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71.
Sulfur-containing scaffold, as a ubiquitous structural motif, has been frequently used in natural products, bioactive chemicals and pharmaceuticals, particularly C−S/N−S bonds are indispensable in many biological important compounds and pharmaceuticals. Development of mild and general methods for C−S/N−S bonds formation has great significance in modern research. Iodine and its derivatives have been recognized as inexpensive, environmentally benign and easy-handled catalysts or reagents to promote the construction of C−S/N−S bonds under mild reaction conditions, with good regioselectivities and broad substrate scope. Especially based on this, several new strategies, such as oxidation relay strategy, have been greatly developed and accelerated the advancement of this field. This review focuses on recent advances in iodine and its derivatives promoted hybridized C−S/N−S bonds formation. The features and mechanisms of corresponding reactions are summarized and the results of some cases are compared with those of previous reports. In addition, the future of this domain is discussed.  相似文献   
72.
For high-throughput screening (HTS) of Bacillus fastidiosus uricase mutants, a practical system was proposed. By error-prone PCR with final 1.5 mM MnCl2, two focused libraries of mutants for A1-V158 and V150-D212 were generated separately. After induced expression of individual clones in 48-well microplates, Escherichia coli cells (BL21) were lyzed by 1.0 M Tris-HCl at pH 9.0 in 96-well microplates at 25 °C for 7.5 ~ 10.5 h; uricase reaction was continuously monitored with 0.15 mM uric acid in 96-well plates by absorbance at 298 nm to estimate V m/K m by kinetic analysis of reaction curve for comparison. V m/K m was resistant to initial uric acid levels with an upper limit 3-fold over that of initial rates. By receiver-operator-characteristic analysis of the recognition of the one of higher activity in uricase pair whose specific activity ratio was 1.8 or 3.3, the area-under-the-curve was comparable to that with cell lysates prepared by sonication treatment. A cutoff for the maximum Youden index was thus developed to recognize positive mutants of 1-fold higher activity. Indeed, mutant L171I/Y182F/Y187F/A193S of higher activity but lower thermostability at pH 7.4 and mutant V144A of higher activity and consistent thermostability were discovered. Therefore, the proposed system was practical for HTS of uricase mutants.  相似文献   
73.
崔洪波  孙君燕 《分析化学》1992,20(7):790-793
本文对微型管状离子选择电极在流动条件下的电化学特征进行了研究,并设计了新的集成微管路离子选择以电极功能块。用此微型装置测定了土壤、血清、水和药物中的K~+、Na~+、pH、Cl~-、F~-、阿托品、东茛菪碱,并和各种标准方法作了比较,获得满意分析结果。  相似文献   
74.
    
A novel and unusual palladium‐catalyzed [4+2] annulation of cyclopropenes with benzosilacyclobutanes is reported. This reaction occurred through chemoselective Si?C(sp2) bond activation in synergy with ring expansion/insertion of cyclopropenes to form new C(sp2)?C(sp3) and Si?C(sp3) bonds. An array of previously elusive bicyclic skeleton with high strain, silabicyclo[4.1.0]heptanes, were formed in good yields with excellent diastereoselectivity under mild conditions. An asymmetric version of the reaction with a chiral phosphoramidite ligand furnished a variety of chiral bicyclic silaheterocycle derivatives with good enantioselectivity (up to 95.5:4.5 er). Owing to the mild reaction conditions, the good stereoselectivity profile, and the ready availability of the functionalized precursors, this process constitutes a useful and straightforward strategy for the synthesis of densely functionalized silacycles.  相似文献   
75.
    
Molecular ferroelectrics have attracted considerable interests because of their easy and environmentally friendly processing, low acoustical impedance and mechanical flexibility. Herein, a molecular thermochromic ferroelectric, N,N′‐dimethyl‐1,4‐diazoniabicyclo[2.2.2]octonium tetrachlorocuprate(II) ([DMe‐DABCO]CuCl4) is reported, which shows both excellent ferroelectricity and intriguing thermochromism. [DMe‐DABCO]CuCl4 undergoes a ferroelectric phase transition from Pca21 to Pbcm at a significantly high Curie temperature of 413 K, accompanied by a color change from yellow to red that is due to the remarkable deformation of [CuCl4]2? tetrahedron, where the ferroelectric and paraelectric phases correspond to yellow and red, respectively. Combined with multiple bistable physical properties, [DMe‐DABCO]CuCl4 would be a promising candidate for next‐generation smart devices, and should inspire further exploration of multifunctional molecular ferroelectrics.  相似文献   
76.
    
Core–shell nanocatalysts are attractive due to their versatility and stability. Here, we describe cobalt nanoparticles encapsulated within graphitic shells prepared via the pyrolysis of a cationic poly‐ionic liquid (PIL) with a cobalt(II) chloride anion. The resulting material has a core–shell structure that displays excellent activity and selectivity in the self‐dehydrogenation and hetero‐dehydrogenation of primary amines to their corresponding imines. Furthermore, the catalyst exhibits excellent activity in the synthesis of secondary imines from substrates with various reducible functional groups (C=C, C≡C and C≡N) and amino acid derivatives.  相似文献   
77.
    
Biological ion channels and ion pumps with sub‐nanometer sizes modulate ion transport in response to external stimuli. Realizing such functions with sub‐nanometer solid‐state nanopores has been an important topic with wide practical applications. Herein, we demonstrate a biomimetic photoresponsive ion channel and photodriven ion pump using a porphyrin‐based metal–organic framework membrane with pore sizes comparable to hydrated ions. We show that the molecular‐size pores enable precise and robust optoelectronic ion transport modulation in a broad range of concentrations, unparalleled with conventional solid‐state nanopores. Upon decoration with platinum nanoparticles to form a Schottky barrier photodiode, photovoltage across the membrane is generated with “uphill” ion transport from low concentration to high concentration. These results may spark applications in energy conversion, ion sieving, and artificial photosynthesis.  相似文献   
78.
    
A dual‐site catalyst allows for a synergetic reaction in the close proximity to enhance catalysis. It is highly desirable to create dual‐site interfaces in single‐atom system to maximize the effect. Herein, we report a cation‐deficient electrostatic anchorage route to fabricate an atomically dispersed platinum–titania catalyst (Pt1O1/Ti1?xO2), which shows greatly enhanced hydrogen evolution activity, surpassing that of the commercial Pt/C catalyst in mass by a factor of 53.2. Operando techniques and density functional calculations reveal that Pt1O1/Ti1?xO2 experiences a Pt?O dual‐site catalytic pathway, where the inherent charge transfer within the dual sites encourages the jointly coupling protons and plays the key role during the Volmer–Tafel process. There is almost no decay in the activity of Pt1O1/Ti1?xO2 over 300 000 cycles, meaning 30 times of enhancement in stability compared to the commercial Pt/C catalysts (10 000 cycles).  相似文献   
79.
    
The combined use of gold as transition metal catalyst and N‐heterocyclic carbene (NHC) as organic catalyst in the same solution for relay catalytic reactions was disclosed. The ynamide substrate was activated by gold catalyst to form unsaturated ketimine intermediate that subsequently reacted with the enals (via azolium enolate intermediate generated with NHC) effectively to form bicyclic lactam products with excellent diastereo‐ and enantio‐selectivities. The gold and NHC coordination and dissociation can be dynamic and tunable events, and thus allow the co‐existence of both active metal and carbene organic catalysts in appreciable concentrations, for the dual catalytic reaction to proceed.  相似文献   
80.
Quantum chemical study has been performed on finite-sized bi-metallic Rh3M alloys, M = Ag, Ir, Pd, Pt, Au, derived from magic cluster, Rh4. Bond length of C–O and N–O are noticed to be elongated in the presence of rhodium alloy clusters. CO2 and NO2 gases are found to be highly adsorbed on Rh3M clusters, which is confirmed by stretching frequency of C–O and N–O. DFT evaluated dipole moment and electronic charge redistribution suggests the sensing capability of CO2 and NO2 gases by Rh3M clusters which is further confirmed by the calculated HOMO–LUMO gap. Mixed rhodium alloy clusters supported on single-wall carbon nanotube (SWCNT) exhibits much higher ability to sense CO2 and NO2. On the other hand, SWCNT@Rh3M shows higher catalytic activity for the activation of CO2 and NO2 in comparison to bare Rh3M because of the higher electronic charge redistribution in the case of SWCNT@Rh3M. In case of SWCNT-supported gas adsorbed clusters, p electrons play a major role in bonding.  相似文献   
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