482 research outputs found

    "What motivates her": motivations for considering labial reduction surgery as recounted on women’s online communities and surgeons’ websites

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    Introduction: Increasing numbers of women are seeking labial reduction surgery. We studied the motivations for considering labial reduction surgery as recounted on women's online communities and surgery provider's websites. Aims: The study analyzed motivations for considering labial reduction surgery expressed by women on online communities, looked at the role of the women's age and nationality, compared findings with motivations indicated on the websites of an international sample of surgery providers, and identified similarities to and differences from what is known from extant studies. Methods: Quantitative content analysis of the posts of 78 American, British, and Dutch women on online communities, and 40 international surgery providers' websites about labial reduction surgery was conducted. Main Outcome Measures: Main outcome measures concerned the incidence and prominence of different motivational categories (functional/emotional and discomfort/enhancement related). Differences in motivations as a function of age, national background, and women's vs. surgeons' stated motivations were tested. Results: Emotional discomfort regarding self‐appearance and social and sexual relationships was found to be the most frequent and most prominent motivation for considering labial reduction surgery on women's online communities, regardless of age and national background. Functional discomfort and desired emotional enhancement ranked second. Very few age or national differences were found. The surgeons' websites recognized functional discomfort more and elaborated upon emotional issues in sexual relationships less than members of the online communities. Conclusions: Feelings of emotional and psychosexual distress in addition to functional distress are a highly prevalent motivation among women considering labial reduction surgery. Emotional distress appears to be greater and more freely emphasized when women communicate on online communities, while functional issues appear to receive greater notice on surgery provider's websites. Zwier S. “What motivates her”: Motivations for considering labial reduction surgery as recounted on women's online communities and surgeons' websites. Sex Med 2014;2:16–23

    Hindered Internal Rotation and Ortho-H2 Enrichment in Trans-Stilbene--H2/D2 Complexes

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    A supersonic free jet expansion has been used to prepare trans-stilbene--H2 and D2 complexes. The cooling in the jet collapses most of the ortho and para H2 and D2 rotational population to the lowest rotational levels of a given nuclear spin symmetry: j = 0 and j = 1. The laser-induced fluorescence excitation spectrum of stilbene--D2 shows a well-resolved doublet at the origin due to stilbene--D2( j = 0) and stilbene--D2( j = 1) complexes. The 4.9 cm-1 splitting of these transitions indicates that the D2 molecule is undergoing hindered internal rotation in the complex and that the barrier to internal rotation changes upon electronic excitation. The relative intensities of the stilbene--D2( j = 0) and stilbene--D2( j = 1) origins depend on the D2concentration in the jet. At low D2 flows the transitions arising from stilbene--D2( j = 1) are favored while at high D2 flows the ( j = 0)/(j = 1) transition intensities approach the 2:1 intensity ratio given by their nuclear spin statistical weights. By contrast, in stilbene--H2 we observe only a single transition at the origin which we assign to stilbene--H2( j = 1). We are able to place an upper bound on the stilbene--H2( j = 0) transition intensity of 5% of the stilbene--H2( j = 1) intensity. Dispersed fluorescence spectra are used to bracket the binding energies of the stilbene--H2/D2 complexes in both ground and excited states

    State Mixing and Vibrational Predissociation in Large Molecule Van Der Waals Complexes: Trans‐Stilbene–X Complexes Where X=He, H2, Ne, and Ar

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    We report a detailed study of vibrational predissociation and intramolecular–intermolecular state mixing in the first excited singlet state of t r a n s‐stilbene van der Waals complexes with helium, hydrogen, neon, and argon. We present evidence that the helium atom in stilbene–He and the H2 molecule in stilbene–H2 possess very low frequency van der Waals bending levels involving delocalization of the complexed species over both phenyl rings. In stilbene–He, the mode‐selective, strong coupling of the out‐of‐plane phenyl ring modes with the pseudotranslation van der Waals modes leads to a dramatic, inhomogeneous broadening of the transitions to several times their breadth in in‐plane vibrations. The observed dispersed fluorescence spectra give product state distributions and internal clock lifetime estimates which can only be made consistent with direct lifetime measurements by assuming extensive state mixing of the intramolecular levels with the van der Waals levels in which the states accessed by the laser are actually only about 30% intramolecular in character. We conclude that in these complexes the processes of intramolecular–intermolecular state mixing (static IVR) and vibrational predissociation are not independent processes but are closely tied to one another. In fact, the vibrational product state distributions observed for the out‐of‐plane phenyl ring levels can best be interpreted as reflecting the percentage van der Waals character in the initially prepared state. In stilbene–H2 the mode selective coupling exhibits itself as a splitting of the out‐of‐plane transitions into a set of 5–6 closely spaced transitions separated by only about 1 cm− 1. The sequence of transitions is suggestive of an in‐plane potential for H2 motion which is nearly flat across the entire length of the stilbene molecule with a small barrier presented by the ethylenic carbons through which the H2 molecule can tunnel. Dispersed fluorescence spectra from these levels point to a two‐tiered coupling scheme with the bound van der Waals levels. In contrast, the out‐of‐plane phenyl transitions in stilbene–Ne and stilbene–Ar possess unusual shifts, but the transitions are narrow once again. In these cases the complexed atom appears to be largely localized over a single phenyl ring

    INFRARED SPECTROSCOPY OF SINGLE-TURN AND DOUBLE-TURN TETHERED ALPHA-HELICES IN THE GAS PHASE: DON'T LET YOUR LEFT HAND KNOW WHAT YOUR RIGHT HAND IS DOING.

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    This talk will describe single-conformation IR and UV spectroscopy of a series of single-turn and double-turn alpha helices as cryo-cooled, gas phase ions. Synthesized samples of tethered pentapeptides are known to form single-turn alpha helices in aqueous solution. When L-amino acids are used, a right-handed single-turn helix is formed while D-amino acids produce a left-handed helix. Due to the tether, these structures are remarkably stable in aqueous solution over a wide range of temperatures, pH, and denaturant. They can be concatenated, making LL, DD, LD, and DL double-turn forms. When a methylated arginine is placed at the C-terminal end of the tethered peptide, single-turn helices are the most stable structure, and are observed exclusively. The spectra in the NH stretch and amide I regions show distinct effects that depend on position along the helix, and the presence or absence of a kink due to concatenation of two opposite-handed helices. We will discuss these spectra and the prospects they offer as scaffolds for studying a wide range of interesting structural and dynamical problems

    BROADBAND MICROWAVE AND COMPUTATIONAL STUDY OF HEXAFLUORO-O-XYLENE: HIGHLY COUPLED CF3 ROTORS

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    The rotational constants and quartic centrifugal distortion coefficients of hexafluoro-o-xylene and all singly 13C isotopologues were precisely determined from the 8 to 18GHz gas phase microwave spectrum. A preliminary r0 structure was determined, reproducing the experimental rotational constants with deviations of no more than 15kHz. Interestingly, rather than the C2v symmetry structure expected intuitively, as in o-xylene, calculations with a variety of methods (B3LYP, CAM-B3LYP, ω\omegaB97XD, MP2, and CCSD(T)) predict a C2 symmetry structure in which the two CF3 groups rotate in opposite directions by about 16 degrees. Analysis of the interactions between the two CF3 groups using an effective fragment potential (EFP) approach identified two major contributions to their interaction, due to exchange repulsion and electrostatic repulsion, with electrostatic repulsion responsible for the barrier at the C2v geometry. SH, SMF, PM and TSZ gratefully acknowledge support for this work from the Department of Energy Basic Energy Sciences Gas Phase Chemical Physics program under Grant No. DE-FG02-96ER14656. YK and LVS gratefully acknowledge support from the National Science Foundation (NSF CHE-1800505). Present address for TSZ: Combustion Research Facility, Sandia National Laboratory, Livermore, CA 94550

    Influence of relative NK-DC abundance on placentation and its relation to epigenetic programming in the offspring

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    Normal placentation relies on an efficient maternal adaptation to pregnancy. Within the decidua, natural killer (NK) cells and dendritic cells (DC) have a critical role in modulating angiogenesis and decidualization associated with pregnancy. However, the contribution of these immune cells to the placentation process and subsequently fetal development remains largely elusive. Using two different mouse models, we here show that optimal placentation and fetal development is sensitive to disturbances in NK cell relative abundance at the fetal–maternal interface. Depletion of NK cells during early gestation compromises the placentation process by causing alteration in placental function and structure. Embryos derived from NK-depleted dams suffer from intrauterine growth restriction (IUGR), a phenomenon that continued to be evident in the offspring on post-natal day 4. Further, we demonstrate that IUGR was accompanied by an overall reduction of global DNA methylation levels and epigenetic changes in the methylation of specific hepatic gene promoters. Thus, temporary changes within the NK cell pool during early gestation influence placental development and function, subsequently affecting hepatic gene methylation and fetal metabolism.Fil: Freitag, Nancy. Medicine University of Berlin; AlemaniaFil: Zwier, M. V.. University of Groningen; PaĂ­ses BajosFil: Barrientos, Gabriela Laura. Medicine University of Berlin; Alemania. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas; ArgentinaFil: Tirado GonzĂĄlez, Irene. Medicine University of Berlin; AlemaniaFil: Conrad, Melanie L.. Medicine University of Berlin; AlemaniaFil: Rose, Matthias. Medicine University of Berlin; AlemaniaFil: Scherjon, S. A.. University of Groningen; PaĂ­ses BajosFil: Plösch, T.. University of Groningen; PaĂ­ses BajosFil: Blois, Sandra M.. Medicine University of Berlin; Alemani

    Infrared Spectroscopy Of H-bonded Bridges Stretched Across The Cis-amide Group: I. Water Bridges

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    The water-containing clusters of oxindole (OI) and 3,4-dihydro-2(1H)-quinolinone (DQ) have been studied in the hydride stretch region of the infrared by the technique of resonant ion-dip infrared spectroscopy (RIDIRS). Both OI and DQ are constrained cis-amides with adjacent N-H and C=O groups between which water can form H-bonded bridges. The hydride stretch fundamentals of OI-W-n with n = 1-3 and DQ-W-n with n = 1, 2 without exception divide up into free OH stretch fundamentals near 3700 cm(-1) and a set of H-bonded bridge fundamentals in the 3200-3450 cm(-1) region. The bridge fundamentals show a distribution of intensities that reflects strong coupling among the XH oscillators in the bridge. When more than one water is involved in the bridge, the bridge fundamentals are unusually broad, with widths of 50-80 cm(-1) full width at half-maximum. Minimum-energy structures, binding energies, vibrational frequencies, and infrared intensities have been calculated by density functional theory with a Becke3LYP functional and a 6-31+G* basis set. The calculated infrared spectra match experiment well, confirming the bridge structures for the clusters. The form of the calculated normal modes provides insight into the nature of the bridge fundamentals
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