The development of an integrated platform to identify breast cancer glycoproteome changes in human serum

Protein glycosylation represents one of the major post-translational modifications and can have significant effects on protein function. Moreover, changes in the carbohydrate structure are increasingly being recognized as an important modification associated with cancer etiology. In this report, we describe the development of a proteomics approach to identify breast cancer related changes in either concentration and/or the carbohydrate structures of glycoprotein(s) present in blood samples. Diseased and healthy serum samples were processed by an optimized sample preparation protocol using multiple lectin affinity chromatography (M-LAC) that partitions serum proteins based on glycan characteristics. Subsequently, three separate procedures, 1D SDS-PAGE, isoelectric focusing and an antibody microarray, were applied to identify potential candidate markers for future study. The combination of these three platforms is illustrated in this report with the analysis of control and cancer glycoproteomic fractions. Firstly, a molecular weight based separation of glycoproteins by 1D SDS-PAGE was performed, followed by protein, glycoprotein staining, lectin blotting and LC–MS analysis. To refine or confirm the list of interesting glycoproteins, isoelectric focusing (targeting sialic acid changes) and an antibody microarray (used to detect neutral glycan shifts) were selected as the orthogonal methods. As a result, several glycoproteins including alpha-1B-glycoprotein, complement C3, alpha-1-antitrypsin and transferrin were identified as potential candidates for further study.     

Development and validation of a highly sensitive LC‐MS/MS‐ESI method for the determination of bicalutamide in mouse plasma: application to a pharmacokinetic study

A highly sensitive, rapid assay method has been developed and validated for the estimation of bicalutamide in mouse plasma using liquid chromatography coupled to tandem mass spectrometry with electrospray ionization in the negative‐ion mode. The assay procedure involves extraction of bicalutamide and tolbutamide (internal standard, IS) from mouse plasma with a simple protein precipitation method. Chromatographic separation was achieved using an isocratic mobile phase (0.2% formic acid:acetonitrile, 35:65, v/v) at a flow rate of 0.5 mL/min on an Atlantis dC₁₈ column (maintained at 40 ± 1°C) with a total run time of 3.0 min. The MS/MS ion transitions monitored were m/z 428.9 → 254.7 for bicalutamide and m/z 269.0 → 169.6 for IS. Method validation was performed as per FDA guidelines and the results met the acceptance criteria. The lower limit of quantitation achieved was 1.04 ng/mL and the linearity range extended from 1.04 to 1877 ng/mL. The intra‐ and inter‐day precisions were in the ranges of 0.49–4.68 and 2.62–4.15, respectively. Copyright © 2012 John Wiley & Sons, Ltd.     

Some New Radical Reactions of Xanthates

Xanthates are convenient precursors of a variety of radicals that can be captured in an inter- or intramolecular fashion. Overall, the process involves rupture of the sulfide C-S bond and addition of the elements of the xanthate to the olefinic trap. The xanthate in the product can be used in another radical sequence or ionically modified in a great variety of ways. S-Propargyl xanthates exhibit a special but interesting behaviour which involves a sigmatropic rearrangement to the corresponding allene and ring closure to a novel betaine.     

Exact solution of a class of nonlinear knapsack problems

We consider a class of nonlinear knapsack problems with applications in service systems design and facility location problems with congestion. We provide two linearizations and their respective solution approaches. The first is solved directly using a commercial solver. The second is a piecewise linearization that is solved by a cutting plane method.     

Analysis of Ti:LiNbO3 zero-gap directional coupler for wavelength division multiplexer/demultiplexer

For the purpose of multichannel integrated-optical wavelength division MUX/DEMUX design, the wavelength tuning method of Ti:LiNbO₃ zero-gap directional coupler is analysed by effective-index based matrix method (EIMM). In this method, first, the 2D refractive index profile of the Ti:LiNbO₃ zero-gap directional coupler is transformed into lateral 1D effective-index profile by WKB method. Finally, matrix method is applied to this effective-index profile and the propagation constants are computed from the resonance peaks of the excitation efficiency versus propagation constant characteristics. It has been shown that the channel wavelength tuning can be achieved by varying the Y-branching angle at the input and output of the device or by a slight variation of two-mode-section length. The method of electro-optic fine tuning of the channel wavelength and channel separation of the device has also been investigated. A cascaded structure with proper parameters for four-channel application is also simulated and the results are presented.     

Simultaneous Spectrophotometric Determination of Imipramine Hydrochloride with Chlordiazepoxide and Nortriptyline Hydrochloride with Fluphenazine Hydrochloride

Spectrophotometry was used with multivariate calibration to simultaneously determine compounds in mixtures. Two antidepressant mixtures were investigated: imipramine hydrochloride and chlordiazepoxide and nortriptyline hydrochloride and fluphenazine hydrochloride. Considerable spectral overlap and large differences in component concentrations were challenges. Since this type of analysis is often performed using complex algorithms, a simple strategy was used here for the simultaneous determination of both mixture components by classical least squares, principal component regression, and partial least squares. Experimental design was used to select the optimum parameters including the wavelength range, sampling interval, software, and derivative order. Accuracy was enhanced by proper wavelength selection. In addition, derivatives of the raw spectra improved the selectivity. The standard deviation, deviation of mean recovery from 100%, and prediction ability of the models were used as the responses. In respect to these terms, first-order derivatization of the spectra and a sampling interval of 1?nm provided the best results. In particular, the low concentration compounds in the mixtures (chlordiazepoxide and fluphenazine) were determined more accurately with precision lower than 3%. The strategy was used for the quality control of pharmaceuticals containing the mixtures without chemical pretreatment.     

Lithium bromide catalyzed solvent free method for synthesis of 2-substituted benzimidazoles and imidazopyridines

<正>The first successful lithium bromide mediated solvent free condensation of arylenediamine and esters to obtain 2-substituted benzimidazole and imidazopyridine in good to excellent yields is described.     

Chemical and Photochemical Water Oxidation Catalyzed by Mononuclear Ruthenium Complexes with a Negatively Charged Tridentate Ligand

Two mononuclear ruthenium complexes [RuL(pic)₃] ( 1 ) and [RuL(bpy)(pic)] ( 2 ) (H₂L=2,6‐pyridinedicarboxylic acid, pic=4‐picoline, bpy=2,2′‐bipyridine) have been synthesized and fully characterized. Both complexes could promote water oxidation chemically and photochemically. Compared with other known ruthenium‐based water oxidation catalysts using [Ce(NH₄)₂(NO₃)₆] (Ce^IV) as the oxidant in solution at pH 1.0, complex 1 is one of the most active catalysts yet reported with an initial rate of 0.23 turnover s^?1. Under acidic conditions, the equatorial 4‐picoline in complex 1 dissociates first. In addition, ligand exchange in 1 occurs when the Ru^III state is reached. Based on the above observations and MS measurements of the intermediates during water oxidation by 1 using Ce^IV as oxidant, [RuL(pic)₂(H₂O)]⁺ is proposed as the real water oxidation catalyst.     

Chiral stationary phases for separation of intermedine and lycopsamine enantiomers from Symphytum uplandicum

Enantioseparation of the pyrrolizidine alkaloid isomers intermedine and lycopsamine, isolated from Symphytum uplandicum, is discussed. The separatory power of two immobilized carbohydrate‐based chiral HPLC columns, Chiralpak IA and IC, in different chromatographic conditions is compared. The study demonstrated the importance of solvent and column selection while developing such chiral HPLC separation methods. The baseline HPLC separation of the two alkaloid isomers in preparatory scale is reported for the first time. The optimized separations were achieved on a Chiralpak IA column with mobile phases of ACN/methanol (80:20) and methanol/methyl‐t‐butyl ether (90:10), both containing 0.1% diethylamine.     

Photocatalytic degradation of an azo reactive dye,Reactive Yellow 84, in water using an industrial titanium dioxide coated media

The photocatalytic degradation of an azo reactive dye, Reactive Yellow 84 (RY84), in aqueous solutions using industrial titanium dioxide coated non-woven paper was studied. The experiments were carried out to investigate the factors that influence the dye photocatalytic degradation, such as adsorption, initial concentration of dye, temperature, and solution pH. The experimental results show that adsorption is an important parameter controlling the apparent kinetics constant of degradation. The photocatalytic degradation rate was favored by a high concentration of solution in respect to Langmuir–Hinshelwood model. The degradation was enhanced by the temperature and was favored in acidic pH range.