Controlled grafting of cellulose esters using SET‐LRP process

Here, we present the first example of application of single‐electron transfer living radical polymerization (SET‐LRP) process to a controlled grafting of cellulose esters, cellulose diacetate (CDA), and cellulose acetate butyrate (CAB). The cellulose ester macroinitiators with various functionality densities have been prepared by acylation of the backbones with 2‐bromoisobutyryl (BrIB) and dichloroacetyl (DCA) groups, respectively. Methacrylate monomers were polymerized using DCA‐functionalized macroinitiators in the presence of pentamethyldiethylene triamine as a ligand. At 30 °C, the reaction is rather slow, reaching about 10% conversion after 3 to 6 h of polymerization, whereas the higher temperature (60 °C) perceptibly speeds up the polymerization so that methyl methacrylate (MMA) conversion is ～30% after 5 h. Graft copolymers with random‐type and diblock‐type grafts having amphiphilic character were also synthesized. For acrylate grafting (BuA and t‐BuA), BrIB‐functionalized macroinitiators are more convenient in a combination with a low concentration of Cu(0) and Me₆TREN as a ligand and polymerization is detectably faster even at the lower temperature than that of MMA. Kinetic studies show “living” character of both the graftings. Important advantages of SET‐LRP, compared with classic ATRP, are (i) higher polymerization rate, (ii) lower extent of recombination of the growing grafts and (iii) negligible coloration of the products with catalytic residua, so that the prepared polymers do not require additional careful purification. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Development and Validation of an LC–ESI-MS Ion-Trap Method for Analysis of Impurities in Transkarbam 12, a Novel Transdermal Accelerant

A new, sensitive LC–MS method for evaluation of the purity of Transkarbam 12 (T12), a novel and highly effective accelerant of transdermal penetration, has been developed and validated. T12 and its impurities (6-aminohexanoic acid, AH, ε-caprolactam, CA, and dodecyl 6-(6-aminohexanamido)hexanoate, DAH) were characterized by MS and MS–MS analysis. Separation was achieved on a 150 mm × 3 mm, 5-μm particle, phenyl–hexyl column. The mobile phase was a gradient prepared from water, formic acid, and acetonitrile. The method was validated within the concentration range 50–250 ng mL^?1; correlation coefficients were >0.998. The accuracy of the method was from 98.6–105.0% for AH, 102.6–104.8% for CA, and 97.9–100.9% for DAH. Precision was in the range 3.19–4.42% for AH, 3.22–5.81% for CA, and 4.8–8.78% for DAH. The selectivity of the method and sample stability were also confirmed. The practical applicability of the method was proven by analysis of T12 bulk substance.     

Light scattering by optically heterogeneous materials: Structural aspects of dichromatic laser speckle patterns

An analysis is given of dichromatic speckle patterns formed by small-angle scattered light in the illumination of optically heterogeneous systems with light of two nearby wavelengths. The existence of the radial-fibrillar appearance of the speckle patterns is explained; it is shown that the occurrence of the radial-fibrillar “structure” corresponds to the measurable correlation of dichromatic speckle patterns as specified by the spectral spatial cross-correlation function of intensity fluctuations. A measurement of speckle-pattern correlation to determine σ_z (the standard deviation of optical path fluctuations due to the passage of coherent light through a layer of heterogeneous material) is described, and the relations between σ_z and the structural parameters for two simple types of heterogeneous materials are discussed. Experimental results obtained with a series of samples of polyethylene filled with CaCO₃ are in comparatively good agreement with theoretical values.     

An acceleration of Erlenkotter-Körkel’s algorithms for the uncapacitated facility location problem

This contribution is focused on an acceleration of branch and bound algorithms for the uncapacitated facility location problem. Our approach is based on the well-known Erlenkotters’ procedures and Körkels’ multi-ascent and multi-adjustment algorithms, which have proved to be the efficient tools for solving the large-sized instances of the uncapacitated facility location problem. These two original approaches were examined and a thorough analysis of their performance revealed how each particular procedure contributes to the computational time of the whole algorithms. These analyses helped us to focus our effort on the most frequent procedures. The unique contribution of this paper is a new dual ascent procedure. This procedure leads to considerable acceleration of the lower bound computation process and reduces the resulting computational time. To demonstrate more efficient performance of amended algorithms we present the results of extensive numerical experiments.     

“On water” ultrasound-assisted one pot efficient synthesis of functionalized 2-oxo-benzo[1,4]oxazines: First application to the synthesis of anticancer indole alkaloid,Cephalandole A

For the first time, an efficient, simple, synthetic green protocol for the one-pot synthesis of functionalized 2-oxo-benzo[1,4]oxazines 24–29 in water under ultrasound irradiation is presented. As compared to conventional methods, the present protocol avoids traditional chromatography and purification steps and furnished the target molecules in excellent yields (upto 98%) with no side products. The methodology was also demonstrated on gram scale synthesis. Moreover, functionalized 2-oxo-quinoxaline analogues 31–33, another class of bio-active heterocyclic scaffolds, were also prepared using this method. For the first time, this protocol was successfully applied in the synthesis of the anticancer indole alkaloid, Cephalandole A 35.     

Surface plasmon resonance biosensor for the detection of VEGFR-1—a protein marker of myelodysplastic syndromes

The surface plasmon resonance (SPR) biosensor system with dispersionless microfluidics for the direct and label-free detection of a soluble vascular endothelial growth factor receptor (sVEGFR-1) is described. The detection approach takes advantage of an affinity interaction between sVEGFR-1 and its ligand, vascular endothelial growth factor (VEGF-A), which is covalently immobilized on the surface of the SPR sensor. The ability of the immobilized VEGF-A to specifically bind the sVEGFR-1 receptor is demonstrated in a buffer. The detection of sVEGFR-1 in 2% human blood plasma is carried out by using the sequential injection approach. The detection limit of 25 ng/mL is achieved. In addition, we demonstrate that the functional surface of the sensor can be regenerated for repeated use.     

5-nitro-2-thienylvinylation. Nucleophilic substitution on 2-(2-bromovinyl)-5-nitrothiophene,new one-step method for preparation of new biologically active ethylenic derivatives of 5-nitro--2-thiophene

A facile method for preparing 2-(2-X-vinyl)-5-nitrothiophene has been established by the reaction of (Z)-2-(2-bromovinyl)-5-nitrothiophene with O, S and N nucleophiles.     

The preparation of conducting polyaniline–silver and poly(p-phenylenediamine)–silver nanocomposites in liquid and frozen reaction mixtures

The oxidation of aniline with silver nitrate in 1 mol L⁻¹ acetic acid at 20 °C yielded a composite of two conducting components, polyaniline and silver; the acceleration with 1 mol% of p-phenylenediamine is needed for efficient synthesis. The yield and molecular weight increased when aniline was copolymerized with 10 mol% p-phenylenediamine. Such product displayed metallic conductivity below 180 K and semiconductor type above this temperature. As the result, the conductivity was the same at 100 and 300 K. The oxidation of p-phenylenediamine alone with silver nitrate also produced a conducting composite having the conductivity of 1,750 S cm⁻¹ despite the assumed nonconductivity of poly(p-phenylenediamine). The present study demonstrates that all oxidations proceeded also in frozen reaction mixtures at −24 °C, i.e., in the solid state. In most cases, molecular weights of polymer component increased, the conductivity of composites with silver improved, to 2,990 S cm⁻¹ for poly(p-phenylenediamine)–silver, and remained high after deprotonation with 1 mol L⁻¹ ammonium hydroxide.