Specific determination of cysteine and penicillamine through cyclization to 2-thioxothiazolidine-4-carboxylic acids

A very simple and highly specific method for the determination of cysteine and penicillamine is presented. Treatment with 1,1'-thiocarbonyldiimidazole in slightly basic solutions converts cysteine rapidly and quantitatively to a very stable derivative, 2-thioxothiazolidine-4-carboxylic acid, which is not formed by thiols or amines. The cyclic derivative has a characteristic UV spectrum with a maximum at 272 nm and it can be quantified by one of two ways. (1) When only inorganic ions and common additives are present, a spectrophotometer or a plate reader capable of handling multiple samples is sufficient to estimate cysteine in the concentration range of 2-150 muM. Penicillamine is determined similarly by cyclization to 5,5-dimethyl-2-thioxothiazolidine-4-carboxylic acid. The method is also applicable to derivatives of cysteine modified only at the carboxyl group. (2) To determine cysteine in complex mixtures, a liquid chromatograph connected to a UV detector is used. The elution is rapid with well-separated peaks for the thiazolidine derivatives. The detection limit is 2 pmole of cysteine or penicillamine per injection and the detector response is linear up to 1 nmole. The usefulness of the method is demonstrated by determining cysteine and penicillamine in capsules and by measuring cysteine in a dietary supplement.     

Surface modified ormosil nanoparticles

Organically modified silanes (ORMOSIL) such as vinyl triethoxysilane readily aggregate in the aqueous cores of reverse micelles where the triethoxysilane moieties are hydrolyzed to form a hydrated silica network and the vinyl groups protruded out from the surface of the nanoparticles toward the hydrophobic side of the micellar interface. These particles are spherical and the size distribution of the particles is relatively narrow, with an average diameter of 87 nm. Surface vinyl silica nanoparticles so formed have been oxidized to surface carboxylic silica nanoparticles, followed by chemical conjugation with polyethyleneglycol amine (PEG amine) through the ethyl-3-(3-dimethylaminopropyl) (EDCI) carbodiimide reaction. The characteristic surface groups have been identified by Fourier transform infrared spectroscopy, while the size and the morphology of the particles have been studied by dynamic light scattering and transmission electron microscopy. It has been found that about 80-85% of the carboxylic groups are PEGylated during the EDCI reaction.     

Solvent control of product diversity in palladium-catalyzed addition of arylboronic acid to aryl aldehydes

In Pd-catalyzed arylboronic acid addition to aryl aldehydes, the expected carbinol or asymmetrical ether can be obtained as the major product by altering aqueous solvent composition. Exploiting this methodology with 2-formylbiphenyls as reaction partner, a fluorene scaffold can be readily constructed in two steps.     

Synthesis of Peptide Cysteine Dimedone Using Fmoc-Cys(Dmd)-OH: Glutathione Cysteine Dimedone as a Probe in Investigating the Sulfenic Acid Mediated Oxidation of Glutathione

Dimedone is the most widely used chemical probe for detection of cysteine sulfenic acid in peptides and proteins. The reaction of dimedone with cysteine sulfenic acid results in the formation of unique cysteine dimedone motif containing thioether bridge. Based on the structure of cysteine dimedone residue in polypeptide, a new building block of Fmoc-Cys(Dmd)-OH was developed for solid phase synthesis of peptide cysteine dimedone. Mass spectrometric sequencing of synthetic peptides have confirmed successful incorporation of cysteine dimedone in peptide chain using HBTU/HOBt as a coupling agent. The new method permits synthesis of peptides containing both cysteine thiol and cysteine dimedone in the same sequence which was difficult to achieve by conventional methods. The synthetic peptide of glutathione cysteine dimedone was used as a standard in probing the air-mediated oxidation of thiol to disulfide form of glutathione. The co-elution of standard peptide and reaction mixture of oxidation of glutathione in presence of dimedone using RP-HPLC have confirmed the formation of glutathione cysteine sulfenic as an intermediate in the air-mediated oxidation of glutathione. The synthetic peptides of cysteine dimedone may find application in the field of redox proteomics and generation of antibodies against modified cysteine residue.     

A soft-segmentation visualization scheme for magnetic resonance images

Prevalent visualization tools exploit gray value distribution in images through modified histogram equalization and matching technique, referred to as the window width/window level-based method, to improve visibility and enhance diagnostic value. The window width/window level tool is extensively used in magnetic resonance (MR) images to highlight tissue boundaries during image interpretation. However, the identification of different regions and distinct boundaries between them based on gray-level distribution and displayed intensity levels is extremely difficult because of the large dynamic range of tissue intensities inherent in MR images. We propose a soft-segmentation visualization scheme to generate pixel partitions from the histogram of MR image data using a connectionist approach and then generate selective visual depictions of pixel partitions using pseudo color based on an appropriate fuzzy membership function. By applying the display scheme in clinical examples in this study, we could demonstrate additional overlapping regions between distinct tissue types in healthy and diseased areas (in the brain) that could help improve the tissue characterization ability of MR images.     

A specific HPLC-UV method for the determination of cysteine and related aminothiols in biological samples

We present a highly selective and sensitive method for the determination of cysteine (Cys) and related aminothiols that play important roles in health and disease. The key step in the analysis is treatment with 1,1′-thiocarbonyldiimidazole (TCDI) that rapidly and quantitatively reacts with both the amino and thiol groups to form stable cyclic dithiocarbamates with intense UV absorption. Cys, homocysteine (hCys), and cysteinylglycine in plasma (75 μl), urine (100 μl), or cerebrospinal fluid (100–500 μl) were determined by separating and measuring their cyclic derivatives by a high performance liquid chromatograph (HPLC) connected to a UV detector. The chromatograms obtained using TCDI contained fewer and better-resolved peaks than those produced by less selective reagents used previously. Using chemically similar 2-methylcysteine as the internal standard, high repeatability (variation of less than 5%) and adequate sensitivity to detect small increments (10–20%) in the concentrations of cysteinylglycine and hCys were achieved. The HPLC method can also be modified to measure -penicillamine (greater than 0.8 μM) in plasma (50 μl) providing a potential method to monitor plasma levels of this drug in patients.     

Separation of 2-butanol–water mixtures by pervaporation through PVA–NYL 66 blend membranes

Blend membranes of poly(vinyl alcohol) (PVA) and nylon 66 (NYL) were synthesized and crosslinked with glutaraldehyde (GA) and assessed for their suitability in dehydrating 2-butanol by pervaporation (PV). These blends were subjected to sorption studies to determine the extent of interaction and degree of swelling in pure liquids as well as binary mixtures. Wide-angle X-ray diffraction (WAXD) and thermal gravimetric analysis (TGA) were carried out to investigate changes in crystallinity and thermal stability, respectively. The effect of experimental parameters such as feed water concentration, permeate pressure and barrier thickness on membrane flux and selectivity was evaluated. The membranes were found to have good potential for breaking the azeotrope of 27.6 wt.% water with a flux of 3.07 kg/m² h 10 μm and selectivity of 26.5. Selectivity was found to improve with decreasing feed water concentration and increasing membrane thickness, whereas opposite trends were observed in case of flux. Higher permeate pressure caused a reduction in both flux and selectivity. These effects were clearly elucidated.     

Nanohybridization of Low-Dimensional Nanomaterials: Synthesis,Classification, and Application

Nanomaterials have attracted much attention from academic to industrial research. General methodologies are needed to impose architectural order in low-dimensional nanomaterials composed of nanoobjects of various shapes and sizes, such as spherical particles, rods, wires, combs, horns, and other non specified geometrical architectures. These nanomaterials are the building blocks for nanohybrid materials, whose applications have improved and will continuously enhance the quality of the daily life of mankind. In this article, we present a comprehensive review on the synthesis, dimension, properties, and present and potential future applications of nanomaterials and nanohybrids. Due to the large number of review articles on specific dimension, morphology, or application of nanomaterials, we will focus on different forms of nanomaterials, such as, linear, particulate, and miscellaneous forms. We believe that almost all the nanomaterials and nanohybrids will come under these three categories. Every form or dimension or morphology has its own significant properties and advantages. These low-dimensional nanomaterials can be integrated to create novel nano-composite material applications for next-generation devices needed to address the current energy crisis, environmental sustainability, and better performance requirements. We discuss the synthesis, properties, and morphology of different forms of nanomaterials (building blocks). Moreover, we elaborate on the synthesis, modification, and application of nanohybrids. The applications of these nanomaterials and nanohybrids in sensors, solar cells, lithium batteries, electronic, catalysis, photocatalysis, electrocatalysis, and bio-based applications will be detailed. The time is now ripe to explore new nanohybrids that use individual nanomaterial components as basic building blocks, potentially affording additionally novel behavior and leading to new, useful applications. In this regard, the combination or integration of linear nanorods/nanowires and spherical nanoparticles to produce mixed-dimensionality, higher-level nanocomposites of greater complexity is an interesting theme, which we explore in this review article.     

Comparison of a branch-and-bound heuristic,a newsvendor-based heuristic and periodic Bailey rules for outpatients appointment scheduling systems

Appointment-based service systems admit limited number of customers at a specific time interval to make service providers more accessible by reducing customers’ waiting time and make the costly resources more productive. A traditional approach suggests the Bailey rule, which assigns one or more customers at the initial block and only one customer at remaining blocks. We prescribe two heuristic approaches and variations of the traditional Bailey rule to appointment scheduling systems with the objective of minimizing total expected costs of delay and idle times between blocks. The first heuristic adopts a branch-and-bound approach using forward dynamic programming and tries to fully enumerate with some restrictions. The second heuristic uses a sequential-inverse newsvendor approach using a starting solution. We conduct numerical tests, which show that both heuristics get near-optimal solutions in a quicker time than a commercial solver, CPLEX and that the second approach gives near-optimal solutions far faster than the first approach. In addition, we suggest the use of a periodic Bailey rule, which can be implemented easily in practice, and provides a close solution to the best result of both heuristics, depending upon cost parameters and service-time variances.