THE PHOTOTOXIC EFFECT OF BENOXAPROFEN AND ITS ANALOGS ON HUMAN ERYTHROCYTES AND RAT PERITONEAL MAST CELLS

Abstract— Benoxaprofen [2-(4-chlorophenyl)-α-methyl-5-benzoxazoleacetic acid] is a phototoxic non-steroidal anti-inflammatory agent. Irradiation of human erythrocytes in the presence of benoxaprofen (8 μ M ) and oxygen resulted in rapid cell lysis which began after 10 min and was complete within 30 min. While photohemolysis was also observed under anerobic conditions, its onset was delayed for more than 20 min and it took nearly 100 min for complete lysis to occur. Photohemolysis was also delayed by butylated hydroxyanisole but was unaffected by reduced glutathione. 1,4-diazabicyclo[2.2.2]octane, D₂O. β-carotene, or superoxide dismutase. The main photoproduct of benoxaprofen, 2-(4-chlorophenyl)-5-ethylbenzoxazole, was almost as effective in causing photohemolysis as benoxaprofen itself. In the presence of UV irradiation, benoxaprofen (10 (μ M ) caused the degranulation of rat peritoneal mast cells and the release of histamine. The release of mast cell histamine may provide a reasonable explanation for the urticarial response to benoxaprofen and irradiation seen in human subjects.     

N-N二甲基甲酰胺/纳米银修饰电极的制备与应用研究

用N-N二甲基甲酰胺和纳米银对导电玻璃(ITO)进行修饰得到了N-N二甲基甲酰胺/纳米银修饰电极。研究了电极的电化学行为,在pH=6.64的PBS缓冲溶液中,盐酸二甲双胍在0.075～0.2mg/mL浓度范围内与氧化峰电流呈现很好的线性关系,线性方程为y=317.19x+30.076,最低检出限为0.000 7mg/mL,线性相关线性系数R2为0.959 5。平行测量5组数据,其RSD值为0.75%,在盐酸二甲双胍缓释片溶液中5次加标回收率平均值为101%。精密度和准确度的分析结果表明方法可应用于药物中盐酸二甲双胍含量的测定。     

Photocytotoxic and anaerobic DNA cleavage activity of binuclear 3,3′-dithiodipropionic acid cobalt(II) complexes having phenanthroline bases

Dicobalt(II) complexes [{(B)Co^II}₂(μ-dtdp)₂] (1–3) of 3,3′-dithiodipropionic acid (dtdp) and phenanthroline bases (B), viz. 1,10-phenanthroline (phen in 1), dipyrido[3,2-d:2′,3′-f]quinoxaline (dpq in 2) and dipyrido[3,2-a:2′,3′-c]phenazine (dppz in 3), have been prepared, characterized and their photo-induced anaerobic DNA cleavage activity studied. The elemental analysis and mass spectral data suggest binuclear formulation of the complexes. The redox inactive complexes have magnetically non-interacting dicobalt(II) core showing magnetic moment of ∼3.9 μ_B per cobalt(II) center. The complexes show good binding propensity to calf thymus DNA giving K_b values within 4.3 × 10⁵–4.0 × 10⁶ M⁻¹. Thermal melting and viscosity data predict DNA groove binding and/or partial intercalative nature of the complexes. The complexes show significant anaerobic DNA cleavage activity in green light under argon atmosphere possibly involving radical species generated from the disulfide moiety in a type-I pathway. The DNA cleavage reaction under aerobic medium in green light is found to involve hydroxyl radical species. The dppz complex 3 exhibits significant photocytotoxicity in HeLa cervical cancer cells with an IC₅₀ value of 2.3 μM in UV-A light of 365 nm, while it is essentially non-toxic in dark giving an IC₅₀ value of >200 μM. A significant reduction of the dark toxicity of the organic dppz base (IC₅₀ = 8.3 μM in dark) is observed on binding to the cobalt(II) center while essentially retaining its photocytotoxicity in UV-A light (IC₅₀ = 0.4 μM).     

Deficiencies of the ferricinium-ferrocene redox couple for estimating transfer energies of single ions

The difference between the partial molal entropies of ferrocene and ferricinium has been determined in nine solvents from the temperature dependence of the formal potential of the ferricinium-ferrocene redox couple using a nonisothermal electrochemical cell arrangement in order to probe possible structural reasons for the limitations of the ferrocene assumption for estimating the transfer thermodynamics of single ions between different solvents. In contrast to the uniformly small positive values of predicted by the Born model, the experimental quantities varied widely from small or even negative values in hydrogen-bonded solvents (–5 to 3 e.u.) to substantially larger values (11–14 e.u.) in dipolar aprotic media. These variations appear to arise chiefly from additional solvent ordering in the vicinity of the ferricinium cation compared to the ferrocene molecule which is enhanced in the aprotic solvents. The variations in between water and a number of nonaqueous solvents provide a predominate contribution to the differences between the free energies of single ion transfer calculated using the ferrocene and alternative extrathermodynamic assumptions.     

Spectrophotometric study of acid-base equilibria of 4-(2-benzothiazolylazo)resorcinol and 4-(2-benzothiazolylazo)salicylic acid in water-organic solvent media

The visible absorption spectra of 4-(2-benzothiazolylazo)resorcinol (BTAR) and 4-(2-benzothiazolylazo)salicylic acid (BTAS) have been recorded in water-organic solvent mixtures in the pH range 0.5–12.0. The organic solvents used are methanol, ethanol,n-propanol, iso-propanol, acetone, dioxane and dimethyl formamide. The spectral changes have been explained in terms of shifts in equilibria among different molecular and ionic species of BTAR and BTAS existing in solution. The pK _a values corresponding to the different ionization steps have been determined at 25°C and I=0.1M (KNO₃) by graphic analysis of the absorbance-pH curves. The results obtained are discussed in terms of the molecular structure of the reagents and the nature of the organic co-solvent used.     

Solvation structure of magnesium,zinc, and alkaline earth metal ions in N,N‐dimethylformamide,N,N‐dimethylacetamide,and their mixtures studied by means of Raman spectroscopy and DFT calculations—Ionic size and electronic effects on steric congestion

The solvation structure of magnesium, zinc(II), and alkaline earth metal ions in N,N‐dimethylformamide (DMF) and N,N‐dimethylacetamide (DMA), and their mixtures has been studied by means of Raman spectroscopy and DFT calculations. The solvation number is revealed to be 6, 7, 8, and 8 for Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺, respectively, in both DMF and DMA. The δ (O C N) vibration of DMF shifts to a higher wavenumber upon binding to the metal ions and the shift Δν(= ν_bound − ν_free) becomes larger, when the ionic radius of the metal ion becomes smaller. The ν (N CH₃) vibration of DMA also shifts to a higher wavenumber upon binding to the metal ions. However, the shift Δν saturates for small ions, as well as the transition‐metal (II) ions, implying that steric congestion among solvent molecules takes place in the coordination sphere. It is also indicated that, despite the magnesium ion having practically the same ionic radius as the zinc(II) ion of six‐coordination, their solvation numbers in DMA are significantly different. DFT calculations for these metalsolvate clusters of varying solvation numbers revealed that not only solvent–solvent interaction through space but also the bonding nature of the metal ion plays an essential role in the steric congestion. The individual solvation number and the Raman shift Δν in DMF–DMA mixtures indicate that steric congestion is significant for the magnesium ion, but not appreciable for calcium, strontium, and barium ions, despite the solvation number of these metal ions being large. Copyright © 2006 John Wiley & Sons, Ltd.     

Morphological evolution of selenium micro‐crystals

A simple solution phase approach using dimethyl formamide (DMF) as solvent is utilized to obtain selenium (Se) microcrystals. Different morphological modifications of the products result from varied reaction environments. Solvothermal treatment of Se with DMF in an autoclave at 170°C yields rod‐like, and feather‐shaped microcrystalline structures while reduction of selenium dioxaide (SeO₂) by DMF generates microspheres at 30°C and 80°C, rods admixed with spherical particles at 120°C and predominantly micro rods at 150°C. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Reference Electrodes in Dimethylformamide

Abstract

An investigation of an Ag/Ag⁺ reference electrode in dimethylformamide solution is reported. Simple preparation, fast response and high exchange current density characterize this reference electrode. The stability of the electrode with time and its temperature coefficient were also studied.     

多金属氧化物立方纳米晶体的可控合成及其与朊蛋白的特异性相互作用

研究表明,在有机小分子二甲基甲酰胺（DMF）的调控作用下Keggin型多金属氧化物在水溶液中形成规则的纳米立方体,随温度改变该纳米立方体转变为空心立方结构．该多金属氧化物纳米立方体可以与朊蛋白（PrP^c）相互作用,产生显著的光散射信号增强,且增强程度在3．36-840ng·mL^-1范围内与朊蛋白浓度呈线性关系．     

Formylation of Secondary Amines with Dimethylformamide Dimethylacetal

Abstract

Secondary amines are formylated by dimethylformamide dimethylacetal, contradicting recent reports on the ethylation of secondary amines by this reagent. This explains why a single derivative is obtained regardless of the alkyl acetal that is used. These formyl derivatives, also formed by reaction with formic acid, are eluted later than the starting material or the corresponding ethyl derivative. Deuterated imipramine and related antidepressants can be prepared by reducing the formyl derivative of the appropriate desalkyl compound with lithium aluminum deuteride.