cssi/SciSciGPT-SciSciNet huggingface dataset:
Investigating the reason for increased postural instability in virtual reality for persons with balance impairments

The objective of this study is to investigate how different visual components of Virtual Reality (VR), such as field of view, frame rate, and display resolution affect postural stability in VR. Although previous studies identified these visual components as some of the primary factors that differ significantly in VR from reality, the effect of each component on postural stability is yet unknown. While most people experience postural instability in VR, it is worse for people with balance impairments (BIs). This may be because they depend more on their visual cues to maintain postural stability. We conducted a study with ten people with balance impairments due to Multiple Sclerosis (MS) and seven people without balance impairments to investigate the effect of different visual components on postural stability. In each condition, we varied one of the visual components and kept all other components fixed. Each participant explored the virtual environment (VE) in a controlled fashion to make sure that the effect of the visual components was consistent for all participants. Results from our study suggest that for people with BIs, decreased field of view and decreased frame rate have significant negative effects on postural stability, but the effect of display resolution is inconclusive. However, for people without BIs, there were no significant differences for any of the visual components. Therefore, VR systems targeting people with balance impairments should focus on improving field of view and frame rate before improving display resolution.
Visual Rhythm and Beat

We present a visual analogue for musical rhythm derived from an analysis of motion in video, and show that alignment of visual rhythm with its musical counterpart results in the appearance of dance. Central to our work is the concept of visual beats --- patterns of motion that can be shifted in time to control visual rhythm. By warping visual beats into alignment with musical beats, we can create or manipulate the appearance of dance in video. Using this approach we demonstrate a variety of retargeting applications that control musical synchronization of audio and video: we can change what song performers are dancing to, warp irregular motion into alignment with music so that it appears to be dancing, or search collections of video for moments of accidentally dance-like motion that can be used to synthesize musical performances.
Workplace Knowledge Flows

We conducted a field experiment in a sales firm to test whether improving knowledge flows between coworkers affects productivity. Our design allows us to compare different management practices and isolate whether frictions to knowledge transmission primarily reside with knowledge seekers, knowledge providers, or both. We find large productivity gains from treatments that reduced frictions for knowledge seekers. Workers who were encouraged to seek advice from a randomly chosen partner during structured meetings had average sales gains exceeding 15%. These effects lasted at least 20 weeks after the experiment ended. Treatments intended to change knowledge providers’ willingness to share information, in the form of incentives tied to partners’ joint output, led to positive—but transitory—sales gains. Directing coworkers to share knowledge raised average productivity and reduced output dispersion between workers, highlighting the role that management practices play in generating spillovers inside the firm.
Inflation and the Boom-Bust Cycle in Corporate Leverage

Financial engineering is an art, not a science. The core of the subject is how to camouflage increases in leverage as the source of raised earnings on equity capital. This article explores how and why demand for financial engineers grows globally under the influence of inflationary U.S. monetary policy and how a boom in their profession contributes importantly to the potentially devastating effect of monetary inflation on economic prosperity. It proceeds to consider the extent to which foreign countries, large or small, would take steps to counter their vulnerability to the financial engineers, with particular reference to the case of the emerging markets and Japan who have experienced at times the maximum impact. Of course, the most effective defense is monetary, but for many reasons detailed here, this has rarely been implemented.
Understanding the Downstream Healthcare Supply Chain: Unpacking Regulatory and Industry Characteristics

Hospital leaders face unprecedented pressure to improve traditional supply chain performance measures such as cost, quality, and customer experience. As such, healthcare executives are increasingly turning to the operations and SCM field to provide thought leadership and establish best practices around coordinating information, material, and financial flows in healthcare delivery. Unfortunately, our learnings from traditional manufacturing, and to some extent other service supply chains, do not always easily port to the downstream healthcare delivery supply chain due to regulatory issues and distinctive characteristics present in this network. Grounded in Institutional Theory, this study conceptualizes the downstream healthcare delivery supply chain, highlights important regulatory pressures that influence this supply chain, and examines the effects of government regulation and the unique characteristics of this network on coordination. In doing so, this conceptual study brings to bear important contextual considerations and motivates novel research areas where the SCM field can make substantial contributions.
Optimal Monetary Policy for the Masses

We study nominal GDP targeting as optimal monetary policy in a simple and stylized model with a credit market friction. The macroeconomy we study has considerable income inequality, which gives rise to a large private sector credit market. There is an important credit market friction because households participating in the credit market use non-state contingent nominal contracts (NSCNC). We extend previous results in this model by allowing for substantial intra-cohort heterogeneity. The heterogeneity is substantial enough that we can approach measured Gini coefficients for income, financial wealth, and consumption in the U.S. data. We show that nominal GDP targeting continues to characterize optimal monetary policy in this setting. Optimal monetary policy repairs the distortion caused by the credit market friction and so leaves heterogeneous households supplying their desired amount of labor, a type of \"divine coincidence\" result. We also further characterize monetary policy in terms of nominal interest rate adjustment.
Measuring Basic Psychological Need Satisfaction and Frustration and Work Engagement of Employees of Divine Word Colleges in Ilocos Region, Philippines

The study wants to determine the effect of basic psychological need satisfaction and basic psychological need frustration toward work engagement of employees of Divine Word Colleges in Ilocos Region, Philippines. In order to support the study, theories were presented which are supported by related literatures and studies. The population of the study were 250 or all employees of the colleges. The study used descriptive correlational research design aided by fact finding inquiry. Questionnaires were used to gather the data. The result revealed that there is a correlation between basic psychological need satisfaction and work engagement. While, basic psychological need frustration, as a whole, does not correlate to the engagement, except relatedness need frustration.
Why haven’t U.S. GAAP and IFRS on insurance contracts converged? Evidence from an unsuccessful joint project

Abstract This study examines the FASB’s and IASB’s unsuccessful joint project on accounting for insurance contracts. It highlights the divergent views the Boards may hold on certain fundamental accounting issues. Further, this study examines how the costs and benefits of accounting standard convergence can vary within an industry, conditional on factors such as prior accounting standards and firms’ global operations. Empirically, U.S. insurers’ negative market reactions to the joint insurance project suggest U.S. investors perceived net costs would outweigh net benefits. This study also finds that market reactions of U.S. insurers were more negative than those of European insurers. The results of cross-sectional analyses indicate that U.S. life insurers perceived higher net costs associated with the joint project, while European insurers with more global revenue perceived higher net benefits. This work illuminates some of the challenges facing standard setters when attempting to develop a globally acceptable set of financial reporting standards.
LIGHT ACTIVE AND STERILE NEUTRINOS FROM COMPOSITENESS

Abstract Neutrinos can have naturally small Dirac masses if the Standard Model singlet right-handed neutrinos are light composite fermions. Theories which produce light composite fermions typically generate many of them, three of which can marry the left-handed neutrinos with small Dirac masses. The rest can serve as sterile states which can mix with the Standard Model neutrinos. We present explicit models illustrating this idea.
Individual Differences in Attributes of Trust in Automation: Measurement and Application to System Design

Computer-based automation of sensing, analysis, memory, decision-making, and control in industrial, business, medical, scientific, and military applications is becoming increasingly sophisticated, employing various techniques of artificial intelligence for learning, pattern recognition, and computation. Research has shown that proper use of automation is highly dependent on operator trust. As a result the topic of trust has become an active subject of research and discussion in the applied disciplines of human factors and human-systems integration. While various papers have pointed to the many factors that influence trust, there currently exists no consensual definition of trust. This paper reviews previous studies of trust in automation with emphasis on its meaning and factors determining subjective assessment of trust and automation trustworthiness (which sometimes but not always are regarded as an objectively measurable properties of the automation). The paper asserts that certain attributes normally associated with human morality can usefully be applied to computer-based automation as it becomes more intelligent and more responsive to its human user. The paper goes on to suggest that the automation, based on its own experience with the user, can develop reciprocal attributes that characterize its own trust of the user and adapt accordingly. This situation can be modeled as a formal game where each of the automation user and the automation (computer) engage one another according to a payoff matrix of utilities (benefits and costs). While this is a concept paper lacking empirical data, it offers hypotheses by which future researchers can test for individual differences in the detailed attributes of trust in automation, and determine criteria for adjusting automation design to best accommodate these user differences.
Financial performance trends of United States Hockey Inc: a resource-dependency approach

Purpose – The purpose of this paper is to examine the 2009 to 2016 financial performance of the US Hockey Inc., using financial effectiveness indicators and financial efficiency ratios. Design/methodology/approach – With the assistance of financial trend analysis, archival data were used to examine the financial performance (evaluated by net income), financial effectiveness (indicated by total assets and total revenues) and financial efficiency (examined by programme services ratios and return on assets) of US Hockey Inc. Findings – On average, the financial performance of the organization was positive ($30,895 net income per year). Financial effectiveness was steady with increases in assets and revenues. Financial efficiency was poor with 79% of revenues spent on programme services and 1.45%average return on asset. Research limitations/implications – The results can be generalized to similar national non-profit sports federations but not corporate sports entities with dissimilar financial goals. Practical implications – The results revealed that national non-profit sports federations can boost their financial performance by maintaining a double strategically focus on both financial effectiveness and financial efficiency. Originality/value – The study used both financial effectiveness and financial efficiency measures to evaluate the financial performances of a national non-profit sports federation – a neglected approach similarstudies. Proposito - El proposito de este documento fue examinar el desempeno financiero de 2009 a 2016 de United States Hockey Inc., utilizando indicadores y ratios de efectividad financiera. Diseno/metodologia/enfoque - Con la ayuda del analisis de tendencias financieras, se utilizaron datos de archivo para examinar el desempeno financiero (evaluado por el ingreso neto), eficacia financiera (indicada por los activos totales y los ingresos totales) y la eficiencia financiera (examinada por los indices de servicios del programa y el rendimiento de los activos) de United States Hockey Inc. Hallazgos - En promedio, el desempeno financiero de la organizacion fue positivo (U$S 30 895, ingreso neto por ano). La efectividad financiera se mantuvo estable con aumentos en activos e ingresos. La eficiencia financiera fue pobre, con el 79% de los ingresos gastados en servicios del programa y un rendimiento promedio del activo del 1.45%. Limitaciones de la investigacion - Los resultados pueden generalizarse a federaciones deportivas nacionales sin fines de lucro similares, pero no a entidades deportivas corporativas con objetivos financieros diferentes. Implicaciones practicas - Los resultados revelaron que las federaciones deportivas nacionales sin fines de lucro pueden aumentar su desempeno financiero al mantener un doble enfoque estrategico, tanto en la eficacia financiera como en la eficiencia financiera. Originalidad/valor - El estudio utilizo medidas de eficacia y eficiencia financieras para evaluar el desempeno financiero de una federacion deportiva nacional sin fines de lucro, un enfoque descuidado en estudios similares.
The Design and Synthesis of a Hapten for 1192U90, a Potential Atypical Antipsychotic Agent

Abstract The design and synthesis of a hapten for a radioimmunoassay procedure for the potential atypical antipsychotic agent 1192U90 (1) is described. The hapten, a butyric acid derivative of ortho-amino benzamide 1192U90, was prepared in five steps starting from 5-hydroxy-2-nitrobenzaldehyde.
The intramolecular Morita–Baylis–Hillman-type alkylation reaction

Abstract From the initial development of a homologous Morita–Baylis–Hillman reaction utilizing epoxides as electrophiles, the method was expanded to enable the exclusively organocatalyzed intramolecular allylation of enones and to develop the intramolecular MBH-type alkylation of activated alkenes. We successfully utilized both enones and unsaturated thioesters as the activated alkene component. This work, carried out using stoichiometric amounts of the trialkylphosphine, gave an array of functionalized five- and six-membered carbocycles in high yields. With the cycloalkylation of enones and thioesters, conditions that allowed the use of substoichometric amounts of the phosphine catalyst were developed. As a result both five- and six-membered rings can be formed efficiently with little to no loss in yield upon comparison to yields obtained when stoichiometric amounts of trialkylphosphines were employed. We isolated, for the first time, an MBH-type intermediate exhibiting unprecedented trans geometry of the phosphonium salt and acyl group.
Efficient synthesis of 3,5-functionalized isoxazoles and isoxazolines via 1,3-dipolar cycloaddition reactions of 1-propargyl- and 1-allylbenzotriazoles

3-Aryl-5-(benzotriazol-1-ylmethyl)- 10a-f and 3-p-methoxyphenyl-5-(α-benzotriazol-1-yl-α-ethoxymethyl)-isoxazole (13) were prepared in high yields by 1,3-dipolar cycloadditions of 1-propargyl-benzotriazole (5) and (α-ethoxypropargyl)benzotriazole (8), respectively, with nitrite oxides 3a-f (prepared in situ from benzohydroximoyl chlorides 2a-f). The benzotriazol-1-ylmethyl moiety was further elaborated by sequential lithiation and reaction with aldehydes, alkyl halides and Michael acceptors. Similar 1,3-cycloadditions using 1-allylbenzotriazole (6) and 1-(α-ethoxyallyl)benzotriazole (7) afforded 3,5-substituted isoxazolines 11b, f and 12 in excellent yields.
Kinetics of the thermal decomposition of ferrocenyl azide: Character of ferrocenyl nitrene

The Arrhenius parameters for the thermal decomposition of ferrocenyl azide in isooctane are A = (5.1 ± 1.4) × 1012 s−1 and Eact = 113.1 ± 0.9 (kJ mol−1) and the rate is relatively insensitive to solvent (isooctane, benzene, acetonitrile: 1:1.7:2.4). The results indicate a relatively nonpolar transition state which is considerably “tighter” than for a normal bond fission reaction. The Arrhenius parameters are comparable to those for aromatic azides and do not offer any support for anchimeric assistance by the iron atom. A kinetic scheme is presented which accounts for the observed products: Nitrogen, ferrocene, aminoferrocene, azoferrocene, and insoluble material. Rates of hydrogen abstraction by the intermediate ferrocenyl nitrene from cyclohexane, benzene, and acetonitrile are used to show that the nitrene is nucleophilic. © 1994 John Wiley & Sons, Inc.
Preparation and Fungitoxicity of Some Trichloro-, Tribromo-, Tetrachloro-, and Tetrabromo-8-Quinolinols

3,5,6-, 3,5,7-, 4,5,7-, and 5,6,7-trichloro- and -tribromo-8-quinolinols as well as 3,5,6,7-tetrachloro- and -tetrabromo-8-quinolinols were prepared and tested against six fungi (Aspergillus niger, Aspergillus oryzae, Myrothecium verrucaria, Trichoderma viride, Mucor cirinelloides, and Trichophyton mentagrophytes) in Sabouraud dextrose broth. The compounds strongly inhibit five fungi but not M. cirinelloides. They are less active than the related dichloro-8-quinolinols which is attributed to steric hindrance.
Potential toxic and carcinogenic chemical contaminants in source‐separated municipal solid waste composts: Review of available data and recommendations

Composting and soil amendment could be an excellent alternative to disposal for the biodegradable fraction of residential, institutional, restaurant and commercial wastes. If done properly, composting fits naturally with traditional recycling, and could become one of the next major steps in solid waste management. Issues of public acceptance and the need to protect human health and the environment will be crucial in the development of municipal composting as a viable solid waste management strategy. Reducing the levels of contaminants in composts will help increase public acceptance of composting, markets for composts and associated ecological benefits. Contaminant levels are usually lower when waste generators separate organic feedstocks for composting than when post‐collection separation techniques are applied to mixed solid wastes. For this reason, source‐separated composting is generally favored by environmentalists — and it has been the focus of this work. It is crucial to keep this point in mind whe...
Perthio- and perseleno-1,3-butadienes, -but-1-ene-3-ynes, and -[3]-cumulenes: one-step syntheses from 1,4-dilithio-1,3-butadiyne.

Treatment of 1,4-dilithio-1,3-butadiyne (1) with dichalcogenides RSSR or RSeSeR affords dithio- and diseleno-1,3-butadiynes (2, 3), perthio- and perseleno-[3]-cumulenes (4, 5), perthio- and perseleno-1,3-butadienes (6, 7), and/or perthio- and perseleno-but-1-ene-3-ynes (8, 9). The products can be controlled by stoichiometry and temperature, by the presence or absence of oxygen, and by choice of the “R” group. By X-ray crystallography, hexa(methylthio)-1,3-butadiene is highly twisted, with a torsion angle [Φ(CCCC)] of 84.7° and an elongated C(2)−C(3) distance of 1.484(3) A.
Pd catalyzed coupling of 1,2-dibromoarenes and anilines: formation of N,N-diaryl-o-phenylenediamines

1,2-Dibromoarenes were coupled with aniline derivatives to yield N,N-diaryl-o-phenylenediamines in moderate to good yield using a palladium/phosphine or palladium/carbene catalyst system. Under similar conditions, 1,2,4,5-tetrabromobenzene was coupled with aniline derivatives to produce the corresponding tetrasubstituted derivatives which are oxidized on workup to yield azophenines. The sequential reaction of two different anilines with 1-chloro-2-iodobenzene afforded mixed N,N-diaryl-o-phenylenediamines.
Cosmic problems for condensed matter experiment

Condensed matter analogs of the cosmological environment have raised the hope that laboratory experiments can be done to test theoretical ideas in cosmology. I will describe Unruh's sonic analog of a black hole (“dumbhole”) that can be used to test Hawking radiation, and some recent proposals on how one might be able to create a dumbhole in the lab. In this context, I also discuss an experiment already done on the helium-3 AB system by the Lancaster group. PACS numbers: 04.70.-s, 67.57.Np.
Kinetics of NiO reduction by H2 and Ni oxidation at conditions relevant to chemical-looping combustion and reforming

Abstract Twenty solid-state kinetic models, including mechanisms dominated by reaction order, geometrical contraction, diffusion, nucleation, random pore growth, as well as the more flexible Sestak–Berggren and Prout–Tompkins models, are reviewed and applied to describe the reduction of unsupported and supported NiO by H2 and the oxidation of supported Ni by air. In an effort to address the inconsistencies in the literature regarding the suitability of each mechanism to describe the kinetics of Ni-based oxygen carriers in chemical-looping, all the models are compared against experimental data from the literature and with in-house experiments at conditions relevant to chemical-looping combustion and reforming with Ni-based oxygen carriers. A statistical approach to compare models of varying fidelity is employed, involving the Akaike Information Criterion and the F-test. The effect of temperature on the selection of the best-suited model is investigated, supplemented by experimental evidence from X-ray diffraction and scanning electron microscopy analyses. This work reveals that unsupported and supported NiO reduction can be described by nucleation and nuclei growth models. The oxidation kinetics of supported Ni is well-predicted by geometrical contraction models. Calcination and high-temperature treatment during oxygen carrier synthesis are shown to significantly affect the reaction kinetics of the oxygen carrier.
Efficient synthesis of trifluoromethylated dihydrochalcones, aryl vinyl ketones and indanones by superelectrophilic activation of 4,4,4-trifluoro/3-(trifluoromethyl)crotonic acids

Abstract Superacid catalyzed electrophilic substitution of arenes using 4,4,4,-trifluoro/3-trifluoromethylcrotonic acids has been investigated. The direct synthesis of various trifluoromethylated dihydrochalcones, aryl vinyl ketones and indanones has been achieved by this methodology. It has been found that the position of the trifluoromethyl group has a profound effect on the nature of the reaction and the products. In the pharmaceutical industry, many fluoroorganics are shown to possess significant biological and therapeutic activities. Therefore, these novel compounds can be considered key intermediates for the preparation of potential biologically active molecules.
Synthesis of 3-substituted xylopyranosides from 2,3-anhydropentosides

The facile regio- and stereoselective epoxide ring-opening of anhydropentosides described herein provides an attractive pathway to 3-substituted analogs of pentosides. Benzyl 2,3-anhydro-β-D-ribopy...
Synthesis of 1,3-butadienes having a nitrogen-containing heterocyclic substituent

Abstract Condensation of γ-(trimethylsilyl)allylborane 2 with aldehydes 3a–f afforded, after base-induced Peterson olefination reaction, the corresponding 1,3-butadienes having a nitrogen-containing heterocyclic substituent.
Mixed Effects Models for Resampled Network Statistics Improves Statistical Power to Find Differences in Multi-Subject Functional Connectivity.

Many complex brain disorders such as Autism Spectrum Disorders exhibit a wide range of symptoms and disability. To understand how brain communication is impaired in such conditions, functional connectivity studies seek to understand individual differences in brain network structure in terms of covariates that measure symptom severity. In practice, however, functional connectivity is not observed but estimated from complex and noisy neural activity measurements. Imperfect subject network estimates can compromise subsequent efforts to detect covariate effects on network structure. We address this problem in the case of Gaussian graphical models of functional connectivity, by proposing novel two-level models that treat both subject level networks and population level covariate effects as unknown parameters. To account for imperfectly estimated subject level networks when fitting these models, we propose two related approaches --- R^2 based on resampling and random effects test statistics, and R^3 that additionally employs random adaptive penalization. Simulation studies using realistic graph structures reveal that R^2 and R^3 have superior statistical power to detect covariate effects compared to existing approaches, particularly when the number of within subject observations is comparable to the size of subject networks. Using our novel models and methods to study parts of the ABIDE dataset, we find evidence of hypoconnectivity associated with symptom severity in Autism Spectrum Disorders, in frontoparietal and limbic systems as well as in anterior and posterior cingulate cortices.
Quality sensitive price competition in spectrum oligopoly

We investigate a spectrum oligopoly where primary users allow secondary access in lieu of financial remuneration. Transmission qualities of the licensed bands fluctuate randomly. Each primary needs to select the price of its channel with the knowledge of its own channel state but not that of its competitors. Secondaries choose among the channels available on sale based on their states and prices. We formulate the price selection as a non-cooperative game and prove that a symmetric Nash equilibrium (NE) strategy profile exists uniquely. We explicitly compute this strategy profile and analytically and numerically evaluate its efficiency. Our structural results provide certain key insights about the unique symmetric NE.
Crystal Structure of a Zinc Sorption Complex of Cd2+-Exchanged Zeolite X Containing Tetrahedral Cd2+4(μ3-Zn0Cd2+Zn0)4 Clusters

The sorption of Zn vapor at 480 C onto fully dehydrated fully Cd{sup 2+}-exchanged zeolite X (Cd{sub 46}Si{sub 100}Al{sub 92}O{sub 384} per unit cell) has been studied at 23 C by single-crystal X-ray diffraction in the cubic space group Fd3 (a{sub 0} = 24.895(3) {angstrom}). In this structure, Cd{sub 46}Si{sub 100}Al{sub 92}O{sub 384}{center_dot}20Zn, Cd{sup 2+} ions are found at five nonequivalent sites, redistributed significantly from 16, 0, 30, 0, 0 in dehydrated Cd{sub 46}-X to 12, 8, 12, 6, 8 (best integers) at sites I, I{prime}, II, III{prime}, and another III{prime} respectively. The 8 Cd{sup 2+} ions at site I{prime} and 8 of the 12 Cd{sup 2+} ions at site II have captured 16 Zn atoms to form two Cd{sub 4}{sup 2+}({mu}{sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} clusters per unit cell. The remaining four Cd{sup 2+} ions at site II have captured the remaining (about four) Zn atoms. Each Cd{sub 4}{sup 2+}({sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} cluster has at its center interpenetrating tetrahedra of (Cd{sup 2+}){sub 4} and (Zn{sup 0}){sub 4} in the sodalite unit, with four terminal Cd{sup 2+}-Zn{sup 0} groups extending radially into the supercage from each of the above Zn{sup 0} atoms; Cd{sup 2+} ions andmore » Zn{sup 0} atoms alternate throughout. The central four Zn{sup 0} atoms form a tetrahedral Zn{sub 4}{sup 0} cluster with Zn-Zn = 2.88(4) {angstrom}, somewhat longer than the 2.66 {angstrom} distance in Zn metal, due perhaps to delocalization of bonding density to adjacent Cd{sup 2+} ions. In each Cd{sub 4}{sup 2+}({mu}{sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} cluster, each sodalite unit Cd{sup 2+} ion has a distorted octahedral environment, 2.566(11) {angstrom} to three framework oxygens at 2.225(8) {angstrom} and axially to two Zn atoms at 2.408(23) {angstrom} and 1.97(5) {angstrom}, respectively. Each sodalite unit Zn atom coordinates tetrahedrally to four Cd{sup 2+} ions; each terminal Zn atom interacts only with one Cd{sup 2+} ion. Surprisingly, no Cd{sup 2+} ions have been reduced by Zn atoms; all Cd{sup 2+} ions are at reasonable bonding distances to framework oxygens, and all Zn atoms are far from framework oxygens. About 12 Cd{sup 2+} ions remained at site I upon Zn sorption; each coordinates octahedrally to six framework oxygens at 2.430(10) {angstrom}. About 6 + 8 = 14 Cd{sup 2+} ions have relocated to two III{prime} sites, 2.46(5) {angstrom} and 2.38(3) {angstrom}, respectively, from framework oxygens.« less
Polyene cyclizations to indole diterpenes. The first synthesis of (+)-emindole SA using a biomimetic approach

Abstract A biomimetic synthesis of the indole diterpene emindole SA (5) has been achieved via Lewis acid promoted polyene cyclization.
1-Boraadamantane blows its top, sometimes. The mono- and polyhomologation of 1-boraadamantane.

1-Boraadamantane·THF (3) reacts with 1 equiv of dimethylsulfoxonium methylide (4) to afford a monohomologated product. The polyhomologation of 1-boraadamantane·THF by ylide 4 followed by oxidative cleavage generates star polymethylene polymers incorporating a cyclohexane core. However, only one-third of the initiators lead to product formation, resulting in an observed degree of polymerization three times higher than expected. The polyhomologation of 3 was found to contain branch points after the fourth and fifth methylene insertions. At the branch points, the propagating species either terminate in tricyclic trialkylborane cages with collapsed, pyramidal inverted boron centers that are unreactive toward ylide or they continue in uninterrupted polymerization and eventually result in the formation of giant “tube-like” structures such as 5.
BIMOLECULAR REACTIONS OF ALKYL HALIDES AND ACYLGERMANES : FORMATION OF KETONES, DIKETONES, AND OTHER PRODUCTS BY RADICAL-RADICAL REACTION

Abstract Reactions of alkyl halides (R1X) with acyltriphenylgermanes (R2COGePh3) under radical conditions provide mixtures of ketones (R1COR2), diketones (R2COCOR2), alkanes (R1H) and alkenes. These products arise from radical-radical reactions, and the results suggest that bimolecular addition reactions of alkyl radicals to acylgermanes are too slow to propagate radical chains.
Chiral N-phosphonyl imine chemistry: asymmetric 1,2-additions of allylmagnesium bromides

Abstract Chiral N -phosphonyl homoallylic amines were synthesized by the reaction of allylmagnesium bromide with chiral N -phosphonyl imines. The C 2 -symmetric chiral N -phosphonyl group was optimized for this reaction. Excellent yields and good diastereoselectivities were obtained for eight examples.
Palladium-catalyzed conversion of benzylic and allylic halides into α-aryl and β,γ-unsaturated tertiary amides by the use of a carbamoylsilane

Treatment of allylic and benzylic halides with N,N-dimethylcarbamoyl(trimethyl)silane in the presence of tetrakis(triphenylphosphine)palladium(0) affords tertiary amides, which arise from the replacement of the halogen by the N,N-dimethylcarbamoyl group.
SLiM 3: Forward Genetic Simulations Beyond the Wright–Fisher Model

With the desire to model population genetic processes under increasingly realistic scenarios, forward genetic simulations have become a critical part of the toolbox of modern evolutionary biology. The SLiM forward genetic simulation framework is one of the most powerful and widely used tools in this area. However, its foundation in the Wright-Fisher model has been found to pose an obstacle to implementing many types of models; it is difficult to adapt the Wright-Fisher model, with its many assumptions, to modeling ecologically realistic scenarios such as explicit space, overlapping generations, individual variation in reproduction, density-dependent population regulation, individual variation in dispersal or migration, local extinction and recolonization, mating between subpopulations, age structure, fitness-based survival and hard selection, emergent sex ratios, and so forth. In response to this need, we here introduce SLiM 3, which contains two key advancements aimed at abolishing these limitations. First, the new non-Wright-Fisher or "nonWF" model type provides a much more flexible foundation that allows the easy implementation of all of the above scenarios and many more. Second, SLiM 3 adds support for continuous space, including spatial interactions and spatial maps of environmental variables. We provide a conceptual overview of these new features, and present several example models to illustrate their use.
Protein tertiary structure modeling driven by deep learning and contact distance prediction in CASP13

Predicting residue-residue distance relationships (eg, contacts) has become the key direction to advance protein structure prediction since 2014 CASP11 experiment, while deep learning has revolutionized the technology for contact and distance distribution prediction since its debut in 2012 CASP10 experiment. During 2018 CASP13 experiment, we enhanced our MULTICOM protein structure prediction system with three major components: contact distance prediction based on deep convolutional neural networks, distance-driven template-free (ab initio) modeling, and protein model ranking empowered by deep learning and contact prediction. Our experiment demonstrates that contact distance prediction and deep learning methods are the key reasons that MULTICOM was ranked 3rd out of all 98 predictors in both template-free and template-based structure modeling in CASP13. Deep convolutional neural network can utilize global information in pairwise residue-residue features such as coevolution scores to substantially improve contact distance prediction, which played a decisive role in correctly folding some free modeling and hard template-based modeling targets. Deep learning also successfully integrated one-dimensional structural features, two-dimensional contact information, and three-dimensional structural quality scores to improve protein model quality assessment, where the contact prediction was demonstrated to consistently enhance ranking of protein models for the first time. The success of MULTICOM system clearly shows that protein contact distance prediction and model selection driven by deep learning holds the key of solving protein structure prediction problem. However, there are still challenges in accurately predicting protein contact distance when there are few homologous sequences, folding proteins from noisy contact distances, and ranking models of hard targets.
Utility of neodymium diiodide as a reductant in ketone coupling reactions.

The viability of NdI2 as a one-electron reducing agent in organic synthesis has been examined by studying coupling reactions between alkyl chlorides and ketones and aldehydes.
Evolutionary Proteomics Reveals Distinct Patterns of Complexity and Divergence between Lepidopteran Sperm Morphs

Spermatozoa are one of the most strikingly diverse animal cell types. One poorly understood example of this diversity is sperm heteromorphism, where males produce multiple distinct morphs of sperm in a single ejaculate. Typically, only one morph is capable of fertilization and the function of the nonfertilizing morph, called parasperm, remains to be elucidated. Sperm heteromorphism has multiple independent origins, including Lepidoptera (moths and butterflies), where males produce a fertilizing eupyrene sperm and an apyrene parasperm, which lacks a nucleus and nuclear DNA. Here we report a comparative proteomic analysis of eupyrene and apyrene sperm between two distantly related lepidopteran species, the monarch butterfly (Danaus plexippus) and Carolina sphinx moth (Manduca sexta). In both species, we identified ∼700 sperm proteins, with half present in both morphs and the majority of the remainder observed only in eupyrene sperm. Apyrene sperm thus have a distinctly less complex proteome. Gene ontology (GO) analysis revealed proteins shared between morphs tend to be associated with canonical sperm cell structures (e.g., flagellum) and metabolism (e.g., ATP production). GO terms for morph-specific proteins broadly reflect known structural differences, but also suggest a role for apyrene sperm in modulating female neurobiology. Comparative analysis indicates that proteins shared between morphs are most conserved between species as components of sperm, whereas morph-specific proteins turn over more quickly, especially in apyrene sperm. The rapid divergence of apyrene sperm content is consistent with a relaxation of selective constraints associated with fertilization and karyogamy. On the other hand, parasperm generally exhibit greater evolutionary lability, and our observations may therefore reflect adaptive responses to shifting regimes of sexual selection.
Iodoacetoxylation of Glycals Using Cerium(IV) Ammonium Nitrate, Sodium Iodide, and Acetic Acid: Stereoselective Synthesis of 2-Deoxy-2-iodo-α-mannopyranosyl Acetates

The reactions of glycals with ceric(IV) ammonium nitrate and sodium iodide in the presence of acetic acid provides 2-deoxy-2-iodo-α-mannopyranosyl acetates with good stereoselectivity. In the majority of the cases examined, the selectivity was considerably better than that from reactions using N-iodosuccinimide and HOAc.
Enantioselective Synthesis of the Macrolide Antibiotic Oleandomycin Aglycon

The stereochemical and heterofunctional complexity of the polypropionate-derived macrolide antibiotics poses a formidable challenge for stereoselective synthesis, and these target structures have provided the stimulus for the development of a host of new enantioand diastereoselective bond constructions.1 In this paper we illustrate, in the context of an efficient synthesis of oleandolide aglycon (1),2 how polypropionate chains may be rapidly assembled using the chiral â-ketoimide building block 2 and its associated aldol reaction methodology recently developed in these laboratories.3,4 As illustrated in Scheme 1, the synthesis plan relied upon â-ketoimide 2 for the construction of both the C1-C8 and C9C14 oleandolide fragments. Concurrent application of a sequential aldol reduction strategy to both fragments established 8 of the 10 requisite stereocenters, while an imide enolate alkylation reaction was employed to control the lone C6 stereocenter in the C5-C8 subunit. In the final stereoselective transformation, the introduction of the C8-epoxide with the desired stereochemistry was effected through the directed VO(acac)2/t-BuO2H epoxidation of the 9-(S)-allylic alcohol prior to macrocyclization.5,6 This last step becomes much more challenging to implement when it is postponed until after macrocycle construction as the two previous syntheses of oleandolide have revealed.2 The synthesis of the C1-C8 fragment began with the titaniummediated syn aldol reaction between aldehyde 47 and â-ketoimide 2 (Scheme 2).3a,8 This double stereodifferentiating reaction (eq 1) proceeded in excellent yield with high anti Felkin diastereoselection. Treatment of aldol adduct 5 with Zn(BH4)2 established the C5-hydroxyl stereocenter Via a chelate-controlled
Medicaid Work Requirements — Results from the First Year in Arkansas

Medicaid Work Requirement in Arkansas Arkansas was among several states that implemented Medicaid work requirements. Results from surveys of low-income adults suggest that work requirements were as...
N-demethylation of (±)-6β-acetoxy-3-tropinone. Synthesis of (±)-6β-acetoxynortropane

Nortropinone 5, prepared from 3 by N-demethylation with trichloroethyl chloroformate, followed by deprotection of carbamate 4 with zinc in acetic acid, served as a starting material to prepare the N-protected 6-acetoxy ketones 7 and 9–12, and alcohols 6 and 8. Nortropane 16 was prepared from 3 by decarbonylation via dithioketal 13 followed by N-demethylation, and from 10 by decarbonylation via dithioketal 14. When ethanol was used in the desulfurization of 14 instead of tetrahydrofuran, substantial amounts of the N-ethylated amine 17 were produced.
Bench-Top Synthesis of Solid-State Copper(I) Sulfides, KCu7-xS4 (x = 0.0, 0.12, 0.34), via Nonaqueous Electrochemistry

Whiskers of the pseudo-one-dimensional copper(I) sulfide series, KCu7-xS4 (x = 0−0.34), are grown by an electrochemical reaction via anodic dissolution of copper in a nonaqueous solution of K2Sn/Cu...
Much improved upper limit for the rate constant for the reaction of O2+ with N2.

The rate constant for the reaction of O 2 + with N 2 to produce NO + plus NO has been measured at 423, 523, and 623 K in a turbulent ion flow tube. Much improved upper limits for this reaction at the three temperatures are 2, 4, and 10 x 10 -21 cm 3 s -1 , respectively. These results should render this reaction irrelevant when modeling all plasmas involving atmospheric gases.
Nonparametric generalized fiducial inference for survival functions under censoring

Fiducial Inference, introduced by Fisher in the 1930s, has a long history, which at times aroused passionate disagreements. However, its application has been largely confined to relatively simple parametric problems. In this paper, we present what might be the first time fiducial inference, as generalized by Hannig et al. (2016), is systematically applied to estimation of a nonparametric survival function under right censoring. We find that the resulting fiducial distribution gives rise to surprisingly good statistical procedures applicable to both one sample and two sample problems. In particular, we use the fiducial distribution of a survival function to construct pointwise and curvewise confidence intervals for the survival function, and propose tests based on the curvewise confidence interval. We establish a functional Bernstein-von Mises theorem, and perform thorough simulation studies in scenarios with different levels of censoring. The proposed fiducial based confidence intervals maintain coverage in situations where asymptotic methods often have substantial coverage problems. Furthermore, the average length of the proposed confidence intervals is often shorter than the length of competing methods that maintain coverage. Finally, the proposed fiducial test is more powerful than various types of log-rank tests and sup log-rank tests in some scenarios. We illustrate the proposed fiducial test comparing chemotherapy against chemotherapy combined with radiotherapy using data from the treatment of locally unresectable gastric cancer.
Massive mining of publicly available RNA-seq data from human and mouse.

RNA sequencing (RNA-seq) is the leading technology for genome-wide transcript quantification. However, publicly available RNA-seq data is currently provided mostly in raw form, a significant barrier for global and integrative retrospective analyses. ARCHS4 is a web resource that makes the majority of published RNA-seq data from human and mouse available at the gene and transcript levels. For developing ARCHS4, available FASTQ files from RNA-seq experiments from the Gene Expression Omnibus (GEO) were aligned using a cloud-based infrastructure. In total 187,946 samples are accessible through ARCHS4 with 103,083 mouse and 84,863 human. Additionally, the ARCHS4 web interface provides intuitive exploration of the processed data through querying tools, interactive visualization, and gene pages that provide average expression across cell lines and tissues, top co-expressed genes for each gene, and predicted biological functions and protein–protein interactions for each gene based on prior knowledge combined with co-expression.
Synthesis of 9-alkylidene-9H-fluorenes by a novel, palladium-catalyzed cascade reaction of aryl halides and 1-aryl-1-alkynes.

In the presence of a palladium catalyst and NaOAc, aryl iodides react with 1-aryl-1-alkynes to afford 9-alkylidene-9H-fluorenes in good yields. The products from this reaction are highly dependent on the base employed. This process appears to involve (1) oxidative addition of the aryl iodide to Pd(0), (2) alkyne insertion, (3) rearrangement of the resulting vinylic palladium intermediate to an arylpalladium species, and (4) aryl−aryl coupling with simultaneous regeneration of the Pd(0) catalyst. Consistent with this mechanism is the fact that 9-alkylidene-9H-fluorenes can also be prepared by the Pd-catalyzed rearrangement of 1,1-diaryl-2-iodo-1-alkenes.
MECP2 regulates cortical plasticity underlying a learned behaviour in adult female mice

Neurodevelopmental disorders are marked by inappropriate synaptic connectivity early in life, but how disruption of experience-dependent plasticity contributes to cognitive and behavioural decline in adulthood is unclear. Here we show that pup gathering behaviour and associated auditory cortical plasticity are impaired in female Mecp2het mice, a model of Rett syndrome. In response to learned maternal experience, Mecp2het females exhibited transient changes to cortical inhibitory networks typically associated with limited plasticity. Averting these changes in Mecp2het through genetic or pharmacological manipulations targeting the GABAergic network restored gathering behaviour. We propose that pup gathering learning triggers a transient epoch of inhibitory plasticity in auditory cortex that is dysregulated in Mecp2het. In this window of heightened sensitivity to sensory and social cues, Mecp2 mutations suppress adult plasticity independently from their effects on early development.
DNA methylation signature of smoking in lung cancer is enriched for exposure signatures in newborn and adult blood

Smoking impacts DNA methylation genome-wide in blood of newborns from maternal smoking during pregnancy and adults from personal smoking. We compared smoking-related DNA methylation in lung adenocarcinoma (61 never smokers, 91 current smokers, and 238 former smokers) quantified with the Illumina450k BeadArray in The Cancer Genome Atlas with published large consortium meta-analyses of newborn and adult blood. We assessed whether CpG sites related to smoking in blood from newborns and adults were enriched in the lung adenocarcinoma methylation signal. Testing CpGs differentially methylated by smoke exposure, we identified 296 in lung adenocarcinoma meeting a P < 10−4 cutoff, while previous meta-analyses identified 3,042 in newborn blood, and 8,898 in adult blood meeting the same P < 10−4 cutoff. Lung signals were highly enriched for those seen in newborn (24 overlapping CpGs, Penrichment = 1.2 × 10−18) and adult blood (66 overlapping CpGs, Penrichment = 1.2 × 10−48). The 105 genes annotated to CpGs differentially methylated in lung tumors, but not blood, were enriched for RNA processing ontologies. Some epigenetic alterations associated with cigarette smoke exposure are tissue specific, but others are common across tissues. These findings support the value of blood-based methylation biomarkers for assessing exposure effects in target tissues.