NITROSYL FERROUS CHELATES——FTIR STUDY ON THE COORDINATION OF NITRIC OXIDE TO FERROUS CHELATES IN AQUEOUS SOLUTIONS

Fourier transform infrared spectroscopic studies of coordination compounds of a series of ferrous aminopolyphosphonates and aminopolyacetates with nitric oxide in aqueous solutions have been described for the first time. The polydentate ligands considered include: nitrilotrimethylenephosphonic acid (NTMP), ethylenediaminetetramethylenephosphonic acid (EDTMP), triethylenetetraaminehexaacetic acid (TTHA), diethylenetriaminepentaacetic acid (DTPA), trans-1,2-cyclohexylenedinitrilotetraacetic acid (CyDTA), ethylenedioxydiethylenedinitrilotetraacetic acid (EGTA) and nitrilotriacetic acid (NTA).By examining the spectra of ~(14)NO and ~(15)NO complexes in both D_2O and H_2O solutions, the characteristic frequencies of N-O vibration in the nitrosyls were assigned. A "red" shift of N-O stretching vibration frequency in the chelates was observed as compared with the aquacomplex [Fe(H_2O)_5(NO)]~(2+). With the aid of FTIR technique, the redox reaction of the nitrosyls with sulfite and oxygen were studied. The coor     

丝氨酸织组膜电极的研究

利用猪肝组织膜配合氨气敏电极,研制了丝氨酸生物催化传感电极。丝氨酸浓度的测定范围为5.1×10~(-5)～3.2×10~(-3)mol/L,检出限为3.1×10~(-5)mol/L。研究和讨论了电极的最佳工作条件,并测定了实验条件下酶催化反应的米氏常数Km。该电极用于合成样品分析,效果满意。     

(1R,2S)或(1S,2R)-1,2-二苯基-2-氨基乙醇衍生物手性配体的合成及其用于不对称催化反应

重点报道了以（１Ｒ，２Ｓ）或（１Ｓ，２Ｒ）－１，２－二苯基－２－氨基乙醇衍生物手性配体的合成及其用于不对称催化反应的研究，如去氢氨基酸的氢化、醛的乙基锌加成、酮的还原、活泼亚甲基化合物的烷基化、醛的硅腈化和瑞福马斯基反应等．研究了手性配体的结构、底物和反应条件等对上述反应的对映选择性和催化活性的影响．     

新型二氢色原酮拼接多环吡咯螺环氧化吲哚类化合物的 无催化剂合成及其抗白血病活性

以取代的3-羧酸活化色酮、靛红与消旋脯氨酸为原料，乙腈为溶剂，依次经1,3-偶极子[3+2]环加成和脱羧反应，合成了8个新型的二氢色原酮拼接多环吡咯螺环氧化吲哚类化合物 (3a~3h)，产率68%~87%, dr值15/1~20/1,其结构经¹H NMR, ¹³C NMR和HR-MS（ESI-TOF）表征。采用MTT法研究了3a~3h对人白血病细胞(K562)的体外抑制活性。结果表明：化合物3d,3f, 3g对K562具有一定的抑制活性(IC₅₀=46.3~69.4 μmol·L^-1)。     

第十五华沙国际金属有机化学讨论会

本文从(一)金属有机化合物的合成、结构及反应性的研究、(二)新颖、独特和官能化配体的研究、(三)金属原子簇合物化学、(四)催化、(五)有机硅化学、(六)其他研究领域等六个方面做了阐述。本届讨论会较全面地体现了从上届会议以来国际金属有机化学的研究进展及发展趋势。这届会议的成功举行,不仅强化了各国金属有机化学家间的学术交流而且增进了各国人民之间的友好情谊。     

[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

甲胺在择形分子筛催化剂上的选择性合成

考察了同晶置换改性丝光沸石和金属表面活性改性ＨＺＳＭ－５对甲醇胺化反应的催化性能，发现两种改性方法都可以降低三甲胺（ＴＭＡ）选择性，提高一甲胺（ＭＭＡ）与二甲胺（ＤＭＡ）的选择性，两种方法都是通过分子筛外表面改性以实现择形性调变的，同晶置换改性可使丝光沸石的强酸性发生显著变化，而强Ｂ酸中心是丝光沸石催化胺化反应的活性中心。     

CATIONIC CONDUCTIVITY FOR THE CROSSLINKED P [OLIGO (OXYETHYLENE) METHACRYLATE-COoMETHACRYLOYL ALKYLSULFONIC ACID LITHIUM]

Crosslinked copolymers with single Li~+-ionic conductivity were prepared from oligo (oxyethylene) methacrylate (MEO_n), methacryloyl alkylsulfonic acid lithium (SAMLi), and oligo (oxyethylene) dimethacrylate (DMEO_n). Li~+-ionic conductivity of the copolymer is improved by crosslinking and presented as a function of polymerization degree (n) in MEO_n, comonomeric salt concentration (O/Li), and crosslinking degree. The crosslinked copolymer P (0.7 MEO_(14)-0.3DMEO_(14)-SHMLi) without other small molecular additives exhibits an optimum Li~+-ionic conductivity of 1.2×10~(-6) S/cm at 25℃. Dc polarization test in the cell composed of Li/copolymer/Li shows a constant dc ionic conductivity which closes gradually to the ac one with decreasing dc polarization potential.     

新显色剂4,4′-二偶氮苯重氮氨基偶氮苯测定水中微量锌的研究

本文报告在四硼酸钠体系中和Triton X-100存在下,锌与新显色剂4,4′-二偶氮苯重氮氨基偶氮苯有灵敏的显色反应。红色络合物在525nm处摩尔吸光系数为1.63×10~5L·mol~(-1)·cm~(-1),并研究了测定锌的各种条件和40余种共存离子对测定的影响。     

树状催化剂在不对称氢转移反应中的回收循环使用研究

以(1S,2R)-降麻黄碱为核心的第三代手性树状催化剂在对苯乙酮的不对称氢转移反应中可以方便的回收并循环使用. 该树状催化剂可以一共使用3次而保持对映选择性基本不变.