Atomically precise hydrido gold nanoclusters are extremely rare but interesting due to their potential applications in catalysis. By optimization of molecular precursors, we have prepared an unprecedented N-heterocyclic carbene-stabilized hydrido gold nanocluster, [Au 24 (NHC) 14 Cl 2 H 3 ] 3+ . This cluster comprises a dimer of two Au 12 kernels, each adopting an icosahedral shape with one missing vertex. The two kernels are joined through triangular faces, which are capped with a total of three hydrides. The hydrides are detected by electrospray ionization mass spectrometry and nuclear magnetic resonance spectroscopy, with density functional theory calculations supporting their position bridging the six uncoordinated gold sites. The reactivity of this Au 24 H 3 cluster in the electrocatalytic reduction of CO 2 is demonstrated and benchmarked against related catalysts.
Herein, we describe
the synthesis of a toroidal Au
10
cluster stabilized by
N
-heterocyclic carbene and
halide ligands
via
reduction of the corresponding
NHC–Au–X complexes (X = Cl, Br, I). The significant
effect of the halide ligands on the formation, stability, and further
conversions of these clusters is presented. While solutions of the
chloride derivatives of Au
10
show no change even upon heating,
the bromide derivative readily undergoes conversion to form a biicosahedral
Au
25
cluster at room temperature. For the iodide derivative,
the formation of a significant amount of Au
25
was observed
even upon the reduction of NHC–Au–I. The isolated bromide
derivative of the Au
25
cluster displays a relatively high
(
ca
. 15%) photoluminescence quantum yield, attributed
to the high rigidity of the cluster, which is enforced by multiple
CH−π interactions within the molecular structure. Density
functional theory computations are used to characterize the electronic
structure and optical absorption of the Au
10
cluster.
13
C-Labeling is employed to assist with characterization of
the products and to observe their conversions by NMR spectroscopy.
The open components separation technique (CST) for hernia repair allows for autologous tissue repair with approximation of the midline fascia in patients with complex hernias. CST requires creation of large undermining skin flaps, whereas the endoscopic component separation technique (ECST) is performed without division of the epigastric perforating vessels and may minimize wound morbidity. A review of patient demographics and outcome measures of patients undergoing CST and ECST between November 2008 and February 2010 was performed. Twenty-five patients were identified who underwent either CST (14 patients) or ECST (11 patients). There were no differences in body mass index (CST 34.8 kg/m2, ECST 37.5 kg/m2, P = 0.45), operating room times (CST 268 minutes, ECST 252 minutes, P = 0.54), or hospital length of stay (CST 5 days, ECST 5.8 days, P = 0.78). Wound complications occurred less with ECST (9 vs 57%, P = 0.03). The time to resolution of wound complications in ECST was reduced * 1 vs 4 months). No recurrences were seen in either group with a mean follow-up of 4months (range, 1 to 12 months). ECST and CST require similar operative times and hospital lengths of stay. ECST is associated with reduced wound complications compared with CST. Short-term recurrence rates with CST and ECST are comparable.
Receiving a telephone call about breast cancer diagnosis may be the norm rather than the exception in health care today. Trends in practice, as well as current best practices based primarily on expert opinion, may not provide optimal care for women diagnosed with breast cancer. Patient outcome research to guide future practice, such as the impact of modes of delivery of bad news, is urgently needed to determine appropriate patient-centered approaches for notification of breast cancer diagnoses.
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