Parabens determination with a hybrid FIA/HPLC system with ultra-short monolithic column

The combination of an ultra-short C18 monolithic column (5 mm long) with a flow injection analysis (FIA) scheme results in a versatile and efficient system that has been used for the chromatographic determination of four preservatives — methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben (BP). The separation is carried out by using two carriers, A and B, consisting of a mixture of ACN: water in different proportions. The described procedure is able to separate the analytes in only 150 s. The applicable concentration range, detection limit and the relative standard deviation were the following: for MP from 1.6 × 10^-5 to 1.1 × 10^-3 M; 4.8 × 10^-4 M; 0.65%; for EP between 3.7 × 10^-5 and 2.0 × 10^-3 M; 1.2 × 10^-5 M; 1.2%; for PP between 3.9 × 10^-5 and 2.0 × 10^-3 M; 1.2 × 10^-5 M; 1.2%; and for BT between 6.0 × 10^-5 and 2.0 × 10^-3 M; 1.8 × 10^-5 M; 1.8%. The method was applied and validated satisfactorily for the determination of these parabens in commercial cosmetics samples, comparing the results with those obtained by HPLC reference method.     

Polymer fractionation using chromatographic column packed with novel regenerated cellulose beads modified with silane

Novel microporous beads with the particle size of about 90 microm were prepared, for the first time, from cellulose and konjac glucomannan (RC/KGM3) in 1.5 M NaOH/0.65 M thiourea aqueous solution by emulsification method. The microporous beads were then modified with silane to avoid the adsorption of polymers containing hydroxyl groups, coded as RC/KGM3-Si. A preparative size-exclusion chromatographic (SEC) column (500 mm x 20 mm) was packed with RC/KGM3-Si, and its exclusion limit and fractionation range of the stationary phase were, respectively, weight-average molecular masses (Mw) of 4.8 x 10(5) g/mol and 5.3 x 10(3)-4.8 x 10(5) g/mol for polystyrene in tetrahydrofuran. The preparative SEC column was used to fractionate poly(epsilon-caprolactone) (PCL, Mw = 8.31 x 10(4) g/mol polydispersity index d= 1.55) in tetrahydrofuran and a polysaccharide PC3-2 (Mw = 1.21 x 10(5) g/mol, d= 1.70) in 0.05 M NaOH aqueous solution, respectively. The Mw values of the fractions determined by analytical SEC combined with laser light scattering were from 1.2 x 10(4) to 1.84 x 10(5) for PCL and from 8.5 x 10(4) to 2.13 x 10(5) for PC3-2, as well as d from 1.2 to 1.5. The results indicated that the preparative SEC has good fractionation efficiency in both organic solvent and alkaline aqueous solution for the various polymers.     

The determination of hydrazobenzene by the die method with hydrogen peroxide catalyzed with vanadium

Hydrazobenzene cannot be oxidized to azobenzene with hydrogen peroxide in ethanol-containing medium. Vanadium(V) ions catalyze the oxidation; in their presence the reaction takes place rapidly. A thermometric (DIE) method was developed for the determination of hydrazobenzene, based on the oxidation reaction with hydrogen peroxide catalyzed by vanadium(V). The reaction is initiated by the addition of the solution of the catalyst, which is applied in small amount (100l). Thus, the application of the immersion pipette is not necessary. The standard deviation of the determination is ±0.42 mg hydrazobenzene in 50 ml ethanol.

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Zusammenfassung Hydrazobenzol kann in Äthanolhaltigem Medium mit Wasserstoffperoxid nicht zu Azobenzol oxidiert werden. Vanadium(V)-ionen katalysierten die Oxidation, in ihrer Gegenwart vollzieht sich die Reaktion rasch. Der Autor entwickelt eine thermometrische (DIE) Methode zur Bestimmung von Hydrazobenzol, die auf der durch Vanadium(V)-katalysierten Oxidationsreaktion mit Wasserstoffperoxid beruht. Die Reaktion wird durch Zugabe der in kleinen Mengen (1001) angewandten Katalysatorlösung ausgelöst. Dadurch erübrigt sich der Einsatz von Immersionspipetten. Die Standardabweichung betrÄgt ± 0.42 mg Hydrazobenzol in 50 ml Äthanol.

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Résumé L'hydrazobenzène ne peut pas Être oxydé par l'eau oxygénée dans un milieu contenant de l'éthanol. Les ions vanadium(V) catalysent l'oxydation et la réaction a Heu à grande vitesse en leur présence. Les auteurs ont développé une méthode thermométrique (DIE) afin d'effectuer le dosage de l'hydrazobenzène. Cette méthode repose sur la réaction d'oxydation par l'eau oxygénée en présence de vanadium(V) comme catalyseur. La réaction est initiée par addition de la solution du catalyseur utilisée en faible quantité (100l). Ainsi, l'emploi d'une pipette d'immersion n'est pas nécessaire. L'écart-type du dosage est ±0.42 mg d'hydrazobenzène dans 50 ml d'éthanol.

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. (V) . () , , (V). (100l) . . ±0.42 50 .

     

Reaction of CCl4 with o- and m-carboranylmagnesium iodides,and with phenyl- and methylmagnesium iodides

Conclusions Together with RCl, substantial amounts of RI are formed when RMgI (o- and m-carboranylmagnesium iodides, C₆H₅MgI and CH₃MgI) is reacted with CCl₄. A mixture of o-, m-RCB₁₀H₁₀CCl and o-, m-RCB₁₀·H₁₀CBr is formed when o- and m-RCB₁₀H₁₀CMgBr is reacted with CCl₄.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2312–2314, October, 1971.     

Reactions of benzofurazan oxide with amines—I : Reduction with diethylamine

The reactions of benzofurazan oxide with diethylamine gave a complex mixture from which quinoxaline-1,4-dioxide (10–15%), o-benzoquinone dioxime (5%), benzofurazan (5–10%), 1-hydroxy-2-methyl-benzimidazole-3-oxide (3%), o-nitrosoaniline (5%), o-nitroaniline (<3%), 3-methylbenzotriazine (5%), 3-methyl-benzotriazine-4-oxide (10%), and o-nitrophenyl-N,N-diethyl hydrazine (10%) were isolated.The formation of these products seems to have a common pathway that involves the reduction of benzofurazan oxide and the oxidation of diethylamine.     

四种阴离子的毛细管电泳电导检测(英文)

 采用柠檬酸 柠檬酸钠作为缓冲体系 ,使用负高压 ,对Cl-,NO3 -,HCO3 -和H2 PO4 -等 4种常见阴离子进行了分离检测 ,研究了缓冲剂的种类、浓度、pH值及操作电压对分离的影响。在选定的条件下 ,4种离子的定量线性范围 :Cl-5 0× 10 -5mol/L～ 2 5× 10 -3 mol/L ,NO3 -6 0× 10 -5mol/L～ 2 0× 10 -3 mol/L ,HCO3 -5 0× 10 -6mol/L～ 2 0× 10 -4 mol/L ,H2 PO4 -6 0× 10 -5mol/L～ 1 0× 10 -3 mol/L ;检出限 :Cl-1 5× 10 -5mol/L ,NO3 -3 0×10 -5mol/L ,HCO3 -1 0× 10 -6mol/L ,H2 PO4 -2 0× 10 -5mol/L ;峰面积的RSD (n =6 ) :Cl-3 1% ,     

Interactions of beta-lactoglobulin with sodium decylsulfonate, decyltriethylammonium bromide, and their mixtures

The interactions of beta-lactoglobulin (BLG) with anionic surfactant sodium decylsulfonate (C10SO3), cationic surfactant decyltriethylammonium bromide (C10NE), and the mixtures of cationic-anionic surfactants (C10NE-C10SO3) were investigated by circular dichroism (CD) and fluorescence methods. At pH 7.0, C10NE and the C10NE-rich surfactant mixtures of C10NE-C10SO3 could form precipitates with BLG, while C10SO3, equimolar mixtures of C10NE-C10SO3, or C10SO3-rich mixtures of C10NE-C10SO3 form homogeneous solutions with BLG. CD observed that both C10NE and C10SO3 could change the BLG structure. The effects of the mixtures of C10NE-C10SO3 on BLG structure depended on the ratio of C10NE to C10SO3. The C10NE-rich or the C10SO3-rich mixtures of C10NE-C10SO3 could significantly affect BLG structure, while the equimolar mixtures of C10NE-C10SO3 exhibited weaker interaction with BLG. Fluorescence measurements showed that both C10NE and C10SO3 could induce the enhancement of fluorescence of BLG, and C10NE enhanced the BLG fluorescence more than C10SO3 did. The effect of the mixtures of C10NE-C10SO3 on the fluorescence of BLG became stronger with the increase of the molar fraction of C10NE in C10NE-C10SO3 mixtures.     

Bisquaternary-drug membrane electrodes with high sensitivity

The construction and performance characteristics of ion-selective plastic membrane electrodes for succinylcholine, hexamethonium and decamethonium are described. The electrodes, based on ion-pair complexes with triphenylstillbenyl borate (TPSB), show near-Nernatian responses over the range 10^?2–10^?6 M or less, with very low limits of detection at around 10^?7 M. The responses are not affected by pH in the range 2–10. The selectivity relative to some inorganic ions, amino acids, neurotransmitters, drugs and various drug excipients is reported.     

Diclofenac derivatives with insulin-sensitizing activity

A series of diclofenac derivatives were synthesized.The insulin-sensitizing activity of 28 new compounds was evaluated in 3T3- L1 cells.The compounds 10a and 10f exhibited similar insulin-sensitizing activity with positive drug rosiglitazone.     

新型安培检测毛细管电泳微系统

将电极、６ｃｍ分离毛细管、缓冲池、检测池集成于８．４×５．０ｃｍ有机玻璃片上,制作了一个毛细管电泳微系统。以碳纤维微盘电极作为工作电极,采用三电极体系柱端检测了１×１０－４ｍｏｌ／Ｌ多巴胺（ＤＡ）,具有良好的重现性,检测限３．６×１０－８ ｍｏｌ／Ｌ,线性范围５×１０－７～１×１０－４ｍｏｌ／Ｌ,并在该系统上分离了邻苯二酚（ＣＡ）和多巴胺的混合物。     

Synthesis of vinyl polymers with pendant phenoxazinyl group

Vinyl monomers bearing phenoxazine units, were synthesized: 2-vinyl-phenoxazine starting with phenoxazine in a five-step synthesis; 3-acrylamido- or 3-methacrylamido-phenoxazines with or without 10-PhCH₂ or 10-Me-substituent starting with o-benzylideneaminophenol or o-anisidine via 3-aminophenoxazines; and 3-(p-styrenesulfonamido)phenoxazines with or without 10-PhCH₂- or 10-Me-substituent, also via 3-aminophenoxazines. Polymerizations of these noval monomers proceeded smoothly, except those having no 10-substituent. Changes of the visible absorption spectrum of iodine in THF with addition of the polymers and oligomers thus prepared were considerable, with the appearance of new absorption peaks for polymers with 10-Me-substituent.     

Antioxidants determination with laccase

The spectrophotometric method of antioxidants determination using recombinant laccase Polyporus pinsitus (rPpL) and Myceliophthora thermophila (rMtL) was developed. The method includes simultaneous oxidation of the antioxidant and high reactive laccase substrate producing chromophoric radical cation. As laccase substrates ABTS and other high reactive phenoxazine derivatives: 2-phenoxazin-10-yl-ethanol (PET), 3-phenoxazin-10-yl-propane-1-sulfonic acid (PPSA) and 3-phenoxazin-10-yl-propionic acid (PPA) were used. The kinetic data were analysed using a scheme of simultaneous oxidation of the antioxidant and the substrate.In a range of (0.9-7.3) × 10⁻⁶ M of Trolox the measurings recovered 91 and 99% of the antioxidant if ABTS and both laccases were used. The recovery varied between 82 and 124% if phenoxazine derivatives were used. The antioxidant activity determined in rich with antioxidants food samples, i.e. date-palm, black raisin, golden raisin, skin of red grape, dice of red grape, fitted the literature data.     

Unlabeled Fluoroimmunoassay with a Europium Chelate

Unlabeled fluoroimmunoassay with a europium chelate is described. The recommended method is simple because the complicated labeling process is omitted. The recovery of some samples ranges from 91 to 111%. The relative standard deviation of the method is less than 10%. The detection limit is about 10⁻¹⁰mol liter⁻¹antigen.     

Nafion修饰电极测定5-羟色胺

５－羟色胺（５－ＨＴ）属于吲哚胺类神经递质［１］,当人在病理状态时５－ＨＴ的量将会发生显著变化,如精神分裂症［２］病人血液中的５－ＨＴ比正常人少,因此,５－ＨＴ的测定对于某些疾病的诊断及病理学的研究具有重要意义．５－ＨＴ的测定方法主要为ＨＰＬＣ法．Ｈ...     

Condensation of N-ethylpiperid-4-one with benzaldehyde

Reaction of N-ethylpiperid-4-one with benzaldehyde and KOH in 65% aqueous methanol gives 2,7-diethyl-10a-hydroxy-9-phenyl-4-(phenylmethylene)-2,7-diaza-10-oxa-1,2,3,4,5,6,7,8,8a, 10a-decahydroanthracene. In the presence of HCl/EtOH, 3,5-bis(phenylmethylene)-1-ethylpiperid-4-one is formed. In the presence of HCl/AcOH, 2,7-diethyl-9-phenyl-4,5-bis(phenylmethylene)-2,7-diaza-10-oxa-1,2,3,4,5,6,7,8-octahydroanthracene is formed.Center for the Chemistry of Medicinal Agents, All-Russian Chemicopharmaceutical Institute, Moscow 119815. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1247–1249, September, 1998.     

Determination of copper with neocuproine by thermal-lens spectrometry

Conditions for the spectrophotometric determination of copper with 2,9-dimethyl-l,10-phenan-throline (neocuproine) in the presence of ascorbic acid in a water-ethanol solution (9 : 1) at pH 4.5–5.0 have been found. The detection limit is 3 x 10^-6 M. The concentration range is from 4.4 x 10^-6 to 3 x 10^-4 M. Conditions for the determination of copper(I) with neocuproine by thermal lens spectrometry have been proposed. The detection limit is 4 x 10^-7 M. The concentration range is from 7 x 10^-7 to 6 x 10^-5 M. Iron(II) at concentrations as high asn x 10^-4 M does not interfere with the determination of copper. Changes in the conditions for the photometric reaction associated with passing from spectrophotometric measurements to thermal lensing are discussed.     

Halfsandwich Transition Metal Complexes with 1,2-dichalcogenolate Carboranes

Mononuclear halfsandwich transition metal complexes (Cp*M) are useful model compounds in which one hemisphere of the coordination shell is blocked by the voluminous Cp* ring. In the protected space below the Cp* ligand, one or two 1,2-dicarba-closo-dodecarborane-1,2-dichalcogenolate ligands can be accommodated, e.q. a mono-dichalcogenolate carborane halfsandwich iridium complexes Cp*Ir(E₂C₂B₁₀H₁₀)(E=S, Se)[l] and bis-dichalcogenolate carborane rhenium or tungsten complexes Cp*Re(E₂C₂B₁₀H₁₀)₂(E=S, Se,Te),[Li(THF)₄] [Cp*W(E₂C₂B₁₀H₁₀)₂] (E=S, Se).     

甲酸根掺杂立方体溴碘化银微晶乳剂的增感效应研究

使用反馈式微机控制双注仪,在晶体生长不同时期,依次加入不同量碘盐和一定量甲酸盐,制得了两个系列的溴碘化银乳剂:一系列为碘含量分别为乳剂颗粒总银量的0、2×10^-2、3×10^-2、4×10^-2和5×10^-2I^-mol/Ag mol的溴碘化银颗粒乳剂;另一系列为碘含量与上述系列乳剂相同,并掺杂有1×10^-4mol/Ag mol甲酸根的溴碘化银颗粒乳剂.对其感光性能的测试结果表明,经过化学敏化和光谱增感后,甲酸根掺杂的溴碘化银乳剂较未掺杂甲酸根的乳剂,感光度显著提高,在一定量的I^-掺杂范围内(0-4×10^-2I^-mol/Ag mol),灰雾没有明显增加.     

Compatibilization of polyethylene/polyamide 6 blends with functionalized polyethylenes prepared with metallocene catalyst

Metallocene catalyst technology was utilized to prepare functionalized polyethylenes, which were used as compatibilizers in polyethylene/polyamide 6 (40/60) blends. Polymerization of ethylene with 10-undecen-1-ol, 10-undecenoic acid, or N-methyl-10-undecenylamine resulted in ethylene copolymers with a small amount (0.2–1.2 mol %) of functionalized side chains. The blends were prepared in a twin-screw midiextruder, and injection molded with a mini-injection molding machine. The effect of the new compatibilizers on morphology and mechanical and thermal properties was studied. Toughness as well as stiffness and strength increased significantly with an addition of 10 wt % compatibilizer. Morphology became much more uniform, and crystallization and melting behavior changed. The Molau test with FTIR analysis was used to determine that the desired reactions between the compatibilizer and polyamide had actually taken place. The results showed functionalized polyethylenes prepared with metallocene catalysts to act as effective compatibilizers in polyethylene/polyamide 6 blends. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3099–3108, 1999     

流动注射-化学发光法测定富马酸依美斯汀

在酸性条件下,KMnO4与甲醛能够产生微弱的化学发光,而富马酸依美斯汀的存在能够大大增强该化学发光强度;结合流动注射技术,建立了测定富马酸依美斯汀的流动注射-化学发光新方法。该方法的线性范围分别为3.0×10-8～2.0×10-7g/mL,2.0×10-7～1.0×10-6g/mL和1.0×10-6～8.0×10-6g/mL。检出限为1.0×10-8g/mL,对2.0×10-6g/mL富马酸依美斯汀滴眼液平行测定11次,其相对标准偏差为1.3%。该方法已成功应用于滴眼液中富马酸依美斯汀的含量测定。