Untersuchungen zum Mechanismus der- mit N-Halogenaminen und Fe(II) initiierten Redox-Polymerisation

Ohne Zusammenfassung     

Structure of 72,74Se at high spin

Lifetimes of high spin states up to { }=22⁺ in the yrast positive parity bands have been measured to investigate the shape evolution with increasing spin in ^{72, 74}Se. The Q _t values derived from these measurements indicate that prolate shape stabilizes for ⁷²Se, while a triaxial shape develops for ⁷⁴Se at higher spins. Comparison of the observed trend in Q _t with spin for ^{72, 74}Se with that of the corresponding kryptones isotones emphasizes the stability provided by N=38 prolate shell gap even at high rotational frequency.     

Phase synchronization of instrumental music signals

Signal analysis is one of the finest scientific techniques in communication theory. Some quantitative and qualitative measures describe the pattern of a music signal, vary from one to another. Same musical recital, when played by different instrumentalists, generates different types of music patterns. The reason behind various patterns is the psycho-acoustic measures – Dynamics, Timber, Tonality and Rhythm, varies in each time. However, the psycho-acoustic study of the music signals does not reveal any idea about the similarity between the signals. For such cases, study of synchronization of long-term nonlinear dynamics may provide effective results. In this context, phase synchronization (PS) is one of the measures to show synchronization between two non-identical signals. In fact, it is very critical to investigate any other kind of synchronization for experimental condition, because those are completely non identical signals. Also, there exists equivalence between the phases and the distances of the diagonal line in Recurrence plot (RP) of the signals, which is quantifiable by the recurrence quantification measure τ-recurrence rate. This paper considers two nonlinear music signals based on same raga played by two eminent sitar instrumentalists as two non-identical sources. The psycho-acoustic study shows how the Dynamics, Timber, Tonality and Rhythm vary for the two music signals. Then, long term analysis in the form of phase space reconstruction is performed, which reveals the chaotic phase spaces for both the signals. From the RP of both the phase spaces, τ-recurrence rate is calculated. Finally by the correlation of normalized tau-recurrence rate of their 3D phase spaces and the PS of the two music signals has been established. The numerical results well support the analysis.     

Lifetimes of nuclear excited states with neutron gated recoil distance method

A motor driven plunger has been constructed for measuring lifetimes of nuclear excited states in pico second region. An array consisting of six neutron detectors was used to clean up γ-spectra obtained with CS-HPGe detectors. Lifetimes of low excited states in neutron deficient nuclei with low production cross-section e.g.⁸¹Y,⁷⁷Kr and⁷⁸Rb are reported.     

A Comprehensive Computational Investigation into the Conserved Virulent Proteins of Shigella species Unveils Potential Small-Interfering RNA Candidates as a New Therapeutic Strategy against Shigellosis

Shigella species account for the second-leading cause of deaths due to diarrheal diseases among children of less than 5 years of age. The emergence of multi-drug-resistant Shigella isolates and the lack of availability of Shigella vaccines have led to the pertinence in the efforts made for the development of new therapeutic strategies against shigellosis. Consequently, designing small-interfering RNA (siRNA) candidates against such infectious agents represents a novel approach to propose new therapeutic candidates to curb the rampant rise of anti-microbial resistance in such pathogens. In this study, we analyzed 264 conserved sequences from 15 different conserved virulence genes of Shigella sp., through extensive rational validation using a plethora of first-generation and second-generation computational algorithms for siRNA designing. Fifty-eight siRNA candidates were obtained by using the first-generation algorithms, out of which only 38 siRNA candidates complied with the second-generation rules of siRNA designing. Further computational validation showed that 16 siRNA candidates were found to have a substantial functional efficiency, out of which 11 siRNA candidates were found to be non-immunogenic. Finally, three siRNA candidates exhibited a sterically feasible three-dimensional structure as exhibited by parameters of nucleic acid geometry such as: the probability of wrong sugar puckers, bad backbone confirmations, bad bonds, and bad angles being within the accepted threshold for stable tertiary structure. Although the findings of our study require further wet-lab validation and optimization for therapeutic use in the treatment of shigellosis, the computationally validated siRNA candidates are expected to suppress the expression of the virulence genes, namely: IpgD (siRNA 9) and OspB (siRNA 15 and siRNA 17) and thus act as a prospective tool in the RNA interference (RNAi) pathway. However, the findings of our study require further wet-lab validation and optimization for regular therapeutic use for treatment of shigellosis.     

An XRD characterization of the thermal degradation of polyacrylonitrile

Thermal degradation of polyacrylonitrile (PAN) has been studied by combined differential thermal analysis, thermogravimetry, and XRD analysis. On the basis of the experimental observations, it has been suggested that the intramolecular polymerization of nitrile groups to a conjugated polyimine structure is initially limited to only the amorphous zone of PAN, which involves little evolution of off-gases. Polymerization of nitrile group in the crystalline zone starts with the melting of crystallites with the evolution of off-gases from the amorphous-crystalline zone interface. ©1995 John Wiley & Sons, Inc.     

Triplet excited states and radical intermediates formed in electron pulse radiolysis of amino-substituted fluorenones

Electron pulse radiolysis of four differently substituted amino derivatives of fluorenone, namely, 1-amino-, 2-amino- 3-amino-, and 4-aminofluorenone, has been carried out to study the effect of structure on the spectroscopic and kinetic characteristics of the triplet excited states as well as the transient free radical intermediates formed under reducing and oxidizing conditions. The triplet states of these compounds have been generated in benzene by pulse radiolysis and in other solvents by flash photolysis technique and their spectral and kinetic properties have been investigated. Hydrated electron (e_aq⁻) has been found to react with these fluorenone derivatives to form the anion radical species with a diffusion-controlled rate constant. The spectral and kinetic properties of the transient ketyl and anion radicals have been studied by generating them in aqueous solutions of suitable pH. The pK_a values of ketylanion radical equilibria are in the range of 6.8–7.7 for these derivatives. The oxidized species have been generated by reaction with the azide radical. Hydrogen atom adducts as well as the cation radicals of these derivatives have also been generated by pulse radiolysis and characterized.     

Synthesis, characterisation and mass spectrometric fragmentation of O-(chlorodifluoroacylated) alcohols

An indirect and uncatalysed esterification of chlorodifluoroacetic acid with polyfluoro and hydrocarbon alcohols has been developed. The method which involves the reaction between sodium chlorodifluoroacetate and alcohols in dimethylformamide (DMF) is particularly facile with polyfluorinated alcohols resulting in esters in 71-85% yield. The esters have been characterised on the basis of ¹H and ¹⁹F NMR and mass spectral data. The electron impact (EI) mass spectrometric fragmentation of these polyfluorinated esters have shown some interesting features which have been substantiated by using tandem mass spectrometry.     

Mechanistic studies of thiol-dimethylsulfoxide initiated polymerization of methylmethacrylate from endgroup analysis

Summary Endgroup analysis of polymethylmethacrylate obtained by initiation with thiol-dimethyl sulfoxide systems has been carried out using dye-techniques developed in our laboratory. Thiols used are 2-mercaptoethylamine hydrochloride, 2-mercaptoethanol, thioglycolic acid and n-butane thiol. The first three thiols incorporated amine, hydroxyl and carboxyl endgroup respectively to the extent of about one per macromolecule, while the last one as expected produced none of the above functional endgroups in the polymer. In the light of endgroup results initiation through thiyl radicals has been suggested. Probable termination mechanism has also been discussed.

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Zusammenfassung Die Endgruppenanalyse von Polymethylmethacrylat, das durch Initiierung mit Thioldimethylsulfoxid-Systemen hergestellt war, wurde unter Anwendung unserer in unserem Labor entwickelten Färbungstechnik durchgeführt. Die verwendeten Thiole waren 2-Mercaptoäthylaminhydrochlorid, 2-Mercaptoäthanol, Thioglykolsäure und N-Butandiol. Die ersten drei Thiole fügten Amin-Hydroxyl- und Carboxyl-Endgruppen respektiv bis zum Betrag von etwa einer pro Makromolekül ein, während das letztere wie erwartet keine der oben genannten funktionalen Endgruppen im Polymer erzeugte. Aufgrund dieser EndgruppenResultate wird auf eine Initiierung durch Thiylradikale geschlossen. Der wahrscheinliche Abbruchmechanismus wird ebenfalls diskutiert.