bluuebunny/crossref_metadata_2025 huggingface dataset:
Pedal Cutaneous Manifestations of Tuberous Sclerosis
Authors: Johnson Rachel E. , Avramaut Kimberly
Published: September 2017

This case report concerns a patient with a painful soft-tissue mass on his fourth toe. He was evaluated for this soft-tissue mass and was diagnosed as having tuberous sclerosis. The podiatric physician should be able to evaluate a patient with a lower-extremity complaint and relate whether this complaint may correlate with a systemic disorder. This case report will make the podiatric physician more aware of tuberous sclerosis and the manifestations of the disorder.
Fundamental bound on the persistence and capacity of short-term memory stored as graded persistent activity
Authors: Koyluoglu Onur Ozan , Pertzov Yoni , Manohar Sanjay , Husain Masud , Fiete Ila R
Published: September 2017

It is widely believed that persistent neural activity underlies short-term memory. Yet, as we show, the degradation of information stored directly in such networks behaves differently from human short-term memory performance. We build a more general framework where memory is viewed as a problem of passing information through noisy channels whose degradation characteristics resemble those of persistent activity networks. If the brain first encoded the information appropriately before passing the information into such networks, the information can be stored substantially more faithfully. Within this framework, we derive a fundamental lower-bound on recall precision, which declines with storage duration and number of stored items. We show that human performance, though inconsistent with models involving direct (uncoded) storage in persistent activity networks, can be well-fit by the theoretical bound. This finding is consistent with the view that if the brain stores information in patterns of persistent activity, it might use codes that minimize the effects of noise, motivating the search for such codes in the brain.
A new target for G protein signaling
Authors: Csanády László
Published: September 2017

G protein-coupled receptor stimulation inhibits TRPM3 channel activity through direct binding of the Gβγ subunit to the channel.
Testing and Evaluation of Health Care Applications of Large Language Models
Authors: Bedi Suhana , Liu Yutong , Orr-Ewing Lucy , Dash Dev , Koyejo Sanmi , Callahan Alison , Fries Jason A. , Wornow Michael , Swaminathan Akshay , Lehmann Lisa Soleymani , Hong Hyo Jung , Kashyap Mehr , Chaurasia Akash R. , Shah Nirav R. , Singh Karandeep , Tazbaz Troy , Milstein Arnold , Pfeffer Michael A. , Shah Nigam H.
Published: October 2024

Importance

Large language models (LLMs) can assist in various health care activities, but current evaluation approaches may not adequately identify the most useful application areas.

Objective

To summarize existing evaluations of LLMs in health care in terms of 5 components: (1) evaluation data type, (2) health care task, (3) natural language processing (NLP) and natural language understanding (NLU) tasks, (4) dimension of evaluation, and (5) medical specialty.

Data Sources

A systematic search of PubMed and Web of Science was performed for studies published between January 1, 2022, and February 19, 2024.

Study Selection

Studies evaluating 1 or more LLMs in health care.

Data Extraction and Synthesis

Three independent reviewers categorized studies via keyword searches based on the data used, the health care tasks, the NLP and NLU tasks, the dimensions of evaluation, and the medical specialty.

Results

Of 519 studies reviewed, published between January 1, 2022, and February 19, 2024, only 5% used real patient care data for LLM evaluation. The most common health care tasks were assessing medical knowledge such as answering medical licensing examination questions (44.5%) and making diagnoses (19.5%). Administrative tasks such as assigning billing codes (0.2%) and writing prescriptions (0.2%) were less studied. For NLP and NLU tasks, most studies focused on question answering (84.2%), while tasks such as summarization (8.9%) and conversational dialogue (3.3%) were infrequent. Almost all studies (95.4%) used accuracy as the primary dimension of evaluation; fairness, bias, and toxicity (15.8%), deployment considerations (4.6%), and calibration and uncertainty (1.2%) were infrequently measured. Finally, in terms of medical specialty area, most studies were in generic health care applications (25.6%), internal medicine (16.4%), surgery (11.4%), and ophthalmology (6.9%), with nuclear medicine (0.6%), physical medicine (0.4%), and medical genetics (0.2%) being the least represented.

Conclusions and Relevance

Existing evaluations of LLMs mostly focus on accuracy of question answering for medical examinations, without consideration of real patient care data. Dimensions such as fairness, bias, and toxicity and deployment considerations received limited attention. Future evaluations should adopt standardized applications and metrics, use clinical data, and broaden focus to include a wider range of tasks and specialties.
Early Warning Scores With and Without Artificial Intelligence
Authors: Edelson Dana P. , Churpek Matthew M. , Carey Kyle A. , Lin Zhenqiu , Huang Chenxi , Siner Jonathan M. , Johnson Jennifer , Krumholz Harlan M. , Rhodes Deborah J.
Published: October 2024

Importance

Early warning decision support tools to identify clinical deterioration in the hospital are widely used, but there is little information on their comparative performance.

Objective

To compare 3 proprietary artificial intelligence (AI) early warning scores and 3 publicly available simple aggregated weighted scores.

Design, Setting, and Participants

This retrospective cohort study was performed at 7 hospitals in the Yale New Haven Health System. All consecutive adult medical-surgical ward hospital encounters between March 9, 2019, and November 9, 2023, were included.

Exposures

Simultaneous Epic Deterioration Index (EDI), Rothman Index (RI), eCARTv5 (eCART), Modified Early Warning Score (MEWS), National Early Warning Score (NEWS), and NEWS2 scores.

Main Outcomes and Measures

Clinical deterioration, defined as a transfer from ward to intensive care unit or death within 24 hours of an observation.

Results

Of the 362 926 patient encounters (median patient age, 64 [IQR, 47-77] years; 200 642 [55.3%] female), 16 693 (4.6%) experienced a clinical deterioration event. eCART had the highest area under the receiver operating characteristic curve at 0.895 (95% CI, 0.891-0.900), followed by NEWS2 at 0.831 (95% CI, 0.826-0.836), NEWS at 0.829 (95% CI, 0.824-0.835), RI at 0.828 (95% CI, 0.823-0.834), EDI at 0.808 (95% CI, 0.802-0.812), and MEWS at 0.757 (95% CI, 0.750-0.764). After matching scores at the moderate-risk sensitivity level for a NEWS score of 5, overall positive predictive values (PPVs) ranged from a low of 6.3% (95% CI, 6.1%-6.4%) for an EDI score of 41 to a high of 17.3% (95% CI, 16.9%-17.8%) for an eCART score of 94. Matching scores at the high-risk specificity of a NEWS score of 7 yielded overall PPVs ranging from a low of 14.5% (95% CI, 14.0%-15.2%) for an EDI score of 54 to a high of 23.3% (95% CI, 22.7%-24.2%) for an eCART score of 97. The moderate-risk thresholds provided a median of at least 20 hours of lead time for all the scores. Median lead time at the high-risk threshold was 11 (IQR, 0-69) hours for eCART, 8 (IQR, 0-63) hours for NEWS, 6 (IQR, 0-62) hours for NEWS2, 5 (IQR, 0-56) hours for MEWS, 1 (IQR, 0-39) hour for EDI, and 0 (IQR, 0-42) hours for RI.

Conclusions and Relevance

In this cohort study of inpatient encounters, eCART outperformed the other AI and non-AI scores, identifying more deteriorating patients with fewer false alarms and sufficient time to intervene. NEWS, a non-AI, publicly available early warning score, significantly outperformed EDI. Given the wide variation in accuracy, additional transparency and oversight of early warning tools may be warranted.
tVNS alters inflammatory response in adult VPA‐induced mouse model of autism: evidence for sexual dimorphism
Authors: Gök Dağıdır Hale , Bukan Neslihan , Bahcelioglu Meltem , Çalıkuşu Ayşen , Alim Ece , Dizakar Saadet Özen , Topa Elif , Bolay Hayrunnisa
Published: October 2024

Autism is a neurodevelopmental disorder with limited treatment alternatives and which incidence is increasing. Some research suggests that vagus nerve simulation might lead to the reduction of certain symptom. Therefore, we aimed to examine the effect of bilateral transcutaneous auricular vagus nerve stimulation (tVNS) on the inflammatory response in an adult valproic acid (VPA) induced mouse (C57BL6) model of autism for the first time. The autism model was induced by oral VPA administration (600 mg·kg−1) to C57BL/6 pregnant mice on E12.5 days. The study included three groups: the VPA Transcutaneous Auricular Stimulation Group (VPA + tVNS), the VPA Control Group (VPA + sham), and the Healthy Control Group (Control + sham). Each group included 16 mice (8 M/8 F). Our results show that serum IL‐1β and IL‐6 levels were significantly higher in male VPA‐exposed mice than controls. However, IL‐1β was significantly lower, and IL‐6, TNF‐ α, and IL‐22 were not different in female VPA‐exposed mice compared to the control group. Brain NLRP3 levels were significantly higher in both sexes in the VPA autism model (P < 0.05). tVNS application increased brain NLRP3 levels in both sexes and reduced serum IL‐1β levels in male mice. We conclude that cytokine dysregulation is associated with the VPA‐induced adult autism model, and the inflammatory response is more pronounced in male mice. tVNS application altered the inflammatory response and increased brain NLPR3 levels in both sexes. Further studies are needed to understand the beneficial or detrimental role of the inflammatory response in autism and its sexual dimorphism.
Dried blood spot improves global access to aquaporin‐4‐IgG testing for neuromyelitis optica
Authors: Vorasoot Nisa , Abdulrahman Yahya J. , Mateen Farrah , Fryer James P. , Redenbaugh Vyanka , Sagen Jessica A. , Musubire Abdu K. , Jenkins Sarah M. , Gorsh Amy P. , Chen John J. , Zekeridou Anastasia , McKeon Andrew , Flanagan Eoin P. , Mills John R. , Pittock Sean J.
Published: October 2024

Objective

This study aimed to evaluate the diagnostic accuracy of dried blood spot (DBS) compared with conventional serum Aquaporin‐4‐IgG (AQP4‐IgG) testing.

Methods

Prospective multicenter diagnostic study was conducted between April 2018 and October 2023 across medical centers in the United States, Uganda, and the Republic of Guinea. Neuromyelitis optica spectrum disorder (NMOSD) patients and controls collected blood on filter paper cards along with concurrent serum samples. These samples underwent analysis using flow cytometric live‐cell‐based assays (CBA) and enzyme‐linked immunosorbent assay (ELISA) to determine AQP4 serostatus. The accuracy of AQP4‐IgG detection between DBS and serum (gold standard) was compared.

Results

Among 150 participants (47 cases, 103 controls), there was a strong correlation between DBS and serum samples (Spearman's correlation coefficient of 0.82). The AUC was 0.97 (95% CI: 0.92–0.99). AQP4‐IgG detection through DBS showed 87.0% sensitivity (95% CI: 0.74–0.95) and 100% specificity (95% CI: 0.96–1.00) using CBA, and 65.2% sensitivity (95% CI: 0.43–0.84) and 95.2% specificity (95% CI: 0.76–0.99) using ELISA. Serum ELISA demonstrated 69.6% sensitivity (95% CI: 0.47–0.87) and 98.4% specificity (95% CI: 0.91–0.99). The stability of DBS in detecting AQP4‐IgG persisted over 24 months for most cases.

Interpretation

The DBS represents a viable alternative for detecting AQP4‐IgG in resource‐limited settings to diagnose NMOSD, offering high sensitivity and specificity comparable to serum testing. Moreover, DBS has low shipping costs, is easy to administer, and is suitable for point‐of‐care testing.
Regulating Local Electron Distribution of Cu Electrocatalyst via Boron Doping for Boosting Rapid Absorption and Conversion of Nitrate to Ammonia
Authors: Liu Wenjing , Chen Jie , Wei Yuao , He Yuxuan , Huang Yuting , Wei Mo , Yu Yingjie , Yang Nan , Zhang Weina , Zhang Linghai , Saleem Faisal , Huo Fengwei
Published: October 2024

The electrochemical reduction of nitrate to ammonia (NO3RR) is an effective route to ammonia synthesis with the characteristics of low energy input. However, the complex multi‐electron/proton transfer pathways associated with this reaction may trigger the accumulation of competitive by‐products. Herein, boron (B)‐doped Cu electrode (denoted as B–Cu2O/Cu/CP) as “all‐in‐one” catalyst is prepared by one‐step electrodeposition strategy. Caused by the B doping, the charge redistribution and local coordination environment of Cu2O/Cu species are modulated, resulting in the exposure of active sites on the Cu2O/Cu/CP catalyst. In‐situ Fourier transform infrared spectroscopy and theoretical investigations demonstrate that both Cu2O and Cu sites modulated by B can effectively enhance the adsorption of NO3− and facilitate the conversion of intermediate by‐products, thus promoting the direct reduction of NO3− to NH3. Consequently, a remarkable Faradaic efficiency of 92.74% can be obtained on B–Cu2O/Cu/CP catalyst with minimal accumulation of by‐products. It is expected that this work, based on the heterogeneous B doping, will open a maneuverable and versatile way for the design of effective catalysts.
Photonic Synapse of CrSBr/PtS2 Transistor for Neuromorphic Computing and Light Decoding
Authors: Khan Muhammad Asghar , Khan Muhammad Farooq , Nasim Muhammad , Elahi Ehsan , Rabeel Muhammad , Asim Muhammad , Rehmat Arslan , Pervez Muhammad Hamza , Rehman Shania , Kim Honggyun , Eom Jonghwa
Published: October 2024

Field effect transistors based on 2D layered material have gained significant potential in emerging technologies, such as neuromorphic computing and ultrafast memory response for artificial intelligence applications. This study proposes a facile approach to fabricate an optoelectronic artificial synapse for neuromorphic computing and light‐decoding information system by utilizing the 2D heterostructure of CrSBr/PtS2 to overcome circuit complexity. The CrSBr layer serves as a trapping layer, while PtS2, mounted on top of CrSBr, acts as a channel layer. PtS2 exhibits n‐type semiconductor behavior with a hysteresis that varies with the thickness of the underlying CrSBr layer. The heterostructure device, featuring a 96.3 nm thick CrSBr layer, exhibited a large memory window of 11.9 V when the gate voltage is swept from −10 V to +10 V. Various synaptic behaviors are effectively demonstrated, including paired‐pulse facilitation, excitatory postsynaptic current, optical spike number and intensity‐dependent plasticity using laser light at a wavelength of 365 nm. The device achieves 26 distinct output signals depending on the intensity of the incident laser light, ranging from 10 to 385 mW cm−2, enabling its applications for light‐decoded information security systems. Thus, the investigation presents a unique approach to artificial intelligence and cybersecurity systems.
All‐In‐One Photonic Crystals With Multi‐Stimuli‐Chromic, Color‐Recordable, Self‐Healable, and Adhesive Functions
Authors: Yu Siyi , Ma Dekun , Qi Chenze , Yang Dongpeng , Huang Shaoming
Published: October 2024

Fabricating photonic crystals (PCs) with dynamic multi‐stimuli‐responsive structural colors, recordable colors, and self‐healable properties is significant for their emerging applications, yet remains a big challenge. Here, an all‐in‐one multifunctional PC (MFPC) film with outstanding mechanochromic, thermochromic, solvatochromic, color/shape‐recordable, self‐healable, and adhesive functions is designed and prepared by simply non‐close‐assembling silica particles into the unique 2‐[[(Butylamino)carbonyl]oxy]ethyl acrylate (BCOEA) followed by photopolymerization. The success is mainly due to the rational combination of non‐close‐packing structures and BCOEA's characteristics, including its urethane groups with numerous sacrificial hydrogen bonds, temperature‐dependent refractive index, swellable and deformable polymer network, as well as low glass‐transition temperature. The MFPC's hue and color saturation can be reversibly and dynamically modulated by strain/pressure/solvents and temperature, respectively, thereby realizing visually and spectrally sensing these stimuli. More interestingly, the color‐responsiveness combined with other functions endows MFPCs with fascinating emerging applications, including multilayer optical filters, inkless printing, reconfigurable multicolor patterns, stretching‐based anti‐counterfeiting, etc. This work offers a new perspective for designing next‐generation smart photonic materials and will facilitate their all‐round applications.
High‐Gain and Tunable Linear Photodetection in 2D Tunneling Heterostructures Through Potential Engineering
Authors: Wei Laijiang , Wu Zhiming , Wei Yuchao , Li Chunyu , Fu Ziyi , Han Jiayue , Yang Xiutao , Xie Jinling , Tian Zexing , Zhou Hongxi , Wang Jun
Published: October 2024

2D materials are extensively employed in the fabrication of high‐performance photodetectors owing to their exceptional physical properties. However, most 2D material photodetectors fail to sustain high gain under intense illumination due to the limited intrinsic trap states. Here, an n‐n type Bi2O2Se/SnSe2 van der Waals tunneling heterojunction photodetector with a detection range from visible to near‐infrared (VIS‐NIR) is presented. Under reverse bias, the heterojunction induces a significant electron barrier and hole potential well, ensuring low leakage current and ample hole defect states. Therefore, the photodetector demonstrated a responsivity of 1636.3 AW−1 and a detectivity of 1.39  ×  1014 Jones under 660 nm illumination, maintaining a tunable linear dynamic range (LDR) of ≈74.7 dB. This performance is attributed to the hole potential well‐suppressing the recombination of photogenerated carriers, thereby enhancing the device's gain. Furthermore, the tunneling of photogenerated electrons within the heterojunction's space charge region under bias enables rapid response (75.1 and 15.6 µs). In summary, the study introduces a novel strategy to overcome the limited detection capabilities of 2D devices under intense illumination, characterized by outstanding linearity for rapid detection and high‐resolution imaging.
Tissue‐Compatible and Lubricated Hydrogel Catheter with Promising Activity Against Polymicrobial Infections for Ventilator‐Associated Pneumonia Prevention
Authors: Kong Xiangren , Guo Gang , Yiming Burebi , Hu Jia Yu , Zheng Qiang , Li Tian Yu , Wu Zi Liang , Qian Jin
Published: October 2024

Endotracheal intubation is a vital means of saving critically ill patients. However, the inserted catheter often causes tissue damage and the formation of tenacious biofilms containing drug‐resistant bacteria and fungi, leading to severe ventilator‐associated pneumonia (VAP). Currently, the resolution of VAP is usually based on antibiotic treatment and lacks targeted prophylaxis. Here, a quaternary phosphonium salts functionalized hydrogel catheter that enhances tissue compatibility yet inhibits complex and tenacious pathogens in the catheter, thus preventing VAP is reported. By copolymerizing the quaternary phosphonium electrolyte and acrylic acid monomers, the hydrogel catheter demonstrates good shape‐supporting ability, and its strength and modulus can be adjusted over a wide range to meet the needs of different ages. Moreover, it possesses good tissue compatibility, antifouling properties, stable lubrication capability, and superior hydrophilicity, which may mitigate tissue damage caused by contact. Importantly, the hydrogel catheter demonstrates potent broad‐spectrum intrinsic antimicrobial activity, eradicating nearly 99% of multi‐drug resistant bacteria and 80% of fungi. To validate its role in preventing VAP, the real VAP pathogenesis process is mimicked, establishing a polymicrobial infections model considering time effects. The results prove that the hydrogel catheter effectively inhibits the invasion of various drug‐resistant pathogens and prevents biofilm formation.
Controlling Cell Interactions with DNA Directed Assembly
Authors: Mathis Katelyn , Chan Clement T. Y. , Meckes Brian
Published: October 2024

The creation of complex cellular environments is critical to mimicking tissue environments that will play a critical role in next‐generation tissue engineering, stem cell programming, and therapeutic screening. To address this growing need, techniques capable of manipulating cell–cell and cell‐material interactions are required that span single‐cell to 3D tissue architectures. DNA programmed assembly and placement of cells present a powerful technique for the bottom‐up synthesis of living microtissues for probing key questions in cell–cell and cell‐material‐driven behaviors through its refined control over placement and architecture. This review examines the current state of the art in the programming of cellular interactions with DNA and its applications spanning tissue model building, fundamental cellular biology, and cell manipulation for measurements across a host of applications.
Measurement of Enhanced Spin‐Orbit Coupling Strength for Donor‐Bound Electron Spins in Silicon
Authors: Krishnan Radha , Gan Beng Yee , Hsueh Yu‐Ling , Huq A.M. Saffat‐Ee , Kenny Jonathan , Rahman Rajib , Koh Teck Seng , Simmons Michelle Y. , Weber Bent
Published: October 2024

While traditionally considered a deleterious effect in quantum dot spin qubits, the spin‐orbit interaction is recently being revisited as it allows for rapid coherent control by on‐chip AC electric fields. For electrons in bulk silicon, spin‐orbit coupling (SOC) is intrinsically weak, however, it can be enhanced at surfaces and interfaces, or through atomic placement. Here it is showed that the strength of the spin‐orbit coupling can be locally enhanced by more than two orders of magnitude in the manybody wave functions of multi‐donor quantum dots compared to a single donor, reaching strengths so far only reported for holes or two‐donor system with certain symmetry. These findings may provide a pathway toward all‐electrical control of donor‐bound spins in silicon using electric dipole spin resonance (EDSR).
Dressing AgNWs with MXenes Nanosheets: Transparent Printed Electrodes Combining High‐Conductivity and Tunable Work Function for High‐Performance Opto‐Electronics
Authors: Ju Zhongshi , Chen Yusheng , Li Peng , Ma Jiangang , Xu Haiyang , Liu Yichun , Samorì Paolo
Published: October 2024

High‐work function transparent electrodes (HWFTEs) are key for establishing Schottky and Ohmic contacts with n‐type and p‐type semiconductors, respectively. However, the development of printable materials that combine high transmittance, low sheet resistance, and tunable work function remains an outstanding challenge. This work reports a high‐performance HWFTE composed of Ag nanowires enveloped conformally by Ti3C2Tx nanosheets (TA), forming a shell‐core network structure. The printed TA HWFTEs display an ultrahigh transmittance (>94%) from the deep‐ultraviolet (DUV) to the entire visible spectral region, a low sheet resistance (<15 Ω sq−1), and a tunable work function ranging from 4.7 to 6.0 eV. The introduction of additional oxygen terminations on the Ti3C2Tx surface generates positive dipoles, which not only increases the work function of the TA HWFTEs but also elevates the TA/Ga2O3 Schottky barrier, resulting in a high self‐powered responsivity of 18 mA W−1 in Ga2O3 diode DUV photodetectors, as demonstrated via experimental characterizations and theoretical calculations. Furthermore, the TA HWFTEs‐based organic light‐emitting transistors exhibit exceptional emission brightness of 5020 cd m−2, being four‐fold greater than that in Au electrodes‐based devices. The innovative nano‐structure design, work function tuning, and the revealed mechanisms of electrode‐semiconductor contact physics constitute a substantial advancement in high‐performance optoelectronic technology.
Physical Field Effects to Suppress Polysulfide Shuttling in Lithium–Sulfur Battery
Authors: Feng Junan , Shi Chuan , Zhao Xiaoxian , Zhang Ying , Chen Shuangqiang , Cheng Xinbing , Song Jianjun
Published: October 2024

Lithium–sulfur batteries (LSB) with high theoretical energy density are plagued by the infamous shuttle effect of lithium polysulfide (LPS) and the sluggish sulfur reduction/evolution reaction. Extensive research is conducted on how to suppress shuttle effects, including physical structure confinement engineering, chemical adsorption strategy, and the design of sulfur redox catalysts. Recently, the rational design to mitigate shuttle effects and enhance reaction kinetics based on physical field effects has been widely studied, providing a more fundamental understanding of interactions with sulfur species. Herein, the physical field effect is focused and their methods and mechanisms of interaction are summarized systematically with LPS. Overall, the working principle of LSB system, the origin of the shuttle effect, and kinetic trouble in LSB are briefly described. Then, the mechanism and application of rational design of materials based on physical field effect concepts and the external physical field‐assisted LSB are elaborated, including electrostatic force, built‐in electric field, spin state regulation, strain engineering, external magnetic field, photoassisted and other physical field‐assisted strategies are pivotally elaborated and discussed. Finally, the potential directions of physical field effects in enhancing the performance and weakening the shuttle effect of high‐energy LSB are summarized and anticipated.
Versatile Metamaterial: Exploring the Resonances of Symmetry‐Protected Modes for Multitasking Functionality
Authors: Boublouh Souhaïla , Suarez Miguel , Gao Feng , Belkhir Abderrahmane , Khelif Abdelkrim , Baida Fadi
Published: October 2024

In this work, an experimental study supported by numerical modeling that demonstrates the possibility of exciting Symmetry Protected‐Bound states In the Continuum (SP‐BICs) in a 1D silicon grating fabricated on a lithium niobate substrate is presented. bBoth transverse electric and magnetic polarization states are investigated, leading to the excitation of four quasi‐ Bound states In the Continuum (quasi‐BIC) resonances, exhibiting distinct behaviors. Under standard illumination conditions (plane of incidence perpendicular to the 1D grating lines), two of these resonances are highly sensitive to illumination conditions, while the other two resonances involving unconventional illumination directions (plane of incidence parallel to the grating lines) are more robust to the angle of incidence, but just as sensitive to external stresses in terms of resonance wavelength and quality factor. Additionally, temperature detection is experimentally demonstrated with a Sensitivity of ST = 0.81∼nm °C−1, a state‐of‐the‐art value achieved due to significant electromagnetic field enhancement inside the lithium niobate substrate at the quasi‐BIC resonance. These findings pave the way for their use in various sensing applications (such as biology, electromagnetic, and temperature sensing), as well as nonlinear applications like second harmonic generation, and electro‐ and acousto‐optic modulation.
Abnormal Response of Indirect Excitons to Non‐Uniform Elastic Strain in MoS2 Flakes
Authors: Yue Xinxin , Zhang Lifu , Chen Xiang , Ji Shaozheng , Liu Fang , Feng Min , Deng Shibin , Hu Zhenpeng , Yan Yuan , Fu Xuewen
Published: October 2024

Regulating the electronic structures and carrier dynamics in 2D materials via elastic strain is a fascinating avenue for tailoring their optoelectronic properties at atomic scale. Here, the abnormal response of indirect excitons to non‐uniform elastic strain in MoS2 flakes is reported. The non‐uniform elastic strain in the MoS2 flakes is introduced by transferring them to pre‐prepared convex cross structures on a SiO2/Si substrate, where the topography and strain distribution are determined by atomic force microscopy and Raman spectroscopy, respectively. It is observed that the emission energy of the indirect excitons shows an unexpected blue‐shift followed by a red‐shift with increasing the local tensile strain, which is in sharp contrast to the linear red‐shift of the direct excitons. Density functional theory calculations reveal that the abnormal energy shift of the indirect excitons in the MoS2 flakes arises from the strain‐induced competition between two indirect bandgap transitions and the spatial exciton funnel effect in the non‐uniform strain field. This work provides new insights into the elastic strain effect on the indirect excitons in 2D semiconductors, which possesses potential applications in flexible optoelectronic devices.
Multiple Energy Transfer Modes From o‐Carborane Dyad Induced by Synergetic Conformational Regulations and Intense Circularly Polarized Luminescence in Self‐Assembly Aggregates
Authors: Li Junfeng , Chen Yu , Wu Wei , Ma Jiamian , Shi Shunan , Deng Yuhang , Lai Wen‐Yong
Published: October 2024

Photothermal modulated excited conformations in traditional optoelectronic materials have been extensively investigated for the manipulation of emissive properties. However, photoinduced molecular synergetic conformational changes, which are promising for controlling intramolecular energy transfer modes through molecular orbital breaking, are never been explored. Herein, a novel o‐carborane dyad composed of carbazole units as electron donors and triazine derivatives as electron acceptors is demonstrated to achieve conformation‐dependent emissions and abundant emissions via synergetic conformational changes. Notably, the resulting dyad exhibited multiple conformational changes that induced emissions through different energy transfer modes involved “through space” and “through bond.” Exactly, the electron spin from singlet to triplet state took a flip accompanied by molecular orbitals from π–π molecular orbitals in the space charge transfer style to π and σ molecular orbitals in the bond charge transfer mode. The circularly polarized luminescence (CPL) properties are systematically investigated, exhibiting intense CPL with large glum values. These results provide novel perspectives for elucidating the complicated emission changes in aggregated states, as well as unique perspectives on the relationship between molecular conformations, energy transfer modes, and molecular orbital breaking.
Highly Refractive Transparent Half‐Heuslers for Near Infrared Optics and Their Material Design
Authors: Ishii Akihiro , Katsuragi Ruon , Tanaka Satoru , Oikawa Itaru , Imura Masaaki , Takamura Hitoshi
Published: October 2024

Advanced control of light focusing, reflection, and transmission is possible with highly refractive transparent materials; however, such materials are difficult to discover because of the negative correlation between the refractive index and the optical band gap. This study elucidates half‐Heuslers as highly refractive transparent materials, considering their densely packed crystal structures comprising both covalent and ionic bonds with d orbitals. Theoretical calculations revealed that 22 ternary half‐Heusler systems (αβγ) exhibited higher refractive indices with wider band gaps than conventional high‐refractive‐index‐transparent materials in the near‐infrared region. The key to achieving a high index and wide gap is aligning α‐d and β‐d levels within a small lattice frame given by small γ elements to the verge of forming Γ‐point conduction band minimum. Experimental examinations revealed that α and γ elements with low and high melting points are preferred for the thin‐film preparation of the well‐ordered half‐Heuslers. Highly refractive transparent half‐Heuslers and their material designs expedite post‐silicon technology for controlling near‐infrared light.
Chiral SPINOL‐Derived Borophosphate‐Catalyzed Asymmetric 1,4‐Reduction of Exocyclic α,β‐Unsaturated Ketones
Authors: Cui Wenhui , Meng Fanjing , Zhang Zengfeng , Han Zhuting , Cao Yang
Published: October 2024

An asymmetric 1,4‐reduction of exocyclic α,β‐unsaturated ketones, yielding diverse optically active α‐substituted tetralones, has been achieved using a chiral SPINOL‐derived borophosphate catalyst. The enantioselectivity‐determining step of the reaction involves the protonation of a highly active boron enolates intermediate. This catalytic reduction system, comprising chiral SPINOL‐derived borophosphate and pinacolborane, has potential for broader application in other asymmetric reduction reactions.
Hydrofluoroether Synthesis through One‐Pot Anodic Iodoalkoxylation of Alkenes
Authors: Becerra‐Ruiz Martin , Winterson Bethan , Pérez Edwin G. , Wirth Thomas
Published: October 2024

The incorporation of carbon‐fluorine bonds can profoundly influence the chemical and physical properties of drugs, agrochemicals, and materials. Different methods allow the installation of CF3, CF2H units and C−F bonds including trifluoro‐ and difluoromethoxylations, reflecting the limited diversity of reactions available to synthetic chemists. We introduce the 2,2,2‐trifluoroethoxy group through an electro‐oxidative iodination of alkenes as a versatile substituent for fluorine chemists. An iodoarene serves as an unusual iodine source facilitating the 1,2‐iodoalkoxylation of a broad range of industrially relevant aliphatic alkenes in high yields (31–98%) showing high Markovnikov regioselectivity.
Cross‐Scale Process Intensification of Spindle CuO Supported Tungsten Single‐Atom Catalysts toward Enhanced Electrochemical Hydrogen Production
Authors: Chang Chaoqun , Li Xiaodong , Wei Shizhong , Zhao Yang , Gong Lihua , Zhang Yonghui , Liu Jian , Gong Feilong
Published: October 2024

Process intensification engineering of electrocatalysts is crucial to facilitate electrocatalytic reaction, while its cross‐scale modulation is of great challenge. Herein, the spindle CuO supported tungsten single‐atom catalysts (W SACs) with tunable mesoscale electric field and atomic‐scale coordination structure are reported toward enhanced electrochemical hydrogen evolution process. Finite element analysis indicates the mesoscale electric field can be enhanced by tailoring the tip angle of spindle configuration from 74° to 27°, enhancing hydrogen production rate by 5 times. Based on the density functional theory calculations, the configuration regulation also triggers the increase of coordination number of W–O, which increases charge transfer and downshifts d‐band center, stabilizing W sites and optimizing hydrogen desorption process. The optimized WSA/CuO‐27 exhibits much better hydrogen evolution activity (η100 = 94 mV) and stability (200 mA cm−2 for 120 h) than as‐prepared WSA/CuO‐56 and WSA/CuO‐74 analogues. Impressively, the anion exchange membrane electrolyzer fabricated with the WSA/CuO‐27 presents excellent activity comparable to that of commercial electrocatalysts, and also delivers an ultra‐low attenuation of 0.085 mA cm−2 h−1 at 300 mA cm−2 after continuous electrocatalysis for 120 h. This work inspires the design of high‐efficiency supported metal catalysts for electrochemical synthesis via the cross‐scale process intensification engineering.
The Role and Impact of Rooftop Photovoltaics in the Norwegian Energy System under Different Energy Transition Pathways
Authors: Myhre Stine Fleischer , Rosenberg Eva
Published: October 2024

This study focuses on investigating the impact and cost‐competitiveness of solar power in a highly hydropower‐driven northern energy system. The goal is to assess the role of rooftop photovoltaics (PV) in the Norwegian energy system toward 2050 under different energy transition pathways. Energy system analysis is conducted using the IFE‐TIMES‐Norway model, with an integrated detailed representation of rooftop PV based on the tilt and azimuth of existing rooftops in Norway. A thorough sensitivity analysis is conducted to illustrate how investment in rooftop PV varies under different system and parameter conditions and to disclose important barriers for PV in similar energy systems. The results show that when PV investments are facilitated, solar power can potentially stand for 56% of all new investments, resulting in a share of 10% of the total electricity generation. With less competition from onshore wind power and favorable investment parameters, especially lowering the demand for the rate of return, the investments in PV will be four times higher and reach their full potential in commercial and apartment buildings by 2050. Additionally, the results highlight that the cost parameter functions as a barrier to other solutions that facilitate increased PV investments, such as flexibility and energy storage.
KIF11 Variants Associated With Novel Renal System Involvement—Two Cases That Expand the Phenotypic Spectrum of Microcephaly With or Without Chorioretinopathy, Lymphedema, or Impaired Intellectual Development
Authors: Gonzalez Tessa , Tyler Rebecca C. , Schilter Kala F. , McCarrier Julie , Muriello Michael , Basel Donald , Reddi Honey V.
Published: October 2024

Pathogenic variants in KIF11 are linked to microcephaly with or without chorioretinopathy, lymphedema, or impaired intellectual development (MCLMR). To our knowledge, renal phenotypes have not been described in the literature in association with KIF11‐related disorders. This study is a case report of two probands with heterozygous pathogenic variants in KIF11 who presented with the common clinical features of MCLMR but also had additional renal involvement not previously reported as associated phenotypes of MCLMR, elucidating phenotypic expansion of this syndrome.
Evaluation and treatment of rhinosinusitis with primary antibody deficiency in children: Evidence‐based review with recommendations
Authors: Makary Chadi A. , Azar Antoine , Gudis David , Crawford Anna , Hannikainen Paavali , Kim Jean , Joe Stephanie , Kimple Adam J. , Lam Kent , Lee Jivianne T. , Luong Amber U. , Marcus Sonya , McArdle Erica , Mullings Warren , Peppers Brian P. , Lewandrowski Callum , Lin Sandra Y. , Ramadan Hassan H. , Rose Austin S. , Ryan Lindsey , Toskala Elina , Baroody Fuad M.
Published: October 2024

Background

There is clear evidence that prevalence of primary antibody deficiency (PAD) is higher in children with chronic rhinosinusitis (CRS) than in the general population. The purpose of this multi‐institutional and multidisciplinary evidence‐based review with recommendations (EBRR) is to thoroughly review the literature on rhinosinusitis with PAD, summarize the existing evidence, and provide recommendations on the evaluation and management of rhinosinusitis in children with PAD.

Methods

The PubMed, Embase, and Cochrane databases were systematically reviewed from inception through December 2023. Studies on the evaluation and management of rhinosinusitis in PAD patients were included. An iterative review process was utilized in accordance with EBRR guidelines. Levels of evidence and recommendations on the evaluation and management principles for PAD were generated.

Results

A total of 50 studies were included in this evidence‐based review. These studies were evaluated on the incidence of PAD in rhinosinusitis patients, the incidence of rhinosinusitis in PAD patients, and on the different treatment modalities used and their outcome. The aggregate quality of evidence varied across the reviewed domains.

Conclusion

Based on the currently available evidence, the incidence of PAD in children with recalcitrant CRS can be significantly elevated. Despite the presence of multiple studies addressing rhinosinusitis and PAD, the level of evidence supporting different treatment options continues to be lacking. Optimal management requires a multidisciplinary approach through collaboration with clinical immunology. There is need for higher level studies that compare different treatments in children with PAD and rhinosinusitis.
Transient transition from Stable to Dissipative Assemblies in Response to the Spatiotemporal Availability of a Chemical Fuel
Authors: Kar Haridas , Chen Rui , Das Krishnendu , Prins Leonard J.
Published: October 2024

The transition from inactive to active matter implies a transition from thermodynamically stable to energy‐dissipating structures. Here, we show how the spatiotemporal availability of a chemical fuel causes a thermodynamically stable self‐assembled structure to transiently pass to an energy‐dissipating state. The system relies on the local injection of a weak affinity phosphodiester substrate into an agarose hydrogel containing surfactant‐based structures templated by ATP. Injection of substrate leads to the inclusion of additional surfactant molecules in the assemblies leading to the formation of catalytic hotspots for substrate conversion. After the local disappearance of the substrate as a result of chemical conversion and diffusion the assemblies spontaneously return to the stable state, which can be reactivated upon the injection of a new batch of fuel. The study illustrates how a dissipating self‐assembled system can cope with the intermittent availability of chemical energy without compromising long‐term structural stability.
NHC‐Catalyzed Aldimine Umpolung/6π‐Electrocyclization Cascade to Access Tetracyclic Dihydrochromeno Indoles
Authors: Das Rohan Chandra , Gupta Priyanshu , Chakraborty Sukriyo , Jindal Garima , Biju Akkattu T.
Published: October 2024

The umpolung of aldimines using N‐heterocyclic carbenes (NHCs) is less explored compared to the established polarity reversal of aldehydes. Described herein is an NHC‐catalyzed imine umpolung /6π‐electrocyclization cascade, which leads to the atom‐ and pot‐economic synthesis of biologically important dihydrochromeno indoles. For the first time, the nucleophilic aza‐Breslow intermediates have been intercepted with unactivated alkynes. Preliminary mechanistic and DFT studies shed light on the role of the phenolic −OH moiety in promoting the addition of the aza‐Breslow intermediate to the unactivated alkyne via an intramolecular proton transfer in a stepwise manner. DFT studies also support the regioselectivity preference for the 5‐exo‐dig cyclization pathway, leading to the exclusive formation of the indole products. Moreover, a comparison of Gibbs free energies provides insight into a thermodynamically preferred 6π‐electrocyclization over a competing oxa‐Michael pathway. Further, this strategy is applied to the formal synthesis of a Hepatitis C Virus (HCV) NS5A inhibitor in a step‐economical method.
Interception of Alkynyl Tetracoordinate Borons with Sulfur Electrophiles beyond the Zweifel Pathway
Authors: Ma Xingxing , An Yuanbiao , Li Luo , Cai Meihui , Song Qiuling
Published: October 2024

Zweifel reaction is a powerful strategy to construct olefins from alkenyl tetracoordinate borons in organoboron chemistry, however, it usually only involves one functional group migration and then undergoes an elimination process affording alkenes or alkynes exclusively. Herein, we disclose several intriguing interception of alkynyl tetracoordinate borons with sulfur electrophiles. Wherein, the substituted benzothiophenes are accessed by consecutive 1,2‐migrations and intramolecular electrophilic substitution, meanwhile, the challenging and elusive five/four‐membered boracycles are easily assembled, and an approach to alkenyl sulfides with good stereoselectivity was developed as well. Moreover, by adding readily available deuterium sources, the tetrasubstituted deuterated alkenyl sulfides with high deuteration rates are constructed. These protocols not only improve atom economy by prohibiting the elimination of Zweifel intermediate, but also enrich the reaction modes of alkynyl tetracoordinate borons achieving versatile value‐added sulfur‐containing molecules. Mechanistic investigations illustrate that dichlorosulfoxide (SOCl2) and dialkylaminosulfur trifluoride‐type reagents (DAST‐type) as surfur sources could promote dual 1,2‐aryl migration of alkynyl tetracoordinate borons, which are distinct from traditional Zweifel reaction, and the regulation of steric hindrance could also make four‐membered boracycles and alkenyl sulfides feasible. And these transformations feature novel reaction modes and unusual reaction mechanisms with valuable products in high efficiency.
A Tricyclic Framework with Integrated B←N and Cyano Dual Functionalization for Superior n‐Type Organic Electronics
Authors: Jiang Zhen , Liu Di , Wang Yang , Song Wei , Yan Dongsheng , Ge Ziyi , Liu Yunqi
Published: October 2024

n‐Type conjugated polymers featuring low‐lying lowest unoccupied molecular orbital (LUMO) energy levels are essential for achieving high‐performance n‐type organic thin‐film transistors (OTFTs) and organic thermoelectrics (OTEs). However, the synthesis of acceptors with strong electron‐withdrawing characteristics presents a significant challenge. Herein, a peripheral functionalization strategy is employed on the tricyclic framework anthracene by introducing dual N,O‐bidentate BF2/B(CN)2 groups to enhance its electron‐withdrawing capability. This approach successfully navigates synthetic challenges, leading to the development of two novel acceptor building blocks: DBNF and DBNCN. Compared to the counterparts with a single N,O‐bidentate BF2/B(CN)2 moiety, DBNF and DBNCN exhibit an extended π‐backbone, enhanced molecular packing, and improved electron‐withdrawing properties. Utilizing these innovative acceptor monomers, copolymers, PDBNF and PDBNCN, are synthesized, which exhibit considerably suppressed LUMO ≈−4.0 eV. The deep LUMO of PDBNF together with its favourable bimodal packing orientation leads to remarkable electron mobility of 3.04 cm2 V−1 s−1 with improved stability in OTFTs. Importantly, efficient n‐doping in OTEs is achieved with PDBNCN, exhibiting exceptional conductivity of 95.5 S cm−1 and a maximum power factor of 147.8 μW m−1 K−2—among the highest reported for solution‐processed n‐type polymers. This work underscores the effectiveness of introducing dual B←N and cyano functionalities in attaining high‐performance n‐type plastic electronics.
A Fluorinated Imide‐Functionalized Arene Enabling a Wide Bandgap Polymer Donor for Record‐Efficiency All‐Polymer Solar Cells
Authors: An Mingwei , Liu Qian , Jeong Sang Young , Liu Bin , Huang Enmin , Liang Qiming , Li Henan , Zhang Guangye , Woo Han Young , Niu Li , Guo Xugang , Sun Huiliang
Published: October 2024

All‐polymer solar cells (all‐PSCs) present compelling advantages for commercial applications, including mechanical durability and optical and thermal stability. However, progress in developing high‐performance polymer donors has trailed behind the emergence of excellent polymer acceptors. In this study, we report a new electron‐deficient arene, fluorinated bithiophene imide (F‐BTI) and its polymer donor SA1, in which two fluorine atoms are introduced at the outer β‐positions in the thiophene rings of BTI to fine‐tune the energy levels and aggregation of the resulting polymers. SA1 exhibits a deep HOMO level of −5.51 eV, a wide bandgap of 1.81 eV and suitable miscibility with the polymer acceptor. Polymer chains incorporating F‐BTI result in a highly ordered π–π stacking and favorable phase‐separated morphology within the all‐polymer active layer. Thus, SA1 : PY‐IT‐based all‐PSCs exhibit an efficiency of 16.31 % with excellent stability, which is further enhanced to a record value of 19.33 % (certified: 19.17 %) by constructing ternary device. This work demonstrates that F‐BTI offers an effective route for developing new polymer materials with improved optoelectronic properties, and the emergence of F‐BTI will change the scenario in terms of developing polymer donor for high‐performance and stable all‐PSCs.