Synthesis and structural characterization of block and random low molecular weight copolymers composed of L-lactic acid and isosorbide succinate moieties

Isosorbide succinate moieties were incorporated into poly(L-lactide) (PLLA) backbone in order to obtain a new class of biodegradable polymer with enhanced properties. This paper describes the synthesis and characterization of four types of low molecular weight copolymers. Copolymer I was obtained from monomer mixtures of L-lactide, isosorbide, and succinic anhydride; II from oligo(L-lactide) (PLLA), isosorbide, and succinic anhydride; III from oligo(isosorbide succinate) (PIS) and L-lactide; and IV from transesterification reactions between PLLA and PIS. MALDI-TOFMS and 13C-NMR analyses gave evidence that co-oligomerization was successfully attained in all cases. The data suggested that the product I is a random co-oligomer and the products II-IV are block co-oligomers.Resíduos de succinato de isosorbídeo foram incorporados na cadeia principal de poli(L-lactídeo) (PLLA) visando a obtenção de uma nova classe de polímeros biodegradáveis com propriedades melhoradas. Este artigo descreve a síntese e caracterização de quatro tipos de copolímeros de baixa massa molar. O copolímero I foi obtido da mistura dos monômeros L-lactídeo, isosorbídeo e anidrido succínico; II do oligo(L-lactídeo) (PLLA), isosorbídeo e anidrido succínico; III do oligo(succinato de isosorbídeo) (PIS) e L-lactídeo; e IV de reações de transesterificação entre PLLA e PIS. Análises de MALDI-TOFMS e 13C-NMR apresentaram evidências de que cooligomerização foi alcançada em todos os casos. Os dados sugerem que o produto I é um cooligômero aleatório e que os produtos II-IV são cooligômeros em bloco.CNPqCoordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES)FAPES

Assembling of xyloglucans and lectin onto si wafers and onto amino-terminated surfaces

Immobilization of xyloglucans extracted from Hymenaea coubaril (HXG) and Tamarindus indica seeds (TXG) on Si/SiO2 wafers or amino-terminated wafers from aqueous solution at concentration of 0.5 g L-1 and pH 3.5 has been investigated by means of ellipsometry and atomic force microscopy (AFM) measurements. Experiments were carried out under equilibrium conditions (adsorption) and non-equilibrium conditions (casting). Under equilibrium conditions neither TXG nor HXG chains adsorbed from solution onto Si/SiO2 surfaces, indicating that negatively charged SiO- groups on the surface do not attract XG chains. Casting TXG and HXG solutions onto Si/SiO2 surfaces led to layers (2.4 ± 0.4) nm and (3.8 ± 0.9) nm thick, respectively. TXG and HXG adsorbed onto amino-terminated surfaces forming layers (1.0 ± 0.1) nm and (1.3 ± 0.1) nm thick, respectively. Upon casting solutions of TXG and HXG onto amino-terminated surfaces, aggregates and fibrils appeared more frequently on the surface, increasing the mean thickness and roughness values. Regardless the substrate, HXG chains tended to form thicker layers than TXG chains did. This trend can be explained with basis on the molecular characteristics of HXG, namely, higher molecular weight and persistence length. The adsorption isotherms of concanavalin A (Con A) onto HXG- and TXG-covered amino-terminated wafers presented maximum adsorbed amount of (3.3 ± 0.3) mg m-2. AFM images shown Con A molecules as small entities densely packed on the surface. The presence of fibrils and aggregates was observed only when the TXG and HXG surfaces were prepared by casting. There ConA molecules adsorbed predominantly on regions free of fibrils and aggregates

Ultrathin cellulose ester films: preparation, characterization and protein immobilization

In this study cellulose acetate butyrate (CAB) and carboxymehtylcellulose acetate butyrate (CMCAB) films adsorbed onto silicon wafers were characterized by means of ellipsometry, atomic force microscopy (AFM), sum frequency generation spectroscopy (SFG) and contact angle measurements. The adsorption behavior of lysozyme (LIS) or bovine serum albumin (BSA) onto CAB and CMCAB films was investigated. The amounts of adsorbed LIS or BSA onto CMCAB films were more pronounced than those onto CAB films due to the presence of carboxymethyl group in the CMCAB structure. Besides, the adsorption of BSA molecules on CMCAB films was more favored than that of LIS molecules. Antimicrobial effect of LIS bound to CAB or CMCAB layers was evaluated using Micrococcus luteus as substrate.FAPESPCNPqCoordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES

Competitive adsorption of wellbores corrosion inhibitor onto steel, esmectite and sandstone

A commercial corrosion inhibitor used in petroleum production was characterized by means of infrared spectroscopy and energy dispersive spectroscopy (EDS). Predicting the adsorption behavior of corrosion inhibitor onto steel, sandstone and esmectite is the key to improve working conditions. In this study, the adsorption kinetics of inhibitor formulations in HCl 15% or in Mud Acid (HCl 13,5% and ammonium bifluoride) onto steel, sandstone and esmectite was determined by means of spectrophotometry. Kinetic parameters indicated that adsorption of inhibitor in the presence of bifluoride was favored. Moreover, the adsorption constant rate was the largest when the substrate was esmectite.FAPESPCNP

Macroporous MnO2 electrodes obtained by template assisted electrodeposition for electrochemical capacitors

Macroporous MnO2 electrodes prepared by template-assisted electrodeposition using spherical polystyrene colloidal particles are studied. The wettability of such electrodes by a LiClO4 aqueous electrolyte is measured by the contact angle technique. Cyclic voltammetry experiments are performed in order to evaluate the use of these electrodes for electrochemical capacitor applications. The specific capacity obtained is about 60% higher than that obtained for flat MnO2 surfaces showing that, in spite of the wettability being lower, some penetration of the electrolyte into the pores must occur, increasing the electroactive area with respect to the flat electrode. Furthermore, the macroporous electrode showed excellent electrochemical stability, with neither a capacitance decrease nor a loss of morphology, after 1000 cycles

Basic science232. Certolizumab pegol prevents pro-inflammatory alterations in endothelial cell function

Background: Cardiovascular disease is a major comorbidity of rheumatoid arthritis (RA) and a leading cause of death. Chronic systemic inflammation involving tumour necrosis factor alpha (TNF) could contribute to endothelial activation and atherogenesis. A number of anti-TNF therapies are in current use for the treatment of RA, including certolizumab pegol (CZP), (Cimzia ®; UCB, Belgium). Anti-TNF therapy has been associated with reduced clinical cardiovascular disease risk and ameliorated vascular function in RA patients. However, the specific effects of TNF inhibitors on endothelial cell function are largely unknown. Our aim was to investigate the mechanisms underpinning CZP effects on TNF-activated human endothelial cells. Methods: Human aortic endothelial cells (HAoECs) were cultured in vitro and exposed to a) TNF alone, b) TNF plus CZP, or c) neither agent. Microarray analysis was used to examine the transcriptional profile of cells treated for 6 hrs and quantitative polymerase chain reaction (qPCR) analysed gene expression at 1, 3, 6 and 24 hrs. NF-κB localization and IκB degradation were investigated using immunocytochemistry, high content analysis and western blotting. Flow cytometry was conducted to detect microparticle release from HAoECs. Results: Transcriptional profiling revealed that while TNF alone had strong effects on endothelial gene expression, TNF and CZP in combination produced a global gene expression pattern similar to untreated control. The two most highly up-regulated genes in response to TNF treatment were adhesion molecules E-selectin and VCAM-1 (q 0.2 compared to control; p > 0.05 compared to TNF alone). The NF-κB pathway was confirmed as a downstream target of TNF-induced HAoEC activation, via nuclear translocation of NF-κB and degradation of IκB, effects which were abolished by treatment with CZP. In addition, flow cytometry detected an increased production of endothelial microparticles in TNF-activated HAoECs, which was prevented by treatment with CZP. Conclusions: We have found at a cellular level that a clinically available TNF inhibitor, CZP reduces the expression of adhesion molecule expression, and prevents TNF-induced activation of the NF-κB pathway. Furthermore, CZP prevents the production of microparticles by activated endothelial cells. This could be central to the prevention of inflammatory environments underlying these conditions and measurement of microparticles has potential as a novel prognostic marker for future cardiovascular events in this patient group. Disclosure statement: Y.A. received a research grant from UCB. I.B. received a research grant from UCB. S.H. received a research grant from UCB. All other authors have declared no conflicts of interes

Biomass Enzymatic Hydrolysis

Production of ethanol from biomass fermentation has gained much attention recently. Biomass cellulosic material is first converted into glucose either by chemical or by enzymatic process, and then glucose is fermented to ethanol. Considering the current scenario, where many efforts are devoted for the search of green routes to obtaining ethanol from renewable sources, this review presents the relationship between structure and properties of cellulosic material, pre-treatments and hydrolysis of cellulosic material, and structure and function of cellulase enzyme complex

Effect of humidity and solvent vapor phase on cellulose esters films

In the present study the effect of relative humidity (RH) during spin-coating process on the structural characteristics of cellulose acetate (CA), cellulose acetate phthalate (C-A-P), cellulose acetate butyrate (CAB) and carboxymethyl cellulose acetate butyrate (CMCAB) films was investigated by means of atomic force microscopy (AFM), ellipsometry and contact angle measurements. All polymer solutions were prepared in tetrahydrofuran (THF), which is a good solvent for all cellulose esters, and used for spin-coating at RH of (35 +/- A 5)%, (55 +/- A 5)% or (75 +/- A 5)%. The structural features were correlated with the molecular characteristics of each cellulose ester and with the balance between surface energies of water and THF and interface energy between water and THF. CA, CAB, CMCAB and C-A-P films spin-coated at RH of (55 +/- A 5)% were exposed to THF vapor during 3, 6, 9, 60 and 720 min. The structural changes on the cellulose esters films due to THF vapor exposition were monitored by means of AFM and ellipsometry. THF vapor enabled the mobility of cellulose esters chains, causing considerable changes in the film morphology. In the case of CA films, which are thermodynamically unstable, dewetting was observed after 6 min exposure to THF vapor. On the other hand, porous structures observed for C-A-P, CAB and CMCAB turned smooth and homogeneous after only 3 min exposure to THF vapor.Rede Nanobiotec CAPESRede Nanobiotec CAPESProReitoria de Graduacao (Programa Ensinar com Pesquisa), Universidade de Sao PauloPro-Reitoria de Graduacao (Programa Ensinar com Pesquisa), Universidade de Sao PauloCNPqCNPqFAPESPFAPES