Imaging of high-amylose starch tablets. 3. Initial diffusion and temperature effects

The penetration of water into cross-linked high amylose starch tablets was studied at different temperatures by nuclear magnetic resonance (NMR) imaging, which follows the changes occurring at the surface and inside the starch tablets during swelling. It was found that the swelling was anisotropic, whereas water diffusion was almost isotropic. The water proton image profiles at the initial stage of water penetration were used to calculate the initial diffusion coefficient. The swelling and water concentration gradients in this controlled release system show significant temperature dependence. Diffusion behavior changed from Fickian to Case II diffusion with increasing temperature. The observed phenomena are attributed to the gelatinization of starch and the pseudo-cross-linking effect of double helix formation.     

Preparation and characteristics of high-amylose corn starch/pectin blend microparticles: A technical note

Summary and Conclusions  The HACS/pectin blend microparticles were prepared by spray-drying technique to obtain effective targeted drug release to the colon. The mean particle size of the micro-particles (plain and blend) that were prepared in the present study was between 5.8 and 7.3 μm. The microparticles were positively charged (ζ potential was in the range of 20.3 to 30.8), and the encapsulation efficiency was between 80.1% and 94.7%. The blending of HACS with pectin improved the encapsulation efficiency and decreased the drug dissolution in the gastric condition (pH 1.2) from the pectin-based microparticles. Results of the drug release study indicated that the colonic-controlled drug delivery could be obtained from spray-dried HACS/pectin blend microparticles, and the drug release mechanism was found to be by diffusion or erosion or a combination of both. Published: September 30, 2005.     

Properties of a plasticised starch blend. Part 1: Influence of moisture content on fracture properties

The effect of moisture content on tensile and fracture properties of a plasticised starch/high molecular weight polyol blend was investigated. A wide range of mechanical behaviour was achieved by varying slightly the water uptake of this material. At low moisture content, the Young’s modulus was 3800 MPa and the yield stress, 54 MPa. When the moisture content reached 15 wt%, their values dropped, respectively, to around 1500 MPa and 21 MPa. As the material behaviour varies greatly over the moisture content range, two fracture mechanics techniques were employed: the linear elastic fracture mechanics approach to characterise brittle behaviour and the essential work of fracture method to investigate a more ductile material. At low moisture content, the measured strain energy release rate at fracture, J_Q was very low and showed little dependency on the moisture content. As the moisture content increases, the material becomes increasingly ductile and displayed a brittle-to-ductile transition at 12% of moisture content, which corresponded to the glass transition temperature of the added polyol.     

Effect of water content on the gelatinisation temperature of sago starch

Differential scanning calorimetry (DSC) has been used to study gelatinisation phenomena of sago starch. Two endothermic transitions were observed for starch heated in the presence of a limited amount of water (starch/water=37–50%w/w). These transitions appear to be due to co-operative effects of water-mediated melting of starch crystallites, remaining crystallites and/or amylopectin crystallites. At a water content of 50%, evidence of M₁ endotherm was observed and 85°C represents the effective T_m at the end of melting of native sago starch. The effect of starch concentration on the shape of these two endotherms was studied for sago starch. The experimental data were treated thermodynamically by applying equations describing phase transition of semi-crystalline polymers. The T⁰_m value obtained by extrapolation to v₁=0 was 390.6 K for sago.     

NMR imaging of high-amylose starch tablets. 1. Swelling and water uptake

Pharmaceutical tablets made of modified high-amylose starch have a hydrophilic polymer matrix into which water can penetrate with time to form a hydrogel. Nuclear magnetic resonance imaging was used to study the water penetration and the swelling of the matrix of these tablets. The tablets immersed in water were imaged at different time intervals on a 300 MHz NMR spectrometer. Radial images show clearly the swelling of the tablets and the water concentration profile. The rate constants for water diffusion and the tablet swelling were extracted from the experimental data. The water diffusion process was found to follow case II kinetics at 25 degrees C. NMR imaging also provided spin density profiles of the water penetrating inside the tablets.     

The retrogradation of waxy maize starch extrudates: effects of storage temperature and water content

The effects of water content and storage temperature on the kinetics of the retrogradation of nonexpanded waxy maize starch extrudates were studied using (1)H pulsed NMR and wide-angle X-ray diffraction. The increase in crystallinity observed by XRD was accompanied by a decrease in the relaxation times of the solid-like component of the NMR free induction and the spin-echo decays, and an increase in the contribution of the solid-like component to the total signal. The dependence of the rate of starch retrogradation on the storage temperature showed the typical "bell-shaped" behavior, which was successfully modeled using the Lauritzen-Hoffman theory of crystallization of chain-folded polymers. This theory was extended to model the effect of water content on the rate of isothermal crystallization by exploiting the ten-Brinke and Karasz, and the Flory equations to describe the dependence of the glass-transition and the melting temperatures on water content.     

A small-angle X-ray scattering study of the absorption of water into the starch granule

Analysis of the shape of the small-angle X-ray scattering (SAXS) intensity profiles obtained from suspensions of wheat starch granules in water gives information on the amount of absorption into the different regions of the granule. At room temperature, less water is absorbed into the granules the higher the starch concentration. At 51°C, the beginning of the gelatinisation region, lower amounts of water are absorbed when the concentration of starch is high and there is less loss of crystalline order. In an excess of water, co-operative melting occurs, whereas, with less water, the absorption is insufficient to destabilise the crystalline order. The beam damage at room temperature is reflected in a slight increase in order, possibly due to rearrangement after chain scission.     

Influence of extrusion and digestion on the nanostructure of high-amylose maize starch

An in-depth characterization of the structural changes undergone by high-amylose starch after extrusion and digestion with a pancreatic alpha-amylase has been carried out. The combination of USAXS, SAXS, XRD, and SEM techniques has provided a wide "picture" of the morphological transformations of starch, covering a length scale from approximately 0.3 nm to approximately 230 microm. Depending on the extrusion conditions, either gelatinization was attained ("mild" conditions) or single-amylose helix formation was induced ("extreme" conditions). SAXS experiments demonstrated that upon contacting the extruded materials with water, retrogradation took place. A new type of molecular organization with a characteristic repeat length of 5 nm was observed in the dry resistant starch fractions from the extruded high-amylose starch. The crystalline morphology of the resistant starch fractions, as observed by XRD, varied from B-type crystallinity for the "mild" extruded starch to a mixture of C- and V-type crystallinity in the case of "extreme" extrusion.     

The influence of temperature and moisture contents regimes on the aerobic microbial activity of a biosolids composting blend

To understand the relationships between temperature, moisture content, and microbial activity during the composting of biosolids (municipal wastewater treatment sludge), well-controlled incubation experiments were conducted using a 2-factor factorial design with six temperatures (22, 29, 36, 43, 50, and 57 degrees C) and five moisture contents (30, 40, 50, 60, and 70%). The microbial activity was measured as O2 uptake rate (mg g(-1) h(-1)) using a computer controlled respirometer. In this study, moisture content proved to be a dominant factor impacting aerobic microbial activity of the composting blend. Fifty percent moisture content appeared to be the minimal requirement for obtaining activities greater than 1.0 mg g(-1) h(-1). Temperature was also documented to be an important factor for biosolids composting. However, its effect was less influential than moisture content. Particularly, the enhancement of composting activities induced by temperature increment could be realized by increasing moisture content alone.     

Water permeability of plant cuticles: The effect of temperature on diffusion of water

The effect of temperature on water permeability of plant cuticles (astomatous Citrus leaf cuticles) has been investigated. The Arrhenius plot (logarithm of the permeability coefficient vs. 1/temperature) has two linear portions that intersect at 44° C. Evidence is presented to show that this intersection represents the solid/liquid phase transition of cuticular lipids. As the Arrhenius plot has only one phase transition in the temperature range of 5 to 80° C, it appears that all soluble cuticular lipids in the cuticle are present as a homogeneous mixture rather than as individual layers differing in composition. This view is supported by electron spin resonance evidence showing homogenous distribution of spin label fatty acids. The original distribution of soluble cuticular lipids is irreversibly altered by heating cuticular membranes above the transition temperature. This is accompanied by an irreversible increase in water peremeability, demonstrating the importance of the structure of cuticular lipids with regard to cuticular permeability.Abbreviations CM cuticular membranes - MX polymer matrix - SCL soluble cuticular lipids - MES morpholinoethane sulphonic acid - J flux - ESR electron spin resonance - THO tritiated water     

Investigation into the diffusion of water into HEMA-co-MOEP hydrogels

Cross-linked homopolymers and copolymers of 2-hydroxyethyl methacrylate, HEMA, and ethylene glycol methacrylate phosphate, MOEP, have been synthesized, and the diffusion of water into these systems has been investigated. Only polymers with 0-20 mol % MOEP exhibited ideal swelling behavior as extensive fracturing occurred in the systems with greater than 20 mol % MOEP as the polymers began to swell during water sorption. Gravimetric studies were used in conjunction with magnetic resonance imaging of the diffusion front to elucidate the diffusion mechanism for these systems. In the case of the cross-linked HEMA homopolymer gels, the water transport mechanism was determined to be concentration-independent Fickian diffusion. However, as the fraction of MOEP in the network increased, the transport mechanism became increasingly exponentially concentration-dependent but remained Fickian until the polymer consisted of 30 mol % MOEP where the water transport could no longer been described by Fickian diffusion.     

Effect of temperature and moisture content on Egyptian peanut seed-borne fungi

In peanut seeds adjusted to various levels of moisture content (8.5 %, 13,5 %, 17.5 % and 21 % on a dry-weight basis) and stored for six months at 5°, 15°, 28° and 45 °C, seed-borne fungi were monthly identified and counted using the dilution plate method, and the germinability of seeds was tested. The total count of seed-borne fungi (recovered at 28 °C) increased regularly and the germinability declined with the rise moisture content and with the lengthening of the storage period. At 5°, 15° and 28 °C,A. fumigatus was almost the most dominant fungal species followed by several fungi such asAspergillus flavus, A. niger, A. terreus, Penicillium funiculosum, P. notatum, Pyrenochaeta decipians andScopulariopsis brevicaulis. The degree of dominance of each fungal species depended upon the conditions of storage and the length of storage period.A. flavus gained its highest count in seeds adjusted to 13.5 % stored at 15 °C for 1 month.Penicillium predominated at 17.5 % and 21 %, and at 13.5 % and 17.5 % when the seeds were stored for long periods at 5° and 15 °C respectively.The total count of thermophilic fungi (recovered at 45 °C) significantly increased with the rise of moisture content and with the lengthening of the storage period between 1 and 2 months and regularly declined after 4 months.A. fumigatus was so extremely dominant that it was the main component of the total fungal flora. Several fungi truly thermophilic were isolated also. They were,Mucor pusillus, Humicola grisea var.thermoidae, H. insolens, H. lanuginosa (Thermomyces lanuginosus) andSporotrichum thermophile.     

Effect of orientation on the physical properties of potato amylose and high-amylose corn starch films

The effect of orientation on the properties of amylose and starch films was studied in order to determine if film strength, flexibility, and water resistance could be improved. Potato amylose and high (70%) amylose corn starch were peracetylated, cast into films, stretched in hot glycerol 1-6 times the original length, and deacetylated. Molecular orientation of potato amylose films was much higher than for high-amylose corn starch films as determined by optical birefringence. For potato amylose films, orientation resulted in large increases in tensile strength and elongation but little change in modulus. For high-amylose corn starch films, tensile strength and modulus did not change with draw ratio but elongation to break increased from about 8% to 27% as draw ratio increased from 1 to 5. Scanning electron micrographs revealed many small crazes in the drawn starch films, suggesting that the improved film toughness was due to energy dissipation during deformation of the crazes. Annealing of drawn films at 100% humidity resulted in partial crystallization and improved wet strength.     

Characteristic moisture curves and maximum water content of two crop residues

Limited data are available relating water potential () to crop residue water content (), although this relationship is important to study decomposition and moisture retention of the residue layer in no-till systems and other agricultural situations where residues are used. The objectives of this study were (i) to determine the characteristic moisture curves of rye (Secale cereale L.) and clover residues (Trifolium incarnatum L.), and (ii) to determine residue characteristics that can predict maximum water content of crop residues. Air-dried residues were separated into leaves and stems, cut into 0.5 cm length pieces and saturated with distilled water. Pieces of the drained residues were dried to various water contents in the laboratory and then transferred into thermocouple psychrometer chambers. Characteristic moisture functions of the type = a ^–b, where a and b are empirical constants, were fitted to the data. The characteristic moisture curves had a similar shape to that of a Cecil sandy loam soil used as an example; however, while plant residues were able to retain up to 4.3 g H₂O g^–1, the mineral soil retained only 0.22 g H₂O g^–1. Soluble carbohydrate concentration can be used as a practical index to estimate maximum water content of residues, given the good relationship between both variables (R ² = 0.92).     

A simple autoradiographic technique for studying diffusion of water into seeds

Visual observations on rates and modes of water penetration into black bean seeds and into wheat and sorghum kernels during conditioning were accomplished by an autoradiographic procedure that eliminates a freezing microtome and liquid and stripping film emulsions. Seeds soaked in tritiated H₂O were hand sectioned before freeze-quenching in liquid N₂ and subsequent block autoradiography on nuclear medicine film.     

Small molecule diffusion into swelling iota-carrageenan gels: a fluorescence study

Small molecule diffusion into Iota-Carrageenan gel was studied by using steady-state fluorescence (SSF) technique. Pyranine, dissolved in water was used as fluorescence probe. Fluorescence emission intensity, I(p), and scattered light intensity, I(sc), were monitored to study diffusion and swelling processes at various temperatures respectively. Fickian and Li-Tanaka models were elaborated to produce diffusion, D, and collective diffusion, D(0), coefficients. Diffusion and swelling activation energies were also obtained and found to be 20.5 kj mol(-1) and 28.2 kj mol(-1), respectively.     

Impact of vegetation removal on the temperature and moisture content of red wood ant nests

We studied the influence of vegetation growing on red wood ant, Formica polyctena, hills and its removal, by cutting, on the temperature and moisture content of the nests. Vegetation was removed from half of nests (n = 10) in June and August. Generally, ant hills were small (0.1–1.1 m³) and their daily temperature fluctuations and moisture (16–38%) were low. The centre temperature of ant hills was positively correlated with ambient air temperature. Daily temperatures peaked at 13:00 and slowly decreased until 09:00 then increased again until 13:00. Nest moisture content was not related to nest volume. All the ant hills were covered with Reed Grass (Calamagrostis arundinacea) that grows through nests and reaches about 185–1085 g/dcm² of dry matter. Dry vegetation matter (g/dcm² of anthill surface) was the same on cut and uncut nests as well because all ant hills were under long-term management (vegetation removal) for at least 10 years. Although vegetation removal did not result in an immediate increase in the temperature of denuded ant hills removal did results in higher daily and night temperatures during the July-September period. The moisture content of nests with undisturbed and intact vegetation was the same. The dry matter content of vegetation strongly affected their moisture content. However, temperature at the inside centre of nests decreased as vegetation dry matter increased, i.e. there was a statistically negative correlation between temperature and moisture. The results support removing grass as a suitable management tool to facilitate the survival of wood ants. Received 30 December 2007; revised 22 April 2008; accepted 10 June 2008.     

Intramolecular esterification by lipase powder in microaqueous benzene: effect of moisture content

In view of the biochemical reaction catalyzed by enzyme powder suspended in a water-insoluble organic solvent, an equation was derived to estimate the amount of water bound to the enzyme powder. With this equation, an apparent adsorption isotherm between free water (water freely dissolved in benzene) and bound water (water bound to crude lipase powder of Pseudomonas fluorescens) was obtained. A direct lactonization reaction (synthesis of cyclopentadenolide from 15-hydroxypen-tadecanoic acid) catalyzed by crude lipase powder of Pseudomonas fluorescens was carried out batchwise in microaqueous benzene at 40oC. A kinetic model of the enzymatic reversible lactonization reaction was derived, from which the effect of moisture content on the initial reaction rate with a fully hydrated enzyme was mathematically expressed. The observed initial reaction rate first increased, then decreased with increasing moisture content, giving rise to the maximum rate at a certain level of the moisture content. The drop in the reaction rate at lower moisture content was due to a lesser hydration of the enzyme molecule (hydration-limited) and the decrease in the reaction rate at higher moisture content was attributed to the dependence of the true initial rate of the reversible reaction on the moisture content (true reversible reaction limited), and could be simulated by the kinetic model. The equilibrium yield approached 100% at a lower moisture content.