四种新型单取代氨基酸四苯基卟啉锌配合物的合成和光谱表征

本文合成了四种新的单取代氨基酸四苯基卟啉锌配合物Zn［Val-TPP］、Zn［Glu-TPP］、Zn［Tyr-TPP］和Zn［Trp-TPP］。通过化学分析和元素分析确定了配合物的组成,研究了它们的紫外、红外、荧光和激光拉曼光谱。     

Molecular Recognition of Chiral Zinc Porphyrin with Amino Acid Esters

One kind of novel chiral porphyrin and its zinc complex were synthesized and characterized. The molecular recognition of chiral zinc porphyrin towards amino acid esters in CHCl₃ was investigated by UV‐vis spectral titration method. The associative constants of the molecular recognition reactions were all K_D>K_L and followed the order of K(PheOMe)>K(LeuOMe)>K(ValOMe)>K(AlaOMe) in host (Zn(L‐BocTyr)TAPP). Circular dichroism spectra were used to explain chiral molecular recognition. The minimal energy conformation of host‐guest molecular system was sought by molecular dynamics method. The molecular recognition process of this host‐guest system was calculated by quantum chemistry and the results were explained by the experiments     

氨基酸卟啉锌配合物对氨基酸酯的分子识别研究

用紫外可见吸收光谱滴定方法研究了一种新型的苏氨酸卟啉锌配合物(主体)对氨基酸酯(客体)的分子识别.这种锌卟啉可以与氨基酸酯形成 1:1和 1:2的两种加合物.氨基酸酯的氨基首先与氨基酸残基的羧基作用形成 1:1的加合物,然后与锌卟啉的中央锌原子配位形成 1:2的加合物,客体分子与主体分子上的氨基酸残基之间的排斥作用以及主客体之间的色散力作用是主体分子能识别客体分子的另外两种作用。     

环糊精-苯丙氨酸超分子体系的包合现象与分子识别

通过紫外-可见光谱探讨了水溶液中α-环糊精(CD 1),β-CD 2,七(2, 6-二-o-甲基)-β-CD 3和γ-CD 4与D-、L-、D,L-苯丙氨酸(Phe)形成超分子包合物的稳定常数(K)。手性或外消旋苯丙氨酸与同一主体结合能力的强弱顺序为:L- >D,L- >D-Phe,各体系的K_L/K_D值在1.65～3.01之间,给出了较好的异构体分离。但三种形式的苯丙氨酸与这些主体的缔合常数均较小(K< 3×10²mol·L^-1)。就不同主体而言,K值的次序为:3 >1 >4 >2,并不完全等同于K_L/K_D的顺序:2 >1 >3 >4。     

Zn(AA)SO4·H2O(AA=Thr,Phe,Val,Met)在水和丙酮混合溶剂中的结晶动力学研究

Zincisanecessarylifeelementinhumanbody．L－α－aminoacidisthebasicunitofproteinrelatedwithlife．L－α－Thr（Threonine），L－α－Phe（Phenylalanine），L－α－Val（Valine）andL－α－Met（Methionine）arein－dispensabletolifewhichhavetobeabsorbedfromfoodbecausetheycannotbesynthesizedinhumanbody．Thecomplexesofzincsaltswithα－aminoacidasad－ditivehaveawideapplicationinmedicine，foodstuffandcosmetics犤１～３犦．Thesynthesismethodsofthecom－plexesofzincsaltswithα－aminoacidhavebeenre－viewed犤…     

新型手性酪氨酸修饰的锌卟啉对氨基酸酯的分子识别研究

合成并表征了一种L型Boc酪氨酸修饰的自由卟啉(L-BocTyrTAPP)及其锌卟啉配合物Zn(L-BocTyr)TAPP.通过紫外-可见光谱滴定法,研究了手性锌卟啉配合物与四对对映异构的手性氨基酸酯客体在CHCl₃中的分子识别行为.实验结果表明,在分子识别的过程中,缔合常数顺序均为D型略大于L型,且按K(PheOMe)>K(AIaOMe)>K(ValOMe)>K(LeuOMe)的顺序依次减小.同时,利用园二色光谱进一步阐述手性分子识别过程.此外,采用分子力学方法搜索了主客体体系的最低能量构象,从理论上对实验本质进行较深入的探讨.     

Tunable fluorescent sensing of cysteine and homocysteine by intramolecular charge transfer

An amphiphilic oligo p-phenylene derivative (DCHO) bearing electron-donating group (–NH(CH₂)₂OH) and electron-withdrawing group (–CHO) has been synthesised and characterised. The sensing characteristics of this probe (DCHO) for cysteine (Cys) and homocysteine (Hcy) are studied in a mixture solution of DMSO–HEPES by UV–vis and fluorescence spectra. ¹H NMR, MALDI-TOF and UV–vis titration experiments proved that thiazolidine and thiazinane derivatives were formed. The highly Cys/Hcy-selective fluorescence hypsochromic shift (>110 nm) can be observed due to the switching of intramolecular charge transfer, leading to potential fabrication of ratiometric fluorescent detection of Cys/Hcy.     

(1R,3R)-1-氨基-1,3-二羧基环丁烷衍生物桥联环糊精与一组低分子量多肽之间的包合行为

The interactions between several peptides with low molecular weight (guest, NH₂-Arg-Arg-Trp-Trp-H 2; NH₂-Arg-Trp-Arg-Trp-H 3; NH₂-Trp-Arg-Arg-Trp-H 4; NH₂-Arg-Arg-Trp-Trp-Trp-Trp-H 5; NH₂-Trp-Trp-Arg-Arg- Trp-Trp-H 6; NH₂-Arg-Arg-Trp-Trp-Trp-Trp-Trp-Trp-H 7; NH₂-Arg-Arg-Trp-Trp-Trp-Trp-Trp-Trp-Trp-Trp-H 8) and β-cyclodextrin dimer (host, 1) bridged with the derivative of (1R, 3R)-1-aminocyclobutane-cis-1,3-dicar- boxylic acid were investigated by using fluorescence polarization method in buffer aqueous solution (pH 7.4) at 298K. The binding constants of the cyclodextrin dimer 1 to the guests 2-8 were determined. It was shown that there was a cooperative action of the two cavities of a cyclodextrin dimer in the binding of large substrates, and that the structure and properties of amino acid in the peptides played very important roles in the synergic complexation between host and guest.     

氨基酸席夫碱配合物的制备及性能研究进展

研究表明,某些含有-N=CH-基团的有机化合物具有一定的抗癌作用,它与某些金属生成配合物后效果更加显著。氨基酸是组成酶和蛋白质的基本单元,与含活泼羰基的化合物形成含有多个强电负性配位原子的席夫碱,此类席夫碱具有较强的配位能力和多样的配位模式的优点,研究其与金属离子配位所形成配合物可以为研究抗肿瘤、抗癌药物提供信息。80年代以来,有不少关于研究过渡金属离子与氨基酸席夫碱配合物的合成和性质的报道,并进行了大量生物生理活性的研究旧剖。本文综述了近年来国内外有关氨基酸席夫碱配合物的制备及其性能应用。     

A Series of Mononuclear Complexes Constructed from Transition Metals and Amino Acid Derived Ligands: Syntheses, Structures and Photoluminescence

Eight neutral mononuclear complexes constructed from transition metals （M = Co（Ⅱ）, Ni（Ⅱ）, Cu（Ⅱ）, Zn（Ⅱ）, Cd（Ⅱ）） and ligands N-（2-pyridylmethyl）-L-phenylalanine （L-Hpmpa） and N-（2-pyridylmethyl）-L-tyrosine （L-Hpmtyr） have been synthesized by both hydrothermal and conventional room temperature reactions. Four of them have been structurally characterized by single-crystal X-ray diffractions. They are： [Co（L-pmpa）2·2H2O] 1, [Ni（L-pmpa）2·2H2O] 2, [Cu（L-pmpa）2·2H2O] 3 and [Cu（L-pmtyr）2·2H2O] 4. Single-crystal X-ray analysis, IR and elemental analysis revealed that complexes 1, 2 and 3 are isostructural. Powder X-ray diffraction, IR and elemental analysis revealed that complexes 4, 5 （Zn[L-pmtyr]2·2H2O）, 6 （Cd[L-pmtyr]2·2H2O）, 7 （Co[L-pmtyr]2·2H2O） and 8 （Ni[L-pmtyr]2·2H2O） are isostructural. The photoluminescence properties of L-Hpmtyr ligand, compounds 5 and 6 were also investigated.     

硫酸锌与α-氨基酸的相化学及其新相的合成和表征

α 氨基酸锌作为添加剂在药物、食品和化妆品等方面都有广阔的应用前景[1,2 ] 。有关氨基酸锌的合成方法前文[3] 已述及。而用相平衡方法研究锌盐与氨基酸的配合行为的相化学[4] ,对新型配合物 ,特别是固液异成分化合物的合成有指导意义。本文对ＺｎＳＯ4与人体必需而非自生的Ｌ 亮氨酸 (Ｌ Ｌｅｕ)、Ｌ 色氨酸 (Ｌ Ｔｒｙ)、Ｌ 苏氨酸 (Ｌ Ｔｈｒ)和Ｌ 缬氨酸 (Ｌ Ｖａｌ)在水中的等温溶度性质进行了研究 ,构制了其相图 ,讨论了未形成化合物的原因。合成了未见报道的Ｚｎ(Ｌｅｕ)ＳＯ4·0 .5Ｈ2 Ｏ ,Ｚｎ(Ｖａｌ)ＳＯ4·Ｈ2 Ｏ和固态配合物…     

氨基酸单取代酞菁锌的合成与表征

以单羧基β-取代酞菁锌和王氏氨基树脂为原料,合成了2种氨基酸单取代酞菁锌:2-L-苯丙氨酸-羧基-β-单取代酞菁锌和2-L-组氨酸-羧基-β-单取代酞菁锌,其结构经UV-Vis,IR,MS和元素分析表征。     

甘氨酸锌相对分子质量与锌含量标准的研讨

甘氨酸锌是新一代氨基酸系列补锌产品,在国标GB2760-1996食品添加剂卫生标准中被确定为食品营养强化剂,其备注中对甘氨酸锌中的锌含量标注为31．8％。作者通过对甘氨酸锌产品的研制和结构分析认为此值有误,应予更正。含结晶水的甘氨酸锌相对分子质量为231．51,锌含量为28．24％;不含结晶水的甘氨酸锌相对分子质量为213．51,锌含量为30．62%。     

含氨基酸席夫碱的5-氟尿嘧啶衍生物的合成及其抗肿瘤活性

以N 1-(2-四氢呋喃烷基)-5-氟尿嘧啶为原料, 与1,4-二溴丁烷反应, 得到N¹-(2-四氢呋喃烷基)-N³-(4-溴丁基)-5-氟尿嘧啶(2), 最后与氨基酸席夫碱的钾盐缩合, 得到13个新的目标化合物3. 其结构经IR, ¹H NMR, MS和元素分析确证. 初步的体外抗肿瘤试验结果表明, 目标化合物具有一定的抗肿瘤活性.     

Conformation Diversity of Complexes Constructed by N-（2-Pyridylmethyl）-phenylalanine and Zn（Ⅱ）

Four configurationally and conformationally related Zn（II） complexes with a tridentate ligand namely, N-（2-pyridylmethyl）-phenylalanine （Hpmpa）, have been synthesized by hydrothermal reactions. [Zn（L-α-pmpa）2·HaO] 1： orthorhombic, space group P21212 with a = 15.1091（7）, b = 16.2417（8）, c = 5.9972（3） A, V= 1471.70（12）A^3, Z = 2, Mr = 593.97, Dc = 1.340 g/cm^3,μ = 0.879 mm^-1, F（000） = 620, Rint= 0.0205, R = 0.0450 and wR = 0.1578 for 3102 observed reflections with I 〉 2σ（I）; [Zn（D-α-pmpa）2·2H2O] 2： orthorhombic, space group P21212 with a = 15.1023（6）, b = 16.2516（7）, c = 6.0024（2）A, V= 1473.21（10）A^3, Z = 2, Mr = 611.98, Dc = 1.380 g/cm^3,μ = 0.882 mm^-1, F（000） = 640, Rint= 0.0337, R = 0.0484 and wR = 0.1435 for 2408 observed reflections with I 〉 2σ（I）; [Zn（L-β-pmpa）2] 3： monoclinic, space group C2/c with a = 27.8667（5）, b = 5.60350（10）, c = 19.9636（2）A β = 120：2210（10）°, V = 2693.66（7）A^3, Z = 4, Mr = 575.95, De= 1.420 g/cm^3,μ = 0.955 mm^-1, F（000） = 1200, Rint= 0.0345, R = 0.0358 and wR = 0.1135 for 2251 observed reflections with I 〉 2σ（I）; and [Zn（D-β-pmpa）2] 4. They are all mononuclear discrete structures. The influence of temperature and pH on the conformation of structures has been investigated. Moreover, the photoluminescent properties of compounds 1 and 3 are also reported.