Synthesis of EPDM-g-MAN by suspension graft copolymerization and its toughening effect on SAN resin

Suspension graft copolymerization of methyl methacrylate and acrylonitrile onto ethylene–propylene–diene terpolymer (EPDM) was carried out under different reaction conditions. A series of graft products of EPDM-graft-methyl methacrylate and acrylonitrile (EPDM-g-MAN), characterized by Fourier-transform infrared spectroscopy, was blended separately with styrene–acrylonitrile (SAN) resin to investigate their toughening effect on SAN matrix. The relationship between the polarity of EPDM-g-MAN and toughness of EPDM-g-MAN/SAN resin blends (AEMS) was evaluated. The compatibility and morphologies of AEMS were probed by dynamic mechanical analysis, transmission electron microscopy, and scanning electron microscopy to determine the toughing mechanism of the blends. Thermogravimetry results showed that the thermal stability of AEMS was enhanced with the incorporation of EPDM-g-MAN graft copolymer.     

Composition and pH dependence on aggregation of SiO2–PVA suspension for the synthesis of porous SiO2–PVA nanocomposite

Porous monolithic SiO₂–poly(vinyl alcohol) (PVA) nanocomposites were fabricated by drying an SiO₂–PVA suspension. Depending on the amount of added PVA and pH value of the suspension, the Brunauer–Emmett–Teller surface areas, total pore volumes, and mean pore radii of the (100 ? x)SiO₂–xPVA (x = 0, 10, 20, 30 wt%) nanocomposites were 102–313 m² g^?1, 0.61–1.42 cm³ g^?1, and 8.1–14.7 nm, respectively. Some cracks were observed in the monolithic SiO₂–PVA nanocomposite, affected by the pore size. To elucidate crack generation, the correlation between the dispersion/aggregation in the SiO₂–PVA suspension and the pore size distribution of the nanocomposite was evaluated in terms of the added PVA amount and pH value. At x = 20 and pH 3, the SiO₂ particles and PVA aggregated in the suspension. The preparation of crack-free monolithic SiO₂–PVA nanocomposites was possible using the aggregated suspension owing to the low capillary force during drying because of the relatively large pores.     

A Novel 3-D Nanoporous Ce(III) Metal-Organic Framework with Terephthalic Acid; Thermal,Topology, Porosity and Structural Studies

This study describes the synthesis, crystal structure, porosity, and thermal stability of a new three-dimensional nano-porous metal-organic framework, [Ce₂(tp)₃(DMF)₂(DMSO)₂]_n, 1, (H₂tp = terephthalic acid, DMF = dimethyl formamid, DMSO = dimethyl sulfoxide). Compound 1 was synthesized by the solvothermal reaction of Ce(NO₃)₃·6H₂O and H₂tp and was then characterized by single-crystal X-ray diffraction and infrared spectroscopy. Structural analysis of 1 showed that Ce(III) ion has coordination number nine in a distorted mono-capped square anti-prismatic geometry. Gas sorption studies revealed a relatively reversible type-I isotherm characteristic of a porous material with surface area, pore volume, and average pore size of 179.4 m² g^?1, 0.73 cm³ g^?1, and 3.8 Å, respectively.     

The efficient removal of dyes over magnetic Ni embedded on mesoporous graphitic carbon material

Magnetically separable Ni embedded on graphitic mesoporous carbon (NMC) material was fabricated through a facile “sol–gel” route using glucose, nickle nitrate, poly(ethylene glycol)–poly(propylene glycol)–poly(ethylene glycol) (P123) and tetraethyl orthosilicate as carbon source, catalyst and magnetic precursor, soft template and porogen. The obtained NMC material exhibited highly graphitic degree with high surface area of 790 m² g^?1, large pore size at 3.9 nm and pore volume of 0.69 cm³ g^?1. The saturation magnetization was enhanced to 6.82 emu g^?1 because of aggregation of magnetic Ni particles to clusters. NMC material showed excellent removal to Rhodamine B and the adsorption capacity reached to 168.1 mg g^?1 within 120 min. NMC material could be easily separated by an external magnet and reused after ethanol extraction.     

Rheological behavior of a LDPE/PS/SBS blending melt

The dynamic rheological behaviors are measured by small amplitude oscillatory shear on a rotational rheometer for a low-density polyethylene (LDPE)/polystyrene (PS)/styrene–butadiene–styrene (SBS) block copolymer blend with the tool of cole–cole plot. The morphology of the blend is measured by scanning electron microscope (SEM) micrograph, the storage moduli–angular frequency (G′–ω) data are fit by the Palierne model, and the relaxation time spectrum is investigated. The storage modulus and loss modulus of the LDPE/PS/SBS blend at low frequency increase when the weight ratio LDPE/PS increases from 10/90, reaches a maximum of 30/70, and drops thereafter. The cole–cole plots of some blends (10/90/3, 70/30/3, 90/10/3 and 100/0/3) have only one main arc due to compatibilizing effect of the SBS, and those of other blends (0/100/3, 30/70/3 and 50/50/3) have a second arc or a long tail besides the main arc probably due to phase separation. The SEM micrographs of the LDPE/PS/SBS = 10/90/3, 30/70/3, 50/50/3 show sea-island, semi-co-continuous and co-continuous structure, respectively. G′–ω curve of two LDPE/PS/SBS = 30/70/3 and 50/50/3 blends shows a power law, and the power index is much lower than one (0.748 and 0.817), respectively, showing a co-continuous morphology also verified by the SEM micrographs. The experimental data of G′–ω curve of the LDPE/PS/SBS blends are fit by Palierne model, the deviation between the fit line and the experimental data increases gradually as the LDPE/PS weight ratio decreases from 90/10 to 10/90. For the LDPE/PS/SBS blends, the weighted relaxation spectra τH (τ)–τ show a main as well as a second arc or tail; the former corresponding to the relaxation of PS phase and the latter corresponding to that of LDPE phase. Due to the compatibilizing effect of SBS the relaxation time and spectrum strength of LDPE/PS = 50/50 (wt) blends are both increased.     

Complete mineralization of the antibiotic amoxicillin by electro-Fenton with a BDD anode

On April 30, 2014, the World Health Organization’s first global report on the presence of antibiotics in waters focused on their negative consequences, which may include the growth of microorganisms with antimicrobial resistance. The β-lactam antibiotic amoxicillin (AMX) is widely used in human and veterinary medicine, and it has been recently detected in sewage treatment plants and effluents. In this paper, the degradation of acidic aqueous solutions of AMX by electro-Fenton process has been studied at constant current. Experiments have been performed in an undivided cell equipped with a carbon-felt cathode and a Pt or boron-doped diamond (BDD) anode. In such systems, the organic molecules are mainly oxidized by hydroxyl radical (^?OH) simultaneously formed on the anode surface from water oxidation as well as in the bulk from Fenton’s reaction between Fe²⁺ catalyst and electrogenerated H₂O₂. The decay and mineralization of AMX was monitored by means of high performance liquid chromatography (HPLC) and TOC measurements. The evolution of the concentration of the final aliphatic carboxylic acids and inorganic ions like ammonium, nitrate and sulfate was assessed by HPLC and ion chromatography, respectively. The effect of the anode material, initial AMX concentration and current density was thoroughly studied. The AMX decay always followed a pseudo-first-order kinetics using either Pt or BDD, and the apparent rate constant increased with applied current. A quicker mineralization was reached with BDD because of the larger production of active ^?OH. The absolute rate constant between hydroxyl radical and AMX determined by the competition kinetics method using p-hydroxybenzoic acid as the reference compound was found to be (2.02 ± 0.01) × 10⁹ M^?1 s^?1.     

Preparation and characterization of equimolar SiO2–Al2O3–TiO2 ternary aerogel beads

Crack-free mesoporous equimolar SiO₂–Al₂O₃–TiO₂ ternary aerogel beads have been synthesized and characterized. Silica sol, alumina sol, and titania sol were synthesized individually to prevent the formation of inhomogeneous structure due to the different hydrolization and polymerization rate of individual precursor. After mixing these three types of acidic sols, SiO₂–Al₂O₃–TiO₂ ternary beads were prepared by the ball dropping method. The ternary aerogel beads were typically mesoporous, showing high surface area (305 m² g^?1), large pore volume (1.32 cm³ g^?1), and high surface acid amount (0.884 mmol NH₃ g^?1). Moreover, the acid sites of the ternary aerogel beads showed higher thermal stability than those of binary aerogel beads. Gradient drying (GD), supercritical drying (SD), ambient drying (AD), extended aging (EA) and hydrophobic modifying drying (HM) have been employed to investigate the effects of drying method on the characteristics of the aerogel beads. The surface areas of the ternary aerogel beads obtained by different drying methods decrease in the sequence EA > HM > GD > SD > AD. The ternary aerogel beads have been characterized by scanning electron microscopy, nitrogen adsorption, X-ray powder diffraction, Fourier-transform infrared spectroscopy (FTIR), solid-state NMR, temperature-programmed desorption measurements, pyridine adsorption FTIR, and differential scanning calorimetry.     

Selected factors influencing neurohormonal regulation of sex pheromone production inHeliothis species

Sex pheromone production and release in females ofHeliothis species exhibit a diel periodicity. Phermone production is controlled by a hormone, the pheromone biosynthesis activating neuropeptide (PBAN). Release of PBAN to activate pheromone production follows a circadian rhythm. InH. zea females, mating terminates pheromone production. An unidentified hemolymph-borne factor is transferred from the male to the female during mating. It is speculated that this factor interacts with the release mechanism of PBAN to prevent further production of the pheromone following mating. Wild females ofH. phloxiphaga (reared from larvae collected in the field) did not produce or release the sex pheromone unless kept in association with the host plant. Pheromone production could be induced in these females by the injection of PBAN. It is suggested that a signal from the host plant is essential to trigger the release of PBAN to induce pheromone production.     

Reversible addition-fragmentation chain transfer polymerization of vinyl acetate and vinyl pivalate in supercritical carbon dioxide

Two highly supercritical CO₂-soluble, poly(vinyl acetate) (PVAc)-based macro-reversible addition-fragmentation chain transfer (RAFT) agents were synthesized. The RAFT agents were used for the first time in RAFT/macromolecular design via the interchange of xanthates (MADIX) and polymerization of vinyl acetate (VAc) and vinyl pivalate (VPi) in supercritical carbon dioxide (scCO₂). A homopolymer PVAc and a block copolymer PVAc-b-PVPi made by RAFT/MADIX polymerization were characterized, and the effects of time and RAFT agents on polymerization were examined. For the 8.4 wt% RAFT agent in VAc, the molecular mass (M _n ) of homopolymer PVAc was 26,000 g mol^?1 and PDI was 1.35. For the copolymerization of VPi using 9.8 wt% PVAc-RAFT agent in VPi for 24 h, the M _n and PDI of PVAc-b-PVPi reached 32,400 g mol^?1 and 1.42, respectively. These results suggest that the polydispersity can be controlled during the clean production of PVAc and PVPi by RAFT/MADIX polymerization in scCO₂.     

Oil absorbency of cellulose/butylmethacrylate graft polymer fibers

Cotton pulp cellulose and butyl methacrylate were used as the main raw materials to synthesize cellulose/butylmethacrylate graft polymer (Cell-g-PBMA) via homogeneous ATRP method, after which the graft polymer was dissolved in N,N-dimethylacetamide to prepare a spinning solution, and the novel oil-absorbent Cell-g-PBMA graft polymer fibers were spun by wet-spinning method. The morphology of the polymer fibers before and after oil absorption was analyzed using a high-powered microscope and scanning electron microscope and the saturated oil absorption rate as well as buoyancy recovery of the fiber products were also studied. The results showed that Cell-g-PBMA polymer fibers had a rough surface and exhibited a void network structure that was specific to oil-absorbent materials. The saturated absorption rates of the Cell-g-PBMA polymer fibers for crude oil, vegetable oil, dichloromethane and diesel were 96.5, 78.7, 38.4, and 27.2 g/g, respectively, which were about 3–6 times that of a commercial polypropylene sorbent. The Cell-g-PBMA fibers also displayed excellent oil/water selectivity and high buoyancy recovery in the clean-up of oil over water. Its excellent oil absorbency demonstrated oil absorbent characteristics of both traditional oil-absorbing materials and synthetic oil-absorbing resins, rendering it an excellent fibrous oil-absorbent material.     

Self-assembled HPW/silica–alumina mesoporous nanocomposite as catalysts for oxidative desulfurization of fuel oil

Mesoporous silica–alumina–polyoxometalate (HPW/SiO₂–Al₂O₃) nanocomposite materials with silica–aluminum molar ratios of 10–80 have been successfully synthesized by evaporation induced self-assembly method with non-ionic surfactant P123 as template agent. The surface areas and pore sizes of the obtained HPW/SiO₂–Al₂O₃ materials are in the range of 509–623 m² g^?1 and 3.6–3.8 nm, respectively, with different silica–aluminum molar ratios. The incorporated polyoxometalate clusters preserve their intact Keggin structure into the mesoporous frameworks. The Py–FTIR investigations indicate that the surface acidity of catalysts gradually increases with an increase in the percentage of aluminium, and the Lewis acidity sites are predominant. The nanocomposites were used as catalysts, and H₂O₂ as oxidant for oxidative desulfurization (ODS) of model fuel, which was composed of benzothiophene (BT), petroleum ether and benzene. The results show that the adsorption capacity and ODS performance of catalysts have close relationship with their surface acidity. An appropriate amount of Lewis acidity sites can contribute to the selective oxidation of the BT due to the preferential adsorption of BT on the catalyst surface, while the Brönsted acidity sites have a negative impact on the selective oxidation of the BT. As a result, the mesoporous HPW/SiO₂–Al₂O₃ with silica–aluminum molar ratio of 50 shows the highest selectivity for BT oxidation in the presence of benzene and has achieved the goal of desulfurization. In addition, the catalyst shows excellent reusing ability, which makes it a promising catalyst in ODS process.     

Unsaturated fatty acids in the postnatally developing rat lung

Fatty acid desaturase activity specific for the C-9 position is present in lung microsomes prepared from rats of all ages. This activity is significantly lower in neonatal rat lung compared with adult lung. A rapid increase in C-9 fatty acid desaturase activity seen at the approximate time of weaning may be related to a decrease in the polyunsaturated fatty acid (PUFA) content of the diet as the rat begins to consume laboratory chow instead of mother's milk. The 900×g supernatant fraction of rat lung parenchymal cell homogenates is capable of incorporating linoleate, linolenate, and arachidonate into both triacylglycerols and phospholipids. Lung tissue from rats less than 20 days old incorporates these PUFA into phospholipids at a greater rate than lung, tissue from adult rats. The incorporation of these PUFA into phospholipids in neonatal lung tissue occured at a greater rate than their incorporation into triacylglycerols. In contrast, lung tissue from adult rats incorporated PUFA into triacylglycerols at a greater rate than into phospholipids. These data show that PUFA, known to be elevated in neonatal rat lungs, are used primarily for phospholipid biosynthesis in neonatal lung tissue whereas in adult lung tissue they are preferentially esterified to glycerol.     

Electrospinning of chitosan/poly(lactic acid-co-glycolic acid)/hydroxyapatite composite nanofibrous mats for tissue engineering applications

Electrospinning, which is a fiber fabrication technique using electrical forces to produce fibers with diameters ranging from nanometers to several micrometers, can be used to prepare materials mimicking the extracellular matrix proteins for potential use as tissue engineering scaffolds. In this study, nanofibrous mats of chitosan (CH) and poly(lactic acid-co-glycolic acid) (PLGA) having fiber diameters between 167 to 525 nm, and containing hydroxyapatite (HAp), were prepared by electrospinning technique. Morphological, chemical, thermal and degradation tests and cell affinity tests were carried out. Chitosan mats were stable in aqueous media and showed degradability in the presence of lysozyme. In PBS solution, PLGA mats disintegrated completely in 2 weeks. Meanwhile, CH-PLGA mats containing equal amounts of both CH and PLGA fibers and CH-PLGA-HAp samples containing 20 % HAp lost 50 and 40 % of their initial weight in 4 weeks, respectively. Cell culture tests showed that all electrospun fibrous mats promoted SaOs-2 cell attachment and proliferation. However, cell proliferation on CH-PLGA-HAp fibrous mats was higher compared to the others after 7 days demonstrating the positive effect of HAp on cell affinity properties compared to pristine CH or PLGA fibrous scaffolds.     

Recovery of N applied as 15N-manure or 15N-gliricidia biomass by maize,cotton and cowpea

Proper management of N applied in fertilizers is important to optimize crop production and to avoid negative environmental impacts. The best way to study N dynamics in the soil plant system is to use fertilizers labeled with ¹⁵N. Recoveries of nitrogen following fertilization with ¹⁵N-labeled goat (Capra hircus L.) manure and gliricidia (Gliricidia sepium Jacq. Walp) biomass were evaluated in a greenhouse experiment with three successive planting cycles of three crops: maize (Zea mays L.), cotton (Gossypium hirsutum L.), and cowpea (Vigna unguiculata (L.) Walp.). Each 1 kg soil pot received 8 g (equivalent to 20 Mg ha^?1) of either manure (12.3 mg g^?1 of N) or gliricidia (37.8 mg g^?1 of N). Plants were harvested 50 days after germination and real (¹⁵N) and apparent recoveries of the applied N were determined. Biomass and N amounts in the cotton and maize crops in all three cycles were higher with gliricidia application than with manure, except for cotton in the first cycle. The biomass of cowpea was also higher with gliricídia in the first and second cycles but the amount of N was significantly higher only in the second cycle. In the first cycle, the largest recoveries of ¹⁵N were obtained with gliricidia, for all three crops, but in the second and third cycles recoveries were greater with manure, so that the real recoveries of gliricidia and manure were similar (cotton, 35 and 37 %; maize, 27 and 26 %; and cowpea, 41 and 38 % of the applied N, respectively). Estimates of apparent recoveries were different from the real ones and therefore inadequate for cotton and cowpea. The fast release of N from gliricidia prunings and, on the other hand, the strong residual effect of goat manure-N to subsequent cropping cycles should be considered by farmers in their fertilization strategies.     

Hot Topics in Silicon Chemistry

The symposium “Silicones and Silicone-Modified Materials VI” was hosted by the American Chemical Society (ACS) during the 243 ^rd National Meeting & Exposition in San Diego, California, USA (March 25 ?29, 2012). At this “Silicones VI” symposium, I circulated a blank notepad and I then asked the members of the audience for responses to the question “What are the three hot topics in silicon chemistry in March 2012?” These responses are given herein along with a brief discussion of how they may guide us in our future teaching, research and service.     

Polymorphism of hydrogenated canola oil

The polymorphism of hydrogenated Canola oil was investigated using X-ray diffraction. The effects of hydrogenation conditions (selective: 200 C; 48 kPa hydrogen pressure, and nonselective: 160 C; 303 kPa) and degree of unsaturation on the transformation β′ → β are discussed. A densitometer was used to follow the changes in the relative density of the characteristic short spacings, in an attempt to present a semiquantitative measure of β′ « β transformation during storage. The samples studied were selectively and nonselectively hydrogenated Canola oils of iodine values (IV) 70 and 60, respectively. Among the 4 samples, the selectively hydrogenated sample with IV 70 was the most stable and the nonselectively hydrogenated sample with IV 60 the least stable.     

Effect of nafion membrane thickness on performance of vanadium redox flow battery

The performance of vanadium redox ow batteries (VRFBs) using different membrane thicknesses was evaluated and compared. The associated experiments were conducted with Nafion® 117 and 212 membranes that have 175 and 50 μm of thickness, respectively. The charge efficiency (CE) and energy efficiency (EE) of VRFB using Nafion® 117 were higher than those of VRFB using Nafion® 212, while power efficiency was vice versa. In terms of amounts of charge and discharge that are measured in different charging current densities, the amounts in VRFB using Nafion® 212 are more than that in VRFB using Nafion® 117. To further characterize the effect of membrane thickness on VRFB performance, electrochemical impedance spectroscopy (EIS) and UV-vis. spectrophotometer (UV-vis) were used. In EIS measurements, VRFB using Nafion® 117 was more stable than that using Nafion® 212, while in UV-vis measurements, vanadium crossover rate of VRFB usingNafion® 212 (0.0125M/hr) was higher than that of VRFB using Nafion® 117 (0.0054 M/hr). These results are attributed to high crossover rate of vanadium ion in VRFB using Nafion® 212. With these results, vanadium crossover plays more dominant role than electrochemical reaction resistance in deciding performance of VRFB in condition of different membranes.     

Lipids in chinese medicine. Characterization of allcis 5,11,14,17-eicosatetraenoic acid inBiota orientalis seed oil and a study of oxo/furanoid esters derived fromBiota oil

The fatty acid composition ofBiota orientalis seed oil consists of palmitic (5.1%), stearic (3.4%), oleic (15.3%), linoleic (25.6%), linolenic (34.7%), C20:3(11c,14c,17c) 4.9%, and C20:4(5c,11c,14c,17c) 10.5%. The unsaturated fatty esters derived fromBiota oil were epoxidized and subsequently treated with NaI-PrI-DMSO. Chromatographic separation of the complex product mixture revealed the presence of C18-oxo, C18-furanoid, and C18-and C20-oxo-furanoid esters. Epoxidation of a pure sample of C20:4(5c,11c,14c,17c) followed by NaI-PrI-DMSO treatment gave a mixture of C20-dioxo-furanoid esters. The positions of the oxo and furanoid groups in the various derivatives were determined by GC/MS analysis.     

Gossypol analysis in cottonseed oil by HPLC

Gossypol in cottonseed oil was selectively separated by the extraction of cottonseed oil with a hexane and N,N dimethyl formamide:water (2∶1, v/v) solvent mixture. After filtration, the extract was injected into the HPLC with the elution time less than 15 min. The spectrophotometric method showed 2 to 5 times higher values of gossypol content in different types of glanded cottonseed oil than did the HPLC method. This is probably due to the gossypol derivatives and coloring interferences reacting with p-anisidine to develop color and increasing the absorbance reading, whereas gossypol was separated and detected in the HPLC method.     

Rapid analysis of dimer acid by HPLC/FID

A method was developed for the rapid analysis of polymerized fatty acids (dimer acid) using normal phase HPLC with a flame ionization detector (FID). The use of analytical scale HPLC with the FID is a significant limprovement over existing methodology for dimer analysis. The HPLC analysis takes only 25 min per sample, with no derivatization required. The FID response is linear for dimer samples from 10% to 90% monomer content. Absolute measurement precision is typically less than 0.5 area percent. Recovery of synthetic dimer blends averaged 102%. Results for the analysis of commercial dimer acid are comparable to those obtained using an HPLC/gravimetric method. The HPLC/FID method is applicable to the analysis of crude dimer as well as the finished dimer product.