摘要:

AbstractOrganometallic linkage of heteroaromatic compounds provided a means of synthesizing complicated combinations of heteroaromatic compounds; not only nucleophilic aromatic substitution, but also “ArCu/ArHal linkage”, “organometallic oxidative linkage”, and “metal amide linkage” have been employed. The heterocyclopolyaromatic compounds are made of one, two, or three kinds of heteroaromatic species as ring members. These syntheses illustrate the construction of heterocycles from large, performed structural units. Competition experiments showed that the reactivity typical of the individual species is enhanced in open‐chain combinations (ArNu)nand (ArE)n(ArNu, ArE: nucleo‐ and electrophilic heteroaromatic systems, respectively); the opposite situation is mostly encountered in the case of ArNuAEcombinations.—Cycloocta[1,2‐b:4,3‐b′5,6‐b″:8,7‐b‴]tetrathiophene, the only heterocyclopolyaromatic system yet to have been studied in detail, proved surprisingly inclined

ISSN:0570-0833    

DOI:10.1002/anie.197900013

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

摘要:

AbstractTitration represents the quantitative determination of a chemical change in response to the variation in concentration of a standrad. Information on reaction parameters is usually obtained from an analysis of the shape of the titration curve. In this paper the derivatives of titration functions with respect to concentration variables and with respect to equilibrium parameters are compared with one another. The latter can be determined directly from amplitudes and time constants of the dynamic responses to equilibrium perturbations, brought about by fast alterations of temperature, pressure or electirc field.Three general situations have to be distinguished: 1. If the interaction is very strong (i.e.the complex stability is high:K→ ∞), the (average) number of sample praticles can be counted directly by means of their reaction with a calibrated number of standard particles.—2. If, on the contrary, the interaction is weak (i.e.the complex stability is low), the sample will react quantitatively only in the presence of a large excess of standard; the half‐way point of which provides a direct measure of the binding constant.—3. Only for moderate interactions can individual curves characteristic of the binding strength be observed. The limiting cases 1 and 2 yield titration curves which reflect only the general class to which the system belongs.The dynamical procedures are fairly insensitive in case 1, which represents the classical end‐point situation and is most suitable for quantitative anlaysis,i.e.for a determination of sample concentrations. For case 2, the classical and dynamical techniques yield comparable information: mass‐action parameters are obtained from the extrema of the curves, which occur only in the presence of an excess of the standard. In case 3 the dynamical treatment provides a more direct access to the equilibrium constants, and also to the enthalpies or volumes of reaction as well as to the rate constants. The advantage of the dynamic method is due to the fact that in the two derivatives of the titration function dTi/d lnqand dTi/d lnp(whereqis the titration variable,i.e.the ratio of standard and sample concentration, andpthe mass‐action parameter,i.e.a reduced binding constant) the terms resulting from a differentiation with respect topare more closely related to the reaction parameters than those following from a variation ofq.The dynamic analysis is generalized for applications to multiple‐step titration processes, where it allows for the measurement fo equilibrium and rate parameters ofindividualsteps. A uniform representation utilizing trigonometric functions was chosen which expresses clearly the singualr character of the end‐point. The relations are summarized intabular form. They provide in conjunction with the illustrations the basis for a com

ISSN:0570-0833    

DOI:10.1002/anie.197900201

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

摘要:

AbstractThe Principal material used in optics is glass. Plastics can only gain acceptance in optics if they have properties not encountered with glass or if a desired article can be produced more rationally from a plastic. An example of the first case is provided by UV light guides consisting of a quartz glass core surrounded by a plastic cladding; there is no glass with a sufficiently low refractive index. Examples of the second case are viewfinder optics for camerás and lenses for sunglasses and industrial safety spectacles

ISSN:0570-0833    

DOI:10.1002/anie.197900491

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

ISSN:0570-0833    

DOI:10.1002/anie.197900591

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

ISSN:0570-0833    

DOI:10.1002/anie.197900601

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

ISSN:0570-0833    

DOI:10.1002/anie.197900611

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

ISSN:0570-0833    

DOI:10.1002/anie.197900621

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

ISSN:0570-0833    

DOI:10.1002/anie.197900631

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

ISSN:0570-0833    

DOI:10.1002/anie.197900651

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

ISSN:0570-0833    

DOI:10.1002/anie.197900661

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY