Unified Total Synthesis, Stereostructural Elucidation, and Biological Evaluation of Sarcophytonolides.

Sarcophytonolides are cembranolide diterpenes isolated from the soft corals of genus Sarcophyton. Unified total synthesis of sarcophytonolides C, E, F, G, H, and J and isosarcophytonolide D was achieved. The synthetic routes feature NaHMDS- or SmI2-mediated fragment coupling, alkoxycarbonylallylation, macrolactonization, and transannular ring-closing metathesis. These total syntheses led to the absolute configurational confirmation of sarcophytonolide H, elucidation of sarcophytonolides C, E, F, and G, and revision of sarcophytonolide J and isosarcophytonolide D. We also evaluated the antifouling activity and toxicity of the synthetic sarcophytonolides H and J and their analogues as well as the cytotoxicity of the synthetic sarcophytonolides and the key synthetic intermediates.

Relationship between Subjective Grip Strength and Physical Functioning among Community-Dwelling Older Women.

This study investigated the relationship between subjective grip strength and physical function in community-dwelling older women. Subjective grip strength was assessed using a questionnaire, and physical function and body composition were compared between groups with strong and weak subjective grip strength. Additionally, the two groups were compared in those with mild cognitive impairment (MCI) and those with normal cognitive function, respectively. The results showed significant differences in grip strength (p < 0.001), 30 s chair-stand (CS-30) test (p = 0.039), timed up-and-go (TUG) test (p = 0.027), maximal gait speed (p = 0.029), and skeletal muscle mass (p < 0.001). Older adults with normal cognitive function showed significant differences in grip strength (p < 0.001), quadriceps muscle strength (p < 0.009), one-leg standing time (p = 0.041), CS-30 (p = 0.002), TUG (p = 0.014), gait speed (p = 0.006), and skeletal muscle mass (p = 0.003). Older adults with low subjective grip strength had lower physical function and skeletal muscle mass. However, no items showed significant differences between groups among older adults with MCI. Thus, subjective grip strength is an indicator of an overall decline in physical function and a reduction in skeletal muscle mass in older adults, and cognitive function should be considered when assessing subjective grip strength in older adults.

Pre-and postoperative factors associated with functional outcomes in patients with posterior malleolar fractures.

INTRODUCTION: Recent studies on posterior malleolar fractures mainly focus on the reduction quality and fixation of the posterior fragment since it contributes to ankle stability and articular congruency. However, the association of pre-and postoperative factors considering the whole ankle joint in postoperative functional outcomes remains unclear. Therefore, this study aimed to examine the association between pre-and postoperative variables for postoperative functional outcomes in patients with posterior malleolar fragments (classified as Haraguchi type I or II) and considered the association between reduction and fixation for small posterior malleolar fragments of less than 25% of the intra-articular surface. METHODS: This multicenter retrospective cohort study included 110 adult patients who underwent internal fixation for ankle fractures with posterior malleolar fragments. The primary outcome was the American Orthopaedic Foot and Ankle Society (AOFAS) score 12-months postoperatively. As pre-and postoperative variables, the preoperative demographic data, radiographic findings, operative method, postoperative radiographic findings, and complications were evaluated. In addition, univariable and multivariable logistic regression analyses were conducted to examine the association between pre-and postoperative variables and AOFAS scores. RESULTS: Twenty-four (21.8%) cases had postoperative complications. Univariate analysis showed that age was significantly according to AOFAS score-stratified groups in patients with Haraguchi type II fractures. Multivariable logistic regression analysis using bootstrapping in the Haraguchi type II group showed that postoperative complications were significantly associated with low AOFAS scores, indicating poor functionality. In both fracture types, postoperative complications had the highest odds ratio among the explanatory variables. In patients with small posterior malleolar fragments, fragment reduction, fixation, and ankle stability were not associated with AOFAS scores. CONCLUSIONS: Our results suggest that postoperative complications were associated with AOFAS scores at postoperative 12 months in patients with ankle fractures with posterior malleolar fragments. In patients with small posterior malleolar fragments, reduction and fixation were not associated with AOFAS scores. Therefore, clinical decisions for posterior fragment fixation should be made based on the possible risk of complications related to the surgical procedures in addition to the posterior malleolar fragment size.

Scanning near-field optical spectroscopy and carrier transport based analysis in mesoscopic regions for two-dimensional semiconductors.

The measurements of photoexcited transport in mesoscopic regimes reveal the states and properties of mesoscopic systems. In this study, we focused on direct measurements of electromagnetic energy transports in the mesoscopic regions and constructed a scanning tunnelling microscope-assisted multi-probe scanning near-field optical microscope spectroscopy system. After producing an emission energy map through a single-probe measurement, two-probe measurement enables us to observe and analyse carrier transport characteristics. It suggests that exciton generation and transport in the mesoscopic region of semiconductors with quantum structure changes, such as the bias of dopant, affect the excited carrier emission recombination process. The measured probability density of the carrier transported with quantum effects can be used for applications in natural intelligence research by combining it with the analysis using tournament structures. Our developed measurement and analysis methods are expected to clarify the details of carrier's behaviour in the mesoscopic region in various materials and lead to applications for novel optoelectronic devices.

Effect of Early vs Delayed Surgical Treatment on Motor Recovery in Incomplete Cervical Spinal Cord Injury With Preexisting Cervical Stenosis: A Randomized Clinical Trial.

Importance: The optimal management for acute traumatic cervical spinal cord injury (SCI) is unknown. Objective: To determine whether early surgical decompression results in better motor recovery than delayed surgical treatment in patients with acute traumatic incomplete cervical SCI associated with preexisting canal stenosis but without bone injury. Design, Setting, and Participants: This multicenter randomized clinical trial was conducted in 43 tertiary referral centers in Japan from December 2011 through November 2019. Patients aged 20 to 79 years with motor-incomplete cervical SCI with preexisting canal stenosis (American Spinal Injury Association [ASIA] Impairment Scale C; without fracture or dislocation) were included. Data were analyzed from September to November 2020. Interventions: Patients were randomized to undergo surgical treatment within 24 hours after admission or delayed surgical treatment after at least 2 weeks of conservative treatment. Main Outcomes and Measures: The primary end points were improvement in the mean ASIA motor score, total score of the spinal cord independence measure, and the proportion of patients able to walk independently at 1 year after injury. Results: Among 72 randomized patients, 70 patients (mean [SD] age, 65.1 [9.4] years; age range, 41-79 years; 5 [7%] women and 65 [93%] men) were included in the full analysis population (37 patients assigned to early surgical treatment and 33 patients assigned to delayed surgical treatment). Of these, 56 patients (80%) had data available for at least 1 primary outcome at 1 year. There was no significant difference among primary end points for the early surgical treatment group compared with the delayed surgical treatment group (mean [SD] change in ASIA motor score, 53.7 [14.7] vs 48.5 [19.1]; difference, 5.2; 95% CI, -4.2 to 14.5; P = .27; mean [SD] SCIM total score, 77.9 [22.7] vs 71.3 [27.3]; P = .34; able to walk independently, 21 of 30 patients [70.0%] vs 16 of 26 patients [61.5%]; P = .51). A mixed-design analysis of variance revealed a significant difference in the mean change in ASIA motor scores between the groups (F1,49 = 4.80; P = .03). The early surgical treatment group, compared with the delayed surgical treatment group, had greater motor scores than the delayed surgical treatment group at 2 weeks (mean [SD] score, 34.2 [18.8] vs 18.9 [20.9]), 3 months (mean [SD] score, 49.1 [15.1] vs 37.2 [20.9]), and 6 months (mean [SD] score, 51.5 [13.9] vs 41.3 [23.4]) after injury. Adverse events were common in both groups (eg, worsening of paralysis, 6 patients vs 6 patients; death, 3 patients vs 3 patients). Conclusions and Relevance: These findings suggest that among patients with cervical SCI, early surgical treatment produced similar motor regain at 1 year after injury as delayed surgical treatment but showed accelerated recovery within the first 6 months. These exploratory results suggest that early surgical treatment leads to faster neurological recovery, which requires further validation. Trial Registration: ClinicalTrials.gov Identifier: NCT01485458; umin.ac.jp/ctr Identifier: UMIN000006780.

Total synthesis of two possible diastereomers of (+)-sarcophytonolide C and its structural elucidation.

Stereoselective and parallel total syntheses of two possible diastereomers of (+)-sarcophytonolide C have been accomplished. Macrolactonization and transannular ring-closing metathesis (RCM) were the key transformations. Detailed comparisons of their (1)H and (13)C NMR data and specific rotation with those of the natural product allowed the absolute configuration of (+)-sarcophytonolide C to be determined.