链状双苯基噁二唑基乙烯光化学性质的研究

本文合成了 1 ,n 双 [4 [2 [2 ( 5 苯基 1 ,3,4 二唑基 ) ]乙烯基 ]苯氧基 ]烷烃(n分别为 3,4,6 )和 2 ,2′ 双 [4 [2 [2 ( 5 苯基 1 ,3,4 二唑基 ) ]乙烯基 ]苯氧基 ]乙醚 4个未见文献报导的链状双杂芳基乙烯化合物及其参比物 4 [2 [2 ( 5 苯基 1 ,3,4 二唑基 ) ]乙烯基 ]苯甲醚。用元素分析、紫外、红外、核磁和质谱表征了化合物的结构并用紫外吸收光谱跟踪研究了其在稀溶液中的光化学性质。结果发现 :上述化合物在高压汞灯照射下可同时发生反顺异构化和 [2 2 ]分子内光二聚两种反应 ,前者迅速可逆 ,后者缓慢且不可逆。其分子内光二聚体在短波长紫外光照射下极易进行逆 [2 2 ]光解开环反应而得到原来的化合物。另外 ,上述化合物的分子内光二聚反应和光解开环反应可反复进行多次 ,再现性较好 ,此类化合物在光信息储存方面具有潜在应用前景     

Synthesis and Anti-Candida Activity of Cobalt(II) Complexes of Benzene-1,2-Dioxyacetic Acid (bdoaH(2)). X-Ray Crystal Structures of [Co(bdoa)(H(2)O)(3)] 3.5H(2)O and {[CO(phen)(3)](bdoa)}(2)24H(2)O (phen = 1,10-Phenanthroline)

Co(CH(3)CO(2))(2)4H(2)O reacts with benzene-1,2-dioxyacetic acid (bdoaH(2)) to give the Co(2+) complexes [Co(bdoa)(H(2)O)(3)]H(2)O (1a) and [Co(bdoa)(H(2)O)(3)] 3.5H(2)O (1b). Subsequent reaction of 1a with 1,10- phenanthroline produces [CO(phen)(3)] bdoa10H(2)O (2a) and {[CO(phen)(3)](bdoa)}(2)24H(2)O (2b). Molecular structures of 1b and 2b were determined crystallographically. In 1b the bdoa(2-)- ligates the metal by two carboxylate oxygens and two ethereal oxygens, whereas in 2b the bdoa(2-) is uncoordinated. The Mn(2+) and Cu(2+) complexes [Mn(bdoa)(phen)(2)]H(2)O (3) and [Cu(pdoa)(imid)(2)] (4) were also synthesised, 1a-4 and other metal complexes of bdoa H(2) (metal = Mn(2+), Co(2+) ,Cu(2+), Cu(+) ) were screened for their ability to inhibit the growth ofhe yeast Candida albicans. Complexes incorporating the 1,10-phenanthroline ligand were the most active.     

On the transformation of (S)-2-hydroxypropylphosphonic acid into fosfomycin in Streptomyces fradiae--a unique method of epoxide ring formation

(1S,2S)- and (1R,2S)-2-hydroxy-[1-D(1)]propylphosphonic acid were synthesised from (1S,2S)-2-benzyloxy-[1-D(1)]propanol, which was obtained by horse liver alcohol dehydrogenase catalysed reduction of the corresponding aldehyde. When (1S,2S)-2-hydroxy-[1-D(1)]propylphosphonic acid was fed to Streptomyces fradiae, the deuterium was retained to the same extent in fosfomycin (cis-epoxide) and its co-metabolite trans-epoxide. Removal of the hydrogen (deuterium) atom from the C-1 atom of deuterated 2-hydroxypropylphosphonic acids is a stereospecific process (the hydrogen atom of (S)-2-hydroxypropylphosphonic acid is pro-R). The formation of the O--C-1 bond of fosfomycin occurs with net inversion of configuration, the formation of the O--C-1 bond of the trans-epoxide with net retention.     

Analysis of sulphur-containing indigoid dyes as leuco forms by NMR spectroscopy

The NMR spectra of different types of sulphur-containing indigoid dyes as leuco forms (i.e. reduced forms or 'vats') in deuterium oxide are recorded and discussed. NMR spectroscopy provides an expeditious technique for identification, structure elucidation and purity control of these dyes. The regio-selective exchange of halogen for deuterium or hydrogen in indigo derivatives was successfully adapted to thioindigos and [indole-(2')]-[thionaphthene-(2)]-indigos. The reaction is useful as supplementary method for structure analysis and renders access to new selectively deuterated dyes. Care must be observed with the concentration of reducing agents and pH values in vat dyeing process in order to avoid further reduction of the leuco forms. The 'overreduction' of leuco forms of [acenaphthene-(1')]-[thionaphthene-(2)]-indigos was followed by NMR spectroscopy and interpreted.     

色满酮类化合物的合成及其抗炎活性研究

设计合成了4种色满酮类化合物,并利用熔点、红外光谱、核磁共振氢谱等手段确定了其结构。采用二甲苯致小鼠耳肿胀法,测定了该化合物的抗炎活性,实验结果表明在200mg／kg剂量下所合成的3个目标化合物6-[2-（4-吗啉基）乙氧基]色满酮、6-[（喹啉-2-基）甲氧基]色满酮、7-[2-（4-吗啉基）乙氧基]色满酮对二甲苯所致小鼠耳肿胀具有显著的抑制作用。     

Polyimide–polysiloxane block copolymers synthesized from α, ω-(3-aminophenoxy) terminated poly[oxy(dimethylsilyl)-1,4-phenylene(dimethylsilylene)]s

A method has been worked out for the synthesis of α,ω-(3-aminophenoxy) terminated poly[oxy(dimethylsilyl)-1,4-phenylene(dimethylsilylene)]oligomers with controlled molecular weight. From these oligomers were synthesized polyimide-polysiloxane block copolymers via a transimidization route, with polyimide moieties based on 2-aminopyridine terminated 5,5′-oxybis-1,3-isobenzofuranedione-4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline oligomers. The copolymers obtained show higher thermooxidative stability in comparison with copolymers having siloxane moiety based on α,ω-aminopropyl or α,ω-arylamine terminated poly(dimethylsiloxane) oligomers.     

Oxygen Radical Scavenger Activity, EPR, NMR, Molecular Mechanics and Extended-Hückel Molecular Orbital Investigation of the Bis(Piroxicam)Copper(II) Complex

The oxygen radical scavenger activity (ORSA) of [Cu(II)(Pir)(2)] (HPir = Piroxicam = 4-hydroxy -2- methyl -N-2- pyridyl -2H- 1,2-benzothiazine -3- carboxamide 1,1-dioxide) was determined by chemiluminescence of samples obtained by mixing human neutrophils (from healthy subjects) and [Cu(II)(Pir)(2)(DMF)(2)] (DMF = N,N -dimethylformammide) in DMSO/GLY/PBS (2:1:2, v/v) solution (DMSO = dimethylsulfoxide, GLY = 1,2,3-propantriol, PBS = Dulbecco's buffer salt solution). The ratio of the residual radicals, for the HPir (1.02.10(-4)M) and [Cu(II)(Pir)(2)(DMF)(2)] (1.08.10(-5)M)/HPir (8.01.10-(-5)M) systems was higher than 12 (not stimulated) [excess of piroxicam was added (Cu/Pir molar ratio approximately 1:10) in order to have most of the metal complexed as bischelate]. In contrast, the ratio of residual radicals for the CuCl(2) (1.00.10(-5)M) and [Cu(II)(Pir)(2)(DMF)(2)] (1.08.10(-5)M)/Hpir (8.01.10(-5)M)system was 5. The [Cu(II)(Pir)(2)] compound is therefore a stronger radical scavenger than either HPir or CuCl(2). A molecular mechanics (MM) analysis of the gas phase structures of neutral HPir, its zwitterionic (HPir(+-)) and anionic (Pir(-)) forms, and some Cu(II)-piroxicam complexes based on X-ray structures allowed calculation of force constants. The most stable structure for HPir has a ZZZ conformation similar to that found in the Cu(II) (and Cd(II) complexes) in the solid state as well as in the gas phase. The structure is stabilized by a strong H bond which involves the N(amide)-H and O(enolic) groups. The MM simulation for the [Cu(II)(Pir)(2)(DMF)(2)] complex showed that two high repulsive intramolecular contacts exist between a pyridyl hydrogen atom of one Pir(-) molecule with the O donor of the other ligand. These interactions activate a transition toward a pseudo-tetrahedral geometry, in the case the apical ligands are removed. On refluxing a suspension of [Cu(II)(Pir)(2)(DMF)(2)] in acetone a brown microcystalline solid with the Cu(Pir)(2).0.5DMF stoichiometry was in fact prepared. (13)C spin-lattice relaxation rates of neutral, zwitterionic and anionic piroxicam, in DMSO solution are explained by the thermal equilibrium between the three most stable structures of the three forms, thus confirming the high quality of the force field. The EPR spectrum of [Cu(II)(Pir)(2)(DMF)(2)] (DMSO/GLY, 2:1, v/v, 298 and 110 K) agrees with a N2O2+O2 pseudo-octahedral coordination geometry. The EPR spectrum of [Cu(II)(Pir)(2).0.5DMF agrees with a pseudo-tetrahedral coordination geometry. The parameters extracted from the room temperature spectra of the solution phases are in agreement with the data reported for powder and frozen solutions. The extended-Hückel calculations on minimum energy structures of [Cu(II)(Pir)(2)(DMF)(2)] and [Cu(II)(Pir)(2)] (square planar) revealed that the HOMOs have a relevant character of d(x) (2)-y(2). On the other hand the HOMO of a computer generated structure for [Cu(II)(Pir)(2)] (pseudo-tetrahedral) has a relevant character of d(xy) atomic orbital. A d(xy) orbital is better suited to allow a dpi-ppi interaction to the O(2) (-) anion. Therefore this work shows that the anti-inflammatory activity of piroxicam could be due in part to the formation of [Cu(II)(Pir)(2)] chelates, which can exert a SOD-like activity.     

Synthese von 2-[Benzazolyl-(2)]-3,3-bis-(alkylthio)-acrylnitrilen und Umsetzungen mit N-Nucleophilen

Synthesis of 2-[Benzazolyl-(2)]-3,3-bis-(alkylthio)-acrylnitriles and Their Reactions with N-Nucleophiles The reactions of benzazolyl-(2)-acetonitriles 1 (1H-benzimidazolyl-, 1-methylbenzimidazolyl-, benzoxazolyl- and benzothiazolyl-) with carbon disulfide in the presence of sodium hydride in dimethylsulfoxide and methylation yield the 2-[benzazolyl-(2)]-3,3-bis-(alkylthio)-acrylonitriles 3 – 5 reacting with amines to the keten-S,N-acetals 6 – 9 . If dinucleophilic reagents are used heterocyclic systems 10 – 14 are formed.     

1,2,3-Triazabutadiene. XIII. UV-vis-spektroskopische Untersuchungen zur Protonierung Z-E-isomerer 1-Aryl-3-[3-methylbenzthiazolinyliden-(2)]- und 1-Aryl-3-[1,3-dimethylbenzimidazolinyliden-(2)]-triazene

1,2,3-Triazabutadienes. XIII. U.V.-vis-Spectroscopic Investigations of the Protonation of Z-E-Isomeric 1-Aryl-3-[3-methylbenzthiazolinyliden-(2)]- and 1-Aryl-3-[1,3-dimethylbenzimidazolinyliden-(2)]-triazenes The u.v.-vis absorption spectra of Z-E-isomeric 1-aryl-3-[3-methylbenzthiazolinyliden-(2)]- and 1-aryl-3-[1,3-dimethyl-benzimidazolinyliden-(2)]-triazenes 1–3 resp. 4 show a pronounced halochromic effect in the presence of acids. The reason is the protonation of the N¹-atom of the triazabutadiene chain whereby the energetically favourable structure of a diazatrimethine is formed. The magnitude of the halochromic effect depends on the substituents in the aryl and benzo residue and on the Z-E-structure of the compounds.     

High Efficiency Electrochemiluminescence for Copper(II) and Cadmium(II) Pyrazolate Polymers

Journal of Inorganic and Organometallic Polymers and Materials - Two new coordination polymers, namely, [Cu2(L)2(4,4′-bpy)]n (1) and [Cd(HL)Cl(1,10′-phen)]n (2)...     

Enzymatic fluorination in Streptomyces cattleya takes place with an inversion of configuration consistent with an SN2 reaction mechanism

The stereochemical course of the recently isolated fluorination enzyme from Streptomyces cattleya has been evaluated. The enzyme mediates a reaction between the fluoride ion and S- adenosyl-L-methionine (SAM) to generate 5'-fluoro-5'-deoxyadenosine (5'-FDA). Preparation of (5'R)-[5-(2)H(1)]-ATP generated (5'R)-[5-(2)H(1)]-5'-FDA in a coupled enzyme assay involving SAM synthase and the fluorinase. The stereochemical analysis of the product relied on (2)H NMR analysis in a chiral liquid-crystalline medium. It is concluded that the enzyme catalyses the fluorination with an inversion of configuration consistent with an S(N)2 reaction mechanism.     

Protein-binding Properties of two Antitumour Ru(III) Complexes to Human Apotransferrin and Apolactoferrin

The interaction of two ruthenium(III) complexes exhibiting high anticancer activity - namely trans-Indazolium(bisindazole) tetrachlororuthenate(III), Hlnd[RuInd(2)Cl(4)], and trans-Imidazolium (bisimidazole) tetrachlororuthenate(III), Hlm[RuIm(2)Cl(4)], - with human serum apotransferrin has been investigated through spectroscopic and chromatographic techniques with the ultimate goal of preparing adducts with good selectivity for cancer cells due to the fact that tumour cells express high amounts of transferrin receptors on their cell surface. Whereas the binding of Hlm[RuIm(2)Cl(4)] to human serum apotransferrin takes several hours, Hlnd[RuInd(2)Cl(4)], the less toxic complex, gives rise to a well defined 2:1 complex within a few minutes. Hlnd[RuInd(2)Cl(4)] will react with apotransferrin only in the presence of bicarbonate, this anion dictating the kinetic and mechanistic characteristics of protein-binding. Circular dichroism studies had previously indicated that binding of both Ru(III) complexes occurs around the unoccupied iron(III) binding sites; this result is now confirmed by preliminary X-ray data of Hlnd[RuInd(2)Cl(4)] and Hlm[RuIm(2)Cl(4)] bound to apolactoferrin, a related iron protein. The crystallograhic data reveals that binding of both complexes takes place at histidine residues, and that the ligand (indazole) remains bound in the case of Hlnd[RuInd(2)Cl(4)].     

Novel 4-amino bis-pyridinium and bis-quinolinium derivatives as choline kinase inhibitors with antiproliferative activity against the human breast cancer SKBR-3 cell line

Choline kinase (ChoK) is the first enzyme in the CDP-choline pathway that synthesizes phosphatidylcholine, the major phospholipid in eukaryotic cell membranes. Human ChoK has three isoforms: ChoKα1, α2, and β. Specific inhibition of ChoKα has been reported to selectively kill tumor cells. In this study, ten new symmetrical bis-pyridinium and bis-quinolinium derivatives were synthesized and tested for their ability to inhibit human ChoKα2. These compounds have electron-releasing groups at position 4 of the pyridinium or quinolinium rings. 1,1'-[(Butane-1,3-diylbis(benzene-1,4-diylmethylene)]bis[4-(4-bromo-N-methylanilino)pyridinium)] dibromide and 1,1'-(biphenyl-3,3'-diylmethylene)bis[7-chloro-4-(perhydroazepine-1-yl)quinolinium] dibromide were identified as highly potent ChoK inhibitors with IC(50) values of 80 nM. Kinetic enzymatic assays indicated a mixed and predominantly competitive mechanism of inhibition for these compounds, which exhibited strong antiproliferative activity (EC(50) 1 μM) against the human breast cancer SKBR3 cell line.     

Synthesis, characterization and biological activity of trans-platinum(II) and trans-platinum(IV) complexes with 4-hydroxymethylpyridine

The synthesis and chemical characterization of two new trans platinum complexes, trans-[PtCl(2)NH(3)(4-hydroxymethylpyridine)] (1) and trans-[PtCl(4)NH(3)(4-hydroxymethylpyridine)] (2) are described. Their ability to interact with 5'-GMP by themselves and in the presence of reducing agents in the case of trans-[PtCl(4)NH(3)(4-hydroxymethylpyridine)] were tested. Circular dichroism, electrophoretic mobility in agarose gel, and atomic force microscopy studies showed that the interaction of complex 1 with DNA is stronger than that of complex 2. Cytotoxicity tests against HL-60 tumor cells also showed higher activity for trans-[PtCl(2)NH(3)(4-hydroxymethylpyridine)] than for trans-[PtCl(4)NH(3)(4-hydroxymethylpyridine)]. Complex 1 presents similar behavior to cisplatin, but with a lower IC(50) at 24 h. Complex 1 also showed high apoptosis induction.     

A [meso-tetrakis(4-sulfonatophenyl)porphyrinato]zinc(ii) complex as an oral therapeutic for the treatment of type 2 diabetic KKA(y) mice

We prepared and characterized [meso-tetrakis(4-sulfonatophenyl)porphyrinato]zinc(II) ([Zn(tpps)]), and investigated its in vitro insulin-mimetic activity and in vivo hypoglycemic effect in type 2 diabetic KKA(y) mice. The results were compared with those of previously proposed insulin-mimetic zinc(II) complexes and zinc sulfate (ZnSO(4)). The in vitro insulin-mimetic activity of [Zn(tpps)] was considerably better than that of bis(allixinato)zinc(II) ([Zn(alx)(2)]), bis(maltolato)zinc(II) ([Zn(mal)(2)]), bis(2-aminomethylpyridinato)zinc(II) ([Zn(2-ampy)(2)](2+)), and ZnSO(4). In particular, the order of in vitro insulin-mimetic activity of the complexes was determined to be: [Zn(tpps)]>[Zn(alx)(2)]>[Zn(mal)(2)]>[Zn(2-ampy)](2+)>ZnSO(4). [Zn(tpps)] normalized the hyperglycemia of KKA(y) mice within 21 days when administered orally at doses of 10-20 mg (0.15-0.31 mmol) Zn per kg body mass for 28 days. In addition, metabolic syndromes such as insulin resistance, the degree of renal disturbance, and the degree of liver disturbance were significantly improved in [Zn(tpps)]-treated KKA(y) mice relative to those administered with saline and ZnSO(4). The improvement in diabetes was validated by the results of oral glucose-tolerance tests and the decrease in the HbA(1c) level observed. In contrast, ZnSO(4) and the ligand H(2)tpps did not lower the elevated blood glucose level under the same experimental conditions. Based on these observations, [Zn(tpps)] is proposed to be the first orally active zinc(II)-porphyrin complex for the efficacious treatment of not only type 2 diabetes but also metabolic syndromes in animals.     

Copolymeric systems bearing side-chain thioxanthone and α-aminoacetophenone moieties as photoinitiators for ultraviolet-curable pigmented coatings

Copolymers of 1-(4-morpholinophenyl)-2-benzyl-2-[N-methyl-N-(3-meth-acryloyloxy propyl)]aminopropan-1-one and of 1-(4-morpholinophenyl)-2-benzyl-2-[N-methyl-N-(3-methacryloyloxypropyl)]aminobutan-1-one with 1-[(2-methacryloyloxy)ethoxycarbonyl]thioxanthone were prepared and structurally characterized. The above systems were also checked in the ultraviolet cure of an acrylic mixture upon irradiation over 380 nm, thus simulating the conditions of a TiO₂-pigmented formulation. The curing results were compared with those obtained in the presence of the mixtures of the corresponding homopolymers as well as of their low-molecular-weight models. The copolymeric systems display synergistic effects of activity with respect to the structural models but show lower photoinitiation efficiency against the homopolymers mixtures. These data are discussed and interpreted in terms of structural requirements and photochemical mechanistic aspects of the above systems. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2247–2258, 1997     

Polymerization characteristics of a dye of anthraquinone

A technical dye of the anthraquinone type was analyzed by GPC, mass spectroscopy, and elemental analysis. Along with the polymerizable component, N-[4-amino-3-methoxyanthraquinonyl-(1)] methacrylamide (I), it contained a saturated admixture, N-[4-amino-3-methoxyanthraquinonyl-(1)]-2-chloro-2-methylpropionamide (II). The homopolymerization of I was carried out, and admixture II was isolated and characterized. The copolymerization of the dye with styrene and methyl methacrylate was verified, and the retardation effect of II on the polymerization of these monomers was evaluated.     

A DFT study of electronic structures, energies, and molecular properties of lithium bis[croconato]borate and its derivatives

Theoretical studies on electrolyte salts, lithium bis[croconato(2-)]borate (LBCB) and its derivatives, lithium [croconato(2-) salicylato(2-)]borate (LCSB), and bis[salicylato(2-)]borate (LBSB) are carried out using density functional theory (DFT) method and B3LYP theory level for the first time. Bidentate structures involving two oxygen atoms are preferred. Based on these conformations, a linear correlation was observed between the highest occupied molecular orbital (HOMO) energies and the limiting oxidation potentials measured by linear sweep voltammetry, which supports experimental results that strongly electron-withdrawing substituent anions are more resistant against oxidation than their organic counterparts. The correlations were also observed between ionic conductivity and binding energy, solubility and theoretical set of parameters of anion_, thermal stability and the hardness (η)_. Wave function analyses have been performed by natural bond orbital (NBO) method to further investigate the cation-anion interactions.     

Novel polymeric photoinitiators bearing side-chain α-aminoacetophenone moieties for ultraviolet-curable pigmented coatings

New polymeric photoinitiators with pendant α-aminoacetophenone moieties, such as the homopolymers of 1-(4-morpholinophenyl)-2-benzyl-2-[N-methyl-N-(3-methacryloyloxypropyl)]aminopropan-1-one and of 1-(4-morpholinophenyl)-2-benzyl-2-[N-methyl-N-(3-methacryloyloxypropyl)]aminobutan-1-one have been prepared and fully characterized. Their photoinitiation activity has been also checked in the ultraviolet cure of a standard acrylic mixture, under irradiation over 380 nm, thus simulating the absorption conditions of a TiO₂-pigmented coating formulation. The results have been compared with those found by using the corresponding low-molecular-weight structural models, purposely synthesized. The activity data obtained are discussed and related to the structural requirements of the above systems. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2237–2246, 1997     

Polypyridyl CoII-Curcumin Complexes as Photoactivated Anticancer and Antibacterial Agents

Four new Co^II complexes, [Co(bpy)₂(acac)]Cl ( 1 ), [Co(phen)₂(acac)]Cl ( 2 ), [Co(bpy)₂(cur)]Cl ( 3 ), [Co(phen)₂(cur)]Cl ( 4 ), where bpy=2,2’-bipyridine ( 1 and 3 ), phen=1,10-phenanthroline ( 2 and 4 ), acac = acetylacetonate ( 1 and 2 ), cur=curcumin monoanion ( 3 and 4 ) have been designed, synthesized and fully characterized. The X-ray crystal structures of 1 and 2 indicated that the CoN₄O₂ core has a distorted octahedral geometry. The photoactivity of these complexes was tuned by varying the π conjugation in the ligands. Curcumin complexes 3 and 4 had an intense absorption band near 435 nm, which made them useful as visible-light photodynamic therapy agents; they also showed fluorescence with λ_em≈565 nm. This fluorescence was useful for studying their intracellular uptake and localization in MCF-7 breast cancer cells. The acetylacetonate complexes ( 1 and 2 ) were used as control complexes to understand the role of curcumin. The white-light-triggered anticancer profiles of the cytosol targeting complexes 3 and 4 were investigated in detail. These non-dark toxic complexes displayed significant apoptotic photo-cytotoxicity (under visible light) against MCF-7 cells through ROS generation. The control complexes 1 and 2 did not induce significant cell death in the light or dark. Interestingly, 1-4 produced a remarkable antibacterial response upon light exposure. Overall, the reported results here can increase the boundary of the Co^II-based anticancer and antibacterial drug development.