Nolan to Wesley, 28 June 1957

Professional correspondenc

Tracking the Amide I and αCOO− Terminal ν(C=O) Raman Bands in a Family of L-Glutamic Acid-Containing Peptide Fragments: A Raman and DFT Study

The E-hook of β-tubulin plays instrumental roles in cytoskeletal regulation and function. The last six C-terminal residues of the βII isotype, a peptide of amino acid sequence EGEDEA, extend from the microtubule surface and have eluded characterization with classic X-ray crystallographic techniques. The band position of the characteristic amide I vibration of small peptide fragments is heavily dependent on the length of the peptide chain, the extent of intramolecular hydrogen bonding, and the overall polarity of the fragment. The dependence of the E residue’s amide I ν(C=O) and the αCOO− terminal ν(C=O) bands on the neighboring side chain, the length of the peptide fragment, and the extent of intramolecular hydrogen bonding in the structure are investigated here via the EGEDEA peptide. The hexapeptide is broken down into fragments increasing in size from dipeptides to hexapeptides, including EG, ED, EA, EGE, EDE, DEA, EGED, EDEA, EGEDE, GEDEA, and, finally, EGEDEA, which are investigated with experimental Raman spectroscopy and density functional theory (DFT) computations to model the zwitterionic crystalline solids (in vacuo). The molecular geometries and Boltzmann sum of the simulated Raman spectra for a set of energetic minima corresponding to each peptide fragment are computed with full geometry optimizations and corresponding harmonic vibrational frequency computations at the B3LYP/6-311++G(2df,2pd) level of theory. In absence of the crystal structure, geometry sampling is performed to approximate solid phase behavior. Natural bond order (NBO) analyses are performed on each energetic minimum to quantify the magnitude of the intramolecular hydrogen bonds. The extent of the intramolecular charge transfer is dependent on the overall polarity of the fragment considered, with larger and more polar fragments exhibiting the greatest extent of intramolecular charge transfer. A steady blue shift arises when considering the amide I band position moving linearly from ED to EDE to EDEA to GEDEA and, finally, to EGEDEA. However, little variation is observed in the αCOO− ν(C=O) band position in this family of fragments

Redefining the Social Geography of Community STI Risk: An Ecological Study of the Association, Mediators, and Moderators of Area-Level Prostitution Arrests

Background: Core groups such as sex workers have been implicated in contributing to higher area STI risk but no studies have analyzed mediators and moderators of this relationship using population data. Objectives: Assess the overall association of area-level prostitution and STI risk, and mediators and moderators of the relationship. Methods: Point-level prostitution and drug arrests were geocoded and aggregated by Census blockgroup. Chlamydia (CT), gonorrhea (GC), syphilis and incident HIV positive test results were aggregated by blockgroup after eliminating same-organism positive tests within 14 days of an initial positive test. Census data also defined moderators: blockgroups with >75% black and >20% Latino (top decile) and >60% below 200% of the federal poverty line (top quartile). Negative binomial and zero-inflated negative binomial regressions were used to estimate incident rate ratios (IRR) of each STI. Results: There was a dose-response relationship between prostitution arrest blockgroup quintiles and IRR of each STI. In models including drug arrest data, this association was completely eliminated. Though % black blockgroup composition had significant interaction with prostitution arrest rates and with respect to its relationship with STI IRR, % Latino did not consistently have this association. Blockgroups with proportions of low minority and low poverty had highest drug arrest IRR for each STI. In these areas, prostitution arrest IRR were only significant for CT and GC and were consistently lower than drug arrest IRRs. Conclusions: Though prostitution arrests are associated with STI risk, this relationship is mediated by drug arrests. Associations of both arrest rates are strongest in low minority, low poverty communities, indicating that high baseline STI prevalence is not moderated by levels of drug and prostitution arrests. Implications for Programs, Policy, and Research: These data suggest that important relationships exist for prostitution and, to a greater degree, drug arrests within communities traditionally defined as ‘low-risk’

Synthesis of methanediol [CH2(OH)2]: The simplest geminal diol

Geminal diols—organic molecules carrying two hydroxyl groups at the same carbon atom—have been recognized as key reactive intermediates by the physical (organic) chemistry and atmospheric science communities as fundamental transients in the aerosol cycle and in the atmospheric ozonolysis reaction sequence. Anticipating short lifetimes and their tendency to fragment to water plus the aldehyde or ketone, free geminal diols represent one of the most elusive classes of organic reactive intermediates. Here, we afford an exceptional glance into the preparation of the previously elusive methanediol [CH2(OH)2] transient—the simplest geminal diol—via energetic processing of low-temperature methanol–oxygen ices. Methanediol was identified in the gas phase upon sublimation via isomer-selective photoionization reflectron time-of-flight mass spectrometry combined with isotopic substitution studies. Electronic structure calculations reveal that methanediol is formed via excited state dynamics through insertion of electronically excited atomic oxygen into a carbon–hydrogen bond of the methyl group of methanol followed by stabilization in the icy matrix. The first preparation and detection of methanediol demonstrates its gas-phase stability as supported by a significant barrier hindering unimolecular decomposition to formaldehyde and water. These findings advance our perception of the fundamental chemistry and chemical bonding of geminal diols and signify their role as an efficient sink of aldehydes and ketones in atmospheric environments eventually coupling the atmospheric chemistry of geminal diols and Criegee intermediate

Use of Cell Phone Diaries to Understand Risk Contexts of Sexual Events Among Female Sex Workers

Background Data collection using mobile technologies, such as cell phones, allows more frequent and real-time data collection and is less prone to recall bias. We describe the feasibility of using twice daily cell phone diaries to capture contextual features of STI/HIV-risk that could impact disease acquisition among female sex workers (FSW). Methods Women engaging in transactional sex in the prior 90 days were recruited utilising incentivized snowball sampling. Participants completed STI testing and baseline/exit surveys. Over 4-weeks, they completed twice-daily electronic diaries assessing event-level sexual behaviour, condom use, and drug use. Weekly in-person interviews used open-ended questions to explore geographical characteristics of sexual encounter locations as well as acceptability of event-level monitoring. Results 25/26 participants (median age 43.5 years) completed the 4-week study. At baseline, 27% tested positive for a STI. Participants completed 84.5% of 1,518 expected surveys and 95% of 106 expected interviews. Patterns of diary compliance were stable over time. Partnered sexual activity was captured in 21.4% of diaries. At the participant-level, most reported giving oral sex (84.7%) or vaginal sex (96.1%); fewer (19.2%) reported engaging in anal sex. Among women reporting partnered sexual behaviour with any partner type (i.e., new/regular customers, romantic partners), using condoms was reported 39.2%, 45.5% and 83.3% of the time for giving oral sex, vaginal sex, and anal sex respectively. At the event-level, the frequency of giving oral sex, vaginal sex or anal sex did not significantly change over time. Conclusions It is feasible to engage and retain FSW in a technologically-advanced study to characterise risk contexts of sexual events. Adherence to study protocol was high indicating event-level monitoring using cell phone based diaries is acceptable. These data can be utilised to improve our understanding of the individual, relational and environmental factors that influence STI/HIV acquisition among FSW

Bisphenol A exposure in Mexico City and risk of prematurity: a pilot nested case control study

Abstract Background Presence of Bisphenol A (BPA) has been documented worldwide in a variety of human biological samples. There is growing evidence that low level BPA exposure may impact placental tissue development and thyroid function in humans. The aim of this present pilot study was to determine urinary concentrations of BPA during the last trimester of pregnancy among a small subset of women in Mexico City, Mexico and relate these concentrations to risk of delivering prematurely. Methods A nested case-control subset of 60 participants in the Early Life Exposure in Mexico to ENvironmental Toxicants (ELEMENT) study in Mexico City, Mexico were selected based on delivering less than or equal to 37 weeks of gestation and greater than 37 weeks of gestation. Third trimester archived spot urine samples were analyzed by online solid phase extraction coupled with high performance liquid chromatography isotope dilution tandem mass spectrometry. Results BPA was detected in 80.0% (N = 48) of the urine samples; total concentrations ranged from < 0.4 μg/L to 6.7 μg/L; uncorrected geometric mean was 1.52 μg/L. The adjusted odds ratio of delivering less than or equal to 37 weeks in relation to specific gravity adjusted third trimester BPA concentration was 1.91 (95%CI 0.93, 3.91, p-value = 0.08). When cases were further restricted to births occurring prior to the 37th week (n = 12), the odds ratio for specific-gravity adjusted BPA was larger and statistically significant (p < 0.05). Conclusions This is the first study to document measurable levels of BPA in the urine of a population of Mexican women. This study also provides preliminary evidence, based on a single spot urine sample collected during the third trimester, that pregnant women who delivered less than or equal to 37 weeks of gestation and prematurely (< 37 weeks) had higher urinary concentrations of BPA compared to women delivering after 37 weeks.http://deepblue.lib.umich.edu/bitstream/2027.42/78251/1/1476-069X-9-62.xmlhttp://deepblue.lib.umich.edu/bitstream/2027.42/78251/2/1476-069X-9-62.pdfPeer Reviewe

BioMaPS: A Roadmap for Success

The manuscript outlines the impact that our National Science Foundation Interdisciplinary Training for Undergraduates in Biological and Mathematical Sciences program, BioMaPS, has had on the students and faculty at Murray State University. This interdisciplinary program teams mathematics and biology undergraduate students with mathematics and biology faculty and has produced research insights and curriculum developments at the intersection of these two disciplines. The goals, structure, achievements, and curriculum initiatives are described in relation to the effects they have had to enhance the study of biomathematics

Psychometric Evaluation of the HIV Stigma Scale in a Swedish Context

Background HIV-related stigma has negative consequences for infected people's lives and is a barrier to HIV prevention. Therefore valid and reliable instruments to measure stigma are needed to enable mapping of HIV stigma. This study aimed to evaluate the psychometric properties of the HIV stigma scale in a Swedish context with regard to construct validity, data quality, and reliability. Methods The HIV stigma scale, developed by Berger, Ferrans, and Lashley (2001), was distributed to a cross-sectional sample of people living with HIV in Sweden (n = 194). The psychometric evaluation included exploratory factor analysis together with an analysis of the distribution of scores, convergent validity by correlations between the HIV stigma scale and measures of emotional well-being, and an analysis of missing items and floor and ceiling effects. Reliability was assessed using Cronbach's α. Results The exploratory factor analysis suggested a four-factor solution, similar to the original scale, with the dimensions personalised stigma, disclosure concerns, negative self-image, and concerns with public attitudes. One item had unacceptably low loadings and was excluded. Correlations between stigma dimensions and emotional well-being were all in the expected direction and ranged between −0.494 and −0.210. The instrument generated data of acceptable quality except for participants who had not disclosed their HIV status to anybody. In line with the original scale, all subscales demonstrated acceptable internal consistency with Cronbach's α 0.87–0.96. Conclusion A 39-item version of the HIV stigma scale used in a Swedish context showed satisfactory construct validity and reliability. Response alternatives are suggested to be slightly revised for items assuming the disclosure of diagnosis to another person. We recommend that people that have not disclosed should skip all questions belonging to the dimension personalised stigma. Our analysis confirmed construct validity of the instrument even without this dimension