cssi/SciSciGPT-SciSciNet huggingface dataset:
State dependent ring polymer molecular dynamics for investigating excited nonadiabatic dynamics

A recently proposed nonadiabatic ring polymer molecular dynamics (NRPMD) approach has shown to provide accurate quantum dynamics by incorporating explicit state descriptions and nuclear quantizations. Here, we present a rigorous derivation of the NRPMD Hamiltonian and investigate its performance on simulating excited state nonadiabatic dynamics. Our derivation is based on the Meyer-Miller-Stock-Thoss mapping representation for electronic states and the ring-polymer path-integral description for nuclei, resulting in the same Hamiltonian proposed in the original NRPMD approach. In addition, we investigate the accuracy of using NRPMD to simulate the photoinduced nonadiabatic dynamics in simple model systems. These model calculations suggest that NRPMD can alleviate the zero-point energy leakage problem that is commonly encountered in the classical Wigner dynamics and provide accurate excited state nonadiabatic dynamics. This work provides a solid theoretical foundation of the promising NRPMD Hamiltonian and demonstrates the possibility of using the state-dependent RPMD approach to accurately simulate electronic nonadiabatic dynamics while explicitly quantizing nuclei.
Evaluating the effect of data standardization and validation on patient matching accuracy.

Objective This study evaluated the degree to which recommendations for demographic data standardization improve patient matching accuracy using real-world datasets. Materials and methods We used 4 manually reviewed datasets, containing a random selection of matches and nonmatches. Matching datasets included health information exchange (HIE) records, public health registry records, Social Security Death Master File records, and newborn screening records. Standardized fields including last name, telephone number, social security number, date of birth, and address. Matching performance was evaluated using 4 metrics: sensitivity, specificity, positive predictive value, and accuracy. Results Standardizing address was independently associated with improved matching sensitivities for both the public health and HIE datasets of approximately 0.6% and 4.5%. Overall accuracy was unchanged for both datasets due to reduced match specificity. We observed no similar impact for address standardization in the death master file dataset. Standardizing last name yielded improved matching sensitivity of 0.6% for the HIE dataset, while overall accuracy remained the same due to a decrease in match specificity. We noted no similar impact for other datasets. Standardizing other individual fields (telephone, date of birth, or social security number) showed no matching improvements. As standardizing address and last name improved matching sensitivity, we examined the combined effect of address and last name standardization, which showed that standardization improved sensitivity from 81.3% to 91.6% for the HIE dataset. Conclusions Data standardization can improve match rates, thus ensuring that patients and clinicians have better data on which to make decisions to enhance care quality and safety.
SNAP and Paycheck Cycles

It is well documented that individuals do not spend the Supplemental Nutrition Assistance Program (SNAP) benefits smoothly over the month after receipt. Rather, recipients spend a disproportionate share of benefits at the beginning of the benefit month. This has costs for recipients and stores. There is also evidence that other income streams, such as Social Security and paychecks, are not spent smoothly. The presence of these other income streams may bias estimates of the effects of this SNAP cycle on consumption for working SNAP beneficiaries and those who receive other government benefits. We use data from United States Department of Agriculture's National Household Food Acquisition and Purchase Survey to explore how the SNAP cycle is affected by accounting for these other income streams. We find suggestive evidence that the cycle is more pronounced for workers who are paid on a weekly or monthly basis, but little evidence that cycles in other income streams mitigate or exacerbate the SNAP cycle.
A Randomized Controlled Trial of Interleaved Mathematics Practice.

We report the results of a preregistered, cluster randomized controlled trial of a mathematics learning intervention known as interleaved practice. Whereas most mathematics assignments consist of a block of problems devoted to the same skill or concept, an interleaved assignment is arranged so that no 2 consecutive problems require the same strategy. Previous small-scale studies found that practice assignments with a greater proportion of interleaved practice produced higher test scores. In the present study, we assessed the efficacy and feasibility of interleaved practice in a naturalistic setting with a large, diverse sample. Each of 54 7th-grade mathematics classes periodically completed interleaved or blocked assignments over a period of 4 months, and then both groups completed an interleaved review assignment. One month later, students took an unannounced test, and the interleaved group outscored the blocked group, 61% versus 38%, d = 0.83. Teachers were able to implement the intervention without training, and they later expressed support for interleaved practice in an anonymous survey they completed before they knew the results of the study. Although important caveats remain, the results suggest that interleaved mathematics practice is effective and feasible. (PsycINFO Database Record (c) 2019 APA, all rights reserved)
Equity in college physics student learning: A critical quantitative intersectionality investigation

We investigated the intersectional nature of race/racism and gender/sexism in broad scale inequities in physics student learning using a critical quantitative intersectionality. To provide transparency and create a nuanced picture of learning, we problematized the measurement of equity by using two competing operationalizations of equity: Equity of Individuality and Equality of Learning. These two models led to conflicting conclusions. The analyses used hierarchical linear models to examine student's conceptual learning as measured by gains in scores on research-based assessments administered as pretests and posttests. The data came from the Learning About STEM Student Outcomes' (LASSO) national database and included data from 13,857 students in 187 first-semester college physics courses. Findings showed differences in student gains across gender and race. Large gender differences existed for White and Hispanic students but not for Asian, Black, and Pacific Islander students. The models predicted larger gains for students in collaborative learning than in lecture-based courses. The Equity of Individuality operationalization indicated that collaborative instruction improved equity because all groups learned more with collaborative learning. The Equality of Learning operationalization indicated that collaborative instruction did not improve equity because differences between groups were unaffected. We discuss the implications of these mixed findings and identify areas for future research using critical quantitative perspectives in education research.
International Taxation and Production Outsourcing

This paper studies the effects of international taxation on multinational firms' production outsourcing strategies, which has attracted recent attention from both practitioners and legislators. We find that under the territorial tax system, the presence of global tax disparity may result in subtle changes of a firm's production outsourcing strategy. In particular, the tax consideration can make the firm more inclined to keep material procurement in house and use buy-sell arrangement to retain profit in low tax jurisdictions. Such an effect can not only cause the firm to choose a more expensive material supplier but also overproduce the products. Therefore, besides the general concern of income shifting, tax considerations can further lead to operational distortions. We show that to reduce tax disparity while preventing tax exemption for shifted foreign profit may lead to a win-win outcome for the firm and the stakeholders. The firm will make more efficient operational decisions to obtain a higher after-tax profit at certain reduced tax rate, while the home country stakeholders can receive more tax income. Interestingly, the foreign contract manufacturer may also benefit from such a change.
Dense products in fundamental groupoids

Infinitary operations, such as products indexed by countably infinite linear orders, arise naturally in the context of fundamental groups and groupoids. Despite the fact that the usual binary operation of the fundamental group determines the operation of the fundamental groupoid, we show that, for a locally path-connected metric space, the well-definedness of countable dense products in the fundamental group need not imply the well-definedness of countable dense products in the fundamental groupoid. Additionally, we show the fundamental groupoid $$\Pi _1(X)$$ has well-defined dense products if and only if X admits a generalized universal covering space.
Analysis of Risk Factor Domains in Psychosis Patient Health Records

Readmission after discharge from a hospital is disruptive and costly, regardless of the reason. However, it can be particularly problematic for psychiatric patients, so predicting which patients may be readmitted is critically important but also very difficult. Clinical narratives in psychiatric electronic health records (EHRs) span a wide range of topics and vocabulary; therefore, a psychiatric readmission prediction model must begin with a robust and interpretable topic extraction component. We created a data pipeline for using document vector similarity metrics to perform topic extraction on psychiatric EHR data in service of our long-term goal of creating a readmission risk classifier. We show initial results for our topic extraction model and identify additional features we will be incorporating in the future.
Studies on solid solutions based on layered honeycomb-ordered phases P2-Na2M2TeO6 (M=Co, Ni, Zn)

Three complete solid solutions between the layered phases P2-Na2M2TeO6 (M=Co, Ni, Zn) have been prepared by conventional solid state method and investigated through X-ray diffraction, magnetism and optical measurements. All compositions are characterized by a M2+/X6+ honeycomb ordering within the slabs and crystallize in a hexagonal unit cell. However, a structural transition based on a different stacking is observed as nickel (space group P63/mcm) is substituted by zinc or cobalt (space group P6322). All compositions exhibit a paramagnetic Curie–Weiss behavior at high temperatures; and the magnetic moment values confirm the presence of Ni2+ and/or Co2+ cations. The low-temperature antiferromagnetic order of Na2Ni2TeO6 and Na2Co2TeO6 is suppressed by zinc substitution. The color of the obtained compositions varies from pink, to light green and white when M=Co, Ni, Zn, respectively.
The single mitochondrion of the kinetoplastid parasite Crithidia fasciculata is a dynamic network

Mitochondria are central organelles in cellular metabolism. Their structure is highly dynamic, allowing them to adapt to different energy requirements, to be partitioned during cell division, and to maintain functionality. Mitochondrial dynamics, including membrane fusion and fission reactions, are well studied in yeast and mammals but it is not known if these processes are conserved throughout eukaryotic evolution. Kinetoplastid parasites are some of the earliest-diverging eukaryotes to retain a mitochondrion. Each cell has only a single mitochondrial organelle, making them an interesting model for the role of dynamics in controlling mitochondrial architecture. We have investigated the mitochondrial division cycle in the kinetoplastid Crithidia fasciculata. The majority of mitochondrial biogenesis occurs during the G1 phase of the cell cycle, and the mitochondrion is divided symmetrically in a process coincident with cytokinesis. Live cell imaging revealed that the mitochondrion is highly dynamic, with frequent changes in the topology of the branched network. These remodeling reactions include tubule fission, fusion, and sliding, as well as new tubule formation. We hypothesize that the function of this dynamic remodeling is to homogenize mitochondrial contents and to facilitate rapid transport of mitochondria-encoded gene products from the area containing the mitochondrial nucleoid to other parts of the organelle.
Controlling Stereoselection in Aza-Cope-Mannich Reactions

The synthesis of 2-substituted cis-octahydroindolones from the reaction of cis-2-amino-1-alkenylcyclopentanols with aldehydes was studied to examine whether stereoselection in the aza-Cope–Mannich reaction could be controlled by the nature of the nitrogen substituent. 2-Alkylamino-1-(1-phenylethenyl)cyclopentanols 7 and 8, which contain nitrogen substituents of widely differing size (Me and CHPh2), were condensed with four aldehydes to give oxazolidines 9a–d and 10a-c. Rearrangement of these intermediates at 23–60 °C, in the presence of 0.9 equiv of (±)-10-camphorsulfonic acid in acetonitrile, gave cis-octahydroindolones 11a-d and 12a–c in yields of 77–95%. Using a combination of single-crystal X-ray crystallography, 1H nOe measurements, and comparisons with known materials it was established that the N-methyl oxazolidines 9a–d provided exclusively cis-octahydroindolones having the 2-substituent trans to the angular substituents, while N-benzhydryl analogs 10a–c provided exclusively the all-cis products 12a–c. These results are interpreted to mean: (1) When the nitrogen substituent is small (Me), the stereochemistry-determining [3,3]-sigmatropic rearrangement occurs preferentially through a transition-state topography having the R2 substituent oriented quasiequatorially (14 15 16); (2) When this substituent is large (CHPh2), destabilizing steric interactions between the vicinal R1 and R2 substituents causes the rearrangement to occur preferentially through the alternate iminium ion stereoisomer (17 18 19).
Novel Synthetic Approach to the 8,10-Dimethyl anti-syn-anti-Perhydrophenanthrene Skeleton

An efficient and highly stereocontrolled approach to the 8,10-dimethyl anti-syn-anti-perhydrophenanthrene carbon skeleton starting with the Wieland−Miescher ketone is described. The approach centers on a Diels−Alder−angular methylation−deoxygenation sequence.
High-resolution data-driven model of the mouse connectome

Knowledge of mesoscopic brain connectivity is important for understanding inter- and intraregion information processing. Models of structural connectivity are typically constructed and analyzed wit...
Solid State Properties of Fullerenes and Fullerene-Based Materials

Publisher Summary This chapter provides an introduction of fullerenes by comparing gas phase and solid state properties, examining thin film and bulk crystal growth, and doping with alkali metals and other atoms. The fullerenes are all-carbon molecules with a closed-cage structure and nearly spherical appearance. These cages are derived from 12 pentagons and an appropriate number of hexagons. The chapter also discusses the electronic structure of correlated-electron systems in fullerenes, relating the electronic properties and vibrational properties to superconductivity. Early descriptions of fullerene formation suggested that small carbon chains would grow by the sequential addition of carbon radicals. Finally, the chapter discusses the latest additions to the fullerene family—namely, endofullerenes, tubes, and the buckyonions.
Synthesis of acyclic nucleoside analogs of 6-substituted 2-aminopurines and 2-amino-8-azapurines†

Several new acyclonucleoside purine and 8-azapurine analogs have been prepared from 2-amino-4,6-dichloropyrimidine (1) and 3-amino-1,2-propanediol (2a) and 4-amino-1-butanol (2b), respectively, as the starting materials. The new target compounds are: 2-amino-6-chloro-9-(2,3-dihydroxypropyl)purine (6a), 2-amino-6-chloro-9-(4-hydroxybutyl)purine (6b), 2-amino-6-chloro-9-(2,3-dihydroxypropyl)-8-azapurine (7a), 2-amino-6-chloro-9-(4-hydroxybutyl)-8-azapurine (7b), 9-(2,3-dihydroxypropyl)-8-azaguanine (8a), 9-(4-hydroxybutyl)-8-azaguanine (8b), 9-(2,3-dihydroxypropyl)-8-azathioguanine (9a), and 9-(4-hydroxybutyl)-8-azathioguanine (9b). Also, the requisite intermediate pyrimidine derivatives, 2,5-diamino-4-(2,3-dihydroxypropylamino)-6-chloropyrimidine (5a) and 2,5-diamino-4-(4-hydroxybutylamino)-6-chloropyrimidine (5b) are novel.
The synthesis of N-arylcyclopropylamines via palladium-catalyzed C–N bond formation

Abstract A variety of N-arylcyclopropylamines has been prepared in one step, by the Pd2(dba)3/BINAP/NaOtBu-catalyzed amination of an aryl bromide with cyclopropylamine. Compounds bearing the N-aryl substitutent (phenyl, 4-methylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-chlorophenyl, 1-napthyl, 9-anthryl, 9-phenanthryl, and 3-pyridyl) were prepared in isolated yields ranging from 43 to 99%. Overall, this chemistry represents a vast improvement over the previous multi-step procedures for the synthesis of compounds of this type.
Null Infinity Waveforms from Extreme-Mass-Ratio Inspirals in Kerr Spacetime

We describe the hyperboloidal compactification for Teukolsky equations in Kerr spacetime. We include null infinity on the numerical grid by attaching a hyperboloidal layer to a compact domain surrounding the rotating black hole and the orbit of an inspiralling point particle. This technique allows us to study, for the first time, gravitational waveforms from large- and extreme-mass-ratio inspirals in Kerr spacetime extracted at null infinity. Tests and comparisons of our results with previous calculations establish the accuracy and efficiency of the hyperboloidal layer method.
Intrinsic cooperativity potentiates parallel cis-regulatory evolution

Sometimes evolution repeats itself. For example, independent butterfly species can evolve the same warning pattern to ward off predators. In many cases, the reason that a certain trait crops up again and again in parallel evolution is unknown. One example is from the evolution of fungi, where a particular DNA sequence appeared several times independently in a large range of genes in different fungus species. This DNA sequence binds to a protein called Mcm1, which regulates nearby genes. Exactly why this DNA sequence has evolved in parallel so often in fungi has not been clear until now. Researchers want to find out what is so special about this DNA binding sequence for Mcm1, as there are many other proteins that could do the same job. Now, Sorrells et al. investigated this further by testing whether a binding site for another protein Rap1 often found close by had a role to play. Experiments using 162 different fungus species showed that Mcm1 binding sites had evolved 12 times in parallel. Rap1 and Mcm1 did indeed turn out to work together to regulate nearby genes. The two proteins interact with a large protein complex critical for activating genes. As a result, Mcm1 binding sites are more likely to evolve and play a role in gene regulation in different species when they are located near Rap1 binding sites. This could explain why this particular DNA sequence has evolved in parallel so many times. The same principle may apply to other genetic sequences involved in parallel evolution. With this understanding, it could be possible to predict when and where this event might occur in the future in fungi. This could be particularly useful for working towards being able to predict and anticipate the evolution of drug-resistant fungal pathogens.
Neomarinone, and new cytotoxic marinone derivatives, produced by a marine filamentous bacterium (actinomycetales)

Abstract Neomarinone (1), a novel metabolite possessing a new sesquiterpene- and polyketide-derived carbon skeleton, and several derivatives, 3–5, of the marinone class of naphthoquinone antibiotics, were isolated from the fermentation broth of a taxonomically-novel marine actinomycete (strain #CNH-099). The structures of the new compounds were determined by comprehensive NMR and mass spectral analyses. Neomarinone (1) and several of the marinone derivatives were shown to be moderately cytotoxic toward human cancer cells in in vitro testing.
Thin Film Growth of Transparent p‐type CuAlO2

Recent results suggests that may be a p‐type transparent conductor, but thin film synthesis is difficult because of the complex phase diagram. We report a robust method of making c‐axis oriented thin films. Thin film precursors of were deposited on sapphire (001) substrates by radio‐frequency sputtering and by pulsed‐laser deposition. Subsequent annealing in air at in a closed crucible containing and powders yielded nearly phase‐pure, biaxially textured . The film were p‐type and transparent with a gap of . ©1999 The Electrochemical Society
Phosphine-Catalyzed Allylic Substitution of Morita−Baylis−Hillman Acetates: Synthesis of N-Protected β-Aminophosphonic Acid Esters

A series of N-protected β-amino phosphonic acid esters have been prepared by phosphine-catalyzed allylic substitution of 2-(diethylphosphonyl)-substituted allylic acetates employing 4,5-dichloropht...
Colloquium: Opportunities in nanomagnetism

Nanomagnetism is the discipline dealing with magnetic phenomena specific to structures having dimensions in the submicron range. This Colloquium addresses the challenges and scientific problems in this emerging area, including its fabrication strategies, and describes experiments that explore new spin-related behaviors in metallic systems as well as theoretical efforts to understand the observed phenomena. As a subfield of nanoscience, nanomagnetism shares many of the same basic organizing principles such as geometric confinement, physical proximity, and chemical self-organization. These principles are illustrated by means of several examples drawn from the quests for ultrastrong permanent magnets, ultra-high-density magnetic recording media, and nanobiomagnetic sensing strategies. As a final example showing the synergetic relationships to other fields of science, this Colloquium discusses the manipulation of viruses to fabricate magnetic nanoparticles.
New synthesis of isoxazolidines

A new synthesis of 5-substituted isoxazolidines was developed by direct isoxazolidine ring formation of allylic hydroxylamines under acidic conditions. The cyclization process is an electrophilic SN1 type reaction. The formed carbocation intermediate is stabilized by electron rich groups (i.e., phenyl). A moiety that mediates oxonium ion formation (i.e., para-methoxy) accelerates the rate of product formation.
The Influence of Higher-Order Epistasis on Biological Fitness Landscape Topography

The effect of a mutation on the organism often depends on what other mutations are already present in its genome. Geneticists refer to such mutational interactions as epistasis. Pairwise epistatic effects have been recognized for over a century, and their evolutionary implications have received theoretical attention for nearly as long. However, pairwise epistatic interactions themselves can vary with genomic background. This is called higher-order epistasis, and its consequences for evolution are much less well understood. Here, we assess the influence that higher-order epistasis has on the topography of 16 published, biological fitness landscapes. We find that on average, their effects on fitness landscape declines with order, and suggest that notable exceptions to this trend may deserve experimental scrutiny. We conclude by highlighting opportunities for further theoretical and experimental work dissecting the influence that epistasis of all orders has on fitness landscape topography and on the efficiency of evolution by natural selection.
Trace Metal Imaging of Sulfate-Reducing Bacteria and Methanogenic Archaea at Single-Cell Resolution by Synchrotron X-Ray Fluorescence Imaging

Metal cofactors are required for many enzymes in anaerobic microbial respiration. This study examined iron, cobalt, nickel, copper, and zinc in cellular and abiotic phases at the single-cell scale for a sulfate-reducing bacterium (Desulfococcus multivorans) and a methanogenic archaeon (Methanosarcina acetivorans) using synchrotron X-ray fluorescence microscopy. Relative abundances of cellular metals were also measured by inductively coupled plasma mass spectrometry. For both species, zinc and iron were consistently the most abundant cellular metals. M. acetivorans contained higher nickel and cobalt content than D. multivorans, likely due to elevated metal requirements for methylotrophic methanogenesis. Cocultures contained spheroid zinc sulfides and cobalt/copper sulfides.
Mass-surveillance without the State: Strongly Undetectable Algorithm-Substitution Attacks.

We present new algorithm-substitution attacks (ASAs) on symmetric encryption that improve over prior ones in two ways. First, while prior attacks only broke a sub-class of randomized schemes having a property called coin injectivity, our attacks break all randomized schemes. Second, while prior attacks are stateful, ours are stateless, achieving a notion of strong undetectability that we formalize. Together this shows that ASAs are an even more dangerous and powerful mass surveillance method than previously thought. Our work serves to increase awareness about what is possible with ASAs and to spur the search for deterrents and countermeasures. 1 Department of Computer Science & Engineering, University of California San Diego, 9500 Gilman Drive, La Jolla, California 92093, USA. Email: mihir@eng.ucsd.edu. URL: http://cseweb.ucsd.edu/~mihir/. Supported in part by NSF grants CNS-1116800 and CNS-1228890 and a gift from Microsoft. This work was done in part while Bellare was visiting the Simons Institute for the Theory of Computing, supported by the Simons Foundation and by the DIMACS/Simons Collaboration in Cryptography through NSF grant CNS-1523467. 2 Department of Computer Science & Engineering, University of California San Diego, 9500 Gilman Drive, La Jolla, California 92093, USA. Email: jsjaeger@eng.ucsd.edu. URL: http://cseweb.ucsd.edu/~jsjaeger/. Supported in part by NSF grants CNS-1116800 and CNS-1228890. 3 Department of Computer Science & Engineering, University of California San Diego, 9500 Gilman Drive, La Jolla, California 92093, USA. Email: dakane@eng.ucsd.edu. URL: http://cseweb.ucsd.edu/~dakane/.
Reward Prediction Error Modulates Saccade Vigor

Movement vigor, defined as the reciprocal of the latency from availability of reward to its acquisition, changes with reward magnitude: movements exhibit shorter reaction time and increased velocity when they are directed toward more rewarding stimuli. This invigoration may be due to release of dopamine before movement onset, which has been shown to be modulated by events that signal reward prediction error (RPE). Here, we generated an RPE event in the milliseconds before movement onset and tested whether there was a relationship between RPE and vigor. Human subjects (both sexes) made saccades toward an image. During execution of the primary saccade, we probabilistically changed the position and content of that image, encouraging a secondary saccade. On some trials, the content of the secondary image was more valuable than the first image, resulting in a positive RPE (+RPE) event that preceded the secondary saccade. On other trials, this content was less valuable (-RPE event). We found that reaction time of the secondary saccade was affected in an orderly fashion by the magnitude and direction of the preceding RPE event: the most vigorous saccades followed the largest +RPE, whereas the least vigorous saccades followed the largest -RPE. Presence of the secondary saccade indicated that the primary saccade had experienced a movement error, inducing trial-to-trial adaptation. However, this learning from movement error was not modulated by the RPE event. The data suggest that RPE events, which are thought to transiently alter the release of dopamine, modulate the vigor of the ensuing movement.SIGNIFICANCE STATEMENT Does dopamine release in response to a stimulus serve to invigorate the ensuing movement? To test this hypothesis, we relied on the fact that reward prediction error (RPE) is a strong modulator of dopamine. Our innovation was a task in which an RPE event occurred precisely before onset of a stimulus-driven movement. We probabilistically produced a combination of large or small, negative or positive RPE events and observed that saccade vigor carried a robust signature of the preceding RPE event: high vigor saccades followed +RPE events, whereas low vigor saccades followed -RPE events. This suggests that in humans, vigor is partly controlled through release of dopamine in the moments before onset of a movement.
Deconstructing isolation-by-distance: the genomic consequences of limited dispersal

Geographically limited dispersal can shape genetic population structure and result in a correlation between genetic and geographic distance, commonly called isolation-by-distance. Despite the prevalence of isolation-by-distance in nature, to date few studies have empirically demonstrated the processes that generate this pattern, largely because few populations have direct measures of individual dispersal and pedigree information. Intensive, long-term demographic studies and exhaustive genomic surveys in the Florida Scrub-Jay (Aphelocoma coerulescens) provide an excellent opportunity to investigate the influence of dispersal on genetic structure. Here, we used a panel of genome-wide SNPs and extensive pedigree information to explore the role of limited dispersal in shaping patterns of isolation-by-distance in both sexes, and at an exceedingly fine spatial scale (within ~10 km). Isolation-by-distance patterns were stronger in male-male and male-female comparisons than in female-female comparisons, consistent with observed differences in dispersal propensity between the sexes. Using the pedigree, we demonstrated how various genealogical relationships contribute to fine-scale isolation-by-distance. Simulations using field-observed distributions of male and female natal dispersal distances showed good agreement with the distribution of geographic distances between breeding individuals of different pedigree relationship classes. Furthermore, we built coalescent simulations parameterized by the observed dispersal curve, population density, and immigration rate, and showed how incorporating these extensions to Malecot's theory of isolation-by-distance allows us to accurately reconstruct observed sex-specific isolation-by-distance patterns in autosomal and Z-linked SNPs. Therefore, patterns of fine-scale isolation-by-distance in the Florida Scrub-Jay can be well understood as a result of limited dispersal over contemporary timescales.
A selective procedure for α-alkenylation of enones involving Pd-catalyzed alkenyl-alkenyl coupling and its application to a convergent and efficient synthesis of nakienone B

Abstract A convergent and efficient synthesis of a marine natural product, nakienone B (1), was achieved using a new protocol for α-alkenylation of enones involving Pd-catalyzed coupling of alkenylzincs with alkenyl iodides. This protocol features (i) avoidance of acidic conditions and (ii) flexibility in charge affinity pattern with respect to the two akenyl groups to be coupled.
Transition-metal-free synthesis of (Z)-3-ylidenephthalides from 2-acyl-benzoic acids

Abstract We report a highly efficient method for the synthesis of (Z)-3-ylidenephthalides via intramolecular cyclization of readily available 2-acyl-benzoic acids mediated by TSTU at room temperature. Using this method, diversely substituted (Z)-3-ylidenephthalides have been generated in good to excellent yields. The application of the method is highlighted by gram-scale preparation of the antiplatelet drug n-butylphthalide.
The allenic Alder-ene reaction : constitutional group selectivity and its application to the synthesis of ovalicin

The scope of the novel allenic Alder-ene reaction using Rh(I) and Ir(I) catalysts has been extended to differentially substituted 1,1,3-trisubstituted allenes. This allenyl substitution pattern can give three possible cross-conjugated triene products. The selectivity of this transformation can be controlled by varying reaction temperature, solvent, and catalyst. Progress toward the synthesis of ovalicin using this triene forming protocol is described.
Reproducible Bioconductor workflows using browser-based interactive notebooks and containers

Objective Bioinformatics publications typically include complex software workflows that are difficult to describe in a manuscript. We describe and demonstrate the use of interactive software notebooks to document and distribute bioinformatics research. We provide a user-friendly tool, BiocImageBuilder, that allows users to easily distribute their bioinformatics protocols through interactive notebooks uploaded to either a GitHub repository or a private server. Materials and methods We present four different interactive Jupyter notebooks using R and Bioconductor workflows to infer differential gene expression, analyze cross-platform datasets, process RNA-seq data and KinomeScan data. These interactive notebooks are available on GitHub. The analytical results can be viewed in a browser. Most importantly, the software contents can be executed and modified. This is accomplished using Binder, which runs the notebook inside software containers, thus avoiding the need to install any software and ensuring reproducibility. All the notebooks were produced using custom files generated by BiocImageBuilder. Results BiocImageBuilder facilitates the publication of workflows with a point-and-click user interface. We demonstrate that interactive notebooks can be used to disseminate a wide range of bioinformatics analyses. The use of software containers to mirror the original software environment ensures reproducibility of results. Parameters and code can be dynamically modified, allowing for robust verification of published results and encouraging rapid adoption of new methods. Conclusion Given the increasing complexity of bioinformatics workflows, we anticipate that these interactive software notebooks will become as necessary for documenting software methods as traditional laboratory notebooks have been for documenting bench protocols, and as ubiquitous.
The NOvA Experiment: Status and Outlook

The NOvA long-baseline neutrino oscillation experiment is currently under construction and will use an upgraded NuMI neutrino source at Fermilab and a 14-kton detector at Ash River, Minnesota to explore the neutrino sector. NOvA uses a highly active, finely segmented detector design that offers superb event identification capability, allowing precision measurements of ν_e/ν_e appearance and ν_µ/ν_µ disappearance, through which NOvA will provide constraints on θ_13, θ_23, |Δm^2_(atm)|, the neutrino mass hierarchy, and the CP-violating phase δ. In this article, we review NOvA's uniquely broad physics scope, including sensitivity updates in light of the latest knowledge of θ_13, and we discuss the experiment's construction and operation timeline.
Enhancing Interconnect Reliability and Performance by Converting Tantalum to 2D Layered Tantalum Sulfide at Low Temperature

The interconnect half-pitch size will reach ≈20 nm in the coming sub-5 nm technology node. Meanwhile, the TaN/Ta (barrier/liner) bilayer stack has to be >4 nm to ensure acceptable liner and diffusion barrier properties. Since TaN/Ta occupy a significant portion of the interconnect cross-section and they are much more resistive than Cu, the effective conductance of an ultrascaled interconnect will be compromised by the thick bilayer. Therefore, 2D layered materials have been explored as diffusion barrier alternatives. However, many of the proposed 2D barriers are prepared at too high temperatures to be compatible with the back-end-of-line (BEOL) technology. In addition, as important as the diffusion barrier properties, the liner properties of 2D materials must be evaluated, which has not yet been pursued. Here, a 2D layered tantalum sulfide (TaSx ) with ≈1.5 nm thickness is developed to replace the conventional TaN/Ta bilayer. The TaSx ultrathin film is industry-friendly, BEOL-compatible, and can be directly prepared on dielectrics. The results show superior barrier/liner properties of TaSx compared to the TaN/Ta bilayer. This single-stack material, serving as both a liner and a barrier, will enable continued scaling of interconnects beyond 5 nm node.
Total Synthesis of Immunosuppressants: Unified Strategies Exploiting Dithiane Couplings and σ-Bond Olefin Constructions†

Although the immunomodulator cyclosporin A (CsA, 1)1 has engendered dramatic progress in organ transplantation, recurrent clinical complications have stimulated an ongoing search for more potent and less toxic agents. The discovery of FK506 (2)2 and the reinvestigation of rapamycin (3)3 and demethoxyrapamycin (4)4 heralded major advances in immunosuppressant research; not only are these natural products more potent than CsA, but they also selectively inhibit two distinct steps in the immune response. CsA and FK506, bound to immunophilins cyclophilin A and FKBP, respectively, prevent cells from entering the G1 phase of the cell cycle, whereas the rapamycin-FKBP complex blocks progression into the S phase. The molecular biology, immunology and phar-
Ni(II) Tol-BINAP-Catalyzed Enantioselective Michael Reactions of β-Ketoesters and Unsaturated N-Acylthiazolidinethiones

The enantioselective addition of β-ketoesters to unsaturated N-acylthiazolidinethiones catalyzed by Ni(II) Tol-BINAP Lewis acid complexes is reported. Notable features of this reaction are its oper...
Fundamental Studies of P(GeH3)3, As(GeH3)3, and Sb(GeH3)3: Practical n-Dopants for New Group IV Semiconductors

We introduce a new chemical approach to the incorporation of high concentrations of active n-dopant atoms into group-IV semiconductors via low temperature, low cost, high efficiency routes involving carbon-free single-source inorganic hydrides. Controlled substitution of As into Ge-based semiconductors is made possible by the use of As(GeH3)3, which furnishes structurally and chemically compatible AsGe3 molecular cores. As(GeH3)3 is synthesized in high purity yields (∼75%) via a new single-step method based on reactions of GeH3Br and As[Si(CH3)3]3, circumventing the need for toxic and unstable starting materials as used in earlier approaches. We demonstrate the development of a viable route to the entire family of compounds M(GeH3)3 {M = P, As, Sb}, suitable for doping or superdoping applications of a wide range of functional materials. The structural, vibrational, and thermochemical properties of M(GeH3)3 are simulated for the first time via density functional theory calculations using both all-electron ...
Search for Yield in Large International Corporate Bonds : Investor Behavior and Firm Responses

Emerging market corporations have significantly increased their borrowing in international markets since 2008. We show that this increase was driven by large-denomination bond issuances, most of them with face value of exactly US$500 million. Large issuances are eligible for inclusion in important international market indexes. These bonds appeal to institutional investors because they are more liquid and facilitate targeting market benchmarks. We find that the rewards of issuing index-eligible bonds rose drastically after 2008. Emerging market firms were able to cut their cost of funds by roughly 100 basis points by issuing bonds with a face value equal to or greater than US$500 million relative to smaller bonds. Firms contemplating whether to take advantage of this cost saving face a tradeoff: they can benefit from the lower yields associated with large, index-eligible bonds, but they pay the potential cost of having to hoard low-yielding cash assets if their investment opportunities are less than US$500 million. Because of the post-2008 “size yield discount,” many companies issued index-eligible bonds, while substantially increasing their cash holdings. The willingness to issue large bonds and hoard cash was greater for firms in countries with high carry trade opportunities that reduced the cost of holding cash. We present evidence suggesting that these post-2008 behaviors reflected a search for yield by institutional investors into higher-risk securities. These patterns are not apparent in the issuance of investment grade bonds by firms in developed economies. Institutional subscribers to the NBER working paper series, and residents of developing countries may download this paper without additional charge at www.nber.org.
Shill bidding and trust

Abstract Shill bidding occurs when the seller enters a bid for her own item. A bidder forms expectations about whether the seller is participating and must decide whether to trust that she is not engaging in what may be viewed as an unkind practice. A trusting individual can be expected to respond differently than an untrusting one. Auctions with the potential for shill bidding allow for trust to be expressed. We design an experiment considering first and second-price auctions with and without the potential for shill bidding. A Trust Game is used to measure trust. We document that the potential for shill bidding leads to lower bids being submitted. Heterogeneous effects are explored. Bidding behavior can be explained in part by one’s level of trust and expectations of other’s trust. In first-price auctions, less trusting individuals submit lower bids and respond to the potential for shill bidding by lowering their bids. In second-price auctions, subjects with lower expectations of the trust others have bid less and respond to shill bidding by further lowering their bid. Second, sellers engage in shill bidding but rarely win. Third, the potential for shill bidding adversely affects revenue and allocative efficiency.
A TRIPHOSPHOLYL-SUBSTITUTED PHOSPHINE

Abstract Tris(2,3,4,5-tetramethylphospholyl)phosphine (1) has been prepared via the reaction of Li(PC4Me4) with PCl3. The structure of 1 was determined by single-crystal X-ray diffraction: triclinic, space group P with a = 8.795(2), b = 11.489(2), c = 14.557(3) A, α = 72.89(3), β = 88.92(3), γ = 67.69(3)°, V = 1293.4(7) A3 and Z = 2.
Nanocomposite Materials for Optical Applications

A substantial amount of work has been carried out in the area of nanocomposite materials for optical applications. Composites are typically constructed by embedding an optically functional phase into a processable, transparent matrix material. By doing so, the optical properties can be utilized in more technologically important forms such as films and fibers. This review covers many areas of optical composite research to date. Composites with second- and third-order nonlinearities and laser amplification properties are discussed with examples from the recent literature. Other composites, including transparent magnets, may be made using similar structures. The principles used to construct these composites may have important technological applications soon and are therefore summarized in this review.
Sequential cross-metathesis/phosphorus-based olefination : stereoselective synthesis of 2,4-dienoates

Abstract A variety of stereodefined 2,4-dienoates have been prepared in a stereoselective manner by sequencing olefin cross-metathesis (CM) with phosphorus-based olefination reactions (Wittig and Horner–Wadsworth–Emmons) in good yield using commercially available reagents.
Improved methodology for the asymmetric alkylation of aldehydes employing bis(sulfonamide) complexes

Abstract We report an improved procedure for the asymmetric transfer of alkyl groups from zinc to aldehydes utilizing bis(sulfonamide) ligands. The new methodology is easier to perform and, in some cases, provides the alcohol products with higher enantioselectivities than the original methodology.
Dicationic intermediates involving protonated amides: dual modes of reactivity including the acylation of arenes.

In the Bronsted superacid CF3SO3H (triflic acid), amides are able to form reactive, dicationic electrophiles. It is shown that these dicationic intermediates participate in two distinctly different types of electrophilic reactions. The protonated amide increases the reactivity of an adjacent electrophilic group, and the protonated amide group itself shows enhanced reactivity arising from an adjacent cationic charge. In the latter case, several types of amides are even capable of reacting with benzene by Friedel−Crafts acylation.
Automated summarization evaluation (ASE) using natural language processing tools

Summarization is an effective strategy to promote and enhance learning and deep comprehension of texts. However, summarization is seldom implemented by teachers in classrooms because the manual evaluation of students’ summaries requires time and effort. This problem has led to the development of automated models of summarization quality. However, these models often rely on features derived from expert ratings of student summarizations of specific source texts and are therefore not generalizable to summarizations of new texts. Further, many of the models rely of proprietary tools that are not freely or publicly available, rendering replications difficult. In this study, we introduce an automated summarization evaluation (ASE) model that depends strictly on features of the source text or the summary, allowing for a purely text-based model of quality. This model effectively classifies summaries as either low or high quality with an accuracy above 80%. Importantly, the model was developed on a large number of source texts allowing for generalizability across texts. Further, the features used in this study are freely and publicly available affording replication.
SYNTHESIS OF FLUORINATED OLEFINS VIA THE PALLADIUM CATALYZED CROSS-COUPLING REACTION OF 1-FLUOROVINYL HALIDES WITH ORGANOBORANES

Abstract The palladium catalyzed cross-coupling reaction of 1-fluorovinyl halides 1–4 with organoboranes proceeds under Suzuki conditions with retention on configuration to give 1-substituted 1-fluoroolefins 6–8 in good to excellent yields.
Alkynyliodonium Salts in Organic Synthesis. Dihydrofuran Formation via a Formal Stevens Shift of a Carbon Substituent within a Disubstituted-Carbon Oxonium Ylide

The addition of p-toluenesulfinate to the silyl, 1-furanyl, and 1-pyranyl ethers of 1-hydroxybut-3-ynyl(phenyl)iodonium triflate triggers a sequence of reactions that ultimately delivers 2-substituted 3-p-toluenesulfonyldihydrofuran products in variable yields. A putative 1,2-group shift within an unsaturated oxonium ylide (Stevens rearrangement) accounts for the oxygen-to-carbon transfer of the ether substituent. Deuterium labeling studies clarify the mechanistic course of this shift by providing evidence consistent with intramolecular substituent transfer and by identifying the primary source of the proton that intercepts the ylide in the major yield-limiting process.
Silent Springs: The Nature of Water and Israel’s Military Occupation

Drawing on interviews with, and observations of, officials from Israel’s Nature and Park Authority, fieldworkers from environmental and human rights nonprofits, and local Palestinian farmers, this ...