Pretransitional electro-optic response of 6CB liquid crystal in the isotropic phase

In this work, the electro-optic response of a 6CB liquid crystal layer is studied using a sensitive differential technique. The layer is held at a temperature just above the nematic to isotropic phase transition. Transverse magnetic (p) polarized light incident on the cell is coupled to guided modes in the liquid crystal layer using prism coupling. The modes manifest themselves as sharp dips in the reflectivity as the angle of incidence is scanned. When a low frequency sinusoidal voltage is applied to the cell, the resonant mode shapes and excitation angles are altered at a frequency which is twice that of the applied field, resulting in a modulation of the reflectivity for a given angle of incidence. By synchronous observation of the modulated signal, a differential signal is recorded. Comparing the data with modelling generated from multilayer optics theory, two effects are then quantified. The first of these is an induced birefringence, varying quadratically with applied voltage, which is well understood and can be expressed in terms of Landau-de Gennes theory. The second is a field induced perturbation in the imaginary part of the optical permittivity, δε_i, which implies a modification of the light scattering properties of the liquid crystal. The measurement of the latter effect is, as far as we know, a novel one, being only made possible by the remarkable sensitivity of the synchronous differential technique.     

Freezing temperatures and densities of solutions of some hydrocarbons and sodium oleate inN-methylacetamide. Evidence for a solvophobic interaction

The freezing temperatures and densities (at 31°C) of solutions of octane, nonane, decane, 3,3-diethylpentane, and sodium oleate inN-methylacetamide (NMA) have been measured. The molality of the freezing solution was calculated from the density. The solubilities of octane, nonane, and decane inN-methylacetamide are also reported. Apparent molal volumes calculated from the densities are close to the values in the pure hydrocarbons and are not strong functions of the concentration. This indicates the absence of any unusual packing effect. The calculated free energies of transfer of the hydrocarbons from pure hydrocarbon to NMA solution are much less negative than the corresponding values for water, showing that the bulk solvophobic interaction inN-methylacetamide is smaller than in water. This is consistent with the freezing temperatures of sodium oleate which show that micelles do not form below 0.1 mole-kg^–1. The osmotic coefficients of the hydrocarbons calculated from the freezing temperatures showed negative deviations from ideality that were larger for the hydrocarbons with the higher molecular weights. Two estimates of the pairwise solvophobic interaction inN-methylacetamide indicate that it is also smaller than in water. The solvophobic effect in this solvent does not include the large entropy and enthalpy effects found in aqueous solutions.     

Salting-in of alcohols in aqueous solutions by tetraalkylammonium bromides at the freezing temperature

The freezing-point depression of the ternary systems tetraalkylammonium bromides-t-butanol-water for the first five homologs of R₄NBr was measured. In the case of Bu₄NBr, the effect of size of the alcohol (methahol ton-butanol) was also investigated. From the corresponding freezing-point data for the binary systems the apparent salting constants were calculated. The true salting constantsk _s were obtained by extrapolation to infinite dilution. These are all very close to zero at the freezing temperature. From the corresponding thermochemical data the temperature dependence ofk _s was calculated, and above 5°C all the R₄NBr salts int-butanol; the salting-in increases with temperature and with the size of the hydrophobic cations. The scaled-particle theory is at present the only one which can account semiquantitatively for the temperature dependence of the salting-in effect. On leave of absence from Chemistry Department, The University, Sheffield S3 7HF, England To whom correspondence should be addressed.     

International Review of Science Solid State Chemistry,Inorganic Chemistry Series Two,Vol. 10 : Consultant Editor H.J. Emeleus FRS,Volume Editor L.E.J. Roberts,Butterworths, London, 1975, pp. 264, price £13.00

Complexes of nicotinic and isonicotinic acids and their deuterated analogues with pyridine, 4-Me pyridine and N Me imidazole have been examined by IR spectroscopy. Strong hydrogen bonding between an O atom of the acid and the N atom of the base with the H atom lying closer to the O atom, is present in all systems.     

DNA typing in hereditary disease.

An increasing number of hereditary diseases are becoming amenable to diagnosis by analysis of DNA as the responsible genes are located and identified. Gel electrophoresis of DNA fragments plays a central role in the diagnosis of hereditary disease. Electrophoretic separation of differently sized fragments enables the characterization or typing of normal variants which are known to be genetically linked to disease genes. For some diseases it is possible to directly detect mutations by DNA electrophoresis. Deletion mutants may be detected by a restriction fragment of altered size or by a failure to amplify a coding region with the polymerase chain reaction. Carriers of small deletions, involving a few base pairs, may be identified by DNA amplification which produces heteroduplexes that show characteristic, anomalous electrophoretic migration. Mutations that alter restriction sites also alter the sizes of restriction fragments. Common disease mutations that alter a single base pair may be detected using a pair of reactions with normal and mutant oligonucleotides under conditions where a perfect match is necessary for hybridization, amplification or ligation. Alternatively a mismatched oligonucleotide primer may be designed to generate a restriction site with either the normal or mutant allele, following DNA amplification. Finally a number of techniques are available that are useful as screening tools for novel mutations.     

On the calculation of the satellite peaks observed in the high energy photoelectron spectra of small molecules

The shake-up peaks which are observed to high binding energy of the main photoionization peak in the high energy photoeletron spectra of CO (carbon and oxygen core holes), H₂O and NH₃ have been interpreted by an extension of the singly excited configuration interaction method used previously in the study of the low-lying excited states of these molecules. The results obtained provide a good interpretation of the experimental spectra of these molecules in terms of many shake-up states. It is concluded that relaxed orbitals and an extensive basis set, including diffuse functions, should be used in the calculations in order to obtain good results.     

Chemical microscopy of some toxicologically important alkaloids

Zusammenfassung Die Arbeit beschäftigt sich mit der systematischen Untersuchung des Verhaltens der auf Seite 250 aufgezählten, bei toxikologischen Untersuchungen häufiger angetroffenen Alkaloidbasen gegenüber 50 Reagenzien. Die auf dem Objektträger erhaltenen Niederschläge wurden mikroskopisch untersucht und gegebenenfalls durch die Bestimmung einfach und rasch zu erfassender Eigenschaften der Kristalle, wie Profilwinkel, Einfachbrechung, Doppelbrechung, Auslöschungswinkel, Pleochroismus, und Verhalten gegenüber dem Gipsblättchen weiters charakterisiert.Eine Durchsicht der Liste der Reagenzien (S. 251 ff.) zeigt, daß außer altbekannten Alkaloidreagenzien eine größere Zahl von bisher wenig oder gar nicht zur Alkaloiderkennung benutzten Reagenzien studiert wurde. Eine systematische Untersuchung des Verhaltens einer möglichst großen Zahl der häufiger angetroffenen Basen erschien erforderlich, da die Spezifität einer Probe nur auf Grundlage der Kenntnis des Verhaltens des Reagens gegenüber allen anderen in Frage kommenden Stoffen sichergestellt werden kann.Die zur Erkennung der Basen nützlichen Reaktionsbilder sind in Tafeln (S. 323 ff.), nach Reagenzien angeordnet, gesammelt. Der systematische Bericht der Untersuchungsbefunde (S. 256) ist nach den Alkaloidbasen eingeteilt. Eine kurze Zusammenfassung betreffend die für jede Base bestgeeigneten Nachweisverfahren ist jeweils am Ende des der Base gewidmeten Kapitels gegeben.Die Nützlichkeit der studierten Reagenzien für die Erkennung von Alkaloidbasen wird zum Abschluß zusammenfassend besprochen (S. 315). Die Reagenzien Brom-Bromnatrium, Perchlorsäure, Kaliumbromid, Stannochlorid, Titanochlorid, Kaliumjodaurit, Natriumbromaurat, Platinbrom-wasserstoffsäure, Kaliumbrommercurat, Zinnchlorwasserstoffsäure und Palladiumbromwasserstoffsäure geben mit mehreren Basen kristalline Niederschläge, die durch Aussehen und Eigenschaften die Erkennung der Basen ermöglichen. Kaliumxanthat, Wismutchlorid, Rhodiumtrichlorid, Rutheniumtrichlorid und Cadmiumjodid erzeugen mit nur je zwei der untersuchten Alkaloidbasen gut kristallisierte Niederschläge, und die folgenden Reagenzien erscheinen durchaus spezifisch: Kupferron gibt nur mit-Eucain einen kristallinen Niederschlag; primäres Kaliumphthalat und Kaliumantimonyltartrat erzeugen nur mit Strychnin Kristallisationen; Cocain ist das einzige Alkaloid, das ein kristallisiertes Jodargentat gab, und lediglich bei Strychnin konnte ein eindeutig kristalliner Niederschlag mit HSbCl₄ erhalten werden.Fulton hat darauf hingewiesen, daß Reagenzien, die mit Brucin, Strychnin und Cocain keine Fällungen geben, nicht als allgemeine Alkaloidreagenzien in Betracht gezogen werden können, da sie wahrscheinlich auch mit anderen Basen keine Niederschläge zu erzeugen imstande sein dürften. Es wird nun darauf hingewiesen, daß Reagenzien, die mit den obgenannten drei Alkaloiden versagen, doch studiert werden sollten, da die Möglichkeit besteht, daß sie mit einem anderen Alkaloid einen spezifischen Nachweis geben.

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Résumé (L) Le présent travail étudie systématiquement le comportement (signalé page 250) des alcaloides les plus courants en toxicologie, vis à vis de 50 réactifs.Le précipité obtenu sur porte objet est examiné microscopiquement et éventuellement caractérisé par détermination simple et rapide des propriétés cristallines telles que le profil angulaire, la simple et double réfringence, l'angle d'extinction, le pleochroisme et son comportement en présence d'une lame de gypse.L'examen de la liste (p. 251) révèle qu'un grand nombre de réactifs peu ou pas du tout utilisés jusqu'ici dans l'identification des alcaloides ont été étudiés à côté des réactifs usuels, bien connus. Une étude systématique du comportement du plus grand nombre possible des bases les plus courantes s'imposait, parce que la spécificité d'un essai n'est établie avec certitude que si l'on connait la façon dont se comporte le réactif vis à vis de toutes les autres substances qui interviennent dans l'essai.Le Tableau (p. 323) donne tous les schémas de réaction nécessaires à l'identification des alcaloides, en prenant les réactifs comme base de classification.L'exposé des résultats de la recherche est subdivisé d'après les bases alcaloidiques (p. 256).Chaque chapitre se rapportant à un alcaloide déterminé se termine par un court résumé des procédés d'identification les mieux appropriés.La justification de l'emploi des réactifs étudiés est finalement discutée (p. 315) sous une forme résumée.Les précipités cristallins dont l'aspect et les propriétés permettent l'identification des bases, sont obtenus par les réactifs suivants: le bromo-bromure de sodium, l'acide perchlorique, le bromure de potassium, le chlorure stanneux et titaneux, l'iodoaurite de potassium, le bromoaurate de sodium, l'acide bromoplatinique, le bromomercurate de potassium, les acides chlorostannique et bromopalladique.Les réactifs suivants ne donnent de précipité cristallin qu'avec deux bases alcaloides étudiées: le xanthate de potassium, le chlorure de bismuth, le trichlorure de rhodium, de ruthénium et l'iodure de cadmium. Les réactifs suivants sont apparus comme spécifiques: le cupferron ne donne de précipité cristallin qu'avec la b-Eucaine; le phtalate acide de potassium et le tartrate de potassium et d'antimonyle ne fournissent de précipité cristallin qu'avec la strychnine; la cocaine est le seul des alcaloides formant un iodoargentate et enfin, la strychnine a donné un précipité cristallin avec HSbCl₄.Fulton avait avancé que les réactifs ne précipitant pas avec la brucine, la strychnine et la cocaine ne pouvaient pas être considérés comme des réactifs généraux des alcaloides, parce que vraisemblablement ils se comportent de même avec d'autres alcaloides. Le présent travail démontre la nécessité d'étudier des réactifs, même s'ils ne précipitent pas ces trois alcaloides, parce qu'ils peuvent avec d'autres alcaloides, donner lieu à des réactions spécifiques.

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The work herein reported represents a portion of that presented by Mr.Wood as his dissertation in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Polytechnic Institute of Brooklyn.     

Effect of photochemical oxidation on polypropylene phosphorescence

Phosphorescence from polyolefins was studied from the aspects of excitation and emission wavelength and lifetime. Effects of photochemical oxidation on polypropylene phosphorescence are discussed in contrast to the effects of thermal oxidation.     

Pre-Validation and Performance Prediction Using Pressure Monitoring to Evaluate HPLC Method Development Changes

HPLC methods for pharmaceutical analysis evolve from method development to commercial product testing. The majority of development and validation takes place in an R&D setting, followed by transfer to commercial sites that execute test methods on a routine basis. There is a growing need to increase confidence and probability that developed methods will be successful both during validation and long-term use with products, particularly when introducing new or unfamiliar technologies. An HPLC method pre-validation and performance prediction plan is presented using model pharmaceutical ingredients in prototype liquid formulations. The pre-validation includes limited linearity, repeatability in sample matrix, precision, carry-over, and selectivity. The performance prediction involves injecting large numbers of worst-case samples and monitoring five critical parameters: retention time, tailing factor, resolution, efficiency, and system pressure. Parameter results are assessed with respect to precision and/or system performance. In a proof of principle model, the performance prediction data demonstrate that system suitability parameters remain constant during injections of prepared samples; however, the system pressure increases over time. These underlying data indicate a potential trend prior to method validation. As a result, sample preparation and HPLC condition modifications are evaluated using pressure plots as a key performance metric.