Study on disulfur-backboned nucleic acids:Part Ⅳ.Efficient synthesis of 3',5'-dithio-2'-deoxyguanosine

<正>An efficient and novel method for synthesizing 3′,5′-dithio-2′-deoxyguanosine was described.In this method normal guanosine was used as the starting material.A very efficient procedure was used to synthesize 2-O-tosylguanosine 1,which used 0.1 eq.DBTO instead of 2 eq.1 was treated with LTBH to give 9-(2-deoxy-β-D-threo-pentofuranosyl)guanine 2.2 could be easily turned to the target compound.     

Total synthesis of endothelin 1 by microwave-assisted solid phase method

<正>A microwave-assisted solid phase synthesis for endothelin 1 is presented.Reduced endothelin 1 was synthesized efficiently on Wang resin under microwave irradiation using Fmoc/tBu orthogonal protection strategy.The whole peptide was cleaved from the resin and two disulphide bridges were formed under air oxidation at room temperature.The purity and efficiency of synthesizing the peptide is much higher than other methods used before.     

Effect of L64 on the Phase Behavior of 1-Dodecyl-3-methylimidazolium Chloride/Water System

Phase behavior of ternary system involving surfactant‐like ionic liquid 1‐dodecyl‐3‐methylimidazolium chloride ([C₁₂mim]Cl), water, and nonionic surfactant PEO‐PPO‐PEO block copolymer (Pluronic L64) is investigated at 25°C. Hexagonal (H₁) and lamellar liquid crystal phase (Lα) are found in [C₁₂mim]Cl/H₂O/L64 system by using polarized optical microscopy (POM), small‐angle X‐ray scattering (SAXS) techniques and ²H NMR spectra. The phase structure (H₁ phase), which is formed in [C₁₂mim]Cl/H₂O binary system, is not changed when L64 with a low concentration is added. However, phase transitions will occur from hexagonal to multiphases of H₁ and cubic phases (C), then to Lα+C phases with constant [C₁₂mim]Cl/H₂O ratio and increasing L64 concentration. Moreover, at given L64 (5%, 20%) concentration, the lattice parameter of H₁ or Lα phase decreases with increasing [C₁₂mim]Cl/H₂O ratio. Fourier transform infrared (FTIR) spectra indicate that the H‐bonded network comprising an imidazolium ring, chloride ion and water formed in [C₁₂mim]Cl/H₂O binary system is disrupted upon addition of L64. This is helpful to the phase transition, due to the decreasing of interfacial curvature induced by dehydration of hydrated layer after the addition of PEO block of L64.     

Effect of electron-withdrawing units on triphenylamine-based small molecules for solution-processed organic solar cells

Organic small molecules(TPA-BT3T,TPA-PT3T,and TPA-DFBT3T)using triphenylamine as a donor unit,terthiophene as a bridge,and benzo-2,1,3-thiadiazole(BT),[1,2,5]thiadiazolo[3,4-c]pyridine(PT)or 5,6-difluorobenzo[c][1,2,5]thiadiazole(DFBT)as an acceptor unit were designed and synthesized through Suzuki coupling reactions.These molecules exhibited good thermal stability with decomposition temperatures over 380°C and broad absorption from 300 to 700 nm.Photovoltaic devices were fabricated with these small molecules as donors and PC71BM as an acceptor.The TPA-BT3T based devices exhibited a power conversion efficiency of 2.89%,higher than those of the TPA-PT3T-and TPA-DFBT3T-based devices(1.34%and1.54%respectively).The effects of electron-withdrawing units on absorption,energy level,charge transport,morphology,and photovoltaic properties also were investigated.     

Determination of the Interaction of Arsenic and Human Serum Albumin by Online Microdialysis Coupled to LC with Hydride Generation Atomic Fluorescence Spectroscopy

Study on the stoichiometry and affinity of the arsenicals bound to HSA is an important step toward a better understanding of arsenic toxic effects. After incubation of As^III or As^V with HSA at the physiological conditions (pH 7.43 and 37 °C), the free arsenicals and arsenic-HSA complexes were separated and detected by the combined techniques of microdialysis and liquid chromatography with hydride generation atomic fluorescence spectroscopy (MD–LC–HGAFS). The decrease of As^III peak response rather than As^V indicated that HSA reacted with As^III but not As^V. The binding plots indicated that the binding between HSA and As^III was in Scatchard pattern when the concentration ratios of As^III to HSA were ≤1:1. The strong binding sites (n ₁) were 1.6 and the stability constant (K ₁) was 1.54 × 10⁶ M⁻¹. When the concentration ratios of As^III to HSA were >1:1, the binding was in Plasvento pattern with the stability constant K ₂ ≅ 0 and no specific binding of As^III with HSA. On the contrary, As^V did not show binding with HSA. The results showed that As^III reacted with HSA more readily than As^V, which provides a chemical basis for arsenic toxicity.

     

三角波强加载下延性金属多次层裂破坏问题

基于应力瞬时断裂判据和Tuler-Butcher损伤累积判据，分析了没有升压的简单三角波强加载下延性金属的多次层裂破坏问题。分析结果显示:层裂片的厚度随着冲击波宽度与强度的比值的增大而增大，材料的破坏深度小于冲击波宽度的一半；在强冲击加载下，材料的破坏深度约为冲击波宽度的一半。