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161.
Vladimir Bershtein Vladimir Gun'ko Larisa Egorova Natalia Guzenko Eugene Pakhlov Valery Ryzhov Vladimir Zarko 《Macromolecular Symposia》2010,296(1):541-549
Interfacial interactions and dynamics were studied in silica and alumina core-poly(vinyl pyrrolidone) (PVP) shell nanoparticles with different shell thicknesses starting from 1-2 nm (monolayer); their geometry and structural organization were comprehensively characterized by several techniques. Far- and mid-IR spectroscopy, combined with DSC activation analysis of the glass transition, allowed to register hydrogen bonding and Lewis/Brønsted interactions, and the multi-modal glass transition dynamics in PVP nanoshells, as well as their interrelationship. For PVP monolayer, only a few “abnormal” modes constituted glass transition which covered the temperature range from 80 to 230 °C, with varying the activation energy by an order of magnitude. 相似文献
162.
Over the past 30 years, optics well known to the physicist have been identified in their multitudes in nature. Multilayer reflectors, diffraction gratings, liquid crystals and structures that scatter light—devices explained using “simple” optical theory—have been found in animals with a diversity of designs. For many years the potential to employ these designs commercially has been clear, although only one optical device in animals has been taken through to the manufacture stage—the fly-eye antireflector. Now, with the beginnings of “complex” optical study in biological specimens, and consequent identification of photonic band gaps, animal reflectors are being taken seriously as promising first stages in the design process of optical engineers. However, natural photonic crystals are often highly complex structures at the nano-scale that may lie beyond the limits of current engineering. This in turn justifies the study of cellular engineering—maybe we can also exploit the flawless processes of manufacture employed by animals. 相似文献
163.
A new, one-step procedure for the generation of azomethine ylides, 4 and 20, via chloroiminium salts, 3 and 19, is reported. The generation of the azomethine ylides was confirmed by their trapping with dimethyl acetylenedicarboxylate (DMAD) which, upon spontaneous 1,4-dehydrochlorination, gave the corresponding pyrroles 17 and 21. 相似文献
164.
Ran Zhang Natalia Pavlovna Bondarenko Chuan Fu Yang 《Mathematical Methods in the Applied Sciences》2021,44(1):124-139
In this paper, we consider the Sturm–Liouville equation with the jump conditions inside the interval (0,π). The inverse problem is studied, which consists in recovering operator coefficients from two spectra, corresponding to different boundary conditions. We prove the uniqueness theorem and provide necessary and sufficient conditions for solvability of the inverse problem. We also obtain the oscillation theorem for the eigenfunctions of the considered discontinuous boundary value problem. 相似文献
165.
María J. Culzoni Agustina V. Schenone Natalia E. Llamas Mariano Garrido Maria S. Di Nezio Beatriz S. Fernández Band Héctor C. Goicoechea 《Journal of chromatography. A》2009,1216(42):7063-7070
A fast chromatographic methodology is presented for the analysis of three synthetic dyes in non-alcoholic beverages: amaranth (E123), sunset yellow FCF (E110) and tartrazine (E102). Seven soft drinks (purchased from a local supermarket) were homogenized, filtered and injected into the chromatographic system. Second order data were obtained by a rapid LC separation and DAD detection. A comparative study of the performance of two second order algorithms (MCR-ALS and U-PLS/RBL) applied to model the data, is presented. Interestingly, the data present time shift between different chromatograms and cannot be conveniently corrected to determine the above-mentioned dyes in beverage samples. This fact originates the lack of trilinearity that cannot be conveniently pre-processed and can hardly be modelled by using U-PLS/RBL algorithm. On the contrary, MCR-ALS has shown to be an excellent tool for modelling this kind of data allowing to reach acceptable figures of merit. Recovery values ranged between 97% and 105% when analyzing artificial and real samples were indicative of the good performance of the method. In contrast with the complete separation, which consumes 10 mL of methanol and 3 mL of 0.08 mol L−1 ammonium acetate, the proposed fast chromatography method requires only 0.46 mL of methanol and 1.54 mL of 0.08 mol L−1 ammonium acetate. Consequently, analysis time could be reduced up to 14.2% of the necessary time to perform the complete separation allowing saving both solvents and time, which are related to a reduction of both the costs per analysis and environmental impact. 相似文献
166.
Highly correlated ab initio quartic force fields (QFFs) are used to calculate the equilibrium structures and predict the spectroscopic parameters of three HC(2)N isomers. Specifically, the ground state quasilinear triplet and the lowest cyclic and bent singlet isomers are included in the present study. Extensive treatment of correlation effects were included using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted as CCSD(T). Dunning's correlation-consistent basis sets cc-pVXZ, X = 3,4,5, were used, and a three-point formula for extrapolation to the one-particle basis set limit was used. Core-correlation and scalar relativistic corrections were also included to yield highly accurate QFFs. The QFFs were used together with second-order perturbation theory (PT) (with proper treatment of Fermi resonances) and variational methods to solve the nuclear Schro?dinger equation. The quasilinear nature of the triplet isomer is problematic, and it is concluded that a QFF is not adequate to describe properly all of the fundamental vibrational frequencies and spectroscopic constants (though some constants not dependent on the bending motion are well reproduced by PT). On the other hand, this procedure (a QFF together with either PT or variational methods) leads to highly accurate fundamental vibrational frequencies and spectroscopic constants for the cyclic and bent singlet isomers of HC(2)N. All three isomers possess significant dipole moments, 3.05 D, 3.06 D, and 1.71 D, for the quasilinear triplet, the cyclic singlet, and the bent singlet isomers, respectively. It is concluded that the spectroscopic constants determined for the cyclic and bent singlet isomers are the most accurate available, and it is hoped that these will be useful in the interpretation of high-resolution astronomical observations or laboratory experiments. 相似文献
167.
Ivan Kralji Natalia Barboy Jean-Pierre Leicknam‡ 《Photochemistry and photobiology》1979,30(6):631-633
Abstract— Singlet oxygen (l O2 ) formed in the photolysis of neutral aqueous micellar (with Triton X-100) solution of chlorophyll a (dissolved inside the micelle) is detected in the aqueous phase by a test using imidazole in the presence of p -nitrosodimethylaniline. The quantum yield of l O2 diffusing out of the micelle into the aqueous phase is also determined [θ(l O2 ) ⋍ 0.70–0.85]. 相似文献
168.
Marina Huber-Gedert Dr. Michał Nowakowski Dr. Ahmet Kertmen Dr. Lukas Burkhardt Dr. Natalia Lindner Dr. Roland Schoch Dr. Regine Herbst-Irmer Dr. Adam Neuba Lennart Schmitz Tae-Kyu Choi Dr. Jacek Kubicki Prof. Dr. Wojciech Gawelda Prof. Dr. Matthias Bauer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(38):9905-9918
A new base metal iron-cobalt dyad has been obtained by connection between a heteroleptic tetra-NHC iron(II) photosensitizer combining a 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine with 2,6-bis(3-methyl-imidazol-2-ylidene)-4,4′-bipyridine ligand, and a cobaloxime catalyst. This novel iron(II)-cobalt(III) assembly has been extensively characterized by ground- and excited-state methods like X-ray crystallography, X-ray absorption spectroscopy, (spectro-)electrochemistry, and steady-state and time-resolved optical absorption spectroscopy, with a particular focus on the stability of the molecular assembly in solution and determination of the excited-state landscape. NMR and UV/Vis spectroscopy reveal dissociation of the dyad in acetonitrile at concentrations below 1 mM and high photostability. Transient absorption spectroscopy after excitation into the metal-to-ligand charge transfer absorption band suggests a relaxation cascade originating from hot singlet and triplet MLCT states, leading to the population of the 3MLCT state that exhibits the longest lifetime. Finally, decay into the ground state involves a 3MC state. Attachment of cobaloxime to the iron photosensitizer increases the 3MLCT lifetime at the iron centre. Together with the directing effect of the linker, this potentially makes the dyad more active in photocatalytic proton reduction experiments than the analogous two-component system, consisting of the iron photosensitizer and Co(dmgH)2(py)Cl. This work thus sheds new light on the functionality of base metal dyads, which are important for more efficient and sustainable future proton reduction systems. 相似文献
169.
170.
Natalia Tiessen Dr. Nico Schwarze Mira Keßler Beate Neumann Dr. Hans-Georg Stammler Prof. Dr. Berthold Hoge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(43):11041-11044
While alkyl-substituted siloxanes are widely known, virtually nothing is known about perfluoroalkyl siloxanes and their congener species, the silanols and silanolates. We recently reported on the tris(pentafluoroethyl)silanide ion, [Si(C2F5)3]−, which features Lewis amphoteric character deriving from the pentafluoroethyl substituents and their strong electron-withdrawing properties. Transferring this knowledge, we investigated the Lewis amphoteric behavior of the tris(pentafluoroethyl)silanolate, [Si(C2F5)3O]−. In order to examine such Lewis amphoteric behavior, we first developed a strategy for the synthesis of the corresponding silanol Si(C2F5)3OH, which readily condenses at room temperature to the hexakis(pentafluoroethyl)disiloxane, (C2F5)3SiOSi(C2F5)3. Deprotonation of Si(C2F5)3OH employing a sterically demanding phosphazene base allows the characterization of the first example of a dimeric triorganosilanolate: the dianionic hexakis(pentafluoroethyl)disilanolate, [{Si(C2F5)3O}2]2−, implies Lewis amphoteric character of the monomeric [Si(C2F5)3O]− anion. 相似文献