cssi/SciSciGPT-SciSciNet huggingface dataset:
Privacy Risk in Machine Learning: Analyzing the Connection to Overfitting

Machine learning algorithms, when applied to sensitive data, pose a distinct threat to privacy. A growing body of prior work demonstrates that models produced by these algorithms may leak specific private information in the training data to an attacker, either through the models' structure or their observable behavior. However, the underlying cause of this privacy risk is not well understood beyond a handful of anecdotal accounts that suggest overfitting and influence might play a role. This paper examines the effect that overfitting and influence have on the ability of an attacker to learn information about the training data from machine learning models, either through training set membership inference or attribute inference attacks. Using both formal and empirical analyses, we illustrate a clear relationship between these factors and the privacy risk that arises in several popular machine learning algorithms. We find that overfitting is sufficient to allow an attacker to perform membership inference and, when the target attribute meets certain conditions about its influence, attribute inference attacks. Interestingly, our formal analysis also shows that overfitting is not necessary for these attacks and begins to shed light on what other factors may be in play. Finally, we explore the connection between membership inference and attribute inference, showing that there are deep connections between the two that lead to effective new attacks.
Sketching Linear Classifiers over Data Streams

We introduce a new sub-linear space sketch---the Weight-Median Sketch---for learning compressed linear classifiers over data streams while supporting the efficient recovery of large-magnitude weights in the model. This enables memory-limited execution of several statistical analyses over streams, including online feature selection, streaming data explanation, relative deltoid detection, and streaming estimation of pointwise mutual information. Unlike related sketches that capture the most frequently-occurring features (or items) in a data stream, the Weight-Median Sketch captures the features that are most discriminative of one stream (or class) compared to another. The Weight-Median Sketch adopts the core data structure used in the Count-Sketch, but, instead of sketching counts, it captures sketched gradient updates to the model parameters. We provide a theoretical analysis that establishes recovery guarantees for batch and online learning, and demonstrate empirical improvements in memory-accuracy trade-offs over alternative memory-budgeted methods, including count-based sketches and feature hashing.
Faulted Phase Location Identification for Adjustable Speed Drives in High-Resistance Grounding System

High-resistance grounding (HRG) is preferred in many industrial applications where continual operation during ground fault conditions is critical. However, there are some drawbacks for the traditional HRG detection methods to locate a ground fault in adjustable speed drive systems. The existing methods cannot detect or identify which phase faulted once the drive has HRG fault. A leakage flux linkage detection-based method for HRG fault identification is proposed in this paper. It will be used to identify the faulted phase of the drive.
ABE-VIEW: Android Interface for Wireless Data Acquisition and Control

Advances in scientific knowledge are increasingly supported by a growing community of developers freely sharing new hardware and software tools. In this spirit we have developed a free Android app, ABE-VIEW, that provides a flexible graphical user interface (GUI) populated entirely from a remote instrument by ascii-coded instructions communicated wirelessly over Bluetooth. Options include an interactive chart for plotting data in real time, up to 16 data fields, and virtual controls including buttons, numerical controls with user-defined range and resolution, and radio buttons which the user can use to send coded instructions back to the instrument. Data can be recorded into comma delimited files interactively at the user’s discretion. Our original objective of the project was to make data acquisition and control for undergraduate engineering labs more modular and affordable, but we have also found that the tool is highly useful for rapidly testing novel sensor systems for iterative improvement. Here we document the operation of the app and syntax for communicating with it. We also illustrate its application in undergraduate engineering labs on dynamic systems modeling, as well as for identifying the source of harmonic distortion affecting electrochemical impedance measurements at certain frequencies in a novel wireless potentiostat.
Human Papillomavirus Vaccine Initiation for Adolescents Following Rhode Island’s School-Entry Requirement, 2010–2016

Objectives. To assess changes in human papillomavirus (HPV) vaccine initiation for adolescent girls and boys in Rhode Island compared with all other states.Methods. We estimated the gender-specific...
Information Technology in the Property Market

Abstract Information technology is increasingly being utilized in the property market. This paper examines how sensitive house transaction prices are to online price estimates using data collected from Zillow. We find that online property price estimates strongly predict transaction prices even when observable and unobservable house and neighborhood characteristics are controlled for. In addition, we find evidence that suggests that online price estimates may have a direct impact on transaction prices.
On configuration spaces and Whitehouse's lifts of the Eulerian representations

Abstract S. Whitehouse's lifts of the Eulerian representations of S n to S n + 1 are reinterpreted, topologically and ring-theoretically, building on the first author's work on A. Ocneanu's theory of permutohedral blades.
On criteria for rook equivalence of Ferrers boards

Abstract In Bloom and Saracino (2018) we introduced a new notion of Wilf equivalence of integer partitions and proved that rook equivalence implies Wilf equivalence. In the present paper we prove the converse and thereby establish a new criterion for rook equivalence. We also refine two of the standard criteria for rook equivalence and establish another new one involving what we call nested sequences of L’s.
Contextual Parameter Generation for Universal Neural Machine Translation

We propose a simple modification to existing neural machine translation (NMT) models that enables using a single universal model to translate between multiple languages while allowing for language specific parameterization, and that can also be used for domain adaptation. Our approach requires no changes to the model architecture of a standard NMT system, but instead introduces a new component, the contextual parameter generator (CPG), that generates the parameters of the system (e.g., weights in a neural network). This parameter generator accepts source and target language embeddings as input, and generates the parameters for the encoder and the decoder, respectively. The rest of the model remains unchanged and is shared across all languages. We show how this simple modification enables the system to use monolingual data for training and also perform zero-shot translation. We further show it is able to surpass state-of-the-art performance for both the IWSLT-15 and IWSLT-17 datasets and that the learned language embeddings are able to uncover interesting relationships between languages.
Performance Analysis of Plug-and-Play ADMM: A Graph Signal Processing Perspective

The Plug-and-Play (PnP) alternating direction method of multiplier (ADMM) algorithm is a powerful image restoration framework that allows advanced image denoising priors to be integrated into physical forward models to generate high-quality image restoration results. However, despite the enormous number of applications and several theoretical studies trying to prove convergence by leveraging tools in convex analysis, very little is known about why the algorithm is doing so well. The goal of this paper is to fill the gap by discussing the performance of PnP ADMM. By restricting the denoisers to the class of graph filters under a linearity assumption, or more specifically the symmetric smoothing filters, we offer three contributions: First, we show conditions under which an equivalent maximum- a-posteriori optimization exists; second, we present a geometric interpretation and show that the performance gain is due to an intrinsic predenoising characteristic of the PnP prior; and third, we introduce a new analysis technique via the concept of consensus equilibrium, and provide interpretations to problems involving multiple priors.
The Effects of Local Industrial Pollution on Students and Schools

Using detailed education data for 1996–2012 from the state of Florida, we examine whether pollution from local Toxic Release Inventory (TRI) sites affects student achievement and high-stakes accountability school rankings. Using event study and difference-in-differences designs, we compare students attending schools within one mile of a TRI site that opens or closes to students attending schools between one and two miles away. We find that being exposed to air pollution is associated with 0.024 of standard deviation lower test scores, increased likelihood of suspension from school, and increased likelihood that a school’s overall high-stakes accountability ranking will drop.
Voltage effects on the stability of Pd ensembles in Pd-Au/Au(111) surface alloys.

The catalytic performance of multimetallic electrodes is often attributed to a beneficial combination of ligand, strain, and ensemble effects. Understanding the influence of the electrochemical environment on the stability of the alloy surface structure is thus a crucial component to the design of highly active and durable electrocatalysts. In this work, we study the effects of an applied voltage to electrocatalytic Pd–Au/Au(111) surface alloys in contact with a model continuum electrolyte. Using planewave density functional theory, two-dimensional cluster expansions are parameterized and used to simulate dilute Pd–Au surface alloys under electrochemical conditions via Metropolis Monte Carlo within an extended canonical ensemble. While Pd monomers are stable at all potentials considered, different extents of surface electrification are observed to promote the formation of Pd dimers and trimers, as well as clusters of Pd monomers. We find that the relative proportion of monomer, dimer, and trimer surface fractions is in good agreement with in situ scanning tunneling microscopy measurements. The further development and refinement of the approaches described herein may serve as a useful aid in the development of next-generation electrocatalysts.
Prolonged noxious stimulation increases periaqueductal gray NMDA mRNA expression: a hybridization study using two different rat models for nociception.

The density and distribution of N-methyl-D-aspartate receptor (NMDAR1) mRNA expression in the rat midbrain Periaqueductal gray (PAG) following exposure to unilateral peripheral inflammation or chronic constrictive injury (CCI) as models for chronic peripheral nociception were examined using thein situ hybridization technique. The NMDAR1 hybridization signal intensities increased significantly in the ventrolateral areas of the caudal and middle thirds of the PAG after 3 days of Complete Freund’s Adjuvant (CFA) injection. Likewise, rats subjected to CCI showed significant increases in hybridization signal intensities in comparison to sham operated animals in both the ipsi and contra-lateral ventrolateral quadrants of the caudal and middle thirds of the PAG. In the caudal dorsal raphe, the CFA and the CCI treated animals showed a significant increase in signal hybridization compared to control and sham operated groups while the rostral dorsal raphe showed no significant changes in either CCI or CFA treated groups. In contrast, there was no significant change in signal intensity of NMDAR1 mRNA in the dorsal subdivisions of the PAG following either CCI or CFA treatment. These results demonstrate significant bilateral increase in NMDAR1 mRNA expression in the ventrolateral areas of the caudal and middle thirds of the PAG and the caudal half of the dorsal raphe following chronic nociception. The up-regulation phenomenon may constitute a reactive mechanism against chronic neuropathic pain in the PAG.
Sinogram interpolation for sparse-view micro-CT with deep learning neural network

In sparse-view Computed Tomography (CT), only a small number of projection images are taken around the object, and sinogram interpolation method has a significant impact on final image quality. When the amount of sparsity - the amount of missing views in sinogram data – is not high, conventional interpolation methods have yielded good results. When the amount of sparsity is high, more advanced sinogram interpolation methods are needed. Recently, several deep learning (DL) based sinogram interpolation methods have been proposed. However, those DL-based methods have mostly tested so far on computer simulated sinogram data rather experimentally acquired sinogram data. In this study, we developed a sinogram interpolation method for sparse-view micro-CT based on the combination of U-Net and residual learning. We applied the method to sinogram data obtained from sparse-view micro-CT experiments, where the sparsity reached 90%. The interpolated sinogram by the DL neural network was fed to FBP algorithm for reconstruction. The result shows that both RMSE and SSIM of CT image are greatly improved. The experimental results demonstrate that this sinogram interpolation method produce significantly better results over standard linear interpolation methods when the sinogram data are extremely sparse.
Longitudinal Analysis of Refractive Errors in Premature Children during the First Three Years of Life

To examine the longitudinal behavior of refractive errors in both retinopathy of prematurity (ROP) and non-ROP screened premature children during the first three years of life. This retrospective c...
Norm Contestation, Robustness, and Replacement

The collaborative project reported in this special issue has sought to move beyond any straightforward connection between norm violation or norm contestation, on the one hand, and norm robustness on the other. Instead, the effects of contestation on norm robustness are conditioned by characteristics of norm challengers and norm defenders, by the nature of the contestation, and by features of norm institutionalization and embeddedness. This contribution assesses the case studies in light of the framing conjectures. It draws broad conclusions, indicates areas where general conclusions are not yet possible, and points out directions for further theoretical development and empirical investigation.
Systematic Design of Decentralized Algorithms for Consensus Optimization

We propose a separation principle that enables a systematic way of designing decentralized algorithms used in consensus optimization. Specifically, we show that a decentralized optimization algorithm can be constructed by combining a non-decentralized base optimization algorithm and decentralized consensus tracking. The separation principle provides modularity in both the design and analysis of algorithms under an automated convergence analysis framework using integral quadratic constraints (IQCs). We show that consensus tracking can be incorporated into the IQC-based analysis. The workflow is illustrated through the design and analysis of a decentralized algorithm based on the alternating direction method of multipliers.
The impact of proficiency testing information and error aversions on the weight given to fingerprint evidence

Fingerprint examiners regularly participate in tests designed to assess their proficiency. These tests provide information relevant to the weight of fingerprint evidence, but no prior research has directly examined how jurors react to proficiency testing information. Using a nationally representative sample of American adults, we examined the impact of proficiency testing information on the weight given to the opinions of fingerprint examiners by mock jurors considering a hypothetical criminal case. The fingerprint examiner's level of performance on a proficiency test (high, medium, low, or very low), but not the type of error committed on the test (false positive identifications, false negative identifications, or a mix of both types of error), affected the weight that jury-eligible adults gave to an examiner's opinion that latent fingerprints recovered from a crime scene matched the defendant's fingerprints, which in turn affected judgments about the defendant's guilt. Jurors who had no information about proficiency gave similar weight to the testimony as jurors exposed to highly proficient examiners, suggesting that jurors assume fingerprint examiners perform at high levels of proficiency unless informed otherwise. We also found that a plurality of Americans deems false acquittals just as aversive as false convictions and a significant minority deems false acquittals more serious. These differences in error aversions predicted differences in evidentiary assessments, suggesting that error aversions of jurors may play an important role in criminal trials.
The FechDeck: A Hand Tool for Exploring Psychophysics

Learning the methods of psychophysics is an essential part of training for perceptual experimentation, and hands-on experience is vital, but gaining this experience is difficult because good tools for learning are not available. The FechDeck is an ordinary deck of playing cards that has been modified to support learning the methods of psychophysics. Card backs are printed with noise patterns that span a range of densities. Faces are augmented with line segments arranged in “L” patterns. Jokers are printed with ruled faces and with backs that serve as standards. Instructions provided with the FechDeck allow users to perform threshold experiments using Fechner's methods of adjustment, limits, and constant stimuli; scaling experiments using Thurstone's ranking, paired comparison, and successive categories methods; and Stevens's magnitude estimation method. Spreadsheets provided with the deck support easy data entry and meaningful data analysis. An online repository supporting the FechDeck has been established to facilitate dissemination and to encourage open source development of the deck.
Double Half-Heuslers

Summary Since their discovery around a century ago, multi-functional half-Heusler semiconductors have been studied extensively as three-component systems (nominal formula XYZ) with valence balanced compositions. From the very same set of elements and stability rules, we explore a much larger phase space of possible quaternary double (X′X″Y2Z2, X2Y′Y″Z2, and X2Y2Z′Z″), triple (X2′X″Y3Z3), and quadruple (X3′X″Y4Z4) half-Heusler compounds. Using reliable, first-principles thermodynamics on a selection (365) of previously unexplored compositions, we predict more quaternary compounds (131) than those predicted or reported extensively for the ternary systems (84). In comparison to state-of-the-art ternary half-Heusler thermoelectrics, for which performance is limited by their intrinsically high thermal conductivity (κ), κ in double half-Heuslers is dominated by smaller group velocity phonons and limited by disorder scattering. The double half-Heusler Ti2FeNiSb2 was synthesized and confirmed to have a significantly lower κ than TiCoSb, thereby providing a better starting point for thermoelectric efficiency optimization.
Data-driven management of post-transplant medications: An ambiguous partially observable markov decision process approach

Problem definition: Organ-transplanted patients typically receive high amounts of immunosuppressive drugs (e.g., tacrolimus) as a mechanism to reduce their risk of organ rejection. However, because...
Assessing fire-blocking effectiveness of barrier fabrics in the cone calorimeter:

Cone calorimetry experiments of on flexible polyurethane foam and flexible polyurethane foam covered with a variety of fire-blocking barrier fabrics were used to characterize and rank the effective...
Two-Color Volumetric Imaging of Neuronal Activity of Cortical Columns

To capture the emergent properties of neural circuits, high-speed volumetric imaging of neural activity at cellular resolution is needed. Here, we introduce wavelength multiplexing to perform fast volumetric two-photon imaging of cortical columns (>2,000 neurons in 10 planes at 10 vol/s), using two different calcium indicators, an electrically tunable lens and a spatial light modulator. We image the activity of neuronal populations from layers 2/3 to 5 of primary visual cortex from awake mice, finding a lack of columnar structures in orientation responses and revealing correlations between layers which differ from trial to trial. We also simultaneously image functional correlations between presynaptic layer 1 axons and postsynaptic layer 2/3 neurons. Wavelength multiplexing enhances high-speed volumetric microscopy and can be combined with other optical multiplexing methods to easily boost imaging throughput.
Variance Reduction in Gradient Exploration for Online Learning to Rank

Online Learning to Rank (OL2R) algorithms learn from implicit user feedback on the fly. The key to such algorithms is an unbiased estimate of gradients, which is often (trivially) achieved by uniformly sampling from the entire parameter space. Unfortunately, this leads to high-variance in gradient estimation, resulting in high regret during model updates, especially when the dimension of the parameter space is large. In this work, we aim at reducing the variance of gradient estimation in OL2R algorithms. We project the selected updating direction (i.e., the winning direction) into a space spanned by the feature vectors from examined documents under the current query (termed the "document space" for short), after an interleaved test. Our key insight is that the result of an interleaved test is solely governed by a user's relevance evaluation over the examined documents. Hence, the true gradient introduced by this test is only reflected in the constructed document space, and components of the proposed gradient which are orthogonal to the document space can be safely removed, for variance reduction purpose. We prove that this projected gradient is still an unbiased estimation of the true gradient, and show that this lower-variance gradient estimation results in significant regret reduction. Our proposed method is compatible with all existing OL2R algorithms which rank documents using a linear model. Extensive experimental comparisons with several state-of-the-art OL2R algorithms have confirmed the effectiveness of our proposed method in reducing the variance of gradient estimation and improving overall ranking performance.
Dimensionally reduced one-dimensional chains of TiSe2

TiSe2(en) is prepared by dissolution of Se powder and NaBH4 in en followed by injection of TiCl4 (1.
Thermal Reactions of 8-Methylbicyclo[4.2.0]oct-2-enes: Competitive Diradical-Mediated [1,3] Sigmatropic, Stereomutation, and Fragmentation Processes

At 275 °C, 8-exo-methylbicyclo[4.2.0]oct-2-ene (1a) undergoes a [1,3] sigmatropic rearrangement to 5-methylbicyclo[2.2.2]oct-2-enes, of which the orbital symmetry-allowed si product is only marginally favored over the forbidden sr product; that is, si/sr is 2.4. Accompanying the [1,3] shift are significant amounts of epimerization and fragmentation. The 8-endo epimer 1b, which yields no [1,3] product, experiences primarily direct fragmentation and secondarily epimerization. A diradical intermediate can account for all such observations.
Synthesis and Structure Determination of a New Organically Templated Scandium Fluorophosphate Framework and Its Indium Analogue

Two new isostructural scandium and indium phosphate frameworks, (C6H14N2)M4F2(PO4)4·4H2O (M = Sc, In), have been synthesized from hydrothermal conditions using an organic amine, 1,4-diazabicyclo[2.2.2]octane (DABCO), as a template. Their structures have been determined by single-crystal X-ray diffraction and supported by solid-state magic-angle spinning (MAS) NMR spectroscopy. They crystallize in the P21/n space group with a = 10.283(2) A, b = 12.698(2) A, c = 17.864(3) A, and β = 102.761(3)° and a = 10.280(2) A, b = 12.700(2) A, c = 17.860(4) A, and β = 102.47(3)° for Sc- and In-compounds, respectively. They are built from corner-sharing M octahedra and P tetrahedra which form eight- and six-membered channels along the b-axis. The channels are occupied by organic templates and water molecules. All PO4 groups share four corners with M polyhedra, resulting in a fully connected framework. The local environments around P, F, and Sc atoms in the Sc-compound were carefully examined by 31P MAS, 19F MAS, 45Sc MA...
Increased Axonal Bouton Stability during Learning in the Mouse Model of MECP2 Duplication Syndrome

MECP2 duplication syndrome is an X-linked form of syndromic autism caused by genomic duplication of the region encoding methyl-CpG-binding protein 2 (MECP2). Mice overexpressing MECP2 demonstrate social impairment, behavioral inflexibility, and altered patterns of learning and memory. Previous work showed abnormally increased stability of dendritic spines formed during motor training in the apical tuft of primary motor cortex (area M1) corticospinal neurons in the MECP2 duplication mouse model. In the current study, we measure the structural plasticity of axonal boutons in layer 5 pyramidal neuron projections to layer 1 of area M1 during motor training. In wild-type littermate control mice, we find that during rotarod training the bouton formation rate changes minimally, if at all, while the bouton elimination rate more than doubles. Notably, the observed upregulation in bouton elimination with training is absent in MECP2 duplication mice. This result provides further evidence of an imbalance between structural stability and plasticity in this form of syndromic autism. Furthermore, the observation that axonal bouton elimination more than doubles with motor training in wild-type animals contrasts with the increase of dendritic spine consolidation observed in corticospinal neurons at the same layer. This dissociation suggests that different area M1 microcircuits may manifest different patterns of structural synaptic plasticity during motor training.
Synthesis of Mixed Thiophene/Furan Oligomers by Stille Coupling

A series of mixed thiophene/furan oligomers have been synthesized via organometallic Stille coupling. In some cases, beside cross-coupling products, symmetrical coupling products were isolated. Oligomers consisting of up to 11 rings were obtained. Attempts to prepare macrocycles with 10 thiophene and furan units were not successful.
Effects of mutation and selection on plasticity of a promoter activity in Saccharomyces cerevisiae.

Phenotypic plasticity is an evolvable property of biological systems that can arise from environment-specific regulation of gene expression. To better understand the evolutionary and molecular mechanisms that give rise to plasticity in gene expression, we quantified the effects of 235 single-nucleotide mutations in the Saccharomyces cerevisiae TDH3 promoter (PTDH3) on the activity of this promoter in media containing glucose, galactose, or glycerol as a carbon source. We found that the distributions of mutational effects differed among environments because many mutations altered the plastic response exhibited by the wild-type allele. Comparing the effects of these mutations with the effects of 30 PTDH3 polymorphisms on expression plasticity in the same environments provided evidence of natural selection acting to prevent the plastic response in PTDH3 activity between glucose and galactose from becoming larger. The largest changes in expression plasticity were observed between fermentable (glucose or galactose) and nonfermentable (glycerol) carbon sources and were caused by mutations located in the RAP1 and GCR1 transcription factor binding sites. Mutations altered expression plasticity most frequently between the two fermentable environments, with mutations causing significant changes in plasticity between glucose and galactose distributed throughout the promoter, suggesting they might affect chromatin structure. Taken together, these results provide insight into the molecular mechanisms underlying gene-by-environment interactions affecting gene expression as well as the evolutionary dynamics affecting natural variation in plasticity of gene expression.
Conformationally constrained thyroliberin analogs: a novel electrochemical route to a key rigid Pro-Phe building block

Abstract An anodic amide oxidation has been employed in the synthesis of a rigid Pro-Phe building block. The key electrochemical step allowed for the functionalization of a proline derivative and led to an annulation procedure for conveniently constructing the bicyclic ring system used to lock the dipeptide building block into a specific conformation.
Attenuation of Influenza A Virus Disease Severity by Viral Coinfection in a Mouse Model

Influenza viruses and rhinoviruses are responsible for a large number of acute respiratory viral infections in human populations and are detected as copathogens within hosts. Clinical and epidemiological studies suggest that coinfection by rhinovirus and influenza virus may reduce disease severity and that they may also interfere with each other's spread within a host population. To determine how coinfection by these two unrelated respiratory viruses affects pathogenesis, we established a mouse model using a minor serogroup rhinovirus (rhinovirus strain 1B [RV1B]) and mouse-adapted influenza A virus (A/Puerto Rico/8/1934 [PR8]). Infection of mice with RV1B 2 days before PR8 reduced the severity of infection by a low or medium, but not high, dose of PR8. Disease attenuation was associated with an early inflammatory response in the lungs and enhanced clearance of PR8. However, coinfection by RV1B did not reduce PR8 viral loads early in infection or inhibit replication of PR8 within respiratory epithelia or in vitro Inflammation in coinfected mice remained focal compared to diffuse inflammation and damage in the lungs of mice infected by PR8. The timing of RV1B coinfection was a critical determinant of protection, suggesting that sufficient time is needed to induce this response. Finally, disease attenuation was not unique to RV1B: dose-dependent coinfection by a murine coronavirus (mouse hepatitis virus strain 1 [MHV-1]) also reduced the severity of PR8 infection. Unlike RV1B, coinfection with MHV-1 reduced early PR8 replication, which was associated with upregulation of beta interferon (IFN-β) expression. This model is critical for understanding the mechanisms responsible for influenza disease attenuation during coinfection by unrelated respiratory viruses.IMPORTANCE Viral infections in the respiratory tract can cause severe disease and are responsible for a majority of pediatric hospitalizations. Molecular diagnostics have revealed that approximately 20% of these patients are infected by more than one unrelated viral pathogen. To understand how viral coinfection affects disease severity, we inoculated mice with a mild viral pathogen (rhinovirus or murine coronavirus), followed 2 days later by a virulent viral pathogen (influenza A virus). This model demonstrated that rhinovirus can reduce the severity of influenza A virus, which corresponded with an early but controlled inflammatory response in the lungs and early clearance of influenza A virus. We further determined the dose and timing parameters that were important for effective disease attenuation and showed that influenza disease is also reduced by coinfection with a murine coronavirus. These findings demonstrate that coinfecting viruses can alter immune responses and pathogenesis in the respiratory tract.
Efficient cu-catalyzed asymmetric conjugate additions of alkylzincs to trisubstituted cyclic enones.

The first examples of efficient catalytic asymmetric conjugate addition (ACA) of alkylzincs to trisubstituted cyclic enones is disclosed. These Cu-catalyzed reactions proceed efficiently with five- and seven-membered ring substrates to afford the desired products in ≥95% ee. Intermediate enolates can be trapped with alkyl halides to generate a quaternary stereogenic center. The requisite chiral ligand is prepared from commercially available materials and can be used in situ without further purification in the presence of commercial grade (CuOTf)2·PhMe.
Dipyrrolidinomethylaminophosphoric acid triamide (DPMPA) as an activator for the samarium diiodide-mediated reduction of alkyl and aryl halides

Abstract The use of the conjugate base of dipyrrolidinomethylaminophosphoric triamide (DPMPA−) as an activator of samarium diiodide is reported. This phosphoramidate has been shown to be a very potent ligand, allowing for the efficient, low-temperature reduction of alkyl and aryl chlorides. Reductive cyclizations of haloalkenylnaphthalenes are also reported.
Allylic etherification via Ir(I)/Zn(II) bimetallic catalysis.

An efficient allylic etherification of aliphatic alcohols with allylic carbonates has been achieved by an iridium catalysis using stoichiometric zinc alkoxides or a two-component bimetallic catalytic system where the Ir(I) catalyst acts on allylic carbonates to generate electrophiles while aliphatic alcohols are separately activated by Zn(II) coordination to function as nucleophilies. This reaction occurs with complete regiospecificity and tolerates a wide range of functional groups.
Advanced Soft Magnetic Materials for Magnetic Recording Heads and Integrated Inductors

High performance magnetic heads, inductors and transformers, indispensable to information technology encompassing from information storage, portable power delivery, to wireless communication, require soft magnetic films with low coercivities, high permeability, and large ferromagnetic resonance frequencies. The Fe-Co-N-based films have a ferromagnetic resonance frequency of >1 GHz at zero-bias field, showing great promise for applications in write heads and integrated inductors in a frequency range of >1 GHz. Magnetization dynamics measurements at sub-nanosecond scale have been performed on Fe-Co-N high saturation soft magnetic films with Permalloy nanolayer seeds having a saturation magnetization of 24 kG. The high frequency behavior appears to be affected by magnetic anisotropy dispersion. One of the biggest challenges facing integration of magnetic material onto silicon is the compatibility of magnetics with standard silicon processing techniques. Integrated inductors were realized using ground planes of Co-Ta-Zr (p=100μΩ-cm). The magnetic properties of Co-Ta-Zr showed no change even after undergoing high temperature processing. Inductors with 1μm Co-Ta-Zr produced inductance values up to 60% higher than the air core inductors at frequencies up to 1.4 GHz.
Palladium-Catalyzed Arylation of Enynes and Electron-Deficient Alkynes Using Diaryliodonium Salts

A new single-pot procedure for the synthesis of aryl alkynes is described. Palladium catalyzes the coupling reaction of diaryliodonium compounds with enynes and electron-deficient alkynes to give aryl alkynes in good yields.
Novel Sandwiched Intermetallic Selenoantimonates: Soft Synthesis and Characterization of Cu2SbSe3·0.5en and Cu2SbSe3·en†

Two novel two-dimensional (layered) intermetallic copper selenoantimonates Cu2SbSe3·0.5en (I) and Cu2SbSe3·en (II), have been prepared by soft solvothermal reactions of CuCl, SbCl3, and Se with A2Se (A = Na, K) in the presence of ethylenediamine. Single-crystal X-ray diffraction analyses show that both structures crystallize in the monoclinic crystal system. Compound I belongs to the P21/n (no. 14) space group with a = 6.399(1) A, b = 18.858(4) A, c = 6.786(1) A, β = 113.23(3)°, Z = 4, V = 752.5(2) A3, and II belongs to the Pn (no. 7) space group with a = 6.321(2) A, b = 11.841(2) A, c = 6.932(2) A, β = 111.59(2)°, Z = 2, V = 482.4(2) A3. Both compounds consist of Cu2SbSe3 layers separated by free ethylenediamine molecules. The intermetallic layers are very similar in I and II, but the orientations of the solvent molecules are different. Both compounds contain copper atoms of mixed-valence, Cu(I) and Cu(II), and both are semiconductors with intermediate band gaps (∼1.6 eV).
Ba2HgS5—A Molecular Trisulfide Salt with Dumbbell-like (HgS2)2– Ions

Ba2HgS5 was synthesized by cooling a molten mixture of BaS, HgS, and elemental sulfur. It crystallizes in the orthorhombic Pnma space group with a = 12.190(2) A, b = 8.677(2) A, c = 8.371(2) A, and dcalc = 4.77 g cm–3. Its crystal structure consists of isolated dumbbell-shaped (HgS2)2– and v-shaped S32– ions. These molecular anions are charge-balanced by Ba2+ cations. Raman spectroscopy shows three strong bands originating from symmetric, asymmetric, and bending vibrational modes of the S32– ions. X-ray photoelectron spectroscopic analysis confirms the presence of the trisulfide species. Ba2HgS5 has a bandgap of ∼2.4 eV. Electronic band structure calculations show that the bandgap is defined essentially by the p-orbitals of the sulfur atoms of the S32– group.
Lewis acid-catalyzed Meyer–Schuster reactions: methodology for the olefination of aldehydes and ketones

Abstract In principle, the most efficient and atom-economical means of converting an aldehyde or ketone into the homologated α,β-unsaturated ester is through addition/rearrangement sequences involving acetylenic π-bonds (Scheme 1). Implementation of such a strategy for the synthesis of α,β-unsaturated esters is presented: addition of ethoxyacetylene followed by scandium(III) triflate-catalyzed Meyer–Schuster rearrangement reaction. Stereoselectivities range from good to excellent in the formation of disubstituted α,β-unsaturated esters from aldehydes (Table 3). The two-stage olefination of even the most hindered ketones proceeds with near perfect efficiency (Table 4).
TDG regulates cell cycle progression in human neural progenitors

Background: As cells divide, they must both replicate their DNA and generate a new set of histone proteins. The newly synthesized daughter strands and histones are unmodified, and must therefore be covalently modified to allow for transmission of important epigenetic marks to daughter cells. Human pluripotent stem cells (hPSCs) display a unique cell cycle profile, and control of the cell cycle is known to be critical for their proper differentiation and survival. A major unresolved question is how hPSCs regulate their DNA methylation status through the cell cycle, namely how passive and active demethylation work to maintain a stable genome. Thymine-DNA glycosylase ( TDG ), an embryonic essential gene, has been recently implicated as a major enzyme involved in demethylation. Methods : We use human pluripotent stem cells and their derivatives to investigate the role of TDG in differentiation and proliferation. To perform loss of function of TDG, RNA Interference was used. To study the cell cyle, we engineered human pluripotent stem cells to express the FUCCI tool which marks cells at various stages of the cell cycle with distinct patterns of fluorescent proteins. We also used cell cycle profiling by FACS, and DNA methylation analysis to probe a connection between DNA demethylation and cell cycle. Results : Here we present data showing that TDG regulates cell cycle dynamics in human neural progenitors (NPCs) derived from hPSCs, leading to changes in cell cycle related gene expression and neural differentiation capacity. These data show that loss of TDG function can block differentiation by driving proliferation of neural progenitors. We also identify specific cell cycle related genes whose expression changes upon loss of TDG expression. Conclusions: These observations suggest that TDG and active demethylation play an important role in hPSC cell cycle regulation and differentiation.
Diastereoselective Synthesis of 2,4-Disubstituted Tetrahydropyranols and Ethers via a Prins-Type Cyclization Catalyzed by Scandium Triflate

Abstract The reaction of aldehydes with homoallylic alcohols catalyzed by scandium triflate gives rise to the formation of 2-substituted tetrahydropyran-4-ols and ethers in good overall yields and with ‘all- cis ’ configurations and high diastereoselectivities. The stereochemistries of these products were assigned with the assistance of coupling constants and NOE. Factors affecting the reaction have been examined in detail. The reaction was found to be most effective in chloroform. Various aromatic and aliphatic aldehydes underwent the cyclization smoothly. A catalytic cycle for this reaction has been proposed.
Catenation of Heterocyclic Non-Kekulé Biradicals to Tetraradical Prototypes of Conductive or Magnetic Polymers

Methods are described for the synthesis of bis-diazene precursors of catenated tetraradicals. Photodeazetation in a low-temperature matrix of the N-tosylpyrrole member of the series (13) gives mainly the monodeazetated biradical 34, which is characterized by its ESR spectrum as a triplet species. Determination of the absolute number of spins present and analysis of the kinetics of the photolysis show that the tetraradical 12 is present to the extent of only 0.2−0.5% of the concentration of the biradical. The spectrum of the tetraradical 12 therefore cannot be observed under these conditions, and its spin remains unknown. Photodeazetation of the bis-diazene precursor (35) in the thiophene series gives successively the green monodeazetated biradical 36 and the (also green) bis-deazetated tetraradical 11. The reactions of compound 11 with alkenes in thawed matrices and its lack of an ESR spectrum characterize the species as a singlet. The tetraradical 11 is a prototype of a nonclassical polymeric conductor. ...
Microwave enhanced greener synthesis of indazoles via nitrenes

Non-traditional methods (grinding, water-based biphasic reactions, microwave chemistry) were used for the preparation of Schiff bases from several amines and 2-nitrobenzaldehydes. These nitro compounds were allowed to react with triethyl phosphite under microwave irradiation for the generation of nitrenes that underwent insertion reactions to form indazoles. This procedure constitutes an energy-efficient, greener chemistry version of the Cadogan reaction for nitrene-based formation of nitrogen heterocycles.
Magnetic Disorder in the Frustrated Antiferromagnet Jarosite Arising from the H3O+···OH- Interaction

Iron jarosite solid solutions with varying K+/H 3 O+ ratios have been prepared and their magnetic properties investigated. The jarosite samples, with formulas K x (H 3 O) 1-x Fe 3 (OH)6(SO 4 ) 2 , (0 < x < 1), have been characterized by means of IR spectroscopy, elemental analysis and SQUID magnetic measurements. The ordering temperatures T max of these spin-frustrated antiferromagnets generally decrease with increasing content of interlayer hydronium ions. Magnetic disorder resulting from an interaction between the interlayer hydronium ions and the intralayer Fe 3+ -OH-Fe 3+ groups appears to be responsible for the decrease in T max values with an increasing hydronium content. The H 3 O + ··OH - interaction appears to exercise a more significant impact on the magnetic disorder in jarosites than the extent occupancy of the magnetic Fe 3+ ions.
Quantitative proteome-based guidelines for intrinsic disorder characterization

Intrinsically disordered proteins fail to adopt a stable three-dimensional structure under physiological conditions. It is now understood that many disordered proteins are not dysfunctional, but instead engage in numerous cellular processes, including signaling and regulation. Disorder characterization from amino acid sequence relies on computational disorder prediction algorithms. While numerous large-scale investigations of disorder have been performed using these algorithms, and have offered valuable insight regarding the prevalence of protein disorder in many organisms, critical proteome-based descriptive statistical guidelines that would enable the objective assessment of intrinsic disorder in a protein of interest remain to be established. Here we present a quantitative characterization of numerous disorder features using a rigorous non-parametric statistical approach, providing expected values and percentile cutoffs for each feature in ten eukaryotic proteomes. Our estimates utilize multiple ab initio disorder prediction algorithms grounded on physicochemical principles. Furthermore, we present novel threshold values, specific to both the prediction algorithms and the proteomes, defining the longest primary sequence length in which the significance of a continuous disordered region can be evaluated on the basis of length alone. The guidelines presented here are intended to improve the interpretation of disorder content and continuous disorder predictions from the proteomic point of view.
Two new noncentrosymmetric (NCS) polar oxides: syntheses, characterization, and structure-property relationships in BaMTe2O7 (M = Mg2+ or Zn2+).

Two new noncentrosymmetric (NCS) polar oxides, BaMgTe2O7 and BaZnTe2O7, have been synthesized and characterized, with their crystal structures determined by single crystal X-ray diffraction. The is...
Synthesis and Unusual Chemical Reactivity of Certain Novel 4,5-Disubstituted 7-Benzylpyrrolo[2,3-d][1,2,3]triazines

The fact that only two pyrrolo[2,3-d][1,2,3]triazines heterocycles had been reported in the literature prompted us to initiate studies designed to provide additional members of this ring system. Initial attempts to prepare additional derivatives of the 7-unsubstituted pyrrolo[2,3-d][1,2,3]triazin-4-ones were limited by their low chemical reactivity. Subsequently, 7-benzyl-5-carboxamidopyrrolo[2,3-d][1,2,3]triazin-4-one (16) was prepared from diethyl 2-nitropyrrole-3,4,-dicarboxylate via an alkylation, ammonolysis, reduction and intramolecular diazocoupling sequence. Conversion of 16 into 7-benzyl-4-(1,2,4-triazol-1-yl)pyrrolo[2,3-d][1,2,3]triazine-5-carbonitrile (17) was accomplished, and nucleophilic displacements of the 4-triazol-1-yl group were studied. Treatment of 17 with NH3/CH3CN gave a mixture of 4-amino-7-benzylpyrrolo[2,3-d][1,2,3]triazine-5-carbonitrile (19) and 2-amino-1-benzylpyrrole-3,4-dicarbonitrile (21). A mechanism to account for the formation of this mixture is described along with stud...
Bis-S-acyl-2-thioethyl (sate)-bearing monophosphate prodrug of β-L-FD4C as potent anti-HBV agent

Abstract The S-acyl-2-thioethyl (SATE)-bearing 5′-monophosphate prodrug of β-L-FD4C (8) was synthesized and evaluated for its activity against HBV in the 2.2.15 cell line. This pronucleotide (8) exhibited an excellent inhibitory effect against HBV with an EC50 value that is more than eight fold lower than that of the parent nucleoside (4) under some assay conditions. It is also important to note that pronucleotide (8) was capable of inhibiting HBV replication by 90%; whereas its parent, β-L-FD4C (4), could only inhibit virus replication no greater than 70% in the same assay. When evaluated in the standard cytotoxicity assay in CEM cell line, pronucleotide (8) exhibited an IC50 value of 52 μM, which was four times less toxic than parent β-L-FD4C (4) (IC50 = 13 μM).
Advanced Materials: Trends and Possibilities in Liquid Crystalline Polymers

During the past ten years there has been a sharp increase in interest in the opportunities afforded by R & D in the field of specialty polymers. Interest is mainly being shown in two distinct categories of polymers, namely, (a) polymers which are used in very small quantities to fulfill critical needs as a part of device system, and (b) high-performance engineering polymers which significantly extend their mechanical and thermal properties for structural applications. The first category ranges from advanced resists and insulating layers for microelectronic devices to membranes for filtration systems. The second category encompasses improved matrices for advanced composites as well as liquid crystalline polymers. In the present paper an overview is first given of the emerging opportunities for advanced materials and particularly specialty polymers. The status of work on liquid crystalline copolyesters is then discussed with special emphasis on one of the major problems confronting this field, namely interpreting the microstructure of the copolyesters.