cssi/SciSciGPT-SciSciNet huggingface dataset:
Discovery of Alpha-Gal-Containing Antigens in North American Tick Species Believed to Induce Red Meat Allergy

Development of specific IgE antibodies to the oligosaccharide galactose-α-1, 3-galactose (α-gal) following tick bites has been shown to be the source of red meat allergy. In this study, we investigated the presence of α-gal in four tick species: the lone-star tick (Amblyomma americanum), the Gulf-Coast tick (Amblyomma maculatum), the American dog tick (Dermacentor variabilis), and the black-legged tick (Ixodes scapularis) by using a combination of immunoproteomic approach and, carbohydrate analysis. Anti-α-gal antibodies identified α-gal in the salivary glands of both Am. americanum and Ix. scapularis, while Am. maculatum and De. variabilis appeared to lack the carbohydrate. PNGase F treatment confirmed the deglycosylation of N-linked α-gal-containing proteins in tick salivary glands. Immunolocalization of α-gal moieties to the salivary secretory vesicles of the salivary acini also confirmed the secretory nature of α-gal-containing antigens in ticks. Am. americanum ticks were fed on human blood (lacks α-gal) using a silicone membrane system to determine the source of the α-gal. N-linked glycan analysis revealed that Am. americanum and Ix. scapularis have α-gal in their saliva and salivary glands, but Am. maculatum contains no detectable quantity. Consistent with the glycan analysis, salivary samples from Am. americanum and Ix. scapularis stimulated activation of basophils primed with plasma from α-gal allergic subjects. Together, these data support the idea that bites from certain tick species may specifically create a risk for the development of α-gal-specific IgE and hypersensitivity reactions in humans. Alpha-Gal syndrome challenges the current food allergy paradigm and broadens opportunities for future research.
Dilute surfactants for wettability alteration and enhanced oil recovery in carbonates

Abstract The effectiveness of dilute nonionic surfactant was evaluated in this study for wettability alteration and enhanced oil recovery (EOR) in carbonates by performing a suite of measurements such as aqueous stability, surface tension, phase behavior, interfacial tension (IFT), zeta potential, contact angle, and microscopic dynamic oil liberation. Two different brines, low salinity and high salinity, were used at 0.1 wt% surfactant concentration. These measurements were conducted at elevated temperature using the rock and crude oil samples from a carbonate reservoir. The dilute concentration of polymer has also been used together with surfactant in both high salinity and low salinity brines to quantify the effects of wettability alteration on microscopic oil liberation efficiency in carbonates. The compatibility of nonionic surfactant was demonstrated in high salinity brine at reservoir temperature. The critical micelle concentrations were found to be very low in both low salinity and high salinity brines. The phase behavior results showed the formation of middle phase microemulsion and correspondingly low interfacial tensions in high salinity brine. The contact angle data indicated the ability of nonionic surfactant to significantly alter the wettability of carbonate from oil-wet to either intermediate wet or less oil-wet in high salinity brine whereas only marginal wettability alterations from oil-wet to less oil-wet were obtained in low salinity brine. The increasing negative zeta potentials and the alteration of charge polarity from positive to negative were observed at crude oil-brine and calcite/brine interfaces, respectively due to surfactant in the high salinity brine. The microscopic equilibrium degree of crude oil liberation from carbonate surface was found to be about 20% higher with high salinity surfactant-polymer solution when compared to the low salinity surfactant-polymer solution. Such higher oil release efficiency obtained with high salinity surfactant-polymer solution can be attributed to the beneficial effects of surfactant induced wettability alteration and IFT reduction mechanisms in the high salinity brine to favorably alter both capillary and adhesion forces for efficient EOR in carbonates.
Understanding Dataset Design Choices for Multi-hop Reasoning.

Learning multi-hop reasoning has been a key challenge for reading comprehension models, leading to the design of datasets that explicitly focus on it. Ideally, a model should not be able to perform well on a multi-hop question answering task without doing multi-hop reasoning. In this paper, we investigate two recently proposed datasets, WikiHop and HotpotQA. First, we explore sentence-factored models for these tasks; by design, these models cannot do multi-hop reasoning, but they are still able to solve a large number of examples in both datasets. Furthermore, we find spurious correlations in the unmasked version of WikiHop, which make it easy to achieve high performance considering only the questions and answers. Finally, we investigate one key difference between these datasets, namely span-based vs. multiple-choice formulations of the QA task. Multiple-choice versions of both datasets can be easily gamed, and two models we examine only marginally exceed a baseline in this setting. Overall, while these datasets are useful testbeds, high-performing models may not be learning as much multi-hop reasoning as previously thought.
Integrative Social Contracts Theory

Difficult moral issues in economic life, such as evaluating the impact of hostile takeovers and plant relocations or determining the obligations of business to the environment, constitute the raison d'etre of business ethics. Yet, while the ultimate resolution of such issues clearly requires detailed, normative analysis, a shortcoming of business ethics is that to date it has failed to develop an adequate normative theory.1 The failing is especially acute when it results in an inability to provide a basis for fine-grained analyses of issues. Both general moral theories and stakeholder theory seem incapable of expressing the moral complexity necessary to provide practical normative guidance for many business ethics contexts.
The role of scale-induced round numbers and goal specificity on goal accomplishment perceptions

Goal progress can be measured using different scales (e.g., lbs., kg, oz., inches lost in weight loss domain). Despite considerable research on perceived goal progress, little is known about the effects of measurement scales on the mental representation of goal attainment. We present three studies across various domains (e.g., monetary earnings, loyalty rewards, games) which demonstrate that, when the goal is not specific, the expression of progress as a round number on a certain scale leads to a higher sense of accomplishment compared with expression of identical progress as a non-round number on a different scale. We further show that this effect is moderated by goal and whether the level of actual progress made is high or low. When the goal is specific, scale-induced round numbers lead to higher perceived accomplishment at lower progress levels, whereas, when the goal is not specific, they lead to higher perceived accomplishment at higher progress levels.
A system for real-time interactive analysis of deep learning training

Performing diagnosis or exploratory analysis during the training of deep learning models is challenging but often necessary for making a sequence of decisions guided by the incremental observations. Currently available systems for this purpose are limited to monitoring only the logged data that must be specified before the training process starts. Each time a new information is desired, a cycle of stop-change-restart is required in the training process. These limitations make interactive exploration and diagnosis tasks difficult, imposing long tedious iterations during the model development. We present a new system that enables users to perform interactive queries on live processes generating real-time information that can be rendered in multiple formats on multiple surfaces in the form of several desired visualizations simultaneously. To achieve this, we model various exploratory inspection and diagnostic tasks for deep learning training processes as specifications for streams using a map-reduce paradigm with which many data scientists are already familiar. Our design achieves generality and extensibility by defining composable primitives which is a fundamentally different approach than is used by currently available systems.
Novel synthetic oleanane and ursane triterpenoids with various enone functionalities in ring A as inhibitors of nitric oxide production in mouse macrophages.

We initially randomly synthesized about 60 oleanane and ursane triterpenoids as potential anti-inflammatory and cancer chemopreventive agents. Preliminary screening of these derivatives for inhibition of production of nitric oxide induced by interferon-γ in mouse macrophages revealed that 3-oxooleana-1,12-dien-28-oic acid (B-15) showed significant activity (IC50 = 5.6 μM). On the basis of the structure of B-15, 19 novel olean- and urs-12-ene triterpenoids with a 1-en-3-one functionality having a substituent at C-2 in ring A have been designed and synthesized. Among them, 3-oxooleana-1,12-diene derivatives with carboxyl, methoxycarbonyl, and nitrile groups at C-2 showed higher activity than the lead compound B-15. In particular, 2-carboxy-3-oxooleana-1,12-dien-28-oic acid (3) had the highest activity (IC50 = 0.07 μM) in this group of triterpenoids. The potency of 3 was similar to that of hydrocortisone (IC50 = 0.01 μM), although 3 does not act through the glucocorticoid receptor. Interesting structure−acti...
Master equation models for the pressure- and temperature-dependent reactions HO + NO2 → HONO2 and ho + NO2 → HOONO

Data for the reactions between OH and NO2 have been modeled using a multiwell, multichannel master equation approach. In this work, new ab initio quantum chemical results for cis−cis- and trans−perp-HOONO at the QCISD(T)/cc-pVDZ level are used with the multiple-well, multiple-channel master equation approach in order to model the data between 220 and 430 K in both He and N2. The results are in good agreement with the experimental data over the entire ranges of temperature and pressure. The contribution from HOONO is evaluated for the experimental conditions. It is also evaluated for the conditions described by the U.S. Standard Atmosphere (1976). Although the HONO2 pathway dominates over all atmospheric conditions, up to ∼20% of the reaction is predicted to yield HOONO near the tropopause. If the atmospheric fate of HOONO is different than that of HONO2, this can affect atmospheric chemistry models.
Fuel Cell Thermal Management: Modeling, Specifications, and Correct-by-Construction Control Synthesis

The safe and efficient operation of fuel cells requires thermal management. The goal of this paper is to algorithmically synthesize a provably correct controller for a fuel cell thermal management system. We begin by developing a control-oriented model for the thermal management system of a fuel cell stack. Then, we list the requirements associated with thermal management and formalize them using linear temporal logic. The model and the requirements are then used for controller synthesis with an abstraction-based technique. To make the abstraction-based synthesis algorithm computationally efficient, some structural properties of the fuel cell system dynamics are identified and leveraged. Finally, the closed-loop system behavior with the synthesized controller is demonstrated via simulations.
Selective isomerization of aryl substituted epoxides to aldehydes via iron Lewis acid catalysis

Abstract The iron Lewis acid [(η5-C5H5)Fe(CO)2(THF)]+BF4− (2) catalyzes the ring opening isomerization of aryl substituted epoxides (1) to aldehydes (3) in excellent yield.
Azomethine ylides from tin-substituted cyclic carbinol amides: a new route to highly substituted pyrrolizidines.

Addition of organolithium and organomagnesium reagents to N-(tri-n-butylstannylmethyl)phthalimides yields N-(tri-n-butylstannylmethyl) cyclic carbinol amides, which form azomethine ylides upon treatment with HF·pyridine. This novel route to azomethine ylides allows rapid access to highly functionalized pyrrolizidines (1,2,3,9b-tetrahydropyrrolo[2,1-a]isoindol-5-ones).
Multidirectional digital scanned light-sheet microscopy enables uniform fluorescence excitation and contrast-enhanced imaging

Light-sheet fluorescence microscopy (LSFM) has emerged as a powerful method for rapid and optically efficient 3D microscopy. Initial LSFM designs utilized a static sheet of light, termed selective plane illumination microscopy (SPIM), which exhibited shadowing artifacts and deteriorated contrast due to light scattering. These issues have been addressed, in part, by multidirectional selective plane illumination microscopy (mSPIM), in which rotation of the light sheet is used to mitigate shadowing artifacts, and digital scanned light-sheet microscopy (DSLM), in which confocal line detection is used to reject scattered light. Here we present a simple and passive multidirectional digital scanned light-sheet microscopy (mDSLM) architecture that combines the benefits of mSPIM and DSLM. By utilizing an elliptical Gaussian beam with increased angular diversity in the imaging plane, mDSLM provides mitigation of shadowing artifacts and contrast-enhanced imaging of fluorescently labeled samples.
Macroscopic quantum mechanics: theory and experimental concepts of optomechanics

Rapid experimental progress has recently allowed the use of light to prepare macroscopic mechanical objects into nearly pure quantum states. This research field of quantum optomechanics opens new doors towards testing quantum mechanics, and possibly other laws of physics, in new regimes. In the first part of this article, I will review a set of techniques of quantum measurement theory that are often used to analyse quantum optomechanical systems. Some of these techniques were originally designed to analyse how a classical driving force passes through a quantum system, and can eventually be detected with an optimal signal-to-noise ratio—while others focus more on the quantum-state evolution of a mechanical object under continuous monitoring. In the second part of this article, I will review a set of experimental concepts that will demonstrate quantum mechanical behaviour of macroscopic objects—quantum entanglement, quantum teleportation and the quantum Zeno effect. Taking the interplay between gravity and quantum mechanics as an example, I will review a set of speculations on how quantum mechanics can be modified for macroscopic objects, and how these speculations—and their generalizations—might be tested by optomechanics.
Reinforcement Knowledge Graph Reasoning for Explainable Recommendation

Recent advances in personalized recommendation have sparked great interest in the exploitation of rich structured information provided by knowledge graphs. Unlike most existing approaches that only focus on leveraging knowledge graphs for more accurate recommendation, we aim to conduct explicit reasoning with knowledge for decision making so that the recommendations are generated and supported by an interpretable causal inference procedure. To this end, we propose a method called Policy-Guided Path Reasoning (PGPR), which couples recommendation and interpretability by providing actual paths in a knowledge graph. Our contributions include four aspects. We first highlight the significance of incorporating knowledge graphs into recommendation to formally define and interpret the reasoning process. Second, we propose a reinforcement learning (RL) approach featured by an innovative soft reward strategy, user-conditional action pruning and a multi-hop scoring function. Third, we design a policy-guided graph search algorithm to efficiently and effectively sample reasoning paths for recommendation. Finally, we extensively evaluate our method on several large-scale real-world benchmark datasets, obtaining favorable results compared with state-of-the-art methods.
Birch reduction of 3,4-dihydro-8-hydroxy-3-methylisocoumarin (mellein). Expeditious syntheses of (±)-ramulosin and a spruce budworm toxin

Abstract A three-step conversion of (±)-mellein (1) to (±)-ramulosin (6) in 41% overall yield is described. A synthesis of the spruce budworm toxin 7 also is reported.
The consequences of strain release in the norbornyl subunit of isodicyclopentadiene on cycloaddition stereochemistry. Further evidence that orbital tilting serves as the key determinant of contrasteric π-facial selectivity

Abstract Diels-Alder cycloadditions to 2 and 3 occur preferentially from the top face in contra-distinction to the behavior of isodicyclopentadiene (1). This reversal in facial stereoselectivity is shown not to arise from torsional constraints, but to be consistent with the overriding of steric effects by orbital tilting in 1.
Mediation of Photochemical Reactions of 1-Naphthyl Phenylacylates by Polyolefin Films. A ‘Radical Clock’ to Measure Rates of Radical-Pair Cage Recombinations in ‘Viscous Space’

Abstract The fates of phenylacyl/1-naphthoxy singlet radical pairs generated upon irradiation of 1-naphthyl phenylacetate (1a) and 1-naphthyl 2-phenylpropanoate (1b) in three unstretched and stretched polyethylene films and isotactic and syndiotactic polypropylene films have been investigated. From dynamic fluorescence measurements, the primary locus of reactions by 1 is within amorphous regions of the films. The reaction cages afforded by these media inhibit escape of the radical pairs and mediate their reorientational motions leading to photo-Fries and related products. In essence, the cages act as stiff-walled templates. In addition, a method is described to measure the rate constants for the singlet radical pairs. Thus, the rate constants (leading to the keto precursors) of the 2-phenylacyl-1-naphthols from the radical pairs of 1 (>108 s−1) are >6 times the rate constants for the 4-isomers. Film stretching increases this selectivity but there is no obvious correlation between the rate of the in-cage radical pair recombinations and macroscopic polymer, properties such as degree of crystallinity and frequency of branched chains. By contrast, formation of (the keto precursors of) 2-benzylic-1-naphthols (from in-cage recombinations after phenylacyl decarbonylation) is slower than for the 4-benzyl-1-naphthols.
Formation of two-dimensional electron and hole gases at the interface of half-Heusler semiconductors

Heuslers are a prominent family of multi-functional materials that includes semiconductors, half metals, topological semimetals, and magnetic superconductors. Owing to their same crystalline structure, yet quite different electronic properties and flexibility in chemical composition, Heusler-based heterostructures can be designed to show intriguing properties at the interface. Using electronic structure calculations, we show that two dimensional electron or hole gases (2DEG or 2DHG) form at the interface of half-Heusler (HH) semiconductors without any chemical doping. We use CoTiSb/NiTiSn as an example, and show that the 2DEG at the TiSb/Ni(001) termination and the 2DHG at the Co/TiSn(001) termination are intrinsic to the interface, and hold rather high charge densities of 3x10^14 carriers/cm^2. These excess charge carriers are tightly bound to the interface plane and are fully accommodated in transition-metal d sub-bands. The formation of 2DEG and 2DHG are not specific to the CoTiSb/NiTiSn system; a list of combinations of HH semiconductors that are predicted to form 2DEG or 2DHG is provided based on band alignment, interface termination, and lattice mismatch.
Thyroid hormone coordinates developmental trajectories but does not underlie developmental truncation in danionins.

Background Differences in postembryonic developmental trajectories can profoundly alter adult phenotypes and life histories. Thyroid hormone (TH) regulates metamorphosis in many vertebrate taxa with multiphasic ecologies, and alterations to TH metabolism underlie notable cases of paedomorphosis in amphibians. We tested the requirement for TH in multiple postembryonic developmental processes in zebrafish, which has a monophasic ecology, and asked if TH production was compromised in paedomorphic Danionella. Results We showed that TH regulates allometric growth in juvenile zebrafish, and inhibits relative head growth. The lateral line system showed differential requirements for TH: the hormone promotes canal neuromast formation and inhibits neuromast proliferation in the head, but causes expansion of the neuromast population in the trunk. While Danionella morphology resembled that of larval zebrafish, the two Danionella species analyzed were not similar to hypothyroid zebrafish in their shape or neuromast distribution, and both possessed functional thyroid follicles. Conclusions Although zebrafish do not undergo a discrete ecological transformation, we found that multiple tissues undergo transitions in developmental trajectories that are dependent on TH, suggesting the TH axis and its downstream pathways as likely targets for adaptation. Nonetheless, we found no evidence that evolutionary paedomorphosis in Danionella is the result of compromised TH production.
Michael addition reactions of α-acyloxy nitrile anions

Abstract The Michael addition reactions of α-acyloxy nitrile anions with Michael acceptors are followed by a shift of the acyl group to the α-carbon of the Michael acceptor. Michael acceptors such as acrylates, acrylonitrile and methyl vinyl ketone can be used. Acetoxy nitriles are selectively deprotonated α to the nitrile.
Mercury Monoxide: A Systematic Investigation of Its Ground Electronic State

One of the possible key products in the oxidation and transport of atmospheric mercury is mercury monoxide, HgO. In the present work, large-scale multireference configuration interaction, as well as coupled cluster, wave functions have been used in conjunction with a series of correlation consistent basis sets to calculate the near-equilibrium potential energy functions of the first two electronic states of HgO. In the absence of spin−orbit coupling, the lowest 1Σ+ and 3Π states are nearly isoenergetic with a binding energy with respect to ground-state atoms of only 2−3 kcal/mol at the estimated complete basis set limit. After spin−orbit coupling effects are accurately included, the resulting X0+ state has a D0 of just 4.0 kcal/mol, leading to a ΔHf(0 K) of 70.4 kcal/mol. These values are in stark contrast to the currently accepted experimental values. The implications of these results to atmospheric mercury chemistry are briefly discussed.
Olefin metathesis by molybdenum imido alkylidene catalysts

Abstract A “well-defined” alkylidene complex of the type Mo(CHCMe2Ph)(N-2,6-i-Pr2C6H3)[OCMe(CF3)2]2 has proven to be a useful initiator in catalytic olefin metathesis reactions of interest to organic chemists. A variety of related molybdenum imido alkylidene complexes can be prepared readily from a common precursor. This article is a summary of what is known about the details of the steps in a metathesis reaction catalyzed by complexes of the type Mo(CHR′)(NAr)(OR)2, and how the activity and stability of complexes of this type change upon altering each of the ligands in the pseudo-tetrahedral species. Some recent asymmetric ring-closing metathesis reactions are also discussed briefly.
Sulfur ylides via decarboxylation of carboxymethylsulfonium betaines: a novel and mild protocol for the preparation of oxiranes.

A novel protocol for the generation of sulfur ylides is described. The overall process involves thermal decarboxylation of a carboxymethylsulfonium betaine to give a sulfur ylide that, in the prese...
Superior Fe-ZSM-5 catalyst for selective catalytic reduction of nitric oxide by ammonia

Nitrogen oxides in the exhaust gases from combustion of fossil fuels remain a major source for air pollution and acid rain. The current technology for reducing NO{sub x} (NO + NO{sub 2}) emissions from power plants is selective catalytic reduction (SCR) with ammonia in the presence of oxygen. For the SCR reaction, V{sub 2}O{sub 5} + WO{sub 3} (or MoO{sub 3}) supported on TiO{sub 2} are the commercial catalysts. The mechanism of the reaction on the vanadia catalysts has been studied extensively, and several different mechanisms have been proposed. Ion-exchanged zeolite catalysts have also been studied, e.g., Fe-Y, Cu-ZSM-5, and Fe-ZSM-5, but the reported activities were lower than that of the commercial vanadia catalysts. The SCR technology based on vanadia catalysts is being used in Europe and Japan and is being quickly adopted in the US. However, problems associated with vanadia catalysts remain, e.g., high activity for oxidation of SO{sub 2} to SO{sub 3}, toxicity of vanadia, and formation of N{sub 2}O at high temperature. Hence, there are continuing efforts in developing new catalysts. In this paper, the authors report a superior Fe-ZSM-5 catalyst that is much more active than the commercial vanadia catalysts and does not have the deficienciesmore » that are associated with the vanadia catalysts.« less
Preparation and biological activity of 24-epi-26,26,26,27,27,27-hexafluoro-1α,25-dihydroxyvitamin D2

A new fluorinated analog of vitamin D2, 24-epi-26, 26, 26, 27, 27, 27-hexafluoro-1α, 25-dihydroxyvitamin D2, was efficiently synthesized starting from (R)-4-isopropyl-3-propionyl-2-oxazolidinone with high stereochemical control.In all four physiological test systems, the fluorinated vitamin D2 analog was found to be slightly less active than 1α, 25-dihydroxyvitamin D3.
Titanium(IV) halide mediated coupling of alkoxides and alkynes: an efficient and stereoselective route to trisubstituted (E)-alkenyl halides.

Alkoxide C−O bond cleavage occurs readily at room temperature in the presence of titanium(IV) halide. Capture of the resultant carbocation by alkynes provides an efficient route to trisubstituted (E)-alkenyl halides with high stereoselectivity.
Does Acculturation Matter? End-of-Life Care Planning and Preference of Foreign-born Older Immigrants in the United States.

Background and objectives Advance care planning (ACP) is a critical component of health care affecting the quality of later life. Responding to the increase in the older immigrant population in the United States, this empirical study explored the racial/ethnic gaps in ACP behaviors among older immigrants and examined the end-of-life (EOL) care planning and preferences of foreign-born immigrant older adults focusing on race/ethnicity, acculturation, health need factors, and enabling social factors (financial capability, public assistance, and informal supports) after controlling predisposing factors (sociodemographic characteristics). Research design and methods Using a subsample from the National Health and Aging Trends Study 2011 and 2012, hierarchical logistic regression models of the EOL plan and preferences were examined with 50 multiple imputation data sets (n = 232). Results Descriptive statistics reveal lower ACP engagement of immigrants from racial/ethnic minority groups. In logistic models, however, only Black immigrants were less likely than Whites to have EOL conversations. Among acculturation factors, age at immigration was only negatively associated with having a durable power of attorney for health, but not significantly associated with other ACP behaviors. Instead, health and social factors, primarily need in health and informal support (i.e., number of coresidents and receiving financial help from family members), were associated with different types of ACP components. Receiving public assistance (i.e., receiving Medicaid and SSI) were positively associated with EOL treatment preferences. Discussion and implications Older foreign-born immigrants, in general, showed lower ACP engagement than the overall older population. Moreover, minority immigrants were lower on ACP engagement than both White immigrants. This study highlights the need for formal and informal assistance for enhancing EOL planning for older immigrants. Adding to the culturally competent approach, policy efforts should address social and health factors that accrued throughout individuals' life spans and affect older immigrants' EOL preparation and care.
The i3+3 design for phase I clinical trials

The traditional rule-based design, 3 + 3, has been shown to be less likely to achieve the objectives of dose-finding trials when compared with model-based designs. We propose a new rule-based desig...
Wire-like diruthenium σ-alkynyl compounds and charge mobility therein

Described in this short review is the chemistry of wire-like diruthenium σ-alkynyl species, which are promising building blocks for organometallic molecular wires. Two series of carbon-rich compounds have been studied: (a) polyyn-diyls with diruthenium capping units, and (b) bi-ferrocenes with a diruthenium alkynyl bridge. Investigations of both the charge transfer process across the polyyn-diyls and the role of diruthenium cores in enhancing charge mobility are achieved through X-ray structure determination, spectroscopic, voltammetric and spectroelectrochemical measurements.
The use of borane–amine adducts as versatile palladium-catalyzed hydrogen-transfer reagents in methanol

Abstract The scope of borane–amine adducts as reducing agents is broadened through palladium-catalyzed methanolysis capable of reducing a wide variety of functional groups. Hence, borane mediated reduction of a benzamide followed by a tandem methanolysis/hydrogenolysis of the resulting borane–benzylamine adduct allows chemoselective removal of an N -benzoyl in the presence of an O -benzoyl.
Enzymatic resolution of diols derived from p -benzoquinones

Abstract An efficient enzymatic resolution of racemic 4-acetoxy-2,3-dibromo-5-cyclohexen-1-ol in organic solvent is described. The methodology is extended to the synthesis of a series of highly functionalized enantiopure intermediates derived from various substituted p-benzoquinones.
Consecutive Rh(I)-catalyzed Alder-ene/Diels–Alder/Diels–Alder reaction sequence affording rapid entry to polycyclic compounds

Abstract Conversion of acyclic allenynes to polycyclic compounds using consecutive transition metal catalyzed carbon–carbon bond forming reactions in a single chemical operation is described. Reaction of an allenyne with a Rh(I) catalyst affords a cross-conjugated triene via a formal Alder-ene reaction. The triene then participates in a Rh(I)-catalyzed intramolecular [4+2] cycloaddition reaction to generate a new conjugated diene. An external dienophile is added to this diene which then undergoes a second [4+2] cycloaddition reaction to afford a complex polycyclic ring system. This reaction sequence demonstrates the synthetic potential of allenynes and cross conjugated trienes and highlights the rapid increases in molecular complexity that are possible by one-pot sequential transition metal catalyzed carbon–carbon bond forming reactions.
Rieke zinc as a reducing agent for common organic functional groups

The ability of Rieke zinc to reduce common organic functional groups has been studied. Nitrobenzene, conjugated aldehydes, arylacetylenes, and phenylpropiolates are readily reduced under mild conditions. Benzonitrile, alkylacetylenes, ketones, unconjugated aldehydes, and alkenes are not reduced.
Quickest Visibility Queries in Polygonal Domains

Let s be a point in a polygonal domain $${\mathcal {P}}$$ of $$h-1$$ holes and n vertices. We consider a quickest visibility query problem. Given a query point q in $${\mathcal {P}}$$ , the goal is to find a shortest path in $${\mathcal {P}}$$ to move from s to seeq as quickly as possible. Previously, Arkin et al. (SoCG 2015) built a data structure of size $$O(n^22^{\alpha (n)}\log n)$$ that can answer each query in $$O(K\log ^2 n)$$ time, where $$\alpha (n)$$ is the inverse Ackermann function and K is the size of the visibility polygon of q in $${\mathcal {P}}$$ (and K can be $$\varTheta (n)$$ in the worst case). In this paper, we present a new data structure of size $$O(n\log h + h^2)$$ that can answer each query in $$O(h\log h\log n)$$ time. Our result improves the previous work when h is relatively small. In particular, if h is a constant, then our result even matches the best result for the simple polygon case (i.e., $$h=1$$ ), which is optimal. As a by-product, we also have a new algorithm for a shortest-path-to-segment query problem. Given a query line segment $$\tau $$ in $${\mathcal {P}}$$ , the query seeks a shortest path from s to all points of $$\tau $$ . Previously, Arkin et al. gave a data structure of size $$O(n^22^{\alpha (n)}\log n)$$ that can answer each query in $$O(\log ^2 n)$$ time, and another data structure of size $$O(n^3\log n)$$ with $$O(\log n)$$ query time. We present a data structure of size O(n) with query time $$O\big (h\log \frac{n}{h}\big )$$ , which also favors small values of h and is optimal when $$h=O(1)$$ .
Synthesis and biological evaluation of 9‐thia‐5,10‐dideazafolic acid

The folate analogue, 9-thia-5,10-dideazafolic acid (3b), was obtained in an efficient two-step procedure in an overall yield of 60%. The previously unknown intermediate dimethyl-thiocarbamic acid S-(2-amino-3,4-dihydo-4-oxo-pyrido[2,3-d]pyrimidin-6-yl) ester (5) was prepared via the condensation of 2,6-diamino-3H-pyrimidin-4-one and S-(2-malonaldehyde)-1,1,3,3-tetramethylthiouronium bromide (4). Compound 5, in a one pot procedure, was deprotected using sodium hydroxide and then coupled to diethyl N-[(4-chloromethyl)benzoyl]-L-glutamate, followed by saponification of the ethyl esters to give the 9-thia-5,10-dideazafolic acid (3b). Compound 3b was a potent inhibitor of human 5-aminoimidazole-4-carboxamide ribonucleotide transformylase (Ki of 8 ± 5 μM) and showed no inhibition of human glycinamide ribonu-cleotide transformylase at concentrations as high as 50 μM. Compound 3b was screened by the National Cancer Institute Developmental Therapeutics Program against 60 human tumors and was found to be active against a leukemia RPMI-8226 cell line where the LC50 was 1 μM.
Adaptive introgression from distant Caribbean islands contributed to the diversification of a microendemic adaptive radiation of trophic specialist pupfishes

Rapid diversification often involves complex histories of gene flow that leave variable and conflicting signatures of evolutionary relatedness across the genome. Identifying the extent and source of variation in these evolutionary relationships can provide insight into the evolutionary mechanisms involved in rapid radiations. Here we compare the discordant evolutionary relationships associated with species phenotypes across 42 whole genomes from a sympatric adaptive radiation of Cyprinodon pupfishes endemic to San Salvador Island, Bahamas and several outgroup pupfish species in order to understand the rarity of these trophic specialists within the larger radiation of Cyprinodon. 82% of the genome depicts close evolutionary relationships among the San Salvador Island species reflecting their geographic proximity, but the vast majority of variants fixed between specialist species lie in regions with discordant topologies. Top candidate adaptive introgression regions include signatures of selective sweeps and adaptive introgression of genetic variation from a single population in the northwestern Bahamas into each of the specialist species. Hard selective sweeps of genetic variation on San Salvador Island contributed 5 times more to speciation of trophic specialists than adaptive introgression of Caribbean genetic variation; however, four of the 11 introgressed regions came from a single distant island and were associated with the primary axis of oral jaw divergence within the radiation. For example, standing variation in a proto-oncogene (ski) known to have effects on jaw size introgressed into one San Salvador Island specialist from an island 300 km away approximately 10 kya. The complex emerging picture of the origins of adaptive radiation on San Salvador Island indicates that multiple sources of genetic variation contributed to the adaptive phenotypes of novel trophic specialists on the island. Our findings suggest that a suite of factors, including rare adaptive introgression, may be necessary for adaptive radiation in addition to ecological opportunity.
Synthesis of 3‐alkylcarbonyloxymethyl derivatives of 5‐fluorouracil

3-Alkylcarbonyloxymethyl derivatives of 5-fluorouracil have been synthesized starting with 1-ethyloxy-carbonyl-5-fluorouracil. Alkylation of the starting material with alkylcarbonyloxymethyl iodides, generated from the corresponding chlorides by the Finkelstein reaction, in the presence of 1,8-bis(dimethyl-amino)naphthalene followed by deprotection with 1,1-dimethylethylamine gave good yields (50-60%) of the target derivatives after column chromatography. A 90% yield of 3-acetyloxymethyl-5-fluorouracil was obtained when the corresponding commercially available bromide was used, instead of the in situ generated iodide, and the product could be isolated from the crude reaction by crystallization. An alternate path of sequential alkylation of 5-fluorouracil with alkylcarbonyloxymethyl chlorides in the presence of tertiary amines, exhibiting different reactivities towards the chlorides, gave an excellent yield of 1-acetyloxymethyl-3-propionyloxymethyl-5-fluorouracil in the one instance it was attempted, but subsequent deprotection of the 1-position with methylamine gave only a 24% yield of 3-propionyloxymethyl-5-fluorouracil.
Ground State and Transition State Contributions to the Rates of Intramolecular and Enzymatic Reactions

reactions, rate enhancements of 108 M have been observed (Table 1).2 Intramolecular reactions where severe ground state strain is relieved upon formation of the transition state are known to be as large as 1016 M.3 Kirby4 has compiled a compendium of intramolecular reactions and has pointed out the relationship of rate to exothermicity. The importance of ground state conformations and the lack of translational entropy in intramolecular and enzymatic reactions have drawn attention from Menger5 and ourselves, while Jencks and Page6 have offered an explanation based on entropic driving forces stemming from the freezing out of motions and the dampening of vibrational frequencies in the transition state. Houk,7 in a scholarly study, has provided a correlation between rate constants for certain lactonization reactions and transition state stabilization. We provide here an account of our recent computational results8-10 dealing with the driving forces for enzymatic and intramolecular reactions. We introduce8 the term near attack conformation (NAC) to define the required conformation for juxtaposed reactants to enter a transition state (TS). The greater the mole fraction of reactant conformations that are present as NACs, the greater the rate constant. Rate constants for bond making and breaking in enzymatic reactions depend on, (i) the fraction of E‚S present as NACs, (ii) the change in solvation of reactant species within the NAC, as compared to water, and (iii) electrostatic forces11 which can stabilize the TS. The latter may include hydrogen bonds and metal ligation. Covalency in metal ligation and hydrogen bonding (low barrier hydrogen bonding12) most probably are introduced in the ground state. These features are best appreciated when ground state conformations and TS structures can be examined separately.
Three-component synthesis of disubstituted 2H-pyrrol-2-ones: preparation of the violacein scaffold

Abstract An efficient, three-component, microwave-mediated cyclization to prepare the 3,5-disubstituted 2H-pyrrol-2-one core of the bis-indole alkaloid, violacein, is described. Preliminary results indicate an iterative, thermally driven, condensation of a γ-ketoester, ammonium acetate, and isatin in polyethylene glycol. This methodology is an effective and environmentally benign route to prepare a series of violacein analogs in good overall yields.
Monocyte and Macrophage Subtypes as Paired Cell Biomarkers for Coronary Artery Disease

NEW FINDINGS What is the central question of this study? Are circulating monocyte markers correlated with their derived macrophage polarization patterns and coronary artery disease severity? What is the main finding and its importance? There was an inverse relationship between circulating CD16+ monocytes (high) and M2 macrophages (low) that marked coronary disease severity, and the differences in polarization of macrophages were seen despite a week of cell culture ex vivo. This study highlights the importance, and potential prognostic implications, of circulating monocyte and descendant macrophage phenotypes in coronary artery disease. ABSTRACT Monocytes and macrophages are central to atherosclerosis, but how they combine to mark progression of human coronary artery disease (CAD) is unclear. We tested whether patients' monocyte subtypes paired with their derived macrophage profiles were correlated with extent of CAD. Peripheral blood was collected from 40 patients undergoing cardiac catheterization, and patients were categorized as having no significant CAD, single vessel disease or multivessel disease according to the number of affected coronary arteries. Mononuclear cells were measured for the monocyte markers CD14 and CD16 by flow cytometry, and separate monocytes were cultured into macrophages over 7 days and measured for the polarization markers CD86 and CD206. At baseline, patients with a greater CAD burden were older, with higher rates of statin, β-blocker and antiplatelet drug use, whereas other characteristics were similar across the spectrum of coronary disease. CD16+ (both intermediate and non-classical) monocytes were elevated in patients with single vessel and multivessel disease compared with those without significant CAD (P < 0.05), whereas regulatory M2 macrophages (CD206+ ) were decreased in patients with single vessel and multivessel disease (P < 0.001). An inverse relationship between paired CD16+ monocytes and M2 macrophages marked CAD severity. On multivariable linear regression, CAD severity was associated, along with age and traditional cardiovascular risk factors, with CD16+ monocytes (directly) and M2 macrophages (inversely). Circulating monocytes may influence downstream polarization of lesional macrophages, and these measures of monocyte and macrophage subtypes hold potential as biomarkers in CAD.
Do Health Insurance Mandates Spillover to Education? Evidence from Michigan's Autism Insurance Mandate.

Abstract Social programs and mandates are usually studied in isolation, but unintended spillovers to other areas can impact individual behavior and social welfare. We examine the presence of spillovers from health care policy to the education sector by studying how health insurance coverage affects the education of students with Autism Spectrum Disorder (ASD). We leverage a state mandate that increased insurance coverage of ASD-related services, which often are provided by both the private sector and within public schools. The mandate primarily affected coverage for children with private health insurance, so we proxy for private insurance coverage with students’ economic disadvantage status and estimate effects via triple-differences. While we find little change in ASD identification, the mandate crowds-out special education supports for students with ASD. A lack of short-run impact on achievement supports our crowd-out interpretation and indicates that the mandate had little net effect on the academic achievement of ASD students.
Computing Bottleneck Distance for 2-D Interval Decomposable Modules

Computation of the interleaving distance between persistence modules is a central task in topological data analysis. For 1-D persistence modules, thanks to the isometry theorem, this can be done by computing the bottleneck distance with known efficient algorithms. The question is open for most n-D persistence modules, n>1, because of the well recognized complications of the indecomposables. Here, we consider a reasonably complicated class called 2-D interval decomposable modules whose indecomposables may have a description of non-constant complexity. We present a polynomial time algorithm to compute the bottleneck distance for these modules from indecomposables, which bounds the interleaving distance from above, and give another algorithm to compute a new distance called dimension distance that bounds it from below.
Evaluating the Robustness of Neural Networks: An Extreme Value Theory Approach

The robustness of neural networks to adversarial examples has received great attention due to security implications. Despite various attack approaches to crafting visually imperceptible adversarial examples, little has been developed towards a comprehensive measure of robustness. In this paper, we provide a theoretical justification for converting robustness analysis into a local Lipschitz constant estimation problem, and propose to use the Extreme Value Theory for efficient evaluation. Our analysis yields a novel robustness metric called CLEVER, which is short for Cross Lipschitz Extreme Value for nEtwork Robustness. The proposed CLEVER score is attack-agnostic and computationally feasible for large neural networks. Experimental results on various networks, including ResNet, Inception-v3 and MobileNet, show that (i) CLEVER is aligned with the robustness indication measured by the $\ell_2$ and $\ell_\infty$ norms of adversarial examples from powerful attacks, and (ii) defended networks using defensive distillation or bounded ReLU indeed achieve better CLEVER scores. To the best of our knowledge, CLEVER is the first attack-independent robustness metric that can be applied to any neural network classifier.
Distributed Linearized Alternating Direction Method of Multipliers for Composite Convex Consensus Optimization

Given an undirected graph $\mathcal {G}=(\mathcal {N},\mathcal {E})$ of agents $\mathcal {N}=\lbrace 1,\ldots,N\rbrace$ connected with edges in $\mathcal {E}$ , we study how to compute an optimal decision on which there is consensus among agents and that minimizes the sum of agent-specific private convex composite functions $\lbrace \Phi _i\rbrace _{i\in \mathcal {N}}$ , where $\Phi _i\triangleq \xi _i + f_i$ belongs to agent- $i$ . Assuming only agents connected by an edge can communicate, we propose a distributed proximal gradient algorithm (DPGA) for consensus optimization over both unweighted and weighted static (undirected) communication networks. In one iteration, each agent- $i$ computes the prox map of $\xi _i$ and gradient of $f_i$ , and this is followed by local communication with neighboring agents. We also study its stochastic gradient variant, SDPGA, which can only access to noisy estimates of $\nabla f_i$ at each agent- $i$ . This computational model abstracts a number of applications in distributed sensing, machine learning and statistical inference. We show ergodic convergence in both suboptimality error and consensus violation for the DPGA and SDPGA with rates $\mathcal {O}(1/t)$ and $\mathcal {O}(1/\sqrt{t})$ , respectively.
Deep multimodal semantic embeddings for speech and images

In this paper, we present a model which takes as input a corpus of images with relevant spoken captions and finds a correspondence between the two modalities. We employ a pair of convolutional neural networks to model visual objects and speech signals at the word level, and tie the networks together with an embedding and alignment model which learns a joint semantic space over both modalities. We evaluate our model using image search and annotation tasks on the Flickr8k dataset, which we augmented by collecting a corpus of 40,000 spoken captions using Amazon Mechanical Turk.
A note on the relationship between the Szlenk and w^*-dentability indices of arbitrary w^*-compact sets

We prove the optimal estimate between the Szlenk and \(w^*\)-dentability indices of an arbitrary \(w^*\)-compact subset of the dual of a Banach space. For a given \(w^*\)-compact, convex subset K of the dual of a Banach space, we introduce a two player game the winning strategies of which determine the Szlenk index of K. We give applications to the \(w^*\)-dentability index of a Banach space and of an operator.