高精度散射光度滴定法测定诺氟沙星的含量

用四苯硼钠标准溶液作滴定剂,采用高精度散射光度滴定法测定了诺氟沙星的含量,并将测定结果与非水滴定法、非水电位滴定法和高效液相色谱法的测定结果进行比较。结果表明：用本方法测定诺氟沙星的含量具有较高的准确度、精密度和良好的线性,且不受其降解产物的干扰。     

On-line identification of trans- and cis-resveratrol by nonaqueous capillary electrophoresis/fluorescence spectroscopy at 77 K

This work presents a novel method for the accurate determining trans- and cis-resveratrol (3,5,4'-trihydroxystilbene) by nonaqueous capillary electrophoresis/fluorescence spectroscopy at 77 K. The proposed method permits not only the separation of resveratrol isomers, but also ensures that on-line spectra are readily distinguishable and unambiguously assigned. The experimental results also indicate that the effect of nonaqueous capillary electrophoresis buffer and low-temperature technique increase the detection limit by more than 150-fold.     

Non-aqueous determination of inorganic salts

The procedures suggested for the determination of salts in nonaqueous solutions have been limited almost wholly to the analysis of amine salts and salts of the alkali and alkaline earth metals. Other salts are usually assayed by a variety of specific cationic or anionic procedures. By the proposed method, salts of all types can be determined titrimetrically so long as the compound will participate in an anion-exchange reaction. The procedure simply involves acidification of the salt with an excess of a strong acid, addition of a nonaqueous solvent and a differentiating potentiometric titration. Carbonate and hydroxide impurities do not interfere in the analysis and the solubility difficulties experienced in other nonaqueous procedures are not encountered in this method.     

拟静态沸点计法测定非水电解质溶液的渗透系数

本文将非分析循环沸点计［1，2］和拟静态方法[3]应用于非水电解质溶液体系的渗透系数的测定，建立了一套拟静态沸点计法测定非水电解质溶液渗透系数的实验装置．经NaCl、NaBr两个甲醇盐溶液体系的检验，相对标准误差小于1％，与传统的苦态法和等压法比较，拟静态沸点计法是一种快速、准确、方便的方法．用该装置分别测定了29巳15K时，＊d、Me。＊Q和BU4＊Br甲酸盐溶液渗透系数，实验值用Pitier方程关联，用关联得到的Pitier相互作用参数计算了盐的活度系数．1实验部分1．1实验原理在等温的条件下，电解质溶液处于汽液平衡时，如果测出…     

Thermodynamic characteristics,structure, and interactions of L-proline in aqueous solutions of alcohols and urea

The enthalpies of dissolution of imino acid L-proline in aqueous solutions of methanol, 2-propanol, ethylene glycol, glycerin, and urea are measured by the calorimetric method at 313.15 K. Enthalpic parameters of the interaction of L-proline with nonaqueous components are calculated and compared with the data at 298.15 K. It is found that the sign of the heat capacity parameter of the pair and ternary interactions depends on whether the nonaqueous solvent component is a destroyer or stabilizer of the water structure. Partial molar heat capacities of proline in mixed solvents are obtained by the integral dissolution heat method. Temperature changes in the reduced enthalpy and entropy of the proline solution are determined at an increase in the temperature from 298 K to 313 K. It is shown that there is entropyenthalpy compensation at temperature changes in the characteristics during dissolution.     

Simultaneous separation of organomercury species by nonaqueous capillary electrophoresis using methanol containing acetic acid and imidazole

A simple and rapid nonaqueous capillary electrophoresis method for simultaneous separation of four kinds of mercury species, namely inorganic mercury, methylmercury, ethylmercury, and phenylmercury, is reported. The effective mobilities of organomercury in aqueous and nonaqueous electrolytes were compared. Imidazole was confirmed not only as a co-ion for the separation but also as an online complexing reagent for mercury species. The optimum conditions for separation were achieved by using methanol solvent containing 0.15 M acetic acid and 15 mM imidazole as electrolyte. The sensitive detection of mercury species was accomplished at 191 nm.     

Silver (I)-Mediated Separations by Nonaqueous Capillary Electrophoresis: Nonaqueous Argentation Electrophoresis

This study represents the first application of Ag(I) charge transfer complexation in nonaqueous capillary electrophoresis. This method applies the principles of argentation chromatography to nonaqueous electrophoretic separations and is termed “nonaqueous argentation electrophoresis”. Since the separations are performed in 100% nonaqueous media, the advantages of nonaqueous solvents, such as enhanced solubility and flexibility in selectivity enhancement, compared to an aqueous or mixed hydroorganic solvent, are realized. A variety of compounds were separated. Qualitatively, the separation of eleven sulfonamides in 100% acetonitrile is shown to improve greatly upon the addition of Ag(I). These results also show that nonaqueous argentation electrophoresis provides fast, well-resolved separations of compounds, such as N-containing heterocyclics, that can selectively complex with Ag(I). Migration data and separation selectivities of these compounds by nonaqueous argentation electrophoresis were compared to previous aqueous argentation electrophoresis results. Selectivities were found to be significantly different for the two separation media. Ag(I) complexation provides an effective means of manipulating selectivity in nonaqueous capillary electrophoresis.     

Nonaqueous capillary electrophoresis of dextromethorphan and its metabolites

This study deals with the nonaqueous capillary electrophoretic separation of dextromethorphan and its metabolites using a methanolic background electrolyte. The optimization of separation conditions was performed in terms of the resolution of dextromethorphan and dextrorphan and the effect of separation temperature, voltage, and the characteristics of the background electrolyte were studied. Complete separation of all analytes was achieved in 40 mM ammonium acetate dissolved in methanol. Hydrodynamic injection was performed at 3 kPa for 4 s. The separation voltage was 20 kV accompanied by a low electric current. The ultraviolet detection was performed at 214 nm, the temperature of the capillary was 25°C. These conditions enabled the separation of four analytes plus the internal standard within 9 min. Further, the developed method was validated in terms of linearity, sensitivity, and repeatability. Rat liver perfusate samples were subjected to the nonaqueous capillary electrophoretic method to illustrate its applicability.     

Separation and determination of phospholipids in plant seeds by nonaqueous capillary electrophoresis

A method has been developed for the separation and determination of phospholipids by nonaqueous capillary electrophoresis in a separation medium of acetonitrile-2-proponol (3:2, v/v), 0.3% acetic acid and 60 mM ammonium acetate. To optimize the separation conditions, the composition of separation medium including alcohols, acetic acid, n-hexane and ammonium acetate was studied. The solvation interaction and ion-dipole interaction were also investigated. The contents of phospholipids in soybean, sunflower, peanut, apricot kernel, filbert and walnut were determined by the recommended method. The results obtained by the nonaqueous capillary electrophoreses were in good agreement with those determined by micellar electrokinetic chromatography.     

Calculations of the solubility of gases in mixed nonaqueous solvents within the framework of the theory of molecular association

A method for calculating the solubility of gases in mixed nonaqueous solvents was suggested. The method was based on the theory of molecular association and the simple lattice model. It allowed the solubility of gases in mixed nonaqueous solvents to be calculated only using molecular association parameters and the mutual exchange energy ω_AB determined from the data on phase equilibria in mixed solvents.     

Optimization and validation of a nonaqueous micellar electrokinetic chromatography method for determination of polycyclic musks in perfumes

A nonaqueous micellar electrokinetic chromatography method was developed for determination of Tonalide®, Galaxolide®, and Traseolide® polycyclic musks (PCMs). These compounds are widely used as fragrance ingredients in cosmetics. The method was optimized by using a three variable Box‐Behnken experimental design and response surface methodology. A modified chromatographic response function was defined in order to adequately weigh the terms in the response function. After optimization of experimental conditions, an electrolyte solution of 195 mM SDS and 40 mM NaH₂PO₄ in formamide was selected for the separation of the three PCMs, and the applied voltage was fixed at 30 kV. The nonaqueous MEKC method was then checked in terms of linearity, limits of detection and quantification, repeatability, intermediate precision and accuracy, providing appropriate values (i.e. RSD values for precision never exceeding 7%, and accuracy 96–107%). Nonaqueous MEKC for determination of the selected compounds was successfully applied to the analysis of commercial perfume samples.     

Determination of xanthohumol in hops (Humulus lupulus L.) by nonaqueous CE

Xanthohumol (XN) is a prenylated chalcone with antimutagenic and anticancer activity from hops. A nonaqueous reverse polarity capillary electrophoretic method for the determination of XN in hop extract was developed and validated. The optimal parameters were a 64.5 cm long fused-silica capillary with 50 microm id at 25 degrees C; 30 kV negative voltage (anode at detector side of the capillary); nonaqueous buffer with 75 mM NaOH and 50 mM boric acid in methanol; hydrodynamical injection with 10 mbar for 40 s; and detection at 440 nm. XN, isoxanthohumol (IX), colupulone, adlupulone, and n-lupulone were well resolved on the electropherogram. The LOD for XN was 0.05 mg/L and RSD for peak area was below 3%. The amount of XN in different samples of hop pellets varied from 0.14 to 0.42%.     

On-line stacking techniques for the nonaqueous capillary electrophoretic determination of acrylamide in processed food

In the present study, field amplified sample stacking (FASS) techniques in the nonaqueous capillary electrophoresis method (NACE) were introduced for the on-line concentration of the acrylamide to improve acrylamide detection at 210 nm by diode-array detection. Acetonitrile (ACN) as a nonaqueous solvent permits acrylamide to be protonated through the change of its acid-base chemistry, allowing capillary electrophoretic separation of this compound. Choosing 30 mmol L(-1) HClO(4), 20 mmol L(-1) NaClO(4), 218 mmol L(-1) CH(3)COOH in ACN as the separation electrolyte and employing sample stacking methods, the LOD value of acrylamide was decreased to 2.6 ng mL(-1) with electrokinetic injection and 4.4 ng mL(-1) with hydrodynamic injection. Optimized stacking conditions were applied to the determination of acrylamide in several foodstuffs. The method is simple, rapid, inexpensive, and widely applicable for the determination of acrylamide in food samples.     

Phase stabilization of ammonium nitrate by double addition of potassium nitrate and melamine

Methods for providing stabilization of ammonium nitrate and expanding the application field of this oxidizing agent in gas-generating compositions used for various purposes were sought for. The results of a study of the physicochemical properties of ammonium nitrate with a melamine–potassium nitrate double additive introduced by mechanical mixing and crystallization from an aqueous (nonaqueous) solution at the boiling point are presented. The phase diagrams of the ammonium nitrate–melamine and ammonium nitrate–melamine–potassium nitrate systems, based on the results of a differential-thermal analysis, demonstrated that a phase-stable ammonium nitrate can be formed by using the method of crystallization from an aqueous (nonaqueous) solution at the boiling point. The resulting samples were examined by IR spectroscopy and X-ray diffraction analysis, and a conclusion was made that a new thermodynamically stable phase can be formed in the system with individual additives, and the introduction of a double additive leads to a combined effect: a thermodynamically stable crystal structure is formed, with the simultaneous slowing down of the nucleation and growth of a new phase in the course of a phase transformation.     

Novel Synthesis of CeO2 Nanoparticles Within Formamide/Tri(ethyleneglycol)monododecyl Ether/n-Octane Nonaqueous Microemulsion Systems

The present study evaluates a new method to prepare Cerium oxide (CeO₂) nanoparticles by formamide/tri(ethyleneglycol)monododecyl ether (C₁₂E₃)/n-octane oil-continuous nonaqueous microemulsion. The effect of the polar phase (formamide/water) on the phase behavior, drop size, and conductivity behavior of the reverse microemulsion were investigated. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize the phase and morphology of synthesized CeO₂ nanoparticles. It was found that the CeO₂ powders synthesized within nonaqueous microemulsions and aqueous microemulisons had an average particle size of 30–50 nm and 15–40 nm, respectively. The experimental results indicate the formation mechanism of CeO₂ nanoparticles in formamide nonaqueous microemulsion and aqueous microemulsion is similar, and the formamide nonaqueous microemulsion can be used as nanoreactors for preparation of nanoparticles.     

The electrical conductivity and surface conduction of consolidated rock cores

A fully computerized high-pressure and high-temperature core holder device is simultaneously used to determine the electrical conductivity, zeta potential, and surface conductivity of consolidated rock cores in aqueous and nonaqueous systems. The total electrical conductivity of rock cores was determined by coupling streaming current and potential measurements. This shows that neglecting the surface conductivity Ksigma is crucial to converting the streaming potential into zeta potentials. It is observed that plots of the core total conductivity as a function of the electrolyte conductivity KL exhibit two behaviors. At low ionic strength, the core conductivity clearly depends on the contribution of surface conductivity behind the slip plane, whereas at higher ionic strength, the magnitude of the surface conductivity becomes negligible. The electrical conductivity of rock cores was found to be in good agreement with the O'Brien theory and the Briggs method. The contribution of the stagnant layer to the surface conductivity in nonaqueous systems has been shown to be significant. This shows that the stagnant layer displays significantly different behavior in different nonaqueous systems, depending on the core porosity and the double-layer overlap. The results indicate that the application of electrokinetics in petroleum reservoirs can provide important insights into reservoir fluid flow characterization.     

Nonaqueous capillary electrophoresis method for the analysis of gleevec and its main metabolite in human urine

The viability of nonaqueous capillary electrophoresis (NACE) was investigated for determination of gleevec and its main metabolite in human urine using a fused-silica capillary. Baseline separation of the studied solutes was obtained using a nonaqueous solution composed of 12 mM ammonium acetate and 87.6 mM acetic acid in methanol-acetonitrile (ACN) (80:20, v:v) providing analysis time shorter than 3 min. Different aspects including stability of the solutions, linearity, accuracy and precision were studied in order to validate the method in the urine matrix. Detection limits of 24 microg L(-1) for gleevec and its metabolite were obtained. A robustness test of the method was carried out using the Plackett-Burman fractional factorial model with a matrix of 15 experiments. The developed method is simple, rapid and sensitive and has been used to determine gleveec and its metabolite at clinically relevant levels in human urine. Before NACE determination, a solid-phase extraction (SPE) procedure with a C18 cartridge was necessary. Real determination of these analytes in two patient urines were done.     

Redox reactions in nonaqueous media determination of amines via dithiocarbamate formation and iodine monobromide titrations

A simple and accurate nonaqueous oxidimetric method of wide applicability has been developed for the determination of primary and secondary amines after their quantitative conversion with carbon disulphide in acetonitrile to the alkylammonium alkyldithiocarbamates, which are titrated with iodine monobromide solution also in acetonitrile at room temperature. The endpoint is detected visually by the yellow tint imparted to the solution by the first drop of oxidant solution in excess; and potentiometrically by using a bright platinum wire indicator electrode, and antimony or modified calomel reference electrode. The method is simple, rapid, accurate, and widely applicable.     

Nonaqueous capillary electrophoresis-mass spectrometry for separation of venlafaxine and its phase I metabolites

Aqueous and nonaqueous capillary electrophoresis (NACE) were investigated for separation of venlafaxine, a new second-generation antidepressant, and its three phase I metabolites. Working at basic pH, around the venlafaxine pKa value, was effective in resolving the investigated drugs, but created considerable peak tailing. To overcome electrostatic interactions between analytes and silanol groups, investigations were also carried out at acidic pH. However, despite the addition of up to 50% v/v of organic solvents (e.g., methanol or acetonitrile), complete separation of the studied compounds was not possible. NACE was found to be an appropriate alternative to resolve venlafaxine and its metabolites simultaneously. Using a conventional capillary (fused-silica, 64.5 cm length, 50 microm inner diameter), and a methanol-acetonitrile mixture (20/80 v/v) containing 25 mM ammonium formate and 1 M formic acid, complete resolution of these closely related compounds was performed in less than 3.5 min. Selectivity, efficiency and separation time were greatly affected by the organic solvent composition. As the electric current generated in nonaqueous medium was very low, the electric field was further increased by reducing the capillary length. This allowed a baseline resolution of venlafaxine and its three metabolities in 0.7 min. Selectivity was compared in aqueous and nonaqueous media in relation to the acid-base properties of the analytes as well as to the solvation degree. Finally, the method successfully coupled on-line to mass spectrometry with electrospray ionization interface allowed significant sensitivity enhancement.     

非水毛细管电泳测定黄连饮片中5种生物碱

建立了一种非水毛细管电泳(NACE)同时测定黄连饮片生品与炮制品中小檗碱、巴马汀、药根碱、木兰碱和黄连碱含量的方法。分别考察了非水溶剂、缓冲液体系及其浓度和pH、运行电压、运行温度和检测波长等条件对实验结果的影响。在优化的实验条件下,选择非水毛细管电泳分离模式,以40 mmol/L乙酸钠-40 mmol/L乙酸铵的无水甲醇缓冲溶液(pH 5.8)为电泳介质,未涂渍标准熔融石英毛细管(64.5 cm×75 μm,有效长度56 cm)为分离通道,检测波长为254 nm,分离电压为25 kV,压力进样(5 kPa×6 s),柱温为20 ℃。结果显示,5种生物碱在20 min内可实现基线分离,加标回收率为98.37%～101.03%。该方法简单、准确,重现性较好,可用于黄连饮片内在质量的评价和控制。