基于氨基化石墨烯量子点荧光比率法超灵敏检测辣根过氧化物酶

荧光比率法超灵敏检测辣根过氧化物酶传感器的构建主要基于酶催化邻苯二胺氧化生成2,3-二氨基吩嗪,生成的2,3-二氨基吩嗪能猝灭氨基化石墨烯量子点440nm处的荧光强度,同时伴随2,3-二氨基吩嗪本身在553nm处的荧光信号增强。随着辣根过氧化物酶浓度的增加,2,3-二氨基吩嗪位于553nm处的荧光不断增强且氨基化石墨烯量子点440nm处的荧光逐渐减弱,形成荧光比率信号。当辣根过氧化物酶浓度在2~800fM范围时,其荧光比率信号与辣根过氧化物酶的浓度具有较好的线性关系,对辣根过氧化酶的检出限为0.21fM。该传感器具有良好的选择性和抗干扰能力,并能实现检测过程的可视性。     

辣根过氧化物酶催化过氧化氢氧化邻苯二胺反应动力学的研究

本文对辣根过氧化物酶催化过氧化氢与氧化邻苯二胺合成 2 ,3 二氨基吩嗪反应动力学进行了研究。首先是用辣根过氧化物酶催化过氧化氢氧化邻苯二胺合成了氧化产物 ,并且对反应条件、酸度 ,温度 ,邻苯二胺 ,过氧化氢与辣根过氧化物酶不同的摩尔比等进行了研究。用紫外 可见光谱、红外光谱以及元素分析法对该产物进行了表征 ,结果表明 ,其产物为 2 ,3 二氨基吩嗪。然后用紫外可见分光光度法 ,根据Michaelis Menten(M M )方程研究了辣根过氧化物酶催化过氧化化氢氧化邻苯二胺反应 ,选择了最佳实验条件 ,确定了最大吸收波长λ =4 4 6 3nm ,pH =4 85和反应温度t=2 2℃ ,进行了一系列实验 ,从而确定了体系的反应级数 ,其结果表明 ,这个反应可以视为单底物反应进行处理 ,并且在实验和理论方面作出了论证 ,并且还求出Km =6 0 2× 10 - 3mol·L- 1 ,vm =7 2× 10 - 2 ΔA·min- 1 。     

沙蚕磷草酸盐的合成与光谱精征

用１－二甲氨基２,３－二氯丙烷和Ｏ,Ｏ－二甲基－二硫代磷酸盐反应合成了一种新的有机磷杀虫剂沙蚕磷,还制备了它的草酸盐。用＾１Ｈ、＾１３Ｃ核磁共振波谱,红外光谱及质谱法表征了沙蚕磷草酸盐的分子结构,结果表明反应产物是１,３－二取代产物。     

沙蚕磷草酸盐的合成与光谱表征

用１－二甲氨基－２,３－二氯丙烷和Ｏ,Ｏ－二甲基－二硫代磷酸盐反应合成了一种新的有机磷杀虫剂沙蚕磷,还制备了它的草酸盐。用１Ｈ、１３Ｃ核磁共振波谱、红外光谱及质谱法表征了沙蚕磷草酸盐的分子结构,结果表明反应产物是１,３－二取代产物。沙蚕磷的分子结构为（ＣＨ３）２Ｎ＋ＨＣＨ［ＣＨ２ＳＰ（Ｓ）（ＯＣＨ３）２］２Ｃ２Ｏ４Ｈ－［Ｏ,Ｏ,Ｏ′,Ｏ′－四甲基－Ｓ,Ｓ′－（２－Ｎ,Ｎ－二甲氨基丙撑）－双－二硫代磷酸酯草酸盐］。     

三水合氯化(2,3-二氨基-5H-吩嗪)的合成及晶体结构研究

合成了化合物三水合氯化(2,3-二氨基-5H-吩嗪)[C12H11N 4Cl-1·3(H2O1)],采用元素分析、NMR、IR、UV对其结构进行了表征.并用X射线单晶衍射仪确定了它的晶体结构,化合物属三斜晶系,空间群Pi,晶胞参数a=0.68123(8)nm,b=0.98861(11)nm,c=1.13066(13)nm,a=74.496(2)°,β=76.890(2)°,γ=82.817(2)°;V=0.71295(14)nm3,Dc=1.401g/cm3,Z=2,F(000)=316,μ=0.281mm-1.     

2,4—二氨基—1,3—环丁烷二酮分子的二阶超极化率和电子相关效应

在６－３１Ｇ＊＊水平上优化了２,４－二氨基－１,３－环丁烷二酮（ＮＤＱ）的分子构型,并计算了振动频率。分别用有限场方法（ＦＦ）及耦合微扰方法（ＣＰＨＦ）在ａｂ ｉｎｉｔｉｏ／４－３１Ｇ＋ｐｂ／ｐ水平上计算值较ＲＨＦ增大９％和７８％。用三态模型对计算结果进行了分析。     

“皮革奶”中L-羟脯胺酸的测定

用硫酸水解试样,再过滤、稀释水解产物。产物经氯胺T氧化后,与对二甲氨基苯甲醛反应生成红色化合物,用分光光度计进行比色测定。本法测定＂皮革奶＂中L-羟脯氨酸的含量可操作性强,适合批量检测。     

用二维NMR变换谱定量地研究氘代DMSO和氘代氯仿中小肽活泼质子的交换动力

用核磁共振二维交换谱方法研究了类肽化合物Ｃｂｚ－Ｔｙｒ－ＯＣ６Ｈ１３中活泼质子的交换动力学,结果表明,在ＤＭＳＯ－ｄ６和ＣＤＣｌ３溶液中,四种活泼质子与溶剂中残留水的交换快慢顺序为：Ｓｅｒ－ＯＨ〉Ｔｙｒ－ＯＨ〉Ｓｅｒ－ＮＨ〉Ｔｙｒ－ＮＨ,在此基础上,对氨基酸中氨基所处的局部环境进行了讨论。     

超声波辐照下N,N,N’,N’-四甲基二氨基二苯 甲烷的合成研究

本文报道了Ｎ,Ｎ,Ｎ’,Ｎ’－四甲基二氨基二苯甲烷的催化合成反应研究,讨论了超声空化场对氨基苯磺酸和阴离子表面活性剂等条件对该反应的催化作用。     

荧光光度法测定雨水中的H2O2含量

研究了在pH4.48的HAc-NaAc缓冲溶液中,邻苯二胺(OPDA)与过氧化氢反应生成新物质2,3-二氨基吩嗪(DAPN)的荧光光谱变化,通过跟踪DAPN的荧光强度建立了过氧化氢测定的新方法,该方法由于采用二元体系,实验操作简单,灵敏度较高。实验结果表明,过氧化氢含量在9.0×10-7～3.6×10-5mol.L-1范围内与荧光强度的变化呈良好的线性关系,线性方程为:F=1.15c(μmol.L-1) 398.6,相关系数r=0.9991,最低检出限为2.7×10-7mol.L-1(3Ds/斜率,n=11)。对含量为7.5×10-6mol.L-1和3.0×10-5mol.L-1的H2O2的标准溶液进行了11次平行测定,其相对标准偏差分别为2.2%和1.0%。考察了多种共存离子的影响。该方法用于雨水中微量H2O2的测定,测定结果令人满意。     

Cl+HD反应产物的极化与态分布

利用准经典轨线理论 ,在BW 2和G3两个势能面上 ,研究了Cl +HD反应的动力学 .计算结果表明 ,产物的转动取向对势能面及反应体系的质量因子非常敏感 .在BW 2势能面上 ,计算的两个产物的转动取向强于在G3势能面上计算的结果 ,而无论是在BW 2势能面上还是在G3势能面上 ,DCl产物的取向都强于HCl产物的取向 .计算结果还表明 ,在不同的势能面上反应物的转动激发对反应的影响有着显著的不同 .在BW 2势能面上 ,反应物的初始转动激发有利于Cl+HD反应的进行 ;而在G3势能面上 ,反应物的初始转动激发消弱了反应的反应性     

Theoretical study of the mechanism of cycloaddition reaction between dichloromethylene silylene and formaldehyde

The mechanism of cycloaddition reaction between singlet dichloromethylene silylene and formaldehyde has been investigated using a MP2/6-31G* method, including geometry optimization and vibrational analysis for the stationary points on the potential energy surface. The energies of different conformations are calculated by CCSD(T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that the cycloaddition reaction between singlet dichloromethylene silylene and formaldehyde has three competitive dominant reaction channels: (1) the two reactants first form a highly strained three-membered ring intermediate INT1c, which then isomerizes to an active four-membered ring product P1 via a transition state TS1c by ring-increasing reaction; Subsequently, P1 further reacts with formaldehyde to form the more stable silapolycyclic product P2; (2) the two reactants first form a four-membered ring intermediate INT1b by the [2?+?2] cycloaddition reaction, which then isomerizes to the four-membered ring product P3.1 via a transition state TS3.1, resulting from the chlorine transfer reaction; (3) INT1b further reacts with formaldehyde to form a silapolycyclic intermediate INT4, which then isomerizes to a silapolycyclic product P₄ via a transition state TS4.     

新型含能富勒烯衍生物的合成研究

 利用N-甲基甘氨酸、2，4-二硝基苯甲醛和C₆₀反应，合成分离出了含有两个硝基的新型富勒烯吡咯烷衍生物1，并对其工艺条件进行了研究，探讨了反应物剂量比、温度和时间对产物1产率的影响，得到了合成产物1的最佳工艺条件：反应物剂量比为1∶2∶6、温度为95 ℃、反应时间为40 h，此时产物1产率可达到65.8%（以消耗的C₆₀计）。同时用¹H NMR、FT-IR、MS、UV-Vis等光谱手段确定了产物1的分子结构。     

Ab initio Study of the Potential Energy Surface and Product Branching Ratios for Reaction of O(1D) with C2H5Cl

用QCISD(T)/6-311++G(d,p)//MP2/6-31G(d,p)方法研究了O(1D)与CH3CH2Cl的反应．计算表明此反应存在一个插入-消去机理．此反应先形成IM1和IM2两个中间体,两个中间体再分解成各种产物．用RRKM理论计算了碰撞能分别为0、20.9、41.8、62.7、83.6、104.5和125.4 kJ/mol时通过IM1、IM2分解的各个通道的分支比率．IM1的主要分解产物是HCl,IM2的主要分解产物是CH2OH．因为IM1比IM2稳定,HCl很可能是反应的主要产物．计算结果能够提供反应机理而且可以对以后的实验提供可能的解释．     

Isomers of OCS and their reaction with H2O on singlet potential energy surface

The isomers of the carbonyl sulfide (OCS) molecule are investigated in detail at CCSD(T)/cc-pVTZ//MP2/6-311++G(2d,2p) level of theory. One cyclic isomer was identified along with three different linear minima of the OCS molecule. Three interconversion transition states were also located between cyclic and linear forms of OCS. Among these four isomers, the singlet potential energy surface (PES) for the molecule–molecule reaction between the three most energetically favoured isomers of OCS and H₂O has been explored theoretically at the CCSD(T)/cc-pVTZ//MP2/6-311++G(2d,2p) level. This singlet PES comprises of three paths. Path 1 is the reaction of linear OCS molecule with water producing the major product P1 (CO₂?+?H₂S), minor product P2 (S?+?HCOOH) and two isomers via 14 minima and 15 transition states. The Path 2 is an isomerization process in which cyclic isomer of OCS reacts with water molecule via another initial barrierless aduct producing five isomers of the OCS–H₂O system through five interconversion transition states. The reaction of linear COS isomer with water is shown in Path 3. This path produces the radicals SH and COOH from another COS–H₂O complex via a transition state. Among these three products, the product P1 is energetically most favoured. The overall exothermicity of the product channels for the formation of major product P1 on PES is calculated to be about 10.60?kcal/mol possessing initial high entrance barriers of 45.48 and 55.47?kcal/mol in two possible pathways. As the process is favoured thermodynamically but not kinetically, the reaction is expected to be very slow.     

Product polarization distribution: Stereodynamics of the reaction of atom H and radical NH

The product angular momentum polarization of the reaction of H+NH is calculated via the quasiclassical trajectory method (QCT) based on the extended London-Eyring-Polanyi-Sato (LEPS) potential energy surface (PES) at a collision energy of 5.1 kcal/mol. The calculated results of the vector correlations are denoted by using the angular distribution functions. The polarization-dependent differential cross sections (PDDCSs) demonstrate that the rotational angular momentum of the product H₂ is aligned and oriented along the direction perpendicular to the scattering plane. Vector correlation shows that the angular momentum of the product H₂ is aligned in the plane perpendicular to the velocity vector. It suggests that the reaction proceeds preferentially when the reactant velocity vector lies in a plane containing all three atoms. The orientation and alignment of the product angular momentum affects the scattering direction of the product molecules. The polarization-dependent differential cross sections (PDD-CSs) reveal that scattering is predominantly in the backward hemisphere.     

Surface aligned ion-molecule reaction: direct observation of initial and final ion momenta

An ion-molecule reaction has been studied by measuring the momentum of both the reactant and the product ions. This is carried out in an ordered molecular film of CD3I where electron stimulated desorption causes the reaction CD+3+ CD3I--> C2D+5+DI. The close similarity of the normal momentum of CD+3 and C2D+5 indicates that a sticky collision occurs in which, to within 10%, the momentum of the reactant ion is transferred to the momentum of the product ion. The measurement represents the first use of molecularly aligned species to study momentum effects in an ion-molecule reaction.     

新型香豆素-7，8-环磷酰胺衍生物的合成与NMR研究

以7-羟基香豆素为原料,经过Mannich反应化学选择性地得到了8位的7-羟基香豆素Mannich碱,然后在三乙胺存在的条件下,与磷酰二氯氮芥发生环合反应得到了一种新型的香豆素-7,8-环磷酰胺衍生物. 通过中间产物Mannich碱和目标产物的NMR图谱,都证实了Mannich反应的化学选择性位点是7-羟基香豆素的8位而不是6位;通过DEPT、¹H-¹H COSY,HSQC和HMBC等2D NMR技术对目标化合物的¹H 和¹³C NMR数据进行了全归属和较详细的解析.      

共焦拉曼光谱对疏水基底上Mg(CH3COO)2液滴与CO2非均相反应动力学过程的观测

本文利用共焦拉曼光谱在球形液滴的表面和中心可聚焦两次的特性, 观测了不同RH(relative humidity, 相对湿度)下疏水基底上Mg(CH3COO)2液滴与CO2在液滴表面和中心的反应情况。结果表明, 反应生成的产物为碱式碳酸镁。当RH约73%时, 液滴表面和中心生成的产物的量差别不大; 当RH约65%时, 表面和中心的差别较RH约73%时明显; 而当RH降至约58%时, 表面和中心的差别则变得非常明显。由于Mg(CH3COO)2液滴在较低相对湿度下会形成胶态结构, 引起传质受阻, 从而使得CO2由液滴表面扩散到内部变得越来越困难, 最终导致液滴表面生成的产物比中心多。