Synthesis,Crystal Structure,and Selected Properties of [Au(S2CNH2)2]SCN: A Precursor for Gold Macro-Needles Consisting of Gold Nanoparticles Glued by Graphitic Carbon Nitride

A new preparation route is developed for the synthesis of needle-like crystals of [Au(S₂CNH₂)₂]SCN, which avoids disproportionation of the Au^I salt used as a starting material. In the crystal structure, the two crystallographically independent Au^III centers are in a square-planar environment of two S₂CNH₂ ligands. The Hirshfeld surface analysis reveals the presence of noncovalent intermolecular S⋅⋅⋅S interactions, which are essential for the spatial arrangement of the molecules. Density functional theory (DFT) calculations including dispersion and damping corrections result in a unit cell volume very close to the value determined experimentally. Thermal decomposition in an inert atmosphere generates black needles with lengths of up to 500 μm. X-ray powder diffraction and pair distribution function analyses demonstrate that the needles are composed of nanosized crystals with a volume-weighted average domain size of 20(1) nm. According to results of X-ray photoemission experiments, the black needles are covered by a nitrogen-rich carbon nitride with composition near (CN)₂N. ¹³C solid-state NMR investigations indicate that two different carbon species are present, with signals corresponding well to heptazine units as in melon and triazine units as in poly(triazin imide) type compounds. Scanning transmission electron microscopy tomography evidences that the needles are composed of slightly elongated nanoparticles.     

Synthesis and Pd-catalyzed coupling of1-C-stannylated glycals

Abstract

1-Tributylstannyl glycals were applied as versatile tools in the Pd(0)-mediated synthesis of glycal phthalonitrile conjugates. Likewise, selective homo-coupling of 1-tributylstannyl glycals furnishing C1-C1’ linked glycal dimers was investigated by using Pd(II)-species. For both Stille type couplings the rate-accelerating effect of copper(I) thiophene-2-carboxylate (CuTC) was exploited. The synthesis of stannylated glycal precursors was significantly improved by establishing a one-pot two-step procedure via glycosyl sulfoxides.     

Influence of Phytochemical Reductive Capacity on Ultraviolet–visible Spectroscopic Behavior of Silver Nanoparticles

ABSTRACT

A widely used method for obtaining silver nanoparticles uses plant extracts for reduction because of the presence of phytochemicals such as terpenoids, tannins, and flavonoids. Extracts of Flores sambuci, Hypericum perforatum, Lavandula angustifolia, Origanum vulgare, Rosmarinus officinalis, and Salvia officinalis were used for generating silver nanoparticles. The ultraviolet–visible spectra of silver nanoparticle solutions were correlated with variations of phytochemical characteristics to evaluate the plant extracts. These parameters were the antioxidant activity, total flavonoids, total tannins, total terpenoids, and total phenolics. Correlations between measurements of extracts’ phytoreductive characteristics were explained using Pearson coefficients. The results showed medium linear positive correlations for total tannins with the spectra of silver nanoparticle solutions. The antioxidant activity and total terpenoids presented medium linear negative correlations. Pearson coefficients between total phenolics and relative areas from ultraviolet–visible spectra from 350 to 600?nm were close to zero indicating no linear correlation.     

The dirichlet problem in lipschitz domains for higher order elliptic systems with rough coefficients

We study the Dirichlet problem, in Lipschitz domains and with boundary data in Besov spaces, for divergence form strongly elliptic systems of arbitrary order with bounded, complex-valued coefficients. A sharp corollary of our main solvability result is that the operator of this problem performs an isomorphism between weighted Sobolev spaces when its coefficients and the unit normal of the boundary belong to the space VMO.     

Invariance for stochastic differential systems with time-dependent constraining sets

The first part of this article presents invariance criteria for a stochastic differential equation whose state evolution is constrained by time-dependent security tubes. The key results of this section are derived by considering an equivalent problem where the square of distance function represents a viscosity solution to an adequately defined partial differential equation. The second part of the paper analyzes the broader context when solutions are constrained by more general time-dependent convex domains. The approach relies on forward stochastic variational inequalities with oblique reflection, the generalized subgradients acting as a reacting process that operates only when the solution reaches the boundary of the domain.     

Channel capacities via p-summing norms

In this paper we show how the metric theory of tensor products developed by Grothendieck perfectly fits in the study of channel capacities, a central topic in Shannon's information theory. Furthermore, in the last years Shannon's theory has been fully generalized to the quantum setting, and revealed qualitatively new phenomena in comparison. In this paper we consider the classical capacity of quantum channels with restricted assisted entanglement. These capacities include the classical capacity and the unlimited entanglement-assisted classical capacity of a quantum channel. Our approach to restricted capacities is based on tools from functional analysis, and in particular the notion of p  -summing maps going back to Grothendieck's work. Pisier's noncommutative vector-valued _Lp$L_p$ spaces allow us to establish the new connection between functional analysis and information theory in the quantum setting.     

Maximal regularity for the Lamé system in certain classes of non-smooth domains

The aim of this article is twofold. On the one hand, we study the well-posedness of the Lamé system ${-\mu\Delta-\mu'\nabla{\rm div} }The aim of this article is twofold. On the one hand, we study the well-posedness of the Lamé system -mD-m￠?div{-\mu\Delta-\mu'\nabla{\rm div} } in L ^q (Ω), where Ω is an open subset of \mathbbRⁿ{{\mathbb{R}}^n} satisfying mild regularity assumptions and the Lamé moduli μ, μ′ are such that μ > 0 and μ + μ′ > 0. On the other hand, we prove the analyticity of the semigroup generated by the Lamé operator as well as the maximal regularity property for the time-dependent Lamé system equipped with a homogeneous Dirichlet boundary condition based on off-diagonal estimates.     

Multivariate Hierarchical Copulas with Shocks

A transformation to obtain new multivariate hierarchical copulas, starting with an arbitrary copula, is introduced. In addition to the hierarchical structure, the presented construction principle explicitly supports singular components. These may be interpreted as the effect of local or global shocks to the underlying random variables. A large spectrum of dependence patterns can be achieved by the presented transformation, which seems promising for practical applications. Moreover, copulas arising from this construction are similarly admissible with respect to analytical tractability and sampling routines as the original copula. Finally, several well-known families of copulas may be interpreted as special cases.     

Saturated models in institutions

Saturated models constitute one of the powerful methods of conventional model theory, with many applications. Here we develop a categorical abstract model theoretic approach to saturated models within the theory of institutions. The most important consequence is that the method of saturated models becomes thus available to a multitude of logical systems from logic or from computing science. In this paper we define the concept of saturated model at an abstract institution-independent level and develop the fundamental existence and uniqueness theorems. As an application we prove a general institution-independent version of the Keisler–Shelah isomorphism theorem “any two elementarily equivalent models have isomorphic ultrapowers” (assuming Generalized Continuum Hypothesis).