Silver Clusters in Zeolites: From Self-Assembly to Ground-Breaking Luminescent Properties.

Interest for functional silver clusters (Ag-CLs) has rapidly grown over years due to large advances in the field of nanoscale fabrication and materials science. The continuous development of strategies to fabricate small-scale silver clusters, together with their interesting physicochemical properties (molecule-like discrete energy levels, for example), make them very attractive for a wide variety of applied research fields, from biotechnology and the environmental sciences to fundamental chemistry and physics. Apart from useful catalytic properties, silver clusters (Agn, n < 10) were recently shown to also exhibit exceptional optical properties. The optical properties and performance of Ag-CLs offer strong potential for their integration into appealing micro(nano)-optoelectronic devices. To date, however, the rational design and directed synthesis of Ag-CLs with specific functionalities has remained elusive. The inability for rational design stems mainly from a lack of understanding of their novel atomic-scale phenomena. This is because accurately studying silver cluster systems at such a scale is hindered by the perturbations introduced during exposure to various experimental probes. For instance, silver possesses a strong tendency to cluster and form ever-larger Ag aggregates while probed with high-energy electron beams and X-ray irradiation. As well, there exists a need to provide a stabilizing environment for which Agnδ+ clusters can persist, setting up a complex interacting guest-host system, as isolated silver clusters are confined within a suitable hosting medium. Fundamental research into Agnδ+ formation mechanisms and their important optical properties is paramount to establishing truly informed synthesis protocols. Over recent years, we have developed several protocols for the ship-in-a-bottle synthesis of highly luminescent Ag-CLs within the microporous interiors of zeolite frameworks. This approach has yielded materials displaying a wide variety of optical properties, offering a spectrum of possible applications, from nano(micro)photonic devices to smart luminescent labels and sensors. The versatility of the Ag-zeolite multicomponent system is directly related to the intrinsic and complex tunability of the system as a whole. There are several key zeolite parameters that confer properties to the clusters, namely, the framework Si/Al ratio, choice of counterbalancing ions, silver loading, and zeolite topology, and cannot be overlooked. This Account is intended to shed light on the current state-of-the-art of luminescent Ag-CLs confined in zeolitic matrices, emphasizing the use of combinatorial approaches to overcome problems associated with the correct characterization and correlation of their structural, electronic, and photoluminescence properties, all to establish the important design principles for developing functional silver-zeolite-based materials. Additionally, examples of emerging applications and future perspectives for functional luminescent Ag-zeolite materials are addressed in this Account.

Tunable white emission of silver-sulfur-zeolites as single-phase LED phosphors.

Metal clusters confined inside zeolite materials display remarkable luminescent properties, making them very suitable as potential alternative phosphors in white LED applications. However, up to date, only single-color emitters have been reported for luminescent metal-exchanged zeolites. In this study, we synthesized and characterized white emitting silver-sulfur zeolites, which show a remarkable color tunability upon the incorporation of silver species in highly luminescent sulfur-zeolites. Via a combined steady-state and time-resolved photoluminescence spectroscopy characterization, we suggest that the observed luminescence and tunability arise from the presence of two different species. The first associated to an orange-red emitting silver cluster (Ag-CL), whereas the second is related to a blue-white emitting S-Ag-species. The relative contribution of both luminescent species depends on the synthesis procedure. It was shown that the formation of the blue-white emitting S-Ag-species is favored upon a heat-treatment of the samples.

The biomechanical performance of bone block and soft-tissue posterior cruciate ligament graft fixation with interference screw and cross-pin techniques.

PURPOSE: The purpose of this study was to evaluate the biomechanical properties of 4 different graft fixation constructs on the tibial side of the posterior cruciate ligament with reconstruction by use of an Achilles tendon graft. METHODS: Biomechanical testing of 4 different fixation techniques was performed on 20 human cadaveric tibias and Achilles tendons. Cross-pin fixation with bone blocks (group A), interference screw fixation with bone blocks (group B), cross-pin fixation of soft tissue with backup fixation (group C), and interference screw fixation of soft tissue with backup fixation (group D) were tested. The tibia-graft fixation complex was cyclically loaded between 50 N and 250 N at 1 Hz for 1,000 cycles. After cycling, the amount of graft displacement was determined by measuring the change in grip-to-grip distance. The complex was then loaded to failure at 1 mm/s, and maximum failure load, stiffness, and mode of failure were determined. RESULTS: Group C had a higher maximum failure load and stiffness than groups A and B (P < .05 and P < .001, respectively) but poor results for displacement (P < .05 and P < .05, respectively). The failure modes were bone block fracture, graft laceration, or cross-pin fracture in the cross-pin groups and graft pullout in the interference screw groups. CONCLUSIONS: Our study suggests that maximum failure load and stiffness of hybrid fixation for Achilles tendon graft are comparable to those of both single calcaneal bone plug fixation methods that we studied. However, tendon graft displacement was significantly greater regardless of fixation method when compared with bone plug fixation. CLINICAL RELEVANCE: Hybrid fixation for soft-tissue graft on the tibial fixation site provides comparable biomechanical properties of bone-to-bone fixation.

Giant Electron-Phonon Coupling and Deep Conduction Band Resonance in Metal Halide Double Perovskite.

The room-temperature charge carrier mobility and excitation-emission properties of metal halide perovskites are governed by their electronic band structures and intrinsic lattice phonon scattering mechanisms. Establishing how charge carriers interact within this scenario will have far-reaching consequences for developing high-efficiency materials for optoelectronic applications. Herein we evaluate the charge carrier scattering properties and conduction band environment of the double perovskite Cs2AgBiBr6 via a combinatorial approach; single crystal X-ray diffraction, optical excitation and temperature-dependent emission spectroscopy, resonant and nonresonant Raman scattering, further supported by first-principles calculations. We identify deep conduction band energy levels and that scattering from longitudinal optical phonons- via the Fröhlich interaction-dominates electron scattering at room temperature, manifesting within the nominally nonresonant Raman spectrum as multiphonon processes up to the fourth order. A Fröhlich coupling constant nearing 230 meV is inferred from a temperature-dependent emission line width analysis and is found to be extremely large compared to popular lead halide perovskites (between 40 and 60 meV), highlighting the fundamentally different nature of the two "single" and "double" perovskite materials branches.

Photophysical Pathways in Highly Sensitive Cs2 AgBiBr6 Double-Perovskite Single-Crystal X-Ray Detectors.

The sensitive detection of X-rays embodies an important research area, being motivated by a common desire to minimize the radiation doses required for detection. Among metal halide perovskites, the double-perovskite Cs2 AgBiBr6 system has emerged as a promising candidate for the detection of X-rays, capable of high X-ray stability and sensitivity (105 µC Gy-1 cm-2 ). Herein, the important photophysical pathways in single-crystal Cs2 AgBiBr6 are detailed at both room (RT) and liquid-nitrogen (LN2 T) temperatures, with emphasis made toward understanding the carrier dynamics that influence X-ray sensitivity. This study draws upon several optical probes and an RT excitation model is developed which is far from optimal, being plagued by a large trap density and fast free-carrier recombination pathways. Substantially improved operating conditions are revealed at 77 K, with a long fundamental carrier lifetime (>1.5 µs) and a marked depopulation of parasitic recombination pathways. The temperature dependence of a single-crystal Cs2 AgBiBr6 X-ray detecting device is characterized and a strong and monotonic enhancement to the X-ray sensitivity upon cooling is demonstrated, moving from 316 µC Gy-1 cm-2 at RT to 988 µC Gy-1 cm-2 near LN2 T. It is concluded that even modest cooling-via a Peltier device-will facilitate a substantial enhancement in device performance, ultimately lowering the radiation doses required.

Medial open wedge high tibial osteotomy: the effect of the cortical hinge on posterior tibial slope.

BACKGROUND: High tibial osteotomy can affect the posterior tibial slope in the sagittal plane because of the triangular configuration of the proximal tibia. However, the effect of the location of cortical hinge on posterior tibial slope has not been previously described. HYPOTHESIS: Posterolateral location of the cortical hinge will increase posterior tibial slope after medial open wedge osteotomy, and lateral location of the cortical hinge will not affect the change of the posterior tibial slope. STUDY DESIGN: Controlled laboratory study. METHODS: We performed incomplete valgus open wedge osteotomy on 12 paired knees of 6 fresh-frozen human cadavers (age, 63.4 + or - 7.5 years) using an OrthoPilot navigation system. The left and right legs of each specimen were randomly assigned to a posterolateral (group A) or a lateral (group B) cortical hinge group. Changes in mean medial proximal tibial angle, posterior tibial slope, and opening wedge angle were measured and compared after surgery. RESULTS: In group A, mean medial proximal tibial angle changed from 84.37 degrees + or - 2.8 degrees to 93.48 degrees + or - 3.06 degrees (P = .028); mean posterior tibial slope increased significantly from 8.71 degrees + or - 0.81 degrees to 12.16 degrees + or - 0.84 degrees (P = .031); and mean wedge angle was 1.92 degrees + or - 0.46 degrees . In group B, mean medial proximal tibial angle changed from 82.98 degrees + or - 2.53 degrees to 90.89 degrees + or - 3.25 degrees (P = .027); mean posterior tibial slope changed from 9.19 degrees + or - 1.11 degrees to 9.78 degrees + or - 1.27 degrees (P = .029); and mean wedge angle was 7.25 degrees + or - 0.72 degrees . CONCLUSION: The location of the intact cortical hinge affects the posterior tibia slope. During medial open wedge osteotomy, the change of posterior tibial slope was larger in the posterolateral than in the lateral cortical hinge group. CLINICAL RELEVANCE: To prevent the unintentional increase of the posterior tibial slope, special attention should be paid to locate the intact cortical hinge on the lateral, not the posterolateral, side of the tibia.