Arthroscopic superior capsule reconstruction augmentation using a semitendinosus autograft in massive reparable rotator cuff tears.

Background: Arthroscopic superior capsule reconstruction (SCR) augmentation is a viable treatment option for massive reparable cuff tears. This study aimed to retrospectively compare clinical and imaging outcomes of patients with reparable massive rotator cuff tears after arthroscopic rotator cuff repair (ARCR) with those after SCR augmentation using a semitendinosus autograft. Methods: We retrospectively compared 50 patients with massive reparable rotator cuff tears who underwent ARCR and SCR augmentation (n = 25 each). Patients were clinically followed up for at least 2 years, and the American Shoulder and Elbow index, other patient-reported outcomes, active range of motion, and radiography and magnetic resonance imaging findings were assessed. Results: At the final follow-up, both patient groups showed significant improvements in forward elevation in range of motion and visual analog scale scores. Improvements in the American Shoulder and Elbow scores in the SCR augmentation group were significantly superior to those in the ARCR group (48.3 and 28.9, P < .01). There was a significant difference in the retear rate between the SCR augmentation group and ARCR group (20% and 56%, respectively; P = .009). Conclusion: Our study demonstrated that patient-reported outcomes and retear rates in patients who underwent SCR augmentation with rotator cuff repair for massive rotator cuff tears significantly improved compared with those in patients who underwent ARCR without augmentation. Augmentation with semitendinosus autografting during rotator cuff repair represents a solution for patients with massive reparable rotator cuff tears.

Pincer-Supported Perfluororhodacyclopentanes: High Nucleophilicity of the M-CF Bond.

Perfluororhodacyclopentane supported by PBP pincer ligand PBP-RhIII (CF2 )4 (2) was prepared from PBP-RhI -PPh3 (1) and tetrafluoroethylene (TFE). By scXRD analysis, it was revealed that the Rh-CF bond trans to the boryl ligand was largely elongated compared to the one in the apical position. Although M-CF bonds of perfluorometallacyclopentanes are known to be very stable, 2 shows high reactivity toward hydrogenolysis, iodinolysis and protonolysis, thanks to the strong trans-effect of the highly σ-donating boryl ligand. Analogous PCP pincer complex PCP-RhIII (CF2 )4 (4) showed slower reaction rate both in oxidative cyclization with TFE and hydrogenolysis of Rh-CF bond. Catalytic production of 1,1,2,2,3,3,4,4-octafluorobutane from two TFE and hydrogen in one pot was achieved via repetitive oxidative cyclization of TFE and Rh followed by the hydrogenolysis of Rh-CF bonds. This report demonstrates the possible application of PBP-pincer skeleton to the preparation of fluorinated compounds from TFE.

Evaluation of hypervascularity in synovitis of the shoulder using ultrasound: comparison of preoperative ultrasound findings and intraoperative arthroscopic findings.

Background: Synovitis of the shoulder causes pain; however, it is difficult to accurately determine the area and degree of synovitis from preoperative images. This study investigated the correlation between intraoperative arthroscopic findings and preoperative power Doppler ultrasonography (PDUS) findings for synovitis evaluation. Methods: Forty patients (mean age = 62.0 years; 24 men and 16 women) underwent arthroscopic surgery for partial rotator cuff tears. Three observation areas were evaluated: rotator interval (RI), subacromial bursa, and bicipital groove. The Doppler flow areas and PDUS grade were measured one day before surgery. Arthroscopic findings were visualized intraoperatively and classified into 3 groups: pale, pink, and red. The correlation between the arthroscopic classification and PDUS findings was analyzed. Results: The correlation between intraoperative arthroscopic classification and preoperative PDUS findings, Doppler flow area and PDUS grade, was high for the RI (r = 0.82, 0.70). There was no correlation for the subacromial bursa (r = 0.01, -0.02) and the bicipital groove (r = -0.03, 0.3). Conclusion: Hypervascularity findings in the PDUS were highly correlated with arthroscopic color classification in the RI. Therefore, visualization of hypervascularity in the RI area could be a reliable measure for the assessment of glenohumeral synovitis in patients with partial-thickness rotator cuff tear.

Single-Step Construction of the anti-Deoxypropionate Motif from Propylene: Formal Total Synthesis of the Cuticular Hydrocarbons Isolated from Antitrogus parvulus.

Reported herein is the single-step construction of an anti-configured deoxypropionate motif by syndiospecific propylene oligomerization catalyzed by a Cs -symmetric zirconocene complex. After oligomerization, oxidation of the oligomers by oxygen afforded oligopropylene alcohols in a single step. This strategy was applied to the single-step preparation of rel-(2R,4S,6R,8S)-2,4,6,8-tetramethylundecan-1-ol, the racemic mixture of the synthetic fragment of the cuticular hydrocarbons isolated from the cane beetle Antitrogus parvulus.

One-step catalytic asymmetric synthesis of all-syn deoxypropionate motif from propylene: Total synthesis of (2R,4R,6R,8R)-2,4,6,8-tetramethyldecanoic acid.

In nature, many complex structures are assembled from simple molecules by a series of tailored enzyme-catalyzed reactions. One representative example is the deoxypropionate motif, an alternately methylated alkyl chain containing multiple stereogenic centers, which is biosynthesized by a series of enzymatic reactions from simple building blocks. In organic synthesis, however, the majority of the reported routes require the syntheses of complex building blocks. Furthermore, multistep reactions with individual purifications are required at each elongation. Here we show the construction of the deoxypropionate structure from propylene in a single step to achieve a three-step synthesis of (2R,4R,6R,8R)-2,4,6,8-tetramethyldecanoic acid, a major acid component of a preen-gland wax of the graylag goose. To realize this strategy, we focused on the coordinative chain transfer polymerization and optimized the reaction condition to afford a stereo-controlled oligomer, which is contrastive to the other synthetic strategies developed to date that require 3-6 steps per unit, with unavoidable byproduct generation. Furthermore, multiple oligomers with different number of deoxypropionate units were isolated from one batch, showing application to the construction of library. Our strategy opens the door for facile synthetic routes toward other natural products that share the deoxypropionate motif.