Changes in Utilization of Birth Control and PrEP During COVID-19 in the USA: A Mixed-Method Analysis.

In the USA, the COVID-19 pandemic has created challenges beyond the direct consequences of the infection. Because of shifting resources in response to need, many domains within the healthcare sector unrelated to COVID-19 have had interrupted abilities to provide care. In the current study, we focus on preventative sexual health care during the pandemic. In a sample of 511 (mean age = 27.7) people, we examined quantitative data regarding continuation and discontinuation of birth control and PrEP during the pandemic, along with qualitative data illustrating the underlying reasons for participants' (dis)continuation. Results showed that most (92.5%) of birth control users reported continuation of their birth control, with the predominant reasons reported being use for health reasons, long-acting reversible contraceptive use, access to remote healthcare services, and increased vigilance over pregnancy prevention. Conversely, around half (52.6%) of PrEP-using participants reported already discontinuing or planning to discontinue their PrEP regimen. Temporary abstinence and concerns about accessing in-person health care were the predominant reasons for PrEP discontinuation. These results have implications for both researchers and sexual healthcare providers. Disruptions to preventative sexual health care should be considered in ongoing research about patient needs, and healthcare providers may wish to consider particular challenges faced by PrEP users concerning re-start and continuation.

Structural elucidation of triacylglycerol using online acetone Paternò-Büchi reaction coupled with reversed-phase liquid chromatography mass spectrometry.

Triacylglycerol (TG) is a class of lipids that is responsible for energy storage and cell metabolism in biological systems; it is found in relatively high abundances in biological fluids such as human plasma. Due to structural complexity, analyzing TGs using shotgun lipidomic approaches is challenging because of the presence of multiple fatty acyl compositional isomers. In this work, reversed-phase liquid chromatography (RPLC) was used for separation of TG species due to the capability of separating lipids based on fatty acyl chain lengths and degrees of unsaturation. RPLC alone does not provide structurally informative information for the location of carbon-carbon double-bonds (C[double bond, length as m-dash]Cs) without using synthesized standards that correspond to each species analyzed. The Paternò-Büchi (PB) reaction was employed online to confidently characterize the location of C[double bond, length as m-dash]Cs within lipid species via photo-initiated modification of the alkene group with acetone, which was later subjected to electrospray ionization (ESI) and tandem mass spectrometry (MS/MS) to form signature fragmentation peaks. This online RPLC-PB-MS/MS system was able to distinguish fatty acyl level and C[double bond, length as m-dash]C level isomeric species. The systems allowed for the identification of 46 TG molecular species in human plasma with confident C[double bond, length as m-dash]C location assignment in fatty acyls at a limit of identification of 50 nM.

In-depth structural characterization of phospholipids by pairing solution photochemical reaction with charge inversion ion/ion chemistry.

Shotgun lipid analysis based on electrospray ionization-tandem mass spectrometry (ESI-MS/MS) is increasingly used in lipidomic studies. One challenge for the shotgun approach is the discrimination of lipid isomers and isobars. Gas-phase charge inversion via ion/ion reactions has been used as an effective method to identify multiple isomeric/isobaric components in a single MS peak by exploiting the distinctive functionality of different lipid classes. In doing so, fatty acyl chain information can be obtained without recourse to condensed-phase separations or derivatization. This method alone, however, cannot provide carbon-carbon double bond (C=C) location information from fatty acyl chains. Herein, we provide an enhanced method pairing photochemical derivatization of C=C via the Paternò-Büchi reaction with charge inversion ion/ion tandem mass spectrometry. This method was able to provide gas-phase separation of phosphatidylcholines and phosphatidylethanolamines, the fatty acyl compositions, and the C=C location within each fatty acyl chain. We have successfully applied this method to bovine liver lipid extracts and identified 40 molecular species of glycerophospholipids with detailed structural information including head group, fatty acyl composition, and C=C location. Graphical Abstract ᅟ.

Localization of cyclopropyl groups and alkenes within glycerophospholipids using gas-phase ion/ion chemistry.

Shotgun lipid analysis using electrospray ionization tandem mass spectrometry (ESI-MS/MS) is a common approach for the identification and characterization of glycerophohspholipids GPs. ESI-MS/MS, with the aid of collision-induced dissociation (CID), enables the characterization of GP species at the headgroup and fatty acyl sum compositional levels. However, important structural features that are often present, such as carbon-carbon double bond(s) and cyclopropane ring(s), can be difficult to determine. Here, we report the use of gas-phase charge inversion reactions that, in combination with CID, allow for more detailed structural elucidation of GPs. CID of a singly deprotonated GP, [GP - H]- , generates FA anions, [FA - H]- . The fatty acid anions can then react with doubly charged cationic magnesium tris-phenanthroline complex, [Mg(Phen)3 ]2+ , to form charge inverted complex cations of the form [FA - H + MgPhen2 ]+ . CID of the complex generates product ion spectral patterns that allow for the identification of carbon-carbon double bond position(s) as well as the sites of cyclopropyl position(s) in unsaturated lipids. This approach to determining both double bond and cyclopropane positions is demonstrated with GPs for the first time using standards and is applied to lipids extracted from Escherichia coli.

Examining differences in menstrual and intimate care product use by race/ethnicity and education among menstruating individuals.

Introduction: United States consumers spend over two billion dollars a year on intimate care products. These products, along with scented menstrual products, are marketed for odor control, perceived "freshness," and vaginal/vulvar cleanliness. However, these scent-altering products may increase exposure to carcinogenic and endocrine-disrupting chemicals. Prior research has not adequately characterized demographic differences in product use. The objective of our study is to examine racial/ethnic and educational differences in menstrual and intimate care product use among people who menstruate. Methods: We pooled data from two US-based cross sectional studies to examine demographic characteristics and product use in 661 participants aged 18-54 years. Participants reported use of scented and unscented menstrual products (tampons, sanitary pads, and menstrual cups) and intimate care products (vaginal douches, sprays, wipes, and powders). We examined differences by race/ethnicity and education using log-binomial regression and latent class analysis (LCA), which can identify groups based on product use patterns. Results: Our sample was 33.4% Black, 30.9% Latina, 18.2% White, and 16.2% another identity. Approximately half the population had a bachelor's degree or more; 1.4% identified as transgender and 1.8% as non-binary. In adjusted models, scent-altering products (i.e., scented menstrual and intimate care products) were more likely to be used by those with less formal education (p < 0.05). Unscented menstrual products were more likely to be used by those with more formal education. Compared to Black participants, White participants were more likely to use unscented tampons and menstrual cups and less likely to use douches and wipes (p < 0.05). Using LCA we identified two groups: one more likely to use scent-altering products, and a second more likely to use unscented menstrual products. Less education and older age, but not race/ethnicity, was significantly associated with membership in the group more likely to use scent-altering products. While sex/gender composition did not statistically vary across groups, all non-binary participants fell in the unscented menstrual product group. Discussion: Lower educational attainment was consistently associated with greater use of scent-altering menstrual and intimate care products. Future research should examine associations between body odor stigma, product use, and health risks at intersections of race, class, and gender.

Coupling Headgroup and Alkene Specific Solution Modifications with Gas-Phase Ion/Ion Reactions for Sensitive Glycerophospholipid Identification and Characterization.

Shotgun lipidomics provides sensitive and fast lipid identification without the need for chromatographic separation. Challenges faced by shotgun analysis of glycerophospholipids (GPs) include the lack of signal uniformity across GP classes and the inability to determine the carbon-carbon double bond (C═C) location within the fatty acyl chains of an unsaturated species. Two distinct derivatization strategies were employed to both enhance the ionization of GPs, via trimethylation enhancement using 13C-diazomethane (13C-TrEnDi), as well as determine location of double bonds within fatty acyl chains, employing an in-solution photochemical reaction with acetone (via the Paternò-Büchi reaction). The modified GPs were then subjected to positive ion mode ionization via electrospray ionization, producing uniform ionization efficiencies for different classes of GP species. The GPs were charge inverted via gas-phase ion/ion reactions and sequentially fragmented using ion trap collision-induced dissociation (CID). The CID of the species led to fragmentation producing diagnostic ions indicative of C═C bond location. The approach enabled enhanced ionization and the identification of phosphatidylcholine and phosphatidylethanolamine species at the C═C level in a bovine lipid extract.

Uncovering Structural Diversity of Unsaturated Fatty Acyls in Cholesteryl Esters via Photochemical Reaction and Tandem Mass Spectrometry.

Mass spectrometry analysis of cholesteryl esters (CEs) faces several challenges, with one of them being the determination of the carbon-carbon double bond (C=C) locations within unsaturated fatty acyl chains. Paternὸ-Büchi (PB) reaction, a photochemical reaction based on the addition of acetone to C=C, is capable of C=C location determination when coupled with tandem mass spectrometry (MS/MS). In this study, the PB reaction conditions were tailored for CEs and subsequent nanoelectrospray ionization (nanoESI). A solvent system containing acetone/methanol/dichloromethane/water (40/30/20/10, volume ratios) and 100 µM LiOH was determined to be optimal, resulting in reasonable PB reaction yield (~30%) and good ionization efficiency (forming lithium adduct of CEs). Collision-induced dissociation (CID) of the PB reaction products produced characteristic fragment ions of CE together with those modified by the PB reactions, such as lithiated fatty acyl ([FA + Li]+) and its PB product ([FA - PB + Li]+). MS3 CID of [FA - PB + Li]+ led to abundant C=C diagnostic ion formation, which was used for C=C location determination and isomer quantitation. A PB-MS3 CID approach was developed and applied for CE analysis from human plasma. A series of unsaturated CEs was identified with specific C=C locations within fatty acyl chains. Absolute quantitation for each CE species was achieved including coexisting C=C location isomers, such as Δ9 and Δ11 isomers of CE 18:1 and ω-6 and ω-3 isomers of CE 18:3. These results show that PB-MS/MS is useful in uncovering structural diversity of CEs due to unsaturation in fatty acyls, which is often undetected from current lipid analysis approach. Graphical Abstract ᅟ.