HNCS与C_2H(X~2Π)反应微观动力学的理论研究

用量子化学密度泛函理论的UB3LYP/6-311 G鄢鄢方法和高级电子相关的UQCISD(T)/6-311 G鄢鄢方法研究了异硫氰酸(HNCS)与乙炔基自由基(C2H(X2Π))反应的微观机理.采用双水平直接动力学方法IVTST-M,获取反应的势能面信息,应用正则变分过渡态理论并考虑小曲率隧道效应,计算了在250～2500K温度范围内反应的速率常数.研究结果表明,HNCS与C2H(X2Π)反应为多通道、多步骤的复杂反应,共存在三个可能的反应通道,主反应通道为通过分子间H原子迁移,生成主要产物NCS C2H2.反应速率常数随温度升高而增大,表现为正温度效应.速率常数计算中变分效果很小.在低温区隧道效应对反应速率的贡献较大,反应为放热反应.     

酞菁键合硅胶的制备及分离取代酞菁异构体

制备和表征了一种新的酞菁键合硅胶，三-β-(辛巯基)-β-(磺酰胺基)-酞菁铜键合硅胶。研究了该键合酞菁硅胶作为HPLC固定相的基本色谱性能。实验结果表明，该固定相可以分离四-α-(2，2，4-三甲基-3-戊氧基)酞菁(铜、镍)的4种异构体，也可以观察到四-α-(2，2，4-三甲基-3-戊氧基)无金属酞菁的4种异构体，而商业C₁₈(VERTEX Eurospher)却只能观察到两组峰，表明这种酞菁键合硅胶固定相在分析、分离一些取代酞菁异构体方面比商业C₁₈具有更好的分离效果。     

分散固相萃取结合气相色谱-高分辨质谱快速筛查酱油中多种氯丙醇

建立了酱油中1，3-二氯-2-丙醇、2，3-二氯-1-丙醇、3-氯-1，2-丙二醇和2-氯-1，3-丙二醇的分散固相萃取-气相色谱-高分辨质谱快速筛查检测方法。样品采用乙酸乙酯提取，提取液浓缩后经N-丙基乙二胺净化，气相色谱-高分辨质谱测定，内标法定量。结果表明，该方法对于酱油中4种氯丙醇的定量限为0.5~10 μg/kg。在3个浓度水平下的加标回收率为78%~103%；相对标准偏差均不大于8.8%。该方法快速、简便、准确、灵敏，可作为酱油中4种氯丙醇的有效检测方法。     

基于非生物折叠体的分子识别

利用分子自组装的方法控制大分子量的线性有机分子的构象是物理有机化学一个富于挑战性的研究课题. 近年来, 化学家已经成功利用不同的分子内非共价键作用力如氢键和疏溶剂作用等诱导线性分子的折叠乃至螺旋构象的产生. 综述了近年来这种新的非生物二级结构形式在分子识别研究中的应用.     

Highly Efficient One-Pot Synthesis of 2-Arylmethyl N-Substituted Anilines via Yb（OTf）3 Catalyzed Three-Component Reaction

An efficient method has been developed for one-pot three-component coupling reactions of various aldehydes, 1-cyclohexen-2-one, and primary or secondary amines in the presence of a catalytic amount of Yb（OTf）3 under mild conditions to afford the corresponding 2-arylmethyl N-substituted anilines in good yields. In addition, the catalyst was easily recovered and could be reused for at least four cycles without any loss of activity.     

糠酸一步催化法制备四氢糠酸甲酯

以糠酸、甲醇、氢气为原料,采用连续流动固定床微反应器,Pd-Ni/γ-Al2O3为催化剂,使糠酸一步加氢甲酯化生成α-四氢糠酸甲酯.研究了反应的温度,压力,气、液体流速,进料流量等因素对催化反应的影响.结果表明:在1.5MPa,250℃,氢气空速3300 h-1,液体空速3.0 h-1(氢油比为50)时,糠酸转化率为96.6%,四氢糠酸甲酯的选择性97.2.0%,产率94.0%.催化剂稳定性较好,连续运转280小时后未见活性下降.该反应体系活性高,选择性好,反应压力低,催化剂性能稳定,操作简单,产物易分离.     

方酸染料在远红光区／近红外区对纳米晶二氧化钛电极的高效敏化作用

Four para-dialkylaminophenyl （PDAAP1-PDAAP4） bearing carboxyl groups were studied for application to the dye-sensitized solar cells （DSC）. It was found the short spacer CH2 between carboxyl and dialkylaminophenyl chromophore in PDAAP3 and PDAAP4 led to highly efficient monochromatic incident photon-to-current conversion efficiencies （IPCE）, however the long alkyl group C4H9 attached on aniline moieties in PDAAP2 and PDAAP4 favored improvement of open-circuit photovoltage. Thus, the solar cell sensitized by PDAAP4, having both short carboxyl groups CH2COOH and long alkyl groups C4H9, exhibited the IPCE maximum of 73% at 670 nm and overall energy conversion efficiency η of 3.06%, representing the highest IPCE and η values so far in dialkylaminophenyl-based organic dye-sensitized semiconductor solar cells. Taking advantage of the highly efficient sensitizing ability of PDAAP4 in far-red region, the data of IPCE above 630 nm of the solar cells were improved greatly by cosensitization with both N3 and PDAAP4. The influences of the TiO2 film thickness and the concentration of 4-tert-butylpyridine （TBP） in electrolyte were also investigated.     

Synthesis and Crystal Structure of 3,3,6,6-Tetramethyl-N-hydroxy-9-ethyl-1,8-dioxo-1,2,3,4,5,6,7,8,9,10-decahydroacridine

1 INTRODUCTION 1,4-Dihydropyridines (1,4-DHPs) are well-knowncompounds because of their pharmacological pro-perty as calcium channel modulators[1, . The che- 2]mical modifications, such as the introduction of dif-ferent substituents[3, or heteroatoms[5], of the DHP 4]ring have allowed the expansion of researches onthe structure-activity relationship to gain new in-sights into the molecular interactions at the receptorlevel. In fact, it is well established th…     

表面含磷酸的介孔分子筛P-SBA-15的合成及其性能评价

采用后合成法，将磷酸固载在纯硅介孔分子筛SBA-15表面上。利用X射线衍射（XRD）、红外光谱（IR）、氮气吸附 脱咐法（BET）分析方法表征催化剂的物理性能。结果表明，催化剂P-SBA-15在高温焙烧后保持了稳定的介孔分子筛SBA-15结构，该催化剂的比表面积和孔径分别为605.45m2/g和5.576nm（磷硅摩尔比5%）。选用十一碳烯酸与异丙醇的酯化反应对催化剂P-SBA-15的催化反应性能进行评价，同时与其他几种微孔沸石分子筛催化剂催化性能相比表明，磷酸改性的介孔分子筛P SBA 15是合成十一烯酸异丙酯较为理想的固体酸催化剂，考察了催化剂的稳定性。     

免疫亲和柱净化/柱前衍生化-高效液相色谱荧光检测法测定粮谷中的T-2毒素

建立了免疫亲和柱净化/柱前衍生化-高效液相色谱荧光检测器测定粮谷中T-2毒素含量的方法。样品经甲醇-水(体积比为80∶20)混合溶剂提取,通过免疫亲和柱(IAC)净化,以氰酸蒽(1-AN)为衍生化试剂、4-二甲基氨基吡啶(DMAP)为催化剂进行衍生,以ZORBAX Eclipse XDB-C18 柱为分离柱,乙腈-水(体积比为80∶20)为流动相进行高效液相色谱分离及荧光检测，荧光检测的激发波长为381 nm，发射波长为470 nm。T-2毒素的质量浓度为0.01~1.5 mg/L时与峰高呈良好的线性,相关系数为0.9985。在0.01~1.5 μg/g添加水平下，回收率为79.7%~94.5%,相对标准偏差小于7%；检出限（S/N＝3）为0.01 μg/g。该方法净化效果好,灵敏度高,操作简便快速。