bluuebunny/crossref_metadata_2025 huggingface dataset:
Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes
Authors: Brandès Stéphane , David Gabriel , Suspène Clément , Corriu Robert J. P. , Guilard Roger
Published: January 2007

We report the exceptional reactivity towards dioxygen of a nanostructured organic–inorganic hybrid material due to the confinement of copper cyclam within a silica matrix. The key step is the metalation reaction of the ligand, which can occur before or after xerogel formation through the sol–gel process. The incorporation of a CuII center into the material after xerogel formation leads to a bridged CuI/CuII mixed‐valence dinuclear species. This complex exhibits a very high affinity towards dioxygen, attributable to auto‐organization of the active species in the solid. The remarkable properties of these copper complexes in the silica matrix demonstrate a high cooperative effect for O2 adsorption; this is induced by close confinement of the two copper ions leading to end‐on μ‐η1:η1‐peroxodicopper(II) complexes. The anisotropic packing of the tetraazamacrocycle in a lamellar structure induces an exceptional reactivity of these copper complexes. We show for the first time that the organic–inorganic environment of copper complexes in a silica matrix fully model the protecting role of protein in metalloenzymes. For the first time an oxygenated dicopper(II) complex can be isolated in a stable form at room temperature, and the reduced Cu2I,I species can be regenerated after several adsorption–desorption cycles. These data also demonstrate that the coordination scheme and reactivity of the copper cyclams within the solid are quite different from that observed in solution.
Reaktionstechnische Untersuchungen zur Umesterung der ionischen Flüssigkeit 1‐Ethyl‐3‐methylimidazoliumethylsulfat ([EMIM][EtOSO3])
Authors: Himmler S. , Hörmann S. , Obert K. , Wasserscheid P.
Published: January 2007

Ionische Flüssigkeiten (ILs) sind neuartige Lösungsmittel, die auf Grund ihrer interessanten und zum Teil einzigartigen Eigenschaftskombinationen für vielfältige Anwendungen interessante Hilfsstoffe, Betriebsmittel oder Funktionsmaterialien darstellen. Die Tatsache, dass ionische Flüssigkeiten bisher hauptsächlich batchweise bzw. im Labormaßstab hergestellt werden, beschränkt zum einen ihre Verfügbarkeit für den großtechnischen Einsatz und wirkt sich zum anderen unvorteilhaft auf die Produktpreise aus. Am Beispiel der Umesterung der kommerziell im Tonnenmaßstab verfügbaren ionischen Flüssigkeit [EMIM][EtOSO3] mit verschiedenen Alkoholen wird ein Weg aufgezeigt, um kostengünstig unterschiedliche Alkylsulfatschmelzen herzustellen. Zudem wird durch kinetische und thermodynamische Untersuchungen des Reaktionssystems die Basis für eine Weiterentwicklung des Syntheseverfahrens hin zu einer kontinuierlichen Synthese geschaffen.
Thin Films Composed of Multiwalled Carbon Nanotubes, Gold Nanoparticles and Myoglobin for Humidity Detection at Room Temperature
Authors: Qi Zhi‐mei , Wei Mingdeng , Honma Itaru , Zhou Haoshen
Published: January 2007

Optically transparent and electrically conductive nanocomposite thin films consisting of multiwalled carbon nanotubes (MWCNTs), gold nanoparticles (GNPs) and myoglobin molecules that glue GNPs and MWCNTs together are fabricated for the first time on glass substrates from aqueous solution. The nanocomposite thin film is capable of varying its resistance, impedance or optical transmittance at room temperature in response to changes in ambient humidity. The conductometric sensitivity to relative humidity (RH) of the nanocomposite thin film is compared with those of the pure and Mb‐functionalized MWCNT layers. The pure MWCNT layer shows a small increase in its resistance with increasing RH due to the effect of p‐type semiconducting nanotubes present in the film. In contrast, a four times higher sensitivity to RH is observed for both the nanocomposite and Mb‐functionalized MWCNT thin films. The sensitivity enhancement is attributable to swelling of the thin films induced by water absorption in the presence of Mb molecules, which increases the inter‐nanotube spacing and thereby causes a further increase of the film resistance. A humidity change as low as ΔRH=0.3 % has been readily detected by conductometry using the nanocomposite thin film.
Geometry Dependence of Spin–Spin Couplings in Cyanamide by DFT Analysis
Authors: van Mourik Tanja , Dingley Andrew J.
Published: January 2007

There have been numerous theoretical and experimental investigations examining NMR parameters related to non‐amino NH⋅⋅⋅N H‐bonded moieties in both biological and chemical contexts. In contrast, little information on the geometry dependence of NMR parameters related to the biologically important H‐bond donor amino group is available. Herein, the geometric dependencies of the one‐bond amino NH spin–spin coupling constants [1J(NH)] in the cyanamide monomer and dimer have been computed with B3LYP and the aug‐cc‐pVTZ‐su0 basis set. In an isolated planar cyanamide molecule, the |1J(NH)| couplings were found to increase as the NH bond lengthened. In contrast, in the planar cyanamide dimer the size of the H‐bonded amino NH coupling (|1J(NdHd)|) decreased with increasing NdHd bond length. The |1J(NdHd)| coupling was larger than the |1J(NdHfree)| coupling for NdHd distances up to 1.18 Å (for a fixed NdHfree distance of 1.006 Å). Hence, the decrease of |1J(NH)| with increasing NH distance, as well as the larger value of |1J(NdHd)| compared to |1J(NdHfree)|, were only observed for situations where the amino group is involved in an H‐bonding interaction. This is attributed to electron redistribution induced by the presence of the second cyanamide molecule. Similar electron‐redistribution effects are thought to be responsible for the observed distance dependence of computed 1J(NH) couplings of H‐bonded amino groups in near‐planar G‐quartet structures. Here, the |1J(NH)| couplings of the amino NH bonds decreased with increasing NH bond length whereas the |1J(NdHd)| couplings are approximately 7 Hz larger than the |1J(NdHfree)| couplings, despite the longer NdHd bond length.
The Active Intermediates of Non‐Heme‐Iron‐Based Systems for Catalytic Alkene Epoxidation with H2O2/CH3COOH
Authors: Duban Eduard A. , Bryliakov Konstantin P. , Talsi Evgenii P.
Published: January 2007

Iron complexes with aminopyridine ligands [FeII(BPMEN)(CH3CN)2](ClO4)2 (1) [BPMEN = N,N′‐dimethyl‐N,N′‐bis(2‐pyridylmethyl)‐1,2‐diaminoethane] and [FeII(TPA)(CH3CN)2](ClO4)2 (2) [TPA = tris(2‐pyridylmethyl)amine] are rare examples of iron‐based catalysts for selective olefin epoxidation with H2O2/CH3COOH combination. Using 1,2H NMR and EPR spectroscopy, it was shown that the active species of the catalytic systems 1/H2O2/CH3COOH and 2/H2O2/CH3COOH are mononuclear iron(IV)‐oxido complexes [(BPMEN)FeIV=O(S)]2+ and [(TPA)FeIV=O(S)]2+, respectively (S = solvent molecule). These intermediates are formed via decomposition of the corresponding acylperoxido complexes [(L)FeIII(O3CCH3)]2+ (L = BPMEN or TPA). The acylperoxido complex [(BPMEN)FeIII(O3CCD3)]2+ was identified in the catalytic system 1/H2O2/CD3COOD by 2H NMR spectroscopy. The improved epoxidation activity and selectivity of the catalytic systems 1/H2O2/CH3COOH and 2/H2O2/CH3COOH, with respect to 1/H2O2 and 2/H2O2, is caused by the effective formation of intermediates [(L)FeIV=O(S)]2+ via decomposition of the acylperoxido complexes [(L)FeIII(O3CCH3)]2+.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Biotrickling filtration of air contaminated with ethanol
Authors: Avalos Ramirez Antonio , Jones J Peter , Heitz Michele
Published: January 2007

A biotrickling filter (BTF) for treating high ethanol loads was operated for one year and the effect of operating conditions was studied. The BTF was operated in a range of ethanol inlet concentrations of 0.2–15.0 g m−3 and at three different residence times (30, 65 and 130 s). The experiments show that removal efficiency decreased with increasing ethanol inlet concentration and decreasing air residence time. Removal efficiency varied in the range of 60–100%. A maximum elimination capacity of 970 g m−3 h−1 was obtained for an inlet load of 1610 g m−3 h−1. At a constant residence time, the carbon dioxide (CO2) production rate varied with ethanol inlet concentration. BTF presented the maximum CO2 production rate in the range of inlet concentration of 3.0–7.0 g m−3. Two strategies for controlling biomass accumulation were applied: one consisted in periodical washing; the other combined periodical washing with nutrient starvation by consuming less water and energy. Both strategies led to maintaining the BTF stable, with high adaptability and reproducibility. Copyright © 2007 Society of Chemical Industry
Automated mass correction and data interpretation for protein open‐access liquid chromatography‐mass spectrometry
Authors: Wagner Craig D. , Hall John T. , White Wendy L. , Miller Luke A. D. , Williams Jon D.
Published: January 2007

Characterization of recombinant protein purification fractions and final products by liquid chromatography‐mass spectrometry (LC/MS) are requested more frequently each year. A protein open‐access (OA) LC/MS system was developed in our laboratory to meet this demand. This paper compares the system that we originally implemented in our facilities in 2003 to the one now in use, and discusses, in more detail, recent enhancements that have improved its robustness, reliability, and data reporting capabilities. The system utilizes instruments equipped with reversed‐phase chromatography and an orthogonal accelerated time‐of‐flight mass spectrometer fitted with an electrospray source. Sample analysis requests are accomplished using a simple form on a web‐enabled laboratory information management system (LIMS). This distributed form is accessible from any intranet‐connected company desktop computer. Automated data acquisition and processing are performed using a combination of in‐house (OA‐Self Service, OA‐Monitor, and OA‐Analysis Engine) and vendor‐supplied programs (AutoLynx, and OpenLynx) located on acquisition computers and off‐line processing workstations. Analysis results are then reported via the same web‐based LIMS. Also presented are solutions to problems not addressed on commercially available, small‐molecule OA‐LC/MS systems. These include automated transforming of mass‐to‐charge (m/z) spectra to mass spectra and automated data interpretation that considers minor variants to the protein sequence—such as common post‐translational modifications (PTMs). Currently, our protein OA‐LC/MS platform runs on five LC/MS instruments located in three separate GlaxoSmithKline R&D sites in the US and UK. To date, more than 8000 protein OA‐LC/MS samples have been analyzed. With these user friendly and highly automated OA systems in place, mass spectrometry plays a key role in assessing the quality of recombinant proteins, either produced at our facilities or bought from external sources, without dedicating extensive amounts of analyst resource. Copyright © 2007 John Wiley & Sons, Ltd.
Rock hyraces: a cause of San rock art deterioration?
Authors: Prinsloo Linda C.
Published: January 2007

San rock art sites are found throughout southern Africa, many showing signs of deterioration. In order to conserve this invaluable heritage, a long‐term multidisciplinary project has been launched to monitor the rate of their deterioration and determine the various chemical processes that are possibly contributing to the decay. This study was initiated to establish if Raman spectroscopy could contribute to this project and since rock hyrax colonies live in close proximity to many of these archaeological sites, the possible influence of their metabolic products on the deterioration process was investigated.

The precipitates from the urine of rock hyraces were analysed with Raman and Fourier‐transform infrared (FTIR) spectroscopy. Where the urine was in contact with the faeces, the precipitates are a mixture of vaterite (a rare polymorph of CaCO3) and the hydrated salt calcium monohydrocalcite (also rarely found in nature). On areas where this contact is at a minimum the common and stable polymorph of CaCO3, calcite, is the main component. SEM micrographs and XRD analysis support the Raman and FTIR results.

XRD, FTIR and preliminary GC‐MS analyses of hyraceum, the fossilised mixture of faeces and urine, identified an inorganic phase (potassium chloride, with small concentrations of other salts, e.g. vaterite and weddelite) and an organic phase, which is a cocktail of various aromatic compounds, mainly amides, alcohols and acids. These compounds could contribute to the crystallisation of these rare carbonates, as well as other uncommon salts detected on the cave walls, such as syngenite. The presence of phosphates in the urine may further act as a stabilizing agent. Copyright © 2007 John Wiley & Sons, Ltd.
Raman scattering, luminescence, and absorption edge under hydrostatic pressures of layered BiI3 and SbI3
Authors: Saitoh A.
Published: January 2007

Raman scattering from BiI3 and SbI3 crystals has been studied at hydrostatic pressures up to 2 GPa. The wavenumbers monotonically increased with pressure for all modes in BiI3. Although both crystals belong to the same space group, the pressure coefficients of SbI3 were significantly different from those of BiI3. At pressure P0 = 0.92 ± 0.01 GPa, the pressure coefficients of all modes changed. Above P0, all modes in SbI3 had positive pressure coefficients as they have in BiI3. By comparing this unusual behavior of the Raman lines in SbI3 around P0 with the results in BiI3 and comparing the two lattice structures, we suggest that the type of bonding of SbI3 changes to become more ionic and hence more similar to the bonding of BiI3. This change in structure is supported by changes in the bandwidth of the self‐trapped exciton (STE) luminescence and the slope of the absorption edge photon energy versus pressure. Copyright © 2007 John Wiley & Sons, Ltd.
Detection of pig derivatives in food products for halal authentication by polymerase chain reaction –restriction fragment length polymorphism
Authors: Aida Azmi A , Che Man Yaakob B , Raha Abdul R , Son Radu
Published: January 2007

A method for detection of the presence of pig derivatives in three types of food products—sausages and casings, bread and biscuits—using polymerase chain reaction–restriction fragment length polymorphism (PCR‐RFLP) analysis of a conserved region in the mitochondrial (mt) cytochrome b (cyt b) gene was developed. Genomic DNA of sausages and casings, bread and biscuits were extracted. The genomic DNA from the food products were found to be of good quality for the sausages and produced clear PCR products on the amplification of the mt cyt b gene of approximately 360 base pairs (bp). However, no genomic DNA was detected from the casing samples and poor quality of genomic DNA was extracted from bread and biscuits. No amplification of mt cyt b gene was produced from bread and biscuit samples. To differentiate between samples, the amplified PCR products were digested with restriction enzyme (RE) BsaJI, resulting in species‐specific RFLP. The cyt b PCR‐RFLP species identification assay gave excellent results for detection of pork adulteration in food products and is a potentially reliable technique to avoid species adulteration or fraudulent species substitution for halal authentication. Copyright © 2006 Society of Chemical Industry
Comparative study of polyphenolic content and antiradical activity of cloudy and clear apple juices
Authors: Oszmianski Jan , Wolniak Michal , Wojdylo Aneta , Wawer Iwona
Published: January 2007

Clear and cloudy apple juices from Idared and Champion varieties were studied for their radical‐scavenging effects. The polyphenolic content and composition of the juices before and after thiolysis were determined by high‐performance liquid chromatography with diode array detection. Cloudy juices, especially that prepared from Champion variety, had a higher content of procyanidins than clear juices. Radical‐scavenging activity was measured by electron paramagnetic resonance (EPR) spectroscopy using the stable 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) radical. All juices showed long‐lasting radical‐scavenging activity, and EPR spectra were recorded over time to follow the reaction kinetics. Scavenging of DPPH showed pseudo‐first‐order kinetics, which might be expected in the presence of polymerised antioxidants that prevent closer contact between the DPPH radical and hydroxyl groups. The content of polymeric procyanidins showed a linear dependence on the rate constant, suggesting that these compounds are mainly responsible for time‐extended radical‐scavenging activity. The antioxidant properties of apple juices were much better reproduced by EPR spectroscopy than by UV–visible measurements. The former method is especially sensitive to the concentration of polymerised or bound procyanidins, whilst the latter method requires transparent (clear) samples. Apple juices, especially cloudy ones, are a rich source of natural antioxidants that may be used in the pharmaceutical or food industry. Copyright © 2006 Society of Chemical Industry
Influence of coffee/water ratio on the final quality of espresso coffee
Authors: Andueza Susana , Vila María A , Paz de Peña M , Cid Concepción
Published: January 2007

Espresso coffee is a polyphasic beverage in which the physico‐chemical and sensory characteristics obviously depend on both the selection of ground roasted coffee and the technical conditions of the percolation process. The aim of this work was to evaluate the influence of the coffee/water ratio on the physico‐chemical and sensory quality of espresso coffee. Furthermore, the influence of botanical varieties (Arabica and Robusta) and the type of roast (conventional and torrefacto) on the selection of coffee/water ratio was studied. The relationship between pH and the perception of acidity intensity is discussed in relation to the influence of the coffee/water ratio, type of coffee and roast. The optimisation of other technical parameters in previous studies seemed to minimise the influence of an increase in the coffee/water ratio on the extraction of soluble and solid compounds. In fact, only some sensory attributes, such as bitterness, astringency and burnt, acrid and earthy/musty flavours were proposed as relevant to the selection of 6.5 g 40 mL−1 or 7.5 g 40 mL−1 in conventional roasted coffees (Arabica 100% and Robusta blend), and 6.5 g 40 mL−1 in torrefacto roasted coffees. On the other hand, the addition of sugar during the roasting process in torrefacto roast coffees seemed to contribute to a higher generation of acids, melanoidins and other compounds by the Maillard reaction or caramelisation, which led us to select the lowest coffee/water ratio. Copyright © 2006 Society of Chemical Industry
Utilisation of fruit fibres in conventional and reduced‐fat cooked‐meat sausages
Authors: García M Luisa , Cáceres Ester , Selgas M. Dolores
Published: January 2007

The effect of several fruit dietary fibres on the sensory properties of conventional and reduced‐fat cooked‐meat sausages is studied. Fruit fibres were assayed at 15 and 30 g kg−1 concentrations. The energy value reduction of the final products was close to 30%. Instrumental measurements of colour and texture were performed. Sensory properties were estimated by hedonic tests. A correlation principal component analysis was performed. The results of textural analysis showed that the differences between batches were mainly related to the fat content. However, sensory analysis indicated that the most appreciated batches were those manufactured with orange fibre, although their colour was more yellow than the remainder. As a consequence, it is possible to manufacture conventional and hypocaloric cooked sausages containing fruit fibres mainly at a concentration of 15 g kg−1 of fibre and obtain a sensorial acceptable product. Copyright © 2006 Society of Chemical Industry
Prediction of sensory textural properties from rheological analysis for process cheeses varying in emulsifying salt, protein and moisture contents
Authors: Everard Colm D , O'Donnell Colm P , O'Callaghan Donal J , Sheehan Elizabeth M , Delahunty Conor M , O'Kennedy Brendan T , Howard Vincent
Published: January 2007

Textural characteristics of process cheeses varying in emulsifying salt (disodium phosphate), protein and moisture contents were evaluated by rheological compression using texture profile analysis and by sensory evaluation. The primary objective of this study was to predict sensory textural parameters using instrumental rheological parameters. All sensory parameters correlated with one or more instrumental parameters, e.g. rheological firmness versus sensory firmness (R = 0.98, P < 0.001), rheological chewiness versus sensory rubbery (R = 0.92, P < 0.001) and rheological chewiness versus sensory chewy (R = 0.86, P < 0.001). Partial least squares calibration models were developed for each of nine sensory parameters using instrumental parameters. Principal component analysis of instrumental and sensory parameters illustrated relationships among parameters. It was shown that instrumental parameters could be used to supplement sensory evaluation of process cheese texture. Increasing emulsifying salt content increased firmness, springiness and chewiness and decreased adhesiveness, mouthcoating and mass formation. Increasing protein content resulted in increased fracture strain and stress and chewiness and decreased melting. Increasing moisture content increased cohesiveness and decreased firmness and chewiness. Copyright © 2007 Society of Chemical Industry
Semi‐dilute solutions of hydroxypropyl guar gum: Viscosity behaviour and thixotropic properties
Authors: Zhang Li‐Ming , Kong Tao , Hui Peter S
Published: January 2007

Semi‐dilute solutions of hydroxypropyl guar gum (HPGG), the most widely used derivative of naturally occurring guar galactomannan, were investigated with respect to their viscosity, yield stress and thixotropy. It was found that the shear‐dependent viscosity behaviour under various HPGG concentrations, added salts and temperature could be well described by the Cross viscosity model. The zero‐shear‐rate viscosity was observed to change with HPGG concentration according to a power‐law function, and decease with the increase of temperature according to an Arrhenius‐type equation. The addition of salts (KCl and CaCl2) lowered the zero‐shear‐rate viscosity. The HPGG solutions of high concentration showed a higher degree of thixotropy while the addition of salt lowered the thixotropic property. Copyright © 2007 Society of Chemical Industry
NMR assignments of unusual flavonoids from the kino of Eucalyptus citriodora
Authors: Freitas Marinalva Oliveira , Lima Mary Anne S. , Silveira Edilberto R.
Published: January 2007

Two unusual flavonoids, 3,5,4′,5″‐tetrahydroxy‐7‐methoxy‐6‐[1‐(p‐hydroxy‐phenyl)ethyl]flavanone (1) and 3,5,7,4′,5″‐pentahydroxy‐6‐[1‐(p‐hydroxy‐phenyl)ethyl] flavanone (2), were isolated from the kino of Eucalyptus citriodora. Structural elucidation of the new compounds were established on the basis of spectral data, particularly by the use of 1D NMR and several 2D shift‐correlated NMR pulse sequences (1H, 1H‐COSY, HMQC, HMBC). Copyright © 2007 John Wiley & Sons, Ltd.
Complete 1H and 13C NMR assignments of the epimeric menthane‐1‐carboxylic acids
Authors: Dillner Debra K. , Traficante Daniel D.
Published: January 2007

Complete NMR analyses with full assignments for 1H and 13C NMR spectral data for both epimers of menthane‐1‐carboxylic acid are described. The NMR properties of the recently synthesized axial isomer had not been previously described, and through use of a variety of 1D and 2D techniques, additional information is provided for the equatorial isomer. As well as assignments of chemical shifts, homonuclear coupling constants were determined for the equatorial isomer and most of coupling constants were measured for the axial isomer. Published in 2007 by John Wiley & Sons, Ltd.
Saturated amine oxides: Part 8†. Hydroacridines: Part 27‡. Effects of N‐oxidation and of N‐quaternization on the 15N NMR chemical shifts of N‐methylpiperidine‐derived mono‐, bi‐, and tricycloaliphatic tertiary amines
Authors: Potmischil Francisc , Duddeck Helmut , Nicolescu Alina , Deleanu Calin
Published: January 2007

The 15N chemical shifts of 13 N‐methylpiperidine‐derived mono‐, bi‐ and tricycloaliphatic tertiary amines, their methiodides and their N‐epimeric pairs of N‐oxides were measured, and the contributions of specific structural parameters to the chemical shifts were determined by multilinear regression analysis. Within the examined compounds, the effects of N‐oxidation upon the 15N chemical shifts of the amines vary from +56 ppm to +90 ppm (deshielding), of which approx. +67.7 ppm is due to the inductive effect of the incoming N+O− oxygen atom, whereas the rest is due to the additive shift effects of the various C‐alkyl substituents of the piperidine ring. The effects of quaternization vary from −3.1 ppm to +29.3 ppm, of which approx. +8.9 ppm is due to the inductive effect of the incoming N+CH3 methyl group, and the rest is due to the additive shift effects of the various C‐alkyl substituents of the piperidine ring. The shift effects of the C‐alkyl substituents in the amines, the N‐oxides and the methiodides are discussed. Copyright © 2007 John Wiley & Sons, Ltd.
Lifestyle, occupation, and whole bone morphology of the pre‐Hispanic Maya coastal population from Xcambó, Yucatan, Mexico
Authors: Wanner Isabel S. , Sosa Thelma Sierra , Alt Kurt W. , Blos Vera Tiesler
Published: January 2007

The present bioarchaeological study examines the external diaphyseal geometric properties of humeri, radii, femora and tibiae of the Classic period skeletal population of Xcambó, Yucatan, Mexico. The diaphysial proportions are evaluated using a biomechanical approach together with data from the material context and other osteological information. Our intent is to provide new answers to questions concerning lifestyle, domestic labour division and subsistence strategies of this coastal Maya settlement that was inhabited from the Late and Terminal Preclassic (300 BC–350 AD) to the Postclassic Period (900–1500 AD).

Our results provide evidence for a marked sexual division of labour when compared with values from contemporaneous inland populations. The overall male and female loading patterns differ remarkably in terms of form and in bilateral comparison. A high directional asymmetry in the upper limbs is evident among males, a condition related to maritime transportation and trading activities. On the other hand, female upper limbs are characterized by very low side differences. Forces on the arms of women were probably dominated by food processing, in particular the grinding of grains or seeds. In the lower limbs, males show significantly higher anteroposterior bending strengths, which can be explained by greater engagement in transportation tasks and carrying heavy loads. In the course of the Classic period (350–900 AD), diachronic changes affect the male sample only, which suggests a shift of occupational pattern and physical demands. This shift, in turn, reflects Xcambó's changing role as the centre of a densifying settlement area and its place in the trading activities of northern Yucatan. Other topics of discussion relate to general regional trends and local prehispanic subsistence strategies. Our conclusions emphasize the value of geometric long bone analysis in the reconstruction of activity patterns and lifestyles in ancient coastal settlements. Copyright © 2007 John Wiley & Sons, Ltd.
Treatment decision difficulties and post‐operative distress predict persistence of psychological morbidity in Chinese women following breast cancer surgery
Authors: Lam Wendy WT , Chan Miranda , Ka Hung Wai , Fielding Richard
Published: January 2007

Background: The patterns and determinants of longer‐term psychological morbidity in women following breast cancer surgery have not been described for Chinese populations.

Methods: Chinese women were assessed at 3‐days, 4‐months and 8‐months following breast surgery, on treatment decision‐making difficulty (TDMD), satisfaction with treatment outcome (E‐OI), self efficacy (GSeS), optimism (C‐LOT‐R), consultation satisfaction (C‐MISS‐R), physical symptom distress (PSD) and psychological morbidity (CHQ‐12) and compared using polynomial logistic models.

Results: Of 303/405 women providing complete data, 33% received chemotherapy and 26% radiotherapy. GSeS, CLOTR and TDMD scores were moderate. Though the proportion of women meeting psychological morbidity case‐criteria declined from 78% (95% Confidence Interval 73–83%) at Baseline to 64% (59–69%) at 8‐months, almost 50% (44–54%) of women remained distressed over the 8‐month period. After adjustment for demographic and clinical factors, severity of psychological morbidity at 4‐months was predicted by PSD, disappointment and higher Baseline CHQ12, and among moderate/severe cases only, greater TDMD and pessimistic outlook. At 8‐months, CHQ12 scores were predicted by PSD, Baseline CHQ‐12, and difficulties with TDM.

Conclusion: TDM difficulties, early post‐surgical psychological and physical symptom distress indicate risk for prolonged distress in Chinese women following breast cancer surgery. Copyright © 2007 John Wiley & Sons, Ltd.
Assessment of the importance of glenohumeral peripheral mechanics by practicing physiotherapists
Authors: Kirby Kenneth , Showalter Chris , Cook Chad
Published: January 2007

Background and Purpose. Physiotherapists develop clinical reasoning theories and applied manual therapy skills through a variety of educational exposures. No studies have assessed the importance of selected theories such as the convex–concave rule, capsular pattern and scapulohumeral rhythm during clinical decision‐making by physiotherapists. The present study investigated which variables physiotherapists considered were associated with the importance of these theories during practice and investigated physiotherapists' perception of translational motion biomechanics of the glenohumeral (GH) joint. Method. Six hundred and sixty physiotherapists in the USA volunteered to participate in this study. Using ologit regression analyses, the identifier themes and clinical background characteristics were associated with importance of peripheral biomechanics in manual therapy application and reliability/validity of the scapulohumeral rhythm theory in predicting pathological sequences of the shoulder complex. An intraclass correlation coefficient (ICC) was used to determine agreement regarding necessary translation of the GH joint for normal movement. Results. The majority of physiotherapists indicated that all theories were important or very important during treatment decision‐making and reported frequent utilization. Regression models identified that the importance placed on peripheral biomechanics was negatively influenced by academic qualification (bachelors and masters degrees) and gender (men were less likely to report that scapulohumeral rhythm was a reliable/valid predictor of shoulder pathology). ICC values identified excellent agreement among clinicians regarding translational motion. Conclusions. The importance of biomechanics of the periphery for use, validation and frequency was based heavily on adoption of selected theories of glenohumeral movements despite evidence that suggests the theories lack validity. Copyright © 2007 John Wiley & Sons, Ltd.
The physiotherapy management of patients undergoing thoracic surgery: a survey of current practice in Australia and New Zealand
Authors: Reeve Julie , Denehy Linda , Stiller Kathy
Published: January 2007

Background and Purpose. Physiotherapy is considered an essential component of the management of patients after thoracotomy, yet the type of interventions utilized, and evidence for their efficacy, has not been established. The aim of the present study was to ascertain the current physiotherapy management of patients undergoing thoracotomy and the factors influencing practice among different providers. Method. A purpose‐designed postal questionnaire was distributed to senior physiotherapists in all thoracic surgical units throughout Australia and New Zealand (n = 57). Results. A response rate of 81% was obtained (n = 46). Pre‐operatively, 16 respondents (35%) reported assessing all thoracotomy patients. The majority of respondents (n = 44; 96%) indicated that all patients were seen by physiotherapists after surgery, with 29 respondents (63%) performing prophylactic physiotherapy interventions to prevent post‐operative pulmonary complications. Respondents reported that physiotherapy treatment was usually commenced on day one post‐operatively (n = 37; 80%) with the most commonly used treatment interventions being deep breathing exercises, the active cycle of breathing techniques, cough, forced expiration techniques and sustained maximal inspirations. Most respondents reported that patients first sat out of bed (n = 41; 89%), commenced shoulder range of movement (n = 23; 50%) and walking (n = 32; 70%) on day one post‐operatively. The majority of respondents reported that they offered no post‐operative pulmonary rehabilitation (n = 25; 54%), outpatient follow‐up (n = 43; 94%) or post‐thoracotomy pain management (n = 40; 87%). Respondents indicated that personal experience, literature recommendations and established practice were the factors which most influenced physiotherapy practice. Conclusion. Most patients after thoracotomy receive physiotherapy assessment and/or treatment in the immediate post‐operative period, but only one‐third were routinely seen pre‐operatively and relatively few were reviewed following discharge from hospital. Further studies are required to guide physiotherapists in determining the efficacy of their practices for patients undergoing thoracotomy. Copyright © 2007 John Wiley & Sons, Ltd.
Auxetic behaviour from rotating semi‐rigid units
Authors: Grima J. N. , Zammit V. , Gatt R. , Alderson A. , Evans K. E.
Published: January 2007

Auxetics (i.e. systems with negative Poisson's ratios) exhibit the unexpected feature of becoming fatter when stretched and narrower when compressed. This property is highly desirable as it imparts many beneficial effects on the material's macroscopic properties. Recent research suggests that in an idealised scenario, systems composed of connected ‘rigid squares’ can exhibit auxetic behaviour (Poisson's ratio = –1) due to a mechanism involving relative rotation of the squares. This paper shows through force‐field based molecular modelling simulations that although ‘rotating squares’ are responsible for negative Poisson's ratios in various zeolite frameworks, in these real materials, the squares are not rigid and the auxeticity is not as pronounced as in the ‘idealised’ model. In view of this, a new model system made from connected ‘semi‐rigid’ squares is proposed and analytical equations for the mechanical properties of this new model system are derived and discussed. It will be shown that the Poisson's ratios in this new model are highly dependent on the extent of rigidity of the squares and the direction of loading. It will also be shown that this new model provides a better description for the behaviour of auxetic zeolite frameworks than the original ‘rotating rigid squares’ model. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
On the existence of negative pressure states
Authors: Imre Attila R.
Published: January 2007

Although pressure is usually believed to be an always positive quantity, negative pressure states exists since the beginning of the Universe and they have been studied since Huygens. These states are metastable and therefore mistakenly thrown out from calculations and neglected in experiments as non‐existing or unaccessible ones although they exist and they can be accessed. Recent theories suggest that normal materials (without any special structure) under negative pressure can be auxetic. In this short review paper we would like to demonstrate the existence of negative pressure states and discuss the limiting negative pressure for condensed matters (liquids and solids). (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Novel structure and swelling dynamics of nanocomposite ultrathin films
Authors: Mukherjee M. , Singh A.
Published: January 2007

Structure and swelling dynamics of ultrathin films of CdS–polyacrylamide nanocomposite material were studied using gravimetric techniques and X‐ray reflectivity. Ultrathin films of the polymer and the nanocomposite were coated on hydrophilic Si(100) substrate using spin coating. The thickness of the composite films vary non‐monotonically with spinning speed and were found to lie in discrete “bands” of thicknesses separated by “forbidden regions” unlike pure polymer films. Modified internal structure of the coils due to polymer–particle interaction was found to play a significant role in describing the novel features of the nanocomposite films. To study the mass uptake, the films were exposed to the H2O vapour and the weights of the films were recorded as functions of exposure time. The observed non‐Fickian transport was explained in terms of alignment of free volume due to confinement of restricted polymer chains. To study swelling dynamics, the films were exposed to the H2O vapour and X‐ray reflectivity scans were collected as functions of exposure time. The swelling dynamics of the nanocomposite films were explained in terms of a model which takes into account the polymer‐particle interaction. A fraction of polymer segments that are in direct contact with the nanoparticles observed slower dynamics as compared to the free chain swelling. Larger values of excluded volume parameters corresponding to restricted segments as compared to the free segments were explained in terms of enhancement of monomer‐monomer interaction through particle attachment. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Strain rate dependence of stiffness and Poisson's ratio of auxetic open cell PU foams
Authors: Pastorino P. , Scarpa F. , Patsias S. , Yates J. R. , Haake S. J. , Ruzzene M.
Published: January 2007

The paper describes the manufacturing and tensile testing of auxetic (negative Poisson's ratio) thermoplastic polyurethane and polyester urethane foams, under quasi‐static and constant strain rate loading. The foams are produced from conventional flexible polyurethane basis following a manufacturing route developed in previous works. The Poisson's ratio behaviour over compressive strain has been analyzed using an Image Data processing technique based on Edge Detection from digital images recorded using camcorders and high speed cameras. The measurements indicate that higher strain rate loading implies stiffening effects on the stress–strain curves, and significant increase of the magnitudes of the Poisson's ratios with increasing compressive strains. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Young's and shear moduli and Poisson's ratio for elastic media of high and middle symmetry
Authors: Paszkiewicz T. , Wolski S.
Published: January 2007

Using bases of fourth rank tensorial bases of [V2]2 symmetry elaborated by Walpole we obtained expressions for inverse of Young's modulus E (n), inverse of shear modulus G (m, n) and Poisson's ratio v (m, n), which depend on components of the stiffness tensor S, on direction cosines of vectors n of uniaxial load and the vector m of lateral strain with crystalline symmetry axes. Crystalline media of high and medium symmetries are considered. Such representation yields decomposition of the above elastic characteristics to isotropic and anisotropic parts. Expressions for Poisson's coefficient are well suited for studying the property of auxeticity. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Exploration of high and negative Poisson's ratio elastomer‐matrix laminates
Authors: Peel L. D.
Published: January 2007

Elastomer‐matrix composites show promise for high Poisson's ratio and negative Poisson's ratio (auxetic) applications due to high orthotropy. There are approximately five orders of magnitude between the axial stiffness of high modulus graphite fibres and the stiffness of low durometer elastomers. Although the maximum Poisson's ratio for isotropic elastomers is 0.5, it is easily shown that inplane Poisson's ratios twice unity can be obtained with a graphite/epoxy angle‐ply laminate at 25°. Chou and others have predicted inplane Poisson's ratios greater than 7 for certain cord‐rubber combinations. Peel previously predicted inplane Poisson's ratios higher than 32 and less than –60. Preliminary experimental results have produced inplane Poisson's ratios as high as 14. Certain combinations of un‐balanced highly orthotropic laminates may also produce inplane negative Poisson's ratios. Inplane Poisson's ratios, experimentally obtained from two laminate configurations with approximately the same axial stiffness are compared. A symmetric, balanced laminate produced an inplane Poisson's ratio of 3.7; while an unbalanced laminate with an equivalent axial stiffness produced an average inplane Poisson's ratio of –1.5. Certain high and negative Poisson's ratio elastomer‐matrix laminates appear to have quasi anti‐symmetric relationships about 0°, although laminate designers may consider dual angle‐ply laminates to be the more likely counterpart to the unbalanced dual angle auxetic laminates. Unbalanced symmetric laminates experience significantly more inplane shear deformation when axially loaded than their balanced counterparts. The high shear may be desirable for damping applications, but less desirable otherwise. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Stability of elastic material with negative stiffness and negative Poisson's ratio
Authors: Xinchun Shang , Lakes Roderic S.
Published: January 2007

Stability of cuboids and cylinders of an isotropic elastic material with negative stiffness under partial constraint is analyzed using an integral method and Rayleigh quotient. It is not necessary that the material exhibit a positive definite strain energy to be stable. The elastic object under partial constraint may have a negative bulk modulus K and yet be stable. A cylinder of arbitrary cross section with the lateral surface constrained and top and bottom planar surfaces is stable provided the shear modulus G > 0 and –G /3 < K < 0 or K > 0. This corresponds to an extended range of negative Poisson's ratio, –∞ < ν < –1. A cuboid is stable provided each of its surfaces is an aggregate of regions obeying fully or partially constrained boundary conditions. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Computer simulation of heat transfer through a ferrofluid
Authors: Strek Tomasz , Jopek Hubert
Published: January 2007

The viscous, two‐dimensional, incompressible and laminar time dependent heat transfer flow through a ferromagnetic fluid is considered in this paper. The flow takes place in channel between two parallel flat plates under the influence of the magnetic dipole located below the channel. It is assumed that there are no electric field effects and the variation in the magnetic field vector, which could occur due to temperature gradients within the ferrofluid, is negligible. This magneto‐thermo‐mechanical problem is governed by dimensionless equations. Results are obtained using computational fluid dynamics code COMSOL with modifications to account for the magnetic term (the Kelvin body force or the thermal power) when needed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Screening of some medicinal plants from cameroon for β‐Lactamase inhibitory activity
Authors: Gangoué‐Piéboji Joseph , Baurin Stéphane , Frère Jean‐Marie , Ngassam Pierre , Ngameni Bathelemy , Azebaze Anatole , Pegnyemb Dieudonné Emmanuel , Watchueng Jean , Goffin Colette , Galleni Moreno
Published: January 2007

In efforts to find new bioactive β‐lactamase inhibitors, this study investigated 16 Cameroonian plants belonging to 10 families which were evaluated for anti‐β‐lactamase activity. The investigation showed that extracts 2, 6, 3 and 5 of the 16 plants investigated presented interesting in vitro β‐lactamase inhibition (over 90%), respectively, of the β‐lactamases TEM‐1, OXA‐10, IMP‐1 and P99. These extracts were from Mammea africana (all β‐lactamases), Garcinia lucida, G. kola (OXA‐10, IMP‐1 and P99), Bridelia micrantha (OXA‐10, P99), Ochna afzelii (OXA‐10, P99), Prunus africana (IMP‐1) and Adenia lobata (TEM‐1). After elimina tion of tannins (according to the European Pharmacopoeia) the extracts from B. micrantha, G. lucida and M. africana were tested further for their anti‐β‐lactamase activity. The extracts from B. micrantha and G. lucida exhibited potent inhibitory activity, respectively, of β‐lactamase OXA‐10 (IC50 = 0.02 mg/mL) and P99 (IC50 = 0.01 mg/mL). The anti‐β‐lactamase activity of M. africana extract was weak. The isolation and the structural elucidation of the active constituents of G. lucida and B. micrantha will provide useful leads in the development of β‐lactamase inhibitors. Copyright © 2007 John Wiley & Sons, Ltd.
Atractylenolide I and atractylenolide III inhibit Lipopolysaccharide‐induced TNF‐α and NO production in macrophages
Authors: Li Cui‐qin , He Lang‐Chong , Jin Ju‐qing
Published: January 2007

In order to clarify the mechanism involved in the antiinflammatory activity of atractylenolide I and atractylenolide III from the rhizomes of Atractylodes macrocephala Koidz, their effects on tumor necrosis factor‐α (TNF‐α) and nitric oxide (NO) production in peritoneal macrophages were examined. Atractylenolide I and atractylenolide III decreased the TNF‐α level in LPS‐stimulated peritoneal macrophages in a dose‐dependent manner, their IC50 values were 23.1 µm and 56.3 µm, respectively. RT‐PCR analysis indicated that they inhibited TNF‐α mRNA expression. Furthermore, they inhibited NO production in LPS‐activated peritoneal macrophages, the IC50 value of atractylenolide I was 41.0 µm, and the inhibition ratio of 100 µm of atractylenolide III was 45.1% ± 6.2%. The activity analysis of inducible nitric oxide synthase (iNOS) indicated that they could inhibit the activity of iNOS, their IC50 values were 67.3 µm and 76.1 µm, respectively. Western blot analysis showed that atractylenolide I and atractylenolide III attenuated LPS‐induced synthesis of iNOS protein in the macrophages, in parallel. These results imply that the antiinflammatory mechanism of atractylenolide I and atractylenolide III may be explained at least in part, by the inhibition of TNF‐α and NO production. Atractylenolide I showed more potent inhibition than atractylenolide III in the production of TNF‐α and NO in LPS‐activated peritoneal macrophages. So, atractylenolide I could be a candidate for the development of new drugs to treat inflammatory diseases accompanied by the overproduction of TNF‐α and NO. Copyright © 2007 John Wiley & Sons, Ltd.