A growing number of copper(II) complexes have been identified as suitable candidates for biomedical applications.Here, we show that the biocompatibility and stability of copper(II) complexes can be tuned by directed ligand design and complex geometry. We demonstrate that azamacrocycle-based chelators that envelope copper(II) in a five-coordinate, distorted trigonalbipyramidal structure are more chemically inert to redox-mediated structural changes than their six-coordinate, Jahn−Teller-distorted counterparts, as evidenced by electrochemical, crystallographic, electron paramagnetic resonance, and density functional theory studies. We further validated our hypothesis of enhanced inertness in vitro and in vivo by employing Cu-64 radiolabeling of bifunctional analogues appended to a prostate-specific membrane antigen targeting dipeptide. The corresponding Cu-64 complexes were tested for stability in vitro and in vivo, with the five-coordinate system demonstrating the greatest metabolic stability among the studied picolinate complex series.

Lead halide perovskite nanocrystals (NCs) have recently drawn considerable attention in the fields of materials science and nanotechnology. However, a major drawback of these NCs is the reliance on toxic lead, which hinders widespread application. Herein, a new class of lead‐free perovskite NCs, that is, lanthanide double perovskite (Ln‐DP) NCs, with f‐orbital‐induced optical properties, is introduced. The Pr‐, Ce‐, Tb‐, Eu‐, Sm‐, and Yb‐based Ln‐DP NCs display narrow d→f and f→f emissions ranging from the UV‐C to the near‐infrared spectral region. Experimental data and calculations reveal that the emissive Ln‐DP NCs exhibit small molecule‐like electronic absorptions: f→d atomic transitions or ligand‐to‐metal charge transfer transitions. Last, it is demonstrated that by alloying Ln compositions in the DP NCs, new materials with unique and improved optical properties can be obtained. These Ln‐DP NCs are promising for optical sensing and lighting, and as components in optoelectronic and/or magneto‐fluorescent devices.

Background: Previous studies comparing stability between single- and double-row arthroscopic bony Bankart repair techniques focused only on the measurements of tensile forces on the bony fragment without re-creating a more physiologic testing environment. Purpose: To compare dynamic stability and displacement between single- and double-row arthroscopic repair techniques for acute bony Bankart lesions in a concavity-compression cadaveric model simulating physiologic conditions. Study Design: Controlled laboratory study. Methods: Testing was performed on 13 matched pairs of cadaveric glenoids with simulated bony Bankart fractures with a defect width of 25% of the inferior glenoid diameter. Half of the fractures were repaired with a double-row technique, and the contralateral glenoids were repaired with a single-row technique. To determine dynamic biomechanical stability and ultimate step-off of the repairs, a 150-N load and 2000 cycles of internal-external rotation at 1 Hz were applied to specimens to simulate early rehabilitation. Toggle was quantified throughout cycling with a coordinate measuring machine. Three-dimensional spatial measurements were calculated. After cyclic loading, the fracture displacement was measured. Results: The bony Bankart fragment–glenoid initial step-off was found to be significantly greater ( P < .001) for the single-row technique (mean, 896 µm; SD, 282 µm) compared with the double-row technique (mean, 436 µm; SD, 313 µm). The motion toggle was found to be significantly greater ( P = .017) for the single-row technique (mean, 994 µm; SD, 711 µm) compared with the double-row technique (mean, 408 µm; SD, 384 µm). The ultimate interface displacement was found to be significantly greater ( P = .029) for the single-row technique (mean, 1265 µm; SD, 606 µm) compared with the double-row technique (mean, 795 µm; SD, 398 µm). Conclusion: Using a concavity-compression glenohumeral cadaveric model, we found that the double-row arthroscopic fixation technique for bony Bankart repair resulted in superior stability and decreased displacement during simulated rehabilitation when compared with the single-row repair technique. Clinical Relevance: The findings from this study may help guide surgical decision-making by demonstrating superior biomechanical properties (improved initial step-off, motion toggle, and interface displacement) of the double-row bony Bankart repair technique when compared with single-row fixation. The double-row repair construct demonstrated increased stability of the bony Bankart fragment, which may improve bony Bankart healing.

N-oxides can amplify the performance of a lanthanum aminobisphenolate catalyst in the ring-opening polymerization (ROP) of rac-β-butyrolactone (rac-BBL) to unprecedented levels (TOF / Pm ; At RT: 1,900 h-1 /...

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Background: Bony Bankart lesions can be encountered during treatment of shoulder instability. Current arthroscopic bony Bankart repair techniques involve intra-articular suture placement, but the effect of these repair techniques on the integrity of the humeral head articular surface warrants further investigation. Purpose: To quantify the degree of humeral head articular cartilage damage secondary to current arthroscopic bony Bankart repair techniques in a cadaveric model. Study Design: Controlled laboratory study. Methods: Testing was performed in 13 matched pairs of cadaveric glenoids with simulated bony Bankart fractures, with a defect width of 25% of the glenoid diameter. Half of the fractures were repaired with a double-row technique, while the contralateral glenoids were repaired with a single-row technique. Samples were subjected to 20,000 cycles of internal-external rotation across a 90° arc at 2 Hz after a compressive load of 750 N, or 90% body weight (whichever was less) was applied to simulate wear. Cartilage defects on the humeral head were quantified through a custom MATLAB script. Mean cartilage cutout differences were analyzed by the Wilcoxon rank-sum test. Results: Both single- and double-row repairs showed macroscopic damage. The histomorphometric analysis demonstrated that the double-row technique resulted in a significantly ( P = .036) more chondral damage (mean, 57,489.1 µm2; SD, 61,262.2 µm2) than the single-row repair (mean, 28,763.5 µm2; SD, 24,4990.2 µm2). Conclusion: Both single-row and double-row arthroscopic bony Bankart fixation techniques resulted in damage to the humeral head articular cartilage in the concavity-compression model utilized in this study. The double-row fixation technique resulted in a significantly increased cutout to the humeral head cartilage after simulated wear in this cadaveric model. Clinical Relevance: This study provides data demonstrating that placement of intra-articular suture during arthroscopic bony Bankart repair techniques may harm the humeral head cartilage. While the double-row repair of bony Bankart lesions is more stable, it results in increased cartilage damage. These findings suggest that alternative, cartilage-sparing arthroscopic techniques for bony Bankart repair should be investigated.

Homoleptic yttrium and lanthanum complexes of bis(phosphineoxide) methanides, RE(HPhL)3 and RE2(HMeL)6, promote the first rare-earth mediated Horner-Wittig and acid-base chemistry consistent with multifunctional reactivity (Lewis-acid/Brønstedbase).

Background Total shoulder arthroplasty with second generation porous tantalum glenoid implants (Trabecular Metal™) has shown good short-term outcomes, but mid-term outcomes are unknown. This study describes the clinical, radiographic, and patient-rated mid-term outcomes of total shoulder arthroplasty utilizing cemented Trabecular Metal™ glenoid components. Methods Patients who underwent anatomic total shoulder arthroplasty with cemented Trabecular Metal™ glenoid components for primary osteoarthritis were identified for minimum five-year follow-up. The primary outcome measure was implant survival; secondary outcome measures included patient-rated outcome scores, shoulder range of motion findings, and radiographic analysis. Results Twenty-seven patients were enrolled in the study. Twenty-one patients had full radiographic follow-up. Mean follow-up was 6.6 years. There was 100% implant survival. Shoulder range of motion significantly improved and the mean American Shoulder and Elbow Society score was 89.8. There was presence of metal debris radiographically in 24% of patients. Twenty-nine percent of patients had evidence of radiolucency. Fourteen percent of patients had moderate superior subluxation. Conclusion Total shoulder arthroplasty with second generation cemented Trabecular Metal™ glenoid components yielded good outcomes at mean 6.6-year follow-up. Metal debris incidence and clinical outcomes were similar to short-term findings. The presence of metal debris did not significantly affect clinical outcomes. Continued observation of these patients will elucidate longer-term implant survival.