Proton relay in cyclic 7‐hydroxyquinoline–(alcohol)2 complexes (see picture) has been explored in nonpolar solvents. The asymmetric triple proton transfer has an unusually large, temperature‐independent, and viscosity‐dependent kinetic isotope effect. Heavy‐atom motions (wavy arrow) of solvent and bridging molecules allow proton tunneling by assisting the complex to reach the optimal precursor configuration.

Older women are generally more sedentary and less active than older men, but little is known about the specific factors underlying the differences between the genders in physical activity (PA). The purpose of this study was to compare men and women regarding their household leisure time PA, walking activity, and personal and environmental factors related to physical activity. Self-administered questionnaires were completed by 276 older adults recruited from senior centers. Findings revealed that women were less active overall but more involved in household activities. The women's personal and environmental factors represented poor conditions for PA, and as a result they engaged in lower levels of PA than men.

The doses of donor-derived natural killer (NK) cells that can be given safely after human leukocyte antigen (HLA)-haploidentical hematopoietic cell transplantation (HCT) remain to be defined. Forty-one patients (ages 17 to 75 years) with hematologic malignancy underwent HLA-haploidentical HCT after reduced-intensity conditioning containing busulfan, fludarabine, and antithymocyte globulin. Cell donors (ages 7 to 62 years) underwent growth factor-mobilized leukapheresis for 3 to 4 days. Cells collected on the first 2 to 3 days were used for HCT, whereas those collected on the last day were CD3-depleted and cultured into NK cells using human interleukins-15 and -21. These NK cells were then infused into patients twice at 2 and 3 weeks after HCT at an escalating doses of .2 × 10(8) cells/kg of body weight (3 patients), .5 × 10(8) cells/kg (3 patients), 1.0 × 10(8) cells/kg (8 patients), and ≥ 1.0 × 10(8) cells/kg or available cells (27 patients). At all dose levels, no acute toxicity was observed after NK cell infusion. After HLA-haploidentical HCT and subsequent donor NK cell infusion, when referenced to 31 historical patients who had undergone HLA-haploidentical HCT after the same conditioning regimen but without high-dose NK cell infusion, there was no significant difference in the cumulative incidences of major HCT outcomes, including engraftment (absolute neutrophil count ≥ 500/μL, 85% versus 87%), grade 2 to 4 acute graft-versus-host disease (GVHD, 17% versus 16%), moderate to severe chronic GVHD (15% versus 10%), and transplantation-related mortality (27% versus 19%). There was, however, a significant reduction in leukemia progression (74% to 46%), with post-transplantation NK cell infusion being an independent predictor for less leukemia progression (hazard ratio, .527). Our findings showed that, when given 2 to 3 weeks after HLA-haploidentical HCT, donor-derived NK cells were well tolerated at a median total dose of 2.0 × 10(8) cells/kg. In addition, they may decrease post-transplantation progression of acute leukemia.

Bridging alcohols, tunneling protons: The intrinsic proton‐transfer dynamics of cyclic H‐bonded 1:1 7‐azaindole/alcohol complexes in n‐alkanes has been investigated at the lowest‐lying excited singlet state with variation of alcohol, solvent, isotope, and temperature by using static and time‐resolved spectroscopy. The proton transfer occurs asymmetrically, and the rate is governed by tunneling although it is assisted by heavy‐atom motions.

Any role for reduced-intensity conditioning (RIC) before hematopoietic cell transplantation (HCT) from a human leukocyte antigen (HLA)-haploidentical donor remains to be defined. We therefore assessed 83 patients (age, 16-70 years): 68 with acute leukemia (including 34 in remission and 34 with refractory disease) and 15 patients with myelodysplastic syndrome, in HCT trials using RIC with busulfan, fludarabine, and antithymocyte globulin. The HLA-haploidentical donors, offspring (n ‫؍‬ 38), mothers (n ‫؍‬ 24), or siblings (n ‫؍‬ 21) of patients, underwent leukapheresis after receiving granulocyte colony-stimulating factor, and donated cells were transplanted without further manipulation. Cyclosporine and methotrexate were given for GVHD prophylaxis. The cumulative incidences of neutrophil engraftment, grade 2 to 4 acute GVHD, chronic GVHD, and transplantation-related mortality after HCT, were 92%, 20%, 34%, and 18%, respectively. After a median follow-up time of 26.6 months (range, 16.8-78.8 months), the event-free and overall survival rates were 56% and 45%, respectively, for patients with acute leukemia in remission; 9% and 9%, respectively, for patients with refractory acute leukemia; and 53% and 53%, respectively, for patients with myelodysplastic syndrome. HCT from an HLA-haploidentical family member resulted in favorable outcomes when RIC containing antithymocyte globulin was performed. This study is registered at www.clinicaltrials.gov as #NCT00521430 and #NCT00732316. (Blood. 2011;118(9):2609-2617)

The excited-state tautomerization dynamics of 7-hydroxyquinoline in the water pools of reverse micelles has been investigated by monitoring time-resolved fluorescence spectra and kinetics as well as static absorption and emission spectra with a variation of water content and isotopic fractionation. The normal and the tautomeric species are found to reside preferentially in the bound- and the free-water regions of the micelles, respectively. The excited-state tautomerization of the normal species in the bound-water layers is suggested to occur via two different channels, depending on rotamers at the moment of excitation. The cis tautomerizes via proton relay from the enol group to the imino group along a hydrogen-bonded water bridge, unusual in water but common in alcohols, whereas the trans tautomerizes via the stepwise individual acid-base reactions of two prototropic groups as found in bulk water. Proton relay can take place because water in the pools has substantially reduced polarity and disrupted hydrogen-bond networks compared with bulk water.

Novel complexes 1 and 2 based on N-heterocyclic carbenes, which are analogous to Ru(bpy)(3)(2+) and Ru(terpy)(2)(2+), respectively, were synthesized. The complex, which is analogous to Ru(terpy)(2)(2+), exhibited promising photoluminescence properties with a long lifetime of 820 ns in acetonitrile and 3100 ns in water at room temperature, respectively. In addition, ab initio calculations were carried out.

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