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1.
Li  Han  Jintao  Feng  Wang  Zhen  Jia  Yan  Li  Peng  Yao  Cuixia  Qu  Zongjin 《Journal of fluorescence》2022,32(5):1825-1832

The development of fluorescent probes for nitroreductase (NTR) has received intense attention because of its biological significance and wide application. In this work, a novel fluorescent probe for the detection of NTR in aqueous solution was designed and synthesized on a 1,8-naphthalimide scaffold. In the presence of NTR and nicotinamide adenine dinucleotide (NADH) under physiological conditions, the probe was converted into a 4-hydroxy-1,8-naphthalimide derivative and exhibited a sharp fluorescence enhancement at 550 nm, with a high selectivity for NTR over various analytes. The detection limit for NTR was determined to be 9.8 ng/ml by this probe. Due to its low signal background, this probe showed?>?70-fold fluorescence enhancement. Theoretical calculations revealed that the reason for the fluorescence quenching of this probe is the photoinduced electron transfer (PET) from both the nitrobenzene and morpholine groups to the naphthalimide fluorophore.

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2.
Ternary clusters (NH3)·(H2SO4)·(H2O)n have been widely studied. However, the structures and binding energies of relatively larger cluster (n > 6) remain unclear, which hinders the study of other interesting properties. Ternary clusters of (NH3)·(H2SO4)·(H2O)n, n = 0-14, were investigated using MD simulations and quantum chemical calculations. For n = 1, a proton was transferred from H2SO4 to NH3. For n = 10, both protons of H2SO4 were transferred to NH3 and H2O, respectively. The NH4+ and HSO4 formed a contact ion-pair [NH4+-HSO4] for n = 1-6 and a solvent separated ion-pair [NH4+-H2O-HSO4] for n = 7-9. Therefore, we observed two obvious transitions from neutral to single protonation (from H2SO4 to NH3) to double protonation (from H2SO4 to NH3 and H2O) with increasing n. In general, the structures with single protonation and solvated ion-pair were higher in entropy than those with double protonation and contact ion-pair of single protonation and were thus preferred at higher temperature. As a result, the inversion between single and double protonated clusters was postponed until n = 12 according to the average binding Gibbs free energy at the normal condition. These results can serve as a good start point for studies of the other properties of these clusters and as a model for the solvation of the [H2SO4-NH3] complex in bulk water.  相似文献   
3.
An accurate potential energy surface for the ground electronic state of SH3 system has been constructed with 41,882 high level ab initio energy points and the neural network fitting method. The time-dependent wave packet method has been used to calculate the first state-to-state differential cross sections for the title reaction up to 1.2 eV in full dimensions, based on the reactant–product decoupling scheme. It is found that the majority of H2S are produced in the ground vibrational state, with a large fraction of available energy for the reaction ending up as product translational motion. The differential cross sections at the threshold energy are dominated by a very narrow peak in the backward direction. With the increase of collision energy, the width of the angular distribution increases considerably, which is a typical feature of a direct reaction via abstract mechanism, similar to the H2 + OH → H2O + H reaction. © 2018 Wiley Periodicals, Inc.  相似文献   
4.
在新的全域势能面上, 用准经典轨线方法细致地研究了O(1D)+CD4多通道化学反应的动力学.这个势能面是用交换不变多项式方法基于MRC+Q/aug-cc-pVTZ从头算点拟合得到的.通过计算得到了产物OD+CD3、D+CD2OD/CD3O和D2+DCOD/D2CO的分支比、平动能分布以及角度分布,结果显示理论与实验吻合得较好, 从而说明了这个反应的同位素取代效应很小. 研究表明,O(1D)+CD4反应是经过陷入的抽取机理发生的: 最初主要通过D原子的抽取,并不是之前人们认为的直接C-D键的插入形成CD3OD中间物后再进而解离成各个产物通道.  相似文献   
5.
6.
Si(111) electrode has been widely used in electrochemical and photoelectrochemical studies. The potential dependent measurements of the second harmonic generation (SHG) were performed to study Si(111) electrode interface. At different azimuthal angles of the Si(111) and under different polarization combinations, the curve of the intensity of SHG with extern potential has a different form of line or parabola. Quantitative analysis showed that these differences in the potential-dependence can be explained by the isotropic and anisotropic contribution of the Si(111) electrode. The change in the isotropic and anisotropic contribution of the Si(111) electrode may be attributed to the increase in the doping concentration of Si(111) electrodes.  相似文献   
7.
This extensive theoretical study employed the spin‐flip density functional theory (SFDFT) method to investigate the photoisomerization of 11‐cis‐retinal protonated Schiff base (PSB11) and its minimal model tZt‐penta‐3,5‐dieniminium cation (PSB3). Our calculated results indicate that SFDFT can perform very well in describing the ground‐ and excited‐state geometries of PSB3 and PSB11. We located the conical intersection (CI) point and constructed the photoisomerization reaction path of PSB3 and PSB11 by using the SFDFT method. To further verify the SFDFT results, we computed the energy profiles along the constructed linearly interpolated internal coordinate (LIIC) pathways by using high‐level theoretical methods, such as the EOM‐CCSD, CR‐EOM‐CCSD(T), CASPT2, NEVPT2, and XMCQDPT2 methods. The SFDFT method predicts that the photoisomerization of PSB3 is barrierless, in accordance with previous complete‐active‐space self‐consistent‐field (CASSCF) results. However, an energy barrier is predicted along the LIIC pathways of PSB11. This finding is different from previous CASSCF results and may indicate that the photoisomerization of PSB11 in gas phase is similar to that in solution. However, the higher spin contamination of the SFDFT method in the vicinity of the CI point caused the located CI geometry to deviate from that of the real CI. In addition, the LIIC pathways are only approximations to the minimum energy path (MEP). Thus, further experimental and theoretical studies are needed to verify the existence of an energy barrier along the photoisomerization reaction path of PSB11 in gas phase. © 2013 Wiley Periodicals, Inc.  相似文献   
8.
运用分子动力学模拟,研究了腺苷酸(激动剂)与A2AAR腺苷受体蛋白的相互作用和配体结合诱导的蛋白动力学变化.识别了与腺苷酸结合力强于0.5kcal/mol的关键基团:A63^2.61,I66^2.64,V84^3.32,L85^3.33,T88^3.36,F168^5.29,M177^5.38,L249^6.51,H250^6.52和N253^6.55,观察到腺苷酸没有与L167^5.28相互作用,这一结果支持了L167^5.28是抑制剂特异性结合位点,不与激动剂结合.未结合配体(激动剂或抑制剂)的单体A2AAR和腺苷酸结合后的A2AAR在构象上有三个不同功能性开关.腺苷酸结合可以诱导A2AAR腺苷受体蛋白的构象调整,使得三个功能性开关器件的构象与单体A2AAR不同.  相似文献   
9.
The hydration of NaCl has been widely studied and believed to be important for understanding the mechanisms of salt dissolution in water and the formation of ice nucleus, cloud, and atmospheric aerosols. However, understanding on the poly-NaCl ion pair interacting with water is very limited. Here, we investigated the adsorption of water molecules on (NaCl)3, using both theoretical calculations and anion photoelectron spectroscopy measurements. The calculated vertical detachment energies and the experimental ones agree well with each other. Furthermore, we found that, for neutral (NaCl)3(H2O) n (n = 2–7) clusters, the water-doped cuboid and structures formed by adding water molecules on the Na–Cl edges of the cuboid are energetically favored; water molecules preferentially bind to the Na–Cl edge if the NaCl ion pair has larger partial charges than others. We also found the anionic structures are more various compared with neutral ones, and the Na+ and Cl? ions are hydrated more easily in the anionic clusters than in the corresponding neutrals.  相似文献   
10.
All-inorganic zero-dimensional (0D) metal halides have recently received increasing attention due to their excellent photoluminescence (PL) performance and high stability. Herein, we present the successful doping of copper(I) into 0D Cs2ZnBr4. The incorporating of Cu+ cations enables the originally weakly luminescent Cs2ZnBr4 to exhibit an efficient blue emission centered at around 465 nm, with a high photoluminescence quantum yield (PLQY) of 65.3 %. Detailed spectral characterizations, including ultrafast transient absorption (TA) techniques, were carried out to investigate the effect of Cu+ dopants and the origin of blue emission in Cs2ZnBr4:Cu. To further study the role of the A-site cation and halogen, A2ZnCl4:Cu (A=Cs, Rb) were also synthesized and found to generate intense sky-blue emission (PLQY≈73.1 %). This work represents an effective strategy for the development of environmentally friendly, low-cost and high-efficiency blue-emitting 0D all-inorganic metal halides.  相似文献   
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