Utilizing Paper-Based Devices for Antimicrobial-Resistant Bacteria Detection

Antimicrobial resistance (AMR), the ability of a bacterial species to resist the action of an antimicrobial drug, has been on the rise due to the widespread use of antimicrobial agents. Per the World Health Organization, AMR has an estimated annual cost of USD 34 billion in the US and is predicted to be the number one cause of death worldwide by 2050. One way AMR bacteria can spread, and by which individuals can contract AMR infections, is through contaminated water. Monitoring AMR bacteria in the environment currently requires that samples be transported to a central laboratory for slow and labor intensive tests. We have developed an inexpensive assay using paper-based analytical devices (PADs) that can test for the presence of β-lactamase-mediated resistance. To demonstrate viability, the PAD was used to detect β-lactam resistance in wastewater and sewage and identified resistance in individual bacterial species isolated from environmental water sources.     

L-Proline Functionalized Polymers Prepared by RAFT Polymerization and Their Assemblies as Supported Organocatalysts

We have prepared a range of well-defined copolymers of styrene and L-proline functionalized styrene (5-11 kDa) using reversible addition-fragmentation chain transfer (RAFT) polymerization techniques and explored their use in supported catalysis. Upon deprotection of the L-proline functionalities, the solution self-assembly of these copolymers was investigated in mixed solvent systems. The resulting assemblies were characterized by dynamic light scattering, transmission electron microscopy (on graphene oxide substrates, along with cryo-TEM and tomography), and scanning electron microscopy. The application of these functional assemblies as supported catalysts for the aldol condensation reaction was explored using cyclohexanone and 4-nitrobenzaldehyde. The rate and selectivity of solution catalysis in our self-assembled system were comparable to those of L-proline, and a significant advantage of our system was that the polymer support could be utilized at lower catalyst loadings with comparable activity and also could be recycled a number of times while maintaining activity and selectivity.     

Evidence for a one-electron mechanistic regime in dirhodium-catalyzed intermolecular C-H amination

Swift and energy efficient conversion of chemical feedstocks to pharmaceuticals and agrochemicals requires the development of new methods to add nitrogen functionality to unfunctionalized organic substrates. Dirhodium-catalyzed insertion of nitrene species into C-H bonds is a promising new method, the main drawback of which is the currently limited understanding of the catalytic mechanism. Herein, cyclic voltammetry and controlled potential electrolysis measurements have enabled us to solve many of the mechanistic mysteries of intermolecular C-H amination catalyzed by [Rh(2)(esp)(2)] (esp=α,α,α',α'-tetramethyl-1,3-benzenedipropanoate). The primary result is that, in addition to a simple nitrene-transfer mechanism that dominates the early stages of the reaction, another mechanism is available that relies on sequential proton-coupled electron transfer steps. Whereas the nitrene-transfer mechanism requires the use of expensive, atom-inefficient oxidants, we show that simple one-electron oxidants such as Ce(4+) may be used to achieve catalytic C-H amination via the one-electron mechanistic regime.     

Determination of fat-soluble vitamins and carotenoids in standard reference material 3280 multivitamin/multielement tablets by liquid chromatography with absorbance detection

The concentrations of selected fat-soluble vitamins and carotenoids in Standard Reference Material (SRM) 3280 Multivitamin/Multielement Tablets have been determined by two independent LC methods, with measurements performed by the National Institute of Standards and Technology (NIST). This SRM has been prepared as part of a collaborative effort between NIST and the National Institutes of Health Office of Dietary Supplements. The SRM is also intended to support the Dietary Supplement Ingredient Database that is being established by the U.S. Department of Agriculture. The methods used at NIST to determine the concentration levels of vitamins A and E, and beta-carotene in the SRM used RPLC with absorbance detection. The relative precision of these methods ranged from 2 to 8% for the analytes measured. SRM 3280 is primarily intended for use in validating analytical methods for the determination of selected vitamins, carotenoids, and elements in multivitamin/multielement tablets and similar matrixes.     

Measurement of heterogeneous reaction rates: three strategies for controlling mass transport and their application to indium-mediated allylations

We describe three new strategies for determining heterogeneous reaction rates using photomicroscopy to measure the rate of retreat of metal surfaces: (i) spheres in a stirred solution, (ii) microscopic powder in an unstirred solution, and (iii) spheres on a rotating shaft. The strategies are applied to indium-mediated allylation (IMA), which is a powerful tool for synthetic chemists because of its stereoselectivity, broad applicability, and high yields. The rate-limiting step of IMA, reaction of allyl halides at indium metal surfaces, is shown to be fast, with a minimum value of the heterogeneous rate constant of 1 × 10(-2) cm/s, an order of magnitude faster than the previously determined minimum value. The strategies described here can be applied to any reaction in which the surface is retreating or advancing, thereby broadening the applicability of photomicroscopy to measuring heterogeneous reaction kinetics.     

Compact Differences of Composition Operators in Several Variables

When φ and ψ are linear–fractional self-maps of the unit ball B _N in \mathbb C^N,N 3 1{{\mathbb C}^N,N\geq 1}, we show that the difference C_j-C_y{C_{\varphi}-C_{\psi}} cannot be non-trivially compact on either the Hardy space H ²(B _N ) or any weighted Bergman space A²_a(B_N){A^2_{\alpha}(B_N)}. Our arguments emphasize geometrical properties of the inducing maps φ and ψ.     

A highly reactive mononuclear non-heme manganese(IV)-oxo complex that can activate the strong C-H bonds of alkanes

A mononuclear non-heme manganese(IV)-oxo complex has been synthesized and characterized using various spectroscopic methods. The Mn(IV)-oxo complex shows high reactivity in oxidation reactions, such as C-H bond activation, oxidations of olefins, alcohols, sulfides, and aromatic compounds, and N-dealkylation. In C-H bond activation, the Mn(IV)-oxo complex can activate C-H bonds as strong as those in cyclohexane. It is proposed that C-H bond activation by the non-heme Mn(IV)-oxo complex does not occur via an oxygen-rebound mechanism. The electrophilic character of the non-heme Mn(IV)-oxo complex is demonstrated by a large negative ρ value of -4.4 in the oxidation of para-substituted thioanisoles.     

Aluminum foils: the contrasting characters of hyperconjugation and steric repulsion in aluminum dimetallocenes

The novel sandwich complex Cp2*Al2I2, which was recently synthesized by Minasian and Arnold, has been characterized using ab initio and density functional methods. A large family of related compounds was also investigated. Although a few Al(II)–Al(II) bonds are known, this is the first such bond to be supported by Cp-type ligands. In addition, in the remarkable Cp4*Al4 synthesis by Roesky, Cp2*Al2I2 is the Al(II) intermediate; Cp4*Al4 is important as a precursor to novel organoaluminum species. Halogen and ligand effects on the Al–Al bond in Cp2*Al2I2 were systematically explored by studying a series of 20 Cp2*Al2I2 derivatives using density functional theory with relativistic basis sets for the halogens. Comparison was made with the focal point treatment, which uses extrapolation to estimate the full configuration interaction and complete basis set limit energy. Torsional potential energy curves, natural population analyses, and enthalpies of hydrogenation were computed. Using the focal point approach, torsional barriers were computed with 0.05 kcal mol(–1) uncertainty. The interplay of steric and electronic effects on the torsional potential energy curves, enthalpies of dehydrogenation reactions, and geometries is discussed. In species with small ligands (R = H, Me), hyperconjugative effects determine the torsional landscape, whereas steric repulsions dominate in species with Cp* alkyl ligands. Species with Cp ligands represent an intermediate case, thus providing insight into how ligands modulate the structures and properties of small metal clusters.     

Fluoroalkyl and alkyl chains have similar hydrophobicities in binding to the "hydrophobic wall" of carbonic anhydrase

The hydrophobic effect, the free-energetically favorable association of nonpolar solutes in water, makes a dominant contribution to binding of many systems of ligands and proteins. The objective of this study was to examine the hydrophobic effect in biomolecular recognition using two chemically different but structurally similar hydrophobic groups, aliphatic hydrocarbons and aliphatic fluorocarbons, and to determine whether the hydrophobicity of the two groups could be distinguished by thermodynamic and biostructural analysis. This paper uses isothermal titration calorimetry (ITC) to examine the thermodynamics of binding of benzenesulfonamides substituted in the para position with alkyl and fluoroalkyl chains (H(2)NSO(2)C(6)H(4)-CONHCH(2)(CX(2))(n)CX(3), n = 0-4, X = H, F) to human carbonic anhydrase II (HCA II). Both alkyl and fluoroalkyl substituents contribute favorably to the enthalpy and the entropy of binding; these contributions increase as the length of chain of the hydrophobic substituent increases. Crystallography of the protein-ligand complexes indicates that the benzenesulfonamide groups of all ligands examined bind with similar geometry, that the tail groups associate with the hydrophobic wall of HCA II (which is made up of the side chains of residues Phe131, Val135, Pro202, and Leu204), and that the structure of the protein is indistinguishable for all but one of the complexes (the longest member of the fluoroalkyl series). Analysis of the thermodynamics of binding as a function of structure is compatible with the hypothesis that hydrophobic binding of both alkyl and fluoroalkyl chains to hydrophobic surface of carbonic anhydrase is due primarily to the release of nonoptimally hydrogen-bonded water molecules that hydrate the binding cavity (including the hydrophobic wall) of HCA II and to the release of water molecules that surround the hydrophobic chain of the ligands. This study defines the balance of enthalpic and entropic contributions to the hydrophobic effect in this representative system of protein and ligand: hydrophobic interactions, here, seem to comprise approximately equal contributions from enthalpy (plausibly from strengthening networks of hydrogen bonds among molecules of water) and entropy (from release of water from configurationally restricted positions).     

Asymmetric hydroamination of aminoallenes catalyzed by titanium and tantalum complexes of chiral sulfonamide alcohol ligands

A series of bidentate sulfonamide alcohol ligands with varying steric and electronic properties was synthesized. The titanium and tantalum complexes of these ligands, prepared in situ from either Ti(NMe₂)₄ or Ta(NMe₂)₅, were used as catalysts for the asymmetric hydroamination of 6-methyl-hepta-4,5-dienylamine, giving exclusively the α-vinylpyrrolidine product. The titanium derived catalysts gave products with low stereoselectivity, up to 11%ee favoring (+)-2-(2-methyl-propenyl)-pyrrolidine, while the tantalum derived catalysts gave products with higher and opposite stereoselectivity, up to 34%ee favoring (−)-2-(2-methyl-propenyl)-pyrrolidine.