Ion-Exchangeable Microporous Polyoxometalate Compounds with Off-Center Dopants Exhibiting Unconventional Luminescence.

The synthesis of luminescent polyoxometalates (POMs) typically relies on the assembly of POM ligands with rare earth or transition metals, placing significant constraints on the composition, structure, and hence the luminescence properties of the resultant systems. Herein, we show that the ion-exchange strategy can be used for the synthesis of novel POM-based luminescent materials. We demonstrate that introducing bismuth ions into an ion-exchangeable, microporous POM compound yields an unconventional system luminescing in the near-infrared region. Experimental characterization, coupled with quantum chemical calculations, confirms that bismuth ions site-specifically occupy an off-center site in the lattice, and have an asymmetric coordination geometry unattainable by other means, thus giving rise to peculiar emission. Our findings offer an effective strategy for the synthesis of POM-based luminescent materials, and the design concept may potentially be adapted to the creation of POM-based systems with other functionalities.

Visible-Light-Driven Intermolecular [2+2] Cycloadditions between Coumarin-3-Carboxylates and Acrylamide Analogs.

This paper reports a room temperature visible-light-driven protocol for the intermolecular [2+2] cycloadditions between coumarin-3-carboxylates and acrylamides analogs by an energy-transfer process. Using an iridium complex FIrPic as a photosensitizer and a 3 W blue LED as a light source, an array of cyclobutabenzocypyranones were prepared in moderate to excellent yields.

Construction of Polyfunctionalized 6-5-5 Fused Tricyclic Carbocycles via One-Pot Sequential Semipinacol Rearrangement/Michael Addition/Henry Reaction.

A novel one-pot semipinacol rearrangement/Michael addition/Henry reaction of vinylogous α-ketols with nitroolefins has been achieved through the promotion of two Lewis acids, namely, TMSOTf and TiCl4, at temperatures between 0 and -78 °C. A range of synthetically challenging polyfunctionalized 6-5-5 and 7-5-5 fused tricyclic carbocycles bearing up to five continuous stereocenters, including one quaternary carbon center, are rapidly constructed in moderate to good yields with good to high diastereoselectivities in most cases.

Development of bifunctional organocatalysts and application to asymmetric total synthesis of naucleofficine I and II.

The proline-type organocatalysts has been efficiently employed to catalyze a wide range of asymmetric transformations; however, there are still many synthetically useful and challenging transformations that remain unachievable in an asymmetric fashion. Herein, a chiral bifunctional organocatalyst with a spirocyclic pyrrolidine backbone-derived containing fluoro-alkyl and aryl sulfonamide functionalities, are designed, prepared, and examined in the asymmetric Mannich/acylation/Wittig reaction sequence of 3,4-dihydro-ß-carboline with acetaldehyde, acyl halides, and Wittig reagents. As a result, the spirocyclic pyrrolidine trifluoromethanesulfonamide catalyst can facilitate this versatile sequence as demonstrated by 18 examples displaying excellent enantioselectivity (up to 94% ee), as well as moderate to good yields (up to 54% over 3 steps). As a practical application, the asymmetric total synthesis of naucleofficine I (1a) and II (1b) in ten steps have been accomplished.

3D conformal radiotherapy combined with transcatheter arterial chemoembolization for hepatocellular carcinoma.

AIM: To compare transcatheter arterial chemoembolization (TACE) and 3D conformal radiotherapy (3D-CRT) with TACE monotherapy in hepatocellular carcinoma (HCC). METHODS: We searched all the eligible studies from the Cochrane Library, PubMed, Medline, Embase, and CNKI. The meta-analysis was performed to assess the survival benefit, tumor response, and the decline in α-fetoprotein (AFP) level. According to the heterogeneity of the studies, pooled OR with 95%CI were calculated using the fixed-effects or random-effects model. An observed OR > 1 indicated that the addition of 3D-CRT to TACE offered survival benefits to patients that could be considered statistically significant. Statistical analyses were performed using Review Manager Software. RESULTS: Ten studies met the criteria to perform a meta-analysis including 908 HCC participants, with 400 patients in the TACE/3D-CRT combination group and 508 in the TACE alone group. TACE combined with 3D-CRT significantly improved 1-, 2- and 3-year overall survival compared with TACE monotherapy (OR = 1.87, 95%CI: 1.37-2.55, P < 0.0001), (OR = 2.38, 95%CI: 1.78-3.17, P < 0.00001) and (OR = 2.97, 95%CI: 2.10-4.21, P < 0.00001). In addition, TACE plus 3D-CRT was associated with a higher tumor response (complete remission and partial remission) (OR = 3.81; 95%CI: 2.70-5.37; P < 0.00001), and decline rates of AFP level (OR = 3.24, 95%CI: 2.09-5.02, P < 0.00001). CONCLUSION: This meta-analysis demonstrated that TACE combined with 3D-CRT was better than TACE monotherapy for patients with HCC, which needs to be confirmed by large multicenter trials．

[Retrospective analysis on total hip arthroplasty for the treatment of developmental dysplasia of the hip in 29 adults].

OBJECTIVE: To study the results of the total hip arthroplasty (THA) in the treatment of developmental dysplasia of the hip (DDH) with severe osteoarthritis in adults. METHODS: From March 2004 to February 2011, 29 patients (32 hips) with DDH were treated by THA with an cementless cup. There were 11 males and 18 females,with an average age of 52.6 years (ranging from 37 to 73 years). Unilateral DDH occurred in 26 patients and bilateral DDH occurred in 3 patients. Based on the Crowe classification, there were 18 hips in 17 patients of type I ,7 hips in 6 patients of type II, 4 hips in 3 patients of type III, 3 hips in 3 patients of type IV. Except for 3 patients with bilateral DDH, the other patients' ill lower limbs were 1 to 6 cm shorter than the healthy lower ones. RESULTS: All the patients were followed up,and the duration ranged from 8 months to 5.3 years(averaged 3.7 years) without infection, dislocation, and sciatic nerves injury after the operation. One patient with proximal femoral fracture, intraoperation used wire binding, after 4 years of follow-up, fracture healed without evidence of prosthesis loosening. All grafts and subtrochanteric osteotomy healing were achieved. In 21 patients, the pain was completely relieved and the function of the hip joints was good. Five patients still had mild limping, but reduced significantly than preoperation. In 3 patients, the ill lower limbs were more than 1 cm shorter than the healthy lower ones and the other patients' ill lower limbs were less than 1 cm shorter than the healthy lower ones. Two patients' lower limbs were lengthened 4 to 5 cm. The Harris scores were 43.6 +/- 7.1 preoperatively and 86.7 +/- 5.3 postoperatively (P < 0.05). CONCLUSION: THA with deepening the medial wall of the acetabulum at the true acetabulum, according to different characteristics of Crowe classification, using different operation program, cementless cup in adult could obtain favorable results.