Poly(ethylene-co-methyl acrylate)/poly(caprolactone) triol blends for drug delivery systems: characterization and drug release

Poly(ethylene-co-methyl acrylate) (EMA) and poly (caprolactone) triol (PCL-T) blends, a biodegradable aliphatic polyester with low molecular weight and moderate water solubility containing diltiazem hydrochloride (DZ) were studied in terms of the thermal and morphological properties, and drug release mechanism. An increase in the PCL-T content in the EMA/PCL-T/DZ films decreased the degree of DZ crystallinity. Drug release from these films is temperature-dependent, and it is possible to modify the drug release rate by adjusting the EMA/PCL-T composition of the blends. The mechanism of drug release is governed by PCL-T melting and PCL-T leaching from EMA matrix.

Application of ftir in the determination of acrylate content in poly(sodium acrylate-co-acrylamide) superabsorbent hydrogels

Hydrogels have been prepared by free-radical solution copolymerization of acrylamide and sodium acrylate (NaAc), with molar ratio ranging from 25/75 to 80/20, respectively, using methylene bisacrylamide as the crosslinking agent. A FTIR spectroscopy procedure to determine the acrylate/acrylamide ratio in these hydrogels was proposed based on absorbance at 1410 cm-1 (nCOO-) and 2940 cm-1 (nCH and nCH2). A straight line with a good linear correlation coefficient (0.998) was obtained by plotting the acrylate content (Ac%) versus relative absorbance (Arel = A1410/A2940). Results were confirmed by the amount of sodium cation released in acid medium determined by atomic absorption spectrometry.

Síntese e caracterização de copolímeros de cadeia lateral derivados de acrilatos de 4,5-di-hidroisoxazol e do (-)-mentol

Five monomers 5-[4-(5-cyano-4,5-dihydroisoxazol-3-yl)phenoxy]undecyl acrylate (7a); n-alkyl 3-{4-[5-(acryloyloxyundecyl)oxyphenyl]}-4,5-dihydroisoxazole-5-carboxylate (7b,c for n-butyl and n-hexyl, respectively); 3-{4-[5-(acryloyloxyundecyl) oxyphenyl]}-4,5-dihydroisoxazole-5-carboxylic acid (7d) and (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl acrylate (9) and the corresponding copolymers 10a-d,11 and homopolymers 12 from 7a and 13 from 9 were designed and synthesized. Except for acrylate 9 which is derived from (-)-menthol, all of the monomers belong to the series containing the isoxazoline ring linked to the acrylate unit by a flexible spacer chain of eleven methylene units. They presented low glass temperature and despite birefringence behavior, these copolymers showed no mesomorphic properties.

DFT study on low molecular weight α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene and α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene S-oxide bridged derivatives

The equilibrium geometries of α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene (DBDT) and α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene S-oxide (DBDTO) were studied at the DFT level of theory with a standard 6-311G* basis set. The molecular structures of the DBDT series were more planar than the corresponding DBDTO series, as revealed by dihedral angles. The UV-visible absorption calculated at TD-DFT/6-311G* showed two absorption peaks for all the molecules except C=S and C=O bridged molecules. In DBDTOs, C=S and C=O bridged molecules showed three and four absorption peaks, respectively. The DBDTOs had lower band gaps and longer wavelengths compared to the corresponding DBDTs.

NOVEL SUPERABSORBENT HYDROGEL COMPOSITE BASED ON POLY(ACRYLAMIDE-CO-ACRYLATE)/NONTRONITE: CHARACTERIZATION AND SWELLING PERFORMANCE

A novel superabsorbent hydrogel (SH) composite based on a poly(acrylamide-co-acrylate) matrix filled with nontronite (NONT), a Fe(III)-rich member of the smectite group of clay minerals, is described in this manuscript. A variety of techniques, including FTIR, XRD, TGA, and SEM/EDX, were utilized to characterize this original composite. Experimental data confirmed the SH composite formation and suggested NONT was completely dispersed in the polymeric matrix. Additionally, NONT improved the water uptake capacity of the final material, which exhibited fast absorption, low sensitivity to the presence of salt, high water retention and a pH sensitive properties. These preliminary data showed that the original SH composite prepared here possesses highly attractive properties for applications in areas such as the agriculture field, particularly as a soil conditioner.

Nodulação e crescimento de variedades de soja RR sob aplicação de glyphosate, fluazifop-p-butyl e fomesafen

O objetivo deste trabalho foi avaliar os efeitos causados por aplicações dos herbicidas glyphosate, fluazifop-p-butyl e fomesafen, em diferentes formas de aplicação, sobre a nodulação e o crescimento inicial de duas variedades de soja RR. Os tratamentos foram organizados em arranjo fatorial 6 x 2, no qual foram avaliadas seis formas de aplicação de herbicida (testemunha sem herbicida, aplicação seqüencial de fomesafen/fomesafen, aplicação seqüencial de fomesafen/[fomesafen+fluazifop-p-butyl], fluazifop-p-butyl em aplicação única, aplicação seqüencial de glyphosate/glyphosate e glyphosate em aplicação única) e duas variedades de soja (BRS 245 RR e BRS 247 RR). Com relação à nodulação, a aplicação seqüencial de fomesafen/fomesafen foi a forma mais seletiva. A variedade BRS 245 RR mostrou-se mais tolerante do que a variedade BRS 247 RR às aplicações dos herbicidas. Número e matéria seca de nódulos da variedade BRS 247 RR são reduzidos por aplicações em dose única de fluazifop-p-butyl e glyphosate.

Mycorrhizal Association and Microbial Activity of Soil Cultivated with Cassava After Application of Mesotrione and Fluazifop-p-Butyl

Soil is a very heterogeneous environment that allows the establishment of wide range of microorganisms populations, whose balance is affected by biotic and abiotic factors. This study has aimed to assess the effect of doses of mesotrione and fluazifop-p-butyl herbicides and two assessment periods on microbial activity and biomass of soil cultivated with cassava Cacau-UFV cultivar, besides the root colonization by arbuscular mycorrhizal fungi. Two trials were conducted in a protected environment where was realized post-emergence application of mesotrione in the doses of 72, 108, 144 and 216 g ha-1 and fluazifop-p-butyl in the doses of 100, 150, 200 and 300 g ha-1, besides a control without application. Soil samples were collected for determination of soil respiratory rate (RR), microbial biomass carbon (MBC), metabolic quotient (qCO2), and colonization of roots by arbuscular mycorrhizal fungi at the 30 and 60 days after applications (DAA) of the herbicides. Fluazifop-p-butyl increased the RR, MBC and the percentage of cassava roots colonized by mycorrhizal fungi in the assessment performed at 60 DAA. The larger effects of mesotrione on soil microbial indicators were up to 30 DAA, being the changes minimized at 60 DAA. It is concluded that the herbicides alter the soil microbial indicators, with effects dependent of the product, of dose applied and also of the period of assessment.

Molecular Basis for Resistance to Fluazifop-P-Butyl in Itchgrass (Rottboellia cochinchinensis) from Costa Rica

Rottboellia cochinchinensis is an annual grass weed species known as itchgrass, or "caminadora" in America´s Spanish speaking countries, and has become a major and troublesome weed in several crops. The application of fluazifop-P-butyl at recommended rates (125 g a.i. ha-1) was observed to be failing to control itchgrass in a field in San José, Upala county, Alajuela province, Costa Rica. Plants from the putative resistant R. cochinchinensis population survived fluazifop-P-butyl when treated with 250 g a.i. ha-1 (2X label rate) at the three- to four-leaf stage under greenhouse conditions. PCR amplification and sequencing of partial carboxyl transferase domain (CT) of the acetyl-CoA carboxylase (ACCase) gene were used to determine the molecular mechanism of resistance. A single non-synonymous point mutation from TGG (susceptible plants) to TGC (putative resistant plants) that leads to a Trp-2027-Cys substitution was found. This Trp-2027-Cys mutation is known to confer resistance to all aryloxyphenoxyproprionate (APP) herbicides to which fluazifop-P-butyl belongs. To the best of our knowledge, this is the first report of fluazifop-P-butyl resistance and a mutation at position 2027 for a Costa Rican R. cochinchinensis population.

A study of the thermal decomposition of allyl t-butyl peroxide and 3-hydroperoxy-1-propene (allyl hydroperoxide) in toluene /|nby Krishnankutty Nair V. G. -- 260 St. Catharines [Ont. : s. n.],

Kinetics and product studies of the decompositions of allyl-t-butyl peroxide and 3-hydroperoxy- l-propene (allyl hydroperoxide ) in tolune were investigated. Decompositions of allyl-t-butyl peroxide in toluene at 130-1600 followed first order kinetics with an activation energy of 32.8 K.cals/mol and a log A factor of 13.65. The rates of decomposition were lowered in presence of the radical trap~methyl styrene. By the radical trap method, the induced decomposition at 1300 is shown to be 12.5%. From the yield of 4-phenyl-l,2- epoxy butane the major path of induced decomposition is shown to be via an addition mechanism. On the other hand, di-t-butYl peroxyoxalate induced decomposition of this peroxide at 600 proceeded by an abstraction mechanism. Induced decomposition of peroxides and hydroperoxides containing the allyl system is proposed to occur mainly through an addition mechanism at these higher temperatures. Allyl hydroperoxide in toluene at 165-1850 decomposes following 3/2 order kinetics with an Ea of 30.2 K.cals per mole and log A of 10.6. Enormous production of radicals through chain branching may explain these relatively low values of E and log A. The complexity of the reaction is indicated a by the formation of various products of the decomposition. A study of the radical attack of the hydro peroxide at lower temperatures is suggested as a further work to throw more light on the nature of decomposition of this hydroperoxide.

The kinetics and mechanism of the thermal decomposition of sec-Butyl peroxide in liquid phase /|nby Sandor Szilagyi. -- 260 St. Catharines, Ont. : [s. n.],

Re~tes artd pJ~oducts of tllerma]. d,ecom.position of sec-butyl peroxide at 110 - 150°C i.n four solvents h,ave been determined. The d,ecompos i tion vJas sb.o\'\Tn to be tlnlmolecl.llar wi tho energies of activation in toluene, benzene, and cyclohexane of 36 .7-+ 1.0, 33.2 +- 1..0, 33.t~) +.. 1.0 I'(:cal/mol respectively. The activation energy of thermal decomposition for the d,et.1terated peroxide was found to be 37.2 4:- 1.0 KC8:1/1TIol in toluene. A.bo1J.t 70 - 80/~ ol~ tJJ.e' pl~od.1..1CtS could, be explained by kn01rJ11 reactions of free allcoxy raclicals J and very littJ...e, i.f allY, disPl"Opox~tiol'lation of tll10 sec-butoxy radica.ls in t116 solvent cage could be detected. The oth,er 20 - 30% of the peroxide yielded H2 and metb.:'ll etb..yl 1{etol1e. Tl1.e yield. o:f H2 "'lIas unafJ:'ected by the nature or the viscosity of the solvent, but H2 was not formed when s-t1U202 lrJaS phctolyzed. in tolttene at 35°C nor 'tl!Jrl.en the peroxide 1;'JaS tl1.ermally o..ecoJnposed. in the gas p11ase. ~pC-Dideutero-~-butYlperoxide was prepared and decomposed in toluene at 110 - 150°C. The yield of D2 was about ·•e1ne same 248 the yield. of I{2 from s-Bu202, bU.t th.e rate of decomposition (at 135°C) 1iJas only 1/1.55 as fast. Ivlecl1.anisms fOl') J:1ydrogen produ.ction are discussed, but none satisfactorily explains all the evidence.

Formulation of emulsion systems for the preparation of butyl rubber gloves

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Improved Mechanical Properties of NR/EPDM and NR/Butyl Blends by Precuring EPDM and Butyl

Ethylene-propylene-diene rubber (EPDM) and isobutylene-isoprene rubber (IIR) were compounded, precured to a low degree, and then were blended with natural rubber (NR). The compounding ingredients for NR were then added and the final curing was done. NR/ EPDM and NR/IIR blends, prepared using this method, were found to possess much improved mechanical properties as compared to their conventional counterparts. The optimum precuring crosslink density that has to be given to the EPDM and IIR phases has been determined.

Photophysical and Electrochemical Investigations on Photoconducting Poly(6-tert-butyl-3,4-dihydro-2H- 1,3-benzoxazine)

Poly(6-tert-butyl-3,4-dihydro-2H-1,3-benzoxazine) was synthesized by thermally activated cationic ring opening polymerization. The structure of the polymer was confirmed by spectral and thermal studies. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were estimated using cyclic voltammetry and optical absorption. Modulated photocurrent measurement technique was employed to study the spectral and field dependence of photocurrent. Photocurrent of the order of 1.5 micro A/m2 was obtained for polymer at a biasing electric field of 40 V/mico m.

Selective Methyl Tert-Butyl Ether Synthesis over Metal Exchanged Pillared Clays

Iron and mixed iron aluminium pillared montmorillonites prepared by partial hydrolysis method was subjected to room temperature exchange with transition metals of the first series. The materials exhibit good structural as well as thermal stability. Exchanged metals were found to be present inside the porous network, in the environs of the pillars. Mixed pillaring resulted in the intercalation of Al 13 like polymers in which Al is partially substituted by Fe. The acidic structure was followed by temperature programmed desorption of ammonia and cumene cracking test reaction. Weak and medium sites overshadow the strong sites in all systems. However, exchange with metals increases the number of strong sites. The prepared materials are efficient catalysts for gas phase MTBE synthesis. The catalytic activity can be well correlated with the total amount of weak and medium acid sites.

Optical properties of phthalocyanine molecules in cyano acrylate polymer matrix

Optical absorption and emission spectral studies of various phthalocyanine molecules, viz., LaPc, NdPc, SmPc, EuPc, CuPc and ZnPc in a polymer matrix of cyano acrylate are reported for the first time. All the absorption spectra show an intense B band (Soret) in the UV region followed by a weaker Q band in the visible region. The positions of the Q and B bands are found to have dependence on the metallic substitution. Values of the important spectral parameters, viz., molar extinction coefficient (ϵ), oscillator strength (f), radiative transition rate and decay time of the excited singlet state are also presented and compared with other solid matrices. The recorded fluorescence spectrum shows two broad emission bands in the case of NdPc, whereas for ZnPc only a very weak band is observed. The absence of emission bands for the other metallated phthalocyanines is attributed to increased spin orbit interaction and intersystem crossing.