Polymer matrix controlled release systems: Influence of polymer carrier and temperature on water uptake and protein release

The release of bovine serum albumin (BSA) from two types of ethylene-co-vinyl acetate (EVAc) polymer matrices was studied over the temperature range 4–50°C. Protein release and weight change of the matrices were evaluated in uitro. The copolymers were characterized using differential scanning calorimetry (DSC) and thermomechanical analysis (TMA). During release, the devices initially exhibit a rapid increase in weight to a maximum, followed by a more gradual decrease for the duration of the release. The time to the maximum weight and the magnitude of the maximum weight gain are temperature dependent. These effects are related to the temperature-dependent diffusivity of the BSA and elastic modulus of the EVAc. The DSC and TMA reveal melting of the crystalline phase of the polymer. The corresponding loss of mechanical integrity of the polymer leads to anomalous weight gains at these temperatures. The observed swelling and release is explained by a model in which the osmotic pressure of the protein within the pore network causes elastic deformation of the polymer matrix.     

Chemo‐enzymatic synthesis of α‐terpineol thioacetate and thiol derivatives and their use as flavouring compounds

Reaction of (R,S)‐α‐terpineol with thioacetic acid in food‐grade n‐hexane resulted into two α‐terpineol thioacetate derivatives with the same molecular weight. After 5 h of reaction time, (R,S)‐α‐terpineol was completely transformed and the mixture analysed by different chromatographic techniques. The aroma character of the α‐terpineol thioacetates was described as exotic, sweet, blackcurrant, roasted and sulphury. Of eight lipases and two esterases assayed, only non‐immobilized pig liver esterase (PLE) hydrolysed α‐terpineol thioacetates into the corresponding α‐terpineol thiols. When reactions were performed in 0.2 m phosphate buffer at pH 8.0 and 30 °C with non‐immobilized PLE, α‐terpineol thiols were produced in an optimal yield of 88% after 24 h of reaction time. The aroma character of α‐terpineol thiols was described as green, exotic and fresh grapefruit. Flavouring powders were prepared by freeze‐drying the α‐terpineol thioacetates and α‐terpineol thiols in the presence of maltodextrine. Preliminary applications showed that these flavouring preparations could be used to improve the flavour quality of lighter cooked notes and tropical fruit aromas. Copyright © 2014 John Wiley & Sons, Ltd.     

Chemical structure of arsenic and chromium in CCA-treated wood: implications of environmental weathering

Chromated copper arsenate (CCA) has been used to treat lumber for over 60 years to increase the expected lifetime of CCA-treated wood. Because of the toxicity of the arsenic and chromium used in CCA treatment, regulatory and public attention has become focused on the potential risks from this exposure source. In particular, exposure of children to arsenic from CCA-treated wood used in decks and play sets has received considerable attention. X-ray Absorption Spectroscopy (XAS) was used to evaluate the chemical structure of As and Cr in three samples of CCA-treated materials: newly treated wood, aged wood (5 years as decking), and dislodgeable residue from aged (1-4 years as decking) CCA-treated wood. The form of the Cr and As in CCA-treated material is the same in fresh and aged samples, and between treated wood and dislodged residue. In all cases, the dominant oxidation state of the two elements is As(V) and Cr(III), and the local chemical environment of the two elements is best represented as a Cr/As cluster consisting of a Cr dimer bridged by an As(V) oxyanion. Long-term stability of the As/Cr cluster is suggested by its persistence from the new wood through the aged wood and the dislodgeable residue.     

Volatile compounds,quality attributes,mineral composition and pericarp structure of South African litchi export cultivars Mauritius and McLean's Red

BACKGROUND: The aim of this research was to identify the differences in volatile compounds, mineral composition, quality parameters and pericarp structure (at different fruit developmental stages) between two South African litchi export cultivars, Mauritius and McLean's Red, in order to provide a better understanding of the plant intraspecific variation. RESULTS: Citronellol and geraniol were predominant in the aroma profile of cv. Mauritius and conferred characteristic floral, rose, citrus and fruity aromas. In cv. McLean's Red, germacrene D was predominant in the sesquiterpene fraction. Germacrene D and muurolene are associated with a woody smell. Cv. Mauritius had lower soluble solid content/titratable acidity ratio and higher ascorbic acid content than cv. McLean's Red. Cv. McLean's Red had lower pericarp hue angle and higher anthocyanin concentration, which correlated negatively. Significant differences in fruit mineral content and pattern of cuticle accumulation were noted between the two cultivars. The parallel cuticular lines formed a network with intercellular ridges and heavy wax deposits in cv. McLean's Red. Cv. Mauritius showed higher weight loss at 25 °C, suggesting that the dense wax deposits and cuticle structure in cv. McLean's Red could limit moisture loss. CONCLUSION: This investigation shows evidence for the lack of sweet and rose‐like fragrance in litchi cv. McLean's Red. It is the first study to compare volatile compounds responsible for the differing aromas of two South African litchi cultivars. Litchi cultivar improvement and breeding programmes are focused on expansion of the season and yield. The reported information is useful for selection of cultivars and for cultivar breeding programmes focusing on fruit quality and storage potential. Copyright © 2008 Society of Chemical Industry     

Second-derivative variance minimization method for automated spectral subtraction

A new second-derivative variance minimization (SDVM) procedure is used to automatically extract spectra of a dilute component (solute) from a mixture whose spectrum is dominated by a major component (solvent). This procedure involves the subtraction of Savitzky-Golay second-derivative preprocessed pure solvent and mixture spectra by minimizing the variance of the difference spectrum. The resulting undifferentiated output spectra contain primarily features associated with the solute and/or solute-induced perturbations of the solvent. The SDVM method is found to outperform several related methods, including a previously proposed derivative minimization method, as demonstrated using 1000 randomly generated solute/solvent synthetic spectral pairs and experimental Raman spectra of dilute solutions of benzene in n-hexane and water in acetone. The former experimental solution produced SDVM difference spectra containing benzene bands with virtually no n-hexane interference, while the latter revealed water-induced shifts in acetone spectral features. Several other types of SDVM applications, such as the spectroscopic analysis of layered composites, are discussed.     

Habitat relationships of subadult humpback chub in the Colorado River through Grand Canyon: spatial variability and implications of flow regulation

We examined subadult humpback chub densities along 24 kms of the Colorado River in the Grand Canyon to: (1) identify geomorphic conditions in the study area; (2) determine associations between subadult humpback chub (<200 mm TL) habitat use and geomorphic differences; and (3) determine how discharge, during base flow conditions, was related to subadult humpback chub habitat conditions. Habitat was categorized at two nested spatial scales: geomorphic reach and shoreline type. Within reaches, shoreline types were categorized according to geomorphology. We measured water depth, velocity and cover attributes along all shoreline types over a range of discharges to determine if habitat quality of reaches and shoreline types varied with discharge. Reaches 1 and 3 had narrow, deep corridors, whereas Reach 2 was a wide, shallow reach. Among shoreline types, depth, velocity and cover varied; however, differences were not consistent between reaches. Fish densities also varied among shoreline types and reaches. Vegetation, talus and debris fan shorelines had the highest densities of subadult humpback chub in a pattern similar to that of cover. In addition, subadult humpback chub presence was associated with a high frequency of cover regardless of shoreline designation. However, these relationships explained little of the overall variation in subadult densities. Lack of a strong association between fish density and geomorphology may be partially due to effects of discharge on habitat quality. The overall trend among shorelines (without regard to type) showed that cover decreased with increasing discharge, whereas depth and velocity increased. However, no consistent pattern between discharge and depth, velocity and cover among individual shoreline types was evident. Vegetated shorelines, consisting mainly of non-native tamarisk (Tamarix chinensis), had nearly twice the fish densities of talus and debris fan. Reasons are discussed as to why subadult humpback chub occupy naturalized habitat like vegetated shorelines in greater densities than natural habitats. The relationships observed in this study have important implications for humpback chub recovery and management of the Colorado River through Grand Canyon. © 1998 John Wiley & Sons, Ltd.     

Autologous resurfacing

Background: There is a discrepancy between the interest in joint‐reconstructions and the current knowledge about the healing‐processes involved. Major reconstructions are performed with osteosynthesized allografts and fresh allografts for cartilage. Objectives: The main question to be answered is: what do we know about metaphyseal and epiphyseal cancellous bone healing, contact healing of the subchondral bone and its influence on cartilage healing? Can we achieve healing of all four compartments in contact? Purpose: The purpose is to systematically investigate through animal testing the healing processes of metaphyseal and epiphyseal bone, including the subchondral bone and the healing of cartilage of press‐fit‐inserted grafts, considering nondemineralized high‐resolution histology. Material and Methods: Primary cancellous‐bone healing of osteosynthesized hemi‐osteotomies was studied in 13 canine tibial heads, the contact healing was investigated in 7 dogs and 18 giant‐rabbits comparing contact‐healing of press‐fit‐inserted autologs cylindrical grafts with empty defects applying the wet‐grinding diamond‐technology. Bench‐experiments on the epiphyseal bones of swine including pullout‐tests of cylindrical grafts formed the basis for validation of that press‐fit diamond technology. Results: Primary metaphyseal and epiphyseal contact healing, including hyaline cartilage, was found in all compartments of the meta‐and epiphysis in the precisely performed experiments. The press‐fit principle, which employs cylindrical grafts and diamond instrumentation featuring a difference of 15/100 mm between graft and recipient bed, achieved high loads between 73.48 and 178.95 N (mean value 118.16 and standard deviation 32.79) in the pullout tests. Conclusion: Autologous press‐fit grafting with alignment of the bony baseplate using wet‐grinding precision has attained promising histo‐morphological results. Microsc. Res. Tech., 78:40–51, 2015. © 2014 Wiley Periodicals, Inc.     

A Single Second Shell Amino Acid Determines Affinity and Kinetics of Linagliptin Binding to Type 4 Dipeptidyl Peptidase and Fibroblast Activation Protein

Drugs targeting type 4 dipeptidyl peptidase (DPP-4) are beneficial for glycemic control, whereas fibroblast activation protein alpha (FAP-α) is a potential target for cancer therapies. Unlike other gliptins, linagliptin displays FAP inhibition. We compared biophysical and structural characteristics of linagliptin binding to DPP-4 and FAP to better understand what differentiates linagliptin from other gliptins. Linagliptin exhibited high binding affinity (K_D) and a slow off-rate (k_off) when dissociating from DPP-4 (K_D 6.6 pM; k_off 5.1×10⁻⁵ s⁻¹), and weaker inhibitory potency to FAP (K_D 301 nM; k_off>1 s⁻¹). Co-structures of linagliptin with DPP-4 or FAP were similar except for one second shell amino acid difference: Asp663 (DPP-4) and Ala657 (FAP). pH dependence of enzymatic activities and binding of linagliptin for DPP-4 and FAP are dependent on this single amino acid difference. While linagliptin may not display any anticancer activity at therapeutic doses, our findings may guide future studies for the development of optimized inhibitors.     

Deoxygenation of Bio‐oil from Calcium‐Rich Paper‐Mill Waste

De‐inking sludge, an ash‐rich recycling paper solid waste, is generated in huge amounts. The catalytic deoxygenation potential of calcium‐based de‐inking sludge in co‐pyrolysis mode with wood and its neat thermal conversion to sustainable biofuels are investigated. Wood, de‐inking sludge, and their blends are processed in a thermocatalytic reforming (TCR) system. In the presence of de‐inking sludge, the oxygen content in the organic phase decreases and the bio‐oil calorific value improves as compared to the neat wood‐derived bio‐oil. The TCR processing of neat de‐inking sludge produces a bio‐oil with low oxygen content and higher calorific value.