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991.
Complex formation ability and stability of both weak and super-weak acids was studied by mean of in silico determined thermodynamic data of the complexes. While weak acids act like Brønsted acids forming hydrogen bond type Brønsted complexes, super-weak acids form Lewis complexes via van der Waals interaction. Unlike in the former type, upon complexation, C-H distances changes insignificantly, yet the complex formation is energy driven in the terms of zero-point corrected Energies, ΔE zp < 0 kcal mol?1, which supports the Lewis complex formation, with the exception of CH4, an extremely “weak acid”. 相似文献
992.
Effect of halogen bonding on supramolecular assembly and photophysical properties of diaryl oxalates
Dong-En Wu Yang-Hui Luo Man-Ning Wang Qing-Ling Liu Gao-Ju Wen Ling-Jun Zhu Chang-Po Fan Bai-Wang Sun 《Structural chemistry》2017,28(6):1731-1742
In order to determine the effect of halogen bonding on supramolecular assemblies and photophysical properties of diaryl oxalates, diaryl oxalate itself and its derivatives with fluorine, chlorine, bromine, and iodine substituents in the p-position of phenyl rings were studied and compared. Their single-crystal structures were studied by geometrical analysis and theoretical calculation. The study reveals that different halogen bonds are formed with respect to different halogen atoms, such as C…F and X…X (bromine and iodine atoms) interactions, and molecular stacking modes would be affected by halogen bonds directly. Comparative studies of photophysical properties in dilute solution and solid state indicate that halogen substitutions would not affect the emission processes of diaryl oxalates in dilute solution; this is not the case for their solid state. This work has demonstrated that halogen bonds play an important role in regulating structures and photophysical properties of diaryl oxalates. 相似文献
993.
Mansur B. Ibrahim Rami Suleiman Mohammed Fettouhi Bassam El Ali 《Transition Metal Chemistry》2017,42(1):1-8
A palladium(II)-bis(oxazoline) complex supported on silica (Pd-BOX-Si) was prepared, characterized and applied as a catalyst in Mizoroki–Heck cross-coupling reactions. The bis(oxazoline) (BOX) ligand has a hydroxyl group that can be anchored to 4-benzyl chloride-functionalized silica gel, followed by the coordination of palladium(II) chloride. The catalytic activity and the recyclability of Pd-BOX-Si have been investigated in the production of cinnamic acid derivatives via Mizoroki–Heck coupling reactions of acrylates with aryl halides; The Pd-BOX-Si catalyst demonstrated excellent catalytic activity. Characterization of the recycled Pd-BOX-Si catalyst revealed its good stability under the reaction conditions employed. 相似文献
994.
Yong-Ming Cui Lu Qiao Yi Li Qian Wang Wu Chen Wen-Xuan Yan 《Transition Metal Chemistry》2017,42(1):51-56
A series of dioxomolybdenum(VI) complexes with similar hydrazone ligands have been prepared, specifically [MoO2L1(MeOH)] (1), [MoO2L2(MeOH)] (2) and [MoO2L3(MeOH)] (3), where L1, L2 and L3 are the dianionic forms of 2-chloro-N′-(2-hydroxybenzylidene)benzohydrazide, 2-chloro-N′-(2-hydroxy-5-methylbenzylidene)benzohydrazide and N′-(3-bromo-5-chloro-2-hydroxybenzylidene)-2-chlorobenzohydrazide, respectively. The complexes were characterized by physicochemical and spectroscopic methods and also by single-crystal X-ray determination. The hydrazone ligands coordinate to the Mo atoms through their phenolate O, imine N and enolic O atoms. The Mo atoms are six-coordinated in octahedral geometries. The complexes show high catalytic activities and selectivities in the epoxidation of cyclohexene with tert-butylhydroperoxide as primary oxidant. 相似文献
995.
Xiao-Xu Song Chong-Chen Wang Xue-Yan Xu Huan-Ping Jing Peng Wang Shi-Jie Gao 《Transition Metal Chemistry》2017,42(2):181-191
Four coordination complexes of copper(II) and iron(II), namely [CuCl(phen)2](5-NO2-Hipa)·2H2O (BUC-10), [Cu(phen)(3,4-H2dczpb)(H2O)]·H2O (BUC-11), [Fe(phen)(L)(H2O)]2 (BUC-12), and [Fe(phen)3](3,4-H3dczpb)2·0.6H2O (BUC-13) (phen = 1,10-phenanthroline; 5-NO2-H2ipa = 5-nitroisophthalic acid; 3,4-H4dczpb = 3,4-dicarboxyl-(3′,4′-dicarboxylazophenyl) benzene; L = 6,12-dihydroxy-1,2,6,12-tetrahydroindazolo[2,1-a]indazole-1,7-dicarboxylic acid), have been synthesized under hydrothermal conditions. All four complexes were characterized by single-crystal X-ray diffraction, FTIR, elemental analysis and UV–Vis diffuse reflection spectroscopy. The photocatalytic performances of the complexes for decomposition of methylene blue under UV irradiation were also investigated. 相似文献
996.
Thales R. de Moura Sahra L. Cavalcanti Paulo R. D. V. de Godoy Elza T. Sakamoto-Hojo Fillipe V. Rocha Eduardo T. de Almeida Victor M. Deflon Antonio E. Mauro Adelino V. G. Netto 《Transition Metal Chemistry》2017,42(6):565-574
Complexes of the type cis-[PdX2(imzt)(PPh3)] {imzt = imidazolidine-2-thione; PPh3 = triphenylphosphine; X = Cl (1), Br (2), I (3), SCN (4)} have been synthesized and characterized by elemental analyses, molar conductance, IR and 1H NMR spectroscopies. The complex 1·MeOH was obtained from the reaction of [PdCl2(CH3CN)2], imidazolidine-2-thione and triphenylphosphine in CHCl3/CH3OH. Complexes 2·MeOH, 3 and 4 were prepared by metathesis of the chlorido ligands in 1 with bromide, iodide and thiocyanate, respectively. Elemental analyses showed good agreement with the expected mononuclear compositions, while the molar conductivities of the complexes in DMF were consistent with their nonelectrolytic nature. NMR spectra confirmed coordination of the imidazolidine-2-thione and triphenylphosphine ligands. Single-crystal X-ray diffraction determination of 1·CH3OH showed that the coordination geometry around PdII is nearly square planar, with the chlorido ligands in a cis configuration. All four complexes have been tested in vitro by XTT assay for their cytotoxicity against human glioblastoma cell line (U87MG). The binding of 1 with guanosine was studied by 1H NMR spectroscopy, revealing that the coordination takes place via N7. 相似文献
997.
Metalloproteins have inspired chemists for many years to synthesize artificial catalysts that mimic native enzymes.As a complementary approach to studying native enzymes or making synthetic models,biosynthetic approach using small and stable proteins to model native enzymes has offered advantages of incorporating non-covalent secondary sphere interactions under physiological conditions.However,most biosynthetic models are restricted to natural amino acids.To overcome this limitation,incorporating unnatural amino acids into the biosynthetic models has shown promises.In this review,we summarize first synthetic,semisynthetic and biological methods of incorporates unnatural amino acids(UAAs)into proteins,followed by progress made in incorporating UAAs into both native metalloproteins and their biosynthetic models to fine-tune functional properties beyond native enzymes or their variants containing natural amino acids,such as reduction potentials of azurin,O_2 reduction rates and percentages of product formation of HCO models in Mb,the rate of radical transport in ribonucleotide reductase(RNR)and the proton and electron transfer pathways in photosystemⅡ(PSⅡ).We also discuss how this endeavour has allowed systematic investigations of precise roles of conserved residues in metalloproteins,such as Metl21 in azurin,Tyr244 that is cross-linked to one of the three His ligands to CuB in HCO,Tyr122,356,730 and 731 in RNR and TyrZ in PSⅡ.These examples have demonstrated that incorporating UAAs has provided a new dimension in our efforts to mimic native enzymes and in providing deeper insights into structural features responsible high enzymatic activity and reaction mechanisms,making it possible to design highly efficient artificial catalysts with similar or even higher activity than native enzymes. 相似文献
998.
Solid phase peptide synthesis (SPPS) based on Fmoc chemistry has become a commonly used technique in peptide chemistry, as it can be easily conducted using automated machine, and not requiring highly toxic HF in comparison to Boc-SPPS. With the fast development in the emerging field of protein chemical synthesis, many efforts have been endeavored aiming to find more efficient methods for preparing peptide fragments required in ligation reactions. This review briefly summarizes recent advances in the engineering and modification of Fmoc-SPPS-derived peptides, which can be used as the N-terminal fragments in a native chemical ligation (NCL) or NCL-type ligation reactions. 相似文献
999.
Tinghai Yan Haijun Bin Yankang Yang Lingwei Xue Zhi-Guo Zhang Yongfang Li 《中国科学:化学(英文版)》2017,60(4):537-544
The medium band gap donor-acceptor(D-A) copolymer J61 based on bi(alkylthio-thienyl)benzodithiophene as donor unit and fluorobenzotriazole as acceptor unit and thiophene as π-bridge has demonstrated excellent photovoltaic performance as donor material in nonfullerene polymer solar cells(PSCs) with narrow bandgap n-type organic semiconductor ITIC as acceptor.For studying the effect of π-bridges on the photovoltaic performance of the D-A copolymers,here we synthesized a new D-A copolymer J61-F based on the same donor and acceptor units as J61 but with furan π-bridges instead of thiophene.J61-F possesses a deeper the highest occupied molecular orbital(HOMO) level at-5.45 eV in comparison with that(-5.32 eV) of J61.The non-fullerene PSCs based on J61-F:ITIC exhibited a maximum power conversion efficiency(PCE) of 8.24%with a higher open-circuit voltage(V_(oc)) of 0.95 V,which is benefitted from the lower-lying HOMO energy level of J61-F donor material.The results indicate that main chain engineering by changing π-bridges is another effective way to tune the electronic energy levels of the conjugated D-A copolymers for the application as donor materials in non-fullerene PSCs. 相似文献
1000.
Ag@C core–shell structure composites were successfully synthesized by hydrothermal method, and then Ag nanoparticles were decorated on the surface of Ag@C by reduction of AgNO3. The morphology, composition and structure of the Ag@C@Ag composites were characterized by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and X-ray diffraction (XRD). Cyclic voltammetry and amperometry were used to evaluate the electrocatalytic performance of the Ag@C@Ag/GCE for detection of H2O2. Meanwhile, a new electrochemical method of zero current potentiometry was used for electrochemical detection of H2O2. The linear range and the detection limit were from 0.2 to 10, and 0.07 μM, respectively. 相似文献