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  • 1
    Online Resource
    Online Resource
    Wiley ; 2017
    In:  Rapid Communications in Mass Spectrometry Vol. 31, No. 19 ( 2017-10-15), p. 1633-1640
    In: Rapid Communications in Mass Spectrometry, Wiley, Vol. 31, No. 19 ( 2017-10-15), p. 1633-1640
    Abstract: Methylation protocols commonly call for acidic, hot conditions that are known to promote organic 1 H/ 2 H exchange in aromatic and aliphatic C–H bonds. Here we tested two such commonly used methods and compared a third that avoids these acidic conditions, to quantify isotope effects with each method and to directly determine acidic‐exchange rates relevant to experimental conditions. Methods We compared acidic and non‐acidic methylation approaches catalyzed by hydrochloric acid, acetyl chloride and EDCI (1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide)/DMAP (4‐dimethylaminopyridine), respectively. These were applied to two analytes: phthalic acid (an aromatic) and octacosanoic acid (an aliphatic). We analyzed yield by gas chromatography/flame ionization (GC/FID) and hydrogen and carbon isotopic compositions by isotope ratio mass spectrometry (GC/IRMS). We quantified the 1 H/ 2 H exchange rate on dimethyl phthalate under acidic conditions with proton nuclear magnetic resonance ( 1 H‐NMR) measurements. Results The δ 2 H and δ 13 C values and yield were equivalent among the three methods for methyl octacosanoate. The two acidic methods resulted in comparable yield and isotopic composition of dimethyl phthalate; however, the non‐acidic method resulted in lower δ 2 H and δ 13 C values perhaps due to low yields. Concerns over acid‐catalyzed 1 H/ 2 H exchange are unwarranted as the effect was trivial over a 12‐h reaction time. Conclusions We find product isolation yield and evaporation to be the main concerns in the accurate determination of isotopic composition. 1 H/ 2 H exchange reactions are too slow to cause measurable isotope fractionation over the typical duration and reaction conditions used in methylation. Thus, we are able to recommend continued use of acidic catalysts in such methylation reactions for both aliphatic and aromatic compounds.
    Type of Medium: Online Resource
    ISSN: 0951-4198 , 1097-0231
    URL: Issue
    Language: English
    Publisher: Wiley
    Publication Date: 2017
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    detail.hit.zdb_id: 58731-X
    SSG: 11
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  • 2
    In: Geobiology, Wiley, Vol. 19, No. 2 ( 2021-03), p. 162-172
    Abstract: The vertical distribution of subseafloor archaeal communities is thought to be primarily controlled by in situ conditions in sediments such as the availability of electron acceptors and donors, although sharp community shifts have also been observed at lithological boundaries suggesting that at least a subset of vertically stratified Archaea form a long‐term genetic record of coinciding environmental conditions that occurred at the time of sediment deposition. To substantiate this possibility, we performed a highly resolved 16S rRNA gene survey of vertically stratified archaeal communities paired with paleo‐oceanographic proxies in a sedimentary record from the northern Red Sea spanning the last glacial–interglacial cycle (i.e., marine isotope stages 1–6; MIS1‐6). Our results show a strong significant correlation between subseafloor archaeal communities and drastic paleodepositional changes associated with glacial low vs. interglacial high stands (ANOSIM; R  = .73; p  = .001) and only a moderately strong correlation with lithological changes. Bathyarchaeota, Lokiarchaeota, MBGA, and DHVEG‐1 were the most abundant identified archaeal groups. Whether they represented ancient cell lines from the time of deposition or migrated to the specific sedimentary horizons after deposition remains speculative. However, we show that the majority of sedimentary archaeal tetraether membrane lipids were of allochthonous origin and not produced in situ. Slow post‐burial growth under energy‐limited conditions would explain why the downcore distribution of these dominant archaeal groups still indirectly reflect changes in the paleodepositional environment that prevailed during the analyzed marine isotope stages. In addition, archaea seeded from the overlying water column such as Thaumarchaeota and group II and III Euryarchaeota, which were likely not have been able to subsist after burial, were identified from a lower abundance of preserved sedimentary DNA signatures, and represented direct markers of paleoenvironmental changes in the Red Sea spanning the last six marine isotope stages.
    Type of Medium: Online Resource
    ISSN: 1472-4677 , 1472-4669
    URL: Issue
    Language: English
    Publisher: Wiley
    Publication Date: 2021
    detail.hit.zdb_id: 2113509-5
    SSG: 12
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  • 3
    In: Pharmacoepidemiology and Drug Safety, Wiley, Vol. 31, No. 6 ( 2022-06), p. 605-613
    Abstract: In response to the opioid crisis, opioid analgesic guidelines and prescribing limits have proliferated. The purpose of this narrative review is to examine evidence from studies evaluating the patient or public health impact of federal and state opioid analgesic prescribing guidelines and laws, describe gaps and challenges in current research, and highlight opportunities for improving future research. Methods We focused on evidence from a literature review covering 2013 through 2019. We identified 30 studies evaluating opioid analgesic thresholds based on federal policies and guidelines, state laws, and Medicaid state plans that attempt to influence the course of patient care at or when the limit is exceeded (e.g., prior authorization). Results Most studies evaluated changes in prescribing or dispensing patterns of opioid analgesics, largely finding decreases in prescribing after policy enactment. Fewer studies evaluated patient or public health outcomes beyond changes in prescribing and dispensing patterns; results were infrequently stratified by potentially important sociodemographic and clinical factors. No studies assessed the potential for adverse patient outcomes for which we have emerging evidence of harms. Conclusions We describe knowledge gaps and propose opportunities for future research to sufficiently assess the potential impact and unintended consequences of opioid analgesic prescribing laws, regulations, guidelines, and policies.
    Type of Medium: Online Resource
    ISSN: 1053-8569 , 1099-1557
    URL: Issue
    Language: English
    Publisher: Wiley
    Publication Date: 2022
    detail.hit.zdb_id: 1491218-1
    SSG: 15,3
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