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We have realized a quantum walk in momentum space with a rubidium spinor Bose-Einstein condensate by applying a periodic kicking potential as a walk operator and a resonant microwave pulse as a coin toss operator. The generated quantum walks appear to be stable for up to ten steps and then quickly transit to classical walks due to spontaneous emissions induced by laser beams of the walk operator. We investigate these quantum to classical walk transitions by introducing well controlled spontaneous emissions with an external light source during quantum walks. Our findings demonstrate a scheme to control the robustness of the quantum walks and can also be applied to other cold atom experiments involving spontaneous emissions.

In order to meet decarbonisation goals and implement a genuinely sustainable circular economy model, the chemical industry needs to transition from fossil to renewable sources of carbon. Current chemical production is dominated by petroleum where this largely uniform feedstock is separated using a q...

Jack Lewis was born and educated in Lancashire. He rose rapidly to become a highly renowned chemist who helped to pioneer the development of modern inorganic chemistry. He was one of the small group of scientists who led the expansion of inorganic chemistry from its renaissance, inspired by Professor Ron Nyholm in the mid 1950s, through the syntheses and study of new transition-metal and organometallic complexes. Their characterization was accomplished through the perceptive application of the newly available physical techniques of spectroscopy (electronic, vibrational and nuclear magnetic resonance), magnetism, mass spectrometry and X-ray diffraction. Jack completed his PhD at the University of Nottingham in 1952, and then held academic appointments in close succession at the University of Sheffield, Imperial College, London, and University College London (UCL) before being appointed Professor of Chemistry at the University of Manchester in early 1962. He returned to UCL as Professor of Chemistry for the period 1967–70 before being appointed the 1970 Professor of Chemistry at the University of Cambridge, a position that he held until 1995, when he was granted emeritus status. His dedication to the study and furtherance of inorganic chemistry was profound and his research achievements were made all the more remarkable when one considers his substantial additional high-profile responsibilities. In 1975 Jack became the first Warden of the newly established Robinson College in Cambridge, where he shaped and guided a progressive academic community until his retirement in 2001. Furthermore, his skill as a highly effective debater also took him, in 1989, to the House of Lords, where as a Life Peer he represented science with great enthusiasm and distinction until a few months before his death. He was a most effective chairman of the Royal Commission on Environmental Pollution from 1985 to 1992.

The 21st century will see fundamental changes in chemical manufacturing and chemical use worldwide. The growing appreciation that we cannot continue to use resources as though they were unlimited is a vital part of sustainability and must be recognized within green chemistry. The latest and more holistic green chemistry metrics for pharmaceutical processes accommodate this concern as one of the key impacts to take into consideration.

Jack Lewis was truly a Man for all Seasons. Prodigious energy combined with a deep understanding of his subject made Jack one of the true founding fathers of Modern Inorganic Chemistry. His contributions to a wide range of areas for over sixty years established him as one of the leading Chemists of his generation and this was recognised by awards from leading Scientific Societies throughout the World.

Two-channel tunable white lighting (TWL) systems represent the next wave of solid-state lighting (SSL) systems and promise flexibility in light environment while maintaining the high reliability and luminous efficacy expected with SSL devices. TWL systems utilize LED assemblies consisting of two different LED spectra (i.e., often a warm white assembly and a cool white assembly) that are integrated into modules. While these systems provide the ability to adjust the lighting spectrum to match the physiology needs of the task at hand, they also are a potentially more complex lighting system from a performance and reliability perspective. We report an initial study on the reliability performance of such lighting systems including an examination of the lumen maintenance and chromaticity stability of warm white and cool white LED assemblies and the multi-channel driver that provides power to the assemblies. Accelerated stress tests including operational bake tests conducted at 75°C and 95°C were used to age the LED modules, while more aggressive temperature and humidity tests were used for the drivers in this study. Small differences in the performance between the two LED assemblies were found and can be attributed to the different phosphor chemistries. The lumen maintenances of both LED assemblies were excellent. The warm white LED assemblies were found to shift slightly in the green color direction over time while the cool white LED assemblies shifted slightly in the yellow color direction. The net result of these chromaticity shifts is a small, barely perceptible reduction in the tuning range after 6,000 hours of exposure to an accelerating elevated temperature of 75°C.

The next wave of LED lighting technology is likely to be tunable white lighting (TWL) devices which can adjust the colour of the emitted light between warm white (∼ 2700 K) and cool white (∼ 6500 K). This type of lighting system uses LED assemblies of two or more colours each controlled by separate driver channels that independently adjust the current levels to achieve the desired lighting colour. Drivers used in TWL devices are inherently more complex than those found in simple SSL devices, due to the number of electrical components in the driver required to achieve this level of control. The reliability of such lighting systems can only be studied using accelerated stress tests (AST) that accelerate the aging process to time frames that can be accommodated in laboratory testing. This paper describes AST methods and findings developed from AST data that provide insights into the lifetime of the main components of one-channel and multi-channel LED devices. The use of AST protocols to confirm product reliability is necessary to ensure that the technology can meet the performance and lifetime requirements of the intended application.

A pastel painting considered to have been painted by renowned Russian artist Natalia Goncharova in c. 1913 has been shown by Raman microscopy of the pigments to have been painted after 1952, with the identification of dioxazine violet. The implications of this discovery are discussed. This result highlights the need for reliable and perceptive dating procedures for valuation purposes.

High-throughput continuous hydrothermal flow synthesis was used to manufacture 66 unique nanostructured oxide samples in the Ce-Zr-Y-O system. This synthesis approach resulted in a significant increase in throughput compared to that of conventional batch or continuous hydrothermal synthesis methods. The as-prepared library samples were placed into a wellplate for both automated high-throughput powder X-ray diffraction and Raman spectroscopy data collection, which allowed comprehensive structural characterization and phase mapping. The data suggested that a continuous cubic-like phase field connects all three Ce-Zr-O, Ce-Y-O, and Y-Zr-O binary systems together with a smooth and steady transition between the structures of neighboring compositions. The continuous hydrothermal process led to as-prepared crystallite sizes in the range of 2-7 nm (as determined by using the Scherrer equation).

The key contributions of the four great Nobel Laureates - Lord Rayleigh, Sir William Ramsay, Lord Rutherford and Sir Chandrasekhara Raman - to the understanding of light scattering, to the identification and classification of the rare gases, and to the discovery in 1928 of the Raman effect are outlined. The interactions between these scientists are explored, in particular those of Rayleigh with Ramsay (in establishing the physics and chemistry of the rare gases), Ramsay with Rutherford (on studies of the radioactivity of radium dibromide and on the discovery of radon and its position in the periodic table), and Rutherford with Raman (in supporting Raman's career via the Royal Society and as a nominee for the Nobel Prize). The resilience and dedication of these scientific pioneers is emphasised, noting in particular that Rutherford and Raman emerged with success from unlikely backgrounds and from countries far removed from the then centres of scientific excellence. Key developments from 1928 onwards in the light sources used for the excitation of Raman spectra and in the detectors of Raman scattered radiation are outlined. Attention is drawn to the mounting number of scientific areas which continue to be opened up by Raman microscopy and many other derived techniques such as SERS, TERS, etc.

Non-destructive pigment analysis by Raman microscopy (RM) and portable X-ray fluorescence (pXRF) has been carried out on some Bolognese illuminations and cuttings chosen to represent the beginnings, evolution and height of Bolognese illuminated manuscript production. Dating to the thirteenth and fourteenth centuries and held in a private collection, the study provides evidence for the pigments generally used in this period. The results, which are compared with those obtained for other north Italian artwork, show the developments in usage of artistic materials and technique. Also addressed in this study is an examination of the respective roles of RM and pXRF analysis in this area of technical art history. This article is part of the themed issue ‘Raman spectroscopy in art and archaeology’.

The arc discharge method has been used hitherto to encapsulate metal-containing structures within carbon nanotubes 1 , 2 , the arrangement of the nanotube walls playing an important role in the process. We show that KCl can be generated in the space between nanotube walls by treating potassium-intercalated uncapped tubes with CCl4. A relationship between the KCl crystal domain and the hexagonal carbon network is thought to give rise to preferential formation of a 100 plane perpendicular to the tube axes.

Novel W–Nb–S composite inorganic nanotubes have been generated by replacing W in the S–W–S sandwich layers of WS2 by Nb. The tubes are uniform, with the Nb concentration 10 atom%. Raman spectral features of the tubes are described.

Two remarkable men, Ernest Rutherford in New Zealand and Chandrasekhara Raman in India, had very demanding early backgrounds from which most would fail to emerge with distinction. Yet, each rose to the top in science, Rutherford being awarded the Nobel Prize in Chemistry in 1908 and Raman the Nobel Prize in Physics in 1930. Their fascinating lives overlapped in interesting ways. There were many hurdles that each needed to overcome, mainly due to the early lack of both finance and good research facilities, and each required fortitude, resilience, industry and insight. The careers of both scientists should be an inspiration to today's students. Copyright © 2011 John Wiley & Sons, Ltd.

A sample of archaeological iron slag from Northern Zimbabwe was characterised by Raman microscopy (RM) and electron beam analysis (EBA). The phases identified in a slag found at an ironmaking site not only reflect the chemical composition of the slag but can also provide crucial information regarding the reconstruction and interpretation of the metallurgical operations, such as the prevailing redox conditions in a furnace at the time of cooling. Free iron oxides, such as haematite, magnetite and wustite, are important indicators of these redox conditions. But while classical techniques of phase identification can be used to identify the different iron oxides, they cannot distinguish between dissimilar oxidation states due to their non-stoichiometric nature, and also the effect of substituting elements in iron oxides. RM proved invaluable in both respects. By combining the results provided by RM and EBA, it was possible to identify (1) the free iron oxides, haematite and magnetite in the original ore, and magnetite and wustite in the slag, (2) oxidised magnetite and wustite, characterized by a shift to higher wavenumbers of their intense characteristic Raman bands and (3) Al3+-substituted magnetite and a solid solution between magnetite and hercynite (FeAl2O4). This pilot study aims to develop a model that enables close identification of the redox conditions by analysing the free iron oxides from a variety of smelting processes. It is hoped that this will provide an independent and quantifiable criterion to distinguish smithing slags (more oxidising) from smelting slags (more reducing), and to understand better the actual smelting process that transforms highly oxidised iron ore to fully reduced iron metal.

High-throughput continuous hydrothermal flow synthesis has been used as a rapid and efficient synthetic route to produce a range of crystalline nanopowders in the Ce–Zn oxide binary system. High-resolution powder X-ray diffraction data were obtained for both as-prepared and heat-treated (850°C for 10 h in air) samples using the new robotic beamline I11, located at Diamond Light Source. The influence of the sample composition on the crystal structure and on the optical and physical properties was studied. All the nanomaterials were characterized using Raman spectroscopy, UV–visible spectrophotometry, Brunauer–Emmett–Teller surface area and elemental analysis (via energy-dispersive X-ray spectroscopy). Initially, for ‘as-prepared’ Ce 1− x Zn x O y , a phase-pure cerium oxide (fluorite) structure was obtained for nominal values of x =0.1 and 0.2. Biphasic mixtures were obtained for nominal values of x in the range of 0.3–0.9 (inclusive). High-resolution transmission electron microscopy images revealed that the phase-pure nano-CeO 2 ( x =0) consisted of ca 3.7 nm well-defined nanoparticles. The nanomaterials produced herein generally had high surface areas (greater than 150 m 2 g −1 ) and possessed combinations of particle properties (e.g. bandgap, crystallinity, size, etc.) that were unobtainable or difficult to achieve by other more conventional synthetic methods.

Raman microscopy has been used to identify the pigments decorating three valuable items owned by the Worshipful Company of Barbers (established in 1308 in London), one being a large leather screen dating to before 1712, the other two being illuminated title pages of books of ordinances of the Company dating to 1605 and 1658. Pigments which could not be fully characterised by this technique (particularly the green paints) have also been subject to XRF or SEM–EDX analysis. The combined analytical approach has shown that the pigments identified on all three items are typical of those in use as artists’ pigments in the 17th C and include azurite, indigo, vermilion, red lead, pink and yellow lakes, verdigris, lead white, calcite (and chalk), gypsum, carbon-based black, and gold and silver leaf. However in the case of the screen alone, restoration in the 1980s has been carried out with different pigments – haematite, phthalocyanine green, rutile, and a mixture of azurite, malachite and barium sulfate. This work constitutes the first in-depth study of painted leatherwork and demonstrates that the palette used for this purpose is similar to that used on other works of art of the same date. It has also allowed the original colour schemes of the decorations to be determined where pigment degradation has occurred. The combined analysis has also provided a more complete understanding of the materials used for, or on, objects to which access is limited.

Italian medieval and Renaissance manuscript cuttings and miniatures from the Victoria and Albert Museum were analyzed by Raman microscopy to compile a database of pigments used in different periods and different Italian regions. The palette identified in most manuscripts and cuttings was found to include lead white, gypsum, azurite, lazurite, indigo, malachite, vermilion, red lead, lead tin yellow (I), goethite, carbon, and iron gall ink. A few of the miniatures, such as the historiated capital “M” painted by Gerolamo da Cremona and the Petrarca manuscript by Bartolomeo Sanvito, are of exceptional quality and were analyzed extensively; some contained unusual materials. The widespread usage of iron oxides such as goethite and hematite as minor components of mixtures with azurite is particularly notable. The use of a needle-shaped form of iron gall ink as a pigment rather than a writing material was established by both Raman microscopy and x-ray fluorescence spectroscopy for the Madonna and Child by Franco de’ Russi.

A novel and rapid and continuous hydrothermal route to the synthesis of extensive ultra-thin 2D sodium titanate (Na(2)Ti(3)O(7)) nano-sheets using a superheated water flow at 450 degrees C and 24.1 MPa as a crystallizing medium is described. High resolution electron microscopy of the sheets revealed that they were a few layers thick and largely uncurled, highly crystalline despite their very short time under hydrothermal flow conditions. The sodium titanate sheets possessed excellent photocatalytic activity for decolourisation of methylene blue dye.

TiO2 doped with various loadings of nitrogen was prepared by nitridation of a nano-TiO2 powder in an ammonia/argon atmosphere at a range of temperatures from 400 to 1100 °C. The nano-TiO2 starting powder was produced in a continuous hydrothermal flow synthesis (CHFS) process involving reaction between a flow of supercritical water and an aqueous solution of a titanium salt. The structures of the resulting nanocatalysts were investigated using powder X-ray diffraction (XRD) and Raman spectroscopy. Products ranging from N-doped anatase TiO2 to phase-pure titanium nitride (TiN) were obtained depending on post-synthesis heat-treatment temperature. The results suggest that TiN started forming when the TiO2 was heat-treated at 800 °C, and that pure phase TiN was obtained at 1000 °C after 5 h nitridation. The amounts and nature of the Ti, O and N at the surface were determined by X-ray photoelectron spectroscopy (XPS). A shift of the band-gap to lower energy and increasing absorption in the visible light region, were observed by increasing the heat-treatment temperature from 400 to 700 °C.

Five miniatures by the so-called ‘Spanish Forger’ were acquired by the Victoria and Albert Museum in 2008. Believed to be authentic medieval miniatures until the mid-twentieth century, they are now considered to have been painted around the end of the nineteenth and the beginning of the twentieth century. To investigate this attribution and to gather detailed knowledge about the materials used by the artist, a comprehensive pigment analysis by Raman microscopy and X-ray fluorescence was carried out. Although traditional materials such as vermilion, carbon black, red lead, lead white and indigo were identified, many others (chrome yellow, Scheele's green, emerald green and ultramarine blue) are modern and synthetic pigments, a result which provides a firm scientific basis for stating that the miniatures are forgeries. Copyright © 2009 John Wiley & Sons, Ltd.

Metallic bismuth, pyrite (FeS2), and specular hematite (Fe2O3) were found to have been used extensively on two miniatures taken from the Book of Hours of Louis XII by Jean Bourdichon, painter at the Royal Court of France between the end of the 15th and the beginning of the 16th centuries. These unusual materials were identified, together with thirteen other more traditional pigments and dyes, by Raman microscopy and X-ray fluorescence. Pyrite was found in many areas, suggesting that it may have been deliberately added as a pigment. The luminary quality of both miniatures was enhanced by the extensive use of shell gold throughout, but other less common materials such as specular hematite and mosaic gold were also utilized. Metallic bismuth was used, alone or in admixture with other pigments, to create a soft gray color. Its identification as a paint material was complemented by the study of the optical and visual properties of standard samples of metallic bismuth and several bismuth compounds. Evidence for the use of a bismuth pencil was also found.

Nanosized TiO2 powder of high surface area was prepared from an aqueous solution of titanium(IV) bis(ammonium lactato) dihydroxide using a continuous hydrothermal flow synthesis (CHFS) reactor which uses superheated water at 400 degrees C and 24.1 MPa as a crystallizing medium. Freeze-dried nano-TiO2 was heat-treated in air over a range of temperatures and then the resulting powders were characterized using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), BET surface area measurement, and Raman spectroscopy. The particle size of the 'as-prepared' TiO2 made using CHFS was ca. 4.8 nm (by HR-TEM), and grew with increasing heat-treatment temperature. It was found that the onset of the anatase-rutile transition of heat-treated nano-TiO2 in air occurred at 500 degrees C and reached 100% rutile at 900 degrees C. The Raman band (E-g) at similar to 150 cm(-1) of anatase (nano-TiO2) softens as the particle size increases with heat-treatment temperature (up to 600 degrees C). The photocatalytic activity of the TiO2 powders for the decolourisation of methylene blue dye was assessed. The effects of nano-TiO2 anatase-rutile phase composition, crystallinity, and crystallite size on the catalytic activity were investigated. (C) 2008 Elsevier B.V. All rights reserved.

SUMMARY Extension is a method of education for farm people who are already operating farm businesses. Farm management extension is the teaching of the facts and concepts of business management. Interest must be created in a subject so that an extension programme may be planned. Economic conditions now make it more important for farmers to consider the business concepts of farming and thus create interest in farm management. Farm account book studies, survey studies and enterprise studies help to provide a basis for continuing this interest. Farm extension workers must have both the basic facts of operation of the farms in their area and the basic input-output data in order to indicate the way of profit maximization of farms and enterprises of the area. The facts can be obtained from farm account book studies, cost studies and special enterprise survey studies. Input-output data can be provided by studies which include all relevant physical facts of production, by other studies designed to obtain factor-product curves and by controlled experiments carried on in co-operation with technical agricultural research workers. Price outlook information and other special information on particular phases of the management of the farm which may affect management decisions are also needed by the extension workers. Farm management extension workers teach decision-making. Research work which provides simple methods of evaluating the present farm business position and of budgeting for profit maximization are useful in teaching this subject. Linear programming provides a method of evaluating budgets and is useful for establishing standards, but the presentation should be simple and recommendations should also be based on the experience of the extension worker.

Fermentation of livestock manure for the production of biogas is not economically viable given current and prospective energy prices, as long as the residue from the fermentation process is used on agricultural land as a source of crop nutrients. An alternative use of the residue is to separate out the solid fraction for use as a source of protein and minerals for livestock. This alternative was evaluated for a commercial beef feedlot in Ontario, and was found to provide attractive returns using feed replacement values for the residue solids, even when a zero value was attributed to the biogas, and when real interest rates reached 7 percent. Economies of size were also found.

The non-figurative illumination in five Islamic religious manuscripts of the 16th to 18th centuries held in the National Art Library (NAL) at the Victoria and Albert Museum were analysed by Raman microscopy (RM) and X-ray fluorescence (XRF) to determine the pigments used in each case and to establish whether the range of pigments evolved with time. The pigments identified include lazurite, red lead, vermilion, orpiment and a carbon-based black, which were found on all five manuscripts without exception, as well as lead white, malachite, atacamite, haematite, pararealgar, indigo and Prussian blue, which were found on a more limited number of manuscripts. The presence of gold-based gilding was also established. This range of pigments differs in only a few respects from those already established for Islamic secular manuscripts of the same period. We may conclude that the range of pigments remained stable during the 16th and 17th centuries and began to expand in the 18th century through the introduction of synthetic pigments. On a 16th-century manuscript analysed in this study, the intermediate phase formed by the light-induced degradation of realgar into pararealgar was also identified. Copyright © 2008 John Wiley & Sons, Ltd.

In an attempt to validate the Vinland Map as a genuine 15th century work, Garman Harbottle (2008) claims to review critically, and thereby discredit, the archaeometric research undertaken on the Map's ink by Walter McCrone (1974-1999) and Brown and Clark (2002). In this paper we outline and discuss the numerous arguments that are presented by Harbottle, all of which we find to be misleading or at best highly questionable.

Scanning electron microscopy/energy dispersive X-ray analysis has earlier shown that the white background layer (slip) on painted pottery sherds (Yangshao culture, Henan, China, 4200 BC) is composed of kaolinitic clay containing titanium in the assumed form of TiO 2 at just 1 wt%. The same samples of white slip have now been studied by Raman microscopy, revealing bands characteristic of anatase, but none from the majority species, the matrix of kaolinitic clay. These results highlight the extraordinarily intense Raman scattering from even trace amounts of anatase and thus the need to recognise that, although the colours of archaeological artefacts are almost always determined by the nature of the matrix, the Raman spectrum may be determined by a highly scattering trace component such as anatase. The significance of anatase as a potential date-marker pigment on works of art and archaeological artefacts is discussed.

The impact of Raman microscopy on the study of artwork and archaeological artefacts is outlined. Important recent case studies are presented to illustrate the power of the technique to answer – either alone or in conjunction with other techniques – key questions of great art historical, conservational, cultural, archaeological and scientific interest. Raman microscopy also offers, via pigment identification, the possibility of testing the attribution of artwork, a matter which should be of great concern to galleries, auction houses and museums.

Six ninth-century stucco fragments from Samarra, Iraq, and now part of the Victoria and Albert Museum collections, were analysed non-destructively and in situ in the Museum by Raman microscopy in order to determine the identities of the pigments thereon. Carbon black, haematite, gypsum, indigo, lazurite, lead white, orpiment, pararealgar, red lead, vermilion and the As 4 S 4 χ-phase were detected. The detection of several arsenic-containing pigments (orpiment, pararealgar and the As 4 S 4 χ-phase), known to be poisonous and carcinogenic, has prompted strict health and safety protocols to be used when the objects are handled by museum staff or displayed in the galleries. This scientific study is the first to be carried out on any of the Samarra finds.

The enormous strides that have been made at the Arts/Science interface by the meticulous application of Raman microscopy to the study of artwork and archaeological artefacts are outlined. Important recent case studies are presented to illustrate the power of the technique to answer key questions of great art historical, conservational, cultural, restorational, archaeological and scientific interest.

T.P. Quinn, D.M. Eggers, J.H. Clark, and H.B. Rich, Jr. Abstract: In 2004 and 2005, exceptionally large runs of sockeye salmon (Oncorhynchus nerka) to the Alagnak River system in Bristol Bay, Alaska, coincided with weak runs to the nearby Kvichak River system. Restricted fishing to pro- tect the Kvichak populations resulted in densities on the Alagnak River system's spawning grounds that were 11.5-fold (in 2004) and 9.0-fold (in 2005) above the long-term (1956-2003) average. Carcass sampling indicated that 23% (2004) and 44% (2005) of the potential egg deposition was lost to prespawning mortality or incomplete spawning in the Alagnak populations. Much lower levels of egg retentions were observed in spawning populations in the Kvichak River and Wood River systems, where the runs did not appreciably exceed the escapement goals, indicating that density-dependent spawning failure may have occurred. However, in 2005, significantly higher egg retention rates were observed in the Alagnak River system despite slightly lower densities than in 2004, indicating that environmental pro- cesses (probably low river levels and high temperatures) influenced prespawning mortality as well. More limited sam- pling in 2006 revealed only 3% egg retention in one of the Alagnak populations, but the combination of lower density and cooler conditions did not allow us to determine the relative contributions of these two factors to spawning failure.

Twenty-three paintings by Henrique Pousao—a 19th century Portuguese painter—belonging to the collection of Museu Nacional Soares dos Reis, Porto, Portugal, were analysed by Raman microscopy. The fine focus of a 100× objective allowed the visualisation and individual identification of small grains. As a result, thirty-seven compounds, namely, anatase, barium white, basic lead sulfate, brochantite, cadmium red, cadmium yellow, calcium carbonate, carbon-based black, celadonite, chrome green, chrome orange, chrome yellow, cobalt blue, cochineal lake, copper sulfide, emerald green, iron(III) oxyhydroxide, iron(III) oxide, kaolinite, lead antimonate yellow, lead carbonate, lead white, lead sulfate, madder lake, malachite, Prussian blue, quartz, realgar/pararealgar, red lead, rutile, Scheele's green, strontium yellow, ultramarine blue, vermilion, viridian, zinc white and zinc yellow, were identified. Not all these compounds are pigments; some are extenders, others trace components and others probably products of reactions between pigments. Special attention was given to the Raman characterisation of celadonite, chrome orange, basic lead sulfate and lead antimonate yellow. Complementary techniques were used to confirm the identities of certain pigments and to characterise reference samples. Pousao, whose work has not previously been studied spectroscopically, was found to have used a remarkably wide range of pigments over his painting periods, without showing significant preference for any particular set of pigments. Copyright © 2007 John Wiley & Sons, Ltd.

The present study examined the association between guideline-derived asthma control and health-related quality of life, assessed using the Asthma Quality of Life Questionnaire (AQLQ), in patients with uncontrolled asthma whose treatment was directed towards achieving the highest possible level of control. The present randomised, double-blind, parallel-group study compared the efficacy of fluticasone propionate (FP) and salmeterol/fluticasone propionate combination (SFC) in achieving two composite, guideline-derived measures of control: total control (TC) and well-controlled (WC) asthma. Not achieving these levels was classed as not well-controlled (NWC). Doses were augmented until patients achieved TC or reached the maximum dose. This dose was maintained for the remainder of the study. AQLQ was assessed at baseline and at each clinic visit. AQLQ scores improved throughout the study, reaching near-maximal levels in patients achieving TC and WC, and 52-week mean scores in the three control groups were statistically significantly different. Clinically meaningful improvements (mean change from baseline) were: TC group (SFC 1.9, FP 1.8), WC (SFC 1.5, FP 1.5) and NWC (SFC 1.0, FP 0.9). In conclusion, the treatment aimed at controlling asthma improves the health-related quality of life to levels approaching normal. The difference in Asthma Quality of Life Questionnaire scores between total control and well-controlled confirms that patients distinguish even between these high levels of control.

The present authors explored the relationship between asthma control status, as measured by a derived Asthma Control TestTM (ACT) score, and the utilisation and cost of healthcare in Europe. Data were derived from a European survey of asthma patients. Frequency of healthcare resource use was identified from the dataset and per-patient mean cost of asthma management estimated. Drug costs were not available. The ACT score was derived from questions in the survey identical or similar to the items comprising the ACT. An ACT score was derived for 2,268 patients, of whom 48% (1,078) scored

The binding and functional properties of adenosine receptor ligands were compared in Chinese hamster ovary cells transfected with human adenosine A(3) receptors. Inhibition of [(125)I]-aminobenzyl-5'-N-methylcarboamidoadenosine ([(125)I]-AB-MECA) binding by adenosine receptor ligands was examined in membrane preparations. Inhibition of forskolin-induced cAMP accumulation by agonists was measured using a cAMP enzyme immunoassay. The rank order of agonist potency for both assays was N(6)-(3-iodobenzyl)-adenosine-5'-N-methyluronamide (IB-MECA) > 5'-N-ethylcarboxamidoadenosine (NECA) > (-)-N(6)-[(R)-phenylisopropyl] adenosine (R-PIA) > 4-aminobenzyl-5'-N-methylcarboxamidoadenosine (AB-MECA) > N(6)-cyclopentyl adenosine (CPA) > adenosine. The radioligand binding rank order of antagonist potency was N-[9-chloro-2-(2-furanyl)[1,2,4]-triazolo[1,5-c]quinazolin-5-benzeneacetamide (MRS1220) > 1,3-dipropyl-8-cyclopentylxanthine (DPCPX) > 8-phenyltheophylline (8-PT) > 8-(p-sulfophenyl)-theophylline (8-SPT). MRS1220 competitively inhibited the effect of IB-MECA on cAMP production, with a K(B) value of 0.35 nm. These data are characteristic of adenosine A(3) receptors. The absence of Mg(2+) and presence of guanosine 5'-(gamma-thio)triphosphate (GTPgammaS) significantly reduced agonist binding inhibition potency, indicating binding to high- and low-affinity states. The IB-MECA, NECA and R-PIA IC(50) values were greater for the cAMP assay than for radioligand binding, suggesting an efficient stimulus-response transduction pathway.

Ten archaeological Punic make-up samples from Tunisia dating from the 4th to the 1st centuries BC were analysed by several techniques including Raman microscopy and synchrotron X-ray diffraction in order to determine their compositions. Eight samples were red and found to contain either quartz and cinnabar or quartz and haematite. The remaining two samples were pink, the main diffracting phase in them being quartz. Examination of these two samples by optical microscopy and by illumination under a UV lamp suggest that the pink dye is madder. These findings reveal the identities of the materials used by Carthaginians for cosmetic and/or ritual make-up purposes.

The Arabic treatise ‘Kitāb Gharā’ib al-funūn wa-mulaḩ al-‘uyūn’ (‘The Book of Curiosities…’), which contains a series of important early maps and celestial diagrams has recently been acquired by The Bodleian Library. Previous examination of the text and paper has led to the suggestion that the manuscript is an early thirteenth-century copy of a treatise compiled in the late eleventh century in Egypt. The pigments and inks used for the illustrations on 11 folios selected from the treatise have been analysed using Raman spectroscopy in order to determine their compositions; SEM-EDX analysis has been used to help identify one of the green pigments as a copper-based pigment. The combined analysis shows that the palette is relatively small in comparison with the wide range of colours observable, and consists almost exclusively of cinnabar (or its synthetic equivalent, vermilion), orpiment, lazurite, indigo, a carbon-based black, basic lead carbonate (‘lead white’) and a copper-based green pigment, possibly a form of verdigris (found in only one of the maps). The only comparable study (but by diffuse reflectance spectroscopy) of Arabic material was that of 17 Arabic manuscripts from the eighth to the fifteenth century at the Bibliotheque nationale de France; that study revealed a rather different range palette, which commonly included minium (red lead), copper green and azurite, and mostly excluded indigo. However, 14 of the French manuscripts in the study were Qurans, and therefore not strictly comparable with the Bodleian manuscript, which is from a secular tradition. One of the three secular manuscripts in the French study, a thirteenth-century north African treatise (manuscript BN Arabe 2221), did have a remarkably similar palette to that of the Bodleian manuscript. This is a very small sample base from which to draw substantial conclusions, but the analysis of ‘The Book of Curiosities’ forms a valuable starting point on which to build our knowledge of the production of Arab manuscripts from this location and date. Copyright © 2006 John Wiley & Sons, Ltd.

A Persian book of poetry—a poetic history of Shah Isma'il—by Mirza Kasim, dating to A.D. 1541, has been studied by Raman microscopy in order to explore the palette used at this time in Persia. The palette was found to include lazurite, indigo, red lead, vermilion, haematite, carbon black, orpiment, lead white and gold. The palette thus differs from that of another contemporary book of Persian poetry, most notably by the inclusion of indigo, and from that of a 1537–1538 Persian codex by the use of an intimate orpiment/indigo mixture for green rather than the copper-based mineral malachite. The palette also differs in a few respects from that of a Persian Herati manuscript of A.D. 1530 in that the latter uses an intimate mixture of orpiment and lazurite for green and does not include either haematite or indigo. Copyright © 2006 John Wiley & Sons, Ltd.

The Raman spectra of nine variants of ‘verdigris’ (organo-copper complexes) synthesized recently by different methods have been measured at room temperature and at 150 K. The spectra are all characterized by a strong band at ca 2935 cm−1 and weaker bands at 3010, 2985, 2935, 1550, 1445, 1415, 1350 and 940 cm−1 at both temperatures; the majority of spectra also feature bands at 220 and 140 cm−1. The features in the 3000–4000 cm−1 and 900–50 cm−1 regions of the spectra show the greatest differences from sample to sample: those in the high wavenumber region relate directly to the nature of the hydrogen bonding in each sample, while those in the lower region reflect the variations in the Cu–O bonding and crystal structures of each sample. The characteristic bands present in the 900–3000 cm−1 region are sufficient for the identification of a sample as a particular form of verdigris. Copyright © 2006 John Wiley & Sons, Ltd.

The Raman spectrum of natural PbS has been shown to exhibit features related to the IR-active (Raman forbidden) LO phonons and to allowed scattering by two phonons. In order to confirm the vibrational nature of these features, and their peculiar temperature dependence, we compare here the spectra obtained for natural samples (i.e. mineral as well as synthetic with the natural isotopic abundance) with those measured for crystals prepared from highly enriched 34 S. The observed isotopic shifts confirm the vibrational nature of the structures mentioned above. We have also measured the spectra of synthetic samples of PbS annealed at several different pressures of sulphur. Because of their non-stoichiometric sulphur content they have carrier concentrations (either electrons or holes) in the 1×10 17 –3×10 18 carriers/cm 3 range (as determined from their IR reflection spectra). The measured spectra, as well as their temperature dependence, do not depend on the bulk carrier concentration, a fact that must result from surface pinning of the Fermi level within the fundamental energy gap. We finally discuss the apparent paradox of why the IR spectra reveal coupled LO-phonon–plasmon modes whereas the Raman spectra exhibit the bare LO-phonons.

The pigments identified on four beautiful icons painted by Constantin Ieromonachou during the late 17th century in churches of the medieval city of Voskopoja (Moschopolis) in south-east Albania have been identified. The analysis was carried out to establish whether the same pigments were used on all the icons and whether this information could form a basis for future restorations. Total reflection X-ray fluorescence (TXRF) and Raman microscopy (RM) were both used to identify the pigments and the combination of techniques minimised the number and amount of samples which needed to be taken from each icon for the analyses. The main pigments identified were white lead, carbon black, indigo, gold, red ochre, red lead, ochre, gypsum, vermilion and a copper-based green.

Raman and infrared microscopy have been used to characterise the black pigments on prehistoric Southwest American black-on-white pottery. Conclusive spectroscopic evidence for the use of carbon-based paints on these sherds has been provided using the Raman technique. Maghaemite (γ-Fe 2 O 3 ) and magnetite (Fe 3 O 4 ), found alternatively or mixed with a carbonaceous pigment, were also identified on some sherds. Infrared measurements indicated that little, if any, organic material from biogenic precursors of the black pigment or from pigment binding agents remained in the paints. These spectroscopic results were obtained rapidly and non-destructively on unprepared samples, and the resulting data complement, and in some instances correct, paint type conclusions drawn from studies involving techniques such as XRD, SEM-EDX, and XPS.

A series of compounds of the form [M(2)L(4)] and [[((t)()BuCO(2))(3)M(2)](2)(mu-L')] have been made where M = Mo or W, L = a thienyl, bithienyl, or terthienyl carboxylate, and L' = a corresponding thienyl dicarboxylate. The electronic absorption spectra are reported and the electronic structures discussed. Intense metal-to-ligand charge transfer bands traverse the visible and near-IR regions of the electronic absorption spectrum. The compounds show reversible metal-based oxidations and quasireversible ligand-based reductions. The molecular structure of Mo(2)(O(2)C-2-Th)(4).2THF is reported, on the basis of a single crystal X-ray diffraction study. These compounds provide insight into the expected properties of related dimetalated polythiophenes incorporating MM quadruple bonds.

A detailed investigation of iron oxide inclusions in a 19th century Russian platinum coin is presented. Such coins represent the products of the first industrial-scale purification of platinum metal. The processed metal is far from pure, however, and two types of iron oxide inclusions are identified by electron microprobe and Raman microscopy. The results show that the inclusions mainly consist of magnetite and haematite. The Raman band of magnetite at 668 cm −1 was found to shift to about 680 cm −1 with an increase in the average oxidation state of the iron. It is concluded that the iron oxides are formed during the heating of the platinum metal powder in the manufacturing process.

Improvements in the instrumentation for dispersive and interferometric Fourier transform (FT) Raman microscopy have overcome many of the earlier limitations of these techniques, thus opening the way for their widespread and routine utilisation in archaeometry laboratories. The use of Raman spectroscopy for identifying and studying archaeological materials has flourished in recent years, but the resulting articles have seldom been published in the archaeology literature, thus limiting their impact on the field. Therefore, this article covers concisely the theory and instrumentation of Raman microscopy and then comprehensively reviews the many applications of this technique in archaeometric research. The significant advances made in archaeological science through the use of Raman microscopy are highlighted, but many areas requiring further research, such as the generation of more extensive and reliable spectral libraries and the surmounting of obstacles in the analysis of certain classes of historical materials, are also revealed.

An extremely rare used 1847 1d orange–red Mauritian stamp, a rare 1847 2d deep blue unused stamp, a 1913 reproduction 2d stamp, early forgeries and 1858–1862 Britannia-type Mauritian stamps were analysed using Raman microscopy in order to determine the identities of the pigments on the stamps. That in the printing ink of the 1d stamp was identified to be lead(II,IV) oxide (‘red lead’), with a cancel mark composed of carbon-based black. Prussian blue was identified as having been used in the genuine and reproduction 2d issues, these being distinguished only by the presence of crystals of ultramarine blue dispersed between the paper fibres of the genuine issues. The 4d green Britannia-type stamp is pigmented with ‘chrome green’, a mixture of Prussian blue and chrome yellow, and the 6d ‘vermilion’ Britannia-type stamp is pigmented with vermilion. Raman microscopy was shown to be a rapid, highly specific and non-destructive technique for the expertising of stamps whose authenticity is in question via the precise identification of the pigments used on the surface of each stamp and dispersed between the paper fibres. Copyright © 2004 John Wiley & Sons, Ltd.