Schiff base

摘要： The cathode of biofuel cell reduces molecular oxygen to water using four electrons, an enzyme of multicopper oxidase family, laccase, is contained, though its electron transfer efficiency from the electrode resulted in rate determining process. To improve this electron, transfer via mediators, we have investigated several mediator metal complexes between the electrode and laccase, in particular hydrophobic pocket on the surface. We have discussed DFT computational results and selected experimental data of new Mn(III/II) Schiff base complexes having redox active (anthraquinone) ligands and photochromic (azobenzene) ligands about azobenzene moiety at the sole molecular level. Moreover, we carried out computational docking simulation of laccase and complexes considering trans-cis photoisomerization (electronic states) and Weigert effect (molecular orientation to fit better) of azobenzene moiety. Additionally, actual experimental data also presented to indicate the expected merits for mediators.

摘要： 以N,N’-邻羟亚苄基-4,5-二甲基邻苯二胺为配体合成一个新型Schiff-base Mn(Ⅱ)配合物,通过红外、单晶衍射对其进行了结构表征.用琼脂扩散法测定Mn(Ⅱ)配合物对临床分离耐药真菌的抑菌圈大小,微量稀释法测定配合物对上述菌株的最低抑菌浓度[minimum inhibitory concentration(MIC)]、最低杀细菌浓度[minimum bactericidal concentration(MBC)].抑菌试验结果表明,Mn(Ⅱ)金属配合物对一般临床分离真菌白念592、白念103和耐氟康唑临床分离真菌白念Z2901、白念Z2503和白念649具有良好的抑菌效果,其与氟康唑联合对抑制白念649和白念Z2901具有有协同杀菌作用.

摘要： The reaction of bis-[2-amino-4-pheny1-5-thiazolyl] disulfide with 5-nitro-salicylaldehyde in absolute ethanol resulted in the formation of a new Schiff base ligand H2L (1). Characterization of the ligand was performed by FT-IR, 1H NMR, 13C NMR, UV-Vis, elemental analysis and single crystal X-ray diffraction. The ligand, (1), possesses a disulfide –S–S– bridge of 2.1121 (3) ? length, and the molecule adopts a cis-conformation around this bond. In the crystal structure of (1), an intramolecular O–H···N hydrogen bond with D… A distance of 2.69 (3) ? was present. The reaction of (1) with Co(NO3)2·6H2O and CuCl2·2H2O in methanol afforded the corresponding metal complexes. The obtained solids were further investigated by elemental analysis and UV-Vis titration that confirmed the formation of [CoL] and [ClCuHL] complexes. However, recrystallizaion of the Co(II) complex in dimethylsulfoxide caused the complete hydrolysis of the imine bond and afforded a Co(II) complex in which two 5-nitro-salicylaldehyde and two DMSO molecules were coordinated to the central metal in an octahedral fashion. This structure (2) was also confirmed by single crystal X-ray analysis.

摘要： 为了探讨天然产物儿茶素能否抑制甘油醛Fenton反应诱导的BSA非酶糖基化,采用Girard's reagentT实验检测儿茶素抑制甘油醛代谢产物的抑制作用;构建甘油醛/Fenton反应诱导的牛血清白蛋白(BSA)非酶糖基化模型,并探讨儿茶素、N-乙,酰半胱氨酸(NAC)、氨基胍(AG)和吡哆胺对此模型非酶糖基化的抑制作用.结果儿茶素和NAC可抑制甘油醛在Fenton反应条件下的代谢产物;NAC和AG可抑制甘油醛诱导牛血清白蛋白(BSA)形成的Schiff base,儿茶素、NAC和AG可抑制甘油醛诱导形成的羧甲基赖氨酸(CML).

摘要： 以L-酪氨酸甲酯盐酸盐为原料,通过格氏反应合成了一种手性β-氨基醇;以水杨醛为原料,通过溴代反应合成了3,5-二溴水杨醛和5-溴水杨醛;将手性β-氨基醇和溴代水杨醛在乙醇中缩合,制备了两种手性三齿Schiff-base配体.产物的结构经IR,1H NMR,13C NMR和MS表征确定.将配体应用于催化不对称Henry反应中,考察其在不同反应条件下的催化性能,在最优化的反应条件下,不同底物均获得了较好的催化效果,产率最高达95％,ee值最高达90％.

摘要： A new Schiff-base compound derived from 1, 2, 4-triazole was synthesized with a high yield. Potentiometric responses of poly(vinyl) chloride(PVC) electrode based on this ligand as neutral ionophore showed high sensitivity and selectivity towards Hg2+ ion. Effects of different plasticizers and amounts of ion-exchanger on the potentiometric response property of Hg2+ -selective electrode (Hg2+ -ISE) were discussed. The result indicated that, under the optimal membrane composition [PVC: 32.70, o-NPOE: 65.39, ionphore: 0.99, ion-exchanger: 0.92, (w : w)], a good Nernstian response slope of (29. 3 + 0. 3 ) mV/dec was obtained for Hg2 + in a wide concentration range of 1.0 × 10-6 -3.0 × 10-4 moL/L with a detection limit of 2. 6 × 10-7 mol/L. Except for silver ion, most of alkali metal, alkaline earth metal and other common transition metal ions didn't interfere the performance of the membrane electrode. The fabricated Hg2+ - ISE can be used in a wide pH range of 2. 8 -5.6 with a fast response time of less than 12 s and can be used for 3 month without any obvious change in potentiometric response. The proposed electrode was also successfully applied as indicator electrode in the potentiometric detection of Hg2+ in lab water by standard addition method and the results were confirmed by ICP- MS.%高产率合成了一种新的Schiff-base结构化合物,并将其表征为高选择性聚合物膜汞离子选择性电极载体.考察了不同增塑剂及离子交换剂对膜电极响应性能的影响,在最佳膜组分条件下测得该电极对汞离子的线性响应范围为1.0×10-6 ～3.0×10-4 mol/L,响应斜率为(29.3±0.3) mV/dec,检出限为2.6×10-7 mol/L;该电极响应速率快(小于12 s),可在较宽的pH范围内(pH 2.8 ～5.6)使用,且其它常见碱金属、碱土金属以及过渡金属离子对该测试电极的干扰小;可准确检测自来水中汞离子的浓度.

摘要： PVP, a synthetic polymer and chitosan, a natural polymer are biocompatible and have presented a great variety of interesting properties for cosmetic, biomedical, pharmaceutical and biotechnological applications, Many alternatives to improve the polymer propeties has been made as bleeding polymers, for example. In this work, two different techniques of hydrogel attainment were used: one from mixtures of acid aqueous cosolutions of chitosan and PVP, whose resultant films and solutions were irradiated, afterwards, by ultraviolet radiation (λ = 254 nm), another one from the reaction of poly (N-vinyl-2-pyrrolidone-co-acrolein)-a novel copolymer synthesized in our biomaterials laboratory-and chitosan. In the first one alternatives it was possible produce hydrogels directly from mixtures of aqueous acidic co-solutions of both polymers. In the second one, the attainment of hydrogels from Schiff base has proved to be an effective methodology for the production of hydrogels, showing good values of gel content and swelling.

摘要： The Schiff base form of the 4-acylpyrazolone ligand was immobilized on the silica surface by reaction of 3-aminopropyl silica with 4-acetyl-5-methyl-2-phenyl-2,4-dihydro-pyrazol-3-one in 97% yield, producing grafted silica with 0.77 mmol/g ligand loading. This surface modified silica was shown to be selective in the adsorption of Yb3+ ions from dilute aqueous solutions, for which 98% adsorption was observed from a 1.0×10-5 mol/L aq. solution at pH 6.7, after 24 h at room temperature. Six other lanthanides studied Eu3+, Gd3+, Nd3+, Tb3+, Sm3+ and La3+ showed moderate to weaker adsorptions of 39%, 28%, 16%, 12%, 11% and 5% respectively under similar conditions.

摘要： A new chiral Schiff base derived from carbohydrate, methyl-4,6-O-benzylidene-3- deoxy-3-(salicylideneamino)-α-D-altropyranoside, has been synthesized by reacting methyl 3-ami- no-4,6-O-benzylidene-3-deoxy-α-D-altropyranoside with salicylaldehyde in methanol and charac- terized by IR, 1H NMR, 13C NMR, MS, elemental analysis, and X-ray crystal structure analysis.The crystal belongs to orthorhombic, space group P212121 with a = 8.0856(16), b = 10.786(2), c = 22.690(5) -, V = 1978.8(7) -3, Z = 4, Mr = 385.40, Dc = 1.294 g/cm3, μ = 0.095 mm-1, F(000) = 816, the final R = 0.0379 and wR = 0.0811 for 2597 independent reflections.In the title compound, the pyrano-ring adopts a twisted 1C4 chair conformation.

摘要： A novel end-to-end azido-bridged polynuclear Schiff-base copper(H) complex,[Cu(C12H15Br2N2O)(N3)]n, was prepared and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction.The crystal belongs to the orthorhombic system, space group Pbcn with a = 24.588(5), b = 10.377(2), c = 13.022(3)(A),V= 3322.6(12)(A)3, Z = 8, Dc = 1.874 g/cm3, Mr= 468.65, λ(MoKα) = 0.71073 (A),μ= 6.130 mm-1, F(000) = 1832, R = 0.0637 and wR = 0.1176.The Cu atom in the complex is five-coordinated in a square pyramidal geometry by three donoratoms of the Schiff-base ligand, and two N atoms from two bridging azide ligands.The [2,4-dibromo-6-[(3-dimethylaminopropylimino)methyl]phenolato]copper(Ⅱ) units are linked by the bridging azide ligands, giving zigzag polymeric chains with backbones of the [-Cu-N-N-N-Cu]n type running along the b axis.

摘要： 具有长发射态寿命的过渡金属络合物越来越多的被应用在功能分子材料的设计上，如联吡啶钌络合物在分子氧传感方面得到了广泛的应用【1]，环金属化(Cyclometalated)络合物如Ir(Ⅲ)和Pt(Ⅱ)的络合物则被广泛应用在OLED功能器件的设计上【2】，等等。西氟碱(Schiff base)的过渡金属络合物，特别是Pt(Ⅱ)络合物具有较长的三重态寿命[3,4】，尽管此类物质无论在合成与结构修饰上都易于实现，但对其氧传感性能的研究却未见报导。本文合成了一系列西氟碱铂络合物，并对其氧传感性能进行了详细研究。我们发现通过对西氟碱配体进行简单的修饰，其对氧气的响应程度(Ksv 值)即可提高6倍(Ksv 值从0.00313 Torr-1 提高到0.01887 Torr-1)。

摘要： 具有长发射态寿命的过渡金属络合物越来越多的被应用在功能分子材料的设计上，如联吡啶钌络合物在分子氧传感方面得到了广泛的应用【1]，环金属化(Cyclometalated)络合物如Ir(Ⅲ)和Pt(Ⅱ)的络合物则被广泛应用在OLED功能器件的设计上【2】，等等。西氟碱(Schiff base)的过渡金属络合物，特别是Pt(Ⅱ)络合物具有较长的三重态寿命[3,4】，尽管此类物质无论在合成与结构修饰上都易于实现，但对其氧传感性能的研究却未见报导。本文合成了一系列西氟碱铂络合物，并对其氧传感性能进行了详细研究。我们发现通过对西氟碱配体进行简单的修饰，其对氧气的响应程度(Ksv 值)即可提高6倍(Ksv 值从0.00313 Torr-1 提高到0.01887 Torr-1)。

摘要： 具有长发射态寿命的过渡金属络合物越来越多的被应用在功能分子材料的设计上，如联吡啶钌络合物在分子氧传感方面得到了广泛的应用【1]，环金属化(Cyclometalated)络合物如Ir(Ⅲ)和Pt(Ⅱ)的络合物则被广泛应用在OLED功能器件的设计上【2】，等等。西氟碱(Schiff base)的过渡金属络合物，特别是Pt(Ⅱ)络合物具有较长的三重态寿命[3,4】，尽管此类物质无论在合成与结构修饰上都易于实现，但对其氧传感性能的研究却未见报导。本文合成了一系列西氟碱铂络合物，并对其氧传感性能进行了详细研究。我们发现通过对西氟碱配体进行简单的修饰，其对氧气的响应程度(Ksv 值)即可提高6倍(Ksv 值从0.00313 Torr-1 提高到0.01887 Torr-1)。

摘要： 具有长发射态寿命的过渡金属络合物越来越多的被应用在功能分子材料的设计上，如联吡啶钌络合物在分子氧传感方面得到了广泛的应用【1]，环金属化(Cyclometalated)络合物如Ir(Ⅲ)和Pt(Ⅱ)的络合物则被广泛应用在OLED功能器件的设计上【2】，等等。西氟碱(Schiff base)的过渡金属络合物，特别是Pt(Ⅱ)络合物具有较长的三重态寿命[3,4】，尽管此类物质无论在合成与结构修饰上都易于实现，但对其氧传感性能的研究却未见报导。本文合成了一系列西氟碱铂络合物，并对其氧传感性能进行了详细研究。我们发现通过对西氟碱配体进行简单的修饰，其对氧气的响应程度(Ksv 值)即可提高6倍(Ksv 值从0.00313 Torr-1 提高到0.01887 Torr-1)。

摘要： 采用阴离子作为模板，将N，N'-(2-胺基苯基)-2，6-二甲酰亚胺吡啶和1，3-二(2-甲酰苯氧基)-2-丙醇与5，5-亚甲基水杨醛分别缩合得到[1+1]和[2+2]的Schiff-base 大环化合物1和2.，并对其进行了晶体结构解析。

摘要： 采用阴离子作为模板，将N，N'-(2-胺基苯基)-2，6-二甲酰亚胺吡啶和1，3-二(2-甲酰苯氧基)-2-丙醇与5，5-亚甲基水杨醛分别缩合得到[1+1]和[2+2]的Schiff-base 大环化合物1和2.，并对其进行了晶体结构解析。

摘要： 采用阴离子作为模板，将N，N'-(2-胺基苯基)-2，6-二甲酰亚胺吡啶和1，3-二(2-甲酰苯氧基)-2-丙醇与5，5-亚甲基水杨醛分别缩合得到[1+1]和[2+2]的Schiff-base 大环化合物1和2.，并对其进行了晶体结构解析。

摘要： 本文首次将超声应用于Salen金属配合物的制备过程中,在超声条件下分别合成了手性及非手性的Salen金属配合物:N,N'-双水杨醛缩乙二胺钴、N,N'-双水杨醛缩乙二胺锰和(S,S)-N,N'-双(水杨醛)-1,2二苯基乙二胺钴,通过元素分析、红外光谱、核磁进行了表征.讨论了反应时间、温度、以及超声波声强对产率的影响,并与常规的合成方法进行了比较.研究结果表明:在合成过程中采用变幅杆式超声波发生器,以乙醇做溶剂,Schiffbase与醋酸盐在60°C下超声波声强为4×10-3W·cm-2左右时反应较短时间即可获得所需的Salen金属配合物,其配位时间大大减少,其中配体和醋酸锰的配位时间由原来的12h缩短到2.5h,反应温度的也由80°C降低到60°C,并且获得95％的产率.

摘要： 本文首次将超声应用于Salen金属配合物的制备过程中,在超声条件下分别合成了手性及非手性的Salen金属配合物:N,N'-双水杨醛缩乙二胺钴、N,N'-双水杨醛缩乙二胺锰和(S,S)-N,N'-双(水杨醛)-1,2二苯基乙二胺钴,通过元素分析、红外光谱、核磁进行了表征.讨论了反应时间、温度、以及超声波声强对产率的影响,并与常规的合成方法进行了比较.研究结果表明:在合成过程中采用变幅杆式超声波发生器,以乙醇做溶剂,Schiffbase与醋酸盐在60°C下超声波声强为4×10-3W·cm-2左右时反应较短时间即可获得所需的Salen金属配合物,其配位时间大大减少,其中配体和醋酸锰的配位时间由原来的12h缩短到2.5h,反应温度的也由80°C降低到60°C,并且获得95％的产率.

摘要： 本文首次将超声应用于Salen金属配合物的制备过程中,在超声条件下分别合成了手性及非手性的Salen金属配合物:N,N'-双水杨醛缩乙二胺钴、N,N'-双水杨醛缩乙二胺锰和(S,S)-N,N'-双(水杨醛)-1,2二苯基乙二胺钴,通过元素分析、红外光谱、核磁进行了表征.讨论了反应时间、温度、以及超声波声强对产率的影响,并与常规的合成方法进行了比较.研究结果表明:在合成过程中采用变幅杆式超声波发生器,以乙醇做溶剂,Schiffbase与醋酸盐在60°C下超声波声强为4×10-3W·cm-2左右时反应较短时间即可获得所需的Salen金属配合物,其配位时间大大减少,其中配体和醋酸锰的配位时间由原来的12h缩短到2.5h,反应温度的也由80°C降低到60°C,并且获得95％的产率.