bluuebunny/crossref_metadata_2025 huggingface dataset:
Association of Social Isolation With Hospitalization and Nursing Home Entry Among Community-Dwelling Older Adults
Authors: Pomeroy Mary Louise , Cudjoe Thomas K. M. , Cuellar Alison E. , Ihara Emily S. , Ornstein Katherine A. , Bollens-Lund Evan , Kotwal Ashwin A. , Gimm Gilbert W.
Published: July 2023

Importance

Social isolation is associated with adverse health outcomes, yet its implications for hospitalization and nursing home entry are not well understood.

Objective

To evaluate whether higher levels of social isolation are associated with overnight hospitalization, skilled nursing facility stays, and nursing home placement among a nationally representative sample of community-dwelling older adults after adjusting for key health and social characteristics, including loneliness and depressive symptoms.

Design, Setting, and Participants

This observational cohort study included 7 waves of longitudinal panel data from the Health and Retirement Study, with community-dwelling adults aged 65 years or older interviewed between March 1, 2006, and June 30, 2018 (11 517 respondents; 21 294 person-years). Data were analyzed from May 25, 2022, to May 4, 2023.

Main Outcomes and Measures

Social isolation was measured with a multidomain 6-item scale (range, 0-6, in which a higher score indicates greater isolation). Multivariate logistic regressions were performed on survey-weighted data to produce national estimates for the odds of self-reported hospitalization, skilled nursing facility stays, and nursing home placement over time.

Results

A total of 57% of this study’s 11 517 participants were female, 43% were male, 8.4% were Black, 6.7% were Hispanic or Latino, 88.1% were White, 3.5% were other (“other” includes American Indian or Alaska Native, Asian or Pacific Islander, and other race, which has no further breakdown available because this variable was obtained directly from the Health and Retirement Study), and 58.2% were aged 65 to 74 years. Approximately 15% of community-dwelling older adults in the US experienced social isolation. Higher social isolation scores were significantly associated with increased odds of nursing home placement (odds ratio, 2.01; 95% CI, 1.21-3.32) and skilled nursing facility stays (odds ratio, 1.16; 95% CI, 1.06-1.28) during 2 years. With each point increase in an individual’s social isolation score, the estimated probability of nursing home placement or a skilled nursing facility stay increased by 0.5 and 0.4 percentage points, respectively, during 2 years. Higher levels of social isolation were not associated with 2-year hospitalization rates.

Conclusions and Relevance

This cohort study found that social isolation was a significant risk factor for nursing home use among older adults. Efforts to deter or delay nursing home entry should seek to enhance social contact at home or in community settings. The design and assessment of interventions that optimize the social connections of older adults have the potential to improve their health trajectories and outcomes.
Consumption of Soft Drinks and Overweight and Obesity Among Adolescents in 107 Countries and Regions
Authors: Hu Huan , Song Jing , MacGregor Graham A. , He Feng J.
Published: July 2023

Importance

Soft drink consumption is associated with weight gain in children and adolescents, but little is known about the association between soft drink consumption and prevalence of the overweight and obesity in adolescents.

Objective

To investigate the association of soft drink consumption with overweight and obesity in adolescents enrolled in school (hereafter, school-going adolescents) using country-level and individual-level data.

Design, Setting, and Participants

This cross-sectional study used data from 3 cross-sectional studies including 107 countries and regions that participated in the Global School-Based Student Health Survey (2009-2017), the European Health Behavior in School-Aged Children study (2017-2018), and the US Youth Risk Behavior Survey (2019).

Exposure

Daily soft drink consumption (consuming soft drinks 1 or more times per day or not).

Main Outcome and Measure

Overweight and obesity defined by the World Health Organization Growth Reference Data.

Results

Among the 107 countries and regions, 65 were low- and middle-income, and 42 were high-income countries and regions, with a total of 405 528 school-going adolescents (mean [SD] age, 14.2 [1.7] years; 196 147 [48.4%] males). The prevalence of overweight and obesity among adolescent students varied from 3.3% (95% CI, 2.6 to 4.1) in Cambodia to 64.0% (95% CI, 57.0 to 71.6) in Niue, and the prevalence of adolescent students consuming soft drinks 1 or more times per day varied from 3.3% (95% CI, 2.9 to 3.7) in Iceland to 79.6% (95% CI, 74.0 to 85.3) in Niue. There was a positive correlation between the prevalence of daily soft drink consumption and the prevalence of overweight and obesity (R, 0.44; P < .001). The pooled analysis using individual-level data also showed a statistically significant association between daily soft drink consumption and overweight and obesity (daily soft drink consumption vs nondaily soft drink consumption), with an odds ratio of 1.14 (95% CI, 1.08 to 1.21) among school-going adolescents.

Conclusions and Relevance

In this study of 107 countries and regions, the prevalence of daily consumption of soft drinks was associated with the prevalence of overweight and obesity among adolescent students. Our results, in conjunction with other evidence, suggest that reducing soft drink consumption should be a priority in combating adolescent overweight and obesity.
Comparative Effectiveness of Anticoagulants in Patients With Cancer-Associated Thrombosis
Authors: Riaz Irbaz Bin , Fuentes Harry , Deng Yihong , Naqvi Syed Arsalan Ahmed , Yao Xiaoxi , Sangaralingham Lindsey R. , Houghton Damon E. , Padrnos Leslie J. , Shamoun Fadi E. , Wysokinski Waldemar E. , McBane Robert D.
Published: July 2023

Importance

Patterns of clinical utilization and comparative effectiveness of anticoagulants for cancer-associated thrombosis (CAT) remain largely unexplored.

Objectives

To assess patterns of and factors associated with anticoagulant use and to evaluate the comparative effectiveness of contemporary anticoagulants in patients with active cancer in a clinical setting.

Design, Setting, and Participants

This retrospective cohort study obtained deidentified OptumLabs electronic health record claims data from January 1, 2012, to September 30, 2019. Adult patients (≥18 years of age) with a primary cancer diagnosis (except skin cancer) during at least 1 inpatient or 2 outpatient visits within 6 months before the venous thromboembolism (VTE) date were included. Data were analyzed from April 2020 to September 2021.

Exposures

The patients were grouped according to the anticoagulant prescribed: (1) direct oral anticoagulants (DOACs), (2) low-molecular-weight heparin (LMWH), and (3) warfarin.

Main Outcomes and Measures

Odds ratios (ORs) were used to present the association between factors of interest and utilization of anticoagulants. Main efficacy outcomes included risk of VTE recurrence and all-cause mortality. Main safety outcomes included the risk of hospitalization due to major bleeding. Relative treatment effect estimates were expressed as hazard ratios (HRs) with 95% CIs.

Results

This study included 5100 patients (mean [SD] age, 66.3 [12.3] years; 2670 [52.4%] women; 799 [15.7%] Black, 389 [7.6%] Hispanic, and 3559 [69.8%] White individuals). Overall, 2512 (49.3%), 1488 (29.2%), and 1460 (28.6%) filled prescriptions for DOACs, LMWH, and warfarin, respectively. The median (IQR) treatment duration was 3.2 (1.0-6.5) months for DOACs, 3.1 (1.0-6.8) months for warfarin, and 1.8 (0.9-3.8) months for LWMH. Patients with lung (OR, 2.07; 95% CI, 1.12-3.65), urological (OR, 1.94; 95% CI,1.08-3.49), gynecological (OR, 4.25; 95% CI, 2.31-7.82), and colorectal (OR, 2.26; 95% CI, 1.20-4.32) cancer were associated with increased prescriptions for LMWH compared with DOACs. LMWH (HR, 1.47; 95% CI, 1.14-1.90) and warfarin (HR, 1.46; 95% CI, 1.13-1.87) were associated with an increased risk of VTE recurrences compared with DOACs. LMWH was associated with an increased risk of major bleeding (HR, 2.27; 95% CI, 1.62-3.20) and higher all-cause mortality (HR, 1.61; 95% CI, 1.15-2.25) compared with DOACs.

Conclusions and Relevance

In this comparative effectiveness study of claims-based data, patients with CAT received anticoagulation for a remarkably short duration in clinical settings. DOACs was associated with a lower risk of VTE recurrence, major bleeding, and mortality. Warfarin may still be considered for patients with contraindications to DOACs and those with poor persistence on LMWH.
Characteristics of Emergency Department Visits Among Older Adults With Dementia
Authors: Gerlach Lauren B. , Martindale Jonathan , Bynum Julie P. W. , Davis Matthew A.
Published: July 2023

This cross-sectional study examines emergency department use among older adults with Alzheimer disease and related dementias.
Considering Patient Sex in Prescribing CGRP Receptor Antagonists for Short-Term Treatment of Migraine
Authors: Porreca Frank , Dodick David W.
Published: July 2023

This Viewpoint describes the relevance of sex-specific differences in the treatment of migraine, including in evidence from trials of CGRP therapeutics, and the clinical implications for decision-making in practice and trial design.
Documenting Psychosocial Problems in Children’s Electronic Health Records
Authors: Dubowitz Howard , Kressly Susan J.
Published: July 2023

This Viewpoint describes why knowledge of a child’s environment is critical for optimal care and why it is important that this information be documented in a child’s electronic health record.
Power of Representation in Educational Materials: Teaching Cutaneous Lupus Across Skin Tones in an Interactive Module
Authors: Tinianow Alex , Sous Dana , Abreu Damien , Scharff Trisha B. , Thomashow Michael , Bayliss Susan , Goglin Sarah , Monroe Joe R. , Mwanthi Muithi , Jones Heather A. , Zickuhr Lisa
Published: July 2023

Objective

Clinicians report low confidence assessing cutaneous lupus erythematosus (CLE) lesions, especially for patients who identify as Black, Indigenous, and People of Color (BIPOC) who are historically excluded from educational materials. To address this, we created an online, interactive module teaching an approach to assessing CLE across skin tones and measured its impact on medical knowledge and confidence.

Methods

Our team created a module with case‐based methods to introduce an approach to CLE, common mimicking rashes, and tips for photographing cutaneous lesions in BIPOC. Graduate medical trainees from five academic institutions completed the module. Using surveys and pre–post testing, we assessed changes in medical knowledge and clinical confidence along with learner satisfaction, comparing responses using Wilcoxon‐signed rank tests and chi square analysis. We assessed the module's representation of light, medium, and dark skin tones with chi square analysis.

Results

The module represented light, medium, and dark skin tones (χ2 = 4.788, P = 0.091) among 102 images (77.5%, n = 79) were novel images from authors’ personal libraries. Ninety‐four participants completed the postmodule test and evaluation survey. Analyses revealed significant improvement in medical knowledge identifying serologic studies associated with subacute CLE (χ2 = 14.035, P < 0.001) and describing how to photograph rashes (χ2 = 38.211, P < 0.001). Participants reported improved confidence across all learning objectives after module completion (P < 0.001).

Conclusion

This module is the first to introduce an approach to assessing CLE across skin tones, effectively increasing medical knowledge and confidence among graduate medical trainees.
Design of Graphdiyne and Holey Graphyne‐Based Single Atom Catalysts for CO2 Reduction With Interpretable Machine Learning
Authors: Ren Manman , Guo Xiangyu , Zhang Shengli , Huang Shiping
Published: July 2023

Using electrochemical CO2 reduction reaction (CO2RR) to synthesize value‐added hydrocarbons provides a useful solution for environmental issues and energy crisis. However, this process is impeded by the low activity and selectivity of electrocatalysts toward targeted products. Employing density functional theory computations, the graphdiyne and holey graphyne supported single‐atom catalysts (SACs, M/GDY and M/HGY) are demonstrated to be the promising candidates for the CO2RR. By taking full elemental diversity of metal sites across the periodic table, 25 catalysts are found to effectively activate CO2 and inhibit competitive hydrogen evolution, and 8 of them show higher activity for CH4 production than Cu(211). Remarkably, changing supports are found to greatly affect limiting potentials and reaction pathways, even leading to an “inert‐active” transition for some metal centers. The resulting SACs, including Mn/GDY, Co/HGY, Ru/GDY, and Os/GDY, can achieve high activity with low limiting potentials of ≈ −0.22 to −0.58 V. Machine learning enables to identify the critical role of the polarized charge and magnetic moment of metal atoms in affecting the activity. The built machine learning model also shows an interpretable capability to predict the activity of the other types of SACs, offering a great promise to quick screening of high‐performance SACs.
Fluorination‐Induced Multi‐Enhancement of a Nano‐Photosensitizer for Deep Photodynamic Therapy against Hypoxia Tumor
Authors: Wei Kai , Wu Yanxin , Zheng Xian , Ma Guiping , Ji Chendong , Yin Meizhen
Published: July 2023

Organic dyes hold great promise for application in photodynamic therapy (PDT). However, they currently face challenges such as inadequate photodynamic activity, limited tumor penetration, and constraints imposed by tumor hypoxia. Here, a facile and efficient strategy is presented for multi‐enhanced PDT through the fluorination of a squarylium indocyanine dye‐based photosensitizer (FCy). The amphiphilic FCy features perfluorooctane and PEG‐biotin moieties conjugated to a squarylium indocyanine core. In aqueous environments, FCy spontaneously self‐assembles into stable nano‐sized photosensitizers (FCy NPs), demonstrating a high oxygen loading ability attributable to the presence of perfluoroalkyl groups. Consequently, the aggregation of squarylium indocyanine dyes remarkably boosts the photodynamic effect, yielding a 15‐fold improvement in singlet oxygen quantum yield. Owing to the perfluoroalkyl group, FCy NPs exhibit increased endoplasmic reticulum (ER)‐ accumulating abilities, which further induce ER stress upon laser irradiation and enhance the PDT effect. Furthermore, the superior deep tumor penetration ability of FCy NPs is confirmed through both in vitro and in vivo studies. With efficient oxygen supply to the deep tumor regions, FCy NPs demonstrate potent imaging‐guided PDT against hypoxia tumors. The study substantiates the enhanced ER‐accumulating ability of the perfluoroalkyl group and presents a facile fluorination strategy for the multi‐enhancement of photosensitizers.
All‐In‐One Optoelectronic Neuristor Based on Full‐vdW Two‐Terminal Ferroelectric p–n Heterojunction
Authors: Ci Wenjuan , Xue Wuhong , Wang Peng , Yin Wenhui , Wang Xiaoling , Shi Lei , Zhou Peng , Xu Xiaohong
Published: July 2023

Photoelectric synaptic devices with optical sensing capability are of great importance in simulating human vision systems. Especially realizing all‐in‐one vision neuristor on silicon based new materials and principles is being pursued. 2D van der Waals (vdW) materials have the unique advantage of arbitrary stacking on demand. Herein, a full‐vdW two‐terminal 2D ferroelectric α‐In2Se3/SnSe p–n heterojunction is proposed to construct an optoelectronic neuristor to simulate visual synaptic functions. Implementation of these simulations is attributed to the co‐modulation of the electrical polarization reconfigurable built‐in electric field caused by p–n junction and photo‐inducing ferroelectric polarization switching. These functions include ultra‐high paired‐pulse facilitation  index (457%), short synaptic plasticity, long synaptic plasticity, and retina‐like optical adaptations. The high PPF is crucial for high‐precision decoding and processing of visual information. Meanwhile, the classical Pavlovian conditioned reflexes associated with associative learning are also emulated showing the ability of the device to handle complex electrical and optical inputs. This study demonstrates that two‐terminal ferroelectric p–n heterojunctions have great potential in high‐precision multifunctional optoelectronic visual synaptic devices.
Bandgap Engineering of BiIns Nanowire for Wide‐Spectrum, High‐Responsivity, and Polarimetric‐Sensitive Detection
Authors: Zhang Fen , Mo Zhangxun , Cui Baocheng , Liu Shuo , Xia Qinglin , Li Bo , Li Linwei , Zhang Zhengwei , He Jun , Zhong Mianzeng
Published: July 2023

Optical devices based on alloying semiconductors offer a plethora of new possibilities for detection across a broad spectrum. Among these devices, nanowire‐based devices have gained much attention due to their remarkable specific surface area properties in terms of material synthesis, device structure, and performance. In this work, (BixIn1−x)2S3 nanowires are designed by controlling the ratio of Bi and In atoms. The atomic ratio directly affects the electronic band structure of the crystal, thereby further optimizing the performance of optoelectronic devices. According to the experimental results, Bi1.28In0.72S3 nanowire‐based photodetectors obtain the most excellent photoresponse performance. The typical device demonstrates a spectral response from deep ultraviolet (DUV 254 nm) to near‐infrared (NIR 1064 nm) and achieves a maximum dichroic ratio of photoresponse of 1.5 under polarization‐angle‐sensitive detection in the 266–808 nm range. It also exhibits a photoresponse of 10.1 A W−1 and a photodetectivity of 5.7 ×  1010 Jones under 532 nm light irradiation. Additionally, the photodetector displays a fast response speed with a rise/fall time of 5/4.7 ms. Finally, “CSU” and puppy images produced by this device further demonstrate the effectiveness of alloying semiconductors in creating wide‐spectrum, high‐responsivity, fast‐response, and polarimetric‐sensitive photodetectors.
Superoxide Dismutase‐Like Regulated Fe/Ppa@PDA/B for Synergistically Targeting Ferroptosis/Apoptosis to Enhance Anti‐Tumor Efficacy
Authors: Ding Xin , Wang Zidong , Yu Qiying , Michał Nowicki , Roman Szewczyk , Liu Yi , Peng Na
Published: July 2023

The cell apoptosis pathway of sonodynamic therapy (SDT) is usually blocked, resulting in limited therapeutic efficacy, therefore, the development of new methods for sensitizing targeted ferroptosis and promoting apoptosis is of great significance to improve the anti‐tumor efficacy of SDT. Herein, mesoporous Fe3O4 nanoparticles (NPs) are synthesized for loading pyropheophorbide‐a (ppa), surface‐coated by polydopamine (PDA) and further anchored with tumor‐targeting moieties of biotin to obtain Fe/ppa@PDA/B NPs. Fe/ppa@PDA/B displayes pH/ultrasound (US) responsive release properties, and magnetic resonance imaging (MRI) functions. Moreover, Fe3O4 NPs of Fe/ppa@PDA/B as the Fe source for ferroptosis, enhances ferroptosis sensitivity by consuming glutathione (GSH) and producing hydroxyl radical (OH). The quinone groups of PDA layer on Fe/ppa@PDA/B own free electrons, which led to effective superoxide dismutase (SOD) action through superoxide anion (O2−) disproportionation to hydrogen peroxide (H2O2) and oxygen (O2), thus, overcame hypoxia of SDT and promoted ·OH generation by Fe ions under US trigger, synergistically improves ferroptosis and apoptosis to enhance the anti‐tumor efficacy of SDT both in vitro and in vivo. The anti‐tumor strategy of synergistic apoptosis and ferroptosis induce by GSH depletion and self‐sufficient O2 regulated by SOD provides a new idea for enhancing SDT efficacy.
Mechanism for Generating H2O2 at Water‐Solid Interface by Contact‐Electrification
Authors: Berbille Andy , Li Xiao‐Fen , Su Yusen , Li Shunning , Zhao Xin , Zhu Laipan , Wang Zhong Lin
Published: July 2023

The recent intensification of the study of contact‐electrification at water‐solid interfaces and its role in physicochemical processes lead to the realization that electron transfers during water‐solid contact‐electrification can drive chemical reactions. This mechanism, named contact‐electro‐catalysis (CEC), allows chemically inert fluorinated polymers to act like single electrode electrochemical systems. This study shows hydrogen peroxide (H2O2) is generated from air and deionized water, by ultrasound driven CEC, using fluorinated ethylene propylene (FEP) as the catalyst. For a mass ratio of catalyst to solution of 1:10000, at 20 °C, the kinetic rate of H2O2 evolution reaches 58.87 mmol L−1 gcat−1 h−1. Electron paramagnetic resonance (EPR) shows electrons are emitted in the solution by the charged FEP, during ultrasonication. EPR and isotope labelling experiments show H2O2 is formed from hydroxyl radicals (HO•) or two superoxide radicals (O2•−) generated by CEC. Finally, it is traditionally believed such radicals migrate in the solution by Brownian diffusion prior to reactions. However, ab‐initio molecular dynamic calculations reveal the radicals can react by exchanging protons and electrons through the hydrogen bonds network of water, i.e., owing to the Grotthuss mechanism. This mechanism can be relevant to other systems, artificial or natural, generating H2O2 from air and water.
Enhancing the Biocompatibility of Additively Manufactured Ti‐6al‐4 V Eli with Diamond‐Like Carbon Coating
Authors: Yick Samuel , Reneman Jake , Martin Philip J. , Evans Margaret D.M. , Bean Penelope A. , Söhnel Tilo , Tse Nicholas M. K. , Bendavid Avi
Published: July 2023

Orthopedic implants provide patients with an opportunity to regain functionality lost from illness, disease, or injury. Recent advancements in additive manufacturing (AM) techniques have allowed for the increased customization of Ti‐6Al‐4V ELI (extra low interstitials) implants to complement natural variations in the human anatomy. Yet, the low bioactivity of Ti‐6Al‐4 V ELI and possible adverse effects from the leeching of aluminum and vanadium complicate the post‐operation recovery process. In this work, Ti‐6Al‐4 V ELI samples are printed using the electron beam melt technique in two directions and coated with diamond‐like carbon (DLC) to examine whether their biological properties can be improved. By conducting in vitro studies with Saos‐2 osteosarcoma cells, the effects of morphology and surface chemistry are correlated to the bioactivities of the coated and uncoated samples. The outcome of the study suggested that DLC coating is a viable method for controlling the surface bioactivity of a material. It indicates that a carbon coating, along with an appropriate topography, has the potential to promote the proliferation and maturity of bone cells and hence enhance the performance of additively manufactured products in next‐generation biomedical applications.
The Effect of Phosphorylcholine Coatings on Ice Growing and Melting
Authors: Münch Alexander S. , Fritzsche Tina , Göbel Michael , Simon Frank , Uhlmann Petra
Published: July 2023

The creation of novel approaches to reduce the icing of devices is of economic, technical, and ecological interest. Passive deicing approaches based on thin polymer layers show high potential. (Super)hydrophilic films, characterized by high swelling and surface energy, exhibit a self‐lubricating interfacial layer that can influence ice adhesion. For this purpose, a polymer layer consisting of zwitterionic 2‐methacryloyloxyethyl phosphorylcholine (MPC) and glycidyl methacrylate (GMA) is presented and investigated with respect to its icing behavior. The dependence of the swelling behavior of these layers on temperature and a stabilization of the swelling even at low temperatures is shown and can be directly influenced by the grafting conditions, which have a significant impact on the resulting ice thickness and deicing performance. In addition to the formation of a thinner ice layer, the polymer coatings grafted for 16 h are characterized by excellent deicing performance, resulting in consistently very low ice layer thicknesses in repeated icing–deicing cycles compared to the investigated reference SiO2. Due to these properties, the developed film has high application potential as a coating for heat exchangers, as it enables a reduction of the time between defrosting cycles and the distance between the plates, resulting in energy and material savings.
Zeolitic Imidazole Framework Derived Cobalt Phosphide/Carbon Composite and Waste Paper Derived Porous Carbon for High‐Performance Supercapattery
Authors: Sundriyal Shashank , Dubey Prashant , Mansi  , Gupta Bhavana , Holdynski Marcin , Bonarowska Magdalena , Deep Akash , Shrivastav Vishal , Nogala Wojciech
Published: July 2023

Metal–organic frameworks (MOFs) derived nanostructures receive immense research focus due to its high porosity, conductivity, and structural tailrolability features. In this work, porous Zeolitic Imidazole Framework‐67 (ZIF‐67) to synthesize cobalt phosphide/carbon composite (ZCoPC) that serves as a positive electrode is utilized. Furthermore, porous and conductive office paper derived carbon (OPC) are utilized as a negative electrode to make a hybrid system. The metalloid characteristics, high conductivity, and good porosity of ZCoPC material makes it a high‐performance battery like electrode. ZCoPC electrode achieves maximum specific capacity of 192.6 mAh g−1 at 1 A g−1 using 1 m potassium hydroxide (KOH) electrolyte. Furthermore, surface and diffusion charge participation investigation are also undergone for ZCoPC electrode that helps in determining the actual charge dynamics occurring in the electrode. In addition, a supercapattery device is assembled using ZCoPC as battery electrode and OPC as supercapacitor electrode. The as fabricated OPC//ZCoPC hybrid supercapattery device delivers extraordinary energy density of 31.6 Wh kg−1 with a power density of 700 W kg−1 and also a long cycle life of 92.3% even after 10,000 charge–discharge cycles. Hence, these outcomes demonstrate that the synergy of porous MOF derived metal phosphide and OPC electrodes are beneficial for supercapattery devices.
Controlling Photoinduced H2 Release from Freestanding Borophane Sheets Under UV Irradiation by Tuning B–H Bonds
Authors: Hikichi Miwa , Takeshita Junpei , Noguchi Natsumi , Ito Shin‐ichi , Yasuda Yukihiro , Ta Luong Thi , Rojas Kurt Irvin M. , Matsuda Iwao , Tominaka Satoshi , Morikawa Yoshitada , Hamada Ikutaro , Miyauchi Masahiro , Kondo Takahiro
Published: July 2023

Hydrogen boride (HB), a freestanding 2D hydrogenated‐borophene (borophane) polymorph, is synthesized via ion exchange. HB sheets with a B/H atomic ratio of 1.0 are confirmed to contain three‐center–two‐electron B–H–B bonds and two‐center–two‐electron terminal B–H bonds. The optical properties of HB sheets are expected to be tunable by changing the BHB/BH bond ratio, which alters the electronic structure of HB sheets; however, this is not yet achieved. This study demonstrates that controlling the BHB/BH bond ratio in the HB sheets is possible without altering the hydrogen content by adjusting the volume of ion‐exchange resin during synthesis, thus enabling the tuning of the photoinduced H2 release under UV irradiation. Furthermore, the fluorescence intensity correlates with the absorbance ratio of the BHB and BH vibrational modes. Increasing the BHB/BH bond ratio enhances the luminescence intensity, whereas reducing it enhances the photoinduced H2 release rate under UV irradiation. The ability to control the BHB/BH bond ratio of HB sheets provides new avenues for optimizing their properties for various applications, including hydrogen storage and photocatalysis.
Domain Boundary Formation Within an Intercalated Pb Monolayer Featuring Charge‐Neutral Epitaxial Graphene
Authors: Schädlich Philip , Ghosal Chitran , Stettner Monja , Matta Bharti , Wolff Susanne , Schölzel Franziska , Richter Peter , Hutter Mark , Haags Anja , Wenzel Sabine , Mamiyev Zamin , Koch Julian , Soubatch Serguei , Rosenzweig Philipp , Polley Craig , Tautz Frank Stefan , Kumpf Christian , Küster Kathrin , Starke Ulrich , Seyller Thomas , Bocquet Francois C. , Tegenkamp Christoph
Published: July 2023

The synthesis of new graphene‐based quantum materials by intercalation is an auspicious approach. However, an accompanying proximity coupling depends crucially on the structural details of the new heterostructure. It is studied in detail the Pb monolayer structure after intercalation into the graphene buffer layer on the SiC(0001) interface by means of photoelectron spectroscopy, x‐ray standing waves, and scanning tunneling microscopy. A coherent fraction close to unity proves the formation of a flat Pb monolayer on the SiC surface. An interlayer distance of 3.67 Å to the suspended graphene underlines the formation of a truly van der Waals heterostructure. The 2D Pb layer reveals a quasi ten‐fold periodicity due to the formation of a grain boundary network, ensuring the saturation of the Si surface bonds. Moreover, the densely‐packed Pb layer also efficiently minimizes the doping influence by the SiC substrate, both from the surface dangling bonds and the SiC surface polarization, giving rise to charge‐neutral monolayer graphene. The observation of a long‐ranged () reconstruction on the graphene lattice at tunneling conditions close to Fermi energy is most likely a result of a nesting condition to be perfectly fulfilled.
Facet‐Dependent Interfacial and Photoelectrochemical Properties of TiO2 Nanoparticles
Authors: Zabara Mohammed Ahmed , Yarar Kaplan Begüm , Alkan Gürsel Selmiye , Yürüm Alp
Published: July 2023

The photoelectrochemical properties of titanium dioxide (TiO2) nanoparticles are directly related to the presence of certain facets. The synthesis of such particles is challenged using volatile and sensitive precursors utilizing shape capping agents. In this study, an easier two‐step synthesis technique for the preparation of well‐specified morphology TiO2 nanocrystals from TiO2 powder is demonstrated. The facet‐dependent Fermi level and flat band potential of the prepared particles are calculated and their photoelectrochemical properties are investigated by Cu2+ and Pb2+ photo/electrodeposition. From Cu2+ electrodeposition, it is shown that the presence of {100} and {001} facets in cubic morphology facilitates the electrodeposition with progressive nucleation mechanisms, while the presence of {101} facet in octahedral geometry follows instantaneous nucleation mechanisms. The activity of electroreduction is also related to the flat‐band potential which shows the highest activity in Pb2+ electrodeposition for octahedron nanostructure due to the alignment of the reduction potential to the edge of the flat band. Photodeposition of Cu2+ and Pb2+ ions shows identical trends to electrodeposition indicating the facets influence in ion adsorption and structure of the bandgap of morphological TiO2. The findings emphasize the importance of facet‐dependent surface adsorption and bandgap structure designing faceted TiO2 nanoparticles for tailored applications.
Planar Coupled Nanocavities for Efficient Solar Spectrum Engineering
Authors: Jin Shenghao , Yi Fan , Xu Jianming , Wang Boxiang , Zhao Changying
Published: July 2023

Tailoring the solar spectrum is critical for energy devices including solar cells and colorful radiative coolers, requiring additional photonic structures with manipulation capabilities adaptable to different application circumstances. However, existing photonic structures cannot effectively balance the trade‐offs between these energy devices' primary functionality, coloration, and visible transparency. Here, a series of planar coupled nanocavities (PCNs) are designed and fabricated, which can manipulate the solar spectrum of energy devices more versatilely than conventional planar multilayers. By judiciously designing and tailoring the coupling effect in the PCNs, the transmissive colors of the PCNs can occupy 99.9% of the sRGB area provided the benchmark for window applications is achieved (average visible transmittance, AVT > 25%), while 25.4% of the sRGB area can be covered by the reflective colors of sub‐ambient radiative coolers with PCNs. Moreover, when serving as the semitransparent electrodes of colorful organic solar cells (OSCs), the PCNs can provide a significantly larger color gamut than commonly used multilayered electrodes under different performance benchmarks. Remarkably, the PCNs can even locally break the trade‐offs between the power conversion efficiency (PCE) and AVT and electrode conductivity of the OSCs. The proposed PCNs provide a promising route for delicately tailoring the solar spectrum with simple multilayered structures.
A Universal Assembly Strategy of All‐Inorganic Non‐Layered Perovskite Single Crystals for High‐Responsivity Photodetectors
Authors: Hong Enliu , Li Ziqing , Cao Fa , Deng Xiaolei , Zhang Xinyu , Fang Xiaosheng
Published: July 2023

Non‐layered all‐inorganic perovskite single crystals (AIPSCs) have ultralow trap density and exceptional optoelectronic properties, which can be used for developing high‐performance perovskite optoelectronic devices with high efficiency and stability. However, there is a lack of comprehensive insight and universal principles to guide the preparation of high‐quality AIPSCs. Herein, a universal liquid–air interfacial assembly strategy is proposed for synthesizing non‐layered AIPSCs, in virtue of which a series of AIPSCs including whole structural dimensions from 0D to 3D are acquired. Specially, the CsPbI3 AIPSCs exhibit an ultrathin thickness of 40 nm, and the CsPbBr3 AIPSCs show ultra‐narrow PL FWHM of 11 nm. Photodetectors (PDs) based on CsPbBr3 show excellent performance with responsivity up to 120 A W−1 and detectivity exceeding 2 × 1013 Jones. Moreover, vertically integrated heterojunctions of mixed‐dimensions are fabricated, and the 2D/3D heterostructure PDs further display enhanced self‐powered characteristics. This work provides general synthetic guidance toward the synthesis of non‐layered AIPSCs and promotes their application in AIPSCs‐based optoelectronics.
Tunable Photoluminescence of Bismuth‐ and Trivalent‐Lanthanide‐Doped Monolayer Perovskite Oxide Nanosheets
Authors: Awaya Keisuke , Hatakeyama Kazuto , Ida Shintaro
Published: July 2023

Multicolor photoluminescent Bi0.4Ln0.1Na0.5Ta2O72− nanosheets (Ln = Eu, Tb, Dy, Sm, La) are prepared by delaminating an Aurivillius‐phase layered perovskite, Bi2.4Ln0.1Na0.5Ta2O9. Both Bi3+ and Ln3+ (except La3+) successfully function as luminescent centers under UV‐light illumination (λex. = 240–340 nm), which result in a photoluminescence color that can be tuned by changing the lanthanide doping. The emission spectra are influenced by pH because the energy distribution to Ln3+ or to Bi3+ is different in acidic or in basic solutions. Freestanding Bi0.4Ln0.1Na0.5Ta2O72− nanosheet membranes are prepared by vacuum filtration, and the relationship between the photoluminescence and structural properties of the nanosheet membranes is investigated. The results indicate that differences in the electron orbitals involved in the photoluminescence of Bi3+ (6s2–6s6p) and Ln3+ (4fn–4fn) influence the responsiveness to changes in the environment surrounding those luminescent centers.
Upconversion Luminescence Reversible Modulation of Photochromic Ba2YTaO6 Double Perovskite Phosphors Toward Anticounterfeiting Application
Authors: Feng Rongbao , Bai Xue , Zi Yingzhu , Song Youyan , Zhao Heping , Cun Yangke , Liu Yue , Qiu Jianbei , Song Zhiguo , Huang Anjun , Xu Zan , Yang Zhengwen
Published: July 2023

Double perovskite (DP) phosphors attract extensive attention due to their potential applications in the field of optoelectronics. Photochromism‐induced luminescence modulation can extend their application fields. However, designing and preparing DP phosphors with expected photochromic and luminescent properties is still challenging. Herein, the photochromic Ba2YTaO6: Yb3+, Er3+, Co2+ DP with upconversion luminescence properties is developed. The color of the sample turns from white to pink upon 254 nm UV light irradiation, which is fast fading upon 473 nm laser illumination. The mechanism of photochromism is related to the formation of color centers, and the doping of Co2+ ions is crucial for the improvement of photochromism, which is from the increasing of traps depth, the oxygen vacancies, and the carrier concentration of the matrix caused by Co2+ doping. The upconversion luminescence of Er3+ ions can be reversibly modulated by the photochromic effect, exhibiting excellent reproducibility and high stability. The potential application of photochromic Ba2YTaO6: Yb3+, Er3+, Co2+ phosphor is demonstrated in the field of anticounterfeiting and three‐dimensional (3D) artwork. This work not only offers insight into the photochromic mechanism of DP but also presents guidance for developing other photochromic DP phosphors.
Laser Promoting Oxygen Vacancies Generation in Alloy via Mo for HMF Electrochemical Oxidation
Authors: Liu Junbo , Tao Shengyang
Published: July 2023

It is well known that nickel‐based catalysts have high electrocatalytic activity for the 5‐hydroxymethylfurfural oxidation reaction (HMFOR), and NiOOH is the main active component. However, the price of nickel and the catalyst's lifetime still need to be solved. In this work, NiOOH containing oxygen vacancies is formed on the surface of Ni alloy by UV laser (1J85‐laser). X‐ray absorption fine structure (XAFS) analyses indicate an interaction between Mo and Ni, which affects the coordination environment of Ni with oxygen. The chemical valence of Ni is between 0 and 2, indicating the generation of oxygen vacancies. Density functional theory (DFT) suggests that Mo can increase the defect energy and form more oxygen vacancies. In situ Raman electrochemical spectroscopy shows that Mo can promote the formation of NiOOH, thus enhancing the HMFOR activity. The 1J85‐laser electrode shows a longer electrocatalytic lifetime than Ni‐laser. After 15 cycles, the conversion of HMF is 95.92%.
Scalable, Patternable Glass‐Infiltrated Ceramic Radiative Coolers for Energy‐Saving Architectural Applications
Authors: Jeon Seung Kyu , Kim June Tae , Kim Min Seong , Kim In Soo , Park Sung Jin , Jeong Hyeondeok , Lee Gil Ju , Kim Yeong Jae
Published: July 2023

A huge concern on global climate/energy crises has triggered intense development of radiative coolers (RCs), which are promising green‐cooling technologies. The continuous efforts on RCs have fast‐tracked notable energy‐savings by minimizing solar absorption and maximizing thermal emission. Recently, in addition to spectral optimization, ceramic‐based thermally insulative RCs are reported to improve thermoregulation by suppressing heat gain from the surroundings. However, a high temperature co‐firing process of ceramic‐based thick film inevitably results in a large mismatch of structural parameters between designed and fabricated components, thereby breaking spectral optimization. Here, this article proposes a scalable, non‐shrinkable, patternable, and thermally insulative ceramic RC (SNPT‐RC) using a roll‐to‐roll process, which can fill a vital niche in the field of radiative cooling. A stand‐alone SNPT‐RC exhibits excellent thermal insulation (≈0.251 W m−1 K−1) with flame‐resistivity and high solar reflectance/long‐wave emissivity (≈96% and 92%, respectively). Alternate stacks of intermediate porous alumina/borosilicate (Al2O3‐BS) layers not only result in outstanding thermal and spectral characteristics, causing excellent sub‐ambient cooling (i.e., 7.05 °C cooling), but also non‐shrinkable feature. Moreover, a perforated SNPT‐RC demonstrates its versatility as a breathable radiative cooling shade and as a semi‐transparent window, making it a highly promising technology for practical deployment in energy‐saving architecture.
Controllable and Reproducible Growth of Transition Metal Dichalcogenides by Design of Experiments
Authors: Heiserer Stefan , Eder Peter , Ó Coileáin Cormac , Biba Josef , Stimpel‐Lindner Tanja , Bartlam Cian , Rührmair Ulrich , Duesberg Georg S.
Published: July 2023

Controllable and reproducible synthesis of 2D materials is crucial for their future applications. Chemical vapor deposition (CVD) promises scalable and high‐quality growth of 2D materials. However, to optimize CVD growth, multiple parameters have to be carefully selected. Design of experiments (DoE) is a consistent and versatile tool to optimize all parameters simultaneously in a controlled way. This study exploits DoE statistical approaches to show how the CVD growth of transition metal dichalcogenides (TMDs) can be optimized, using tungsten disulfide as an example. A designed set of 29 different processes is used to cover the entire parameter space. The resulting growth output is characterized in terms of material morphology for factors such as single crystal size and continuous film size. The nonlinear model used to fit the output as a function of input parameters provides crucial insights into the nontrivial CVD process ensuring easy and systematic growth optimization. The predicted processes show successful optimization with respect to both the resulting material and the process stability. This powerful technique can be adapted for different setups and other TMD materials.
Topochemical Syntheses of Polyarylopeptides Involving Large Molecular Motions: Frustrated Monomer Packing Leads to the Formation of Polymer Blends
Authors: Raju Cijil , Mridula Kozhukunnon , Srinivasan Nikitha , Kunnikuruvan Sooraj , Sureshan Kana M.
Published: July 2023

We report the topochemical syntheses of three polyarylopeptides, wherein triazolylphenyl group is integrated into the backbone of peptide chains. We synthesized three different monomers having azide and arylacetylene as end‐groups from glycine, L‐alanine and L‐valine. We crystallized these monomers and the crystal structures of two of them were determined by single‐crystal X‐ray diffractometry. Due to the steric constraints, both of these monomers crystallized with two molecules, viz. conformers A and B, in the asymmetric unit. Consistently, in both cases, the A‐conformers are antiparallelly π‐stacked and B‐conformers are parallelly slip‐stacked, exploiting weak interactions. Though the arrangements of molecules in the pristine crystals were unsuitable for topochemical reaction, upon heating, they undergo large motion inside the crystal lattice to reach a transient reactive orientation and thereby the self‐sorted conformer stacks react to give a blend of triazole‐linked polyarylopeptides having two different linkages. Due to the large molecular motion inside crystals, the product phase loses its crystallinity.
Bioorthogonal Reaction‐Mediated Tumor‐Selective Delivery of CRISPR/Cas9 System for Dual‐Targeted Cancer Immunotherapy
Authors: Yang Jingjing , Yang Kaiyong , Du Shiyu , Luo Wen , Wang Chao , Liu Hongmei , Liu Kunguo , Zhang Zhibin , Gao Yanfeng , Han Xin , Song Yujun
Published: July 2023

CRISPR system‐assisted immunotherapy is an attractive option in cancer therapy. However, its efficacy is still less than expected due to the limitations in delivering the CRISPR system to target cancer cells. Here, we report a new CRISPR/Cas9 tumor‐targeting delivery strategy based on bioorthogonal reactions for dual‐targeted cancer immunotherapy. First, selective in vivo metabolic labeling of cancer and activation of the cGAS‐STING pathway was achieved simultaneously through tumor microenvironment (TME)‐biodegradable hollow manganese dioxide (H‐MnO2) nano‐platform. Subsequently, CRISPR/Cas9 system‐loaded liposome was accumulated within the modified tumor tissue through in vivo click chemistry, resulting in the loss of protein tyrosine phosphatase N2 (PTPN2) and further sensitizing tumors to immunotherapy. Overall, our strategy provides a modular platform for precise gene editing in vivo and exhibits potent antitumor response by boosting innate and adaptive antitumor immunity.
Modulating Electronic Structures of Iron Clusters through Orbital Rehybridization by Adjacent Single Copper Sites for Efficient Oxygen Reduction
Authors: Qi Chunhong , Yang Haoyu , Sun Ziqi , Wang Haifeng , Xu Na , Zhu Guihua , Wang Lianjun , Jiang Wan , Yu Xiqian , Li Xiaopeng , Xiao Qi , Qiu Pengpeng , Luo Wei
Published: July 2023

The atom‐cluster interaction has recently been exploited as an effective way to increase the performance of metal‐nitrogen‐carbon catalysts for oxygen reduction reaction (ORR). However, the rational design of such catalysts and understanding their structure‐property correlations remain a great challenge. Herein, we demonstrate that the introduction of adjacent metal (M)−N4 single atoms (SAs) could significantly improve the ORR performance of a well‐screened Fe atomic cluster (AC) catalyst by combining density functional theory (DFT) calculations and experimental analysis. The DFT studies suggest that the Cu−N4 SAs act as a modulator to assist the O2 adsorption and cleavage of O−O bond on the Fe AC active center, as well as optimize the release of OH* intermediates to accelerate the whole ORR kinetic. The depositing of Fe AC with Cu−N4 SAs on nitrogen doped mesoporous carbon nanosheet are then constructed through a universal interfacial monomicelles assembly strategy. Consistent with theoretical predictions, the resultant catalyst exhibits an outstanding ORR performance with a half‐wave potential of 0.92 eV in alkali and 0.80 eV in acid, as well as a high power density of 214.8 mW cm−2 in zinc air battery. This work provides a novel strategy for precisely tuning the atomically dispersed poly‐metallic centers for electrocatalysis.
Visible‐Light‐Induced Control over Reversible Single‐Chain Nanoparticle Folding
Authors: Maag Patrick H. , Feist Florian , Truong Vinh X. , Frisch Hendrik , Roesky Peter W. , Barner‐Kowollik Christopher
Published: July 2023

We introduce a class of single‐chain nanoparticles (SCNPs) that respond to visible light (λmax=415 nm) with complete unfolding from their compact structure into linear chain analogues. The initial folding is achieved by a simple esterification reaction of the polymer backbone constituted of acrylic acid and polyethylene glycol carrying monomer units, introducing bimane moieties, which allow for the photochemical unfolding, reversing the ester‐bond formation. The compaction and the light driven unfolding proceed cleanly and are readily followed by size exclusion chromatography (SEC) and diffusion ordered NMR spectroscopy (DOSY), monitoring the change in the hydrodynamic radius (RH). Importantly, the folding reaction and the light‐induced unfolding are reversible, supported by the high conversion of the photo cleavage. As the unfolding reaction occurs in aqueous systems, the system holds promise for controlling the unfolding of SCNPs in biological environments.
Magnetite dopamine‐decorated copper (Fe3O4@PDA/CuCl2): A robust and reusable catalyst for promoting green synthesis of benzimidazoles and benzothiazoles
Authors: Badbedast Mehran , Khalili Dariush , Abdolmaleki Amir , Norouzi Fereshteh
Published: July 2023

A one‐pot and efficient catalytic protocol has been developed to synthesize pharmaceutically critical 2‐substituted benzimidazoles and benzothiazoles using magnetite dopamine‐supported copper nanoparticles (Fe3O4@PDA/CuCl2) as a heterogeneous catalyst. This selective transformation proceeds via oxidative cross‐coupling of readily available benzylic amines witho‐phenylenediamine/2‐aminothiophenol. This one‐pot green method proceeds smoothly, under mild conditions, avoids the usage of toxic metals, tolerates a variety of functionalities, and is amenable to gram scale. Furthermore, this easy‐to‐prepare magnetic nanocatalyst can be separated by magnetic decantation after the reaction, thereby making it more sustainable.