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.     

Novel rotor position extraction based on carrier frequency component method (CFCM) using two reference frames for IPM drives

In this paper a novel interior permanent-magnet (IPM) motor's rotor position extraction method from the carrier-frequency component signal, derived from pulsewidth-modulated (PWM) inverter switching, using two reference frames is presented. This method has been utilized for IPM motor vector control without a mechanical rotor position detector, extracting rotor position angle from the switching carrier-frequency (10 kHz) component current. It is effective for IPM motors, which have magnetic saliency, sinusoidal distributed stator winding, and are supplied by a PWM voltage-source inverter. The performance of two IPM motors' vector control without mechanical rotor position detector utilizing this method has been investigated. Experimental results demonstrating good dynamic and steady-state performance achieved are presented and discussed.     

Dietary oxysterols are incorporated in plasma triglyceride-rich lipoproteins, increase their susceptibility to oxidation and increase aortic cholesterol concentration of rabbits

Early fatty streaks and advanced lesions are characterized by the deposition of cholesterol and cholesterol oxidation products (oxysterols). Oxysterols have been shown to be cytotoxic and pro-atherogenic compared to cholesterol and are found in cholesterol-rich processed foods. The consumption of dietary oxysterols may be significant in the onset and development of vascular disease. In order to study the short term effects of low levels of ingested dietary oxysterols on lipoprotein and aortic cholesterol and oxysterol levels, rabbits were fed either standard chow, chow supplemented with 1.0% oxidized cholesterol (containing 6% oxysterols), or 1.0% purified cholesterol (control). To determine the distribution and uptake of oxysterols after a 2-week dietary period, triglyceride-rich plasma lipoproteins, low density lipoproteins and aorta were analyzed by GC-MS. The concentration of 7beta-hydroxycholesterol was similar in all groups but the oxidized cholesterol-fed animals showed five times the concentration of 5alpha,6alpha-epoxycholesterol and double the level of 7-ketocholesterol in triglyceride-rich lipoproteins compared to the purified cholesterol-fed animals. The presence of 7-ketocholesterol in LDL was exclusive to animals fed the oxidized cholesterol diet. In addition, oxidation of triglyceride-rich lipoproteins was significantly greater in rabbits fed oxidized cholesterol compared to the pure cholesterol-fed animals. The oxidized cholesterol-fed animals also had a 64% increase in total aortic cholesterol, despite lower plasma cholesterol levels compared to the pure cholesterol control animals. Taken together these results suggest that dietary oxysterols may substantially increase the atherogenicity of lipoproteins.     

Modeling the diffusion-adsorption kinetics of 1-methylcyclopropene (1-MCP) in apple fruit and non-target materials in storage rooms

The purpose of this research was to model the kinetics of adsorption of 1-methylcyclopropene (1-MCP) in apple fruit and non-target solid materials found in apple storage rooms. The process was described by Fick’s second law of diffusion of the gas through the pores of the material coupled with adsorption kinetics of the gas on the material’s binding sites. A finite element formulation of the model, describing the diffusion and adsorption mechanisms separately, was first developed. The values of the relevant parameters were estimated based on headspace measurements of the decrease of 1-MCP in jars containing the different materials. The headspace concentration of 1-MCP was measured using gas chromatography. Apple fruit (Golden Delicious and Jonagold) and the following bin construction materials were investigated: high density polyethylene (HDPE), oak, poplar wood and card lining. The range in the magnitude of the diffusion coefficient, adsorption coefficient, and concentration of active sites in the various solids was 10,000-, 8-, and 30-fold, respectively.     

Luminescent Mononuclear and Dinuclear Iridium(III) Cyclometalated Complexes Immobilized in a Polymeric Matrix as Solid-State Oxygen Sensors

Oxygen quenching of the luminescence of mononuclear and dinuclear Ir(III) cyclometalated complexes immobilized in the pPEGMA matrixes has been studied. Linear Stern-Volmer plots, even when experiments at different emission wavelengths have been performed, were evidenced. Despite the different luminescence lifetimes of the chromophores in the absence of quencher, similar Stern-Volmer slopes have been calculated. This behavior was tentatively interpreted by taking into account the size and charge of the chromophores. Increased sizes and lower charges seem to enhance the sensitivity of the systems. Such findings could be of interest for the design of new solid-state luminescent oxygen sensors with improved performance.     

Soil nutrient maps of Sub-Saharan Africa: assessment of soil nutrient content at 250 m spatial resolution using machine learning

Spatial predictions of soil macro and micro-nutrient content across Sub-Saharan Africa at 250 m spatial resolution and for 0–30 cm depth interval are presented. Predictions were produced for 15 target nutrients: organic carbon (C) and total (organic) nitrogen (N), total phosphorus (P), and extractable—phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), sodium (Na), iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), aluminum (Al) and boron (B). Model training was performed using soil samples from ca. 59,000 locations (a compilation of soil samples from the AfSIS, EthioSIS, One Acre Fund, VitalSigns and legacy soil data) and an extensive stack of remote sensing covariates in addition to landform, lithologic and land cover maps. An ensemble model was then created for each nutrient from two machine learning algorithms—random forest and gradient boosting, as implemented in R packages ranger and xgboost—and then used to generate predictions in a fully-optimized computing system. Cross-validation revealed that apart from S, P and B, significant models can be produced for most targeted nutrients (R-square between 40–85%). Further comparison with OFRA field trial database shows that soil nutrients are indeed critical for agricultural development, with Mn, Zn, Al, B and Na, appearing as the most important nutrients for predicting crop yield. A limiting factor for mapping nutrients using the existing point data in Africa appears to be (1) the high spatial clustering of sampling locations, and (2) missing more detailed parent material/geological maps. Logical steps towards improving prediction accuracies include: further collection of input (training) point samples, further harmonization of measurement methods, addition of more detailed covariates specific to Africa, and implementation of a full spatio-temporal statistical modeling framework.     

The impact of natural and artificial weathering on the visual,colour and structural changes of seven tropical woods

This study investigates the effects of wood weathering on changes in its macroscopic and colour characteristics in connection with changes in its molecular and anatomical structure. Seven hardwoods suitable for outdoor architecture—bangkirai, cumaru, cumaru rosa, ipé, jatobá, kusia, and massaranduba—were exposed to the exterior out of ground contact for 1–36 months according to EN 927-3, and for 1–12 weeks in Xenotest with water spraying according to partly modified EN 927-6. With prolonged weathering, the following changes occurred in the top surfaces of all tropical woods: (1) visual—creation of longitudinal macro-cracks, (2) spectrophotometry and CIE-L ^? a ^? b ^? —darkening in exterior exposure mainly due to pollutants, except for ipé, and vice versa lightening in Xenotest, as well as greening and blueing in both modes of exposure, (3) FTIR—faster decrease of guaiacyl than syringyl lignin, absolute decrease of conjugated and unconjugated carbonyl groups in the newly formed lignin-polysaccharide-extractive substrate in the photo-oxidized and washed-out cell walls, and decrease of cellulose crystallinity, (4) SEM—damaging of cell-walls by micro-cracks, and their degradation by thinning. Connections between changes of the individual characteristics of weathered woods, for example, between the colour (ΔE*, etc.) and the molecular structure (carbonyls, etc.), were also determined.     

Experimental and Numerical Investigation of Airflow Inside Refrigerated Shipping Containers

During transportation of fruits and vegetables, factors such as temperature, air exchange, humidity levels, packaging design and stacking arrangements in the reefer (refrigerated shipping container) are extremely important to maintain the cold chain. In this study, the airflow distribution inside two types of refrigerated shipping containers (T-bar floor and flat floor) used for transporting fresh fruit handling were investigated. Computational fluid dynamics (CFD) model of airflow was developed and experimentally validated. Measurements of air velocities were taken from 222 sample positions inside a full-size reefer. The validated model was then implemented to study the effects of container designs and operational conditions on airflow pattern and distribution. High and low evaporator speed scenarios of the two reefer designs (T-bar floor and flat floor) were investigated. The result showed that airflow distribution in the two container designs were markedly different. Good agreement was found between measured and predicted values of air velocities. The air exchange rate in the rear part of the reefers for the two designs were compared. For the flat floor reefer, the air exchange was 0.2 m³ h^?1 while for the T-bar floor, it was 0.6 m³ h^?1. Also, in the primary recirculation region, (between 3 and 8 m from the inlet side) the average vertical air velocity was higher in the T-bar floor reefer (0.04 m s^?1) than in the flat floor reefer (0.01 m s^?1). As a result, reefer with T-bar floor design exhibited a noticeable reduction of air recirculation zone and enhanced uniform vertical air movement compared to the reefer with flat floor design.     

Undoped, nitrogen-doped and boron-doped multiwalled carbon nanotube/poly(vinyl alcohol) composite as active layer in simple hydrostatic pressure sensors

We report on hydrostatic pressure sensors prepared using 10 % w/w multiwalled carbon nanotube (MWCNT)/poly(vinyl alcohol) composites. Three types of carbon nanotubes were used in the composites: undoped MWCNTs, nitrogen-doped MWCNTs and boron-doped MWCNTs (B-MWCNTs). The sensor response was tested using an alternating current input, measuring the capacitance and conductance outputs. The sensors based on the three composites show a linear capacitance and conductance sensitivity pressure dependence in the range 50–120 kPa, but a higher sensitivity to pressure dependence above this interval. The highest angular coefficient of the sensitivity, which reached 0.092 kPa^?1, was observed for the capacitance sensitivity of the B-MWCNT based composite.