Radiative cooling and indoor light management enabled by a transparent and self-cleaning polymer-based metamaterial.

Transparent roofs and walls offer a compelling solution for harnessing natural light. However, traditional glass roofs and walls face challenges such as glare, privacy concerns, and overheating issues. In this study, we present a polymer-based micro-photonic multi-functional metamaterial. The metamaterial diffuses 73% of incident sunlight, creating a more comfortable and private indoor environment. The visible spectral transmittance of the metamaterial (95%) surpasses that of traditional glass (91%). Furthermore, the metamaterial is estimated to enhance photosynthesis efficiency by ~9% compared to glass roofs. With a high emissivity (~0.98) close to that of a mid-infrared black body, the metamaterial is estimated to have a cooling capacity of ~97 W/m2 at ambient temperature. The metamaterial was about 6 °C cooler than the ambient temperature in humid Karlsruhe. The metamaterial exhibits superhydrophobic performance with a contact angle of 152°, significantly higher than that of glass (26°), thus potentially having excellent self-cleaning properties.

Determining Structures of Layer-by-Layer Spin-Coated Zinc Dicarboxylate-Based Metal-Organic Thin Films.

Thin films of crystalline solids with substantial free volume built from organic chromophores and metal secondary building units (SBUs) are promising for engineering new optoelectronic properties through control of interchromophore coupling. Zn-based SBUs are especially relevant in this case because they avoid quenching the chromophore's luminescence. We find that layer-by-layer spin-coating using Zn acetate dihydrate and benzene-1,4-dicarboxylic acid (H2BDC) and biphenyl-4,4'-dicarboxylic acid (H2BPDC) linkers readily produces crystalline thin films. However, analysis of the grazing-incidence wide-angle X-ray scattering (GIWAXS) data reveals the structures of these films vary significantly with the linker, and with the metal-to-linker molar ratio used for fabrication. Under equimolar conditions, H2BPDC creates a type of structure like that proposed for SURMOF-2, whereas H2BDC generates a different metal-hydroxide-organic framework. Large excess of Zn2+ ions causes the growth of layered zinc hydroxides, irrespective of the linker used. Density functional theory (DFT) calculations provide structural models with minimum total energy that are consistent with the experimentally observed diffractograms. In the broader sense, this work illustrates the importance in this field of careful structure determination, e. g., by utilizing GIWAXS and DFT simulations to determine the structure of the obtained crystalline metal-organic thin films, such that properties can be rationally engineered and explained.

Influence of acromioclavicular joint arthritis on outcomes after reverse total shoulder.

Background: Although substantial motion at the acromioclavicular joint (ACJ) occurs during overhead shoulder motion, the influence of ACJ arthritis on postoperative outcomes of patients undergoing reverse total shoulder arthroplasty (rTSA) is unclear. We assessed the influence of ACJ arthritis, defined by degenerative radiographic changes, and its severity on clinical outcomes after primary rTSA. Methods: We conducted a retrospective review of a prospectively collected shoulder arthroplasty database of patients that underwent primary rTSA with a minimum 2-year clinical follow-up. Imaging studies of included patients were evaluated to assess ACJ arthritis classified by radiographic degenerative changes of the ACJ; severity was based upon size and location of osteophytes. Both the Petersson classification and the King classification (a modified Petersson classification addressing superior osteophytes and size of the largest osteophyte) were used to evaluate the severity of degenerative ACJ radiographic changes. Severe ACJ arthritis was characterized by large osteophytes (≥2 mm). Active range of motion (ROM) in abduction, forward elevation, and external and internal rotation as well as clinical outcome scores (American Shoulder and Elbow Surgeons Shoulder, Constant, Shoulder Pain and Disability Index, simple shoulder test, University of California, Los Angeles scores) were assessed both preoperatively and at the latest follow-up; outcomes were compared based on severity of ACJ arthritis. Multivariable linear regression models were used to determine whether increasing severity of ACJ arthritis was associated with poorer outcomes. Results: A total of 341 patients were included with a mean age of 71 ± 8 years and 55% were female. The mean follow-up was 5.1 ± 2.4 years. Preoperatively, there were no differences in outcomes based on the severity of ACJ pathology. Postoperatively, there were no differences in outcomes based upon the severity of ACJ arthritis except for greater preoperative to postoperative improvement in active internal rotation in patients with normal or grade 1 ACJ arthritis vs. grade 2 and 3 (3 ± 2 vs. 1 ± 2 and 1 ± 3, P = .029). Patients with ACJ arthritis and osteophytes ≥2 mm had less favorable Shoulder Pain and Disability Index scores, corresponding to greater pain (-49.3 ± 21.5 vs. -41.3 ± 26.8, P = .015). On multivariable linear regression, increased severity of ACJ arthritis was not independently associated with poorer postoperative ROM or outcome scores. Conclusion: Overall, our results demonstrate that greater ACJ arthritis severity score is not associated with poorer outcome scores and has minimal effect on ROM. However, patients with the largest osteophytes (≥2 mm) did have slightly worse pain postoperatively. Radiographic presence of high-stage ACJ arthritis should not alter the decision to undergo rTSA.

High Quantum Yield Shortwave Infrared Luminescent Tracers for Improved Sorting of Plastic Waste.

More complete recycling of plastic waste is possible only if new technologies that go beyond state-of-the-art near-infrared (NIR) sorting are developed. For example, tracer-based sorting is a new technology that explores the upconversion or down-shift luminescence of special tracers based on inorganic materials codoped with lanthanide ions. Specifically, down-shift tracers emit in the shortwave infrared (SWIR) spectral range and can be detected using a SWIR camera preinstalled in a state-of-the-art sorting machine for NIR sorting. In this study, we synthesized a very efficient SWIR tracer by codoping Li3Ba2Gd3 (MoO4)8 with Yb3+ and Er3+, where Yb3+ is a synthesizer ion (excited near 976 nm) and Er3+ emits near 1550 nm. Fine-tuning of the doping concentration resulted in a tracer (Li3Ba2Gd(3-x-y)(MoO4)8:xYb3+, yEr3+, where x = 0.2 and y = 0.4) with a high photoluminescence quantum yield for 1550 nm emission of 70% (using 976 nm excitation). This tracer was used to mark plastic objects. When the object was illuminated by a halogen lamp and a 976 nm laser, the three parts could be easily distinguished based on reflectance and luminescence spectra in the SWIR range: a plastic bottle made of polyethylene terephthalate, a bottle cap made of high-density polyethylene, and a label made of the tracer Li3Ba2Gd3(MoO4)8:Yb3+, Er3+. Importantly, the use of the tracer in sorting may require only the installation of a 976 nm laser in a state-of-the-art NIR sorting system.

Solar-pumped fiber laser using a solid-state luminescent solar collector.

We have developed a fully planar solar-pumped fiber laser using a solid-state luminescent solar collector (LSC). This laser does not use any focusing device, such as a lens or mirror; thus, it can lase without tracking the sun. Our developed device with an aperture of 30 cm emits 15 mW, corresponding to an optical-to-optical conversion efficiency of 0.023% and a collection efficiency of 0.21 W/m2. A 12-fold improvement over a previously developed liquid LSC is achieved by combining the total internal reflection of the solid-state LSC with dielectric multilayer mirrors. The observed laser power is in good agreement with that predicted via numerical simulation, demonstrating the effectiveness of our proposed method.

Structure and luminescence properties of Dy3+ doped quaternary tungstate Li3Ba2Gd3(WO4)8 for application in wLEDs.

Quaternary tungstates with the composition Li3Ba2Gd3(WO4)8 doped with different concentrations of Dy3+ (from 0.5 to 10 at%) were prepared by the solid-state reaction method at 900 °C. Their structural, spectroscopic and optical properties were studied systematically in this work. X-ray diffraction analysis confirmed the crystallization of Li3Ba2Gd3(WO4)8 to have a monoclinic structure (sp. gr. C2/c); the lattice constants for 1 at% doping concentration of Dy3+ are a = 5.2126(2) Å, b = 12.7382(1) Å, c = 19.1884(3) Å, Vcalc = 1273,40(4) Å3 and ß = a × c = 91.890(9)°. The first principles calculations for the undoped crystal revealed a direct bandgap of 2.45 eV, which is very close to the experimental one. The identified broad, and strong excitation peak at 450 nm indicates that Li3Ba2Gd3(WO4)8:Dy3+ phosphors are suitable to be pumped by a blue laser diode (LD). Under excitation at 445 nm, the phosphor showed a stronger luminescence peak at 575 nm which corresponds to the Dy3+:4F9/2 → 6H13/2 transition, and three weaker emissions peaks at 477, 661, and 750 nm. Meanwhile, the effect of different Dy3+ contents on the luminescence properties was investigated. The optimum concentration to minimize the quenching effect was 4 at% and the critical distance is 31.209 Å. The phosphor emitted strong greenish-yellow light situated at (0.425, 0.472) in CIE coordinates with a color temperature of 3652 K. All the measured luminescence lifetime curves exhibited a single-exponential nature. Excellent thermal stability was found for this tungstate phosphor (the activation energy is 0.352 ± 0.01 eV). The measured absolute photoluminescence quantum yield was around 10.5%. The results presented in this work show that Li3Ba2Gd3(WO4)8:Dy3+ phosphors with strong yellow emission are promising candidates for white-light emitting LED (wLED) applications.

Preventing cation intermixing enables 50% quantum yield in sub-15 nm short-wave infrared-emitting rare-earth based core-shell nanocrystals.

Short-wave infrared (SWIR) fluorescence could become the new gold standard in optical imaging for biomedical applications due to important advantages such as lack of autofluorescence, weak photon absorption by blood and tissues, and reduced photon scattering coefficient. Therefore, contrary to the visible and NIR regions, tissues become translucent in the SWIR region. Nevertheless, the lack of bright and biocompatible probes is a key challenge that must be overcome to unlock the full potential of SWIR fluorescence. Although rare-earth-based core-shell nanocrystals appeared as promising SWIR probes, they suffer from limited photoluminescence quantum yield (PLQY). The lack of control over the atomic scale organization of such complex materials is one of the main barriers limiting their optical performance. Here, the growth of either homogeneous (α-NaYF4) or heterogeneous (CaF2) shell domains on optically-active α-NaYF4:Yb:Er (with and without Ce3+ co-doping) core nanocrystals is reported. The atomic scale organization can be controlled by preventing cation intermixing only in heterogeneous core-shell nanocrystals with a dramatic impact on the PLQY. The latter reached 50% at 60 mW/cm2; one of the highest reported PLQY values for sub-15 nm nanocrystals. The most efficient nanocrystals were utilized for in vivo imaging above 1450 nm.

Absolute quantum yield for understanding upconversion and downshift luminescence in PbF2:Er3+,Yb3+ crystals.

The search for new materials capable of efficient upconversion continues to attract attention. In this work, a comprehensive study of the upconversion luminescence in PbF2:Er3+,Yb3+ crystals with different concentrations of Yb3+ ions in the range of 2 to 7.5 mol% (Er3+ concentration was fixed at 2 mol%) was carried out. The highest value of upconversion quantum yield (ϕUC) 5.9% (at 350 W cm-2) was found in the PbF2 crystal doped with 2 mol% Er3+ and 3 mol% Yb3+. Since it is not always easy to directly measure ϕUC and estimate the related key figure of merit parameter, saturated photoluminescence quantum yield (ϕUCsat), a method to reliably predict ϕUCsat can be useful. Judd-Ofelt theory provides a convenient way to determine the radiative lifetimes of the excited states of rare-earth ions based on absorption measurements. When the luminescence decay times after direct excitation of a level are also measured, ϕUCsat for that level can be calculated. This approach is tested on a series of PbF2:Er3+,Yb3+ crystals. Good agreement between the estimates obtained as above and the directly experimentally measured ϕUCsat values is demonstrated. In addition, three methods of Judd-Ofelt calculations on powder samples were tested and the results were compared with Judd-Ofelt calculations on single crystals, which served as the source of the powder samples. Taken together, the results presented in our work for PbF2:Er3+,Yb3+ crystals contribute to a better understanding of the UC phenomena and provide a reference data set for the use of UC materials in practical applications.

π-Complexation and C-H hydrogen bonding in the formation of colored cocrystals.

The present study evaluates the potential combination of charge-transfer electron-donor-acceptor π-π complexation and C-H hydrogen bonding to form colored cocrystals. The crystal structures of the red 1:1 cocrystals formed from the isomeric pyridines 4- and 3-{2-[4-(dimethylamino)phenyl]ethynyl}pyridine with 1-[2-(3,5-dinitrophenyl)ethynyl]-2,3,5,6-tetrafluorobenzene, both C14H4F4N2O4·C15H14N2, are reported. Intermolecular interaction energy calculations confirm that π-stacking interactions dominate the intermolecular interactions within each crystal structure. The close contacts revealed by Hirshfeld surface calculations are predominantly C-H interactions with N, O, and F atoms.

Cystadenofibroma with Mullerian-Type Epithelium and Stroma in the Liver: A Report of an Unusual Diagnosis and Discussion of Possible Etiologies.

Primary cystic neoplasms in the liver with ovarian type stroma typically represent mucinous cystic neoplasms. These tumors contain a cuboidal to columnar epithelium with variably mucinous cytoplasm. To the best of our knowledge, there are no reports of primary hepatic cystic neoplasms with ovarian-type stroma and ciliated epithelial lining. We describe a case of a 53-year-old woman with a history of a multicystic mass in the right hepatic lobe that did not communicate with the biliary tree. The tumor contained multiple cysts with large papillae lined with ciliated Mullerian epithelium and subepithelial ovarian-type stroma.

The Longitudinal Impact Of A Multistate Commercial Accountable Care Program On Cost, Use, And Quality.

The prevalence of accountable care organizations (ACOs) has grown significantly across Medicare and commercial payers in the past decade, but there are limited insights regarding the effect of ACOs on costs in the commercial population. We used longitudinal administrative claims data over the course of nineteen calendar quarters from 2016 to 2021 to assess the ongoing incremental impact of Elevance Health's commercial ACO program on cost and use across fifteen US states. We also analyzed the program's impact on spending subcategories (inpatient, outpatient, professional, and pharmacy) and measured differences in quality performance. The program was associated with incremental savings during this period. Incremental savings were greater in the fully insured population relative to the administrative services only population and were due to outpatient and pharmacy savings. ACO providers had superior quality performance measures relative to contracted providers not participating in ACOs. Payers should be aware of the potential for diminishing marginal returns of ACO contracting on containing health care costs.

Limitation of room temperature phosphorescence efficiency in metal organic frameworks due to triplet-triplet annihilation.

The effect of triplet-triplet annihilation (TTA) on the room-temperature phosphorescence (RTP) in metal-organic frameworks (MOFs) is studied in benchmark RTP MOFs based on Zn metal centers and isophthalic or terephthalic acid linkers (ZnIPA and ZnTPA). The ratio of RTP to singlet fluorescence is observed to decrease with increasing excitation power density. Explicitly, in ZnIPA the ratio of the RTP to fluorescence is 0.58 at 1.04 mW cm-2, but only 0.42 at (the still modest) 52.6 mW cm-2. The decrease in ratio is due to the reduction of RTP efficiency at higher excitation due to TTA. The density of triplet states increases at higher excitation power densities, allowing triplets to diffuse far enough during their long lifetime to meet another triplet and annihilate. On the other hand, the shorter-lived singlet species can never meet an annihilate. Therefore, the singlet fluorescence scales linearly with excitation power density whereas the RTP scales sub-linearly. Equivalently, the efficiency of fluorescence is unaffected by excitation power density but the efficiency of RTP is significantly reduced at higher excitation power density due to TTA. Interestingly, in time-resolved measurements, the fraction of fast decay increases but the lifetime of long tail of the RTP remains unaffected by excitation power density. This may be due to the confinement of triplets to individual grains, leading decay to be faster until there is only one triplet per grain left. Subsequently, the remaining "lone triplets" decay with the unchanging rate expressed by the long tail. These results increase the understanding of RTP in MOFs by explicitly showing the importance of TTA in determining the (excitation power density dependent) efficiency of RTP. Also, for applications in optical sensing, these results suggest that a method based on long tail lifetime of the RTP is preferable to a ratiometric approach as the former will not be affected by variation in excitation power density whereas the latter will be.

Pyoderma Gangrenosum Masquerading as Wound Infection in the Early Postoperative Period After Lumbar Spine Deformity Correction Surgery.

The development of pyoderma gangrenosum (PG) after surgical site trauma is a rare, poorly understood immunologic phenomenon. PG is an immunologic disorder characterized by lymphocytic infiltration of the dermis that can manifest with skin necrosis and ulceration. This rare phenomenon can mimic surgical site infection (SSI) when it occurs in the perioperative period and in the region of surgical wounds. Within the neurosurgical literature, only two cases of postoperative PG have been reported to our knowledge. We describe the clinical features and treatment of PG in the case of a 65-year-old man who underwent a three-stage surgical approach for intractable mechanical low back pain on hospital days (HDs) 1 and 2, and who subsequently developed PG around all three surgical sites in the immediate postoperative period (HD 8). The physical and laboratory findings and surgical and pharmacologic treatments are detailed. The patient was initially treated for presumed SSI, started on broad-spectrum antibiotics, and underwent surgical wound debridement twice, without resolution of symptoms. The diagnosis of PG was ultimately made by a consulting dermatologist on HD 17. The patient was started on systemic immunosuppression with steroids during his initial hospitalization; symptoms resolved within two weeks of the index surgery. Although PG is a rare entity, we suggest that it be considered in the differential diagnosis of nonhealing surgical wounds. Familiarity with PG may help mitigate unnecessary surgical morbidity and reduce the length of hospital stays and unnecessary use of antibiotics.

Dual-color dynamic anti-counterfeiting labels with persistent emission after visible excitation allowing smartphone authentication.

A significant impediment to the deployment of anti-counterfeiting technologies is the reliance on specialized hardware. Here, anti-counterfeiting labels are developed that are both excited and detected using a smartphone. The persistent luminescence pattern and color changes on the timescale of hundreds of milliseconds to seconds. The labels can be authenticated by comparing still images from the red and green channels of video acquired at known times after flashlight excitation against expected reference patterns. The labels are based on a green-emitting SrAl2O4: Eu2+,Dy3+ (SAED), and red-emitting CaS:Eu2+ phosphors whose lifetimes are varied: (i) for SAED from 0.5 to 11.7 s by annealing the commercial material in air; and (ii) CaS:Eu2+ from 0.1 to 0.6 s by varying the dopant concentration. Examples of anti-counterfeiting labels exhibiting changing emission patterns and colors on a seven-segment display, barcode, and emoji are demonstrated. These results demonstrate that phosphors with visible absorption and tunable persistent luminescence lifetimes on the order of hundreds of milliseconds to seconds are attractive for anti-counterfeiting applications as they allow authentication to be performed using only a smartphone. Further development should allow richer color shifts and enhancement of security by embedding further covert anti-counterfeiting features.

Drying and Coating of Perovskite Thin Films: How to Control the Thin Film Morphology in Scalable Dynamic Coating Systems.

Hybrid perovskite photovoltaics combine high performance with the ease of solution processing. However, to date, a poor understanding of morphology formation in coated perovskite precursor thin films casts doubt on the feasibility of scaling-up laboratory-scale solution processes. Oblique slot jet drying is a widely used scalable method to induce fast crystallization in perovskite thin films, but deep knowledge and explicit guidance on how to control this dynamic method are missing. In response, we present a quantitative model of the drying dynamics under oblique slot jets. Using this model, we identify a simple criterion for successful scaling of perovskite solution printing and predict coating windows in terms of air velocity and web speed for reproducible fabrication of perovskite solar cells of ∼15% in power conversion efficiency─in direct correlation with the morphology of fabricated thin films. These findings are a corner stone toward scaling perovskite fabrication from simple principles instead of trial and error optimization.

Cubic versus hexagonal - phase, size and morphology effects on the photoluminescence quantum yield of NaGdF4:Er3+/Yb3+ upconverting nanoparticles.

Upconverting nanoparticles (UCNPs) are well-known for their capacity to convert near-infrared light into UV/visible light, benefitting various applications where light triggering is required. At the nanoscale, loss of luminescence intensity is observed and thus, a decrease in photoluminescence quantum yield (PLQY), usually ascribed to surface quenching. We evaluate this by measuring the PLQY of NaGdF4:Er3+,Yb3+ UCNPs as a function of size (ca. 15 to 100 nm) and shape (spheres, cubes, hexagons). Our results show that the PLQY of α-phase NaGdF4 Er3+,Yb3+ surpasses that of ß-NaGdF4 for sizes below 20 nm, an observation related to distortion of the crystal lattice when the UCNPs become smaller. The present study also underlines that particle shape must not be neglected as a relevant parameter for PLQY. In fact, based on a mathematical nucleus/hull volumetric model, shape was found to be particularly relevant in the 20 to 60 nm size range of the investigated UCNPs.

BODIPY-pyrene donor-acceptor sensitizers for triplet-triplet annihilation upconversion: the impact of the BODIPY-core on upconversion efficiency.

Triplet-triplet annihilation upconversion (TTA-UC) is an important type of optical process with applications in biophotonics, solar energy harvesting and photochemistry. In most of the TTA-UC systems, the formation of triplet excited states takes place via spin-orbital interactions promoted by heavy atoms. Given the crucial role of heavy atoms (especially noble metals, such as Pd and Pt) in promoting intersystem crossing (ISC) and, therefore, in production of UC luminescence, the feasibility of using more readily available and inexpensive sensitizers without heavy atoms remains a challenge. Here, we investigated sensitization of TTA-UC using BODIPY-pyrene heavy-atom-free donor-acceptor dyads with different numbers of alkyl groups in the BODIPY scaffold. The molecules with four and six alkyl groups are unable to sensitize TTA-UC in the investigated solvents (tetrahydrofuran (THF) and dichloromethane (DCM)) due to negligible ISC. In contrast, the dyad with two methyl groups in the BODIPY scaffold and the dyad with unsubstituted BODIPY demonstrate efficient intersystem crossing (ISC) of 49-58%, resulting in TTA-UC with quantum yields of 4.7% and 6.9%, respectively. The analysis of the elementary steps of the TTA-UC process indicates that heavy-atom-free donor-acceptor dyads are less effective than their noble metal counterparts, but may equal them in the future if the right combination of solvent, donor-acceptor sensitizer structure, and new luminescent molecules as TTA-UC emitters can be found.

Harvesting Sub-bandgap Photons via Upconversion for Perovskite Solar Cells.

Lanthanide-based upconversion (UC) allows harvesting sub-bandgap near-infrared photons in photovoltaics. In this work, we investigate UC in perovskite solar cells by implementing UC single crystal BaF2:Yb3+, Er3+ at the rear of the solar cell. Upon illumination with high-intensity sub-bandgap photons at 980 nm, the BaF2:Yb3+, Er3+ crystal emits upconverted photons in the spectral range between 520 and 700 nm. When tested under terrestrial sunlight representing one sun above the perovskite's bandgap and sub-bandgap illumination at 980 nm, upconverted photons contribute a 0.38 mA/cm2 enhancement in the short-circuit current density at lower intensity. The current enhancement scales non-linearly with the incident intensity of sub-bandgap illumination, and at higher intensity, 2.09 mA/cm2 enhancement in current was observed. Hence, our study shows that using a fluoride single crystal like BaF2:Yb3+, Er3+ for UC is a suitable method to extend the response of perovskite solar cells to near-infrared illumination at 980 nm with a subsequent enhancement in current for very high incident intensity.

Interface Pattern Engineering in Core-Shell Upconverting Nanocrystals: Shedding Light on Critical Parameters and Consequences for the Photoluminescence Properties.

Advances in controlling energy migration pathways in core-shell lanthanide (Ln)-based hetero-nanocrystals (HNCs) have relied heavily on assumptions about how optically active centers are distributed within individual HNCs. In this article, it is demonstrated that different types of interface patterns can be formed depending on shell growth conditions. Such interface patterns are not only identified but also characterized with spatial resolution ranging from the nanometer- to the atomic-scale. In the most favorable cases, atomic-scale resolved maps of individual particles are obtained. It is also demonstrated that, for the same type of core-shell architecture, the interface pattern can be engineered with thicknesses of just 1 nm up to several tens of nanometers. Total alloying between the core and shell domains is also possible when using ultra-small particles as seeds. Finally, with different types of interface patterns (same architecture and chemical composition of the core and shell domains) it is possible to modify the output color (yellow, red, and green-yellow) or change (improvement or degradation) the absolute upconversion quantum yield. The results presented in this article introduce an important paradigm shift and pave the way toward the emergence of a new generation of core-shell Ln-based HNCs with better control over their atomic-scale organization.