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961.
962.
Feng‐You Hao Yong‐Fang Zhao Xiao‐Gong Jing Xin‐Ying Li Feng‐Li Liu 《International journal of quantum chemistry》2007,107(6):1502-1507
Ab initio quantum chemical calculations have been performed on X2Cl? and X2Cl (X = C, Si, Ge) clusters. The geometrical structures, vibrational frequencies, electronic properties and dissociation energies are investigated at the Hartree–Fock (HF), Møller–Plesset second‐ and fourth‐order (MP2, MP4), CCSD(T) level with the 6‐311+G(d) basis set. The X2Cl (X = C, Si, Ge) and X2Cl? (X = Si, Ge) take a bent shape obtained at the ground state, while C2Cl? has a linear structure. The impact on internal electron transfer between the X2Cl and the corresponding anional clusters is studied. The three different types of electron affinities (EAs) at the CCSD(T) are reported. The most reliable adiabatic electronic affinities, obtained at the CCSD(T)/cc‐pvqz level of theory, are predicted to be 3.30, 2.62, and 1.98 eV for C2Cl, Si2Cl, and Ge2Cl, respectively. The calculated EAs of C2Cl and Ge2Cl are in good agreement with theoretical results reported. The correlation effects and basis sets effects on the geometrical structures and dissociation energies are discussed. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
963.
Design, synthesis, and binding affinities of pyrrolinone-based somatostatin mimetics 总被引:1,自引:0,他引:1
Smith AB Charnley AK Mesaros EF Kikuchi O Wang W Benowitz A Chu CL Feng JJ Chen KH Lin A Cheng FC Taylor L Hirschmann R 《Organic letters》2005,7(3):399-402
[structure: see text] Tetrapyrrolinone somatostatin (SRIF) mimetics (cf. 1), based on a heterochiral (D,L-mixed) pyrrolinone scaffold, were designed, synthesized, and evaluated for biological activity. The iterative synthetic sequence, incorporating the requisite functionalized coded and noncoded amino acid side chains, comprised a longest linear synthetic sequence of 23 steps. Binding affinities at two somatostatin receptor subtypes (hsst 4 and 5) reveal micromolar activity, demonstrating that the d,l-mixed pyrrolinone scaffold can be employed to generate functional mimetics of peptide beta-turns. 相似文献
964.
With the advent of the big data era, information storage and security are becoming increasingly important. However, high capacity information storage and multilevel anti-counterfeiting are typically difficult to achieve simultaneously. To address this challenge, herein, two electrochromic and electrofluorochromic dual-functional polymers with aggregation-induced emission (AIE) characteristics were rationally designed and facilely prepared. Upon applying voltages, the absorption and fluorescence spectra of the AIE polymers can undergo reversible changes, accompanied by variation of their color and emission. By utilizing the controllable characteristics of the polymers, dual-mode display devices were fabricated via a simple spraying technique. More interestingly, a four-dimensional color code device was constructed by adding color change multiplexing to the two-dimensional space, thereby achieving high capacity information storage. Moreover, the color code device can also be applied in the multilevel anti-counterfeiting area. The encrypted information can be dynamically converted under different voltages. Thus, the AIE polymers show great promise for applications in multidimensional information storage and dynamic anti-counterfeiting, and the design strategy may provide a new avenue for advanced information storage and high security technology.By using electrical stimuli-responsive AIE polymers, dual-mode display devices, multidimensional information storage and anti-counterfeiting devices were constructed. 相似文献
965.
Nonlinear optical (NLO) crystals assembled with conventional non-π-conjugated tetrahedral functional building units (FBUs), generally referring to [PO4] and [BO4], usually exhibit weak nonlinearity and poor birefringence. It is currently proposed that partially substituting oxygen atoms with fluoride atoms in these FBUs could enhance these crucial properties. Hence, we investigated for the first time the NLO-related properties of NH4BAsO4F (ABAF), which was constructed from tetrahedral [BO3F] and [AsO4] FBUs, and enhancements of these properties were observed in this material, that is large second-harmonic generation (SHG) response (2 × KDP) and improved birefringence (0.03 at 1064 nm). Notably, both SHG coefficient and birefringence of ABAF exceeded those of a great majority of phosphates, sulfates, or boron phosphates and achieved a preferable balance. It is interesting that ABAF shows vast structural similarities to the typical NLO crystals Sr2Be2B2O7 (SBBO) and KBe2BO3F2 (KBBF), which might be the partial reason why it showed improvement in these vital properties. This work may afford some inspiration for enhancing the key performances of NLO crystals assembled with non-π-conjugated tetrahedra.We report a new nonlinear optical crystal assembled exclusively with tetrahedral functional building units in which enhanced birefringence (Δn) and second-harmonic generation (deff) were observed. 相似文献
966.
Yubin Xue Shun‐Chang Liu Xinsheng Liu Yusi Yang Yimin Zhang Ding‐Jiang Xue Jin‐Song Hu 《中国化学》2020,38(4):356-360
Colloidal quantum dots (CQDs) are attractive absorber materials for high‐efficiency photovoltaics because of their facile solution processing, bandgap tunability due to quantum confinement effect, and multi‐exciton generation. To date, all published performance records for PbS CQDs solar cells have been based on the conventional hot‐injection synthesis method. This method usually requires relatively strict conditions such as high temperature and the utility of expensive source material (pyrophoric bis(trimethylsilyl) sulfide (TMS‐S)), limiting the potential for large‐scale and low‐cost synthesis of PbS CQDs. Here we report a facile room‐temperature synthetic method to produce high‐quality PbS CQDs through inexpensive ionic source materials including Pb(NO3)2 and Na2S in the presence of triethanolamine (TEA) as the stabilizing ligand. The PbS CQDs were successfully prepared with an average particle size of about 5 nm. Solar cells based on the as‐synthesized PbS CQDs show a preliminary power conversion efficiency of 1.82%. This room‐temperature and low‐cost synthesis of PbS CQDs will further benefit the development of solution‐processed CQD solar cells. 相似文献
967.
Zhang Qiang Mao Sifeng Li Weiwei Huang Qiushi Feng Shuo Hong Zhanying Lin Jin-Ming 《中国科学:化学(英文版)》2020,63(6):865-870
Cancer metastasis is one of the most serious problems for tumor therapy, which is closely related to cell adhesion and deadhesion process. Better comprehension of cell adhesion ability will benefit drug research. Here, a biomimetic microfluidic enzyme digestion method was proposed to gently measure the influence of drugs on cell-matrix adhesion ability at the single cell level.The method can selectively digest the extracellular matrix(ECM) that linked to a single cell, and the trypsin concentration around the cell is relatively uniform and constant, thus the measured cell adhesion strength should be precise. Commercially available anti-cancer agents including 5-fluorouracil(5-FU), actinomycin D(Act D), temozolomide(TMZ) and allicin were evaluated, and the data showed only TMZ and allicin can inhibit cell adhesion significantly under our experiment conditions. The influence of TMZ became more and more obvious as the increase of duration and the effect became prominent only after 6 h adhesion process, which could provide a quick evaluation of whether the drugs are effective to cancer cell(compared with Calcein-AM/PI cell viability test). The adhesion strength of U87 cells decreased when the concentration of TMZ increased, and the effect of TMZ can be effectively inhibited by adding lactic acid to culture medium, which indicated acidic tumor microenvironment could promote drug resistance of tumor cells. Different from conventional evaluation methods which focus on the drugs' influence on cellular viability or metabolism, this work provides a new perspective to study the effect of drugs, which is helpful to enrich the drug evaluation system. 相似文献
968.
Here, we report a new method based on the combination of membrane separation technology and nanomaterial to rapid detection of peptides and protein with MALDI-TOF MS. This method shows advantages as it can inhibit the heterogeneous of sample spot and enhance the target molecular signal intensity. 相似文献
969.
First-second shell interactions in metal binding sites in proteins: a PDB survey and DFT/CDM calculations 总被引:1,自引:0,他引:1
The role of the second shell in the process of metal binding and selectivity in metalloproteins has been elucidated by combining Protein Data Bank (PDB) surveys of Mg, Mn, Ca, and Zn binding sites with density functional theory/continuum dielectric methods (DFT/CDM). Peptide backbone groups were found to be the most common second-shell ligand in Mg, Mn, Ca, and Zn binding sites, followed (in decreasing order) by Asp/Glu, Lys/Arg, Asn/Gln, and Ser/Thr side chains. Aromatic oxygen- or nitrogen-containing side chains (Tyr, His, and Trp) and sulfur-containing side chains (Cys and Met) are seldom found in the second coordination layer. The backbone and Asn/Gln side chain are ubiquitous in the metal second coordination layer as their carbonyl oxygen and amide hydrogen can act as a hydrogen-bond acceptor and donor, respectively, and can therefore partner practically every first-shell ligand. The second most common outer-shell ligand, Asp/Glu, predominantly hydrogen bonds to a metal-bound water or Zn-bound histidine and polarizes the H-O or H-N bond. In certain cases, a second-shell Asp/Glu could affect the protonation state of the metal ligand. It could also energetically stabilize a positively charged metal complex more than a neutral ligand such as the backbone and Asn/Gln side chain. As for the first shell, the second shell is predicted to contribute to the metal selectivity of the binding site by discriminating between metal cations of different ionic radii and coordination geometries. The first-shell-second-shell interaction energies decay rapidly with increasing solvent exposure of the metal binding site. They are less favorable but are of the same order of magnitude as compared to the respective metal-first-shell interaction energies. Altogether, the results indicate that the structure and properties of the second shell are dictated by those of the first layer. The outer shell is apparently designed to stabilize/protect the inner-shell and complement/enhance its properties. 相似文献
970.
Tandem cascade reactions of allylazides and olefinic dipolarophiles to give cis‐fused 2,3,7‐triazabicyclo [3.3.0]octenes ( 5, 6 or 7 ) are reported. Therein, an intermolecular dipolar cycloaddition of azide and alkene gave a triazoline which was followed by isomerization of the triazoline to a diazoester ( 4 ) and then an intramolecular dipolar cycloaddition from the diazo functional group and the double bond in 4 to give 5 . Compound 5 may further more undergo a Michael addition to give 7‐substituted‐ 2,3,7‐ triazabicyclo [3.3.0]oct‐2‐ene ( 6 ) or a tautomerization to give 2,3,7‐triazabicyclo[3.3.0]oct‐3‐ene ( 7 ). The reaction may be manipulated to stop at a particular stage by adopting a suit able solvent or an appropriate temperature. 相似文献