bluuebunny/crossref_metadata_2025 huggingface dataset:
Dual Sub‐Cells Modification Enables High‐Efficiency n–i–p Type Monolithic Perovskite/Organic Tandem Solar Cells
Authors: Yao Qin , Xie Yue‐Min , Zhou Yingzhi , Xue Qifan , Xu Xin , Gao Yujia , Niu Tianqi , Chu Linghao , Zhou Zhisheng , Lin Francis R. , Jen Alex K.‐Y. , Shi Tingting , Yip Hin‐Lap , Cao Yong
Published: January 2023

Monolithic perovskite/organic tandem solar cells (POTSCs) have attracted increasing attention owing to ability to overcome the Shockley–Queisser limit. However, compromised sub‐cells performance limits the tandem device performance, and the power conversion efficiency (PCE) of POTSCs is still lower than their single‐junction counterparts. Therefore, optimized sub‐cells with minimal energy loss are desired for producing high‐efficiency POTSCs. In this study, an ionic liquid, methylammonium acetate (MAAc), is used to modify wide‐bandgap perovskite sub‐cells (WPSCs), and bathocuproine (BCP) is used to modify small‐bandgap organic solar cells. The Ac− group of MAAc can effectively heal the Pb defects in the all‐inorganic perovskite film, which enables a high PCE of 17.16% and an open‐circuit voltage (Voc) of 1.31 V for CsPbI2.2Br0.8‐based WPSCs. Meanwhile, the BCP film, inserted at the ZnO/organic bulk‐heterojunction (BHJ) interface, acts as a space layer to prevent direct contact between ZnO and the BHJ while passivating the surface defects of ZnO, thereby mitigating ZnO defect‐induced efficiency loss. As a result, PM6:CH1007‐based SOSCs exhibit a PCE of 15.46%. Integrating these modified sub‐cells enable the fabrication of monolithic n–i–p structured POTSCs with a maximum PCE of 22.43% (21.42% certified), which is one of the highest efficiencies in such type of POTSCs.
Triplet Excitons and Associated Efficiency‐Limiting Pathways in Organic Solar Cell Blends Based on (Non‐) Halogenated PBDB‐T and Y‐Series
Authors: Grüne Jeannine , Londi Giacomo , Gillett Alexander J. , Stähly Basil , Lulei Sebastian , Kotova Maria , Olivier Yoann , Dyakonov Vladimir , Sperlich Andreas
Published: January 2023

The great progress in organic photovoltaics (OPV) over the past few years has been largely achieved by the development of non‐fullerene acceptors (NFAs), with power conversion efficiencies now approaching 20%. To further improve device performance, loss mechanisms must be identified and minimized. Triplet states are known to adversely affect device performance, since they can form energetically trapped excitons on low‐lying states that are responsible for non‐radiative losses or even device degradation. Halogenation of OPV materials has long been employed to tailor energy levels and to enhance open circuit voltage. Yet, the influence on recombination to triplet excitons has been largely unexplored. Using the complementary spin‐sensitive methods of photoluminescence detected magnetic resonance and transient electron paramagnetic resonance corroborated by transient absorption and quantum‐chemical calculations, exciton pathways in OPV blends are unravelled employing the polymer donors PBDB‐T, PM6, and PM7 together with NFAs Y6 and Y7. All blends reveal triplet excitons on the NFA populated via non‐geminate hole back transfer and, in blends with halogenated donors, also by spin‐orbit coupling driven intersystem crossing. Identifying these triplet formation pathways in all tested solar cell absorber films highlights the untapped potential for improved charge generation to further increase plateauing OPV efficiencies.
Real‐Time Probing and Unraveling the Morphology Formation of Blade‐Coated Ternary Nonfullerene Organic Photovoltaics with In Situ X‐Ray Scattering
Authors: Peng Zhongxiang , Zhang Yaowen , Sun Xiaokang , Zhao Wenchao , Bian Fenggang , Geng Yanhou , Ye Long , Yang Chunming
Published: January 2023

Characterizing the bulk heterojunction (BHJ) morphology of the active layer is essential for optimizing blade‐coated organic solar cells (OSCs). Here, the morphology evolution of a highly efficient ternary polymer:nonfullerene blend PM6:N3:N2200 under different blade coating conditions is probed in real‐time by in situ synchrotron X‐ray scattering and in situ ultraviolet‐visible (UV‐vis) spectroscopy. Besides, the morphology of blade‐coated blend films at different conditions is detailed by ex situ X‐ray scattering and microscopic imaging. The ternary blend film exhibited optimized morphology, such as superior molecular stacking structure and appropriate phase separation structure, and boosted photovoltaic performance of the binary blend, as adding a second polymer component to the host polymer:nonfullerene system can balance nucleation and crystallization of polymers and small molecules, facilitating molecular rearrangement to perfect crystallization. Both binary and ternary blends obtained optimized morphology and photovoltaic properties at medium coating speed, mainly attributed to the movement of the polymer and small molecules at the long crystallization and aggregation stage. These findings help understand morphology formation under film drying and provide guidance for optimizing the morphology in blade‐coated OSCs.
A Nanogenerator Enabled by a Perfect Combination and Synergetic Utilization of Triboelectrification, Charge Excitation and Electromagnetic Induction to Reach Efficient Energy Conversion
Authors: Li Gui , Wang Jian , Fu Shaoke , Shan Chuncai , Wu Huiyuan , An Shanshan , Du Yan , He Wencong , Wang Zhao , Liu Wenlin , Nie Yongjie , Liu Siyang , Wang Ping , Hu Chenguo
Published: January 2023

Triboelectric–electromagnetic hybridized nanogenerator (TEHG) is confirmed as an effective energy harvesting for Internet of Things. However, it is still a great challenge to gain a high‐output triboelectric‐nanogenerator (TENG) and to perfectly combine TENG with electromagnetic generator (EMG). Herein, a TEHG composed of space confined multi‐layer‐stack TENG (SM‐TENG) and stack compression promoted flux change EMG is proposed. The interaction of magnets on the rotor with the magnets on the stator makes contact–separation of the SM‐TENG and changes the magnetic flux of EMG in rotation process, reducing wear and deformation of TENG. A voltage multiplier circuit (VMC) with a Zener diode is employed to enhance SM‐TENG performance and maintain stable output. The output charge and current of four SM‐TENG units reach 3.2 µC and 385 µA at rotatory speed 60 rpm, and the voltage of four EMG reaches 8.09 V. The perfect combination and synergetic utilization of triboelectrification, charge excitation, and electromagnetic induction in a single device are realized. The integrated TEHG can power 12 bulbs (2 W) and 16 thermo‐hygrometers, and a Bluetooth thermo‐hygrometer to transmit wireless signals to a mobile phone. This work provides a new strategy for high efficient integration and utilization various mechanisms in one energy‐harvesting device.
3D Microprinting of Super‐Repellent Microstructures: Recent Developments, Challenges, and Opportunities
Authors: Dong Zheqin , Levkin Pavel. A.
Published: January 2023

Liquid super‐repellent surfaces, characterized by a low liquid–solid contact fraction, allow various liquids to bead up and freely roll off. Apart from liquid repellency, these surfaces feature several unique properties, including inter alia, self‐cleaning, low‐friction, anti‐icing, and anti‐biofouling, making them valuable for a vast array of applications involving liquids. Essential to achieve such super‐repellency is the bio‐inspired reentrant or doubly reentrant micro‐topography. However, despite their unique interfacial properties, the fabrication of these delicate 3D topographies by conventional microfabrication methods is extremely challenging. Recently, emerging 3D microprinting technologies, particularly two‐photon lithography, have brought new scope to this field. With unparalleled design freedom and flexibility, 3D microprinting greatly facilitates the design, testing, and studying of complex 3D microstructures. Here, applications of 3D microprinting in the design and fabrication of super‐repellent microstructures are summarized, with a focus on their remarkable properties, and new functionalities offered by these intricate 3D topographies. Current challenges and new opportunities of emerging 3D microprinting techniques to further advance liquid super‐repellent materials are also discussed.
High‐Tc Realization of Lead‐Free Halide Hybrid Ferroelectrics via Steric Confinement Modulation
Authors: Chen Qin , Jiang Haidong , Fan Yipeng , Li Zhou , Ye Huang , Yao Yunpeng , Chen Shuang , Ji Chengmin , Zhang Shuhua , Luo Junhua
Published: January 2023

Hybrid organic–inorganic perovskite (HOIP) ferroelectrics with high Curie temperature (Tc), typified by the lead halide hybrid perovskite ferroelectrics, are developing rapidly owing to their maneuverable ferroelectricity at high temperatures. However, acquiring high‐Tc lead‐free HOIP ferroelectrics via rational strategy still needs development. In this study, a brand‐new program by modulating the steric confinement in a cuplike cavity to design high‐Tc bismuth‐halide ferroelectrics [H2mdap]BiX5 (H2mdap = N‐Methyl‐1,3‐Propanediamine, X = Cl (1), Br (2), I(3)) is proposed. Emphatically, the Tc enhanced dramatically from 264 K of 3 to 318 K of 2 and 377 K of 1, induced by the substitution of Br and Cl to I, accompanied with an interesting transition from second‐order phase transition (for 3) to the first‐order one (for 1 and 2). The extent of Tc increase is up to 113 K, which far outweighs that of reported Pb‐halide hybrid ferroelectrics. Structural and computational analyses elucidate that this unprecedented improvement of Tc is due to the higher phase transition energy barriers induced by modulating the steric confinement of cuplike cavity via halogen substitution. These results will provide new inspiration for designing high‐Tc lead‐free HOIP ferroelectrics.
Endogenous Electric Field‐Coupled PD@BP Biomimetic Periosteum Promotes Bone Regeneration through Sensory Nerve via Fanconi Anemia Signaling Pathway
Authors: Su Yanlin , Zeng Lian , Deng Rongli , Ye Bing , Tang Shuo , Xiong Zekang , Sun Tingfang , Ding Qiuyue , Su Weijie , Jing Xirui , Gao Qing , Wang Xiumei , Qiu Zhiye , Chen Kaifang , Quan Daping , Guo Xiaodong
Published: January 2023

To treat bone defects, repairing the nerve‐rich periosteum is critical for repairing the local electric field. In this study, an endogenous electric field is coupled with 2D black phosphorus electroactive periosteum to explore its role in promoting bone regeneration through nerves. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) are used to characterize the electrically active biomimetic periosteum. Here, the in vitro effects exerted by the electrically active periosteum on the transformation of Schwann cells into the repair phenotype, axon initial segment (AIS) and dense core vesicle (DCV) of sensory neurons, and bone marrow mesenchymal stem cells are assessed using SEM, immunofluorescence, RNA‐sequencing, and calcium ion probes. The electrically active periosteum stimulates Schwann cells into a neuroprotective phenotype via the Fanconi anemia pathway, enhances the AIS effect of sensory neurons, regulates DCV transport, and releases neurotransmitters, promoting the osteogenic transformation of bone marrow mesenchymal stem cells. Microcomputed tomography and other in vivo techniques are used to study the effects of the electrically active periosteum on bone regeneration. The results show that the electrically active periosteum promotes nerve‐induced osteogenic repair, providing a potential clinical strategy for bone regeneration.
Zero‐Valence Selenium‐Enriched Prussian Blue Nanozymes Reconstruct Intestinal Barrier against Inflammatory Bowel Disease via Inhibiting Ferroptosis and T Cells Differentiation
Authors: Zhu Dongdong , Wu Haitao , Jiang Kai , Xu Yifeng , Miao Zhaohua , Wang Hua , Ma Yan
Published: January 2023

The structural disruption of mechanical barrier and dysfunction of immune barrier in intestinal, are important factors, that aggravate inflammatory bowel disease (IBD). To tackle this challenge, a multifunctional nanozyme capable of scavenging reactive oxygen species (ROS) and inhibiting ferroptosis or T cells differentiation for IBD therapy is here reported. In this work, zero‐valence selenium‐enriched Prussian blue nanozymes (Se‐HMPB nanozymes) are prepared via the hard template method. PB nanozymes with multi‐enzyme activities can effectively scavenge various ROS in inflammatory tissues. Meanwhile, the presence of selenium element endows the glutathione peroxidase activity of Se‐HMPB nanozymes, which can inhibit ferroptosis and reverse the lipid peroxidation of intestinal epithelial cells to protect the intestinal mechanical barrier in ulcerative colitis (UC) model. In addition, selenium supplementation can realize efficient inhibition on the differentiation of T cells in Crohn's disease (CD) model, regulating the intestinal immune barrier. Thus, the Se‐HMPB nanozymes reconstructed intestinal barrier via inhibiting ferroptosis and T cells differentiation in UC and CD models, depicting great potential to alleviate IBD.
Water Spider‐Inspired Nanofiber Coating with Sustainable Scale Repellency via Air‐Replenishing Strategy
Authors: Wang Yixuan , Zhao Ran , He Xiao , Zhang Zhe , Meng Jingxin , Wang Shutao
Published: January 2023

To survive underwater even in severely hypoxic water for a long period, the water spider has to periodically collect and replenish air into the diving bell. Inspired by this natural air‐replenishing strategy, a water spider‐inspired nanofiber (WSN) coating with underwater superaerophilicity displaying excellent and sustainable scalephobic capability is prepared. Air film on the WSN coating can be well‐kept and further employed as the barrier layer for scale repellence. Significantly, scalephobic capability of the WSN coating mainly originates from two aspects: inhibiting interfacial nucleation and reducing interfacial adhesion of scale. Compared with previous studies, this WSN coating achieves excellent and sustainable scale repellence (≈ 98% reduction in scale deposition) even after a one‐month dynamic scaling test. Thus, this air‐replenishing strategy may raise a new avenue for advanced long‐term scalephobic materials.
Confined Water Cluster Formation in Water Harvesting by Metal–Organic Frameworks: CAU‐10‐H versus CAU‐10‐CH3
Authors: van der Veen Monique A. , Canossa Stefano , Wahiduzzaman Mohammad , Nenert Gwilherm , Frohlich Dominik , Rega Davide , Reinsch Helge , Shupletsov Leonid , Markey Karen , De Vos Dirk E. , Bonn Mischa , Stock Norbert , Maurin Guillaume , Backus Ellen H. G.
Published: January 2023

Several metal–organic frameworks (MOFs) excel in harvesting water from the air or as heat pumps as they show a steep increase in water uptake at 10–30 % relative humidity (RH%). A precise understanding of which structural characteristics govern such behavior is lacking. Herein, CAU‐10‐H and CAU‐10‐CH3 are studied with H, CH3 corresponding to the functions grafted to the organic linker. CAU‐10‐H shows a steep water uptake ≈18 RH% of interest for water harvesting, yet the subtle replacement of H by CH3 in the organic linker drastically changes the water adsorption behavior to less steep water uptake at much higher humidity values. The materials’ structural deformation and water ordering during adsorption with in situ sum‐frequency generation, in situ X‐ray diffraction, and molecular simulations are unraveled. In CAU‐10‐H, an energetically favorable water cluster is formed in the hydrophobic pore, tethered via H‐bonds to the framework μOH groups, while for CAU‐10‐CH3, such a favorable cluster cannot form. By relating the findings to the features of water adsorption isotherms of a series of MOFs, it is concluded that favorable water adsorption occurs when sites of intermediate hydrophilicity are present in a hydrophobic structure, and the formation of energetically favorable water clusters is possible.
Pyramidal Hyperbolic Metasurfaces Enhance Spontaneous Emission of Nitrogen‐Vacancy Centers in Nanodiamond
Authors: Zheng Peng , Liang Le , Arora Saransh , Ray Krishanu , Semancik Steve , Barman Ishan
Published: January 2023

Nitrogen‐vacancy (NV) centers in nanodiamond hold great promise for creating superior biological labels and quantum sensing methods. Yet, inefficient photon generation and extraction from excited NV centers restrict the achievable sensitivity and temporal resolution. Herein, an entirely complementary route featuring pyramidal hyperbolic metasurface is reported to modify the spontaneous emission of NV centers. Fabricated using nanosphere lithography, the metasurface consists of alternatively stacked silica–silver thin films configured in a pyramidal fashion, and supports both spectrally broadband Purcell enhancement and spatially extended intense local fields owing to the hyperbolic dispersion and plasmonic coupling. The enhanced photophysical properties are manifested as a simultaneous amplification to the spontaneous decay rate and emission intensity of NV centers. It is envisioned that the reported pyramidal metasurface can serve as a versatile platform for creating chip‐based ultrafast single‐photon sources and spin‐enhanced quantum biosensing strategies, as well as aid in further fundamental understanding of photoexcited species in condensed phases.
Luminescence Temperature Quenching in Mn2+ Phosphors
Authors: van Bunningen Arnoldus J. , Sontakke Atul D. , van der Vliet Ruben , Spit Vincent G. , Meijerink Andries
Published: January 2023

Narrower band red and green emission in phosphor‐converted white light‐emitting diodes (wLEDs) can improve the efficacy and color gamut in lighting and display applications. A promising luminescent ion is Mn2+ that can have both narrowband green (tetrahedral coordination) and red (octahedral coordination) emission. Unlike in earlier lighting applications of Mn2+ phosphors, temperature quenching is important in wLEDs. Insight into the thermal quenching behavior of Mn2+ luminescence is lacking. Here systematic research is reported for a variety of Mn2+‐doped phosphors; a huge variation in the luminescence quenching temperature T50, ranging from 50 K for Mn2+ in ZnTe to 1200 K in MgAl2O4, is revealed. The value T50 shows a positive correlation with the bandgap of the host, but no correlation with the full width half maximum (FWHM) of the emission band, indicating that thermally activated photoionization, not thermal crossover, is the operative quenching mechanism. This is confirmed by thermally stimulated luminescence (TSL) measurements that show a rise in TSL signal following photoexcitation at temperatures around T50 providing evidence that quenching is correlated with generation of free charge carriers. Based on these findings, as a design rule is obtained that for temperature‐stable Mn2+ luminescence in (high power) LEDs a wide‐bandgap host material is required.
Synthesis of 2‐Methylindoles through Ruthenium(II)‐Catalyzed Reaction of Aniline Derivatives with Allylamines
Authors: He Xue‐Yi , Wang Zhong‐Xia
Published: January 2023

The ruthenium(II)‐catalyzed reaction of aniline derivatives with allylamines was carried out, affording 2‐methylindoles via C−H/C−N bond activation. 4,5‐Dimethyl pyrimidin‐2‐yl group attached on the nitrogen atom of anilines is the most effective directing group and N‐allyl‐4‐fluoro‐N‐methylaniline is the optimal allylamine. The cyclization products were obtained in 16% to 96% yields. The method does not require external oxidant. A possible mechanism is proposed.

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MnBr2‐Catalyzed Aerobic Oxyazidation of Fluoroolefins: Access to Fluoroalkylated β‐Hydroxy Aliphatic Azides
Authors: Cai Yingying , Jiang Huanfeng , Zhu Chuanle
Published: January 2023

MnBr2‐catalyzed oxyazidation of fluoroolefins with molecular oxygen and TMSN3 is reported. This method gives rise to various useful fluoroalkylated β‐hydroxy aliphatic azides in 36%–97% yields. Importantly, this protocol features mild conditions, operationally simple, and gram‐scalable, it tolerates various functional groups and has been applied in the synthesis of diverse attractive bioactive compounds and analogous. Mechanism studies enable the detection of the intermediate and indicate that a radical reaction process is involved. The β‐fluoride elimination of α‐fluoroalkylated radicals via radical‐polar crossover pathway was completely inhibited in this reaction.

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Synthesis of Alkylsulfonyl‐Substituted Indolo[2,1‐a]Isoquinolines via Photoredox‐Catalyzed Radical‐Cascade Addition/Sulfonylation/Cyclization with DABCO ⋅ (SO2)2 and Thianthrenium Salts
Authors: Yuan Xin , Liu Jie , Qin Long‐Zhou , Duan Xiu , Wang Jian , Wu Meng‐Yu , Qiu Jiang‐Kai , Guo Kai
Published: January 2023

A direct, visible‐light‐mediated, radical‐cascade addition/sulfonylation/cyclization reaction with DABCO ⋅ (SO2)2 and thianthrenium salts is reported herein. This protocol provides operationally‐convenient access to various sulfonated functionalized indole [2,1‐a] isoquinolines under mild conditions. This transformation features high functional‐group tolerance, operational ease, and broad substrate scope. Preliminary studies reveal that the method undergoes a radical pathway.

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Characterizing Ion Transport in Electrolytes via Concentration and Velocity Profiles
Authors: Mistry Aashutosh , Srinivasan Venkat , Steinrück Hans‐Georg
Published: January 2023

Current flowing through an electrolyte is accompanied by continuum motion of ions and solvent, species concentration profiles, and the electric field. While, historically, the understanding of electrolyte transport has predominantly relied on interpreting macroscopic voltage (or current) measurements, recent advances in imaging and spectroscopic techniques allow velocity and concentration profiles to be probed directly. Such detailed information creates exciting opportunities—ranging from verifying theories describing transport in previously studied Li‐ion electrolytes, to new approaches for measuring properties as well as accurately and precisely quantifying transport in more complex electrolytes. Such emerging directions are herein discussed.
On the role of the macroscopic deformation in liquid film drainage between bubbles
Authors: Song Runci , Zhang Ling , Yi Zhengming , Zhou Yefeng , Yuan Haizhuan , Han Luchang
Published: January 2023

The collision of bubbles in multiphase reactors is critical to bubble size distribution. However, the theoretical models that can reasonably predict collision outcomes and the experimental data that can be used to directly verify the models are still very lacking. We studied the collision of two bubbles in clean water through experiments and theoretical modeling, revealing the mechanism that the collision result shifts from coalescence to rebound with increasing collision velocity. The macroscopic deformation (MacrD) of bubbles is associated with the film drainage via a segmented linear equation as a function of the film radius and initial Weber number. Thus, the current model can reflect the effect of MacrD in a self‐consistent way. The coalescence times and critical coalescence velocities predicted by the model were in good agreement with the experiments. This work provides novel insights into bubble coalescence modeling and serves to improve the accuracy of reactor simulations.
Effects of tree sex, maturity, local abiotic, and biotic neighborhoods on the growth of a subtropical dioecious tree species Diospyros morrisiana
Authors: He Qing , Queenborough Simon A. , Zhang Yonghua , Wang Weitao , Li Buhang , Zhao Kangning , Luo Wenqi , Tang Hui , Lin Wei , Chu Chengjin
Published: January 2023

Premise

Understanding the drivers of the growth in long‐lived woody trees is the key to predicting their responses to and maintaining their populations under global change. However, the role of tree sex and differential investment to reproduction are often not considered in models of individual tree growth, despite many gymnosperm and angiosperm species having separate male and female sexes. Thus, better models of tree growth should include tree sex and life stage along with the abiotic and biotic neighborhoods.

Methods

We used a sex‐specific molecular marker to determine the sex of 2188 individual trees >1 cm DBH of the dioecious tree species Diospyros morrisiana in a 50‐ha subtropical forest plot in China. We used long‐term census data from about 300,000 trees, together with 625 soil samples and 2352 hemispherical photographs to characterize the spatially explicit biotic and abiotic neighborhoods.

Results

We found a male‐biased effective sex ratio and a female‐biased overall population sex ratio of D. morrisiana. No sex spatial segregation was detected for the overall population, mature, or immature trees. Immature trees grew faster than mature trees and females grew slower than males. Further, conspecific neighbors significantly decreased tree growth, while the abiotic neighborhood showed no significant effect.

Conclusions

Our findings suggest that variation in resource allocation patterns within and across individual trees of different sexes and life‐history stages should be more widely accounted for in models of tree growth. In addition, our study highlights the importance of sex‐specific molecular markers for studying populations of long‐lived dioecious tree species.
Insights into the perinatal phenotype of Kabuki syndrome in infants identified by genome‐wide sequencing
Authors: Wigby Kristen , Hammer Monia , Tokita Mari , Patel Priyanka , Jones Marilyn C. , Larson Austin , Bartolomei Frances Velez , Dykzeul Natalie , Slavotinek Anne , Yip Tiffany , Bandres‐Ciga Sara , Simpson Brittany N. , Suhrie Kristen , Shankar Suma , Veith Regan , Bragg Jennifer , Powell Cynthia , Kingsmore Stephen F. , Dimmock David , Maron Jill , Davis Jonathan , Del Campo Miguel
Published: January 2023

Increasing use of unbiased genomic sequencing in critically ill infants can expand understanding of rare diseases such as Kabuki syndrome (KS). Infants diagnosed with KS through genome‐wide sequencing performed during the initial hospitalization underwent retrospective review of medical records. Human phenotype ontology terms used in genomic analysis were aggregated and analyzed. Clinicians were surveyed regarding changes in management and other care changes. Fifteen infants met inclusion criteria. KS was not suspected prior to genomic sequencing. Variants were classified as Pathogenic (n = 10) or Likely Pathogenic (n = 5) by American College of Medical Genetics and Genomics Guidelines. Fourteen variants were de novo (KMT2D, n = 12, KDM6A, n = 2). One infant inherited a likely pathogenic variant in KMT2D from an affected father. Frequent findings involved cardiovascular (14/15) and renal (7/15) systems, with palatal defects also identified (6/15). Three infants had non‐immune hydrops. No minor anomalies were universally documented; ear anomalies, micrognathia, redundant nuchal skin, and hypoplastic nails were common. Changes in management were reported in 14 infants. Early use of unbiased genome‐wide sequencing enabled a molecular diagnosis prior to clinical recognition including infants with atypical or rarely reported features of KS while also expanding the phenotypic spectrum of this rare disorder.
The “good refugee” ideal: How discourses of deservingness permeate Australia's refugee and asylum seeker narratives
Authors: Clark Sal , Haw Ashleigh , Mackenzie Laurel
Published: January 2023

While “good refugee” stories have the potential to soften attitudes toward forcibly displaced people, there are hidden implications associated with this construct that must be considered. Based on 60 qualitative interviews with asylum seekers and refugees, this paper examines the ways forced migrants adopt and reproduce “good refugee” discourses that unintentionally position their belonging as contingent upon upholding narrowly defined, and arbitrary, ideals about deservingness. By critically analysing this discourse, we highlight the importance of reconsidering the construction of refugees' deservingness along moral and neoliberal lines and instead present a case for approaches that focus on rights‐based, humanitarian grounds for refugee resettlement.
Clinical outcomes of posterior tibial tendon sheath ultrasound‐guided corticosteroid injections
Authors: Spencer Mark , Hall Matthew , Schafer Allison , Geaney Lauren E.
Published: January 2023

Objectives

The purpose of this study was to assess the safety of ultrasound‐guided corticosteroid injections into the posterior tibial tendon sheath for posterior tibialis tendinopathy. Secondary outcomes include duration of pain relief, amount of pain relief, need for repeat injections and progression to surgery.

Methods

We retrospectively reviewed all patients in our electronic medical record who underwent a posterior tibial tendon sheath (PTTS) steroid injection between 2015 and 2020 for the diagnosis of posterior tibial tendon dysfunction and/or posterior tibialis tendon insufficiency, and/or ankle pain. Demographic information was obtained from the patient record in addition to MRI data, clinical response to injection based on follow‐up visits, number of total injections and progression to surgery. Thirty‐eight posterior tibial tendon sheath ultrasound‐guided injections were administered in 33 patients who met inclusion criteria during the 5‐year study period.

Results

Thirty‐three patients were included in the study with a total of 38 injections performed. Eighteen of 38 (47%) injections yielded good or better pain relief. Seven of 33 patients (21%) progressed to surgery. There were no reported complications with the 38 performed injections.

Conclusion

Ultrasound‐guided corticosteroid injection into the posterior tibial tendon sheath is a safe nonoperative treatment modality for progressive collapsing foot deformity. The efficacy of the injection appears highly variable with 47% of injections yielding ‘good’ or better clinical results. When evaluating body mass index (BMI), obese patients (BMI ≥30.0) were found to have a more sustained response to injection (P = 0.029) and more pain relief (P = 0.049) than non‐obese patients.
Reproducibility and feasibility of a handheld ultrasound device compared to a standard ultrasound machine in muscle thickness measurements
Authors: Alfuraih Abdulrahman M. , Alqarni Mohammed A. , Alhuthaili Hamad S. , Mubaraki Meshal Y. , Alotaibi Nader N. , Almusalim Fahad M.
Published: January 2023

Objective

To test the feasibility and reproducibility of a handheld ultrasound device (HUD) compared to a standard ultrasound machine for muscle thickness measurements in healthy participants.

Methods

A prospective cross‐sectional study was designed where two novice operators tested the thickness of the vastus lateralis, rectus femoris, and vastus intermedius muscles on recruited asymptomatic participants with no history of muscle diseases. The anterior–posterior thickness of each muscle was measured three times per operator to evaluate intra‐operator reproducibility and using two machines to evaluate inter‐system reproducibility. Scanning started using the HUD followed by the standard system. Intraclass correlation coefficients (ICC) and simple linear regression were used to test for reproducibility and proportional bias respectively.

Results

A total of 33 male participants volunteered to take part in this study with a mean age of 22.7 years (6.8). Intra‐operator reproducibility was almost perfect for both operators on both machines (ICC > 0.80). The measurements difference percentage between the machines ranged from 1.8% to 6.6% and inter‐system reproducibility ICC ranged from 0.815 to 0.927 showing excellent reproducibility. Inter‐operator reproducibility was poor to moderate on both machines (ICC: 0.522–0.849). Regression analysis showed no proportional bias in the measurements. All measurements were completed successfully using the HUD.

Conclusion

The HUD demonstrated excellent accuracy compared to the standard ultrasound machine for measuring thigh muscle thickness.
Controlling the Fluorescence Performance of AIE Polymers by Controlling the Polymer Microstructure
Authors: Xu Jiaxi , Wang Jiayi , Bakr Osman M. , Hadjichristidis Nikos
Published: January 2023

Aggregation‐induced emission (AIE) polymers with expected emission wavelength/color and fluorescence efficiency are valuable in applications. However, most AIE polymers exhibit irregular emission wavelength/color changes compared to the original AIE monomers. Here, we report the synthesis of AIE polymers with unchanged emission wavelength by ring‐opening (co)polymerizations of 4‐(triphenylethenyl)phenoxymethyloxirane (TPEO) and other epoxides or phthalic anhydride. The chemical structures/physical properties of all (co)polymers were characterized by NMR, SEC, MALDI‐TOF, and DSC. The co‐polyether microstructures were revealed by calculating the reactivity ratios and visualized by Monte Carlo simulation. The photoluminescence quantum yields of all the (co)polymers were determined in the solid state. We systematically correlated the fluorescence performance with molecular weights, crystallinity, monomer compositions, glass transition temperatures, side lengths, and flexibility/rigidity.
Supramolecular Self‐Assembly as a Tool To Preserve the Electronic Purity of Perylene Diimide Chromophores**
Authors: Heckelmann Ina , Lu Zifei , Prentice Joseph C. A. , Auras Florian , Ronson Tanya K. , Friend Richard H. , Nitschke Jonathan R. , Feldmann Sascha
Published: January 2023

Organic semiconductors are promising for efficient, printable optoelectronics. However, strong excited‐state quenching due to uncontrolled aggregation limits their use in devices. We report on the self‐assembly of a supramolecular pseudo‐cube formed from six perylene diimides (PDIs). The rigid, shape‐persistent cage sets the distance and orientation of the PDIs and suppresses intramolecular rotations and vibrations, leading to non‐aggregated, monomer‐like properties in solution and the solid state, in contrast to the fast fluorescence quenching in the free ligand. The stabilized excited state and electronic purity in the cage enables the observation of delayed fluorescence due to a bright excited multimer, acting as excited‐state reservoir in a rare case of benign inter‐chromophore interactions in the cage. We show that self‐assembly provides a powerful tool for retaining and controlling the electronic properties of chromophores, and to bring molecular electronics devices within reach.
Second Sphere Effects Promote Formic Acid Dehydrogenation by a Single‐Atom Gold Catalyst Supported on Amino‐Substituted Graphdiyne
Authors: Liu Hong , Zou Haiyuan , Wang Dan , Wang Chuancheng , Li Fan , Dai Hao , Song Tao , Wang Mei , Ji Yongfei , Duan Lele
Published: January 2023

Regulating the second sphere of homogeneous molecular catalysts is a common and effective method to boost their catalytic activities, while the second sphere effects have rarely been investigated for heterogeneous single‐atom catalysts primarily due to the synthetic challenge for installing functional groups in their second spheres. Benefiting from the well‐defined and readily tailorable structure of graphdiyne (GDY), an Au single‐atom catalyst on amino‐substituted GDY is constructed, where the amino group is located in the second sphere of the Au center. The Au atoms on amino‐decorated GDY displayed superior activity for formic acid dehydrogenation compared with those on unfunctionalized GDY. The experimental studies, particularly the proton inventory studies, and theoretical calculations revealed that the amino groups adjacent to an Au atom could serve as proton relays and thus facilitate the protonation of an intermediate Au−H to generate H2. Our study paves the way to precisely constructing the functional second sphere on single‐atom catalysts.
Enantioselective Nickel‐Catalyzed Hydrosilylation of 1,1‐Disubstituted Allenes
Authors: Liu Tao , Mao Xin‐Rui , Song Shuo , Chen Zi‐Yang , Wu Yichen , Xu Li‐Ping , Wang Peng
Published: January 2023

Here, we report the first example of Ni‐catalyzed asymmetric hydrosilylation of 1,1‐disubstituted allenes with high level of regioselectivities and enantioselectivities. The key to achieve this stereoselective hydrosilylation reaction was the development of the SPSiOL‐derived bisphosphite ligands (SPSiPO). This protocol features broad substrate scope, excellent functional group, and heterocycle tolerance, thus provides a versatile method for the construction of enantioenriched tertiary allylsilanes in a straightforward and atom‐economic manner. DFT calculations were performed to reveal the reaction mechanism and the origins of the enantioselectivity.
A Practical and Robust Zwitterionic Cooperative Lewis Acid/Acetate/Benzimidazolium Catalyst for Direct 1,4‐Additions
Authors: Hans Andreas C. , Becker Patrick M. , Haußmann Johanna , Suhr Simon , Wanner Daniel M. , Lederer Vera , Willig Felix , Frey Wolfgang , Sarkar Biprajit , Kästner Johannes , Peters René
Published: January 2023

A catalyst type is disclosed allowing for exceptional efficiency in direct 1,4‐additions. The catalyst is a zwitterionic entity, in which acetate binds to CuII, which is formally negatively charged and serving as counterion for benzimidazolium. All 3 functionalities are involved in the catalytic activation. For maleimides productivity was increased by a factor >300 compared to literature (TONs up to 6700). High stereoselectivity and productivity was attained for a broad range of other Michael acceptors as well. The polyfunctional catalyst is accessible in only 4 steps from N‐Ph‐benzimidazole with an overall yield of 96 % and robust during catalysis. This allowed to reuse the same catalyst multiple times with nearly constant efficiency. Mechanistic studies, in particular by DFT, give a detailed picture how the catalyst operates. The benzimidazolium unit stabilizes the coordinated enolate nucleophile and prevents that acetate/acetic acid dissociate from the catalyst.
Macrocycle‐Based Crystalline Supramolecular Assemblies Built with Intermolecular Charge‐Transfer Interactions
Authors: Wu Jia‐Rui , Wu Gengxin , Li Dongxia , Yang Ying‐Wei
Published: January 2023

Synthetic macrocycles have served as principal tools for supramolecular chemistry, have greatly extended the scope of organic charge transfer (CT) complexes, and have proved to be of great practical value in the solid state during the past few years. In this Minireview, we summarize the research progress on the macrocycle‐based crystalline supramolecular assemblies primarily driven by intermolecular CT interactions (a.k.a. macrocycle‐based crystalline CT assemblies, MCCAs for short), which are classified by their donor–acceptor (D‐A) constituent elements, including simplex macrocyclic hosts, heterogeneous macrocyclic hosts, and host–guest D‐A pairs. Particular attention will be focused on their diverse functions and applications, as well as the underlying CT mechanisms from the perspective of crystal engineering. Finally, the remaining challenges and prospects are outlined.
Enhanced Energy Transfer in A π‐Conjugated Covalent Organic Framework Facilitates Excited‐State Nickel Catalysis
Authors: Fan Yingjie , Kang Dong Won , Labalme Steven , Li Jinhong , Lin Wenbin
Published: January 2023

Covalent organic frameworks (COFs) have received broad interest owing to their permanent porosity, high stability, and tunable functionalities. COFs with long‐range π‐conjugation and photosensitizing building blocks have been explored for sustainable photocatalysis. Herein, we report the first example of COF‐based energy transfer Ni catalysis. A pyrene‐based COF with sp2 carbon‐conjugation was synthesized and used to coordinate NiII centers through bipyridine moieties. Under light irradiation, enhanced energy transfer in the COF facilitated the excitation of Ni centers to catalyze borylation and trifluoromethylation reactions of aryl halides. The COF showed two orders of magnitude higher efficiency in these reactions than its homogeneous control and could be recovered and reused without significant loss of catalytic activity.
Effect of silane‐modified fluorinated graphene on the anticorrosion property of epoxy coating
Authors: Lin Xiuzhou , Chen Xulei , Zhao Shixiong , Dou Baojie , Peng Qiang , Deng Zhiqiang , Emori Wilfred , Gao Xiulei , Fang Zhiwen
Published: January 2023

Fluorinated graphene (FG) is a derivative of graphene with excellent insulating properties, however, the dispersion performance of FG in organic coatings is still a challenge in anti‐corrosion applications. This study aims to propose a simple strategy to effectively improve the dispersion of FG towards enhancing its interfacial compatibility with epoxy resins. FG was modified with amino‐containing 3‐aminopropyl triethoxysilane (APTES) and epoxy terminated 3‐glycidoxypropyl trimethoxysilane (GPTMS). The chemical compositions and microstructures of FG and the silane‐modified FGs were effectively characterized. Moreover, the corrosion resistance and anticorrosion mechanisms of the epoxy coatings modified by FG and silane‐modified FG were systematically studied, and the results showed that the silane coupling agent effectively improved the dispersion of FG in the epoxy coating and enhanced the interface interaction between FG and the epoxy resin, thereby improving the barrier properties of the epoxy coating and preventing the penetration of the corrosive medium. Electrochemical and tribological analyses showed that the APTES‐modified FG (AFG) coating exhibited better anti‐corrosion properties than the GPTMS‐modified FG (GFG) coating, which is attributed to the improvement of its crosslinking density and barrier properties by the reactions between the amino groups on AFG and the epoxy resin.
In vivo monitoring of brain pharmacokinetics and pharmacodynamics with cerebral open flow microperfusion
Authors: Altendorfer‐Kroath Thomas , Hummer Joanna , Birngruber Thomas
Published: January 2023

In vivo investigation of brain pharmacokinetics and pharmacodynamics (PK/PD) is an integral part of neurological drug development. However, drugs intended to act in the brain may reach it at very low concentrations due to the protective effect of the blood–brain barrier (BBB). Consequently, very sensitive measurement methods are required to investigate PK/PD of drugs in the brain. Also, these methods must be capable of continuously assessing cerebral drug concentrations with verifiable intact BBB, as disrupted BBB may lead to compound efflux from blood into brain and to biased results. To date, only a few techniques are available that can sensitively measure drug concentrations in the brain over time; one of which is cerebral open flow microperfusion (cOFM). cOFM's key features are that it enables measurement of cerebral compound concentrations with intact BBB, induces only minor tissue reactions, and that no scar formation occurs around the probe. The membrane‐free cOFM probes collect diluted cerebral interstitial fluid (ISF) samples that are containing the whole molecule spectrum of the ISF. Further, combining cOFM with an in vivo calibration protocol (e.g. Zero Flow Rate) enables absolute quantification of compounds in cerebral ISF. In general, three critical aspects have to be considered when measuring cerebral drug concentrations and recording PK/PD profiles with cOFM: (a) the BBB integrity during sampling, (b) the status of the brain tissue next to the cOFM probe during sampling, and (c) the strategy to absolutely quantify drugs in cerebral ISF. This work aims to review recent applications of cOFM for PK/PD assessment with a special focus on these critical aspects.
Open Innovation for sustainable transition: The case of Enel “Open Power”
Authors: Lippolis Stella , Ruggieri Angelo , Leopizzi Rossella
Published: January 2023

Only in the last years, Sustainable Open Innovation has become a unique issue from the convergence between the concept of Open Innovation and sustainability as well as a challenge for the future business models of companies. Given that the aim to build a more sustainable world is one of the most relevant targets to reach over the world, the present work has focused on how Open Innovation is a catalyst for sustainability, by proposing a model for the case study in an underdeveloped sector, such as the energy one. Specifically, through the analysis of the ENEL case study, the relationship between Open Innovation (OI) and a strategic approach to CSR has emerged. The strategic approach to CSR, guided by open leadership aimed at involving stakeholders and creating shared value, creates an organizational culture and an environment favorable to the development of Open Innovation strategies; furthermore, the Open Innovation processes support the integration of the social, environmental, and economic objectives of companies. The findings show how Open Innovation can address sustainability practices and objectives. Through the application of the framework called SKiN, which provides a qualitative and replicable tool, the study allows to evaluate the organizational permeability as a critical success factor for both sustainability strategies and innovation.
Stabilizing oxygen by high‐valance element doping for high‐performance Li‐rich layered oxides
Authors: Wang Errui , Xiao Dongdong , Wu Tianhao , Wang Boya , Wang Yinzhong , Wu Lingqiao , Zhang Xu , Yu Haijun
Published: January 2023

Lithium‐rich layered oxides (LLOs) with high energy density and low cost are regarded as promising candidates for the next‐generation cathode materials for lithium‐ion batteries (LIBs). However, there are still some drawbacks of LLOs such as oxygen instability and irreversible structure reconstruction, which seriously limit their electrochemical performance and practical applications. Herein, the high‐valence Ta doping is proposed to adjust the electronic structures of transition metals, which form strong Ta‐O bonds and reduce the covalency of Ni‐O bonds, thereby stabilizing the lattice oxygen and enhancing the structural/thermal stabilities of LLOs during electrochemical cycling. As a result, the optimized Ta‐doped LLO can deliver a capacity retention of 80% and voltage decay of 0.34 mV cycle−1 after 650 cycles at 1C. This study enriches the fundamental understanding of the electronic structure adjustment of LLOs and contributes to the optimization of LLOs for high‐energy LIBs.
Rational design of PANI‐modified three‐dimensional dendritic hierarchical porous Cu–Sn nanocomposites as thick anodes with ultrahigh areal capacity and good cycling stability
Authors: Liu Wenbo , Gou Hongmei , Dong Xin , Zhang Shichao , Shi Sanqiang
Published: January 2023

A simple and effective one‐step strategy gives freestanding 3D dendritic hierarchical porous (DHP) Cu–Sn nanocomposites by chemically dealloying a designed Cu35Sn65 (at.%) alloy with dendritic segregation in a specific corrosive solution. A 3D DHP Cu–Sn modified by polyaniline (PANI) further makes the nanocomposites with improved conductivity and structural stability, which are typical of bimodal pore‐size distribution comprising a dendritic micron‐sized ligament‐channel structure with interconnected nanoporous channel walls. The as‐prepared 12 h dealloyed 3D DHP nanocomposites with ca. 200 μm in thickness can serve as binder‐free thick anodes for lithium‐ion batteries (LIBs) and exhibit enhanced Li storage performance with a ultrahigh first reversible capacity of 13.9 mAh cm−2 and an initial CE of 85.8%, good cycling stability with a capacity retention of 73.5% after 50 cycles, and superior rate capability with a reversible capacity of 11.95 mAh cm−2 after high‐rate cycling. These Sn‐based anodes can effectively alleviate the volume variation, enhance the loading of active materials, strengthen the stability of solid electrolyte interphase films, shorten the Li+ migration distance, and improve the electron conductivity. Additionally, the Sn content and areal capacity of the 3D DHP electrode can be tuned by changing the dealloying time of the initial alloy for 3D tin‐based thick anodes with adjustable capacities toward high‐performance LIBs.