Femtosecond real-time probing of reactions. IX. Hydrogen-atom transfer

The real-time dynamics of hydrogen-atom-transfer processes under collisionless conditions are studied using femtosecond depletion techniques. The experiments focus on the methyl salicylate system, which exhibits ultrafast hydrogen motion between two oxygen atoms due to molecular tautomerization, loosely referred to as intramolecular ''proton'' transfer. To test for tunneling and mass effects on the excited potential surface, we also studied deuterium and methyl-group substitutions. We observe that the motion of the hydrogen, under collisionless conditions, takes place within 60 fs. At longer times, on the picosecond time scale, the hydrogen-transferred form decays with a threshold of 15.5 kJ/mol; this decay behavior was observed up to a total vibrational energy of approximately 7200 cm-1. The observed dynamics provide the global nature of the motion, which takes into account bonding before and after the motion, and the evolution of the wave packet from the initial nonequilibrium state to the transferred form along the O-H-O reaction coordinate. The vibrational periods (2pi/omega) of the relevant modes range from 13 fs (the OH stretch) to 190 fs (the low-frequency distortion) and the motion involves (in part) these coordinates. The intramolecular vibrational-energy redistribution dynamics at longer times are important to the hydrogen-bond dissociation and to the nonradiative decay of the hydrogen-transferred form

Application of spectral phase shaping to high resolution CARS spectroscopy

By spectral phase shaping of both the pump and probe pulses in coherent anti-Stokes Raman scattering (CARS) spectroscopy we demonstrate the extraction of the frequencies, bandwidths and relative cross sections of vibrational lines. We employ a tunable broadband Ti:Sapphire laser synchronized to a ps-Nd:YVO mode locked laser. A high resolution spectral phase shaper allows for spectroscopy with a precision better than 1 cm-1 in the high frequency region around 3000 cm-1. We also demonstrate how new spectral phase shaping strategies can amplify the resonant features of isolated vibrations to such an extent that spectroscopy and microscopy can be done at high resolution, on the integrated spectral response without the need for a spectrograph

Single-shot fluctuations in waveguided high-harmonic generation

For exploring the application potential of coherent soft x-ray (SXR) and extreme ultraviolet radiation (XUV) provided by high-harmonic generation, it is important to characterize the central output parameters. Of specific importance are pulse-to-pulse (shot-to-shot) fluctuations of the high-harmonic output energy, fluctuations of the direction of the emission (pointing instabilities), and fluctuations of the beam divergence and shape that reduce the spatial coherence. We present the first single-shot measurements of waveguided high-harmonic generation in a waveguided (capillary-based) geometry. Using a capillary waveguide filled with Argon gas as the nonlinear medium, we provide the first characterization of shot-to-shot fluctuations of the pulse energy, of the divergence and of the beam pointing. We record the strength of these fluctuations vs. two basic input parameters, which are the drive laser pulse energy and the gas pressure in the capillary waveguide. In correlation measurements between single-shot drive laser beam profiles and single-shot high-harmonic beam profiles we prove the absence of drive laser beam-pointing-induced fluctuations in the high-harmonic output. We attribute the main source of high-harmonic fluctuations to ionization-induced nonlinear mode mixing during propagation of the drive laser pulse inside the capillary waveguide

Blame, Symbolic Stigma and HIV Misconceptions are Associated with Support for Coercive Measures in Urban India

This study was designed to examine the prevalence of stigma and its underlying factors in two large Indian cities. Cross-sectional interview data were collected from 1,076 non-HIV patients in multiple healthcare settings in Mumbai and Bengaluru, India. The vast majority of participants supported mandatory testing for marginalized groups and coercive family policies for PLHA, stating that they “deserved” their infections and “didn’t care” about infecting others. Most participants did not want to be treated at the same clinic or use the same utensils as PLHA and transmission misconceptions were common. Multiple linear regression showed that blame, transmission misconceptions, symbolic stigma and negative feelings toward PLHA were significantly associated with both stigma and discrimination. The results indicate an urgent need for continued stigma reduction efforts to reduce the suffering of PLHA and barriers to prevention and treatment. Given the high levels of blame and endorsement of coercive policies, it is crucial that such programs are shaped within a human rights framework

Femtosecond spectral phase shaping for CARS spectroscopy and imaging

Coherent Anti-Stokes Raman Scattering (CARS) is a third-order non-linear optical process that provides label-free, chemically selective microscopy by probing the internal vibrational structure of molecules. Due to the resonant enhancement of the CARS process, faster imaging is possible compared to Raman microscopy. CARS is unaffected by background fluorescence, but the inherent non-resonant background signal can overwhelm the resonant signal. We demonstrate how simple phase shapes on the pump (and probe) beam reduce the background signal and enhance the resonant signal. We demonstrate chemically selective microscopy using these shaped pulses on plastic beads

Controlling the quality factor of a tuning-fork resonance between 9 K and 300 K for scanning-probe microscopy

We study the dynamic response of a mechanical quartz tuning fork in the temperature range from 9 K to 300 K. Since the quality factor Q of the resonance strongly depends on temperature, we implement a procedure to control the quality factor of the resonance. We show that we are able to dynamically change the quality factor and keep it constant over the whole temperature range. This procedure is suitable for applications in scanning probe microscopy.Comment: 5 pages, 6 figure

Can being gay provide a boost in the hiring process? Maybe if the boss is female

Purpose – The purpose of this study was to investigate whether men and women differentially prefer hiring gay and lesbian job applicants relative to equally qualified heterosexual job applicants. Design/methodology/approach – Data were collected from two samples of non-student participants. Each participant evaluated the perceived hirability of an ostensibly real job applicant by reviewing the applicant’s resume. In reality, all participants were randomly assigned to evaluate the same fictitious resume that differed only in the gender and sexual orientation of the applicant. Findings – We find that men perceived gay and lesbian job applicants as less hirable, while women perceived gay and lesbian job applicants as more hirable than heterosexual job applicants. Additionally, we show perceptions of hirability are mediated by perceptions of gay and lesbian job applicants’ competence. Implications – These results show that bias against gays and lesbians is much more nuanced than previous work suggests. One implication is that placing more women in selection roles within organizations could be a catalyst for the inclusion of gay and lesbian employees. Additionally, these results could influence when and how gays and lesbians disclose their gay identities at work. Originality/value –These studies are the first to identify a positive bias in favor of gay and lesbian job applicants. As attitudes toward gays and lesbians become more positive, results like these are important to document as they signal a shift in intergroup relations. These results will also help managers and organizations design selection processes to minimize bias towards applicants. Keywords: gender, sexual orientation, selection, bia

HIV stigma in UK press reporting of a case of intentional HIV transmission

The UK has set itself the ambitious target of zero new HIV transmissions by 2030. HIV stigma is a significant barrier to achieving this target. Media reporting plays an important role in shaping social representations of HIV and of stigma. Between 2016 and 2018, the media in the UK reported on the Daryll Rowe case – the first criminal prosecution for intentional transmission of HIV in the UK. This article examines the way that UK newspapers reported this case, which may have exacerbated HIV stigma. Using Nexis, 178 UK newspaper articles were extracted and subjected to qualitative thematic analysis through a social constructionist lens. Informed by social representations theory, the analysis yielded three discursive themes: (1) Representing the perpetrator through HIV-focussed metaphors; (2) Constructing volitional ambiguity; and (3) Anchoring the lived experience of HIV to misery and death. UK newspapers constructed an ‘evil vs victimhood’ dichotomy in relation to Rowe and the men infected with HIV, respectively. This article argues that news coverage of the Rowe story constructs HIV in ways that are inconsistent with public health messaging. Reporting failed to note innovations in HIV treatment and prevention but instead disseminated stigmatising social representations of HIV. This is important because stigma impedes effective HIV prevention, engagement with HIV care and ultimately our ability to achieve the zero-infections target

Extraction of optical Bloch modes in a photonic-crystal waveguide

We perform phase-sensitive near-field scanning optical microscopy on photonic-crystal waveguides. The observed intricate field patterns are analyzed by spatial Fourier transformations, revealing several guided TE- and TM-like modes. Using the reconstruction algorithm proposed by Ha, et al. (Opt. Lett. 34 (2009)), we decompose the measured two-dimensional field pattern in a superposition of propagating Bloch modes. This opens new possibilities to study specific modes in near-field measurements. We apply the method to study the transverse behavior of a guided TE-like mode, where the mode extends deeper in the surrounding photonic crystal when the band edge is approached

Genetic and Environmental Influences on Individual Differences in Attitudes Toward Homosexuality: An Australian Twin Study

Previous research has shown that many heterosexuals hold negative attitudes toward homosexuals and homosexuality (homophobia). Although a great deal of research has focused on the profile of homophobic individuals, this research provides little theoretical insight into the aetiology of homophobia. To examine genetic and environmental influences on variation in attitudes toward homophobia, we analysed data from 4,688 twins who completed a questionnaire concerning sexual behaviour and attitudes, including attitudes toward homosexuality. Results show that, in accordance with literature, males have significantly more negative attitudes toward homosexuality than females and non-heterosexuals are less homophobic than heterosexuals. In contrast with some earlier findings, age had no significant effect on the homophobia scores in this study. Genetic modelling showed that variation in homophobia scores could be explained by additive genetic (36%), shared environmental (18%) and unique environmental factors (46%). However, corrections based on previous findings show that the shared environmental estimate may be almost entirely accounted for as extra additive genetic variance arising from assortative mating for homophobic attitudes. The results suggest that variation in attitudes toward homosexuality is substantially inherited, and that social environmental influences are relatively minor