Cross-Linking Nitroxide-Mediated Radical Copolymerization from a Bayesian Experimental Design Angle

Summary: In an attempt to collect “meaningful” experimental data in cross-linking nitroxide-mediated radical copolymerization of stryene and divinyl benzene, a Bayesian design approach was used to derive optimal experimental sequences to be carried out in the laboratory. Since a considerable amount of prior knowledge about this polymerization system was already available from previous experimental and modeling efforts, application of the Bayesian design of experiments seemed like a perfect approach. In addition, the implementation of the Bayesian approach would, in principle, result in running fewer experiments, hence saving considerable time and resources.     

Fabrication,characterization, and drug release study of vitamin C–loaded alginate/polyethylene oxide nanofibers for the treatment of a skin disorder

Pigmented purpuric dermatosis (PPD) is a skin disorder mainly seen in the lower limbs. The nanofibrous web has been shown to be an appropriate alternative for the treatment of skin diseases as a drug delivery vehicle. In this study, sodium alginate (SA)/polyethylene oxide (PEO) nanofibers containing vitamin C (VC) were fabricated using both blended electrospinning and core/shell electrospinning. The resultant nanofibers were characterized using Fourier transform infrared spectroscopy and scanning electron microscopy. Enhancing the VC content resulted in increasing the nanofibers diameter. Also, the degradation rate and drug release were investigated. Drug release was evaluated using the in vitro dissolution and permeation method. The degradation rate and the drug release of the core/shell nanofibers were found to be lower than those of the blended nanofibers. The drug release of the extended nanofibers followed a different pattern, indicating that the extension of the nanofibers could be a promising way to control the drug release.     

Applications of Dainshefsky's Dienes in the Asymmetric synthesis of Aza‐Diels‐Alder Reaction

Asymmetric hetero‐Diels‐Alder (AHDA) reactions provide a multitude of opportunities for the highly efficient, regio‐ and stereoselective construction of various heterocycles in enantiomerically pure form. The asymmetric aza‐Diels‐Alder (A‐aza‐DA) reaction using diversely hetero‐dienophiles and hetero‐dienes have been increasingly developed as a valuable method for the synthesis of functionalized nitrogen ring systems. The purpose of this review is to give a detailed discussion of the A‐aza‐DA reaction particularly, the stereoselective reactions of imines as dienophiles with Dainshefsky dienes to obtain optically pure aza‐Diels‐Alder products. The development of stereoselective variants of the reaction make use of imines as the dienophile and Dainshefsky dienes is at the forefront of these studies. This review updates the A‐aza‐DA reactions covering the literature from 1972 till date     

Development and Validation of Salt Gradient CEX Chromatography Method for Charge Variants Separation and Quantitative Analysis of the IgG mAb-Cetuximab

Ion exchange chromatography is widely used for charge variant analysis of proteins, including monoclonal antibodies. In this study, a simple and robust salt gradient cation exchange chromatography was developed and validated for quantitative determination of cetuximab in biopharmaceutical formulations. For this purpose, we investigated the effect of various parameters including buffer composition, column temperature, pH, gradient volume and flow rate on chromatographic separation of charge variants to achieve the acceptable peak separation, and the optimum condition was selected. Validation of the method was done in accordance with the International Conference on Harmonization (ICH) guidelines. The developed method was found to provide a linear regression over the concentration range of 0.06–2.00 mg mL^?1 yielding a correlation coefficient of 0.9972. The limits of detection and quantification for the developed method were 0.02 and 0.06 mg mL^?1, respectively. The intra-day and inter-day precision had relative standard deviation values?≤?2.7%. The robustness of the method was assessed by changes in the applied pH range of buffer, temperature, mobile phase composition, and flow rate. Specificity of the method was confirmed by evaluation of baseline resolution of the mAb variants from product excipients, which showed no interference between excipients and cetuximab. The stability indicating capability of this method was determined using photodegraded, and mechanically and thermally stressed samples. The proposed method could be applied as a simple, precise, and robust quantitative technique which can be reproduced in any labs for the high-throughput quality control and stability assessment of in-process and final product samples.     

Highly selective transport of silver ion through a supported liquid membrane using calix[4]pyrroles as suitable ion carriers

Facilitated transport of silver ion across a supported liquid membrane (SLM) by calix[4]pyrroles, as selective ion carriers, dissolved in kerosene has been investigated. The influences of fundamental parameters affecting the transport of silver ion including ion carrier concentration in the membrane phase, thiosulfate concentration in strip phase, picric acid concentration in the feed phase, stirring speed of aqueous phases, type of membrane solvent and time of transport have been studied. In the presence of thiosulfate as a suitable metal ion acceptor in the strip phase and picrate ion as ion pairing agent in the source phase, transport of silver occurs almost quantitatively after 75 min. The selectivity and efficiency of silver transport from aqueous solution containing Cu²⁺, Mg²⁺, Ni²⁺, Ca²⁺, Zn²⁺, Pb²⁺, Co²⁺, Al³⁺, Hg²⁺, Cd²⁺, Fe³⁺, Fe²⁺ and Cr³⁺ were investigated.     

Effect of gold nanoparticle as a novel nanocatalyst on luminol-hydrazine chemiluminescence system and its analytical application

In this work the catalytic role of unsupported gold nanoparticles on the luminol–hydrazine reaction is investigated. Gold nanoparticles catalyze the reaction of hydrazine and dissolved oxygen to generate hydrogen peroxide and also catalyze the oxidation of luminol by the produced hydrogen peroxide. The result is an intense chemiluminescence (CL) due to the excited 3-aminophthalate anion. In the absence of gold nanoparticles no detectable CL was observed by the reaction of luminol and hydrazine unless an external oxidant is present in the system. The size effect of gold nanoparticles on the CL intensity was investigated. The most intensive CL signals were obtained with 15-nm gold nanoparticles. UV–vis spectra and transmission electron microscopy studies were used to investigate the CL mechanism. The luminol and hydroxide ion concentration, gold nanoparticles size and flow rate were optimized. The proposed method was successfully applied to the determination of hydrazine in boiler feed water samples. Between 0.1 and 30 μM of hydrazine could be determined with a detection limit of 30 nM.     

Highly improved electrocatalytic behavior of sulfite at carbon ionic liquid electrode: application to the analysis of some real samples

The electrocatalytic oxidation of sulfite was investigated at carbon ionic liquid electrode (CILE). This electrode is a very good alternative to previously described electrodes because the electrocatalytic effect is achieved without any electrode modification. Comparative experiments were carried out using carbon paste electrode (CPE) and glassy carbon electrode (GCE). At CILE, highly reproducible and well-defined cyclic voltammograms were obtained for sulfite with a peak potential of 0.55 V vs. Ag/AgCl. Sulfite oxidation at CILE does not result in deactivation of the electrode surface. The kinetic parameters for this irreversible heterogeneous electron transfer process were determined. Under optimal experimental conditions, the peak current response increased linearly with sulfite concentration over the range of 6-1000 μM. The detection limit of the method was 4 μM. The method was applied to the determination of sulfite in mineral water, grape juice and non-alcoholic beer samples.     

Double covers of Kummer surfaces

Besides its construction as a quotient of an abelian surface, a Kummer surface can be obtained as the quotient of a K3 surface by a -action. In this paper, we classify all such K3 surfaces. Our classification is expressed in terms of period lattices and extends Morrison’s criterion of K3 surfaces with a Shioda–Inose structure. Moreover, we list all the K3 surfaces associated to a general Kummer surface and provide very geometrical examples of this phenomenon.     

Dynamic method as a simple approach for wide range pH measurements using optodes

In this paper, a flow system equipped with an optode has been suggested for wide range pH measurements. Triacetyl cellulose was used as the optode membrane in which different pH indicators were immobilized. For extending the pH range, the dynamic response rather than the steady-state response of the optode was measured. Since diffusion is the main process governing the system response, different parameters having influence on diffusion of the analyte into the membrane were optimized. Under the optimum conditions, wide range pH determination (up to 11 pH units) is simply achieved regardless of the pK_a of the pH indicator immobilized in the membrane. To validate the application of the method different indicators with different structures and pK_a values were tested and the results were all confirming the precision and accuracy of the method. The suggested method also has combined advantages of flow systems together with inherent advantages of kinetic systems.