cssi/SciSciGPT-SciSciNet huggingface dataset:
Why Do Stores Drive Online Sales? Evidence of Underlying Mechanisms from a Multichannel Retailer

Traditional retailers are closing down their brick and mortar stores and increasing investments in their online channels. This may not be a beneficial strategy for retailers selling nondigital prod...
Taxing Litigation: Federal Tax Concerns of Personal Injury Plaintiffs and Their Lawyers

This Article addresses the federal tax concerns of personal injury plaintiffs and the lawyers who represent them, typically on a contingency-fee basis. It explains when plaintiffs’ recoveries are taxable for income and employment tax purposes and whether and how those recoveries are required to be reported by defendants to the IRS. It also discusses whether attorney’s fees and costs are deductible by plaintiffs. In addition to these tax planning and compliance issues, the Article also considers when tax evidence might be admissible. Plaintiffs and defendants often try to introduce tax evidence in an effort to increase or decrease, respectively, the amount of damages awarded. These attempts have been met with varying degrees of success, depending on the jurisdiction and context. The Article then addresses the personal tax issues of trial lawyers themselves. Structured attorney fee arrangements, whereby these lawyers attempt to defer tax on contingent fees, are discussed. The tax deductibility of litigation costs advanced by contingent fee lawyers to their clients is considered. Finally, the Article concludes with a discussion of how provisions of the 2017 Tax Act might affect trial lawyers.
The tug-of-war in the laboratory

Abstract The tug-of-war is a multi-battle contest often used to describe extended interactions in economics, operations management, political science, and other disciplines. While there has been some theoretical work, to the best of our knowledge, this paper provides the first experimental study of the tug-of-war. The results show notable deviations of behavior from theory derived under standard assumptions. In the first battle of the tug-of-war, subjects often bid less, while in the follow-up battles, they bid more than predicted. Also, contrary to the prediction, bids tend to increase in the duration of the tug-of-war. Finally, extending the margin necessary to win the tug-of-war causes a greater reduction in bidding than either a decrease in the prize or greater impatience despite all three having the same predicted effect. These findings have implications both for theorists and practitioners.
Deconstructing Difference and Inclusion in Educational Research: Reflections on the International Journal of Qualitative Studies in Education Special Edition on Difference.

Disabled and disability studies scholars and activists have challenged and are challenging the bio- and necro-politics of disability subjectivity through scholarship, art, activism, and online enga...
Evolutionary Optimization of Nondiffracting Helicon Beams

We optimized helicon-like beams in a high resolution imaging sytem with an evolutionary algorithm, achieving a tight intensity profile while largely maintaining self-rotation and nondiffraction. The method promises wide applicability in beam design.
MAC Protocols for Wireless Mesh Networks with Multi-beam Antennas: A Survey

Multi-beam antenna technologies have provided lots of promising solutions to many current challenges faced in wireless mesh networks. The antenna can establish several beamformings simultaneously and initiate concurrent transmissions or receptions using multiple beams, thereby increasing the overall throughput of the network transmission. Multi-beam antenna has the ability to increase the spatial reuse, extend the transmission range, improve the transmission reliability, as well as save the power consumption. Traditional Medium Access Control (MAC) protocols for wireless network largely based on the IEEE 802.11 Distributed Coordination Function (DCF) mechanism, which cannot take the advantages of these unique capabilities of multi-beam antennas. This paper surveys the MAC protocols for wireless mesh networks with multi-beam antennas. The paper first discusses some basic information in designing multi-beam antenna system and MAC protocols, and then presents the main challenges for the MAC protocols in wireless mesh networks compared with the traditional MAC protocols. A qualitative comparison of the existing MAC protocols is provided to highlight their novel features, which provides a reference for designing the new MAC protocols. To provide some insights on future research, several open issues of MAC protocols are discussed for wireless mesh networks using multi-beam antennas.
Rhythmic Food Intake Drives Rhythmic Gene Expression More Potently than the Hepatic Circadian Clock in Mice.

Summary Every mammalian tissue exhibits daily rhythms in gene expression to control the activation of tissue-specific processes at the most appropriate time of the day. Much of this rhythmic expression is thought to be driven cell autonomously by molecular circadian clocks present throughout the body. By manipulating the daily rhythm of food intake in the mouse, we here show that more than 70% of the cycling mouse liver transcriptome loses rhythmicity under arrhythmic feeding. Remarkably, core clock genes are not among the 70% of genes losing rhythmic expression, and their expression continues to exhibit normal oscillations in arrhythmically fed mice. Manipulation of rhythmic food intake also alters the timing of key signaling and metabolic pathways without altering the hepatic clock oscillations. Our findings thus demonstrate that systemic signals driven by rhythmic food intake significantly contribute to driving rhythms in liver gene expression and metabolic functions independently of the cell-autonomous hepatic clock.
High accruals momentum

We examine the information content of high accruals momentum defined as a string of high discretionary accruals for four consecutive years. We find that firms that consistently report high levels of discretionary accruals experience low subsequent returns. The results are robust after we control for annual levels of discretionary accruals for the estimation period of high accruals momentum. Furthermore, the predictive power of the high accruals momentum for future returns is strongly persistent even after the existing accruals anomaly disappears. Our results also show that the high accruals momentum impact is more pronounced for low growth firms, suggesting that the overpricing of stocks with high accruals momentum is driven by managerial discretion to manage earnings.
Identification of new loci for salt tolerance in soybean by high-resolution genome-wide association mapping

Salinity is an abiotic stress that negatively affects soybean [Glycine max (L.) Merr.] seed yield. Although a major gene for salt tolerance was identified and consistently mapped to chromosome (Chr.) 3 by linkage mapping studies, it does not fully explain genetic variability for tolerance in soybean germplasm. In this study, a genome-wide association study (GWAS) was performed to map genomic regions for salt tolerance in a diverse panel of 305 soybean accessions using a single nucleotide polymorphism (SNP) dataset derived from the SoySNP50K iSelect BeadChip. A second GWAS was also conducted in a subset of 234 accessions using another 3.7 M SNP dataset derived from a whole-genome resequencing (WGRS) study. In addition, three gene-based markers (GBM) of the known gene, Glyma03g32900, on Chr. 3 were also integrated into the two datasets. Salt tolerance among soybean lines was evaluated by leaf scorch score (LSS), chlorophyll content ratio (CCR), leaf sodium content (LSC), and leaf chloride content (LCC). For both association studies, a major locus for salt tolerance on Chr. 3 was confirmed by a number of significant SNPs, of which three gene-based SNP markers, Salt-20, Salt14056 and Salt11655, had the highest association with all four traits studied. Also, additional genomic regions on Chrs. 1, 8, and 18 were found to be associated with various traits measured in the second GWAS using the WGRS-derived SNP dataset. A region identified on Chr. 8 was identified to be associated with all four traits and predicted as a new minor locus for salt tolerance in soybean. The candidate genes harbored in this minor locus may help reveal the molecular mechanism involved in salt tolerance and to improve tolerance in soybean cultivars. The significant SNPs will be useful for marker-assisted selection for salt tolerance in soybean breeding programs.
A Tale of Two Polymorphs – Growth and Characterization of α‐LnNiGa4 (Ln = Y, Gd–Yb) and β‐LnNi1–xGa4 (Ln = Tb–Er)

The single crystals of two polymorphs of LnNiGa4, namely, the orthorhombic α-LnNiGa4 (Ln = Y, Gd–Yb) and, a new polymorph, the tetragonal β-LnNi1–xGa4 (Ln = Tb–Er), were successfully grown by using the self-flux method. α-LnNiGa4 (Ln = Y, Gd–Yb) is isostructural to YNiAl4 and can be described as an edge-sharing polyhedral of Ni@Ga7Ln2 (Ln = Y, Gd–Yb) along the ac-plane that is sandwiched between the square nets of the Ga atoms along the b-axis. The structure of β-LnNi1–xGa4 (Ln = Tb–Er) is a distorted variant of the Ce2NiGa10-structure type with a Ni deficiency and multiple Ga split positions and is structurally related to YNiGa3Ge. The magnetic data for β-LnNi1–xGa4 (Ln = Tb–Er) and the transport properties for α-LnNiGa4 (Ln = Y, Gd–Tm) and β-LnNi1–xGa4 (Ln = Tb–Er) are reported. Antiferromagnetic correlations are observed in the magnetic susceptibility of β-LnNi1–xGa4 (Ln = Tb–Er), where the magnetic transitions occurred below 7 K and with effective moments that are consistent with free Ln3+ ions.
The impact of reward on attention in schizophrenia

Traditionally, attention was thought to be directed by either top-down goals or bottom-up salience. Recent studies have shown that the reward history of a stimulus feature also acts as a powerful attentional cue. This is particularly relevant in schizophrenia, which is characterized by motivational and attentional deficits. Here, we examine the impact of reward on selective attention. Forty-eight people with schizophrenia (PSZ) and 34 non-psychiatric control subject (NCS) discriminated the location of a target dot appearing inside a left circle or right circle. The circles were different colors, one of which was associated with reward via pre-training. In the first 2 blocks, targets were equally likely to appear in the left or right circle. In the last 4 blocks, the target was 75% likely on one side, thus allowing us to separately examine how attention was impacted by reward (color) and probability (location). PSZ had slower overall reaction times (RTs) than NCS. Both groups showed robust effects of spatial probability and reward history, with faster RTs for the rewarded color and for the more probable location. These effects were similar in PSZ and NCS. Negative symptom severity correlated with overall RT slowing, but there were no correlations between symptoms and reward-associated biasing of attention. PSZ demonstrated RT slowing but normal reward history and spatial probability-driven RT facilitation. These results are conceptually similar to prior findings showing intact implicit reward effects on response bias, and suggest that implicit processing of reward and probability is intact in PSZ.
Direct synthesis of trimethyl(2-phenoxyethyl)silanes from aromatic fluorides

A direct synthesis of trimethyl(2-phenoxyethyl)silanes from the corresponding aromatic fluorides and 2-(trimethylsilyl)ethanol was developed. A variety of substituents were tolerated and a substitution reaction using 1-bromo-3-chloro-5-fluorobenzene was demonstrated.
New Approach for the General Synthesis of Oxotetrahydroindoles via Intramolecular Cycloadditions of Azomethine Ylides with Tethered Alkynes

A new method for the synthesis of oxotetrahydroindoles has been achieved employing an intramolecular dipolar cycloaddition approach involving mesoionic species (munchnones) with electron-deficient alkynes. The methodology is quite general and convergent as shown by the synthesis of a variety of tri- and tetrasubstituted oxotetrahydroindoles 18, 21, 24, 27, 30, and 34. LiI-based ester cleavage in the presence of an electrophilic acetylenic ketone was critical for formation of the requisite cycloaddition substrates. The cycloaddition is virtually unaffected by the presence of gem-dimethyl groups in the side chain (cf. 38). The presence of a substituted benzyl or a phenethyl moiety on nitrogen, a polarized acetylene, and an appropriate tether between dipole and dipolarophile are essential for obtaining optimal efficiency.
Cation and spin ordering in the n = 1 Ruddlesden-Popper phase La2Sr2LiRuO8

The synthesis and characterization of a polycrystalline sample of the n = 1 Ruddlesden−Popper phase La2Sr2LiRuO8 are reported. X-ray and neutron diffraction show that the six-coordinate sites are occupied by 1:1 ordered xy layers of Li:Ru, and the nine-coordinate sites are occupied by 1:1 ordered layers of La:Sr; a low concentration (7.4%, 9.8% respectively) of anti-site defects was detected on each sublattice. These layers stack in an ordered sequence along z, resulting in an orthorhombic unit cell with a = 5.46001(1), b = 5.45803(1), and c = 25.5410(2) A (space group Imm2) at 290 K. The structure is confirmed by high-resolution transmission electron microscopy, although the presence of stacking faults is revealed. 7Li MAS NMR spectra are consistent with the diffraction data and show that the anti-site defects are not randomly distributed but occur in domains. The sample undergoes a transition to an antiferromagnetic phase at 85 K, with an ordered magnetic moment of 1.58(7) μB per Ru5+ aligned along [001...
Detection and Classification of Hard and Soft Sweeps from Unphased Genotypes by Multilocus Genotype Identity

Positive natural selection can lead to a decrease in genomic diversity at the selected site and at linked sites, producing a characteristic signature of elevated expected haplotype homozygosity. These selective sweeps can be hard or soft. In the case of a hard selective sweep, a single adaptive haplotype rises to high population frequency, whereas multiple adaptive haplotypes sweep through the population simultaneously in a soft sweep, producing distinct patterns of genetic variation in the vicinity of the selected site. Measures of expected haplotype homozygosity have previously been used to detect sweeps in multiple study systems. However, these methods are formulated for phased haplotype data, typically unavailable for nonmodel organisms, and some may have reduced power to detect soft sweeps due to their increased genetic diversity relative to hard sweeps. To address these limitations, we applied the H12 and H2/H1 statistics proposed in 2015 by Garud et al., which have power to detect both hard and soft sweeps, to unphased multilocus genotypes, denoting them as G12 and G2/G1. G12 (and the more direct expected homozygosity analog to H12, denoted G123) has comparable power to H12 for detecting both hard and soft sweeps. G2/G1 can be used to classify hard and soft sweeps analogously to H2/H1, conditional on a genomic region having high G12 or G123 values. The reason for this power is that, under random mating, the most frequent haplotypes will yield the most frequent multilocus genotypes. Simulations based on parameters compatible with our recent understanding of human demographic history suggest that expected homozygosity methods are best suited for detecting recent sweeps, and increase in power under recent population expansions. Finally, we find candidates for selective sweeps within the 1000 Genomes CEU, YRI, GIH, and CHB populations, which corroborate and complement existing studies.
MetaNN: accurate classification of host phenotypes from metagenomic data using neural networks.

Microbiome profiles in the human body and environment niches have become publicly available due to recent advances in high-throughput sequencing technologies. Indeed, recent studies have already identified different microbiome profiles in healthy and sick individuals for a variety of diseases; this suggests that the microbiome profile can be used as a diagnostic tool in identifying the disease states of an individual. However, the high-dimensional nature of metagenomic data poses a significant challenge to existing machine learning models. Consequently, to enable personalized treatments, an efficient framework that can accurately and robustly differentiate between healthy and sick microbiome profiles is needed. In this paper, we propose MetaNN (i.e., classification of host phenotypes from Metagenomic data using Neural Networks), a neural network framework which utilizes a new data augmentation technique to mitigate the effects of data over-fitting. We show that MetaNN outperforms existing state-of-the-art models in terms of classification accuracy for both synthetic and real metagenomic data. These results pave the way towards developing personalized treatments for microbiome related diseases.
Cu-catalyzed N- and O-arylation of 2-, 3-, and 4-hydroxypyridines and hydroxyquinolines.

With use of Cu-based catalysts, 2- and 4-hydroxypyridines were N-arylated in modest to excellent yields. In the case of 2-hydroxypyridine, the use of 4,7-dimethoxy-1,10-phenanthroline, 3, expanded the scope of previous literature reports to include the use of N-containing heteroaryl halides, and 2-substituted aryl halides. In addition, by using a copper catalyst based on 2,2,6,6-tetramethylheptane-3,5-dione, 4, the first N-arylations of 4-hydroxypyridines and O-arylations of 3-hydroxypyridines with aryl bromides and iodides have been accomplished.
The impact of structural variation on human gene expression

Structural variants (SVs) are an important source of human genetic diversity, but their contribution to traits, disease and gene regulation remains unclear. We mapped cis expression quantitative trait loci (eQTLs) in 13 tissues via joint analysis of SVs, single-nucleotide variants (SNVs) and short insertion/deletion (indel) variants from deep whole-genome sequencing (WGS). We estimated that SVs are causal at 3.5-6.8% of eQTLs-a substantially higher fraction than prior estimates-and that expression-altering SVs have larger effect sizes than do SNVs and indels. We identified 789 putative causal SVs predicted to directly alter gene expression: most (88.3%) were noncoding variants enriched at enhancers and other regulatory elements, and 52 were linked to genome-wide association study loci. We observed a notable abundance of rare high-impact SVs associated with aberrant expression of nearby genes. These results suggest that comprehensive WGS-based SV analyses will increase the power of common- and rare-variant association studies.
Organometallic Aspects of Fluoroalkylation Reactions with Copper and Nickel

The development of perfluoroalkylation methods has become increasingly important in synthetic chemistry. However, many of the metal-mediated transformations that occur readily with alkyl substrates can proceed slowly, with limited scope, or not proceed at all with fluoroalkyl derivatives. To develop more sophisticated transformations with fluoroalkyl groups using base metals, a better understanding of their fundamental fluoro-organometallic chemistry is needed. This account describes our recent investigations into the organometallic chemistry of well-defined nickel– and copper–fluoroalkyl complexes, as well as our efforts towards trifluoromethoxylations and trifluoromethylthiolations using those metals. Synthetic routes to the new complexes are discussed, as are their structural and electrochemical properties and chemical reactivities. 1 Introduction 2 Bottling a Copper(I)–Trifluoromethyl Source 3 The Redox Chemistry of Copper– and Nickel–Fluoroalkyl Complexes 4 Nickel- and Copper-Mediated Trifluoromethylthiolations 5 The Organometallic Chemistry of Nickel–Perfluoroalkyl Complexes 6 Outlook
A new synthetic route to boron-10 enriched pentaborane(9) from boric acid and its conversion to anti-10B18H22

Boron-10 enriched boric acid, H310BO3, was converted to the corresponding sodium borohydride, Na10BH4, in essentially quantitative yields, by using slightly modified literature methods involving the formation of butyl borate, (n-OBu)310B, first and then reacting it with NaH in mineral oil. The oxidation reaction of Na10BH4 with I2 in diglyme and subsequent addition/purification in dioxane gave Na[10B3H8]0.3(C4H8O2) that reacted further with NiCl2 in either anhydrous benzene or heavy mineral oil at 110 °C to produce the corresponding 10B5H9 as the first isolated 10B-enriched liquid boron hydride in a laboratory environment. Treatment of this 10B5H9 with NaH or t-BuLi in 2:1 molar ratio underwent a cage expansion reaction to produce the [M]10B9H14 that undergoes a redox reaction in situ with anhydrous NiCl2 in n-hexane to yield the corresponding fused cage anti-10B18H22 as the only solid borane product in 42% yield, thus establishing new synthetic routes for the preparation of 10B-enriched polyhedral boranes.
Selective deprotection of benzyl (Bn) ethers in the presence of para-methoxybenzyl (PMB) ethers

Substituted benzyl ethers have been widely used as readily manipulatable protecting groups for organic synthesis. It is known that electron-rich para-methoxybenzyl (PMB) ethers can be selectively deprotected over benzyl or other electron-poor benzyl ethers under oxidative conditions. In this presentation, we will describe an approach for selective deprotection of benzyl ethers in the presence of PMB ethers under reductive conditions. This new method should complement the existing strategies in the utilization of substituted benzyl ethers in organic synthesis, especially in carbohydrate synthesis.
Synthesis of functionalized pyroglutamic acids, part 1: The synthetic utility of N-acylindole and the ugi reaction with a chiral levulinic acid

A variety of pyroglutamic acid derivatives are readily synthesized via N-acylindole intermediates obtained by the Ugi reaction. For the preparation of functionalized pyroglutamic acid derivatives, the diastereoselectivity of the Ugi 4-center 3-component condensation reaction with a chiral γ-keto acid and convertible isocyanide is described.
Diastereoselective conjugate additions of ethoxyvinyllithium to aromatic and α,β-unsaturated oxazolines

Abstract Ethoxyvinyllithium (EVL) adds cleanly to unsaturated oxazolines, which upon hydrolytic work-up afford the corresponding ketones in high yields and excellent diastereoselectivity.
Enhanced guide-RNA design and targeting analysis for precise CRISPR genome editing of single and consortia of industrially relevant and non-model organisms.

Motivation Genetic diversity of non-model organisms offers a repertoire of unique phenotypic features for exploration and cultivation for synthetic biology and metabolic engineering applications. To realize this enormous potential, it is critical to have an efficient genome editing tool for rapid strain engineering of these organisms to perform novel programmed functions. Results To accommodate the use of CRISPR/Cas systems for genome editing across organisms, we have developed a novel method, named CRISPR Associated Software for Pathway Engineering and Research (CASPER), for identifying on- and off-targets with enhanced predictability coupled with an analysis of non-unique (repeated) targets to assist in editing any organism with various endonucleases. Utilizing CASPER, we demonstrated a modest 2.4% and significant 30.2% improvement (F-test, P < 0.05) over the conventional methods for predicting on- and off-target activities, respectively. Further we used CASPER to develop novel applications in genome editing: multitargeting analysis (i.e. simultaneous multiple-site modification on a target genome with a sole guide-RNA requirement) and multispecies population analysis (i.e. guide-RNA design for genome editing across a consortium of organisms). Our analysis on a selection of industrially relevant organisms revealed a number of non-unique target sites associated with genes and transposable elements that can be used as potential sites for multitargeting. The analysis also identified shared and unshared targets that enable genome editing of single or multiple genomes in a consortium of interest. We envision CASPER as a useful platform to enhance the precise CRISPR genome editing for metabolic engineering and synthetic biology applications. Availability and implementation https://github.com/TrinhLab/CASPER. Contact ctrinh@utk.edu. Supplementary information Supplementary data are available at Bioinformatics online.
Structure, magnetism, and magnetoresistance of the rare-earth transition metal compounds Eu13AMnSb11 (A = Ca, Sr, Ba, and Yb)

The effect of four different dopants (Ca, Sr, Ba, and Yb) on the structural and physical properties of the ternary rare-earth transition metal compound, Eu14MnSb11, has been investigated. The compounds, Eu14-xAxMnSb11 (A = Ca, Sr, Ba, and Yb, x = 1), have been prepared by heating the mixture of stoichiometric amounts of the elements, sealed in a quartz jacketed Ta tube, in a two-zone furnace with Thigh = 1100 °C and Tlow = 1050 °C for 10 days. These compounds are isostructural with the Zintl compound Ca14AlSb11 and crystallize in the tetragonal space group I41/acd, Z = 8. The lattice parameters of the doped compound increase correspondingly as the radius of the metal dopant (A2+) increases. The preference of the dopants onto the four crystallographically inequivalent sites of Eu was examined by single-crystal X-ray diffraction. The magnetization of the compounds has been measured as a function of temperature and applied magnetic field. Temperature-dependent magnetic susceptibility measurement of powder sa...
Identification of Patients in Need of Advanced Care for Depression Using Data Extracted From a Statewide Health Information Exchange: A Machine Learning Approach.

Background: As the most commonly occurring form of mental illness worldwide, depression poses significant health and economic burdens to both the individual and community. Different types of depression pose different levels of risk. Individuals who suffer from mild forms of depression may recover without any assistance or be effectively managed by primary care or family practitioners. However, other forms of depression are far more severe and require advanced care by certified mental health providers. However, identifying cases of depression that require advanced care may be challenging to primary care providers and health care team members whose skill sets run broad rather than deep. Objective: This study aimed to leverage a comprehensive range of patient-level diagnostic, behavioral, and demographic data, as well as past visit history data from a statewide health information exchange to build decision models capable of predicting the need of advanced care for depression across patients presenting at Eskenazi Health, the public safety net health system for Marion County, Indianapolis, Indiana. Methods: Patient-level diagnostic, behavioral, demographic, and past visit history data extracted from structured datasets were merged with outcome variables extracted from unstructured free-text datasets and were used to train random forest decision models that predicted the need of advanced care for depression across (1) the overall patient population and (2) various subsets of patients at higher risk for depression-related adverse events; patients with a past diagnosis of depression; patients with a Charlson comorbidity index of ≥1; patients with a Charlson comorbidity index of ≥2; and all unique patients identified across the 3 above-mentioned high-risk groups. Results: The overall patient population consisted of 84,317 adult (aged ≥18 years) patients. A total of 6992 (8.29%) of these patients were in need of advanced care for depression. Decision models for high-risk patient groups yielded area under the curve (AUC) scores between 86.31% and 94.43%. The decision model for the overall patient population yielded a comparatively lower AUC score of 78.87%. The variance of optimal sensitivity and specificity for all decision models, as identified using Youden J Index, is as follows: sensitivity=68.79% to 83.91% and specificity=76.03% to 92.18%. Conclusions: This study demonstrates the ability to automate screening for patients in need of advanced care for depression across (1) an overall patient population or (2) various high-risk patient groups using structured datasets covering acute and chronic conditions, patient demographics, behaviors, and past visit history. Furthermore, these results show considerable potential to enable preventative care and can be easily integrated into existing clinical workflows to improve access to wraparound health care services.
New Porous Materials from Layered Compounds

Abstract The pillaring of clays has become an established technique of preparing a new class of porous materials. While their promise as cracking catalysts has not been fulfilled, never-the-less they exhibit interesting catalytic behavior. We have extended the technique to the pillaring of many other types of non-clay layered compounds which include phosphates, oxides and layered double hydroxides. This extensiion broadens the field to the point where one can choose the degree of acidity or basicity and framework metals required for specific catalytic processes.
Effect of an Electric Field on the Growth and Optoelectronic Properties of Quasi-One-Dimensional Organic Single Crystals of 1-(Phenylazo)-2-naphthol

Organic single-crystal thin films (2−10 μm thick) of 1-(phenylazo)-2-naphthol (Sudan I) were grown by capillary filling from its molten state (∼133 °C) into cells constructed of two parallel pieces of indium tin oxide (ITO) coated glass followed by slow cooling to room temperature. The solidified crystals were needle-shaped, a few tens of micrometers in diameter, and were aligned parallel to both ITO surfaces. Needle-shaped crystals of Sudan I were also grown from solution. X-ray diffraction analysis revealed a monoclinic crystal with space group, P21/c (No. 14), having a = 5.8225(15), b = 17.377(5), c = 24.598(5) A, β = 92.37(2)°, V = 2486.7(11) A3, Z = 8, ρ = 1.33 g cm-3. The planar molecules are stacked parallel to one another to form molecular columns along the needle axis. The pattern of crystal growth can be changed by the application of an electric field between the two ITO electrodes during solidification to produce crystal needles tilted at an angle relative to the ITO surface. The electrical con...
Preparation of Glycosylated Amino Acids Suitable for Fmoc Solid-Phase Assembly

Many biological interactions and functions are mediated by glycans, consequently leading to the emerging importance of carbohydrate and glycoconjugate chemistry in the design of novel drug therapeutics. Despite the challenges that carbohydrate moieties bring into the synthesis of glycopeptides and glycoproteins, considerable progress has been made during recent decades. Glycopeptides carrying many simple glycans have been chemically synthesized, enzymatic approaches have been utilized to introduce more complex glycans, and most recently native chemical ligation has enabled synthesis of glycoproteins from well-designed peptide and glycopeptide building blocks. Currently, general synthetic methodology for glycopeptides relies on preformed glycosylated amino acids for the stepwise solid-phase peptide synthesis. The formation of glycosidic bonds is of fundamental importance in the assembly of glycopeptides. As such, every glycosylation has to be regarded as a unique problem, demanding considerable systematic research. In this chapter we will summarize the most common chemical methods for the stereoselective synthesis of N- and O-glycosylated amino acids. The particular emphasis will be given to the preparation of building blocks for use in solid-phase glycopeptide synthesis based on the 9-fluorenylmethoxycarbonyl (Fmoc) protective group strategy.
Allenyl azide cycloaddition chemistry. synthesis of pyrrolidine-containing bicycles and tricycles via the possible intermediacy of azatrimethylenemethane species.

Thermolysis of 5-azidoallenes bearing a C(1) methyl group and either an aryl ring or an alkene on C(1) furnishes tricyclic (from the aryl substrates) or bicyclic (from the alkenyl substrates) pyrrolidine products following formal H−CN addition across an intermediate imine. High levels of diastereoselectivity are observed in all cases studied. This reaction cascade presumably passes through unobserved triazoline and azatrimethylenemethane diyl intermediates en route to product.
The halogenolysis of organoboranes

Transmercuration of tri-exo-2-norbornylborane followed by chlorinolysis of the resultant organoborane is a low yield (≤5%) method of producing exo-2-norbornyl chloride. The primary source of this low yield is the inefficient transmercuration of the sterically restricted organoborane. Yields of alkyl halide are substantially higher (up to 63%) when the organoborane undergoes direct chlorinolysis promoted by boron trichloride. Even higher yields (approaching 80%) are obtained when brominolysis of the organoborane is carried out. Controls suggest that at least part of the reason for the higher yield with bromine is due to the greater stability of the product under the reaction conditions. Despite the general retention aspects(exo-borane gives largely exo-halide) of these halogenolyses, deuterium labeling studies show that these reactions are accompanied by substantial Wagner-Meerwein rearrangement, very possibly due to boron trihalide induced rearrangement of the norbornyl halide product
A Density Functional Theory Study of the Gas-Phase Hydrolysis of Dinitrogen Pentoxide

The gas-phase hydrolysis of N2O5 in the clusters of one to four water molecules is investigated by density functional theory calculations. The excess water molecules beyond stoichiometry of the reaction function as a polar solvent medium that stabilizes an ionic pair in the transition state. The reaction energy barrier is progressively diminished by the successive addition of water molecules and is completely eliminated in the cluster of four water molecules, permitting the hydrolysis reaction to proceed directly to products. Atmospheric implications are discussed to understand the reaction mechanisms for the hydrolysis of N2O5 in the gas-phase homogeneous conditions as well as in the heterogeneous conditions.
Binocular Modulation of Monocular V1 Neurons

In humans and other primates, sensory signals from each eye remain separated until they arrive in the primary visual cortex (V1), but their exact meeting point is unknown. In V1, some neurons respond to stimulation of only one eye (monocular neurons), while most neurons respond to stimulation of either eye (binocular neurons). The main input layers of V1 contain most of the monocular neurons while binocular neurons dominate the layers above and below. This observation has given rise to the idea that the two eyes' signals remain separate until they converge outside V1's input layers. Here, we show that, despite responding to only one eye, monocular neurons in all layers, including the input layers, of V1 discriminate between stimulation of their driving eye alone and stimulation of both eyes. Some monocular V1 neurons' responses were significantly enhanced, or facilitated, when both eyes were stimulated. Binocular facilitation within V1's input layers tended to occur at the onset of the visual response, which could be explained by converging thalamocortical inputs. However, most V1 monocular neurons were significantly reduced, or suppressed, to binocular stimulation. In contrast to facilitation, binocular suppression occurred several milliseconds following the onset of the visual response, suggesting that the bulk of binocular modulation involves cortical inhibition. These findings, combined, suggest that binocular signals arise at an earlier processing stage than previously appreciated, as even so-called monocular neurons in V1's input layers encode what is shown to both eyes.
Stability of the Kaczmarz Reconstruction for Stationary Sequences

The Kaczmarz algorithm is an iterative method to reconstruct an unknown vector f from inner products $$\langle f , \varphi _{n} \rangle $$ . We consider the problem of how additive noise affects the reconstruction under the assumption that $$\{ \varphi _{n} \}$$ form a stationary sequence. Unlike other reconstruction methods, such as frame reconstructions, the Kaczmarz reconstruction is unstable in the presence of noise. We show, however, that the reconstruction can be stabilized by relaxing the Kaczmarz algorithm; this relaxation corresponds to Abel summation when viewed as a reconstruction on the unit disc. We show, moreover, that for certain noise profiles, such as those that lie in $$H^{\infty }(\mathbb {D})$$ or certain subspaces of $$H^{2}(\mathbb {D})$$ , the relaxed version of the Kaczmarz algorithm can fully remove the corruption by noise in the inner products. Using the spectral representation of stationary sequences, we show that our relaxed version of the Kaczmarz algorithm also stabilizes the reconstruction of Fourier series expansions in $$L^2(\mu )$$ when $$\mu $$ is singular.
Determination of 77Se-77Se and 77Se-13C J-coupling parameters for the clusters [Re5OsSe8(CN)6]3- and [Re4Os2Se8(CN)6]2-

We have investigated rarely observed 77 Se J-couplings (spin-spin couplings) in the mixed-metal face-capped octahedral clusters [Re 5 OsSe 8 (CN) 6 ] 3- and [Re 4 Os 2 Se 8 (CN) 6 ] 2- at natural abundance. To the best of our knowledge, these are the first observations of Se-Se spin-spin interactions between μ 3 -Se sites, important for stereochemical assignments in hexarhenium analogues, Chevrel phase materials, and similar cluster materials. NMR techniques such as COSY, INADEQUATE, and 2D J-resolved spectroscopy have been used in conjunction to study these interactions. The two isomers (cis and trans) of [Re 4 Os 2 Se 8 (CN) 6 ] 2- were distinguishable, and selective isotopic labeling of [Re 5 OsSe 8 (CN) 6 ] 3- with 13 CN ligands enabled resonances to be assigned by observing the 2 J (Se-M-C) couplings. For [Re 5 OsSe 8 (CN) 6 ] 3- , two different 2 J (Se-M-Se) couplings were measurable on a single cluster, and these are related to one another through spin-spin interactions across a face diagonal or along an edge of the cube of inner selenium ligands. A rigorous analysis based on combinatorial math has been invoked to assign the couplings on the basis of the probability of multiple-spin interactions. The face diagonal association is found to result in a J-coupling interaction larger in magnitude than that from coupling along an edge of the cube-information critical for making stereochemical assignments of selenium sites.
A New Molecular Iodine-Catalyzed Acetalization of Carbonyl Compounds

A new and facile molecular iodine-catalyzed acetalization of carbonyl compounds has been developed. Useful selectivity has also been demonstrated.
Prospective, Real-time Metagenomic Sequencing During Norovirus Outbreak Reveals Discrete Transmission Clusters

Background Norovirus outbreaks in hospital settings are a common challenge for infection prevention teams. Given the high burden of norovirus in most communities, it can be difficult to distinguish between ongoing in-hospital transmission of the virus and new introductions from the community, and it is challenging to understand the long-term impacts of outbreak-associated viruses within medical systems using traditional epidemiological approaches alone. Methods Real-time metagenomic sequencing during an ongoing norovirus outbreak associated with a retrospective cohort study. Results We describe a hospital-associated norovirus outbreak that affected 13 patients over a 27-day period in a large, tertiary, pediatric hospital. The outbreak was chronologically associated with a spike in self-reported gastrointestinal symptoms among staff. Real-time metagenomic next-generation sequencing (mNGS) of norovirus genomes demonstrated that 10 chronologically overlapping, hospital-acquired norovirus cases were partitioned into 3 discrete transmission clusters. Sequencing data also revealed close genetic relationships between some hospital-acquired and some community-acquired cases. Finally, this data was used to demonstrate chronic viral shedding by an immunocompromised, hospital-acquired case patient. An analysis of serial samples from this patient provided novel insights into the evolution of norovirus within an immunocompromised host. Conclusions This study documents one of the first applications of real-time mNGS during a hospital-associated viral outbreak. Given its demonstrated ability to detect transmission patterns within outbreaks and elucidate the long-term impacts of outbreak-associated viral strains on patients and medical systems, mNGS constitutes a powerful resource to help infection control teams understand, prevent, and respond to viral outbreaks.
Structures of three substituted pentacyclo[5.4.0.02, 6.03, 10.05, 9]undecanes and a computational analysis of bond lengths

5-Methyl-2-phenylpentacyclo[5.4.0.02, 6.03, 10.05, 9]undecane-8, 11-dione,5-methyl-2-phenylpentacyclo [5.4.0.02,6.03,10.05,9]undecane-8-one-11-ol,and 5-methyl-2-phenylpentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-diol are three cage compounds which differ only in the oxidation state at C(8) and C(11). The three compounds contain a four-membered, a six-membered, and four five-membered rings fused into a cagelike structure. An X-ray structure analysis shows the C(1)-C(7) and C(9)-C(10) bonds in the diketo cage to be 1.606(2) and 1.586(2) A, which are significantly longer than in the other two molecules. In order to assess the effects of strain, steric, and electronic factors in these compounds, we investigated the unsubstituted parent cage compounds and a series of derivatives by molecular mechanics (MM3), AMPAC (AM1), MOPAC (PM3), and GAUSSIAN 90 calculations. These data suggest that dipolar through space interactions are responsible for the bond elongation and not aπ −→σ * interaction, which has been postulated in parallelπ-systems originating from a common bond. A small degree ofπ −→σ * “through-bond” interaction may contribute to the lengthening in the dimethylene cage analogues.
Diastereocontrol in the Synthesis of 2,3,4-Trisubstituted Pyrrolidines and Tetrahydrofurans via a Palladium(II)-Catalyzed Three-Component Coupling Reaction

The synthesis of trisubstituted pyrrolidines and tetrahydrofurans from boronic acids, allenes, and imines or aldehydes via a five- and a three-step protocol, respectively, is described. The assignment­ of the relative stereochemistry in the pyrrolidines and tetrahydrofurans confirmed the mechanistically significant stereochemical divergence of the palladium-catalyzed three-component coupling reaction. The methodology is applicable to the preparation of combinatorial libraries of pyrrolidines related to pharmaceutical agents and bioactive natural products.
Laser-induced fluorescence spectra of jet-cooled organometallic radicals

Less than ten years ago, the gas phase spectroscopy of organometallic radicals was, except for diatomics and other closely related species, essentially non-existant. The situation changed dramatically with the reports of laser induced fluorescence (LIF) spectra of organometallic radicals by Bemath and co-workers. They prepared a number of species in a Brodia oven reactor wherein a metal vapor, produced from equillibrium heating of a metallic solid, is reacted with a suitable reagent to form an organometallic radical. The species produced were at ambient temperature or above and oftentimes their LIF spectra were quite congested; however, a number of very interesting observations were made concerning their electronic spectra and structure, and the foundation for future experiments was firmly laid. Somewhat after the promising experiments of Bernath and co-workers, our laboratory pioneered the production of similar organometallic radicals in a supersonic free jet expansion. The cooling of the organometallic radicals by the jet to a few degrees Kelvin greatly simplified many of their LIF spectra and allowed for detailed analysis.
Synthesis of a novel cage-functionalized chiral binaphthol host: a potential new agent for enantioselective recognition of chiral ammonium salts

Abstract Optically active, cage-functionalized crown ether ( R )- 3 which contains a 1,1′-bi-2-naphthol moiety has been prepared. Subsequently, the ability of ( R )- 3 to selectively recognize the enantiomers of guest ammonium salts, i.e., 4 and 5 in transport experiments was studied. Host ( R )- 3 displays significantly enhanced enantiomeric selectivity toward complex formation with 4 vis-a-vis complex formation with 5 . The relative energetics of various relevant host–guest complexes have been investigated computationally.
HiCRep: assessing the reproducibility of Hi-C data using a stratum-adjusted correlation coefficient

Hi-C is a powerful technology for studying genome-wide chromatin interactions. However, current methods for assessing Hi-C data reproducibility can produce misleading results because they ignore spatial features in Hi-C data, such as domain structure and distance dependence. We present HiCRep, a framework for assessing the reproducibility of Hi-C data that systematically accounts for these features. In particular, we introduce a novel similarity measure, the stratum adjusted correlation coefficient (SCC), for quantifying the similarity between Hi-C interaction matrices. Not only does it provide a statistically sound and reliable evaluation of reproducibility, SCC can also be used to quantify differences between Hi-C contact matrices and to determine the optimal sequencing depth for a desired resolution. The measure consistently shows higher accuracy than existing approaches in distinguishing subtle differences in reproducibility and depicting interrelationships of cell lineages. The proposed measure is straightforward to interpret and easy to compute, making it well-suited for providing standardized, interpretable, automatable, and scalable quality control. The freely available R package HiCRep implements our approach.
TOTAL SYNTHESIS OF RHIZOXIN D

Abstract The convergent, enantiocontrolled synthesis of a significant antimitotic agent for cancer chemotherapy is presented with completion of rhizoxin diene 2 .
Better to Bend than to Break: Sharing Supply Risk Using the Supply-Flexibility Contract

Problem definition : We analyze a contract in which a supplier who is exposed to disruption risk offers a supply-flexibility contract comprising of a wholesale price and a minimum-delivery fraction...
A review of the relation between species traits and extinction risk

Abstract Biodiversity is shrinking rapidly, and despite our efforts only a small part of it has been assessed for extinction risk. Identifying the traits that make species vulnerable might help us to predict the status for those less known. We gathered information on the relationships between traits and extinction risk from 173 publications, across all taxa, spatial scales and biogeographical regions, in what we think it is the most comprehensive compilation to date. We aimed to identify (1) taxonomical and spatial biases, and (2) statistically robust and generalizable predictors of extinction risk through the use of meta-analyses. Vertebrates and the Palaearctic are the most studied taxon and region because of higher accumulation of data in these groups. Among the many traits that have been suggested to be predictors, only three had enough data for meta-analyses. Two of them are potentially useful in assessing risk for the lesser-known species: regardless of the taxon, species with small range and narrow habitat breadth are more vulnerable to extinction. Contrastingly, body size (the most studied trait) did not present a consistently positive or negative response. We hypothesize that the relationship between body size and extinction risk is shaped by different aspects, namely the phenomena represented by body size depending on the taxonomic group. To increase our understanding of the drivers of extinction, further studies should focus on understudied groups such as invertebrates and fungi and regions such as the tropics and expand the number of traits in comparative analyses that should avoid current biases.