246 research outputs found

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

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    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

    Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazole

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    The vibrational spectra of 5-chlorotetrazole (CN4HCl) isolated in an argon matrix (T ÂŒ 8.5 K) and in the solid state (at room temperature) were studied. The infrared spectrum of monomers of 5-chlorotetrazole isolated in an argon matrix agrees well with the spectrum predicted theoretically (DFT(B3LYP)/6-31G*) for the 2Htautomer of the compound. The bands assigned to the 1H-tautomer appear in the experimental spectrum as very low intensity features. Based on the relative intensities of the bands in the spectra of the 1H- and 2Htautomers, the relative amount of the first tautomer in this matrix can be estimated as 1%. Three matrixes were deposited with different nozzle temperatures and the enthalpy difference between the tautomers DH ÂŒ 8.0 kJ mol 1 was estimated using the Van’t Hoff relation. The internal energy difference between the two tautomers was predicted theoretically (DFT B3LYP/6-31G*) as 12.6 kJ mol 1. This is in reasonable agreement with experimental observations. In the crystalline phase, this compound exists in its 1H-tautomeric form. Accordingly, the IR spectrum of polycrystalline 5-chlorotetrazole is well reproduced by the spectrum predicted theoretically for the 1H- tautomer

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

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    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

    Some limitations in the use of the mitochondrial DNA cytb gene as a molecular marker for phylogenetic and population genetic studies by the example of the Apodemus genus

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    The interpretation of a signal sent by the mtDNA cytb gene as a molecular marker in phylogenetic and population genetic research can be complicated by cumulative influence of parallel mutations, i.e., the entropy of nucleotide sequences. Such a phenomenon impedes differentiation among the effects of hybridization, natural polymorphisms, and artifacts imposed by pseudogenes. We analyzed possible limitations in the use of the mtDNA cytb gene as a molecular marker by the example of the Apodemus genus. For this purpose, the entropy of nucleotide sequences was calculated, and probable tracts of gene conversion were sought in samples of various Apodemus species from Tibet, Korea, south of Russian Primorye, and Western Europe. Many haplotypes were identified as containing tracts of gene conversion. The high level of nucleotide sequence variability was found in species from Tibet, particularly, in A. draco, presumably due to the influence of low effective sizes of populations on the speed of point mutation accumulation and also cytochrome b role in the adaptation to unfavorable environment. The effects of hypervariability in cytb nucleotide sequences of some samplings resulting in entropy growth imitating gene conversion when compared to other species of the genus were analyzed. Examples of possible pseudogene interference among published cytb sequences are provided. It is suggested that the strategy in the use of the mtDNA cytb gene in population genetics and phylogenetics should be adapted to the degree of the gene variability. Emphasis is placed on the necessity of close control over sequencing data

    A content analysis of thinspiration, fitspiration, and bonespiration imagery on social media

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    Background On social media, images such as thinspiration, fitspiration, and bonespiration, are shared to inspire certain body ideals. Previous research has demonstrated that exposure to these groups of content is associated with increased body dissatisfaction and decreased self-esteem. It is therefore important that the bodies featured within these groups of content are more fully understood so that effective interventions and preventative measures can be informed, developed, and implemented. Method A content analysis was conducted on a sample of body-focussed images with the hashtags thinspiration, fitspiration, and bonespiration from three social media platforms. Results The analyses showed that thinspiration and bonespiration content contained more thin and objectified bodies, compared to fitspiration which featured a greater prevalence of muscles and muscular bodies. In addition, bonespiration content contained more bone protrusions and fewer muscles than thinspiration content. Conclusions The findings suggest fitspiration may be a less unhealthy type of content; however, a subgroup of imagery was identified which idealised the extremely thin body type and as such this content should also be approached with caution. Future research should utilise qualitative methods to further develop understandings of the body ideals that are constructed within these groups of content and the motivations behind posting this content

    South Korean Military Service Promotes Smoking: A Quasi-Experimental Design

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    ∙ The authors have no financial conflicts of interest. © Copyright: Yonsei University College of Medicine 2012 This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial Licens

    Foldamers of ÎČ-peptides : conformational preference of peptides formed by rigid building blocks : The first MI-IR spectra of a triamide nanosystem

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    To determine local chirality driven conformational preferences of small aminocyclobutane-1-carboxylic acid derivatives, X-(ACBA) n -Y, their matrix-isolation IR spectra were recorded and analyzed. For the very first time model systems of this kind were deposited in a frozen (~10 K) noble gas matrix to reduce line width and thus, the recorded sharp vibrational lines were analyzed in details. For cis-(S,R)-1 monomer two “zigzag” conformers composed of either a six or an eight-membered H-bonded pseudo ring was identified. For trans-(S,S)-2 stereoisomer a zigzag of an eight-membered pseudo ring and a helical building unit were determined. Both findings are fully consistent with our computational results, even though the relative conformational ratios were found to vary with respect to measurements. For the dimers (S,R,S,S)-3 and (S,S,S,R)-4 as many as four different cis,trans and three different trans,cis conformers were localized in their matrix-isolation IR (MI-IR) spectra. These foldamers not only agree with the previous computational and NMR results, but also unambiguously show for the first time the presence of a structure made of a cis,trans conformer which links a “zigzag” and a helical foldamer via a bifurcated H-bond. The present work underlines the importance of MI-IR spectroscopy, applied for the first time for triamides to analyze the conformational pool of small biomolecules. We have shown that the local chirality of a ÎČ-amino acid can fully control its backbone folding preferences. Unlike proteogenic α-peptides, ÎČ- and especially (ACBA) n type oligopeptides could thus be used to rationally design and influence foldamer’s structural preferences
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