Despite significant developments in mass spectrometry technology in recent years, no routine proteomics sequencing tool is currently available for peptide anions. The use of a molecular open-shell cation is presented here as a possible reaction partner to induce electron transfer dissociation with deprotonated peptide anions. In this negative electron transfer dissociation (NETD) scheme, an electron is abstracted from the peptide anion and transferred to the radical cation. This is demonstrated for the example of the fluoranthene cation, C(16)H(10)(+*), which is reacted with deprotonated phosphorylated peptides in a 3-D ion trap mass spectrometer. Selective backbone cleavage at the C(alpha)-C bond is observed to yield a and x fragments, similarly to electron detachment dissociation (EDD) of peptide anions. Crucially, the phosphorylation site is left intact in the dissociation process, allowing an identification and localization of the post-translational modification (PTM) site. In contrast, NETD using Xe(+*) as the reagent cation results in sequential neutral losses (CO(2) and H(3)PO(4)) from a/x fragments, which complicate the interpretation of the mass spectra. This difference in dissociation behavior can be understood in the framework of the reduced recombination energy of the electron transfer process for fluoranthene, which is estimated at 2.5-4.5 eV, compared to 6.7-8.7 eV for xenon. Similarly to ETD, proton transfer is found to compete with electron transfer processes in NETD. Isotope fitting of the charge-reduced species shows that in the case of fluoranthene-mediated NETD, proton transfer only accounts for <20%, whereas this process highly abundant for Xe(+*) (43 and 82%). Since proton abstraction from Xe(+*) is not possible, this suggests that Xe(+*) ionizes other transient species in the ion trap, which then engage in proton transfer reactions with the peptide anions.
Objective: To determine internal medicine (IM) residents’ knowledge of, attitudes towards, and barriers to prescribing buprenorphine for opioid use disorder (OUD). Methods: We conducted a cross-sectional study of IM residents across all 35 Accreditation Council for Graduate Medical Education (ACGME) accredited Florida IM residency programs. We used an online survey to collect information about resident demographics, substance use curriculums, career interests, content knowledge about diagnosing and managing OUD, and attitudes about and barriers to prescribing buprenorphine for OUD. We used Chi-square test to explore differences in interest in prescribing buprenorphine. We created a composite knowledge score and investigated distribution of knowledge among characteristics via Mann-Whitney U test. Results: There were 161 participants (response rate 16.0%, n = 1008) across 35 programs Seventy-seven percent of residents provided care for patients with OUD more than once per month. Seventy-four percent report no buprenorphine prescribing training. Higher knowledge scores, interest in primary care, being an intern, and caring for patients with OUD more than monthly were associated with interest in obtaining a buprenorphine waiver (P < 0.05). Limited knowledge about OUD was the most important barrier to prescribing buprenorphine. Eighty-nine percent support legislation to deregulate buprenorphine. Conclusions: Knowledge about managing OUD was poor and represented the most commonly cited barrier to prescribing buprenorphine. Residents want to expand their role in treating OUD. Our findings warrant incorporating addiction medicine into residency curriculum standards. Legislation removing the buprenorphine waiver requirement may increase the number of resident buprenorphine prescribers and improve treatment options for patients with opioid addiction.
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