Eumelanin for nature‐inspired UV‐absorption enhancement of plastics

In the human body, the black‐brown biopigment eumelanin blocks harmful ultraviolet (UV) radiation. In the plastics industry, additives are often added to polymers to increase their UV‐absorption properties. We herein report an assessment of the biopigment eumelanin as a nature‐inspired additive for plastics to enhance their UV absorption. Since eumelanin is produced by natural sources and is nontoxic, it is an interesting candidate in the field of sustainable plastic additives. In this work, the eumelanin‐containing films of commercial ethylene–vinyl acetate copolymer, a plastic used for packaging applications, were obtained by melt compounding and compression molding. The biopigment dispersion in the films was improved by means of the melanin free acid treatment. It was observed that eumelanin amounts as low as 0.8 wt% caused an increase of the UV absorption, up to one order of magnitude in the UVA range. We also evaluated the effect of eumelanin on the thermal stability and photostability of the films: the biopigment proved to be double‐edged, working both as UV‐absorption enhancer and photo‐prooxidant, as thermogravimetric analysis and infrared spectroscopy revealed. © 2019 Society of Chemical Industry     

Effects of diet type and supplementation of glucosamine, chondroitin, and MSM on body composition, functional status, and markers of health in women with knee osteoarthritis initiating a resistance-based exercise and weight loss program

Background

The purpose of this study was to determine whether sedentary obese women with knee OA initiating an exercise and weight loss program may experience more beneficial changes in body composition, functional capacity, and/or markers of health following a higher protein diet compared to a higher carbohydrate diet with or without GCM supplementation.

Methods

Thirty sedentary women (54 ± 9 yrs, 163 ± 6 cm, 88.6 ± 13 kg, 46.1 ± 3% fat, 33.3 ± 5 kg/m²) with clinically diagnosed knee OA participated in a 14-week exercise and weight loss program. Participants followed an isoenergenic low fat higher carbohydrate (HC) or higher protein (HP) diet while participating in a supervised 30-minute circuit resistance-training program three times per week for 14-weeks. In a randomized and double blind manner, participants ingested supplements containing 1,500 mg/d of glucosamine (as d-glucosamine HCL), 1,200 mg/d of chondroitin sulfate (from chondroitin sulfate sodium), and 900 mg/d of methylsulfonylmethane or a placebo. At 0, 10, and 14-weeks, participants completed a battery of assessments. Data were analyzed by MANOVA with repeated measures.

Results

Participants in both groups experienced significant reductions in body mass (-2.4 ± 3%), fat mass (-6.0 ± 6%), and body fat (-3.5 ± 4%) with no significant changes in fat free mass or resting energy expenditure. Perception of knee pain (-49 ± 39%) and knee stiffness (-42 ± 37%) was decreased while maximal strength (12%), muscular endurance (20%), balance indices (7% to 20%), lipid levels (-8% to -12%), homeostasis model assessment for estimating insulin resistance (-17%), leptin (-30%), and measures of physical functioning (59%), vitality (120%), and social function (66%) were improved in both groups with no differences among groups. Functional aerobic capacity was increased to a greater degree for those in the HP and GCM groups while there were some trends suggesting that supplementation affected perceptions of knee pain (p < 0.08).

Conclusions

Circuit style resistance-training and weight loss improved functional capacity in women with knee OA. The type of diet and dietary supplementation of GCM provided marginal additive benefits.

Trial Registration

ClinicalTrials.gov: NCT01271218     

Separation of polyolefins based on comonomer content using high‐temperature gradient adsorption liquid chromatography with a graphitic carbon column

This report describes the application of a recently developed polyolefin characterization tool based upon gradient adsorption high‐temperature liquid chromatography (HT‐LC) using a graphitic carbon stationary phase to polyolefin homopolymer and previously unreported copolymer systems. Polyolefin‐based materials find utility in a broad range of applications and are differentiated by parameters such as molecular weight and comonomer content. Polymer comonomer distribution is commonly determined by crystallinity‐based separations (ATREF, CRYSTAF). These techniques, however, are time consuming. In addition, some semicrystalline polymers undergo cocrystallization, impacting the techniques' universal utility. Adsorption‐based HT‐LC can ideally overcome the limitations of crystallinity‐based separations, shedding new light on the composition of randomly‐polymerized polyolefins. In this report the basic separation capability of the adsorption HT‐LC technique, using a graphitic carbon column, is demonstrated for poly (ethylene‐co‐octene) and poly(ethylene‐co‐propylene) systems and compared with select precipitation/redissolution HT‐LC and ATREF results. Select results in this paper are also compared and contrasted to other recent publications on similar separations of polyolefins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal Stability, Phase Evolution, and Crystallization in Si-B-C-N Ceramics Derived from a Polyborosilazane Precursor

Amorphous Si-B-C-N ceramic powder samples obtained by thermolysis of boron-modified polysilazane, {B[C₂H₄Si(H)NH]₃} _n , were isothermally annealed at different temperatures (1400–1800°C) and hold times (3, 10, 30, and 100 h). A qualitative and semiquantitative analysis of the crystallization behavior of the materials was performed using X-ray diffraction (XRD). The phase evolution was additionally followed by ¹¹B and ²⁹Si MAS NMR as well as by FT-IR spectroscopy in transmission and diffuse reflection (DRIFTS) modes. Bulk chemical analyses of selected samples were performed to determine changes in the chemistry/phase composition of the materials. It was observed that silicon carbide is the first phase to nucleate around 1400–1500°C, whereas silicon nitride nucleates at and above 1700°C. Crystallization accelerates with increasing annealing temperature and proceeds with increasing annealing time. Furthermore, the surface area of the powders strongly influences the thermal stability of silicon nitride and thus controls overall chemical and phase composition of the materials on thermal treatment.     

Crystallization of Polymer-Derived Silicon Carbonitride at 1873 K under Nitrogen Overpressure

The chemical stability of an amorphous silicon carbonitride ceramic, having the composition 0.57SiC·0.43Si₃N₄·0.49C is studied as a function of nitrogen overpressure at 1873 K. The ceramic suffers a weight loss at p _N2 < 3.5 bar (1 bar = 100 kPa), does not show a weight change from 3.5 to 11 bar, and gains weight above 11 bar. The structure of the ceramic changes with pressure: it is crystalline from 1 to 6 bar, amorphous at ∼10 bar, and is crystalline above ∼10 bar. The weight-loss transition, at 3.5 bar, is in excellent agreement with the prediction from thermodynamic analysis when the activities of carbon, SiC, and Si₃N₄ are set equal to those of the crystalline forms; this implies that the material crystallizes before decomposition. The amorphous to crystalline transition that occurs at ∼10 bar, and which is accompanied by weight gain, is likely to have taken place by a different mechanism. A nucleation and growth reaction with the atmospheric nitrogen is proposed as the likely mechanism. The supersaturation required to nucleate α-Si₃N₄ crystals is calculated to be 30 kJ/mol.     

CuI and H2O2 Inactivate and FeII Inhibits [Fe]‐Hydrogenase at Very Low Concentrations

[Fe]‐Hydrogenase (Hmd) catalyzes reversible hydride transfer from H₂. It harbors an iron‐guanylylpyridinol as a cofactor with an Fe^II that is ligated to one thiolate, two COs, one acyl‐C, one pyridinol‐N, and solvent. Here, we report that Cu^I and H₂O₂ inactivate Hmd (half‐maximal rates at 1 μM Cu^I and 20 μM H₂O₂) and that Fe^II inhibits the enzyme with very high affinity (K_i=40 nM ). Infrared and EPR studies together with competitive inhibition studies with isocyanide indicated that Cu^I exerts its inhibitory effect most probably by binding to the active site iron‐thiolate ligand. Using the same methods, it was found that H₂O₂ binds to the active‐site iron at the solvent‐binding site and oxidizes Fe^II to Fe^III. Also it was shown that Fe^II reversibly binds away from the active site iron, with binding being competitive to the organic hydride acceptor; this inhibition is specific for Fe^II and is reminiscent of that for the [FeFe]‐hydrogenase second iron, which specifically interacts with H₂.     

Synthesis of random or tapered solution styrene–butadiene copolymers in the presence of sodium dodecylbenzene sulfonate as a polar modifier

Random or tapered solution styrene–butadiene copolymer (SSBR) is very difficult to prepare in an isothermal batch process without the use of polar modifiers because of the diverse reactivity ratios of the styrene and the butadiene in hydrocarbon solvents. In the presence of polar modifiers, the random SSBR can be synthesized by anionic living polymerization with the variety of microstructures, which results in the change of glass transition temperature (T_g). This article will discuss the use of sodium dodecylbenzene sulfonate as a polar modifier in isothermal batch process that controls the microstructure of the SSBR resulting in a random as well as tapered SSBR with low T_g (?67°C to ?80°C). The T_g of SSBR was controlled by the styrene content rather than the microstructure of polybutadiene. Physical properties of SSBR compounding were discussed for tire tread applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of Ultrahigh-Temperature Si–B–C–N Ceramic from Polymeric Waste Gas

A "green" route to ultrahigh-temperature Si–B–C–N ceramic from vacuum-degassing waste gas of polyborosilazane {B[C₂H₄Si(CH₃)NH]₃} _n (T2-1) has been developed. After gas-to-gel transformation, an amorphous ceramic Si_5.3B_1.0C₁₉N_3.7 was derived from the gel by dehydrocoupling and polymer-to-ceramic transformation. The ceramic started to form a nanostructure at 1700°C and resisted thermal degradation up to 2200°C in argon. This suggests that vacuum-degassing waste gases of polymer precursors may be perfect raw materials for various advanced ceramics.     

Obesity: Prevalence,Theories, Medical Consequences,Management, and Research Directions

Obesity and its associated disorders are a growing epidemic across the world. Many genetic, physiological, and behavioral factors play a role in the etiology of obesity. Diet and exercise are known to play a valuable role in the treatment and prevention of obesity and associated disorders such as hypertension, heart disease, and diabetes. Therefore, the purpose of this review is to examine the prevalence, etiology, consequences, and treatment of obesity.     

Biflavonoid-Induced Disruption of Hydrogen Bonds Leads to Amyloid-β Disaggregation

Deposition of amyloid β (Aβ) fibrils in the brain is a key pathologic hallmark of Alzheimer’s disease. A class of polyphenolic biflavonoids is known to have anti-amyloidogenic effects by inhibiting aggregation of Aβ and promoting disaggregation of Aβ fibrils. In the present study, we further sought to investigate the structural basis of the Aβ disaggregating activity of biflavonoids and their interactions at the atomic level. A thioflavin T (ThT) fluorescence assay revealed that amentoflavone-type biflavonoids promote disaggregation of Aβ fibrils with varying potency due to specific structural differences. The computational analysis herein provides the first atomistic details for the mechanism of Aβ disaggregation by biflavonoids. Molecular docking analysis showed that biflavonoids preferentially bind to the aromatic-rich, partially ordered N-termini of Aβ fibril via the π–π interactions. Moreover, docking scores correlate well with the ThT EC₅₀ values. Molecular dynamic simulations revealed that biflavonoids decrease the content of β-sheet in Aβ fibril in a structure-dependent manner. Hydrogen bond analysis further supported that the substitution of hydroxyl groups capable of hydrogen bond formation at two positions on the biflavonoid scaffold leads to significantly disaggregation of Aβ fibrils. Taken together, our data indicate that biflavonoids promote disaggregation of Aβ fibrils due to their ability to disrupt the fibril structure, suggesting biflavonoids as a lead class of compounds to develop a therapeutic agent for Alzheimer’s disease.