Thermal Degradation and Kinetics of Alginate Polyurethane Hybrid Material Prepared from Alginic Acid as a Polyol

Alginate polyurethane hybrid materials are prepared by varying mole ratio of 2, 4-TDI as a di-isocyanate and alginic acid as a polyol in presence of dimethyl sulfoxide (DMSO) as a solvent. FT-IR and ¹³C one-dimensional (1D) solid state NMR (SSNMR) spectroscopy indicates that alginic acid is converted into alginate-polyurethane hybrid material via urethane linkage. Surface morphology of alginate-polyurethane hybrids changes by varying alginic acid: TDI ratio. The peak at near 221 °C in DSC thermogram of alginic acid (Alg) is shifted to higher temperature in alginate-polyurethane hybrid (Algpu1 and Algpu2). TGA study shows that alginate-polyurethane hybrid prepared using alginic acid: TDI = 1:1 (Algpu2) is more stable than alginic acid: TDI = 1:0.5 (Algpu1) at 300 °C. Kinetic analysis was performed to fit with TGA data, where the entire degradation process has been considered as three consecutive 1st order reactions. This study shows that thermal stability of alginate-polyurethane hybrid material was increased by adjusting mole ratio of 2, 4-TDI and alginic acid.     

N235萃取含盐酸性废水中的盐酸

以N235为萃取剂、甲苯为稀释剂萃取模拟含盐酸性废水(简称废水)中的盐酸。最佳实验条件为:振荡时间20 min,初始废水中盐酸浓度0.75～2.45 mol/L,V(N235):V(N235+甲苯)=0.3～0.7,V(N235+甲苯):V(废水)=0.5～1.0。在初始废水中盐酸浓度为1.00 mol/L、不含无机盐、V(N235):V(N235+甲苯)=0.4、V(N235+甲苯):V(废水)=1.0的条件下,振荡20 min后萃取液中盐酸浓度为0.80 mol/L、n(盐酸):n(N235)=0.88。当废水中氯化钠浓度大于2.0 mol/L时,氯化钠的加入对N235萃取盐酸有促进作用;硫酸钠的加入对N235萃取盐酸具有抑制作用。     

Role of Amino Acids on <Emphasis Type="Italic">In Situ</Emphasis> Photografting of Jute Yarn with 3-(Trimethoxysilyl) Propylmethacrylate

To improve the mechanical performance of natural lignocellulosic jute yarn, grafting with [3-(trimethoxysilyl) propylmethacrylate] (TMSPM) monomer has been performed on in situ UV radiation and optimized the monomer concentration (30%) and irradiation time (30 min). Effect of various amino acids (1%) as additives in TMSPM with photografted jute yarn at optimized system has been studied. The polymer loading (PL) and tensile properties like tensile strength (TS) and elongation at break (Eb) of treated samples were enhanced by incorporation of amino acids and the highest properties (TS = 300% and Eb = 386%) achieved by the sample treated with l-Arginine (Arg) with 32.5% PL value. Weak acid like 3% acetic acid and inorganic acid like 1% sulfuric acid were also incorporated in the optimized system of TMSPM grafting and compared their effect on the tensile properties with amino acid treated samples. Water absorption and weathering resistance of treated and untreated samples were also performed and treated sample showed lesser water uptake as well as less weight loss and mechanical properties as compared to untreated samples.     

A Novel Biodegradable Green Poly(l-Aspartic Acid-Citric Acid) Copolymer for Antimicrobial Applications

Poly (l-aspartic acid-citric acid) green copolymers were developed using thermal polymerization of aspartic acid (ASP) and citric acid (CA) followed by direct bulk melt condensation technique. Antibacterial properties of copolymer of aspartic acid based were investigated as a function of citric acid content. This study is focused on the microorganism inhibition performance of aspartic acid based copolymers. Results showed that inhibition properties increase with increasing citric acid content. Characterization of obtained copolymers was carried out with the help of infrared absorption spectra (FTIR), x-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA). The antibacterial activity of copolymers against bacteria like E-coli, Bacillus and pseudomonas was investigated. The copolymers showed excellent antimicrobial activities against three types of microorganisms. Overall studies indicated that the above copolymers possess a broad wound dressing activity against above three types of bacteria and may be useful as antibacterial agents.     

Improving the two-step remediation process for CCA-treated wood: Part I. Evaluating oxalic acid extraction

In this study, three possible improvements to a remediation process for chromated-copper-arsenate- (CCA) treated wood were evaluated. The process involves two steps: oxalic acid extraction of wood fiber followed by bacterial culture with Bacillus licheniformis CC01. The three potential improvements to the oxalic acid extraction step were (1) reusing oxalic acid for multiple extractions, (2) varying the ratio of oxalic acid to wood, and (3) using a noncommercial source of oxalic acid such as Aspergillus niger, which produces oxalic acid as a metabolic byproduct. Reusing oxalic acid for multiple extractions removed significant amounts of copper, chromium, and arsenic. Increasing the ratio of wood to acid caused a steady decline in metal removal. Aspergillus niger removed moderate amounts of copper, chromium, and arsenic from CCA-treated wood. Although A. niger was effective, culture medium costs are likely to offset any benefits. Repeated extraction with commercial oxalic acid appears to be the most cost-effective method tested for the two-step process.     

New biodegradable polyester-copolymers from commodity chemicals with favorable use properties

Copolyesters composed of aliphatic and aromatic compounds were synthesized by the polycondensation of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, sebacic acid, adipic acid, and terephthalic acid. By applying an appropriate ratio of aliphatic to aromatic acids, the synthesized materials proved to be biodegradable, as was verified by several degradation test methods such as aqueous polymer suspension inoculated by a soil eluate (Sturm test), a soil burial test (at ambient temperature), and a composting simulation test at 60°C. The degradability of the polyester-copolymers (measured as weight loss) was investigated with respect to the aliphatic monomer components and the fraction of terephthalic acid. Excellent biodegradability was observed even for copolymers with a content of terephthalic acid up to 56 mol% (of the acid fraction) and melting points in the range up to 140°C. Degradation by chemical hydrolysis of the polyesters was determined independently and was found to facilitate microbial attack significantly only at higher temperatures. The findings demonstrate that biodegradable polymers with advantageous usage properties can easily be manufactured by conventional techniques from commodity chemicals (adipic acid, terephthalic acid, and ethylene glycol or 1,4-butanediol).Dedicated to Prof. J. Klein's 60th birthday.     

粉煤灰制聚合氯化铝铁和白碳黑新工艺

采用粉煤灰制备聚合氯化铝铁和白碳黑.该法共分一次酸浸、碱溶、焙烧、二次酸浸4个阶段.实验确定的最佳工艺条件为:一次酸浸阶段酸溶温度100℃,碱溶阶段m(氢氧化钠):m(活化高硅渣)=0.6,二次酸浸阶段m(碳酸钠):m(灰渣A)=0.8、盐酸质量分数20%.在此条件下Fe~(3+)和Al~(3+)的总浸出率分别为96.54%和86.67%.主要产品聚合氯化铝铁的质量符合GB15892-2003<水处理剂聚氯化铝>的标准;产品白碳黑的质量符合GBl0517-89<沉淀二氧化硅>的标准.     

Biodegradation of acrylic acid polymers and oligomers by mixed microbial communities in activated sludge

The biodegradability (mineralization to carbon dioxide) of acrylic acid oligomers and polymers was studied in activated sludge obtained from continuous-flow activated sludge (CAS) systems exposed to mixtures of low molecular weight (Mw < 8000) poly(acrylic acid)s and other watesoluble polymers [poly(ethylene glycol)s] in influent wastewater. Dilute preparations of activated sludge from the CAS units were tested for their ability to mineralize acrylic acid monomer and dimer, as well as a series of model acrylic acid oligomers and polymers (Mw 500, 700, 1000, 2000, and 4500), as sole carbon and energy sources. Complete mineralization of acrylic acid monomer and dimer was observed in low-biomass sludge preparations previously exposed to the polymer mixture, based on carbon dioxide production and residual dissolved organic carbon analyses. Extensive (though incomplete) degradation was also observed for the low molecular weight acrylic acid oligomers (Mw 500 and 700), but degradation dropped off sharply for the 1000, 2000, and 4500 Mw polymers. Radiochemical (¹⁴C) data also confirmed the low degradation potential of the 1000, 2000, and 4500 Mw materials. Degradation of two commercial poly(ethylene glycol)s at 1000 and 3400 Mw was complete and comparable to that of the acrylic acid monomer and dimer. Our results indicate that mixed populations of activated sludge microorganisms can extensively metabolize acrylic acid oligomers of seven units or less. Complete mineralization, however, could be confirmed only for the monomer and dimer material, and carbon mass balance data suggested that the true molecular weight cutoff for complete biodegradation was significantly less than the 500–700 Mw range tested.     

壳聚糖复合吸附剂对油的吸附性能

以天然可生物降解的壳聚糖和硬脂酸为原料,通过壳聚糖2位氨基与硬脂酸的羧基相互作用,引入疏水烷基链,制备了疏水的壳聚糖-硬脂酸复合吸附剂(简称复合吸附剂),采用傅立叶红外光谱、X射线衍射对复合吸附剂的结构进行表征,并考察了复合吸附剂对油的回收性能.实验结果表明:壳聚糖和硬脂酸以离子形式结合得到复合吸附剂;当硬脂酸与壳聚糖质量比为0.7时,硬脂酸的结合量最大;复合吸附剂对油的吸附量、保油率、脱附率的顺序分别为花生油(14.93 g/g)>甲基硅油(10.71 g/g)>液体石蜡(9.37 g/g),花生油(94.51%)>液体石蜡(90.74%)>甲基硅油(78.69%),花生油(95.62%)>液体石蜡(93.27%)>甲基硅油(90.73%).     

The basic properties of poly(lactic acid) produced by the direct condensation polymerization of lactic acid

Poly(lactic acids) with high molecular weights have been synthesized by direct condensation polymerization of lactic acid. These polymers have good mechanical properties and can be processed into products such as cups, film, and fiber, which can be used as compostable materials. This polymerization method can be applied to the synthesis of copolymers of lactic acid and other hydroxyacids. The properties of poly(lactic acid) and copolymers synthesized by the direct process are different from those of polymers obtained by the conventional lactide process.     

Isolation and Characterization of a <Emphasis Type="Italic">Burkholderia</Emphasis> sp. USM (JCM15050) Capable of Producing Polyhydroxyalkanoate (PHA) from Triglycerides,Fatty Acids and Glycerols

A consortium of microorganisms from oil polluted wastewater sample was cultivated to promote polyhydroxyalkanoate (PHA) accumulation before subjecting the mixed cultures to sucrose density gradient ultracentrifugation. This resulted in the fractionation of the bacterial cells according to their physical features such as size, morphology and/or densities. An isolate was identified as Burkholderia sp. USM (JCM15050), which was capable of converting palm oil products [crude palm kernel oil (CPKO), palm olein (PO), palm kernel acid oil (PKAO), palm stearin (PS), crude palm oil (CPO), palm acid oil (PAO) and palm fatty acid distillate (PFAD)], fatty acids and various glycerol by-products into poly(3-hydroxybutyrate) [P(3HB)]. Up to 70 and 60 wt% of P(3HB) could be obtained when 0.5%(v/v) CPKO and glycerol was fed, respectively. Among the various fatty acids tested, lauric acid followed by oleic acid and myristic acid gave the best cell growth and PHA accumulation. Compared to Cupriavidus necator H16, the present isolate showed better ability to grow on and produce PHA from various glycerol by-products generated by the palm oil industry. This study demonstrated for the first time an isolate that has the potential to utilize palm oil and glycerol derivatives for the biosynthesis of PHA.     

Capillary electrophoretic study of dibasic acids of different structures: Relation to separation of oxidative intermediates in remediation

Dicarboxylic acids are important in environmental chemistry because they are intermediates in oxidative processes involved in natural remediation and waste management processes such as oxidative detoxification and advanced oxidation. Capillary electrophoresis (CE), a promising technique for separating and analyzing these intermediates, has been used to examine a series of dibasic acids of different structures and conformations. This series includes malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, phthalic acid, and trans, trans-muconic acid. The CE parameters as well as structural variations (molecular structure and molecular isomers, buffer composition, pH, applied voltage, injection mode, current, temperature, and detection wavelength) that affect the separations and analytical results have been examined in this study. Those factors that affect the separation have been delineated. Among these parameters, the pH has been found to be the most important, which affects the double-layer of the capillary wall, the electro-osmotic flow and analyte mobility. The optimum pH for separating these dibasic acids, as well as the other parameters are discussed in detail and related to the development of methods for analyzing oxidation intermediates in oxidative waste management procedures.     

Mechanical Properties with the Functional Group of Additives for Starch/PVA Blend Film

This paper deals with the mechanical properties and degree of swelling (DS) of starch/PVA blend film with the functional groups i.e., hydroxyl and carboxyl group, of additives. Starch/PVA blend films were prepared by using the mixing process. Glycerol (GL) with 3 hydroxyl group, sorbitol (SO) with 6 hydroxyl group, succinic acid (SA) with 2 carboxyl group, malic acid (MA) with 1 hydroxyl and 2 carboxyl group, tartaric acid (TA) with 2 hydroxyl and 2 carboxyl group and citric acid (CA) with 1 hydroxyl and 3 carboxyl group were used as additives. The results of measured tensile strength (TS) and elongation (%E) verified that both hydroxyl and carboxyl group as a functional groups increased the flexibility and strength of the film. Values of DS for GL-added and SA-added films were low. However, DS values of the films added MA, TA or CA with both hydroxyl and carboxyl group were comparatively high. When the film was dried at low temperature, the properties of the films were evidently improved. The reason is probably because the hydrogen bonding was activated at low temperature.     

Oxygen Permeability and Biodegradability of Polyuronic Acids Prepared from Polysaccharides by TEMPO-Mediated Oxidation

Polyuronic acids, i.e., amylouronic acid, cellouronic acid and chitouronic acid, were prepared from starch, cellulose and chitin, respectively, by the 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)-mediated oxidation, and their gas-barrier properties and biodegradability were studied in consideration to use the polyuronic acids as flexible packaging films or coating materials. Cellouronic acid and amylouronic acid had excellent oxygen-barrier properties similar to that of poly(vinyl alcohol) (PVA), while chitouronic acid did not. The regular chemical structures of the former two polyuronic acids with no bulky substituents or adducts may have brought about such high oxygen-barrier levels. An oxidized product prepared form fine microcrystalline cellulose by the TEMPO-mediated oxidation was not completely dissolved in water, but became a paste. However, this paste also formed sufficiently smooth films by coating, and had good gas-barrier property. All polyuronic acids prepared were biodegradable; cellouronic acid and chitouronic acid had high degrees of biodegradability, while amylouronic acid had quite low value. These various characteristics are significant for end use of these new polyuronic acids as gas-barrier materials for biodegradable packaging.     

用低品位磷矿制备生态型磷肥

以低品位磷矿、腐植酸（风化煤）和硫酸为原料，研究了制备有效P2O5转化率高、表观物性好的生态型磷肥生产工艺。研究结果表明：在采用传统方法生产过磷酸钙的过程中加入风化煤可明显改善磷肥的表观物性，提高有效P2O5的转化率。制备生态型磷肥的最佳工艺条件：硫酸质量分数60％、硫酸加入量105％、搅拌转速500r／min、反应时间15min、100g磷矿粉中风化煤加入量为8～12g。     

Organic–Inorganic Hybrid Coatings for the Modification of Barrier Properties of Poly(lactic acid) Films for Food Packaging Applications

Organic–inorganic hybrid coatings based on poly(ε-caprolactone), poly(ethylene oxide) or poly(lactic acid) as organic phase and silica from tetraethoxysilane as inorganic phase were prepared by the sol–gel approach. Coatings were applied onto poly(lactic acid) films for food packaging in order to improve its barrier properties towards oxygen and water vapour. All the prepared coatings were dense, homogeneous layers characterized by a good adhesion to the substrate. The permeance of the coating layers resulted one order of magnitude lower than that of the uncoated poly(lactic acid) (PLA) film. The hydrophilic character of the coating did not permit to gain a significant decrease in the water vapour permeance. The perfect visual transparency of the coatings allows their application without worsening of the esthetical properties of the substrate PLA film.     

Recovery of nickel oxide from spent catalyst

This study investigates the possibility of recovering nickel from the spent catalyst (NiO/Al2O3) resulting from the steam reforming process to produce water gas (H2/H2O) in many industries. In the extraction process, nickel is recovered as sulfate using sulfuric acid as a solvent. The considered parameters affecting nickel recovery were acid concentration, temperature and time of digestion solid:liquid ratio, particle size and stirring rate. Nickel was to be directly recovered as a sulfate salt by direct crystallization method. The conversion was 99% at 50% sulfuric acid concentration, solid: liquid ratio (1:12) by weight, particle size less than 500 micron for more than 5 h and 800 rpm at 100 degrees C.     

Poly(Lactic Acid)-co-Aspartic Acid Copolymers: Possible Utilization in Drug Delivery Systems

The synthesis and characterization of poly(lactic acid)-co-aspartic acid copolymers (PLA-co-Asp) were presented. Subsequently, the synthesized PLA-co-Asp copolymers were tested as biodegradable carriers in drug delivery systems. PLA-co-Asp copolymers were synthesized by solution polycondensation procedure, using different molar ratios PLA/l-aspartic acid (2.33/1, 1/1, 1/2.33), manganese acetate and phosphoric acid as catalysts and N,N′-dimethyl formamide (DMF)/toluene as solvent mixture. The copolymers were characterized by FT-IR and ¹H-NMR spectroscopy, gel permeation chromatography (GPC), DSC and TG-DTG analyses. Diclofenac sodium, a non steroidal anti-inflammatory drug was subsequently loaded into PLA-co-Asp copolymers. The in vitro drug release experiments were done by dialysis of the copolymer/drug systems, in phosphate buffer solution (pH = 7.4, at 37 °C) and monitored by UV spectroscopy.     

Improving Water Resistance of Soy-Based Adhesive by Vegetable Tannin

In this research tannic acid was used to prepare soy-based adhesives for making plywood and fiber board. The different resin formulations were analyzed by Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and its derivative as a function of temperature (DTG) and Fourier Transform Infra-red (FTIR) spectroscopy. The results showed that the addition of tannic acid to soy-based adhesive decreased soy-based adhesive viscosity and its pH. The DSC analysis showed that the denaturation temperature of soy-based adhesives decrease by adding tannic acid. The TGA and DTG curves showed that the thermal degradation of soy flour starts above 146 °C. The FTIR spectroscopy results also showed that the soy flour amino acids appeared to react well with tannic acid. Furthermore, delamination and shear strength test results showed the good water resistance of plywood bonded with soy-based tannic acid-modified adhesive. The mechanical and physical properties such as MOR, MOE, IB, and water resistance of fiberboard were improved, by adding tannic acid to the soy-based adhesive.     

Production of Poly(3-hydroxyalkanoate)s by Pseudomonas putida Cultivated in a Glycerol/Nonanoic Acid-Containing Medium

The biosynthesis of poly(3-hydroxyalkanoate) (PHA) by Pseudomonas putida (JCM6160) cultivated in a medium containing glycerol, nonanoic acid, or a glycerol/nonanoic acid mixture as the sole carbon sources was investigated. The PHA content was ~20 % when glycerol was the carbon source. This relatively low content can be attributed to the glycerol end-cap effect and the absence of enzymes that can directly synthesize PHA from acetyl CoA, which is the major metabolite of glycerol. Fatty acids, containing even numbered carbons, are synthesized from acetyl CoA, and they can be used as substrates for PHA synthesis. However, this process also results in decreasing PHA content as fatty acids are siphoned off into other pathways. However, addition of 5 mM nonanoic acid into a 20 mM glycerol-containing medium dramatically increased the PHA content in P. putida, which was 1.3 times larger than the sum of the values found when glycerol and nonanoic acid were each used as the sole carbon source. The PHA, synthesized in the glycerol/nonanoic acid medium, contains 3-hydroxy alkanoate units that have 5, 6, 7, 8, 9, or 10 carbons. The units that contain the even numbered carbons are derived from fatty acids that were produced from glycerol; whereas, the PHA units with the odd numbered carbons are derived from nonanoic acid. Pentanoate units were also found in the polyester derived from glycerol and nonanoic acid, and must have been synthesized indirectly via β-oxidation of nonanoic acid with the assistance of glycerol because pentanoate units were not found in PHA when P. putida was cultivated in the presence of only nonanoic acid.