42 research outputs found

    Discrimination between charge-catalyzed and charge-independent fragmentation processes of cationized poly(n-butyl acrylate).

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    International audienceWhen performing structural investigation of macromolecular systems using tandem mass spectrometry, an important matter is the choice of the cation and how that does affect the tandem mass spectra. Moreover, when studying mechanistic aspects, the role of the adduct ions in the mechanism of the fragmentation processes is often discussed: Is the process charge-induced (more accurately described as charge-catalyzed) or charge-remote (more accurately described as charge-independent). In a previous study[1], we shed light on the catalytic effect of lithium in the case of cationized poly(ethylene glycols) (PEGs). The activation energy of the main fragmentation process for the trimer was shown, by means of Density Functional Theory calculations, to decrease by as much as 0.3 eV in the presence of lithium. To further sketch our picture of the role of cation adducts on the fragmentation of even electron ions, we present in this communication the results obtained on the fragmentation of poly (n-butyl acrylate), PBA, with different alkali ions and various degrees of polymerization. Thus, we present a method to clarify the role of the charge on the fragmentation processes

    Evaluation of the chemical and physical changes induced by KrF laser irradiation of tempera paints

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    A systematic study of the chemical and physical changes induced by exposure to UV (248 nm) excimer laser light of unvarnished tempera paint samples has been undertaken as a part of the research activities included in the European project "Advanced workstation for controlled laser cleaning of artworks". The direct exposure of the paint to the UV laser configures the worst case scenario of laser cleaning, as a thin protective layer of varnish is normally left to minimize the dose of UV radiation that reaches the paint surface. However, in the practice of laser cleaning, there is a need to characterize and quantify the possible effects of direct UV laser irradiation of unvarnished paints. To this purpose, a broad range of techniques have been used including profilometry, colorimetry, optical and vibrational spectroscopic techniques, such as laser-induced fluorescence (LIF), laser-induced breakdown spectroscopy (LIBS), Fourier transform Raman (FTR) and infrared (FTIR), and analytical mass spectrometric techniques, like direct-temperature-resolved mass spectrometry (DTMS) and laser desorption and ionization time of flight mass spectrometry (LDI-TOF). Integration of the results obtained by these techniques allowed the investigation of the nature and degree of change of the irradiated paint systems. These were observed to strongly depend on the type of paint system. © 2003 Éditions scientifiques et médicales Elsevier SAS. All rights reserved

    Controlled UV laser cleaning of painted artworks: S systematic effect study on egg tempera paint samples

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    The Cooperative Research project “Advanced workstation for controlled laser cleaning of artworks” (ENV4-CT98-0787) has yielded important information on the application of UV laser cleaning to paint materials. In the project, in which conservators, researchers and engineers participated, the viability of the laser technique as an additional tool in present conservation practice was investigated. The research was pointed at the definition of the boundary conditions in which laser cleaning can be safely applied. It included a systematic effect study of tempera paint systems. Physical and chemical changes, induced by exposure to UV (248 nm) excimer laser light under various conditions, were evaluated. In parallel, an innovative laser cleaning tool was developed, allowing accurate and controlled removal of superficial layers from paint materials. Both aspects of the project are presented. The presentation of the research focuses on the integration of the results from various analytical techniques, yielding valuable information on the immediate and long-term effects of UV laser radiation on the paint materials. The analytical techniques include colorimetry, spectroscopic techniques, mass spectrometry and profilometry, as well as thermographic and UV transmission measurements. Furthermore, the application of the laser workstation on various painted artworks is shown. This includes the gradual removal of varnish layers and the recovery of original paint colour in fire-damaged paintings.The European Commission is gratefully acknowledged for facilitating the work in the Cooperative Research project “Advanced workstation for controlled laser cleaning of artworks” (ENV4-CT98-0787)

    COSNET-a coherent optical subscriber network

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    A complete coherent multichannel system, designed for application in the local loop, is presented. The concept of a uni- and bidirectional system and its technical realization in a laboratory demonstrator are described. The network control, including frequency management of the bidirectional channels, and network security are discussed. Attention is paid to the scenario for evolution from a narrowband to a complete broadband system. All aspects are integrated in a demonstrator, which is capable of supporting a large number of narrowband and broadband distributive and communicative services. Novel technical solutions for frequency management, data induced polarization switching (DIPS), high-speed encryption, and network signaling are presented

    Structure and function of PspA and Vipp1 N-terminal peptides: Insights into the membrane stress sensing and mitigation

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    The phage shock protein (Psp) response maintains integrity of the inner membrane (IM) in response to extracytoplasmic stress conditions and is widely distributed amongst enterobacteria. Its central component PspA, a member of the IM30 peripheral membrane protein family, acts as a major effector of the system through its direct association with the IM. Under non-stress conditions PspA also negatively regulates its own expression via direct interaction with the AAA + ATPase PspF. PspA has a counterpart in cyanobacteria called Vipp1, which is implicated in protection of the thylakoid membranes. PspA's and Vipp1's conserved N-terminal regions contain a putative amphipathic helix a (AHa) required for membrane binding. An adjacent amphipathic helix b (AHb) in PspA is required for imposing negative control upon PspF. Here, purified peptides derived from the putative AH regions of PspA and Vipp1 were used to directly probe their effector and regulatory functions. We observed direct membrane-binding of AHa derived peptides and an accompanying change in secondary structure from unstructured to alpha-helical establishing them as bona fide membrane-sensing AH's. The peptide-binding specificities and their effects on membrane stability depend on membrane anionic lipid content and stored curvature elastic stress, in agreement with full length PspA and Vipp1 protein functionalities. AHb of PspA inhibited the ATPase activity of PspF demonstrating its direct regulatory role. These findings provide new insight into the membrane binding and function of PspA and Vipp1 and establish that synthetic peptides can be used to probe the structure-function of the IM30 protein family

    The cardiovascular risk profile of middle-aged women with polycystic ovary syndrome

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    Contains fulltext : 220851.pdf (Publisher’s version ) (Open Access)OBJECTIVES: Contradictory results have been reported regarding the association between polycystic ovary syndrome (PCOS) and cardiovascular disease (CVD). We assessed the cardiometabolic phenotype and prevalence of CVD in middle-aged women with PCOS, compared with age-matched controls from the general population, and estimated 10-year CVD risk and cardiovascular health score. DESIGN: A cross-sectional study. PARTICIPANTS: 200 women aged >45 with PCOS, and 200 age-matched controls. MEASUREMENTS: Anthropometrics, insulin, lipid levels, prevalence of metabolic syndrome and type II diabetes. Ten-year Framingham risk score and the cardiovascular health score were calculated, and carotid intima-media thickness (cIMT) was measured. RESULTS: Mean age was 50.5 years (SD = 5.5) in women with PCOS and 51.0 years (SD = 5.2) in controls. Increased waist circumference, body mass index and hypertension were more often observed in women with PCOS (P < .001). In women with PCOS, the prevalence of type II diabetes and metabolic syndrome was not significantly increased and lipid levels were not different from controls. cIMT was lower in women with PCOS (P < .001). Calculated cardiovascular health and 10-year CVD risk were similar in women with PCOS and controls. CONCLUSIONS: Middle-aged women with PCOS exhibit only a moderately unfavourable cardiometabolic profile compared to age-matched controls, even though they present with an increased BMI and waist circumference. Furthermore, we found no evidence for increased (10-year) CVD risk or more severe atherosclerosis compared with controls from the general population. Long-term follow-up of women with PCOS is necessary to provide a definitive answer concerning long-term risk for CVD

    The cardiovascular risk profile of middle-aged women with polycystic ovary syndrome

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    Objectives: Contradictory results have been reported regarding the association between polycystic ovary syndrome (PCOS) and cardiovascular disease (CVD). We assessed the cardiometabolic phenotype and prevalence of CVD in middle-aged women with PCOS, compared with age-matched controls from the general population, and estimated 10-year CVD risk and cardiovascular health score. Design: A cross-sectional study. Participants: 200 women aged >45 with PCOS, and 200 age-matched controls. Measurements: Anthropometrics, insulin, lipid levels, prevalence of metabolic syndrome and type II diabetes. Ten-year Framingham risk score and the cardiovascular health score were calculated, and carotid intima-media thickness (cIMT) was measured. Results: Mean age was 50.5 years (SD = 5.5) in women with PCOS and 51.0 years (SD = 5.2) in controls. Increased waist circumference, body mass index and hypertension were more often observed in women with PCOS (P <.001). In women with PCOS, the prevalence of type II diabetes and metabolic syndrome was not significantly increased and lipid levels were not different from controls. cIMT was lower in women with PCOS (P <.001). Calculated cardiovascular health and 10-year CVD risk were similar in women with PCOS and controls. Conclusions: Middle-aged women with PCOS exhibit only a moderately unfavourable cardiometabolic profile compared to age-matched controls, even though they present with an increased BMI and waist circumference. Furthermore, we found no evidence for increased (10-year) CVD risk or more severe atherosclerosis compared with controls from the general population. Long-term follow-up of women with PCOS is necessary to provide a definitive answer concerning lon
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