Polymer entanglement loss in extensional flow: Evidence from electrospun short nanofibers

High strain rate extensional flow of a semidilute polymer solution can result in fragmentation caused by polymer entanglement loss, evidenced by appearance of short nanofibers during electrospinning. The typically desired outcome of electrospinning is long continuous fibers or beads, but, under certain material and process conditions, short nanofibers can be obtained, a morphology that has scarcely been studied. Here we study the conditions that lead to the creation of short nanofibers, and find a distinct parametric space in which they are likely to appear, requiring a combination of low entanglement of the polymer chains and high strain rate of the electrospinning jet. Measurements of the length and diameter of short nanofibers, electrospun from PMMA dissolved in a blend of CHCl₃ and DMF, confirm the theoretical prediction that the fragmentation of the jet into short fibers is brought about by elastic stretching and loss of entanglement of the polymer network. The ability to tune nanofiber length, diameter and nanostructure, by modifying variables such as the molar mass, concentration, solvent quality, electric field intensity, and flow rate, can be exploited for improving their mechanical and thermodynamic properties, leading to novel applications in engineering and life sciences. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1377–1391     

Antibody modified Bovine Serum Albumin microspheres for targeted delivery of anticancer agent Gemcitabine

Inhibition of the EGFR signaling pathway is one of the attractive therapeutic targets for pancreatic cancer as recent studies demonstrated that EGFR is over‐expressed in pancreatic cancer. In this article we have demonstrated the design of targeted drug delivery system containing Bovine Serum Albumin (BSA) microspheres as delivery vehicle, gemcitabine as anticancer drug and anti‐EGFR (epidermal growth factor receptor) monoclonal antibody as targeting agent. The conjugated BSA microspheres were characterized by several physico‐chemical techniques such as scanning electron microscope, optical microscopy, fluorescent microscopy etc. Administration of these BSA microspheres containing gemcitabine and anti‐EGFR (BSA‐Gem‐EGFR) shows significant inhibition of pancreatic cancer cells (AsPC1) compared to the cells treated with only BSA microspheres, BSA with gemcitabine (BSA‐Gem), and free gemcitabine. This strategy could be used as a generalized approach for the treatment of pancreatic cancer along with other cancers which overexpress EGFR on cell surface. Copyright © 2012 John Wiley & Sons, Ltd.     

Alliin Lyase (Alliinase) from Garlic (Allium sativum)

The garlic plant (Allium sativum) alliinase (EC 4.4.1.4), which catalyzes the synthesis of allicin, was purified to homogeneity from bulbs using various steps, including hydrophobic chromatography. Molecular and biochemical studies showed that the enzyme is a dimer of two subunits of MW 51.5 kDa each. ItsK _m using synthetic S-allylcysteine sulfoxide (+isomer) as substrate was 1.1 mM, its pH optimum 6.5, and its isoelectric point 6.35. The enzyme is a glycoprotein containing 6% carbohydrate. N-terminal sequences of the intact polypeptide chain as well as of a number of peptides obtained after cyanogen bromide cleavage were obtained. Cloning of the cDNAs encoding alliinase was performed by a two-step strategy. In the first, a cDNA fragment (pAli-1-450 bp) was obtained by PCR using a mixed oligonucleotide primer synthesized according to a 6-amino acid segment near theN- terminal of the intact polypeptide. The second step involved screening of garlic λgt11 and λZAPII cDNA libraries withpAli-1, which yielded two clones; one was nearly full length and the second was full length. These clones exhibited some degree of DNA sequence divergence, especially in their 3′ noncoding regions, suggesting that they were encoded by separate genes. The nearly full length cDNA was fused in frame to a DNA encoding a signal peptide from a wheat gliadin, and expressed inXenopus oocytes. This yielded a 50 kDa protein that interacted with the antibodies against natural bulb alliinase. Northern and Western blot analyses showed that the bulb alliinase was highly expressed in bulbs, whereas a lower expression level was found in leaves, and no expression was detected in roots. Strikingly, the roots exhibited an abundant alliinase activity, suggesting that this tissue expressed a distinct alliinase isozyme with very low homology to the bulb enzyme.     

Synthesis of air stable FeCo/C alloy nanoparticles by decomposing a mixture of the corresponding metal-acetyl acetonates under their autogenic pressure

A mixture of Fe(AcAc)(2) and Co(AcAC)(2) was thermolyzed in a closed cell under the autogenic pressure of the reactants. The nature of the products was temperature dependent. The reaction is a one-stage, simple, efficient, and solvent-free method to prepare FeCo alloy nanoparticles protected by a carbon shell. Particle sizes of 60-150 were obtained covered by a carbon layer of 3-4 nm. The air stability of these particles is also demonstrated.     

Relaxation spectra of polymers and phenomena of electrical and hydrophobic recovery: Interplay between bulk and surface properties of polymers

Low‐density polyethylene, polypropylene, and polycarbonate were exposed to cold air plasma treatment. The decay of electret response, hydrophobic recovery, and mechanical relaxation of polymers were studied experimentally. The three‐exponential decay kinetic model was used for the treatment of mechanical and electret responses. The characteristic time scales of mechanical and electret responses turned out to be very close. The “longest” relaxation time, extracted from the experimental study of the hydrophobic recovery, was also close to the corresponding characteristic time spans of electret and mechanical responses. The kinetics of surface processes taking place in polymers is controlled by the mobility of their functional groups, represented by the bulk relaxation spectra. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 198–205     

Polyanhydrides. IV. Unsaturated and crosslinked polyanhydrides

Unsaturated polyanhydrides of the structure ? [? (? CO? CH?CH? COO? )_x? (? CO? R? COO? )_y? ]_n? , were synthesized. The polymers were prepared by either melt or solution polycondensation. Weight average molecular weights of up to 30,000 were obtained. The double bonds remain intact throughout the polymerization process and were available for a secondary reaction to form a crosslinked matrix. Poly(fumaric acid) is crystalline and insoluble in common organic solvents. Copolymers of fumaric acid with aliphatic diacids are less crystalline and soluble in chlorinated hydrocarbons. These copolymers displayed nearly constant degradation rates and drug release rates under physiological conditions. The time for complete degradation of 14 × 1.5 mm discs of poly(fumaric anhydride) and poly(sebacic anhydride) occurred in 2 and 15 days, respectively, while their copolymers degraded within this range. Further crosslinking of the polyanhydrids is demonstrated.