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1.
Synthesis of pure Zinc oxide (ZnO), Copper oxide (CuO) nanoparticles (NPs) and their (ZnO/CuO) nanocomposites (NCs) in 1:1 M ratio were successfully prepared by co-precipitation method. The structural properties of the as synthesized nanoparticles and nanocomposite materials were investigated using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) techniques. Optical band-gap studies were done using UV–Visible absorption spectroscopy. Photovoltaic properties of pure ZnO NPs, CuO NPs and ZnO/CuO NCs coated over a single-crystalline silicon solar cell were carried out to compare improvement of light-conversion efficiency in coated solar cell. The maximum light conversion efficiencies were found to be of 8.02% for CuO (3 mg/ml concentration) and 7.28% for ZnO NPs (3 mg/ml concentration), whereas that of mixed metal nanocomposite CuO/ZnO NCs was found to be 7.62%. at very low concentration of 1 mg/ml. This indicates with low concentration of mixed metal NCs an improvement in light efficiency can be obtained. The enhancement in efficiency could be due to formation of p - n heterojunction by CuO/ZnO NCs composites which enhances the number of electrons and holes participating in conduction on the surface.  相似文献   
2.
One of the most fascinating questions in chemistry is why nature chose CGAT as the alphabet of life. Very likely, such selection was the result of multiple factors and a long period of refinement. Here, we explore how the intermolecular interactions influenced such process, by characterizing the formation of dimers between adenine, theobromine and 4-aminopyrimidine. Using a combination of mass-resolved excitation spectroscopy and DFT calculations, we determined the structure of adenine-theobromine and 4-aminopyrimidine-theobromine dimers. The binding energy of these dimers is very close to the canonical adenine-thymine nucleobases. Likewise, the dimers are able to adopt Watson-Crick conformations. These findings seem to indicate that there were many options available to build the first versions of the informational polymers, which also had to compete with other molecules, such as 4-aminopyrimidine, which does not have a valid attaching point for a saccharide. For some reason, nature did not select the most strongly-bonded partners or if it did, such proto-bases were later replaced by the nowadays canonical CGAT.  相似文献   
3.
The oxidized form of baicalein ( BA ) leads to covalent binding with human amyloid proteins. Such adducts hamper the aggregation and deposition of fibrils. A novel reaction of BA with pentylamine ( PA ) as a model for the lysine side chain is described. This is the first study addressing the atomistic details of a Schiff base reaction with the trihydroxylated moiety of BA . Nuclear magnetic resonance and mass spectrometry approaches clearly indicate the formation of dehydrobaicalein in solution as well as its condensation with PA under aerobic conditions, yielding regioselectively C6-substituted products. The combined results suggest initial ion pair formation between BA and PA , followed by a redox chain reaction: the initiation by oxygen/air; an o-quinone-based chain involving oxidation and reduction steps; and extra off-chain formation of a doubly oxidized product. These mechanistic details support the anti-amyloid activity of BA and endorse its trihydroxyphenyl moiety as a pharmacophore for drug-design studies.  相似文献   
4.
Acyl group migration affects the synthesis, isolation, manipulation and purification of all acylated organic compounds containing free hydroxyl groups, in particular carbohydrates. While several isolated studies on the migration phenomenon in different buffers have been reported, comprehensive insights into the overall migration process in different monosaccharides under similar conditions have been lacking. Here, we have studied the acyl migration in different monosaccharides using five different acyl groups by a combination of experimental, kinetic and theoretical tools. The results show that the anomeric configuration in the monosaccharide has a major influence on the migration rate, together with the relative configurations of the other hydroxyl groups and the nature of the migrating acyl group. Full mechanistic model, based on computations, demonstrates that the acyl migration proceeds through an anionic stepwise mechanism with linear dependence on the [OH] and the pKa of the hydroxyl group toward which the acyl group is migrating.  相似文献   
5.
Fluorene is a classic three-membered polycyclic aromatic hydrocarbon, and it has been widely used in optoelectronic devices. Here we explore a simple and efficient strategy for the derivatization at the 2- and 3- positions in fluorene unit. By introducing different types of substituents, we design two pairs of 2,3-disubstituted fluorene isomers and use them as host materials for phosphorescent organic light-emitting diodes (PHOLEDs). The green PHOLEDs hosted by these fluorene derivatives realize high external quantum efficiencies (EQE) over 20 % with low efficiency roll-off. Particularly, the devices hosted by 2TRz3TPA and 2TPA3TRz achieve nearly 24 % EQE and 104 lm W−1 power efficiency. These results clearly demonstrate that the 2,3-disubstituted fluorene platforms are potentially useful for constructing host materials.  相似文献   
6.
The binding of small gas molecules such as NO and CO plays a major role in the signaling routes of the human body. The sole NO-receptor in humans is soluble guanylyl cyclase (sGC) – a histidine-ligated heme protein, which, upon NO binding, activates a downstream signaling cascade. Impairment of NO-signaling is linked, among others, to cardiovascular and inflammatory diseases. In the present work, we use a combination of theoretical tools such as MD simulations, high-level quantum chemical calculations and hybrid QM/MM methods to address various aspects of NO binding and to elucidate the most likely reaction paths and the potential intermediates of the reaction. As a model system, the H-NOX protein from Shewanella oneidensis (So H-NOX) homologous to the NO-binding domain of sGC is used. The signaling route is predicted to involve NO binding to form a six-coordinate intermediate heme-NO complex, followed by relatively facile His decoordination yielding a five-coordinate adduct with NO on the distal side with possible isomerization to the proximal side through binding of a second NO and release of the first one. MD simulations show that the His sidechain can quite easily rotate outward into solvent, with this motion being accompanied in our simulations by shifts in helix positions that are consistent with this decoordination leading to significant conformational change in the protein.  相似文献   
7.
The cycloaddition of heptafulvalene ( 1 ) with tetracyanoethylene (TCNE) was previously described as an example of an antarafacial cycloaddition, a [π14a2s] process that afforded only the trans cycloadduct by virtue of the edge-to-face approach of TCNE, facilitated by the S shape of 1 . The reaction has been investigated in depth and found not to be a concerted antarafacial process. At low temperature, the reaction is observed to give a mixture of cis and trans cycloadducts as well as a [4+2] cycloadduct. The mixture of products is converted to the trans cycloadduct by equilibration upon warming to room temperature. Studies with diethyl 2,3-dicyanofumarate and -maleate confirmed the formation of cis cycloadducts. DFT studies at the M06-2X/6-311+G(2d,p) SCRF=acetone level of theory show that the originally proposed edge-to-face approach of TCNE to 1 is highly disfavored, whereas a stepwise mechanism involving the addition of TCNE at C2 to form a zwitterion followed by collapse at either C2′ or C7′ is energetically accessible. The Diels-Alder adduct is also formed in a stepwise reaction by competitive addition of TCNE at C4 of 1 . These studies suggest that edge-to-face interactions are prohibitive in even the most favorable cases.  相似文献   
8.
The conformational properties of monosaccharides constitute fundamental features of oligosaccharides. While the energy landscape of monosaccharides can be altered by a specific biochemical environment or by chemical modifications, the analysis of resulting dynamic conformational equilibria is not feasible by experimental means alone. In this work, a series of β-d -xylopyranosides is used to outline how a combination of experimental NMR parameters and computed molecular properties can be used to determine conformers and quantify the composition of conformational equilibria. We demonstrate that identifying the most stable conformers using energy calculations is challenging and computing of NMR shieldings is typically not sensitive enough. On the other hand, computed spin-spin coupling constants for the xyloside ring can be used to unambiguously assign experimental NMR data of dynamic conformational equilibria and quantify the ratio of different conformers in the mixture. As a proof of principle, this procedure allowed to analyze a hitherto unknown dynamic equilibrium of a diamino-xyloside as a precursor of a molecular switch.  相似文献   
9.
It is clear that the field of organocatalysis is continuously expanding during the last decades. With increasing computational capacity and new techniques, computational methods have provided a more economic approach to explore different chemical systems. This review offers a broad yet concise overview of current state-of-the-art studies that have employed novel strategies for catalyst design. The evolution of the all different theoretical approaches most commonly used within organocatalysis is discussed, from the traditional approach, manual-driven, to the most recent one, machine-driven.  相似文献   
10.
A mathematical model of simultaneous cobalt deposition and hydrogen evolution was developed and applied to the electroreduction process of 5 mM Co2+ ions investigated by cyclic voltammetry (CV) technique at different hydrogen ion concentrations (pH=2, 3, 4). The kinetic parameters of such a complex process were determined, and the validity of the model and its sensitivity to changes in individual parameters were verified. The relative value of the approximate standard deviation (ASD%) was used to determine the degree of fit of the model to the experimental data. The catalytic effect of cobalt on the hydrogen evolution process was comprehensively confirmed.  相似文献   
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