Stacking and Electrostatic Interactions Drive the Stereoselectivity of Silylium‐Ion Asymmetric Counteranion‐Directed Catalysis

Computational analysis shows that the enantioselectivity of asymmetric Lewis‐acid organocatalysis of the Diels–Alder cycloaddition of cyclopentadiene to cinnamates arises from stacking interactions that favor the addition of the diene to the more hindered face of the dienophile, while electrostatic interactions control the diastereoselectivity by selectively stabilizing the endo transition state. These results not only explain the stereoselectivity of these silylium‐ion‐ACDC reactions but should also guide the development of more effective ion‐pairing asymmetric organocatalysts.     

Self‐Assembly of the Cyclic Lipopeptide Daptomycin: Spherical Micelle Formation Does Not Depend on the Presence of Calcium Chloride

The cyclic lipopeptide Daptomycin, used as a treatment for infections where antimicrobial resistance is observed, is shown to self‐assemble into spherical micelles above a critical aggregation concentration. Micelles are observed either in the absence or presence of CaCl₂, in contrast to claims in the literature that CaCl₂ is required for micellization.     

An agent-based model of organizational ambidexterity decisions and strategies in new product development

Organizational ambidexterity, defined as the pursuit of both exploitation and exploration, has become an important topic in the study of organizations, especially in innovation management theory. Previous literature has not focused on the strategic (game-theoretic) aspects of organizational ambidexterity or on its decision-making aspects. Little is known about how or even whether the decision to adopt ambidexterity is competitively advantageous in the presence of diverse strategies that competitors may adopt. This facet of the subject is inherently game-theoretic; the value of a decision by one firm depends in part on decisions made by other firms. This paper initiates systematic investigation of these strategic aspects, including the overall performance of available strategies. Specifically, this study examines questions of ambidexterity-related strategy performance in the context of new product development. The main contributions are (1) to introduce and make available to the research community an agent-based model and decision support system that captures many of the key aspects and tradeoffs, which have been identified in the literature, of the exploration–exploitation dilemma faced by firms in the new product development process, with a focus on organizations’ product investment decisions and (2) to report on results obtained from the model, calibrated with available data from the literature, augmented by new data collected from interviews with practitioners.     

Low rank approximation in G0W0 calculations

The single particle energies obtained in a Kohn-Sham density functional theory (DFT) calculation are generally known to be poor approximations to electron excitation energies that are measured in transport, tunneling and spectroscopic experiments such as photo-emission spectroscopy. The correction to these energies can be obtained from the poles of a single particle Green’s function derived from a many-body perturbation theory. From a computational perspective, the accuracy and efficiency of such an approach depends on how a self energy term that properly accounts for dynamic screening of electrons is approximated. The G₀W₀ approximation is a widely used technique in which the self energy is expressed as the convolution of a noninteracting Green’s function (G₀) and a screened Coulomb interaction (W₀) in the frequency domain. The computational cost associated with such a convolution is high due to the high complexity of evaluating W₀ at multiple frequencies. In this paper, we discuss how the cost of G₀W₀ calculation can be reduced by constructing a low rank approximation to the frequency dependent part of W₀. In particular, we examine the effect of such a low rank approximation on the accuracy of the G₀W₀ approximation. We also discuss how the numerical convolution of G₀ and W₀ can be evaluated efficiently and accurately by using a contour deformation technique with an appropriate choice of the contour.     

Swellable polymer films containing Au nanoparticles for point-of-care therapeutic drug monitoring using surface-enhanced Raman spectroscopy

Large (10 × 10 cm) sheets of surface-enhanced Raman spectroscopy (SERS) active polymer have been prepared by stabilising metal nanoparticle aggregates within dry hydroxyethylcellulose (HEC) films. In these films the aggregates are protected by the polymer matrix during storage but in use they are released when aqueous analyte droplets cause the films to swell to their gel form. The fact that these “Poly-SERS” films can be prepared in bulk but then cut to size and stored in air before use means that they provide a cost effective and convenient method for routine SERS analysis. Here we have tested both Ag and Au Poly-SERS films for use in point-of-care monitoring of therapeutic drugs, using phenytoin as the test compound. Phenytoin in water could readily be detected using Ag Poly-SERS films but dissolving the compound in phosphate buffered saline (PBS) to mimic body fluid samples caused loss of the drug signal due to competition for metal surface sites from Cl⁻ ions in the buffer solution. However, with Au Poly-SERS films there was no detectable interference from Cl⁻ and these materials allowed phenytoin to be detected at 1.8 mg L⁻¹, even in PBS. The target range of detection of phenytoin in therapeutic drug monitoring is 10–20 mg L⁻¹. With the Au Poly-SERS films, the absolute signal generated by a given concentration of phenytoin was lower for the films than for the parent colloid but the SERS signals were still high enough to be used for therapeutic monitoring, so the cost in sensitivity for moving from simple aqueous colloids to films is not so large that it outweighs the advantages which the films bring for practical applications, in particular their ease of use and long shelf life.     

Mass spectrometry‐based proteomics of oxidative stress: Identification of 4‐hydroxy‐2‐nonenal (HNE) adducts of amino acids using lysozyme and bovine serum albumin as model proteins

Modification of proteins by 4‐hydroxy‐2‐nonenal (HNE), a reactive by‐product of ω6 polyunsaturated fatty acid oxidation, on specific amino acid residues is considered a biomarker for oxidative stress, as occurs in many metabolic, hereditary, and age‐related diseases. HNE modification of amino acids can occur either via Michael addition or by formation of Schiff‐base adducts. These modifications typically occur on cysteine (Cys), histidine (His), and/or lysine (Lys) residues, resulting in an increase of 156 Da (Michael addition) or 138 Da (Schiff‐base adducts), respectively, in the mass of the residue. Here, we employed biochemical and mass spectrometry (MS) approaches to determine the MS “signatures” of HNE‐modified amino acids, using lysozyme and BSA as model proteins. Using direct infusion of unmodified and HNE‐modified lysozyme into an electrospray quadrupole time‐of‐flight mass spectrometer, we were able to detect up to seven HNE modifications per molecule of lysozyme. Using nanoLC‐MS/MS, we found that, in addition to N‐terminal amino acids, Cys, His, and Lys residues, HNE modification of arginine (Arg), threonine (Thr), tryptophan (Trp), and histidine (His) residues can also occur. These sensitive and specific methods can be applied to the study of oxidative stress to evaluate HNE modification of proteins in complex mixtures from cells and tissues under diseased versus normal conditions.     

Fell拓扑,Choquet容量和遍历的 Choquet容量系统

本文描述了Fell 拓扑的结构与收敛条件,重新确立了关于随机集的Choquet 定理在概率论中的重要作用,并提出了不变Choquet 容量的概念。此外,利用环面上的双曲自同构和随机映射,具体构造了一个遍历的Choquet 容量系统,且进一步探讨了这种系统的动力性态。     

On induced Ramsey numbers for k‐uniform hypergraphs

Let denote the complete k‐uniform k‐partite hypergraph with classes of size t and the complete k‐uniform hypergraph of order s. One can show that the Ramsey number for and satisfies when t = s^o(1) as s →∞. The main part of this paper gives an analogous result for induced Ramsey numbers: Let be an arbitrary k‐partite k‐uniform hypergraph with classes of size t and an arbitrary k‐graph of order s. We use the probabilistic method to show that the induced Ramsey number (i.e. the smallest n for which there exists a hypergraph such that any red/blue coloring of yields either an induced red copy of or an induced blue copy of ) satisfies . © 2015 Wiley Periodicals, Inc. Random Struct. Alg., 48, 5–20, 2016     

Hydrodynamic Rocking Disc Electrode Study of the TEMPO‐mediated Catalytic Oxidation of Primary Alcohols

The hydrodynamically thinned diffusion layer at a sinusoidally rocking disc is approximately uniform and can be expressed in terms of a diffusion layer thickness with D, the diffusion coefficient of the redox active species, v, the kinematic viscosity, Θ, the total rocking angle (here 90 degrees), and f, the rocking frequency (ranging here from 0.83 to 25 Hz). For the one‐electron oxidation of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) in aqueous carbonate buffer pH 9.5, it is shown that there is quantitative agreement between the expression for the diffusion layer thickness and experimental data. Next, for seven primary alcohols, the catalytic TEMPO‐mediated oxidation mechanism is investigated under rocking disc conditions. Chemical rate constants are evaluated (by varying the diffusion layer thickness) employing the DigiElch4.F simulation package. Trends in the chemical rate constants (compared with DFT calculations) suggest enhanced reactivity for methanol versus higher primary alcohols and for aromatic versus non‐aromatic primary alcohols. Rocking disc voltammetry allows quantitative mechanistic analysis in the laminar flow regime.     

Visible Light Activation of Boronic Esters Enables Efficient Photoredox C(sp2)–C(sp3) Cross‐Couplings in Flow

We report herein a new method for the photoredox activation of boronic esters. Using these reagents, an efficient and high‐throughput continuous flow process was developed to perform a dual iridium‐ and nickel‐catalyzed C(sp²)–C(sp³) coupling by circumventing solubility issues associated with potassium trifluoroborate salts. Formation of an adduct with a pyridine‐derived Lewis base was found to be essential for the photoredox activation of the boronic esters. Based on these results we were able to develop a further simplified visible light mediated C(sp²)–C(sp³) coupling method using boronic esters and cyano heteroarenes under flow conditions.