Exploring the Substrate Specificity and Enantioselectivity of a Baeyer–Villiger Monooxygenase from Dietzia sp. D5: Oxidation of Sulfides and Aldehydes

Baeyer–Villiger monooxygenases (BVMOs) are valuable enzymes for specific oxyfunctionalization chemistry. They catalyze the oxidation of ketones to esters, but are also capable of oxidizing other chemical functions, namely aldehydes and heteroatoms such as sulfur, nitrogen, selenium and boron. The oxidation specificity and enantioselectivity of a newly characterized BVMO (BVMO4) from a strain of Dietzia towards sulfide- and aldehyde substrates have been studied. BVMO4 could react with sulfides containing an aromatic group. The presence of a substituent on the aromatic group was tolerated when they were in the meta- and para position and the oxidations yielded predominantly the (R)-sulfoxides. Similarly, BVMO4 displayed a higher activity for aldehydes containing a phenyl group, but long aliphatic aldehydes, namely octanal and decanal, were also accepted as substrate by this enzyme. The major oxidation products of the aldehyde substrates were the respective carboxylic acids in contrast to formate ester that was obtained in most of the previous reports. The Baeyer–Villiger oxidation of the substrate 2-phenylpropionaldehyde was studied in further detail and the corresponding acid product was obtained with good regio- and enantioselectivity. This is a unique feature for BVMO4 and is of great interest for further exploration of an alternative biocatalytic process.     

The role of calcium in blended fly ash geopolymers

In this research effort, the role of calcium in geopolymers was investigated through a series of syntheses where a high-calcium fly ash was blended with a low-calcium fly ash. Increased calcium content led to accelerated set-up times, increased compressive strength, and increased product formation. Powder X-ray diffraction results showed the majority of that product to be geopolymer framework with only minor contributions from calcium silicate phases. Thermal analysis confirmed the absence of a calcium silicate hydrate phase. Analysis of fly ash dissolution showed that calcium aided in aluminosilicate dissolution and therefore the geopolymerization reaction. While aiding in this reaction, calcium became incorporated into the pore structure of the geopolymer as a counter-balancing cation, according to ion exchange experiments. Thus, geopolymer synthesis with increased calcium content through the use of a high-calcium fly ash under these experimental conditions produced a quick-setting, strong, calcium incorporated geopolymer material.     

An investigation of the damage mechanisms and fatigue life diagrams of flax fiber-reinforced polymer laminates

In this paper we investigated the fatigue damage of a unidirectional flax-reinforced epoxy composite using infrared (IR) thermography. Two configurations of flax/epoxy composites layup were studied namely, [0]₁₆ unidirectional ply orientation and [±45]₁₆. The high cycle fatigue strength was determined using a thermographic criterion developed in a previous study. The fatigue limit obtained by the thermographic criterion was confirmed by the results obtained through conventional experimental methods (i.e., Stress level versus Number of cycles to failure). Furthermore, a model for predicting the fatigue life using the IR thermography was evaluated. The model was found to have a good predictive value for the fatigue life. In order to investigate the mechanism of damage initiation in flax/epoxy composites and the damage evolution, during each fatigue test we monitored the crack propagation for a stress level and at different damage stages, a direct correlation between the percentage of cracks and the mean strain was observed.     

Determining the Reuse Potential of Components Based on Life Cycle Data

Reuse of components is one of the most efficient strategies for product recovery, which requires reliable methods for assessing the quality and the remaining life of used components. A new methodology, presented in this paper, is based on the trend analysis of lifetime monitoring data. Data with similar trends were grouped and a number of analysis techniques such as Linear Multiple Regression, Dynamic Ordinary Kriging, Universal Kriging and Neural Networks were applied in order to find the most suitable methodology for each group. The methodology was validated by using lifetime monitoring data from a consumer product.     

Drug targeting using low density lipoprotein (LDL): physicochemical factors affecting drug loading into LDL particles

Low density lipoprotein (LDL) has been found suitable as a targeting carrier for cytotoxic drugs. However, higher drug loading into LDL particles without disrupting their native integrity remains a major obstacle. The purpose of this study is to investigate the different physicochemical factors that may affect drug loading and to characterize LDL-drug conjugates. Doxorubicin (Dox) and 3', 5'-O-dipalmitoyl-5-iodo-2'-deoxyuridine (dpIUdR) were used as reference cytotoxic drugs. Drugs were loaded into LDL particles using the dry film method with or without surfactants, liposomal and the direct addition method. The effects of incubation temperature, time and stoichiometry of LDL-drug conjugates on drug loading were investigated. The LDL-drug conjugates were evaluated for their stability and characterized by differential scanning calorimetry (DSC), denatured gel (SDS-PAGE), and electron microscopy (EM). We have suitably incorporated 45+/-10 Dox and 150+/-25 dpIUdR molecules/LDL particle. A seven-fold increase in Dox incorporation was achieved with the liposomal preparation compared to the dry film method. A 4- to 6-h incubation at 37 degreesC was suitable to restore the native structure of LDL particles. No apo B fragmentation of LDL particles was noted on denatured gel. DSC studies showed no change in the Tm of the LDL and the LDL-drug conjugates. An increase in particle size of LDL-dpIUdR, not LDL-Dox was observed in EM compared to the native LDL which may be related to higher incorporation of dpIUdR. The results indicate that physicochemical factors significantly affect drug loading efficiency and may need to be considered to optimize drug incorporation into LDL particles.     

Comments on `A Lyapunov function of two-dimensional linear systems'

The authors show that the function introduced in the above-titled paper by H. Mahgoub and R. Carroll (ibid., vol. AC-31, p.170-172, (1986)) is not a Lyapunov function for a discrete 2-D system     

N-methyl-D-aspartate antagonists, glutamate release inhibitors, 4-aminopyridine at neuromuscular transmission

GLP-1, an incretin hormone of the enteroinsular axis with insulinotropic and glucagonostatic activity, is secreted after nutrient ingestion. GLP-1 is mainly produced by intestinal L-cells in the lower gastrointestinal tract (GIT); simple carbohydrates are absorbed in the upper GIT and alpha-glucosidase inhibition leads to augmented and prolonged GLP-1 release in normal subjects. In a cross-over study, 100 mg acarbose or placebo was administered simultaneously with 100 g sucrose to 11 hyperglycaemic Type 2 diabetic patients poorly controlled with diet and sulphonylureas. Plasma levels of GLP-1, insulin, C-peptide, glugacon, GIP, glucose and H2-exhalation were measured over 6 h. Differences in the integrated responses over the observation period were evaluated by repeated measurement analysis of variance with fasting values used as covariates. With acarbose, sucrose reached the colon 60-90 min after ingestion as indicated by a significant increment in breath hydrogen exhalation (p = 0.005). After an early GLP-1 increment 15 min after sucrose under both conditions, GLP-1 release was prolonged in the acarbose group (p = 0.001; significant from 210 to 360 min.). Initially (0-150 min), glucose (p = 0.001), insulin (p = 0.001), and GIP (p < 0.001) were suppressed by acarbose, whereas later there were no significant differences. Glucagon levels were higher with acarbose in the last 3 h of the 6 h observation period (p = 0.02). We conclude that in hyperglycaemic Type 2 diabetic patients, ingestion of acarbose with a sucrose load leads to elevated and prolonged GLP-1 release.