Additivity of the proton affinity of polysubstituted benzenes: the ipso position

It is shown, by the MP2(fc)/6-31G^{* *}/ /HF/6-31G^* +ZPE(HF/6-31G^*) theoretical model and concomitant use of homodesmic reactions, that the ipso proton affinities in polyfluorinated benzenes follow a simple additivity rule. Performance of the latter is good, as evidenced by a low average absolute deviation Δ_abs = 0.8 kcal/mol from the accurate ab initio results. Additional evidence supporting the additivity concept is provided by good accordance with the experimental proton affinity (PA) for perfluorobenzene. The present approach enables estimates of the ipso PAs of multiply substituted aromatics. It is particularly useful in those systems which involve or atomic groupings with lone pairs of electrons proximate to the aromatic π moiety. The additivity rule of thumb offers a simple rationalization of the ipso proton affinities. The origin of the PA additivity is briefly discussed.     

Improving quality of service in four-channel WDM ethernet passive optical network

Energy-efficiency and green communications have become dominant topics related to access network implementation, since their energy consumption is a major contributor of energy consumption within the Internet. In this paper we analyze an implementation of a new energy-efficient dynamic bandwidth algorithm in a four-channel Wavelength Division Multiplexing Ethernet Passive Optical Network (WDM EPON), in which wavelength assignments take place per service class and not per Optical Network Unit (ONU). The improved Dynamic Bandwidth Allocation (DBA) algorithm introduces independent bandwidth allocation for each wavelength, which results in efficient bandwidth management and utilization. The mathematical model for new DBA algorithm is described, as are changes to the Multi-Point Control Protocol (MPCP), necessary for its implementation. The obtained results show that the redefined DBA algorithm improves Key Performance Indicators (KPIs) and as a consequently enables delivery of enhanced services to end-users. Significant energy savings are achieved without Quality of Service (QoS) degradation, and without network or equipment architecture changes.     

Excitation of Electronic States of CO in Radio-Frequency Electric Field by Electron Impact

Electron impact excitation rate coefficients for singlet and triplet electronic states of the carbon monoxide molecule have been calculated under non-equilibrium conditions in the presence of radio-frequency electric field. A Monte Carlo simulation of electron transport has been performed in order to determine non-equilibrium electron energy distribution functions within one period of applied electric field. By using these distribution functions and corresponding cross sections, the excitation rate coefficients have been calculated for all electronic states of CO in the frequency range from 13.56 up to 500 MHz, at reduced root mean square electric field values ranging from 200 to 700 Td. We expect these rates to be valuable for modeling radio-frequency CO plasmas since excited neutrals exhibit greater chemical reactivity than neutrals in ground electronic state, hence altering many properties of plasma.     

Correlation of the absolute conformation of sec alcohols derived from macrocyclic lactones of resorcylic acid and their stereoselective transacetylation in organic solvents by Pseudomonas fluorescens lipase

Transacetylation of diastereomeric pairs of sec. alcohols, derived from macrocyclic lactones of resorcylic acid; 7,β-trans-zearalenols (1,2, full names., (3S,7R and 3S,7S) trans- 3,4,5,6,9,10-octahydro-7,14,16-trihydroxy-3-methyl-1H-2-benzoxacyclotetradecine-1-ones), 7,β-cis-zearalenols (5,6),and 7,β-zearanols (9,10,full names., (3S,7R and 3S,7S) 3,4,5,6,9,10,11,12-decahydro-714,16-trihydroxy-3-methyl-1H-2-benzoxacyclotetradecine-1-ones) by vinylacetate, catalysed by Pseudomonas sp. and Pseudomonas fluorescens lipase in n-heptane and acetonitrile has been studied. It is highly stereoselective; diastereomeric excess of 7β-O-acetates was usually near 100%. K_M, V_max and specificity constant V_max/K_M do not significantly differ for 7β-stereoisomers 2, 6 and 10. However, they notably change on going from n-heptane to acetonitrile, and the specificity constant drops by factor ca 10-100. The enzyme-bound water is assumed to be partly released in the latter solvent, thus diminishing the interaction with the hydrophilic region of the substrates, and affecting the activity. but not the stereoselectivity of lipases. To correlate the structural and conformational properties of these substrates with unexpectedly high diastereoselectivity of enzymatic transacetylation, the solid state structures of 7β-isomers 2, 4, 6, 10 and 12 have been determined by X-ray analysis. The X-ray structure analysis has revealed that the 7 and 7β isomers possess notably different and in some cases almost mirror-image related absolute conformations around the reactive center. The importance of conformational chirality in the hydrophobic region of these substrates for stereoselection in transacylation by microbial lipases is discussed.     

Comparison of comet assay parameters for estimation of genotoxicity by sum of ranking differences

The genotoxic potential of waters in six rivers and reservoirs from Serbia was monitored in different tissues of chub (Squalius cephalus L. 1758) with the alkaline comet assay. The comet assay, or single-cell gel electrophoresis, has a wide application as a simple and sensitive method for evaluating DNA damage in fish exposed to various xenobiotics in the aquatic environment. Three types of cells, erythrocytes, gill cells, and liver cells, were used for assessing DNA damage. Images of randomly selected cells were analyzed with a Leica fluorescence microscope and image analysis by software (Comet Assay IV Image analysis system, PI, UK). Three parameters (tail length—l, tail intensity—i, and Olive tail moment—m) were analyzed on 1,700 nuclei per cell type. The procedure for sum of ranking differences (SRD) was implemented to compare different types of cells and different parameters for estimation of DNA damage. Regarding our nine different estimations of genotoxicity: tail length, intensity, and moment in erythrocytes (rel, rei, rem), liver cells (rll, rli, rlm), and gill cells (rgl, rgi, rgm), the SRD procedure has shown that the Olive tail moment and tail intensity are (almost) equally good parameters; the SRD value was lower for the tail moment and tail intensity than for tail length in the case of all types of cells. The least reliable parameter was rel; close to the borderline case were rei, rll, and rgl (～5 % probability of random ranking).

Detection of Escherichia coli O157:H7 bacteria by a combination of immunofluorescent staining and capillary electrophoresis

As the number of incidents of bacterial infections continues to rise around the globe, simpler, faster, and more sensitive diagnostic techniques are required to improve the safety of the food supply and to screen for potential bacterial infections in humans. We present here direct and indirect approaches for the detection of bacteria, which are based upon a combination of immunofluorescent staining and capillary electrophoresis. In the direct approach, Escherichia coli O157:H7 bacteria stained with fluorescein-tagged specific antibodies are detected by CE, while in the indirect approach fluorescein-tagged specific antibodies to E. coli are first captured by E. coli O157:H7 bacteria and then released and detected by CE. We have identified suitable bacteria staining and CE protocols, which involved a 10 mM Tris-borate-EDTA (TBE) buffer, 0.25 micro g antibody/1 million bacteria, and capillaries dynamically coated with poly-N-hydroxyethylacrylamide (polyDuramide). We have also successfully detected the presence of E. coli O157:H7 in contaminated meat. The total time required for analysis was 6-8 h, which is less than that realized in most commercial assays presently available.     

A DFT study of pyramidalized alkenes: 7-oxasesquinorbornenes and 7,7′-dioxasesquinorbornenes

  DFT calculations of 7′–oxasesquinorbornenes and 7,7′-dioxasesquinorbornenes using the B3LYP/6–31G* method are reported. All the investigated structures (syn- and anti- derivatives) showed significant non-planarity of the central double bond, with the exception of those anti-derivatives possessing symmetrical structures. The influence of the replacement of the methylene groups at position 7- of the norbornene fragment with oxygen and the introduction of second and third (peripheral) double bonds and benzene rings on the molecular and electronic structures of these molecules have also been investigated. Received: 11 November 2002 / Accepted: 6 June 2002 / Published online: 29 April 2003     

Principal component analysis of the main factors of line intensity enhancements observed in oscillating direct current plasma

Enhancement of emission line intensities by induced oscillations of direct current (DC) arc plasma with continuous aerosol sample supply was investigated using multivariate statistics. Principal component analysis (PCA) was employed to evaluate enhancements of 34 atomic spectral lines belonging to 33 elements and 35 ionic spectral lines belonging to 23 elements. Correlation and classification of the elements were done not only by a single property such as the first ionization energy, but also by considering other relevant parameters. Special attention was paid to the influence of the oxide bond strength in an attempt to clarify/predict the enhancement effect. Energies of vaporization, atomization, and excitation were also considered in the analysis. In the case of atomic lines, the best correlation between the enhancements and first ionization energies was obtained as a negative correlation, with weak consistency in grouping of elements in score plots. Conversely, in the case of ionic lines, the best correlation of the enhancements with the sum of the first ionization energies and oxide bond energies was obtained as a positive correlation, with four distinctive groups of elements. The role of the gas-phase atom-oxide bond energy in the entire enhancement effect is underlined.     

Intermolecular interaction in an open-shell pi-bound cationic complex: IR spectrum and coupled cluster calculations for C2H2+-Ar

The intermolecular potential energy surface (PES) of Ar interacting with the acetylene cation in its (2)Pi(u) ground electronic state is characterized by infrared photodissociation (IRPD) spectroscopy and quantum chemical calculations. In agreement with the theoretical predictions, the rovibrational analysis of the IRPD spectrum of C(2)H(2) (+)-Ar recorded in the vicinity of the antisymmetric CH stretching fundamental (nu(3)) is consistent with a vibrationally averaged T-shaped structure and a ground-state center-of-mass separation of R(c.m.) = 2.86 +/- 0.09 A. The nu(3) band experiences a blueshift of 16.7 cm(-1) upon complexation, indicating that vibrational excitation slightly reduces the interaction strength. The two-dimensional intermolecular PES of C(2)H(2) (+)-Ar, obtained from coupled cluster calculations with a large basis set, features strong angular-radial coupling and supports in addition to a global pi-bound minimum also two shallow side wells with linear H-bound geometries. Bound state rovibrational energy level calculations are carried out for rotational angular momentum J = 0-10 (both parities) employing a discrete variable representation-distributed Gaussian basis method. Effective spectroscopic constants are determined for the vibrational ground state by fitting the calculated rotational energies to the standard Watson A-type Hamiltonian for a slightly asymmetric prolate top.