cssi/SciSciGPT-SciSciNet huggingface dataset:
Political Activism and Research Ethics

Those who care about and engage in politics frequently fall victim to cognitive bias. Concerns that such bias impacts scholarship recently have prompted debates — notably, in philosophy and psychology — on the proper relationship between research and politics. One proposal emerging from these debates is that researchers studying politics have a professional duty to avoid political activism because it risks biasing their work. While sympathetic to the motivations behind this proposal, I suggest several reasons to reject a blanket duty to avoid activism: (1) even if it reduced bias, this duty would make unreasonable demands on researchers; (2) this duty could hinder research by limiting viewpoint diversity; (3) this duty wrongly implies that academia offers a relative haven from bias compared to politics; and (4) not all forms of political activism pose an equal risk of bias. None of these points suggest that researchers should ignore the risk of bias. Rather, researchers should focus on stronger evidence-based strategies for reducing bias than a blanket recommendation to avoid politics.
Plasma-aided manufacturing

Plasma-aided manufacturing is used for producing new materials with unusual and superior properties, for developing new chemical compounds and processes, for machining, and for altering and refining materials and surfaces. Plasma-aided manufacturing has direct applications to semiconductor fabrication, materials synthesis, welding, lighting, polymers, anti-corrosion coatings, machine tools, metallurgy, electrical and electronics devices, hazardous waste removal, high performance ceramics, and many other items in both the high-technology and the more traditional industries in the United States.
A Secure and Efficient Parallel-Dependency RFID Grouping-Proof Protocol

In this time of ubiquitous computing and the evolution of the Internet of Things (IoT), the deployment and development of Radio Frequency Identification (RFID) is becoming more extensive. Proving the simultaneous presence of a group of RFID tagged objects is a practical need in many application areas within the IoT domain. Security, privacy, and efficiency are central issues when designing such a grouping-proof protocol. This work is motivated by our serial-dependent and Sundaresan et al.’s grouping-proof protocols. In this paper, we propose a light, improved offline protocol: parallel-dependency grouping-proof protocol (PDGPP). The protocol focuses on security, privacy, and efficiency. PDGPP tackles the challenges of including robust privacy mechanisms and accommodates missing tags. It is scalable and complies with EPC C1G2.
Small-Data, Large-Scale Linear Optimization with Uncertain Objectives

Optimization applications often depend on a huge number of uncertain parameters. In many contexts, however, the amount of relevant data per parameter is small, and hence, we may only have imprecise...
Heterostructured Approaches to Efficient Thermoelectric Materials

A key challenge for the materials chemist is the development of controllable and straightforward synthetic methodologies that will integrate multiple phases/compositions with scalar designed physical properties. The intent of this Perspective is to give a brief summary of some of the current bulk-scaled approaches that might help guide researchers in the design of optimal heterostructures in large quantity for the further improvement of thermoelectric conversion efficiency. Examples of two-phase combinations on different length scales will be discussed with a focus on the hot carrier filtering effect that results from the selective scattering of carriers with different energies. On the basis of this strategy, heterostructures fabricated by both the bottom-up solution approaches at low temperature and top-down solid-state deposition routes that show promise in improving the thermoelectric figure of merit are highlighted.
Zirconocene-mediated deoxygenative ring contractions of vinyl-substituted carbohydrates: An expedient route to enantiomerically pure, densely functionalized 4-to-8-membered carbocycles

Abstract The recent finding that the powerfully electrophilic zirconocene equivalent known as “Cp 2 Zr” is capable of transforming vinyl furanosides and pyranosides into enantiomerically pure, highly functionalized cis -2-vinyl cyclobutanols and cyclopentanols has been extended in a number of directions. The synthetic potential of this methodology is illustrated by the variety of carbocycles that can be produced, ranging from cyclobutanones, a carbacyclic nucleoside, cyclooctane polyols, and medium-ring carbohydrate mimics. Many of the key transformations are evaluated in terms of transition state energetics.
A High Temperature Liquid Plasma Model of the Sun

In this work, a liquid model of the Sun is presented wherein the entire solar mass is viewed as a high density/high energy plasma. This model challenges our current understanding of the densities associated with the internal layers of the Sun, advocating a relatively constant density, almost independent of radial position. The incompressible nature of liquids is advanced to prevent solar collapse from gravitational forces. The liquid plasma model of the Sun is a non-equilibrium approach, where nuclear reactions occur throughout the solar mass. The primary means of addressing internal heat transfer are convection and conduction. As a result of the convective processes on the solar surface, the liquid model brings into question the established temperature of the solar photosphere by highlighting a violation of Kirchhoff’s law of thermal emission. Along these lines, the model also emphasizes that radiative emission is a surface phenomenon. Evidence that the Sun is a high density/high energy plasma is based on our knowledge of Planckian thermal emission and condensed matter, including the existence of pressure ionization and liquid metallic hydrogen at high temperatures and pressures. Prior to introducing the liquid plasma model, the historic and scientific justifications for the gaseous model of the Sun are reviewed and the gaseous equations of state are also discussed.
A quasi-integral controller for adaptation of genetic modules to variable ribosome demand

The behavior of genetic circuits is often poorly predictable. A gene’s expression level is not only determined by the intended regulators, but also affected by changes in ribosome availability imparted by expression of other genes. Here we design a quasi-integral biomolecular feedback controller that enables the expression level of any gene of interest (GOI) to adapt to changes in available ribosomes. The feedback is implemented through a synthetic small RNA (sRNA) that silences the GOI’s mRNA, and uses orthogonal extracytoplasmic function (ECF) sigma factor to sense the GOI’s translation and to actuate sRNA transcription. Without the controller, the expression level of the GOI is reduced by 50% when a resource competitor is activated. With the controller, by contrast, gene expression level is practically unaffected by the competitor. This feedback controller allows adaptation of genetic modules to variable ribosome demand and thus aids modular construction of complicated circuits. Competition for shared cellular resources often renders genetic circuits poorly predictable. Here the authors design a biomolecular quasi-integral controller that allows gene expression to adapt to variable demand in translation resources.
Proteomic and genomic characterization of a yeast model for Ogden syndrome.

Naa10 is a Nα-terminal acetyltransferase that, in a complex with its auxiliary subunit Naa15, co-translationally acetylates the α-amino group of newly synthetized proteins as they emerge from the ribosome. Roughly 40-50% of the human proteome is acetylated by Naa10, rendering this an enzyme with one of the most broad substrate ranges known. Recently, we reported an X-linked disorder of infancy, Ogden syndrome, in two families harboring a c.109 T > C (p.Ser37Pro) variant in NAA10. In the present study we performed in-depth characterization of a yeast model of Ogden syndrome. Stress tests and proteomic analyses suggest that the S37P mutation disrupts Naa10 function and reduces cellular fitness during heat shock, possibly due to dysregulation of chaperone expression and accumulation. Microarray and RNA-seq revealed a pseudo-diploid gene expression profile in ΔNaa10 cells, likely responsible for a mating defect. In conclusion, the data presented here further support the disruptive nature of the S37P/Ogden mutation and identify affected cellular processes potentially contributing to the severe phenotype seen in Ogden syndrome. Data are available via GEO under identifier GSE86482 or with ProteomeXchange under identifier PXD004923.
Mitsunobu reactions of aliphatic alcohols and bulky phenols

Alkylation of hydrazinedicarboxylate (a Mitsunobu by-product) is not a notable problem in common Mitsunobu alkyl aryl etherification reactions. Good yields can be obtained with a wide range of solvents. However, this side reaction can cause yield reduction for the reactions of sterically hindered phenols and primary alcohols. To suppress the side reaction, solvent effect was investigated. It was found that hydrazinedicarboxylate is about five times less soluble in diethyl ether than in THF, and the yields are improved for ortho-substituted phenols of a wide range of steric hindrance using diethyl ether as the solvent instead of THF which is the more commonly used for Mitsunobu reactions.
A Scalable Route to Trisubstituted (E)-Vinyl Bromides

An effective, readily scalable two-step synthesis of trisubstituted (E)-vinyl bromides involving bromination of α,β-unsaturated lactones followed by hydrolytic fragmentation has been developed. Several trisubstituted (E)-vinyl bromides, including multigram quantities of (+)-(E)-4-bromo-2-methyl-3-pentenol, a synthetic intermediate required for the C(8)−C(11) moieties of (+)-tedanolide (1) and (+)-13-deoxytedanolide (2), illustrate the utility of this protocol.
Direct, facile synthesis of acyl azides and nitriles from carboxylic acids using bis(2-methoxyethyl)aminosulfur trifluoride

A mild, efficient, and practical method for the one-step synthesis of acyl azides from carboxylic acids using bis(2-methoxyethyl)aminosulfur trifluoride is described. The reaction was easily extended to the synthesis of the corresponding nitriles by the inclusion of phosphorous reagents. The method can be applied to the synthesis of optically active nitriles in high yields, and is compatible with fluorous phosphines.
FADS1 and the Timing of Human Adaptation to Agriculture

Variation at the FADS1/FADS2 gene cluster is functionally associated with differences in lipid metabolism and is often hypothesized to reflect adaptation to an agricultural diet. Here, we test the evidence for this relationship using both modern and ancient DNA data. We show that almost all the inhabitants of Europe carried the ancestral allele until the derived allele was introduced ∼8,500 years ago by Early Neolithic farming populations. However, we also show that it was not under strong selection in these populations. We find that this allele, and other proposed agricultural adaptations at LCT/MCM6 and SLC22A4, were not strongly selected until much later, perhaps as late as the Bronze Age. Similarly, increased copy number variation at the salivary amylase gene AMY1 is not linked to the development of agriculture although, in this case, the putative adaptation precedes the agricultural transition. Our analysis shows that selection at the FADS locus was not tightly linked to the initial introduction of agriculture and the Neolithic transition. Further, it suggests that the strongest signals of recent human adaptation in Europe did not coincide with the Neolithic transition but with more recent changes in environment, diet, or efficiency of selection due to increases in effective population size.
Cyclic nitriles: diastereoselective alkylations.

Diastereoselective alkylations of metalated conformationally locked 4-tert-butylcyclohexanecarbonitrile are highly diastereoselective with magnesium and copper counterions but only modestly diastereoselective with lithium as the counterion. Selective generation of diverse metalated nitriles is readily achieved through bromine−magnesium, −copper, and −lithium exchange reactions of the corresponding bromonitrile or, for lithium, by deprotonating the parent nitrile with lithium diethylamide. Collectively, high alkylation stereoselectivities correlate with the retentive alkylations of C-metalated nitriles, whereas N-lithiated nitriles alkylate with modest selectivity, reflecting minimal steric differences in the corresponding axial and equatorial electrophile trajectories.
Low Power Depth Estimation of Rigid Objects for Time-of-Flight Imaging

Depth sensing is useful in a variety of applications that range from augmented reality to robotics. Time-of-flight (TOF) cameras are appealing because they obtain dense depth measurements with minimal latency. However, for many battery-powered devices, the illumination source of a TOF camera is power hungry and can limit the battery life of the device. To address this issue, we present an algorithm that lowers the power for depth sensing by reducing the usage of the TOF camera and estimating depth maps using concurrently collected images. Our technique also adaptively controls the TOF camera and enables it when an accurate depth map cannot be estimated. To ensure that the overall system power for depth sensing is reduced, we design our algorithm to run on a low power embedded platform, where it outputs $640\times 480$ depth maps at 30 frames per second. We evaluate our approach on several RGB-D datasets, where it produces depth maps with an overall mean relative error of 0.96% and reduces the usage of the TOF camera by 85%. When used with commercial TOF cameras, we estimate that our algorithm can lower the total power for depth sensing by up to 73%.
Microtubule bundling by MAP65-1 protects against severing by inhibiting the binding of katanin

The microtubule-severing enzyme katanin (KTN1) regulates the organization and turnover of microtubule arrays by the localized breakdown of microtubule polymers. In land plants, KTN1 activity is essential for the formation of linearly organized cortical microtubule arrays that determine the axis of cell expansion. Cell biological studies have shown that even though KTN1 binds to the sidewalls of single and bundled microtubules, severing activity is restricted to microtubule cross-over and nucleation sites, indicating that cells contain protective mechanisms to prevent indiscriminate microtubule severing. Here, we show that the microtubule-bundling protein MAP65-1 inhibits KTN1-mediated microtubule severing in vitro. Severing is inhibited at bundled microtubule segments and the severing rate of nonbundled microtubules is reduced by MAP65-1 in a concentration-dependent manner. Using various MAP65-1 mutant proteins, we demonstrate that efficient cross-linking of microtubules is crucial for this protective effect and that microtubule binding alone is not sufficient. Reduced severing due to microtubule bundling by MAP65-1 correlated to decreased binding of KTN1 to these microtubules. Taken together, our work reveals that cross-linking of microtubules by MAP65-1 confers resistance to severing by inhibiting the binding of KTN1 and identifies the structural features of MAP65-1 that are important for this activity.
Synthesis of benzo[6,7][1,4]diazepino[1,2-b]indazol-7(6H)-ones and benzo[f]pyrazolo[1,5-a][1,4]diazepin-4-ones via CuI/l-proline catalyzed intramolecular N2-arylation

Abstract Facile intramolecular N2-arylation catalyzed by CuI/ l -proline has been developed to prepare in good to excellent yields a variety of benzo[ f ]pyrazolo[1,5- a ][1,4]diazepin-4-ones and previously unreported benzo[6,7][1,4]diazepino[1,2- b ]indazol-7(6 H )-ones.
A new anionic cyclization reaction: Condensation of benzoate esters with nitriles to give 3-amino-2-inden-1-ones

Abstract A new type of anionic cyclization has been discovered in which the condensation of alkyl benzoates with simple nitriles, induced by an excess of LDA, leads directly to substituted-3-amino-2-inden-1-ones. The corresponding intermediate β-oxonitriles undergo cyclization to give, in most instances, superior yields of the same compounds. Acid hydrolysis of these indenones leads in high yield to the corresponding biologically active (anticoagulant) indandiones.
Synthesis of a second-generation pseudopeptide platform

Abstract A synthetic pathway is presented to a functionalized pseudopeptide molecular platform for use in supramolecular and solution-phase combinatorial chemistry. The platform contains amino acids with quaternary asymmetric centers, the configurations of which are determined by the method of synthesis.
Synthesis, Characterization, and Ion Exchange Behavior of a Framework Potassium Titanium Trisilicate K2TiSi3O9·H2O and Its Protonated Phases

A framework potassium titanium silicate K2TiSi3O9·H2O, compound I, was synthesized by the reaction of a titanium−hydrogen peroxide complex and SiO2 in alkaline media under mild hydrothermal conditions (180 °C). This compound was converted to the corresponding sodium phase, Na2TiSi3O9·H2O (IV) and two proton-containing phases, K1.26H0.74TiSi3O9·1.8H2O (II) and K0.3H1.7TiSi3O9·2.4H2O (III) by ion exchange. These products were characterized by elemental analysis, TGA, FT-IR, MAS 29Si NMR, and X-ray diffraction. The ion exchange behavior of K2TiSi3O9·H2O and K0.3H1.7TiSi3O9·2H2O toward alkali, alkaline earth, and some transition metal ions solutions was studied. A high affinity of the protonic form of titanium trisilicate exchanger for cesium and potassium makes it promising for radionuclide-contaminated groundwater treatment and certain analytical separations. The crystal structure of K2TiSi3O9·H2O was found to be isomorphous with that of the zirconium analogue and contains a framework enclosing two types of...
Synthesis of Azacrown Macrocycles and Related Compounds by a Crablike Cyclization Method: A Short Review

This paper summarizes the application of bis(α-chloroamide)s for the preparation of azamacrocyclic ligands. Bis(α-chloroamide)s look like crabs with two reactive claws so the method is called the c...
Rapid Expansion of Immune-Related Gene Families in the House Fly, Musca domestica

The house fly, Musca domestica, occupies an unusual diversity of potentially septic niches compared with other sequenced Dipteran insects and is a vector of numerous diseases of humans and livestock. In the present study, we apply whole-transcriptome sequencing to identify genes whose expression is regulated in adult flies upon bacterial infection. We then combine the transcriptomic data with analysis of rates of gene duplication and loss to provide insight into the evolutionary dynamics of immune-related genes. Genes up-regulated after bacterial infection are biased toward being evolutionarily recent innovations, suggesting the recruitment of novel immune components in the M. domestica or ancestral Dipteran lineages. In addition, using new models of gene family evolution, we show that several different classes of immune-related genes, particularly those involved in either pathogen recognition or pathogen killing, are duplicating at a significantly accelerated rate on the M. domestica lineage relative to other Dipterans. Taken together, these results suggest that the M. domestica immune response includes an elevated diversity of genes, perhaps as a consequence of its lifestyle in septic environments.
NOVEL NUCLEOSIDES VIA INTRAMOLECULAR FUNCTIONALIZATION OF 2,2'-ANHYDROURIDINE DERIVATIVES

Abstract The generation of novel ribonucleoside analogues derived from 2,2′-anhydrouridines by a 3′-hydroxyl directed intramolecular nucleophilic substitution of the 2′-position is described. The methodology allows for the efficient, regio- and stereoselective elaboration of the 2′-position, often under exceptionally mild reaction conditions.
Spectral contrast optical coherence tomography angiography enables single-scan vessel imaging

Optical coherence tomography angiography relies on motion for contrast and requires at least two data acquisitions per pointwise scanning location. We present a method termed spectral contrast optical coherence tomography angiography using visible light that relies on the spectral signatures of blood for angiography from a single scan using endogenous contrast. We demonstrate the molecular sensitivity of this method, which enables lymphatic vessel, blood, and tissue discrimination.
SOME CHEMISTRY OF AROMATIC FLUORINE CONTAINING RADICAL ANIONS

Abstract A review of the literature and ab initio calculations show that aromatic fluorine containing radical anions do not readily dissociate into aryl radicals and fluoride ions. © 1997 Elsevier Science Ltd.
Integrating Coexpression Networks with GWAS to Prioritize Causal Genes in Maize

Genome-wide association studies (GWAS) have identified loci linked to hundreds of traits in many different species. Yet, because linkage equilibrium implicates a broad region surrounding each identified locus, the causal genes often remain unknown. This problem is especially pronounced in nonhuman, nonmodel species, where functional annotations are sparse and there is frequently little information available for prioritizing candidate genes. We developed a computational approach, Camoco, that integrates loci identified by GWAS with functional information derived from gene coexpression networks. Using Camoco, we prioritized candidate genes from a large-scale GWAS examining the accumulation of 17 different elements in maize (Zea mays) seeds. Strikingly, we observed a strong dependence in the performance of our approach based on the type of coexpression network used: expression variation across genetically diverse individuals in a relevant tissue context (in our case, roots that are the primary elemental uptake and delivery system) outperformed other alternative networks. Two candidate genes identified by our approach were validated using mutants. Our study demonstrates that coexpression networks provide a powerful basis for prioritizing candidate causal genes from GWAS loci but suggests that the success of such strategies can highly depend on the gene expression data context. Both the software and the lessons on integrating GWAS data with coexpression networks generalize to species beyond maize.
The conversion of α-bromo-β-dicarbonyls to vicinal tricarbonyls using dimethyldioxirane and base

Abstract Vicinal tricarbonyls are prepared from α-bromo-β-dicarbonyl precursors by base promoted oxygen transfer from dimethyldioxirane. The α-bromo-β-dicarbonyls were prepared by the reaction of CuBr2 and [hydroxy(tosyloxy)iodo]benzene (Koser’s reagent) with a β-dicarbonyl system.
A New Route to 3-Amino Sugars. A Concise Synthesis of l-Daunosamine and d-Ristosamine Derivatives

An asymmetric aldol strategy has been developed for the synthesis of l-daunosamine and d-ristosamine derivatives starting from noncarbohydrate precursors. Lithium and boron enolate mediated aldol reactions of 12 with O-TBS lactaldehyde gave non-Evans syn and Evans syn aldol products, respectively, with high selectivity. The chemical efficiency of the lithium enolate reactions were higher than the corresponding reactions with the boron enolates. Curtius rearrangement of lactone acids 23 and 26 gave the corresponding N-BOC amino lactones 30 and 32 in 64% and 62%, respectively, with complete retention of configuration. Lactone 30 was converted by a two-step sequence to N-benzoyldaunosamide 40. The overall yield for the amino sugar 40 was 18% over six steps. Similarly, lactone 32 was converted to N-benzoylristosamide 42 with an overall yield of 18% starting from 12.
Benzoate- and Salicylate-Tolerant Strains of Escherichia coli K-12 Lose Antibiotic Resistance during Laboratory Evolution

Escherichia coli K-12 W3110 grows in the presence of membrane-permeant organic acids that can depress cytoplasmic pH and accumulate in the cytoplasm. We conducted experimental evolution by daily diluting cultures in increasing concentrations of benzoic acid (up to 20 mM) buffered at external pH 6.5, a pH at which permeant acids concentrate in the cytoplasm. By 2,000 generations, clones isolated from evolving populations showed increasing tolerance to benzoate but were sensitive to chloramphenicol and tetracycline. Sixteen clones grew to stationary phase in 20 mM benzoate, whereas the ancestral strain W3110 peaked and declined. Similar growth occurred in 10 mM salicylate. Benzoate-evolved strains grew like W3110 in the absence of benzoate, in media buffered at pH 4.8, pH 7.0, or pH 9.0, or in 20 mM acetate or sorbate at pH 6.5. Genomes of 16 strains revealed over 100 mutations, including single-nucleotide polymorphisms (SNPs), large deletions, and insertion knockouts. Most strains acquired deletions in the benzoate-induced multiple antibiotic resistance (Mar) regulon or in associated regulators such as rob and cpxA, as well as the multidrug resistance (MDR) efflux pumps emrA, emrY, and mdtA Strains also lost or downregulated the Gad acid fitness regulon. In 5 mM benzoate or in 2 mM salicylate (2-hydroxybenzoate), most strains showed increased sensitivity to the antibiotics chloramphenicol and tetracycline; some strains were more sensitive than a marA knockout strain. Thus, our benzoate-evolved strains may reveal additional unknown drug resistance components. Benzoate or salicylate selection pressure may cause general loss of MDR genes and regulators. Importance Benzoate is a common food preservative, and salicylate is the primary active metabolite of aspirin. In the gut microbiome, genetic adaptation to salicylate may involve loss or downregulation of inducible multidrug resistance systems. This discovery implies that aspirin therapy may modulate the human gut microbiome to favor salicylate tolerance at the expense of drug resistance. Similar aspirin-associated loss of drug resistance might occur in bacterial pathogens found in arterial plaques.
Temporary in situ aluminum and zinc tethering in Diels-Alder reactions

(formula presented) Temporary tethering using aluminum or zinc in Diels-Alder reactions made possible the use of otherwise "noncompatible" combinations of dienes and dienophiles, resulting in the one-step formation of substituted cyclohexene 1,2-bis-methanols. Excellent regioselectivity and also significant stereoselectivity were obtained.
9-Acylation of 1-acyldipyrromethanes containing a dialkylboron mask for the α-acylpyrrole motif

1,9-Diacyldipyrromethanes are important precursors to porphyrins, yet synthetic access remains limited owing to (1) poor conversion in the 9-acylation of 1-acyldipyrromethanes and (2) handling difficulties because acyldipyrromethanes typically streak upon chromatography and give amorphous powders upon attempted crystallization. A reliable means for converting a dipyrromethane to a 1-acyldipyrromethane−dialkylboron complex was recently developed, where the dialkylboron (BR2) unit renders the complex hydrophobic and thereby facilitates isolation. Herein a refined preparation of 1,9-diacyldipyrromethanes is presented that employs the 1-acyldipyrromethane−BR2 complex as a substrate for 9-acylation. The dialkylboron unit provides protection for the α-acylpyrrole unit. 9-Acylation requires formation of the pyrrolyl−MgBr reagent and the presence of 1 equiv of a nonnucleophilic base to quench the proton liberated upon α-acylation. Reaction of the 1-acyldipyrromethane−BR2 complex (1 equiv) with mesitylmagnesium br...
ANTIMALARIALS : SYNTHESIS OF 4-AMINOQUINOLINES THAT CIRCUMVENT DRUG RESISTANCE IN MALARIA PARASITES

The strategies described here have permitted the synthesis of a series of 4-aminoquinoline antimalarials. Substantive improvements over previous syntheses include nucleophilic substitution with neat amine rather than in phenol, regioselective reductive alkylation to convert the terminal primary amine (12a–20a) on the diaminoalkane side chain to a diethylamino group, and purification by column chromatography with basic alumina. The 1H nmr spectra obtained after regioselective reductive alkylation with sodium borodeuteride (in comparison with sodium borohydride) demonstrated that this reductive alkylation proceeds via formation and subsequent reduction of the corresponding diamides in situ.
Regio- and diastereoselective boron-mediated aldol reactions of chiral α,β,γ,δ-unsaturated N-acyloxazolidinones

Abstract Chiral N-acyloxazolidinones derived from conjugated dienoic acids undergo boron-mediated aldol condensation in good yield and with high regio- and diastereoselectivity to provide a convenient method for introducing a 1,3-diene subunit. The condensation of a homologous triene derivative is also described.
A direct arylation-oxidation route to 3-arylisoindolinone inhibitors of MDM2-p53 interaction

Abstract A route to the MDM2-p53 inhibitor isoindolinone pharmacophore from a pre-formed phthalimide is detailed. The route involves treatment of 3-hydroxy-2-(n-propyl)isoindolinone with a substituted benzene in the presence of triflic acid. The resulting 3-aryl-2-(n-propyl)isoindolinones are then oxidized to the corresponding 3-hydroxy-3-aryl-2-(n-propyl) isoindolinones by treatment with 2,2’-bipyridinium chlorochromate. The benzylic oxidation represents a rather rare oxochromium (VI)-mediated reaction in which a selective C–H to C–OH transformation occurs.
Evaluating Gender Bias in Machine Translation

We present the first challenge set and evaluation protocol for the analysis of gender bias in machine translation (MT). Our approach uses two recent coreference resolution datasets composed of English sentences which cast participants into non-stereotypical gender roles (e.g., “The doctor asked the nurse to help her in the operation”). We devise an automatic gender bias evaluation method for eight target languages with grammatical gender, based on morphological analysis (e.g., the use of female inflection for the word “doctor”). Our analyses show that four popular industrial MT systems and two recent state-of-the-art academic MT models are significantly prone to gender-biased translation errors for all tested target languages. Our data and code are publicly available at https://github.com/gabrielStanovsky/mt_gender.
Crystal Structures, Raman Spectroscopy, and Magnetic Properties of Ba7.5Al13Si29 and Eu0.27Ba7.22Al13Si29

The framework-deficient clathrate phases Ba7.5Al13Si29 and Eu0.27Ba7.22Al13Si29 were prepared using a molten Al flux. Single-crystal X-ray diffraction confirmed the two phases to be clathrate type ...
Synthetic Applications of N‐Sulfonyl Imines

N-Tosyl imines, prepared from aldehydes and N-sulfinyl-p-toluene sulfonamide (Kresze reaction), cyclize with alkenes and vinyl silanes in the presence of a Lewis acid to afford intermediates useful for alkaloid total synthesis.
Synthesis and properties of N7O

The reaction of NOF2+SbF6− with an equimolar amount of HN3 in an anhydrous HF solution at −45 °C produces N3NOF+SbF6−. When an excess of HN3 is used in this reaction, N7O+SbF6− is formed. However, this compound could not be isolated as a solid and rapidly decomposed in a quantitative manner with N2O evolution to N5+SbF6−. This reaction represents a novel and more convenient synthesis for N5+SbF6− because NOF2+SbF6− is more readily accessible than N2F+SbF6− and the N5+ can be labeled in all five positions with 15N by the simple use of terminally singly labeled N3−. The formation of the N7O+ cation was established by isotopic labeling experiments and theoretical calculations. It is shown that the addition of a second azido ligand to the same central atom allows the attack of the negatively charged Nα atom of one ligand by the positively charged Nγ atom of the second ligand, thereby greatly lowering the activation energy barrier toward decomposition and explaining why geminal diazides are much less stable th...
Hydrothermal synthesis of K2PdSe10. Coexistence of two large interpenetrating three-dimensional frameworks of [Pd(Se4)2]2- and [Pd(Se6)2]2-

The hydrothermal reaction of PdCl 2 with K 2 Se 4 in the presence of different KOH and water in the 1:5:5:40 ratio produced K 2 [PdSe 10 ] (I), the first metal polychalcogenide compound containing two interpenetrating three-dimensional frameworks. The black rectangular chunky crystals of I are insoluble in water and most organic solvents. They crystallize in the orthorhombic space group I2 1 2 1 2 1 .
A Resource for the Allele-Specific Analysis of DNA Methylation at Multiple Genomically Imprinted Loci in Mice.

Genomically imprinted loci are expressed mono-allelically, dependent upon the parent of origin. Their regulation not only illuminates how chromatin regulates gene expression but also how chromatin can be reprogrammed every generation. Because of their distinct parent-of-origin regulation, analysis of imprinted loci can be difficult. Single nucleotide polymorphisms (SNPs) are required to accurately assess these elements allele specifically. However, publicly available SNP databases lack robust verification, making analysis of imprinting difficult. In addition, the allele-specific imprinting assays that have been developed employ different mouse strains, making it difficult to systemically analyze these loci. Here, we have generated a resource that will allow the allele-specific analysis of many significant imprinted loci in a single hybrid strain of Mus musculus. This resource includes verification of SNPs present within 10 of the most widely used imprinting control regions and allele-specific DNA methylation assays for each gene in a C57BL/6J and CAST/EiJ hybrid strain background.
AmpUMI: design and analysis of unique molecular identifiers for deep amplicon sequencing.

Motivation Unique molecular identifiers (UMIs) are added to DNA fragments before PCR amplification to discriminate between alleles arising from the same genomic locus and sequencing reads produced by PCR amplification. While computational methods have been developed to take into account UMI information in genome-wide and single-cell sequencing studies, they are not designed for modern amplicon-based sequencing experiments, especially in cases of high allelic diversity. Importantly, no guidelines are provided for the design of optimal UMI length for amplicon-based sequencing experiments. Results Based on the total number of DNA fragments and the distribution of allele frequencies, we present a model for the determination of the minimum UMI length required to prevent UMI collisions and reduce allelic distortion. We also introduce a user-friendly software tool called AmpUMI to assist in the design and the analysis of UMI-based amplicon sequencing studies. AmpUMI provides quality control metrics on frequency and quality of UMIs, and trims and deduplicates amplicon sequences with user specified parameters for use in downstream analysis. Availability and implementation AmpUMI is open-source and freely available at http://github.com/pinellolab/AmpUMI.
Bioreactor Systems for the Production of Optically Active Amino Acids and Alcohols

Industrial enzyme catalytic reactions for the production of useful optically active compounds have been developed. The first example is a unique process for the production of d-p-hydroxyphenylglycine (D-HPG) from d,l-5-p-hydroxyphenylhydantoin. This process involves two immobilized enzyme processes, hydantoinase and N-carbamoyl-d-amino acid amidohydrolase (DCase). A thermophilic bacterium producing thermostable hydantoinase and a mesophilic bacterium producing DCase were isolated, and the thermostability of the latter enzyme was improved by a protein-engineering technique. Both enzymes could be reused in long-term repeated batch reactions as immobilized enzymes for industrial production. The second example is an enzymatic reduction system for the production of optically active alcohols from the corresponding carbonyl compounds. Effective production of ethyl (S)-4-chloro-3-hydroxybutyrate was achieved with high productivity (350 g/L, >99% ee) by constructing the recombinant Escherichia coli overproducing b...
Bureaucratic Politicization, Partisan Attachments, and the Limits of Public Agency Legitimacy: The Venezuelan Armed Forces under Chavismo

Which factors determine support for the armed forces? What is the effect of agency politicization on confidence? Existing studies, which draw largely from bureaucratically neutral militaries, find that interpersonal trust and demographic variables play significant roles in determining public confidence in the armed forces. I argue that this is different for a politicized agency. A loss of bureaucratic neutrality activates voters’ partisan attachments, inducing individuals to judge the agency on the basis of their ties to the governing party or leader. Using survey data from Venezuela, I show that government evaluation has a salient and bifurcated effect on respondents’ perceptions of their armed forces. Respondents sympathetic to the governing leader are more likely to have a favorable view of the military while those identifying as opposition are more likely to have a negative view. The results suggest that politicization of public agencies may impose an upper limit on public support regardless of institutional performance, undermine their representativeness and legitimacy, and weaken their mandates. Resumen ?Cuales factores determinan el apoyo a las fuerzas armadas? ?Cual es el efecto de la politizacion de la institucion en la confianza? Los estudios existentes, que se basan mayoritariamente en militares burocraticamente neutrales, hallan que la confianza interpersonal y la demografia desempenan un papel importante en la determinacion de la confianza publica en las fuerzas armadas. Aqui sostengo que esto es diferente para una agencia politizada. Una perdida de neutralidad burocratica activa los vinculos partidistas de los votantes, induciendo a los individuos a juzgar a la agencia en funcion de sus vinculos con el gobierno. A traves del uso de datos de encuestas publicas en Venezuela, muestro que la evaluacion del gobierno tiene un efecto destacado y bifurcado en las percepciones de los ciudadanos sobre sus fuerzas armadas. Los encuestados que simpatizan con el gobierno tienen mayor probabilidad de una percepcion favorable de los militares y los opositores tienen mayor probabilidad de una percepcion negativa. Los resultados sugieren que la politizacion de los organismos publicos puede imponer un limite al apoyo publico independientemente del desempeno institucional, socavar su representatividad y legitimidad y debilitar sus mandatos.
Cannabis Stock behavior and Investor’s Expectations on the TSX: A Mixed Method Approach

This study examines the behavior of cannabis stock on the Toronto Stock Exchange and why investors are interested in cannabis stock. The theory of heterogeneous beliefs, bounded rationality theory and the theory of addiction grounded the study. We employed basic descriptive statistics and the Kruskal-Wallis test including an in-depth interview of investors using convenience sampling methods. The study findings showed that cannabis stocks exhibit a higher-level of risk volatility when compared to speculative and growth stocks on the Toronto Stock Exchange within the period under investigation. The descriptive statistics result suggest potential diversification benefits between cannabis stocks and growth stocks as both stocks classifications are likely to respond to macroeconomic shocks differently. Other findings show that cannabis stocks share similar characteristics with other speculative stocks but also possess unique features. Finally, investors are interested in cannabis stocks because of its potential for future strong earnings on the platform of the theory of addiction as discussed in the study.
Quantitative Density under Higher Rank Abelian Algebraic Toral Actions

We generalize Bourgain-Lindenstrauss-Michel-Venkatesh’s recent one-dimensional quantitative density result to abelian algebraic actions on higher dimensional tori. Up to finite index, the group actions that we study are conjugate to the action of UK , the group of units of some non-CM number field K, on a compact quotient of K ⊗Q R. In such a setting, we investigate how fast the orbit of a generic point can become dense in the torus. This effectivizes a special case of a theorem of Berend; and is deduced from a parallel measure-theoretical statement which effectivizes a special case of a result by Katok-Spatzier. In addition, we specify two numerical invariants of the group action that determine the quantitative behavior, which have number-theoretical significance. ∗Department of Mathematics, Princeton University, Princeton, NJ 08544, USA; zhirenw@math.princeton.edu
On the geodesic centers of polygonal domains

In this paper, we study the problem of computing Euclidean geodesic centers of a polygonal domain P of n vertices. We give a necessary condition for a point being a geodesic center. We show that there is at most one geodesic center among all points of P that have topologically-equivalent shortest path maps. This implies that the total number of geodesic centers is bounded by the size of the shortest path map equivalence decomposition of P, which is known to be O(n^{10}). One key observation is a pi-range property on shortest path lengths when points are moving. With these observations, we propose an algorithm that computes all geodesic centers in O(n^{11}*log(n)) time. Previously, an algorithm of O(n^{12+epsilon}) time was known for this problem, for any epsilon > 0.
Rigidity and minimizing properties of quasi-local mass

In this article, we survey recent developments in defining the quasi-local mass in general relativity. We discuss various approaches and the properties and applications of the different definitions. Among the expected properties, we focus on the rigidity property: for a surface in the Minkowski spacetime, one expects that the mass should vanish. We describe the Wang-Yau quasi-local mass whose definition is motivated by this rigidity property and by the Hamilton-Jacobi analysis of the Einstein-Hilbert action. In addition, we survey recent results on the minimizing property the Wang-Yau quasi-local mass.
U-PoT: A Honeypot Framework for UPnP-Based IoT Devices

The ubiquitous nature of the IoT devices has brought serious security implications to its users. A lot of consumer IoT devices have little to no security implementation at all, thus risking user's privacy and making them target of mass cyber-attacks. Indeed, recent outbreak of Mirai botnet and its variants have already proved the lack of security on the IoT world. Hence, it is important to understand the security issues and attack vectors in the IoT domain. Though significant research has been done to secure traditional computing systems, little focus was given to the IoT realm. In this work, we reduce this gap by developing a honeypot framework for IoT devices. Specifically, we introduce U-PoT: a novel honeypot framework for capturing attacks on IoT devices that use Universal Plug and Play (UPnP) protocol. A myriad of smart home devices including smart switches, smart bulbs, surveillance cameras, smart hubs, etc. uses the UPnP protocol. Indeed, a simple search on Shodan IoT search engine lists 1,676,591 UPnP devices that are exposed to public network. The popularity and ubiquitous nature of UPnP-based IoT device necessitates a full-fledged IoT honeypot system for UPnP devices. Our novel framework automatically creates a honeypot from UPnP device description documents and is extendable to any device types or vendors that use UPnP for communication. To the best of our knowledge, this is the first work towards a flexible and configurable honeypot framework for UPnP-based IoT devices. We released U-PoT under an open source license for further research on IoT security and created a database of UPnP device descriptions. We also evaluated our framework on two emulated deices. Our experiments show that the emulated devices are able to mimic the behavior of a real IoT device and trick vendor-provided device management applications or popular IoT search engines while having minimal performance ovherhead.
Local curves, wild character varieties, and degenerations

Conjectural results for cohomological invariants of wild character varieties are obtained by counting curves in degenerate Calabi-Yau threefolds. A conjectural formula for E-polynomials is derived from the Gromov-Witten theory of local Calabi-Yau threefolds with normal crossing singularities. A refinement is also conjectured, generalizing existing results of Hausel, Mereb and Wong as well as recent joint work of Donagi, Pantev and the author for weighted Poincar\'e polynomials of wild character varieties.
A Greedy Approach to Adapting the Trace Parameter for Temporal Difference Learning

One of the main obstacles to successful application of reinforcement learning methods is the parameter sensitivity of our core learning algorithms. In many larger scale applications, online computation and the use of function approximation represent key strategies in scaling up reinforcement learning algorithms. In this setting, we have effective and reasonably well understood algorithms for adapting the learning-rate parameter, online during learning. For temporal-difference learning algorithms which we study here, there is yet another parameter, λ, that similarly impacts learning speed and stability in practice. Unfortunately, unlike the learning-rate parameter, λ parametrizes the objective function that temporal-difference methods optimize. Different choices of λ produce different fixed-point solutions, and thus adapting λ online and characterizing the optimization is substantially more complex than adapting the learning-rate parameter. There are no methods available that can achieve (1) incremental updating, (2) compatibility with function approximation, and (3) maintain stability of learning under both on and off-policy sampling. In this paper we contribute a novel objective function for optimizing λ as a function of state rather than time. We derive a new incremental, linear complexity λ-adaption algorithm that does not require offline batch updating or access to a model of the world, and present a suite of experiments illustrating the practicality of our new algorithm in three different settings. Taken together, our contributions represent a concrete step towards black-box application of temporal-difference learning methods in real world problems.
Quantifying spatio-temporal variation of invasion spread

- The spread of invasive species can have far-reaching environmental and ecological consequences. Understanding invasion spread patterns and the underlying process driving invasions are key to predicting and managing invasions. - We combine a set of statistical methods in a novel way to characterize local spread properties and demonstrate their application using simulated and historical data on invasive insects. Our method uses a Gaussian process fit to the surface of waiting times to invasion in order to characterize the vector field of spread. - Using this method, we estimate with statistical uncertainties the speed and direction of spread at each location. Simulations from a stratified diffusion model verify the accuracy of our method. - We show how we may link local rates of spread to environmental covariates for two case studies: the spread of the gypsy moth ( Lymantria dispar), and hemlock woolly adelgid ( Adelges tsugae) in North America. We provide an R-package that automates the calculations for any spatially referenced waiting time data.
The 4-dimensional light bulb theorem

For embedded 2-spheres in a 4-manifold sharing the same embedded transverse sphere homotopy implies isotopy, provided the ambient 4-manifold has no $\BZ_2$-torsion in the fundamental group. This gives a generalization of the classical light bulb trick to 4-dimensions, the uniqueness of spanning discs for a simple closed curve in $S^4$ and $\pi_0(\Diff_0(S^2\times D^2)/\Diff_0(B^4))=1$. In manifolds with $\BZ_2$-torsion, one surface can be put into a normal form relative to the other.