催化动力学光度法测定微量铁

根据铁对过氧化氢氧化酸性铬蓝 K有强烈的催化作用 ,并使之褪色明显的特性 ,研究了最佳实验条件和动力学参数 ,建立了测定痕量铁的新方法。     

C_2(a~3Π_u)自由基与C_2H_6反应的动力学计算

用密度泛函理论B3LYP方法,在6-311G(d,p)基组下,优化得到C2(a3Πu)+C2H6→C2H+C2H5反应各驻点(反应物、过渡态和产物)的几何构型,对其进行振动分析,并计算了它们的能量.在CCSD/6-311G(d,p)水平下单点能计算得到的反应势垒为24.47kJ/mol.采用传统过渡态理论,计算了温度范围50K～2000K的反应速率常数.实验结果表明,随着反应温度的升高,反应速率逐渐升高,反应的平均活化能也随着温度的不断升高而不断增大.     

流动注射光纤荧光动力学法测定锰的研究——Mn（Ⅱ）—ANS-Brig35—NaIO4体系

以ANS-Brig35为荧光指示剂,研究了流动注射和光导纤维技术测定锰的催化动力学分析方法,线性范围为0.1-1.2μg.ml-1,检测下限为0.01μg.ml-1,对0.14μg.ml-1 Mn(Ⅱ)进行测定的相对标准偏差为0.22%,可以实现对茶叶、铝合金中的痕量锰的直接测定。     

氨茶碱的热分解动力学研究

用TG-DTG(热重-微分热重)联用技术研究了氨茶碱片剂在氮气气氛中的热分解行为。首先运用普适法Kissinger和Ozawa法计算了氨茶碱片剂的表观活化能E和指前因子lnA,然后运用一般积分法Coats-Redfern法和Satava-Sestak法推测了主分解阶段的最佳热分解机理,推测出热分解机理为相边界反应,求出了热分解反应的表观活化能和指前因子。几种方法求得的表观活化能和指前因子的平均值分别为113.933KJ/mol,lnA为22.101(1/min).用malek法对所得结果进行了验证,进一步证明所得动力学参数和机理函数的正确性。     

双燃料发动机燃烧模型研究综述

发动机燃烧模型的发展经历了零维模型,准维模型,多雏模型三个阶段。双燃料发动机是气体燃料使用的主要方式,针对国内外双燃料发动机燃烧模型的研究进展和现状,介绍了气体-柴油双燃料发动机的三维燃烧模型应包含的子模型和计算方法。     

THE POLYMERIZATION OF METHYL METHACRYLATE WITH A NEW TIN-BRIDGED YTTROCENE/Al(i-Bu)_3

ＩＮＴＲＯＤＵＣＴＩＯＮＳｉｎｃｅｔｈｅｐｏｌｙｍｅｒｉｚａｔｉｏｎｏｆｍｅｔｈｙｌｍｅｔｈａｃｒｙｌａｔｅ(ＭＭＡ)ｗｉｔｈｒａｒｅｅａｒｔｈｃａｔａｌｙｓｔｓｗａｓｒｅａｌｉｚｅｄｆｏｒｔｈｅｆｉｒｓｔｔｉｍｅｉｎ1991,ａｓｅｒｉｅｓｏｆｎｅｗｒａｒｅｅａｒｔｈｃａｔａｌｙｓｔｓｙｓｔｅｍｓｓｕｃｈａｓＮｄ(Ｐ204)3/Ａｌ(ｉＢｕ)3,Ｎｄ(Ｐ204)3/Ａｌ(ｉＢｕ)3/ＣＣｌ4,Ｎｄ(Ｏｃｔ)3/Ａｌ(ｉＢｕ)3,Ｌｎ(ａｃａｃ)3/ＢｕＭｇＣｌ,Ｙ(ａｃａｃ)3/Ａｌ(ｉＢｕ)3/ＢｕＬｉ,Ｎｄ(ｎａｐｈ)3/ＢｕＬｉ,ａｎｄＮｄ(Ｏ…     

Polymerization of methyl methacrylate with iron-ytterbium dinuclear metallocene catalyst

A novel iron-ytterbium dinuclear catalyst, FcB(MeCp) Yb (MeCp) Cl (Fc: ferrocenyl, B: diethylene ether), was synthesized for the polymerization of methyl methacrylate (MMA). Synergistic effects between the ferrocenyl group and the lanthanocene part were investigated regarding their catalytic behaviors. UV, IR, GPC and NMR were used to characterize the structures of the catalyst and polymer. Kinetic study showed that polymerization is first order in monomer concentration and fractional order (0.78) in the catalyst. The bimetallic complex is a good catalyst for the polymerization of MMA, giving high molecular weight PMMA with 78% syndiotactivity. Project (29774021) supported by NSFC and Laboratory of Rare-Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences     

有机合成反应选择性及其控制策略

有机合成是化学研究领域中最具有魅力的。结构复杂、性质多元、应用广泛的有机物及其合成方法学,让人赞叹与探求。文章用科学方法论总结了有机合成中的化学选择性、区域选择性和立体选择性的规律及其热力学和动力学控制策略,提出了综合利用其控制原理解释或预测竞争性反应产物的基本方法。     

A fast and versatile cross-linking strategy via o-phthalaldehyde condensation for mechanically strengthened and functional hydrogels

Fast and catalyst-free cross-linking strategy is of great significance for construction of covalently cross-linked hydrogels. Here, we report the condensation reaction between o-phthalaldehyde (OPA) and N-nucleophiles (primary amine, hydrazide and aminooxy) for hydrogel formation for the first time. When four-arm poly(ethylene glycol) (4aPEG) capped with OPA was mixed with various N-nucleophile-terminated 4aPEG as building blocks, hydrogels were formed with superfast gelation rate, higher mechanical strength and markedly lower critical gelation concentrations, compared to benzaldehyde-based counterparts. Small molecule model reactions indicate the key to these cross-links is the fast formation of heterocycle phthalimidine product or isoindole (bis)hemiaminal intermediates, depending on the N-nucleophiles. The second-order rate constant for the formation of phthalimidine linkage (4.3 M⁻¹ s⁻¹) is over 3000 times and 200 times higher than those for acylhydrazone and oxime formation from benzaldehyde, respectively, and comparable to many cycloaddition click reactions. Based on the versatile OPA chemistry, various hydrogels can be readily prepared from naturally derived polysaccharides, proteins or synthetic polymers without complicated chemical modification. Moreover, biofunctionality is facilely imparted to the hydrogels by introducing amine-bearing peptides via the reaction between OPA and amino group.     

Associated ACL risk factors differences during an unanticipated volleyball blocking movement

ABSTRACT

The lateral tilt of the arms accompanied by trunk lateral tilt is a typical blocking manoeuvre in volleyball. However, during this unanticipated blocking movement, an associated risk of ACL injury may result. The aim of the present study was to compare associative ACL risk factors at the initial contact and the first and second peak of VGRF during an unanticipated blocking movement with different arm positions. Synchronized kinematic and kinetic data were collected for each trial of each condition. Student paired t-tests and effect size were used to determine differences between two conditions (S – with arms straight up from the body) and (T – with the arms and trunk laterally tilted). The results showed that the T condition significantly decreases knee flexion, increases VGRF at the foot contact, first peak force and increases the valgus moment at the first peak force. The values of the associated risk factors for a non-contact ACL injury appear to be related to the tilted arm position accompanied by trunk tilt towards to right lower limb during landing. The players should be taught to land with greater knee flexion and, if possible, a double-leg landing to decrease right lower limb loading during the blocking manoeuvre.