Preparation and properties of biodegradable foams from starch acetate and poly(tetramethylene adipate-co-terephthalate)

Biodegradable composite foams were prepared by extruding starch acetate, with degree of substitution (DS) 1.78, with poly(tetramethylene adipate-co-terephthalate) (EBC). The foams' chemical structures, thermal behaviors, and microstructures were investigated by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). By measuring these properties, it was found that low EBC contents in the blends favored the miscibility of the two polymers, as characterized by (1) disappearance of EBC carbonyl peak and appearance of hydrogen-bonded EBC carbonyl groups in FTIR spectra; (2) an increase in T_g of starch acetate and the decreases in T_m values of starch acetate and EBC in DSC thermograms; and (3) formation of a homogeneous morphology in SEM. However, large amounts of EBC decreased the miscibility of these two polymers, as reflected by the foams' physical and mechanical properties. With a small amount of EBC, the foams had high radial expansion ratios (RER) and spring indices (SI) and low unit densities and compressibilities. Biodegradation rates of the composite foams decreased with the addition of EBC to starch acetate.     

Dynamic and extensional properties of starch in aqueous dimethylsulfoxide

The effect of starch composition and concentration on the rheological properties of starch in a mixed solvent, water–DMSO, was investigated in dynamic shear and extensional mode. High amylose corn starch containing 70% amylose and 30% amylopectin, common corn starch containing 25% amylose and 75% amylopectin, and waxy corn starch containing about 99% amylopectin were used in this study. Concentrations of 2, 4, 6, and 8% (w/v) in 10% water-90% DMSO (v/v) were used for each starch type. An increase in the amylopectin content of starch from 30 to 99% caused a change in behavior from semidilute solution to viscoelastic solid at a concentration of 8% (w/v). At a concentration of 2%, an increase in the amylopectin content of starch from 30 to 99% caused a change from Newtonian to incipient gel-like behavior. Behavior at intermediate concentrations of 4 and 6% (w/v) varied from semidilute to critical gel-like with increasing amylopectin content. A power-law relaxation was observed for all concentrations of common and waxy corn starches with the slope decreasing with increase in concentrations. A 2% waxy corn starch solution displayed extension thinning behavior, while a 2% high amylose corn starch solution displayed Newtonian behavior.     

Segmental mobility of polymers in starch granules at low moisture contents

The objective of this study was to determine the moisture content at which the segmental mobility of polymers within a starch granule is restricted. Common corn, waxy corn and high amylose corn starch samples were equilibrated to a final water activity of 0.15, 0.33, 0.75 or 0.97. The samples were then exposed to iodine vapor for 24 h and the color, absorption spectra and X-ray diffraction patterns were measured. Stained and unstained granules were also viewed under a bright field and polarized light microscope. The results demonstrate that successive local transitions occur within a granule with increasing moisture contents. Furthermore, the data shows that at moisture contents of about 13%, iodine is able to penetrate the granule and the resulting complex disrupts the crystalline arrangement within the granules. The differences in extent of mobility of polymers between different starch types can potentially illuminate differences in starch structure and architecture.     

不同类型玉米籽粒的营养品质及其与籽粒质地的关系

测定普通玉米、爆裂玉米、糯玉米和甜玉米4种类型玉米籽粒不同发育时期的直链淀粉、支链淀粉、总淀粉、可溶性糖和蛋白的含量,分析这些营养物质与角质率的关系。结果表明：灌浆期间4种类型玉米的直链淀粉、支链淀粉和总淀粉含量呈上升趋势,总蛋白含量呈下降趋势,可溶性糖含量变化规律不明显。爆裂玉米的直链淀粉含量始终最高（4．7％-23．1％）,甜玉米（1．4％-4．6％）和糯玉米（2．3％-4．9％）的始终较低;甜玉米的支链淀粉含量一直最低（15．7％-35．5％）,除授粉10d以外,糯玉米的支链淀粉含量一直最高（65．5％-69．8％）;甜玉米总淀粉含量始终最低（17．1％36.1％）、总蛋白含量（15．2％-26．9％）和授粉30d后的可溶性糖含量最高（14．2％-17．6％）。高蛋白含量可能是爆裂玉米和甜玉米角质率高的原因,糯玉米的角质率低可能与支链淀粉含量高和蛋白积累少有关。     

Extruding foams from corn starch acetate and native corn starch

Because of the hydrophilic characteristics of native starch foams and the cost of modifying starch, the uses of starch and modified starch foams are hindered. To decrease hydrophilicity and cost of starch foams, native corn starch was blended with starch acetate and extruded. A twin-screw mixing extruder was used to produce the foams. Native starch content, screw speed, and barrel temperature had significant effects on molecular degradation of starches during extrusion. The melting temperature of extruded starch acetate/native starch foam was higher (216 degrees C) than that for starch acetate (193.4 degrees C). Strong peaks in the X-ray diffractograms of extruded starch acetate/native starch foam suggested new crystalline regions were formed. Optimum conditions for high radial expansion ratio, high compressibility, low specific mechanical energy requirement, and low water absorption index were 46.0% native starch content, 163 rpm screw speed, and 148 degrees C barrel temperature.     

Internal structure and physicochemical properties of corn starches as revealed by chemical surface gelatinization

The organization of amylose and amylopectin within starch granules is still not well elucidated. This study investigates the radial distribution of amylose and amylopectin in different corn starches varying in amylose content (waxy corn starch (WC), common corn starch (CC), and 50% and 70% amylose corn starches (AMC)). Corn starches were surface gelatinized by 13 M LiCl at room temperature to different extents (approximately 10%, 20%, 30%, and 40%). The gelatinized surface starch and remaining granules were characterized for amylose content, amylopectin chain-length distribution, thermal properties, swelling power (SP), and water solubility index (WSI). Except for the outmost 10% layer, the amylose content in CC increased slightly with increasing surface removal. In contrast, amylose was more concentrated at the periphery than at the core for 50% and 70% AMC. The proportion of amylopectin A chains generally decreased while that of B1 chains generally increased with increasing surface removal for all corn starches. The gelatinization enthalpy usually decreased, except for 70% AMC, whereas the retrogradation enthalpy relatively remained unchanged for CC but increased for WC, 50% and 70% AMC with increasing surface removal. The SP and WSI increased with increasing surface removal for all corn starches, with WC showing a significant increase in SP after the removal of the outmost 10% layer. The results of this study indicated that there were similarities and differences in the distribution of amylose and amylopectin chains along the radial location of corn starch granules with varying amylose contents. More amylose-lipid complex and amylopectin long chains were present at the periphery than at the core for amylose-containing corn starches.     

Quantification of total iodine in intact granular starches of different botanical origin exposed to iodine vapor at various water activities

Iodine has been used as an effective tool for studying both the structure and composition of dispersed starch and starch granules. In addition to being employed to assess relative amylose contents for starch samples, it has been used to look at the molecular mobility of the glucose polymers within intact starch granules based on exposure to iodine vapor equilibrated at different water activities. Starches of different botanical origin including corn, high amylose corn, waxy corn, potato, waxy potato, tapioca, wheat, rice, waxy rice, chick pea and mung bean were equilibrated to 0.33, 0.75, 0.97 water activities, exposed to iodine vapor and then absorbance spectra and LAB color were determined. In addition, a new iodine quantification method sensitive to <0.1% iodine (w/w) was employed to measure bound iodine within intact granular starch. Amylose content, particle size distribution of granules, and the density of the starch were also determined to explore whether high levels of long linear glucose chains and the surface area-to-volume ratio were important factors relating to the granular iodine binding. Results showed, in all cases, starches complexed more iodine as water content increased and waxy starches bound less iodine than their normal starch counterparts. However, much more bound iodine could be measured chemically with waxy starches than was expected based on colorimetric determination. Surface area appeared to be a factor as smaller rice and waxy rice starch granules complexed more iodine, while the larger potato and waxy potato granules complexed less than would be expected based on measured amylose contents. Corn, high amylose corn, and wheat, known to have starch granules with extensive surface pores, bound higher levels of iodine suggesting pores and channels may be an important factor giving iodine vapor greater access to bind within the granules. Exposing iodine vapor to moisture-equilibrated native starches is an effective tool to explore starch granule architecture.     

Pasting viscosity and in vitro digestibility of retrograded waxy and normal corn starch powders

Pasting viscosity and in vitro digestibility of oven-dried powders of waxy and normal corn starch gels (40% solids) retrograded under an isothermal (4 °C) or temperature cycled (4/30 °C) storage were investigated. Temperature cycling induced higher onset temperature for melting of amylopectin crystals than isothermal storage under a differential scanning calorimeter whereas little difference in crystalline type was observed under X-ray diffraction analysis. Temperature cycling caused higher pasting temperature and viscosity for the retrograded starches than isothermal storage. The retrograded waxy corn starch powders exhibited pasting behaviors similar to that of native waxy corn starch. However, the retrograded normal corn starch powders showed very much different pasting patterns with lower pasting viscosity but higher pasting temperature than native starch counterpart. The retrogradation increased slowly digestible starch content without changing resistant starch content, more effectively by the temperature cycling than the isothermal storage.     

Locations of hypochlorite oxidation in corn starches varying in amylose content

The general oxidation mechanism by hypochlorite on starch has been well studied, but the information on the distribution of the oxidation sites within starch granules is limited. This study investigated the locations where the oxidation occurred within corn starch granules varying in amylose content, including waxy corn starch (WC), common corn starch (CC), and 50% and 70% high-amylose corn starch (AMC). Oxidized corn starches were surface gelatinized by 13 M LiCl at room temperature to different extents (approximately 10%, 20%, 30%, and 40%). The surface-gelatinized remaining granules were separated and studied for structural characteristics including carboxyl content, amylose content, amylopectin chain-length distribution, thermal properties, and swelling properties. Oxidation occurred mostly at the amorphous lamellae. More carboxyl groups were found at the periphery than at the core of starch granules, which was more pronounced in oxidized 70% AMC. More amylose depolymerization from oxidation occurred at the periphery of CC. For WC and CC, amylopectin long chains (>DP 36) were more prone to depolymerization by oxidation. The gelatinization properties as measured by differential scanning calorimetry also supported the changes in amylopectin fine structure from oxidation. Oxidized starches swelled to a greater extent than their unmodified counterparts at all levels of surface removal. This study demonstrates that the locations of oxidation and physicochemical properties of oxidized starches are affected by the molecular arrangement within starch granules.     

Supercritical CO2 Foaming of Thermoplastic Materials Derived from Maize: Proof-of-Concept Use in Mammalian Cell Culture Applications

Background

Foams are high porosity and low density materials. In nature, they are a common architecture. Some of their relevant technological applications include heat and sound insulation, lightweight materials, and tissue engineering scaffolds. Foams derived from natural polymers are particularly attractive for tissue culture due to their biodegradability and bio-compatibility. Here, the foaming potential of an extensive list of materials was assayed, including slabs elaborated from whole flour, the starch component only, or the protein fraction only of maize seeds.

Methodology/Principal Findings

We used supercritical CO₂ to produce foams from thermoplasticized maize derived materials. Polyethylene-glycol, sorbitol/glycerol, or urea/formamide were used as plasticizers. We report expansion ratios, porosities, average pore sizes, pore morphologies, and pore size distributions for these materials. High porosity foams were obtained from zein thermoplasticized with polyethylene glycol, and from starch thermoplasticized with urea/formamide. Zein foams had a higher porosity than starch foams (88% and 85%, respectively) and a narrower and more evenly distributed pore size. Starch foams exhibited a wider span of pore sizes and a larger average pore size than zein (208.84 vs. 55.43 μm², respectively). Proof-of-concept cell culture experiments confirmed that mouse fibroblasts (NIH 3T3) and two different prostate cancer cell lines (22RV1, DU145) attached to and proliferated on zein foams.

Conclusions/Significance

We conducted screening and proof-of-concept experiments on the fabrication of foams from cereal-based bioplastics. We propose that a key indicator of foamability is the strain at break of the materials to be foamed (as calculated from stress vs. strain rate curves). Zein foams exhibit attractive properties (average pore size, pore size distribution, and porosity) for cell culture applications; we were able to establish and sustain mammalian cell cultures on zein foams for extended time periods.     

Three-dimensional temporal and spatial distribution of adult Rhyzopertha dominica in stored wheat and corn under different temperatures, moisture contents, and adult densities

Three-dimensional temporal and spatial distributions of adult Rhyzopertha dominica (F.) at adult densities of 1.0, 5.0, and 10.0 adults per kg grain and at 20 +/- 1, 25 +/- 1, and 30 +/- 1 degrees C were determined in 1.5 t bins filled with wheat (Triticum aestivum L.) with 11.0 +/- 0.8, 13.0 +/- 0.6, and 15.0 +/- 0.5% moisture content (wet basis) or corn (Zea mays L.) with 13.0 +/- 0.2% moisture content (wet basis). At each of five sampled locations, grain was separated into three 15-kg vertical layers, and adult numbers in each layer were counted. Inside both corn and wheat, adults did not prefer any location in the same layer except at high introduced insect density in wheat. The adults were recovered from any layer of the corn and >12, 65, and 45% of adults were recovered in the bottom layer of the corn at 20, 25, and 30 degrees C; respectively. However, <1% of adults were recovered in the bottom layer of wheat. Numbers of adults correlated with those in adjacent locations in both vertical and horizontal directions, and the temporal continuous property existed in both wheat and corn. Adults had highly clumped distribution at any grain temperature and moisture content. This aggregation behavior decreased with the increase of adult density and redistribution speed. Grain type influenced their redistribution speed, and this resulted in the different redistribution patterns inside wheat and corn bulks. These characterized distribution patterns could be used to develop sampling plans and integrated pest management programs in stored grain bins.     

土壤水分变化对玉米苗期吸收积累镉的影响

采用土壤盆栽试验研究不同土壤水分含量对玉米苗期吸收积累 Cd的影响。试验结果表明 ,玉米生物量及其吸收 Cd量在玉米不同的生长时期差异较大。2 2 d收获时 ,玉米地上部和地下部生物量均随着田间持水量 (35 %～ 85 % )的增加而提高 ;而 16 d收获时 ,玉米生物量在田间持水量为 35 %和 85 %时比在其它水分时低许多。 16 d和 2 2 d收获时 ,玉米地上部 Cd含量在田间持水量 5 5 %时分别达到最大值 ,5 5 .4 1mg/ kg和 39.33mg/ kg;而在田间持水量 85 %时分别达最小值 ,2 7.97mg/ kg和 2 3.5 2 m g/kg。在玉米根系的影响下 ,土壤溶液 Cd含量基本上随着玉米的不断生长而降低。田间持水量为 6 5 %时的土壤溶液 Cd含量比田间持水量为 75 %和 85 %时大。玉米总吸 Cd量与水分蒸腾量之间呈极显著的线性正相关关系     

Surface esterification of corn starch films: Reaction with dodecenyl succinic anhydride

Surface of corn starch films was modified through esterification using dodecenyl succinic anhydride (DDSA) as reactant. The effects of reaction temperature and time, concentration of alkaline aqueous solution for activating starch, concentration of ethanol diluted DDSA, and time of alkaline aqueous solution treatment on the physical properties related to material’s hydrophilic nature, such as moisture absorption and surface water contact angle, were investigated. It was found that the surface esterification modification significantly reduced the moisture sensitivity and surface hydrophilic character of starch film. Due to the hydroxyl groups in the film surface layer were reacted with DDSA, the equilibrium moisture content of the starch film under 95% RH declined 22% and the surface water contact angle increased up to 82% after surface esterification modification.     

Influence of amylose content on starch films and foams

After extraction of smooth pea starch and waxy maize starch from pure amylose and amylopectin fractions, films with various amylose contents were prepared by casting in the presence of water or water with glycerol. For unplasticized films, a continuous increase in tensile strength (40–70 MPa) and elongation (4–6%) was observed as amylose increased from 0 to 100%. Discrepancies with values obtained for native starches with variable amylose content and different botanical origins were attributable to variations in the molecular weights of components. Taking cell wall properties into account, the values obtained in the laboratory were used to improve the relation between the flexural behavior of extruded foams and the model of cellular solids with open cavities.

The properties of plasticized films were not improved by the presence of glycerol and remained constant when amylose content was higher than 40%. Results are interpreted on the basis of topological differences between amylose and amylopectin.     

不同类型玉米发育籽粒中淀粉合成及相关酶活性比较

以普通玉米、爆裂玉米、甜玉米和糯玉米为试材,分析和比较不同类型的玉米品种之间籽粒发育过程中淀粉合成及相关酶活性的变化。结果表明,淀粉合成速率和蔗糖合成酶(SS)、可溶性淀粉合成酶(SSS)、束缚态淀粉合成酶(GBSS)、淀粉分支酶(SBE)、去分支酶(DBE)活性都呈单峰曲线变化。30～40 DAP,普通玉米的SS活性显著高于其他3种类型;类型间平均和最大SSS活性水平的顺序为普通玉米>糯玉米>爆裂玉米>甜玉米;30～40 DAP,普通玉米GBSS活性最高,糯玉米GBSS活性最低;20～40 DAP,糯玉米SBE活性最高;甜玉米的DBE活性很低,并且在40 DAP完全丧失。淀粉合成速率与SS、SSS、GBSS和SBE活性相关程度比较高,与腺苷二磷酸葡萄糖焦磷酸化酶(AGP酶)和DBE活性相关不显著。推测AGP酶虽然为淀粉合成提供直接前体ADPG,但可能SS活性过低致使其限速作用比AGP酶的还强,AGP酶潜在的限速作用无法表现,SS成为玉米籽粒淀粉合成的限速因子。GBSS对直链淀粉积累起重要的促进作用;SSS和SBE对支链淀粉积累起重要的促进作用。     

不同品种玉米对草地贪夜蛾生长发育及繁殖的影响

为评价新入侵害虫草地贪夜蛾对我国不同品种玉米的为害潜能,本文采用组建实验种群生命表的方法研究了草地贪夜蛾对3种甜质型玉米(穗甜1号、正甜68和华金甜1号)以及3种糯质型玉米(京科糯2000、广黑甜糯和广糯1号)的生存适合度,分析了草地贪夜蛾生物学指标与玉米叶片主要营养物质及粗纤维含量间的相关性。结果表明: 取食甜质型玉米的草地贪夜蛾的幼虫存活率、蛹重、雌成虫产卵量均显著高于取食糯质型玉米;取食甜质型玉米草地贪夜蛾的内禀增长率介于0.1566～0.1843,净生殖力介于187.97～353.35,也均高于取食糯质型玉米(内禀增长率介于0.0998～0.1465,净生殖力介于25.89～95.34),表明取食甜质型玉米的草地贪夜蛾具有更高的种群增长能力。甜质型玉米叶片中主要营养物质维生素C、淀粉、可溶性糖、蛋白质、脂肪、总氨基酸及粗纤维的含量普遍高于糯质型玉米,草地贪夜蛾的净生殖力与维生素C、淀粉、可溶性糖、蛋白质及粗纤维的含量均存在显著正相关关系。草地贪夜蛾在甜质型玉米上具有更高的生存适合度。     

玉米籽粒胚乳细胞增殖及其与淀粉充实的关系

用纤维素酶解离胚乳、滤膜法统计玉米胚乳细胞的数目,进一步借助Logistic方程模拟胚乳细胞增殖动态的结果表明,整个灌浆期间胚乳细胞增殖呈现“慢-快-慢”的变化趋势。授粉15d后,不同类型胚乳的细胞数目依序为普通玉米〉糯玉米〉甜玉米〉爆裂玉米;胚乳细胞数目主要取决于细胞的增殖速率,并与淀粉充实和粒重关系密切。胚乳发育前期以胚乳细胞增殖为主,后期以淀粉积累为主。     

Selected morphological and functional properties of extruded acetylated starch-cellulose foams

Starch acetates with degrees of substitution (DS) of 1.68 and 2.3 were extruded with 10%, 20% and 30% (w/w) cellulose and 20% (w/w) ethanol in a twin screw extruder at 150, 160 and 170 degrees C barrel temperatures and 170, 200 and 230 rpm screw speeds. X-ray diffractogram (XRD), differential scanning calormetry (DSC) and Fourier transform infrared spectroscopy (FTIR) were used to analyze the morphological properties of extruded foams. A central composite response surface design was applied to analyze the effects of starch type, cellulose content, barrel temperature and screw speed on specific mechanical energy requirement of extruding foams and the radial expansion ratio and compressibility of the extruded foams. XRD showed losses of DS starch and cellulose crystallinity and the formation of new complexes. FTIR spectra revealed that functional groups and chemical bonds were maintained after extrusion. Melting temperatures changed significantly when higher DS starch acetate was used. Cellulose content, barrel temperature and screw speed showed significant effects on thermal, physical and mechanical properties of extruded foams and the specific mechanical energy requirement.     

Pasting properties of a heat-moisture treated canna starch in relation to its structural characteristics

Native and moistened canna starches (moisture contents of 15%, 18%, 20%, 22%, and 25%) were heat treated at 100 °C for 16 h. Heat-moisture treatment (HMT) did not alter the shape or size of starch granules. Heat-treated starches showed lower paste viscosity, more stable paste (with no breakdown) and noticeable decrease in setback value compared to untreated native starch. These changes were more obvious when the starch samples contained more moisture. Starch gel morphology investigated by I₂ staining revealed that the granules of untreated native canna starch were completely ruptured, whereas those of HMT22% and HMT25% samples remained in granular form. These gel morphologies were correlated and provided the information to explain the pasting behaviors of treated and untreated canna starches. Shifts of gelatinization endotherms towards higher temperatures (1–8 °C) with broadened peaks following the moisture contents in starch samples were found after HMT. Amylose leaching of treated samples tended to be lower when the moisture content of the samples increased. HMT did not alter crystalline type of canna starch (B-type), but with increase of the moisture, slight reduction of a peak at 5.7° and a fusion of doublet at 22° and 24° were observed.     

A comparative account of conditions for synthesis of sodium carboxymethyl starch from corn and amaranth starch

Conditions for the preparation of carboxymethyl derivatives of corn and amaranth starch were compared. The two starches differed considerably with respect to the optimum conditions such as temperature, pH, time, concentration of sodium monochloroacetate, and starch:liquor ratio. In both cases, isopropyl alcohol was the solvent of choice. Multistage carboxylation was also carried out. Amaranth starch differs from corn starch in two respects. It is waxy in nature and also has a small granule size of 1–2 μm. However, comparison with rice starch, having a granule size of 1–2 μm and potato starch, having a similar amylose content as corn starch showed no correlation between any of these parameters.