Vitamin A microencapsulation within poly(methyl methacrylate)‐g‐polyethylenimine microspheres: Localized proton buffering effect on vitamin A stability

To stabilize vitamin A in a cosmetic/dermatological formulation, we present here a new encapsulation method based on polymer microspheres having a localized “proton‐buffering” capacity. Poly(methyl methacrylate)‐g‐polyethylenimine (PMMA‐g‐PEI) was prepared by direct condensation grafting of PEI onto poly(methyl methacrylate‐co‐methyl acrylic acid). The reaction was confirmed by FT‐IR analysis showing the amide vibration at 1,550 cm^?1. Elemental analysis indicated that the weight content of the grafted PEI was 1.6% (w/w). Vitamin A was encapsulated into PMMA‐g‐PEI microspheres by using an oil‐in‐water (O/W) single emulsion method. The presence of PEI moiety dramatically improved the chemical stability of vitamin A in microspheres. Vitamin A encapsulated within PMMA‐g‐PEI microspheres maintained 91% of its initial activity after 30‐day incubation at 40°C, while only maintaining 60% within plain PMMA microspheres. This study demonstrates that proton‐buffering within hydrophobic polymer matrix is a useful strategy for stabilizing “acid‐labile” active ingredients. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 517–522, 2004     

Kinetics of hydroformylation of 1-decene using homogeneous HRh(CO)(PPh3)3 catalyst: a molecular level approach

The kinetics of hydroformylation of 1-decene using homogenous HRh(CO)(PPh₃)₃ catalyst has been reported in the temperature range of 50–70 °C. The effect of catalyst,P _{H 2},P _CO, and 1-decene concentration on the rate of hydroformylation has been studied. Based on the analysis of initial rate data, a rate equation has been proposed and kinetic parameters evaluated. The activation energy was found to be 11.76 kcal/mol. A molecular level approach to kinetic modelling has also been illustrated. The rate equation derived assuming oxidative addition of H₂ as a rate determining step, has been found to represent the data satisfactorily. The rate parameters for the mechanistic model have been evaluated for the data at 60 °C.NCL Communication No. 5735.     

Metallocene‐based functionalized polyolefins as compatibilizers in polyolefin nanocomposites

This article reports a study of some functionalized polyolefins evaluated as compatibilizers in polyethylene nanocomposites. The functionalized polymers were prepared by direct metallocene‐mediated copolymerizations of ethylene and a functional comonomer. The prepared nanocomposites were evaluated for mechanical and barrier property enhancement. A good combination of mechanical and barrier properties was obtained with the metallocene‐based functionalized polyethylene. The toughness–stiffness balance was better than or comparable to that achieved with conventional functionalized polymers such as maleic anhydride grafted polyethylene. The results also indicated that these metallocene‐based functionalized polyolefins, when used as compatibilizers, could have relatively higher molar masses and lower functionality than those of conventional post‐reactor‐modified compatibilizers, and so the drawbacks associated with the latter could be avoided. Their inherent properties could also further improve the final nanocomposite properties. This was attributed to the more homogeneous nature of metallocene‐catalyzed polymers in comparison with post‐reactor‐modified products. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1094–1100, 2004     

Modification of silica gel,cellulose, and polyurethane with a sterically hindered N‐halamine moiety to produce antimicrobial activity

The sterically hindered amine monomer 4‐[3‐triethoxysilylpropoxyl]‐2,2,6,6‐tetramethylpiperidine has been synthesized and covalently bonded to the surfaces of silica gel particles and cellulose (cotton) and copolymerized in a polyurethane coating formulation. Upon exposure to dilute sodium hypochlorite (household bleach), a very stable N‐Cl bond is formed in situ at the hindered amine nitrogen site. This source of oxidative chlorine provides an antimicrobial function to the silica gel, cotton, and polyurethane. Stability, regenerability, and biocidal efficacy data are presented. The new N‐halamine materials were remarkably effective against Staphylococcus aureus and Escherichia coli O157 : H7 in brief periods of contact. The materials should find application in water treatment and medical applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Surface functionalized colloidal silica particles from an inverse microemulsion sol gel process

Colloidal silica particles are prepared via a sol gel technique carried out in an inverse microemulsion of water in a toluene solution of tetraethoxysilane (TEOS), stabilized by either an anionic surfactant AOT or isopropanol. Functionalized material was obtained using a functional coupling agent (RO)₃Si(CH₂)₃ X, X being a functional group such as methacryloyl, thiol, vinyl, amino group, or a chlorine atom. Functionalization can be carried out either directly via the direct copolycondensation of TEOS and the coupling agent, or in a two-step process involving a core-shell polycondensation of the coupling agent onto preformed silica particles. Kinetic studies of the copolycondensation are carried out using either²⁹Si NMR analysis or liquid chromatography. They show that the consumption of TEOS is more rapid than that of the coupling agent. The materials are characterized both chemically (elemental analysis, FTIR,¹³C and²⁹Si NMR CPMAS analysis), and by their particle size. The silica functionalized with a polymerizable methacryloyl group is encapsulated by a polymer layer in an inverse emulsion polymerization of acrylic acid. After inversion of the emulsion in water, the resulting material is covered with a layer of hydrophobic polymer in a conventional emulsion polymerization.     

Immobilization of biologically active species on PA‐6 foils treated by a dielectric barrier discharge

In the field of biomaterials and biomedical devices, surface activation has been focused on creating functional groups capable of preferential adsorption of biologically active species (proteins, enzymes, cells, drugs, etc.). In this way an interface can be created between the synthetic material and the biological medium, with the aim of increasing the compatibility of the implant with the human organism. In our experiments a dielectric barrier discharge (DBD), in helium at atmospheric pressure, was used as the source of energy capable of creating active centers that render the functionalized surface favorable to immobilization of biological molecules. Retention of immunoglobulin (IgG) and heparin biomolecules on polyamide‐6 (PA‐6) surfaces after treatment by the DBD was analyzed by atomic force microscopy, adhesion evaluation, and measurement of the contact angle titration in order to assess this incorporation on the treated surfaces. The marked adsorption of the biomolecules on the active sites created by DBD on the exposed surfaces also was related to a complex set of processes, such as enhanced roughness, increased surface wettability, and modified distribution of cationic and anionic groups on the treated surfaces. All these factors could promote interfacial interactions between the specific groups of the biomolecules existing in the biological medium and the type of cationic and/or anionic groups present on the surface. The efficiency of the DBD treatment showed that the DBD technique is useful for preactivation of the polymer surface for immobilization of other biologically active species (such as drugs and enzymes). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1985–1990, 2003     

Alder ene functionalization of polyisobutene oligomer and styrene-butadiene-styrene triblock copolymer

The Alder ene functionalization reaction of double bonds containing macromolecules such as polyisobutene oligomer (PIB) and a styrene-butadiene-styrene triblock copolymer (SBS) samples with maleic anhydride (MAH) or diethyl maleate (DEM) as enophiles is described. The analysis of the products by means of different techniques assesses the addition of the polar molecules to the reactive vinylidene units of the polymer with functional degrees (FD) depending on the type of enophile and polymer reactivity. The role of the reaction conditions and the use as Lewis acids as catalysts are discussed in terms of their influence on the addition reaction extent and on the polymer molecular weight.     

Adaptive relationships of epoxide hydrolase in herbivorous arthropods

Epoxide hydrolase catalyzes a simple hydrolysis of reactive cyclic ethers that may otherwise alkylate and impair critical proteins and nucleic acids required for life. Although much less studied than the cytochrome P-450 monooxygenases that produce epoxides, differences in subcellular, tissue, pH, substrate, and inhibitor specificities argue for at least three forms of insect epoxide hydrolase. Increasing numbers of epoxides are being identified as plant allelochemicals, antifeedants, and essential hormones or precursors for herbivorous arthropods, and in many cases an associated alkene to diol pathway of metabolism is found. A role for epoxide hydrolase in arthropod-plant interactions is strongly supported by species comparisons and by age-activity and induction studies. Two major limitations for study in biochemical ecology of epoxide hydrolase are the lack of an effective in vivo inhibitor and a range of commercially available radiolabeled substrates for the enzymes.     

Selective removal of heavy metal ions from aqueous solutions with surface functionalized silica nanoparticles by different functional groups

The industrial silica fume pretreated by nitric acid at 80 °C was re-used in this work. Then, the obtained silica nanoparticles were surface functionalized by silane coupling agents, such as（3-Mercaptopropyl） triethoxysilane（MPTES） and（3-Amincpropyl） trithoxysilane（APTES）. Some further modifications were studied by chloroaceetyl choride and 1,8-Diaminoaphalene for amino modified silica. The surface functionalized silica nanoparticles were characterized by Fourier transform infrared（FI-IR） and X-ray photoelectron spectroscopy（XPS）. The prepared adsorbent of surface functionalized silica nanoparticles with differential function groups were investigated in the selective adsorption about Pb2＋, Cu2＋, Hg2＋, Cd2＋ and Zn2＋ions in aqueous solutions. The results show that the（3-Mercaptopropyl） triethoxysilane functionalized silica nanoparticles（SiO2-MPTES） play an important role in the selective adsorption of Cu2＋ and Hg2＋, the（3-Amincpropyl） trithoxysilane（APTES） functionalized silica nanoparticles（SiO2-APTES） exhibited maximum removal efficiency towards Pb2＋ and Hg2＋, the 1,8-Diaminoaphalene functionalized silica nanoparticles was excellent for removal of Hg2＋ at room temperature, respectively.