CASPT2 and CCSD(T) calculations of dipole moments and polarizabilities of acetone in excited states

The acetone molecule is investigated in its ground state and valence ^1,3n-π*, ^1,3π-π*, and ^1,3σ-π* excited states and Rydberg ^1,3n-3s, ^1,3π-3?, ^1,3n-3p_y and ^1,3π-3p_y states using the CASSCF, CASPT2, and CCSD(T) methods. Equilibrium geometries of excited states are obtained and their changes with respect to the ground state are discussed. For most excited states the C_2v symmetry of the ground state is lowered to the C_s symmetry. A series of valence vertical and adiabatic excitation energies is presented along with excitation energies for Rydberg states. The main body of the paper contains Finite-Field Perturbation Theory (FFPT) calculations of electric properties of the vertically as well as geometry relaxed excited states. Dipole moments of valence excited states decrease significantly upon excitation, being about one half of the ground state dipole moment. Polarizabilities usually change upon excitation much less (increase by about 30%) but hyperpolarizabilities are enhanced up to one or two orders of magnitude. The orientation of the dipole moment is reversed in some vertically excited Rydberg states. Properties of the ground and excited states are discussed considering alterations of the electronic structure and shifts in the geometry.     

The Identification of a Novel Highly Condensed Pentacyclic Heteroaromatic Ring System 1,3,5,5b,6,8,10,10b‐Octaazacyclopenta[h,i]Aceanthrylene and its Application in the Synthesis of 5,7‐Substituted Pyrazolo[4,3‐d]Pyrimidines

Pyrazolo[4,3‐d]pyrimidines are of interest as potential kinase inhibitors. This article describes the formation of a novel highly conjugated, condensed, centrosymmetric heteroaromatic compound, 4,9‐dichloro‐2,7‐diisopropyl‐1,3,5,5b,6,8,10,10b‐octaazacyclopenta[h,i]aceanthrylene ( 3 ), during the chlorination of 5,7‐dihydroxypyrazolo[4,3‐d]pyrimidine ( 1 ) with phenylphosphonic dichloride. The nucleophilic attack of benzylamine on 3 afforded N‐benzyl‐5‐chloro‐3‐isopropyl‐1H‐pyrazolo[4,3‐d]pyrimidin‐7‐amine ( 6 ), which was further substituted to yield a pyrazolo[4,3‐d]pyrimidine analogue of roscovitine, a well‐known cyclin‐dependent kinase inhibitor.     

Pressurised solvent extraction of nitrated derivatives of polycyclic aromatic hydrocarbons from roadside dust

An analytical method based upon the pressurised solvent extraction and gas chromatography and mass spectrometry (GC-MS) for analysis of nitrated derivatives of polycyclic aromatic hydrocarbons (nitro-PAHs) in roadside dust has been developed. Five nitro-PAHs (1-nitronaphthalene, 1-nitropyrene, 9-nitroanthracene, 2-nitrofluorene, 6-nitrochrysene) were chosen for this study because of their variable physical properties and effect on human health. Experiments with spiked inert matrix were used for the best extraction conditions finding. Different extraction conditions (temperature, pressure, solvents and duration of extraction cycle) were examined. The highest recoveries were observed at the extraction pressure of 14?MPa, temperature of 100°C and two cycles of 5?min extraction time, when dichloromethane was used as an extraction solvent. These conditions were applied to the extraction of nitro-PAHs from roadside dust. After extraction the nitro-PAHs fraction was isolated by the silica gel column chromatography. The GC-MS detector was used for analyses of the extracts. Recoveries of nitro-PAHs after extraction from roadside dust ranged from 60% for 9-nitroanthracene to 108% for 6-nitrochrysene.     

Volume Chemistry of Nitrogen in Binary Metal Nitrides and Subnitrides

A comparison of the concept of volume increments created by W. Biltz with that based on quantum mechanical calculations by R.F.W. Bader was performed for crystal structures of binary metal nitrides and ‐subnitrides. The mutual comparison of both concepts permits insights into the bonding relationships of these compounds and reveals the considerable range of volume demand of a strongly polarisable bonding partner, such as the nitride ion. Finally it becomes clear that the Biltz volume increments show a quantum‐chemical relevance in the chemistry of solids.     

Controlled grafting of cellulose esters using SET‐LRP process

Here, we present the first example of application of single‐electron transfer living radical polymerization (SET‐LRP) process to a controlled grafting of cellulose esters, cellulose diacetate (CDA), and cellulose acetate butyrate (CAB). The cellulose ester macroinitiators with various functionality densities have been prepared by acylation of the backbones with 2‐bromoisobutyryl (BrIB) and dichloroacetyl (DCA) groups, respectively. Methacrylate monomers were polymerized using DCA‐functionalized macroinitiators in the presence of pentamethyldiethylene triamine as a ligand. At 30 °C, the reaction is rather slow, reaching about 10% conversion after 3 to 6 h of polymerization, whereas the higher temperature (60 °C) perceptibly speeds up the polymerization so that methyl methacrylate (MMA) conversion is ～30% after 5 h. Graft copolymers with random‐type and diblock‐type grafts having amphiphilic character were also synthesized. For acrylate grafting (BuA and t‐BuA), BrIB‐functionalized macroinitiators are more convenient in a combination with a low concentration of Cu(0) and Me₆TREN as a ligand and polymerization is detectably faster even at the lower temperature than that of MMA. Kinetic studies show “living” character of both the graftings. Important advantages of SET‐LRP, compared with classic ATRP, are (i) higher polymerization rate, (ii) lower extent of recombination of the growing grafts and (iii) negligible coloration of the products with catalytic residua, so that the prepared polymers do not require additional careful purification. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Thermal conductivity of lightweight aggregate based on coal fly ash

The article presents the results of physical and chemical properties of lightweight aggregates (LWA) obtained by the thermal treatments of raw composition based on fly ash, supplied by electric plants from Serbia. The production process of LWA consists of raw material preparation, plastic shaping?Cextrusion, granulation, and thermal treatment at three temperatures: 1100, 1150, and 1200?°C. The final firing temperature (T?=?1150?°C) is chosen based on the mechanical and physical properties of the designed aggregates. The particle-size distribution of the LWAs is unimodal (d????16?mm) while the density value varies from 0.98 to 1.99?g/cm³. The water absorption values are determined by use of two methods: 24?h of soaking in cold water and 5?h of boiling. The thermal conductivity of unbound, fired LWA particles is determined by measuring the amount of axially transferred heat in the stationary state. The obtained value of the LWA thermal conductivity (???=?0.0872?W/mK, T?=?1150?°C) is suitable for the production of structural concrete blocks with improved thermal insulating properties. Because of their high-porosity and -compressive strength values, the designed LWA could be used instead of the conventional aggregates in the production of concrete blocks. Consequently, a real valorization of the waste material such as fly ash in Serbia was established.     

Cubic β-Fe2O3 as the product of the thermal decomposition of Fe2(SO4)3

Hyperfine Interactions - The thermal decomposition of Fe2(SO4)3 in air has been investigated using transmission Mössbauer spectroscopy, CEMS and X-ray powder diffraction. The hexagonal...     

Bicyclic graphs for which the least eigenvalue is minimum

The spread of a graph is defined to be the difference between the greatest eigenvalue and the least eigenvalue of the adjacency matrix of the graph. In this paper we determine the unique graph with minimum least eigenvalue among all connected bicyclic graphs of order n. Also, we determine the unique graph with maximum spread in this class for each n?28.     

Potential antidepressants. Synthesis of 6,11-dihydrodibenzo[b,e]thiepin-11-yl 4-(dimethylamino-methyl)phenyl ketone and of some related compounds

Reactions of dibenzo[b,e]thiepin-11(6H)-one (4) with 2-, 3- and 4-(dimethylaminomethyl)phenylmagnesium bromide afforded the tertiary alcohols 5a,b,c. The aldehydes 7 and 8 gave similarly the secondary alcohols 9a,b,c and 10c . Numerous attempts to prepare the corresponding ketones, especially by oxidation of 9a,b,c and 10c were unsuccessful. Only the oxidation of 9c with tetrabutylammonium chromate in chloroform afforded the desired ketone 16 . Its formation was accompanied by an important side reaction consisting in a cleavage of the “retro-ene-reaction” type leading to compound 11 and the aldehyde 13c which reacted with the chloroform present to give the alcohol 17 . Compounds 5a,b,c, 9a,b,c and 16 were tested as potential antidepressants but with the exception of some effects in the test of potentiation of yohimbine toxicity in mice, they proved inactive in this line.