cssi/SciSciGPT-SciSciNet huggingface dataset:
Text Generation with Exemplar-based Adaptive Decoding

We propose a novel conditioned text generation model. It draws inspiration from traditional template-based text generation techniques, where the source provides the content (i.e., what to say), and the template influences how to say it. Building on the successful encoder-decoder paradigm, it first encodes the content representation from the given input text; to produce the output, it retrieves exemplar text from the training data as “soft templates,” which are then used to construct an exemplar-specific decoder. We evaluate the proposed model on abstractive text summarization and data-to-text generation. Empirical results show that this model achieves strong performance and outperforms comparable baselines.
Part 15++: An Enhanced ID-Based Approach for Etiquette and Enforcement Management in Unlicensed Band

The simple and well-conceived global rules for the unlicensed bands operating in the industrial, scientific, and medical (ISM) band has enabled tremendous product and service innovation. However, the argument can be made that the growing use of unlicensed bands by greater numbers and more heterogenous devices could lead to certain “tragedies of the commons.” The current regulatory approach limits how devices may operate in space-time–frequency along with restriction on transmit power, antenna specification and synchronization. However, if these devices could be better informed about an impending interference through simple alterations to the regulations, then it might be possible to improve both device and overall use of the spectrum. Thus, we propose Part 15++, where unlicensed devices make use of an enhanced identification (ID) mechanism to identify the operator, interferer, victim, and resolution mechanism for a system. With denser and broader use of these bands, we show that creating a common ID method might allow for a more efficient coexistence among heterogeneous technologies. Admittedly, there are numerous benefits and costs to consider with the proposed ID extension, but in this paper, we explore improving throughput followed by a sensitivity analysis on the information provided in the ID structure.
Optimal imprisonment and fines with non-discriminatory sentences

Abstract When considering the optimal combination of monetary sanctions (costless) and imprisonment (costly) as deterrents, the traditional result is that imprisonment should not be imposed until monetary sanctions are completely exhausted. Therefore, imprisonment acts as a mere supplement to maximal fines. We show that, when wealth varies across individuals, it could be efficient to use imprisonment in combination with fines that do not exhaust the wealth of all individuals. The rationale is that, generally, it is impractical to tailor criminal sanctions as a continuous function of individuals’ wealth.
Rookie Mistakes: The Interplay of Teacher Experience and Racial Representation.

A growing body of research has documented the important benefits teachers of color bring to students of color, including higher expectations. Separately, researchers have shown that teachers improv...
Phosphine-Catalyzed Annulation of Thioamides and 2-Alkynoates: A New Synthesis of Thiazolines

The annulation of thioamides with 2-alkynoates and 2,3-dienoates under the catalysis of tri-n-butylphosphine was described. The annulation reaction provided a new entry to thiazolines, particularly those with 2-aryl substituents.
Preparation of functionalized aryl(diallyl)ethoxysilanes and their palladium-catalyzed coupling reactions giving sol–gel precursors

Abstract A series of molecular building blocks containing allylsilyl groups, which can be incorporated into the appropriate sol–gel precursors as fragments, were prepared. The allylsilyl group is retained unchanged over the course of all reactions giving sol–gel precursors and behave as the synthetic equivalent of alkoxysilyl groups toward sol–gel polymerization, but are stable enough to allow purification by silica gel chromatography. These allylsilanes were successfully used as building blocks to construct functional sol–gel precursors via palladium-catalyzed coupling reactions.
Use of EPR spectroscopy to study macromolecular structure and function.

Electron paramagnetic resonance (EPR) spectroscopy is now part of the armory available to probe the structural aspects of proteins, nucleic acids and protein–nucleic acid complexes. Since the mobil...
Synthesis of polymethylene chain-bridged 6-substituted 8-azapurines and related compounds

The synthesis of a series of polymethylene chain-bridged 8-azapurines as potential DNA intercalating agents is described. N,N’-Bis(5-amino-6-chloro-4-pyrimidyl)-1,3-diaminopropane ( III ), N,N”-bis(5-amino-6chloro-4-pyrimidyl)-1,8-diaminooctane ( IV ), and N,N’-bis(5-amino-6-chloro-4-pyrimidyl)-1,12-diaminododecane ( V ) were synthesized from 5-amino-4,6-dichloropyrimidine ( I ) and 1,3-diaminopropane ( II, n = 3), 1,8-diaminooctane ( II, n = 8), and 1,12-diaminododecane ( II, n = 12), respectively, as the starting materials. 1,3-Bis(6-chloro-9-purinyl)propane ( VI ), 1,8-bis(6-chloro-9-purinyl)octane ( VII ), and 1,12-bis(6-chloro-9-purinyl)dodecane ( VIII ) were prepared by acid-catalyzed reaction of the corresponding pyrimidines III-V with triethyl orthoformate in N,N-dimethylacetamide. The polymethylene chain-bridged 6-hydroxy-8-azapurines XII-XIV were obtained via diazotization of the corresponding pyrimidines. The spectral data and other physical properties of the new compounds have been determined.
Stereospecific synthesis of aminocyclitols via cycloadditions of unsymmetrical, optically pure dienes: conduramine A-1 and dihydroconduramine A-1

Abstract Stereospecific synthesis of Conduramine A-1 and Dihydroconduramine A-1 has been achieved by a fully regio- and stereospecific hetero Diels-Alder cycloaddition of a nitrosyl derivative and homochiral 1-halocyclohexadiene diols obtained by microbial oxidation of halobenzenes.
Na2Te3Mo3O16: A New Molybdenum Tellurite with Second-Harmonic Generating and Pyroelectric Properties

The synthesis, structure, and characterization of a new noncentrosymmetric molybdenum tellurite, Na2Te3Mo3O16, are reported. Na2Te3Mo3O16 crystallizes in the noncentrosymmetric monoclinic space group I2 (No. 5, cell choice 3) with a = 7.3373(10) A, b = 11.2668(16) A, c = 8.2369(18) A, and β = 97.387(3)°. The material exhibits a quasi-one-dimensional crystal structure, with each chain consisting of edge-shared MoO6 octahedra that are connected by TeO3 and TeO4 polyhedra. The SHG efficiency of Na2Te3Mo3O16, using 1064 nm radiation, is approximately 500 × α-SiO2 and is phase-matchable (type 1). The strong SHG efficiency is maintained up to the melting temperature. The maximum polarization is 0.189 μC/cm2 at 25 kV/cm, and the pyroelectric coefficient (total effect), p, is −2.6 μC/m2 K.
Yttrocene-catalyzed asymmetric cyclization–hydrosilylation of α,ω-dienes

Abstract (R,S)-BnBpY-H (BnBp={(OC10H6C10H6O)Si(C5H2-2-SiMe3-4-CMe3)2}) is an effective catalyst for the cyclization–hydrosilylation of α,ω-dienes. The cyclization of 1,5-hexadienes and 1,6-heptadienes results in the formation of five- and six-membered rings, respectively, with low to moderate enantioselectivities. Deuterium labeling studies revealed that β-hydride elimination of the cycloalkylmethyl intermediate prior to σ-bond metathesis with the silane did not occur.
Reaction of oxalyl and malonyl chloride with 1,1‐dimethyl‐2‐substituted hydrazides

Recently we reported the reaction of 1,1-dimethyl-4-substituted semicarbazides with phosgene to occur with formation of several new heterocyclic ring systems. Here we report the reaction of several semicarbazides, thiosemicarbazides and related acyl substituted hydrazides with oxalyl chloride and malonyl chloride. These reactions occur with the formation of heterocyclic products which are oxadiazolinones, imidazolidinetriones, 2-thioxoimidazolindine-4,5-diones, and 2-thioxo-1,3-diazine-4,6-diones (2-thioxopyrimidine-4,6-diones).
The Physical Organic Chemistry of Fischer Carbene Complexes

Publisher Summary This chapter deals with the chemistry of the Fischer-type complexes. The key to the rich chemistry of the Fischer carbene complexes is that they can undergo reactions at several sites; they include modification of the carbene fragment, reaction on the side chain or the metal, and insertion of unsaturated organic molecules into the metal–carbon bond. After such elaborations of the carbene complex, removal of the metal to complete the synthesis of the target organic molecule is usually a simple task. The most prominent systems studied so far are the Fischer carbene complexes of the Group 6 metals. The chapter discusses nucleophilic substitution process, for example, the replacement of the MeO group by a group with a different heteroatom, such as an amino or thioalkyl group. This reaction proceeds via a tetrahedral intermediate and is similar to nucleophilic substitutions on carboxylic esters. Another common reaction based on the acidity of the α-carbon proton—that is, the carbon attached to the carbene carbon—has also been discussed in detail. The carbanion that results from the deprotonation of the α-carbon can act as a nucleophile and react with a variety of electrophiles, especially in the presence of Lewis acid catalysis, to form many different products.
Insight on the Sequential Vapor Infiltration Mechanisms of Trimethylaluminum with Poly(methyl methacrylate), Poly(vinylpyrrolidone), and Poly(acrylic acid)

The sequential vapor infiltration (SVI) method, based on atomic layer deposition chemistry, allows the creation of a polymer–inorganic hybrid material through the diffusion of metal–organic vapor reagents into a polymer substrate. This study investigates the reactivity of the ester, amide, and carboxylic acid functional groups of poly(methyl methacrylate) (PMMA), poly(vinylpyrrolidone) (PVP), and poly(acrylic acid) (PAA), respectively, in the presence of trimethylaluminum (TMA) vapor. This work explores the possible reaction mechanisms of these functional groups through in situ Fourier transform infrared spectroscopy and ab initio quantum chemical analysis. At temperatures of ≤100 °C, TMA physisorbs to the carbonyl groups of PMMA. As the temperature is increased, TMA forms a covalent bond with PMMA. TMA physisorbs to PVP and then partially desorbs in the presence of water for all studied temperatures of ≤150 °C. PAA readily reacts with TMA to form a covalent bond with the carbonyl group at 60 °C. This inc...
Efficient synthesis of 4-aminoquinazoline and thieno[3,2-d]pyrimidin-4-ylamine derivatives by microwave irradiation.

A simple, efficient, and high-yielding synthesis of quinazolin-4-ylamine and thieno[3,2-d]pyrimidin-4-ylamine derivatives is reported under microwave irradiation conditions. Reaction conditions including temperature, solvent, and reaction time have been studied. An efficient parallel workup procedure was developed to generate a small library (23 compounds) in a short time period.
Glycerophosphoinositols: Total Synthesis of the First Fluorescent Probe Derivative

The first fluorescent glycerophosphoinositol probe was synthesized in moderate good yield (37%). The total synthesis applied a convergent synthetic strategy involving two successive coupling reactions between the three key moieties: myo-inositol, glycerol, and NBD-aminohexanoic acid.
Inference and visualization of DNA damage patterns using a grade of membership model.

Motivation Quality control plays a major role in the analysis of ancient DNA (aDNA). One key step in this quality control is assessment of DNA damage: aDNA contains unique signatures of DNA damage that distinguish it from modern DNA, and so analyses of damage patterns can help confirm that DNA sequences obtained are from endogenous aDNA rather than from modern contamination. Predominant signatures of DNA damage include a high frequency of cytosine to thymine substitutions (C-to-T) at the ends of fragments, and elevated rates of purines (A & G) before the 5' strand-breaks. Existing QC procedures help assess damage by simply plotting for each sample, the C-to-T mismatch rate along the read and the composition of bases before the 5' strand-breaks. Here we present a more flexible and comprehensive model-based approach to infer and visualize damage patterns in aDNA, implemented in an R package aRchaic. This approach is based on a 'grade of membership' model (also known as 'admixture' or 'topic' model) in which each sample has an estimated grade of membership in each of K damage profiles that are estimated from the data. Results We illustrate aRchaic on data from several aDNA studies and modern individuals from 1000 Genomes Project Consortium (2012). Here, aRchaic clearly distinguishes modern from ancient samples irrespective of DNA extraction, lab and sequencing protocols. Additionally, through an in-silico contamination experiment, we show that the aRchaic grades of membership reflect relative levels of exogenous modern contamination. Together, the outputs of aRchaic provide a concise visual summary of DNA damage patterns, as well as other processes generating mismatches in the data. Availability and implementation aRchaic is available for download from https://www.github.com/kkdey/aRchaic. Supplementary information Supplementary data are available at Bioinformatics online.
Exceptionally Mild, High-Yield Synthesis of α-Fluoro Acrylates

Novel achiral and chiral alkyl α-(1,3-benzothiazol-2-ylsulfonyl)-α-fluoroacetates can be readily synthesized by metalation−fluorination of (1,3-benzothiazol-2-ylsulfonyl)acetates. DBU-mediated condensations of these fluorinated synthons with aldehydes proceed in a facile manner at 0 °C or at room temperature giving high yields of α-fluoro acrylates. Ketones are unreactive under these conditions. The presence of fluorine renders the synthon substantially more reactive compared to the unfluorinated analogue. Reactivity of α-(1,3-benzothiazol-2-ylsulfonyl)-α-fluoroacetate and the Horner−Wadsworth−Emmons reagent (EtO)2P(O)CHFCOOEt has also been compared.
Coextrusion for food ingredients and nutraceutical encapsulation: principles and technology

Abstract: Coextrusion is a physical encapsulation technique used for the formation of core-shell liquid-filled microcapsules. Stationary, centrifugal, vibrating, and submerged coaxial nozzles are used to form compound droplets that harden when the outer liquid shell solidifies through gelling, congealing, or chemically induced solidification. Common coextrusion technologies are capable of producing microcapsules from 150 μm to 8 mm with a liquid payload over 90%. Compatible core materials include aqueous liquids, non-aqueous liquids, slurries, and gases. Production rates range from 1 kg/hr/nozzle to over 15 kg/hr/ nozzle, and scale up is achieved through the use of multiple nozzles.
Global landscape of mouse and human cytokine transcriptional regulation

Cytokines are cell-to-cell signaling proteins that play a central role in immune development, pathogen responses, and diseases. Cytokines are highly regulated at the transcriptional level by combinations of transcription factors (TFs) that recruit cofactors and the transcriptional machinery. Here, we mined through three decades of studies to generate a comprehensive database, CytReg, reporting 843 and 647 interactions between TFs and cytokine genes, in human and mouse respectively. By integrating CytReg with other functional datasets, we determined general principles governing the transcriptional regulation of cytokine genes. In particular, we show a correlation between TF connectivity and immune phenotype and disease, we discuss the balance between tissue-specific and pathogen-activated TFs regulating each cytokine gene, and cooperativity and plasticity in cytokine regulation. We also illustrate the use of our database as a blueprint to predict TF-disease associations and identify potential TF-cytokine regulatory axes in autoimmune diseases. Finally, we discuss research biases in cytokine regulation studies, and use CytReg to predict novel interactions based on co-expression and motif analyses which we further validated experimentally. Overall, this resource provides a framework for the rational design of future cytokine gene regulation studies.
Efficient synthesis of halo indanones via chlorosulfonic acid mediated Friedel–Crafts cyclization of aryl propionic acids and their use in alkylation reactions

Abstract Several halo indanones were synthesized from benzyl Meldrum's acid derivatives in two steps. Although several Lewis acids are effective for the Friedel–Crafts ring-closing reaction on more electron-rich arenes, in the case of the electron-deficient arenes this chemistry is not efficient. Here it is reported that chlorosulfonic acid (used as solvent) is an efficient reagent for cyclization of electron-withdrawing arenes. These molecules are potentially useful for subsequent alkylation reactions. The selective alkylation of 5,7-dibromo indanone is demonstrated using Pd-catalyzed Grignard coupling to provide monoalkylated indanone in good yield.
Concise synthesis of the bacterial DNA primase inhibitor (+) -Sch 642305.

A highly convergent, enantioselective synthesis of (+)-Sch 642305 is presented, which features a Mukaiyama−Michael addition followed by allylation to establish the syn−anti relationship of the three contiguous stereocenters. The 10-membered macrolactone was formed through ring-closing metathesis.
Stereoselective chain extension of (R,R)- or (S,S)-1,2-dicyclohexylethane-1,2-diol trityloxymethylboronate to compounds having three stereogenic centers

Abstract The highly diastereoselective chain extension of (R)- or (S)-(R ∗ ,R ∗ )-1,2- dicyclohexylethane-1,2-diol (‘DICHED’) boronic esters has been applied to enantiomerically pure DICHED [(trityloxy)methyl]boronate to provide possible precursors of kainic acid. A five carbon chain has been assembled having the two critical stereogenic centers in the correct absolute configurations, with the third stereogenic center in a single absolute configuration potentially convertible to the correct amino acid diastereomer. However, peroxidic deboronation of the potential sec-kainic acid precursor took an unexpected course.
Asymmetric C-N Bond Constructions via Crotylsilane Addition Reactions: A Stereocontrolled Route to Dipeptide Isosteres

A new approach to the asymmetric synthesis of (E)-olefin dipeptide isosteres is described based on asymmetric C−N bond constructions resulting from nitronium tetrafluoroborate (NO2BF4) promoted electrophilic nitrations of chiral (E)-crotylsilanes and from a copper(I)-catalyzed enantioselective aziridination of chiral (E)-crotylsilanes. The silane reagents undergo efficient anti-SE‘ additions to the nitrogen-based electrophiles to give the (E)-olefin isosteres in >96% de. The topological bias is principally controlled by the facial bias of the silane reagent. The scope of the methodology was explored via several related crotylsilane derivatives. The (E)-olefin isosteres are nonhydrolyzable, rigid analogs of the peptide linkage in biologically active peptides. The new methodology will facilitate the preparation and study of peptidomimetics since the crotylsilane reagents allow for incorporation of a wide range of functionality on the resulting isosteres.
Structure, Spectra, and Reaction Energies of the Aluminum−Nitrogen (HAl−NH)2 and (H2Al−NH2)2 Rings and the (HAl−NH)4 Cluster

Rings of four-coordinate aluminum and nitrogen are easily synthesized and well studied, as are clusters of four-coordinate Al and N. Only recently, however, have rings that are derivatives of the m...
Ultrafast Reaction between LiH and NH3 during H2 Storage in Li3N

Li3N is a potential H2 storage material due to its high theoretical H2 capacity (10.4 wt %). A critical potential issue regarding this N-based storage material is the generation of NH3, which consumes some H2 and also constitutes a poison for the downstream processes. In this Letter, by using the temperature-programmed decomposition of a two-layer material (LiNH2 and LiH), we demonstrate that NH3 produced via the decomposition of LiNH2 is completely captured by LiH even at very short contact times (25 ms) with the carrier gas. This ultrafast reaction between NH3 and LiH inhibits NH3 formation during the hydrogenation of Li3N and also prevents the NH3 generated during the dehydrogenation of the hydrogenated Li3N to escape into the H2 stream. However, if the hydrogenated Li3N was previously exposed to the atmosphere, some NH3 could escape into the H2 stream during the H2 desorption, due to the partial oxidation of LiH by the water present in air.
Alterations in Cell Motility, Proliferation, and Metabolism in Novel Models of Acquired Temozolomide Resistant Glioblastoma.

Glioblastoma (GBM) is an aggressive and incurable tumor of the brain with limited treatment options. Current first-line standard of care is the DNA alkylating agent temozolomide (TMZ), but this treatment strategy adds only ~4 months to median survival due to the rapid development of resistance. While some mechanisms of TMZ resistance have been identified, they are not fully understood. There are few effective strategies to manage therapy resistant GBM, and we lack diverse preclinical models of acquired TMZ resistance in which to test therapeutic strategies on TMZ resistant GBM. In this study, we create and characterize two new GBM cell lines resistant to TMZ in vitro, based on the 8MGBA and 42MGBA cell lines. Analysis of the TMZ resistant (TMZres) variants in conjunction with their parental, sensitive cell lines shows that acquisition of TMZ resistance is accompanied by broad phenotypic changes, including increased proliferation, migration, chromosomal aberrations, and secretion of cytosolic lipids. Importantly, each TMZ resistant model captures a different facet of the “go” (8MGBA-TMZres) or “grow” (42MGBA-TMZres) hypothesis of GBM behavior. These in vitro model systems will be important additions to the available tools for investigators seeking to define molecular mechanisms of acquired TMZ resistance.
Individual differences in functional brain connectivity predict temporal discounting preference in the transition to adolescence.

Abstract The transition from childhood to adolescence is marked by distinct changes in behavior, including how one values waiting for a large reward compared to receiving an immediate, yet smaller, reward. While previous research has emphasized the relationship between this preference and age, it is also proposed that this behavior is related to circuitry between valuation and cognitive control systems. In this study, we examined how age and intrinsic functional connectivity strength within and between these neural systems relate to changes in discounting behavior across the transition into adolescence. We used mixed-effects modeling and linear regression to assess the contributions of age and connectivity strength in predicting discounting behavior. First, we identified relevant connections in a longitudinal sample of 64 individuals who completed MRI scans and behavioral assessments 2–3 times across ages 7–15 years (137 scans). We then repeated the analysis in a separate, cross-sectional, sample of 84 individuals (7–13 years). Both samples showed an age-related increase in preference for waiting for larger rewards. Connectivity strength within and between valuation and cognitive control systems accounted for further variance not explained by age. These results suggest that individual differences in functional brain organization can account for behavioral changes typically associated with age.
A novel mathematical method for disclosing oscillations in gene transcription: A comparative study

Circadian rhythmicity, the 24-hour cycle responsive to light and dark, is determined by periodic oscillations in gene transcription. This phenomenon has broad ramifications in physiologic function. Recent work has disclosed more cycles in gene transcription, and to the uncovering of these we apply a novel signal processing methodology known as the pencil method and compare it to conventional parametric, nonparametric, and statistical methods. Methods: In order to assess periodicity of gene expression over time, we analyzed a database derived from livers of mice entrained to a 12-hour light/12-hour dark cycle. We also analyzed artificially generated signals to identify differences between the pencil decomposition and other alternative methods. Results: The pencil decomposition revealed hitherto-unsuspected oscillations in gene transcription with 12-hour periodicity. The pencil method was robust in detecting the 24-hour circadian cycle that was known to exist, as well as confirming the existence of shorter-period oscillations. A key consequence of this approach is that orthogonality of the different oscillatory components can be demonstrated. thus indicating a biological independence of these oscillations, that has been subsequently confirmed empirically by knocking out the gene responsible for the 24-hour clock. Conclusion: System identification techniques can be applied to biological systems and can uncover important characteristics that may elude visual inspection of the data. Significance: The pencil method provides new insights on the essence of gene expression and discloses a wide variety of oscillations in addition to the well-studied circadian pattern. This insight opens the door to the study of novel mechanisms by which oscillatory gene expression signals exert their regulatory effect on cells to influence human diseases.
Asymmetric alkylation of 5-alkyl-2-aminothiazolones using a C2-symmetric chiral tetraamine base

Abstract The diastereoselective alkylation of a series of 5-alkyl-2-aminothiazolones utilizing a C 2 -symmetric chiral tetraamine base is reported.
Dehydrogenative Bond-Forming Catalysis Involving Phosphines

This review presents developments in the young field of dehydrogenative coupling reactions of phosphines. Catalytic phosphorus-element bond formation via dehydrocoupling has rapidly expanded since the first discoveries in the mid 1990s. A survey of the available catalysts, P-P and P-E products, and mechanistic understanding is presented with emphasis on the emerging synthetic applications of this reaction.
Integral chains and Bousfield-Kan completion

Working in the Arone-Ching framework for homotopical descent, it follows that the Bousfield-Kan completion map with respect to integral homology is the unit of a derived adjunction. We prove that this derived adjunction, comparing spaces with coalgebra complexes over the associated integral homology comonad, via integral chains, can be turned into a derived equivalence by replacing spaces with the full subcategory of simply connected spaces. In particular, this provides an integral chains characterization of the homotopy type of simply connected spaces.
Concise approach to novel isothiazolidinone phosphotyrosine mimetics: microwave-assisted addition of bisulfite to activated olefins.

A novel and efficient synthesis of isothiazolidinone protein tyrosine phosphatase mimetics is presented. A practical, regiospecific microwave-assisted addition of bisulfite to activated olefins, including unprecedented reactions with styrene derivatives, is highlighted.
The Gut Microbiota Is Associated with Clearance of Clostridium difficile Infection Independent of Adaptive Immunity.

ABSTRACT Clostridium (Clostridioides) difficile, a Gram-positive, anaerobic bacterium, is the leading single cause of nosocomial infections in the United States. A major risk factor for Clostridium difficile infection (CDI) is prior exposure to antibiotics, as they increase susceptibility to CDI by altering the membership of the microbial community enabling colonization. The importance of the gut microbiota in providing protection from CDI is underscored by the reported 80 to 90% success rate of fecal microbial transplants in treating recurrent infections. Adaptive immunity, specifically humoral immunity, is also sufficient to protect from both acute and recurrent CDI. However, the role of the adaptive immune system in mediating clearance of C. difficile has yet to be resolved. Using murine models of CDI, we found that adaptive immunity is dispensable for clearance of C. difficile. However, random forest analysis using only two members of the resident bacterial community correctly identified animals that would go on to clear the infection with 66.7% accuracy. These findings indicate that the indigenous gut microbiota independent of adaptive immunity facilitates clearance of C. difficile from the murine gastrointestinal tract. IMPORTANCEClostridium difficile infection is a major cause of morbidity and mortality in hospitalized patients in the United States. Currently, the role of the adaptive immune response in modulating levels of C. difficile colonization is unresolved. This work suggests that the indigenous gut microbiota is a main factor that promotes clearance of C. difficile from the GI tract. Our results show that clearance of C. difficile can occur without contributions from the adaptive immune response. This study also has implications for the design of preclinical studies testing the efficacy of vaccines on clearance of bacterial pathogens, as inherent differences in the baseline community structure of animals may bias findings.
Expedient acylations of primary and secondary alkyl cyanides to α-substituted β-ketonitriles

Primary and secondary cyanides are efficiently acylated with N-acylbenzotriazoles 3a−f (derived from a variety of acids) to afford the corresponding α-substituted β-ketonitriles 5a−r in 67−96% yields.
Structure and function in organometallic•protein complexes

Abstract Bioorganometallic chemistry is a rapidly growing subfield of organometallic chemistry. One important facet is the study of organometallic•protein complexes that contain a covalent bond between the protein and an organometallic prosthetic group. Structural elucidation of these complexes is being used with increasing frequency to determine exactly where metal binding takes place and to obtain accurate structural information. This review summarizes the structures in this field, highlighting how this information has driven the frontier of this research.
Acid-induced transannular cyclization of 2-methyl- and 10-methyl-5-cyclodecenone

Abstract 2-Methyl- and 10-methyl-5-cyclodecenone were made by anionic oxy-Cope rearrangement of the corresponding 1,2-divinylcyclohexanols, and their transannular cyclizations were induced using trifluoroacetic acid. In each case, a single diastereomer of a trans fused bicyclo[4.4.0]decan-1-ol with an equatorial methyl group was isolated. The methyl substituent at C2 or C10 of the 5-cyclodecenone did not alter the regio- and stereochemistry previously observed for the parent ring system, (E)-5-cyclodecenone. The relative stereochemistry of the products was determined spectroscopically from J-value analysis and NOE.
A Chemistry Cascade: From Physical Organic Studies of Alkoxy Radicals to Alkaloid Synthesis†

In this Perspective, I present a personal account of a succession of chemical projects that I was involved with, each of which triggered or initiated my next research undertaking. It started with my early work in the field of physical organic photochemistry, which, in turn, guided me to my current research dealing with the synthesis of biologically active alkaloids. The article highlights some of the dominant themes of my research program over the past 48 years. Subject matter that is discussed includes the generation of reactive intermediates by photoexcitation, [1,3]-dipolar cycloaddition chemistry, rhodium(II)-catalyzed domino reactions of alpha-diazo carbonyl compounds, intramolecular [4 + 2]-cycloaddition of 2-amidofurans, and the utilization of various thio fragments for the synthesis of nitrogen heterocycles.
Preparation and fungitoxicity of 3,6-dichloro-and 3,6-dibromo-8-quinolinols

3,6-Dichloro- and 3,6-dibromo-8-quinolinols were prepared by direct halogenation of 8-nitroquinoline by N-halosuccinimide in acetic acid or by halogenation of the corresponding 6-halo-8-nitroquinoline prepared via aSkraup reaction. The nitro group was reduced to amino and the amine was hydrolyzed to the phenol in 70% sulfuric acid at 220°C. The fungitoxicity of 3,6-dichloro- and 3,6-dibromo-8-quinolinols, as well as intermediates in their preparation, againstAspergillus niger, Aspergillus oryzae, Myrothecium verrucaria, Trichoderma viride, andMucor cirinelloides was determined. 3,6-dichloro-8-quinolinol is the most fungitoxic analogue of this class of compounds observed to date.
Palladium-catalyzed transfer hydrogenation in alkaline aqueous medium

Abstract Catalytic transfer hydrogenation using palladium(II) chloride, formate and aqueous sodium hydroxide is effective for the reduction of unsaturated carboxylic acids, azalactones, and α-ketocarboxylic acids. This method is convenient, economical, avoids organic solvents, and uses a stable, nonpyrophoric catalyst.
Reinforcement Learning for Interference Avoidance Game in RF-Powered Backscatter Communications

RF-powered backscatter communication is a promising new technology that can be deployed for battery-free applications such as internet of things (IoT) and wireless sensor networks (WSN). However, since this kind of communication is based on the ambient RF signals and battery-free devices, they are vulnerable to interference and jamming. In this paper, we model the interaction between the user and a smart interferer in an ambient backscatter communication network as a game. We design the utility functions of both the user and interferer in which the backscattering time is taken into the account. The convexity of both sub-game optimization problems is proved and the closed-form expression for the equilibrium of the Stackelberg game is obtained. Due to lack of information about the system SNR and transmission strategy of the interferer, the optimal strategy is obtained using the Q-learning algorithm in a dynamic iterative manner. We further introduce hotbooting Q-learning as an effective approach to expedite the convergence of the traditional Q-learning. Simulation results show that our approach can obtain considerable performance improvement in comparison to random and fixed backscattering time transmission strategies and improves the convergence speed of Q-Learning by about 31&#x0025;.
MIND food and speed of processing training in older adults with low education, the MINDSpeed Alzheimer's disease prevention pilot trial

Abstract Background Multiple national organizations and leaders have called for increased attention to dementia prevention in those most vulnerable, for example persons with limited formal education. Prevention recommendations have included calls for multicomponent interventions that have the potential to improve both underlying neurobiological health and the ability to function despite neurobiological pathology, or what has been termed cognitive reserve. Objectives Test feasibility, treatment modifier, mechanism, and cognitive function effects of a multicomponent intervention consisting of foods high in polyphenols (i.e., MIND foods) to target neurobiological health, and speed of processing training to enhance cognitive reserve. We refer to this multicomponent intervention as MINDSpeed. Design MINDSpeed is being evaluated in a 2 × 2 randomized factorial design with 180 participants residing independently in a large Midwestern city. Qualifying participants are 60 years of age or older with no evidence of dementia, and who have completed 12 years or less of education. All participants receive a study-issued iPad to access the custom study application that enables participants, depending on randomization, to select either control or MIND food, and to play online cognitive games, either speed of processing or control games. Methods All participants complete informed consent and baseline assessment, including urine and blood samples. Additionally, up to 90 participants will complete neuroimaging. Assessments are repeated immediately following 12 weeks of active intervention, and at 24 weeks post-randomization. The primary outcome is an executive cognitive composite score. Secondary outcomes include oxidative stress, pro-inflammatory cytokines, and neuroimaging-captured structural and functional metrics of the hippocampus and cortical brain regions. Summary MINDSpeed is the first study to evaluate the multicomponent intervention of high polyphenol intake and speed of processing training. It is also one of the first dementia prevention trials to target older adults with low education. The results of the study will guide future dementia prevention efforts and trials in high risk populations.
Financial storage rights in electric power networks

The decreasing cost of energy storage technologies coupled with their potential to bring significant benefits to electric power networks have kindled research efforts to design both market and regulatory frameworks to facilitate the efficient construction and operation of such technologies. In this paper, we examine an open access approach to the integration of storage, which enables the complete decoupling of a storage facility’s ownership structure from its operation. In particular, we analyze a nodal spot pricing system built on a model of economic dispatch in which storage is centrally dispatched by the independent system operator (ISO) to maximize social welfare. Concomitant with such an approach is the ISO’s collection of a merchandising surplus reflecting congestion in storage. We introduce a class of tradable electricity derivatives—referred to as financial storage rights (FSRs)—to enable the redistribution of such rents in the form of financial property rights to storage capacity; and establish a generalized simultaneous feasibility test to ensure the ISO’s revenue adequacy when allocating such financial property rights to market participants. Several advantages of such an approach to open access storage are discussed. In particular, we illustrate with a stylized example the role of FSRs in synthesizing fully hedged, fixed-price bilateral contracts for energy, when the seller and buyer exhibit differing intertemporal supply and demand characteristics, respectively.
FPGA architecture for deep learning and its application to planetary robotics

Autonomous control systems onboard planetary rovers and spacecraft benefit from having cognitive capabilities like learning so that they can adapt to unexpected situations in-situ. Q-learning is a form of reinforcement learning and it has been efficient in solving certain class of learning problems. However, embedded systems onboard planetary rovers and spacecraft rarely implement learning algorithms due to the constraints faced in the field, like processing power, chip size, convergence rate and costs due to the need for radiation hardening. These challenges present a compelling need for a portable, low-power, area efficient hardware accelerator to make learning algorithms practical onboard space hardware. This paper presents a FPGA implementation of Q-learning with Artificial Neural Networks (ANN). This method matches the massive parallelism inherent in neural network software with the fine-grain parallelism of an FPGA hardware thereby dramatically reducing processing time. Mars Science Laboratory currently uses Xilinx-Space-grade Virtex FPGA devices for image processing, pyrotechnic operation control and obstacle avoidance. We simulate and program our architecture on a Xilinx Virtex 7 FPGA. The architectural implementation for a single neuron Q-learning and a more complex Multilayer Perception (MLP) Q-learning accelerator has been demonstrated. The results show up to a 43-fold speed up by Virtex 7 FPGAs compared to a conventional Intel i5 2.3 GHz CPU. Finally, we simulate the proposed architecture using the Symphony simulator and compiler from Xilinx, and evaluate the performance and power consumption.
Stochastic dual algorithm for voltage regulation in distribution networks with discrete loads

This paper considers power distribution networks with distributed energy resources and designs an incentive-based algorithm that allows the network operator and customers to pursue given operational and economic objectives while concurrently ensuring that voltages are within prescribed limits. Heterogeneous DERs with continuous and discrete control commands are considered. We address four major challenges: discrete decision variables, non-convexity due to a Stackelberg game structure, unavailability of private information from customers, and asynchronous operation. Starting from a non-convex setting, we develop a distributed stochastic dual algorithm that solves a relaxed problem, and prove that the proposed algorithm achieves the global optimal solution of the original problem on average. Feasible values for discrete decision variables are also recovered. Stability of the algorithm is analytically established and numerically corroborated.
Dynamic Transmit Covariance Design in MIMO Fading Systems With Unknown Channel Distributions and Inaccurate Channel State Information

This paper considers dynamic transmit covariance design in point-to-point multiple-input multiple-output fading systems with unknown channel state distributions and inaccurate channel state information subject to both long-term and short-term power constraints. First, the case of instantaneous but possibly inaccurate channel state information at the transmitter (CSIT) is treated. By extending the drift-plus-penalty technique, a dynamic transmit covariance policy is developed and is shown to approach optimality with an $O(\delta)$ gap, where $\delta $ is the inaccuracy measure of CSIT, regardless of the channel state distribution and without requiring knowledge of this distribution. Next, the case of delayed and inaccurate channel state information is considered. The optimal transmit covariance solution that maximizes the ergodic capacity is fundamentally different in this case, and a different online algorithm based on convex projections is developed. The proposed algorithm for this delayed-CSIT case also has an $O(\delta)$ optimality gap, where $\delta $ is again the inaccuracy measure of CSIT.
Virial Theorem in Nonlocal Newtonian Gravity

Nonlocal gravity is the recent classical nonlocal generalization of Einstein’s theory of gravitation in which the past history of the gravitational field is taken into account. In this theory, nonlocality appears to simulate dark matter. The virial theorem for the Newtonian regime of nonlocal gravity theory is derived and its consequences for “isolated” astronomical systems in virial equilibrium at the present epoch are investigated. In particular, for a sufficiently isolated nearby galaxy in virial equilibrium, the galaxy’s baryonic diameter D 0 —namely, the diameter of the smallest sphere that completely surrounds the baryonic system at the present time—is predicted to be larger than the effective dark matter fraction f D M times a universal length that is the basic nonlocality length scale λ 0 ≈ 3 ± 2 kpc.
Mechanism Design for Multi-Type Housing Markets.

We study multi-type housing markets, where there are $p\ge 2$ types of items, each agent is initially endowed one item of each type, and the goal is to design mechanisms without monetary transfer to (re)allocate items to the agents based on their preferences over bundles of items, such that each agent gets one item of each type. In sharp contrast to classical housing markets, previous studies in multi-type housing markets have been hindered by the lack of natural solution concepts, because the strict core might be empty. We break the barrier in the literature by leveraging AI techniques and making natural assumptions on agents' preferences. We show that when agents' preferences are lexicographic, even with different importance orders, the classical top-trading-cycles mechanism can be extended while preserving most of its nice properties. We also investigate computational complexity of checking whether an allocation is in the strict core and checking whether the strict core is empty. Our results convey an encouragingly positive message: it is possible to design good mechanisms for multi-type housing markets under natural assumptions on preferences.
Tutorial on Dynamic Average Consensus: The Problem, Its Applications, and the Algorithms

Technological advances in ad hoc networking and the availability of low-cost reliable computing, data storage, and sensing devices have made scenarios possible where the coordination of many subsystems extends the range of human capabilities. Smart grid operations, smart transportation, smart health care, and sensing networks for environmental monitoring and exploration in hazardous situations are just a few examples of such network operations. In these applications, the ability of a network system to (in a decentralized fashion) fuse information, compute common estimates of unknown quantities, and agree on a common view of the world is critical. These problems can be formulated as agreement problems on linear combinations of dynamically changing reference signals or local parameters. This dynamic agreement problem corresponds to dynamic average consensus, which, as discussed in "Summary," is the problem of interest of this article. The dynamic average consensus problem is for a group of agents to cooperate to track the average of locally available time-varying reference signals, where each agent is capable only of local computations and communicating with local neighbors.
On bodies with directly congruent projections and sections

Let K and L be two convex bodies in R4, such that their projections onto all 3-dimensional subspaces are directly congruent. We prove that if the set of diameters of the bodies satisfies an additional condition and some projections do not have certain π-symmetries, then K and L coincide up to translation and an orthogonal transformation. We also show that an analogous statement holds for sections of star bodies, and prove the n-dimensional versions of these results.
Compact gradient shrinking Ricci solitons with positive curvature operator

In this article, we first derive several identities on a compact shrinking Ricci soliton. We then show that a compact gradient shrinking soliton must be Einstein, if it admits a Riemannian metric with positive curvature operator and satisfies an integral inequality. Furthermore, such a soliton must be of constant curvature.
Measuring, Predicting and Visualizing Short-Term Change in Word Representation and Usage in VKontakte Social Network

Language in social media is extremely dynamic: new words emerge, trend and disappear, while the meaning of existing words can fluctuate over time. Such dynamics are especially notable during a period of crisis. This work addresses several important tasks of measuring, visualizing and predicting short term text representation shift, i.e. the change in a word's contextual semantics, and contrasting such shift with surface level word dynamics, or concept drift, observed in social media streams. Unlike previous approaches on learning word representations from text, we study the relationship between short-term concept drift and representation shift on a large social media corpus - VKontakte posts in Russian collected during the Russia-Ukraine crisis in 2014-2015. Our novel contributions include quantitative and qualitative approaches to (1) measure short-term representation shift and contrast it with surface level concept drift; (2) build predictive models to forecast short-term shifts in meaning from previous meaning as well as from concept drift; and (3) visualize short-term representation shift for example keywords to demonstrate the practical use of our approach to discover and track meaning of newly emerging terms in social media. We show that short-term representation shift can be accurately predicted up to several weeks in advance. Our unique approach to modeling and visualizing word representation shifts in social media can be used to explore and characterize specific aspects of the streaming corpus during crisis events and potentially improve other downstream classification tasks including real-time event detection.