Assessing the physical stability of archival cellulose acetate films by monitoring plasticizer loss

Cellulose acetate film plasticized with diethyl phthalate was subjected to artificial aging regimes and the loss of plasticizer determined by means of Thermogravimetric Analysis and Fourier-transform Infrared Spectroscopy. Alterations in the strain hardening capability of the films was monitored by Dynamic Mechanical Analysis, and the connection between flexibility, strain hardening and the degree of plasticization investigated as a means of monitoring the physical condition of archival cellulose acetate film. It was found that the higher the plasticizer content the greater the ability to strain harden, and therefore the least vulnerable to mechanical damage from archival handling. The correlation between the critical plasticizer content and the working properties of cellulose acetate film provides a means of assessing stability, and highlights artifacts at risk from physical damage

The application of a VUV Fourier transform spectrometer and synchrotron radiation source to measurements of: II. The δ(1,0) band of NO

Line-by-line photoabsorption cross-sections of the NO δ(1,0) band were measured with the VUV Fourier transform spectrometer from Imperial College, London, using synchrotron radiation at Photon Factory, KEK, Japan, as a continuum light source. The analysis of the NO δ(1,0) band provides accurate rotational line positions and term values as well as the photoabsorption cross-sections. The molecular constants of the C(1)2 II level are found to be T0 = 54 690.155±0.03 cm–1, Bv = 1.944 06±0.000 62 cm–1, Dv = (5.91±0.42)×10–5 cm–1, AD = –0.0187±0.0050 cm–1, p = –0.0189±0.0037 cm–1, and q = –0.015 21±0.000 20 cm–1. The sum of the line strengths for all rotational transitions of the NO δ(1,0) band is determined as 4.80×10–15 cm2 cm–1, corresponding to a band oscillator strength of 0.0054±0.0003.published_or_final_versio

The application of a VUV Fourier transform spectrometer and synchrotron radiation source to measurements of: I. the β(9,0) band of NO

State-of-the-art models of the vacuum ultraviolet (VUV) absorbing properties of the atmosphere call for absorption cross sections with detail on the scale of the Doppler widths. As a consequence, spectroscopic data at resolving powers of the order of 10 6 are needed. To meet these requirements in the vacuum ultraviolet region, we have used the VUV Fourier transform spectrometer from Imperial College, London, at the synchrotron radiation facility at Photon Factory, KEK, Japan, to measure photoabsorption cross sections of NO from 195 to 160 nm, and of O 2 from 185 to 175 nm. The analysis of the β(9,0) band (B 2Π r-X 2Π r) of NO provides accurate rotational line positions and term values. Molecular constants of the B(9) 2Π level are T 0=54205.097±0.012cm -1, A=45.320±0.021cm -1, B υ=1.01672±0.00016cm -1, D υ=(10.61±0.32)×10 -6cm -1, and A D=0.00122±0.00011cm -1. The rotational line strengths and the branching ratios are also presented. The band oscillator strength is obtained as f=2.65×10 -4. © 1998 American Institute of Physics.published_or_final_versio

Assessment of the composition and condition of animation cels made from cellulose acetate

Cellulose diacetate and cellulose triacetate cels from animated feature films in the collection of the Walt Disney Animation Research Library were tested by several analytical techniques in order to assess their composition and look for evidence of degradation. Triphenyl phosphate and a range of phthalate plasticizers were identified using pyrolysis-gas chromatography/mass spectrometry, which also showed evidence that evaporation of more volatile plasticizers may have occurred. Plasticizer content measurements by solvent extraction, found to be more accurate than volatile content data from thermogravimetric analysis, revealed there was less residual plasticizer in triacetate cels compared to diacetate cels. Gas chromatography/mass spectrometry, performed to quantify the acetyl content of cels after removal of plasticizers by solvent extraction, revealed some evidence for hydrolysis of the oldest cels, although the reduction could be related to original variations in acetate content from the polymer manufacturers. Use of Fourier-transform infrared spectroscopy to measure deacetylation of the cellulose acetate polymer based on the hydroxyl to carbonyl peak area ratio proved less satisfactory. Moreover, because the cels cannot be measured directly due to interference from plasticizers, non-invasive assessment of deacetylation using a portable instrument would be impossible. The results from this analytical survey provide an important point of reference against which long-term changes in cel composition can be monitored. © 2014 The J. Paul Getty Trust. Published by Elsevier Ltd. All rights reserved

Failing boys and moral panics: perspectives on the underachievement debate

The paper re-examines the underachievement debate from the perspective of the ‘discourse of derision’ that surrounds much writing in this area. It considers the contradictions and inconsistencies which underpin much of the discourse – from a reinterpretation of examination scores, to the conflation of the concepts of ‘under’ and ‘low’ achievement and finally to the lack of consensus on a means of defining and measuring the term underachievement. In doing so, this paper suggests a more innovative approach for understanding, re-evaluating and perhaps rejecting the notion of underachievement

Effects of sample handling and analytical procedures on thyroid hormone concentrations in pregnant women's plasma

Background: Maternal thyroid function is a critical mediator of fetal brain development. Pregnancy-related physiologic changes and handling conditions of blood samples may influence thyroid hormone biomarkers. We investigated the reliability of thyroid hormone biomarkers in plasma of pregnant women under various handling conditions. Methods: We enrolled 17 pregnant women; collected serum and plasma were immediately frozen. Additional plasma aliquots were subjected to different handling conditions before the analysis of thyroid biomarkers: storage at room temperature for 24 or 48 hours before freezing and an extra freeze-Thaw cycle. We estimated free thyroid hormone indices in plasma based on T3 uptake. Results: High correlations between plasma and serum (>0.94) and intraclass correlation coefficients for plasma handling conditions (0.96 to 1.00) indicated excellent reliability for all thyroid hormone biomarkers. Conclusion: Delayed freezing and freeze-Thaw cycles did not affect reliability of biomarkers of thyroid function in plasma during pregnancy. See video abstract at, http://links.lww.com/EDE/B180

Novel mass spectrometric approaches for the analysis of modern oil paint media and organic additives in paintings

Modern unvarnished oil paints in paintings show degradation problems such as bleeding, efflorescence and solvent sensitivity1 which are related to specific lipidic media and additives in the paint. Micro-analytical techniques such as Fourier Transform Infrared Spectroscopy (FTIR) and Gas Chromatography/Mass spectrometry (GCMS) are routinely used for detection of organic materials in oil paints. The type of oil may be determined based on characteristic peak ratios of mainly palmitic and stearic acid, using GCMS. However, the techniques are less specific if other lipidic components are present. Moreover, using standard preparation techniques GCMS provides only limited information about important parameters which reflect the original composition and the state of ageing or degradation through oxidation, hydrolysis and soap formation. In general, a combination of analytical techniques and/or extensive sample pretreatment is required to obtain such information.2,3 This paper discusses 20th C oil paint technology and the organic components that may be present in fresh and dried oil paints. An overview is given of novel mass spectrometric techniques which can be used for detection of these original materials and their drying and degradation products, and compared to GCMS techniques which involve pretreatment and derivatisation procedures

Identidad étnica y redes personales entre jóvenes de Sarajevo

After fieldwork conducted among young people in Sarajevo, we found a relation between the discourses sustained by them and the ethnic categories they use to classify people and to identify themselves. Also we have found that people self-affiliated as "Bosnians" play an important role in the network of multiethnic relationships, in which strong ties, surprisingly, are still very important. Finally we found a relationship between the composition of personal networks and the ethnic discourses that are maintained.Después de un trabajo de campo realizado con un grupo de jóvenes en Sarajevo, hemos constatado la existencia de una relación entre los discursos que sostienen y las categorías étnicas que utilizan tanto para clasificar a los demás como para auto-identificarse. Asimismo hemos encontrado que los jóvenes que se autodenominan "Bosnios" juegan un rol importante en la red de relaciones multiétnicas, en la que los lazos fuertes, sorprendentemente, son muy importantes. Finalmente hemos hallado una relación entre la composición de las redes personales y los discursos étnicos que se sostienen. Vivimos, o creemos vivir, en múltiples "comunidades", imaginadas o no. Al mismo tiempo, el individuo y no el lugar, la familia o el grupo, se sitúa en el centro de la vida social y de las comunicaciones (Cf. Wellman, 2001). En este contexto, inducido por el avance del capitalismo flexible (Castells, 1996), pensamos que para entender adecuadamente la identidad o identidades postuladas por los individuos es necesario estudiar las redes personales y su dinámica. Desde esta perspectiva no podemos hablar de "etnias" o "multietnicidad" sin más precisiones, pues son conceptos basados en una concepción esencialista y estática de la identidad individual. El concepto de "sociedad multiétnica" es utilizado de una manera engañosamente progresista y objetiva, pues lo que en realidad legitima es la existencia de diferencias esenciales entre personas, alejando en lugar de acercar. Sin embargo, somos plenamente conscientes que los discursos esencialistas de la identidad étnica son omnipresentes, con enormes efectos políticos e individuales. Que planteemos que la concepción esencialista de la identidad sea inapropiada desde un punto de vista académico, no significa que ésta no se utilice políticamente y por lo tanto tenga consecuencias formidables en las relaciones sociales. Precisamente el estudio de las redes personales nos permite situarnos en una perspectiva que no utiliza con pretensiones analíticas conceptos "folk", como son los de "etnia", "pueblo" o "nación", sino que los sitúa en el terreno de los discursos sustentados por los actores (y los estados y medios de comunicación) y nos permite contextualizarlos mediante conceptos etic, es decir, impuestos por los investigadores. Sólo así podemos superar las tautologías que abundan en los discursos étnicos

Pollutants Increase Song Complexity and the Volume of the Brain Area HVC in a Songbird

Environmental pollutants which alter endocrine function are now known to decrease vertebrate reproductive success. There is considerable evidence for endocrine disruption from aquatic ecosystems, but knowledge is lacking with regard to the interface between terrestrial and aquatic ecosystems. Here, we show for the first time that birds foraging on invertebrates contaminated with environmental pollutants, show marked changes in both brain and behaviour. We found that male European starlings (Sturnus vulgaris) exposed to environmentally relevant levels of synthetic and natural estrogen mimics developed longer and more complex songs compared to control males, a sexually selected trait important in attracting females for reproduction. Moreover, females preferred the song of males which had higher pollutant exposure, despite the fact that experimentally dosed males showed reduced immune function. We also show that the key brain area controlling male song complexity (HVC) is significantly enlarged in the contaminated birds. This is the first evidence that environmental pollutants not only affect, but paradoxically enhance a signal of male quality such as song. Our data suggest that female starlings would bias their choice towards exposed males, with possible consequences at the population level. As the starling is a migratory species, our results suggest that transglobal effects of pollutants on terrestrial vertebrate physiology and reproduction could occur in birds

HPLC-DAD and HPLC-ESI-Q-ToF characterisation of early 20th century lake and organic pigments from Lefranc archives

The characterisation of atelier materials and of the historical commercial formulation of paint materials has recently gained new interest in the field of conservation science applied to modern and contemporary art, since modern paint materials are subjected to peculiar and often unpredictable degradation and fading processes. Assessing the composition of the original materials purchased by artists can guide not only their identification in works of art, but also their restoration and conservation. Advances in characterisation methods and models for data interpretation are particularly important in studying organic coloring materials in the transition period corresponding to the late 19th-early 20th century, when many such variants or combinations were hypothetically possible in their formulations. There is thus a need for reliable databases of materials introduced in that period and for gaining chemical knowledge at a molecular level related to modern organic pigments, by state-of-the-art protocols. This paper reports on the results of a study on 44 samples of historical colorants in powder and paint tubes, containing both lake pigments and synthetic organic pigments dating from 1890 to 1926. The samples were collected at the Lefranc Archive in Le Mans (France) as a part of Project Futurahma "From Futurism to Classicism (1910-1922). Research, Art History and Material Analysis", (FIRB2012, Italian Ministry of University and Research), and were investigated using an analytical approach based on chromatographic and mass spectrometric techniques. The focus of the chemical analyses was to reveal the composition of the historical organic lake pigments including minor components, to discriminate between different recipes for the extraction of chromophore-containing molecules from the raw materials, and ultimately to distinguish between different formulations and recipes. High performance liquid chromatography (HPLC) with diode array detector (DAD) or electrospray-Quadrupole-Time of Flight tandem mass spectrometry detector (ESI-Q-ToF) were chosen given their considerable capacity to identify such complex and widespread organic materials. Although the inorganic components of the pigments were not taken into account in this survey, the specific molecular profiles provided invaluable information on the extraction procedures or synthetic strategy followed by the different producers, at different times. For instance, the use of Kopp's purpurin and garancine was highlighted, and synthetic by-products were identified. The results provided evidence that the addition of synthetic organic pigments to paint mixtures started from 1910 onwards, but they also suggest that in the formulation of high quality (surfin) colorants, natural products were still preferred. Moreover, in one of the samples the use of murexide as the colouring material was confirmed. This paper presents the first systematic and comprehensive survey on organic lakes and pigments belonging to an historical archive, by both HPLC-DAD and HPLC-ESI-Q-ToF. Specific by-products of synthetic production of pigments, which can act as specific molecular markers for dating or locating a work of art, were also identified for the first time