Initiation system effects in the cationic copolymerization of tetrahydrofuran (THF)

Summary Macromonomeric peroxy initiator, poly tetrahydrofuran (poly-THF=inimer) were synthesized via cationic polymerization of THF by the mono- (t-BuBP) and tetra-bromo methyl benzoyl peroxides (BDBP)/ZnCl₂ initiating system. The macromonomers were characterized by ¹H-NMR, IR, and GPC techniques. Methyl methacrylate (MMA) polymerization initiated by poly-THF inimers at 80°C and different times in bulk gave crosslinked poly-THF-b-polymethyl methacrylate block copolymers. Swelling ratios of the crosslinked block copolymers obtained by taking in same amounts of poly-THF inimer and MMA monomer in CHCl₃ were decreased versus time. It was compared the results obtained from t-BuBP-, BDBP-ZnCl₂ initiating systems with t-BuBP-, BDBP-AgSbF₆ initiating systems for THF monomer. Poly(THF-b-MMA) crosslinked block copolymers containing undecomposed peroxide groups initiated the thermal polymerization of styrene, S, were used to obtain poly(THF-b-MM_A-b-S) crosslinked multicomponent copolymers at 90°C. The crosslinked multi component copolymers were investigated sol-gel analysis and swelling ratios in CHCl₃. "Active" poly(THF-b-MM_A) having peroxygen group were used in the free radical coupling reaction of poly butadien (Poly Bd). Poly(THF-b-MM_A)-polybutadien crosslinked blend soluble graft copolymers were obtained. Received: 31 July 2001/Revised version: 16 June 2002/ Accepted: 5 July 2002     

Molecular Epidemiology of Enteroaggregative Escherichia coli (EAEC) Isolates of Hospitalized Children from Bolivia Reveal High Heterogeneity and Multidrug-Resistance

Enteroaggregative Escherichia coli (EAEC) is an emerging pathogen frequently associated with acute diarrhea in children and travelers to endemic regions. EAEC was found the most prevalent bacterial diarrheal pathogen from hospitalized Bolivian children less than five years of age with acute diarrhea from 2007 to 2010. Here, we further characterized the epidemiology of EAEC infection, virulence genes, and antimicrobial susceptibility of EAEC isolated from 414 diarrheal and 74 non-diarrheal cases. EAEC isolates were collected and subjected to a PCR-based virulence gene screening of seven virulence genes and a phenotypic resistance test to nine different antimicrobials. Our results showed that atypical EAEC (a-EAEC, AggR-negative) was significantly associated with diarrhea (OR, 1.62, 95% CI, 1.25 to 2.09, p < 0.001) in contrast to typical EAEC (t-EAEC, AggR-positive). EAEC infection was most prevalent among children between 7–12 months of age. The number of cases exhibited a biannual cycle with a major peak during the transition from warm to cold (April–June). Both typical and a-EAEC infections were graded as equally severe; however, t-EAEC harbored more virulence genes. aap, irp2 and pic were the most prevalent genes. Surprisingly, we detected 60% and 52.6% of multidrug resistance (MDR) EAEC among diarrheal and non-diarrheal cases. Resistance to ampicillin, sulfonamides, and tetracyclines was most common, being the corresponding antibiotics, the ones that are frequently used in Bolivia. Our work is the first study that provides comprehensive information on the high heterogenicity of virulence genes in t-EAEC and a- EAEC and the large prevalence of MDR EAEC in Bolivia.     

Electron beam penetration of poly (methyl methacrylate)/colemanite composite irradiated at low earth orbit space radiation environment

Poly (methyl methacrylate) modification by colemanite (CMT) addition has ensured beta shielding improvement. This study has connected with space environmental utilization with Kibo Japanese Experiment Module on International Space Station at low earth orbit. Space environment experiment was performed by using Kibo Experiment Handrail Attachment Mechanism–ExHAM. The changes in beta transmission of the composite were examined (by Sr-90 radioisotope) before and after space environmental utilization and details on beta penetration capacity was examined to protect the equipment (used in aviation and aerospace industries) from space radiation. Beta attenuation variations have indicated composite densification with beta attenuation enhancement after CMT addition.     

Antimicrobial Effects of Wine: Separating the Role of Polyphenols,pH, Ethanol,and Other Wine Components

Abstract: While the antimicrobial effectiveness of wine is well documented, relative contributions of the wine components to its antimicrobial activity is controversial. To separate the role of wine phenolics, ethanol, and pH from other wine constituents, the antimicrobial effects of intact wine were compared to that of phenols-stripped wine, dealcoholized wine, ethanol, and low pH applied separately and in combination, against 2 common foodborne pathogens, Salmonella enterica serovar Enteritidis and Escherichia coli. All samples were biochemically characterized with respect to their total phenolics and resveratrol content, antioxidant capacity, ethanol content, and pH. Antioxidative activity of the samples corresponded to their total phenolics content. Except for respective controls, pH and ethanol content were similar in all samples. The order of antibacterial activity of the samples was: intact wine > phenols-stripped wine > dealcoholized wine > combination of ethanol and low pH > low pH > ethanol. Separate application of ethanol or low pH showed negligible antibacterial activity while their combination showed synergistic effect. Antibacterial activity of the samples could not be related to their total phenolics and resveratrol content, antioxidant capacity, ethanol content, or pH. Our study indicates that antimicrobial activity of complex solutions such as intact wine cannot be exclusively attributed to its phenolic or nonphenolic constituents, nor can the antimicrobial activity of wine be predicted on the basis of its particular components.     

Conjugates of poly(N‐isopropyl acrylamide‐co‐acrylic acid) with alanine monopeptide,dipeptide, and tripeptide

A random copolymer of N‐isopropyl acrylamide (NIPAAm) and acrylic acid (AAc) with an AAc content of 3.1 ± 0.19 mmol of carboxylic acid groups per gram of the copolymer and with a number‐average molecular weight of 1400 was synthesized by free‐radical polymerization with 2,2′‐azoisobutyronitrile in dimethylformamide. Then, monopeptide, dipeptide, and tripeptide (i.e., alanine) conjugates of this copolymer were prepared with their carboxyl‐end‐protected (with methyl ester hydrochloride) form of alanine, with a water‐soluble carbodiimide. Of the carboxylic acids, 93, 69, and 57% were conjugated (loaded) with alanine at the monopeptide, dipeptide, and tripeptide conjugation steps, respectively. The chemical structures of the copolymer and conjugates were analyzed by Fourier transform infrared and ¹H‐NMR, which revealed the conjugate formation. Amino acid conjugation caused significant decreases in the lower critical solution temperatures (LCST) of the copolymer, especially at pH 7.4. The LCST values of the dipeptide and tripeptide conjugates of poly(NIPAAm‐co‐AAc) at both pH 4.0 and 7.4 shifted to significantly higher temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2012–2019, 2003     

Stabilization of Polymer‐Hydrogel Capsules via Thiol–Disulfide Exchange

Polymer hydrogels are used in diverse biomedical applications including drug delivery and tissue engineering. Among different chemical linkages, the natural and reversible thiol–disulfide interconversion is extensively explored to stabilize hydrogels. The creation of macro‐, micro‐, and nanoscale disulfide‐stabilized hydrogels commonly relies on the use of oxidizing agents that may have a detrimental effect on encapsulated cargo. Herein an oxidization‐free approach to create disulfide‐stabilized polymer hydrogels via a thiol–disulfide exchange reaction is reported. In particular, thiolated poly(methacrylic acid) is used and the conditions of polymer crosslinking in solution and on colloidal porous and solid microparticles are established. In the latter case, removal of the core particles yields stable, hollow, disulfide‐crosslinked hydrogel capsules. Further, a procedure is developed to achieve efficient disulfide crosslinking of multilayered polymer films to obtain stable, liposome‐loaded polymer‐hydrogel capsules that contain functional enzymatic cargo within the liposomal subcompartments. This approach is envisaged to facilitate the development of biomedical applications of hydrogels, specifically those including fragile cargo.     

Photon transmission method for studying film formation from polstyrene latexes with different molecular weights

A photon‐transmission method was used to probe the evolution of transparency during film formation from polystyrene (PS) particles with different molecular weights. The latex films were formed at room temperature from the PS particles having two different average molecular weights and annealed at elevated temperatures in various time intervals above the glass transition (T_g). Onset temperatures (T_H) at given times (τ_H) for the optical clarity of films formed from low (LM) and high molecular (HM) weight PS particles were used to calculate the healing activation energies for the minor chains and found to be 22.0 ± 0.5 and 27.0 ± 0.6 kcal/mol, respectively. The increase in the transmitted photon intensity, I_tr, above the T_H was attributed to increase in the number of interfaces that disappeared. The Prager–Tirrell (PT) model was employed to interpret the increase in crossing density at the junction surface. The backbone activation energies (ΔE) were measured and found to be 127.8 ± 2.5 kcal/mol for a diffusing polymer chain across the junction surface for LM and HM latex films. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 866–874, 2000     

RAFT polymerization and thiol-ene modification of 2-vinyloxyethyl methacrylate: Towards functional branched polymers

A vinyl functional polymer, viz, poly(vinyloxyethyl methacrylate) (poly(VEMA) was synthesized by the RAFT polymerization of an asymmetric divinyl monomer, VEMA. This polymer, with pendant vinyloxyl groups, was subsequently reacted with three thiol compounds; 2-mercaptoethanol, cysteamine and 3-mercaptoproponic acid via the thiol-ene reactions. The resulting branched polymers contained hydroxyl, amino and carboxylic acid functionalities suitable for further reactions and conjugations.     

Ultrasonography measurement of intrabdominal visceral fat in obese men. Association with alterations in serum lipids and insulinemia

Abdominal obesity and specifically intrabdominal adiposity leads to increase in cardiometabolic risk factors (CMR), independently of body mass index (BMI). In order to examine CMR factors associated with the presence of visceral fat (VF) in individuals with different degrees of overweight/obesity, 154 men, 20 to 60 years of age, attending a at an Industrial Clinic in Venezuela, were evaluated. Ultrasound was used to establish the presence and amount of VF. As expected, VF values were higher as the BMI increased. It was observed that VF was associated positive and significantly with age, abdominal circumference and the degree of insulin resistance (HOMA-IR) in subjects with normal weight as well as in those with overweight and obesity. However, BMI was correlated with VF only in those with normal weight or overweight. In the obese a positive correlation was observed between VF with glycemia and triglycerides, while insulin was correlated with VF only in the subjects with normal weight. Based on the ROC curves, and taking as cut-off point for VF a value of 6 cm, it was possible to predict the presence of hyperglycemia with a 58.6% of sensitivity and 77% of specificity, presence of insulin resistance with 54 % of sensitivity and 78 % specificity, hypertriglyceridemia with 39% of sensitivity and 78% specificity and low HDLc with 45% sensitivity and 77% specificity. The area under the curve for the ROC analysis was greater for visceral fat compared with abdominal circumference for hyperglicemia (0.727 vs. 0.693, p < 0.05) and hypertrigliceridemia (0.678 vs. 0.621, p < 0.05) while the opposite was observed for HOMA-IR (0.74 vs. 0.788, p < 0.05) and for low HDL-c (0.651 vs. 0.668, p < 0.05). We conclude that ultrasound measure of VF, was better in predicting hyperglycemia and hypertriglyceridemia, while abdominal circumference was better predicting insulin resistance and low HDLc and could be useful in the preventive evaluation of individuals at risk for diabetes or cardiovascular disease.