Ln3+ Induced Thermally Activated Delayed Fluorescence of Chiral Heterometallic Clusters Ln2Ag28.

A series of TADF-active compounds: 0D chiral Ln-Ag(I) clusters L-/D-Ln2Ag28-0D (Ln=Eu/Gd) and 2D chiral Ln-Ag(I) cluster-based frameworks L-/D-Ln2Ag28-2D (Ln=Gd) has been synthesized. Atomic-level structural analysis showed that the chiral Ag(I) cluster units {Ag14S12} in L-/D-Ln2Ag28-0D and L-/D-Ln2Ag28-2D exhibited similar configurations, linked by varying numbers of [Ln(H2O)x]3+ (x=6 for 0D, x=3 for 2D) to form the final target compounds. Temperature-dependent emission spectra and decay lifetimes measurement demonstrated the presence of TADF in L-Ln2Ag28-0D (Ln=Eu/Gd) and L-Gd2Ag28-2D. Experimentally, the remarkable TADF properties primarily originated from {Ag14S12} moieties in these compounds. Notably, {Ag14S12} in L-Eu2Ag28-0D and L-Gd2Ag28-2D displayed higher promote fluorescence rate and shorter TADF decay times than L-Gd2Ag28-0D. Combined with theoretical calculations, it was determined that the TADF behaviors of {Ag14S12} cluster units were induced by 4 f perturbation of Ln3+ ions. Specially, while maintaining ΔE(S1-T1) small enough, it can significantly increase k(S1→S0) and reduce TADF decay time by adjusting the type or number of Ln3+ ions, thus achieving the purpose of improving TADF for cluster-based luminescent materials.

Efficacy and safety of the Latarjet procedure for the treatment of athletes with glenoid bone defects ≥ 20%: a single-arm meta-analysis.

BACKGROUND: The shoulder joint is the most commonly dislocated joint in the human body, and the recurrence rate exceeds 50% after nonsurgical treatment. Although surgical treatment reduces the recurrence rate, there is controversy regarding the optimal surgical approach. Previous studies suggest that the Latarjet procedure yields favourable outcomes for specific populations at risk of recurrence, such as competitive athletes with significant glenoid defects. However, most of the existing related research consists of nonrandomized controlled trials with small sample sizes, and there is a lack of strong evidence regarding the efficacy and safety of the Latarjet procedure. METHODS: The PubMed, Embase, Cochrane Library, and Web of Science databases were systematically searched. Athletes with ≥ 20% glenoid defects were selected for inclusion. The following data were extracted: general patient information, instability rates, return to sports (RTS) rates, imaging features (graft positioning rate and graft healing rate), functional assessments [Rowe score, Athletic Shoulder Outcome Scoring System(ASOSS), visual analogue scale (VAS), forward flexion function, and external rotation function], and complications. RESULTS: After excluding suspected duplicate cases, a total of 5 studies were included in this meta-analysis. The studies involved a total of 255 patients, including 237 males (93%) and 18 females (7%). The average age at the time of surgery was 25.4 ± 8.5 years. All the studies had a minimum follow-up period of 2 years, with an average follow-up time of 48.7 ± 18.9 months. The pooled rate of return to sport (RTS) was 94.3% (95% CI: 87.3%, 98.8%), and 86.1% (95% CI: 78.2%, 92.5%) of patients returned to their preoperative level of activity. The pooled redislocation rate was 1.1% (95% CI: 0%, 3.8%). Regarding the imaging results, the combined graft retention rate was 92.1% (95% CI: 88.1%, 95.5%), and the graft healing rate was 92.1% (95% CI: 88%, 95.4%). Postoperative functional evaluation revealed that the combined Rowe score, ASOSS score, and VAS score were 93.7 ± 6.5 points, 88.5 ± 4.4 points, and 1.1 ± 10 points, respectively. The forward flexion and external rotation angles were 170.9 ± 6.9 degrees and 65.6 ± 4.5 degrees, respectively. After excluding one study with unclear complications, the combined complication rate was 9.4% (95% CI: 1.0%, 23.6%). CONCLUSION: For athletes with shoulder instability and a total of ≥ 20% glenoid bone defects, the Latarjet procedure can achieve excellent functional outcomes, with the majority of patients returning to preoperative levels of sports activity. This procedure also leads to a low recurrence rate. Therefore, the Latarjet procedure has been proven to be a safe and effective treatment.

Chiral lanthanide-silver(I) cluster-based metal-organic frameworks exhibiting solvent stability, and tunable photoluminescence.

Due to the lack of effective synthetic strategies, the preparation of chemically stable chiral Ag(I) cluster-based materials for assembly remains challenging. Here, we have developed an approach to synthesize three pairs of chiral Ln-Ag(I) cluster-based metal-organic frameworks (MOFs) named l-LnAg5-3D (Ln = Gd for 1-L, Eu for 2-L, and Tb for 3-L) and d-LnAg5-3D (Ln = Gd for 1-D, Eu for 2-D, and Tb for 3-D) by employing a chiral Ag(I) cluster ({Ag5S6}) as the node and Ln3+ ion as the inorganic linker. Structural analysis revealed that the chiral ligands induced chirality through the entire structure, resulting in a chiral helix arrangement of the C3-symmetric chiral {Ag5S6} nodes and Ln3+ ions. These compounds showed high solvent stability in various polar organic solvents. The solid-state circular dichroism (CD) spectra of compounds l-LnAg5-3D and d-LnAg5-3D exhibited obvious mirror symmetrical peaks. The emission spectra in the solid state revealed that compound 1-L only exhibited the emission peak of {Ag5S6}, while compounds 2-L and 3-L exhibited overlapping peaks of Ln3+ and {Ag5S6} at different excitation wavelengths. This demonstrates the tunable photoluminescence from {Ag5S6} to Ln3+ by introducing different Ln3+ ions and manipulating the excitation wavelengths. The study underscores the enhanced stability of Ag(I) cluster-based MOFs achieved through the incorporation of Ln3+ ions and establishes chiral Ln-Ag(I) cluster-based MOFs as promising candidates for advanced materials with tunable photoluminescence.

Preorganized Nitrogen Sites for Au11 Amidation: A Generalizable Strategy toward Precision Functionalization of Metal Nanoclusters.

Atomically precise metal nanoclusters have received tremendous attention due to their unique structures and properties. Although synthetic approaches to this kind of nanomaterial have been well developed, methods toward precision functionalization of the as-synthesized metal nanoclusters are extremely limited, hindering their interfacial modification and related performance improvement. Herein, an amidation strategy has been developed for the precision functionalization of the Au11 nanocluster based on preorganized nitrogen sites. The nanocluster amidation did not change the number of gold atoms in the Au11 kernel and their bonding mode to the surface ligands but slightly modified the arrangement of gold atoms with the introduction of functionality and chirality, thus representing a relatively mild method for the modification of metal nanoclusters. The stability and oxidation barrier of the Au11 nanocluster are also improved accordingly. The method developed here would be a generalizable strategy for the precision functionalization of metal nanoclusters.

Advanced age is associated with increased adverse outcomes in patients undergoing middle cerebral artery stenting.

Purpose: This study tried to evaluate whether advanced age has an increased incidence of major complications in patients undergoing MCA stenting. Methods: A total of 348 patients who underwent MCA stenting were reviewed from a prospectively maintained database. Ninety-day ischemic stroke, intracerebral hemorrhage, and death outcomes were compared among the young (≤40 years old), middle (41-60 years old) and old (≥61 years old) groups. Univariate analysis and multivariable logistic regression analysis were used to investigate different variables associated with 90-day major adverse events. Kaplan-Meier analysis was performed to determine long-term outcomes during follow-up. Results: The incidence of 90-day ischemic stroke was 9.26% in the old group, 2.86% in the middle group, and 0% in the young group (P = 0.024). The incidence of all 90-day major adverse events was 3.33% in patients ≤40 years old, 19.90% in patients 41-60 years old, and 24.07% in patients ≥61 years old, with statistical significance (P = 0.04). Advanced age was associated with increased 90-day ischemic stroke (OR = 1.074, 95% CI: 1.019-1.132, P = 0.007; adjusted OR: 1.071, 95% CI: 1.008-1.138, P = 0.026) and 90-day death (OR = 1.072, 95% CI: 1.012-1.135, P = 0.018; adjusted OR: 1.095, 95% CI: 1.015-1.182, P = 0.018). Meanwhile, advanced age was also associated with decreased long-term survival and ischemic stroke-free survival during follow-up. Conclusion: Our data indicated that MCA stenting in elderly patients is associated with a high risk of adverse events and should be cautiously considered.

[Screening and identification of steroidal saponins-producing endophytes from Paris polyphylla var. chinensis Franch].

Two endophytic strains SS01 and SS02 with the potential for producing steroidal saponins were isolated from the underground stems of Paris polyphylla var. chinensis Franch. The TLC comparison indicated that there are 3 sports with similar R(f) between the metabolites of SS01 and the saponins of Paris polyphylla var. chinensis Franch. And there are 2 sports with similar R(f) between the metabolites of SS02 and the saponins of Paris polyphylla var. chinensis The and that biochemical SS01 Franch. characteristics of morphology, physiological belonged showed to Enterobacteriaceae and SS02 belonged to Bacillus sp.. The 16S rDNA of SS01 and SS02 were PCR and sequenced. The accessions of GenBank are AY842143 and AY842144, respectively. The two 16S rDNA phylogenetic trees were constructed by comparing with the published 16S rDNA sequences of the relative bacteria species. In the first phylogenetic tree SS01 and Cedecea davisae DSM 4568 was the closest relative with 98.9% sequence similarity, and in the second phylogenetic tree SS02 and Paenibacillus daejeonensis was the closest relative with 97.7% sequence similarity. According to the phylogenetic analysis they were identified as Cedecea davisae SS01 and Paenibacillus daejeonensis SS02, respectively.