Analysis of protamine peptides in insulin pharmaceutical formulations by capillary electrophoresis

Protamines are a group of highly basic peptides that are sometimes added to insulin formulations to prolong the pharmacological action. In this study, different methods were investigated to identify protamine in insulin formulations. Capillary electrophoresis in aqueous and non‐aqueous media was tested to separate these peptides with very close amino acid sequences. Different buffers (phosphate or formate, both acidified) and various additives (principally negatively charged and neutral surfactants) were investigated to optimize peptide separation. Finally, a micellar electrokinetic capillary chromatography method using a capillary of 120 cm effective length and an aqueous background electrolyte made up of 100 mM phosphate buffer (pH 2) and 50 mM Thesit® gave the best results, providing the separation of the four major protamine peptides within 25 min.     

Transport theory of multiterminal hybrid structures

We derive a microscopic transport theory of multiterminal hybrid structures in which a superconductor is connected to several spin-polarized electrodes. We discuss the non-perturbative physics of extended contacts, and show that such contacts can be well represented by averaging out the phase of the electronic wave function. The intercontact Andreev reflection and elastic cotunneling conductances are identical if the phase can be averaged out, namely in the presence of at least one extended contact. The maximal conductance of a two-channel contact is proportional to (e ²/h)(a ₀/D)²exp[-D/ξ(ω^*)], where D is the distance between the contacts, a₀ the lattice spacing, ξ(ω) is the superconducting coherence length, and ω^* is the cross-over frequency between a perturbative regime ( ω < ω^*) and a non perturbative regime ( ω^* < ω < Δ). Received 18 June 2001 and Received in final form 17 January 2002     

Determination of diflubenzuron and chlorbenzuron in fruits by combining acetonitrile‐based extraction with dispersive liquid–liquid microextraction followed by high‐performance liquid chromatography

In this study, a simple and low‐organic‐solvent‐consuming method combining an acetonitrile‐partitioning extraction procedure followed by “quick, easy, cheap, effective, rugged and safe” cleanup with ionic‐liquid‐based dispersive liquid–liquid microextraction and high‐performance liquid chromatography with diode array detection was developed for the determination of diflubenzuron and chlorbenzuron in grapes and pears. Ionic‐liquid‐based dispersive liquid–liquid microextraction was performed using the ionic liquid 1‐hexyl‐3‐methylimidazolium hexafluorophosphate as the extractive solvent and acetonitrile extract as the dispersive solvent. The main factors influencing the efficiency of the dispersive liquid–liquid microextraction were evaluated, including the extractive solvent type and volume and the dispersive solvent volume. The validation parameters indicated the suitability of the method for routine analyses of benzoylurea insecticides in a large number of samples. The relative recoveries at three spiked levels ranged between 98.6 and 109.3% with relative standard deviations of less than 5.2%. The limit of detection was 0.005 mg/kg for the two insecticides. The proposed method was successfully used for the rapid determination of diflubenzuron and chlorbenzuron residues in real fruit samples.     

Simultaneous derivatization and air-assisted liquid–liquid microextraction of some aliphatic amines in different aqueous samples followed by gas chromatography-flame ionization detection

The paper presents a new method based on simultaneous derivatization and air-assisted liquid–liquid microextraction (AALLME) for the extraction and preconcentration of some aliphatic amines prior to gas chromatography-flame ionization detection (GC-FID). Primary aliphatic amines are derivatized and extracted simultaneously by a fast reaction with butylchloroformate (derivatization agent/extraction solvent) under mild conditions. The mixture of butylchloroformate and aqueous sample solution is rapidly sucked into a 10-mL glass syringe and then is injected into a test tube with conical bottom and the procedure is repeated seven times. After centrifuging the resulted cloudy solution, the derivatized analytes in the sedimented phase are determined by GC-FID. The influence of main factors on the efficiency of derivatization/extraction procedure is studied. Under the optimal conditions, the enrichment factors (EFs) for aliphatic amines are obtained in the range of 248–360 and limits of detection (LODs) are between 0.30 and 2.6 μg L⁻¹. The obtained extraction recoveries ranged from 50 to 72% and the relative standard deviation (RSD) was less than 4.8% for intra-day (n = 6) and inter-days (n = 4) precision. The method is successfully applied to determine some aliphatic amines in environmental water samples.     

Coherent resonant transport through a mesoscopic system with quantum ac microwave field

The time-dependent transport through an ultrasmall quantum dot coupling to two electron reservoirs is investigated. The quantum dot is perturbed by a quantum microwave field (QMF) through gate. The tunneling current formulae are obtained by taking expectation values over coherent state (CS), and SU(1,1) CS. We derive the transport formulae at low temperature by employing the nonequilibrium Green function technique. The currents exhibit coherent behaviors which are strongly associated with the applied QMF. The time-dependent currents appear compound effects of resonant tunneling and time-oscillating evolution. The time-averaged current and differential conductance are calculated, which manifest photon-assisted behaviors. Numerical calculations reveal the similar properties as those in classical microwave field (CMF) perturbed system for the situations concerning CS and squeezed vacuum SU(1,1) CS. But for other squeezed SU(1,1) CS, the tunneling behavior is quite different from the system perturbed by a single CMF through gate. Due to the quantum signal perturbation, the measurable quantities fluctuate fiercely. Received 28 May 1998     

Conjugate gradient method for dual-dual mixed formulations

We deal with the iterative solution of linear systems arising from so-called dual-dual mixed finite element formulations. The linear systems are of a two-fold saddle point structure; they are indefinite and ill-conditioned. We define a special inner product that makes matrices of the two-fold saddle point structure, after a specific transformation, symmetric and positive definite. Therefore, the conjugate gradient method with this special inner product can be used as iterative solver. For a model problem, we propose a preconditioner which leads to a bounded number of CG-iterations. Numerical experiments for our model problem confirming the theoretical results are also reported.

     

Determination of four sulfonylurea herbicides in tea by matrix solid‐phase dispersion cleanup followed by dispersive liquid–liquid microextraction

Matrix solid‐phase dispersion combined with dispersive liquid–liquid microextraction has been developed as a new sample pretreatment method for the determination of four sulfonylurea herbicides (chlorsulfuron, bensulfuron‐methyl, chlorimuron‐ethyl, and pyrazosulfuron) in tea by high‐performance liquid chromatography with diode array detection. The extraction and cleanup by matrix solid‐phase dispersion was carried out by using CN‐silica as dispersant and carbon nanotubes as cleanup sorbent eluted with acidified dichloromethane. The eluent of matrix solid‐phase dispersion was evaporated and redissolved in 0.5 mL methanol, and used as the dispersive solvent of the following dispersive liquid–liquid microextraction procedure for further purification and enrichment of the target analytes before high‐performance liquid chromatography analysis. Under the optimum conditions, the method yielded a linear calibration curve in the concentration range from 5.0 to 10 000 ng/g for target analytes with a correlation coefficients (r²) ranging from 0.9959 to 0.9998. The limits of detection for the analytes were in the range of 1.31–2.81 ng/g. Recoveries of the four sulfonylurea herbicides at two fortification levels were between 72.8 and 110.6% with relative standard deviations lower than 6.95%. The method was successfully applied to the analysis of four sulfonylurea herbicides in several tea samples.     

非饱和土壤水流问题基于POD 方法的降阶有限体积元格式及外推算法实现

利用特征投影分解(proper orthogonal decomposition, 简记为POD) 方法对非饱和土壤水流问题的经典有限体积元格式做降阶处理, 建立一种具有足够高精度维数较低的降阶有限体积元格式, 并给出这种降阶有限体积元解的误差估计和外推算法的实现, 最后用数值例子说明数值结果与理论结果是相吻合的. 进一步表明了基于POD 方法的降阶有限体积元格式对求解非饱和土壤水流问题数值解是可靠和有效的.     

Application of the fractional factorial design in multiple W/O/W emulsions

In presented research, multiple W/O/W emulsions were developed by using experimental design method. A 24-1 fractional factorial design was performed by varying the following input parameters: primary polymeric emulsifier (PEG 30-dipolyhydroxystearate) concentration (0.8% and 2.4%), secondary polymeric emulsifier (Poloxamer 407) concentration (0.8% and 1.2%), electrolyte magnesium sulfate heptahydrate (0.08% and 0.4%) and electrolyte sodium chloride (0.08% and 0.4%). Multiple emulsions were prepared by a two-step emulsification process. Obtained emulsions were characterized with rheological measurements, conductivity and centrifugation tests. Factorial analysis revealed that the concentration of the primary emulsifier was the predominant factor influencing the phase separation, conductivity and maximal apparent viscosity. Additionally, electrolyte magnesium sulfate heptahydrate was more efficient in stabilizing these systems, compared to sodium chloride. The applied fractional factorial design method enabled determination of the optimal concentrations of the primary and secondary emulsifier, as well as the concentration of electrolytes, in order to obtain W/O/W emulsions with desired maximal apparent viscosities, low values of conductivity and without phase separation after centrifugation.     

Polyol‐enhanced dispersive liquid–liquid microextraction coupled with gas chromatography and nitrogen phosphorous detection for the determination of organophosphorus pesticides from aqueous samples,fruit juices,and vegetables

Polyol‐enhanced dispersive liquid–liquid microextraction has been proposed for the extraction and preconcentration of some organophosphorus pesticides from different samples. In the present study, a high volume of an aqueous phase containing a polyol (sorbitol) is prepared and then a disperser solvent along with an extraction solvent is rapidly injected into it. Sorbitol showed the best results and it was more effective on the extraction recoveries of the analytes than inorganic salts such as sodium chloride, potassium chloride, and sodium sulfate. Under the optimum extraction conditions, the method showed low limits of detection and quantification within the ranges of 12–56 and 44–162 pg/mL, respectively. Enrichment factors and extraction recoveries were in the ranges of 2799–3033 and 84–92%, respectively. The method precision was evaluated at a concentration of 10 ng/mL of each analyte, and relative standard deviations were found to be less than 5.9% for intraday (n = 6) and less than 7.8% for interday (n = 4). Finally, some aqueous samples were successfully analyzed using the proposed method and four analytes (diazinon, dimethoate, chlorpyrifos, and phosalone) were determined, some of them at ng/mL level.