含螯合配体的钕配合物的晶体结构

用NdCl_3,NaS_2CNEt_2和Et_4NBr为原料,在甲醇溶剂中反应,生成钕配合物,[Et_4N](Nd(S_2CNEt_2)_4]晶体,用X-射线衍射法测定了配合物的晶体结构。晶体属于单斜晶系,空间群P2_1/n晶胞参数,a=11.704(3)A,b=20.941(3)A,c=17.564(4)A,V=4242.2A~3,Z=4。结构经最小二乘方法修正后偏离因子为R=0.0564.在配合物钕离子是通过8个硫原子配位形成扭曲的NdS_3核的十二面体。井对配合物的红外线光谱和紫外可见光谱也进行了研究。     

含螯合配位体的M-Fe-S系列簇合物的合成,结构和性质研究(M=Mo,W)

本文总结报道了(1) [Et_4N]_3[Mo_2FeS_6(SCH_2CH_2S)_2],(2) [Et_4N]_3[W_2FeS_6(SCH_2CH_2S)_2]_2(3) {[Et_4N]_3[Mo_2FeS_6(SCH_2-CH_2S]_2}_4·CH_3CN和(4) [Et_4N]_4[Mo_2Fe_4S_9(SCH_2CH_2S)_2]四种簇合物的合成,结构和性质研究。在Nicolet R_3 System四圆单晶衍射仪上,用MoK_辐射收集数据,用SHELXTL程序,重原子法解出这些簇合物的晶体结构,用红外光谱、紫外可见光谱和穆斯堡尔谱对簇合物进行了物理性质的测定.同时用循环伏安法对簇合物的氧化还原特性也进行了研究,并结合量子化学计算探讨了簇合物的电子结构和性能之间的关系。     

Characterization of electrospray ionization mass spectrometry for N-diisopropyloxyphosphoryl dipeptide methyl esters

A systematic study of the fragmentation pattern of N-diisopropyloxyphosphoryl (DIPP) dipeptide methyl esters in an electrospray ionization (ESI) tandem mass spectrometry (MS/MS) was presented. A combination of accurate mass measurement and tandem mass spectrometry had been used to characterize the major fragment ions observed in the ESI mass spectrum. It was found that the alkali metal ions acted as a fixed charge site and expelled the DIPP group after transferring a proton to the amide nitrogen. For all the N-phosphoryl dipeptide methyl esters, under the activation of a metal ion, the rearrangement product ion at m/z 163 was observed and confirmed to be the sodium adduct of phosphoric acid mono-isopropyl esters (PAIE), via a specific five-membered penta-co-ordinated phosphorus intermediate. However, no rearrangement ion was observed when a beta-amino acid was at the N-terminal. This could be used to develop a novel method for differentiating isomeric compounds when either alpha- or beta-amino acid are at the N-terminus of peptides. From the [M+Na]+ ESI-MS/MS spectra of N-phosphoryl dipeptide methyl esters (DIPP Xaa1 Xaa2 OMe), the peaks corresponding to the [M+Na Xaa1 C3H6]+ were observed and explained. The [M+Na]+ ESI-MS/MS spectra of N-phosphoryl dipeptide methyl esters with Phe located in the C-terminal, such as DIPPValPheOMe, DIPPLeuPheOMe, DIPPIlePheOMe, DIPPAlaPheOMe and DIPPPhePheOMe, had characteristic fragmentation. Two unusual gas-phase intramolecular rearrangement mechanisms were first proposed for this fragmentation. These rearrangements were not observed in dipeptide methyl ester analogs which did not contain the DIPP at the N-terminal, suggesting that this moiety was critical for the rearrangement.     

Covalently immobilized aminonaphthalimide as fluorescent carrier for the preparation of optical sensors

By replacing the hydrogen of the 4-amino group of a 4-amino-1,8-naphthalimide derivative with an N-acryloxyethyl group, the fluorophore has been covalently immobilized on an optical sensor surface by UV photopolymerization. The optical sensor obtained can be used for the determination of picric acid. The linear range and detection limit of the sensor are 9.80x10(-7)-1.96x10(-4) mol L(-1) and 7.1x10(-7) mol L(-1), respectively. Leaching of the fluorophore from the membrane is effectively prevented by covalent immobilization, resulting in a sensor with a relatively long lifetime. The response time of the sensor is short, and the reproducibility and reversibility are good. The sensor has been used for the indirect determination of the chloroquine content of pharmaceutical tablets.     

稀土-蛋氨酸配合物的热力学

在25 ℃和μ=0.15 mol·L~(-1)[NaCl]条件下, 用pH电位法测定了L-蛋氨酸的质子化常数、15个稀土元素与该配体生成配合物的稳定常数。表明稀土与L-蛋氨酸可生成1:1配合物。讨论了“四分组效应”及钇的位置。用量热滴定法直接测定了稀土与L-蛋氨酸生成1:1配合物的△H_(101)值, 计算了△S_(101)和△G_(101)值。     

溶胶-凝胶模板法合成SmFeO3纳米线

通过阳极氧化在质量分数为0.3 mol·L^-1草酸溶液中制得多孔氧化铝膜。经5%（质量分数）的磷酸扩孔处理得到具有孔径大小均一,排列有序,并具有一定厚度的阳极氧化铝模板（AAO）。用溶胶-凝胶法在氧化铝模板中制备了直径约为50 nm的有序SmFeO3纳米线阵列。用扫描电镜（SEM）、透射电镜（TEM）和X射线衍射仪（XRD）对SmFeO3纳米线的形貌、结构以及相组成进行了分析。结果发现：纳米线的长度受控于氧化铝模板的厚度,直径与氧化铝模板的孔径相等。同时分析了纳米线的形成机制。     

La和Nd在其氯化物熔体中的电化学腐蚀

稀土金属在其氯化物熔盐中的自腐蚀是导致电解制备稀土金属时电流效率降低的一个重要原因。但由于实验技术上的困难,有关这方面的研究报道不多。本文将在水溶液体系中常用的电化学弱极化测量腐蚀速度及电化学参数的方法用之于La、Nd在其氯化物熔盐体系中的腐蚀,表明同样适用。     

EFFECT OF CATALYST CONCENTRATION ON CATALYTIC PERFORMANCE IN LIQUID PHASE DIMETHYL ETHER SYNTHESIS FROM SYNGAS

利用ＺＳＭ－５型沸石可将轻烃选择性地转化为苯，甲苯和二甲苯。ＨＺＳＭ－５催化剂上丙烷转化率和芳烃选择性都很低，但在ＨＺＳＭ－５上添加Ｇａ或Ｐｔ－Ｇａ（双金属改性）后丙烷转化率和芳烃选择性都有很大提高。实验结果表明，Ｇａ／ＨＺＳＭ－５催化剂经氢气高温预处理后，其上的Ｂｒｏ．．ｎｓｔｅｄ酸中心数目减少。铂的加入促进了镓物种的还原，而还原的镓物种可以中和相当一部分催化剂表面Ｂｒ．ｎｓｔｅｄ酸中心，然后形成高度不饱和的催化活性中心。这些中心可以作为Ｌｅｗｉｓ中心，从丙烷和反应中间产物中拔除Ｈ－，使丙烷高选择性地生成芳烃     

Synthesis of SAPO-41 from a new reproducible route using H3PO3 as the phosphorus source and its application in hydroisomerization of n-decane

In the new reproducible route, phosphorous acid (H₃PO₃) or the mixture of H₃PO₃ and phosphoric acid (H₃PO₄) are used as the phosphorus source to synthesize microporous silicoaluminophosohates. It is found that gels containing H₃PO₃ favor the formation of SAPO-41 materials. With only H₃PO₃ as the phosphorus source, pure SAPO-41 phase can be prepared with high crystallinity. When the mixture of H₃PO₃ and H₃PO₄ is used as the phosphorus source, the crystallization of SAPO-41 can be accelerated. Raman and XRD results show that SAPO-41 can be formed after crystallizing for 12 h. The dosage of the template di-n-propylamine (DPA) can be reduced in the mixed phosphorus source system. The SAPO-41 has been used to prepare catalysts for the hydroisomerization of n-decane. High selectivity of isomerization (89.5%) has been observed even at high conversion (88%) over the Pt/SAPO-41.