The first electrophilic Pd(II)-catalyzed allylic C H alkylation is reported, providing a novel method for formation of sp3-sp3 C C bonds directly from C H bonds. A wide range of aromatic and heteroaromatic linear (E)-alpha-nitro-arylpentenoates are obtained as single olefin isomers in excellent yields directly from terminal olefin substrates and methyl nitroacetate. The use of DMSO as a pi-acidic ligand was found to be crucial for promoting functionalization of the pi-allylPd intermediate. Products from this reaction are valuable synthetic intermediates and are readily transformed to amino esters via selective reduction and optically enriched alpha,alpha-disubstituted amino acid precursors via asymmetric conjugate addition.
Published data on the use of extracorporeal membrane oxygenation (ECMO) as a supportive measure during or immediately after cardiopulmonary resuscitation (CPR) in adults (older than 18 years) shows mixed results. To assess the clinical outcomes of the use of ECMO in this modality and to look for predictors of mortality, we performed a meta-analysis (MA) of individual patients collected from observational studies. An electronic PubMed search restricted to English-language publications between 1990 and 2007, using a consensus restrictive criterion, retrieved 141 titles. After full text evaluation, 11 clinical series and nine case reports were considered appropriate and included in our MA. Data on 135 individually identified adult patients (male:female = 1.6:1) were collected. Median age for the group was 56 years (range 18-83), and the median ECMO run was 54 hours (range 0-3881). Overall survival to hospital discharge was 40% (54 of 135). The most common diagnosis leading to cardiac arrest was acute myocardial infarction (46 of 135 patients). Compared with the youngest group (17-41 years), odds ratio (OR) for mortality was higher for age group 41-56 years (OR 2.9 95%; CL, 1.6-8.2) and those older than 67 years (OR 3.4%; 95% CL, 1.2-9.7). Duration of ECMO support measured in days was also a predictor of mortality, with significant better outcome for those supported between 0.875 and 2.3 days (OR 0.2; 95% CL, 0.07-0.6). There was a negative trend in survival when manual CPR lasted >30 minutes without prompt ECMO initiation (OR 1.9; 95% CL, 0.9-4.2). This work confirms the expectations for a better survival when E-CPR is used in younger patients, for shorter periods of time and after expeditious implementation during or immediately after manual CPR. Neurologic sequelae and other major complications, although suspected to be high, are poorly described in the reviewed literature.
Abstract-Spatially-coupled low-density parity-check (LDPC) codes, which were first introduced as LDPC convolutional codes, have been shown to exhibit excellent performance under low-complexity belief-propagation decoding. This phenomenon is now termed threshold saturation via spatial coupling. Spatiallycoupled codes have been successfully applied in numerous areas. In particular, it was proven that spatially-coupled regular LDPC codes universally achieve capacity over the class of binary memoryless symmetric (BMS) channels under belief-propagation decoding. Recently, potential functions have been used to simplify threshold saturation proofs for scalar and vector recursions. In this paper, potential functions are used to prove threshold saturation for irregular LDPC and low-density generator-matrix codes on BMS channels, extending the simplified proof technique to BMS channels. The corresponding potential functions are closely related to the average Bethe free entropy of the ensembles in the large-system limit. These functions also appear in statistical physics when the replica method is used to analyze optimal decoding.
BACKGROUND Cold-stored whole blood (CWB) provides a balance of red blood cells, plasma, and platelets in less anticoagulant volume than standard blood component therapy (BCT). We hypothesize that patients receiving CWB along with BCT have improved survival compared with patients receiving only BCT. METHODS We performed a dual-center case-match study of trauma patients who received CWB and BCT at two urban, Level-I Trauma Centers. Criteria to receive CWB included boys 16 years of older, women older than 50 years, SBP less than 90 mm Hg, and identifiable source of hemorrhage. We performed a 2:1 propensity match against any trauma patient who received 1 unit or greater of packed red cells during their initial trauma bay resuscitation. Endpoints included trauma bay mortality, 30-day mortality, laboratory values at 4 hours and 24 hours, and overall blood product utilization. Comparisons were made with Wilcoxon-ranked sum and Fisher's exact test, p less than 0.05 was significant. RESULTS Between both institutions, a total of 107 patients received CWB during the study period with 91 being matched to 182 BCT patients for analysis. Hemodynamic parameters of the patients in both groups at the time of presentation were similar. The CWB patients had higher mean hemoglobin (10 ± 2 g/dL vs. 11 ± 2 g/dL; p < 0.001) and hematocrit (29.2 ± 6.1% vs. 32.1 ± 5.8%; p < 0.001) at 24 hours. Importantly, trauma bay mortality was less in CWB patients (8.8% vs. 2.2%;p = 0.039). Thirty-day mortality was not different in CWB patients, and there were no differences in the total amount of blood products transfused at the 4-hour and 24-hour periods. CONCLUSION Cold-stored whole blood offers the benefit of a balanced resuscitation with improved trauma bay survival and higher mean hemoglobin at 24 hours. A larger, prospective study is needed to determine whether it has a longer-term survival benefit for severely injured patients. LEVEL OF EVIDENCE Therapeutic, level III.
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