Synthesis of magnetic nanocomposite microparticles for binding of chlorinated organics in contaminated water sources

In this work, the development of novel magnetic nanocomposite microparticles (MNMs) via free radical polymerization for their application in the remediation of contaminated water is presented. Acrylated plant-based polyphenols, curcumin multiacrylate (CMA) and quercetin multiacrylate (QMA), were incorporated as functional monomers to create high affinity binding sites for the capture of polychlorinated biphenyls (PCBs), as a model pollutant. The MNMs were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, dynamic light scattering, and UV–visible spectroscopy. The affinity of these novel materials for PCB 126 was evaluated and fitted to the nonlinear Langmuir model to determine binding affinities (K_D). The results suggest the presence of the polyphenolic moieties enhances the binding affinity for PCB 126, with K_D values comparable to that of antibodies. This demonstrates that these nanocomposite materials have promising potential as environmental remediation adsorbents for harmful contaminants.     

Influence of HMTA ligand in MMA AGET ATRP emulsion polymerization

Interactions of hexamethylenetetramine ligand in atom transfer radical polymerization initiated by activator generated by electron transfer were studied. Polymerization of methyl methacrylate was done using two-step experimental procedure in 2 L emulsion batch reactor at 50, 60, and 80°C. The selection of reactant ratios was quite challenging for a reactor of this size. Replicate runs were conducted for data reproducibility purpose. Gravimetry method and gel permeation chromatography were used to determine monomer conversion, Mn, and PDI of polymer samples. PMMA produced was also characterized by means of dynamic light scattering, Fourier-transform infrared spectroscopy and nuclear Magnetic Resonance spectroscopy. Results showed high monomer conversion up to 93% and Mn ranging 243–274 kg/mol with PDI from 1.45 to 1.60. Besides, combining HMTA with sodium dodecyl sulfate, an anionic surfactant, a well-controlled polymer with a lower Mn of 201 kg/mol and PDI of 1.56 was obtained in 3 hr reaction time.     

Synthesis,characterization and rheological properties of multiblock associative copolymers by RAFT technique

Polymer Bulletin - Preparation of associating multiblock copolymer electrolytes mediated by radical addition–fragmentation chain transfer (RAFT) technique has been evaluated and reported in...     

Interpolymer radical coupling: A toolbox complementary to controlled radical polymerization

The current review focuses on the relevance and practical benefit of interpolymer radical coupling methods. The latter are developing rapidly and constitute a perfectly complementary macromolecular engineering toolbox to the controlled radical polymerization techniques (CRP). Indeed, all structures formed by CRP are likely to be prone to radical coupling reactions, which multiply the available synthetic possibilities. Basically, the coupling systems can be divided in two main categories. The first one, including the atom transfer radical coupling (ATRC), silane radical atom abstraction (SRAA) and cobalt-mediated radical coupling (CMRC), relies on the recombination of macroradicals produced from a dormant species. The second one, including atom transfer nitroxide radical coupling (ATNRC), single electron transfer nitroxide radical coupling (SETNRC), enhanced spin capturing polymerization (ESCP) and nitrone/nitroso mediated radical coupling (NMRC), makes use of a radical scavenger in order to promote the conjugation of the polymer chains. More than a compilation of macromolecular engineering achievements, the present review additionally aims to emphasize the particularities, synthetic potential and present limitations of each system.     

Novel bis(methylimidazolium)alkane bolaamphiphiles as templates for supermicroporous and mesoporous silicas

A series of bis-cationic bolaamphiphiles were synthesized containing N-methylimidazolium head-groups, separated by alkyl chains of 12, 16 and 24 methylene units. Their critical micelle concentrations were determined with subsequent flooding experiments revealing the tendency for the formation of hexagonal mesophases at high surfactant concentrations. The surfactants were employed as templates for silica formation, at ca. four times their critical micelle concentrations, permitting super-microporous and nanoparticulate mesoporous silicas to be prepared. Silica surface areas ranged from 500 to 1000 m² g⁻¹, and pore diameters (D_TEM) from 10 to 22 Å. Analysis of the materials by small angle X-ray diffraction indicated that, in the case of the template possessing 24 methylene units, the silica obtained exhibited a 2D hexagonal pore arrangement.     

Gallium(III) triflate: an efficient and a sustainable Lewis acid catalyst for organic synthetic transformations

Green chemical processes play a crucial role in sustainable development, and efficient recyclable catalysts that can be conveniently applied in various chemical reactions are the key elements for the development of sustainable synthetic processes. Many organic transformations rely on Lewis and Br?nsted acid catalysts, and such molecules have been widely studied in organic synthesis. Over the years, researchers have looked for Lewis acid catalysts that provide high selectivity and high turnover frequency but are also stable in aqueous media and recoverable. Since the first preparation of trifluoromethanesulfonic acid by Hazeldine (triflic acid, HOTf), researchers have synthesized and used numerous metal triflates in a variety of organic reactions. Even though the rare earth metal triflates have played a major role in these studies, the majority of rare earth triflates lack one or more of the primary properties of sustainable catalysts: low cost and easy availability of the metals, easy preparation of triflates, aqueous/thermal stability, recyclability, and catalytic efficiency. In this Account, we describe the synthetic applications of Ga(OTf)(3) and its advantages over similar catalysts. Ga(OTf)(3) can be conveniently prepared from gallium metal or gallium chloride in excess of trifluoromethanesulfonic acid (triflic acid) under reflux. Among many Lewis acid catalysts recently studied, Ga(OTf)(3) is water tolerant and soluble and requires very low catalyst loading to drive various acid-catalyzed reactions including Friedel-Crafts alkylation, hydroxyalkylation, and acylation selectively and efficiently. In many reactions Ga(OTf)(3) demonstrated high chemo- and regioselectivity, high yields, excellent stability, and recyclability. We successfully synthesized many biologically active heterocycles and their fluoroanalogs under mild conditions. Many challenging reactions such as the ketonic Strecker reactions proceed efficiently via Ga(OTf)(3) catalysis. Because it is stable in water, this catalyst provides the opportunity to study substrates and develop new synthetic protocols in aqueous media, significantly reducing the production of hazardous waste from organic solvents and toxic catalyst systems.     

Effect of betaine supplementation on cycling sprint performance

Purpose

To examine the effect of betaine supplementation on cycling sprint performance.

Methods

Sixteen recreationally active subjects (7 females and 9 males) completed three sprint tests, each consisting of four 12 sec efforts against a resistance equal to 5.5% of body weight; efforts were separated by 2.5 min of cycling at zero resistance. Test one established baseline; test two and three were preceded by seven days of daily consumption of 591 ml of a carbohydrate-electrolyte beverage as a placebo or a carbohydrate-electrolyte beverage containing 0.42% betaine (approximately 2.5 grams of betaine a day); half the beverage was consumed in the morning and the other half in the afternoon. We used a double blind random order cross-over design; there was a 3 wk washout between trials two and three. Average and maximum peak and mean power were analyzed with one-way repeated measures ANOVA and, where indicated, a Student Newman-Keuls.

Results

Compared to baseline, betaine ingestion increased average peak power (6.4%; p < 0.001), maximum peak power (5.7%; p < 0.001), average mean power (5.4%; p = 0.004), and maximum mean power (4.4%; p = 0.004) for all subjects combined. Compared to placebo, betaine ingestion significantly increased average peak power (3.4%; p = 0.026), maximum peak power max (3.8%; p = 0.007), average mean power (3.3%; p = 0.034), and maximum mean power (3.5%; p = 0.011) for all subjects combined. There were no differences between the placebo and baseline trials.

Conclusions

One week of betaine ingestion improved cycling sprint power in recreationally active males and females.     

Food group intake patterns and nutrient intake vary across low-income Hispanic and African American preschool children in Atlanta: a cross sectional study

ABSTRACT: BACKGROUND: The food group intake patterns of low income Hispanic and African American preschool children are not well documented. The aim of this study was to perform a food group intake analysis of low income minority preschool children and evaluate how macronutrient and micronutrient intake compares to Dietary Reference Intakes (DRI). METHODS: A cross sectional study design using three-day food diaries analyzed by dietary analysis software (Nutrient Database System for Research) was used. Children were recruited from well-child clinics at Children's Healthcare of Atlanta at Hughes Spalding and North Dekalb Grady Satellite Clinic, Atlanta, GA. Low-income, African American and Hispanic preschool age children (n = 291) were enrolled. A total of 105 completed the 3-day food diaries were returned and analyzed. Chi-squared tests were used to assess demographic variables. The mean percentage of intake per day of specific food groups and sub-groups were obtained (servings of given food group/total daily servings). Food intake data and proportion of children meeting DRIs for macro- and micronutrients were stratified by race/ethnicity, nutritional status, and caloric intake, and were compared using t-tests. Regression models controlling for age, BMI and sex were obtained to assess the effect of total caloric intake upon the proportional intake of each studied food group. RESULTS: The mean age of African American children was 2.24 [PLUS-MINUS SIGN] 1.07 years and Hispanic children 2.84 [PLUS-MINUS SIGN] 1.12 years. African Americans consumed more kcal/kg/day than Hispanics (124.7 [PLUS-MINUS SIGN] 51 vs. 96.9 [PLUS-MINUS SIGN] 33, p < 0.05). Hispanics consumed more fruits (22.0 [PLUS-MINUS SIGN] 10.7% vs. 14.7 [PLUS-MINUS SIGN] 13.7%, p < 0.05), while African Americans consumed more grains (25.7 [PLUS-MINUS SIGN] 7.8% vs. 18.1 [PLUS-MINUS SIGN] 6.4%, p < 0.05), meats (20.7 [PLUS-MINUS SIGN] 9.0% vs. 15.4 [PLUS-MINUS SIGN] 6.1%, p < 0.05), fats (9.8 [PLUS-MINUS SIGN] 5.4% vs. 7.0 [PLUS-MINUS SIGN] 5.8%, p < 0.05), sweet drinks (58.7 [PLUS-MINUS SIGN] 17.1% vs. 41.3 [PLUS-MINUS SIGN] 14.8%, p < 0.05) and low-fat dairy products (39.5 [PLUS-MINUS SIGN] 19.3% vs. 28.9 [PLUS-MINUS SIGN] 12.6%, p < 0.05). Among Hispanics, the proportional intake of fruits, fats and grains varied by total caloric intake, while no difference by total caloric intake was found for the dietary patterns of African Americans. Micronutrient intake also differed significantly between African American and Hispanic children. CONCLUSIONS: Food group intake patterns among low-income children differ by ethnic group. There is a need for more research to guide program design and target nutritional interventions for this population.     

Cloning and heterologous expression of three type II PKS gene clusters from Streptomyces bottropensis

Mensacarcin is a potent cytotoxic agent isolated from Streptomyces bottropensis. It possesses a high content of oxygen atoms and two epoxide groups, and shows cytostatic and cytotoxic activity comparable to that of doxorubicin, a widely used drug for antitumor therapy. Another natural compound, rishirilide A, was also isolated from the fermentation broth of S. bottropensis. Screening a cosmid library of S. bottropensis with minimal PKS-gene-specific primers revealed the presence of three different type II polyketide synthase (PKS) gene clusters in this strain: the msn cluster (mensacarcin biosynthesis), the rsl cluster (rishirilide biosynthesis), and the mec cluster (putative spore pigment biosynthesis). Interestingly, luciferase-like oxygenases, which are very rare in Streptomyces species, are enriched in both the msn cluster and the rsl cluster. Three cosmids, cos2 (containing the major part of the msn cluster), cos3 (harboring the mec cluster), and cos4 (spanning probably the whole rsl cluster) were introduced into the general heterologous host Streptomyces albus by intergeneric conjugation. Expression of cos2 and cos4 in S. albus led to the production of didesmethylmensacarcin (DDMM, a precursor of mensacarcin) and the production of rishirilide A and B (a precursor of rishirilide A), respectively. However, no product was detected from the expression of cos3. In addition, based on the results of isotope-feeding experiments in S. bottropensis, a putative biosynthesis pathway for mensacarcin is proposed.     

Design of novel FN3 domains with high stability by a consensus sequence approach

The use of consensus design to produce stable proteins has been applied to numerous structures and classes of proteins. Here, we describe the engineering of novel FN3 domains from two different proteins, namely human fibronectin and human tenascin-C, as potential alternative scaffold biotherapeutics. The resulting FN3 domains were found to be robustly expressed in Escherichia coli, soluble and highly stable, with melting temperatures of 89 and 78°C, respectively. X-ray crystallography was used to confirm that the consensus approach led to a structure consistent with the FN3 design despite having only low-sequence identity to natural FN3 domains. The ability of the Tenascin consensus domain to withstand mutations in the loop regions connecting the β-strands was investigated using alanine scanning mutagenesis demonstrating the potential for randomization in these regions. Finally, rational design was used to produce point mutations that significantly increase the stability of one of the consensus domains. Together our data suggest that consensus FN3 domains have potential utility as alternative scaffold therapeutics.