Diorganotin(IV) dithiocarbamate complexes as chromogenic sensors of anion binding

One dinuclear chlorodiphenyltin (IV) dithiocarbamate complex (1) and four mononuclear complexes of general formula Ph₂Sn(S₂CNR)Cl (2, 3, 5, and 6) have been synthesized and characterized both in solid-state and solution. X-ray structures for complexes 1, 3 and 6 demonstrated a five-coordination geometry around of tin atoms, in which dithiocarbamate ligand chelates asymmetrically the metal center. As shown by ¹¹⁹Sn NMR spectroscopy, five-coordination geometry observed in the solid-state remains in solution. The stability of these chlorodiphenyltin(IV) dithiocarbamate complexes in the presence of biologically relevant anions such as acetate, dicarboxylates of general formula ^?OOC-(CH₂)_n-COO^? (n = 2–8), dihydrogenphosphate, hydrogensulfate, and halides has been examined in acetonitrile solutions. For all of these organotin(IV) complexes the displacement of the coordinated ligands (i.e., chloride and dithiocarbamate) from the organotin(IV) moiety occurred in the presence of monoanions like acetate, dihydrogenphosphate, hydrogensulfate and fluoride. A stepwise mechanism for ligand exchange is proposed based on UV–Vis, ¹H, ¹³C and ¹¹⁹Sn spectroscopic data, as well as mass spectrometry. From UV–Vis titration experiments it was found that dicarboxylates with small spacers like malonate and succinate, acted differently in the exchange of the dithiocarbamate group in comparison to other monoanionic O donor ligands or dicarboxylates with longer chains, perhaps by following an intramolecular displacement of the coordinated ligand.The lability of these organotin(IV) dithiocarbamate compounds in solution hampers their use as stably host for anions, however, by taking advantage of the intrinsic chromogenic properties of free dithiocarbamate anions, or by attaching dithiocarbamate groups to well-known fluorescent moieties such as antracene, these complexes can sense the presence of O-donor anions at very low concentrations by displacement of the metal-coordinated dithiocarbamate.     

Superpositional Quantum Network Topologies

We introduce superposition-based quantum networks composed of (i) the classical perceptron model of multilayered, feedforward neural networks and (ii) the algebraic model of evolving reticular quantum structures as described in quantum gravity. The main feature of this model is moving from particular neural topologies to a quantum metastructure which embodies many differing topological patterns. Using quantum parallelism, training is possible on superpositions of different network topologies. As a result, not only classical transition functions, but also topology becomes a subject of training. The main feature of our model is that particular neural networks, with different topologies, are quantum states. We consider high-dimensional dissipative quantum structures as candidates for implementation of the model.     

Modification of the defect structure and electrophysical properties in zinc selenide crystals under the action of an alternating electric field

Modifications in the structure and electrophysical properties of ZnSe crystals subjected to a high alternating electric field of industrial frequency are investigated. It is established that such an action changes their defect structure and dielectric parameters. The latter exhibit different dependences on temperature and photoexcitation wavelength. The modifications are caused by ionic conduction, which is associated with local anomalies in the electric and elastic subsystems of the crystals.     

Irreversible electrostatic deposition of CdTe quantum dots on glassy carbon electrodes from colloidal solutions

Journal of Solid State Electrochemistry - Cadmium telluride quantum dots (CdTe-QDs) can be deposited from colloidal solutions on glassy carbon (GC) electrodes potentiostatically. The immobilization...     

Homoallylic <Emphasis Type="Italic">o</Emphasis>-halobenzylamines: asymmetric diversity-oriented synthesis of benzo-fused cyclic amines

The presence of a halogen atom in the proximity of a homoallylic amine, obtained by asymmetric addition of allylzinc bromide to the corresponding tert-butyl sulfinimine, makes them versatile building blocks suitable to participate in several palladium-catalyzed processes, such as the intramolecular Heck reaction or the Sonogashira cross-coupling. The thus obtained ortho-alkynyl derivatives display two unsaturated functional groups which may be further modified by means of the intramolecular Pauson–Khand reaction or the ring-closing enyne metathesis. In this way, a variety of benzo-fused amines can be obtained in 2–3 steps from readily available starting materials.     

Acid–Base Pairs in Lewis Acidic Zeolites Promote Direct Aldol Reactions by Soft Enolization

Hf‐, Sn‐, and Zr‐Beta zeolites catalyze the cross‐aldol condensation of aromatic aldehydes with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled molecules confirm that acid‐base pairs in the Si‐O‐M framework ensemble promote soft enolization through α‐proton abstraction. The Lewis acidic zeolites maintain activity in the presence of water and, unlike traditional base catalysts, in acidic solutions.     

Large conformal metrics with prescribed sign-changing Gauss curvature

Let \((M,g)\) be a two dimensional compact Riemannian manifold of genus \(g(M)>1\). Let \(f\) be a smooth function on \(M\) such that

$$\begin{aligned} f \ge 0, \quad f\not \equiv 0, \quad \min _M f = 0. \end{aligned}$$

Let \(p_1,\ldots ,p_n\) be any set of points at which \(f(p_i)=0\) and \(D^2f(p_i)\) is non-singular. We prove that for all sufficiently small \(\lambda >0\) there exists a family of “bubbling” conformal metrics \(g_\lambda =e^{u_\lambda }g\) such that their Gauss curvature is given by the sign-changing function \(K_{g_\lambda }=-f+\lambda ^2\). Moreover, the family \(u_\lambda \) satisfies

$$\begin{aligned} u_\lambda (p_j) = -4\log \lambda -2\log \left( \frac{1}{\sqrt{2}} \log \frac{1}{\lambda }\right) +O(1) \end{aligned}$$

and

$$\begin{aligned} \lambda ^2e^{u_\lambda }\rightharpoonup 8\pi \sum _{i=1}^{n}\delta _{p_i},\quad \text{ as } \lambda \rightarrow 0, \end{aligned}$$

where \(\delta _{p}\) designates Dirac mass at the point \(p\).

     

On the Constraints Defining BPS Monopoles

We discuss the explicit formulation of the transcendental constraints defining spectral curves of SU(2) BPS monopoles in the twistor approach of Hitchin, following Ercolani and Sinha. We obtain an improved version of the Ercolani-Sinha constraints, and show that the Corrigan-Goddard conditions for constructing monopoles of arbitrary charge can be regarded as a special case of these. As an application, we study the spectral curve of the tetrahedrally symmetric 3-monopole, an example where the Corrigan-Goddard conditions need to be modified. A particular 1-cycle on the spectral curve plays an important rôle in our analysis.