Synthesis,structure and stereochemistry of diiodide complexes (E)[(η5-t-BuC5H3)Fe(CO)2I]2 (E = Me2Si,Me2SiSiMe2, and Me2SiOSiMe2)

Reactions of diiron complexes (E)[⁵-t-BuC₅H₃)Fe(CO)]₂(-CO)₂ [E = Me₂Si (1), Me₂SiSiMe₂ (2), and Me₂SiOSiMe₂ (3)] with iodine in CHCl₃ yielded diiodide complexes (E)[⁵-t-BuC₅H³)Fe(CO)₂I]₂ [E=Me₂Si (5), Me₂SiSiMe₂ (6), and Me₂SiOSiMe₂ (7)]. Like (1–3), complexes (5–7) also exists as mixtures of cis and trans isomers even though the Fe–Fe bond in (1–3) has been cleaved. When the pure isomers (1–3) reacted with iodine respectively in CHCl₃, the cis isomers (1c–3c) yielded only the cis products (5c–7c), whereas the trans isomers (1t–3t) yielded only the trans isomers (5t–7t). This indicates that iodination of bridged diiron complexes is stereospecific. Similar treatment of trans-(Me₂Si)[{⁵-t-(heptyl)C₅H₃}Fe(CO)]₂(-CO)₂ (4t) with iodine gave only the trans product (Me_2Si)[{⁵-t-(heptyl)C₅H₃}Fe(CO)₂I]₂ (8t). The molecular structure of (5t) was determined by X-ray diffraction.     

Ultrasensitive small molecule fluorogenic probe for human heparanase

Heparanase (HPA) is a critical enzyme involved in the remodeling of the extracellular matrix (ECM), and its elevated expression has been linked with diseases such as various types of cancer and inflammation. The detection of heparanase enzymatic activity holds tremendous value in the study of the cellular microenvironment, and search of molecular therapeutics targeting heparanase, however, no structurally defined probes are available for the detection of heparanase activity. Here we present the development of the first ultrasensitive fluorogenic small-molecule probe for heparanase enzymatic activity via tuning the electronic effect of the substrate. The probe exhibits a 756-fold fluorescence turn-on response in the presence of human heparanase, allowing one-step detection of heparanase activity in real-time with a picomolar detection limit. The high sensitivity and robustness of the probe are exemplified in a high-throughput screening assay for heparanase inhibitors.

Heparanase, a critical enzyme involved in the remodeling of the extracellular matrix, activates a disaccharide probe HADP to give a strong fluorescence signal.     

烯烃羰化—步制醇铑系催化新体系的研究

羰基铑催化剂由于其加氢性能较弱，在羰基化反应的研究中，通常仅作为烯烃氢甲酰化制醛的催化剂。产物中得不到醇。本文则报道了以Ｒｈ＿２（ＡｃＯ）＿４和Ｒｈ＿６（ＣＯ）＿１６为催化剂，在一个反应器内进行烯烃氢甲酰化，加氢制醇的研究。系统考察了Ｒｈ／Ｐｂｕ＿３／ＥｔＯＨ催化体系受各种反应条件的影响。在最佳反应条件下，烯烃转化率达１００％。对醇选择性亦在９９．５％以上，正异构比在２以上．为烯烃一步制醇建立了铑系催化新体系。文中并利用红外光谱测定了反应过程的催化剂物种．实验证明，由烯烃一步制醇是由烯烃首先进行氢甲酰化反应，然后由生成的醛进一步加氢成醇的一个串联反应过程。前一步骤反应速度较快，２ｈ内可使９５％以上的烯烃转化为醛，后面由醛加氢成醇则进行缓慢，在１００—１２０℃下，至少２２ｈ，才能使醛全部转化为醇。     

A Quantum Chemical Study of N14 Cluster

Ab initio molecular orbital theory and density functional theory have been employed to study N₁₄ cluster with low spin at the HF/6-31G*, B3LYP/6-31G*, B3PW91/6-31G*, BP86/6-31G*, and BHLYP/6-31G* levels of theory. Twelve isomers were studied, including one previously investigated cage molecule. The most stable isomer of N₁₄ is a C _2h -symmetric molecule that contains two separated five-membered nitrogen rings connected by a —N=N—N=N— bridge. The second, third, and fifth most stable isomers each have one five-membered nitrogen ring. The theoretical results suggest that the five-membered nitrogen ring gives rise to a particularly stable structural unit, and the more side chains that the five-membered nitrogen ring links with, the less stable the structure will become.     

β-内酰胺类抗生素酶促合成新进展

β-内酰胺类抗生素的合成在制药工业中占据重要的地位, 相关的酶促合成方法研究备受关注; 酶促合成显著提高合成效率, 减少三废的排放, 是实现绿色合成的有效方法. 综述了近年来β-内酰胺类抗生素酶促合成研究的新进展, 包括一锅合成法、原位产物排出法、介质技术和酶固定化方法.     

Experimental and theoretical studies of rate coefficients for the reaction O(3P)+CH3OH at high temperatures

Rate coefficients of the reaction O((3)P) + CH(3)OH in the temperature range of 835-1777 K were determined using a diaphragmless shock tube. O atoms were generated by photolysis of SO(2) with a KrF excimer laser at 248 nm or an ArF excimer laser at 193 nm; their concentrations were monitored via atomic resonance absorption excited by emission from a microwave-discharged mixture of O(2) and He. The rate coefficients determined for the temperature range can be represented by the Arrhenius equation, k(T) = (2.29 +/- 0.18) x 10(-10) exp[-(4210 +/- 100)T] cm(3) molecule(-1) s(-1); unless otherwise noted, all the listed errors represent one standard deviation in fitting. Combination of these and previous data at lower temperature shows a non-Arrhenius behavior described as the three-parameter equation, k(T) = (2.74 +/- 0.07) x 10(-18)T(2.25 +/- 0.13) exp[-(1500 +/- 90)T] cm(3)molecule(-1) s(-1). Theoretical calculations at the Becke-3-Lee-Yang-Parr (B3LYP)6-311 + G(3df,2p) level locate three transition states. Based on the energies computed with coupled clusters singles, doubles (triples) [CCSD(T)]/6-311 + G(3df,2p)B3LYP6-311 + G(3df,2p), the rate coefficients predicted with canonical variational transition state theory with small curvature tunneling corrections agree satisfactorily with the experimental observations. The branching ratios of two accessible reaction channels forming OH + CH(2)OH (1a) and OH + CH(3)O (1b) are predicted to vary strongly with temperature. At 300 K, reaction (1a) dominates, whereas reaction (1b) becomes more important than reaction (1a) above 1700 K.     

镓在氨基吡啶树脂上的吸附行为及机理

前文已报道了氨基吡啶树脂对AuCl_4~-、PtCl_6~(2-)的吸附性。本文报道4-氨基吡啶树脂对镓的吸附行为与机理。在6mol/L HCl条件下,对镓的氯络阴离子(GaCl_4~-)有很好的吸附性。并能定量洗脱。测得静态吸附容量为351.15mg/g树脂,用化学法及红外光谱等方法,测得4-氨基吡啶树脂吸附镓(Ⅲ)的基本参数。     

TEOS-MTES基SiO2溶胶微结构的SAXS研究

正硅酸乙酯(TEOS)为前驱体,在碱性条件下制备含有无定形SiO2颗粒的溶胶,以甲基三乙氧基硅烷(MTES)在酸性条件下获得聚甲基硅氧链,二者混合后应用同步辐射X射线进行混合溶胶的SAXS散射强度测定,计算了溶胶的平均回转半径、平均粒径、两相界面层厚度、散射体体积分数、两相间比表面积等参数,辅以光子相关光谱法(PCS)和透射电子显微镜(TEM)观测溶胶粒度,证实SiO2颗粒被MTES混合物连接成族团.实验发现所测混合溶胶样品均表现出对Porod定理的负偏离,说明溶胶中颗粒与溶剂之间存在很明显的两相间界面层.     

电渗流与缓冲液浓度之间数学关系的线性表达

It was believed that electroosmotic mobility μeo is inversely proportional to the square root of the ionic strength L But the linear relationship for regression analysis was expressed differently in different papers. The paper studied the linear expression of the mathematical relationship between μeo and c （background buffer concentration） by mathematical transform and real experimental data.μeo values of fused silica capillary were determined in four buffer systems. Their experimental conditions were controlled carefully for decreasing temperature difference AT and pH difference ApH in 50 μm ID capillary, in which no double layer overlap existed. The linear relationship between the reciprocal of electroosmotic mobility and the square root of concentration （or ionic strength） was derived by mathematical method. The regression analysis of experimental data was shown to well correspond to the relationship. The constants in regression equation could be well defined and the calculated results were acceptable.     

铜基催化剂的制备方法对草酸二乙酯加氢反应的影响

草酸二乙酯加氢性成乙二醇的反应过程中，所用的铜基催化剂是由Ｃｕ（ＮＯ３）２与硅溶胶凝法制得的。本文考察了该催化剂的ＴＰＲ特性，结果表明，随着催化剂中Ｃｕ／ＳｉＯ２值的增大，其ＴＰＲ主峰ＴＭ峰温有所升高，这意味着催化剂的还原温度随Ｃｕ／ＳｉＯ２值的增大而提高。用ＸＲＤ和ＸＰＳ等手段对该催化剂还原后铜的含量及价态进行了考察，表明用胶凝法制备的铜基催化剂，还原后存在Ｃｕ＾ｏ和Ｃｕ＾＋两种价态。结合活性评