Fluorescence of Kryptofix 5 metal complexes

Kryptofix 5 forms complexes with a variety of metal cations. The coordination with the crown ether moiety affects only slightly the emission wavelength of the free Kryptofix 5 ligand (λ_max = 425 nm) in a buffer (pH = 9) solution, but the emission intensity of this blue fluorescence can increase strongly upon complex formation, probably owing to the rigidity of the complex. This applies e.g. to Ba^2 +, Zn^2 +, Cd^2 +, Hg^2 +, Ag⁺ and La^3 +. A second group of metal ions such as Al^3 +, Pb^2 +, Sb^3 +, Bi^3 +, Te^4 +, Gd^3 + and Th^4 + causes a large red shift of the fluorescence of free Kryptofix 5 to approximately λ_max = 500 nm. This green fluorescence resembles that of Kryptofix 5 in acidic solution. It is suggested, that the second group of metal ions is also coordinated to the pyridine nitrogen atoms of the quinoline substituents.     

浅谈氟试剂分光光度法测定水中氟化物

在用氟试剂分光光度法测定水中氟化物过程中,不同版本的检验书籍其显色剂的加入方法有所不同,其中一种方法是将各种显色剂按先后顺序分别加入(方法A),另一种方法是将显色剂临用前混合后一次性加入(方法B).为确定哪一种显色剂的加入方法更佳,特做了一系列的对比实验,结果表明方法B比方法A更加方便、省时,而且其标准曲线的相关系数、加标回收率和测定结果重现性都相对要高些;另外,显色时间选择1 h较佳.     

水杨醛缩对羟基苯甲酰肼及其配合物的荧光研究

将Schiff碱与金属盐在一定的条件下反应,生成了具有稳定的结构和生物活性的配合物.该类配合物被广泛应用于药学、催化和分析化学等领域.本实验设计合成了水杨醛缩对羟基苯甲酰肼Schiff碱配体(H2L)及其10种金属配合物.采用红外光谱、元素分析、热重-差热分析对Schiff碱配体及其配合物进行了表征.并对目标化合物的荧光活性进行了初步测定.     

Colorimetric chemosensor for Ni2+ based on alizarin complexone and a cationic polyelectrolyte in aqueous solution

A new and convenient chemosensor for detecting Ni²⁺ in aqueous buffer has been developed by mixing an anionic organic dye, alizarin complexone (ALC) and a cationic polyelectrolyte, poly(diallyldimethylammonium chloride) (PDADMAC). After addition of Ni²⁺, the chemosensor exhibits a remarkable bathochromic shift with a significant color change from red to blue, while other metal ions did not induce such a change. The color change may be attributed to the aggregate formation of an ALC-based Ni²⁺ complex on the surface of PDADMAC. The results showed that the ALC and PDADMAC mixture can be applied to detect Ni²⁺ selectively with colorimetric changes. This investigation can lead to the construction of new chemosensors by facile and simple mixture of a water-soluble dye and an oppositely charged polyelectrolyte. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47496.     

New polymeric Schiff base and its metal complexes

A novel polymeric Schiff base was synthesized by the reaction of a Schiff base from 2,4‐dihydroxy benzaldehyde and aniline with acryloyl chloride and was polymerized in methyl ethyl ketone at 70°C with benzoyl peroxide as a free‐radical initiator. Polychelates were obtained in an alkaline solution of poly(2‐hydroxy‐4‐acryloyloxy‐N‐phenylbenzylidine) with aqueous solutions of metal ions such as Cu(II), Ni(II), Co(II), Ca(II), Cd(II), Mn(II), and Zn(II). The polymeric Schiff base and polychelates were characterized with elemental analysis and spectral studies. The elemental analysis of the polychelates suggested that the metal‐to‐ligand ratio was 1:2. The IR spectral data of the polychelates indicated that the metals were coordinated through the nitrogen and oxygen of the phenolic ? OH group. Diffuse reflectance spectra, electron paramagnetic resonance, and magnetic moment studies revealed that the polychelates of the Cu(II) complex were square‐planar, those of the Ni(II), Mn(II), and Co(II) complexes were octahedral, and those of the Ca(II), Cd(II), and Zn(II) complexes were tetrahedral. X‐ray diffraction studies revealed that the polychelates were highly crystalline. The thermal properties of the Schiff base and polychelates were also examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 494–500, 2004     

Synthesis and properties of novel end-functionalized polybutylacrylate and its metal complexes

Summary Well-defined polybutylacrylate (PBA) was prepared by atom transfer radical polymerization (ATRP). A novel end-functionalized PBA (macromolecular ligand) was synthesized via PBA bonded with thiocarbamide. Since thiocarbamide possesses strong chelating ability, end-functionalized PBA possesses some new properties such as coordination with metallic ions. After metallic ions were introduced into it, two kinds of end-functionalized PBA metal complexes were got. The structure and property of PBA, end-functionalized PBA and its metal complexes were characterized by ¹H NMR, UV, GPC, Atomic Emission Spectrometry (AES), Cyclic Voltammogram (CV) and Dielectric Constant. The results indicate that the properties of end-functionalized PBA with well-defined structure were improved greatly by introducing a small quantity of transitional metallic ions into it. The novel end-functionalized PBA metal complexes exhibit stable electrochemical activity, dielectric property and have a good prospect in many fields as functional polymer.     

Synthesis and properties of functionalized β-cyclodextrin copolymer and its metal complexes

Summary A novel copolymer was synthesized successfully via polymerization of part (6-O-butene diacid ester)-β-cyclodextrin and styrene. Because the carboxyl groups of the new copolymer possess a strong chelating ability, the copolymer is capable of coordinating with metal ions. Utilizing this new ability, the copolymer metal complexes containing Cu(II) and Ag(I) were synthesized. The structures and properties of the copolymer and its metal complexes were characterized by IR, UV, MS, ¹³C NMR, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), electron spin resonance (ESR), and cyclic voltammetry (CV). The results show that the novel copolymer metal complexes were composed of the desired metal ion, polystyrene, and the functionalized β-cyclodextrin (β-CD). Furthermore, they possess stable electrochemical activity and are paramagnetic.     

新型含羧基卟啉及其金属配合物的合成

合成了5－（间羰基苯甲酸）－氨基苯基－10,15,20－三苯基卟啉（m-CPTPP)及其锌（Ⅱ）、铁（Ⅲ）、铜（Ⅱ）配合物,并通过质谱、元素分析、IR、UV－Vis、^1HNMR、荧光光谱等对其进行了考察。     

Antiviral metal complexes

The initial events (virus adsorption and fusion with the cells) in the replicative cycle of human immunodeficiency virus (HIV) can serve as targets for the antiviral action of metal-binding compounds such as polyanionic compounds (polysulfates, polysulfonates, polycarboxylates, polyoxometalates, and sulfonated or carboxylated metalloporphyrins), bicyclams and G-octet-forming oligonucleotides. The adsorption and fusion of HIV with its target cells depends on the interaction of the viral envelope glycoproteins (gp 120) with the receptors (CD4, CXCR4) at the outer cell membrane. We are currently investigating how the aforementioned compounds interfere with these viral glycoproteins and/or cell receptor.     

Properties of grafted polymer metal complexes as ion exchangers and its electrical conductivity

A polyelectrolyte has been prepared, as a potential proton exchange polymer, by grafting acrylic acid/acrylamide (AAc/AAm) and acrylic acid/acrylonitrile (AAc/AN) comonomers onto a low‐density polyethylene film via gamma irradiation. The developed polymers were characterized by evaluating their physico‐chemical properties such as ion exchange capacity (IEC) and electrical conductivity as functions of grafting yield. The grafted film at different compositions was characterized by Fourier transform infrared, thermogravimetric analysis, and scanning electron microscopy. IEC of the grafted film at grafting % 191 and monomer concentration ratio 50:50 for (LDPE‐g‐AAc/AAm) was found to be more than that for (LDPE‐g‐AAc/AN). The electrical conductivity was found to be greatly affected by the comonomer composition, were it increased as the degree of grafting increased for all grafted films. After alkaline treatment with 3% KOH (3% potassium hydroxide), the electrical conductivity of the grafted films found to be increased. The presence of potassium as counter ion maximized the electrical conductivity of the grafted films. The electrical conductivity of Cu‐membrane complexes was higher than that of both Co (cobalt) and Ni (Nickel) complexes. It has been indicated that, the electrical conductivity increased by increasing both Cu ion content and temperature. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers.     

Hormone anchored metal complexes. 1. Synthesis, structure, spectroscopy and in vitro antitumor activity of testosterone acetate thiosemicarbazone and its metal complexes

Testosterone acetate thiosemicarbazone (TATSC, 17-beta-hydroxyandrost-4-one acetate thiosemicarbazone) was synthesized and characterized by single crystal X-ray structure determination. The copper and platinum complexes of this steroid derivative were synthesized and characterized by spectroscopy and electrochemiatry. The in vitro activity of these compounds against human breast cancer cell line MCF-7 was tested. The highest activity was found for the [Pt(TATSC)Cl(1)] followed by [Cu(TATSC)Cl(2)] and the ligand in compariosn with cisplatin.     

含二茂铁基Schiff碱及其金属 配合物的合成、表征及抑菌活性

通过双乙酰基二茂铁和水合肼合成双乙酰基二茂铁双肼腙配体,然后分别与Cu(Ⅱ),Ni(Ⅱ),Zn(Ⅱ),Pb(Ⅱ),Cd(Ⅱ)合成金属配合物。配体及其金属配合物通过摩尔电导、元素分析、IR和1HNMR进行了表征。所有化合物进行了抗菌活性测试,结果表明,化合物都具有一定的抗菌活性,金属配合物2a~2f比其配体有更高的抗菌活性,其中,CdL(CH3COO)2(2f)的抗菌活性最高。     

Synthesis,characterization, and thermal stability of azomethine oligomer and its metal complexes

The oxidative polycondensation reaction conditions of N,N′‐bis[(2‐hydroxy‐1‐naphthyl)methylene]urea (2‐HNMU) has been accomplished using NaOCl, H₂O₂, and air O₂ oxidants in an aqueous alkaline medium. The structures of the obtained monomer and oligomer were confirmed by FTIR, UV–vis, ¹H NMR, ¹³C NMR, and elemental analysis. The characterization was made by TG‐DTA, size exclusion chromatography (SEC), and solubility tests. At the optimum reaction conditions, the yield of oligo‐N,N′‐bis[(2‐hydroxy‐1‐naphthyl)methylene]urea (O‐2‐HNMU) was found to be 95% (for air O₂ oxidant), 51% (for H₂O₂ oxidant), 96% (for NaOCl oxidant). According to the SEC analysis, the number‐average molecular weight (M_n), weight‐average molecular weight (M_w), and polydispersity index values of O‐2‐HNMU was found to be 1036, 1225 g/mol, and 1.182, respectively, using H₂O₂, and 765, 1080 g/mol, and 1.412, respectively, using air O₂, and 857, 1105 g/mol, and 1.289, respectively, using NaOCl. TG‐DTA analyses showed that O‐2‐HNMU was more stable than 2‐HNMU. According to TG analyses, the carbonaceous residue of 2‐HNMU and O‐2‐HNMU was found to be 0.49% and 2.11% at 1000°C, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

硫氮杂冠醚大环配体及其过渡金属配合物的合成与表征

合成了一种新的含硫氮杂冠醚大环配体4,5：13,14－二苯并－9－甲基－3,15－二氧－20－硫－7,11－二氮双环[15.2.1]二十环－1（19）,17－二烯,及其过渡金属Cu(II),Ni(II),Hg(II),Co(II)和Mn(II)的配合物,用元素分析,红外光谱,核磁共振谱,质谱和电导测定等手段表征了这些化合物,发现配体中氧原子和氮原子均与金属离子配位。     

硫代磷酰二腙及其配合物的合成和生物活性

合成了一种硫代磷酰二腙配体(H2L)及其Mn(Ⅱ)、Fe(Ⅱ)、Co(Ⅱ)配合物,所合成的配体及配合物均用元素分析、摩尔电导、UV、IR等手段进行了表征,对配体还用MS和1HNMR进行了结构表征。测定了化合物的杀虫活性以及对水稻幼苗细胞超氧化物歧化酶(SOD)活力的影响,表明这些化合物具有一定杀虫活性并能激活水稻细胞SOD。     

Polymer anchored metal complexes

Summary Pyromellitic dianhydride and dipyridyl/dipyridylamine have been polycondensed in presence of anhydrous ZnCl₂ under selective conditions. Fe(III), Cr(III), Co(II), Ni(II) and Cu(II) complexes of the polycondensates have been prepared. Tentative structures for PMDA-DP (DPA)-M complexes have been proposed on the basis of elemental IR and electronic spectral analyses.     

Multinuclear metal nucleobase complexes

Of all properties of metal nucleobase complexes, formation of multinuclear species appears to be an outstanding feature. After a brief introduction into well known polymeric metal nucleobase complexes, three aspects recently Studied in our laboratory will be dealt with in more detail: (i) Heteronuclear complexes derived from trans-[(amine)(2)Pt(1-MeC)(2)](2+) (1-MeC=1-methylcytosine). They form, e. g. with Pd(II) or Hg(II), upon single deprotonation of the exocyclic amino group of each 1-MeC ligand, compounds of type trans-[(amine)(2)Pt(1-MeC-)(2)MY](n+), displaying Pt-M bond formation. (ii) Cyclic nucleobase complexes derived from cis-a(2)Pt(II). A cyclic compound of composition {[(en)Pt(UH-N(1),N(3))](4)}(4+) (UH=monoanion of unsubstituted uracil) is presented and the analogy with organic calix-[4]-arenes is pointed out. (iii) Cyclic nucleobase complexes from trans-a(2)Pt(II). Possible ways for the preparation of macrocyclic nucleobase complexes containing trans-a(2)Pt(II) linkages are outlined and precursors and intermediates are presented.     

负载型TiO2 制备及其对茜素红的降解研究

以钛酸四丁酯和正硅酸乙酯为前驱体、冰醋酸为水解抑制剂，用溶胶-凝胶法制备纳米TiO₂/SiO₂复合物。通过X-射线衍射、红外光谱和比表面积仪等测试手段进行了分析，结果表明，纳米TiO₂ /SiO₂粒子焙烧后主要以锐钛型存在，有Ti—O—Si键的产生，复合粒子的比表面积达到389 m²·g^－1。光催化结果表明，n(Ti)∶n(Si)=3和焙烧温度为700 ℃的TiO₂/SiO₂粒子对茜素红溶液的降解性能最好。利用气质联用仪对降解产物进行了分析。     

槲皮素金属配合物的研究进展

槲皮素具有广泛的生物活性和多方面的药理作用,有完整的大π键共轭体系、强配位氧原子及合适的空间构型,可与多种金属离子螯合成稳定的环状配合物。研究表明:槲皮素金属配合物具有抗癌、抗炎、抗氧化、清除自由基和降血糖等作用。槲皮素金属配合物生物活性明显高于槲皮素,药理作用显著。综述了槲皮素金属配合物的研究进展,介绍了槲皮素与主族、副族和稀土金属元素形成配合物的研究现状,为此类化合物的研究提供科学依据。