Biomedical subjects

R L Zuckerman

Publications and source records attributed to R L Zuckerman.

6 recordsLinked to original sources

PubMed2000

Zirconium-mediated metathesis of imines: a study of the scope, longevity, and mechanism of a complicated catalytic system.

By kinetically stabilizing imidozirconocene complexes through the use of a sterically demanding ligand, or by generating a more thermodynamically stable resting state with addition of diphenylacetylene, we have developed transition metal-catalyzed imine metathesis reactions that are mechanistically analogous to olefin metathesis reactions catalyzed by metal carbene complexes. When 5 mol % of Cp*Cp(THF)Zr=N(t)Bu is used as the catalyst precursor in the metathesis reaction between PhCH=NPh and p-TolCH=N-p-Tol, a 1:1:1:1 equilibrium mixture with the two mixed imines p-TolCH=NPh and PhCH=N-p-Tol is generated in C(6)D(6) at 105 degrees C. The catalyst was still active after 20 days with an estimated 847 turnovers (t(1/2) 170 m; TON = 1.77 h(-1)). When the azametallacyclobutene Cp(2)Zr(N(Tol)C(Ph)=C(Ph)) is used as the catalyst precursor under similar reaction conditions, a total of 410 turnovers are obtained after 4 days (t(1/2) 170 m; TON = 4.3 h(-1)). An extensive kinetic and equilibrium analysis of the metallacyclobutene-catalyzed metathesis of PhCH=N-p-Tol and p-F-C(6)H(4)CH=N-p-F-C(6)H(4) was carried out by monitoring the concentrations of imines and observable metal-containing intermediates over time. Numerical integration methods were used to fit these data to a detailed mechanism involving coordinatively unsaturated (16-electron) imido complexes as critical intermediates. Examination of the scope of reaction between different organic imines revealed characteristic selectivity that appears to be unique to the zirconium-mediated system. Several zirconocene complexes that could generate the catalytically active "CpCp'Zr=NAr" (Cp' = Cp or Cp*) species in situ were found to be effective agents in the metathetical exchange between different N-aryl imines. N-Alkyl aldimines were found to be completely unreactive toward metathesis with N-aryl aldimines, and metathesis reactions involving the two N-alkyl imines TolCH=NPr and PhCH=NMe gave slow or erratic results, depending on the catalyst used. Metathesis was observed between N-aryl ketimines and N-aryl aldimines, but for N-aryl ketimine substrates, the catalyst resting state consists of zirconocene enamido complexes, generated by the formal C-H activation of the alpha position of the ketimine substrates.

Journal Article↗

PubMed2000

Effectiveness of remifentanil versus traditional fentanyl-based anesthetic in high-risk outpatient surgery.

STUDY OBJECTIVE: To determine if remifentanil would offer a superior hemodynamic and recovery profile compared to the current standard of care, which implements a fentanyl-based technique. DESIGN: Randomized, single-blind study. SETTING: Outpatient center associated with tertiary care center. PATIENTS: 75 outpatients undergoing microsuspension laryngoscopy. INTERVENTIONS: Patients were randomized to either a remifentanil induction (0.5 microg/kg/min) and maintenance (0.25 microg/kg/min) versus fentanyl (maximum of 250 microg) as the only opioid. All patients received propofol as part of the induction and maintenance with or without the use of nitrous oxide. MEASUREMENTS: Assessment of hemodynamics [heart rate (HR) and blood pressure(BP)], presence of perioperative myocardial ischemia on ambulatory electrocardiographic monitoring, and time to discharge. MAIN RESULTS: Significantly fewer patients in the remifentanil group demonstrated episodes of tachycardia (HR > 100 beats per min) compared to the fentanyl group (14% vs. 40%, p<0.05), with significantly fewer episodes of tachycardia and hypertension per patient. Recovery profiles between the two groups did not show clinically significant differences. CONCLUSIONS: Remifentanil, a new short-acting opioid, offers excellent hemodynamic control for brief, intense outpatient procedures performed in high-risk patients; however, its use was not associated with any improvement in recovery profiles.

Aged↗

PubMed1997

A randomized, double-blind, dose-response comparison of epidural fentanyl versus sufentanil analgesia after cesarean section.

This study was designed to determine and compare the dose-response characteristics, speed of onset, and relative potency of single-dose epidural fentanyl (F) and sufentanil (S) for postoperative pain relief. Eighty women undergoing cesarean section (C/S) with epidural 2% lidocaine with epinephrine (1:200,000) were randomly assigned to receive double-blind epidural administration of F (25, 50, 100, or 200 microg) or S (5, 10, 20, or 30 microg) (n = 10 per group) upon complaint of pain postoperatively. Visual analog scales (VAS, 0-100 mm) were used to assess pain and sedation at baseline; at 3, 6, 9, 12, 15, 20, 25, 30, 45, and 60 min; and every 30 min until further analgesia was requested. The study was terminated at 30 min if satisfactory analgesia was not achieved. Side effects were recorded. A dose-response was demonstrated for both opioids. F 25 microg and S 5 microg were ineffective, with significantly fewer women achieving VAS scores <10 mm (P < 0.05 compared with F 100 or 200 microg and S 20 or 30 microg). F 100 and 200 microg and S 20 and 30 microg all achieved VAS scores <10 mm in all women with no differences in time to 50% reduction in VAS (mean 11-16 min) and no differences in duration of analgesia (mean 117-138 min). The 50% and 95% effective dose values for each opioid to achieve a VAS score <10 mm were F 33 microg and 92 microg and S 6.7 microg and 17.5 microg. There were no differences among groups in sedation scores or side effects. Our data suggest that the relative analgesic potency of epidural S:F is approximately 5 and that there are no differences between the opioids in the onset, duration, and effectiveness of analgesia when equianalgesic doses are administered postoperatively after lidocaine anesthesia for C/S.

Adult↗

PubMed1994

Anesthesia in obstetrics.

Some of the topics which have generated particular interest in obstetric anesthesia recently include the effects of epidural anesthesia on the progress of labor, the efficacy of volume preloading prior to spinal anesthesia for cesarean section, and the use of intraspinal opioids and of alpha-2 adrenergic agonists for labor analgesia.

Analgesia, Epidural↗

PubMed1991

Effect of halothane on arrhythmogenic responses induced by sympathomimetic agents in single rat heart cells.

The combination of catecholamines and halothane has long been recognized as arrhythmogenic. The purpose of this study was to evaluate whether the mechanism of this interaction originates at the single cell level. The incidence of spontaneous contractile waves occurring between stimulated beats (interbeat waves), early aftercontractions, and late aftercontractions was measured in rat myocytes exposed to sympathomimetics with and without halothane. Each of these endpoints in single cells has the potential to produce arrhythmias in multicellular preparations. Interbeat waves and late aftercontractions were observed with isoproterenol (1 X 10(-7) M) and norepinephrine (1-3 X 10(-7) M). The incidence of these phenomena was significantly reduced in the presence of 0.30 mM halothane. Early aftercontractions occurred in the presence of isoproterenol (1 X 10(-7) M), norepinephrine (1-3 X 10(-7) M), and phenylephrine (5-10 X 10(-6) M). There was a statistically significant decrease in the incidence of early aftercontractions in the presence of 0.30 mM halothane. These results indicate that the mechanism behind the clinically observed increased arrhythmogenicity of catecholamines with halothane does not arise at the level of single ventricular cells because halothane inhibited sympathomimetic-induced arrhythmogenic activity in this model. The probable mechanisms rather include altered impulse propagation, which might lead to phenomena such as reentry.

Animals↗

PubMed1989

Iatrogenic factors in "managed" psychotherapy.

The clinical implications of the "case-manager" system are explored through a detailed case presentation. It is demonstrated that the introduction of a third person into the therapeutic relationship compromises the therapeutic alliance and the transference. Under such conditions psychotherapy is impossible.

Adult↗