Energy distribution among reaction products. H + NOCl,H + ICl

The infrared chemiluminescence technique has been used to obtain k(V′, R′, T′) (V′, R′, Tt? are product vibrational, rotational and translational energies) for the reactions (i) H + ClNO → HCl + NO (energy-release E_tot′ = 68.5 kcal mole^?1) and (ii) H + CII → HCl + I (E_tot′ = 55.8 kcal mole^?1). Reaction (i) exhibits inefficient conversion of energy-release into vibration in the new bond, characteristic of a light attacking atom reacting on a repulsive energy-surface. Reaction (ii) has a bimodal HCl product-energy-distribution suggesting that 18% of the reaction proceeds by direct attack at the Cl end of CII to yield low V′ and R′, and 82% by indirect reaction from the 1 end to give high V′ and R′.     

Steady Impact Factor Growth for MDPI Open Access Journals

For the past three years MDPI has announced the newly released impact factors for its Open Access journals by the means of an annual editorial [1-3]. In 2012 we are-once again-pleased to report that the growth of the impact factors of MDPI's Open Access journals continues. This year's edition of the Journal Citation Reports (JCR), which is published annually by Thomson Reuters, includes 10 journals published by MDPI, including three that have received their first official Impact Factors-International Journal of Environmental Research and Public Health (IJERPH), Materials and Nutrients. Table 1 reports the latest Impact Factors for 2011. Figure 1 graphically depicts the evolution of the Impact Factors for four MDPI open access journals that have received Impact Factors in the past. Table 2 reports the ranking of the MDPI journals within the subject categories of the Science Citation Index Expanded (SCIE).     

Electron energy loss spectroscopy (EELS) of H2O,H2S,H2Se and H2Te

Electronic excitation in H₂O, H₂S, H₂Se and H₂Te molecules has been studied by the EELS technique. Spectra of H₂S and H₂Se are remarkably similar with the 1b₁-nd transition most intense. The intensity of the first transition 1b₁-nsa₁ decreases through H₂O to H₂Se and this transition is absent in H₂Te. Transitions observed by EELS have been compared with optical absorption studies. A correlation diagram of the occupied and the excited states has been provided for these four molecules by making use of UVPES and EELS.     

Mono- and sesquiterpenoids of the oleoresin ofPinus koraiensis andP. pumila. crystal structure of 1β,4αH,7αH,10βH-Guaiane-5α,14-diol

The composition of the mono- and sesquiterpenoids of the oleoresin of two species of conifers of thePinaceae family has been studied. In the oleoresin ofPinus koraiensis Sieb. et Zucc. 10 oxidized monoterpenoids, 18 sesquiterpene hydrocarbons, and six sesquiterpene alcohols have been identified. In theoleoresin ofPinus pumila (Pall.) Rg1. 10 monoterpene hydrocarbons, six oxidized monoterpenoids, 14 sesquiterpene hydrocarbons, and four sesquiterpene alcohols have been found. The structure of 1β,4αH,7αH,10βH-guaiane-5α,14-diol, one of the hydroboration-oxidation products of an unidentified sesquiterpene alcohol isolated from both oleoresins, has been determined by x-ray structural analysis.     

Electrophoretic determination of phenyl and p-bromophenyl substituted 1H,2H,3H,4H-pyrido[4,3-d]pyrimidinium diiodobromides

Phenyl and p-bromophenyl substituted 1H,2H,3H,4H-pyrido[4,3-d]pyrimidinium diiodobromides have been identified and determined by capillary zone electrophoresis on an unmodified quartz capillary. It has been found that an increase in the number of bromine atoms in the structure of 1H,2H,3H,4H-pyrido[4,3-d]pyrimidinium derivatives consecutively decreases the electrophoretic mobility of the cations. The developed method makes possible the determination pyrido[4,3-d]pyrimidinium derivatives in the concentration range (0.03–0.25) mM with the c _min (3.1–10.0) μM.     

Spectroscopic investigation of the composition of electrospun titania nanofibers. E. T. Bender,P. Katta,G. G. Chase and R. D. Ramsier. Surface and Interface Analysis, 2006; 38, 1252–1256

The original article to which this Erratum refers was published in Surface and Interface Analysis Vol. 38, No. 9, 2006, pages 1252–1256. Copyright © 2006 John Wiley & Sons, Ltd.     

Metal ions in biological systems, vol. 2, metal ligand complexes : ed. by H. Sigel, Dekker, New York, 1973, xiv + 294 pages, $25.25

The kinetic isotope effect for β-hydride elimination from alkyliridium(I) complexes has bee found to be k_H/k_D = 2.28 ± 0.20.     

A New Flavanone from Chromolaena tacotana (Klatt) R. M. King and H. Rob,Promotes Apoptosis in Human Breast Cancer Cells by Downregulating Antiapoptotic Proteins

Chromolaena tacotana is a source of flavonoids with antiproliferative properties in human breast cancer cells, the most common neoplasm diagnosed in patients worldwide. Until now, the mechanisms of cell death related to the antiproliferative activity of its flavonoids have not been elucidated. In this study, a novel flavanone (3′,4′-dihydroxy-5,7-dimethoxy-flavanone) was isolated from the plant leaves and identified by nuclear magnetic resonance (NMR) and mass spectrometry (MS). This molecule selectively inhibited cell proliferation of triple-negative human breast cancer cell lines MDA-MB-231 and MCF-7 whit IC₅₀ values of 25.3 μg/mL and 20.8 μg/mL, respectively, determined by MTT assays with a selectivity index greater than 3. Early and late pro-apoptotic characteristics were observed by annexin-V/7-AAD detection, accompanied by a high percentage of the Bcl-2 anti-apoptotic protein inactivated and the activation of effector Caspase-3 and/or 7 in breast cancer cells. It was verified the decreasing of XIAP more than Bcl-2 anti-apoptotic proteins expression, as well as the XIAP/Caspase-7 and Bcl-2/Bax complexes dissociation after flavanone treatment. Docking and molecular modeling analysis between the flavanone and the antiapoptotic protein XIAP suggests that the natural compound inhibits XIAP by binding to the BIR3 domain of XIAP. In this case, we demonstrate that the new flavanone isolated from leaves of Chomolaena tacotana has a promising and selective anti-breast cancer potential that includes the induction of intrinsic apoptosis by downregulation of the anti-apoptotic proteins XIAP and Bcl-2. New studies should deepen these findings to demonstrate its potential as an anticancer agent.     

Determination of long-range intermolecular interaction energies using RPA/moment function methods. Application to H2O,H2O2 and H2O/H2O2 mixtures

The fully expanded expression for the Boltzmann-averaged pairwise intermolecular interaction energy of two molecules of arbitrary symmetry in the long-range (interaction < kT) limit has recently been determined explicitly as a series in r⁻ⁿ (r is the intermolecular separation) for n < 11. The resultant expression contains only multipolar products (point moment functions: PMFs) and energy terms which are characteristic of the ground state and excitation properties of the isolated molecules. These quantities are determined for H₂O and H₂O₂ using the single particle-hole RPA method, and the interaction energy contributions determined by direct state summation. Static electric dipole polarizabilities are determined as a by-product of the procedure, and are shown to agree closely with finite field results using a comparable basis. For the chiral H₂O₂/H₂O₂ system, the r⁻⁶ and r⁻⁹ discrimination energies are also calculated, suggesting that the r⁻⁹ contributions could well exceed the r⁻⁶ discriminatory terms for separations less than 20 au.     

(Trifluoromethyl)germanes. Preparation and properties of (CF3)2GeHX (X = H,D, F,Cl, Br,I, CH3) and CF3GeHnX3-n (X = H,D, CF2H,CH3)

The hydrogenation of (CF₃)_nGeX_4-n (X = halogen, n = 1–3) with NaBH₄ in an acidic medium has been investigated. Deuteration with NaBD₄ and D₃PO₄ gave the partially deuterated species CF₃GeH_nD_3-n and (CF₃)₂GeH_nD_2-n in reasonable isotopic purity. The (CF₃)₂GeHBr was isolated and converted into the halides (CF₃)₂GeHX (X = F, Cl, I) by treatment with AgX or HX. Insertion of CF₂ into a GeH bond has been observed, and (CF₃)(CF₂H)GeH₂ has been characterized. Direct alkylation of GeH bonds was brought about by reaction with a mixture of RI and R′₂Zn (R, R′= CH₃, C₂H₅), and the methyl(trif]uoromethyl)germanes CF₃GeH₂(CH₃), CF₃GeH(CH₃)₂ and (CF₃)₂GeH(CH₃) were isolated. For R = CD₃, R′ = CH₃ the product distribution can be accounted in terms of two competing mechanisms.     

Book Reviews

Abstract

HANDBOOK FOR ESTIMATING PHYSICOCHEMICAL PROPERTIES OF ORGANIC COMPOUNDS, by M. Reinhard and A. Drefal, 228 pages, J. Wiley, New York (1999). ISBN 0—471—172634. UK £ 210.00

THE CHEMISTRY OF POLLUTION, by G. Fellenberg, 192 pp. J. Wiley & Sons, Chichester, U.K. (1999). ISBN 0—471—980889. UK£ 24,95.

NATURAL ATTENUATION OF FUELS AND CHLORINATED SOLVENTS IN THE SUBSURFACE, by T.H. Wiedemeier, H.S. Rifai, C.J. Newell and J.T. Wilson, 617 pages, J. Wiley, New York (1999). ISBN 0—471—19749—1. UK £ 58.50

UNDERSTANDING OUR ENVIRONMENT, 3^rd, edition, edited by R.M. Harrison, 445 pages, The Royal Society of Chemistry, Cambridge (UK) (1999). ISBN 0—85404—584—8. UK£ 19.95

ENDOCRINE DISRUPTING CHEMICALS, Vol. 12 of Issues in Environmental Science and Technology, edited by R.E. Hester and R.H. Harrison, 152 pages, Royal Society of Chemistry, Cambridge (U.K.) (1999). ISBN 0—85404—255—5. UK£ 25,00

METHOD PERFORMANCE STUDIES FOR SPECIATION ANALYSIS. by P. Quevauviller, 271 pages, The Royal Society of Chemistry, Cambridge (U.K.) (1998). ISBN 0—85404—467—1. UK£ 59.50

GLOBAL AQUATIC AND ATMOSPHERIC ENVIRONMENT, by H.D. Kumar and D.P. Häder, 393 pages, Springer, Berlin (1999). ISBN 3—540—65369—4. USD 229.00

BIOACCUMULATION. New Aspects and Developments, edited by B. Beek, 284 pages, Springer, Heidelberg, 2000. ISBN 3—540—62575. USD 143.00

INTERLABORATORY STUDIES AND CERTIFIED REFERENCE MATERIALS FOR ENVIRONMENTAL ANALYSIS. The BCR approach, by Ph. Quevauviller and E.A. Maier, 558 pages, Elsevier Science, Amsterdam NL, (1999). ISBN 0—444—82389—1. USD 251.50 (Euro 224.62).     

Calculation of the hyperfine spectrum for H2Ne,H2Ar,H2Kr dimers.

The weakly bound dimers H₂Ne, Ar, Kr are treated such that the H₂, rotation (quantum number j) remains unperturbed except for orientational effects. The orientation of the ortho H₂(j = 1) is mainly influenced by the anisotropic forces between the dimer constituents. We develop a method which allows to extract from a measured hyperfine dimer transition the value of a simple molecular parameter containing mainly the strength of the anisotropic interaction sandwiched between the dimer-stretch vibrational eigenfunctions. An analytic expression is derived permitting an easy comparison between measurements and results from simple model potentials. In addition, where necessary due to the existence of quasi-bound states, the influence of continuum states can be properly taken into account, by our method.     

A Review of: “SEPARATION AND PURIFICATION TECHNIQUES IN BIOTECHNOLOGY Frederick J. Dechow Noyes Publications,Park Ridge,NJ, August 31, 1989, hardbound, 490 pages, $72.00.”

Abstract

J. Turková Elsevier, Amsterdam, 1993; hardbound, XVIII + 796 pages, $282.75     

Vibrational spectra and normal coordinate analysis of CF3 compounds: Part XLVI. Synthesis,vibrational spectra,normal coordinate analysis and electron diffraction investigation of the cis isomer of hexafluoroazomethane

The hitherto unknown cis isomer of hexafluoroazomethane has been prepared by the reaction of CICN with AgF₂ under mild conditions. It isomerizes rapidly to the trans isomer when exposed to daylight, but is stable in the dark. The compound has been characterized by NMR and UV spectra. Infrared and Raman spectra have been recorded and assigned with the assistance of a normal coordinate analysis. The molecular structure of cis-CF₃NNCF₃ has been determined by gas phase electron diffraction, and a planar CNNC skeleton, d(NN) 1.229(8) Å, d(CN) 1.494(5) Å, and ∠NNC 122.1(8)° has been established. Compared with the trans isomer, the higher sterc strain due to F?F repulsions is released by a ∮.03 Å d(CN) lengthening and a 9° widening of the NNC angle.     

Book Reviews

Abstract

WATER AND WATER ANALYSIS (in German: Wasser und Wasseruntersuchung), 2nd revised edition in the Series “Laboratory Books in Chemistry”, by Leonhard A. Hiitter, A-6060 Hall in Tirol, Austria, 344 pages (including 38 figures, 34 tables, 43 pages with newest literature references and other informations (regulations, addresses) mainly from Germany, Austria and Switzerland, and a good index of nine pages), carton cover, format 227 × 165 mm, ISBN 3-425-05075-3, Verlag Diesterweg/Salle, D-6000 Frankfurt/Main and Sauerlander, CH-5000 Aarau (1984), DM 48.00

AQUATIC TOXICOLOGY, Volume 2 of a Series, edited by Laverne J. Weber, Marine Science Center, Oregon State University, Newport, Oregon, U.S.A., 236 pages (including 7 tables, 33 figures, references (mainly of the 1970's) added to each chapter, and a valuable subject index of 6 pages), linen, format 243 × 163 mm, ISBN 0-89004-439-2, Raven Press, New York 10036 (1984), US $55.00

TOXICITY TESTING, NEW APPROACHES AND APPLICATIONS IN HUMAN RISK ASSESSMENT, edited by Dr. A. P. Li et al., Enviromental Health Laboratory Monsanto Company, St. Louis, Missouri, U.S.A., 295 pages (including 37 tables, 49 figures, newest references added to each contribution, discussion statements, a good subject index of six pages, and an address list of contributors), linen, format 241 × 162mm, ISBN 0-88167-083-9, Raven Press, New York (1983/1985), US $50.50

HEALTH RISKS TO FEMALE WORKERS IN OCCUPATIONAL EXPOSURE TO CHEMICAL AGENTS, by Prof. Dr. Reinier L. Zielhuis et al., Coronel Laboratorium, Universiteit van NL-1054 BW Amsterdam, The Netherlands, 132 pages (including 30 tables, references added to each chapter, an appendix on recent data, but no subject index), soft cover, format 242 × 165mm, ISBN 3-540- 13579-0, Springer-Verlag, Berlin-Heidelberg-New York-Tokyo (1984), DM 70.00, or approximately US $24.60

IS THE SOIL DYING (in German: Stirbt der Boden)? GDI-Series Man-Nature-Environment, by Dr. Volker Hauff et al., D-5300 Bonn, 250 pages (including 49 figures, 34 tables, an author index of two pages, but no subject index), soft cover, format 241 × 171 mm, no ISBN-number, GDI-Buchhandlung, CH-8803 Riischlikon, Switzerland (1985), SFr. 50.00

THE HANDBOOK OF ENVIRONMENTAL CHEMISTRY, PARTS C and D, edited by Prof. Dr. Otto Hutzinger, Chair of Ecological Chemistry and Geochemistry, D-8580 Bayreuth, linen, format 248 × 170 mm, Springer-Verlag Berlin-Heidelberg-New York-Tokyo (1985).     

Group IB organometallic chemistry: XXXV. Crystal and molecular structure of [Cu4(4-MeC6H4)-MeC-C(C6H4NMe2-2)2(C6H4NMe2-2)2], a tetranuclear organocopper compound containing bridging alkenyl and aryl groups

The crystal and molecular structure of the title compound has been determined by a single crystal X-ray diffraction study using standard Patterson and Fourier methods. The structure was refined by a block-diagonal least-square procedure to a finalR value of 0.16 for 3454 reflections. Crystals are monoclinic, space groupP2₁/c, witha 14.007(5), b 12.224(5), c 28.358(8)A?, β 99.60(1)°, andZ - 4.The molecule consists of a central rhombus-type core of copper atoms to which the alkenyl and aryl groups are bound in a bridging fashion (two electron-three center bonding). The two alkenyl and the two aryl groups each occupy adjoining edges of the Cu₄ core. The dimethylamino groups of the alkenyl ligand coordinate to copper, whereas those of the bridging aryl ligand are free. As a result the copper core is made up of copper atoms which are alternatingly two- and three-coordinate.The structure is discussed in terms of structural information now available for organocopper compounds. The geometry of the Cu₂C (bridge) moiety in organocopper cluster compounds as expected varies little with the nature of the bridging one-electron organo ligand (alkyl, alkenyl, alkynyl or aryl).     

Advances in Catalysis. Volume 25; edited by D.D. Eley, H. Pines, and P.B. Weisz, Academic Press, New York, San Francisco and London, 1976, xii + 457 pages, $42.50

Photolysis of 1,2-divinyl- and 1-phenyl-2-vinyltetramethyldisilane and 1-phenylethenylpentamethyldisilane has been investigated. All three compounds afforded a new type of silicon—carbon double-bonded intermediate via photorearrangement of a silyl group to the terminal carbon of a vinyl group.     

Advances in inorganic chemistry and radiochemistry,vol. 18: Edited by H.J. Emeléus and A.G. Sharpe,Academic Press,New York/San Francisco/London, 1976, vii + 414 pages, $35.50.

The catinic complex trans-[FeCl(CCHPh)(depe)₂]⁺ (depe = bis(diethylphosphino)ethane has been prepared by interaction of trans-[FeCl₂(depe)₂] with penylacetylene in methanol solution in the presence of NaX (X = BPh₄ or PF₆.     

Chlorinated long-chain fatty acids. Their properties and reactions—VI : Kinetics and mechanisms of base-catalyzed dehydrochlorination of sodium threo,threo-9,10,12,13-tetrachlorooctadecanoate

The base-catalyzed dehydrochlorination of sodium threo,threo-9,10,12,13-tetra-chlorooctadecanoate has been carried out in aqueous ethylene glycol solutions. During the first reaction step two chlorine atoms are eliminated nearly simultaneously as hydrogen chloride whereas the third and fourth chlorine atoms are released separately. The relative rates of these three reaction steps at 130°C are 497,41 and 1, respectively. The possible reaction mechanisms have been discussed in light of the kinetic results and product analyses which showed that the dehydrochlorination results mainly in conjugated diene-yne systems.