Positive Identification of UV-Generated, Non-Hydrogen-Bonded Isomers of o-Hydroxybenzaldehyde and o-Hydroxyacetophenone

Non-hydrogen-bonded isomers were photogenerated by UV (λ > 335 nm) irradiation of o-hydroxybenzaldehyde (salicylaldehyde) and o-hydroxyacetophenone monomers isolated in low-temperature Ar matrixes. These photoisomerizations were found to be photoreversible. Upon shorter wavelength (λ > 235 nm or λ > 270 nm) UV irradiation, the initial forms of the compounds (with intramolecular hydrogen bonds) were partially repopulated. The structures of the photogenerated non-hydrogen-bonded isomers of both compounds were positively identified by comparison of their IR spectra with the spectra theoretically calculated [at the DFT(B3LYP)/6-311++G(2d,p) level] for all possible non-hydrogen-bonded isomers of the studied compounds. The experimental IR spectra of the photoproducts generated from o-hydroxybenzaldehyde and o-hydroxyacetophenone are very well reproduced only by the theoretical spectra predicted for the isomers with both OH and formyl (or acetyl) groups rotated by 180°, with respect to the initial, most stable hydrogen-bonded conformer. Excellent agreement between experiment and theoretical prediction provides a basis for a very reliable identification of the photoproduced isomers of o-hydroxybenzaldehyde and o-hydroxyacetophenone

Preferred Conformers and Photochemical (λ > 200 nm) Reactivity of Serine and 3,3-Dideutero-Serine In the Neutral Form

A systematic investigation of the conformational potential energy surface of neutral serine [HOCH2CHNH2COOH] and 3,3-dideutero-serine [HOCD2CHNH2COOH] was undertaken, revealing the existence of 61 different minima. The structures and vibrational spectra of the most stable conformers, which were estimated to have relative energies within 7 kJ mol-1 and account for ca. 93% of the total conformational population at room temperature, were calculated at both the MP2 and DFT/BLYP levels of theory with the 6-311++G(d,p) basis-set and used to interpret the spectroscopic data obtained for the compounds isolated in low-temperature inert matrixes. The assignment of the main spectral infrared features observed in the range 4000−400 cm-1 to the most stable conformers of serine was undertaken. In addition, UV irradiation (λ > 200 nm) of the matrix-isolated compounds was also performed, leading to decarboxylation, which was found to be strongly dependent on the conformation assumed by the reactant molecule

Generation of mice with a conditional allele of the p120 Ras GTPase-activating protein

p120 Ras GTPase-activating protein (RasGAP) encoded by the rasa1 gene in mice is a prototypical member of the RasGAP family of proteins involved in negative-regulation of the p21 Ras proto-oncogene. RasGAP has been implicated in signal transduction through a number of cell surface receptors. In humans, inactivating mutations in the coding region of the RASA1 gene cause capillary malformation arteriovenous malformation. In mice, generalized disruption of the rasa1 gene results in early embryonic lethality associated with defective vasculogenesis and increased apoptosis of neuronal cells. The early lethality in this mouse model precludes its use to further study the importance of RasGAP as a regulator of cell function. Therefore, to circumvent this problem, we have generated a conditional rasa1 knockout mouse. In this mouse, an exon that encodes a part of the RasGAP protein essential for catalytic activity has been flanked by loxP recognition sites. With the use of different constitutive and inducible Cre transgenic mouse lines, we show that deletion of this exon from the rasa1 locus results in effective loss of expression of catalytically-active RasGAP from a variety of adult tissues. The conditional rasa1 mouse will be useful for the analysis of the role of RasGAP in mature cell types. genesis 45:762–767, 2007. © 2007 Wiley-Liss, Inc.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/57536/1/20354_ftp.pd

The quality assessment of different geolocalisation methods for a sensor system to monitor structural health of monumental objects

Cultural heritage objects are affected by a wide range of factors causing their deterioration and decay over time such as ground deformations, changes in hydrographic conditions, vibrations or excess of moisture, which can cause scratches and cracks formation in case of historic buildings. The electromagnetic spectroscopy has been widely used for non-destructive structural health monitoring of concrete structures. However, the limitation of this technology is a lack of geolocalisation in the space for multispectral architectural documentation. The aim of this study is to examine different geolocalisation methods in order to determine the position of the sensor system, which will then allow to georeference the results of measurements performed by this device and apply corrections to the sensor response, which is a crucial element required for further data processing related to the object structure and its features. The classical surveying, terrestrial laser scanning and SfM photogrammetry methods were used in this investigation at three test sites. The methods were reviewed and investigated. The results indicated that TLS technique should be applied for simple structures and plain textures, while the SfM technique should be used for marble-based and other translucent or semi-translucent structures in order to achieve the highest accuracy for geolocalisation of proposed sensor system

Photoinduced transformation of matrix-isolated methyl 2-pyrone-3-carboxylate into methyl 2-pyrone-5-carboxylate via intramolecular hydrogen shift in open-ring aldehyde-ketene

Abstract Photochemical transformations of methyl 2-pyrone-3-carboxylate (mp3c) were studied by matrix-isolation technique. The dominating primary photoreaction induced by UV (k > 295 nm) light was a-bond cleavage leading to open-ring aldehyde-ketene. Another reaction characteristic of a-pyrones, isomerisation to the Dewar form, did not occur for mp3c. The ring-opening photoreaction was followed by intramolecular hydrogen shift and subsequent ring-closure reaction converting the aldehyde-ketene into methyl 2-pyrone-5-carboxylate (mp5c). Upon prolonged UV irradiation, mp3c completely transformed into mp5c and its Dewar isomer Dmp5c. Unequivocal identification of mp5c and Dmp5c photoproducts was enabled by exact knowledge of their experimental IR spectra, recorded in separate experiments

Combination of the Photogrammetric and Microwave Remote Sensing for Cultural Heritage Documentation and Preservation– Preliminary Results

Nowadays, cultural heritage is an integral part of modern societies and it is necessary to preserve the tangible and intangible evidences of the past. Cultural heritage objects and sites are being devastated by natural causes and human acts. There are many existing techniques for structural health monitoring, but in the cultural heritage area, there is a need for a non-destructive measurements. The main advantages and drawbacks of some of these technologies have been presented for both laser scanner and photogrammetry techniques. The aim of this article is to present the integration of existing methods for spatial documentation (classical surveying, laser scanner, photogrammetry) and structures health monitoring using electromagnetic spectroscopy. The multi-sensor platform was developed to characterise and analyse various building materials such as marble, sandstone and bricks. The spatial techniques were used for generation of architectural documentation and geolocalisation of the multi-sensor platform. The preliminary results demonstrated that the proposed technology enables commonly used image and rage-based surface measurements as well as measurements through the entire structure for more detailed analysi

The review of methods for documentation, management and sustainability of cultural heritage. Case study: Museum of King Jan III’s Palace at Wilanów

All countries around the world are blessed with particularly rich cultural heritage. Nowadays, many researchers are exploring different methods for documentation, management and sustainability of cultural heritage. The aim of this article is to review the state of the art documentation, management and sustainability techniques in the field of cultural heritage based on the case study in the Museum of King Jan III’s Palace at Wilanów. Various 2D/3D image- and range-based methods are discussed demonstrating their applications and drawbacks. The geographical information system (GIS) is presented as a method for management, storage and maintenance of cultural heritage documentation

The efficacy of social role models to increase motivation to obtain vaccination against hepatitis B among men who have sex with men

This study assessed the effects of role models in persuasive messages about risk and social norms to increase motivation to obtain hepatitis B virus (HBV) vaccination in men who have sex with men (MSM). MSM at risk for HBV in The Netherlands (N = 168) were recruited online via a range of websites and were randomly assigned to one of four conditions in a 2 (risk communication: yes and no) × 2 (social norms communication: yes and no) factorial design. In each condition, participants subsequently provided self-completed assessments of their perceived risk of HBV infection, perceived social norms regarding HBV vaccination and their intention to obtain vaccination against HBV. Risk communication and social norms communication that used social role models were effective in significantly increasing men's intention to obtain vaccination against HBV. No additive effect was found for a combined message. Mediation analyses showed that communications influenced intention via perceived risk and social norms. Findings extend previous theorizing and research and show that both role model-based risk communication and social norms communication can be effective in increasing intentions to obtain HBV vaccination in MSM. This knowledge contributes to the development of effective health promotion to increase HBV vaccination in MSM. © The Author 2010