bluuebunny/crossref_metadata_2025 huggingface dataset:
In situ micro‐Raman spectroscopy on minerals on‐site in the Grotto Hall of the New Palace, Park Sanssouci, in Potsdam
Authors: Ziemann Martin A.
Published: September 2006

Questions of identity and provenance of minerals that are parts of masterpieces in museums have become increasingly important in mineralogical and historical studies. Detailed investigations of valuable and unique objects require on‐site, nondestructive and noninvasive methods because touching or removing them may cause irreparable damage. A mobile Raman‐microprobe has been used to meet these demands for truly in situ mineralogical studies of the large collection of minerals and rocks of the Prussian kings in the Grotto Hall (Grottensaal) of the New Palace (Neues Palais), Park Sanssouci in Potsdam. Minerals on the walls of the Grotto Hall were analyzed to identify them and thereby to complete the data bank of the collection. Fluid and solid inclusions in the interior of a large quartz crystal have been studied to provide evidence of the provenance of the crystal. The fluid inclusions contain aqueous saline solutions, whereas the solid inclusions are needles of anhydrite with a length of about 1.5 mm. The quartz probably originated from an area in the eastern Alps, from the surroundings of Bad Gastein, Austria. This is the first on‐site and in situ study of inclusions below the surface of a mineral with a mobile Raman‐microprobe outside a laboratory. Copyright © 2006 John Wiley & Sons, Ltd.
Raman and ATR‐FTIR spectroscopies applied to the conservation of archaeological Baltic amber
Authors: Shashoua Yvonne , Degn Berthelsen Mai‐Britt Lund , Nielsen Ole Faurskov
Published: September 2006

A recent survey suggested that the National Museum of Denmark had more than 17 000 pieces of amber in its collections. It also concluded that 45% of the amber in the collections exhibit deterioration, manifested by surface crazing, powdering and discolouration. Although the chemical composition of Baltic amber has been investigated, and it is known to comprise an alkyd polymer containing 8% succinic acids and terpenoid components, degradation pathways have not been defined. It is important that the amber collections are preserved for future study and enjoyment, and a preventive conservation strategy is under development. Such an approach involves controlling the environment in which the objects are stored to slow the rate of deterioration. Experience at the Natural History Museum, London, suggested that the rate of degradation was related to relative humidity (RH) of the storage environment. In this study, Raman and attenuated total reflection‐Fourier transform infrared (ATR‐FTIR) spectroscopies were used to quantify and compare the extent of deterioration of amber after thermal ageing at various levels of RH. ATR‐FTIR spectra provided information about surfaces, because the electromagnetic radiation penetrated only the upper few microns of the amber, whereas Raman spectra reflected chemical changes at the millimetre level.

Raman spectra showed a loss in CC groups on ageing of the amber samples at all levels of RH, while ATR‐FTIR spectra indicated an increase in the concentration of carbonyl for the same samples. Bands corresponding to unsaturated carbon bonds (1646 cm−1) were strong in Raman spectra and weak in FTIR spectra, while the opposite was true for bands representing carbonyl groups (1730 cm−1). The findings were attributed to reaction of oxygen with unsaturated carbon–carbon bonds in the terpenoid components of amber that formed acids containing carbonyl groups (dehydroabietic and 7‐oxodehydroabietic acids). ATR‐FTIR spectroscopy suggested that the rate of deterioration was slowed by high RH, although further investigations are required. Copyright © 2006 John Wiley & Sons, Ltd.
Introduction to Raman microscopy of prehistoric rock paintings from the Sierra de las Cuerdas, Cuenca, Spain
Authors: Hernanz Antonio , Gavira‐Vallejo José M. , Ruiz‐López Juan F.
Published: September 2006

Selected pictographs from the prehistoric painting panel 2 of Cueva del Tío Modesto shelter in the Sierra de las Cuerdas (Henarejos, Cuenca, Spain) were studied by Raman microscopy in order to determine the chemical composition of the pigments used. Hematite (α‐Fe2O3) was found as the main component. The hematite particle size of one motif is much smaller than that observed for the others. No binders were found. A blue‐greyish crust extends over the whole panel. Whewellite, weddellite and amorphous carbon were identified in this crust. The Triassic sandstone on which the paintings are made is found to suffer from a flaking process. Therefore, flakes of the rocky substratum were studied, and α‐quartz, whewellite, magnetite and gypsum were found. A micro‐stratigraphic study of the flakes revealed channels of gypsum from one side of the flake to the other. This result supports the mechanism proposed for this sandstone weathering process. Copyright © 2006 John Wiley & Sons, Ltd.
Waterlogged archaeological wood—chemical changes by conservation and degradation
Authors: Christensen M. , Frosch M. , Jensen P. , Schnell U. , Shashoua Y. , Nielsen O. F.
Published: September 2006

Conservation of waterlogged archaeological wooden artefacts from the Nydam Bog in the southern part of Denmark was investigated by Raman spectroscopy. Two different conservation methods were used: the cellosolve/petroleum method and the polyethylene glycol (PEG)/freeze‐drying method. Conservation with cellosolve/petroleum at both room and elevated temperatures was used to preserve archaeological arrows made from pinewood and ash wood. The double bonds in lignin were affected by the warm treatment. Holocellulose in the archaeological wooden arrows had decomposed completely. A band around 180 cm−1 in the R(v)‐representation of the low‐wavenumber Raman spectrum was used to monitor the presence of water in PEG2000 with a structure like the one in ‘free’ bulk water. The lignin/PEG2000 relative band intensities were used to make a quantitative estimate of the wood/PEG2000 ratio in a PEG2000 impregnated piece of hardwood. A decreasing degradation of holocellulose was observed from the surface to the centre of an oak piece from the Kolding Cog, built around 1200 A.D. A broad background was observed in the spectra recorded close to the surface of the plank. A similar, very intense, broad background was seen in untreated collapsed ash wood from the Nydam Bog. This broad background, most probably arising from fluorescence, was too intense to allow a Raman spectrum to be seen. In these cases, ATR‐FTIR spectroscopy is a valuable complementary tool in studies of waterlogged archaeological wood, confirming that holocellulose degrades more rapidly than lignin. Copyright © 2006 John Wiley & Sons, Ltd.
A study of medieval illuminated manuscripts by means of portable Raman equipments
Authors: Bersani Danilo , Lottici Pier Paolo , Vignali Francesca , Zanichelli Giuseppa
Published: September 2006

The pigments used in five important medieval illuminated manuscripts (Ms. Pal.6; Ms. Pal. 159; Ms. Pal. 212; Ms. Parm. 1650; Ms. Parm. 3063), all held in the Biblioteca Palatina in Parma (Italy), were analysed in situ by portable micro‐Raman instruments supplied by Renishaw and Horiba Jobin‐Yvon. In spite of a strong fluorescence background, different pigments were identified and important information on the pigment palette used in the manuscript illumination, helpful to clarify the history of the artworks, was obtained. Differences in the pigments used, suggesting late interventions, were found. In particular, an addition was identified in the Ms. Pal. 212 manuscript (Bruges—15th century), and late interventions were found in the coat of arms of Barbara of Brandenburg in her breviary (Ms. Pal. 6). A different origin for some rubrics and illumination was found in Ms. Parm. 3063, a 12th century Psalter, whereas common palettes for the different artists were confirmed for Ms. Parm. 1650 and for Ms. Pal. 159. Copyright © 2006 John Wiley & Sons, Ltd.
Micro‐Raman study of red decorations in French faiences of the 18th and 19th centuries
Authors: Marco de Lucas M. C. , Moncada F. , Rosen J.
Published: September 2006

Obtaining the red color was a technical and economic challenge for the French faience manufactories in the 18th and 19th centuries. The tendency of the red hematite to turn into drab brown during the firing process explains the difficulty in obtaining this color. Red decorations in shards coming from the four production centers of faience manufacturing during this period—Rouen (northwest), Nevers (central), Thiviers (southwest) and Argonne (northeast)—have been studied by means of micro‐Raman spectroscopy, scanning electron microscopy (SEM) and energy‐dispersive X‐ray spectroscopy (EDX). Among them, Thiviers appears to be the leader thanks to a particular reddish sandstone called ‘Grès de Thiviers’ (GT) available in the region. This material is composed of α‐quartz grains cemented by goethite (α‐FeOOH), leading to red hematite during the firing process. Raman spectra revealed that GT was also used by the Nevers manufactories in the middle of the 19th century instead of other methods used in the middle of the 18th century based on the mixture of Naples yellow with iron oxides. Manufactories in the north of France at Rouen and Argonne did not employ GT, but Naples yellow together with iron oxides or other pigments as ‘bol d'Arménie’. Copyright © 2006 John Wiley & Sons, Ltd.
Micro‐Raman study of aluminium‐bearing hematite from the slip of Gaul sigillata wares
Authors: Zoppi A. , Lofrumento C. , Castellucci E. M. , Dejoie C. , Sciau Ph.
Published: September 2006

The presence of sub‐microscopic Al‐Fe2O3 and Fe‐Al2O3 impure crystallites in the slip of sigillata wares from La Graufesenque (southern France) has recently been demonstrated by micro‐structural analyses, posing new questions about manufacturing processes and technological skills. To clarify the chemical composition and the spatial distribution of such phases within the slip, five representative sigillata wares were investigated by micro‐Raman spectroscopy. The recorded spectra show the typical hematite bands, though the Raman peaks are broadened and shifted, which agrees with a disordered phase. This is also reflected in a signal at 670 cm−1, while a shoulder close to 430 cm−1 is attributed to point defects, in agreement with the substitution of Fe atoms by Al atoms. A corundum spectrum was not detected indeed, probably hidden by the more intense hematite one. Spectral parameters were then estimated by a curve‐fitting analysis. Their comparison indicates a similarity among the investigated slips as well as uniformity within the slip layer. This suggests an awareness of the control of the production process among the local craftsmen. The spectral interpretation was assisted by reference spectra acquired on artificially doped hematite and corundum powder samples, which were used for probing the doping effect on the vibrational features of the pure crystallites. Copyright © 2006 John Wiley & Sons, Ltd.
Raman study of a ‘Tabula Colorum Physiologica’ in a 1686 printed journal
Authors: Baraldi Pietro , Fagnano Concezio , Bensi Paolo
Published: September 2006

A Table painted in 1686 with spots of colors on paper was investigated. It appears that the Table is composed of pure pigments, and their mixtures in a 1:1 proportion. However, there were some problems when analyzing the pure compounds and the mixtures, due to the interaction of some pigments, as degradation had occurred. Possible explanations of the nature of the compound are analyzed and discussed. Copyright © 2006 John Wiley & Sons, Ltd.
Evidence for the degradation of an alloy pigment on an ancient Italian manuscript
Authors: Aceto Maurizio , Agostino Angelo , Boccaleri E. , Crivello F. , Garlanda A. Cerutti
Published: September 2006

An unusual metallic pigment was identified on an ancient Italian manuscript containing theHomilies on the Gospelsof Gregory the Great, belonging to the Archive and Chapter Library of Vercelli (Italy) and datable to the IX century. Green uncial text and part of decoration on this manuscript were described as ‘being of golden fashion’ in a book written at the beginning of XX century. Investigations carried out with portable XRF and Raman instruments revealed that the green colouration is actually the result of a marked degradation process that has altered the original composition of the pigment, an alloy of copper, lead and zinc. Probably because of the conditions of storage of the manuscript, the pigment tarnished owing a chemical process that could resemble the infamous ‘bronze disease’: that is, the conversion of metallic copper into inorganic salts. Measurements were performed bothin situ, i.e. directly on the manuscript, and on small fragments of ink collected from the page gutters. Copyright © 2006 John Wiley & Sons, Ltd.
Fuzzy logic: a technique to Raman spectra recognition
Authors: Castanys Tutzó M. , Perez‐Pueyo R. , Soneira M. J. , Ruiz Moreno S.
Published: September 2006

This paper presents two strategies based on fuzzy logic to identify unknown Raman spectra. Following the guidelines of visual inspection, it would be possible to compare the whole spectrum of the analyzed sample with the spectra of standard materials or, once the wavenumber positions of the bands of the unknown spectrum are localized, to compare them with those of the reference spectra. In both cases, it is necessary to have a database in which either the whole standard spectrum or the position of their bands are stored. In order to automate and to facilitate the task of comparison and identification of Raman spectra, two fuzzy logic systems are proposed. In one case, the designed fuzzy logic system uses a similarity index that quantifies the likeness between the compared spectra to find out to which material can the unknown spectrum correspond. In the other case, the proposed fuzzy logic system identifies the analyzed material, searching for the coincidence on the position of their bands with those of the considered standard materials. In both cases, the identification of artistic pigments can be achieved from their Raman spectra in a systematic and objective way. Copyright © 2006 John Wiley & Sons, Ltd.
Raman spectroscopic analysis of mediaeval wall paintings in the Palencia region, Spain
Authors: Villar S. E. Jorge , Edwards H. G. M. , Medina J. , Perez F. Rull
Published: September 2006

The use of Raman spectroscopic techniques for the analysis of wall paintings and frescoes has been reported previously. In this paper we present for the first time the Raman study of a collection of three wall paintings attributed to the same artist, dating from the XVth century, and a fourth wall painting dated three centuries earlier, all of them located in the same area, namely Palencia in northern Spain. From the results obtained here we can conclude that there is an identifiable recipe for the different colours and pigment tonalities, which had been maintained during the centuries regardless of the artistic origin of the work and did not seem to have been subjected to external influences. Also, the use of expensive pigments by the artist(s) is identified with the local importance of the figure, more than with the established religious hierarchy. Copyright © 2006 John Wiley & Sons, Ltd.
Raman spectroscopic analysis of a unique linen artefact: the HMS Victory Trafalgar sail
Authors: Edwards Howell G. M. , Nikhassan Nik F. , Farwell Dennis W. , Garside Paul , Wyeth Paul
Published: September 2006

The Battle of Trafalgar took place in 1805 and is generally accepted to mark the last occasion of combat between major fleets of sailing ships, when a combined Franco‐Spanish force of 33 battleships was defeated by a British fleet of 27 battleships blockading Cadiz and the approaches to the Mediterranean Sea. The HMS Victory Trafalgar sail, the fore‐topsail from Admiral Lord Nelson's flagship, was severely damaged and has since suffered significant natural deterioration. As the only extant early 19th century sail in the world, it is a unique artefact and arguably Britain's foremost maritime textile treasure. Prior to its display at the bicentennial exhibition in 2005, the sail was analysed by Raman spectroscopy. Complementary tensile tests were also completed on loose yarn from around the damaged areas. The mechanical data and Raman spectral comparisons suggest a good correspondence between the historic sailcloth and surrogate specimens. The latter were prepared by subjecting modern linen canvas to a four‐stage regime of artificial ageing in an attempt to reproduce the weakened state of the 200‐year‐old sailcloth, and provide model material to help appreciate the properties of the historic canvas. Detailed analysis suggests that certain Raman signatures are characteristic of ageing and may correlate with reduced performance of the fabric, suggesting that the technique could offer a non‐destructive approach to informing the preservation of a national textile heritage. Copyright © 2006 John Wiley & Sons, Ltd.
Preliminary investigations by Raman microscopy of prehistoric pigments in the wall‐painted cave at Roucadour, Quercy, France
Authors: Ospitali Francesca , Smith David C. , Lorblanchet Michel
Published: September 2006

Raman microscopy (RM) was applied to an ongoing study of prehistoric pigments employed in Palaeolithic wall paintings in the Roucadour Cave (France). Micro‐samplings were carried out on parts of red or black painted figures representing animals and also negative human hands.

These first analyses showed that in all the red micro‐samples, the main pigment is haematite. Where the tone was dark red, well‐formed crystals of haematite were identified, but magnetite, Mn oxide and carbon grains were also found. An intermediate mineral phase structurally in‐between goethite and haematite was also identified. In red samples, the yellowish hydrated species goethite was also detected. A great quantity of white, greyish‐white and yellowish‐white crystals were present in the pigment, and many of them were identified as calcite or quartz.

The black pigments were constituted of well‐formed crystals of Mn oxyhydroxide in some black micro‐samples. Suggestions are made for the identification of some mineral species (bixbyite, hollandite, nsutite) but there is still much uncertainty on this topic. In others, amorphous carbon grains were utilised as the main pigment. This distinction is important for orienting the research towards a subsequent investigation by radiocarbon dating.

Traces of anatase were found in black pigments, as were traces of rutile and gypsum in red pigments. It is interesting that haematite occurs in all the black pigments, black because of the great content of C or of Mn oxyhydroxide, and that several red pigments contain minor carbon, such that each pigment is a mixture with at least five different species in most micro‐samples. These data are compatible with the possibility that the prehistoric artists used naturally‐occurring impure geological materials (e.g. (Fe,Mn)‐ochre rocks) and natural biological materials (e.g. wood or oil to make charcoal or soot), but it cannot exclude the fact that they may have treated the raw materials and/or manufactured mixtures of purer materials. Copyright © 2006 John Wiley & Sons, Ltd.
Comparison of germanium oxide fibers with silica and sapphire fiber tips for transmission of erbium: YAG laser radiation
Authors: Polletto Travis J. , Ngo Anthony K. , Tchapyjnikov Alexei , Levin Ken , Tran Danh , Fried Nathaniel M.
Published: September 2006

Background and Objectives

Endoscopic applications of the Erbium:YAG laser have been limited due to the lack of a suitable optical fiber delivery system. The purpose of this study was to compare the transmission of Er:YAG laser radiation through germanium oxide trunk fibers with silica and sapphire fiber tips for potential use in contact tissue ablation during endoscopy.

Study Design/Materials and Methods

Er:YAG laser radiation with a wavelength of 2.94 µm, pulse length of 300 microseconds, pulse energies from 5 to 1,360 mJ, coupled into pulse repetition rates of 3–10 Hz, was through 1‐m‐long germanium oxide fibers with either 1‐cm‐long, 550‐µm‐diameter silica or sapphire tips.

Results

Transmission through the germanium oxide/sapphire fibers measured 65±5% compared with 55±4% for the germanium oxide/silica fibers (P<0.05). The damage threshold for the hybrid fibers averaged 309± 44 mJ and 126±43 mJ, respectively (n = 7 fibers each) (P<0.05). The highest pulse energies transmitted through the fibers were 700 mJ and 220 mJ, respectively.

Conclusions

Improved index‐matching of the trunk fiber and fiber tip at 2.94 µm resulted in higher transmission and damage thresholds for the germanium oxide/sapphire fibers. The germanium oxide/sapphire fiber may represent a promising mid‐infrared optical fiber delivery system for use in endoscopic applications of the Er:YAG laser requiring a flexible, biocompatible, and robust fiber delivery system for contact tissue ablation. Lasers Surg. Med. 38:787–791, 2006. © 2006 Wiley‐Liss, Inc.
Fabrication and Characterization of an Organic‐Inorganic Gradient Surface made by Polymethylsilsesquioxane (PMSQ)
Authors: Liu Haiyun , Xu Jian , Li Yanfang , Li Baiyu , Ma Jun , Zhang Xiaoli
Published: September 2006

Summary: A simple method for the fabrication of a chemical composition gradient from organic to inorganic by the pyrolysis of a polymethylsilsesquioxane (PMSQ) thin film in a gradient temperature field is reported. The resultant chemical gradient surface demonstrates gradual changes in wettability, and slight microstructural changes are observed along the substrate.

FT‐IR spectra of gradient PMSQ surface along the length from the unheated side to the heated side.

magnified image

FT‐IR spectra of gradient PMSQ surface along the length from the unheated side to the heated side.
Metal ion retention from aqueous solution using the ultrafiltration technique: preparation, retention capacity of copolymers of N‐maleimide derivatives with β‐methylhydrogen itaconate and metal complexes
Authors: Pizarro Guadalupe del C , Marambio Oscar G , Jeria‐Orell Manuel , Huerta Margarita R , Rodríguez Oscar O , Olea‐Azar Claudio , Rivas Bernabé L , Habicher Wolf D
Published: September 2006

Chlorophenylmaleimide (Cl‐PhMI) and N‐maleoylglycine (N‐MG) with β‐methylhydrogen itaconate (β‐MHI) were copolymerized by radical polymerization, and their metal ion retention capacity (MRC) and thermal behavior were studied. The copolymers were obtained by varying the mole fraction of Cl‐PhMI or N‐MG in the feed from 0.25 to 0.75. The monomer reactivity ratios, r1 and r2, were determined using the Kelen–Tüdös method. The molecular weight and polydispersity were also determined. The capacity to remove several metal ions, such as Cu(II), Cr(III), Co(II), Zn(II), Ni(II), Pb(II), and Fe(III), in aqueous phase was determined using the liquid‐phase polymer‐based retention technique. Inorganic ion interactions with the hydrophilic polymer were determined as a function of pH and the filtration factor. The MRC depends strongly on the pH. Metal ion retention increased with increases in pH and the content of β‐MHI units in the macromolecular backbone. The copolymers and polymer–metal complexes of transition metal ions were characterized using elemental analysis, Fourier transform infrared spectroscopy, 1H NMR, and electron paramagnetic resonance spectroscopy. The maximum MRC of Cu(II) ions of poly(Cl‐PhMI‐co‐β‐MHI) varied from 240 to 260 mg g−1, while the MRC of Cu(II) ions of poly(N‐MG‐co‐β‐MHI) varied from 270 to 318 mg g−1 at pH 5 and pH 7. The thermal behavior of the copolymers and polymer–metal complexes was studied using differential scanning calorimetry and thermogravimetry techniques under nitrogen atmosphere. The copolymers have a lower thermal decomposition temperature than the polymer‐metal complex for the same copolymer composition. The thermal behavior may be correlated with the copolymer composition. Copyright © 2006 Society of Chemical Industry
Autodiffusion: a novel method for emitter formation in crystalline silicon thin‐film solar cells
Authors: Wolf A. , Terheiden B. , Brendel R.
Published: September 2006

The in situ formation of an emitter in monocrystalline silicon thin‐film solar cells by solid‐state diffusion of dopants from the growth substrate during epitaxy is demonstrated. This approach, that we denote autodiffusion, combines the epitaxy and the diffusion into one single process. Layer‐transfer with porous silicon (PSI process) is used to fabricate n‐type silicon thin‐film solar cells. The cells feature a boron emitter on the cell rear side that is formed by autodiffusion. The sheet resistance of this autodiffused emitter is 330 Ω/□. An independently confirmed conversion efficiency of (14·5 ± 0·4)% with a high short circuit current density of (33·3 ± 0·8) mA/cm2is achieved for a 2 × 2 cm2large cell with a thickness of (24 ± 1) µm. Transferred n‐type silicon thin films made from the same run as the cells show effective carrier lifetimes exceeding 13 µs. From these samples a bulk diffusion lengthL > 111 µm is deduced. Amorphous silicon is used to passivate the rear surface of these samples after the layer‐transfer resulting in a surface recombination velocity lower than 38 cm/s. Copyright © 2006 John Wiley & Sons, Ltd.
Free radical polymerization with catalytic chain transfer: Using NMR to probe the strength of the cobalt–carbon bond in small molecule model reactions
Authors: Morrison David A. , Davis Thomas P. , Heuts Johan P. A. , Messerle Barbara , Gridnev Alexei A.
Published: September 2006

This work examines cobalt–carbon bond formation between the cobalt (II) macrocycle, (tetrakis(p‐methoxyphenyl)porphyrinato)cobalt (II), (TAP)Co, and a variety of radicals derived from vinyl compounds to facilitate a better understanding of the various factors affecting the cobalt–carbon bond strength in catalytic chain transfer polymerization. The reaction of (TAP)Co with the following vinylic molecules was studied: methacrylonitrile, cyclohexene, methyl methacrylate, styrene, methyl acrylate, vinyl acetate, vinyl benzoate, methyl crotonate, cis‐2‐pentenenitrile, and ethyl α‐hydroxymethacrylate. Different concentrations of each vinylic compound were added to (TAP)Co and 2,2′‐azobis(isobutyronitrile) in CDCl3 at 60 °C. The ratio of Co(III) to Co(II) and the nature of the radical bound to the cobalt macrocycle were determined via nuclear magnetic resonance measurements. Several factors are shown to affect the reaction of the radical and the cobalt (II) species (and hence the strength of the cobalt–carbon bond in the resulting compound). These factors are as follows: the number of pathways by which a radical may be derived from the vinyl compound; the variety of radicals that can be produced from the vinylic molecule; the stability of the radical(s) generated; and the relative propagation rate of the vinyl compound. A discussion on the relevance of this study to the behavior of different monomers in catalytic chain transfer reactions is included. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6171–6189, 2006
Multi‐center nature of ethylene polymerization catalysts based on 2,6‐bis(imino)pyridyl complexes of iron and cobalt
Authors: Kissin Yury V. , Qian Changtao , Xie Guangyong , Chen Yaofeng
Published: September 2006

2,6‐Bis(imino)pyridyl complexes of Fe and Co in combination with methylalumoxane form very active homogeneous catalytic systems for polymerization of ethylene. GPC analysis of the polymers prepared with the complexes indicates that the Co complexes produce single‐center catalysts whereas the Fe complexes produce catalysts with numerous types of active centers. Different centers in the latter catalyst systems respond differently to reaction conditions such as the reaction duration, the [MAO]:[Fe] ratio, the ethylene concentration, etc. The article examines the effects of reaction variables on the performance of both types of catalysts and proposes an explanation for the complex behavior of the catalysts derived from the Fe complexes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6159–6170, 2006
Facile synthesis and high optical activity of poly(1‐pentyne)s carrying amino‐acid pendant groups
Authors: Lai Lo Ming , Lam Jacky W. Y. , Tang Ben Zhong
Published: September 2006

1‐Pentynes containing different amino acid moieties and pendant terminal groups {HCC(CH2)2CONHC(R′)HCO2CH3, where R′ = CH3, CH2CH(CH3)2, CH2C6H5, and HCC(CH2)2CONHC[CH2CH(CH2)3]HCO2‐(1R,2S,5R)‐(+)‐menthol} have been designed and synthesized. The polymerizations of the monomers are effected by organorhodium catalysts, giving soluble polymers with moderate molecular weights in satisfactory yields. The structures and properties of the polymers have been characterized and evaluated with infrared, nuclear magnetic resonance, thermogravimetric analysis, circular dichroism, and ultraviolet analyses. All the polymers are thermally stable (≥300 °C) and show strong circular dichroism signals at ∼310 nm because of the helicity of the polyene backbone. The circular dichroism and ultraviolet absorptions of the polymers can be tuned with a solvent. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6190–6201, 2006
A bicyclic conjugated diene monomer, tetrahydroindene, for cationic polymerization and a novel alicyclic hydrocarbon polymer with heat resistance
Authors: Mizuno Naomi , Satoh Kotaro , Kamigaito Masami , Okamoto Yoshio
Published: September 2006

This study was directed toward the cationic polymerization of tetrahydroindene (i.e., bicyclo[4.3.0]‐2,9‐nonadiene), a bicyclic conjugated diene monomer, with a series of Lewis acids, especially focusing on the synthesis of high‐molecular‐weight polymers and subsequent hydrogenation for novel cycloolefin polymers with high service temperatures. EtAlCl2 or SnCl4 induced an efficient and quantitative cationic polymerization of tetrahydroindene to afford polymers with relatively high molecular weights (number‐average molecular weight > 20,000) and 1,4‐enchainment bicyclic main‐chain structures. The subsequent hydrogenation of the obtained poly(tetrahydroindene) with p‐toluenesulfonyl hydrazide resulted in a saturated alicyclic hydrocarbon polymer with a relatively high glass transition (glass‐transition temperature = 220 °C) and improved pyrolysis temperature (10% weight loss at 480 °C). The new diene monomer was randomly copolymerized with cyclopentadiene at various feed ratios in the presence of EtAlCl2 to give novel cycloolefin copolymers, which were subsequently hydrogenated into alicyclic copolymers with variable glass‐transition temperatures (70–220 °C). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6214–6225, 2006
Copolymerization of carbon dioxide and cyclohexene oxide with zinc/β‐ketoiminato complexes: Investigating the influence of the electron structure of zinc/β‐ketoiminato complexes on the catalytic activity and resultant copolymer properties
Authors: Liu Binyuan , Tian Chunying , Zhang Li , Yan Weidong , Zhang Wenjun
Published: September 2006

A series of LZnX zinc/β‐ketoiminato complexes [L = CH3C(OH)C(CH2CHCH2)C(CH3)NAr (L1), CH3C(OH)C(CH2CH2CN)C(CH3)NAr (L2), CH3C(OH)C(CH2C6H5)C(CH3)NAr (L3), or CH3C(OH)CHC(CH3)NAr (L4); Ar = 2,6‐iPr2C6H3; and initiation group X = alcoholate or acetate (for L1) or alcoholate (for L2–L4)] were synthesized, and their activities toward the copolymerization of carbon dioxide with cyclohexene oxide were determined. The 3‐position substituents on the β‐ketoiminato ligand backbone of the zinc/β‐ketoiminato complexes played an important role not only in the catalytic activity but also in the intrinsic viscosity, chemical composition, and refined microstructure of the resultant copolymers. The order of the catalytic activity of L1ZnX with different initiation groups (X = OMe, OiPr, or OAc) was L1Zn (OiPr) > L1Zn (OMe) > L1Zn (OAc), being the opposite of the order of the leaving ability of the initiation groups. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6243–6251, 2006
Michael addition polymerizations of difunctional amines (AA′) and triacrylamides (B3)
Authors: Wang Ding , Zheng Zhiju , Hong Chunyan , Liu Ye , Pan Caiyuan
Published: September 2006

Novel hyperbranched poly(amido amine)s containing tertiary amines on the backbones and acryl or secondary amines as the surface groups were successfully synthesized via the Michael addition polymerizations of a triacrylamide [1,3,5‐triacryloylhexahydro‐1,3,5‐triazine (TT)] and a difunctional amine [n‐butylamine (BA)] NMR techniques were used to clarify the structures of hyperbranched polymers and polymerization mechanism. The reactivity of the secondary amine formed in situ was much lower than that of the primary amines in BA. When the feed molar ratio was 1:1 TT/BA, the secondary amine formed in situ was almost kept out of the reaction before the BA (AA′) and TT (B3) monomers were consumed, and this led to the formation of A′B2 intermediates containing one secondary amine group and two acryl groups. The self‐polymerization of the A′B2 intermediates produced hyperbranched polymers bearing acryl as surface groups. For the polymerization with the feed molar ratio of 1:2 TT/BA, A′2B intermediates containing one acryl group and two secondary amine groups were accumulated until self‐polymerization started; the self‐polymerization of the intermediates formed hyperbranched polymers with secondary amines as their surface groups. Modifications of surface functional groups were studied to form new hyperbranched polymers. The hyperbranched poly(amido amine)s were amorphous. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6226–6242, 2006
Psychosocial registry for persons with cancer: a method of facilitating quality of life and symptom research
Authors: Daly Barbara J. , Douglas Sara L. , Foley Helen , Lipson Amy , Liou Chiou‐Fang [Emily] , Bowman Karen , Kwilosz Donna , Koroukian Siran , O'Toole Elizabeth , Smyth Kathleen , Townsend Aloen , VonGruenigen Vivian , Rose Julia
Published: September 2006

Research focused on the psychosocial aspects of the experience of persons with cancer and their family caregivers is hampered by the methodological challenges inherent in quality of life research. A data registry offers a potential solution to many of these problems in providing a large, comprehensive database, using standardized instruments. We report here our preliminary experience with establishing a Psychosocial Registry designed to advance research in the psychological, social, and spiritual aspects of quality of life of newly diagnosed cancer patients and their family caregivers. The first six months of enrollment demonstrated that the majority of newly diagnosed patients approached for consent (68%) and their primary family caregiver (92%) were willing to participate in the registry; of these, 80% also agreed to be contacted in the future for additional studies. Face‐to‐face interview was the preferred method of data collection. Our preliminary experience suggests that continuation of the registry with the current modest level of resources would generate a sample of approximately 1000 patients in three years. The long‐range goal is to establish a national psychosocial data registry that will enroll patients at diagnosis and follow them through the entire cancer experience, including end of life or survivorship. Copyright © 2006 John Wiley & Sons, Ltd.
Seeking informed consent to cancer clinical trials; evaluating the efficacy of doctor communication skills training
Authors: Brown R. F. , Butow P. N. , Boyle F. , Tattersall M. H. N.
Published: September 2006

Introduction: Clinical trials have come to be regarded as the gold standard for treatment evaluation. However, many doctors and their patients experience difficulties when discussing trial participation, leading to poor accrual to trials and questionable quality of informed consent. We have previously developed a communication skills training program based on a typology for ethical communication about Phase II and III clinical trials within four categories. The training program consisted of a 1 day experiential workshop that included didactic teaching, exemplary video and role play. The aim of this study was to evaluate the effectiveness of the communication skills training workshop.

Method: Oncologists were recruited from three major teaching hospitals conducting oncology outpatient clinics in three Australian capital cities. Ten oncologists and 90 of their adult cancer patients who were eligible for a Phase II or III clinical trial participated. Ninety informed consent consultations were audiotaped before (n = 59) and after (n = 31) training, and fully transcribed. The presence or absence of each domain component was coded and these were summed within categories. A coding manual was produced which enabled standardization of the coding procedure. Patients completed questionnaires before and after the consultation, and doctors completed a short measure of satisfaction after the consultation.

Results: Doctors increased their use of some aspects of shared decision‐making behavior (t87 = −1.945, p = 0.05) and described some aspects of essential ethical/clinical information more commonly. In addition they used less coercive behaviors (z = −1.976, p = 0.048). However, they did not provide more clinical information or structure their consultations in the recommended fashion. Patients in the post‐training cohort reported more positive attitudes to clinical trials, but other outcomes were not affected by the intervention.

Conclusions: This short training programme demonstrated limited success in improving the oncologist's communication skills when gaining informed consent. A larger randomized controlled trial of extended training is now underway. Copyright © 2006 John Wiley & Sons, Ltd.
Physicians are different when they learn communication skills: influence of the locus of control
Authors: Libert Yves , Merckaert Isabelle , Reynaert Christine , Delvaux Nicole , Marchal Serge , Etienne Anne‐Marie , Boniver Jacques , Klastersky Jean , Scalliet Pierre , Slachmuylder Jean‐Louis , Razavi Darius
Published: September 2006

Purpose: Although it is widely recognised that educational interventions may be more effective for people with an ‘internal’ Locus of Control (who believe that life outcomes are controlled by their own characteristics or actions) compared to people with an ‘external’ Locus of Control (who believe that life outcomes are controlled by external forces such as luck, fate or others), no study has yet assessed the influence of physicians' Locus of Control (LOC) on communication skills learning. This study aims to test the hypothesis that, in a communication skills training program, physicians with an ‘internal’ LOC would demonstrate communication skills acquisition to a greater degree than those with an ‘external’ LOC.

Methods: A non‐randomised longitudinal intervention study was conducted between January 1999 and April 2001. Sixty‐seven volunteer physicians from private and institutional practice in Belgium participated in a learner‐centred, skills‐focused, practice‐oriented communication skills training program. Communication skills changes were assessed in 2 standardised simulated interviews before and after training (one two‐person and one three‐person interview). Communication skills were assessed using the Cancer Research Campaign Workshop Evaluation Manual. Physicians' LOC was assessed using the Rotter I‐E scale. Communication skills changes of the upper and lower third of physicians in respect of their scores on this scale were compared using group by time repeated measures of variance.

Results: In the two‐person and three‐person interviews, changes in the use of open directive questions were more important among physicians with an “internal” LOC compared with changes observed among physicians with an ‘external’ LOC (P=0.066 and P=0.004, respectively). In the three‐person interview, changes in the use of directive questions, assessing functions and moderate feelings stated explicitly were more important among physicians with an ‘internal’ LOC compared with changes observed among physicians with an ‘external’ LOC (P= 0.001; P=0.002 and P=0.011 respectively).

Conclusion: This study shows that physicians' LOC is a psychological characteristic that could influence the efficacy of a communication skills training program. This evidence supports the idea that a psychological characteristic such as ‘internal’ LOC may facilitate communication skills acquisition through physicians' belief that communication with patients may be controlled by physicians themselves. Copyright © 2006 John Wiley & Sons, Ltd.
Multifaceted psychosocial intervention program for breast cancer patients after first recurrence: feasibility study
Authors: Akechi Tatsuo , Taniguchi Koji , Suzuki Shimako , Okamura Masako , Minami Hironobu , Okuyama Toru , Furukawa Toshiaki A. , Uchitomi Yosuke
Published: September 2006

We developed a novel multifaceted psychosocial intervention program which involves screening for psychological distress and comprehensive support including individually tailored psychotherapy and pharmacotherapy provided by mental health professionals. The purpose of the present study was to investigate the feasibility of the intervention program and its preliminary usefulness for reducing clinical psychological distress experienced by patients with recurrent breast cancer. The subjects who participated in the 3 months intervention program completed psychiatric diagnostic interview and several self‐reported measures regarding psychological distress, traumatic stress, and quality of life. The assessments were conducted before the intervention (T1), after the intervention (T2), and 3 months after the intervention (T3). A total of 50 patients participated in the study. The rates of participation in and adherence to the intervention program were 85 and 86%, respectively. While the proportion of psychiatric disorders at T2 (11.6%) was not significantly different from that at T1 (22.0%) (p = 0.15), the proportion of that at T3 (7.7%) had significantly decreased compared with that at T1 (p = 0.005). The novel intervention program is feasible, is a promising strategy for reducing clinically manifested psychological distress and further controlled studies are warranted. Copyright © 2006 John Wiley & Sons, Ltd.
Molecular and functional changes of pulmonary surfactant in response to hyperoxia
Authors: Dombrowsky Heike , Tschernig Thomas , Vieten Gertrud , Rau Gunnar A. , Ohler Florian , Acevedo Christa , Behrens Clemens , Poets Christian F. , von der Hardt Horst , Bernhard Wolfgang
Published: September 2006

Surfactant comprises phosphatidylcholine (PC) together with anionic phospholipids, neutral lipids, and surfactant proteins SP‐A to‐D. Its composition is highly specific, with dipalmitoyl‐PC, palmitoyl‐myristoyl‐PC, and palmitoyl‐palmitoleoyl‐PC as its predominant PC species, but with low polyunsaturated phospholipids. Changes in pulmonary metabolism and function in response to injuries depend on their duration and whether adaptation can occur. We examined in rats prolonged (7 days) versus acute (2 days) exposure to non‐lethal oxygen concentrations (85%) with respect to the composition and metabolism of individual lung phospholipid molecular species. Progressive inflammation, structural alteration, and involvement of type II pneumocytes were confirmed by augmented bromodeoxyuridine incorporation, broadening of alveolar septa, and increased granulocyte, macrophage, SP‐A, and SP‐D concentrations. Surfactant function was impaired after 2 days, but normalized with duration of hyperoxia, which was attributable to inhibition but not to alteration in SP‐B/C concentrations. Phospholipid pool sizes and PC synthesis by lung tissue, as assessed by [methyl‐3H]‐choline incorporation, were unchanged after 2 days, although after 7 days they were elevated 1.7‐fold. By contrast, incorporation of labeled PC into tissue pools of surfactant and lung lavage fluid decreased progressively. Moreover, concentrations of arachidonic acid containing phospholipids were augmented at the expense of saturated palmitoyl‐myristoyl‐PC and dipalmitoyl‐PC. We conclude a persisting impairment in the intracellular trafficking and secretion of newly synthesized PC, accompanied by a progressive increase in alveolar arachidonic acid containing phospholipids in spite of recovery of acutely impaired surfactant function and adaptive increase of overall PC synthesis. Pediatr Pulmonol. 2006, 41:1025–1039. © 2006 Wiley‐Liss, Inc.
A comparison of the prevalence of urinary incontinence in girls with cystic fibrosis, asthma, and healthy controls
Authors: Prasad S.A. , Balfour‐Lynn I.M. , Carr S.B. , Madge S.L.
Published: September 2006

Urinary incontinence (UI) is recognized as a significant problem in adult females with cystic fibrosis and can often have a marked impact on day‐to‐day activities. The prevalence and severity of UI in the pediatric cystic fibrosis (CF) female population is less clear and there are no comparative data with healthy children or children with other respiratory disorders. An anonymous self‐completed semi‐structured questionnaire was used to study the prevalence rates of UI in girls with CF aged between 11 and 17 and compared it to age‐matched asthmatic and healthy girls. The prevalence of UI in girls with CF was significantly higher (17/51, 33%) than the asthmatic (4/25, 16%) and healthy girls (2/27, 7%) (P = 0.02). It may manifest as early as 11 years of age and is associated with increasing lung disease. Surprisingly it is perceived as a relatively minor problem in terms of the distress it causes. Pediatric CF clinics should be routinely addressing UI as a potential problem in all girls from the age of 11 years. Pediatr Pulmonol. 2006, 41:1065–1068. © 2006 Wiley‐Liss, Inc.
Assessment of inhalation technique and determinants of incorrect performance among children with asthma
Authors: Walia Mandeep , Paul Lincy , Satyavani A. , Lodha Rakesh , Kalaivani Mani , Kabra S.K.
Published: September 2006

The objective of our study was to evaluate the pressurized metered dose inhaler (pMDI) with holding chamber technique of asthmatic children attending out patient pediatric chest clinic and determine factors associated with incorrect technique. All patients had previously received instructions regarding inhalation technique. The inhalation technique was assessed on a five‐point checklist, four of which were considered essential. Two hundred and thirteen children (mean ± SD age, 7.3 ± 3.8 years; 151 boys) completed the study. Children were using their inhaler for a median duration of 6 months (range 1–96 months). One hundred and eighty‐eight patients (88.3%) performed all essential steps correctly. The commonest mistake among the essential steps was not shaking the inhaler (n = 21, 9.9%) followed by inability to make a tight seal around the mouthpiece of the holding chamber (n = 12, 5.6%). Correct technique was not affected by gender, asthma severity and socio‐economic indices: education level of parents, percapita monthly income, rural or urban background. Our study indicates that a large majority of children from a developing country setting, irrespective of lower education and income levels can be successfully educated to appropriately use inhalation device. Inhalation performance is not affected by socio‐economic background of the patients. Comprehensive inhalation instructions and monitoring at each visit are however critical to ensure reliable and consistent performance of correct technique among asthmatic children. Pediatr Pulmonol. 2006, 41:1082–1087. © 2006 Wiley‐Liss, Inc.