Diagnostic accuracy of pancreatic stone protein in patients with sepsis: a systematic review and meta-analysis.

BACKGROUND: Sepsis is a common syndrome of multiorgan system dysfunction secondary to the dysregulated inflammatory response to infection. The role of pancreatic stone protein (PSP) in diagnosing sepsis has been investigated in previous studies. The meta-analysis aimed to comprehensively investigate the diagnostic value of PSP in identifying sepsis. METHODS: PubMed, Web of Science, Embase, Cochrane Library, and China National Knowledge Infrastructure (CNKI), were systematically searched. Studies investigating the diagnostic performance of PSP were included. Pooled sensitivity, specificity, positive Likelihood Ratio (+ LR) and negative Likelihood Ratio (-LR), diagnostic odds ratio (DOR), and area under the curve (AUC) of summary receiver operating characteristic (SROC) were calculated. RESULTS: The sensitivity of PSP was 0.88 (95% CI: 0.77-0.94), and the pooled specificity was 0.78 (95% CI: 0.65-0.87). Pooled + LR, -LR, and DOR were 4.1 (2.3, 7.3), 0.16 (0.07, 0.34), and 26 (7, 98). The AUC value for the SROC of PSP was 0.90 (0.87, 0.92). The pooled sensitivity, specificity, + LR and - LR, and DOR for PSP among neonates were 0.91 (95% CI: 0.84, 0.96), 0.66 (95% CI: 0.58, 0.74), 3.97 (95% CI: 0.53, 29.58), 0.13 (95% CI: 0.02, 1.00), and 31.27 (95% CI: 0.97, 1004.60). CONCLUSIONS: This study indicates that PSP demonstrated favorable diagnostic accuracy in detecting sepsis. Well-designed studies are warranted to ascertain the value of PSP measurement to guide early empirical antibiotic treatment, particularly in neonates.

Breaking Conventional Site Selectivity in C-H Bond Activation: Selective sp3 versus sp2 Silylation by a Pincer-Based Pocket.

A deeply ingrained assumption in the conventional understanding and practice of organometallic chemistry is that an unactivated aliphatic C(sp3)-H bond is less reactive than an aromatic C(sp2)-H bond within the same molecule given that they are at positions unbiasedly accessible for activation. Herein, we demonstrate that a pincer-ligated iridium complex catalyzes intramolecular dehydrogenative silylation of the unactivated δ-C(sp3)-H (δ to the Si atom) with exclusive site selectivity over typically more reactive ortho δ-C(sp2)-H bonds. A variety of tertiary hydrosilanes undergo δ-C(sp3)-H silylation to form 5-membered silolanes, including chiral silolanes, which can undergo further oxidation to produce enantiopure ß-aryl-substituted 1,4-diols. Combined computational and experimental studies reveal that the silylation occurs via the Si-H addition to a 14-electron Ir(I) fragment to give an Ir(III) silyl hydride complex, which then activates the C(sp3)-H bond to form a 7-coordinate, 18-electron Ir(V) dihydride silyl intermediate, followed by sequential reductive elimination of H2 and silolane. The unprecedented site selectivity is governed by the distortion energy difference between the rate-determining δ-C(sp3)-H and δ-C(sp2)-H activation, although the activation at sp2 sites is much more favorable than sp3 sites by the interaction energy.

A concise access to bridged [2,2,1] bicyclic lactones with a quaternary stereocenter via stereospecific hydroformylation.

Chiral bridged [2,2,1] bicyclic lactones are privileged structural units in pharmaceutics and bioactive nature products. However, the synthetic methods for these compounds are rare. Here we report an efficient method for enantioselective construction of bridged [2,2,1] bicyclic lactones bearing a quaternary stereocenter via Rh-catalyzed asymmetric hydroformylation/intramolecular cyclization/pyridium chlorochromate (PCC) oxidation. By employing a hybrid phosphine-phosphite chiral ligand, a series of cyclopent-3-en-1-ols are transformed into corresponding γ-hydroxyl aldehydes with specific syn-selectivity. Then, hemiacetals form in situ and oxidation with PCC in one-pot affords bridged [2,2,1] bicyclic lactones in high yields and excellent enantiomeric excess. Replacing the hydroxyl group by an ester group, cyclopentanecarbaldehydes with a chiral all-carbon quaternary stereocenter in the γ-position can be generated efficiently.

Rhodium-Catalyzed Enantioselective Anti-Markovnikov Hydroformylation of α-Substituted Acryl Acid Derivatives.

Rhodium-catalyzed asymmetric anti-Markovnikov hydroformylation of α-substituted acrylates/acrylamides has been developed. By employing the Rh/(S,S)-DTBM-YanPhos complex, a series of ß-chiral linear aldehydes were obtained in high yields (up to 94% yield) and high enantioselectivities (up to 96% ee). The utility of this methodology is demonstrated by a gram-scale reaction and a concise synthetic route to chiral γ-butyrolactone.