The fundamental nature of Ti(III) complexes generated in tetrahydrofuran by reduction of Cp(2)TiCl(2) has been clarified by means of cyclic voltammetry and kinetic measurements. While the electrochemical reduction of Cp(2)TiCl(2) leads to the formation of Cp(2)TiCl(2)(-), the use of metals such as Zn, Al, or Mn as reductants affords Cp(2)TiCl and (Cp(2)TiCl)(2) in a mixture having a dimerization equilibrium constant of 3 x 10(3) M(-)(1), independent of the metal used. Thus, we find it unlikely that the trinuclear complexes or ionic clusters known from the solid phase should be present in solution as previously suggested. The standard potentials determined for the redox couples Cp(2)TiCl(2)/Cp(2)TiCl(2)(-), (Cp(2)TiCl)(2)(+)/(Cp(2)TiCl)(2), Cp(2)TiCl(+)/Cp(2)TiCl, and Cp(2)Ti(2+)/Cp(2)Ti(+) increase in the order listed. However, the reactivity of the different Ti(III) complexes is assessed as (Cp(2)TiCl)(2) greater, similar Cp(2)TiCl approximately Cp(2)Ti(+) >> Cp(2)TiCl(2)(-) in their reactions with benzyl chloride and benzaldehyde. None of the reactions proceed by an outer-sphere electron transfer pathway, and clearly the inner-sphere character is much higher in the case of Cp(2)Ti(+) than for (Cp(2)TiCl)(2), Cp(2)TiCl, and in particular Cp(2)TiCl(2)(-). As to the electron acceptor, the inner-sphere character increases, going from benzyl chloride to benzaldehyde, and it is suggested that the chlorine atom in benzyl chloride and the oxygen atom in benzaldehyde may function as bridges between the reactants in the transition state.

Patients exposed to a surgical safety checklist experience better postoperative outcomes, but this could simply reflect wider quality of care in hospitals where checklist use is routine.

The mechanism for the electrochemical reduction of titanocene dihalides, Cp 2 TiX 2 (X ) Cl, Br, I), in tetrahydrofuran has been described successfully using a common mesh scheme. On the basis of simulations of recorded cyclic voltammograms it has been possible to evaluate a number of thermodynamic and kinetic parameters for the species involved: i.e., Cp 2 TiX 2 -, (Cp 2 TiX) 2 , Cp 2 TiX, and Cp 2 Ti + . In general, the standard potentials of the oxidized titanium-based species increase (i.e. become less negative) in the orders Cp 2 TiX 2 , (Cp 2 TiX) 2 + , Cp 2 TiX + , CpTi 2+ and X ) Cl, Br, I. From the extracted data pertaining to electrochemically reduced solutions of Cp 2 TiX 2 , it becomes evident that while Cp 2 TiX 2 -is the major constituent for X ) Cl, Cp 2 TiX and (Cp 2 TiX) 2 are the main species in the cases of X ) Br, I. The presence of (Cp 2 TiX) 2 is surprising, as the solvent tetrahydrofuran was believed to be capable of breaking the weak dimeric structure. Kinetic investigations of the reactions between electrochemically reduced solutions of Cp 2 TiX 2 and benzyl chloride show that the reactive species are Cp 2 TiX and (Cp 2 TiX) 2 , with almost no contribution from Cp 2 TiX 2 -, even in the case of X ) Cl.

Background and purpose — Telemedicine could allow patients to be discharged more quickly after surgery and contribute to improve fast-track procedures without compromising quality, patient safety, functionality, anxiety, or other patient-perceived parameters. We investigated whether using telemedicine support (TMS) would permit hospital discharge after 1 day without loss of self-assessed quality of life, loss of functionality, increased anxiety, increased rates of re-admission, or increased rates of complications after hip replacement.Patients and methods — We performed a randomized controlled trial involving 72 Danish patients in 1 region who were referred for elective fast-track total hip replacement between August 2009 and March 2011 (654 were screened for eligibility). Half of the patients received a telemedicine solution connected to their TV. The patients were followed until 1 year after surgery.Results — Length of stay was reduced from 2.1 days (95% CI: 2.0–2.3) to 1.1 day (CI: 0.9–1.4; p < 0.001) with the TMS intervention. Health-related quality of life increased in both groups, but there were no statistically significant differences between groups. There were also no statistically significant differences between groups regarding timed up-and-go test and Oxford hip score at 3-month follow-up. At 12-month follow-up, the rates of complications and re-admissions were similar between the groups, but the number of postoperative hospital contacts was lower in the TMS group.Interpretation — Length of postoperative stay was shortened in patients with the TMS solution, without compromising patient-perceived or clinical parameters in patients undergoing elective fast-track surgery. These results indicate that telemedicine can be of value in fast-track treatment of patients undergoing total hip replacement.