Synthesis and characterization of highly flexible thermoplastic films from cyanoethylated corn distillers dried grains with solubles

Corn distillers dried grains with solubles (DDGS) can be made into highly flexible thermoplastic films without the need for plasticizers. DDGS is an abundantly available coproduct of ethanol production that is inexpensive ($80-130/ton) compared to most of the polymers used for thermoplastic applications. In this research, oil-and-zein-free DDGS was cyanoethylated using acrylonitrile, and cyanoethylation conditions were optimized to obtain high percent weight gain of up to 42%. Cyanoethylated DDGS was characterized using (1)H NMR, FTIR, DSC, and TGA. Cyanoethylated DDGS was compression molded into thermoplastic films, and the tensile properties of the films were studied. It was found that DDGS films with elongation as high as 38% and strength of 14 MPa could be obtained without the use of any plasticizers. Alternatively, films with strength as high as 651 MPa but with relatively low elongation (2.5%) were obtained by varying the extent of cyanoethylation. This research showed that cyanoethylation could be a viable approach to develop biothermoplastics from biopolymers for applications such as packing films, extrudates, and resins for composites.     

Graft polymerization of native chicken feathers for thermoplastic applications

Inexpensive and biodegradable thermoplastics were developed through graft polymerization of native chicken feather with methyl acrylate as a potential substitute for petroleum products. Poultry feathers are available in large quantities at a low price. However, natural chicken feathers have poor thermoplasticity, cannot be used to develop thermoplastic products, have very limited industrial applications, and are often considered as solid wastes. In this research, the effects of graft polymerization conditions, such as molar ratio of NaHSO(3) to K(2)S(2)O(8), initiator and monomer concentrations, pH, temperature and time of polymerization, on grafting parameters, that is, the conversion of monomer to polymer, grafting percentage, and grafting efficiency were evaluated. Methyl acrylate was found to be successfully grafted onto functional groups on the surfaces of the chicken feathers, and optimal graft polymerization conditions were also obtained. The feather-g-poly(methyl acrylate) developed showed good thermoplasticity, and feather films had substantially higher tensile properties than soy protein isolate and starch acetate films.     

Acetylation of soybean lecithin and identification of components for solubility in supercritical carbon dioxide

There is a growing interest to develop environmentally friendly surfactants for utilization with supercritical carbon dioxide (scCO2), which is a "green" solvent with many industrial applications. The goal of the present work was to separate the commonly used soybean lecithin into a phospholipid-rich fraction, acetylate this fraction, and then test its solubility in scCO2 to gauge its suitability as a surfactant for potential scCO2-based applications. Soybean lecithin was first purified by fractionation using acetone and ethanol and then acetylated with acetic anhydride. The acetylated lecithin was further purified by fractionation with acetone to separate the acetylated fraction from the nonacetylated fraction. High-performance liquid chromatography and electrospray ionization mass spectrometry were utilized to characterize these fractions. The various acetylated phospholipid fractions were then tested for solubility in scCO2 under various pressures and temperatures using both a cloud-point and a Fourier transform infrared apparatus. Acetylation was found to increase the solubility of the phospholipids in scCO2, and N-acetylated phosphatidylethanolamine (NAc-PE) was found to be the most soluble component of the acetylated phospholipids.     

Extraction, characterization of components, and potential thermoplastic applications of camelina meal grafted with vinyl monomers

Camelina meal contains oil, proteins, and carbohydrates that can be used to develop value-added bioproducts. In addition to containing valuable polymers, coproducts generated during the production of biofuels are inexpensive and renewable. Camelina is a preferred oilseed crop for biodiesel production because camelina is easier to grow and provides better yields. In this research, the components in camelina meal were extracted and studied for their composition, structure, and properties. The potential of using the camelina meal to develop thermoplastics was also studied by grafting various vinyl monomers. Oil (19%) extracted from camelina meal could be useful for food and fuel applications, and proteins and cellulose in camelina meal could be useful in the development of films, fibers, and thermoplastics. Thermoplastic films developed from grafted camelina meal had excellent wet tensile properties, unlike thermoplastics developed from other biopolymers. Camelina meal grafted with butylmethacrylate (BMA) had high dry and wet tensile strengths of 53.7 and 17.3 MPa, respectively.     

热塑性辐照玉米淀粉薄膜的制备及表征

为了提高热塑性淀粉基薄膜的力学性能,采用0、10、20、30、40、50 kGy 6个剂量的~(60)Co-γ射线对玉米淀粉进行辐照处理,研究辐照对玉米淀粉结构、颗粒尺寸的影响;并以辐照玉米淀粉为原材料,采用挤出造粒、熔融吹塑法制备热塑性辐照玉米淀粉薄膜,研究辐照剂量对热塑性薄膜力学性能、表面形貌的影响。结果表明,~(60)Co-γ射线能够有效破坏玉米淀粉分子内、分子间氢键,降低玉米淀粉的刚性;能够有效减小玉米淀粉的颗粒尺寸,增加玉米淀粉的加工流动性。随着辐照剂量的增加,热塑性辐照玉米淀粉薄膜的力学性能不断增加;未熔融颗粒不断减少,表面形貌更加均匀、平整。综合考虑热塑性辐照玉米淀粉薄膜的力学性能和钴源能耗,40kGy剂量辐照的玉米淀粉制备的热塑性淀粉基降解薄膜更具有实用价值。本研究结果为辐照玉米淀粉制造热塑性降解薄膜提供了理论依据和实际参考。     

Biological activity of acetylated phenolic compounds

In recent years an effort has been made to isolate and identify biologically active compounds that are included in the Mediterranean diet. The existence of naturally occurring acetylated phenolics, as well as studies with synthetic ones, provide evidence that acetyl groups could be correlated with their biological activity. Platelet activating factor (PAF) is implicated in atherosclerosis, whereas its inhibitors seem to play a protective role against cardiovascular disease. The aim of this study was to examine the biological activity of resveratrol and tyrosol and their acetylated derivatives as inhibitors of PAF-induced washed rabbit platelet aggregation. Acetylation of resveratrol and tyrosol was performed, and separation was achieved by HPLC. Acetylated derivatives were identified by negative mass spectrometry. The data showed that tyrosol and its monoacetylated derivatives act as PAF inhibitors, whereas diacetylated derivatives induce platelet aggregation. Resveratrol and its mono- and triacetylated derivatives exert similar inhibitory activity, whereas the diacetylated ones are more potent inhibitors. In conclusion, acetylated phenolics exert the same or even higher antithrombotic activity compared to the biological activity of the initial one.     

Antimicrobial and physicochemical properties of chitosan-HPMC-based films

To prepare composite films from biopolymers with anti-listerial activity and moisture barrier properties, the antimicrobial efficiency of chitosan-hydroxy propyl methyl cellulose (HPMC) films, chitosan-HPMC films associated with lipid, and chitosan-HPMC films chemically modified by cross-linking were evaluated. In addition, the physicochemical properties of composite films were evaluated to determine their potential for food applications. The incorporation of stearic acid into the composite chitosan-HPMC film formulation decreased water sensitivity such as initial solubility in water and water drop angle. Thus, cross-linking of composite chitosan-HPMC, using citric acid as the cross-linking agent, led to a 40% reduction in solubility in water. The water vapor transfer rate of HPMC film, approximately 270 g x m(-2) x day(-1) x atm(-1), was improved by incorporating chitosan and was further reduced 40% by the addition of stearic acid and/or cross-linking. Anti-listerial activity of films was determined on solid medium by a numeration technique. Chitosan-HPMC-based films, with and without stearic acid, inhibited the growth of Listeria monocytogenes completely. On the other hand, a loss of antimicrobial activity after chemical cross-linking modification was observed. FTIR and 13C NMR analyses were then conducted in order to study a potential chemical modification of biopolymers such as a chemical reaction with the amino group of chitosan. To complete the study, the mechanical properties of composite films were determined from tensile strength assays.     

Occurrence of naturally acetylated lignin units

This work examines the occurrence of native acetylated lignin in a large set of vascular plants, including both angiosperms and gymnosperms, by a modification of the so-called Derivatization Followed by Reductive Cleavage (DFRC) method. Acetylated lignin units were found in the milled wood lignins of all angiosperms selected for this study, including mono- and eudicotyledons, but were absent in the gymnosperms analyzed. In some plants (e.g., abaca, sisal, kenaf, or hornbeam), lignin acetylation occurred at a very high extent, exceeding 45% of the uncondensed (alkyl-aryl ether linked) syringyl lignin units. Acetylation was observed exclusively at the gamma-carbon of the lignin side chain and predominantly on syringyl units, although a predominance of acetylated guaiacyl over syringyl units was observed in some plants. In all cases, acetylation appears to occur at the monomer stage, and sinapyl and coniferyl acetates seem to behave as real lignin monomers participating in lignification.     

Partially carboxymethylated feather keratins. 1. Properties in aqueous systems

Feather keratins were extracted from chicken feathers with an aqueous solution of urea and 2-mercaptoethanol. The keratin solution obtained was dialyzed to remove the reagents. Upon dialysis, extensive protein aggregation occurred. To obtain stable solutions or dispersions in water, cysteine residues were modified prior to dialysis with iodoacetamide, iodoacetic acid, or bromosuccinic acid, thereby blocking free thiol groups and introducing hydrophilic groups. For the development of biodegradable materials with good mechanical properties from these biopolymers, disulfide bonds between the keratin molecules are needed. Therefore, cysteine residues were only partially modified by using different reagent/cysteine molar ratios. The reaction rate constants of iodoacetate with glutathione and 2-mercaptoethanol were successfully used to predict the degree of modification of keratin cysteine. It was shown that, for carboxymethylated keratin, fewer aggregates were formed for higher degrees of cysteine modification, while more protein was present as oligomers. Aggregates and oligomers were stabilized through intermolecular disulfide bonds.     

Effect of Temperature on Moisture Barrier Efficiency of Monoglyceride Edible Films in Cereal‐Based Composite Foods

The effects of temperature on moisture transfer within a composite food consisting of a sponge cake (SC) separated from a high moisture content agar gel (AG) by an acetylated monoglyceride (AMG1 and AMG2) film were investigated through moisture content profile experiments. A diffusion model was successfully used to predict moisture transfer within various composite foods (AG/SC, AG/AMG1/SC, and AG/AMG2/SC). The barrier efficiencies of the two hydrophobic films studied were reduced by temperature increase due to activation of diffusivity and equilibrium water sorption. Despite the low melting point of highly acetylated monoglyceride films, their barrier efficiency appeared to be less sensitive to temperature than monoglyceride films with a lower degree of acetylation. Consequently, in poor storage temperature conditions, these latter monoglyceride films seemed to be more effective in enhancing the shelf‐life of the composite food studied here.     

Infrared spectroscopic investigations of humic substances and their metal complexes

A study has been made on the infrared spectra of lowland peats and purified humic, hymatomelanic and fulvic acids, as well as their acetylated derivatives and metal complexes. Extraction and purification may modify humic acids of untreated peats only to a small extent. Acetylation of fulvic and humic acids with acetic acid anhydride resulted mainly in the reaction of phenolic hydroxyl and quinone groups. Similarities of the spectra of the individual humic substances point to similar structures, differing only in the number of functional groups and the degree of aggregation. Metals are bound by humic substances mainly in metalcarboxylate bonds. The degree to which these bonds are ionic or covalent can be determined by the antisymmetric carboxylate stretching frequencies.     

Effect of Modified Oat Starch and Protein on Batter Properties and Quality of Cake

Starch and protein separated from oat were chemically modified using cross‐linking and acetylation protocols for starch, and deamidation and succinylation for protein isolate. Cross‐linking decreased swelling power of starch, whereas syneresis increased, but cross‐linking does not have a significant effect on gelatinization temperature. Acetylation increased swelling power, but gelatinization temperature and syneresis diminished. Deamidation and succinylation increased nitrogen solubility index, emulsion activity, foaming capacity, and water and oil binding capacity. Emulsion stability did not change with deamidation and it diminished with succinylation, while foaming stability decreased with both treatments. Acetylated starch and two types of modified proteins were substituted for 5, 10, 15, and 20% of oat flour to bake cake samples and then physical properties of the cakes were measured. Acetylated starch increased batter viscosity, cake volume, and whiteness of cake crust. Increased level of deamidated protein produced cakes with lower batter viscosity, higher volume, and darker color (increase in redness). Application of higher levels of succinylated protein led to higher batter viscosity and lightness, and lower cake volume. Therefore, substitution of deamidated protein and acetylated starch can improve cake properties.     

Development of an iron chelating polyethylene film for active packaging applications

Metal-promoted oxidation reactions are a major cause of food quality deterioration. Active packaging offers novel approaches to controlling such oxidation for the purpose of extending shelf life. Herein, we report modification of the surface of polyethylene (PE) films to possess metal chelating activity. Metal chelating carboxylic acids were introduced to the film surface using cross-linking agents [polyethylenimine (PEI) or ethylenediamine (ED)] to increase the number of available carboxylic acids. ATR-FTIR, contact angle, dye assay, and iron chelating assay were used to characterize changes in surface chemistry after each functionalization step. The chelator poly(acrylic acid) (PAA) was attached to the surface at a density of 9.12 ± 0.71 nmol carboxyl groups/cm2, and exhibited an iron chelating activity. The results indicate that PAA-modified PE films might have a higher affinity to Fe3? than Fe2? with the optimum binding pH at 5.0. Such inexpensive active packaging materials are promising in food industry for the preservation of liquid and semiliquid food products and have application in heavy metal chelation therapy for biomedical materials as well.     

Partially carboxymethylated feather keratins. 2. Thermal and mechanical properties of films

Free cysteine thiol groups of keratin extracted from chicken feathers were partially carboxymethylated with iodoacetic acid (25-76% cysteine modification). Stable dispersions were used for the preparation of films by solution casting. Glycerol was used as a plasticizer (0.05-0.47 g/g of keratin), and films were stored at a constant relative humidity (20, 30, 50, 70, or 90%). The degree of crystallinity in the films was higher when more cysteine residues were carboxymethylated. The films displayed an optimum in mechanical properties at approximately 50% cysteine carboxymethylation. The tensile strength at this optimum was 25 MPa, the E modulus, 350 MPa, and the elongation at break, 50%. Probably, this optimum was the result of both a decreasing amount of disulfide bonds and an increasing degree of crystallinity for higher degrees of cysteine modification. The influences of a higher amount of glycerol and of different storage conditions on the mechanical properties of films from keratin with a defined degree of cysteine modification were also investigated.     

玉米秸秆液化制备生物高聚物材料的研究(英)

该研究旨在探讨低温生物质液化技术及液化产物应用的可能性。以玉米秸秆为原料在酸性、常压条件下快速液化成多羟基化合物，再以多羟基化合物为原料合成一系列的聚合材料。采用不同的有机溶剂，在稀硫酸的催化作用下，对不同的温度下生物质的液化效果进行研究。同时探讨了液化有机溶剂同生物质物料的混合比率对液化过程的影响。试验表明，碳酸乙烯酯比乙烯醇具有较高的液化率。优化试验结果表明，在较佳的液化效果下， 有机溶剂同玉米秆的混合比率为3∶1，反应温度160℃，稀硫酸浓度3%，反应时间2.5 h。液化产物经稀释、调节pH值、过滤、臭氧氧化一系列过程的处理后得到具有高活性多羟基聚合物。阐述了以多羟基聚合物制备各种生物聚合物材料如聚酯薄膜、聚胺酯泡沫和颗粒板的方法。聚酯薄膜是多羟基化合物上的羟基和多元酸上的羧基通过酯化反应形成的；聚胺酯泡沫通过多羟基化合物上的羟基和二异氰酸酯反应形成。研究表明以多羟基化合物和多元酸（酐）形成的聚酯型胶粘剂适合于制造颗粒板。     

Widening the problem of lead poisoning to a South-American top scavenger: Lead concentrations in feathers of wild Andean condors

Lead poisoning is not a new threat for wild birds, but it is now playing an important role in shaping raptor populations. Studies have been focused mainly on Europe, North-America, and Japan, but little is known about the situation in South-America. Lead is a serious threat for wildlife, especially for long-lived species. Nevertheless, no information is available for wild Andean condor (Vultur gryphus) populations. This species, which lives throughout the Andes Mountains, is endangered mainly in the north though it is having problems throughout its distribution. We evaluated lead exposure in the Andean condor by a non-destructive method using feathers. We determined lead concentration from 152 feathers, collected in 15 communal roosts distributed throughout almost all condor’s range in Patagonia (ca. 1500 km north–south). We also looked for the origin of this lead through the analysis of lead isotope composition of feathers and ammunition. We present here the first reference data on lead concentration for a raptor population from Argentina. Lead concentrations were generally low, however, some individuals had concentrations several times above the overall mean (up to 21 μg/g). Our results suggest that lead might come from a mix of two types of ammunition sources, one used for big game and another for hare hunting. Andean condors are at the top of the food chain, thus all the other medium-to-large sized scavengers and predators from this area can be also exposed to this threat. We highlight the need to change hunting policies in Argentina, and in other South-American countries, including the banning of lead ammunitions to protect carnivores consuming hunted animals.     

Antioxidant activity and diffusion of catechin and epicatechin from antioxidant active films made of poly(L-lactic acid)

Active membranes and food packaging containing antioxidants like catechin and epicatechin, combined with the use of materials made of biopolymers obtained from renewable sources, could create a novel alternative to reduce oxidation in food, pharmaceutical, and cosmetic products. Poly(94% L-lactic acid) films containing 1.28% catechin and 1.50% epicatechin were extruded in a pilot plant-scale extrusion machine. The diffusion kinetics of catechin and epicatechin into 95% ethanol at 20, 30, 40, and 50 °C and 50% ethanol at 40 °C displayed Fickian release behavior and diffusion coefficients between 0.5 and 50 × 10(-11) cm(2)/s. According to the Arrhenius equation, the energy of activation for the diffusion of catechin and epicatechin in the films was 110.43 and 98.92 kJ/mol, respectively. The antioxidant activity of the films was measured in methanol extracts containing 46.42 μg/mL of catechin and 57.52 μg/mL of epicatechin as 32.90 and 36.68% of scavenging the 2,2-diphenyl-1-picrylhydrazyl radical, respectively.     

Alkaline Amendment for the Enhancement of Compost Degradation for Polylactic Acid Biopolymer Products

This research evaluates the addition of alkaline amendments to enhance the degradation of polylactic acid polymers (PLA) in compost conditions. The use of compostable biopolymers is increasing in part because they are advertised as compostable. However, PLA degrades slowly compared to the organic wastes in compost and even when processed in commercial composting facilities may not fully break down. This results in the accumulation of biopolymers in compost facilities and increased difficulty in identifying and removing contamination from traditional plastics. Alkaline amendments were used to accelerate the degradation of two PLA products in compost conditions. Six flasks containing food scraps, compost inoculant, and an alkaline amendment were set up as bioreactors with half containing clear PLA and the others including opaque PLA. The six bioreactors were incubated for 22 days. The mass loss and final visual inspection, including microscopy, showed increased degradation within the bioreactors containing the alkaline treatments. These results show that the addition of alkaline amendment to composting systems may enable more effective processing of biopolymers, expanding the range and quantity of wastes that can be processes. The enhanced degradation of biopolymers in compost may enable greater diversion rates for institutions and cities by enabling the acceptance of biopolymers and any mixed organics stream which includes biopolymers wastes.     

Avian Urine: Its Potential as a Non-Invasive Biomonitor of Environmental Metal Exposure in Birds

Current non-invasive biomonitoring techniques to measure heavy metal exposure in free ranging birds using eggs, feathers and guano are problematic because essential metals copper (Cu) and zinc (Zn) deposited in eggs and feathers are under physiological control, feathers accumulate metals from surface contamination and guano may contain faecal metals of mixed bioavailability. This paper reports a new technique of measuring lead (Pb), Cu and Zn in avian urate spheres (AUS), the solid component of avian urine. These metal levels in AUS (theoretically representing the level of metal taken into the bloodstream, i.e. bioavailable to birds) were compared with levels in eggs (yolk and shell), feathers and whole guano from chickens (Gallus gallus domesticus) exposed to a heavy metal-contaminated soil (an allotment soil containing Pb 555?mg?kg^?1 dry mass (dm), Cu 273?mg?kg^?1?dm and Zn 827?mg?kg^?1?dm). The median metal levels (n?=?2) in AUS from chickens exposed to this contaminated soil were Pb 208???g?g^?1 uric acid, Cu 66???g?g^?1 uric acid and Zn: 526???g?g^?1 uric acid. Lead concentrations in egg yolk and shell samples (n?=?3) were below the limit of detection (<2?mg?kg^?1), while Cu and Zn were only consistently detected in the yolk, with median values of 3 and 70?mg?kg^?1 (dm), respectively, restricting the usefulness of eggs as a biomonitor. Feathers (n?=?4) had median Pb, Cu and Zn levels respectively of 15, 10 and 140?mg?kg^?1 (dm), while whole guano samples (n?=?6) were 140, 70 and 230?mg?kg^?1 (dm). Control samples were collected from another chicken flock; however, because they had no access to soil and their diet was significantly higher in Cu and Zn, no meaningful comparison was possible. Six months after site remediation, by top soil replacement, the exposed chickens had median Pb, Cu and Zn levels respectively in whole guano (n?=?6) of 30, 20 and 103?mg?kg^?1 (dm) and in AUS (n?=?4) of 147, 16 and 85???g?g^?1 uric acid. We suggest the persistent high Pb level in AUS was a consequence of bone mobilised for egg production, releasing chronically sequestered Pb deposits into the bloodstream. In contrast, AUS levels of Cu and Zn (metals under homeostatic control and sparingly stored) had declined, reflecting the lower current exposure. However because pre- and post-remediation samples were measured using different methods carried out at different laboratories, such comparisons should be guarded. The present study showed that metals can be measured in AUS, but no assessment could be made of availability or uptake to the birds because tissue and blood samples were not concomitantly analysed. A major short coming of the study was the inappropriate control group, having no access to uncontaminated soil and being fed a different diet to the exposed birds. Furthermore guano and urine analysis should have been carried out on samples from individual birds, so biological (rather than just technical) variation of metal levels could have been determined. Future studies into using AUS for biomonitoring environmental heavy metals must resolve such experimental design issues.     

Properties and Microstructure of Zein Sheets Plasticized with Palmitic and Stearic Acids

Interest in biodegradable materials for packaging and agricultural uses has grown in recent years. Plant proteins have been proposed as inexpensive, renewable, and abundant feedstock. Corn zein was investigated based on value-added considerations and on the unique thermoplastic and hydrophobic properties of zein. Films prepared from zein are known to be tough and resistant, but also hard and brittle, thus requiring the addition of plasticizers to improve flexibility. The objectives of this research were to study the tensile properties, water absorption, and microstructure of zein sheets plasticized with palmitic and stearic acids. Both palmitic and stearic acids showed similar effects as plasticizers of zein. Tensile strength of zein sheets increased with the addition of low levels of plasticizers. However, beyond a critical point, tensile strength decreased with further addition of fatty acids. Water absorption decreased continuously with increasing fatty acid content. Kinetic parameters indicated fatty acids decreased water absorption by decreasing the saturation level of zein sheets. Coating zein with flax oil decreased the rate of water absorption by sealing off surface pores. Scanning electron micrographs of zein sheets showed the development of layered structures as fatty acid content increased. Zein-fatty acid layers were believed to be responsible for the increased tensile strength of plasticized zein sheets and to have contributed to increased resistance to water absorption.