Catalytic transformation of aliphatic alcohols to corresponding esters in O2 under neutral conditions using visible-light irradiation

Selective oxidation of aliphatic alcohols under mild and base-free conditions is a challenging process for organic synthesis. Herein, we report a one-pot process for the direct oxidative esterification of aliphatic alcohols that is significantly enhanced by visible-light irradiation at ambient temperatures. The new methodology uses heterogenerous photocatalysts of gold–palladium alloy nanoparticles on a phosphate-modified hydrotalcite support and molecular oxygen as a benign oxidant. The alloy photocatalysts can absorb incident light, and the light-excited metal electrons on the surface of metal nanoparticles can activate the adsorbed reactant molecules. Tuning the light intensity and wavelength of the irradiation can remarkably change the reaction activity. Shorter wavelength light (<550 nm) drives the reaction more efficiently than light of longer wavelength (e.g., 620 nm), especially at low temperatures. The phosphate-exchanged hydrotalcite support provides sufficient basicity (and buffer) for the catalytic reactions; thus, the addition of base is not required. The photocatalysts are efficient and readily recyclable. The findings reveal the first example of using “green” oxidants and light energy to drive direct oxidative esterification of aliphatic alcohols under base-free, mild conditions.

Overfitting Bayesian mixture models with an unknown number of components

This paper proposes solutions to three issues pertaining to the estimation of finite mixture models with an unknown number of components: the non-identifiability induced by overfitting the number of components, the mixing limitations of standard Markov Chain Monte Carlo (MCMC) sampling techniques, and the related label switching problem. An overfitting approach is used to estimate the number of components in a finite mixture model via a Zmix algorithm. Zmix provides a bridge between multidimensional samplers and test based estimation methods, whereby priors are chosen to encourage extra groups to have weights approaching zero. MCMC sampling is made possible by the implementation of prior parallel tempering, an extension of parallel tempering. Zmix can accurately estimate the number of components, posterior parameter estimates and allocation probabilities given a sufficiently large sample size. The results will reflect uncertainty in the final model and will report the range of possible candidate models and their respective estimated probabilities from a single run. Label switching is resolved with a computationally light-weight method, Zswitch, developed for overfitted mixtures by exploiting the intuitiveness of allocation-based relabelling algorithms and the precision of label-invariant loss functions. Four simulation studies are included to illustrate Zmix and Zswitch, as well as three case studies from the literature. All methods are available as part of the R package Zmix, which can currently be applied to univariate Gaussian mixture models.

Prolonged hyperinsulinemia affects metabolic signal transduction markers in a tissue specific manner

Insulin dysregulation is common in horses although the mechanisms of metabolic dysfunction are poorly understood. We hypothesized that insulin signaling in striated (cardiac and skeletal) muscle and lamellae may be mediated through different receptors as a result of receptor content, and that transcriptional regulation of downstream signal transduction and glucose transport may also differ between tissues sites during hyperinsulinemia. Archived samples from horses treated with a prolonged insulin infusion or a balanced electrolyte solution were used. All treated horses developed marked hyperinsulinemia and clinical laminitis. Protein expression was compared across tissues for the insulin receptor and insulin-like growth factor 1 receptor (IGF-1R) by immunoblotting. Gene expression of metabolic insulin-signaling markers (insulin receptor substrate 1, Akt2, and glycogen synthase kinase 3 beta [GSK-3β]) and glucose transport (basal glucose transporter 1 and insulin-sensitive glucose transporter 4) was evaluated using real-time reverse transcription polymerase chain reaction. Lamellar tissue contained significantly more IGF-1R protein than skeletal muscle, indicating the potential significance of IGF-1R signaling for this tissue. Gene expression of the selected markers of insulin signaling and glucose transport in skeletal muscle and lamellar tissues was unaffected by prolonged hyperinsulinemia. In contrast, the significant upregulation of Akt2, GSK-3β, GLUT1, and GLUT4 gene expression in cardiac tissue suggested that the prolonged hyperinsulinemia induced an increase in insulin sensitivity and a transcriptional activation of glucose transport. Responses to insulin are tissue-specific, and extrapolation of data across tissue sites is inappropriate.

The effect of light on cognitive performance of partially sleep-deprived young drivers

Sleepiness remains a primary cause of road crashes, the major cause of death in young adults. Light is known to produce a direct alerting effect, but little is known about its effects on sleepy drivers. This study aimed to compare the effect of blue-green light and caffeine on young drivers’ cognitive performance after chronic-partial sleep loss.

Tyrosine kinase inhibitors (nibs)

Traditional chemotherapy involves cytotoxic agents that indiscriminately target all rapidly-dividing cells. This can lead to significant side effects as healthy cells are also targeted.

Where have all the zebras gone? The pedestrian ranks lowest in the food chain of Kathmandu's urban jungle

This article presents an overview of pedestrian environment in Kathmandu, Nepal to briefly discuss some of the emerging problems. It argues that pedestrian ranks lowest in the food chain of Kathmandu's urban jungle as there is too little concern shown by the government agencies in improving the quality of the street space for walkers.

Evaluation of the Red Light Camera Program and the Owner Onus Legislation

Red light cameras were introduced in Victoria in August 1983, with the intention of reducing the number of accidents that result from motorists disobeying red traffic signals at signalised intersections. Accident data from 46 treated and 46 control sites from 1981 to 1986 were analysed. The analysis indicated that red light camera use resulted in a reduction in the incidence of right angle accidents, and in the number of accident casualties. Legislation was introduced in March 1986 to place the onus for red light camera offences onto the vehicle owner. This legislation was intended to improve Police efficiency and therefore increase the number of red light cameras in operation. Data supplied by the Police indicated that these aims have beneficial road safety effects.

Report on Red Light Camera Program: Operation from July 1988 to December 1989

EXECUTIVE SUMMARY (excerpts) The red light camera (RLC) program commenced in July 1988, with five cameras operating at 15 sites in metropolitan Adelaide. This report deals with the first eighteen months of operation, to December 1989. A number of recommendations have been made… PROGRAM EVALUATION … In 1989 dollars, the program was estimated to have achieved an accident reduction benefit of $1.4m in the first 12 months of operation, which is almost twice the benefit expected using the assumptions made when selecting the sites. (There are 8 recommendations, mostly specific to the particular program characteristics)

The Red Light Camera Evaluation - Interim Report - July 1985

Red light cameras were introduced in August 1983 to deter run-the-red offences and therefore to reduce the incidence of right-angle accidents at signalised intersections in Melbourne. This report was prepared after two years of operation of the program. It provides a detailed account of the technical aspects of the program, but does not provide any detailed, evaluative analyses of accident data.

Fire resistance of light gauge steel frame wall systems lined with gypsum plasterboards

Light gauge steel frame (LSF) wall systems are increasingly used in residential and commercial buildings as load bearing and non-load bearing elements. Conventionally, the fire resistance ratings of such building elements are determined using approximate prescriptive methods based on limited standard fire tests. However, recent studies have shown that in some instances real building fire time-temperature curves could be more severe than the standard fire curve, in terms of maximum temperature and rate of temperature rise. This has caused problems for safe evacuation and rescue activities, and in some instances has also lead to the collapse of buildings earlier than the prescribed fire resistance. Therefore a detailed research study into the performance of LSF wall systems under both standard fire and realistic fire conditions was undertaken using full scale fire tests to understand the fire performance of different LSF wall configurations. Both load bearing and non-load bearing full scale fire tests were performed on LSF walls configurations which included single layer, double layer, externally insulated wall panels made up of different steel sections and thicknesses of gypsum plasterboards. The non-load bearing fire test results were utilized to understand the factors affecting the fire resistance of LSF walls, while loading bearing fire test results led to development of simplified methods to predict the fire resistance ratings of load bearing LSF walls exposed to both standard and realistic design fires. This paper presents the results of full scale experimental study and highlights the effects of standard and realistic fire conditions on fire performance of LSF walls.

Sustainable conversion of cellulosic biomass to chemicals under visible-light irradiation

For the first time, the conversion of crystalline cellulose to valuable chemicals was enhanced by visible-light irradiation using zeolite-based gold nanoparticles (Au-NPs). This plasmon-enhanced photocatalytic conversion significantly improved processing efficiency and achieved a high yield of 60% at relatively low temperature. Moreover, the photocatalytic properties of the photocatalysts varied with the light intensity and the irradiation wavelength.

Evaluation of polymorphisms in predicted target sites for micro RNAs differentially expressed in endometriosis

Previous microarray analyses identified 22 microRNAs (miRNAs) differentially expressed in paired ectopic and eutopic endometrium of women with and without endometriosis. To investigate further the role of these miRNAs in women with endometriosis, we conducted an association study aiming to explore the relationship between endometriosis risk and single-nucleotide polymorphisms (SNPs) in miRNA target sites for these differentially expressed miRNAs. A panel of 102 SNPs in the predicted miRNA binding sites were evaluated for an endometriosis association study and an ingenuity pathway analysis was performed. Fourteen rare variants were identified in this study. We found SNP rs14647 in the Wolf-Hirschhorn syndrome candidate gene1 (WHSC1) 3'UTR (untranslated region) was associated with endometriosis-related infertility presenting an odds ratio of 12.2 (95% confidence interval = 2.4-60.7, P = 9.03 x 10(-5)). SNP haplotype AGG in the solute carrier family 22, member 23 (SLC22A23) 3'UTR was associated with endometriosis-related infertility and more severe disease. With the individual genotyping data, ingenuity pathways analysis identified the tumour necrosis factor and cyclin-dependant kinase inhibitor as major factors in the molecular pathways. Significant associations between WHSC1 alleles and endometriosis-related infertility and SLC22A23 haplotypes and the disease severe stage were identified. These findings may help focus future research on subphenotypes of this disease. Replication studies in independent large sample sets to confirm and characterize the involvement of the gene variation in the pathogenesis of endometriosis are needed.

Changes in straylight and corneal light scattering in a newly diagnosed case of type 2 diabetes

Visual problems may be the first symptoms of diabetes. There have been several reports of transient changes in refraction of people newly diagnosed with diabetes. Visual acuity and refraction may be affected when there are ocular biometric changes. Small but significant biometrical changes have been found by some authors during hyperglycaemia and during reduction of hyperglycaemia.[4] Here, we describe a case of type 2 diabetes that was detected from ocular straylight and intraocular thickness measurements...

Robust nanostructured silver and copper fabrics with localized surface plasmon resonance property for effective visible light induced reductive catalysis

Inspired by high porosity, absorbency, wettability and hierarchical ordering on the micrometer and nanometer scale of cotton fabrics, a facile strategy is developed to coat visible light active metal nanostructures of copper and silver on cotton fabric substrates. The fabrication of nanostructured Ag and Cu onto interwoven threads of a cotton fabric by electroless deposition creates metal nanostructures that show a localized surface plasmon resonance (LSPR) effect. The micro/nanoscale hierarchical ordering of the cotton fabrics allows access to catalytically active sites to participate in heterogeneous catalysis with high efficiency. The ability of metals to absorb visible light through LSPR further enhances the catalytic reaction rates under photoexcitation conditions. Understanding the mode of electron transfer during visible light illumination in Ag@Cotton and Cu@Cotton through electrochemical measurements provides mechanistic evidence on the influence of light in promoting electron transfer during heterogeneous catalysis for the first time. The outcomes presented in this work will be helpful in designing new multifunctional fabrics with the ability to absorb visible light and thereby enhance light-activated catalytic processes.