Structure of electrolyte solutions sorbed in carbon nanospaces, studied by the replica RISM theory

The replica RISM theory is used to investigate the structure of electrolyte solutions confined in carbonized polyvinylidene chloride (PVDC) nanoporous material, compared to bulk electrolyte solution. Comparisons are made between the models of electrolyte solution sorbed in the carbonized PVDC material and a single carbon nanosphere in bulk electrolyte solution. Particular attention is paid to the chemical potential balance between the species of the sorbed electrolyte solution and the bulk solution in contact with the nanoporous material. As a result of the strong hydrophobicity of the carbonized PVDC material in the absence of activating chemical groups, the densities of water and ions sorbed in the material are remarkably low compared to those in the ambient bulk solution. The interaction between water molecules and cations becomes strong in nanospaces. It turns out that, in carbon nanopores, a cation adsorbed at the carbon surface is fully surrounded by the hydration shell of water molecules which separates the cation and the surface. Distinctively, an anion is adsorbed in direct contact with the carbon surface, which squeezes a part of its hydration shell out. The tendency increases toward smaller cations, which are characterized as "positive hydration" ions. In the bulk, cations are not hydrated so strongly and behave similarly to anions. The results suggest that the specific capacitance of an electric double-layer supercapacitor with nanoporous electrodes is intimately related to the solvation structure of electrolyte solution sorbed in nanopores, which is affected by the microscopic structure of the nanoporous electrode.     

Addition of diphenylphosphinoyl azide to [60]fullerene

The reaction of [60]fullerene with diphenylphosphinoyl azide in toluene or ino-dichlorobenzene in the presence of traces of water affords 2-[N-(diphenylphosphoryl)amino]-1-hydroxy[60]fullerene This reaction in THF gives a mixture of (N-diphenylphosphoryl)[60]fullerenol[1,2-b]aziridine and a product of partial hydrolysis of the bisadduct of phosphorylated azide and fullerene. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2168–2172, November, 1999.     

Recyclization of 2-imino-2H-1-benzopyrans by the action of nucleophilic reagents 4. Use of 2-(N-aroylhydrazono)coumarin-3-carboxamides for the synthesis of 3-(1,3,4-oxadiazol-2-yl)coumarins

A new method for the synthesis of 3-(1,3,4-oxadiazol-2-yl)coumarins is proposed. It is based on the recyclization of 2-(N-aroylhydrazono)coumarin-3-carboxamides, which are readily obtained by the reaction of 2-iminocoumarin-3-carboxamides with arenecarboxylic hydrazides in an acidic medium. Advantages of the given method over alternative synthetic schemes were shown. Proposals on the mechanism of reaction were made.For Communication 3, see [1].Ukrainian Pharmaceutical Academy, Khar'kov 310002. Khar'kov State University, Khar'kov 310077, Ukraine. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 190–193, February, 1999.     

ortho‐Fluoroazobenzenes: Visible Light Switches with Very Long‐Lived Z Isomers

Improving the photochemical properties of molecular photoswitches is crucial for the development of light‐responsive systems in materials and life sciences. ortho‐Fluoroazobenzenes are a new class of rationally designed photochromic azo compounds with optimized properties, such as the ability to isomerize with visible light only, high photoconversions, and unprecedented robust bistable character. Introducing σ‐electron‐withdrawing F atoms ortho to the N?N unit leads to both an effective separation of the n→π* bands of the E and Z isomers, thus offering the possibility of using these two transitions for selectively inducing E/Z isomerizations, and greatly enhanced thermal stability of the Z isomers. Additional para‐electron‐withdrawing groups (EWGs) work in concert with ortho‐F atoms, giving rise to enhanced separation of the n→π* transitions. A comprehensive study of the effect of substitution on the key photochemical properties of ortho‐fluoroazobenzenes is reported herein. In particular, the position, number, and nature of the EWGs have been varied, and the visible light photoconversions, quantum yields of isomerization, and thermal stabilities have been measured and rationalized by DFT calculations.     

Analysis of the Operation of Thermonuclear Inverted-Corona Targets with an Ultrathin Working Layer at the Iskra-5 Laser Facility

Journal of Experimental and Theoretical Physics - We report on the results of experiments performed on the Iskra-5 laser facility for studying the effect of the polydeuteroethylene (CD2)n working...     

Detection of a single electron in xenon-based electroluminescent detectors

It is experimentally shown that a single ionization electron can be detected by various xenon-based electroluminescent detectors with optical readout, such as a high-pressure cylindrical gas counter, a two-phase detector with gas amplification, and a two-phase detector with a plane-parallel and uniform electric field. The sensitivity of the detectors was 7, 18, and 15 photoelectrons respectively. The coordinate resolution of the two-phase detector for electrons resulting from field emission at the cathode was σ _X,Y = 5.2 mm.     

Fabrication of 2D–3D photonic crystal heterostructures by glancing angle deposition

We fabricate 2D–3D photonic crystal heterostructures based on the silicon [001]-diamond:1 square spiral geometry using glancing angle deposition. We compare the normal incidence reflection properties of the fabricated 2D–3D heterostructures to simulated spectra generated using finite-difference time-domain calculations. Reflection peaks are observed, resulting from the presence of a photonic band gap, and defect modes are created by the 2D layer. Deterioration of the reflectance peaks with increased number of vertical spiral periods is observed. A series of square spiral structures are fabricated with a varying number of vertical periods to quantify the degradation of reflection peaks. At normal light incidence, a maximum reflection peak is observed from the film with three vertical periods. Beyond three spiral rotations, deterioration of the substrate-plane periodicity causes scattering losses.     

Synthesis of spiro-fused (C5)-pyrazolino-(C6)-triazinones, a new heterocyclic system

Reaction of 4-hydrazinoquinazoline with 2,4-diketoesters gives the corresponding 3-acylmethyl-2H-[1,2,4]triazino[2,3-c]quinazolin-2-ones in a one-step procedure via cyclocondensation-Dimroth-like rearrangement. Spectroscopic studies as well as X-ray analysis reveal that the obtained triazinoquinazolines exist in their ketoimine tautomeric form. Treatment of these compounds with hydrazine hydrate affords 3′-(2-aminophenyl)-3-(het)aryl-spiro[pyrazoline-5,6′(1′H)-1,2,4-triazin]-5′(4′H)-ones or 5-(het)arylpyrazole-3-carboxylic acid hydrazides depending on the reaction conditions. The structure of the spiro-heterocycles was elucidated by means of single-crystal X-ray analysis and confirmed by spectroscopic investigations.     

Epitaxial growth of a graphene single crystal on the Ni(111) surface

The thermally controlled synthesis of graphene from propylene molecules on the Ni(111) surface in ultrahigh vacuum is studied by scanning tunneling microscopy and density functional theory. It is established that the adsorption of propylene on Ni(111) atomic terraces at room temperature results in the dehydration of propylene molecules with the formation of single-atomic carbon chains and in the complete dissociation of propylene at the edges of atomic steps with the subsequent diffusion of carbon atoms below the surface. The annealing of such a sample at 500°С leads to the formation of multilayer graphene islands both from surface atomic chains and by the segregation of carbon atoms collected in the upper nickel atomic layers. The process of formation of an epitaxial graphene monolayer until the complete filling of the nickel surface is controllably observed. Atomic defects seen on the graphene surface are interpreted as individual nickel atoms incorporated into graphene mono- or bivacancies.     

Chiral Monolithic Silica-Based HPLC Columns for Enantiomeric Separation and Determination: Functionalization of Chiral Selector and Recognition of Selector-Selectand Interaction

This review draws attention to the use of chiral monolithic silica HPLC columns for the enantiomeric separation and determination of chiral compounds. Properties and advantages of monolithic silica HPLC columns are also highlighted in comparison to conventional particle-packed, fused-core, and sub-2-µm HPLC columns. Nano-LC capillary monolithic silica columns as well as polymeric-based and hybrid-based monolithic columns are also demonstrated to show good enantioresolution abilities. Methods for introducing the chiral selector into the monolithic silica column in the form of mobile phase additive, by encapsulation and surface coating, or by covalent functionalization are described. The application of molecular modeling methods to elucidate the selector–selectand interaction is discussed. An application for enantiomeric impurity determination is also considered.