bluuebunny/crossref_metadata_2025 huggingface dataset:
On pseudo-rotation in (AsCH3)5 and (AsCF3)5
Authors: Wells E. J. , Ferguson R. C. , Hallett J. G. , Peterson L. K.
Published: May 2006

Two internal rearrangement processes can be deduced from the temperature dependences of the 1H and 19F nuclear magnetic resonance (n.m.r.) spectra of the asymmetric puckered five-membered ring compounds (AsCH3)5, (AsCF3)5, and (PCF3)5. The first is a fast "butterfly" motion of the ring puckering which yields a time-averaged plane of symmetry perpendicular to the ring through the puckered atom. This motion could not be stopped in any of the three compounds by cooling, even to −130 °C in the case of (AsCF3)5. The second is a slow pseudo-rotation, or a rotation of the perpendicular symmetry plane around the ring yielding a time-averaged fivefold rotation axis. There is a choice between two mechanisms for this second rearrangement, either a "clickstop" process in which the puckering progresses around the ring by one position at a time, or a "pancake" process in which the puckering drops randomly into any one of the five ring positions from a planar transition state. This choice can be resolved for this cyclic permutation process by appeal to the n.m.r. lineshapes. The present data for (AsCH3)5 favor the "clickstop" mechanism in spite of a competing intermolecular process at elevated temperatures with other components in the system which are in equilibrium with the ring compound.
Densities and magnetic susceptibilities of thallium amalgams
Authors: Foley W. T. , Chiu Rebecca Fai-Ying , Delorey John R.
Published: May 2006

not available
Effect of solvent and anion upon the proton magnetic resonance spectrum of the 1-methylpyridinium ion
Authors: Reynolds W. F. , Priller U. R.
Published: May 2006

The proton magnetic resonance spectra of 1-methylpyridinium bromide and iodide have been measured over a range of concentrations in different solvents. It is found that, with the exception of acetonitrile solutions, the infinite dilution chemical shifts are related to solvent dielectric constant. Extrapolated shifts for a nonpolar medium agree with previously calculated chemical shifts for the pyridinium ion. Proton chemical shifts in concentrated solutions are affected by cation–anion interactions. These interactions are interpreted in terms of ion pair formation.
Synthesis of 6-O-α- and β-D-xylopyranosyl-D-mannopyranose. (Glycosidation of α-and β-D-xylopyranosyl chloride 2,3,4-tri(chlorosulfate))
Authors: Jennings H. J.
Published: May 2006

Crystalline β-D-xylopyranosyl chloride 2,3,4-tri(chlorosulfate) has been prepared by the reaction of sulfuryl chloride with D-xylose. Anomerization of β-D-xylopyranosyl chloride 2,3,4-tri(chlorosulfate) yielded crystalline α-D-xylopyranosyl chloride 2,3,4-tri(chlorosulfate). Both α- and β-D-xylopyranosyl chlorides gave high yields of their inversion products on methyl glycosidation (Königs–Knorr conditions) demonstrating the non-participating properties of the chlorosulfate group. Using modified Königs–Knorr conditions β-D-xylopyranosyl chloride 2,3,4-tri(chlorosulfate) was condensed with 1,2,3,4-tetra-O-acetyl-β-D-mannopyranose to give predominantly 6-O-α-D-xylopyranosyl-D-mannopyranose. A similar condensation using α-D-xylopyranosyl chloride 2,3,4-tri(chlorosulfate) did not yield the analogous 6-O-β-D-xylopyranosyl-D-mannopyranose, therefore, for comparative purposes it was synthesized by the method of Bredereck and co-workers (1).
Temperature dependence of chemical shifts of protons in hydrogen bonds. Experimental evidence on an intramolecular hydrogen bond
Authors: Schaefer T. , Kotowycz G.
Published: May 2006

A temperature dependence of the chemical shift of the hydroxyl proton in the strong intramolecular hydrogen bond in 3,5-dichlorosalicylaldehyde is observed in carbon tetrachloride and benzene-d6 solutions. Its magnitude of 0.25 to 0.30 × 10−2 p.p.m. per ° C over a range of 100 °C is in agreement with the model described by Muller and Reiter (1).
Nuclear overhauser effect studies on fumaria alkaloids
Authors: Saunders J. K. , Bell R. A. , Chen C.-Y. , MacLean D. B. , Manske R. H. F.
Published: May 2006

The nuclear Overhauser effect has been used to confirm the structures proposed for two alkaloids isolated from Fumaria officinalis L.
Polarographic reduction of some Schiff bases in dimethylformamide. Part II. Some further theoretical considerations
Authors: Benson H. G. , Scott J. M. W.
Published: May 2006

The ordinary Hückel molecular orbital (H.m.o.) method and the linear combination of molecular orbitals (l.c.m.o.) method in a perturbational form have been used to calculate the π-electron energy levels appropriate to a series of 24 Schiff bases (S.b.'s) of the type ArCH=NAr′, where Ar— and Ar—′ are unsubstituted aryl groups. The energy levels calculated by both the H.m.o. and l.c.m.o. treatments are shown to give a satisfactory account of the polarographic data for the S.b.'s reported in Part I of the present series. However, the l.c.m.o. method appears to offer a deeper insight into the variation of the half-wave potentials for the first electron transfer with the structure of the S.b.
Ionic association and the Fuoss–Onsager conductance equation: aqueous KI
Authors: Andalaft E. , Tomkins R. P. T. , Janz G. J.
Published: May 2006

Results are reported for a reevaluation of the data for aqueous KI solutions using a modified application of the 1957 Fuoss–Onsager conductance equation in which it is reduced to a one-parameter equation with KA as the unknown. A single value of å is sufficient to account for the concentration dependence of conductance over the temperature range, 5–55 °C, and a small, but nevertheless finite, degree of ionic association is thus predicted for KI in aqueous solutions.
Synthesis of optically active deacetyl anisomycin
Authors: Wong C. M. , Buccini J. , Raa J. Te
Published: May 2006

Optically active (−)-deacetyl anisomycin and the enantiomer (+)-deacetyl anisomycin were synthesized starting with (+)-2R 3R tartaric acid. The asymmetric centers of the tartaric acid correspond to the C-2 and C-3 asymmetric centers of anisomycin. N-Benzyl tartarimide (3) was attacked by the Grignard reagent of anisyl chloride followed by lithium aluminium hydride reduction to give two diols (7) and (8) separated by thin-layer chromatography. The diol (8) was debenzylated giving the natural (−)-deacetyl anisomycin. The diol (7) was converted into the epoxide (10) by selective acetylation of the C-4 hydroxy group followed by treatments with phosphorus pentachloride and sodium ethoxide. Opening of the epoxide ring of 10 in boiling acetic acid followed by basic hydrolysis gave (+)-N-benzyl deacetyl anisomycin (11) which was debenzylated to give (+)-deacetyl anisomycin.
Reactions of ozonides. VII. Isolation and oxidation of ozonolysis products from 1-decene
Authors: Diaper Dennis G. M.
Published: May 2006

1-Decene ozonide (1) was isolated by column chromatography of the mixed products of ozonation of 1-decene (2) in several nonpolar solvents. 1-Methoxy- (3) and 1-tertiary butoxynonane-1-hydroperoxide (4) were similarly obtained. The thin-layer chromatographic separation of these products from each other and from other ozonation products was examined. Compounds 3 and 4 were smoothly oxidized to di-(1-alkoxyalkyl)peroxides by Ce(IV). The stoichiometry of this reaction, examined by isothermal calorimetry, was 1:1. Compounds 1,3, and 4 were oxidized by CF3CO3H and by other oxidizing agents to nonanoic acid with chain degradation loss of 2–30%.
Temperature dependence of proton magnetic resonance solvent shifts. 3,5-Dichlorosalicylaldehyde in carbon tetrachloride and benzene
Authors: Kotowycz G. , Schaefer T.
Published: May 2006

The ring proton chemical shifts of 3,5-dichlorosalicylaldehyde as a function of temperature in carbon tetrachloride and benzene solutions indicate that if there is association with solvent molecules in benzene solution, then there is also association with carbon tetrachloride solvent molecules. The aldehydic proton shift shows a much smaller (relative) temperature dependence in the carbon tetrachloride solution.
The nature of the coordination bond in metal complexes of substituted pyridine derivatives. III. 4-Methylpyridine complexes of some divalent transition metal ions
Authors: Brewer D. G. , Wong P. T. T. , Sears M. C.
Published: May 2006

Previous papers in this series investigated the nature of the coordination bond in copper(II) and zinc(II) complexes of 4-substituted pyridines by infrared spectroscopy. In this paper, the investigation has been extended to complexes of 4-methylpyridine with cobalt(II), manganese(II), and nickel(II). The geometry of the solid complexes is assigned, and the force constants associated with the metal–nitrogen bond were calculated from a normal coordinate analysis. The validity of the previously introduced Rπ parameter in these systems is discussed.
Intermolecular association and dielectric relaxation in some liquid amides
Authors: Dannhauser Walter , Johari Gyan P.
Published: May 2006

The equilibrium dielectric constants of three isomeric N-methylvaleramides are reported over a wide range of temperature. Analysis of the data in terms of Kirkwood's correlation factor suggests that the liquids are extensively associated into linear chains and that the extent of association is essentially independent of the size and shape of the alkyl group. Dielectric dispersion was measured (0.5–200 MHz) for these compounds as well as the isomeric N-butylacetamides and also N-ethylacetamide. The dispersion loci all follow the Debye equation and the relaxation times show a specific dependence on the size and shape of the alkyl group, but not on whether it is in the acid or the amine position. Activation energies for relaxation, viscous flow, and conduction are compared and the nature of liquid N-mono-substituted amides is discussed.
The chlorosulfuric acid solvent system. Part II. The solutes SeCl4 and TeCl4; evidence for the formation of the SeCl3+ and TeCl3+ ions
Authors: Robinson E. A. , Ciruna J. A.
Published: May 2006

From the results of electrical conductivity measurements on solutions in chlorosulfuric acid and the Raman spectra of solutions in chlorosulfuric acid (and fluorosulfuric acid) it is shown that SeCl4 and TeCl4 ionize quantitatively in these strong acid solutions to give the SeCl3+ and TeCl3+ cations.By comparison of the spectra with the vibrational spectra of solid SeCl4 and solid TeCl4, reported by other workers, it is suggested that the solids contain covalent MCl4 molecules rather than the ionic species MCl3+•Cl−, suggested previously.
Theoretical calculations of hot-spot initiation in explosives
Authors: Bruckman Jr. H. J. , Guillet J. E.
Published: May 2006

The heat balance equations for the thermal decomposition of hot spots in explosives have been solved using an iterative computer method. This yields a value of Tc, the critical temperature for hot-spot initiation, which is a function of the size and duration of the hot spot and of the physical and chemical properties of the explosive. It is demonstrated that there is a strong correlation between the ranking of explosives in terms of shock sensitivity and their ranking in terms of Tc. In general explosives having low values of Tc are more sensitive to shock and other forms of accidental initiation than those having high values.Using the computer program, it was shown that the major factor affecting Tc was not the energy released in the explosion, but the rate of decomposition, as expressed in terms of the parameters A and Ea in the Arrhenius equation. Consideration of reagent depletion also indicated certain limits beyond which the heat production cannot be maintained for the time necessary to initiate explosion and insensitivity should result. Considerations of this type could be used to predict safe handling procedures for explosives.
Square planar metal complexes of thiosemicarbazide
Authors: Haines Roland A. , Sun Kenneth K. W.
Published: May 2006

Square planar complexes of nickel(II), palladium(II), and platinum(II) containing the ligand thiosemicarbazide (Htsc) have been studied. Both the cis and trans geometric isomers have been obtained for the complexes with the general formula [M(tsc)2]2+ while only the trans isomer was obtained for the neutral species [M(tsc)2]. Infrared and diffuse reflectance spectra are presented and discussed with reference to the stereochemistry of the complexes.
The mercury (63P1) photosensitized hydrogenation of ethylene. Kinetics of the reaction C2H5 + H2 = C2H6 + H
Authors: Reid L. E. , Roy D. J. Le
Published: May 2006

A quantitative study has been made of the reaction of ethyl radicals with molecular hydrogen in the gas phase in the temperature range 240 to 320 °C. The mercury (63Pi) photosensitized decomposition of hydrogen in the presence of ethylene was used to generate ethyl radicals. Extinction coefficients for the absorption of 2537 Å by mercury vapor were measured and Beer's law was shown to be obeyed under the experimental conditions used. The corrections required to allow for the nonuniformity of radical concentrations in the cell were small. After delineating the experimental conditions necessary to minimize secondary reactions, the rate constant (cm3 mole−1 s−1) for the reaction C2H5 + H2 = C2H6 + H was found to be given by log10k = 12.57 − 13.7/θ. Experiments in the presence of added carbon dioxide showed the absence of hot radical effects at the working pressure of 92 Torr of hydrogen.
Photolysis of some alkyl-1-pyrazolines
Authors: Moore Ralph , Mishra Anupama , Crawford Robert J.
Published: May 2006

The direct and photosensitized photolysis of six methylated-1-pyrazolines is described. Examination of the products suggests that direct photolysis leads to an excited singlet trimethylene, whereas a triplet is produced on benzophenone photosensitization. The trimethylene produced from 4 and 5 is related to the intermediates produced on addition of triplet methylenes to cis- and trans-2-butene. Evidence is presented to support the claim that no intermediate is involved in the addition of singlet methylene to cis-and trans-2-butene.
Addition of carbethoxynitrene to trans- and cis-propenylbenzene and the ring-opening of the resulting aziridines
Authors: Nozaki H. , Okuyama Y. , Fujita S.
Published: May 2006

Carbethoxynitrene (1) generated thermally from ethyl azidoformate adds stereospecifically to trans- and cis-propenylbenzene. Ring-opening of the aziridines thus produced, proceeds with inversion at the phenyl-substituted carbon in dry acetic acid, while the reaction in aqueous acetic acid occurs with no stereospecificity.
Substitutions électrophiles en série naphtalénique. V. Sur le di-t-butyl-2,6 naphtalène
Authors: Richer Jean-Claude , Baskevitch Nicolas , Erichomovitch Lucien , Chubb Francis L.
Published: May 2006

not available
Synthesis of abnormal peptides: cyclization of Nα-formyltryptophyl residue to 3,4-dihydro-β-carboline-3-carboxylic acid residue in acidic media
Authors: Previero Aldo , Coletti-Previero Maria-Antonia , Barry Léo-G.
Published: May 2006

The intramolecular reaction of Nα-formyltryptophan to 3,4-dihydro-β-carboline-3-carboxylic acid is realized with high yield either in trifluoroacetic acid or in formic acid – concentrated hydrochloric acid solutions. Optically active products are obtained when formylated L- or D-tryptophan are used as starting compounds. The experimental conditions employed are highly specific and the cyclization of Nα-formyltryptophyl residue is realized also in peptides without secondary lytic reactions. The general behavior of Nα-formyltryptophan in formic acid solutions is discussed.
The preparation of methyl 4-deoxy-3-O-methyl-α, β-DL-threo-pentopyranoside
Authors: Sweet F. , Brown R. K.
Published: May 2006

not available
Luciduline: a unique type of Lycopodium alkaloid
Authors: Ayer W. A. , Masaki N. , Nkunika D. S.
Published: May 2006

The isolation and determination of the structure of luciduline, C13H21ON, an alkaloid present among the weak bases of Lycopodium lucidulum Michx, is described. Chemical and physical evidence which suggests structure 9 for luciduline is presented. An X-ray diffraction study on O-p -bromobenzoyl-dihydroluciduline confirmed this hypothesis and defined the stereochemistry of the methyl group at C-8. The complete structure of luciduline, including absolute configuration, is thus represented by 1. A possible mode of biosynthesis of luciduline, which is a new type of Lycopodium alkaloid, is discussed. The mass spectra of luciduline and some of its derivatives are interpreted in terms of structure 1.
Sur la réduction par LiAlH4 de quelques dérivés de l'hydroxyméthylène-2 triméthyl-3,5,5 cyclohexanone
Authors: Richer Jean-Claude , MacDougall William A.
Published: May 2006

not available
Preparation of 15-hydroxypentadecanoic acid by means of condensation reaction via β-ketosulfoxide
Authors: Nozaki H. , Mori T. , Kawanisi M.
Published: May 2006

Basic condensation of 1,12-dodecanolide with methylsulflnylcarbanion (DMSO−) gives a β-keto-sulfoxide 2 which is ethoxycarbonylmethylated and the product is converted to 15-hydroxypentadecanoic acid (6) in a 46% overall yield based on the lactone. Another β-ketosulfoxide 9 is prepared by condensation of methyl 10-undecenoate with DMSO− and is subjected to the Michael condensation with methyl acrylate. Treatment of the adduct gives 14-pentadecenoic acid (13) in a 38% overall yield based on the undecenoate.
Nuclear magnetic resonance studies of ketone•BF3 complexes. II. The boron trifluoride catalyzed condensation of acetone
Authors: Gillespie R. J. , Hartman J. S.
Published: May 2006

A detailed study of the reactions of the acetone•BF3 complex in excess acetone has been carried out by "F nuclear magnetic resonance (n.m.r.) spectroscopy. It is shown that rapid reversible fluorine exchange processes occur in solution, in addition to the slower aldol condensation–dehydration reaction. Two of the new 19F absorptions which appear during the reaction are shown to arise from BF3 complexes of donors which are formed by condensation and dehydration of acetone. The rate of the aldol condensation reaction is shown to fall off markedly as an increasing proportion of the BF3 becomes complexed with water; thus BF3 catalysis of the reaction appears to depend on the existence of a ketone–BF3 donor–acceptor bond. 1H and 19F n.m.r. studies of the acetone•BF3 complex in methylene chloride throw some light on the apparent greatly decreased reactivity of the complex in this solvent. Evidence is presented for the reversibility of the first step of the condensation reaction.
Complexes mixtes de la sérine et de l'arginine
Authors: Israeli Julius , Cecchetti Maria
Published: May 2006

not available
Electron spin resonance of fluorine-substituted nitro-aromatic anion radicals
Authors: Fischer P. H. H. , Zimmermann H.
Published: May 2006

Electron spin resonance spectra have been observed for anion radicals derived from 2-fluoro-nitro-benzene, 3-fluoro-nitrobenzene, 2,4-difluoro-nitrobenzene, 2,5-difluoro-nitrobenzene, 4-fluoro-2-nitro-phenol, 2-fluoro-6-nitrophenol, and 3-fluoro-6-nitrophenol. All radicals were generated electrolytically in dimethoxyethane/acetonitrile solution, acetonitrile, or dimethylformamide. The radicals are generally quite stable with the exception of those from 2-fluoro-6-nitrophenol and 3-fluoro-6-nitrophenol, the latter decaying with a half-life of approximately 6 min. All spectra can be interpreted completely, and coupling constants are assigned by comparison to related compounds and consistency arguments.
Mechanism of decarboxylation of substituted salicylic acids. II. Kinetics and 13C-carboxyl kinetic isotope effects in nitrobenzene–quinoline mixtures
Authors: Bourns A. N. , Buccini J. , Dunn G. E. , Rodewald W.
Published: May 2006

The decarboxylation of 4-methylsalicylic acid in dilute solutions of quinoline in nitrobenzene at 200 °C is first order with respect to the salicylic acid and first order with respect to quinoline. The pseudo-first-order rate constant reaches a maximum at 0.25 M quinoline, then decreases as the quinoline concentration increases. The 13C-carboxyl kinetic isotope effect, 100(k12/k13 − 1), is 2.2% in pure quinoline and 0.7% in 0.02 M quinoline. It is therefore concluded that the mechanism proposed in Part I of this series involves three steps: ionization of the salicylic acid to a quinolinium salicylate ion pair, reversible protonation by quinolinium ion of the salicylate ion at carbon 1 of the aromatic ring, and loss of carbon dioxide from the protonated salicylate ion. In dilute quinoline solution the second step is slow, while in pure quinoline the third step becomes rate determining.
A method for the calculation of surface and interfacial tensions from the shape of pendent drops
Authors: Lomas H.
Published: May 2006

A classical capillary equation is applied to the shape of the portion of a pendent drop on the opposite side to the source, and the interfacial tension is calculated by the use of a simple computer program.
FTIR SPECTRAL ANALYSIS ON HEAVY METAL BORATE GLASSES
Authors: KARTHIKEYAN B.
Published: May 2006

Inorganic heavy metal borate glasses were prepared through the melt quenching technique. Two sets of glasses were prepared, the compositions are (wt.%) 35 Bi 2 O 3+(50-x) B 2 O 3+15 Na 2 O +x PbO , where x=0, 10, 20, 30 and 35 MO +30 Na 2 O +35 B 2 O 3 ( MO = Bi 2 O 3, PbO , ZnO ). The FTIR structural analysis was made. These glasses have different borate groups and it mainly depends on the modifier/metal ion concentration. The influence of heavy metal and transition metal ion on the borate network were also identified.
Distinct Short-Term and Long-Term Adaptation to Reduce Saccade Size in Monkey
Authors: Robinson Farrel R. , Soetedjo Robijanto , Noto Christopher
Published: May 2006

In monkeys, saccades that repeatedly overshoot their targets adapt to become smaller by the time the monkey has made 1,000–2,000 saccades. In life, adaptation must keep movements accurate for long periods of time. Previous work describes only saccade adaptation that occurs within a few hours. Here we describe long-term saccade adaptation elicited in three monkeys by 19 days of training. Each day a monkey made saccades to track 16° leftward and rightward target movements. During saccades, the target stepped back toward its starting position 6.4° (40%) in two monkeys or 8° (50%) in the third. After each day's adaptation, we blindfolded the monkey with goggles and returned it to its cage overnight. We found that adapting saccades for 19 days elicited significantly larger, long-lasting reduction in saccade size than did adapting for only 1 day. Further, after 19 days of adaptation we could elicit additional, apparently normal, short-term reduction in saccade size by increasing the size of the intra-saccade target movement. In contrast, we could elicit only small additional size reduction after only 1 day of adaptation. A simple model using separate short- and long-term adaptation mechanisms can reproduce many of the features of saccade gain exhibited by monkeys during a 19-day adaptation. We conclude that there is a long-term saccade-adaptation mechanism that is distinct from the well-characterized short-term system and that this newly recognized system is responsible for long-term maintenance of saccade accuracy.
Differential regional gene expression from cardiac dyssynchrony induced by chronic right ventricular free wall pacing in the mouse
Authors: Bilchick Kenneth C. , Saha Sudip K. , Mikolajczyk Ed , Cope Leslie , Ferguson Will J. , Yu Wayne , Girouard Steven , Kass David A.
Published: May 2006

Routine clinical right ventricular pacing generates left ventricular dyssynchrony manifested by early septal shortening followed by late lateral contraction, which, in turn, reciprocally stretches the septum. Dyssynchrony is disadvantageous to cardiac mechanoenergetics and worsens clinical prognosis, yet little is known about its molecular consequences. Here, we report the influence of cardiac dyssynchrony on regional cardiac gene expression in mice. Mice were implanted with a custom-designed miniature cardiac pacemaker and subjected to 1-wk overdrive right ventricular free wall pacing (720 beats/min, baseline heart rate 520–620 beats/min) to generate dyssynchrony (pacemaker: 3-V lithium battery, rate programmable, 1.5 g, bipolar lead). Electrical capture was confirmed by pulsed-wave Doppler and dyssynchrony by echocardiography. Gene expression from the left ventricular septal and lateral wall myocardium was assessed by microarray (dual-dye method, Agilent) using oligonucleotide probes and dye swap. Identical analysis was applied to four synchronously contracting controls. Of the 22,000 genes surveyed, only 18 genes displayed significant ( P < 0.01) differential expression between septal/lateral walls >1.5 times that in synchronous controls. Gene changes were confirmed by quantitative PCR with excellent correlations. Most of the genes ( n = 16) showed greater septal expression. Of particular interest were seven genes coding proteins involved with stretch responses, matrix remodeling, stem cell differentiation to myocyte lineage, and Purkinje fiber differentiation. One week of iatrogenic cardiac dyssynchrony triggered regional differential expression in relatively few select genes. Such analysis using a murine implantable pacemaker should facilitate molecular studies of cardiac dyssynchrony and help elucidate novel mechanisms by which stress/stretch stimuli due to dyssynchrony impact the normal and failing heart.
Conjugate gradient algorithm and fractals
Authors: Sahari Mohamed Lamine , Djellit Ilhem
Published: May 2006

This work is an extension of the survey on Cayley′s problem in case where the conjugate gradient method is used. We show that for certain values of parameters, this method produces beautiful fractal structures.
A fixed point theorem for a class of differentiable stable operators in banach spaces
Authors: Azhmyakov Vadim
Published: May 2006

We study Frèchet differentiable stable operators in real Banach spaces. We present the theory of linear and nonlinear stable operators in a systematic way and prove solvability theorems for operator equations with differentiable expanding operators. In addition, some relations to the theory of monotone operators in Hilbert spaces are discussed. Using the obtained solvability results, we formulate the corresponding fixed point theorem for a class of nonlinear expanding operators.
Mean convergence theorems and weak laws of large numbers fordouble arrays of random variables
Authors: Van Thanh Le
Published: May 2006

For a double array of random variables {Xmn,  m ≥  1,  n ≥  1}, mean convergence theorems and
weak laws of large numbers are established. For the mean
convergence results, conditions are provided under which
where {amnij; m, n, i, j ≥ 1} are constants, and
{kn, n ≥ 1} and {ln, n ≥ 1} are sequences of
positive integers. The weak law results provide conditions for
to hold where {Tm, m ≥ 1} and {τn, n ≥ 1} are sequences of positive integer‐valued random
variables. The sharpness of the results is illustrated by
examples.
Systemic and Local CC Chemokines Production in aMurine Model of Listeria monocytogenes Infection
Authors: Bubonja Marina , Wraber Branka , Brumini Gordana , Gobin Ivana , Veljkovic Danijela , Abram Maja
Published: May 2006

Repeated intragastric inoculation of Listeria
monocytogenes into BALB/c mice resulted in prolonged bacteraemia
and severe hepatic infection. Bacteria could also be isolated from
the brain tissue of all experimental mice. During the inflammatory
process, chemokine concentrations typically increased at the local
site in comparison to the systemic level. The liver‐to‐serum ratio
was more pronounced in the case of macrophage inflammatory protein
1α (MIP‐1α), suggesting its role in the inflammatory response in
the liver. The ratio of brain‐to‐serum concentration of monocyte
chemoattractant protein 1 (MCP‐1) remained the same as in the
control animals, while it was lower in the infected mice, both in
the case MIP‐1α and in the case of regulated on activation, normal
T cell expressed and secreted (RANTES). This is in correlation
with slight inflammatory infiltrates found in the brain tissue
early in infection.
Recidivism Among Spousal Abusers
Authors: Hendricks Bryan , Werner Todd , Shipway Lee , Turinetti Greg J.
Published: May 2006

The relative effectiveness of two interventions for dealing with 200 court-referred spousal abusers is examined. The overall failure rate is 17.5%, with most recidivism occurring during the first 6 months after treatment. Offenders who completed a 14-week group treatment program called SAFE manifest significantly lower rates of recidivism (10.6%) than do offenders who did not complete the mandated treatment (38.8%). Some high-risk clients are referred to a cognitive restructuring treatment program called R&R, and those completing both programs (despite their high-risk status) have a recidivism rate of only 23.5%. Prediction of recidivism is difficult, with the LSI-R scores correctly predicting only 66% of the outcomes, using a cut score of 11.5. The exploration of other predictors is encouraged.
Introduction
Authors: Kelly Michael
Published: May 2006

The introduction to this special number of French Cultural Studiespresents the key themes in the articles it contains, focusing on writers, intellectuals and the colonial experience. It sets them in the context of a reappraisal of Empire in both France and Britain, expressed in the recent French law obliging schools to recognise the benefits of the French colonial enterprise, and in related developments in Britain. French writers and intellectuals of the colonial period were concerned with issues of the benefits of civilisation, the universal spread of republican humanism, and the practical and theoretical implications of inter-imperial rivalries, especially with Britain. When they criticised colonial practice, it was in the name of the same values of civilisation that underlay the ‘civilising mission’ of colonialism. In a modulated discourse, these issues continue to inform the way governments and intellectuals view the mission of leading industrial countries to bring the benefits of Western values to the rest of the world. An understanding of how earlier generations of French writers thought about the colonial experience may be relevant to a reflection on similar current concerns.
Emmanuel Mounier and the Awakening of Black Africa
Authors: Kelly Michael
Published: May 2006

Emmanuel Mounier, Director of the Catholic review Esprit, was a pioneering participant in criticising French colonial activities. The debates of the 1940s were strongly framed by France's ‘mission to civilise’ its colonies, which was supported by universal humanist aspirations but was also criticised as masking policies of exploitation and oppression. The resulting tensions are well demonstrated by Emmanuel Mounier's book L'Éveil de l'Afrique noire, published after a visit to several areas of French West Africa in the spring of 1947, at a crucial moment in France's relations with its colonies. This article focuses on the components published in Esprit, Combat, and Présence africaine, which outlined the positive roles that France could play in the region, but warned against the dangers if opportunities were missed, and recognised the particular difficulties confronting the rising African elites. A closer examination of the discursive strategies he deployed shows that Mounier's frame of reference remained within the paternalist paradigm of republican humanism, and that he saw France's role as a duty to guide the development of Africa. However, in the myths and metaphors he adopted, a more radical vision can be identified, which expressed an underlying anti-colonialism.
Conceptions of Perfectionism and Interpersonal Problems
Authors: Slaney Robert B. , Pincus Aaron L. , Uliaszek Amanda A. , Wang Kenneth T.
Published: May 2006

This study examined two conceptions of perfectionism in relation to interpersonal problems. Two hundred and seventy-nine undergraduate participants completed the Almost Perfect Scale-Revised (APS-R) and the Dyadic Almost Perfect Scale (DAPS). The authors used empirically derived discriminant functions (APS-R) and cluster analysis (DAPS) to identify three groups for both measures: adaptive and maladaptive perfectionists and nonperfectionists. Analyses of group profiles were performed on the Inventory of Interpersonal Problems Circumplex (IIP-C) scales using the structural summary method for circumplex data. APS-R and DAPS groups were compared on interpersonal problems endorsement and IIP-C profile characteristics. For both measures, results supported the hypotheses that maladaptive perfectionists would exhibit elevated profiles reflecting hostile-dominant and friendly-submissive interpersonal problems, whereas the adaptive perfectionists would exhibit low profile elevation indicative of interpersonal adjustment. Overall, results supported Slaney and colleagues’ (2001) model of perfectionism and provided evidence for the validity of the APS-R and DAPS.
Curfews: No More Hanging Around
Authors: Walsh Charlotte
Published: May 2006

This article examines the recent extension of the scope of youth curfews. A critical analysis of the desirability of this widening of status laws is then offered, with an initial focus on libertarian issues, followed by a consideration of the predicted efficacy of youth curfews in the field of crime control. As the use of youth curfews has been prevalent in the United States since their revival in the early 1990s, a comparative analysis is possible. It is argued that the use of youth curfews is questionable both in terms of their implications for human rights and freedoms and as regards their utility.
Youth Crime, the ‘Parenting Deficit’ and State Intervention: A Contextual Critique
Authors: Goldson Barry , Jamieson Janet
Published: May 2006

On 1 June 2000 a new court order was implemented in England and Wales. The Parenting Order provided for the extension of state intervention (primarily through youth justice agencies) into ‘family life’. We have recently completed research with regard to youth justice parenting initiatives, and during the course of our research, our interest in, and concern with, the broader question of ‘parenting’, ‘parental responsibility’ and the ‘parenting deficit’ consolidated. This article sets out our principal concerns by locating the new statutory powers within their wider context. By tracing their historical antecedents, theoretical foundations and policy expressions we aim to critique the latest developments in state intervention. Similarly, by analysing the material circumstances of the parents who are targeted by such intervention, and reviewing the means by which children, young people and parents conceive such intervention, we argue that the new powers essentially comprise an extension of punitiveness underpinned by stigmatising and pathologising constructions of working class families.
Welfare versus Justice - Again!
Authors: Smith Roger
Published: May 2006

This article reviews recent developments in government policy designed to provide an integrated framework for children’s services, in the light of the continuing and long-running debate between principles of welfare and justice. It is noted that at the level of policy, it has repeatedly been argued that responding to the offences of children and providing for their welfare are inseparable. However, this apparent consensus has resulted in a range of different service structures and delivery systems over the years, characterised by ‘turf wars’ amongst policy-makers and practitioners, and unintended consequences in terms of damaging outcomes for children. The article suggests that the most recent policy initiatives from government leave this tension unresolved; and it concludes that alternative rationales need to be developed to inform interventions with children who offend.
The Use of Electronic and Human Surveillance in a Multi-Modal Programme
Authors: Moore Robin
Published: May 2006

The Intensive Supervision and Surveillance Programme, which was introduced in England and Wales in 2001, combines intensified supervision with regular surveillance in an attempt to bring structure to the lives of our most persistent and serious young offenders. While both the ‘electronic tag’ and ‘human trackers’ have been commonly used forms of ‘surveillance’ for young people on the programme, trackers have proved most effective in ensuring their completion, with the tag proving more acceptable to the young people when combined with this human element.
Understanding ‘What Works’: Accredited Cognitive Skills Programmes for Young Offenders
Authors: Cann Jenny , Falshaw Louise , Friendship Caroline
Published: May 2006

This research assessed effectiveness of prison-based cognitive skills programmes for young offenders in England and Wales, using reconviction as the outcome measure. Reconviction rates were compared between offenders who started a programme (N= 1,534) and a matched comparison group who did not (N= 1,534). Programme participation did not lead to a statistically significant reduction in reconviction, at one- or two-years following discharge. However, when offenders who dropped out of a programme and their matched comparisons were excluded from analysis, the one-year reconviction rate for programme completers was statistically significantly lower (p <0.05).
Human CD34+ cells expressing the inv(16) fusion protein exhibit a myelomonocytic phenotype with greatly enhanced proliferative ability
Authors: Wunderlich Mark , Krejci Ondrej , Wei Junping , Mulloy James C.
Published: May 2006

The t(16:16) and inv(16) are associated with FAB M4Eo myeloid leukemias and result in fusion of the CBFB gene to the MYH11 gene (encoding smooth muscle myosin heavy chain [SMMHC]). Knockout of CBFβ causes embryonic lethality due to lack of definitive hematopoiesis. Although knock-in of CBFB-MYH11 is not sufficient to cause disease, expression increases the incidence of leukemia when combined with cooperating events. Although mouse models are valuable tools in the study of leukemogenesis, little is known about the contribution of CBFβ-SMMHC to human hematopoietic stem and progenitor cell self-renewal. We introduced the CBFβ-MYH11 cDNA into human CD34+ cells via retroviral transduction. Transduced cells displayed an initial repression of progenitor activity but eventually dominated the culture, resulting in the proliferation of clonal populations for up to 7 months. Long-term cultures displayed a myelomonocytic morphology while retaining multilineage progenitor activity and engraftment in NOD/SCID-B2M-/- mice. Progenitor cells from long-term cultures showed altered expression of genes defining inv(16) identified in microarray studies of human patient samples. This system will be useful in examining the effects of CBFβ-SMMHC on gene expression in the human preleukemic cell, in characterizing the effect of this oncogene on human stem cell biology, and in defining its contribution to the development of leukemia.
Calcium adsorption and displacement: characterization of lipid monolayers and their interaction with membrane-active peptides/proteins
Authors: Hagge Sven O , Hammer Malte U , Wiese Andre , Seydel Ulrich , Gutsmann Thomas
Published: May 2006

Background

The first target of antimicrobial peptides (AMPs) is the bacterial membrane. In the case of Gram-negative bacteria this is the outer membrane (OM), the lipid composition of which is extremely asymmetric: Whereas the inner leaflet is composed of a phospholipid mixture, the outer leaflet is made up solely from lipopolysaccharides (LPSs). LPS, therefore, represents the first target of AMPs. The binding and intercalation of polycationic AMPs is driven by the number and position of negatively charged groups of the LPS. Also, proteins other than cationic AMPs can interact with LPS, e.g. leading eventually to a neutralization of the endotoxic effects of LPS. We compared different biophysical techniques to gain insight into the properties of the electrical surface potentials of lipid monolayers and aggregates composed of LPSs and various phospholipids and their interaction with peptides and proteins.

Results

The net negative charge calculated from the chemical structure of the phospholipid and LPS molecules is linearly correlated with the adsorption of calcium to two-dimensional lipid monolayers composed of the respective lipids. However, the ζ-potentials determined by the electrophoretic mobility of LPS aggregates can only be interpreted by assuming a dependence of the plane of shear on the number of saccharides and charged groups. Various peptides and proteins were able to displace calcium adsorbed to monolayers.

Conclusion

To characterize the electrical properties of negatively charged phospholipids and LPSs and their electrostatic interaction with various polycationic peptides/proteins, the adsorption of calcium to and displacement from lipid monolayers is a suitable parameter. Using the calcium displacement method, the binding of peptides to monolayers can be determined even if they do not intercalate. The interpretation of ζ-potential data is difficulty for LPS aggregates, because of the complex three-dimensional structure of the LPS molecules. However, the influence of peptides/proteins on the ζ-potential can be used to characterize the underlying interaction mechanisms.
Four genomic islands that mark post-1995 pandemic Vibrio parahaemolyticus isolates
Authors: Hurley Catherine C , Quirke AnneMarie , Reen F Jerry , Boyd E Fidelma
Published: May 2006

Background

Vibrio parahaemolyticus is an aquatic, halophilic, Gram-negative bacterium, first discovered in 1950 in Japan during a food-poisoning outbreak. Infections resulting from consumption of V. parahaemolyticus have increased globally in the last 10 years leading to the bacterium's classification as a newly emerging pathogen. In 1996 the first appearance of a pandemic V. parahaemolyticus clone occurred, a new O3:K6 serotype strain that has now been identified worldwide as a major cause of seafood-borne gastroenteritis.

Results

We examined the sequenced genome of V. parahaemolyticus RIMD2210633, an O3:K6 serotype strain isolated in Japan in 1996, by bioinformatic analyses to uncover genomic islands (GIs) that may play a role in the emergence and pathogenesis of pandemic strains. We identified 7 regions ranging in size from 10 kb to 81 kb that had the characteristics of GIs such as aberrant base composition compared to the core genome, presence of phage-like integrases, flanked by direct repeats and the absence of these regions from closely related species. Molecular analysis of worldwide clinical isolates of V. parahaemolyticus recovered over the last 33 years demonstrated that a 24 kb region named V. parahaemolyticus island-1 (VPaI-1) encompassing ORFs VP0380 to VP0403 is only present in new O3:K6 and related strains recovered after 1995. We investigated the presence of 3 additional regions, VPaI-4 (VP2131 to VP2144), VPaI-5 (VP2900 to VP2910) and VPaI-6 (VPA1254 to VPA1270) by PCR assays and Southern blot analyses among the same set of V. parahaemolyticus isolates. These 3 VPaI regions also gave similar distribution patterns amongst the 41 strains examined.

Conclusion

The 4 VPaI regions examined may represent DNA acquired by the pandemic group of V. parahaemolyticus isolates that increased their fitness either in the aquatic environment or in their ability to infect humans.
How effective is tetracaine 4% gel, before a peripherally inserted central catheter, in reducing procedural pain in infants: a randomized double-blind placebo controlled trial [ISRCTN75884221]
Authors: Lemyre Brigitte , Sherlock Rebecca , Hogan Debora , Gaboury Isabelle , Blanchard Colline , Moher David
Published: May 2006

Background

Procedural pain relief is sub-optimal in infants, especially small and vulnerable ones. Tetracaine gel 4% (Ametop®, Smith-Nephew) provides pain relief in children and larger infants, but its efficacy in smaller infants and for peripherally inserted central catheters (PICC) remains uncertain. The objective of this trial was to assess the safety and efficacy of tetracaine gel on the pain response of very low birth weight (VLBW) infants during insertion of a PICC.

Methods

Medically stable infants greater than or equal to 24 weeks gestation, requiring a non-urgent PICC, were included. Following randomization and double blinding, 1.1 g of tetracaine or placebo was applied to the skin for 30 minutes. The PICC was inserted according to a standard protocol. Pain was assessed using the Premature Infant Pain Profile (PIPP). A 3-point change in the pain score was considered clinically significant, leading to a sample size of 54 infants, with 90% statistical power. Local skin reactions and immediate adverse cardiorespiratory events were noted. The primary outcome, PIPP score at 1 minute, was analysed using an independent Student's t-test.

Results

Fifty-four infants were included, 27 +/- 2 weeks gestation, 916 +/- 292 grams and 6.5 +/- 3.2 days of age. Baseline characteristics were similar between groups. The mean PIPP score in the first minute was 10.88 in the treatment group as compared to 11.74 in the placebo group (difference 0.86, 95% CI -1.86, 3.58). Median duration of crying in non-intubated infants was 181 seconds in the tetracaine group compared to 68 seconds in the placebo group (difference -78, 95% CI -539, 117). Local skin erythema was observed transiently in 4 infants (3 in the treatment and 1 in the placebo group). No serious harms were observed.

Conclusion

Tetracaine 4% when applied for 30 minutes was not beneficial in decreasing procedural pain associated with a PICC in very small infants.
Inhibition of homologous recombination repair with Pentoxifylline targets G2 cells generated by radiotherapy and induces major enhancements of the toxicity of cisplatin and melphalan given after irradiation
Authors: Bohm Lothar
Published: May 2006

The presentation reviews the modus operandi of the dose modifying drug Pentoxifylline and the dose enhancement factors which can be achieved in different cell types. Preclinical and clinical data show that Pentoxifylline improves the oxygenation of hypoxic tumours and enhances tumour control by irradiation. In vitro experiments demonstrate that Pentoxifylline also operates when oxygen is not limiting and produces dose modifying factors in the region of 1.2 – 2.0. This oxygen independent effect is poorly understood. In p53 mutant cells irradiation induces a G2 block which is abrogated by Pentoxifylline. The enhancement of cell kill observed when Pentoxifylline and irradiation are given together could arise from rapid entry of damaged tumour cells into mitosis and propagation of DNA lesions as the result of curtailment of repair time. Recovery ratios and repair experiments using CFGE after high dose irradiation demonstrate that Pentoxifylline inhibits repair directly and that curtailment of repair time is not the explanation. Use of the repair defective xrs1 and the parental repair competent CHO-K1 cell line shows that Pentoxifylline inhibits homologous recombination repair which operates predominantly in the G2 phase of the cell cycle. When irradiated cells residing in G2 phase are exposed to very low doses of cisplatin at a toxic dose of 5 %. (TC: 0.05) massive toxicity enhancements up to a factor of 80 are observed in melanoma, squamous carcinoma and prostate tumour cell lines. Enhancements of radiotoxicity seen when Pentoxifylline and radiation are applied together are small and do not exceed a factor of 2.0. The capacity of Pentoxifyline to inhibit homologous recombination repair has not as yet been clinically utilized. A suitable application could be in the treatment of cervical carcinoma where irradiation and cisplatin are standard modality. In vitro data also strongly suggest that regimes where irradiation is used in combination with alkylating drugs may also benefit.