cssi/SciSciGPT-SciSciNet huggingface dataset:
Management of Preexisting Diabetes in Pregnancy: A Review.

Importance The presence of preexisting type 1 or type 2 diabetes in pregnancy increases the risk of adverse maternal and neonatal outcomes, such as preeclampsia, cesarean delivery, preterm delivery, macrosomia, and congenital defects. Approximately 0.9% of the 4 million births in the United States annually are complicated by preexisting diabetes. Observations Women with diabetes have increased risk for adverse maternal and neonatal outcomes, and similar risks are present with type 1 and type 2 diabetes. Both forms of diabetes require similar intensity of diabetes care. Preconception planning is very important to avoid unintended pregnancies and to minimize risk of congenital defects. Hemoglobin A1cgoals are less than 6.5% at conception and less than 6.0% during pregnancy. It is also critical to screen for and manage comorbid illnesses, such as retinopathy and nephropathy. Medications known to be unsafe in pregnancy, such as angiotensin-converting enzyme inhibitors and statins, should be discontinued. Women with obesity should be screened for obstructive sleep apnea, which is often undiagnosed and can result in poor outcomes. Blood pressure goals must be considered carefully because lower treatment thresholds may be required for women with nephropathy. During pregnancy, continuous glucose monitoring can improve glycemic control and neonatal outcomes in women with type 1 diabetes. Insulin is first-line therapy for all women with preexisting diabetes; injections and insulin pump therapy are both effective approaches. Rates of severe hypoglycemia are increased during pregnancy; therefore, glucagon should be available to the patient and close contacts should be trained in its use. Low-dose aspirin is recommended soon after 12 weeks’ gestation to minimize the risk of preeclampsia. The importance of discussing long-acting reversible contraception before and after pregnancy, to allow for appropriate preconception planning, cannot be overstated. Conclusions and Relevance Preexisting diabetes in pregnancy is complex and is associated with significant maternal and neonatal risk. Optimization of glycemic control, medication regimens, and careful attention to comorbid conditions can help mitigate these risks and ensure quality diabetes care before, during, and after pregnancy.
Gender Differences in Work Motivation of Public Basic Education in Metro Vigan and Caoayan, Philippines and Job Satisfaction

The study wanted to determine the differences in work motivation and job satisfaction of male and female teachers and to determine the relationship between work motivation and job satisfaction. To carry out such purpose, related literatures and studies were reviewed to support the theory of the study and proper methodology was followed. The study used descriptive correlational method of research design and aided by fact finding inquiry. The population of the study were 263 teachers. of basic public schools of Metro Vigan and Caoayan. Questionnaires were used to gather the data and to treat the data statistically, mean, t-test and Pearson r were used. Mean was to measure the level of motivation and job satisfaction and t-test was used to measure the difference and Pearson r was used to determine the correlation. The study found that work motivation and job satisfaction of basic public schools in Metro Vigan and Caoayan is very high and there was no correlation between work motivation of both gender and job satisfaction. It also found that there was no difference between job satisfaction of male and female teachers and as whole, there was no difference between work motivation of both genders but taking it singly, there was a difference between work motivation of both genders in terms of integrated regulation.
Walking With Leg Blood Flow Restriction: Wide-Rigid Cuffs vs. Narrow-Elastic Bands.

Background: Blood flow restriction (BFR) training is becoming a popular form of exercise. Walking exercise in combination with pressurized wide-rigid (WR) cuffs elicits higher cardiac workload and a vascular dysfunction due presumably to reperfusion injury to the endothelium. In contrast, narrow-elastic (NE) BFR bands may elicit different hemodynamic effects. Therefore, we compared the acute cardiovascular responses to two distinct forms of BFR training during light-intensity exercise. Methods and Results: 15 young healthy participants (M=9, F=6) performed 5 bouts of 2-minute walking intervals at 0.9 m/s with a 1-minute rest and deflation period with either WR, NE, or no bands placed on upper thighs. Cuff pressure was inflated to 160 mmHg in WR cuffs and 300 mmHg in NE bands while no cuffs were used for the control. Increases in heart rate and arterial blood pressure were greater (p<0.05) in the WR than the NE and control conditions. Double product increased to a greater extent in the WR than in the NE and control conditions. Increases in perceived exertion and blood lactate concentration were greater (p<0.05) in the WR compared with the NE and control conditions (p<0.05), while no differences emerged between the NE and control conditions. There were no changes in arterial stiffness or brachial artery flow-mediated dilation after all three trials. Conclusion: Use of wide-rigid BFR cuffs resulted in a marked increase in blood pressure and myocardial oxygen demand compared with narrow-elastic BFR bands, suggesting that narrow-elastic bands present a safer alternative for at-risk populations to perform BFR exercise. Clinical Trial Registration: This study was registered in the Clinicaltrials.gov (NCT03540147).
Dynamics of Proton Transfer from Radical Cations. Addition−Elimination or Direct Proton Transfer?

Kinetic studies including the evaluation of deuterium kinetic isotope effects and Arrhenius activation energies implicate an addition−elimination mechanism for the proton transfer reaction between 9-methylanthracene radical cation and 2,6-lutidine in acetonitrile−Bu4NPF6 (0.1 M) and in dichloromethane−Bu4NPF6 (0.2 M). Isotopic substitution of D for H at the 10-position results in inverse deuterium kinetic isotope effects (kH/kD) equal to 0.83 due to nucleophilic attack on the radical cation by 2,6-lutidine. Primary kH/kD of 3.5−5.9 were observed for D3 substitution in the 9-methyl group. The addition−elimination mechanism involves unimolecular rearrangement of the initially formed adduct to give the product of proton transfer, 9-anthracenylmethyl radical. Oxidation of the latter followed by reaction with 2,6-lutidine affords N-(9-anthracenylmethyl)-2,6-lutidinium ion, which was isolated as the perchlorate salt. A comparison of kinetic data from reactions of both 9-methyl and 9,10-dimethylanthracene radica...
Addition/oxidative rearrangement of 3-furfurals and 3-furyl imines: new approaches to substituted furans and pyrroles.

Furans and pyrroles are important synthons in chemical synthesis and are commonly found in natural products, pharmaceutical agents, and materials. Introduced herein are three methods to prepare 2-substituted 3-furfurals starting from 3-furfural, 3-bromofuran, and 3-vinylfurans. Addition of a variety of organolithium, Grignard, and organozinc reagents (M-R) to 3-furfural provides 3-furyl alcohols in high yields. Treatment of these intermediates with NBS initiates a novel oxidative rearrangement that results in the installation of the R group in the 2 position of the 2-substituted 3-furfurals. Likewise, metalation of 3-bromofuran with n-BuLi and addition to benzaldehyde provides a furyl alcohol that is converted to 2-phenyl 3-furfural upon oxidative rearrangement. Enantioenriched disubstituted furans can be prepared starting with the Sharpless asymmetric dihydroxylation of 3-vinylfurans. The resulting enantioenriched diols undergo the oxidative rearrangement to furnish enantioenriched 2-substituted 3-furfur...
Arnoamines A and B, New Cytotoxic Pentacyclic Pyridoacridine Alkaloids from the Ascidian Cystodytes sp.

Two new cytotoxic pyridoacridine alkaloids, arnoamines A (1) and B (2), have been isolated from the ascidian Cystodytes sp. collected in the vicinity of Arno Atoll, Republic of Marshall Islands. Compounds 1 and 2 are proposed to be the first members of a new class of pentacyclic pyridoacridine alkaloids possessing a pyrrole ring fused to the pyridoacridine ring system. The structures of 1 and 2 were proposed on the basis of the interpretation of spectroscopic data, particularly those obtained from HMBC and NOE NMR experiments. The arnoamines were unexpectedly found to incorporate deuterium at C-10 and C-11 of the pyrrole ring when dissolved in CDCl3/TFA-d.
Carbon Inputs From Riparian Vegetation Limit Oxidation of Physically Bound Organic Carbon Via Biochemical and Thermodynamic Processes

In light of increasing terrestrial carbon (C) transport across aquatic boundaries, the mechanisms governing organic carbon (OC) oxidation along terrestrial-aquatic interfaces are crucial to future climate predictions. Here, we investigate biochemistry, metabolic pathways, and thermodynamics corresponding to OC oxidation in the Columbia River corridor using ultra-high resolution C characterization. We leverage natural vegetative differences to encompass variation in terrestrial C inputs. Our results suggest that decreases in terrestrial C deposition associated with diminished riparian vegetation induce oxidation of physically-bound OC. We also find that contrasting metabolic pathways oxidize OC in the presence and absence of vegetation and--in direct conflict with the priming concept--that inputs of water-soluble and thermodynamically favorable terrestrial OC protects bound-OC from oxidation. In both environments, the most thermodynamically favorable compounds appear to be preferentially oxidized regardless of which OC pool microbiomes metabolize. In turn, we suggest that the extent of riparian vegetation causes sediment microbiomes to locally adapt to oxidize a particular pool of OC, but that common thermodynamic principles govern the oxidation of each pool (e.g., water-soluble or physically-bound). Finally, we propose a mechanistic conceptualization of OC oxidation along terrestrial-aquatic interfaces that can be used to model heterogeneous patterns of OC loss under changing land cover distributions.
Simple but robust improvement in multivoxel pattern classification.

Multivoxel pattern analysis (MVPA) typically begins with the estimation of single trial activation levels, and several studies have examined how different procedures for estimating single trial activity affect the ultimate classification accuracy of MVPA. Here we show that the currently preferred estimation procedures impart spurious positive correlations between the means of different category activity estimates within the same scanner run. In other words, if the mean of the estimates for one type of trials is high (low) in a given scanner run, then the mean of the other type of trials is also high (low) for that same scanner run, and the run-level mean across all trials therefore shifts from run to run. Simulations show that these correlations occur whenever there is a need to deconvolve overlapping trial activities in the presence of noise. We show that subtracting each voxel’s run-level mean across all trials from all the estimates within that run (i.e., run-level mean centering of estimates), by cancelling out these mean shifts, leads to robust and significant improvements in MVPA classification accuracy. These improvements are seen in both simulated and real data across a wide variety of situations. However, we also point out that there could be cases when mean activations are expected to shift across runs and that run-level mean centering could be detrimental in some of these cases (e.g., different proportion of trial types between different runs).
The first example of Nazarov reactions of vinyl cumulenyl ketones.

α-Lithio cumulenyl ethers can be prepared in situ and converted to α-allenyl cyclopentenones. Isomerization of the product of one such reaction has led to a furanyl cyclopentenone, the core structure of nakadomarin A.
Resistance diagnostics as a public health tool to combat antibiotic resistance: A model-based evaluation.

Rapid point-of-care resistance diagnostics (POC-RD) are a key tool in the fight against antibiotic resistance. By tailoring drug choice to infection genotype, doctors can improve treatment efficacy while limiting costs of inappropriate antibiotic prescription. Here, we combine epidemiological theory and data to assess the potential of resistance diagnostics (RD) innovations in a public health context, as a means to limit or even reverse selection for antibiotic resistance. POC-RD can be used to impose a nonbiological fitness cost on resistant strains by enabling diagnostic-informed treatment and targeted interventions that reduce resistant strains’ opportunities for transmission. We assess this diagnostic-imposed fitness cost in the context of a spectrum of bacterial population biologies and find that POC-RD have a greater potential against obligate pathogens than opportunistic pathogens already subject to selection under “bystander” antibiotic exposure during asymptomatic carriage (e.g., the pneumococcus). We close by generalizing the notion of RD-informed strategies to incorporate carriage surveillance information and illustrate that coupling transmission-control interventions to the discovery of resistant strains in carriage can potentially select against resistance in a broad range of opportunistic pathogens.
Heavy-tailed prior distributions for sequence count data: removing the noise and preserving large differences.

MOTIVATION In RNA-seq differential expression analysis, investigators aim to detect those genes with changes in expression level across conditions, despite technical and biological variability in the observations. A common task is to accurately estimate the effect size, often in terms of a logarithmic fold change (LFC). RESULTS When the read counts are low or highly variable, the maximum likelihood estimates for the LFCs has high variance, leading to large estimates not representative of true differences, and poor ranking of genes by effect size. One approach is to introduce filtering thresholds and pseudocounts to exclude or moderate estimated LFCs. Filtering may result in a loss of genes from the analysis with true differences in expression, while pseudocounts provide a limited solution that must be adapted per dataset. Here, we propose the use of a heavy-tailed Cauchy prior distribution for effect sizes, which avoids the use of filter thresholds or pseudocounts. The proposed method, Approximate Posterior Estimation for generalized linear model, apeglm, has lower bias than previously proposed shrinkage estimators, while still reducing variance for those genes with little information for statistical inference. AVAILABILITY AND IMPLEMENTATION The apeglm package is available as an R/Bioconductor package at https://bioconductor.org/packages/apeglm, and the methods can be called from within the DESeq2 software. SUPPLEMENTARY INFORMATION Supplementary data are available at Bioinformatics online.
The synthesis of 8-substituted tetracycline derivatives, the first 8-position carbon–carbon bond

Abstract The synthesis of C8-functionalized tetracyclines using Stille coupling is described. These derivatives are the first reported with a carbon–carbon bond in the 8-position of a tetracycline negating total synthesis routes to 8-substituted tetracyclines.
Nano-Structured Materials for Next Generation Fuel Cells and Photoelectrochemical Devices

Progress in achieving improved performance in the generation and utilization of hydrogen depends on our ability to identify materials with optimized electrical and (photo)- electrochemical performance. Given their high volume fraction of interfaces, high chemical stability and versatility (ionic, electronic, optical property control), nanocrystalline electroceramic materials are of growing interest for advanced energy conversion and storage technologies. As grain size decreases towards the Debye length and grain boundaries come in closer proximity, space charge properties begin to dominate, resulting in modified charge transport. Through systematic variation of grain boundary properties by heterogeneous indiffusion of cations, the electronic and ionic carrier profiles in the space charge region may be altered. The relationships between space charge potential and defect profiles in the space charge regions are quantitatively analyzed, and implications for nano-ionic materials in thin film solid oxide fuel cells are discussed. From the standpoint of photoelectrochemical water splitting for hydrogen generation, optimizing the band gap, band alignments, and transport properties while retaining stability has remained a challenging objective. Novel nanocrystalline composite structures are discussed which exhibit features amenable to optimization of required properties and electrical measurements to determine key transport properties of titanium dioxide nanopowder, a photoanode material are introduced.
Insights into the binding mode of MEK type-III inhibitors. A step towards discovering and designing allosteric kinase inhibitors across the human kinome

Protein kinases are critical drug targets for treating a large variety of human diseases. Type-III kinase inhibitors have attracted increasing attention as highly selective therapeutics. Thus, understanding the binding mechanism of existing type-III kinase inhibitors provides useful insights into designing new type-III kinase inhibitors. In this work, we have systematically studied the binding mode of MEK-targeted type-III inhibitors using structural systems pharmacology and molecular dynamics simulation. Our studies provide detailed sequence, structure, interaction-fingerprint, pharmacophore and binding-site information on the binding characteristics of MEK type-III kinase inhibitors. We hypothesize that the helix-folding activation loop is a hallmark allosteric binding site for type-III inhibitors. Subsequently, we screened and predicted allosteric binding sites across the human kinome, suggesting other kinases as potential targets suitable for type-III inhibitors.
High-field and high-frequency EPR

This introductory essay surveys the motivation for high-field/high-frequency electron paramagnetic resonance (HFEPR), and identifies some of the technology needed to further develop HFEPR. For many spin systems HFEPR increases resolution of the EPR spectra, makes the spectra more nearly first-order, thus simplifying interpretation, and/or changes the motional regime or relaxation times that dominate important features of the spectra. In other cases, spectra can only be seen at high field. Applications of HFEPR range over most problems that involve unpaired electrons in materials sciences, chemistry, physics, and biology. Applications of HFEPR will be enhanced by improvements in resonators, lower-noise sources and detectors, and fast switches for pulse experiments.
Secure and reliable connectivity in heterogeneous wireless sensor networks

We consider a wireless sensor network secured by a heterogeneous random key predistribution scheme and investigate its reliability against both link and node failures. The heterogeneous random key predistribution scheme is a lightweight security mechanism proposed to secure sensor networks that include nodes with varying levels of resources, features, or connectivity requirements; e.g., regular nodes vs. cluster heads. To capture the reliability of the network against both link and node failures, we consider the case when each link fails independently with probability 1 − α and present conditions (in the form of zero-one laws) on how to scale the parameters of the resulting network so that it is k-connected with high probability, i.e., the network remains connected even if any k − 1 nodes fail or leave the network. Collectively, we obtain a network that is reliable against the probabilistic failure of each link and against the failure of any k − 1 nodes. We present numerical results to support these conditions in the finite-node regime.
Total Synthesis of (+)-Epoxydictymene. Application of Alkoxy-Directed Cyclization to Diterpenoid Construction

An enantioselective synthesis of (+)-epoxydictymene (1) is reported. Condensation of the enantiopure aldehydo ester 5 with (S)-3-isopropylcyclopentenyllithium proceeds selectively to afford 13. Once this lactone was methylenated with the Tebbe reagent, the newly formed allyl vinyl ether was induced into Claisen rearrangement under catalysis with triisobutylaluminum. Sequential hydroboration−oxidation of the resulting dicyclopentacyclooctenone derivative was followed by angular methylation and deoxygenation of the carbonyl functionality. Following epimerization at C-11, an α-hydroxyl was introduced regio- and stereoselectively. Some functional group manipulation led to 57 and 58, both of which underwent efficient cyclization to deliver the complete framework of the target molecule when irradiated with visible light in cyclohexane solution containing iodosobenzene diacetate and iodine. The generality of this key reaction, which efficiently constructs the strained oxabicyclo[3.3.0]octane subunit of 1, is dem...
Iodohexahydropyridoindolones. Formation and reactivity

Described herein is the generation and use of iodohexahydropyridoindolines and their free radical atom transfer reactions with aryl acetylenes to generate quaternary substituted pyridoindolones.
Lewis Acid Behavior of ReO2F3: Synthesis of (ReO2F3)∞, ReO2F4-, Re2O4F7-, Re3O6F10-, and ReO2F3(CH3CN) and Study by NMR Spectroscopy, Raman Spectroscopy, and Density Functional Theory Calculations; and X-ray Structures of [Li][ReO2F4], [K][Re2O4F7], [K][Re2O4F7]·2ReO2F3, [Cs][Re3O6F10], and ReO3F(CH3CN)2·CH3CN†

The reaction of Re2O7 with XeF6 in anhydrous HF provides a convenient route to high-purity ReO2F3. The fluoride acceptor and Lewis base properties of ReO2F3 have been investigated leading to the formation of [M][ReO2F4] [M = Li, Na, Cs, N(CH3)4], [K][Re2O4F7], [K][Re2O4F7]·2ReO2F3, [Cs][Re3O6F10], and ReO2F3(CH3CN). The ReO2F4-, Re2O4F7-, and Re3O6F10- anions and the ReO2F3(CH3CN) adduct have been characterized in the solid state by Raman spectroscopy, and the structures [Li][ReO2F4], [K][Re2O4F7], [K][Re2O4F7]·2ReO2F3, [Cs][Re3O6F10], and ReO3F(CH3CN)2·CH3CN have been determined by X-ray crystallography. [Li][ReO2F4] crystallizes in the tetragonal system, space group P421m, with a = 4.727(3) A, c = 8.880(7) A, V = 198.4(7) A3, and Z = 2 at 24 °C, R1 = 0.0378, and wR2 = 0.1029. [K][Re2O4F7] crystallizes in the monoclinic system, space group P2/n, with a = 5.4990(11) A, b = 5.1530(10) A, c = 14.753(3) A, β = 95.68°, V = 415.99(14) A3, and Z = 2 at 20 °C, R1 = 0.0473, and wR2 = 0.1200. [K][Re2O4F7]·2ReO2F3...
Pd(DIPHOS)2-Catalyzed Cross-Coupling Reactions of Organoborons with Free or Polymer-Bound Aryl Halides†

Bis[1,2-bis(diphenylphosphino)ethane]palladium(0) [Pd(DIPHOS)2] catalyzes cross-coupling reactions of free or polymer-bound aryl halides with organoboron compounds to produce biaryls in overall yields of 60-96%.
Hybridization and postzygotic isolation promote reinforcement of male mating preferences in a diverse group of fishes with traditional sex roles

Behavioral isolation is thought to arise early in speciation due to differential sexual and/or natural selection favoring different preferences and traits in different lineages. Instead, behavioral isolation can arise due to reinforcement favoring traits and preferences that prevent maladaptive hybridization. In darters, female preference for male coloration has been hypothesized to drive speciation, because behavioral isolation evolves before F1 inviability. However, as with many long-lived organisms, the fitness of second-generation hybrids has not been assessed because raising animals to adulthood in the laboratory is challenging. Of late, reinforcement of male preferences has been implicated in darters because male preference for conspecific females is high in sympatry but absent in allopatry in multiple species pairs. The hypothesis that reinforcement accounts for behavioral isolation in sympatry assumes that hybridization and postzygotic isolation are present. Here, we used genomic and morphological data to demonstrate that hybridization is ongoing between orangethroat and rainbow darters and used hybrids collected from nature to measure postzygotic barriers across two hybrid generations. We observed sex ratio distortion in adult F1s and a dramatic reduction in backcross survival. Our findings indicate that selection to avoid hybridization promotes the evolution of male-driven behavioral isolation via reinforcement in this system.
On the optimal trimming of high-throughput mRNA sequence data

The widespread and rapid adoption of high-throughput sequencing technologies has afforded researchers the opportunity to gain a deep understanding of genome level processes that underlie evolutionary change, and perhaps more importantly, the links between genotype and phenotype. In particular, researchers interested in functional biology and adaptation have used these technologies to sequence mRNA transcriptomes of specific tissues, which in turn are often compared to other tissues, or other individuals with different phenotypes. While these techniques are extremely powerful, careful attention to data quality is required. In particular, because high-throughput sequencing is more error-prone than traditional Sanger sequencing, quality trimming of sequence reads should be an important step in all data processing pipelines. While several software packages for quality trimming exist, no general guidelines for the specifics of trimming have been developed. Here, using empirically derived sequence data, I provide general recommendations regarding the optimal strength of trimming, specifically in mRNA-Seq studies. Although very aggressive quality trimming is common, this study suggests that a more gentle trimming, specifically of those nucleotides whose Phred score <2 or <5, is optimal for most studies across a wide variety of metrics.
MicroScope: ChIP-seq and RNA-seq software analysis suite for gene expression heatmaps

Heatmaps are an indispensible visualization tool for examining large-scale snapshots of genomic activity across various types of next-generation sequencing datasets. However, traditional heatmap software do not typically offer multi-scale insight across multiple layers of genomic analysis (e.g., differential expression analysis, principal component analysis, gene ontology analysis, and network analysis) or multiple types of next-generation sequencing datasets (e.g., ChIP-seq and RNA-seq). As such, it is natural to want to interact with a heatmap’s contents using an extensive set of integrated analysis tools applicable to a broad array of genomic data types. We propose a user-friendly ChIP-seq and RNA-seq software suite for the interactive visualization and analysis of genomic data, including integrated features to support differential expression analysis, interactive heatmap production, principal component analysis, gene ontology analysis, and dynamic network analysis. MicroScope is hosted online as an R Shiny web application based on the D3 JavaScript library: http://microscopebioinformatics.org/ . The methods are implemented in R, and are available as part of the MicroScope project at: https://github.com/Bohdan-Khomtchouk/Microscope .
Base-catalyzed reaction between isatins and N-Boc-3-pyrrolin-2-one

Abstract The base-catalyzed reaction between isatins and N -Boc-3-pyrrolin-2-one yields Morita–Baylis–Hillman (MBH) adducts instead of the expected aldol products in good to high yields (up to 97%). Various organic and inorganic bases are efficient catalysts for this reaction. Our study excluded the Morita–Baylis–Hillman mechanism for the formation of the MBH-type products. The MBH products are most likely formed as a result of the subsequent isomerization of the original aldol products between isatins and N -Boc-3-pyrrolin-2-one.
A practical and stereoselective synthesis of (+/−)-trans-4-benzyloctahydropyrrolo[3,4-b][1,4]oxazine

Starting from commercially available cis-epoxysuccinic acid (I) a facile stereoselective synthesis of title compound (V) is described.
Stereo- and regioselective synthesis of 1,3-diaryl-3-chloro-1-propanols via the reaction of aryl aldehydes with styrene and (E)-β-methylstyrene

Reactions of aryl aldehydes with styrene and (E)-β-methylstyrene in the presence of phenylboron dichloride regioselectively generate 1,3-diaryl-3-chloro-1-propanols and 1,3-diaryl-3-chloro-2-methyl-1-propanols in good to excellent yields with high stereoselectivity.
Amine-directed intramolecular hydroacylation of alkenes and alkynes

Abstract Medium-ring heterocycles are prepared via an amine-directed, rhodium(I)-catalyzed intramolecular hydroacylation. The presence of an allyl substituent on the amine accelerates the reaction and increases product yields.
Preparation of Keto-Isoxazole Polyketide Synthons

The Dess-Martin periodinane (DMP) oxidation of alcohols, proceeds in good to excellent yield in the presence of the isoxazole ring, and other nitrogen-containing functional groups. The DMP route allows for the preparationof highly branched polyketide synthetic equivalents.
Preparation of Optically Active 2-(Trifluoromethyl)alkan-1-ols by Catalytic Asymmetric Hydrogenation

The hydrogenation of (E)-2-(trifluoromethyl)alk-2-en-1-ols catalyzed by Ru-2, 2'-bis(diphynylphosphino)-1, 1'-binaphthyl (Ru-BINAP) and Rh-BINAP was carried out with good enantiomeric excess (71-83% ee). Ru-BINAP-catalyzed hydrogenation converted 2-(trifluoromethyl)acrylic acid to the corresponding saturated acid whose esterification and reduction provided optically active 2-(trifluoromethyl)propan-1-ol in 80% ee.
Migration of groups from zirconium to boron: Aspects of synthesis and utility

Abstract The hydrozirconation of alkenes or alkynes yields the dicyclopentadienyl alkyl- or alkenylzirconium chloride, respectively, in high yields and with high regioselectivity. The reaction of these organozirconium compounds with a boron halide results in the exchange of the halogen and organic group, forming the organoborane. We report here a systematic investigation of the transmetallation of organic groups from zirconium to a variety of boron compounds. The migration is facile to a variety of boron halides, yielding structurally different types of alkyl or alkenylboranes in good to high yields. Exploiting the unique reactivity and selectivity of the hydrozirconation reaction for the preparation of organoboranes expands the range of potential of both metals for synthesis.
Health and Education Expenditures in Russia, the Baltic States, and the Other Countries of the Former Soviet Union

Russia, the Baltic states and the other countries of the former Soviet Union inherited health and education systems that were in need of substantial structural and financial reform. In spite of a sharp decline of real resources, this reform has barely begun. While health and education have not suffered disproportionate cuts, employment has been maintained, with real wages sharply compressed, purchases of materials reduced and energy-related spending taking a greater share of resources in many countries. Structural and financial reform would include reducing staffing and physical capacity, while increasing expenditures for materials and wages for the more highly qualified.
Optimum mixed-state discrimination for noisy entanglement-enhanced sensing

We propose a structured receiver for optimum mixed-state discrimination in quantum illumination target detection, paving the way for entanglement-enhanced minimum-error-probability sensing in an entanglement-breaking environment.
Codestitcher: inter-procedural basic block layout optimization

Modern software executes a large amount of code. Previous techniques of code layout optimization were developed one or two decades ago and have become inadequate to cope with the scale and complexity of new types of applications such as compilers, browsers, interpreters, language VMs and shared libraries. This paper presents Codestitcher, an inter-procedural basic block code layout optimizer which reorders basic blocks in an executable to benefit from better cache and TLB performance. Codestitcher provides a hierarchical framework which can be used to improve locality in various layers of the memory hierarchy. Our evaluation shows that Codestitcher improves the performance of the original program (already optimized with O3 and link time optimizations) by 3% to 25% (on average, by 10%) on 5 widely used applications with large code sizes: MySQL, Clang, Firefox, PHP server, and Python. It gives an additional improvement of 4% over LLVM's PGO and 3% over PGO combined with the best function reordering technique. For profiling, Codestitcher does not need instrumentation. Instead it uses branch history samples which are collected during the execution of the original program. Codestitcher's profiling and trace processing together incur an average overhead of 22.5%, compared to an average overhead of 90% from LLVM's PGO.
Symmetry in the sequence of approximation coefficients

Let $\{a_n\}_1^\infty$ and $\{\theta_n\}_0^\infty$ be the sequences of partial quotients and approximation coefficients for the continued fraction expansion of an irrational number. We will provide a function $f$ such that $a_{n+1} = f(\theta_{n\pm1},\theta_n)$. In tandem with a formula due to Dajani and Kraaikamp, we will write $\theta_{n \pm 1}$ as a function of $(\theta_{n \mp 1}, \theta_n)$, revealing an elegant symmetry in this classical sequence and allowing for its recovery from a pair of consecutive terms.
Diagrams for relative trisections

We establish a correspondence between trisections of smooth, compact, oriented $4$--manifolds with connected boundary and diagrams describing these trisected $4$--manifolds. Such a diagram comes in the form of a compact, oriented surface with boundary together with three tuples of simple closed curves, with possibly fewer curves than the genus of the surface, satisfying a pairwise standardness condition. This should be thought of as the $4$--dimensional analog of a sutured Heegaard diagram for a sutured $3$--manifold. We also give many foundational examples.
Some remarks on the lonely runner conjecture

The lonely runner conjecture of Wills and Cusick, in its most popular formulation, asserts that if $n$ runners with distinct constant speeds run around a unit circle $\R/\Z$ starting at a common time and place, then each runner will at some time be separated by a distance of at least 1/(n+1) from the others. In this paper we make some remarks on this conjecture. Firstly, we can improve the trivial lower bound of 1/(2n) slightly for large n, to (1/(2n)) + (c \log n)/(n^2 (\log\log n)^2) for some absolute constant c>0; previous improvements were roughly of the form (1/(2n)) + c/n^2. Secondly, we show that to verify the conjecture, it suffices to do so under the assumption that the speeds are integers of size n^{O(n^2)}. We also obtain some results in the case when all the velocities are integers of size O(n).
Real-Time Integrity Indices in Power Grid: A Synchronization Coefficient Based Clustering Approach

We propose a new methodology based on modularity clustering of synchronization coefficient, to identify coherent groups of generators in the power grid in real-time. The method uses real-time integrity indices, i.e., the Generators Connectivity Index (GCI) that represents how generators are coherently strong within the groups, the Generator Splitting Index (GSI) that reveals to what extent the generators in different groups tend to swing against the other groups, and the System Separation Index (SI) which discloses the overall system separation status. We demonstrate how these integrity indices can be used to study the dynamic behavior of the power system. Furthermore, a comparison analysis is conducted between the synchronization coefficient (KS) and the generator rotor angle correlation coefficient (CC). The proposed indices demonstrate the dynamic behavior of power system following occurrence the faults and thus represent a promising approach in power system islanding studies. Our methodology is simple, fast, and computationally attractive. Simulation case performed on IEEE 118-bus systems demonstrates the efficacy of our approach.
Building state-of-the-art distant speech recognition using the CHiME-4 challenge with a setup of speech enhancement baseline

This paper describes a new baseline system for automatic speech recognition (ASR) in the CHiME-4 challenge to promote the development of noisy ASR in speech processing communities by providing 1) state-of-the-art system with a simplified single system comparable to the complicated top systems in the challenge, 2) publicly available and reproducible recipe through the main repository in the Kaldi speech recognition toolkit. The proposed system adopts generalized eigenvalue beamforming with bidirectional long short-term memory (LSTM) mask estimation. We also propose to use a time delay neural network (TDNN) based on the lattice-free version of the maximum mutual information (LF-MMI) trained with augmented all six microphones plus the enhanced data after beamforming. Finally, we use a LSTM language model for lattice and n-best re-scoring. The final system achieved 2.74\% WER for the real test set in the 6-channel track, which corresponds to the 2nd place in the challenge. In addition, the proposed baseline recipe includes four different speech enhancement measures, short-time objective intelligibility measure (STOI), extended STOI (eSTOI), perceptual evaluation of speech quality (PESQ) and speech distortion ratio (SDR) for the simulation test set. Thus, the recipe also provides an experimental platform for speech enhancement studies with these performance measures.
Moonshots for aging.

As the global population ages, there is increased interest in living longer and improving one's quality of life in later years. However, studying aging - the decline in body function - is expensive and time-consuming. And despite research success to make model organisms live longer, there still aren't really any feasible solutions for delaying aging in humans. With space travel, scientists and engineers couldn't know what it would take to get to the moon. They had to extrapolate from theory and shorter-range tests. Perhaps with aging, we need a similar moonshot philosophy. And though "shot" might imply medicine, perhaps we need to think beyond medical interventions. Like the moon once was, we seem a long way away from provable therapies to increase human healthspan (the healthy period of one's life) or lifespan (how long one lives). This review therefore focuses on radical proposals. We hope it might stimulate discussion on what we might consider doing significantly differently than ongoing aging research.
Distributed Coordinated Control of Large-Scale Nonlinear Networks∗

Abstract We provide a distributed coordinated approach to the stability analysis and control design of large-scale nonlinear dynamical systems by using a vector Lyapunov functions approach. In this formulation the large-scale system is decomposed into a network of interacting subsystems and the stability of the system is analyzed through a comparison system. However finding such comparison system is not trivial. In this work, we propose a sum-of-squares based completely decentralized approach for computing the comparison systems for networks of nonlinear systems. Moreover, based on the comparison systems, we introduce a distributed optimal control strategy in which the individual subsystems (agents) coordinate with their immediate neighbors to design local control policies that can exponentially stabilize the full system under initial disturbances. We illustrate the control algorithm on a network of interacting Van der Pol systems.
Asymptotic Analysis of Mean Field Games with Small Common Noise

In this paper, we consider a mean field game (MFG) model perturbed by small common noise. Our goal is to give an approximation of the Nash equilibrium strategy of this game using a solution from the original no common noise MFG whose solution can be obtained through a coupled system of partial differential equations. We characterize the first order approximation via linear mean-field forward-backward stochastic differential equations whose solution is a centered Gaussian process with respect to the common noise. The first order approximate strategy can be described as follows: at time $t \in [0,T]$, applying the original MFG optimal strategy for a sub game over $[t,T]$ with the initial being the current state and distribution. We then show that this strategy gives an approximate Nash equilibrium of order $\epsilon^2$.
Discretization of time-dependent quantum systems: real-time propagation of the evolution operator

We discuss time-dependent quantum systems on bounded domains. Our work may be viewed as a framework for several models, including linear iterations involved in time-dependent density functional theory, the Hartree-Fock model, or other quantum models. A key aspect of the analysis of the algorithms is the use of time-ordered evolution operators, which allow for both a well-posed problem and its approximation. The approximation theorems obtained for the time-ordered evolution operators complement those in the current literature. We discuss the available theory at the outset, and proceed to apply the theory systematically in later sections via approximations and a global existence theorem for a nonlinear system, obtained via a fixed point theorem for the evolution operator. Our work is consistent with first-principle real-time propagation of electronic states, aimed at finding the electronic responses of quantum molecular systems and nanostructures. We present two full 3D quantum atomistic simulations using t...
Twin Learning for Similarity and Clustering: A Unified Kernel Approach.

Many similarity-based clustering methods work in two separate steps including similarity matrix computation and subsequent spectral clustering. However similarity measurement is challenging because it is usually impacted by many factors, e.g., the choice of similarity metric, neighborhood size, scale of data, noise and outliers. Thus the learned similarity matrix is often not suitable, let alone optimal, for the subsequent clustering. In addition, nonlinear similarity often exists in many real world data which, however, has not been effectively considered by most existing methods. To tackle these two challenges, we propose a model to simultaneously learn cluster indicator matrix and similarity information in kernel spaces in a principled way. We show theoretical relationships to kernel k-means, k-means, and spectral clustering methods. Then, to address the practical issue of how to select the most suitable kernel for a particular clustering task, we further extend our model with a multiple kernel learning ability. With this joint model, we can automatically accomplish three subtasks of finding the best cluster indicator matrix, the most accurate similarity relations and the optimal combination of multiple kernels. By leveraging the interactions between these three subtasks in a joint framework, each subtask can be iteratively boosted by using the results of the others towards an overall optimal solution. Extensive experiments are performed to demonstrate the effectiveness of our method.
Commissioning and performance results of the WFIRST/PISCES integral field spectrograph

Direct imaging of exoplanets has become a priority in the field of exoplanet discovery and characterization due to its ability to directly obtain evidence about a planet’s atmosphere and some bulk properties. Features such as atmospheric composition, structure and clouds are just some of the planetary properties obtainable from directly imaged spectra. However, detecting and observing spectra of exoplanets using direct imaging is challenging due to the combination of extreme star to planet contrast ratios and the relatively small apparent physical separation between a host star and an orbiting planet. Detection of Earth-sized planets in reflected visible light requires contrast ratios of 1010, while even detection of Jupiter-sized planets and large young self-luminous planets requires contrast ratios of 108 and 106, respectively. Consequently, direct detection of exoplanets requires observing strategies which push the boundaries of high contrast imaging. The use of coronagraphy to occult a host star has been combined with adaptive optics (AO) technology to yield a particularly promising means of potentially achieving the required contrast ratios in regions close-in enough to the host star. Ground based adaptive optics systems such as The Gemini Planet Imager (GPI)1 and Spectro-Polarimetric High-contrast Exoplanet REsearch (SPHERE)2 instrument have been able to achieve contrast ratios nearing 107 using post-processing techniques3, 4 and have yielded a number of direct detections of young self-luminous planets. Advancing these technologies onto a space based platform immune to the difficulties posed by the effects of Earth’s atmosphere is the next step in accessing even larger contrast ratios.
Joint Uplink and Downlink Coverage Analysis of Cellular-based RF-powered IoT Network

Ambient radio frequency (RF) energy harvesting has emerged as a promising solution for powering small devices and sensors in massive Internet of Things (IoT) ecosystem due to its ubiquity and cost efficiency. In this paper, we study joint uplink and downlink coverage of cellular-based ambient RF energy harvesting IoT where the cellular network is assumed to be the only source of RF energy. We consider a time division-based approach for power and information transmission where each time-slot is partitioned into three sub-slots: 1) charging sub-slot during which the cellular base stations (BSs) act as RF chargers for the IoT devices, which then use the energy harvested in this sub-slot for information transmission and/or reception during the remaining two sub-slots; 2) downlink sub-slot during which the IoT device receives information from the associated BS; and 3) uplink sub-slot during which the IoT device transmits information to the associated BS. For this setup, we characterize the joint coverage probability , which is the joint probability of the events that the typical device harvests sufficient energy in the given time slot and is under both uplink and downlink signal-to-interference-plus-noise ratio (SINR) coverage with respect to its associated BS. This metric significantly generalizes the prior art on energy harvesting communications, which usually focused on downlink or uplink coverage separately. The key technical challenge is in handling the correlation between the amount of energy harvested in the charging sub-slot and the information signal quality (SINR) in the downlink and uplink sub-slots. Dominant BS-based approach is developed to derive tight approximation for this joint coverage probability. Several system design insights including comparison with regularly powered IoT network and throughput-optimal slot partitioning are also provided.
Edge-Unfolding Nearly Flat Convex Caps

The main result of this paper is a proof that a nearly flat, acutely triangulated convex cap C in R^3 has an edge-unfolding to a non-overlapping polygon in the plane. A convex cap is the intersection of the surface of a convex polyhedron and a halfspace. "Nearly flat" means that every outer face normal forms a sufficiently small angle f < F with the z^-axis orthogonal to the halfspace bounding plane. The size of F depends on the acuteness gap a: if every triangle angle is at most pi/2 {-} a, then F ~~ 0.36 sqrt{a} suffices; e.g., for a=3Â°, F ~~ 5Â°. The proof employs the recent concepts of angle-monotone and radially monotone curves. The proof is constructive, leading to a polynomial-time algorithm for finding the edge-cuts, at worst O(n^2); a version has been implemented.