Effect of Interphase Properties on Isothermal and Non-isothermal Crystallization Behavior of Poly(lactic acid)/Acetylated Starch Blends.

The effect of interphase properties on the crystallization behavior of blends of poly(lactic acid) (PLA)/acetylated starch (AS) with different degrees of substitution (DSs) was investigated. Under isothermal crystallization conditions, the rate of crystallization was higher for PLA/DS0.5 and lower for PLA/DS1.5 and PLA/DS2.5 when compared to PLA. In contrast, non-isothermal crystallization behavior indicated a slower rate of crystallization of PLA/DS0.5 and a faster rate of crystallization of PLA/DS1.5 and PLA/DS2.5 compared to PLA at the highest cooling rate (5 °C/min). The potential relationship between crystallization behavior and interphase properties and interphase thickness and formation of rigid amorphous fraction in the interphase, was investigated. The formation of a rigid amorphous fraction in PLA/DS1.5 and a thick interphase in PLA/DS2.5 prevented the formation of crystals on the dispersed phase and interrupted the crystallization under isothermal conditions. Hydrogen bonding in the PLA/DS1.5 blend and hydrophobic interactions in the PLA/DS2.5 blend may facilitate the crystallization at high cooling rates under non-isothermal conditions. Small-angle X-ray scattering analysis revealed the presence of a smaller lamellar structure in PLA/AS blends. The largest amorphous phase among blends was observed for the PLA/DS1.5 blend, which can be attributed to the hydrogen bonding in the interphase region of this blend.

Poly(lactic acid)/acetylated starch blends: Effect of starch acetylation on the material properties.

This study investigated the acetylation of starch to improve its processability and compatibility with poly(lactic acid). The temperature at the maximum rate of degradation increased by 3.2% for poly(lactic acid) blends containing acetylated starch degree of substitution 2.5 compared to the blend containing neat starch. A biphasic morphology with distinct dispersed phase was predicted and observed experimentally for all blends except the blend containing acetylated starch degree of substitution 3. Acetylated starch induced plasticization and nucleation for all degree of substitution. The blend containing acetylated starch degree of substitution 2.5 had higher tensile strength (26%), and toughness (29%) compared to the blend containing neat starch. The superior mechanical properties of the blend containing acetylated starch degree of substitution 2.5 are attractive for medical implant applications. The continuous microstructure and transparency characteristics of the blend containing acetylated starch degree of substitution 3 are attractive for packaging applications.

Fluorescence spectroscopy and principal component analysis of soy protein hydrolysate fractions and the potential to assess their antioxidant capacity characteristics.

The potential of intrinsic fluorescence and principal component analysis (PCA) to characterize the antioxidant capacity of soy protein hydrolysates (SPH) during sequential ultrafiltration (UF) and nanofiltration (NF) was evaluated. SPH was obtained by enzymatic hydrolysis of soy protein isolate. Antioxidant capacity was measured by Oxygen Radical Absorbance Capacity (ORAC) and Folin Ciocalteau Reagent (FCR) assays together with fluorescence excitation-emission matrices (EEM). PCA of the fluorescence EEMs revealed two principal components (PC1-tryptophan, PC2-tyrosine) that captured significant variance in the fluorescence spectra. Regression models between antioxidant capacity and PC1 and PC2 displayed strong linear correlations for NF fractions and a weak linear correlation for UF fractions. Clustering of UF and NF fractions according to ORACFPCA and FCRFPCA was observed. The ability of this method to extract information on contributions by tryptophan and tyrosine amino acid residues to the antioxidant capacity of SPH fractions was demonstrated.

Drying of Durum Wheat Pasta and Enriched Pasta: A Review of Modeling Approaches.

Models on drying of durum wheat pasta and enriched pasta were reviewed to identify avenues for improvement according to consumer needs, product formulation and processing conditions. This review first summarized the fundamental phenomena of pasta drying, mass transfer, heat transfer, momentum, chemical changes, shrinkage and crack formation. The basic equations of the current models were then presented, along with methods for the estimation of pasta transport and thermodynamic properties. The experimental validation of these models was also presented and highlighted the need for further model validation for drying at high temperatures (>-100°C) and for more accurate estimation of the pasta diffusion and mass transfer coefficients. This review indicates the need for the development of mechanistic models to improve our understanding of the mass and heat transfer mechanisms involved in pasta drying, and to consider the local changes in pasta transport properties and relaxation time for more accurate description of the moisture transport near glass transition conditions. The ability of current models to describe dried pasta quality according to the consumers expectations or to predict the impact of incorporating ingredients high in nutritional value on the drying of these enriched pasta was also discussed.

A Meta-Analysis of Enriched Pasta: What Are the Effects of Enrichment and Process Specifications on the Quality Attributes of Pasta?

Pasta products enriched with ingredients to improve their nutritional value or functionality have become increasingly popular, and substantial research efforts have been directed towards the development of new enriched pasta products. In this work, a meta-analysis was conducted to quantify the impact of enrichment and process specifications on the quality attributes of pasta. A literature search revealed 66 studies on enriched pasta. Process specifications and quality attributes, namely proximate composition, dough, drying, cooking, and mechanical properties, color, and sensory attributes, were extracted from the studies and compiled in a data set. Analysis of the data set revealed significant differences between pasta enriched with high-fiber ingredients and pasta enriched with pulse flour. High-fiber ingredients generally preserved the quality attributes of pasta more effectively than pulse flour. Comparisons based on the drying temperature showed that high drying temperatures generally improve the cooking properties of enriched pasta. Sensory evaluations indicated that enrichment levels below 10% generally do not affect consumer acceptance, but higher enrichment levels significantly decrease it. Pearson correlation coefficients showed that the gelatinization temperature and Farinograph properties are useful indicators of the mechanical properties and sensory attributes of pasta. The meta-analysis revealed the need to better understand the impact of the processing history of the enrichment ingredient on the quality attributes and the health benefits of enriched pasta.

Fluorescence analysis of NOM degradation by photocatalytic oxidation and its potential to mitigate membrane fouling in drinking water treatment.

This study examined the photocatalytic oxidation of natural organic matter (NOM) as a method to mitigate membrane fouling in drinking water treatment. ZnO and TiO2 photocatalysts were tested in concentrations ranging from 0.05 g L(-1) to 0.5 g L(-1). Fluorescence peaks were used as the primary method to characterize the degradation of three specific NOM components - fulvic acid-like humic substances, humic acid-like humic substances, and protein-like substances during photocatalytic oxidation. Fluorescence peaks and Liquid Chromatography-Organic Carbon Detection (LC-OCD) analysis indicated that higher NOM degradation was obtained by photocatalytic oxidation with ZnO than with TiO2. Treatment of the feed water by ZnO photocatalytic oxidation was successful in reducing considerably the extent of hydraulically reversible and irreversible membrane fouling during ultrafiltration (UF) compared to feed water treatment with TiO2. Fouling during UF of water subjected to photocatalytic oxidation appeared to be caused by low molecular weight constituents of NOM generated during photocatalytic oxidation.

Flaxseed-Enriched Cereal-Based Products: A Review of the Impact of Processing Conditions.

The properties of cereals products, bread, pasta, muffins, cookies, cakes, and bars, enriched with flaxseed, were reviewed to highlight suitable processing conditions for the production of high-quality flaxseed-enriched products with the desired health attributes. The review highlights the contrasting effect of flaxseed enrichment on the mechanical and physical properties of cereal products according to product type, flaxseed enrichment level, and processing history. Flaxseed lipids remain stable for most processing and storage conditions, presumably due to the significant antioxidant properties of lignans, but information is lacking on the impact of home-handling, such as bread toasting, on lipid oxidation. Cereal products enriched with flaxseed generally exhibit similar or improved shelf life compared to equivalent products with no flaxseed enrichment, suggesting that flaxseed may limit starch retrogradation, maintain moisture content, and delay microbial growth. Sensory analysis shows lower organoleptic properties of most cereal products containing flaxseed, but similar consumer acceptance for cereal products without and with flaxseed enrichment up to 15% is reported in the literature. This review indicates the need to better understand the impact of flaxseed enrichment on product microstructure and to conduct an extensive assessment of the health effects of flaxseed-enriched products, since very few studies have focused on the quantification of the bioaccessibility, bioavailability, and activity of flaxseed bioactive compounds for a variety of processing conditions and product formulation.

Characterizing natural colloidal/particulate-protein interactions using fluorescence-based techniques and principal component analysis.

Characterization of the interactions between natural colloidal/particulate- and protein-like matter is important for understanding their contribution to different physiochemical phenomena like membrane fouling, adsorption of bacteria onto surfaces and various applications of nanoparticles in nanomedicine and nanotoxicology. Precise interpretation of the extent of such interactions is however hindered due to the limitations of most characterization methods to allow rapid, sensitive and accurate measurements. Here we report on a fluorescence-based excitation-emission matrix (EEM) approach in combination with principal component analysis (PCA) to extract information related to the interaction between natural colloidal/particulate- and protein-like matter. Surface plasmon resonance (SPR) analysis and fiber-optic probe based surface fluorescence measurements were used to confirm that the proposed approach can be used to characterize colloidal/particulate-protein interactions at the physical level. This method has potential to be a fundamental measurement of these interactions with the advantage that it can be performed rapidly and with high sensitivity.

Reversible and irreversible low-pressure membrane foulants in drinking water treatment: Identification by principal component analysis of fluorescence EEM and mitigation by biofiltration pretreatment.

With the increased use of membranes in drinking water treatment, fouling--particularly the hydraulically irreversible type--remains the main operating issue that hinders performance and increases operational costs. The main challenge in assessing fouling potential of feed water is to accurately detect and quantify feed water constituents responsible for membrane fouling. Utilizing fluorescence excitation-emission matrices (EEM), protein-like substances, humic and fulvic acids, and particulate/colloidal matter can be detected with high sensitivity in surface waters. The application of principal component analysis to fluorescence EEMs allowed estimation of the impact of surface water constituents on reversible and irreversible membrane fouling. This technique was applied to experimental data from a two year bench-scale study that included thirteen experiments investigating the fouling potential of Grand River water (Ontario, Canada) and the effect of biofiltration pre-treatment on the level of foulants during ultrafiltration (UF). Results showed that, although the content of protein-like substances in this membrane feed water (=biofiltered natural water) was much lower than commonly found in wastewater applications, the content of protein-like substances was still highly correlated with irreversible fouling of the UF membrane. In addition, there is evidence that protein-like substances and particulate/colloidal matter formed a combined fouling layer, which contributed to both reversible and irreversible fouling. It is suggested that fouling transitions from a reversible to an irreversible regime depending on feed composition and operating time. Direct biofiltration without prior coagulant addition reduced the protein-like content of the membrane feed water which in turn reduced the irreversible fouling potential for UF membranes. Biofilters also decreased reversible fouling, and for both types of fouling higher biofilter contact times were beneficial.

Probing protein colloidal behavior in membrane-based separation processes using spectrofluorometric Rayleigh scattering data.

One of the primary problems in membrane-based protein separation is membrane fouling. In this study we explored the feasibility of employing Rayleigh light scattering data from fluorescence studies combined with chemometric techniques to determine whether a correlation could be established with membrane fouling phenomena. Membrane flux was measured in a dead-end UF filtration system and the effect of protein solution properties on the flux decline was systematically investigated. A variety of proteins were used as a test case in this study. In parallel, the colloidal behavior of the protein solutions was assessed by employing multiwavelength Rayleigh scattering measurements. To assess the usefulness of Rayleigh scattering measurements for probing the colloidal behavior of proteins, a protein solution of beta-lactoglobulin was used as a base-case scenario. The colloidal behavior of different beta-lactoglobulin solutions was inferred based on published data for this protein, under identical solution conditions, where techniques other than Rayleigh scattering had been used. Using this approach, good agreement was observed between scattering data and the colloidal behavior of this protein. To test the hypothesis that a high degree of aggregation will lead to increased membrane fouling, filtration data was used to find whether the Rayleigh scattering intensity correlated with permeate flux changes. It was found that for protein solutions which were stable and did not aggregate, fouling was reduced and these solutions exhibited reduced Rayleigh scattering. When the aggregation behavior of the solution was favored, significant flux declines occurred and were highly correlated with increased Rayleigh scattering.

Identifying fouling events in a membrane-based drinking water treatment process using principal component analysis of fluorescence excitation-emission matrices.

The identification of key foulants and the provision of early warning of high fouling events for drinking water treatment membrane processes is crucial for the development of effective countermeasures to membrane fouling, such as pretreatment. Principal foulants include organic, colloidal and particulate matter present in the membrane feed water. In this research, principal component analysis (PCA) of fluorescence excitation-emission matrices (EEMs) was identified as a viable tool for monitoring the performance of pre-treatment stages (in this case biological filtration), as well as ultrafiltration (UF) and nanofiltration (NF) membrane systems. In addition, fluorescence EEM-based principal component (PC) score plots, generated using the fluorescence EEMs obtained after just 1hour of UF or NF operation, could be related to high fouling events likely caused by elevated levels of particulate/colloid-like material in the biofilter effluents. The fluorescence EEM-based PCA approach presented here is sensitive enough to be used at low organic carbon levels and has potential as an early detection method to identify high fouling events, allowing appropriate operational countermeasures to be taken.

Monitoring the fractionation of a whey protein isolate during dead-end membrane filtration using fluorescence and chemometric methods.

During membrane-based separation of proteins, changes in protein concentration of the permeate and retentate streams occurs over time. The current work proposes a new approach for monitoring the changes in concentrations of proteins in both permeate and retentate by making use of data collected using fluorescence spectroscopy and intrinsic protein fluorescence analyzed by multivariate statistical techniques. Whey protein isolate consists mainly of alpha-lactalbumin (alpha-LA), beta-lactoglobulin (beta-LG), and small proportion of bovine serum albumin (BSA) and was used as a model system in this study. A fiber optic probe (FOP) was used to acquire multiwavelength fluorescence spectra for permeate and retentate streams at different times during UF-based separation of the components from a multicomponent solution. Multivariate regression models were developed for predicting the concentrations of alpha-LA, beta-LG, and BSA by establishing a calibration model between data acquired using the FOP and the corresponding protein concentration levels measured by size-exclusion chromatography. The model was validated using FOP data that were not previously used for calibration of the regression models. This comparison showed that concentrations of alpha-LA, beta-LG, and BSA could be predicted directly from FOP data within reasonable accuracy by making use of multivariate calibration tools. This approach has several attractive features including that it is nondestructive, fast, and relatively simple to perform. This technique has potential practical applications as it could offer the opportunity for in situ monitoring of membrane filtration processes by tracking individual protein transmission and selectivity of fractionation.

Effect of pore size, shear rate, and harvest time during the constant permeate flux microfiltration of CHO cell culture supernatant.

The influence of the shear rate, the membrane pore size, and the age of the culture at time of harvest on transmembrane pressure (TMP) increase and membrane fouling during the microfiltration of a Chinese Hamster Ovary (CHO) cell culture supernatant was investigated. A hollow fiber microfiltration system operated at constant permeate flux was used. The highest TMP increase with filtration time was observed for the small membrane pore size (0.20 microm) operated at the higher shear rate (8,000 s(-1)). Furthermore, the high overall fouling observed with the small membrane pore size was also associated with the highest irreversible fouling and the most significant decrease of predicted open pore area. The predicted reduction in open pore area obtained with the combined pore blockage and cake formation mechanism could explain the observed TMP profiles. Based on the overall membrane fouling, the long-term irreversible fouling and the initial fouling rate, derived from an empirical curve fitting, no effect of the time of harvest was observed but a dependence of the initial fouling rate on the shear rate was identified. Treatment of the fouled membrane with water showed the presence of a more significant reversible fouling at high shear rates and increased irreversible fouling with smaller membrane pore size. It is recommended to use the large membrane pore size (0.45 microm) and the low shear rate (4,000 s(-1)) to minimize fouling associated with the soluble components of serum-free CHO cell culture supernatant.

Fluorescence-based soft-sensor for monitoring beta-lactoglobulin and alpha-lactalbumin solubility during thermal aggregation.

A soft-sensor for monitoring solubility of native-like alpha-lactalbumin (alpha-LA) and beta-lactoglobulin (beta-LG) and their aggregation behavior following heat treatment of mixtures under different treatment conditions was developed using fluorescence spectroscopy data regressed with a multivariate Partial Least Squares (PLS) regression algorithm. PLS regression was used to correlate the concentrations of alpha-LA and beta-LG to the fluorescence spectra obtained for their mixtures. Data for the calibration and validation of the soft sensor was derived from fluorescence spectra. The process of thermal induced aggregation of beta-LG and alpha-LA protein in mixtures, which involves the disappearance of native-like proteins, was studied under various treatment conditions including different temperatures, pH, total initial protein concentration and proportions of alpha-LA and beta-LG. It was demonstrated that the multivariate regression models used could effectively deconvolute multi-wavelength fluorescence spectra collected under a variety of process conditions and provide a fairly accurate quantification of respective native-like proteins despite the significant overlapping between their emission profiles. It was also demonstrated that a PLS model can be used as a black-box prediction tool for estimating protein aggregation when combined with simple mass balances.

Carbohydrate and mineral removal during the production of low-phytate soy protein isolate by combined electroacidification and high shear tangential flow ultrafiltration.

In this work, soy protein isolates were produced by a combination of electroacidification and high shear tangential flow hollow fiber ultrafiltration with a 100 kDa membrane under constant pressure. The filtration performance was evaluated by comparing the filtration time and the final product composition for an electroacidified (pH 6) and a non-electroacidified (pH 9) soy protein extract. The removal of carbohydrates during the filtration was always consistent with the theoretical predictions (based on free permeability assumption) for both the electroacidified and the non-electroacidified feeds. A higher removal of calcium, magnesium, and phytic acid was achieved during the filtration of the electroacidified feed compared to the non-electroacidified feed. However, the electroacidification pretreatment had a negative impact on the permeate flux and resulted in more significant membrane fouling with correspondingly longer filtration times. A discontinuous diafiltration enhanced the removal of carbohydrates and minerals, thus yielding a product with higher protein content but was unable to improve the permeate flux for the electroacidified feed.

Fluorescence spectroscopy as a tool for monitoring solubility and aggregation behavior of beta-lactoglobulin after heat treatment.

Denaturation and aggregation of whey proteins are of interest to the food and pharmaceutical industry due to the importance of final structure in functionality, impact on food texture, and the chemical stability of the final product. In this study, we demonstrate the potential of fluorescence spectrometry combined with multivariate chemometric methods for quantifying solubility and aggregation behavior of beta-lactoglobulin (beta-LG); a major whey protein and a frequent food ingredient. Heat-induced aggregation of beta-LG was studied under different conditions including pH, temperature and heating durations. Results showed very good agreement between the fluorescence-based predictions and measurements obtained by HPLC and gravimetric analysis regardless of the conditions. Standard normal variate (SNV), a signal preprocessing and filtering tool, was found to enhance the predictive accuracy and robustness of the fluorescence-based model.

Calcium interacts with antifreeze proteins and chitinase from cold-acclimated winter rye.

During cold acclimation, winter rye (Secale cereale) plants accumulate pathogenesis-related proteins that are also antifreeze proteins (AFPs) because they adsorb onto ice and inhibit its growth. Although they promote winter survival in planta, these dual-function AFPs proteins lose activity when stored at subzero temperatures in vitro, so we examined their stability in solutions containing CaCl2, MgCl2, or NaCl. Antifreeze activity was unaffected by salts before freezing, but decreased after freezing and thawing in CaCl2 and was recovered by adding a chelator. Ca2+ enhanced chitinase activity 3- to 5-fold in unfrozen samples, although hydrolytic activity also decreased after freezing and thawing in CaCl2. Native PAGE, circular dichroism, and Trp fluorescence experiments showed that the AFPs partially unfold after freezing and thawing, but they fold more compactly or aggregate in CaCl2. Ruthenium red, which binds to Ca(2+)-binding sites, readily stained AFPs in the absence of Ca2+, but less stain was visible after freezing and thawing AFPs in CaCl2. We conclude that the structure of AFPs changes during freezing and thawing, creating new Ca(2+)-binding sites. Once Ca2+ binds to those sites, antifreeze activity, chitinase activity and ruthenium red binding are all inhibited. Because free Ca2+ concentrations are typically low in the apoplast, antifreeze activity is probably stable to freezing and thawing in planta. Ca2+ may regulate chitinase activity if concentrations are increased locally by release from pectin or interaction with Ca(2+)-binding proteins. Furthermore, antifreeze activity can be easily maintained in vitro by including a chelator during frozen storage.

Survey of bandage lens use in North America, October-December 2002.

PURPOSE: The purpose of this work was to report the findings of a survey of current modes of bandage lens (BL) use by optometrists and ophthalmologists in Canada and the United States in 2002. METHODS: Two thousand voluntary surveys were sent to ophthalmic practitioners across the United States and Canada. The survey contained a questionnaire with 15 questions about the practitioner's background and BL-prescribing trends and views. It also contained a 10-patient list with parameters such as patient profile, BL type, and pharmaceutical use. RESULTS: Seventy-two percent of those opthalmic practitioners who returned surveys have prescribed soft contact lenses for therapeutic purposes. BLs are most often used for corneal wound healing and for managing postoperative complications. Pharmaceuticals are concomitantly administered in more than 81% of the patients treated with BLs. The most commonly prescribed pharmaceuticals are antibiotics (47.5% of patients) and antiinflammatory drugs (42% of patients). ACUVUE and Focus Night & Day lenses are the most popular choices for BLs. Most respondents (93%), regardless of whether they routinely prescribed BLs, would be interested in a BL that could deliver a topical pharmaceutical drug. CONCLUSIONS: The results from the survey indicated that BL use is prevalent across North America. The BL-prescribing habits of North American practitioners indicate that there is a strong interest and need for a drug-delivering therapeutic soft contact lens.