Unsymmetrical tetraarenoporphines

Zinc complexes of unsymmetrical tetraarenoporphines and their oxidized forms were synthesized by condensation of mixtures of phthalic and naphthalene-2,3-dicarboxylic acid imides with sodium acetate or malonic acid in the presence of zinc acetate. Metal-free compounds were obtained by treatment of benzene solutions of the zinc complexes with gaseous hydrogen chloride. The electronic, PMR, x-ray electron, IR, and mass spectra of the synthesized compounds are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1351–1357, October, 1988.     

具有π共轭骨架的Salen-卟啉型同、异双核配合物的合成及谱学性质

设计合成了两类具有π共轭骨架的Salen-卟啉型配体及金属配合物. 以Salen-卟啉半体及相应的醛为原料, 运用金属模板法合成了单核镍和双核镍Salen-卟啉型金属配合物. 在单核镍的基础上可得到异双核镍、锌Salen-卟啉型金属配合物. 通过核磁共振氢谱(¹H NMR)、紫外-可见(UV-Vis)光谱、傅里叶变换红外(FTIR)光谱、电喷雾质谱(ESI-MS)和荧光光谱等多种谱学手段对其结构进行了表征. 研究表明, 单核镍及异双核镍、锌配合物中, 镍离子落入Salen 部分的配位空腔, 而锌离子则是与卟啉部分形成锌卟啉大环结构。由于卟啉环流效应及分子π共轭结构的影响, 导致配体上的氢原子的化学位移向高场或低场移动. 当金属离子与配体配位之后,卟啉部分的紫外-可见光谱的Soret带和Q带均发生显著变化, 而荧光则出现猝灭现象.     

Nano-sized Cu(II) and Zn(II) complexes and their use as a precursor for synthesis of CuO and ZnO nanoparticles: A study on their sonochemical synthesis,characterization, and DNA-binding/cleavage,anticancer, and antimicrobial activities

Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)₂] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2.     

DNA与生物碱类化合物非共价作用的负离子电喷雾质谱研究(Ⅰ)

目前,临床上使用的许多抗病毒药物均是通过与DNA,RNA发生相互作用破坏其结构,进而影响基因调控与表达的功能,表现出抗病毒活性。因此,核酸与药物分子相互作用的研究对阐述抗病毒药物的作用机理,以及对药物的体外筛选都具有重要的意义．电喷雾电离质谱作为一种软电离手段,可将溶液中生物分子与药物分子的非共价复合物转为气相进行分析,再现其生理状态,使其成为分子水平上进行药物筛选的最佳方法和在分子水平上筛选中药抗病毒活性成分的理想工具,本文选择合成了与SARS病毒相关的DNA片段作为抗病毒药物筛选的靶分子,用电喷雾质谱技术,通过对靶分子与5种生物碱的非共价复合作用,探讨了生物质谱方法用于药物筛选的可行性。     

‘Two-point’-bound supramolecular complexes from semi-rigidified dipyridine receptors and zinc porphyrins

Two linear compounds 1 and 2 have been designed and synthesized as new receptors for zinc porphyrins. Both compounds consist of two folded aromatic amide moieties, which are connected with an acetylene linker in 1 or directly in 2. The rigid conformations of their folded moieties are stabilized by intramolecular tri-centered hydrogen bonding, while the whole molecule adopts a ‘S’- or ‘C’-styled conformation depending on the relative orientation of the two rigid moieties. Two pyridine units are introduced at the ends of 1 and 2 for the complexation of zinc porphyrin guests. Although the ¹H NMR investigation indicated that both compounds can bind two zinc porphyrin guests at high concentrations (≥5 mM) in chloroform, the UV-vis studies revealed that, at low concentration of 1 and 2 (4 μM), both compounds complex one zinc porphyrin guest to form structurally unique ‘two-point’-bound 1:1 complexes. The association constants of the 1:1 complexes have been determined with the UV-vis titration experiments.     

Synthesis of meso-tetraalkyltetrabenzoporphines

Stable complexes of zinc meso-tetralkyltetrabenzoporphines with tribenzylamine have been obtained by the template tetramerization of 3-R-methylenephthalimidines with zinc acetate in the presence of tribenzylamine or by the reaction of potassium phthalimide with the corresponding alkylmalonic acids. The structures of the compounds synthesized have been confirmed by their electronic absorption spectra, and in some cases also by their mass spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 61–64, January, 1984.     

<Emphasis Type="Italic">meso</Emphasis>-Quinolyl-substituted Tetrabenzoporphins. Synthesis and Properties

Prolonged heating of phthalimide with 2-methylquinoline in the presence of zinc oxide afforded zink complexes of meso-tri-, di- and monoquinolyltetrabenzoporphins. Alternative preparation methods were developed for some among these compounds. The corresponding porphins were prepared by treating complexes with hydrochloric acid. The spectral characteristics of compounds synthesized were investigated.__________Translated from Zhumal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 306–311.Original Russian Text Copyright © 2005 by Galanin, Kudrik, Lebedev, Aleksandriiskii, Shaposhnikov.     

Synthesis and properties of zinc complexes of meso-hexadecyloxy-substituted tetrabenzoporphyrin and tetrabenzoazaporphyrins

The hexadecyloxyacetic acid was prepared by alkylation of glycolic acid. Proceeding from the acid obtained zinc complexes were synthesized of meso-trans-di(hexadecyloxy)tetra-benzoporphyrin, meso-tetra(hexadecyloxy)tetrabenzoporphyrin, and also of meso-hexadecyloxytetrabenzoazaporphyrins. The spectral properties of compounds synthesized were investigated.     

Synthesis and spectral properties of <Emphasis Type="Italic">meso</Emphasis>-phenyltetrabenzoazaporphyrins containing triphenylmethyl groups

4-(p-Triphenylmethylphenoxy)isoindoline-1,3-diimine was synthesized starting from 4-(p-triphenylmethylphenoxy)phthalodinitrile obtained by the reaction of 4-nitrophthalodinitrile with 4-(triphenylmethyl)phenol. The former was reacted with phenylacetic acid in the presence of zinc oxide to obtain zinc complexes of meso-phenyltetrabenzoazaporphyrins containing triphenylmethyl groups. Spectral properties of the synthesized compounds were studied.     

Synthesis and characterization of 4-(alkylaminoisonitrosoacetyl)biphenyls and their complexes

Three new substituted 4-(alkylaminoisonitrosoacetyl)biphenyls (ligands) derived from 4-biphenylhydroxymoyl chloride and corresponding amines were synthesized. The following aromatic and aliphatic amines were used for ligands: ethanolamine, 2-amino-4-methylphenol, and 2-(aminomethyl)pyridine. Mononuclear or binuclear cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), and lead(II) complexes with these ligands were synthesized. These compounds were characterized by elemental analyses, AAS, infrared spectra, and magnetic susceptibility measurements. The ligands were additionally characterized by ¹H NMR. The results suggest that the ligands act as tridentate ligands. The text was submitted by the authors in English.     

Synthesis, characterization and photophysical properties of novel tetrasubstituted phthalocyaninato zinc derivatives

Peripherally tetraimido-substituted phthalocyaninato zinc compounds 1-3 were synthesized through the reaction of tetraamino-substituted phthalocyaninato zinc with 4-Br-1,8-naphthalic anhydride, 4-hexahydropyridine-1,8-naphthalic anhydride and 4-morpholine-1,8-naphthalic anhydride, respectively. The compounds were characterized by MS, ¹H NMR, UV-vis, IR and elemental analysis, the results of which were consistent with the proposed structures. The effects of substitutes, acid/base and solvents on the UV-vis spectra of the new complexes were discussed in detail.     

Synthesis and characterization of heteroleptic Schiff base transition metal complexes: a study of anticancer,antimicrobial, DNA cleavage and anti-TB activity

In search of effective bioactive compounds, we have synthesized the new Co(II), Ni(II), and Cu(II) complexes of the Schiff base derived from 8-formyl-7-hydroxy-4-methylcoumarin and 2-hydrazino benzothiazole and characterized by analytical, spectroscopic (IR, NMR, UV–vis, Mass), magnetic, powder X-ray diffraction data (PXRD) and TGA studies. Elemental analysis suggests the stoichiometry of the synthesized complexes and the solution electronic spectral study revealed the octahedral geometry of the compounds. Thermal analysis shows the presence of water molecule outside the coordination sphere and powder-XRD patterns have been studied to test the degree of crystallinity of the complexes and unit cell calculations were made. All the synthesized compounds were tested against human ovarian cancer cell line (PA-1). The synthesized metal complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to free ligand (LH). The results of the DNA-cleavage activity suggest that the ligand and its metal complexes can cleave CT-DNA at different degrees. Further, anti-tuberculosis activity was done using microplate almar blue assay. Among all these synthesized compounds, the Cu(II) complex exhibits good cleaving ability compared to other newly synthesized metal complexes.     

Synthesis and characterization of some metal complexes of isonitroso-2-acetylnaphthalene derivative

Nickel(II), copper(II), and zinc(II) complexes with the Schiff base obtained from isonitroso-2-acetylnaphthalene and 1,2-phenylenediamine were synthesized. The compounds were characterized by elemental analyses, FT-IR, UV-Vis, and ¹H and ¹³C NMR spectra, conductance measurements, magnetic susceptibility measurements, and thermal analysis. The results suggest tetradentate coordination of the symmetrical Schiff base ligand through the two oxime oxygen atoms and two azomethine nitrogen atoms. The molar conductance data showed that the synthesized complexes are non-electrolytes.     

Synthesis,photophysics, and photochemistry of peripherally Schiff base-zinc complex substituted zinc phthalocyanine

The content of this work is based on the introduction of the salicylhydrazone-zinc complexes into the phthalocyanine core. The reaction of the salicylhydrazone substituted ZnPc (1) with the related zinc(II) salt in basic conditions in DMF yielded bis[bis(salicyhydrazone)phenoxy)zinc(II)] phthalocyaninato zinc(II) (5) in which two salicylhydrazone-Zn complexes are linked through oxygen bridges to the macrocyclic core as three-nuclear complex. The novel compound synthesized in this study was fully characterized by general spectroscopic techniques such as FT-IR, UV-vis, ¹H NMR, ¹³C NMR, elemental analysis and mass spectroscopy. In addition, spectral, photophysical (fluorescence quantum yields), and photochemical (generation of singlet oxygen and photo stability under light irradiation) properties of newly synthesized phthalocyanine (5) and the starting Pcs molecules used to obtain this molecule were investigated in DMSO solutions, comparatively.     

Synthesis,Spectral, and Coordination Properties of Halogen-Substituted Tetraarylporphyrins

2,3,7,8,12,13,17,18-Ocatbromo-5,10,15,20-tetra-(4-chloroprienyl)porphyrin and 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetra-(4-bromophenyl)porphyrin have been synthesized. The obtained compounds have been identified by electronic absorption and ¹H NMR spectroscopy as well as mass spectrometry. The complex-forming properties of the synthesized porphyrins in the zinc acetate (II)-acetonitrile system at 278–298 K have been studied. Kinetic parameters of the formation of the corresponding zinc complexes in acetonitrile have been determined.

     

Selectively Enhanced Retention of Neutral Iron(II) Complex in RP-LC with o-Hydroxy Pyrimidylazo Compounds as Precolumn Derivatizing Reagent

The diazo component of o-hydroxy heterocyclic azo compounds showed a remarkable effect on the retention of their neutral complexes of iron and nickel as a precolumn derivatizing reagent in the separation of metal ions by RP-HPLC using an octadecyl-bonded silica gel column. High resolutions of iron and nickel complexes were obtained with pyrimidyl derivatives. Acetonitrile-water or acetone-water was more suitable as a mobile phase than alcohol-water with regard to the separation of these metal ions. Thermodynamic study showed that the difference in transfer enthalpies of iron and nickel complexes from the mobile phase to the stationary phase dominated the resolution of two complexes with pyrimidyl compounds. High resolutions obtained by use of pyrimidyl compounds were ascribed to selectively enhanced retention of the iron complexes from the comparison with the retentions of the zinc complexes.     

3,5-di-tert-butyl-1,4-benzoquinone ferrocenoylhydrazone and its zinc(II), palladium(II), and mercury(II) complexes: Structure and properties

A new ligand system, 3,5-di-tert-butyl-1,4-benzoquinone ferrocenoylhydrazone, was synthesized and its complexes with zinc(II), Hg(II), and palladium(II) were prepared. The compounds were studied by IR, electron absorption, and ¹H NMR spectroscopy. Structure of the compounds obtained is discussed.     

Isolation and characterization of main group and late transition metal complexes using orthometallated imine ligands

Several late transition metal and main group orthometallated imine complexes were synthesized by utilizing ortholithiated imine precursors. Magnesium, aluminum, zinc, copper(I), and tin(IV) complexes were isolated and characterized. Subsequent reactions with electrophiles such as Ph(2)PCl, MeI and I(2) yielded several functionalized products, including a new iminophosphine ligand and its corresponding copper(I) complex. The coordination modes of the orthometallated imine ligands, as well as the structures of the metal complexes, were studied in the solid state using small molecule X-ray diffraction when possible.     

Synthesis and properties of [4-(triphenylmethyl)phenoxy]acetic and 3-[4-(triphenylmethyl)phenoxy]propionic acids and their condensation with phthalimide leading to <Emphasis Type="Italic">meso</Emphasis>-substituted tetrabenzoporphyrins

Condensation of 4-(triphenylmethyl)phenol with monochloroacetic and 3-bromopropionic acids gave, respectively, [4-(triphenylmethyl)phenoxy]acetic and 3-[4-(triphenylmethyl)phenoxy]propionic acids which reacted with phthalimide in the presence of zinc acetate to produce meso-substituted zinc tetrabenzoporphyrins having bulky triphenylmethyl groups in the substituent. The corresponding free ligands were obtained by demetalation of the zinc complexes. Spectral properties of the synthesized compounds were studied.     

Chelating Polymers. III. Chelating Monomers and Polymers from s-Triazinyl Substituted Hydrazinoacetic Acids

The model chelating compounds β-[2,4-bis(dimethylamino)-s-triazin-6-yl] hydrazinoacetic acid, β-[2,4-bis(dimethylaniino)-s-triazind-yl] hydrazino-N, N-diacetic acid, 2,4-bis(dimethylamino)-s-triazin-6-yl-aminoacetic acid, and 2,4-bis(dimethylamino)-s-triazin-6-yl-iminodiacetic acid have been synthesized and characterized by composition analysis, infrared spectroscopy, and potentiometric titration data. The copper(II), nickel(II), cobalt(II), zinc(II), magnesium(II), and palladium(II) complexes of the first two model compounds, and the copper, nickel, cobalt, and zinc complexes of the third and fourth model compounds have been prepared. The infrared absorption spectra of the model compounds and their complexes were recorded for the range 3800 to 600 cm^?1, and the assignment of pertinent bands was made by comparison with reported infrared correlations. In those cases where applicable, shifts in the NH stretching vibration and carboxylate stretching vibration frequencies of the metal complexes were compared to those of the proper references and used as an indication of possible chelation effects in the metal complexes.

The aldehyde-reactable β-[2,4-diarnino-s-triazin-6-y1] hydrazinoacetic acid was also prepared and characterized; its polymers were prepared by the reaction of both the free ligand and its copper(II) complex with formaldehyde. Qualitative studies on the reaction of these polymers with metal ions and on the ease of metal ion elution from the polymers indicate that t h is a promising chelating polymer system.