Theoretical investigation of the scope of sequential ligand tuning using a bifunctional scorpionate tris(1,2,4-triazolyl)borate-based architecture

The donor properties of a series of tripodal mixed N-donor/carbene ligands derived through sequential alkylation of hydrotris(1,2,4-triazolyl)borate have been investigated by density functional theory (DFT) methods. The structures of complexes of the form [Mo(L)(CO)₃]⁻ were optimized (L = [HB(1,2,4-triazolyl)_n(1,2,4-triazol-5-ylidene)_3−n]⁻ (n = 0-3), hydrotris(pyrazolyl)borate, hydrotris(3,5-dimethylpyrazolyl)borate and hydrotris(imidazol-2-ylidene)borate) and ν_CO frequencies for these complexes and partial charges of their Mo(CO)₃ fragments were determined. Results show that ligand donation is highly tunable when compared to similar experimentally known ligands with a shift in the symmetric ν_CO stretching mode of −39 cm⁻¹ on going from the tris(1,2,4-triazolyl)borate complexes to that of the triscarbene hydrotris(1,2,4-triazol-5-ylidene) and an increase in partial charge (distributed multipole analysis) of the Mo(CO)₃ fragment from −0.23 to −0.48.     

Crystal structure based design of signal enhancement schemes for solid-state NMR of insensitive half-integer quadrupolar nuclei

A combination of density functional and optimal control theory has been used to generate amplitude- and phase-modulated excitation pulses tailored specifically for the (33)S nuclei in taurine, based on one of several reported crystal structures. The pulses resulted in significant signal enhancement (stemming from population transfer from the satellite transitions) without the need for any experimental optimization. This allowed an accurate determination of the (33)S NMR interaction parameters at natural abundance and at a moderate magnetic field strength (11.7 T). The (33)S NMR parameters, along with those measured from (14)N using frequency-swept pulses, were then used to assess the accuracy of various proposed crystal structures.     

Accurate mass and nuclear magnetic resonance identification of bisphenolic can coating migrants and their interference with liquid chromatography/tandem mass spectrometric analysis of bisphenol A

Two unknown compounds were previously determined to be potential interferences in liquid chromatography/tandem mass spectrometry (LC/MS/MS) analysis of bisphenol A (BPA) in canned infant formula. Both yielded two identical MS/MS transitions to BPA. The identities of the unknowns were investigated using accurate mass LC/MS, LC/MS/MS, and elemental formula and structures proposed. Exact identities were confirmed through purification or synthesis followed by (1)H and (13)C nuclear magnetic resonance (NMR) experiments, as well as comparisons of one unknown with commercial standards. Comparisons of negative ion electrospray ionization (ESI) MS/MS and accurate mass spectra suggested both unknowns to be structurally identical (to BPA and each other). Positive ion ESI spectra confirmed both were larger molecules, suggesting that in the negative mode they likely fragmented to the deprotonated BPA ion in the source [corrected]. Elemental composition of positive ion accurate mass spectra and NMR analysis concluded the unknowns were oxidized forms of the known epoxy can coating monomer, bisphenol A diglycidyl ether (BADGE). One of the unknowns, 2,2-[bis-4-(2,3-dihydroxypropoxy)phenyl]propane, commonly known as BADGE*2H(2)O, is widely reported as an epoxy-phenolic can coating migrant, but has not been suggested to interfere with the MS/MS analysis of BPA. The other unknown, 2-[4-(2,3-dihydroxypropoxy)phenyl]-2-[4'-hydroxyphenyl]propane, or the oxidized form of bisphenol A monoglycidyl ether (BAMGE*H(2)O), has not been previously reported in food or packaging.     

Green chemiluminescence from a bis-cyclometalated iridium(III) complex with an ancillary bathophenanthroline disulfonate ligand

The reaction of a fluorinated iridium complex with cerium(IV) and organic reducing agents generates an intense emission with a significant hypsochromic shift compared to contemporary chemically-initiated luminescence from metal complexes.     

Membrane assisted passive sampler for triazine compounds in water bodies--characterization of environmental conditions and field performance

This article reports the integration of the fiber optic-particle plasmon resonance (FO-PPR) biosensor with a microfluidic chip to reduce response time and improve detection limit. The microfluidic chip made of poly(methyl methacrylate) had a flow-channel of dimensions 4.0 cm × 900 μm × 900 μm. A partially unclad optical fiber with gold or silver nanoparticles on the core surface was placed within the flow-channel, where the volume of the flow space was about 14 μL. Results using sucrose solutions of various refractive indexes show that the refractive index resolution improves by 2.4-fold in the microfluidic system. The microfluidic chip is capable of delivering a precise amount of biological samples to the detection area without sample dilution. Several receptor/analyte pairs were chosen to examine the biosensing capability of the integrated platform: biotin/streptavidin, biotin/anti-biotin, DNP/anti-DNP, OVA/anti-OVA, and anti-MMP-3/MMP-3. Results show that the response time to achieve equilibrium can be shortened from several thousand seconds in a conventional liquid cell to several hundred seconds in a microfluidic flow-cell. In addition, the detection limit also improves by about one order of magnitude. Furthermore, the normalization by using the relative change of transmission response as the sensor output alleviate the demand on precise optical alignment, resulting in reasonably good chip-to-chip measurement reproducibility.     

Smoothed aggregation multigrid solvers for high-order discontinuous Galerkin methods for elliptic problems

We develop a smoothed aggregation-based algebraic multigrid solver for high-order discontinuous Galerkin discretizations of the Poisson problem. Algebraic multigrid is a popular and effective method for solving the sparse linear systems that arise from discretizing partial differential equations. However, high-order discontinuous Galerkin discretizations have proved challenging for algebraic multigrid. The increasing condition number of the matrix and loss of locality in the matrix stencil as p increases, in addition to the effect of weakly enforced Dirichlet boundary conditions all contribute to the challenging algebraic setting.     

Decarboxylative Palladium(II)‐Catalyzed Synthesis of Aryl Amidines from Aryl Carboxylic Acids: Development and Mechanistic Investigation

A fast and convenient synthesis of aryl amidines starting from carboxylic acids and cyanamides is reported. The reaction was achieved by palladium(II)‐catalysis in a one‐step microwave protocol using [Pd(O₂CCF₃)₂], 6‐methyl‐2,2′‐bipyridyl and trifluoroacetic acid (TFA) in N‐methylpyrrolidinone (NMP), providing the corresponding aryl amidines in moderate to excellent yields. The protocol is very robust with regards to the cyanamide coupling partner but requires electron‐rich ortho‐substituted aryl carboxylic acids. Mechanistic insight was provided by a DFT investigation and direct ESI‐MS studies of the reaction. The results of the DFT study correlated well with the experimental findings and, together with the ESI‐MS study, support the suggested mechanism. Furthermore, a scale‐out (scale‐up) was performed with a non‐resonant microwave continuous‐flow system, achieving a maximum throughput of 11 mmol h^?1 by using a glass reactor with an inner diameter of 3 mm at a flow rate of 1 mL min^?1.     

Pebbling Graphs of Fixed Diameter

Given a configuration of indistinguishable pebbles on the vertices of a connected graph G on n vertices, a pebbling move is defined as the removal of two pebbles from some vertex, and the placement of one pebble on an adjacent vertex. The m‐pebbling number of a graph G, , is the smallest integer k such that for each vertex v and each configuration of k pebbles on G there is a sequence of pebbling moves that places at least m pebbles on v. When , it is simply called the pebbling number of a graph. We prove that if G is a graph of diameter d and are integers, then , where denotes the size of the smallest distance k dominating set, that is the smallest subset of vertices such that every vertex is at most distance k from the set, and, . This generalizes the work of Chan and Godbole (Discrete Math 208 (2008), 15–23) who proved this formula for . As a corollary, we prove that . Furthermore, we prove that if d is odd, then , which in the case of answers for odd d, up to a constant additive factor, a question of Bukh (J Graph Theory 52 (2006), 353–357) about the best possible bound on the pebbling number of a graph with respect to its diameter.     

Restricted Normal Cones and Sparsity Optimization with Affine Constraints

The problem of finding a vector with the fewest nonzero elements that satisfies an underdetermined system of linear equations is an NP-complete problem that is typically solved numerically via convex heuristics or nicely behaved nonconvex relaxations. In this paper we consider the elementary method of alternating projections (MAP) for solving the sparsity optimization problem without employing convex heuristics. In a parallel paper we recently introduced the restricted normal cone which generalizes the classical Mordukhovich normal cone and reconciles some fundamental gaps in the theory of sufficient conditions for local linear convergence of the MAP algorithm. We use the restricted normal cone together with the notion of superregularity, which is inherently satisfied for the affine sparse optimization problem, to obtain local linear convergence results with estimates for the radius of convergence of the MAP algorithm applied to sparsity optimization with an affine constraint.