The iron(III) complexes of tetra amidato macrocyclic ligands (TAMLs) ([Fe{1-X1-2-X2C6H2-4,5-(NCOCMe2NCO)2CR2}(OH2)]- , 1: X1 = X2 = H, R2 = Me2 (a), R2 = (CH2)2 (b); X1 = X2 = Cl, R2 = F2 (c), etc.), which the proton is known to demetalate at pH < 3, are also subject to catalyzed demetalation by Brønsted acid buffer components at pH 4-9 such as H2PO4-, HSO3-, and CH3CO2H, HO2CCH2CO2-. Buffers based on pyridine (py) and tris(hydroxymethyl)aminomethane (TRIS) are catalytically inactive. Where reactions proceed, the products are demetalated TAMLs and iron species of variable composition. Pseudo-first-order rate constants for the demetalation (kobs) are linear functions of the acid concentrations, and the effective second-order rate constants k1,eff have a hyperbolic dependence on [H+] (k1,eff = a1[H+]/(b1+[H+]). The rate of demetalation of 1a in H2PO4-/HPO42- buffer is appreciable, but the kobs values for 1b and 1c are immeasurably low, showing that the rates are strongly affected by the CR2 or "tail" fragments, which are known to potently affect the TAML basicity. The reactivities of 1 depend insignificantly on the aromatic ring or "head" group of 1. The proposed mechanism involves precoordination of the acidic buffer species followed by hydrolysis. The demetalating abilities of buffer species depend on their structures and acidities. Thus, although pyridine-2-carboxylic (picolinic) acid catalyzes the demetalation, its 3- and 4-isomers (nicotinic and isonicotininc acids) are inactive. The difference is rationalized to result from the ability that only coordinated picolinic acid has to deliver a proton to an amidato nitrogen in an intramolecular manner. The reaction order in picolinic acid equals one for 1a and two for 1b. For 1b, "inactive" pyridine and nicotinic acid speed up the demetalation in the presence of picolinic acid, suggesting that the second order arises from the axial binding of two pyridine molecules, one of which must be picolinic acid. The binding of pyridine- and imidazole-type ligands was confirmed by UV/vis equilibrium measurements and X-ray crystallography. The implications of these mechanistic findings for designing superior Fe-TAML oxidation catalysts and catalyst formulations are discussed using the results of DFT calculations.
BackgroundPeripheral regional anesthesia and analgesia may increase the efficiency of ambulatory surgical centers by reducing pain and preventing nausea and vomiting, which are important modifiable causes of prolonged postanesthesia care unit (PACU) length of stay. We hypothesized that the use of peripheral nerve blocks (PNB) was associated with shorter PACU length of stay in ambulatory surgery.MethodsIn this retrospective cohort study, we analyzed data from adult ambulatory surgical cases, in which PNB was a viable anesthetic option (ie, was routinely performed for these procedures), at an academic medical center between 2008 and 2018. We assessed the association between the use of PNB and the primary endpoint of PACU length of stay. As key secondary endpoint, we compared intraoperative opioid doses. Analyses were adjusted for patient demographics, comorbidities and intraoperative factors.ResultsA total of 57 040 cases were analyzed, of whom 13 648 (23.9%) received a PNB. The use of PNB was associated with shorter PACU length of stay (a decrease of 7.3 min, 95% CI 6.1 to 8.6, p<0.001). This association was most pronounced in surgeries of long duration (decrease of 11.2 min, 95% CI 9.0 to 13.4) and in patients undergoing leg and ankle procedures (decrease of 15.1 min, 95% CI 5.5 to 24.6). Intraoperative opioid doses were significantly lower in patients receiving a nerve block (decrease of 9.40 mg oral morphine equivalents, 95% CI 8.34 to 10.46, p<0.001).ConclusionThe use of PNB significantly reduced PACU length of stay in ambulatory surgical patients, which may in part be attributed to lower intraoperative opioid requirements.
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