摘要:

RSC ANALYTICAL DIVISION THE ANNUAL MEETING on R AND D TOPICS IN ANALYTICAL CHEMISTRY will be held at UMIST on June 26th and 27th, 1984 Papers are invited describing work carried out by postgraduate research students in Universities and Colleges and by young research workers in industrial and other establishments. Contributions are to be presented by the student or his industrial counterpart in a 20-minute lecture. There will also be a poster session in which work can be exhibited and discussed. Those who wish to attend or who have any queries about the meeting should write to the Secretary of the Analytical Division, Royal Society of Chemistry, Burlington House, London, WIV OBN. FEDERATION OF EUROPEAN CHEMICAL SOCIETIES EUROANALYSIS V Cracow, Poland, August 2631,1984 The Scientific Programme of this conference will consist of plenary lectures, keynote lectures and contributed papers and posters as well as special sessions on Computer Based Analytical Chemistry (COBAC I l l ) and Speciation in Trace and Environmental Analysis. The plenary lecturers will be Yu. J. Belyaev, R. E. Dessy, D. Jagner and H. W. Nurnberg, while the keynote lecturers will be J. Buffle, P. Camus, K. Doerfel, Z. Hippe, J. F. K. Huber, T. K. Kantor, R. Kellner, W. E. van der Linden, G. Mouvier and G. Nickless. Abstracts of papers and posters should besubmitted by January 16th, 1984, so that persons wishing to contribute should write immediately to Euroanalysis V, Professor Zygmunt Kowalski, Academy of Mining and Metallurgy, Al. Mickiewicza 30, 30-059 Cracow, Poland.

ISSN:0144-557X    

DOI:10.1039/AP98421FX001

出版商:RSC    

年代:1984

数据来源: RSC

摘要:

2 HONORARY PUBLICITY SECRETARY’S COLUMN Anal. proc., vol. 21 Honorary Publicity Secretary’s Column Conference Format There has been a trend, in recent years, towards the inclusion of a large number of poster presentations at scientific conferences. It has been suggested that the undesirable features of posters can outweigh their advantages, and in view of the fact that the organising committee for SAC 86 (20-25 July, 1986, at Bristol University) is just starting to function, views on the subject of posters at conferences are requested. It would also be of interest to receive views on alternative conference formats such as more streams, shorter oral presentations, more extensive use of preprints, etc. Publications Although the proportion of papers submitted from UK authors to The Analyst remains high, the Editorial Board would like to see still more good papers from the UK, in addition to a good selection from abroad.A special issue of The Analyst containing some of the papers presented at SAC 83 will be published in March 1984. The possibility of collecting the articles concern- ing various aspects of the history of analytical chemistry, published over the years in Analytical Proceedings, into a single volume is being considered by the RSC. The sales of Annual Reports on Analytical Atomic Spectro- scopy have declined slightly. This extremely valuable publication is highly recommended to anyone using analytical atomic spectroscopy of any kind. The modest outlay is easily recovered in saved time and effort and represents only a small fraction of the annual running costs of an atomic spectrometer.The Third Edition of “Official and Standardised Methods of Analysis” will be published in 1984 or 1985. And at the other end of the analytical spectrum, the second book in the RSC series of “paperbacks” will be entitled “Analytical Chemistry” and is to be written by a well known Honorary Publicity Secretary. Meetings and Conferences The February Divisional meeting (on the 8th at the Scientific Societies Lecture Theatre) will concern “The Analysis of Surface Coatings and Raw Materials.” “The Analyst in Court” and the Theophilus Redwood lec- ture, given by Dr. R. L. Williams, are to be seen and heard at the RSC Annudl Congress, April 16th-l9th, in Exeter. While on the subject of Exeter, a meeting in honour of Professor Bishop is to be held there in April 1985, featuring contributions from Professor Bishop’s former students.Such former students are invited to contact the Programmes Secretary, Dr. D. 1. Coomber (via Miss Hutchinson). Professor Bishop remains in the news as he is to present the first L. S. Theobald Lecture, commemorating L. S. Theobald’s long and distin- guished service as a teacher in Analytical Chemistry. This lecture will be given at the Research and Develop- ment Topics meeting, June 26th-27th, at UMIST. This last meeting provides an excellent opportunity to discover the most recent analytical topics being researched in British Polytechnics and Universities. Contributions from younger research workers in industry and Government service are also welcomed. The Divisional AGM and Biennial Formal Dinner will take place in London on March 2nd, 1984, and will feature the retiring President’s address.Future Divisional meetings will include: September 18th-20th, 1984, RSC Autumn Meeting in Hull, AD Symposium on Pharmaceutical Analysis; October, 1984, half-day meeting on Laser Applications; Decem- ber, 1984, Process Control Analysis; and February, 1985, Modified Electrodes. The Scottish Region celebrates its 50th Anniversary in 1984 and is planning a popular lecture to celebrate the occasion. The next in the series of “Flow Analysis” conferences, the third, is scheduled for Birmingham from September 5th-8th, 1985, immediately prior to the IUPAC Congress in Manchester. RSC Awards The Analytical Reactions and Analytical Reagents award (sponsored by BDH Chemicals) has been award- ed to Professor D.T. Burns and the Chromatography and Separations award (sponsored by Whatman) to Professor J. H. Purnell. The Rank Hilger Spectroscopy prize rules are to be revised to allow slightly older candidates to be nominated. Publicity and Public Relations The glossy brochure on Analytical Chemistry, aimed at school students, has been produced and distributed widely throughout Regional and Group membership, teacher centres, etc. Copies can be obtained on request from the Honorary Publicity Secretary. There are still available a small number of the Education and Training Group’s newspaper “Education and Training News,” which was presented at SAC 83. Again these are available free of charge from the Honorary Publicity Secretary. The Schools Lecture programme is well under way and the lecture “Analytical Chemists Make Light Work” will be given at least once in every Region during the 1983/4 session. The lectures will be organised in conjunction with a local student chemical society andor chemistry teachers centre as appropriate. J. F. TYSON

ISSN:0144-557X    

DOI:10.1039/AP9842100002

出版商:RSC    

年代:1984

数据来源: RSC

ISSN:0144-557X    

DOI:10.1039/AP98421BX003

出版商:RSC    

年代:1984

数据来源: RSC

摘要:

January, 1984 CHROMATOGRAPHY - MASS SPECTROMETRY 13 Chromatography - Mass Spectrometry in the Environmental and Life Sciences The following are summaries of six of the papers presented at a Joint Meeting of the Scottish Region, Chroniatographj. and Electrophoresis Group and Joint Pharmaceutical Analysis Group held on March 1st and b n d , 1983, at the University of Edinburgh. The suniniaries are preceded liy a brief note of other features of the meeting by Prof. C. J. W. Brooks.14 CHROMATOGRAPHY - MASS SPECTROMETRY Anal. Proc., Vol. 21 Meeting Note The three scientific sessions included a total of nine lectures, together with two periods occupied by concurrent discussion seminars. The group of speakers included a distinguished visitor from overseas, Professor Karl Ballschmiter of the Department of Analytical Chemistry, University of Ulm, Federal Republic of Germany.The seminars proved very successful, the liveliest interest being elicited by environmental topics and by considerations of modern techniques in sanipling, purification, chromatography and mass spectrometry. Professor Ballschmiter dealt with sample preparation for capillary GC - MS, and participants appreci- ated the chance to draw upon his unique expertise in the analysis of almost every class of organic pollutant. Dr. J. D. Baty’s seminar dealt with the applications of stable isotope-labelled analogues of drugs as internal standards for quantitative analysis and in the study of metabolic pathways. Environmental analysis by GC - MS was discussed in the seminars conducted by Dr.B. Brookes and Mr. S. J. W. Grigson, while microbore LC - MS was the topic in Dr. D. E. Games’s session. Dr. S. J. Gaskell gave a lucid exposition of the analytical capabilities of the various combinations of scanning modes available in modern mass spectrometry systems. i n a Plenary Lecture, Professor C. J. W. Brooks (University of Glasgow) surveyed the role of GC - &IS in the analysis of bio-organic samples, with emphasis on the practical differentia- tion of closely similar compounds. Examples included (i) the selective analysis of tetra- chlorodibenzo-$-dioxins having two chlorine substituents in each benzo ring, based on efficient GLC and on the ion of m / z 176 [C,H,Cl,O,]-• produced via chemical ionisation using oxygen as reagent gas; (ii) the difficulty of distinguishing between sterols with certain structurally or stereochemically isomeric side-chains ; and (iii) the value of appropriate derivatives, and of chemical ionisation, for the characterisation and sensitive detection of prostaglandins and of tlironiboxane B,.The theme was further exemplified by studies in Glasgow in collaboration with Professor T. D. 1’. Lawrie and Mr. J. MacLachlan (Department of Medical Cardiology) on the identification of sterol epoxides in blood plasma. Mr. S. J. \IT. Grigson (Institute of Offshore Engineering, Heriot-Watt University) surveyed the practice and usefulness of analyses of hydrocarbons in marine sediments, exemplified by determinations of triterpanes, steranes and alkylated arenes as indicators of the occurrence and source of oil pollution.Fast atom bombardment (FAB) mass spectrometry was discussed by Dr. R. Large (hl-Scan, Bucks) ; the value of the technique in structural investigations on large biological molecules was well illustrated with reference to peptides, leukotrienes, bleomycins and fungal elicitors of yolygalacturonic acid types, these last compounds yielding molecular ions above nzjz 2 000. Studies on De-acetylation - Re-acetylation Reactions Using Stable Isotopes J. D. Baty, R. G. Willis and Yoke Khim Koh Depavtmepit of BLoclLewical JIedicLrie, iYbnewells Hospital alzd ,IIedLcal Scliool, Dundee, DD1 9SY Acetanailide (see Fig. 1) is largely metabolised in man and other species to paracetamol (see I;ig. 2 ) , which in turn is escreted into the urine as conjugates.Recent work has shown that in a rat liver niicrosomal system the de-acetylation of acetanilide to produce aniline was the major metabolic reaction.’ These iiz i~itvo data would appear to correlate with the in viilo metabolism of acetanilide only if, after de-acetylation, the aniline was re-acetylated to acetanilide. This would have to be a rapid reaction relative to aromatic oxidation. possible metabolic scheme is shown in Fig. 1 . If acetanilide labelled in the acetyl group with deuterium were to be de-acetylated and re-acetylated prior to or after its conversion to paracetamol, the product of this re-acetylation would contain an NHCOCH, group owing to re-acetylation by acetyl-CoA. Consequently, from an inspection of the mass spectra of the residual acetanilide and the paracetamol produced in the reaction, the extent of de-acetylation followed by re-acetylation can be observed.U’e have investigated this reaction in the rat and in man.January , 1984 CHROMATOGRAPHY - MASS SPECTROMETRY NHCOCH3 (CD3) NHCOCH3 (CD3) I 1 Oxidation 1 De-acetylation Acetylation NHCOCH3 I +(j OH I OH YHCOCHj Acetylation ,f+ OH NHCOCH3 I 15 OH 1 2 Fig. 1. Metabolism of acetanilide to aniline and The deuteriomethyl derivative paracetamol in the rat. was used as a substrate in these experiments. An experiment was carried out with ‘three substrates, trideuterioacetanilide, trideuterio- phenacetin and trideuterioparacetamol (Fig. 2). NHCOCD3 4 Deuterioacetanilide NHCOCD3 NHCOCD3 OCzH5 OH Deuteriophenacetin Deuterioparacetamol Fig.2. Substrates for in vivo de-acetylation experi- ments in the rat and man. Two male Wistar rats were used for each experiment with a different substrate. They were given an oral dose (100 mg kg-l) of the substrate and urine was collected over a 24-h period. The urine was hydrolysed and extracted with ethyl acetate as previously described.2 The two forms of acetanilide and the two forms of paracetamol were monitored by GC - MS as their TMS ethers2 and the aniline produced was measured by HPLC., A male volunteer also ingested 50 mg of trideuterioacetanilide and on a separate occasion 50 mg of trideuterio- phenacetin. Urine was collected for the next 8 h and treated as described above. Results None of the substrates showed any exchange of the label in the phosphate buffer (pH 5.4).Any removal of the NHCOCD, group would thus be due to metabolism. We were able to show that in the rat extensive de-acetylation occurred followed by re-acetylation. Table I shows the results of the experiment with trideuterioacetanilide, and Table I1 shows the amount of re-acetylation that occurred with the three substrates. With phenacetin we were unable to monitor the parent compound owing to its rapid metabolism. The amount of re-acetyla- tion of trideuterioacetanilide differed from the amount occurring in the product of oxidation , i . e . , paracetamol. This suggests that the aniline that is produced is oxidised to p-amino- phenol, which is then acetylated to paracetamol. This additional source of re-acetylation would explain the difference in the results between the two compounds.16 CHROMATOGRAPHY - MASS SPECTROMETRY TABLE I Anal.PYOC., Vol. 21 I N V I vo METABOLISM OF TRIDEUTERIOACETANILIDE IN THE RAT Amounts are reported as pmoles in a 24-h urine sample. [ZH,]Acetanilide Acetanilide [ZH,]Paracetamol Paracetamol Aniline Rat 1 .. 1.5 0.6 64.1 37.6 12.7 Rat 2 .. I .4 0.7 57.4 43.1 13.6 In man we observed only a small percentage exchange of acetyl groups (approximately 10%). It may be important to monitor this reaction in people who are fast or slow acetylators of drugs, as the accumulation of amines resulting from de-acetylation reactions may be potentially hazardous. TABLE I1 EXTENT OF DE-ACETYLATION/RE-ACETYLATION FOUND IN THREE DEUTERIATED SUBSTRATES IN THE RAT Re-acetylated paracetamol, y-, Substrate re-acetylation, % f A j r A 7 Substrate Rat 1 Rat 2 Rat 1 Rat 2 [2H,]Acetanilide .. . . .. 37.0 42.9 28.6 33.3 [2H3]Phenacetin . . . . .. 33.7 32.8 - - [ H, ] Parace tam01 .. .. 6.4 8.9 - - References 1. 2. 3. Carlson, G. P., Dziezak, J . D., and Johnson, K. M., Res. Commun. Chem. Pathol. Pharmacol., 1979,25, Baty, J . D., and Robinson, P. R., Biomed. Mass Spectrom., 1976, 3, 60. Sternson, L. A., and Dewitte, W. J . , J . Chromatogr., 1977, 137, 305. 181. Complementary Role of Mass Spectrometry in the Chromatographic Analysis of Environmental Samples K. Ballschmiter Department of Analytical Chemistvy, University of Ulm, Ulm-Donau, Federal Republic of Germany Environmental science deals with multi-matrix and multi-component problems and mostly with concentrations of the looked-for components in the microgram/gram or nanogram/gram range.Outstanding examples of organic trace analysis with environmental samples are the determinations of polychlorobiphenyls (PCBs) or polychlorodibenzodioxins (PCDDs) in a broad spectrum of matrices; 209 single PCB components are possible and about 100 can be found in technical formulations and in the envir0nment.l Seventy-five polychlorodibenzo- dioxins are possible and four are of particular interest owing to their extreme toxicity. Environmental analysis is further complicated by abiotic and biotic degradation in the environment. However specific a determination can be made in mass spectrometry, the basis of any analytical scheme for environmental samples is a set of separation steps.2 The depletion of the matrix alone requires a well designed sequence of separations.The combination of a highly effective mode of separation, especially high-resolution gas chromatography, with a highly specific mode of detection makes the combination of gas chromatography (GC) with mass spectrometry (MS) extremely appealing for environmental analysis. The availability of open-tubular columns of fused silica has removed the psycho- logical barriers often connected with capillary gas chromatography and has made possible theJanuary, 1984 CHROMATOGRAPHY - MASS SPECTROMETRY 17 optimum interfacing of the gas chromatograph with the mass spectrometer. Either the direct inlet into the source or the so called “open coupling,” where only a defined and constant portion (50-80~0) of the GC effluent is brought into the ion source, are standard designs.The “open coupling” has the possibility of cutting off the solvent peak, which can be a major advantage when injection volumes of 2-5 pl are used to obtain an effective “solvent effect” i n j e c t i ~ n . ~ , ~ Considering the mass spectrometer only as a detector clarifies its operational needs- simplicity in operation and servicability, stability in performance and sensitivity in creating the analytical signal-with respect to the ions to be detected. By early 1983 only two major instrument companies had followed this approach. The type of ion source in the mass spectrometer governs the type of analytical signal with which one can operate, Either electron impact or chemical or negative ion chemical ionisa- tion, owing to the variations in fragmentation pattern and ion yields, gives the basis of the analytical signal.In terms of a GC detector, any ionisation process that gives only a few but typical fragments and high yield is to be preferred; it will give both sensitivity and specificity. Specificity of the detection can be sharply increased by using high-resolution mass spectro- metry, but with a consequent trade-off of sensitivity and stability under the operation conditions, coupled with the high cost of the instrumentation. In most instances it is more reasonable to concentrate the analytical efforts on the chromatographic part of a GC - MS combination than on the resolution of the MS part. Whether a full-scan mode (60-600 a.m.u.) or a multiple-ion mode (4-10 ions) is used in GC - MS depends on the analytical problem.Any structure elucidation of unknowns will require the former mode and any detection or search for expected compounds is best carried out by the latter mode. In either instance one should bear in niind that a peak of 2 s width requires a scan time or sum of dwell times of 0.6 s to ensure reasonable integration. Both modes of )IS operation give three basic types of information: (1) retention time; (2) data regarding the molecular structure; and (3) amount. The first type of information is still often overlooked, although a transformation to retention index can standardise the retention time and add further structural aspects to the analytical information. Quantitation by GC - MS should always operate on the basis of keeping all parameters constant, because only in this way can the inherent systematic errors be regarded as similar in the calibration and the analytical runs.One should keep in mind that any fluctuation in the ion yield can strongly distort the quanti- t a t i ~ n . ~ The use of internal standards can improve the quantitation considerably, or even make it possible. Sensitivity in GC - MS, in addition to requiring optimised functioning of the ion source and the ion separation, includes primarily the structural parameters of the molecules to be investig- ated. Strong molecular ions or fragments such as are obtained with many aromatics clearly give optimum sensitivity. Even with an electron-impact source 1-5 pg of an aromatic com- pound can be detected in the multiple-ion mode.In the scan mode it will require 5-10 ng to give a useful mass spectrum. Negative ion chemical ionisation has detection limits well into the femtogram range, if one uses the right molecules for this demonstration. However, its specificity makes it an even more distorting detector than the electron-capture detector, and it strongly overestimates highly chlorinated compounds. As negative ion chemical ionisation includes chemistry in the gas phase, this can be used to create a structurally defined specificity. One drawback of GC - JIS is often overlooked, namely that molecules with undefined frag- mentation patterns and/or low ion yields are nearly invisible in the GC - MS system. A typical example is the polychlorinated terpene Tosaphene, when using an electron-impact source.One should always bear in mind when using a specific detector such as a mass spectro- meter that it only answers the questions being asked. A more general detector such as the flame-ionisation detector (FID) or even the electron-capture detector (ECD) should be run in parallel in environmental science. The ECD is in general about 50 times more sensitive than an electron-impact source and a corresponding dilution or concentration of the samples has to be carried out. Operating a gas chromatograph with either an FID or ECD in parallel with the GC - JIS combination under identical chromatographic conditions can be extremely helpful with environmental samples. Matrix depletion is a multi-functional separation scheme for environmental samples, and consequently one should push the resolution of the chromatography prior to the detection to18 CHROMATOGRAPHY - MASS SPECTROMETRY Anal.Proc., Vol. 21 its highest possible level. In addition to being sound analytical strategy, it helps to optimise the specificity of the detector. However, both the structural information and the information obtained by the gas chromatograph should be used. The MS detector is an extremely helpful positive identification device in environmental science, whereas most other detectors merely detect the analogy between an unknown and a reference standard. References 1. 2. Zell, M., and Ballschmiter, K., Fresrnius 2. Anal. Chem., 1980, 304, 337. Rallschmiter. K., in Nunisto, L., Editor, “Euroanalysis IV, Reviews on Analytical Chemistry,” AkadCmiai Kiad6, Budapest, and Association of Finnish Chemical Societies, Helsinki, 1982, pp.Grob, I<., and Grob, I<., Jr., J . High Resolut. Chromatogr., Chromatogr. Commun., 1978, 1, 57 and 263. Jennings, W. G., Freeman, It. K., and Roney, T. A., J . High Resolut. Chromatogr. Chromatogr. Schafer, W., and Ballschmiter, I<., Frcsrnius 2. Anal. Chrm., 1983, 315, 475. 139-156. 3. 4. 5. Commun., 1978, 1, 215. Techniques for Improved Quantitative Analysis in Environmental Trace Analysis Using Capillary Gas Chromatography - Mass Spectrometry D. E. Wells DA FS, Freshwater Fisheries Laboratory, Pitlochry Over the past 3 years there has been a considerable growth in the number of reports describing the use of capillary columns, particularly fused-silica columns, for the quantitative GC - MS multi-component analysis of contaminants in environmental samples.’ This has made the use of internal standards (IS) mandatory in any serious quantitative determination.Although this is reflected in most branches of medical science (GC - MS Abstracts, 1980-82; in the Clini- cal Chemistry section 73% of the applications used ISs), the same does not appear to be so for environmental science (GC - MS Abstracts, 1980-82; 10% of these applications use 1%). In keeping with medical science some methods have employed isotopic analogues,192 particularly for tetrachlorodibenzo-P- dioxin (TCDD) and polycyclic aromatic hydrocarbons (PAH) determinations, but clearly this cannot be seriously contemplated on financial or logistical grounds for the extensive multi- coniyonent analyses for both pollutants and metabolites in the environmental field.As one of the main sources of error in quantitative capillary GC - MS, apart from tlie initial sampling, occurs during sample introduction, it is often sufficient to add tlie IS just prior to injection. This laboratory uses GC - MS, GC with electron-capture detection (ECD)3 and high-perform- ance liquid chromatography (HPLC) with ultraviolet (UV)4 and fluorescence detection and samples are often cross-checked by a second method. I t was highly desirable to select ISs that were detectable with as many of these systems as possible, as well as fulfilling the usual criteria of purity and stability.The IS was therefore required (i) to have a similar retention time (R,) but be resolved from its analyte(s), (if) to have a limited number of mass spectral fragments, preferably in/z >120 (above the JIS background) and (iii) to be electron capturing or UV absorbing (and/or to fluoresce). The method of sample introduction was also investig- ated and tlie discrimination experienced in the injection of compounds of differing polarity and volatility was considerably improved by replacing the splitless injector with an on-column injector (OCI). The instruinentation used was a Finnigan 9500 GC, fitted with a split/splitless Grob-type injector, interfaced to a Finnigan 320OF 11s and 6100 Data System. The GC column was 25 m ~ 0 . 2 5 inn1 i.d. fused-silica CP Sil5 (Chroinpak UK, London) and installed from the injector through the interface oven directly into the ion source.The split/splitless injector was used in the splitless mode with 20 ml min-l of helium as the purge gas. The split valve was closed, the sample (1 pl) injected at 260 O C , the injector vented after 45 s and the programme coninienced after 1 niin. An OCI-2 on-column injector [SGE (UK), Milton Keynes] was retrofitted to the Finnigan One of the main problems in this field is the choice of IS.January, 1984 CHROMATOGRAPHY - MASS SPECTROMETRY 19 9500 GC oven top, between the end of the interface oven and the GC oven edge using the manufacturer's recommendations. The sample was introduced into the OCI at ambient temperature, using a syringe with a 0.17 mm i.d. fused-silica needle (SGE) through the pneumatic seal.Following insertion and sealing of the syringe needle the carrier gas pressure was permitted to re-establish (10-20 s) before the sample was injected. The injection time was (1 s for 1-p1 samples and 2-3 s for 2-5-pl samples. On-column Injection Following installation of the OCI system, it was tested with a wide variety of mixtures and found to be superior to the splitless system in sensitivity, sample discrimination and repro- ducibility, particularly for relatively less volatile compounds such as some aromatic amines and sulphonamides. Many of these points have been adequately covered by other w o k e r ~ ~ ~ ~ so that this report is confined to additional information only. Grob6 has reported that up to 8 p1 can be injected over a period of 20 s without harmful effects to the column or to the detriment of the chromatography, particularly for chemically bonded phases. Although this holds true for the GC alone, the upper limit on solvent volume for GC - MS, when the column is interfaced directly into the ion source, is about 5 p1 (the more efficient turbomolecular pumps on newer instruments will handle a greater solvent volume).A summary of results obtained for two more difficult analytes is given in Table I. Ter- butryn, a triazine-based aquatic herbicide, and polychlorinated aminodiphenyl ethers (PADs) were both difficult to quantify using the splitless injector, but showed a marked improvement when introduced via the OCI. 9-Bromoanthracene was used as the internal standard for the determination of terbutryn and decachlorobiphenyl (DCBP) for the PADs.TABLE I COMPARISON OF Determinand Terbutryn .. De-ethylterbutryn PADs . . .. DCBP .. . I INJECTION PRECISION USING SPLITLESS AND ON-COLUMN INJECTORS Coefficient of variation (95%) t 7 OCI Split less Internal NO. of , - - * - - I ,-A-$ mlz standard m/z runs RSN* KPAt RSN* RPAt . . 185 9-Bromoanthracene 256 7 2.3 3.9 1.1 16.6 .. 156 256 7 2.5 5.9 2.6 . . 321 DCBP 500 7 1.6 6.1 2.63 20.7 . . 498 DCBP 500 7 - 2.0 - 6.8 * RSN = relative scan number. t RPA = relative peak area. Following Grab's' detailed descriptions of the solvent effects immediately following injection, most workers have chosen to inject their samples in pentane or hexane around ambient temperatures, which is particularly suitable for the analysis of determinands with a wide boil- ing range or for volatile compounds. However, many pesticide residues and industrial pollut- ants are less volatile, eluting from most columns at higher temperatures (>150 "C).For these analyses a successful alternative approach has been to select both the starting tempera- ture and programming rate as determined by the separation requirements of the analytes. A solvent of the appropriate boiling range, within 20 "C of the initial temperature, is selected (Table 11). This approach has been particularly successful when determining less volatile pollutants using multiple-ion monitoring (MIM) , giving fast analysis times and good precision and separation efficiency. There is, however, one particular disadvantage using high-boiling (>lo0 "C) carriers with direct interface capillary GC - MS, where the solvent is not dumped at the interface stage.After a small number of injections, traces of solvent remain on the inner surfaces of the analyser, increasing the background spectra as the samples are injected. This can be troublesome when using decane if a full mass spectrum, extending below 120 a.m.u., is required or if the20 CHROMATOGRAPHY - MASS SPECTROMETRY TABLE I1 Anal. Proc., Vol. 21 SOLVENT SELECTION FOR DIFFERENT INITIAL GC OVEN TEMPERATURES Final sample solvent B.p./"C Pentane . . . . 36 Hexane . . . . . . 69 Isooctane . . . . 99 Octane . . . . . . 126 Decane .. . . 174 GC oven temperature Injection range/"C at injectionlac 30-50 50 65-80 80 95-1 10 100 120-135 130 170-1 85 180 ions monitored in the MIM mode are coincident with the solvent spectrum. On such occasions a lower boiling solvent such as octane was used.This pumped away rapidly and allowed the normal background subtraction techniques to obtain the spectrum of the eluting chrom- atographic peaks. Choice of Internal Standards During the past 2 years a number of ISs have been incorporated into analytical schemes used at this laboratory.* These now cover the analysis of a large number of persistent pesticide residues and non-volatile industrial pollutants. Most of these compounds are readily available, and to date none has been detected in samples taken from Scottish freshwater, coastal and marine environments. The ISs are listed in order of elution (Table 111) obtained on a 25 m x 0.25 mm i.d.CP Sil fused-silica column and cover the temperature range 80-270 "C. The bromohydrocarbons were chosen to cover the lower temperature range as the lower chlorinated aromatics tend to be more widespread at trace levels in the environment. With the exception of mirex, meth- oxychlor and dechlorane, they all have an aromatic nucleus and an intense molecular ion. The halohydrocarbons also give a choice of ions in the molecular cluster at M + 2, M + 4, etc., depending on the number of halogen atoms, which can be particularly useful when it is necessary to avoid a more intense background ion or co-eluting peak. Of the 15 ISs selected, 10 are suitable for GC - ECD analysis, 13 are UV absorbing and 8 fluoresce.TABLE I11 INTERNAL STANDARDS FOR USE WITH GC - MS, GC - ECD AND HPLC ANALYSIS OF PESTICIDE AND INDUSTRIAL POLLUTANT RESIDUES Internal standard [2H,]Naphthalene . . . . o-Dibromobenzene . . . . 2-Bromonaphthalene . . . . 4-Bromodiphenyl ether . . . . [2H,,]Phenanthracene . . . . 2-Bromofluorene . . . . . . 1,2,3,4-Tetrachloronaphthalene [2H,,]Pyrene . . . . . . 9-Bromoanthracene . . . . [2H,,]Chrysene . . . . . . Methoxychlor . . . . . . [2H12]Perylene . . . . . . Decachlorobiphenyl . . . . Dechlorane . . . . . . Mirex . . . . . . . . Masses selected, lnlz 136 236,238 206,208 248,250 188 244,246 264,266 212 256,258 238 2277 272,2747 264 496,498 261,263 Elution order on CP Sil5,* k GC - ECD 3.49 - 3.98 + 10.34 + 18.72 + 21.31 - 26.09 + 28.43 + 32.85 - 33.33 + 44.07 - 45.99 + 47.56 + 55.23 - 57.31 + + - HPLC UV + + + + + + + + + + + + + - - HPLC - + + + + + + + fluorescence - - - - - + - - * Injected a t 100 OC, then programmed at 2 0C min-'.t Base peak is not the molecular ion. Multiple Internal Standards Most analyses reported to date involving ISs have used a single compound, the response of which is related to all eluants in the chromatograph. This has certainly been sufficiently accurate for most isothermal analyses on packed columns and short run times (about 10 min)January, 1984 CHROMATOGRAPHY - MASS SPECTROMETRY 21 using capillary chromatography. However, for multi-component analyses normally associ- ated with capillary columns one IS does not always cover the whole chromatographic range with similar precision.This has been reported by Sauter et aL9 in the analysis of priority pollutants and is further confirmed in this work. A study was completed for a mixture of mothproofing agents currently being determined in this laboratory. In recent years dieldrin has been replaced by Eulan WA New, which has a series of polychlorinated sulphonamidodiphenyl ethers (PCSDs) as active ingredients and a corresponding amine (PAD) as an impurity and as a primary metab~lite.~ Subsequently a series of cis,trans-permethrin-based mothproofers were also marketed. As effluents containing these products were discharged to the same catchment it was desirable to quantify most of these residues in a single chromatogram. Dieldrin, PADS and perrnethrin occur in the same clean-up eluate and were analysed together with TCN, mirex and DCBP as ISs.The results of the reproducibility at two series of concentrations are given in Table IV. The solvent used was decane with 1 pl injected at a column temperature of 80 O C , held for 1 min, followed by programming at 2 “C min-l. The peak areas and scan times were measured and ratioed against each of the three internal standards, in turn. Both the relative scans (relative retention time) and the peak areas exhibit the same trends. The precision of the measure- ment declines as the analyte and IS are separated by an increasing time margin. TABLE IV REPRODUCIBILITY OF PEAK SCAN NUMBER AND AREA FOR MOTHPROOFING AGENTS WITH DIFFERENT INTERNAL STANDARDS Coefficient of variation (95%) Mass on col u nin / Compounds in elution order ng inlz Tetrachloronaphthalcne (TCS) .. 0.1 266 Dieldrin . . . . . . . . 2.0 277 Mirex . . .. .. . . 0.5 272 PADS . . . . .. . . 2.0 321 I’erme thrin . . . . . . 0.2 183 Decachlorobiphenyl (DCBP) . . 2.0 496 0.5 10.0 2.5 10 1 .0 10 r - ’lC9 T---A-- 7 n I<SK* IWAt 7 IS IS 7 IS IS 7 2.9 10.5 7 5.6 7 4.0 9.4 7 3.9 7 4.2 17.8 7 6.8 7 2.0 28.6 7 10.1 7 4.0 12.5 7 13.3 Mirex -A-7 I<SN* l<J?At 4.1 9.6 5.4 0.8 14.0 7.6 IS IS IS IS 0.4 22.0 8.9 1.0 37.8 12.3 1.5 12.8 15.3 DCBP +--7 I<SN* RPAt 4.1 14.8 11.4 1.0 13.2 19.5 1.4 12.6 13.6 1.6 13.2 6.1 0.6 32.4 8.8 IS IS IS IS * I<SX =: relative scan number. t HSA : relative peak area. Conclusions Following the retrofit of the on-column injector to the GC - MS system, superior quantitative results were obtained compared with the splitless injector, particularly for less volatile, non- polar herbicides and pesticides.The final sample solvent can be selected on the basis of the desired chromatography, giving shorter analysis times and minimum delay between injections. The precisions in peak retention timesand areas are markedly improved by the use of multiple internal standards tliat elute within a 10-min time window of the analyte. Many of the internal standards selected can be used with GC - MS, GC - ECD and HPLC with C\’ and fluorescence detection. References 1 .. 131-ooks, C. J . I\‘., liditor, Gas C‘hromatogvafihy - .Wuss Spectvometvy Abstracts, 1980-82, Volumes 11-13, P I t M Science arid Technology Agency, London. 2. Sorlvicki, H. G., I)c\.inc, I ( .I:., ant1 liietla, C. .I., i n \-ail Hall, C. I:., Iiditov, “Mcasurcmcnt of Organic I’ollutants in \\’atcr :inti \\-astc \\‘atcr,” .ISl.lI S‘l1’ 686, I\mcrican Society for Testing and Mater- ials, T’hilatlclphia, lYi!), pp. 1.70-1.51.22 CHROMATOGRAPHY - MASS SPECTROMETRY Anal. Proc., Vol. 21 3. 4. 5. 6. 7. 8. 9. Wells, D. E., and Cowan, A. A, Analyst, 1981, 106, 862. Wells, D. E., and Johnstone, S. J., J . Chvomatogr. Sci., 19'81, 137. Watanabe, C., Tomita, H., Sato, K., Masada, Y., and Hashimoto, K., J . High. Resolut. Chromatgr. Chromatgr. Commun., 1982, 5 , 630. Grob, K., J . HigJt Resolut. Chromatgr. Chromatgr. Commain., 1978, 1, 263. Grob, I<., J . High Resolut. CJwomatgr. Chrotnatgr. Commun., 1978, 1, 57. Wells, D. E., Anal. Pvoc., 1980, 17, 116.Sautcr, A. D., Betowski, L. D., Smith, T. R., Strickler, \'. X., Beimer, K. G., Colly, B. N., and Wilkin- son, J . E., J . HigJz Resolttt. Clivonzatgr. Chvotnatgr. Commun., 1981, 4, 366. Sampling and Gas Chromatography - Mass Spectrometry Analysis of Polar Volatile Organic Pollutants B. 1. Brookes Regional Chemist's Departwient, StvatJiclyde Regional Council, 8 Elliot Place, Glasgow. G3 8E J Water-insoluble Compounds Determinations for volatile water-insoluble compounds (benzene, chloroform, decane, etc.) can be achieved routinely a t parts per lo9 concentrations in both air and water. - I n the simplest methods for air analysis, the air is drawn through a tube containing Tenax GC,I-3 Porapak Q1*4 or graphitised carbon black (GCB) ,5 and, subsequently, the adsorbed compounds are transferred on to the gas chromatography (GC) column by thermal desorption.More powerful adsorbents such as activated charcoal6 are also used but require greater manual dexterity as milligram amounts of the adsorbent and microlitre volumes of extraction solvent must be employed if high recovery efficiencies and high concentration factors are to be obtained. The total cryogenic sampler of Penkett et aL7 is the most elegant technique for the very volatile compounds. I t ensures lOOq/, sampling efficiency and has the greatest freedom from artefacts . Adsorption tube techniques have also been applied to water analysis by bubbling a pure, inert gas through the sample and trapping the vapours in a sample tube.8~~ Water-soluble Compounds Impressive results are obtained for water insolubles with comparative ease and chemists have been tempted to use these same techniques for the water-soluble compounds such as methanol, methylamine and formic acid.However, problems ensue: GCB and Tenax GC, in keeping with their low retention of water vapour, show poor retention of water-soluble com- p o u n d ~ . ~ * ~ Porapak Q, a more powerful adsorbent, can be used for acids and neutrals,'JO although the retention volumes are st+H much less than those of the water-insoluble compounds of similar volatility. Activated charcoal is not generally recommended for water solubles, and the total cryogenic sampler, as developed so far, is unsuitable as the water solubles remain in the water film that has condensed on the walls of the sample vessel.Attempts have been made to use the gas-phase stripping technique for water-soluble compounds in water," but the inherent difficulties of this approach have not been effectively overcome. Vt'hereas the water insolubles can be analysed on an)' non-polar or semi-polar capillary column, different columns are necessary for the different types of water-soluble compounds. Also, as any device suitable for sampling wa ter-soluble compounds will also sample some water, the GC column must be chosen to withstand repeated injections of water. It is therefore a mistake to use the procedures for water insolubles as a starting place for the development of methods for the water solubles. Instead, consideration should first be given to the chemical properties of the compounds.-4 good example of where this has been done is the method of Peters12 for the concentration of volatile water-soluble compounds in water. The sample is heated in a flask and the vapours rise up a short fractionating column to a micro-Soxhlet device built inside a condenser. The system is allowed to come to equilibrium, when 800, of the compound will have been transferred into the Soshlet trap and a concentra- tion factor of sel-era1 liundred achieved. As an alternative to the method of Peters, acids can be concentrated in water samples by There are also problems with the chromatography of water-soluble compounds.January, 1984 CHROMATOGRAPHY - MASS SPECTROMETRY 23 rendering 10 ml of the sample 0.01 N alkaline and reducing the volume by a factor of 100 to 0.1 ml.Bases can be similarly concentrated after rendering the sample 0.01 N a~idic.1~ The equivalent technique for air samples ought to be the condensate sampler, but it can suffer from poor trapping efficiency and consequently other, less general techniques are also employed. Table I gives a summary of the air sampling methods and the analytical procedures. Appropriate combinations of these methods permit most volatile compounds to be analysed in almost any atmosphere or water. Very reactive compounds are an exception as they must be converted into stable derivatives by the sampling technique. The less volatile water- soluble compounds, such as nicotine, also present problems. They can be adsorbed on fine particles in air1* and a specialised sampling device must be used.TABLE I ANALYTICAL TECHNIQUES AND AIR SAMPLING PROCEDURES Limitations of Compound type GC column Air sampling method sampling method* Water insolubles Non-polar' or Tenax G P 3 V semi-bolar capillary Water-soluble neutrals Polar capillary or Chromosorb loll Acids Bases Capillaryls or Chromosorb 101' Triton X-100 - KOHL Chromosorb 102 - KOH17 or KOH-modified capillary'* Activated charcoals GCB5 Porapak Q4 Total cryogenic7 Porapak Ql Silica geP5 Condensate' Porapak Q1 Condensate Alkali bubbler'5 Condensatel Silica gel'5*'* Acid bu bbler13 9 l7 v, w v, w V LV W MA W * The letters indicate that the sampling method is unsuitable for certain compounds or atmospheres as follows: V = very volatile compounds, e.g., methane; LV = less volatile compounds, e.g., naphthalene; W = very wet atmospheres; MA = atmospheres rich in mineral acids such as sulphur dioxide.It is usually preferable to select an analytical technique that permits full scan monitoring, as it provides the most comprehensive data. However, selective ion monitoring (SIM) has the advantage of greater quantitative accuracy and the ability to distinguish co-eluting compounds. The packed columns in Table I may sometimes produce poor results if water- insoluble compounds are co-eluting with water sohbles. This particular problem can be overcome, without resort to capillary columns or SIM, by using a sampling procedure which distinguishes the two types of compound. Fig. 1 shows two analyses for the minor organic components in landfill gas using a Chromosorb 101 column.The first chromatogram was obtained from a Porapak Q sample and most of the alcohols have their analyses impaired by fluorocarbons and hydrocarbons that are also present. In the second chromatogram the interferences have been eliminated by analysing only the aqueous phase of a condensate sample of the same gas. Whatever type of column is used it is generally advantageous to operate at as high a temperature as possible to avoid condensation of water at the head of the column.' With mass spectrometric detection it may also be necessary to restrict the end of the column, or use make-up gas. Derivatisation should be avoided for the analysis of volatiles in environmental samples. This saves the analyst from having to make assumptions about the type of compound he is looking for ; environmental samples are sufficiently complex without the unnecessary addition of reactive chemicals.The analytical methods in Table I give linear calibration graphs for injections in the range 1-100 ng. Water-soluble compounds can therefore be measured by GC - MS at parts per lo9 levels in both air and water. The techniques are simple, but attention must be given to the choice of sampling or concentration method that will suit both the type of compound to be measured and the analytical procedure. For atmospheric samples it must also suit the type of atmosphere.24 CHROMATOGRAPHY - MASS SPECTROMETRY Anal. Proc., Vol. 21 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. (6) w c- i, a I 50 100 150 Temperature/’C Fig.1. Minor components of a landfill gas analysed on a 1 m x 2 mm i.d. 80-100 mesh, Chromosorb 101 column, monitoring m/z 22-220. (a) Porapak Q sample; and (b) aqueous phase of a condensate sample. Peaks: B, = butan-1-01; B, = butan-2-01; D = diethyl ether; E = ethanol; P, = propan-1-01; Pz = propan-2-01; and W = water. References Brookes, B. I., and Young, P. J., Talanta, in the press. Brown, R. H.. and Purnell, C. J., J. Chromatogr., 1979, 178, 79. Pellizzari, E. D., US Environmental Protection Agency, Report Number EPA-600/2-79-057, National Roe, A. B., J . Inst. Water Eng. Sci., 1982, 34, 118. Ciccioli, P., Bertoni, G., Brancaleoni, E., Fratarcangeli, R., and Bruner, F., J. Chromatogr., 1976, 126, Grob, K., and Grob, G., J. Chrornatogr., 1971, 62, 1. Penkett, S.A., Prosser, N. J. D., Rasmussen, R. A., and Khalil, M. A. K., J. Geophys. Res., 1981, 86, Fed. Reg., 1979, 44, No. 233, 69532. Grob, K., Grob, K., Jr., and Grob, G., J. Chrornatogr., 1975, 106, 299. Brookes, B. I., Jickells, S. M., and Nicolson, R. S., J. Assoc. Public Anal., 1978, 16, 101. Ramstad, T., and Nestrick, T. J., Water Res., 1981, 15, 375. Peters, T. L., Anal. Chem., 1980, 52, 211. Mosier, A. R., Andre, C. E., and Viets, F. G.. Jr., Environ. Sci. Technol., 1973, 7 , 642. Brookes, B. I., and Forbes, G. F., Environ. Health Scotl., 1981, 11, No. 4, 12. “NIOSH Manual of Analytical Methods,” US Government Printing Office, Washington, DC, 1983. Hrivnac, M., Sykora-Cechova, L., and Muller-Aerne, M., J. High Resolut. Chromatogr. Chromatogr. Kuwata, K., Yamazaki, Y., and Uebori, M., Anal.Chem., 1980, 52, 1980. Becher, G., J. Chromatogr., 1981, 211, 103. Technical Information Service, US Dept. of Commerce, Springfield, VA, 1979. 757. 5172. Commun., 1981, 4, 323. Microbore Liquid Chromatography - Mass Spectrometry and its Analytical Potential David E. Games, Nicholas J. Alcock and Mark A. McDowaII Department of Chemistry, University College, P.O. Box 78, Cardiff, CF1 1XL Microbore Liquid Chromatography There is considerable current interest in the use of smaller bore columns for high-performance liquid chromatography (LC).1-3 The types of column in use range from packed microbore columns of 0.25-2 mm i.d.4-12 to o p e n - t u b ~ l a r ~ ~ - ~ ~ and packed capillary column^^^^^^ with inner diameters less than 100 pm.Use of smaller bore columns requires modification of the injection, pumping and detection systems used for conventional LC. In addition, specialised techniques are required for the production of suitable columns. These problems are much less formidable if microbore columns are used and suitable injectors, pumps, columns and detectorsJanuar-y , 1984 CHROMATOGRAPHY - ,MASS SPECTKOMETRY 25 are commercially available. The requirements for columns of this type are that the injection volumes should be 1 pl or less, the pumps should be capable of operating down to 10 p1 min-1 and the cell volume of the detector should be of the order of 1 pl or less. Currently the best columns appear to be made from glass-lined stainless stee16s7 or but PTFE10 and fused-silica11J2 columns have also been used.Packing technology has not yet been fully developed and most columns are packed with 10-pm material. A major advantage in using microbore LC is the considerable reduction in solvent costs that can be obtained, e.g., use of a 250 x 1 mm i.d. column with a flow-rate of 50 p1 min-l results in a 9504 reduction in solvent consumption compared with a 250 x 4.5 mm i.d. column with a flow-rate of 1 ml min-l. This means that the use of unusual, expensive solvents can be contemplated for difficult separations, e g . , optically active or deuteriated20 solvents. Other advantages include the obtaining of high plate numbers by connecting columns in series, which can be advantageous when complex mixtures are being studied. The small peak volumes obtained in microbore LC result in increased mass sensitivity with concentration-sensitive detectors.Thus, for the same amount of sample injected on to both a 4.6 and a 1 mm i.d. column, the detector response for the peak eluting from the microbore column is of the order of 20 times greater than that eluting from the conventional column. Finally, because of the lower flow-rates used with microbore columns, coupling of a liquid chromatograph with a mass spectrometer can be undertaken without the necessity to split off some of the column eluent which is necessary with some types of interface. A problem with microbore LC is that there is a decrease in the volume and amount of sample (of the order o f 1 pl and 10 pg, respectively) which can be injected on to the column without affecting chromatographic performance. The first problem can be overcome by the use of pre-column concentration techniques2 and the latter by use of column-switching techniques.21 Combined Liquid Chromatography - Mass Spectrometry (LC - MS) ,4 variety of methods for combining a liquicl chromatograph with a mass spectrometer have Currently three approaches been developed and the area has been extensively ~-eviewed.~~-~~ appear to have particular merit, as follows.Direct Liquid Introduction With this approach a portion of the effluent from the liquid chromatograph is fed into the mass spectrometer ion source where the solvent acts as a chemical ionisation (CI) reagent gas for ionising the solute molecules. Early systems suffered from problems due to blocking of the capillary inlet when low-volatility compounds were being examined.These problems have been 0verconie~8-~~ by use of cooled probes with a membrane having a hole of 1-5 pm diameter, which enables efficient nebulisation of the LC eluent to occur. A second important feature is the incorporation of a desolvation chamber and finally cryogenic pumping is of considerable assistance in handling some polar mobile phases. A potential ability to handle mass spectrometrically very difficult molecules has been shown with the recent obtaining of a negative CI spectrum of vitamin B12.32 It should be noted, however, that the obtaining of on-line LC - )IS data is not as easy as obtaining spectra of samples just introduced in solu- tion. There are many impressive examples of the use of this type of interface in the litera- t ~ r e .~ ~ The main drawbacks are that only a portion of the LC effluent can be handled if conventional LC columns are used, solvents have to be carefully purified and often solvent systems developed for a particular separation cannot be used because they fail to give good CI spectra (this can be a particular problem when gradient elution is used), finally, only CI mass spectral information is obtained. The latter is not necessarily a problem for many types of stud)., C.R. , quantitative studies and additional structural information can be obtained by use of collision induced dissociation with double or triple quadrupole instrument^.^**^^ On the positi\re sick is the lack of thermal decomposition of thermally labile compounds at low levels, wliich has been demonstrated with commercial interfaces of this type.Moving Belt Systems \\'it11 interfaces of this type the effluent is fed on to a continuously moving belt made of Kapton. Solvent is remo\.ed by a heater and in two vacuum locks and the solute is flash vaporised into the mass spectrometer ion source where either electron impact (EI) or CI26 CHROMATOGRAPHY - MASS SPECTROMETRY Anal. Proc., Vol. 22 spectra can be obtained. Three commercial systems are available, two of which enter directly into the mass spectrometer ion ~ o u r c e , ~ ~ ~ ~ ~ and the other is interfaced to the ion source block.38 Two of the system^^^.^^ exhibit very similar behaviour in terms of their ability to handle com- pounds and are suitable for handling compounds that are amenable to direct insertion probe mass spectrometric study.However, problems are encountered owing to thermal decom- position of thermally labile compounds at low levels. The third system3’ is superior in its ability to handle compounds and enables the range to be extended to those compounds which can only be handled by desorption chemical i o n i ~ a t i o n . ~ ~ Systems of this type exhibit good retention of chromatographic integrity and their ability to provide both E I and CI data has proved to be very effective in the identification of known and unknown compounds. They have been extensively used for the solution of a wide range of problems and their utility and problems encountered in their use have recently been reviewed.40 Initial problems in handling aqueous reversed mobile phase systems have now been largely overcome and with recent improvements in detection levels using microbore LC41 this type of interface is ideal for qualita- tive studies of compounds which fall within the ionisation range mentioned earlier.Thermospray Ionisation and Liquid Ion Evaporation As a result of studies of LC - MS using molecular beam techniques a new method for the ionisation of low-volatility compounds which can be introduced into the mass spectrometer in ionic form has been developed.42 The liquid chromatographic effluent passes through a 0.015 mm i.d. stainless-steel tube which is embedded in an electrically heated copper block, a supersonic jet of vapour is produced which traverses the ion source of a mass spectrometer and enters a 1 cm diameter pumping line which is connected to a 300 ml min-1 mechanical vacuum pump.A conical ion exit aperture is connected to the ion source and a high-capacity source heater is embedded in the ion source cavity. The system produces ions without the ion source filament being on but can also be used with it on to produce solvent induced CI spectra. The system has been shown to be capable of providing mass spectral data from a wide range of difficult molecules, c.g., underivatised peptides, nucleotides and vitamin B,,, and impressive sensitivities have been demonstrated with on-line LC - MS of nucleosides. Unlike the other systems described, this type of interface is capable of handling 2 ml min-1 of water.A system based on this approach has recently become commercially available from Finnigzin-MAT and it appears to be the method of choice for handling low-volatility com- pounds that can be ionised in solution. Liquid ion evaporation is a similar technique to thermospray ionisation in that it is an extremely effective technique for handling compounds that are introduced into the mass spectrometer in ionic form.43v44 This technique has been used for LC - MS with an atmos- pheric pressure ion (.\PI) source. Ions that are present in liquid solution are emitted into the .API source bjr use of a strong electric field. In general (SfH)+ or (JI-H)- ions are formed with little fragmentation ; lwwwr, use of collision-induced dissociation with a triple quad- rupole instrument enables further structural information to be obtained.This technique has not yet been as fully developed as thermospray ionisation for LC - 31s but shows consider- able promise for handling low-volatility ionic compounds. Microbore LC - MS Although this approach appears to have little advantage for the third of the approaches to LC - SIS, it has considerable advantages for interfaces of the first two types. The advan- tages with interfaces of the direct liquid introduction type are immediately apparent in that if flow-rates of the order of 20 pl niin-l are used all of the eluent from the LC can be fed into the mass spectrometer ion source, resulting in considerable improvements in detection levels measured in terms of sample injected on-column. One of the problems with this type of interface is that some loss of chromatographic performance occurs unless the column is directly in the interface and special interfaces have to be designed.45 Jlicrobore LC has been used exte~isively~l+-~~ with interfaces of this type and with interfaces of the jet5” and vacuum nebulisingj8-61 types.Although interfaces of the moving belt type are capable of handling higher solvent flow-rates than those of the direct liquid introduction type, problems can be encountered through thermal decomposition or steam distillation of sample at the high temperature required in the infraredJanuary, 1984 CHROMATOGRAPHY - MASS SPECTROMETRY 27 heater to handle high percentage aqueous mobile phases and there are additional problems due to solvent beading on the belt if systems containing over 50% of water are used.Use of a nebulising system to spray sample on to the belt is one solution to the p r ~ b l e m . ~ ~ , ~ ~ Micro- bore LC provides an equally effective ~ o l u t i o n . ~ ~ ~ ~ ~ Our initial studies21 in this area used a JASCO microbore LC system which uses 0.5 mm i.d. PTFE tubing for columns. We were able to develop efficient methods for packing columns of this type, but their performance did match those of conventional columns. However, we were able to show that use of this approach enables better detection limits to be achieved in terms of sample.injected on-column, as with aqueous mobile phases all the column's effluent could be fed on to the interface without the necessity to split off some of the solvent as occurs with conventionalcolumns. In addition, by feeding ethanol on to the belt behind the eluent from the microbore column, high percentage aqueous mobile phases could be readily handled. Recently we41 have explored the use of commercially available glass-lined stainless-steel and stainless-steel columns of 1 mm i.d.and packed with 10-pm material. These columns give considerably improved chromatography equivalent to that obtained from conventional columns packed with similar material. The approach has been used in studies of pesticides and natural products and has also been used with gradient elution64 to study extracts from test well samples taken from landfill sites. In addition to the benefits mentioned earlier by increasing the flow-rate, microbore LC enables fast analysis and flow programming to be per- formed with interfaces of the moving belt type.This type of study would necessitate splitting of some of the column effluent with interfaces of the direct liquid introduction type. Conclusions Microbore LC provides an effective means of reducing solvent costs, improving detection limits and separating complex mixtures. It provides improved detection limits with LC - MS interfaces of the direct liquid and moving belt types and in the latter instance enables aqueous mobile phases to be more effectively handled. Combined LC - MS is currently in a fluid state, interfaces of the moving belt and direct liquid introduction types are effective for handling a wide range of compounds but systems of the thermospray and liquid ion evaporation types appear to be the methods of choice if low- volatility ionic compounds are being investigated.However, use of surface ionisation tech- niques with moving belt systems may also be effective in this area.37 There appear to be five clearly defined areas for LC - MS : (1) compounds that are amenable to gas chromatographic study but are analysed by LC because it is more efficient ; (2) compounds that are thermally labile and decompose on gas chromatography (GC) or do not have sufficient volatility for GC but are amenable to direct insertion probe mass spectrometry ; (3) compounds amenable only to mass spectral study by desorption CI; (4) compounds amenable only to mass spectral study by field desorption, fast atom bom- (5) compounds not currently amenable to mass spectral study.Compounds of classes 1-3 are amenable to study by systems of the direct liquid introduction, moving belt and thermospray types. However, it should be noted that not all systems of the first two types fall into this category. The choice of system depends on the type of study being undertaken. If it is of a qualitative nature then the belt systems appear to have advantages in that they provide data that can be readily compared with those in the literature or computer library to establish identification. However, if compounds are being studied where there is considerable variation in relative amounts problems could occur owing to thermal decomposition of the compounds present in small amounts and the thermospray or direct liquid introduction approach would appear to be preferable.For class 4 and ionic com- pounds thermospray ionisation appears to be the method of choice, although liquid ion evaporation may be equally effective or better but remains to be fully proven. Use of belt systems with surface ionisation may have an application in this area and there are some indications that direct liquid introduction may also be used. Class 5 awaits further develop- bardment or californium-252 plasma desorption ; and28 CHROMATOGRAPHY - MASS SPECTROMETRY Anal. Proc., VoZ. 21 ment in mass spectral instrumentation-the limitations here are not necessarily in the ionisa- tion methods but in the capabilities of mass spectrometers in providing data from molecules of high relative molecular mass.N. J.A. and M.A.M. thank the Analytical Trust Fund of the Royal Society of Chemistry and the SERC and Beecham Pharmaceuticals, respectively, for financial support. We thank the Royal Society and SERC for financial assistance in the purchase of liquid chromato- graphic and mass spectrometric equipment. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. References Novotny, M., Anal. Chem., 1981, 53, 129A. Knox, J. H., J. Chromatogr. Sci., 1980, 18, 453. Guiochon, G., Anal. Chem., 1981, 53, 1318. Scott, R. P. W., and Kucera, P., J. Chromatogr., 1976, 25, 251; 1979, 169, 51; 1979, 185, 27. Scott, R. P. W., J.Chromatogr. Sci., 1980, 18, 49. Ryall, R. R., and Kessler, Jr., H. D., Int. Lab., 1982, June, 68. Tsuji, K., and Binns, R. B., J. Chromatogr., 1982, 253, 227. Vadukul, N. K., and Loscombe, C. R., J. High Resolut. Chromatogr. Chromatogr. Commun., 1982, 5, Hermansson, J., Chromatographia, 1981, 4, 43. Ishii, D., Asai, K., Hibi, K., Jonkuchi, J., and Nagaya, M., J. Chromatogr., 1977, 144, 157. Yang, F. J., J. Chromatogr., 1982, 236, 265. Ishii, D., and Takeuchi, T., J. Chromatogr., 1983, 255, 349. Novotny, M., J. Chromatogr. Sci., 1980, 18, 473. Tsuda, T., Hibi, K., Nakanishi, T., Takeuchi, T., and Ishii, D., J. Chromatogr., 1978, 158, 277. Hibi, K., and Ishii, D., J. Chromatogr., 1980, 189, 179. Ishii, D., and Takeuchi, T., J. Chromatogr. Sci., 1980, 18, 462. Tijssen, R., Bleumer, J.P. A., Smit, A. L. C., and Van Kreveld, M. E., J. Chromatogr., 1981, 218, 137. Yang, F. J., J. Chromatogr. Sci., 1982, 20, 241. McGuffin, V. L., and Novotny, M., J. Chromatogr., 1983, 255, 381. Jinno, K., J. High Resolut. Chromatogr. Chromatogr. Commun., 1982, 5, 364. Games, D. E., Lant, M. S.. Westwood, S. A., Cocksedge, M. J., Evans, N., Williamson, J., and Wood- Arpino, P. J., and Guichon, G., Anal. Chem., 1979, 51, 682A. McFadden, W. H., J. Chromatogr. Sci., 1979, 17, 2; 1980, 18, 97. McFadden, W. H., Anal. Proc., 1982, 19, 258. Games, D. E., Anal. Proc., 1980, 17, 110 and 322. Games, D. E., Biomed. Mass Spectrom., 1981, 8, 454. Games, D. E., in Morris, H. R., Editor, “Soft Ionization Biological Mass Spectrometry,” Heyden, Melera, A., Adv.Mass Spectrom., 1980, 8B, 159. Arpino, P. J., and Guiochon, G., J. Chromatogr., 1979, 185, 529. Arpino, P. J., Krien, P., Vajta, S., and Devant, G., J. Chromatogr., 1981, 203, 117. Arpino, P. J., and Guiochon, G., J. Chromatogr., 1982, 251, 153. Dedieu, M., Juin, C., Arpino, P. J . , and Guiochon, G., Anal. Chew., 1982, 54, 2375. Edmonds, C. G., McCloskey, J. A., and Edmonds, V. A., Biomed. Mass Spectrom., 1983, 10, 237. Henion, J. D., Thomson, B. A., and Dawson, P. H., Anal. Chem., 1982, 54, 451. Voyksner, R. D., Hass, J. R., and Bursey, M. M., Anal. Lett., 1982, 15, 1. Millington, D. S., Yorke, D. A., and Burns, P., Adv. Mass Spectrom., 1980, 8B, 1819. Dobberstein, P., Korte, E., Meyerhoff, G., and Pesch, R., Int. J. Mass Spectrom. Ion Phys., 1983, 46, McFadden, W.H., Schwartz, H. L., and Evans, S., J. Chromatogr., 1976, 122, 389. Games, D. E., McDowall, M. A., and Levsen, K., unpublished work. Alcock, N. J., Eckers, C., Games, D. E., Games, M. P. L., Lant, M. S., McDowall, M. A., Rossiter, M., Alcock, N. J., Corbelli, L., Games, D. E., Lant, M. S., and Westwood, S. A., Biomed. Mass Spectrom., Vestal, M. L., Int. J. Mass Spectrom. Ion Phys., 1983, 46, 193. Thomson, B. A., Iribarne, J. V., and Dziedzic, P. J., Anal. Chem., 1982, 54, 2219. Shushan, B., Fulford, J . E., Thornson, B. A., Davidson, W. R., Danylewych, L. M., Ngo, A., Nac- Brophy, J. J., Nelson, D., and Withers, M. K., Int. J. Mass Spectrom. Ion. Phys., 1980, 36, 205. Henion, J. D., and Maylin, G. A., Biomed. Mass Spectrom., 1980, 7 , 155. Henion, J. D., J.Chromatogr. Sci., 1981, 19, 57. Henion, J. D., and Wachs, T., Anal. Chem., 1981, 53, 1963. Eckers, C., Skrabalak, D. S., and Henion, J.. Clin. Chem., 1982, 28, 1882. Eckers, C., Henion, J . D., Maylin, G. A., Skrabalak, D. S., Vessman, J., Tivert, A. M., and Greenfield. J . C., Int. J . Mass Spectrom. Ion Phys., 1983, 46, 205. 360. hall, B. J., Biomed. Mass Spectrom., 1982, 9, 215. London, 1981, p. 54. 185. Smith, R. W., Westwood, S. A., and Wong, H.-Y., J. Chromatogr., 1982, 251, 165. 1982, 9, 499. son, S., and Tanner, S. D., J. Mass Spectrom. Ion Phys., 1983, 46, 225.January, 1984 CHROMATOGRAPHY - MASS SPECTROMETRY 29 51. 52. 53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. Schafer, K. H., and Levsen, K., J . Chromatogr., 1981, 206, 245. Levsen, K., and Schafer, K.H., Int. J . Mass Spectrom. Ion Phys., 1983, 46, 209. Yanianchi, E., Mizuno, T., and Azuma, K., Shibak Shitsuryo Bunseki, 1980, 28, 227. Krien, P., Devant, G . , and Hardy, M., J . Chromatogr., 1982, 251, 129. Okada, S., and Iida, Y., Shibak Shitsuryo Bunseki, 1981, 29, 287. Bruins, A. P., and Drenth, B. F. H., Int. J . Mass Spectrom. Zon Phys., 1983, 46, 213. Takeuchi, T.. Hirata, Y., and Okumara, Y., Anal. Chem., 1978, 50, 659. Tsuge, S., Hirata, Y., and Takeuchi, T., Anal. Chem., 1979, 51, 166. Yoshida, Y., Yosida, H., Tsuge, S., Takeuchi, T., and Mochizuki, K . , J . High Resolut. Chromatogr. Chromatogr. Commun., 1980, 3, 16. Tsuge, S., Yoshida, Y., Takeuchi, T., Mochizuki, K., Kokubun, N., and Hibi, I<., Chem. Biomed. Environ. Instrum., 1980, 10, 405.Yoshida, H., Matsumoto, K., Itoh, K . , lsuge, S., Hirata, Y., Mochizuki, I<., Kokubun, N., and Yoshida, Y., Fresenius 2. Anal. Chem., 1982,311, 674. Smith, R. D., and Johnson, A. L., Anal. Chem., 1981, 53, 739. Lankmayr, E. P., Hayes, M. J., Karger, 13. L., Vouros, P.,and McGuire, J . M., Znt. J . Mass Spectrom. Foster, M . G . , Meresz, O., Games, D. E., Idant, M. S.,and Westwood, S. A., Biomed. Mass Spectrom., Ion Phys., 1983, 46, 177. 1983, 10, 338. Analysis of Endogenous and Exogenous Compounds in Tumour Tissue by Gas Chromatography- High-resolution Mass Spectrometry Simon J. Gaskell, Heather M. Leith and Brian G. Brownsey Tenovus Instztute for Cancer Research. Welsh Natzonal School of Medicine, Heath, Cardig, CF4 4XX The mechanism of action of natural oestrogens, in common with other steroid hormones, is now considered to involve binding to a specific cytosol receptor protein, transformation of the steroid - receptor complex and translocation to the nucleus.Interaction with the chroma- tin stimulates RNA and DNA synthesis and ultimately promotes protein synthesis and normal cell function and growth. Synthetic anti-oestrogens, now widely used in the treatment of breast cancer, are thought to exert their beneficial effect, at least in part, by sequestering the receptor but failing to elicit a full oestrogenic response. Study of natural oestrogens and synthetic drugs requires a knowledge of circulating concentrations and of the levels achieved in target tissues. The concentrations of oestrogens in blood plasma are low (generally in the pg ml-1 range) and, of this total, only a small proportion is non-protein bound and hence physiologically active.A direct measure of this fraction is obtained by analyses of saliva where the concentrations of oestradiol-17/3, for example, rarely exceed 20 pg ml-I. According- ly, the analyses of natural and synthetic compounds which bind to the oestrogen receptor are particularly demanding in terms of both sensitivity and selectivity. While analyses based on gas chromatography - mass spectrometry (GC - MS) are clearly of great potential for such studies, considerable attention must be given to achieving specificity during both sample work-up and mass spectrometric detection. Sample Work-up Procedures \.\'ork-up procedures where fractionations are based on criteria different from those which apply during GC - 11s characterisation are particularly beneficial.Anion-exchange chromatography, for example, may be used to exploit the weak acidity of the natural oestro- gens (and synthetic oestrogens such as diethylstilboestrol) attributable to their phenolic structure. The use of triet hylammoniohydroxypropyl-Lipidex 5000 was developed by Axelson and Sjovalll and has been applied to the analysis of oestrogens in urine, saliva2 and tissue3 extracts. Fractionation on a single micro-column in sequential reversed-phase, straight-phase and ion exchange modes provides a rapid separation and high degree of sample purification. Cation-exchange chromatography, using sulphoethyl-Sephadex LH-20,4 has been applied to the isolation of the basic anti-oestrogenic drug tamoxifen from extracts of plasma5 and tissue.6 An alternative procedure for the isolation of natural oestrogens is provided by the use of solid-phase coupled antisera.Immunoadsorption, a technique borrowed and adapted from the immunoassaJ-ist, permits the direct extraction of selected analytes fiom a biological fluid or fractionation of tissue extracts. Table I gives the extraction efficiencies, from blood plasma,30 CHROMATOGRAPHY - MASS SPECTROMETRY Anal. Proc., Vol. 21 of various steroids using an oest radiol-l7/3 antiserum coupled to microcellulose and compares the cross-reactions determined conventionally according to the Abraham criteria.’ A typical immunoadsorption procedurea incorporates addition of a suspension of the solid-phase coupled antiserum to the biological fluid, brief incubation, followed by centrifugation and washing of the solid phase with buffer and water.The analyte and coextractants are recovered by methanol stripping, after which the coupled antiserum is available for re-use. The extremely rapid technique is valuable primarily because the stereochemical discrimination implicit in its use complements the subsequent GC - MS characterisation. TABLE I EXTRACTION EFFICIENCIES OF STEROIDS FROM PLASMA USING A CELLULOSE-COUPLED ANTI-OESTRADIOL-17fl SERUM, AND COMPARISON WITH THE CROSS-REACTIVITIES OF THE LIQUID ANTISERUM Data from Teference 8. Steroid Extraction efficiency,* :(, Cross-reaction,? yo Oestradiol-17fi . . .. .. .. .. 81 100 Oestrone .. .. .. .. .. .. 65 24 Oestriol . . .. . . .. .. .. 53 9.5 Testosterone . . .. .. .. .. 3 (0.1 Dehydroepiandrosteroiie . . .. .. . . 3 (0.1 Cortisol . . .. .. . . .. . . <1 - * Extraction of 3H-labelled steroid from 0.5 nil of plasma using 0.5 nil of a suspension of solid-phase-coupled t Determined according to the --\braham criteria,’ with an antiserum dilution of 1 : 150 000. antiscruni a t a dilution of 1 : 100. GC - MS Characterisation and Quantification The sensitivities required for analysis of many steroid hormones and drugs in body fluids and tissues dictate the use of selected ion monitoring (SIM) techniques during GC - MS. The implicit neglect of most of the features of the mass spectrum of the analyte may lead to un- certainty of compound identification and various approaches may be taken to enhance the selectivity of detection.High sensitivi- ties and selectivities have been reported in favourable cases using negative chemical ionisation (CI),s although the exploitation of the technique in the biomedical area is at an early stage. The use of halogenated derivatives estends the range of application of negative CI in the electron-capture mode. Thus, for example, oestradiol-17p bisheptafluorobutyrate may be detected at the low picograni level during GC - negative CIlIS/SIlI of (M-HF)- ions. The use of high 11s resolution during SIJIlO represents a technique of general applicability to increase selectivity of detection. Signal intensities are necessarily reduced but the useful sensitivity, defined as the signal to noise ratio observed during the analysis of biological samples, niay actually be increased owing to the reduction in “chemical noise.’’ The superior selectivity has been demonstrated in analyses of, itttcv d i n , oestradiol-17/3 in blood plasma8 and testosterone in prostatic tissue.ll GC - high resolution W3/SIJl has been used in analyses of the anti-oestrogen taniosifen in blood plasma5 and tumour tissue6 of treated breast cancer patients. The quantitative data were shown to be consistent with the hypothesis of the mechanism of action of the drug as a coinpetitor to oestradiol-17/3 for binding to the oestrogen receptor. More recent studies of the concentrations of the three “classical” oestrogens (oestrone, oestradiol-17/3 and oestriol) in human breast tuniours have further illustrated the value of the high resolution technique. Concentrations are generally low, with levels of oestriol, for example in the range 0-500 pg g-1 in tissue. Netastable peak monitoringllJ2 provides an experimentally simple, although less widely applicable, alternati1.e to high-resolution SIN. ,in appropriate choice of derivative has an important bearing on the sensitivity achie\?ed. -4nalyses of steroids in both tissue and plasma samples have been reported. Further enhancement of selectivity is dependent on an im- proved resolution of the parent ion beam. This may be achieved using one of the recently described configurations of the multiple analyser mass spectronieter ; the value of such instruments in biochemical trace analysis, however, has yet to be demonstrated. The most attractive of these is selective ionisation.January, 1984 EQUIPMENT NEWS The support of the Tenovus Organisation is gratefully acknowledged. 31 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 1 1 . 12. References Axelson, M., and Sjovall, J., J . Steroid Biochem., 1977, 8, 683. Gaskell, S. J., Finlay, E. M. H., and Pike, A. W., Biomed. Mass Spectrom., 1980, 7, 500. Axelson, M., Clark, J. H., Eriksson, H., and Sjovall, J., J . Steroid Biochem., 1981, 14, 1253. Setchell, K. D. R., AlmC, B., Axelson, M., and Sjovall, J., J . Steroid Biochem., 1976, 7, 615. Daniel, C. P., Gaskell, S. J., Bishop, H., and Nicholson, R. I., J . Endocrinol., 1979, 83, 401. Daniel, C. P., Gaskell, S. J., Bishop, H., Campbell, C., and Nicholson, R. I., Eur. J . Cancer CEin. OncoE., Abraham, G. E., J . Clin. EndocrinoZ. Metab., 1969, 29, 866. Gaskell, S. J., and Brownsey, B. G., Clin. Cham., 1983, 29, 677. Markey, S. P., Lewy, A. J., and Colburn, R. W., in De Leenheer, A. P., Roncucci, R. R., and Van Peteghem, C., Editors, “Quantitative Mass Spectrometry in Life Sciences, 11,” Elsevier, Amster- dam, 1978, p. 17. 1981, 17, 1183. Millington, D. S., J . Steroid Biochem., 1975, 6, 239. Gaskell, S. J., Finney, R. W., and Harper, M. E., Biomed. Mass Spectrom., 1979, 6, 113. Gaskell, S. J., and Millington, D. S., Biomed. Mass Spectrom., 1978, 5, 557.

ISSN:0144-557X    

DOI:10.1039/AP9842100013

出版商:RSC    

年代:1984

数据来源: RSC

摘要:

January, 1984 EQUIPMENT NEWS 31 Equipment News Software for X-ray Diffraction New search - match software for the PW 1700 X-ray diffraction system allows the user to create his own reference files. The software can record the number of times that each file has been accessed. Pye Unicam Ltd., York Street, Cambridge, CB12PX. Digital Cassette Recorder for X-ray Diffraction The PM 4202 can be used with the PW 1710 controller - processor to enable many different data baqks to be dumped on cassette tape or selected data banks to be read from tape. Pye Unicam Ltd., York Street, Cambridge, CB12PX. Colour-measurement Software Based on the PU 8800 ultraviolet -visible spectrophoto- meter, the new software for the HP85 computer is available on tape and disc. It provides measurement of colour or colour difference in up to three modes- diffuse or total reflectance and transmission.The system conforms to the requirements of the CIE. Pye Unicam Ltd., York Street, Cambridge, CB12PX. Spectrophotometer The Shimadzu UV120 single-beam instrument is avail- able in both ultraviolet - visible and visible only versions. It is supplied with a four cell sample compart- ment. Available accessories include recorders, thermo- statted systems and the SFU sipper-type flow cell system with a sample size of less than 500 PI and an automatic waste system once the reading has been taken. V. A. Howe & Co. Ltd., 12-14 St. Ann’s Crescent, London, SW18 2LS. Extended Systems for Spectrophotometry Three optional units are available for the Shimadzu UV240 ultraviolet - visible instrument.The OPI-1 and OPI-2 permit operations between measured data and memorised data, allowing subtraction, division and differentiation of spectra. They allow derivation of spectra to any order between first and fourth of stored or real time data. The OPI-3, used with an auto-flow cell and sipper system, gives a completely automated analysis system. V. A. Howe & Co. Ltd., 12-14 St. Ann’s Crescent, London, SW18 2LS. Infrared Spectrophotometer The Shimadzu 408 features a double beam optical system with optical null method, a built-in chart recorder with automatic pen lift, three-stage light source intensity adjustment and adjustable amplifier gain. A range of accessories is available. V. A. Howe & Co. Ltd., 12-14 St. Ann’s Crescent, London, SW18 2LS. Spectrofluorimeter The SFM 25 has a double beam optical system and pre-programmed method files.Four wavelength modes are available-fixed, excitation scan, emission scan and synchroscan. Kontron Instruments Ltd., P.O. Box 88, St. Albans, Hertfordshire, ALl 5JG.32 EQUIPMENT NEWS Anal. Proc., Vol. 21 Spectrophotometer for Environmental Monitoring The Scintrex AAZ-2, designed to analyse trace metals from 10-2Opl samples, is suitable for measuring the effects of acid rain in the field and in the laboratory. Techmation Ltd., 58 Edgware Way, Edgware, Middlesex, HA8 8JP. HPLC Resins A range of resins, consisting of finely sized spherical beads, can be used with water and most organic solvents. Their stability is such that a 4% cross-linked cation and neutral resin can operate at about 1 OOO lb in-2 pressure without bead deformation.The 8% cross-linked resins have been used at about 8 OOO lb in-2. Field Instruments Co. Ltd., 1-5 Baker Street, Wey- bridge, Surrey, KT13 8AE. Syringes Hamilton lo00 series chemically inert gas-tight syringes have a tested accuracy and reproducibility of k 1 YO and have been found to lose less than 3plh-1 at 7 atmospheres. V. A. Howe & Co. Ltd., 12-14 S t . Ann's Crescent, London, SW18 2LS. The Shimadzu-CS 930 'has a data processor and fast recording functions. .it features dual wavelength s m - ning, zig - zag scanning, working curve linearisation and background cornxtion. V. A. Howe & Co. Ltd., 12-14 S t . Ann's Crescent, London, SW18 2LS. Thin-lraw C M o g r a p k y Scan- Conductivity M&ers A range of meters is availahk.The Radiometer CDM83 autoranging instrument measures conductivity from 1.3pScm-1 to i300rnScm-1. The PHM $3 is an autocalibrating pH meter. The CDM 80 is a battery or mains power4 meter measuring from 0.01 yS cm-1 to 200mSc~1-~. There is a PHM 80 pH meter. The 2Q51 conductivity meter has a triple range from 0 to 19.99mS accurate to within 1.5%. V. A. Howe & Co. Ltd,, 12-14 St. Ann's Crescent, London, SW18 2LS. Digital Titration System The Radiometer DTS 833 can be used for all 'types of titration, including selective ion. It can titrate to one, two or more end-points, detect and .printout data for very weak end-points, deliver titrant automatically and titrate whea the end-point potential varies. It can also slow down titrant delivery as the end-point is approachd V.A. Howe & Co. Ltd., 12-14 St. Ann's Crescent, London, SW'18 2LS. pH and Temperature Meter The PHM 9 measures pH from 0 to 14 pH, with a resolution of 0.1, and has a direct temperature measure- ment range from -40 to + 150 "C with 1 .O "C resolution. It features lockable buffer control, allowing caiibration at the start of a day's use. Jenway Ltd., Gransmore Green, Felsted, Dunmow, Essex, CM6 3LB. Infrared Thermograph The Insight 80 series instrument, based on the pyroelec- tric videcon detector, provides thermal pictures on a TV screen in standard PAL 625 line format in the 8-14 pm infrared .band. The system is battery operated. Micron Infrared Systems Ltd., Foster House, Max- well Road, Borehamwood, Hertfordshire, WD6 1JB.PertaMe Muttimeter Tke MPM 2000 system measures temperature, relative humidity, rev min-1 and windspeed. By plugging in different Modumeters it can measure pH, oxygen, pressure, conductivity, etc. Solomat SA, 8 Finnimore Estate, Ottery St. Mary, Devon . Thermal Analysis Instrumentation A range of thermal analysis equipment from Mettler consists of the new FP800 series and the TA3000, which includes a thermal analysis computer containing a data handling software package. A series of application briefs is available. MSE Scientific Instruments, Manor Royal, Crawley, Sussex, RHlO 2QQ.January, 1984 EQUIPMENT NEWS 33 Interface for Particle Size Analysis SediComp, a computer-to-SediGraph interface, is designed to allow any SediGraph 5000ET to be adapted to Apple 11+ and Apple IIe microcomputers.The package includes Apple PC boards, master programme discs, connecting cable and user manual. Micromeritics Instrument Corporation, 5680 Goshen Springs Road, Norcross, GA 30093, USA. Portable Toxic Gas Detectors The Autostep series of instruments use the principle of colorimetric paper-tape analysis. Available initially as a continuous phosgene monitor, Autostep will soon be available for other gases. SKC Ltd., Hamworthy Trading Estate, Dawkins Road, Poole, Dorset, BH15 4JW. Hydrogen Sulphide Monitor Equipment from the Delphian Corporation for the analysis and monitoring of hydrogen sulphide in aqueous solution employs an electrochemical, pH compensated sensing technique. Auriema Ltd., 442 Bath Road, Slough, Berkshire, SL16BB.Balance The Sauter RE 1614 electronic top-pan balance has a mass range of 0-162 g and a tare range of 0-162 g and is readable to 0.1 mg. It is equipped with the Sauter Trend Display for fast, controlled weighing-in. MSE Scientific Instruments, Manor Royal, Crawley, Sussex, R H l O 2QQ. Ultracentrifuge The L8M system features ultra-smooth induction drive, full microprocessor control and an optional RS 232C port for connection t o a minicomputer for control data storage and processing. Linkage to a mainframe com- puter is also possible. Beckman-RIIC Ltd., Progress Road, Sands Indus- trial Estate, High Wycombe, Buckinghamsbire. Centrifuge The Heraeus Christ Cryofuge 8000 features built-in microprocessor control to give 16 centrifugation pro- grammes.It can achieve 0-835Og with a 6 I capacity within 100s. V. A. Howe & Co. Ltd., 12-14 St. Ann’s Crescent, London, SW18 2LS. Microbial Monitoring System The Bactometer Model 123 system is computer assisted and can test up to 512 samples simultaneously. It can measure conductance, capacitance or impedance changes in samples under test. A graphics programme allows six electrical response curves to be displayed simultaneously. An optional digital plotter is available. Bactomatic Ltd., 1 Newtown Industrial Estate, Newtown Road, Henley-on-Thames, Oxfordshire, RG9 IHG. Multi-channel Analyser A unit based on an Apple microcomputer with pro- grammes written in compiled PASCAL has been devel- oped for applications such as particle size distribution analysis.Lablogic., 72 Eldon Street, Wellington Street Indus- trial Estate, Sheffield, S1 4GT. Automated Quality Control System Developed by Hamilton and Ciba - Geigy, the Amica system is capable of sample preparation, automatic samphg and mixing of liquids in variable ratios. Analysis can be performed by photometry, photometric titration or potentiometric titration. V. A. Howe & Co. Ltd., 12-14 St. Ann’s Crescent, London, SW18 2LS. Interface for LABNET The SP9500 contains the software and input - output ports for interfacing a LABNET inter-instrument com- munications network with a variety of external devices such as VDU terminals, Centronics-type printers and micro- and minicomputers. Spectra-Physics Ltd., 17 Brick Knoll Park, St. Albans, Hertfordshire, AL1 5UF.Chart Recorders A range af recorders includes single- and double-pen units. Chart drive is electronically controlled over 11 speeds between 0.lmmmin-1 and lOmrns-’ in both directions, StaH - stop, chart drive, pen lift and event marker can be controlled remotely. V. A. Howe & Co. Ltd., 12-14 St. Ann’s Crescent, London, SW18 2LS. Literature A brochure describes the DU-6 ultraviolet - visible computing scanning spectrophotometer. Details are given of the range of accessories and in-built computing options. Beckman-REIC Ltd., Progress Road, Sands Indus- trial Estate, High Wyeombe, Buckinghamshire. A catalogue lists certified reference materials used for the calibration of optical emission and X-ray fluores- cence spectrometers for the analysis of metals in industry. BNF Metals Technology Centre, Grove Labora- tories, Denchworth Road, Wantage, Oxfordshire, OX12 9BJ.A brochure describes the APD 3520 microprocessor- based control and measuring system for the maker’s X-ray diffractometers. Philips Electronic Instruments Inc., 85 McKee Drive, Mahwah, NJ 07430, USA.34 AMENDMENTS TO FERTILISERS REGULATIOSS Anal. Pt‘OC., VOZ. 21 A compendium of products for liquid chromatography reviews columns and media, giving guidance on their selection. Uniscience Ltd., 12-14 St. Ann’s Crescent, London, SW18 2LS. An application note describes the determination of sequestering agents by ion chromatography. It includes eight chromatograms, details of sample preparation and instrument conditions, and references. Dionex (UK) Ltd., 1st Floor, The Parade, Frimley, Camberley, Surrey, GU16 5HY. The “Guide to Ion Analysis” explains the different types of available electrodes and the methods for which they can be used. The bibliography contains around 1 OOO references. MSE Scientific Instruments, Manor Royal, Crawley, Sussex, RHlO 2 0 0 . A brochure lists over 20 different types of ion-selective electrode, including solid-state, PVC membrane and gas-sensing devices. NWlO 7LU. EDT Research, 14 Trading Estate Road, London, A catalogue reviews the full range of the maker’s analytical instrumentation, giving details of automation developments in ultraviolet - visible, infrared and atomic-absorption spectrophotometry, chromato- graphy and X-ray emission and electrochemical analy- sis. Pye Unicam Ltd., York Street, Cambridge, CB12PX. A booklet describes a wide range of chromatography fittings. Also available are two dictionaries describing products, instrumentation and techniques for spectro- scopy and chromatography. A catalogue gives full details of porous polymer supports and includes the basic theory of gas chromatography and a glossary of chromatographic terms. Field Instrument Co. Ltd., 1-5 Baker Street, Weybridge, Surrey, KT13 8AE.

ISSN:0144-557X    

DOI:10.1039/AP9842100031

出版商:RSC    

年代:1984

数据来源: RSC

摘要:

34 AMENDMENTS TO FERTILISERS REGULATIOSS Anal. Pt'OC., VOZ. 21 Publications Received Methods for the Examination of Waters and Associated Materials. Standing Committee of Analysts (to Review Standard Methods for Quality Control of the Water Cycle); Department of the Environment, National Water Council. HM Stationery Office. Arsenic in Potable Waters by Atomic Absorption Spectrophotometry (Semi-Automatic Method) 1982. Pp. 17. 1983. Price f2.80. ISBN 0 11 751679 1. Formaldehyde, Methanol and Related Compounds in Raw, Waste and Potable Waters, 1982 Tentative Methods. Pp. 47. 1983. Price f4.10. ISBN 0 11 751690 2. Moiybdenum, Especially in Sewage Sludges and Soils by Spectrophotometry 1982. Pp. 17. 1983. Price f2.80. ISBN 0 11 75 1680 5. Analysis of Rubber and Rubber-like Polymers.Third Edition. W. C. Wake, B. K. Tidd and M. J. R. Loadman. Pp. xiv + 330. Applied Science Publishers. 1983. Price f36. ISBN 0 85334 215 6. Chemical Methods in Gas Chromatography. V. G. Berezkin. Journal of Chromatography Library, Volume 24. Pp. x + 313. Elsevier. 1983. Price $73.25 (USA & Canada); DfI190 (Rest of World). ISBN 0 444 41951 9. This book covers the entire field of reaction gas chromatography. Describing the joint use of chemical and chromatographic methods, its nine chapters cover the following topics: derivatization methods for the preliminary treatment of samples for analysis, kinetic methods, pyrolysis - gas chromatographic methods, determination of the carbon skeleton in organic com- pounds, subtraction methods, use of chemically selec- tive stationary liquid phases in gas chromatography,34 AMENDMENTS TO FERTILISERS REGULATIOSS Anal.Pt'OC., VOZ. 21 Publications Received Methods for the Examination of Waters and Associated Materials. Standing Committee of Analysts (to Review Standard Methods for Quality Control of the Water Cycle); Department of the Environment, National Water Council. HM Stationery Office. Arsenic in Potable Waters by Atomic Absorption Spectrophotometry (Semi-Automatic Method) 1982. Pp. 17. 1983. Price f2.80. ISBN 0 11 751679 1. Formaldehyde, Methanol and Related Compounds in Raw, Waste and Potable Waters, 1982 Tentative Methods. Pp. 47. 1983. Price f4.10. ISBN 0 11 751690 2. Moiybdenum, Especially in Sewage Sludges and Soils by Spectrophotometry 1982. Pp. 17. 1983.Price f2.80. ISBN 0 11 75 1680 5. Analysis of Rubber and Rubber-like Polymers. Third Edition. W. C. Wake, B. K. Tidd and M. J. R. Loadman. Pp. xiv + 330. Applied Science Publishers. 1983. Price f36. ISBN 0 85334 215 6. Chemical Methods in Gas Chromatography. V. G. Berezkin. Journal of Chromatography Library, Volume 24. Pp. x + 313. Elsevier. 1983. Price $73.25 (USA & Canada); DfI190 (Rest of World). ISBN 0 444 41951 9. This book covers the entire field of reaction gas chromatography. Describing the joint use of chemical and chromatographic methods, its nine chapters cover the following topics: derivatization methods for the preliminary treatment of samples for analysis, kinetic methods, pyrolysis - gas chromatographic methods, determination of the carbon skeleton in organic com- pounds, subtraction methods, use of chemically selec- tive stationary liquid phases in gas chromatography,36 lsoenzyme Analysis ANALYTICAL PROCEEDINGS $ Q AIral.Proc., Vol. 21 The Sampling of Bulk Materials by R. Smith and G. V. James The literature of analytical chemistry exhaustively covers the many techniques now available to the analyst. Sampling, the one feature common to all analyses, is in contrast only sparsely documented. Comparatively few original papenon this subject have been published in the last f* years, there are very few reviews available, and perhaps as a result sampling is badly neglected in most instructional courses in analytical chemistry. This Monograph will go some way towards filing a gap in the literature and should stimulate interest in the develop ment of sampling as a field of study.Analytical Sciences Monograph No. 8 Hardcover 200pp 0 85186 810 X Price f18.00 (532.00) RSC Mombers f 11.75 Analysis of Airborne Pollutants in Working Atmospheres: The Welding and., Surface Coatings Industries by J. Moreton and N. A. R . Falla This Monograph covers the following: Part I The Welding Industry; Airborne Pollutants in Welding; Sampling of Welding Workshp Atmospheres; Anal* of Welding Fumes and Pollutant Gases. Part II The Surface Coatings Industry: Origin of Airborne Pollutants in the Surface Coatings Industry; Collection and Analysis of Gaseous Atmospheric Pollutants in the Surface Coatings Industry; Collection and Analysis of Particulate Atmospheric Pollutants in the Surface Coatings Industry; Future Trends Relating to Sampling and Analysts in the Welding and Surface Coatings Industries. Analytical Sciences Monograph No.7 Hardcover 192pp 0 85186 860 6 Price €16.50 (530.001 RSC Members €13.25 Dithizone by H. M. N. H. Irving The author of this monograph, who has been closely associated with the development of analytical techniques using this reagent for many years, and who has made extensive investigations into the properties of its compkxes, has gathered together a body of historical and technical data that will be .of interest to many practising analytical chemists. Analytical Sciences Monograph No. 5 Hardcover 112pp 0 85186 787 1 Price f 13.50 ($24.00) RSC Members f10.50 ORDERING: RSCMemberssharMsendmevordrwsto ChmsDy aSmkmon Cutwe, BleddKwse Roed, Letchwmh.Herts SG6 1HN ~ l z T % $ ~ ~ z A : % ~ & ~ of Chemistry by D W. Moss This monograph attempts to draw together the most important experimental techniques which have resulted from the modern recognition that enzymes frequently exist in multiple molecular forms. This monograph also indicates the advantages and limitations in isoenzyme studies of these modern analytical techniques. & i f Contents: Multiple Forms of Enzymes; Separation of Multiple Forms of Enzymes; Selective Inactivation of Multiple Forms of Enzymes; Immunochemistry of Multiple Forms of Enzymes; Catalytic Differences between Multiple Forms of Enzymes; Methods of Obtaining Structural Information; Selection of Methods of Analysis Analytical Sciences Monograph No.6 Hardcover 171pp 0 85186 800 2 Price f 13.00 (523.00) RSC Members f 10.00 Electrothermal Atomization for Atomic Absorption -71 Spectrometry by C. W. Fuller Since the introduction of atomic absorption spectrometry as an analytical technique, by Walsh, in 1953. the use of alternative atomization sources to the flame has been explored. At the present time the two most successful alternatives appear to be the electrothermal atomizer and the inductively-coupled plasma. In this book an attempt has been made to provide the author's views on the historical develop- ment, commercial design features, theory, practical considerations, analytical parameters of the elements, and areas of application of the first of these two techniques, electrothermal atomization. Analytical Sciences Monograph No.4 Hardcover 135pp 0 85186 777 4 Price f 19.50 (535.00) RSC Members f 14.75 h "-J a f f uary , 1984 CONFERENCES AND MEETINGS 37 application of reaction chromatographic methods of elemental analysis, trace analysis and reaction methods of functional group analysis. Reviews of Infrared and Millimeter Waves, Volume 1. Edited by Kenneth J. Button. Pp. viii + 372. Plenum. 1983. Price $45. ISBN 0 306 41260 8. scopy. Methods of quality assessment of intact biolog- ical samples using research composition analysers oper- ating in the visible region are also covered. Most of the references relate to food and agricultural commodities; relevant papers from a large number of different disciplines are included. Analytical Chemistry of Molybdenum.Gordon A. Parker. Pp. viii + 175. Springer-Verlag. 1983. Price DM98; $40.50. ISBN 3 540 12235 4; 0 387 12235 4. Chapters include Detection, Separations, Gravimetric, Titrimetric and Colorimetric Methods, Emission, AA and XRF Spectroscopy, Voltammetry, Catalytic Methods, Radiochemical and Activation Methods, Rock and Mineral Samples, Molybdenum Alloys, Ferrous and Non-ferrous Alloys, Animal, Plant and Soil Samples and Environmental Samples. Table of Spectral Data for Structure Determination of Organic Compounds. E. Pretsch, T. Clerc, J. Seibl and W. Simon (translated from German by K. Biemann). Pp. ix + 316. Springer- Verlag. 1983. Price DM32; $12.70. ISBN 3 540 12406 3; 0 387 12406 3. I3C NMR, lH NMR, IR and UV - visible spectral data are tabulated for a wide range of organic compounds, with numerous annotations.Heteropoly and Isopoly Oxometalates. Michael Thor Pope. Znorganic Chemistry Concepts, Volume 8. Pp. xiv + 180. Springer-Verlag. 1983. Price DM124; $49.30. ISBN 3 540 11889 6; 0 387 11889 6. Electrophoretic Techniques. Edited by Colin F. Simpson and Mary Whittaker. Pp. x + 280. Academic Press. 1983. Price 226; $44. ISBN 0 12 644480 3. Topics covered in this book are Basic Theory (Rilbe), Molecular Characterisation of Proteins (Whittaker and Simpson), Recent Developments in Isoelectric Focus- ing (Fawcett), Analytical Isoelectric Focusing on Cellu- lose Acetate Membranes and Agarose Thin Layers (Ambler), Ultra-thin-layer Isoelectric Focusing (Rad- ola), Gel Immunoelectrophoresis (Kohn), Analytical Isotachophoresis (Everaerts and Verheggen) , Prepara- tive Isotachophoresis (Simpson and Whittaker), Prepa- rative Displacement Electrophoresis (Hampson), Pre- parative Isoelectric Focusing (Hampson) and Free-Flow Electrophoresis (Thomson). Computer Chromatography, Volume 1. Rudolf E. Kaiser and Anthony J. Rackstraw. Chro- matographic Methods. Pp. viii + 171. Huthig. 1983. Price DM54; $25. ISBN 3 7785 0885 7. A Bibliography of Applications of Near Infrared Reflec- tance Spectroscopy to Food Analysis. Compiled by B. G. Osborne. Pp. 56. Flour Milling and Baking Research Association. 1983. Price f 2 (Mem- bers); f12 (Non-members). ISBN 0 907503 01 2. This comprehensive bibliography contains 483 refer- ences on quantitative analysis by near infrared and mid-infrared transmittance and reflectance spectro-

ISSN:0144-557X    

DOI:10.1039/AP984210034b

出版商:RSC    

年代:1984

数据来源: RSC

摘要:

J a f f uary , 1984 CONFERENCES AND MEETINGS 37 Conferences and Meetings 1984 Pittsburgh Conference and Exposition on Analy- tical Chemistry and Applied Spectroscopy March 5-9, 1984, Atlantic City, NJ, USA The symposium titles of the Technical Programme for this year’s conference, which will be held at the Atlantic City Convention Center, are now available. Among them are the following: New Opportunities in Mass Spectrometry; Sample Introduction for Atomic Spec- troscopy, How Can we Do It Better?; Polymer Charac- terisation; Micropole Techniques as Applied to Organic Materials; New Techniques in Electroanalytical Chemistry; Modern Techniques for Industrial Hygiene Monitoring; Modern Liquid Chromatography; Advan- ced Light Sources; New Horizons in Nuclear Magnetic Resonance; Analytical Techniques Using Supercritical Fluids; Industrial Applications of Surface Analysis; Multi-technique Approaches; Practice of Capillary Col- umn Gas Chromatography; and Integrating Software into Laboratory Systems.For further information contact The Pittsburgh Con- ference Inc., 437 Donald Road, Department 5-024, Pittsburgh, PA 15235, USA. Pyrolysis - GC/MS March 28, 1984, Newcastle upon Tyne This meeting is to be organised by the Chromatography Discussion Group. For further information write to Mrs. J. A. Challis, Chromatography Discussion Group, Trent Polytechnic, Burton Street, Nottingham, NG14BU. Third International Workshop on Trace Element Analy- tical Chemistry in Medicine and Biology April 16-18, 1984, Neuherberg, FRG The GSF and the Working Group on Trace Elements in the Life Sciences of the AGF are to hold this meeting at the GSF Research Centre.The purpose of the work- shop is for analysts and biomedical specialists to discuss biomedical applications of trace element analytical research. The trace analysis of zinc, manganese and selenium will be discussed, together with the analysis of the more newly discovered essential trace elements such as lithium, aluminium, nickel, silicon, vanadium and arsenic. Also under discussion will be the role of trace elements in various states and diseases, including cardiovascular diseases, nephrotic diseases, cancer, pregnancy and early infancy. The programme will consist of invited lectures and short contributed papers. For further information contact Dr. P. Schramel, Phys. Techn.Abteilung GSF, Ingolstadter Landstr. 1 , D-8042 Neuherberg, FRG.COURSES 38 Second International Conference on Chromatography and Mass Spectrometry in Biomedical Sciences June 18-20, 1984, Milan, Italy This conference is being organised by the Italian Group for Mass Spectrometry in Biochemistry and Medicine and will be held in the Lecture Room of the Mediocred- ito Lombardo. Persons attending the conference will be able to discuss all the latest aspects of chromatography, mass spectrometry and chromatography - mass spectro- metry and their areas of application, including bioche- mistry, medicine, toxicology, drug research, nutrition science and food safety, forensic science, clinical chemistry and pollution. The proceedings of the con- ference will be published. For further information contact Dr. Alberto Frigerio, Italian Group for Mass Spectrometry in Biochemistry and Medicine, Via Eustachi 36, 20129 Milan, Italy. ATfaL. Proc., VoL. 21

ISSN:0144-557X    

DOI:10.1039/AP9842100037

出版商:RSC    

年代:1984

数据来源: RSC

摘要:

38 COURSES ATfaL. Proc., VoL. 21 The lecturers have practical experience in the use of humidity and moisture measurement devices and in their application in a wide range of industries. The number of people attending is strictly limited so that the members of the lecturing team can give ample time to questions and problems raised by participants during the lectures and demonstrations. For further details contact Conference Unit, Sira Ltd., South Hill, Chislehurst, Kent, BR7 5EH. Courses Statistics for Industry 1984 Programme The 1984 Workshop programme is now available. The venues will be the University of York and the Cairn Hotel, Harrogate. Details of the courses are as follows: “Introduction and Significance Testing (3 days) ,” Janu- ary 18-20, Harrogate, and September 4-6, York; “Statistics for Analytical Chemists,” February 28- March 2, Harrogate, and September 18-21, York; “Introduction and Significance Testing (Intensive) ,” March 28-29, York, and July 3-4, Harrogate; “Statistics in Research and Development,” April 10-13, York, and October 1619, Harrogate; “Design of Experiments,” May 1-4, Harrogate; “Statistics in Sensory Evaluation,” June 12-15, Harrogate; “Analysis of Abnormal Data,” July 9-12, York; “Statistics in Quality Assurance,” November 13-16, Harrogate.Further details can be obtained from Mrs. B. Robin- son, Statistics for Industry (UK) Ltd., 14 Kirkgate, Knaresborough, North Yorkshire. Moisture Measurement in Solids and Gases: Available Techniques and Applications March 13-14 and November 6-7, 1984, Chislehurst To meet continuing demand, the Sira Moisture Mea- surement course is being repeated. The two-day pro- gramme describes and explains available techniques for measuring the moisture content of gases and solids.It is designed to acquaint engineers with a knowledge of the principles, advantages and limitations, and the range of application, of modern techniques for the measurement of moisture in solids and gases. The course is in three main parts: humidity measurement methods; measure- ment of moisture in solids; and calibration of humidity and moisture meters. Although adequate consideration is given both to humidity measurement (moisture in gases) and measurement of moisture in solids, the latter topic occupies a somewhat larger proportion of the programme. 21st Annual Short Summer Course in X-ray Powder Diffraction June 18-22, June 25-29, 1984, Albany, NY, USA This course will be offered at the State University of New York at Albany.It will be instructional and will develop the basic theory and techniques, starting from elementary principles. No previous knowledge or experience is required. The first week will cover basic principles, techniques and practical applications and the second week will continue with further fundamentals and practical applications. The emphasis in the first week will be on camera and film techniques, X-ray instrumentation, especially the diffractometer and its use, identification of powder patterns, multi-phase identification using several indices and fundamentals of quantitative analysis. The second week will cover more advanced principles and techniques with emphasis on diffractometer alignment, complex quantitative analy- sis, complex powder identifications, computer automa- tion of diffractometers and computer search - match methods.Equal time will be devoted to lectures and laboratory problem solving sessions. A suitable amount of time will be set aside for individual sessions. Registration can be made for one (either) week at a registration fee of $800.00 or for the entire two-week session at a registration fee of $1 500.00, payable in US dollars drawn on a US bank. For further information please communicate with Professor Henry Chessin, State University of New York at Albany, Department of Physics, 1400 Washington Avenue, Albany, New York 12222, USA.21st Annual Short Summer Course in X-ray Spectro- metry June 4-8, June 11-15, 1984, Albany, NY, USA Details of this course are mainly as for the X-ray powder diffraction course described above (including charges). The first week will cover basic principles, techniques and practical applications and the second week will continue with further fundamentals and practical appli- cations. Both weeks will illustrate and employ equally the wavelength-dispersive and energy-dispersive methods. The emphasis in the second week will be placed on advanced principles and techniques, absorption-enhancement corrections by several proce- dures, including mathematical methods, computer cal- culations and computer automation of modern X-ray spectrometers. Equal time will be devoted to lectures and laboratory-problem solving sessions. For further information please communicate with Professor Henry Chessin, State University of New York at Albany, Department of Physics, 1400 Washington Avenue, Albany, New York 12222, USA.

ISSN:0144-557X    

DOI:10.1039/AP9842100038

出版商:RSC    

年代:1984

数据来源: RSC

摘要:

January, 1984 ANALYTICAL DIVISION DIARY Analytical Division Diary 39 FEBRUARY Wednesday, lst, 10 a.m.: London Special Techniques Group, jointly with the Computational Physics Group of the Insti- tute of Physics and the Electronic Image Processing Group of the Institute of Elec- trical Engineers. Imaging Techniques. “Introductory to Digital Image Processing,” by R. J . Clarke. “Applications of Image Processing in NDT,” by S. F. Burch. Processing of Images from Spacecraft,” by K. H. Bagot. “Image Reconstruction from Partial Information ,” by M. A. Fiddy. “Scanning Acoustic, Optical and Optoacoustic Microscopy,” by I. Smith. “Emission and Transmission Tomography,” by N. M. Spyrou. “Molecular Graphics and Modelling,” by D. Fincham. Reed Lecture Theatre, Sherfield Building, Imperial College, London, S.W.7.Registration is necessary. Cost for members of participating bodies f25; f30 for non- members. Contact: Mr. J . Huddleston, Building 10.2, Instrumentation and Applied Physics Divi- sion, AERE, Harwell, Oxfordshire, OX11 ORA. (Tel. 0235-24141, Ex. 2030). Wednesday, 8th, 2 p.m.: London AnalyticaZ Division, in conjunction with the Oil The Analysis of Surface Coatings and Raw Materials. “Techniques Used in the Analysis of Titanium Dioxide Pigments,” by R. C. Hutton. “Plasma Erosion in Ultra Rapid Painting Durability Testing,” by N. A. R. Falla. “Clear and Pigmented Coatings for Conservation and Restoration,” by N. H. Tennent. “Paint Examination-A Forensic Scientist’s View ,” by C. M. Jenkins. “Analysis of Surfaces by Small Area X-ray Photo- electron Spectroscopy,” by R.West. Scientific Societies Lecture Theatre, 23 Savile Row (entrance in New Burlington Place), London, W.l. Registration is necessary. Cost f 2 to members of RSC/OCCA and f 4 to non-members. and Colour Chemists Assocation. Contact: Miss P. E . Hutchinson, Analytical Division, Royal Society of Chemistry, Bur- lington House, London, W1V OBN. (Tel. 01-734-9971). Thursday, 9th, 7 p.m.: Moreton North West Region. A Novel Approach to the Analysis of Anti- biotics. Speaker: R. F. Cosgrove. E. R. Squibb & Sons Laboratories, Reeds Registration is necessary; no charge. Contact: Mr. T. E. Hanley, 5 Old Hall Court, Ashton, Near Chester, Cheshire. (Tel. 0829- 51609). Lane, Moreton, Wirral. Wednesday, 15th, 6.30 p.m.: London Microchemical Methods and Education and Discussion on The Place of Micro- and Trace Analysis in Present-day Teaching.The roles of micro- and trace analysis have evolved in different ways but together they encompass many of the “new” trends in analytical chem- istry. They should obviously form a significant part of present-day teaching, although it can be argued how, when and where this should be done. Speaker: J. A. W. Dalziel. The Savoy Tavern, Savoy Street, London, w.c.2. Contact: Mr. P . R. W. Baker, Department of Physical Chemistry, Wellcome Research Laboratories, Langley Court, Beckenham, Kent, BR3 3BS. (Tel. 01-658-2211, Ex. 357). Training Groups. Wednesday, 15th, 10.30 a.m.: Northampton Automatic Methods Group. Analysis in the Cosmetics Industry. Session I: Avon Cosmetics.Welcoming Address by a representative of Avon Tour of Factory and Laboratory Facilities. “Perfumery,” by A. Moss. Session 11: Analysis in the Cosmetics Industry. Papers will be presented on aspects such as Quality Assurance, Fingerprinting of Essential Oils/ Fragrances, Quality Control of Packaging, etc. [continued on p. 40 Cosmetics Ltd.40 ANALYTICAL DIVISION DIARY Anal. Proc., Vol. 21 Analytical Division Diary, continued February, continued Avon Cosmetics Ltd., Nunn Mills Road, North- ampton, NN15PA. Registration is necessary; numbers limited to 40. No charge. Contact: Dr. C. J. Jackson, Health and Safety Executive, Occupational Hygiene Lab- oratory, 403 Edgware Road, London, NW2 6LN. (Tel. 01-450-8911, Ex. 227). Friday, 17th, 5.15 p.m.: Plymouth Western Region, jointly with the Peninsula Hunting the Snark-Recent Developments in Ultra-sensitive Molecular Spectroscopy.Speaker: J. N. Miller. Chemistry Department, The Polytechnic, Plymouth. Contact: Mr. F. W. Sweeting, Wessex Water Authority, Bristol Avon Division, P.O. Box 95, The Ambury, Bath, BA1 2YP. (Tel. Section of the RSC. 0225-313500, EX. 385). Tuesday, 21st, 4.15 p.m.: Loughborough Midlands Region, jointly with the Lough- borough University Students Chemical Society . Analysis of Mary Rose Treasure by X-ray Fluorescence Spectroscopy. Speaker: E. E. Pitt. Lecture Theatre JOOl, Edward Herbert Build- ing, University of Technology, Lough- borough. Contact: Mr. H. E. Brookes. 35 Dunster Road, West Bridgford, Nottingham, NG2 6JE. (Tel. 0602-23 1769). Wednesday, 22nd, 10 a.m.: Warrington North West Region.Recent Developments and Applications in Ion Chromatography . Introductory Lecture by G. I. Goodfellow. “Total pH Control for Optimised Anion Analysis by Single Column Ion Chromatography,” T. Jupille. “Applications of Ion Chromatography in Chemical Manufacturing,” by A. Westwell. “Some Applications of Ion Chromatography Within the British Gas Corporation,” by L. Anthony and R. P. Mounce. “Recent Applications of Ion Interaction Chromato- graphy with Indirect Detection.” by M. Cooke. “The Use of Ion Chromatography in the North West Region Scientific Services of the CEGB,” by R. M. Donaldson, J. C. Greene, J. Greenhalgh and J. D. Tyldesley. “The Role of Automation as Applied to Ion Chroma- tography in the HSE Laboratories,” by C.J. Jackson and J. Ferrett. “Ion Chromatography-Everybody’s Doing it ,” by M. Masters. Lord Daresbury Hotel, Warrington. Registration is necessary. Cost f20 to RSC members, f22 to non-members and f5 to retired members and full-time Regional stu- dents. Contact: Mr. P. Morries, 2 Rothesay Road, Crumpsall, Manchester, M8 6JA. (Tel. 061- 740-7354). Thursday, 23rd, 4.15 p.m.: Aberdeen Scottish Region, jointly with the Aberdeen and North of Scotland Section of the RSC and the Aberdeen University Chemical Society. Of Mosses, Mussels and Micrograms. Many substances entering the environment from human activities are toxic or can cause sub- lethal disorders at low concentrations. Analy- tical chemists are hard pressed to detect and quantify compounds at these low levels.but the analysis of indicator organisms can provide an early warning about a potential pollution prob- lem. Speaker: G. A. Best. Department of Chemistry, University of Aber- deen, Meston Walk, Aberdeen. Contact: Dr. D. E. Wells, DAFS, Freshwater Fisheries Laboratory, Pitlochry, Perthshire. (Tel . 0796-2060). Tuesday and Wednesday, 28th and 29th: Edin- burgh Scottish Region, Chromatography and Electro- phoresis, and Joint Pharmaceutical Analysis Groups, jointly with the Association of Clinical Biochemists. Advances in Chromatography: Pharmaceutical and Clinical Applications. Tuesday 28th- Session I: Microbore Chromatography. “Is Microbore Necessary?” by Professor J . H. Knox. “The Application of Narrow-bore HPLC to Drug [conrinued on p. 41 Analysis,” by R.Gill.January, 1984 ANALYTICAL DIVISION DIARY 41 Analytical Division Diary, continued February, continued “Analysis of Biological Samples Where ‘Microbore’ Seminars I (see list of topics below). Sherry Reception and Conference Dinner, George HPLC is Necessary,” by R. Oliver. Hotel. Wednesday 29th- Session 11: Capillary Chromatography. “New Trends in Capillary Gas Chromatography,” by P. Sandra. “Applications of Capillary Gas Chromatography in the Study of Toxic Compounds,” by E. Bailey. “Selective Detection in Capillary Gas Chromato- graphy in Forensic Science,” by W. Anderson. Session 111: Thin Layer Chromatography. “The Potential of High-performance Thin Layer Chromatography (HPTLC) as a Qualitative Tool,” by W. Ritter. Title to be announced, by J. P.Franke. Seminars I1 (see list of topics below). Session IV: Ion Chromatography and Detection Techniques. “The Determination of Lactate, Pyruvate and 3-Hydroxybutyrate by Ion Chromatography,” by M. Cooke. “The Measurement of Oxalate in Biological Fluids by Ion Chromatography,” by M. Robertson. “Drug and Metabolic Profiling by Rapid Scanning Detectors in High-Performance Liquid Chromato- graphy.” by A. F. Fell and H. P. Scott. “The Trouble with Morphine,” by M. J. Stewart. Seminar topics: “Designs of Flow-through Cells in HPLC” (a 30 min video from speaker’s laboratory), by D. R. Oliver. “Instrumentation for Narrow-bore HPLC,” by R. Gill. “Computer-aided Strategies for Photodiode Array Detection in HPLC,” by A. F. Fell and H. P. Scott. “Sample Introduction in Capillary GC,” by P. Sandra. “Ion Chromatography with Conventional HPLC, Equipment,” by M. Cooke and B. Robertson. “Sample Preparation for HPLC,” by M. Stewart. “Practical HPTLC and (TLC),” by W. Ritter. “Ion-pair Chromatography,” by Professor J. H. Knox. “Selective Detection in Capillary GC,” by W. Anderson. Department of Chemistry, The University, King’s Buildings Campus, West Mains Road, Edinburgh. Registration is necessary. Cost E28 to members of participating bodies, f38 to non-members and &12 to students. Additional charges for accommodation and Conference Dinner. Contact: Dr. D. Simpson, Analysis For Industry, Factories 2/3, Bosworth House, High Street, Thorpe-le-Soken, Essex, C016 OEA. (Tel. 0255-861714).

ISSN:0144-557X    

DOI:10.1039/AP9842100039

出版商:RSC    

年代:1984

数据来源: RSC