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41.
In the Raman spectra of silicon nanocrystals a new anomalous component was detected. Close to the usual first order Raman peak situated for a bulk crystal at 521 cm−1 at room temperature, two peaks arise shifting towards lower energy and demonstrating a huge temperature increase, as measured by the ratio of the Stokes/anti-Stokes peak intensities. This behavior is dependent on the laser power and on the morphology of the nanocrystals. We can exclude, however, confinement effects, although surface enhanced phonon modes could be responsible of such superheating. Alternative explanations are also suggested and discussed. 相似文献
42.
We demonstrate with a minimal example that in Filippov systems (dynamical systems governed by discontinuous but piecewise smooth vector fields) stable periodic motion with sliding is not robust with respect to stable singular perturbations. We consider a simple dynamical system that we assume to be a quasi-static approximation of a higher-dimensional system containing a fast stable subsystem. We tune a system parameter such that a stable periodic orbit of the simple system touches the discontinuity surface: this is the so-called grazing-sliding bifurcation. The periodic orbit remains stable, and its local return map becomes piecewise linear. However, when we take into account the fast dynamics the local return map of the periodic orbit changes qualitatively, giving rise to, for example, period-adding cascades or small-scale chaos. 相似文献
43.
The Allen-Cahn equation ? Δu = u ? u 3 in ?2 has family of trivial singly periodic solutions that come from the one dimensional periodic solutions of the problem ?u″ =u ? u 3. In this paper we construct a non-trivial family of singly periodic solutions to the Allen-Cahn equation. Our construction relies on the connection between this equation and the infinite Toda lattice. We show that for each one-soliton solution to the infinite Toda lattice we can find a singly periodic solution to the Allen-Cahn equation, such that its level set is close to the scaled one-soliton. The solutions we construct are analogues of the family of Riemann minimal surfaces in ?3. 相似文献
44.
Marlena Pięta Jacek Kędzia Dorota Kowalczyk Jakub Wojciechowski Wojciech M. Wolf Tomasz Janecki 《Tetrahedron》2019,75(17):2495-2505
An efficient, versatile, enantioselective synthesis of 1,3-disubstituted and 1,3,6-trisubstituted 5-methylidenedihydrouracils applying Horner-Wadsworth Emmons methodology was developed. Starting 1,3-disubstituted 5-diethoxyphosphoryluracils were subjected to reduction of the double bond or addition of various Grignard reagents and obtained Horner-Wadsworth Emmons reagents were used for the olefination of formaldehyde. Enantioselective synthesis of 1,3,6-trisubstituted 5-methylidenedihydrouracils was accomplished by introducing (R,R)- or (S,S)-di(1-phenylethylamino)phosphoryl groups as chiral auxiliary. Additions of Grignard reagents in the presence of these groups were highly and complimentary diastereoselective (de?~?80%). Further separation of the diastereomeric mixtures by column chromatography enabled synthesis of (R)- and (S)-1,3,6-trisubstituted-5-methylidenedihydrouracils with ee?≥?98%. Furthermore, absolute configuration of the adducts and final products was established using single crystal X-ray analysis. Stereochemical course of the addition reactions is also discussed. 相似文献
45.
Rafal Kruszynski Agata Trzesowska‐Kruszynska 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(12):o624-o629
The 2‐aminobenzothiazole sulfonation intermediate 2,3‐dihydro‐1,3‐benzothiazol‐2‐iminium monohydrogen sulfate, C7H7N2S+·HSO4−, (I), and the final product 2‐iminio‐2,3‐dihydro‐1,3‐benzothiazole‐6‐sulfonate, C7H6N2O3S2, (II), both have the endocyclic N atom protonated; compound (I) exists as an ion pair and (II) forms a zwitterion. Intermolecular N—H...O and O—H...O hydrogen bonds are seen in both structures, with bonding energy (calculated on the basis of density functional theory) ranging from 1.06 to 14.15 kcal mol−1. Hydrogen bonding in (I) and (II) creates DDDD and C(8)C(9)C(9) first‐level graph sets, respectively. Face‐to‐face stacking interactions are observed in both (I) and (II), but they are extremely weak. 相似文献
46.
A major challenge in the area of DNA detection is the development of rapid methods that do not require polymerase chain reaction
(PCR) amplification of the genetic sample. The PCR amplification step increases the cost of the assay, the complexity of the
detection, and the quantity of DNA required for the assay. In this context, methods that are able to perform DNA analyses
with ultrasensitivity have recently been investigated with the aim of developing new PCR-free detection protocols. Functionalized
gold nanoparticles have played a central role in the development of such methods. Here, possibilities offered by functionalized
gold nanoparticle in the ultrasensitive detection of DNA are discussed. The different functionalization protocols available
for gold nanoparticles and the principal DNA detection methods that are able to detect DNA at the femtomolar to attomolar
level are presented. 相似文献
47.
The electronic structure of CO3 is characterized by equation-of-motion and coupled-cluster methods. C(2v) and D(3h) isomers are considered. Vertical excitation energies, transition dipoles, and the molecular orbital character of the excited states are presented for singlet and triplet manifolds. Ground-state equilibrium structures and frequencies are strongly affected by vibronic interactions with low-lying excited states. At D(3h) geometries, the vibronic interactions are enhanced by the Jahn-Teller character of the excited states. The curvature of the potential energy surface and the existence of the D(3h) minimum are very sensitive to the correlation treatment and the basis set. The correlation effects are stronger at D(3h), in agreement with a smaller HOMO-LUMO gap. 相似文献
48.
49.
Conducting polymer (CP) films, used as ion-sensing membranes under open circuit potentiometric conditions, are usually characterised with rather high detection limit, in the range of 10−4-10−5 mol dm−3. This effect is unfavourable, not only from the point of view of CP applications in potentiometry as ion sensitive membranes, but also when these materials are used as ion-to-electron transducers (solid contacts) for ion-selective electrodes. The theoretical considerations presented underline the crucial role of spontaneous processes of polymer charging/discharging—the source of observed high detection limit of sensors comprising CP layer under zero current conditions. Although the mechanism of occurring process is different from that observed for plastic, solvent polymeric based ion-selective electrodes, the ultimate result—alteration of activity of electrolyte at the membrane/solution interface leading to elevation of the detection limit—is the same.The method of estimation of parameters characterising spontaneous charge transfer processes is presented. The values obtained can be used to calculate the resulting polymer/solution interface activity of electrolyte ions, thus the detection limit of CP membrane can be theoretically predicted.A method of lowering of the detection limit of conducting polymer membranes, applying galvanostatic polarisation to compensate the spontaneous process of polymer charging/discharging, is presented.The experimental results obtained for poly(pyrrole), poly(N-methylpyrrole) and poly(3,4-ethylenedioxythiophene) are in good accordance with predictions of the presented model. 相似文献
50.
Namieśnik J Zabiegała B Kot-Wasik A Partyka M Wasik A 《Analytical and bioanalytical chemistry》2005,381(2):279-301
The current state-of-the-art of passive sampling and/or extraction methods for long-term monitoring of pollutants in different environmental compartments is discussed in this review. Passive dosimeters that have been successfully used to monitor organic and inorganic contaminants in air, water, sediments, and soil are presented. The application of new approaches to the determination of pollutants at the sampling stage is discussed. The main milestones in the development of passive techniques for sampling and/or extraction of analytes, and in biomonitors used in environmental analysis, are summarized in this review. Passive samplers and biomonitors are compared. 相似文献