Preparation and characterization of conducting polyaniline layered magnetic nano composite polymer particles

Considering the application potentials of organic materials possessing both conducting and ferromagnetic functions in various electronic devices, an attempt was made to prepare conducting polyaniline (PANI) layered magnetic nano composite polymer particles. Two routes were used to modify magnetic Fe₃O₄ core particles. In one route, seeded emulsion polymerization of methyl methacrylate (MMA) was carried out in presence of nano‐sized Fe₃O₄ core particles. In another route, cross‐linker ethyleneglycol dimethacrylate (EGDM) was used in addition to MMA. The modified composite particles were named as Fe₃O₄/PMMA and Fe₃O₄/P(MMA‐EGDM), respectively. Finally, seeded chemical oxidative polymerization of aniline was carried out in the presence of Fe₃O₄/PMMA and Fe₃O₄/P(MMA‐EGDM) composite seed particles to obtain Fe₃O₄/PMMA/PANI and Fe₃O₄/P(MMA‐EGDM)/PANI composite polymer particles. The modification of Fe₃O₄ core particles was confirmed by electron micrographs, FTIR, UV–visible spectra, X‐ray photoelectron spectra, X‐ray diffraction pattern and thermogravimetric analyses. A comparative study showed that crosslinking of intermediate shell improved the magnetic susceptibility and electrical conductivity of PANI layered magnetic nano composite particles. Copyright © 2013 John Wiley & Sons, Ltd.     

Complementary MS Methods Assist Conformational Characterization of Antibodies with Altered S–S Bonding Networks

As therapeutic monoclonal antibodies (mAbs) become a major focus in biotechnology and a source of the next-generation drugs, new analytical methods or combination methods are needed for monitoring changes in higher order structure and effects of post-translational modifications. The complexity of these molecules and their vulnerability to structural change provide a serious challenge. We describe here the use of complementary mass spectrometry methods that not only characterize mutant mAbs but also may provide a general framework for characterizing higher order structure of other protein therapeutics and biosimilars. To frame the challenge, we selected members of the IgG2 subclass that have distinct disulfide isomeric structures as a model to evaluate an overall approach that uses ion mobility, top-down MS sequencing, and protein footprinting in the form of fast photochemical oxidation of proteins (FPOP). These three methods are rapid, sensitive, respond to subtle changes in conformation of Cys?→?Ser mutants of an IgG2, each representing a single disulfide isoform, and may be used in series to probe higher order structure. The outcome suggests that this approach of using various methods in combination can assist the development and quality control of protein therapeutics.      

Sensory Response and Two-Photon-Fluorescence Study of Regioregular Polythiophene Nanoparticles

Nanoparticles of a regioregular and soluble polythiophene were fabricated by mini-emulsion technique. The fabricated nanoparticles were characterized by optical spectroscopy and dynamic light scattering. The fluorescence quenching of these fabricated nanoparticles with 2,4-dinitrotolune (DNT) in aqueous and organic solutions was investigated. Significant fluorescence quenching was observed. The Stern-Volmer constants were determined to be higher than that of the bulk polymer in solution, indicating that the nanoparticles provide better sensitivity in DNT sensing. Strong two-photon-induced fluorescence was measured from these nanoparticles.     

Horseradish Peroxidase Catalyzed Synthesis of Polycardanol Microcapsules

Polymers synthesized from naturally derived monomers are valuable since they decrease the reliance on petroleum based feed stocks. Cashew nut shell oil (CNSL) is a side-product from processing of edible Cashew nuts of Annacardium occidentale. One of the major components of CNSL is cardanol, which is a phenol derivative having an unsaturated pentadecyl substituent in the ‘meta’ position with varying amount of unsaturation (no double bonds to three double bonds). The substituent in the meta position can also be hydrogenated to yield completely saturated hydrogenated cardanol. Cardanol can be utilized to stabilize the dispersions of oil in water and vice versa since it displays amphiphilic behavior owing to the phenolic head and the C15 aliphatic tail. Here we report the horseradish peroxidase (HRP) catalyzed polymerization of cardanol at oil water interface to obtain polycardanol microcapsules. A synthetic analogue of hydrogenated cardanol, 3-pentadecylphenol (3PDP), was also oxidatively polymerized at the oil-water interface to obtain Poly(3-pentadecylphenol) microcapsules.     

Immobilized Carboxypeptidase A for Sequential Analysis

The use of carboxypeptidase for sequence determination is attractive because of its technical simplicity. In chemical methods all molecules of a peptide are made to go through a degradation cycle before a new cycle is started. In the enzymatic degradation of a protein, the order of the amino acid residues is not necessarily determined in a stepwise fashion but rather from the rate at which the amino acids appear in the digest, i.e., an amino acid appearing faster than another presumably precedes it in the sequence. Under favorable circumstances the rate of appearance of the amino acids released during digestion give sufficient evidence for the C-terminal sequence to be deduced. The present work pertains to a study on the use of immobilized carboxypeptidase A columns for sequential analyses.     

Feasibility of Polyvinyl Alcohol as a Transdermal Drug Delivery System for Terbutaline Sulphate

A series of terbutaline sulphate drug incorporated polyvinyl alcohol (PVA) matrix films were produced by the solvent evaporation method. The effect of xanthan gum and plasticizers (propylene glycol and dibutyl phthalate) on the rate and amount of drug diffusion from PVA membrane across the hydrated cellophane membrane has been evaluated, using an open glass diffusion‐tube. The obtained films were clear, smooth and flexible having sufficient mechanical strength. The mechanical performance of the dry PVA films with xanthan gum and plasticizers were also ascertained. Polyvinyl alcohol‐xanthan gum blends showed a high rate of drug release compared to that of polyvinyl alcohol film alone. Among the two plasticizers employed, propylene glycol showed better permeability. Among different formulations studied, the formulation PVA/xanthan gum/propylene glycol (F7) was found to be an optimized composition for efficient transdermal delivery of the model drug, terbutaline sulphate. The mechanism of drug diffusion has been evaluated using the Peppas model. Stability studies carried out on polymer‐drug formulations revealed that the drug is stable at 40°C and 75% RH for a period of 6 weeks.     

N‐Vinylpyrrolidone and Ethoxyethyl Methacrylate Copolymer: Synthesis,Characterization and Reactivity Ratios

Free radical copolymerization of N‐vinyl‐2‐pyrrolidone with 2‐ethoxyethyl methacrylates was carried out with 2,2′‐azobisisobutyronotrile as an initiator in 1,4‐dioxane. The resulting copolymer was characterized by FTIR, H¹‐NMR and C¹³‐NMR spectroscopic techniques thermal properties of copolymer were determined by DSC and TGA. The reactivity ratios of the monomers were computed by the Fineman‐Rose (F‐R), Kelen‐Tudos (K‐T) and extended Kelen‐Tudos (EK‐T) method at lower conversion, using the data obtained from both FTIR and elemental analysis studies; the results are in good agreement with each other. The average reactivity ratio, Alfrey‐Price Q and e values were found to be r ₁=0.769, r ₂=0.266 and Q ₁=0.0859, e ₁=0.4508, respectively for NVP/EOEMA copolymer. The distribution of monomer sequence along the copolymer chain was calculated using a statistical method based on obtained reactivity ratio. The number average molecular weight and polydispersity were determined by GPC.     

Ethylene spacer-linked bis-acetamidopyridine for dicarboxylic acid recognition and polymeric new wave-like anti-perpendicular arrangement of a host–guest in the solid state

In this paper, 1,2-bis(2-acetamido-6-pyridyl)ethane, receptor 1, having an ethylene spacer is reported to recognise dicarboxylic acids. The binding study in the solution phase is carried out using ¹H NMR (1:1) and UV–vis experiments and in the solid phase by single-crystal X-ray analysis. In ¹H NMR, the downfield shifts of specific amide protons of receptor 1 in 1:1 complexes of receptor and guest diacids, and in the UV–vis experiment, the appearance of an isosbestic point as well as significant binding constants are observed, which thus unambiguously support the complexation of receptor 1 with dicarboxylic acids in solution. Receptor 2, simple 2-acetamido-6-methylpyridine, has lower binding constants than receptor 1 due to cooperative binding of two pyridine amide groups with two acid groups of diacids. In the solid phase, the ditopic receptor 1 shows a grid-like polymeric hydrogen-bonded network that changes to a polymeric wave-like 1:1 anti-perpendicular network instead of the syn–syn polymeric 1:1 (Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett. 2005 (a) Goswami, S., Ghosh, K. and Dasgupta, S. 2000. J. Org. Chem., 65: 1907–1914. (b) Goswami, S.; Ghosh, K.; Mukherjee, R. Tetrahedron2001, 57, 4987–4993. (c) Goswami, S.; Ghosh, K.; Halder, M. Tetrahedron Lett.1999, 40, 1735–1738. (d) Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett.2005, 46, 7187–7191. (e) Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem.2006, 18, 571–574. (f) Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm.2008, 10, 507–517. (g) Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron2008,64, 6426–6433. (h) Goswami, S.; Dey, S.; Jana, S. Tetrahedron2008, 64, 6358–6363 [Google Scholar], 46, 7187–7191), anti–anti polymeric 1:1 (Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem. 2006 (a) Goswami, S., Ghosh, K. and Dasgupta, S. 2000. J. Org. Chem., 65: 1907–1914. (b) Goswami, S.; Ghosh, K.; Mukherjee, R. Tetrahedron2001, 57, 4987–4993. (c) Goswami, S.; Ghosh, K.; Halder, M. Tetrahedron Lett.1999, 40, 1735–1738. (d) Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett.2005, 46, 7187–7191. (e) Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem.2006, 18, 571–574. (f) Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm.2008, 10, 507–517. (g) Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron2008,64, 6426–6433. (h) Goswami, S.; Dey, S.; Jana, S. Tetrahedron2008, 64, 6358–6363 [Google Scholar], 18, 571–574; Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm. 2008, 10, 507–517; Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron 2008, 64, 6426–6433), syn–syn 2:2 (Karle, I.L.; Ranganathan, D.; Haridas, V. J. Am. Chem. Soc. 1997 (a) Garcia-Tellado, F., Goswami, S., Chang, S.K., Geib, S.J. and Hamilton, A.D. 1990. J. Am. Chem. Soc., 112: 7393–7394. (b) Geib, S.J.; Vicent, C.; Fan, E.; Hamilton, A.D. Angew. Chem. Int. Ed. Engl.1993, 32, 119–121. (c) Garcia-Tellado, F.; Geib, S.J.; Goswami, S.; Hamilton, A.D. J. Am. Chem. Soc.1991, 113, 9265–9269. (d) Karle, I.L.; Ranganathan, D.; Haridas, V. J. Am. Chem. Soc.1997, 119, 2777–2783. (e) Moore, G.; Papamicaël, C.; Levacher, V.; Bourguignon, J.; Dupas, G. Tetrahedron2004, 60, 4197–4204. (f) Korendovych, I.V.; Cho, M.; Makhlynets, O.V.; Butler, P.L.; Staples, R.J.; Rybak-Akimova, E.V. J. Org. Chem.2008, 73, 4771–4782. (g) Ghosh, K.; Masanta, G.; Fröhlich, R.; Petsalakis, I.D.; Theodorakopoulos, G. J. Phys. Chem. B2009, 113, 7800–7809 [Google Scholar], 119, 2777–2783) or top–bottom-bound 1:1 (Garcia-Tellado, F.; Goswami, S.; Chang, S.K.; Geib, S.J.; Hamilton, A.D. J. Am. Chem. Soc. 1990 (a) Goswami, S., Ghosh, K. and Dasgupta, S. 2000. J. Org. Chem., 65: 1907–1914. (b) Goswami, S.; Ghosh, K.; Mukherjee, R. Tetrahedron2001, 57, 4987–4993. (c) Goswami, S.; Ghosh, K.; Halder, M. Tetrahedron Lett.1999, 40, 1735–1738. (d) Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett.2005, 46, 7187–7191. (e) Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem.2006, 18, 571–574. (f) Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm.2008, 10, 507–517. (g) Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron2008,64, 6426–6433. (h) Goswami, S.; Dey, S.; Jana, S. Tetrahedron2008, 64, 6358–6363 [Google Scholar], 112, 7393–7394) co-crystals.