Luminol chemiluminescense reaction: a new method for monitoring nitric oxide in vivo

A new method employing a combination of microdialysis sampling and chemiluminescence (CL) detection was developed to monitor nitric oxide (NO) in vivo. A special probe was designed with an interference-free membrane to achieve very high selectivity for NO. High sensitivity was achieved by optimizing the working system and improving the NO sampling time. This system was used in vivo to monitor blood and brain tissue in rats and rabbits. The system is sensitive enough to detect variations of NO formation under different physiological states. The linear valid range of NO determination is 5 nM to 1 μM, with a 3σ detection limit of 1 nM; real NO concentrations in test animals used in this work were found to be in the range of 1-5 nM or even less. Finally, the effects of body temperature, NO donors, Viagra, NO activators, NO cofactors and NO interference (such as O₂) were investigated carefully in different physiological situations.     

Theory of gold on ceria

The great promise of ceria-supported gold clusters as catalysts of the future for important industrial processes, such as the water gas shift reaction, has prompted a flurry of activity aimed at understanding the molecular-level details of their operation. Much of this activity has focused on experimental and theoretical studies of the structure of perfect and defective ceria surfaces, with and without gold clusters of various sizes. The complicated electronic structure of ceria, particularly in its reduced form, means that at present it is highly challenging to carry out accurate electronic structure simulations of such systems. To overcome the challenges, the majority of recent theoretical studies have adopted a pragmatic and often controversial approach, applying the so-called DFT + U technique. Here we will briefly discuss some recent studies of Au on CeO(2){111} that mainly use this methodology. We will show that considerable insight has been obtained into these systems, particularly with regard to Au adsorbates and Au cluster reactivity. We will also briefly discuss the need for improved electronic structure methods, which would enable more rigorous and robust studies in the future.     

Primal and dual linear decision rules in stochastic and robust optimization

Linear stochastic programming provides a flexible toolbox for analyzing real-life decision situations, but it can become computationally cumbersome when recourse decisions are involved. The latter are usually modeled as decision rules, i.e., functions of the uncertain problem data. It has recently been argued that stochastic programs can quite generally be made tractable by restricting the space of decision rules to those that exhibit a linear data dependence. In this paper, we propose an efficient method to estimate the approximation error introduced by this rather drastic means of complexity reduction: we apply the linear decision rule restriction not only to the primal but also to a dual version of the stochastic program. By employing techniques that are commonly used in modern robust optimization, we show that both arising approximate problems are equivalent to tractable linear or semidefinite programs of moderate sizes. The gap between their optimal values estimates the loss of optimality incurred by the linear decision rule approximation. Our method remains applicable if the stochastic program has random recourse and multiple decision stages. It also extends to cases involving ambiguous probability distributions.     

A smoothing algorithm for finite min–max–min problems

We generalize a smoothing algorithm for finite min–max to finite min–max–min problems. We apply a smoothing technique twice, once to eliminate the inner min operator and once to eliminate the max operator. In mini–max problems, where only the max operator is eliminated, the approximation function is decreasing with respect to the smoothing parameter. Such a property is convenient to establish algorithm convergence, but it does not hold when both operators are eliminated. To maintain the desired property, an additional term is added to the approximation. We establish convergence of a steepest descent algorithm and provide a numerical example.     

Short-time vibrational dynamics of metaphosphate glasses

In this paper we present the picosecond vibrational dynamics of a series of binary metaphosphate glasses, namely Na₂O–P₂O₅, MO–P₂O₅ (M=Ba, Sr, Ca, Mg) and Al₂O₃–3P₂O₅ by means of Raman spectroscopy. We studied the vibrational dephasing and vibrational frequency modulation by calculating time correlation functions of vibrational relaxation by fits in the frequency domain. The fitting method used enables one to model the real line profiles intermediate between Lorentzian and Gaussian by an analytical function, which has an analytical counterpart in the time domain. The symmetric stretching modes ν_s(PO₂^?) and ν_s(P–O–P) of the PO₂^? entity of PØ₂O₂^? units and of P–O–P bridges in metaphosphate arrangements have been investigated by Raman spectroscopy and we used them as probes of the dynamics of these glasses. The vibrational time correlation functions of both modes studied are rather adequately interpreted within the assumption of exponential modulation function in the context of Kubo–Rothschield theory and indicate that the system experiences an intermediate dynamical regime that gets only slower with an increase in the ionic radius of the cation-modifier. We found that the vibrational correlation functions of all glasses studied comply with the Rothschild approach assuming that the environmental modulation is described by a stretched exponential decay. The evolution of the dispersion parameter α with increasing ionic radius of the cation indicates the deviation from the model simple liquid indicating the reduction of the coherence decay in the perturbation potential as a result of local short lived aggregates. The results are discussed in the framework of the current phenomenological status of the field.     

Visualization of hydrogen bonding and associated chirality in methanol hexamers

Using a combination of scanning tunneling microscopy (STM) and density functional theory the hydrogen bond directionality and associated chirality of enantiopure clusters is visualized and controlled. This is demonstrated with methanol hexamers adsorbed on Au(111), which depending on their chirality, adopt two distinct molecular footprints on the surface. Controlled STM tip manipulations were used to interconvert the chirality of entire clusters and to break up metastable chain structures into hexamers.     

Hydrogen bonds and van der waals forces in ice at ambient and high pressures

The first principles methods, density-functional theory and quantum Monte Carlo, have been used to examine the balance between van der Waals (vdW) forces and hydrogen bonding in ambient and high-pressure phases of ice. At higher pressure, the contribution to the lattice energy from vdW increases and that from hydrogen bonding decreases, leading vdW to have a substantial effect on the transition pressures between the crystalline ice phases. An important consequence, likely to be of relevance to molecular crystals in general, is that transition pressures obtained from density-functional theory exchange-correlation functionals which neglect vdW forces are greatly overestimated.     

Pomerons and BCFW recursion relations for strings on D-branes

We derive pomeron vertex operators for bosonic strings and superstrings in the presence of D-branes. We demonstrate how they can be used in order to compute the Regge behavior of string amplitudes on D-branes and the amplitude of ultrarelativistic D-brane scattering. After a lightning review of the BCFW method, we proceed in a classification of the various BCFW shifts possible in a field/string theory in the presence of defects/D-branes. The BCFW shifts present several novel features, such as the possibility of performing single particle momentum shifts, due to the breaking of momentum conservation in the directions normal to the defect. Using the pomeron vertices we show that superstring amplitudes on the disc involving both open and closed strings should obey BCFW recursion relations. As a particular example, we analyze explicitly the case of 1→1$1\to 1$ scattering of level one closed string states off a D-brane. Finally, we investigate whether the eikonal Regge regime conjecture holds in the presence of D-branes.     

Geometry + Simulation Modules: Implementing Isogeometric Analysis

Isogeometric analysis (IGA) is a recently developed simulation method that allows integration of finite element analysis (FEA) with conventional computer-aided design (CAD) software [1,3]. This goal requires new software design strategies, in order to enable the use of CAD data in the analysis pipeline. To this end, we have initiated G + SMO (Geometry+Simulation Modules), an open-source, C++ library for IGA. G + SMO is an object-oriented, template library, that implements a generic concept for IGA, based on abstract classes for discretization basis, geometry map, assembler, solver and so on. It makes use of object polymorphism and inheritance techniques to provide a common framework for IGA, for a variety of different basis-types which are available. A highlight of our design is the dimension independent code, realized by means of template meta-programming. Some of the features already available include computing with B-spline, Bernstein, NURBS bases, as well as hierarchical and truncated hierarchical bases of arbitrary polynomial order. These basis functions are used in continuous and discontinuous Galerkin approximation of PDEs over (non-)conforming multi-patch computational (physical) domains. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Circulating Ligands of the Receptor for Advanced Glycation End Products and the Soluble Form of the Receptor Modulate Cardiovascular Cell Apoptosis in Diabetes

We determined whether plasma concentrations of the receptor for advanced glycation end products (RAGE) and the soluble (s) form of RAGE (sRAGE) in healthy individuals and patients with type 2 diabetes (T2D) modulate vascular remodeling. Healthy individuals and patients with T2D were divided into two age groups: young = <35 years old or middle-aged (36–64 years old) and stratified based on normal glucose tolerance (NGT), impaired (IGT), and T2D. Plasma titers of sRAGE, the RAGE ligands, AGEs, S100B, S100A1, S100A6, and the apoptotic marker Fas ligand Fas(L) were measured by enzyme-linked immunosorbent assay (ELISA). The apoptotic potential of the above RAGE ligands and sRAGE were assessed in cultured adult rat aortic smooth muscle cells (ASMC). In NGT individuals, aging increased the circulating levels of AGEs and S100B and decreased sRAGE, S100A1 and S100A6. Middle-aged patients with T2D presented higher levels of circulating S100B, AGEs and FasL, but lower levels of sRAGE, S100A1 and S100A6 than individuals with NGT or IGT. Treatment of ASMC with either AGEs or S100B at concentrations detected in T2D patients increased markers of inflammation and apoptosis. Responses attenuated by concomitant administration of sRAGE. In middle-aged patients with T2D, lower circulating plasma levels of sRAGE may limit decoy and exogenous trapping of deleterious pro-apoptotic/pro-inflammatory RAGE ligands AGEs and S100B, increasing the risk for diabetic complications.