cssi/SciSciGPT-SciSciNet huggingface dataset:
Energy Absorption and Low Velocity Impact Response of Open-Cell Polyurea Foams

The energy absorption and impact attenuation of low density polyurea (PU) foams (140–220 kg/m3) is presented. The stress–strain behavior, energy absorption, cushioning efficiency, and energy return (resilience) are measured at a quasi-static strain rate using an Instron load frame. In addition, the low velocity impact attenuation of the polyurea foams at 5 J and 7 J impact energies were investigated according to the American Society for Testing and Materials (ASTM) test methods F1976. The polyurea foams were then compared with widely used ethylene vinyl acetate (EVA) and thermoplastic polyurethane (TPU) foam technologies at similar densities. The PU foams displayed a 5% increase in cushioning efficiency and 30% greater energy absorption over TPU and EVA foams under quasi-static compression. Under impact testing, PU foams resulted in a reduction of up to 28.6% and 36.9% in peak transmitted impact forces when compared to EVA and TPU foams of the same thickness (20 mm) at 5 J and 7 J, respectively. These properties should allow these materials to have a wide range of cushioning/impact applications, especially as midsoles in athletic footwear.
Non-Linear Reasoning For Invariant Synthesis

The ability of program-analysis tools to identify program invariants is hampered by the capabilities of present-day solvers for handling non-linear arithmetic—including polynomials, exponentials, and logarithms. Improved capabilities for reasoning about non-linear functions would help program analyzers establish important program invariants. For instance, reasoning about exponentials provides a way to find invariants of digital-filter programs; reasoning about polynomials and/or logarithms is needed for establishing invariants that describe the time or memory usage of many well-known algorithms. This paper describes the techniques used in an arithmetic-reasoning kit to represent logarithmic and exponential relationships indirectly, using uninterpreted-function symbols and integrity constraints. It also describes a recurrence-relation solver—used to find invariants of loops—that handles two classes of recurrences: * Ones of the form $x_{n+1} = b*x_n + f(n)$, where $b$ is a constant, and $f(n)$ is a sum of polynomials, exponentials, or products of a polynomial and an exponential. * Ones of the form $\mathbf{y_{n+1}} = \mathbf{A}\mathbf{y_n} + \mathbf{f(n)}$, where $\mathbf{y_n}$ is a vector of variables, $\mathbf{A}$ is a rational matrix, and $\mathbf{f(n)}$ is a vector of functions, where each entry is a sum of polynomials, exponentials, or products of a polynomial and an exponential.
Virtually the Same: Comparing Physical and Virtual Testbeds

Network designers, planners, and security professionals increasingly rely on large-scale testbeds based on virtualization to emulate networks and make decisions about real-world deployments. However, there has been limited research on how well these virtual testbeds match their physical counterparts. Specifically, does the virtualization that these testbeds depend on actually capture real-world behaviors sufficiently well to support decisions?As a first step, we perform simple experiments on both physical and virtual testbeds to begin to understand where and how the testbeds differ. We set up a web service on one host and run ApacheBench against this service from a different host, instrumenting each system during these tests.We define an initial repeatable methodology (algorithm) to quantitatively compare physical and virtual testbeds. Specifically we compare the testbeds at three levels of abstraction: application, operating system (OS) and network. For the application level, we use the ApacheBench results. For OS behavior, we compare patterns of system call orderings using Markov chains. This provides a unique visual representation of the workload and OS behavior in our testbeds. We also drill down into read-system-call behaviors and show how at one level both systems are deterministic and identical, but as we move up in abstractions that consistency declines. Finally, we use packet captures to compare network behaviors and performance. We reconstruct flows and compare per-flow and per-experiment statistics.From these comparisons, we find that the behavior of the workload in the testbeds is similar but that the underlying processes to support it do vary. The low-level network behavior can vary quite widely in packetization depending on the virtual network driver. While these differences can be important, and knowing about them will help experiment designers, the core application and OS behaviors still represent similar processes.
Fast tabulation of challenge pseudoprimes

We provide a new algorithm for tabulating composite numbers which are pseudoprimes to both a Fermat test and a Lucas test. Our algorithm is optimized for parameter choices that minimize the occurrence of pseudoprimes, and for pseudoprimes with a fixed number of prime factors. Using this, we have confirmed that there are no PSW challenge pseudoprimes with two or three prime factors up to $2^{80}$. In the case where one is tabulating challenge pseudoprimes with a fixed number of prime factors, we prove our algorithm gives an unconditional asymptotic improvement over previous methods.
Deep Ahead-of-Threat Virtual Patching

Many applications have security vulnerabilities that can be exploited. It is practically impossible to find all of them due to the NP-complete nature of the testing problem. Security solutions provide defenses against these attacks through continuous application testing, fast-patching of vulnerabilities, automatic deployment of patches, and virtual patching detection techniques deployed in network and endpoint security tools. These techniques are limited by the need to find vulnerabilities before the ‘black hats’. We propose an innovative technique to virtually patch vulnerabilities before they are found. We leverage testing techniques for supervised-learning data generation, and show how artificial intelligence techniques can use this data to create predictive deep neural-network models that read an application’s input and predict in real time whether it is a potential malicious input. We set up an ahead-of-threat experiment in which we generated data on old versions of an application, and then evaluated the predictive model accuracy on vulnerabilities found years later. Our experiments show ahead-of-threat detection on LibXML2 and LibTIFF vulnerabilities with 91.3% and 93.7% accuracy, respectively. We expect to continue work on this field of research and provide ahead-of-threat virtual patching for more libraries. Success in this research can change the current state of endless racing after application vulnerabilities and put the defenders one step ahead of the attackers.
Synthetic Baseload and Intermediate Decarbonization

Synthetic baseload (SBL) generation is power generation at a constant ("baseload") rate by a plant composed of flexible thermal generation, such as a combined cycle gas turbine (CCGT) plant, and one or more sources of variable renewable energy (VRE). The paper uses the notion of SBL as an analytic construct and conducts a high-level (basic business case, exploratory) economic analysis. At current U.S. prices for natural gas and VRE (solar PV and wind power), SBL is in many locations either economically attractive now or close to it. SBL would be unambiguously attractive economically with a price on carbon of $60 per metric ton, or even less in some areas. The paper finds that two distinct approaches to assessing fuel price risk - a decision analysis approach and a hedging approach based on a zero-cost collar - agree that the resulting adjusted cost of natural gas (incorporating the cost of risk) makes SBL widely economically attractive. SBL, whether driven by cost fundamentals or prodded by regulation, affords an economic path to intermediate decarbonization of the electric power system.
Effect of Transit Signal Priority on Bus Service Reliability

Abstract As every user knows buses tend to bunch. To alleviate this problem, transit agencies introduce slack into their schedules and then hold buses back to schedule at pre-established control points along their routes. Unfortunately, this practice retards buses and only works with low frequency systems; i.e., when the headways are long. For higher frequency systems, which effectively operate without a schedule, headway-based control strategies show promise but unfortunately, they also retard buses. To alleviate bus retardation in all its forms, transit signal priority (TSP) is commonly used. Curiously however, the potential of TSP to enhance bus control practices has not been explored in detail. This paper evaluates a form of TSP designed for this purpose. In this version of TSP, which we call conditional signal priority (CSP), buses send priority requests only when the requests improve reliability. The evaluation includes both scheduled (low frequency) systems, and unscheduled (high frequency) systems operated by headways. A mathematical model based on Brownian motion is proposed for the former. This model allows us to optimize the CSP strategy and to develop formulas for the expectation and variance of the steady state deviations from the schedule-with CSP, with conventional TSP and with neither. Simulations confirm the accuracy of these findings. It is found that CSP improves reliability considerably and that it is better for traffic than TSP because it reduces the number of priority requests. For high frequency systems operated with a fixed number of buses CSP is shown to not just improve reliability and reduce the number of priority requests of TSP (by about 50%) but also to reduce the average headway by speeding up the buses. This paper has been accepted for a podium presentation at the 23rd International Symposium on Transportation and Traffic Theory (ISTTT23) July 24-26, 2019 in Lausanne, CH.
The Effect of CIO Virtues on CIO Role Effectiveness

This paper aims to contribute to the concept of ethical CIO leadership through a distinctive focus on virtue ethics. Our research investigates the theoretical significance of CIO virtues on two CIO capabilities and their corresponding influence on the CIO’s role effectiveness in organizations.
Dislocation Arrangement in a Thick LEO GaN Film on Sapphire

Diffraction-contrast TEM, focused probe electron diffraction, and high-resolution X-ray diffraction were used to characterize the dislocation arrangements in a 16µm thick coalesced GaN film grown by MOVPE LEO. As is commonly observed, the threading dislocations that are duplicated from the template above the window bend toward (0001). At the coalescence plane they bend back to lie along [0001] and thread to the surface. In addition, three other sets of dislocations were observed. The first set consists of a wall of parallel dislocations lying in the coalescence plane and nearly parallel to the substrate, with Burgers vector (b) in the (0001) plane. The second set is comprised of rectangular loops with b = 1/3 $$\left[ {11\,\,\bar 20} \right]$$ (perpendicular to the coalescence boundary) which originate in the coalescence boundary and extend laterally into the film on the $$\left( {1{\text{ }}\bar 100} \right)$$ . The third set of dislocations threads laterally through the film along the $$\left[ {1{\text{ }}\bar 100} \right]$$ bar axis with $$1/3\left\langle {11{\text{ }}\bar 20} \right\rangle $$ -type Burgers vectors These sets result in a dislocation density of ∼109 cm−2. High resolution X-ray reciprocal space maps indicate wing tilt of ∼0.5o.
Item-specific delay activity demonstrates concurrent storage of multiple active neural representations in working memory.

Persistent neural activity that encodes online mental representations plays a central role in working memory (WM). However, there has been debate regarding the number of items that can be concurrently represented in this active neural state, which is often called the “focus of attention.” Some models propose a strict single-item limit, such that just 1 item can be neurally active at once while other items are relegated to an activity-silent state. Although past studies have decoded multiple items stored in WM, these studies cannot rule out a switching account in which only a single item is actively represented at a time. Here, we directly tested whether multiple representations can be held concurrently in an active state. We tracked spatial representations in WM using alpha-band (8–12 Hz) activity, which encodes spatial positions held in WM. Human observers remembered 1 or 2 positions over a short delay while we recorded electroencephalography (EEG) data. Using a spatial encoding model, we reconstructed active stimulus-specific representations (channel-tuning functions [CTFs]) from the scalp distribution of alpha-band power. Consistent with past work, we found that the selectivity of spatial CTFs was lower when 2 items were stored than when 1 item was stored. Critically, data-driven simulations revealed that the selectivity of spatial representations in the two-item condition could not be explained by models that propose that only a single item can exist in an active state at once. Thus, our findings demonstrate that multiple items can be concurrently represented in an active neural state.
5-(Trimethylstannyl)-2H-pyran-2-one and 3-(Trimethylstannyl)-2H-pyran-2-one: New 2H-Pyran-2-one Synthons.

5-(Trimethylstannyl)-2H-pyran-2-one (11) and 3-(trimethylstannyl)-2H-pyran-2-one (30), readily prepared from the corresponding bromo-2H-pyran-2-ones, undergo Pd(0)-catalyzed coupling reactions with a variety of enol triflates to give 5- and 3- substituted 2H-pyran-2-ones, respectively. This reaction is applicable to the enol triflates of 14β-hydroxy-17-ketosteroids, and therefore may prove useful in convergent syntheses of lucibufagins and bufadienolides.
New cuprates featuring ladderlike periodic arrays of [Cu3O8]10- trimeric magnetic nanostructures.

A new family of cuprates, Li2Cu3(SiO3)4 (1) and Na2Cu3(GeO3)4 (2), was isolated in molten salt media. The extended lattices contain ladderlike periodic arrays of [Cu3O8]10- magnetic nanostructures. Magnetic properties of the Na2Cu3Ge4-xSixO12 series, where x = 0, 0.86, and 1.72, were systematically studied. The geometrically induced magnetic couplings are tunable upon cation substitution.
Kinetics and mechanisms of the oxidation of hydrazinium ion (N2H5+) by aqueous Br2, Cl2, and BrCl. Electrophilicity scale for halogens and interhalogens.

Very rapid oxidations of N2H5+ by Br2, Cl2, and BrCl are measured by stopped−flow and pulsed−accelerated-flow methods in acidic solutions with excess N2H5+. Second-order rate constants (M-1 s-1) at 25.0 °C, μ = 1.0 M are 1.49 × 107, 1.01 × 108, and 5.6 × 108 for the reactions with Br2, Cl2, and BrCl, respectively. The reactions are postulated to proceed by nucleophilic reaction of N2H5+ with XY electrophiles (XY = Br2, Cl2, BrCl) to form XN2H4+ with Y- and H+ release in the rate-determining step. In the subsequent reactions, we propose that XN2H4+ eliminates X- and H+ rapidly to form N2H3+ and diazine, N2H2, which is oxidized by a second Br2, Cl2, or BrCl to form N2 in fast steps. The stoichiometries are measured and confirmed to be 1:2 for the Cl2 and BrCl reactions. The relative reactivities for the oxidation of N2H5+ by halogens and interhalogens (BrCl > Cl2 > Br2 > ICl ≫ IBr ≫ I2) are used to establish an electrophilicity scale (EXY) for this type of reaction in aqueous solution.
Asymmetric Catalysis with Chiral Porous Metal–Organic Frameworks: Critical Issues

Chiral metal–organic frameworks (MOFs) have shown great promise as highly efficient and recyclable heterogeneous catalysts in asymmetric reactions. Following a brief introduction of basic concepts and potential virtues of MOFs in catalysis, five critical issues pertinent to the fundamental understanding of MOF asymmetric catalysis are discussed: strategies to construct and sustain reagent-accessible channels, framework distortion and characterization of large open channels in MOFs, substrate diffusion through the MOF channels, the dependence of catalytic activities and stereoselectivities on MOF open channel sizes, and detailed elucidation of structure–property relationships via single-crystal-to-single-crystal transformations. A perspective on further development of chiral MOF catalysts in the potential production of optically pure organic molecules is also given.
Synthesis of Aminated Naphthacenetriones: Precursors to Aminated Anthracyclines

Abstract An application of aminoacetaldehyde dialkoxy acetal to introduce an amino fuctionality in the 6 and/or 11 position of the naphthacenetrione ring system, resulting in key intermediates to aminated anthracyclines, is described.
Solid-State Chemistry of a Novel Carbapenem with a Releasable Sidechain

Abstract The solid-state chemistry of amorphous and crystalline forms of a novel cationic 1-β-methyl carbapenem antibiotic 2 is described. The lyophilized chloride salt of 2 ( 2 ·Cl) is amorphous and exhibits moisture-dependent β-lactam hydrolysis rates. Hydrolysis is concomitant with ejection of the sidechain naphthosultam moiety 4 . In the lyophilized solid (with 1.8% w/w water or less), a significant contribution from a Hofmann-like elimination reaction within the sidechain structure to give products 6 and 7 is observed. Another less significant elimination pathway involving loss of acetamide from the sidechain to form 8 is also operating at low residual moisture contents. Co-lyophilization of 2 ·Cl with sucrose decreases the rate of the reactions within the sidechain as well as β-lactam hydrolysis, concomitant with a slight increase in the strength of the glassy lyophilized product based on modulated differential scanning calorimetry (MDSC). Kinetics of degradation of 2 ·Cl lyophilized in the presence of 1% trisodium citrate and 50% weight of sucrose showed a 30–40% increase in overall initial rate of degradation at 25 and 40°C with increasing moisture from 0.3 to 1.1% residual water. Moisture enhances the stability of the N , N ′-dialkyl 1,4-diaza[2.2.2]bicyclooctane (DABCO) sidechain structure in 2 ·Cl, and this protective effect slightly offsets the increase in hydrolysis rate observed with increasing moisture. The crystalline benzenesulfonate trihydrate ( 2 ·PhSO 3 ) was characterized and found to have improved thermal stability in the solid state relative to the amorphous 2 ·Cl, particularly in terms of the elimination pathway.
On the Long-Time Behavior of a Perturbed Conservative System with Degeneracy

We consider in this work a model conservative system subject to dissipation and Gaussian-type stochastic perturbations. The original conservative system possesses a continuous set of steady states and is thus degenerate. We characterize the long-time limit of our model system as the perturbation parameter tends to zero. The degeneracy in our model system carries features found in some partial differential equations related, for example, to turbulence problems.
Scaling of G1 Duration with Population Doubling Time by a Cyclin in Saccharomyces cerevisiae.

The longer cells stay in particular phases of the cell cycle, the longer it will take these cell populations to increase. However, the above qualitative description has very little predictive value, unless it can be codified mathematically. A quantitative relation that defines the population doubling time (Td) as a function of the time eukaryotic cells spend in specific cell cycle phases would be instrumental for estimating rates of cell proliferation and for evaluating introduced perturbations. Here, we show that in human cells, the length of the G1 phase (TG1) regressed on Td with a slope of ≈0.75, while in the yeast Saccharomyces cerevisiae, the slope was slightly smaller, at ≈0.60. On the other hand, cell size was not strongly associated with Td or TG1 in cell cultures that were proliferating at different rates. Furthermore, we show that levels of the yeast G1 cyclin Cln3p were positively associated with rates of cell proliferation over a broad range, at least in part through translational control mediated by a short upstream ORF (uORF) in the CLN3 transcript. Cln3p was also necessary for the proper scaling between TG1 and Td. In contrast, yeast lacking the Whi5p transcriptional repressor maintained the scaling between TG1 and Td. These data reveal fundamental scaling relationships between the duration of eukaryotic cell cycle phases and rates of cell proliferation, point to the necessary role of Cln3p in these relationships in yeast, and provide a mechanistic basis linking Cln3p levels to proliferation rates and the scaling of G1 with doubling time.
A synthetic route to 3-(dialkylamino)phenothiazin-5-ium salts and 3,7-disubstituted derivatives containing two different amino groups

Phenothiazin-5-ium tetraiodide hydrate (2), the suggested oxidation product of phenothiazine with iodine, is treated with two equivalents of a dialkylamine to give 3-(dialkylamino)phenothiazin-5-ium triiodides (3-6). 3,7-Disubstituted phenothiazin-5-ium iodides (7-9) are obtained by the reaction of (3-6) with an amine
Synthesis of n-heteroaryl-7-azabicyclo[2.2.1]heptane derivatives via palladium-bisimidazol-2-ylidene complex catalyzed amination reactions.

A one-step approach to novel N-heteroaryl-substituted-7-azabicyclo[2.2.1]heptanes from readily available heteroaryl halides and 7-azabicyclo[2.2.1]heptane has been achieved. The cross-coupling amin...
Diastereoselective fluorination of chiral imide enolates using N-fluoro-O-benzenedisulfonimide (NFOBS)

Abstract α-Fluoro acids (78–90% ee) and β-fluoro alcohols (89–>95%ee) of well defined stereochemistry are prepared via the diastereoselective fluorination of chiral imide enolates with NFOBS (3).
Synthesis and photoproperties of diamagnetic octabutoxyphthalocyanines with deep red optical absorbance

The synthesis and photoproperties of six new metal 1,4,8,11,15,18,22,25-octabutoxyphthalocyanines and photoproperties of the known, analogous Zn and metal-free phthalocyanines are described. The new compounds are AlPc(OBu){sub 8}OSiEt{sub 3}, GaPc(OBu){sub 8}OSiEt{sub 3}, GePc(OBu){sub 8}(OSiEt{sub 3}){sub 2}, SnPc(OBu){sub 8}(OSiEt{sub 3}){sub 2}, RuPc(OBu){sub 8}(py){sub 2}, and PdPc(OBu){sub 8} (where Pc(OBu){sub 8} represents the octabutoxyphthalocyanine ligand). Benzene-d{sub 6} solutions of all eight of the compounds give NMR spectra showing large ring-current effects. Benzene solutions of the compounds give visible spectra with absorption maxima in the 688-779-nm range having extinction coefficients between 1.0 {times} 10{sup 5} and 2.2 {times} 10{sup 5} M{sup {minus}1} cm{sup {minus}1}. The triplet-state properties of the phthalocyanines in benzene solutions have been measured by laser flash photolysis. The triplet states have absorption maxima in the 550-640-nm range, quantum yields in the 0.1-0.9 range, and lifetimes when the solutions are deaerated in the 0.5-150-{mu}s range. The rate constants for energy transfer from the triplet states of the compounds to O{sub 2} are between 1.3 {times} 10{sup 8} and 2.8 {times} 10{sup 9} M{sup {minus}1} s{sup {minus}1}.
Detecting different oxygen-ion jump pathways in Bi2WO6 with 1- and 2-dimensional 17O MAS NMR spectroscopy

Bismuth tungsten oxide (Bi2WO6) is an m = 1 Aurivillius phase and some of its doped compounds show moderately high oxygen ion conductivity. These materials are structurally related to the more diso...
Amine-catalyzed direct asymmetric Mannich-type reactions

Three chiral cyclic secondary amines are shown to be catalysts for the direct asymmetric Mannich-type reaction of acetone with a variety of preformed aldimines derived from o-anisidine. A simple one-pot three-component reaction procedure consisting of aldehyde, acetone, p-anisidine and an amine catalyst provides the corresponding β-amino ketones with 50–89% ee under very mild conditions.
Synthesis, characterization and solution 113Cd NMR analysis of Cd(II) 1,4,7,10,13-pentaazacyclopentadecane complexes

Two new cadmium(II) complexes of the macrocyclic ligand, 1,4,7,10,13-pentaazacyclopentadecane 5 , have been prepared and characterized. The crystal structure of dichlorocadmium(II) complex 3 was determined and reveals that the Cd(II) is coordinated in a pentagonal bipyramidal array of the five nitrogens of the macrocyclic ring and capped by two trans -chloro ligands. Crystal data for Cd(C 10 H 25 N 5 )Cl 2 –0.5H 2 O are as follows: monoclinic at 20 °C, space group C2/c−C 6 2h (No. 15) with a =22.165(5) A, b =11.439(3) A, c =14.6788(4) A, β =118.75(2)°, V =3262(2) A 3 and Z =8 [ d calcd =1.660 g cm −3 ; μ a (Mo K α )=1.66 mm −1 ]. Solution 1 H, 13 C and 113 Cd NMR studies of complex 3 suggest that in non-polar solvents, such as CDCl 3 , the seven-coordinate structure is maintained, while in aqueous media dissociation of one axial chloride ligand affords a macrocyclic ligand-folded six-coordinate species. This is analogous to the dichloromanganese(II) complex 1 . Folding of the pentaazamacrocyclic ligand 5 is confirmed as a relevant structural motif for this series of complexes by the X-ray structure determination of the bis(nitrate) derivative. Complex 4 [Cd(C 10 H 25 N 5 )NO 3 ]NO 3 reveals a six-coordinate structure with a folded conformation of the macrocyclic ligand. Crystal data for [Cd(C 10 H 25 N 5 )NO 3 ]NO 3 is as follows: orthorhombic at 20 °C, space group P2 1 2 1 2 1 −D 4 2 (No. 19) with a =9.627(2) A, b =12.858(2) A, c =14.003(2) A, V =1733.3(6) A 3 and Z =4 [ d calcd =1.731 g cm −3 ; μ a (Mo K α )=1.30 mm −1 ]. Solution 1 H, 13 C and 113 Cd NMR studies of complex 4 suggest six-coordinate structures in both CDCl 3 and D 2 O, again with the macrocyclic ligand in a folded conformation. Again, this is entirely analogous to the Mn(II) bis(nitrate) complex 2 . 113 Cd NMR shifts are consistent with literature predictions for the types and numbers of coordinating ligands in complexes 3 and 4 in both NMR solvents. Figure options Download full-size image Download as PowerPoint slide
A One-Pot Umpolung Method for Preparation of α-Aryl Nitriles from α-Chloro Aldoximes via Organocuprate Additions to Transient Nitrosoalkenes

Conjugate addition of a variety of aryl lithiocyanocuprates to nitrosoalkenes generated from α-chloro aldoximes, followed by in situ dehydration of the crude α-aryl aldoxime product with N , N ′-dicyclohexylcarbodiimide, affords α-aryl nitriles in good overall yields via a one-pot protocol.
Enantioselective Synthesis of α-Amino Acids from N-Tosyloxy β-Lactams Derived from β-Keto Esters‡

A novel synthetic sequence has been developed to convert simple beta-keto esters into enantiomerically enriched alpha-amino acids. The key features of this sequence include the addition of azide to the C3 position of beta-keto ester derived N-tosyloxy-beta-lactams through a concomitant nucleophilic addition/N-O bond reduction reaction, a mild CsF-induced N1 benzylation of alpha-azido monocyclic beta-lactams, the preparation of alpha-keto-beta-lactams through a novel four-step sequence from the corresponding 3-azido-1-benzyl-beta-lactams, and TEMPO-mediated ring expansion of these compounds to the corresponding N-carboxy anhydrides (NCAs). In addition, the synthesis, isolation, and characterization of unusual 3-imino and 3-chloramino-beta-lactams is reported.
Coin, Currency, and Constitution: Reconsidering the National Bank Precedent

The constitutional debates surrounding the First and Second Banks of the United States generated the first major precedents regarding the scope of federal legislative powers, and their importance continues to resonate today. Eric Lomazoff's important new book, Reconstructing the National Bank Controversy, is the first scholarly study that views the National Bank controversy as a continuous 55-year sequence of events, whose highlights include the adoption of Alexander Hamilton's proposed Bank of the United States in 1791, John Marshall's decision in McCulloch v. Maryland in 1819, and Andrew Jackson's veto of the Second Bank recharter in 1832. Lomazoff persuasively establishes that a Madisonian consensus supporting the creation of the Second Bank in 1816 " largely overlooked by constitutional scholars " was framed in a way that tried, albeit unsuccessfully, to downplay the Necessary and Proper Clause and the idea of implied powers by emphasizing the existence of a federal power to regulate the national currency, linked to the Coinage Clause. The book review goes on to argue that the National Bank controversy demonstrates that many antebellum partisans of limited enumerated powers -- mainstream Jeffersonian Republicans, Jacksonian Democrats, and even James Madison himself -- were quite happy to work around enumerated powers in order to meet the political demands and objectives of the moment. This lends support to the suggestion that enumerationism (the ideology of limited enumerated powers) was never, in practice, the "true" original meaning of the Constitution.
KCuCeTe4 : A new intergrowth rare earth telluride with an incommensurate superstructure associated with a distorted square net of tellurium

The quaternary compound KCuCeTe4 has an ordered intergrowth structure made of KCuTe and CeTe3 layers. The CeTe3 layers have square nets of tellurium atoms which are structurally distorted to give rise to an incommensurate superstructure.
Microwave‐mediated pyrazole fluorinations using selectfluor®

Microwave-mediated electrophilic fluorinations and a new single-pot condensation en route to ring-fluorinated pyrazoles were examined: The monofluorination by these methods was successful for a variety of pyrazoles, with yields ranging from 13% to 75%. While electrophilic aromatic fluorination of 3-CF3 pyrazoles proved largely ineffective, development of a single-pot process overcame this limitation. The microwave-mediated reaction is regioselective; ring fluorination of the heterocycle occurs preferentially over phenyl and alkyl substituents. Alkyl side chain fluorination, when desired, can be modulated by reactant ratios. The single-pot method, which involves acid catalysis by H-TEDA, produces 4-fluoropyrazoles products. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:341–345, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20556
STUDIES ON THE INDIUM-MEDIATED REDUCTION OF IMINES

Indium-ammonium chloride-mediated reduction of imines was investigated and the products were found to be monoamines.
Passenger mutations can accelerate tumour suppressor gene inactivation in cancer evolution

Carcinogenesis is an evolutionary process whereby cells accumulate multiple mutations. Besides the ‘driver mutations’ that cause the disease, cells also accumulate a number of other mutations with ...
Kinase-Targeted Library Design through the Application of the PharmPrint Methodology

The PharmPrint methodology, as modified and implemented by Deanda and Stewart, was prospectively evaluated for use as a virtual high-throughput screening tool by applying it to the design of target-focused arrays. To this end, PharmPrint quantitative structure-activity relationship (QSAR) models for the prediction of AKT1, Aurora-A, and ROCK1 inhibition were constructed and used to virtually screen two large combinatorial libraries. Based on predicted activities, an Aurora-A targeted array and a ROCK1 targeted array were designed and synthesized. One control group per designed array was also synthesized to assess the enrichment levels achieved by the QSAR models. For the Aurora-A targeted array, the hit rate, against the intended target, was 42.9%, whereas that of the control group was 0%. Thus, the enrichment level achieved by the Aurora-A QSAR model was incalculable. For the ROCK1 targeted array, the hit rate against the intended target was 30.6%, whereas that of the control group was 5.10%, making the enrichment level achieved by the ROCK1 QSAR model 6-fold above control. Clearly, these results support the use of the PharmPrint methodology as a virtual screening tool for the design of kinase-targeted arrays.
Synthesis of a Double Alkoxide Precursor to Spinel (MgAl2O4) Directly from Al(OH)3, MgO, and Triethanolamine and Its Pyrolytic Transformation to Spinel

Reaction of Al(OH)3 and MgO or Mg(OH)2 with triethanolamine [TEA, N(CH2CH2OH)3] in ethylene glycol (EG) provides, in one step, access to a polymer-like precursor to spinel. On the basis of high-resolution mass spectroscopy, chemical analysis and 27Al solution NMR, the precursor appears to be a trimetallic double alkoxide consisting of two four-coordinate TEAA1 (alumatrane) moieties linked via a bridging TEA group that enfolds the Mg cation. The 27Al NMR shows only tetracoordinate Al centers (64.8 ppm). The same compound can be prepared stepwise by reaction of tetrameric alumatrane, (TEAAl)4, with Mg and TEA. Product evolution upon pyrolysis was followed as a function of temperature using TGA, DTA, XRD, and diffuse reflectance infrared spectroscopy (DRIFTS). Pyrolysis at 700 °C for 2 h in air appears to produce a γ-Al2O3-MgAl2O4 solid solution and a small amount (<5 wt %, by TGA) of X-ray amorphous MgCO3. Transformation of the solid solution to pure spinel is a function of pyrolysis temperature and time, w...
Synthesis of 5,6-bis(alkyn-1-yl)pyrimidines and related nucleosides

Abstract Sonogashira coupling of 5-iodo-1-methyluracil or 5′- O -TBDMS-5-iodo-2′,3′- O -isopropylideneuridine with alkynes gave 5-(alkyn-1-yl) derivatives that underwent 6-lithiation/iodination to give 5-(alkyn-1-yl)-6-iodo-(1-methyluracil or uridine) intermediates (57–80%). Coupling of the 5-(alkyn-1-yl)-6-iodo intermediates gave 5,6-bis(alkyn-1-yl)pyrimidines and protected nucleosides (51–79%). Two of the 5,6-bis(ethynyl)-1,3-dimethyluracil derivatives underwent Bergman cycloaromatization at 130°C with half-lives of 2–8 h.
Enantioselective synthesis of P-stereogenic benzophospholanes via palladium-catalyzed intramolecular cyclization.

Enantioselective or diastereoselective intramolecular cyclization of functionalized secondary phosphines or their borane adducts catalyzed by chiral Pd(diphosphine) complexes gave P-stereogenic benzophospholanes in up to 70% ee. These results provide a new method for the synthesis of chiral phospholanes, which are valuable ligands in asymmetric catalysis.
Compounds That Contract on Heating

Various mechanisms to explain negative thermal expansion in oxides are presented. Our search for compounds having this unusual property has focused on the mechanism based on transverse thermal motion of oxygen in M−O−M linkages. Such a mechanism can give strong negative thermal expansion over broad temperature ranges. Examples of compounds where this mechanism operates to give negative thermal expansion are ZrW2O8, the Sc2W3O12 family, NbOPO4, AlPO4-17, and faujasite SiO2.
Differential Splicing of ANP32A in Birds Alters Its Ability to Stimulate RNA Synthesis by Restricted Influenza Polymerase.

Summary Adaptation of viruses to their hosts can result in specialization and a restricted host range. Species-specific polymorphisms in the influenza virus polymerase restrict its host range during transmission from birds to mammals. ANP32A was recently identified as a cellular co-factor affecting polymerase adaption and activity. Avian influenza polymerases require ANP32A containing an insertion resulting from an exon duplication uniquely encoded in birds. Here we find that natural splice variants surrounding this exon create avian ANP32A proteins with distinct effects on polymerase activity. We demonstrate species-independent direct interactions between all ANP32A variants and the PB2 polymerase subunit. This interaction is enhanced in the presence of viral genomic RNA. In contrast, only avian ANP32A restored ribonucleoprotein complex assembly for a restricted polymerase by enhancing RNA synthesis. Our data suggest that ANP32A splicing variation among birds differentially affects viral replication, polymerase adaption, and the potential of avian hosts to be reservoirs.
Conformationally constrained bis(oxazoline) derived chiral catalyst: A highly effective enantioselective Diels-Alder reaction

Abstract The reaction of cyclopentadiene with various bidentate dienophiles in the presence of 4–10 mol% of copper(II)-bis(oxazoline) complexes afforded excellent endo/exo selectivity as well as endo enantioselectivity (95–99% ee) and isolated yields. On the other hand, Diels-Alder reaction with Mg(II)-complexes afforded a modest (61% ee) reversal in enantioselectivity.
Structure, Stoichiometry, and Morphology of Bromine Hydrate†

The hydrate of bromine was one of the first clathrate hydrates discovered. It has played a significant role in the development of the solid solution theory of clathrate hydrates, yet its detailed structure remains unknown. This hydrate again has become a test case for two different views of clathrates: the solid solution model, after van der Waals and Platteeuw, that sees clathrates as unstable lattices which derive stability from a minimum degree of cage filling and thus are nonstoichiometric, and a view promoted by Dyadin and Aladko that all large cages in a hydrate structure need to be filled. In light of the latter view, existing data obtained over the last ∼160-year period on the composition and morphology of bromine hydrate would require the existence of four different hydrate structures. Our single crystal diffraction study of 16 different crystals of distinct compositions (Br2·8.62H2O to Br2·10.68H2O) and morphologies showed that there is just a single structure (tetragonal, P42/mnm, a = 23.04 A,...
Recurrent Losses and Rapid Evolution of the Condensin II Complex in Insects

Condensins play a crucial role in the organization of genetic material by compacting and disentangling chromosomes. Based on studies in a few model organisms, the condensins I and II complexes are considered to have distinct functions, with the condensin II complex playing a role in meiosis and somatic pairing of homologous chromosomes in Drosophila. Intriguingly, the Cap-G2 subunit of condensin II is absent in Drosophila melanogaster, and this loss may be related to the high levels of chromosome pairing seen in flies. Here, we find that all three non-SMC subunits of condensin II (Cap-G2, Cap-D3, and Cap-H2) have been repeatedly and independently lost in taxa representing multiple insect orders, with some taxa lacking all three. We also find that all non-Dipteran insects display near-uniform low-pairing levels regardless of their condensin II complex composition, suggesting that some key aspects of genome organization are robust to condensin II subunit losses. Finally, we observe consistent signatures of positive selection in condensin subunits across flies and mammals. These findings suggest that these ancient complexes are far more evolutionarily labile than previously suspected, and are at the crossroads of several forms of genomic conflicts. Our results raise fundamental questions about the specific functions of the two condensin complexes in taxa that have experienced subunit losses, and open the door to further investigations to elucidate the diversity of molecular mechanisms that underlie genome organization across various life forms.
A comparison of Redlich-Kister polynomial and cubic spline representations of the chemical potential in phase field computations

Abstract Free energies play a central role in many descriptions of equilibrium and non-equilibrium properties of solids. Continuum partial differential equations (PDEs) of atomic transport, phase transformations and mechanics often rely on first and second derivatives of a free energy function. The stability, accuracy and robustness of numerical methods to solve these PDEs are sensitive to the particular functional representations of the free energy. In this communication we investigate the influence of different representations of thermodynamic data on phase field computations of diffusion and two-phase reactions in the solid state. First-principles statistical mechanics methods were used to generate realistic free energy data for HCP titanium with interstitially dissolved oxygen. While Redlich-Kister polynomials have formed the mainstay of thermodynamic descriptions of multi-component solids, they require high order terms to fit oscillations in chemical potentials around phase transitions. Here, we demonstrate that high fidelity fits to rapidly fluctuating free energy functions are obtained with spline functions. Spline functions that are many degrees lower than Redlich-Kister polynomials provide equal or superior fits to chemical potential data and, when used in phase field computations, result in solution times approaching an order of magnitude speed up relative to the use of Redlich-Kister polynomials.
From conjugacy classes in the Weyl group to unipotent classes, III

Let G be a connected reductive group over an algebraically closed field of characteristic p. In an earlier paper we defined a surjective map Φp from the set W of conjugacy classes in the Weyl group W to the set of unipotent classes in G. Here we prove three results for Φp. First we show that Φp has a canonical one-sided inverse. Next we show that Φ0 = rΦp for a unique map r. Finally, we construct a natural surjective map from W to the set of special representations of W which is the composition of Φ0 with another natural map and we show that this map depends only on the Coxeter group structure of
On the distribution of the van der Corput sequence in arbitrary base

A central limit theorem with explicit error bound, and a large deviation result are proved for a sequence of weakly dependent random variables of a special form. As a corollary, under certain conditions on the function \(f:[0,1] \rightarrow \mathbb {R}\) a central limit theorem and a large deviation result are obtained for the sum \(\sum _{n=0}^{N-1} f(x_n)\), where \(x_n\) is the base b van der Corput sequence for an arbitrary integer \(b \ge 2\). Similar results are also proved for the \(L^p\) discrepancy of the same sequence for \(1 \le p < \infty \). The main methods used in the proofs are the Berry–Esseen theorem and Fourier analysis.
Resolution Of Conjectures Related To Lights Out! And Cartesian Products

Lights Out! is a game played on a $5 \times 5$ grid of lights, or more generally on a graph. Pressing lights on the grid allows the player to turn off neighboring lights. The goal of the game is to start with a given initial configuration of lit lights and reach a state where all lights are out. Two conjectures posed in a recently published paper about Lights Out! on Cartesian products of graphs are resolved.
On solving large-scale limited-memory quasi-Newton equations

Abstract We consider the problem of solving linear systems of equations arising with limited-memory members of the restricted Broyden class of updates and the symmetric rank-one (SR1) update. In this paper, we propose a new approach based on a practical implementation of the compact representation for the inverse of these limited-memory matrices. Numerical results suggest that the proposed method compares favorably in speed and accuracy to other algorithms and is competitive with several update-specific methods available to only a few members of the Broyden class of updates. Using the proposed approach has an additional benefit: The condition number of the system matrix can be computed efficiently.
Sustainable green networking: exploiting degrees of freedom towards energy-efficient 5G systems

The carbon footprint concern in the development and deployment of 5G new radio systems has drawn the attention to several stakeholders. In this article, we analyze the critical power consuming component of all candidate 5G system architectures—the power amplifier (PA)—and propose PA-centric resource management solutions for green 5G communications. We discuss the impact of ongoing trends in cellular communications on sustainable green networking and analyze two communications architectures that allow exploiting the extra degrees-of-freedom from multi-antenna and massive antenna deployments: small cells/distributed antenna network and massive MIMO. For small cell systems with a moderate number of antennas, we propose a peak to average power ratio-aware resource allocation scheme for joint orthogonal frequency and space division multiple access. For massive MIMO systems, we develop a highly parallel recurrent neural network for energy-efficient precoding. Simulation results for representative 5G deployment scenarios demonstrate an energy efficiency improvement of one order of magnitude or higher with respect to current state-of-the-art solutions.
Intention-Aware Motion Planning Using Learning Based Human Motion Prediction

We present a motion planning algorithm to compute collision-free and smooth trajectories for robots cooperating with humans in a shared workspace. Our approach uses offline learning of human actions and their temporal coherence to predict the human actions at runtime. This data is used by an intention-aware motion planning algorithm that is used to compute a reliable trajectory based on these predicted actions. We highlight the performance of our planning algorithm in complex simulated scenarios and real world scenarios with 7-DOF robot arms operating in a workspace with a human performing complex tasks. We demonstrate the benefits of our intention-aware planner in terms of computing safe trajectories.
On v-positive type transformations in infinite measure

For each vector v we dene the notion of a v-positive type for innite measure-preserving transformations, a renement of positive type as introduced by Hajian and Kakutani. We prove that a positive type transformation need not be (1; 2)-positive type. We study this notion in the context of Markov shifts and multiple recurrence and give several examples.
Early Prediction of Acute Kidney Injury in Critical Care Setting Using Clinical Notes

Acute kidney injury (AKI) in critically ill patients is associated with significant morbidity and mortality. Development of novel methods to identify patients with AKI earlier will allow for testing of novel strategies to prevent or reduce the complications of AKI. We developed data-driven prediction models to estimate the risk of new AKI onset. We generated models from clinical notes within the first 24 hours following intensive care unit (ICU) admission extracted from Medical Information Mart for Intensive Care III (MIMIC-III). From the clinical notes, we generated clinically meaningful word and concept representations and embeddings, respectively. Five supervised learning classifiers and knowledge-guided deep learning architecture were used to construct prediction models. The best configuration yielded a competitive AUC of 0.779. Our work suggests that natural language processing of clinical notes can be applied to assist clinicians in identifying the risk of incident AKI onset in critically ill patients upon admission to the ICU.
NR Wide Bandwidth Operations

The 3GPP is in the process of developing the next generation radio access technology, named New Radio (NR), which will be proposed as a candidate technology for IMT-2020. This article outlines the wide bandwidth operation of NR, among other new features being considered, based on the up-to-date discussions and decisions made in 3GPP standardization meetings. The much wider channel bandwidth of NR, compared to LTE, enables more efficient use of resources than the existing carrier aggregation framework with lower control overhead. The support of multiple sub-carrier spacing options allows NR to operate in a wide range of carrier frequency from sub-6 GHz band to mmWave band with appropriate handling of multi-path delay spread and phase noise depending on the carrier frequency. In addition, the introduction of the new bandwidth part concept allows flexible and dynamic configuration of UE's operating bandwidth, which will make NR an energy-efficient solution despite the support of wide bandwidth. Other NR wideband operation related issues, such as the support of UEs with limited RF capability and frequency domain resource indexing, are also explained in this article.