N-Hydroxy-N-m-tolyl-N′-(2-methyl-5-chloro)phenyl-p-toluamidine hydrochloride (HTMCPTH), a monobasic and bidentate chelating agent which reacts with vanadium(V) in carboxylic acid media to develop a blue-violet complex, has been employed as a highly selective reagent for extraction and direct photometric determination of the metal. Solvent extraction experiments indicate that from aqueous acetic acid (1.0–10.0 M), monochloroacetic acid (0.1–10.0 M), and phenylacetic acid (at pH 0.5–6.0) vanadium(V) is quantitatively extracted into chloroform. Almost all common ions including Fe3+, Cu2+, Ni2+, Co2+, Mn2+, Cr3+, Ti4+, Zr4+, and Mo6+ do not interfere with the proposed method. The procedure has been utilized for accurate determination of vanadium in standard steels. 相似文献
Solutions of CoII salts of organic acids in primary amines absorb molecular oxygen rapidly and irreversibly forming μ-dioxygen—cobalt complexes. Thermolysis leads to a homopolar cleavage of the OO bond with subsequent radical reactions involving ligand amine. After thermolysis the capacity of oxygen uptake is reestablished (catalysis). 相似文献
Reactions of sulphate radical anion (SO·4-) with 4,6-dihydroxy-2-methyl pyrimidine (DHMP), 2,4-dimethyl-6-hydroxy pyrimidine (DMHP), 6-methyl uracil (MU) and 5,6-dimethyl uracil (DMU) have been studied by pulse radiolysis at pH 3 and at pH 10. The transient intermediate spectra were compared with those from the reaction of hydroxyl radical (·OH). It is proposed that SO·4- produces radical cations of these pyrimidines in the initial stage. These radical cations are short-lived except in the case of DMHP where a relatively longer lived radical cation is proposed to be formed. When there is a hydrogen atom attached to the N(1) or N(3) position, a deprotonation from these sites is highly favored. When there is no hydrogen attached to these sites, deprotonation from a substituted methyl group is favored. At acidic pH, deprotonation from nitrogen is observed for DHMP, MU and DMU. At basic pH, the radical cation reacts with OH- leading to the formation of OH adducts. 相似文献
Production of the end products of polygalacturonic acid degradation on a large scale was done by reacting free galacturonic acid with Bacillus pumilus polygalacturonic acid transeliminase (PATE, EC 4.2.2.2) to obtain a mixture of the barium salts of several oligouronides. Small amounts of the unsaturated oligouronides were separated by paper chromatography. Large quantities of unsaturated oligouronides were separated on a AG-1-X8 (formate) column by applying a sample of mixed oligouronides and stepwise elution was carried out with sodium formate buffer (pH 4.7). The unsaturated oligouronides were identified on the basis of chromatographic mobilities, Sephadex gel filtration data, COOH/CHO ratio, thiobarbituric acid-reacting material, bromine uptake, and chemical and enzymatic degradation data as unsaturated tri-, tetra-, and hexagalacturonic acids. The chemical degradation of these unsaturated oligouronides, done with 6 N HCl by heating at 100 degrees for 30 min, gave qualitatively identical products of hydrolysis. These products compared with authentic standards, were identified as galacturonic acid, formic acid, 5-formyl-2-furancarboxylic acid, and 2-furancarboxylic acid. Analysis of the enzymatic breakdown products of the higher unsaturated uronides showed that a minimum of four galacturonic acid units was required for the action of purified endo-PATE from B. pumilus. The unsaturated trimer was not attacked, thus accounting for its accumulation as the major end product of polygalacturonate degradation by this enzyme. 相似文献
Thioacetals and thioketals of various aldehydes and ketones were obtained directly from carbonyl compounds or by a transthioacetalisation process from cyclic O,O-acetals in the presence of dithiols and a catalytic amount of tetrabutylammonium tribromide (TBATB). Chemoselective thioacetalisation of aromatic aldehydes containing an electron-donating group in the presence of an aldehyde containing an electron-withdrawing group, aldehydes in the presence of ketones, aliphatic cyclic ketones in the presence of aromatic ketones and less hindered ketones in the presence of more hindered ketones have been achieved. A cyclic acetal containing an electron-donating group has been chemoselectively transthioacetalised in the presence of an acetal having an electron-withdrawing substituent. These selectivities are due to the intrinsic reactivity of the substrate themselves and are independent of the catalyst and reaction conditions. Shorter reaction times, mild reaction conditions, stability of acid sensitive protecting groups, high efficiencies, facile isolation of the desired products and the catalytic nature of the reagent are the attractive features of the present method. 相似文献
A spectrophotometric method for determination of a microgram quantity of cerium with N-p-tolyl-p-chlorobenzohydroxamic acid is described. The orange-red-colored complex is extracted from chloroform at pH 9 which absorbs between 460 and 465 nm. Beer's law is obeyed at this wavelength. A clean-cut separation from many commonly occurring metal ions is easily accomplished. The system obeys Beer's law within the range of 0.5–28 ppm of cerium(IV). The molar absorptivity of cerium-N-p-tolyl-p-chlorobenzohydroxamic acid complex is 4.5 × 103 liters mol?1 cm?1. 相似文献
The kinetics of vesicle formation from a hydrotrope (sodium xylenesulfonate) solution of a surfactant (Laureth 4) is studied
by the use of a stopped-flow apparatus combined with a dynamic light scattering device to determine vesicle size in the system.
The hydrotrope system studied presents a system with a high surfactant solubilization combined with vesicle formation simply
by dilution with water. The kinetic results show a single exponential decay time. The kinetic analysis indicates that the
vesicles are formed from a molecular solution which resulted from the shear in the stopped-flow device and grow by monomeric
association.
Received: 1 October 1996 Accepted: 22 November 1996 相似文献
Abstract— Hydroxyl radicals ('OH) are scavenged by 1,4-diazabicyclo[2.2.2]octane (DABCO) at a diffusion-controlled rate of 1.25 ± 0.1 × 109 M -1s-1. Unlike other efficient 'OH scavengers which exhibit protection of bacteria against irradiation both in oxic and hypoxic conditions, DABCO has been shown to protect Serratia marcescens and various strains of Escherichia coli only in oxic conditions. DABCO appears to eliminate a component of the sensitization afforded by oxygen in all strains of E. coli tested. The level of this protection increases from ∼15% in the wild type AB 1157 to ∼100% in the recA uvrA mutant AB 2480. It is suggested that DABCO protects against lethal events that can occur on macromolecules other than DNA such as the cell membrane. Results with added glycerol, as well as work in D2O solution, indicate that DABCO is more likely to be acting by scavenging radicals rather than by quenching 1O2. If 1O2 is a component of the sensitization afforded by oxygen, then it is unlikely to be formed in a hydrophilic environment in the cell. 相似文献
The International and European standards for radiation sterilization require evidence of the effectiveness of a minimum sterilization dose of 25 kGy but do not provide detailed guidance on how this evidence can be generated. An approach, designated VDmax, has recently been described and computer evaluated to provide safe and unambiguous substantiation of a 25 kGy sterilization dose. The approach has been further developed into a practical method, which has been subjected to field evaluations at three manufacturing facilities which produce different types of medical devices. The three facilities each used a different overall evaluation strategy: Facility A used VDmax for quarterly dose audits; Facility B compared VDmax and Method 1 in side-by-side parallel experiments; and Facility C, a new facility at start-up, used VDmax for initial substantiation of 25 kGy and subsequent quarterly dose audits. A common element at all three facilities was the use of 10 product units for irradiation in the verification dose experiment.
The field evaluations of the VDmax method were successful at all three facilities; they included many different types of medical devices/product families with a wide range of average bioburden and sample item portion values used in the verification dose experiments. Overall, around 500 verification dose experiments were performed and no failures were observed. In the side-by-side parallel experiments, the outcomes of the VDmax experiments were consistent with the outcomes observed with Method 1.
The VDmax approach has been extended to sterilization doses >25 and <25 kGy; verification doses have been derived for sterilization doses of 15, 20, 30, and 35 kGy. Widespread application of the VDmax method for doses other than 25 kGy must await controlled field evaluations and the development of appropriate specifications/standards. 相似文献
In the present paper an isotropic sample of air-dried elastoidin has been studied considering it to be a non-ideal two-phase densely packed system after the theories by Vonk [1]. The relevant important physical parameters obtained for the sample areE, the width of the transition layer,D, the average periodicity transverse to the layers, S/V, the specific inner surface
1 and
2, the volume fraction of two phases, i. e. matter and void,l1 andl2 the transversal lengths,lr, the range of inhomogeneity,lc, the length of coherence and 2E/D, the volume fraction of the transition layer. The values ofE obtained by two approches as given by Vonk [1] and Ruland [2] show but a small difference indicating the correctness of the analysis. 相似文献