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131.
132.
Monte Carlo (MC) methods are important computational tools for molecular structure optimizations and predictions. When solvent effects are explicitly considered, MC methods become very expensive due to the large degree of freedom associated with the water molecules and mobile ions. Alternatively implicit-solvent MC can largely reduce the computational cost by applying a mean field approximation to solvent effects and meanwhile maintains the atomic detail of the target molecule. The two most popular implicit-solvent models are the Poisson-Boltzmann (PB) model and the Generalized Born (GB) model in a way such that the GB model is an approximation to the PB model but is much faster in simulation time. In this work, we develop a machine learning-based implicit-solvent Monte Carlo (MLIMC) method by combining the advantages of both implicit solvent models in accuracy and efficiency. Specifically, the MLIMC method uses a fast and accurate PB-based machine learning (PBML) scheme to compute the electrostatic solvation free energy at each step. We validate our MLIMC method by using a benzene-water system and a protein-water system. We show that the proposed MLIMC method has great advantages in speed and accuracy for molecular structure optimization and prediction. 相似文献
133.
Liping Zhang Yun Geng Lijuan Li Xiaofan Tong Shi Liu Xingman Liu Zhongmin Su Zhigang Xie Dongxia Zhu Martin R. Bryce 《Chemical science》2021,12(16):5918
Near-infrared (NIR) emitters are important probes for biomedical applications. Nanoparticles (NPs) incorporating mono- and tetranuclear iridium(iii) complexes attached to a porphyrin core have been synthesized. They possess deep-red absorbance, long-wavelength excitation (635 nm) and NIR emission (720 nm). TD-DFT calculations demonstrate that the iridium–porphyrin conjugates herein combine the respective advantages of small organic molecules and transition metal complexes as photosensitizers (PSs): (i) the conjugates retain the long-wavelength excitation and NIR emission of porphyrin itself; (ii) the conjugates possess highly effective intersystem crossing (ISC) to obtain a considerably more long-lived triplet photoexcited state. These photoexcited states do not have the usual radiative behavior of phosphorescent Ir(iii) complexes, and they play a very important role in promoting the singlet oxygen (1O2) and heat generation required for photodynamic therapy (PDT) and photothermal therapy (PTT). The tetranuclear 4-Ir NPs exhibit high 1O2 generation ability, outstanding photothermal conversion efficiency (49.5%), good biocompatibility, low half-maximal inhibitory concentration (IC50) (0.057 μM), excellent photothermal imaging and synergistic PDT and PTT under 635 nm laser irradiation. To our knowledge this is the first example of iridium–porphyrin conjugates as PSs for photothermal imaging-guided synergistic PDT and PTT treatment in vivo.Iridium–porphyrin conjugates assembled in nanoparticles are photosensitizers that exhibit excellent photothermal imaging and synergistic PDT and PTT in vivo. 相似文献
134.
Lei Sun Jiahui Geng Dr. Mengyou Gao Dr. Dehua Zheng Zhongxin Jing Qingyun Zhao Prof. Jianjian Lin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(42):10998-11004
Fe0.95S1.05 with high reactivity and stability was incorporated into WS2 nanosheets via a one-step solvothermal method for the first time. The resulted hybrid catalyst has much higher catalytic activity than WS2 and Fe0.95S1.05 alone, and the optimal WS2/Fe0.95S1.05 hybrid catalyst was found by adjusting the feed ratio. The addition of Fe0.95S1.05 was proven to be able to enhance the hydrogen evolution reaction (HER) activity of WS2, and vice versa. At the same time, it was found that the catalytic effect of the hybrid catalyst was the best when the feed ratio was W : Fe=2 : 1. In other words, we confirmed that there is a synergistic effect between W- and Fe-based sulfide hybrid catalysts, and validated that the reason for the improved HER performance is the strong interaction between the two in the middle sulfur. WS2/Fe0.95S1.05-2 hybrid catalyst leads to enhanced HER activity, which shows a low overpotential of ∼0.172 V at 10 mA cm−2, low Tafel slope of ∼53.47 mV/decade. This study supplies innovative synthesis of a highly active WS2/Fe0.95S1.05 hybrid catalyst for HER. 相似文献
135.
Yibo Zhang Prof. Yuying Zheng Prof. Hongbo Geng Dr. Yang Yang Dr. Minghui Ye Dr. Yufei Zhang Prof. Cheng Chao Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(35):9031-9037
Metal phosphates have been widely explored in lithium ion batteries and sodium ion batteries owing to high theoretical capacities, mild toxicity and low cost. However, their potassium ion battery applications are less reported due to the limited conductivity and the slow diffusion kinetics. Considering these drawbacks, novel structured M2P2O7/C (M=Fe, Co, Ni) nanoflake composites are prepared through an organic-phosphors precursor-assisted solvothermal method and a subsequent high temperature annealing process. The designed Co2P2O7/C composite exhibits the highest rate capacity with 502 mAh g−1 at 0.1 A g−1 and good cyclability for 900 cycles at 1 A g−1 and 2 A g−1 when compared with Ni and Fe based composites. The superior electrochemical performance can be attributed to their unique nanoparticle-assembled nanoflake structure, which can afford enough active sites for K+ intercalation. In addition, the robust pyrophosphate crystal structure and the in situ formed carbon composition also have positive effects on enhancing the long-term cycling performance and the electrode's conductivity. Finally, this organic-phosphors precursor induced simple approach can be applied for easy fabrication of other pyrophosphate/carbon hybrids as advanced electrodes. 相似文献
136.
137.
Crown ether complexes of sodium and potassium 2-(benzotriazol-2-yl)phenolates were synthesized and characterized. In the presence of BnOH these complexes are highly active catalysts for the controlled ring-opening polymerization of rac-lactide. The polymerizations are iso-selective and the Pm of polylactide reached 0.77 when the polymerization was performed in toluene at ?60°C; whereas heterorich-polylactide was obtained when the polymerization was carried out in CH2Cl2 or THF. 相似文献
138.
Matthias Uhl Tanja Geng Philipp A. Schuster Benjamin W. Schick Matthias Kruck Alexander Fuoss Prof. Dr. Alexander J. C. Kuehne Prof. Dr. Timo Jacob 《Angewandte Chemie (International ed. in English)》2023,62(2):e202214927
For sustainable energy storage, all-organic batteries based on redox-active polymers promise to become an alternative to lithium ion batteries. Yet, polymers contribute to the goal of an all-organic cell as electrodes or as solid electrolytes. Here, we replace the electrolyte with a deep eutectic solvent (DES) composed of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) and N-methylacetamide (NMA), while using poly(2,2,6,6-tetramethylpiperidin-1-yl-oxyl methacrylate) (PTMA) as cathode. The successful combination of a DES with a polymer electrode is reported here for the first time. The electrochemical stability of PTMA electrodes in the DES at the eutectic molar ratio of 1 : 6 is comparable to conventional battery electrolytes. More viscous electrolytes with higher salt concentration can hinder cycling at high rates. Lower salt concentration leads to decreasing capacities and faster decomposition. The eutectic mixture of 1 : 6 is best suited uniting high stability and moderate viscosity. 相似文献
139.
Yu Wang Bochun Liang Jiaxiong Zhu Geng Li Qing Li Ruquan Ye Jun Fan Chunyi Zhi 《Angewandte Chemie (International ed. in English)》2023,62(23):e202302583
Constructing a reliable solid-electrolyte interphase (SEI) is imperative for enabling highly reversible zinc metal (Zn0) electrodes. Contrary to conventional “bulk solvation” mechanism, we found the SEI structure is dominated by electric double layer (EDL) adsorption. We manipulate the EDL adsorption and Zn2+ solvation with ether additives (i.e. 15-crown-5, 12-crown-4, and triglyme). The 12-crown-4 with medium adsorption on EDL leads to a layer-structured SEI with inner inorganic ZnFx/ZnSx and outer organic C−O−C components. This structure endows SEI with high rigidness and strong toughness enabling the 100 cm2 Zn||Zn pouch cell to exhibit a cumulative capacity of 4250 mAh cm−2 at areal-capacity of 10 mAh cm−2. More importantly, a 2.3 Ah Zn||Zn0.25V2O5⋅n H2O pouch cell delivers a recorded energy density of 104 Wh Lcell−1 and runs for >70 days under the harsh conditions of low negative/positive electrode ratio (2.2 : 1), lean electrolyte (8 g Ah−1), and high-areal-capacity (≈13 mAh cm−2). 相似文献
140.
在溶剂热条件下,以2-吡啶甲醛肟(HL)为主配体,Zn(OAc)2·2H2O和NiCl2·6H2O为金属盐,合成了一个NiⅡ2ZnⅡ2簇配合物[Ni2Zn2(L)4Cl2(CH3O)2](1),通过元素分析、红外光谱、单晶X射线衍射等对其结构进行了表征。研究了该配合物的磁性及光催化降解染料的性能,结果表明:配合物1属于正交晶系,Pna21空间群,其分子中包含2个NiⅡ离子,2个ZnⅡ离子,4个L-配体,2个Cl-离子和2个CH3O-离子。磁性研究表明NiⅡ…NiⅡ离子间存在弱的反铁磁相互作用。光催化降解染料的研... 相似文献