Boron carboxylate catalysis of homoallylboration.

Boron tris(trifluoroacetate) is identified as the first effective catalyst for the homoallyl- and homocrotylboration of aldehydes by cyclopropylcarbinylboronates. NMR spectroscopic studies and theoretical calculations of key intermediates and transition states both suggest that a ligand-exchange mechanism, akin to our previously reported PhBCl2-promoted homoallylations, is operative. Our experimental and theoretical results also suggest that the catalytic activity of boron tris(trifluoroacetate) might originate from more facile catalytic turnover of the trifluoroacetate ligands (in agreement with DFT calculations) or from a lower propensity for formation of off-pathway reservoir intermediates (as observed by (1)H NMR). This work shows that carboxylates are viable catalytic ligands for homoallyl- and homocrotylations of carbonyl compounds and opens the door to the development of catalytic asymmetric versions of this transformation

A Loosely-Coupled Collaborative Integrated Environmental Modelling Framework

Integration of environmental models requires full support of the modelling community. When a large number of models are integrated, it requires consistency within scale, datasets, and model to model interactions to minimize the uncertainty among the models. The integrated environmental modelling (IEM) framework is a necessary approach to integrate multiple environmental models for a particular study. When modellers cannot afford considerable amount of time to get involved with full and tightly-integrated IEM or an IEM has very short time frame to complete, then a loosely-coupled collaborative IEM environment can provide the benefits of the integrated approach while minimizing the effort of each individual modeller. However, such a framework will require setting rules that all participants must adhere to. These rules address the issues of model inputs and model to model interaction. The framework should also provide value-added functionality to make the IEM framework more transparent and applicable

What has China done for the global refugee problem in the past 20 years? : should China do more?

published_or_final_versionInternational and Public AffairsMasterMaster of International and Public Affair

Application of Knowledge-based Tools in Environmental Decision Support Systems

Decision support system often requires the combined knowledge of multiple domains. A knowledge-based approach is proposed to include not only the process modelling knowledge but also the descriptive knowledge in the integration. Descriptive knowledge such as survey statistics and expert opinions forms the core of a study on the uncertainty of the combined knowledge. It was found that the use of expert systems, neural network and belief causal network assist greatly in the implementation of these concepts. Examples are drawn from the combination of scientific and economic knowledge to solve some acid rain problems.decision support system; knowledge-based system; expert system; causal network

Comprehensive Identification and Modified-Site Mapping of S-Nitrosylated Targets in Prostate Epithelial Cells

Although overexpression of nitric oxide synthases (NOSs) has been found associated with prostate diseases, the underlying mechanisms for NOS-related prostatic diseases remain unclear. One proposed mechanism is related to the S-nitrosylation of key regulatory proteins in cell-signaling pathways due to elevated levels of NO in the prostate. Thus, our primary objective was to identify S-nitrosylated targets in an immortalized normal prostate epithelial cell line, NPrEC.We treated NPrEC with nitroso-cysteine and used the biotin switch technique followed by gel-based separation and mass spectrometry protein identification (using the LTQ-Orbitrap) to discover S-nitrosylated (SNO) proteins in the treated cells. In parallel, we adapted a peptide pull-down methodology to locate the site(s) of S-nitrosylation on the protein SNO targets identified by the first technique. This combined approach identified 116 SNO proteins and determined the sites of modification for 82 of them. Over 60% of these proteins belong to four functional groups: cell structure/cell motility/protein trafficking, protein folding/protein response/protein assembly, mRNA splicing/processing/transcriptional regulation, and metabolism. Western blot analysis validated a subset of targets related to disease development (proliferating cell nuclear antigen, maspin, integrin beta4, alpha-catenin, karyopherin [importin] beta1, and elongation factor 1A1). We analyzed the SNO sequences for their primary and secondary structures, solvent accessibility, and three-dimensional structural context. We found that about 80% of the SNO sites that can be mapped into resolved structures are buried, of which approximately half have charged amino acids in their three-dimensional neighborhood, and the other half residing within primarily hydrophobic pockets.We here identified 116 potential SNO targets and mapped their putative SNO sites in NPrEC. Elucidation of how this post-translational modification alters the function of these proteins should shed light on the role of NO in prostate pathologies. To our knowledge, this is the first report identifying SNO targets in prostate epithelial cells

Inconsistent Adoption of World Health Organization V (2010) Semen Analysis Reference Ranges in the United States Six Years After Publication

Objective To determine the percentage of laboratories in the United States that have adopted the World Health Organization 2010 (WHO 5) semen analysis (SA) reference values six years after their publication. Methods Laboratories were identified via three approaches: using the Clinical Laboratory Improvement Amendments (CLIA) website, the CDC's 2015 Assisted Reproductive Technology Fertility Clinical Success Rate Report, and automated web searches. Laboratories were contacted by phone or email to obtain de-identified SA reports and reference ranges. Results We contacted 617 laboratories in 46 states, of which 208 (26.7%) laboratories in 45 states were included in our analysis. 132 (63.5%) laboratories used WHO 5 criteria, 57 (27.4%) used WHO 4 criteria, and 19 (9.1%) used other criteria. WHO 5 criteria adoption rates varied by geographic region, ranging from 87.5% (35/40) in the Midwest to 50.0% (33/66) in the West. There was a greater adoption rate of WHO 5 reference values in academic affiliated (23/26, 88.5%) compared to non-academic affiliated laboratories (110/182, 60.4%) (P=0.028). Conclusion While the majority of laboratories have adopted WHO 5 criteria following its release six years ago, a large percentage (36.5%) use what is now considered outdated criteria. This variability could result in the characterization of a male's semen values as being “within reference range” at one center and “outside of reference range” at another. This inconsistency in classification may result in confusion for the both patient and physician and potentially shift the burden of infertility evaluation and treatment to the female partner

Application of Knowledge-based Tools in Environmental Decision Support Systems

Decision support system often requires the combined knowledge of multiple domains. A knowledge-based approach is proposed to include not only the process modelling knowledge but also the descriptive knowledge in the integration. Descriptive knowledge such as survey statistics and expert opinions forms the core of a study on the uncertainty of the combined knowledge. It was found that the use of expert systems, neural network and belief causal network assist greatly in the implementation of these concepts. Examples are drawn from the combination of scientific and economic knowledge to solve some acid rain problems

Application of Knowledge-based Tools in Environmental Decision Support Systems

Decision support system often requires the combined knowledge of multiple domains. A knowledge-based approach is proposed to include not only the process modelling knowledge but also the descriptive knowledge in the integration. Descriptive knowledge such as survey statistics and expert opinions forms the core of a study on the uncertainty of the combined knowledge. It was found that the use of expert systems, neural network and belief causal network assist greatly in the implementation of these concepts. Examples are drawn from the combination of scientific and economic knowledge to solve some acid rain problems