CO(υ)高振动激发态向C2H2的振动传能研究

用时间分辨富里叶红外发射谱研究了高振动激发态ＣＯ向Ｃ２Ｈ２的传能，得到了ＣＯ（ｖ＝１－３）各振动态布居及其随时间的变化。利用微分法解出弛豫微分方程组，获得ＣＯ（ｖ＝１－３）向Ｃ２Ｈ２的传能速率常数分别为：２．０±０．１，６．０±０．２和９．４±０．８（１０＾－１３ｃｍ＾３·ｍｏｌｅｃｕｌｅ＾－１·ｓ＾－１）。传能速率随着振动量子数的增加而迅速增加。ＣＯ的振动能应向Ｃ２Ｈ２的对称伸缩模ｖ２近共振Ｖ－     

氟硅烷自组装单分子膜的制备及其摩擦学性能

利用分子自组装技术制备了全氟辛酰胺丙基硅烷单分子膜,用X射线光电子能谱(XPS)对组装膜的表面元素进行了表征;接触角测试表明,该组装膜具有很好的疏水-疏油性,其对水的接触角高达105°,对正十六烷的接触角为50°.摩擦磨损实验结果表明,全氟辛酰胺丙基硅烷自组装单分子膜可以大大降低基片的摩擦系数,使载玻片的摩擦系数从0.85左右降低到0.14左右,而且低负荷下具有很好的耐磨性.     

Aluminum Lon Removal from Monoaluminum Ovotransferrin by Pyrophosphate

The rates at which aluminum was removed from the N- and C-terminal monoaluminum ovotransferrins by pyrophosphate were evaluated by UV difference spectra in 0.01 mol/L Hepes, pH=7.4 and at 37℃. Pesudo first-order rate constants as a function of pyrophosphate concentration were measured. The results indicate that the pathways of aluminum removal are different. For the N-terminal binding site, aluminum removal follows simple saturation kinetics, while the removal of aluminum from the C-terminal binding site reverts to the combination of saturation and first-order kinetics. The saturation component is consistent with a rate-limiting conformational change in the protein as has been reported. We propose that the first-order kinetics mechanism is attributed to a pre-equilibrium process. The rate constants of saturation kinetics are accelerated from both terminals with the addition of 0.1 mol/L chloride to the monoaluminum ovotransferrin solutions, whereas the rates of the first-order kinetics are decreased for the C-terminal binding site. The effect of chloride ionic strength causes a continuing increase on kobs for the N- and C-terminal binding sites. Moreover, the kinetics behavior of the N-terminal is more easily affected by chloride than that of the C-terminal. In the experiment presumably the N-terminal site is apparently kinetically more labile than the C-terminal site.     

茂基稀土胺化物与异氰酸正己酯的反应-{(MeC5H4)2Yb[OC(NPh2)N(n-hexyl)]}2的合成及表征

茂基稀土胺化物(MeCp)2YbNPh2(THF)与异氰酸正己酯(n-HexylNCO)按11摩尔比反应, 分离出产物{(MeC5H4)2Yb[OC(NPh2)N(n-hexyl)]}2. 产物经元素分析和核磁共振表征, 并测定了其晶体结构. 配合物属三斜晶系, R-3空间群, 晶胞参数为a=2.9533(11) nm, b=2.9533(11) nm, c=1.5873(6) nm, V=11.9896(80) nm3, Z=9, Dc=1.562 mg·m-3, μ=3.536 mm-1 (Mo Kα), F(000)=5670, R=0.034, Rw=0.064. 该化合物具有二个对称氧桥的双分子结构, 并存在着由氮原子向中心金属镱分子内配位而形成的三环骨架, 中心金属镱的配位数是九, 整个分子呈中心对称.     

杂环光化学——Ⅺ.1,3-二甲基-6-氮杂胸腺嘧啶和丙酮的光反应

研究了1,3-二甲基-6-氮杂胸腺嘧啶和丙酮的光反应。反应机理中包含有三线态激基复合物和由此相继形成的两个不同结构的双自由基作为反应中间体。最终得到了1:2的加成产物, 即2,2,4,4,6,8,10-七甲基-7,9-二氧代-3,5-二氧杂-1,8,10-三氧杂双环[4,4,0]癸烷(Ⅰ)。     

Thermotropic copolyamides from triethyleneglycol bis (4-carboxyphenyl) ether,aromatic diamines,and p-aminobenzoic acid

It is proposed that depression of the transition temperatures, especially the melting point (T_m), can be achieved by the introduction of a different amide bond structure into the copolyamides of dicarboxylic acids and diamines by copolymerization of aminocarboxylic acids, such as p-aminobenzoic acid. The effect was examined by the amount and distribution of the structure in the copolylamindes. Copolycondensations of PEG₃, p-aminobenzoic acid, and diamines with different chain lengths showed that the structural change of the amide bond in the copolymers, especially its distribution, was more important than its total amount in them. Several types of aminocarboxylic acids were briefly examined to study the effect. © 1994 John Wiley & Sons, Inc.     

Encrypting Chemical Reactivity in Protein Sequences toward Information‐Coded Reactions†

Controlling chemical reactivity has been the central theme in chemistry. Herein, we review the recent progress on the development of genetically encoded protein coupling reactions and their potential applications. The chemical reactivity is encoded in the protein sequences. The information is read out by folding and molecular recognition between two reactive components and subsequently translated into chemical bonding via autocatalysis. It has emerged as a unique way to tune the chemical reactivity and is regarded as one type of information‐coded reactions. Not only has it received many applications such as protein topology engineering, bioconjugation, biomaterials and synthetic biology, but also its principle may be extended beyond protein chemistry to enable new modes of supramolecular interactions that promote chemical bonding and that are simultaneously reinforced by covalent bonds.     

高效液相色谱与原子荧光光谱联用分析汞化合物形态的研究

建立了高效液相色谱与原子荧光光谱联用测定汞化合物形态的分析方法。实验对淋洗液组分浓度、氧化剂和还原剂浓度、载气流速及紫外消解管长度等操作条件进行了优化,获得了令人满意的分析结果。在优化的分离检测条件下,20μg/L的汞化合物标准溶液平行7次进样分析,甲基汞、无机汞和乙基汞的色谱峰高的相对标准偏差(RSD)分别为2.0%、2.9%和2.4%;3种汞化合物的线性范围为10~1000μg/L,25μL进样检出限分别为3、2和4μg/L。用建立的方法测定了脉红螺样品中甲基汞的含量,甲基汞和乙基汞的加标回收率分别为90%和92%。     

硫化物的生物氧化成手性亚砜

描述了硫化物不对称生物氧化成手性亚砜, 主要为氯过氧化物酶、环己酮单氧酶催化有机硫化物氧化成具有光学活性的亚砜的两条酶促反应途径.     

离子交换树脂纯化酪蛋白磷酸肽研究

通过单因素实验和正交试验确定了使用D-201型大孔强碱性阴离子交换树脂纯化酪蛋白磷酸肽(CPPs)的操作条件为：洗脱温度40℃、洗脱酸(HCI)浓度0．2mol／L、洗脱速度2．3ml／min、进样浓度2％(w／v)，进一步应用HPSEC技术分析考察了离子交换树脂纯化后含磷洗脱峰分子量分布情况，并计算了产品氮磷比与纯化收率．