无患子三萜皂苷研究进展

无患子是一种集工业、药用、观赏、生态于一体的多功能综合利用价值极高的经济树种,近年来,由于其具有较高的商业价值和药理活性,受到了广泛的重视。迄今文献中报道的无患子中分离鉴定的三萜皂苷类化合物有71种,具有抗菌、抗肿瘤、保护心脑血管、保护肝脏、抗生育、杀虫等多种生物活性和良好的非离子表面活性作用,在医药、食品保健、日化和农业等领域应用前景广阔。本文对其皂苷的种类、提取与分离及其应用进行了综述,以期为今后无患子的研究、开发与利用提供参考。     

Cure mechanism of novel bismaleimide resins based on fluorene cardo moiety and their thermal properties

In this paper, two novel bismaleimide resins based on 9, 9-bis[4-(4-maleimidophenoxy) phenyl] fluorene (PFBMI), 9, 9-bis[4-(4-maleimidophenoxy)-3-methylphenyl]fluorene (MFBMI), and 2, 2’-diallyl bisphenol A (DABPA) were prepared. Their curing mechanism and curing kinetic were carefully investigated by Differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The thermal mechanical properties of the composites based on these BMI resins and the glass cloth were obtained by Dynamic mechanical analysis (DMA), displaying that the novel resins whose T_g were 296°C and 289°C had excellent thermal performance. In addition, Thermogravimetric analysis (TGA) results showed that both the cured PD and MD resins possessed good thermal stability, and their T_5% were all higher than 410°C.     

Pressure Dependence of the Lattice Distortion in Perovskite La0.5−xBixCa0.5MnO3 (x=0.1, 0.15, 0.2)

The in situ behavior of distorted perovskite La_0.5−xBi_xCa_0.5MnO₃ (x=0.1, 0.15, 0.2) under high pressure has been studied by energy-dispersive X-ray diffraction in a diamond anvil cell. An abnormal change of the 202–040 d-spacing ascribed to the disappearance of the distortion mode Q₂ in the MnO₆ octahedra is observed at 1.2, 1.4, and 1.6 GPa, respectively, and it results in a reduction of the Jahn–Teller distortion commonly existing in the manganites. Effect of the unique 6s² long-pair character of the Bi³⁺ ion on the pressure dependence of the lattice distortion is discussed.     

Kinetic determination of ascorbic acid by the BZ oscillating chemical system

A new analytical method for the determination of ascorbic acid by the perturbation caused by different amounts of ascorbic acid on the BZ oscillating chemical system involving the Ce(IV)-catalyzed reaction between potassium bromate and malonic acid in a acidic medium is proposed. The method relies on the linear relationship between the change in the oscillation amplitude of the chemical system and the concentration of ascorbic acid, which is in this work exposed for the first time. The calibration curve is linearly proportional to the concentration of ascorbic acid over the range 3.5x10(-6)-4.7x10(-4) M, with the regression coefficient is 0.9975. Two different methodologies were used to address the determination. Some aspects of the potential mechanism of action of ascorbic acid on the BZ oscillating chemical system are discussed in detail.     

Dehydrogenative coupling of phenanthroline under hydrothermal conditions: crystal structure of a novel layered vanadate complex constructed of 4,8,10-net sheets: [(2,2'-biphen)Co]V3O8.5

2,2'-Biphenanthroline (2,2'-biphen) formed from 1,10-phenanthroline when a new two-dimensional layered vanadium oxide metal coordination complex, [(2,2'-biphen)Co]V3O8.5, which contains novel 4,8,10-net sheets, was hydrothermally synthesized.     

An unmediated hydrogen peroxide biosensor based on hemoglobin incorporated in a montmorillonite membrane

Hemoglobin was incorporated in a montmorillonite membrane. Electrochemical and spectroscopic studies revealed that the electron transfer reactivity and peroxidase activity of the protein were both enhanced. Nevertheless, its structure was still maintained native-like in the membrane. An unmediated hydrogen peroxide biosensor was accordingly prepared. The calibration plot of this H202 sensor was linear in the range of 1.0 x 10(-6)-6.0 x 10(-4) mol L(-1). The relative standard deviation was 3.1% for six successive determinations at a concentration of 1.0 x 10(-4) mol L(-1). The detection limit was 6.0 x 10(-7) mol L(-1). Possible interferences in real sample analyses are discussed.     

Synthesis of p‐tert‐Butyl‐calix[6] ‐biscrown‐3 via Intramolecular Ring‐closure of 1,4‐Bis (2‐(2‐chloroethoxy) ethoxy) ‐p‐tert‐butyl‐calix[6]arene

With a variation in reaction conditions, 1, 4‐bis (2‐(2‐chloroethoxy)ethoxy)‐calix[6]arene (3) and l,3,5‐tris(2‐(2‐chloroethoxy) ethoxy)‐calix [6] arene (4) or 4 and 4‐chloroethoxyethoxy‐calix[6]crown‐3 (5) were selectively synthesized from p‐tert‐butyl‐calix [6] arene and 2‐(2‐chloroethoxy)ethyltosylate. l,3–4,6‐p‐tert‐butylcalix[6]‐bis‐crown‐3 (6) with (u,u,u,d,d,d) conformation and 1,3–4,5‐p‐tert‐butylcalix[6]‐biscrown‐3 (7) with self‐anchored (u,u, u, u, u, d) conformation were synthesized through an intramolecularly ring‐closing condensation of 1, 4‐bis (2‐(2‐chloroethoxy)ethoxy)‐p‐tert‐butyl‐calix[6]arene (3) in 25% and 15% yield, respectively. Using 5 instead of 3, only 7 was obtained in 65% high yield. 6 and 7 show different complexation properties toward alkali metal and ammonium ions.     

A novel hydrogen‐bonded microporous framework constructed from two different metal complexes

A hydrogen‐bonded coordination supramol­ecule, (meso‐5,7,­7,­12,14,14‐hexa­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐κ⁴N)­nickel(II) [N,N‐o‐phenylenebis­(oxamato)­‐κ⁴O,N,N′,O′]nickelate(II) dihydrate, [Ni(C₁₆H₃₆N₄)][Ni(C₁₀H₄N₂O₆)]·2H₂O or [Ni(meso‐cth)]­[Ni(opba)]·2H₂O, has been prepared and characterized by X‐ray crystallographic analysis. The two complex ions, i.e. [Ni(meso‐cth)]²⁺ and [Ni(opba)]^2?, are hydrogen bonded to each other, resulting in two‐dimensional neutral supramolecular sheets. The sheets stack along the a direction to produce a three‐dimensional architecture with one‐dimensional channels in which hydrogen‐bonded chains of water mol­ecules are included.     

Preparation of CaCO3/Polystyrene Inorganic/Organic Composite Nanoparticles

CaCO₃/polystyrene inorganic/organic composite nanoparticles (50 nm) with a core/shell structure were synthesized in 80% yield by emulsion polymerization. Nanometer CaCO₃ was pretreated with γ‐methacryloxypropyltrimethoxysilane in order to introduce polymerizable groups onto its surface. Soxhlet extraction experiments have shown that only 4% of total encapsulating polystyrene (PS) was removable when the ratio of CaCO₃ to styrene was relatively low (14.8–29.6%), indicating strong adhesion between CaCO₃ and PS.     

硅酸盐中桥联键的机制及其性质的CNDO/2法研究

法计算模型,分析了桥联键的成键机制,解释了硅酸盐的通常性质。以体系总能量随桥角变化关系,解释了硅酸盐矿物及沸石分子筛中桥角Si-O-T出现的范围和几率。 由计算结果还发现,桥氧上具有较高的非键p-电子电荷Q_o~n,并随桥氧的第三配原子性质和距离R(M-O~(br))而变化,使桥氧具有授受电子的双重性质。在此基础上,探讨了沸石分子筛的碳离子催化活性机理,提出了锁与匙匹配原子对的催化活性中心的新观点。