cssi/SciSciGPT-SciSciNet huggingface dataset:
Seeing Things from a Different Angle: Discovering Diverse Perspectives about Claims.

One key consequence of the information revolution is a significant increase and a contamination of our information supply. The practice of fact checking won’t suffice to eliminate the biases in text data we observe, as the degree of factuality alone does not determine whether biases exist in the spectrum of opinions visible to us. To better understand controversial issues, one needs to view them from a diverse yet comprehensive set of perspectives. For example, there are many ways to respond to a claim such as “animals should have lawful rights”, and these responses form a spectrum of perspectives, each with a stance relative to this claim and, ideally, with evidence supporting it. Inherently, this is a natural language understanding task, and we propose to address it as such. Specifically, we propose the task of substantiated perspective discovery where, given a claim, a system is expected to discover a diverse set of well-corroborated perspectives that take a stance with respect to the claim. Each perspective should be substantiated by evidence paragraphs which summarize pertinent results and facts. We construct PERSPECTRUM, a dataset of claims, perspectives and evidence, making use of online debate websites to create the initial data collection, and augmenting it using search engines in order to expand and diversify our dataset. We use crowd-sourcing to filter out noise and ensure high-quality data. Our dataset contains 1k claims, accompanied with pools of 10k and 8k perspective sentences and evidence paragraphs, respectively. We provide a thorough analysis of the dataset to highlight key underlying language understanding challenges, and show that human baselines across multiple subtasks far outperform ma-chine baselines built upon state-of-the-art NLP techniques. This poses a challenge and opportunity for the NLP community to address.
Synthesis of 3-iodobenzo[b]thiophenes via iodocyclization/etherification reaction sequence

Abstract An efficient method was developed for the synthesis of benzo[ b ]thiophene core structure using a two-step, multicomponent reaction resulting in favorable yields. This convergent reaction requires room temperature thus eliminating the harsh reaction conditions usually associated with the synthesis of benzo[ b ]thiophene ring structures. Used in many drugs that treat conditions such as osteoporosis, asthma, and fungal infections, the benzo[ b ]thiophene core structure is of extreme importance to medicinal and pharmaceutical research. The key step in this process involves the use of an iodine as a cyclizing agent that acts simultaneously as a catalyst. Alcohols such as alkyl, allyl, propargyl, and benzylic are employed to prepare a diverse library of 3-iodobenzo[ b ]thiophenes.
Kinetic Investigations Provide Additional Evidence That an Enzyme-like Binding Pocket Is Crucial for High Enantioselectivity in the Bis-Cinchona Alkaloid Catalyzed Asymmetric Dihydroxylation of Olefins

The Sharpless enantioselective dihydroxylation of terminal olefins by OsO4 using the catalytic chiral ligand (DHQD)2PYDZ (1) has been shown to follow Michaelis−Menten kinetics, demonstrating fast reversible formation of a complex of olefin, OsO4, and 1 prior to the rate-limiting conversion to the Os(VI) ester intermediate. There is a good correlation between the observed binding constants, Km, and the degree of enantioselectivity of the dihydroxylation indicating that van der Waals binding of the substrate by 1·OsO4 is important to enantioselective rate enhancement. Inhibition of the oxidation by various compounds has been demonstrated kinetically using Dixon analysis of the data, and Ki values have been determined and correlated with inhibitor structure. The strongest inhibitors are compounds with the ability to coordinate to Os(VIII) of the 1·OsO4 complex while simultaneously binding in the pocket formed by the aromatic subunits of the ligand. Parallelism between Km and Ki values and their relationship ...
New Drosophila Long-Term Memory Genes Revealed by Assessing Computational Function Prediction Methods

A major bottleneck to our understanding of the genetic and molecular foundation of life lies in the ability to assign function to a gene and, subsequently, a protein. Traditional molecular and genetic experiments can provide the most reliable forms of identification, but are generally low-throughput, making such discovery and assignment a daunting task. The bottleneck has led to an increasing role for computational approaches. The Critical Assessment of Functional Annotation (CAFA) effort seeks to measure the performance of computational methods. In CAFA3, we performed selected screens, including an effort focused on long-term memory. We used homology and previous CAFA predictions to identify 29 key Drosophila genes, which we tested via a long-term memory screen. We identify 11 novel genes that are involved in long-term memory formation and show a high level of connectivity with previously identified learning and memory genes. Our study provides first higher-order behavioral assay and organism screen used for CAFA assessments and revealed previously uncharacterized roles of multiple genes as possible regulators of neuronal plasticity at the boundary of information acquisition and memory formation.
Synthesis of Carbocycles via Intramolecular Conjugate Additions: Total Syntheses of Axane Sesquiterpenoids.

Syntheses of (±)-axamide-1 (2) and (±)-axisonitrile-1 (1) are described. The syntheses require 12 steps and 13 steps, respectively, from vinylogous ester 8 and feature the diastereoselective cyclization of unsaturated ester 7 to perhydroindan 5. Some interesting reactions of the organometallic derived from [(trimethylsilyl)methyl]magnesium chloride and cerium trichloride are also described.
Igneous Assimilation and Associated Contact Metamorphism in the Virginia Mining District, New Mexico

The rocks of the Virginia Mining District consist chiefly of basalt of Comanche (?) age intruded by late Cretaceous or early Tertiary porphyritic granodiorite. The granodiorite generally has a dark border, ranging from a fraction of an inch to 20 feet in thickness, that contains a variable amount of augite and much more magnetite than the rock of the main mass. In addition, the plagioclase in the border rock is about 10 per cent more anorthitic than that in the main mass. The differences are interpreted as being the results of partial assimilation of intruded basalt in accordance with Bowen's reaction-principle.
Capturing single-cell heterogeneity via data fusion improves image-based profiling

Single-cell resolution technologies warrant computational methods that capture cell heterogeneity while allowing efficient comparisons of populations. Here, we summarize cell populations by adding features’ dispersion and covariances to population averages, in the context of image-based profiling. We find that data fusion is critical for these metrics to improve results over the prior alternatives, providing at least ~20% better performance in predicting a compound’s mechanism of action (MoA) and a gene’s pathway. A challenge with single-cell resolution methods is that cell heterogeneity should be captured while allowing for comparisons between populations. Here the authors fuse information from the dispersion profiles with the average profiles at the level of profiles’ similarity matrices for single cell imaging data.
Sonochemical Synthesis of C60H2

C60H2 has been synthesized by ultrasonically irradiating solutions of C60 in decahydronaphthalene. This synthesis can be understood as a secondary reaction arising from the production of atomic hyd...
Total synthesis of (+/-)-symbioimine.

The synthesis of (±)-symbioimine (1) has been completed in only 12 linear steps in 8% overall yield. The key step is the treatment of 13b with BF3·Et2O to generate N-carboalkoxydihydropyridinium cation 14b, which undergoes a novel stereospecific intramolecular Diels−Alder reaction to give adduct 16b in 42% yield. Cleavage of the N-Troc group of 16b afforded imine 24b stereospecifically. Cleavage of the TBDMS ethers and sulfation provided (±)-symbioimine (1).
Porphyrins with exocyclic rings. Part 19: Efficient syntheses of phenanthrolinoporphyrins

Abstract 5-Nitro-1,10-phenanthrolines react with isocyanoacetate esters in the presence of DBU in THF to give excellent yields of the corresponding phenanthrolinopyrroles. These were condensed with acetoxymethylpyrroles using catalytic quantities of p-toluenesulfonic acid in acetic acid to give dipyrrylmethanes, but these structures proved to be poorly suited for porphyrin synthesis due to the electron-withdrawing nature of the fused phenanthroline unit. However, phenanthrolinopyrrole ethyl esters could be converted to the corresponding α-unsubstituted pyrroles with KOH in ethylene glycol at 180–190 °C, and these condensed with 2 equiv of acetoxymethylpyrroles in refluxing acetic acid-isopropyl alcohol to give tripyrranes. In a one pot procedure, tripyrrane di-tert-butyl esters were treated with TFA at room temperature to cleave the protective groups, diluted with dichloromethane, reacted with pyrrole dialdehydes and oxidized to afford phenanthrolinoporphyrins in 52–83% yield. These conditions also allow the synthesis of porphyrins with additional fused acenaphthylene or phenanthrene rings. Although the UV–vis spectra for these porphyrins are unexceptional, the presence of an external coordination site allows many potential applications to be considered. Porphyrins with two phenanthroline units could not be prepared by the ‘3+1’ strategy. Instead, α-unsubstituted phenanthrolinopyrroles were reacted with a bis(dimethylaminomethyl)pyrrole in refluxing acetic acid to give moderate yields of the corresponding opp-diphenanthrolinoporphyrins. In one case, a triphenanthrolinoporphyrin and trace amounts of an adj-diphenanthrolinoporphyrin were formed as by-products.
Exploring the genetics of lesion and nodal resistance in pea (Pisum sativum L.) to Sclerotinia sclerotiorum using genome-wide association studies and RNA-Seq

The disease white mold caused by the fungus Sclerotinia sclerotiorum is a significant threat to pea production, and improved resistance to this disease is needed. Nodal resistance in plants is a phenomenon where a fungal infection is prevented from passing through a node, and the infection is limited to an internode region. Nodal resistance has been observed in some pathosystems such as the pea (Pisum sativum L.)-S. sclerotiorum pathosystem. In addition to nodal resistance, different pea lines display different levels of stem lesion size restriction, referred to as lesion resistance. It is unclear whether the genetics of lesion resistance and nodal resistance are identical or different. This study applied genome-wide association studies (GWAS) and RNA-Seq to understand the genetic makeup of these two types of resistance. The time series RNA-Seq experiment consisted of two pea lines (the susceptible 'Lifter' and the partially resistant PI 240515), two treatments (mock inoculated samples and S. sclerotiorum-inoculated samples), and three time points (12, 24, and 48 hr post inoculation). Integrated results from GWAS and RNA-Seq analyses identified different redox-related transcripts for lesion and nodal resistances. A transcript encoding a glutathione S-transferase was the only shared resistance variant for both phenotypes. There were more leucine rich-repeat containing transcripts found for lesion resistance, while different candidate resistance transcripts such as a VQ motif-containing protein and a myo-inositol oxygenase were found for nodal resistance. This study demonstrated the robustness of combining GWAS and RNA-Seq for identifying white mold resistance in pea, and results suggest different genetics underlying lesion and nodal resistance.
Systematic analysis of the Myxococcus xanthus developmental gene regulatory network supports posttranslational regulation of FruA by C-signaling.

Upon starvation Myxococcus xanthus undergoes multicellular development. Rod-shaped cells move into mounds in which some cells differentiate into spores. Cells begin committing to sporulation at 24-30 h poststarvation, but the mechanisms governing commitment are unknown. FruA and MrpC are transcription factors that are necessary for commitment. They bind cooperatively to promoter regions and activate developmental gene transcription, including that of the dev operon. Leading up to and during the commitment period, dev mRNA increased in wild type, but not in a mutant defective in C-signaling, a short-range signaling interaction between cells that is also necessary for commitment. The C-signaling mutant exhibited ~20-fold less dev mRNA than wild type at 30 h poststarvation, despite a similar level of MrpC and only 2-fold less FruA. Boosting the FruA level twofold in the C-signaling mutant had little effect on the dev mRNA level, and dev mRNA was not less stable in the C-signaling mutant. Neither did high cooperativity of MrpC and FruA binding upstream of the dev promoter explain the data. Rather, our systematic experimental and computational analyses support a model in which C-signaling activates FruA at least ninefold posttranslationally in order to commit a cell to spore formation.
Convenient synthesis of heteroaryl-linked benzimidazoles via microwave-assisted boronate ester formation

Abstract N-Substituted 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-benzimidazoles were conveniently accessed via microwave-assisted synthesis. Subsequent Suzuki–Miyaura cross-coupling with heteroaryl halides proceeded to give a wide variety of heteroaryl-substituted benzimidazoles.
Applications of phthalimide photochemistry to macrocyclic polyether, polythioether, and polyamide synthesis.

Irradiation of phthalimides which contain N-linked ω-trimethylsilylmethyl-substituted polyether, polythioether, and polysulfonamide chains results in efficient production of the corresponding macrocyclic polyether, polythioether, and polysulfonamide products. These photocyclization reactions follow sequential single electron transfer (SET)−desilylation pathways. Only in the cases of phthalimides, bearing mixed ether-thioether N-substituents, do these excited-state cyclization reactions proceed with lower degrees of regioselectivity. This is a result of competitive desilylation and α-to-sulfur deprotonation reactions of the zwitterionic diradical intermediates formed by initial SET.
Enantioselective and Diastereoselective Additions of Allylic Stannanes to Aldehydes Promoted by a Chiral (Acyloxy)borane Catalyst

A modified Yamamoto Lewis acid (CAB), prepared from the 2,6-dimethoxybenzoic ester of (R,R)-tartaric acid, and 1.5 equiv of BH3·THF was employed in additions of crotyltributyltin (6) and allyltribu...
Longitudinal study of leukocyte DNA methylation and biomarkers for cancer risk in older adults

Changes in DNA methylation over the course of life may provide an indicator of risk for cancer. We explored longitudinal changes in CpG methylation from blood leukocytes, and likelihood of future cancer diagnosis. Peripheral blood samples were obtained at baseline and at follow-up visit from 20 participants in the Health, Aging and Body Composition prospective cohort study. Genome-wide CpG methylation was assayed using the Illumina Infinium Human MethylationEPIC (HM850K) microarray. Global patterns in DNA methylation from CpG-based analyses showed extensive changes in cell composition over time in participants who developed cancer. By visit year 6, the proportion of CD8+ T-cells decreased (p-value = 0.02), while granulocytes cell levels increased (p-value = 0.04) among participants diagnosed with cancer compared to those who remained cancer-free (cancer-free vs. cancer-present: 0.03 ± 0.02 vs. 0.003 ± 0.005 for CD8+ T-cells; 0.52 ± 0.14 vs. 0.66 ± 0.09 for granulocytes). Epigenome-wide analysis identified three CpGs with suggestive p-values ≤10− 5 for differential methylation between cancer-free and cancer-present groups, including a CpG located in MTA3, a gene linked with metastasis. At a lenient statistical threshold (p-value ≤3 × 10− 5), the top 10 cancer-associated CpGs included a site near RPTOR that is involved in the mTOR pathway, and the candidate tumor suppressor genes REC8, KCNQ1, and ZSWIM5. However, only the CpG in RPTOR (cg08129331) was replicated in an independent data set. Analysis of within-individual change from baseline to Year 6 found significant correlations between the rates of change in methylation in RPTOR, REC8 and ZSWIM5, and time to cancer diagnosis. The results show that changes in cellular composition explains much of the cross-sectional and longitudinal variation in CpG methylation. Additionally, differential methylation and longitudinal dynamics at specific CpGs could provide powerful indicators of cancer development and/or progression. In particular, we highlight CpG methylation in the RPTOR gene as a potential biomarker of cancer that awaits further validation.
Synthesis of water-soluble near-infrared cyanine dyes functionalized with [(succinimido)oxy]carbonyl group

Two hetamethine cyanine dyes suitable for labeling of biomolecules at a primary amino group with a near-infrared chromophore/fluorophore (λmax/(λem = 800/830 nm and 837/864 nm) have been synthesized from readily available starting materials. Despite the high molecular complexity of intermediate and final products, all these compounds have been obtained in an analytically pure form by using crystallization only.
Wealth-destroying states

According to the contract theory of the state, individuals give up their freedom to a specialist in violence who then provides public goods, such as private property rights and collective defense. The predatory perspective views the state as expropriating what it can unless individuals develop institutions of collective action to limit the scope of the state. We extend these economic theories of the state by showing how the behavior of rulers depends on political stability, political constraints, self-governance, and foreign intervention. We use evidence from Afghanistan to illustrate how political instability and the absence of meaningful political constraints enables the predatory state. Foreign aid and foreign military intervention amplify the wealth-destroying features of political institutions. Customary self-governance provides public goods locally but is only a partial defense against predatory rulers and can be overwhelmed by predatory self-governing organizations, especially warlords and the Taliban.
Five-Membered Ring Systems: With More than One N Atom

Abstract The synthesis and chemistry of pyrazoles, imidazoles, 1,2,3-triazoles, 1,2,4-triazoles, and tetrazoles were actively pursued in 2013. No attempt was made to incorporate all the exciting chemistry and biological applications that were published in 2013.
gwasurvivr: an R package for genome-wide survival analysis.

Summary To address the limited software options for performing survival analyses with millions of SNPs, we developed gwasurvivr, an R/Bioconductor package with a simple interface for conducting genome-wide survival analyses using VCF (outputted from Michigan or Sanger imputation servers), IMPUTE2 or PLINK files. To decrease the number of iterations needed for convergence when optimizing the parameter estimates in the Cox model, we modified the R package survival; covariates in the model are first fit without the SNP, and those parameter estimates are used as initial points. We benchmarked gwasurvivr with other software capable of conducting genome-wide survival analysis (genipe, SurvivalGWAS_SV and GWASTools). gwasurvivr is significantly faster and shows better scalability as sample size, number of SNPs and number of covariates increases. Availability and implementation gwasurvivr, including source code, documentation and vignette are available at: http://bioconductor.org/packages/gwasurvivr. Supplementary information Supplementary data are available at Bioinformatics online.
Theoretical principles of multiscale spatiotemporal control of neuronal networks: a complex systems perspective

Success in the fine control of the nervous system depends on a deeper understanding of how neural circuits control behavior. There is, however, a wide gap between the components of neural circuits and behavior. We advance the idea that a suitable approach for narrowing this gap has to be based on a multiscale information-theoretic description of the system. We evaluate the possibility that brain-wide complex neural computations can be dissected into a hierarchy of computational motifs that rely on smaller circuit modules interacting at multiple scales. In doing so, we draw attention to the importance of formalizing the goals of stimulation in terms of neural computations so that the possible implementations are matched in scale to the underlying circuit modules.
A convenient method for regioselective C-5 halogenation of 4(3H)-oxo-7H-pyrrolo[2,3-d]pyrimidines

N-7, O-Disilylation of 4(3H)-oxo-7H-pyrrolo[2,3-d]pyrimidines provides a convenient method for activation of these compounds toward regiospecific halogenation at C-5. The sequence is conveniently carried out without isolation of the silylated derivatives and desilylation is spontaneous upon addition of water to the reaction mixture.
Intramolecular Hetero Diels–Alder Routes to γ-Carboline Alkaloids

Abstract Concise and efficient routes to the carboline alkaloids isocanthine (3), isocanthin-6-one (4), 1-methylisocanthine (5), and 1-methylisocanthin-6-one (6) are reported. In each case, the key synthetic step was an intramolecular hetero Diels–Alder reaction of a 1-aza-1,3-diene with an acetylenic dienophile.
ZEOLITE MEDIATED MICHAEL ADDITION OF 1,3-DICARBONYL COMPOUNDS AND THIOLS

Abstract Zeolites, an environmentally attractive solid catalyst, proves to be an efficient catalyst for Michael addition of several 1, 3-dicarbonyl compounds and thiols as donors with methyl vinyl ketone, acrolein and methyl acrylate as acceptors without any solvent are described.
Evaluating Discourse in Structured Text Representations

Discourse structure is integral to understanding a text and is helpful in many NLP tasks. Learning latent representations of discourse is an attractive alternative to acquiring expensive labeled discourse data. Liu and Lapata (2018) propose a structured attention mechanism for text classification that derives a tree over a text, akin to an RST discourse tree. We examine this model in detail, and evaluate on additional discourse-relevant tasks and datasets, in order to assess whether the structured attention improves performance on the end task and whether it captures a text’s discourse structure. We find the learned latent trees have little to no structure and instead focus on lexical cues; even after obtaining more structured trees with proposed model modifications, the trees are still far from capturing discourse structure when compared to discourse dependency trees from an existing discourse parser. Finally, ablation studies show the structured attention provides little benefit, sometimes even hurting performance.
Sequential Reactions Initiated by Oxidative Dearomatization. Biomimicry or Artifact

Robert Robinson first introduced the concept of biomimetic synthesis in 1917 with a one-pot preparation of tropinone [1]. This remarkable transformation joins three reactants together capitalizing upon the reactive proclivities of polyketides. Because aromatic compounds themselves are the end point of polyketide biosynthetic sequences, which are followed by the action of a few specific tailoring decarboxylative and oxidative enzymes, it is hard to conclude that sequences commencing with dearomatization are indeed ‘biomimetic’ [2]. However, sequential reactions initiated by oxidative phenol dearomatization can often appear as ‘biomimetic’, reaching very complex molecular architectures in short order because the functionality and the stereoand regiochemical tendencies that are programmed into the polyketide intermediates are still efficacious in the corresponding phenol derivatives and in the reactions stemming from these compounds. In this chapter, we examine some of the sequential one-pot reactions initiated by oxidative dearomatization. This discussion is by no means a comprehensive treaty on this topic. However, we attempt to untangle this subject for the benefit of interested chemists by focusing on one-pot oxidative dearomatization sequences commencing from phenols that result in the formation or cleavage of three or more C–C, C–O or C–N bonds. In all of the following schemes, the intermediate formed by the initial oxidative dearomatization undergoes further chemical reactions involving the formation and breakage of two or more bonds. Thus, the examples presented are different from most rudimentary oxidative dearomatization reactions that most often result in the usual quinol and ketal adducts [3].
N-heterocyclic carbenes as highly efficient catalysts for the cyclotrimerization of isocyanates.

A series of N-heterocyclic carbenes (NHCs) were evaluated as potential catalysts for the cyclotrimerization of isocyanates to afford isocyanurates. 1,3-Bis-(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr) was found to be a highly efficient catalyst for the cyclotrimerization of a variety of isocyanates.
SYNTHESIS OF 1,4-DIAMINOCYCLITOLS FROM L-SERINE METHYL ESTER

l-Serine methyl ester hydrochloride was converted to (S)-2-[N-(benzyloxycarbonyl)amino]-3-(tert-butyldimethylsiloxy)propanal (6). Homocoupling of 6 promoted by [V2Cl3(THF)6]2[Zn2Cl6] (1) gave C2-symmetric diol (7). After manipulation of protecting groups and Swern oxidation, 7 was converted to a 1,6-dialdehyde 10. Intramolecular pinacol coupling of 10 with 1 gave a selectively protected 1,4-diamino-2,3,5,6-tetrahydroxycyclohexane, which is the key skeleton of Fortimicin AM and AK.
Discovery and Synthesis of [6-Hydroxy-3-[4-[2-(1-piperidinyl)ethoxy]phenoxy]- 2-(4-hydroxyphenyl)]benzo[b]thiophene: A Novel, Highly Potent, Selective Estrogen Receptor Modulator

Raloxifene, [2-(4-hydroxyphenyl)-6-hydroxybenzo[b]thien-3-yl][4-[2-(1-piperidinyl)ethoxy]phenyl]methanone hydrochloride (2), is representative of a class of compounds known as selective estrogen receptor modulators (SERMs) that possess estrogen agonist-like actions on bone tissues and serum lipids while displaying potent estrogen antagonist properties in the breast and uterus. As part of ongoing SAR studies with raloxifene, we found that replacement of the carbonyl group with oxygen ([6-hydroxy-3-[4-[2-(1-piperidinyl)ethoxy]phenoxy]-2-(4-hydroxyphenyl)]benzo[b]thiophene hydrochloride, 4c) resulted in a substantial (10-fold) increase in estrogen antagonist potency relative to raloxifene in an in vitro estrogen dependent cell proliferation assay (IC50 = 0.05 nM) in which human breast cancer cells (MCF-7) were utilized. In vivo, 4c potently inhibited the uterine proliferative response to exogenous estrogen in immature rats following both sc and oral dosing (ED50 of 0.006 and 0.25 mg/kg, respectively). In ova...
An efficient synthesis of cyclic urethanes from Boc-protected amino acids through a metal triflate-catalyzed intramolecular diazocarbonyl insertion reaction

Abstract A simple and efficient synthesis of cyclic urethanes and related oxazinanones 1a – l from diazoketones 3a – l is described. The transformation involves generation of carbenes by activation of diazo groups using metal triflates in intramolecular diazocarbonyl insertion reactions in high overall yields.
Development of a Friedel−Crafts Triflation

The development of a new variant of the Friedel−Crafts reaction that yields 3-aryl enol triflates is described. The reaction is practical, is atom-economical, and works well with electron-rich arene substrates.
Synthesis of (E)- and (Z)-α-Alkylidene-γ-aryl-γ-butyrolactones via Alkenylalumination of Oxiranes

Alkenylalumination of substituted styrene oxides with [α-(ethoxycarbonyl)alkenyl]diisobutylaluminum, in the presence of BF3·Et2O, affords the corresponding (Z)-α-alkylidene-γ-aryl-γ-hydroxy esters in 81−100% Z-selectivity. Chromatographic separation of isomers, followed by lactonization with trifluoroacetic acid, provides isomerically pure (Z)-α-alkylidene-γ-aryl-γ-butyrolactones in 53−78% overall yield. Isomerization of the (Z)-alkylidene hydroxyl esters using LDA, followed by protonation using a bulky proton source, such as BHT, provides a simple route to the corresponding α-(E)-alkylidene-γ-phenyl-γ-hydroxy esters in 72−78% yield, which were cyclized to obtain the corresponding (E)-butyrolactones in 78−85% yield.
Synthesis, Structure, and Properties of a New Family of Mixed-Framework Chalcohalide Semiconductors: CdSbS2X (X = Cl, Br), CdBiS2X (X = Cl, Br), and CdBiSe2X (X = Br, I)

A new family of quaternary mixed-framework chalcohalide semiconductors has been synthesized by conventional solid-state reactions in an intermediate temperature region of 400−430 °C. These include CdSbS2Cl (1), CdSbS2Br (2), CdBiS2Cl (3), CdBiS2Br (4), CdBiSe2Br (5), and CdBiSe2I (6). Single-crystal structure analyses of this compound series reveal two types of crystal structures depending upon the combination of chalcohalide anions, and they crystallize in an orthorhombic Pnma (type I) and monoclinic C2/m (type II) space group. Type I is adopted by two sulfochlorides, 1 and 3, and one selenobromide, 5. Type II is adopted by two sulfobromides, 2 and 4, and one selenoiodide, 6. Both structure types have slabs built of corner and edge shared Cd-centered CdQ6-xXx (Q = S, Se; X = Cl, Br, I; x = 0, 2, 4) octahedra that resemble the (110) plane of a distorted NaCl-type structure. In the type I structure, this slab contains only CdQ4X2 octahedra, while type II shows alternating CdQ6 and CdQ2X4 octahedra. In both...
Convenient Formation of Diphenylmethyl Esters Using Diphenylmethyl Trichloroacetimidate

Diphenylmethyl trichloroacetimidate is a useful reagent for the protection of carboxylic acids as their corresponding diphenylmethyl esters. These esterifications proceed rapidly without the need for an added catalyst or promoter. A variety of carboxylic acid substrates undergo esterification in excellent yields with the trichloroacetimidate reagent, including substrates possessing acid- or base-sensitive functionality. Protection of a carboxylic acid with a highly enolizable α-stereocenter using diphenylmethyl imidate was also accomplished without racemization.
Stereocontrolled Asymmetric Synthesis of α-Hydroxy-β-amino Acids. A Stereodivergent Approach

The stereocontrolled asymmetric synthesis of α-hydroxy-β-amino acids has been investigated via the Lewis acid-promoted cyanation of (5R,6S)-2-acetoxy-4-(benzyloxycarbonyl)-5,6-diphenyl-2,3,5,6-tetrahydro-4H-1,4-oxazines with trimethylsilyl cyanide. Base-catalyzed hydrolysis of the resulting cyano compounds proceeds with excellent stereoselectivity, providing access to diastereomerically pure oxazine-2-carboxylic acids which were readily converted to each enantiomer of the α-hydroxy-β-amino acids isothreonine and nor-C-statine.
Reductive Coupling of Carbonyl Compounds using Silole and Germole Dianions

Reductive coupling of aryl aldehydes and ketones is induced by silole and germole dianions at −78 °C in THF, and 1,2-diols are obtained as the only or major products.
Anodic Cyclization Reactions: Reversing the Polarity of Ketene Dithioacetal Groups

Intramolecular coupling reactions of ketene dithioacetal groups with enol ether and alcohol nucleophiles have been studied. The reactions were initiated by an anodic oxidation of the ketene dithioacetal and proved to be compatible with the formation of five- or six-member rings, as well as the stereoselective generation of quaternary carbons.
Conjugate Additions to Vinyl-Substituted Aromatic N-Heterocycles

Conjugate or Michael addition to vinyl-substituted aromatic N-heterocycles has been a useful synthetic method for the synthesis of functionalized heterocyclic compounds. A wide variety of heterocycles and nucleophiles undergo this chemistry. Recent work in this area has utilized transition-metal catalysts and some asymmetric synthesis has been accomplished. An overview of this chemistry is presented in this account. 1 Introduction 2 General Aspects 3 Carbon-Centered Nucleophiles 4 Nitrogen-Centered Nucleophile 5 Oxygen and Sulfur Nucleophiles 6 Transition-Metal-Catalyzed Reactions 7 Asymmetric Conjugate Addition 8 Summary and Outlook
WebMeV: A Cloud Platform for Analyzing and Visualizing Cancer Genomic Data

Although large, complex genomic datasets are increasingly easy to generate, and the number of publicly available datasets in cancer and other diseases is rapidly growing, the lack of intuitive, easy-to-use analysis tools has remained a barrier to the effective use of such data. WebMeV (http://mev.tm4.org) is an open-source, web-based tool that gives users access to sophisticated tools for analysis of RNA-Seq and other data in an interface designed to democratize data access. WebMeV combines cloud-based technologies with a simple user interface to allow users to access large public datasets, such as that from The Cancer Genome Atlas or to upload their own. The interface allows users to visualize data and to apply advanced data mining analysis methods to explore the data and draw biologically meaningful conclusions. We provide an overview of WebMeV and demonstrate two simple use cases that illustrate the value of putting data analysis in the hands of those looking to explore the underlying biology of the systems being studied. Cancer Res; 77(21); e11-14. ©2017 AACR.
Local economic freedom and creative destruction in America

Economic freedom facilitates the market selection mechanism that enables the Schumpeterian creative destruction process. I develop a framework depicting how economic freedom, which reduces entry barriers and transaction costs, acts as an external enabler that facilitates the creation of firms and jobs. It also facilitates the market correction device, potentially serving as a disabling force to allow firm and job destruction. Using a novel metropolitan statistical area–level dataset, I investigate empirically the role of local economic freedom on dynamism for a sample of nearly 300 U.S. cities over the period 1972–2012. My results confirm that economic freedom is positively associated with firm and job creation, but it has no effect on firm and job destruction.
Regional data exchange to improve care for veterans after non-VA hospitalization: a randomized controlled trial

Coordination of care, especially after a patient experiences an acute care event, is a challenge for many health systems. Event notification is a form of health information exchange (HIE) which has the potential to support care coordination by alerting primary care providers when a patient experiences an acute care event. While promising, there exists little evidence on the impact of event notification in support of reengagement into primary care. The objectives of this study are to 1) examine the effectiveness of event notification on health outcomes for older adults who experience acute care events, and 2) compare approaches to how providers respond to event notifications. In a cluster randomized trial conducted across two medical centers within the U.S. Veterans Health Administration (VHA) system, we plan to enroll older patients (≥ 65 years of age) who utilize both VHA and non-VHA providers. Patients will be enrolled into one of three arms: 1) usual care; 2) event notifications only; or 3) event notifications plus a care transitions intervention. In the event notification arms, following a non-VHA acute care encounter, an HIE-based intervention will send an event notification to VHA providers. Patients in the event notification plus care transitions arm will also receive 30 days of care transition support from a social worker. The primary outcome measure is 90-day readmission rate. Secondary outcomes will be high risk medication discrepancies as well as care transitions processes within the VHA health system. Qualitative assessments of the intervention will inform VHA system-wide implementation. While HIE has been evaluated in other contexts, little evidence exists on HIE-enabled event notification interventions. Furthermore, this trial offers the opportunity to examine the use of event notifications that trigger a care transitions intervention to further support coordination of care. ClinicalTrials.gov NCT02689076. “Regional Data Exchange to Improve Care for Veterans After Non-VA Hospitalization.” Registered 23 February 2016.
CFO Outside Directorship and Financial Misstatements

SYNOPSIS I study an important accounting consequence—financial misstatements—of CFO outside board membership. I find that firms with CFOs holding outside directorships have a lower likelihood of mi...
Prognostic Variables Associated With Improved Outcomes in Patients With Stage III NSCLC Treated With Chemoradiation Followed by Consolidation Pembrolizumab: A Subset Analysis of a Phase II Study From the Hoosier Cancer Research Network LUN 14-179.

Abstract Introduction The Hoosier Cancer Research Network (HCRN) LUN 14-179 is a phase II trial of consolidation pembrolizumab after concurrent chemoradiation for the treatment of patients with stage III non–small-cell lung cancer (NSCLC). Time to metastatic disease or death (TMDD), progression-free survival (PFS), and overall survival (OS) appear to be superior to that in historical controls of chemoradiation alone. Unfortunately, not all patients benefit from consolidation immunotherapy. We performed a univariate analysis to evaluate variables associated with PFS, metastatic disease, and OS. Patients and Methods We conducted a retrospective analysis of patients enrolled in HCRN LUN 14-179. Data collected included age, sex, stage, smoking status, programmed death ligand 1 status, Grade (G) ≥ 2 versus G ≤ 1 adverse event, G ≤ 2 versus G ≥ 3 pneumonitis, duration of pembrolizumab ( Results From April 2015 to December 2016, 93 patients were enrolled and 92 were included in the efficacy analysis (1 patient was ineligible). For TMDD, improved outcomes might be associated (P Conclusion Stage IIIA and longer duration of pembrolizumab treatment might be associated with prolonged TMDD, PFS, and OS for patients with stage III NSCLC treated with chemoradiation followed by pembrolizumab.
Molecular Engineering of an Alkaline Naphthoquinone Flow Battery

Aqueous organic redox flow batteries (AORFBs) have recently gained significant attention as a potential candidate for grid-scale electrical energy storage. Successful implementation of this technol...
Direct Visualization of Live Zebrafish Glycans via Single-Step Metabolic Labeling with Fluorophore-Tagged Nucleotide Sugars.

Dynamic turnover of cell-surface glycans is involved in a myriad of biological events, making this process an attractive target for in vivo molecular imaging. Metabolic glycan labeling coupled with ‘bioorthogonal chemistry’ has paved the way for visualizing glycans in living organisms. However, a two-step labeling sequence is required, which is prone to tissue penetration difficulties for the imaging probes. Here, by exploring the substrate promiscuity of endogenous glycosyltransferases, we developed a single-step fluorescent glycan labeling strategy by directly using fluorophore-tagged analogs of the nucleotide sugars. Injecting the fluorophore-tagged sialic acid and fucose into the yolk of zebrafish embryos at the one-cell stage enables systematic imaging of sialylation and fucosylation in live zebrafish embryos at distinct developmental stages. From these studies, we obtained insights into the role of sialylated and fucosylated glycans in zebrafish hematopoiesis.
GEOMETRIZATION OF ELECTROMAGNETISM IN TETRAD-SPIN-CONNECTION GRAVITY

The metric-affine Lagrangian of Ponomarev and Obukhov for the unified gravitational and electromagnetic fields is linear in the Ricci scalar and quadratic in the tensor of homothetic curvature. We apply to this Lagrangian the variational principle with the tetrad and spin connection as dynamical variables and show that, in this approach, the field equations are the Einstein–Maxwell equations if we relate the electromagnetic potential to the trace of the spin connection. We also show that, as in the Ponomarev–Obukhov formulation, the generally covariant Dirac Lagrangian gives rise to the standard spinor source for the Einstein–Maxwell equations, while the spinor field obeys the nonlinear Heisenberg–Ivanenko equation with the electromagnetic coupling. We generalize that formulation to spinors with arbitrary electric charges.
Distributed Model Predictive Control based on Goal Coordination for Multi-zone Building Temperature Control

In this paper, a distributed Model Predictive Control (DMPC) strategy is developed for a multi-zone building plant with disturbances. The control objective is to maintain each zone's temperature at a specified level with the minimum cost of the underlying HVAC system. The distributed predictive framework is introduced with stability proofs and disturbances prediction, which have not been considered in previous related works. The proposed distributed MPC performed with 48% less computation time, 25.42% less energy consumption, and less tracking error compared with the centralized MPC. The controlled system is implemented in a smart building test bed.
NON-SPLITTINGS OF SPEEDABLE SETS

An r.e. set $A$ is speedable if for every recursive function, there exists a program enumerating membership in $A$ faster, by the desired recursive factor, on infinitely many integers. We construct a speedable set that cannot be split into speedable sets. This solves a question of Bauerle and Remmel.
Using ACL2 to Verify Loop Pipelining in Behavioral Synthesis.

Behavioral synthesis involves compiling an Electronic System-Level (ESL) design into its Register-Transfer Level (RTL) implementation. Loop pipelining is one of the most critical and complex transformations employed in behavioral synthesis. Certifying the loop pipelining algorithm is challenging because there is a huge semantic gap between the input sequential design and the output pipelined implementation making it infeasible to verify their equivalence with automated sequential equivalence checking techniques. We discuss our ongoing effort using ACL2 to certify loop pipelining transformation. The completion of the proof is work in progress. However, some of the insights developed so far may already be of value to the ACL2 community. In particular, we discuss the key invariant we formalized, which is very different from that used in most pipeline proofs. We discuss the needs for this invariant, its formalization in ACL2, and our envisioned proof using the invariant. We also discuss some trade-offs, challenges, and insights developed in course of the project.
Conducting Highly Principled Data Science: A Statistician's Job and Joy

Abstract Highly Principled Data Science insists on methodologies that are: (1) scientifically justified; (2) statistically principled; and (3) computationally efficient. An astrostatistics collaboration, together with some reminiscences, illustrates the increased roles statisticians can and should play to ensure this trio, and to advance the science of data along the way.
On algebraic solitons for geometric evolution equations on three-dimensional Lie groups

The relationship between algebraic soliton metrics and self-similar solutions of geometric evolution equations on Lie groups is investigated. After discussing the general relationship between algebraic soliton metrics and self-similar solutions to geometric evolution equations, we investigate the cross curvature flow and the second order renormalization group flow on simply-connected, three-dimensional, unimodular Lie groups, providing a complete classification of left invariant algebraic solitons that give rise to self-similar solutions of the corresponding flows on such spaces.
Smooth convergence away from singular sets

We consider sequences of metrics, $g_j$, on a Riemannian manifold, $M$, which converge smoothly on compact sets away from a singular set $S\subset M$, to a metric, $g_\infty$, on $M\setminus S$. We prove theorems which describe when $M_j=(M, g_j)$ converge in the Gromov-Hausdorff sense to the metric completion, $(M_\infty,d_\infty)$, of $(M\setminus S, g_\infty)$. To obtain these theorems, we study the intrinsic flat limits of the sequences. A new method, we call hemispherical embedding, is applied to obtain explicit estimates on the Gromov-Hausdorff and Intrinsic Flat distances between Riemannian manifolds with diffeomorphic subdomains. Seven years after the publication of this paper in CAG, Brian Allen discovered a counter example to the published statement of Theorem 1.3. Note that Theorem 4.6 (which is the key theorem cited in other papers) remains correct. We have added an hypothesis to correct the statement of Theorem 1.3 and its consequences. This v4 includes corrections in blue, an erratum at the end of the introduction, and Brian Allen's example in an appendix. An erratum is also being sent to the journal.
Identifying On-time Reward Delivery Projects with Estimating Delivery Duration on Kickstarter

In Crowdfunding platforms, people turn their prototype ideas into real products by raising money from the crowd, or invest in someone else's projects. In reward-based crowdfunding platforms such as Kickstarter and Indiegogo, selecting accurate reward delivery duration becomes crucial for creators, backers, and platform providers to keep the trust between the creators and the backers, and the trust between the platform providers and users. According to Kickstarter, 35% backers did not receive rewards on time. Unfortunately, little is known about on-time and late reward delivery projects, and there is no prior work to estimate reward delivery duration. To fill the gap, in this paper, we (i) extract novel features that reveal latent difficulty levels of project rewards; (ii) build predictive models to identify whether a creator will deliver all rewards in a project on time or not; and (iii) build a regression model to estimate accurate reward delivery duration (i.e., how long it will take to produce and deliver all the rewards). Experimental results show that our models achieve good performance -- 82.5% accuracy, 78.1 RMSE, and 0.108 NRMSE at the first 5% of the longest reward delivery duration.
A Combinatorial Approach to Multiplicity-Free Richardson Subvarieties of the Grassmannian

We consider Buch's rule for K-theory of the Grassmannian, in the Schur multiplicity-free cases classified by Stembridge. Using a result of Knutson, one sees that Buch's coefficients are related to Mobius inversion. We give a direct combinatorial proof of this by considering the product expansion for Grassmannian Grothendieck polynomials. We end with an extension to the multiplicity-free cases of Thomas and Yong.
A Generalized Linear Transport Model for Spatially-Correlated Stochastic Media

We formulate a new model for transport in stochastic media with long-range spatial correlations where exponential attenuation (controlling the propagation part of the transport) becomes power law. Direct transmission over optical distance τ(s), for fixed physical distance s, thus becomes (1 + τ(s)/a)− a, with standard exponential decay recovered when a → ∞. Atmospheric turbulence phenomenology for fluctuating optical properties rationalizes this switch. Foundational equations for this generalized transport model are stated in integral form for d = 1, 2, 3 spatial dimensions. A deterministic numerical solution is developed in d = 1 using Markov Chain formalism, verified with Monte Carlo, and used to investigate internal radiation fields. Standard two-stream theory, where diffusion is exact, is recovered when a = ∞. Differential diffusion equations are not presently known when a < ∞, nor is the integro-differential form of the generalized transport equation. Monte Carlo simulations are performed in d = 2, a...