Gas chromatography method for the characterization of ethanol steam reforming products

Ethanol steam reforming is a promising reaction for producing fuel cell hydrogen. Depending on catalyst and reaction conditions, mixtures of condensable hydrocarbons and organic and inorganic gases are produced. This paper proposes an economic and effective solution for separating and detecting these compounds employing a gas chromatograph equipped with two columns, two 6-way valves, and two detectors.     

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.     

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.     

A hermetic wireless subretinal neurostimulator for vision prostheses

A miniaturized, hermetically encased, wirelessly operated retinal prosthesis has been developed for preclinical studies in the Yucatan minipig, and includes several design improvements over our previously reported device. The prosthesis attaches conformally to the outside of the eye and electrically drives a microfabricated thin-film polyimide array of sputtered iridium oxide film electrodes. This array is implanted into the subretinal space using a customized ab externo surgical technique. The implanted device includes a hermetic titanium case containing a 15-channel stimulator chip and discrete circuit components. Feedthroughs in the case connect the stimulator chip to secondary power and data receiving coils on the eye and to the electrode array under the retina. Long-term in vitro pulse testing of the electrodes projected a lifetime consistent with typical devices in industry. The final assembly was tested in vitro to verify wireless operation of the system in physiological saline using a custom RF transmitter and primary coils. Stimulation pulse strength, duration, and frequency were programmed wirelessly from a Peripheral Component Interconnect eXtensions for Instrumentation (PXI) computer. Operation of the retinal implant has been verified in two pigs for up to five and a half months by detecting stimulus artifacts generated by the implanted device.     

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.     

Dissociation kinetics of Mn2+ complexes of NOTA and DOTA

The kinetics of transmetallation of [Mn(nota)](-) and [Mn(dota)](2-) was investigated in the presence of Zn(2+) (5-50-fold excess) at variable pH (3.5-5.6) by (1)H relaxometry. The dissociation is much faster for [Mn(nota)](-) than for [Mn(dota)](2-) under both experimental and physiologically relevant conditions (t(?) = 74 h and 1037 h for [Mn(nota)](-) and [Mn(dota)](2-), respectively, at pH 7.4, c(Zn(2+)) = 10(-5) M, 25 °C). The dissociation of the complexes proceeds mainly via spontaneous ([Mn(nota)](-)k(0) = (2.6 ± 0.5) × 10(-6) s(-1); [Mn(dota)](2-)k(0) = (1.8 ± 0.6) × 10(-7) s(-1)) and proton-assisted pathways ([Mn(nota)](-)k(1) = (7.8 ± 0.1) × 10(-1) M(-1) s(-1); [Mn(dota)](2-)k(1) = (4.0 ± 0.6) × 10(-2) M(-1) s(-1), k(2) = (1.6 ± 0.1) × 10(3) M(-2) s(-1)). The observed suppression of the reaction rates with increasing Zn(2+) concentration is explained by the formation of a dinuclear Mn(2+)-L-Zn(2+) complex which is about 20-times more stable for [Mn(dota)](2-) than for [Mn(nota)](-) (K(MnLZn) = 68 and 3.6, respectively), and which dissociates very slowly (k(3)～10(-5) M(-1) s(-1)). These data provide the first experimental proof that not all Mn(2+) complexes are kinetically labile. The absence of coordinated water makes both [Mn(nota)](-) and [Mn(dota)](2-) complexes inefficient for MRI applications. Nevertheless, the higher kinetic inertness of [Mn(dota)](2-) indicates a promising direction in designing ligands for Mn(2+) complexation.     

2,2-Difunctionalization of alkenes via Pd(II)-catalyzed aza-Wacker reactions

N-Ts and N-Boc derivatives of 1,2-diamines and 1,2-amino alcohols are shown to undergo efficient Pd(II)-catalyzed aza-Wacker reactions with a large range of electron-deficient alkenes. The resulting enamine intermediate generally undergoes cyclization with the second heteroatom to form 1,3-heterocycles. The sequence facilitates the rapid synthesis of saturated oxazolidines, imidazolidines, and their derivatives. Use of N-L-valinol derivatives results in highly diastereoselective reactions, where the net stereochemical outcome diverges between N-Ts and N-Boc.     

Vibrations of a chelated proton in a protonated tertiary diamine

Vibrational spectra of the conjugate acid of Me(2)NCH(2)CH(2)CH(2)CH(2)NMe(2) (N,N,N',N'-tetramethylputrescine) have been examined in the gaseous and crystalline phases using Infrared Multiple Photon Dissociation (IRMPD) spectroscopy, Inelastic Neutron Scattering (INS), and high pressure Raman spectroscopy. A band observed near 530 cm(-1) is assigned to the asymmetric stretch of the bridging proton between the two nitrogens, based on deuterium substitution and pressure dependence. The NN distance measured by X-ray crystallography gives a good match to DFT calculations, and the experimental band position agrees with the value predicted from theory using a 2-dimensional potential energy surface. The reduced dimensionality potential energy surface, which treats the ion as though it possesses a linear NHN geometry, shows low barriers to proton transit from one nitrogen to the other, with zero point levels close to the barrier tops. In contrast, two other related systems containing strong hydrogen bonds do not exhibit the same spectroscopic signature of a low barrier hydrogen bond (LBHB). On the one hand, the IRMPD spectra of the conjugate acid ions of the amino acid N,N,N',N'-tetramethylornithine (in which the two nitrogens have different basicities) show fewer bands and no comparable isotopic shifts in the low frequency domain. On the other hand, the IRMPD spectrum of the shorter homologue Me(2)NCH(2)CH(2)CH(2)NMe(2) (N,N,N',N'-tetramethyl-1,3-propanediamine), for which the NHN bond angle deviates substantially from linearity, displays more than one band in the 1100-1400 cm(-1) domain, which vanish as a consequence of deuteration.     

Integrated microfluidic array plate (iMAP) for cellular and molecular analysis

Just as the Petri dish has been invaluable to the evolution of biomedical science in the last 100 years, microfluidic cell assay platforms have the potential to change significantly the way modern biology and clinical science are performed. However, an evolutionary process of creating an efficient microfluidic array for many different bioassays is necessary. Specifically for a complete view of a cell response it is essential to incorporate cytotoxic, protein and gene analysis on a single system. Here we present a novel cellular and molecular analysis platform, which allows access to gene expression, protein immunoassay, and cytotoxicity information in parallel. It is realized by an integrated microfluidic array plate (iMAP). The iMAP enables sample processing of cells, perfusion based cell culture, effective perturbation of biologic molecules or drugs, and simultaneous, real-time optical analysis for different bioassays. The key features of the iMAP design are the interface of on-board gravity driven flow, the open access input fluid exchange and the highly efficient sedimentation based cell capture mechanism (～100% capture rates). The operation of the device is straightforward (tube and pump free) and capable of handling dilute samples (5-cells per experiment), low reagent volumes (50 nL per reaction), and performing single cell protein and gene expression measurements. We believe that the unique low cell number and triple analysis capabilities of the iMAP platform can enable novel dynamic studies of scarce cells.