bluuebunny/crossref_metadata_2025 huggingface dataset:
Modulating the Locally Excited States with a Regulating Substituent for Highly Efficient Red/Near‐Infrared Thermally Activated Delayed Fluorescence Emitters
Authors: Feng Zi‐Qi , Yu You‐Jun , Song Zi‐Yu , Song Min , Zuo Peng , Jiang Zuo‐Quan , Zhou Dong‐Ying , Liao Liang‐Sheng
Published: May 2024

Developing highly efficient red/near‐infrared (NIR) thermally activated delayed fluorescence (TADF) materials is important for organic light‐emitting diodes (OLEDs). Here, two TADF emitters, APTT and APTI, which have the same D/A backbone but different attaching groups at acenaphtho‐[1,2‐b]pyrazine‐8,9‐dicarbonitrile (APDC) core, are reported. The appended regulating groups can not only suppress the D/A rotation due to the space confinement effects but also modulate the locally excited triplet state (3LE). The improved molecular rigidity suppresses the non‐radiative process, accounting for the improved photoluminescence quantum yields (PLQYs), while the modulated 3LE promotes the reverse intersystem crossing (RISC) process due to the high utilization efficiency of triplets. Consequently, both APTT and APTI demonstrate high PLQY and fast RISC process, thereby enhancing TADF efficiency. The doped devices based on APTT and APTI achieve maximum external quantum efficiency (EQEmax) values of 20.5% and 25.4% with emission peaks at 664 and 670 nm, respectively. The non‐doped devices of APTT and APTI achieve the EQEmax of 2.8% and 2.9% with emission peaks at 788 and 794 nm, respectively. Encouragingly, the non‐doped devices of APTI have set new records for near‐infrared TADF OLEDs based on the APDC core. This study provides an efficient approach to modulating the optoelectronic properties of highly efficient NIR TADF OLEDs.
A Highly Optical Anisotropic Hybrid Perovskite for Efficient Manipulation of Light Polarization
Authors: Zheng Jieyu , Song Xianyu , Wu Yiran , Lian Yulong , Li Yanqiang , Xu Qianting , zhou Yang , Wang Ziyi , Wang Lei , Luo Junhua , Zhao Sangen
Published: May 2024

Optical anisotropic (e.g., birefringent) crystals can manipulate the polarization of light and thus are widely applied in modern optical fields. Common birefringent crystals are almost exclusively limited to inorganic oxides with small birefringence. Here, a new 1D hybrid halide perovskite PZPbCl3 (PZ = phenazine) is reported, which consists of perfectly parallel Pb–Cl chains and PZ cations. Remarkably, polarized optical observations show that even a PZPbCl3 crystal with micrometer thickness can modulate the polarized light efficiently. Furthermore, PZPbCl3 exhibits exceptional birefringence up to 0.65@546 nm, which is significantly larger than that of commercial oxide crystals. According to first‐principles calculations and polarizability anisotropy analyses, it is found that this birefringence is mainly ascribed to the linear polymerization of π‐conjugated rings in PZ cations. Due to the rich physical properties and structural diversity of hybrid perovskites, it is believed that the introduction of excellent birefringence into the hybrid perovskites will bring unprecedented opportunities to the future explorations of polarization‐dependent functional materials.
Constructing Lysozyme Protective Layer via Conformational Transition for Aqueous Zn Batteries
Authors: Pan Yifan , Zuo Zhicheng , Jiao Yucong , Wu Peiyi
Published: May 2024

The practical applications for aqueous Zn ion batteries (ZIBs) are promising yet still impeded by the severe side reactions on Zn metal. Here, a lysozyme protective layer (LPL) is prepared on Zn metal surface by a simple and facile self‐adsorption strategy. The LPL exhibits extremely strong adhesion on Zn metal to provide stable interface during long‐term cycling. In addition, the self‐adsorption strategy triggered by the hydrophobicity‐induced aggregation effect endows the protective layer with a gap‐free and compacted morphology which can reject free water for effective side reaction inhibition performance. More importantly, the lysozyme conformation is transformed from α‐helix to β‐sheet structure before layer formation, thus abundant functional groups are exposed to interact with Zn2+ for electrical double layer (EDL) modification, desolvation energy decrease, and ion diffusion kinetics acceleration. Consequently, the LPL renders the symmetrical Zn battery with ultra‐long cycling performance for more than 1200 h under high Zn depth of discharge (DOD) for 77.7%, and the Zn/Zn0.25V2O5 pouch cell with low N/P ratio of 2.1 at high Zn utilization of 48% for over 300 cycles. This study proposes a facile and low‐cost method for constructing a stable protective layer of Zn metal for high Zn utilization aqueous devices.
Interfacially Enhanced Superconductivity in Fe(Te,Se)/Bi4Te3 Heterostructures
Authors: Chen An‐Hsi , Lu Qiangsheng , Hershkovitz Eitan , Crespillo Miguel L. , Mazza Alessandro R. , Smith Tyler , Ward T. Zac , Eres Gyula , Gandhi Shornam , Mahfuz Meer Muhtasim , Starchenko Vitalii , Hattar Khalid , Lee Joon Sue , Kim Honggyu , Moore Robert G. , Brahlek Matthew
Published: May 2024

Realizing topological superconductivity by integrating high‐transition‐temperature (TC) superconductors with topological insulators can open new paths for quantum computing applications. Here, a new approach is reported for increasing the superconducting transition temperature by interfacing the unconventional superconductor Fe(Te,Se) with the topological insulator Bi–Te system in the low‐Se doping regime, near where superconductivity vanishes in the bulk. The critical finding is that the of Fe(Te,Se) increases from nominally non‐superconducting to as high as 12.5 K when Bi2Te3 is replaced with the topological phase Bi4Te3. Interfacing Fe(Te,Se) with Bi4Te3 is also found to be critical for stabilizing superconductivity in monolayer films where can be as high as 6 K. Measurements of the electronic and crystalline structure of the Bi4Te3 layer reveal that a large electron transfer, epitaxial strain, and novel chemical reduction processes are critical factors for the enhancement of superconductivity. This novel route for enhancing TC in an important epitaxial system provides new insight on the nature of interfacial superconductivity and a platform to identify and utilize new electronic phases.
Supersoft Norbornene‐Based Thermoplastic Elastomers with High Strength and Upper Service Temperature
Authors: Cater Henry L. , Allen Marshall J. , Linnell Mark I. , Rylski Adrian K. , Wu Yudian , Lien Hsu‐Ming , Mangolini Filippo , Freeman Benny D. , Page Zachariah A.
Published: May 2024

With over 6 million tons produced annually, thermoplastic elastomers (TPEs) have become ubiquitous in modern society, due to their unique combination of elasticity, toughness, and reprocessability. Nevertheless, industrial TPEs display a tradeoff between softness and strength, along with low upper service temperatures, typically ≤100 °C. This limits their utility, such as in bio‐interfacial applications where supersoft deformation is required in tandem with strength, in addition to applications that require thermal stability (e.g., encapsulation of electronics, seals/joints for aeronautics, protective clothing for firefighting, and biomedical devices that can be subjected to steam sterilization). Thus, combining softness, strength, and high thermal resistance into a single versatile TPE has remained an unmet opportunity. Through de novo design and synthesis of novel norbornene‐based ABA triblock copolymers, this gap is filled. Ring‐opening metathesis polymerization is employed to prepare TPEs with an unprecedented combination of properties, including skin‐like moduli (<100 kPa), strength competitive with commercial TPEs (>5 MPa), and upper service temperatures akin to high‐performance plastics (≈260 °C). Furthermore, the materials are elastic, tough, reprocessable, and shelf stable (≥2 months) without incorporation of plasticizer. Structure–property relationships identified herein inform development of next‐generation TPEs that are both biologically soft yet thermomechanically durable.
Superdurable Full‐Life Superhydrophobic Composite Block
Authors: Wang Shanlin , Zhao Zhimeng , Yu Qiang , Li Pengfei , Zhou Fei , Xu Chao , Zhao Xiaofeng , Teng Yuancheng
Published: May 2024

Superhydrophobic materials are attractive for industrial development but plagued by poor mechanical stability. Herein, a superdurable full‐life superhydrophobic composite block is designed and fabricated by embedding near‐zero contractive superhydrophobic silica aerogel into a rigid iron‐nickel foam structured similarly to a regular dodecahedron. The synergistic protection afforded by these materials ensures superrobust mechanical stability for the composite block, which features a high compressive strength of up to ≈7.4 MPa, and ultralow Taber abrasion of down to ≈0.567 mm after withstanding 50 000 cycles, and highly efficient water harvesting capability of up to ≈3114.3 mg min−1 cm−2 at a supercooling degree of 40 K. This robust material system provides a novel strategy to design superhydrophobic materials capable of withstanding extreme conditions, including high temperature, humidity, pressure, and abrasion.
The Power of Synergism: A Novel Drug Combination for Improved Therapy of Glioblastoma
Authors: Maravajjala Kavya Sree , Kothekar Ameya , Roy Aniruddha
Published: May 2024

One of the biggest obstacles in treating glioblastoma multiforme (GBM) is the plasticity and adaptability of GBM cells, which renders monotherapy ineffective. Novel drug combinations that target multiple pathways are required to overcome this challenge. In the current study, the PI3K/AKT/mTOR pathway is identified as a crucial component in GBM cell survival using the KEGG database and literature search. Hence, it is hypothesized that a potential synergistic therapy can be achieved by targeting different stages of this pathway by combining disulfiram (DSF) and 7‐ethyl‐10‐hydroxycamptothecin (SN‐38). The efficacy of this drug combination is evaluated using 2D and 3D in vitro assays, which exhibited a significant synergism with 5 × 104 times lower IC50 than that of temozolomide (TMZ), the gold‐standard drug. The combination treatment increases intracellular ROS (reactive oxygen species) production, and ROS inhibition by using N‐Acetyl Cysteine (NAC) reduced the cytotoxicity substantially, indicating that ROS played a crucial role in the synergistic cytotoxicity. The combination treatment inhibited GBM cell proliferation, migration, and stem cell marker expression. Mechanistically, the DSF+SN‐38 combination is found to increase p53 expression, inhibit PI3K signaling, and activate caspase 9. Altogether, this study demonstrates that the DSF+SN‐38 combination can present a promising therapeutic strategy for treating GBM.
In‐Plane Combination of Micropillars with Distinct Aspect Ratios to Resist Overload‐Induced Adhesion Failure
Authors: Li Dongwu , Li Ruozhang , Yuan Kangbo , Chen Ao , Guo Ning , Xu Chao , Zhang Wenming
Published: May 2024

Bioinspired micropillar adhesives have shown broad application prospects in space capture and docking, due to their strong adhesion, good environmental adaptability, and reusability. However, when performing space missions, unavoidable contact collision with target objects may cause large deformation of the micropillars, resulting in the loss of adhesion ability. This study reports a novel micropillar adhesive through the in‐plane combination of micropillars (IPCM) with different aspect ratios, consisting of small pillars for retaining strong adhesion and large ones for resisting overload‐induced adhesion failure. It is demonstrated that the IPCM array can still maintain 85% of the adhesion peak after static large deformation compared to a general micropillar array composed of the same pillars. The impact of element size and layout of the IPCM, as well as detachment velocity on adhesion performance under high preload is discussed. Furthermore, finite element contact analysis qualitatively reproduces the experimentally observed micropillar deformations and attributes the overload‐induced adhesion failure to the redistribution of surface normal stress. Finally, the potential application of the IPCM in dynamic capture is demonstrated on different objects. The proposed IPCM opens up new design concepts for practical applications of bioinspired adhesives in space capture and docking.
Field Induced Off‐State Instability in InGaZnO Thin‐Film Transistor and its Impact on Synaptic Circuits
Authors: Kang Minseung , Cho Ung , Kang Jaehyeon , Han Narae , Seo Hyeong Jun , Yang Jee‐Eun , Shin Seokyeon , Kim Taehyun , Kim Sangwook , Jeong Changwook , Kim Sangbum
Published: May 2024

Charge storage synaptic circuits employing InGaZnO thin‐film transistors (IGZO TFTs) and capacitors are a promising candidate for on‐chip trainable neural network hardware accelerators. However, IGZO TFTs often exhibit bias instability. For synaptic memory applications, the programming transistors are predominantly exposed to asymmetric off‐state biases, and a unique field‐dependent on‐current reduction under off‐scenario is observed which may result in programming current variation. Further examination of the phenomenon is conducted with transmission line‐like method and degradation recovery tests, and current reduction can be attributed to contact resistance increase by charge trapping in the source and drain electrode and the channel region. The current decrease is subsequently formulated with a stretched exponential model with bias‐dependent parameters for quantitative circuit analysis under off‐state degradation. A neural network hardware acceleration simulator is utilized to assess the complicated impact the off‐state current degradation could instigate on on‐chip trainable IGZO TFT‐based synapse arrays. The simulation results generally demonstrate deteriorated training accuracy with aggravated off‐state instability, and the accuracy trend is elucidated from the perspective of weight symmetry point.
Achieving Near‐Ideal Subthreshold Swing in P‐Type WSe2 Field‐Effect Transistors
Authors: Ali Fida , Choi Hyungyu , Ali Nasir , Hassan Yasir , Ngo Tien Dat , Ahmed Faisal , Park Won‐Kyu , Sun Zhipei , Yoo Won Jong
Published: May 2024

The pursuit of near‐ideal subthreshold swing (SS) ≈ 60 mV dec−1 is a primary driving force to realize the power‐efficient field‐effect transistors (FETs). This challenge is particularly pronounced in 2D material‐based FETs, where the presence of a large interface trap density (Dit) imposes limitations on electrostatic control, consequently escalating power consumption. In this study, the gate controllability of 2D FETs is systematically analyzed by fabricating pre‐patterned van der Waals (vdW)‐contacted p‐FETs, varying the WSe2 channel thickness from monolayer to ten‐layer. As a result, the channel thickness is optimized to achieve efficient gate controllability while minimizing Dit. The findings demonstrate negligible hysteresis and excellent subthreshold swing (SSmin) close to the thermal limit (≈60 mV dec−1), with a corresponding Dit of ≈1010 cm−2 eV−1, comparable to Dit values observed in state‐of‐the‐art Si transistors, when utilizing WSe2 channel thicknesses ≥ five‐layer. However, reducing the WSe2 channel thickness below the trilayer, SSmin (≈91 mV dec−1) deviates from the thermal limit, attributed to a comparatively higher Dit (≈1011 cm−2 eV−1), despite the still lower than values reported for surface‐contacted 2D transistors. Furthermore, all devices exhibit consistent p‐type characteristics, featuring a high ION/IOFF ratio, high mobility, and excellent electrical stability confirmed over several months.
Long‐term exposure to air pollution and road traffic noise and incidence of dementia in the Danish Nurse Cohort
Authors: Tuffier Stéphane , Zhang Jiawei , Bergmann Marie , So Rina , Napolitano George Maria , Cole‐Hunter Thomas , Maric Matija , Antic Sonja , Brandt Jørgen , Ketzel Matthias , Loft Steffen , Lim Youn‐Hee , Andersen Zorana Jovanovic
Published: May 2024

INTRODUCTION

We examined the association of long‐term exposure to air pollution and road traffic noise with dementia incidence in the Danish Nurse Cohort.

METHODS

Female nurses were followed for dementia incidence (hospital contact or medication prescription) from 1993/1999 to 2020. Air pollution and road traffic noise levels were estimated at nurses’ residences, and their associations with dementia were examined using Cox regression models.

RESULTS

Of 25,233 nurses 1409 developed dementia. Particulate matter with a diameter of ≤2.5 µm (PM2.5) was associated with dementia incidence, after adjusting for lifestyle, socioeconomic status, and road traffic noise (hazard ratio [95% confidence interval] 1.35 [1.15–1.59] per interquartile range of 2.6 µg/m3). There was no association of PM2.5 with dementia in physically active nurses. Association with road traffic noise diminished after adjusting for PM₂.₅ (1.02 [0.93–1.11] per 7.6 dB).

DISCUSSION

Long‐term exposure to air pollution increases risk of dementia, and physical activity may moderate this risk.

Highlights

Long‐term exposure to air pollution was associated with increased risk of dementia among female nurses from the Danish Nurse Cohort.

Association of air pollution with dementia was independent of road traffic noise.

Association of road traffic noise with dementia diminished after adjusting for air pollution.

Physical activity moderated adverse effects of air pollution on dementia.
Blood biomarkers of Alzheimer's disease in the community: Variation by chronic diseases and inflammatory status
Authors: Valletta Martina , Vetrano Davide Liborio , Rizzuto Debora , Winblad Bengt , Canevelli Marco , Andersson Sarah , Dale Matilda , Fredolini Claudia , Fratiglioni Laura , Grande Giulia
Published: May 2024

INTRODUCTION

We explored the variations of blood biomarkers of Alzheimer's disease (AD) by chronic diseases and systemic inflammation.

METHODS

We explored the association of AD blood biomarkers with chronic diseases and systemic inflammation (interleukin‐6 [IL‐6]), in 2366 dementia‐free participants of the Swedish National Study on Aging and Care‐in Kungsholmen, using quantile regression models.

RESULTS

A greater number of co‐occurring chronic diseases was associated with higher concentrations of phosphorylated‐tau 181 (p‐tau181), total‐tau (t‐tau), neurofilament light chain (NfL), and glial fibrillary acidic protein (GFAP) (p < 0.01). Anemia, kidney, cerebrovascular, and heart diseases were associated with variations in the levels of AD blood biomarkers. Participants in the highest (vs. lowest) interleukin‐6 (IL‐6) tertile had higher NfL concentration. Systemic inflammation amplified the associations between several chronic diseases and p‐tau181, t‐tau, NfL, and GFAP.

DISCUSSION

In the community, the concentration of AD blood biomarkers varies in relation to medical conditions and systemic inflammation. Recognizing these influences is crucial for the accurate interpretation and clinical implementation of blood biomarkers.

Highlights

Participants with a complex clinical profile (i.e., multiple co‐occurring diseases or specific disease combinations) display elevated levels of AD blood‐biomarkers.

Anemia, heart, cerebrovascular, and kidney diseases are associated with variations is the levels of AD blood biomarkers in cognitively intact older adults.

Systemic inflammation amplifies the association between several chronic diseases and AD blood biomarkers.
A Bioorthogonal Dual Fluorogenic Probe for the Live‐Cell Monitoring of Nutrient Uptake by Mammalian Cells
Authors: Wang Yixuan , Torres‐García Diana , Mostert Thijmen P. , Reinalda Luuk , Van Kasteren Sander I.
Published: May 2024

Cells rely heavily on the uptake of exogenous nutrients for survival, growth, and differentiation. Yet quantifying the uptake of small molecule nutrients at the single cell level is difficult. Here we present a new approach to studying the nutrient uptake in live single cells using Inverse Electron‐Demand Diels Alder (IEDDA) chemistry. We have modified carboxyfluorescein‐diacetate‐succinimidyl esters (CFSE)—a quenched fluorophore that can covalently react with proteins and is only turned on in the cytosol of a cell following esterase activity—with a tetrazine. This tetrazine serves as a second quencher for the pendant fluorophore. Upon reaction with nutrients modified with an electron‐rich or strained dienophile in an IEDDA reaction, this quenching group is destroyed, thereby enabling the probe to fluoresce. This has allowed us to monitor the uptake of a variety of dienophile‐containing nutrients in live primary immune cell populations using flow cytometry and live‐cell microscopy.
Functionalization of Supramolecular Polymers by Dynamic Covalent Boroxine Chemistry
Authors: Preuss Marco D. , Schnitzer Tobias , Jansen Stef A. H. , Meskers Stefan C. J. , Kuster Tom H. R. , Lou Xianwen , Meijer E. W. , Vantomme Ghislaine
Published: May 2024

Molecular scaffolds that enable the combinatorial synthesis of new supramolecular building blocks are promising targets for the construction of functional molecular systems. Here, we report a supramolecular scaffold based on boroxine that enables the formation of chiral and ordered 1D supramolecular polymers, which can be easily functionalized for circularly polarized luminescence. The boroxine monomers are quantitatively synthesized in situ, both in bulk and in solution, from boronic acid precursors and cooperatively polymerize into 1D helical aggregates stabilized by threefold hydrogen‐bonding and π–π stacking. We then demonstrate amplification of asymmetry in the co‐assembly of chiral/achiral monomers and the co‐condensation of chiral/achiral precursors in classical and in situ sergeant‐and‐soldiers experiments, respectively, showing fast boronic acid exchange reactions occurring in the system. Remarkably, co‐condensation of pyrene boronic acid with a hydrogen‐bonding chiral boronic acid results in chiral pyrene aggregation with circularly polarized excimer emission and g‐values in the order of 10−3. Yet, the electron deficiency of boron in boroxine makes them chemically addressable by nucleophiles, but also sensitive to hydrolysis. With this sensitivity in mind, we provide first insights into the prospects offered by boroxine‐based supramolecular polymers to make chemically addressable, functional, and adaptive systems.
Circularly Polarized Room Temperature Phosphorescence through Twisting‐Induced Helical Structures from Polyvinyl Alcohol‐Based Fibers Containing Hydrogen‐Bonded Dyes
Authors: Liu Qin , Liu Xiaoqing , Yu Xiaoxiao , Zhang Xinhai , Zhu Meifang , Cheng Yanhua
Published: May 2024

Room temperature phosphorescence (RTP) materials have garnered significant attention owing to its distinctive optical characteristics and broad range of potential applications. However, the challenge remains in producing RTP materials with more simplicity, versatility, and practicality on a large scale, particularly in achieving chiral signals within a single system. Herein, we show that a straightforward and effective combination of wet spinning and twisting technique enables continuously fabricating RTP fibers with twisting‐induced helical chirality. By leveraging the hydrogen bonding interactions between polyvinyl alcohol (PVA) and quinoline derivatives, along with the rigid microenvironment provided by PVA chains, typically, Q‐NH2@PVA fiber demonstrates outstanding phosphorescent characteristics with RTP lifetime of 1.08 s and phosphorescence quantum yield of 24.6 %, and the improved tensile strength being 1.7 times than pure PVA fiber (172±5.82 vs 100±5.65 MPa). Impressively, the transformation from RTP to circularly polarized room temperature phosphorescence (CP‐RTP) is readily achieved by imparting left‐ or right‐hand helical structure through simply twisting, enabling large‐scale production of chiral Q‐NH2@PVA fiber with dissymmetry factor of 10−2. Besides, an array of displays and encryption patterns are crafted by weaving or seaming to exemplify the promising applications of these PVA‐based fibers with outstanding adaptivity in cutting‐edge anti‐counterfeiting technology.
Adaptive Reaktion bei der Lösung von flexiblen Molekülen: Oligohydrate von 4‐Hydroxy‐2‐butanon
Authors: Li Meng , Li Wenqin , Pérez Cristóbal , Lesarri Alberto , Grabow Jens‐Uwe
Published: May 2024

Durch Wasser hervorgerufene Strukturveränderungen spielen eine zentrale Rolle in der Chemie und Biologie, sind aber auf molekularer Ebene nach wie vor schwer vorherzusagen, zu messen und zu kontrollieren. Hier untersuchen wir in der Gasphase die größenabhängige Wasseraggregation am flexiblen Molekül 4‐Hydroxy‐2‐butanon und modellieren die Konformationsanpassungsfähigkeit flexibler Substrate an Wirtswassergerüste, sowie die Präferenzen für sequentielles Tröpfchenwachstum. Das Experiment wurde mittels breitbandiger Rotationsspektroskopie durchgeführt und mit quantenchemischen Berechnungen nachvollzogen. Experimentell wurden vom Di‐ bis zum Pentahydrat (4‐Hydroxy‐2‐butanon‐(H2O)n=2–5) zwei verschiedene Isomere beobachtet, einschließlich der 18O‐Isotopologen für die Di‐ und Trihydrate. Um Wassermoleküle effektiv unterzubringen, verändert sich interessanterweise das schwere Atomgerüst von 4‐Hydroxy‐2‐butanon in jedem beobachteten Isomer und entspricht nicht der stabilen Konformation des freien Monomers. Alle Solvate gehen von der Alkoholgruppe (Protonendonor) aus, behalten aber die Carbonylgruppe als sekundären Bindungspunkt bei. Die Wassergerüste ähneln stark denen in reinen Wasserclustern und balancieren zwischen der Fähigkeit von 4‐Hydroxy‐2‐butanon, die Orientierung und Position der Wassermoleküle zu steuern, und der Fähigkeit von Wasser, die Konformation des Monomers zu modulieren. Die vorliegende Arbeit liefert somit eine genaue molekulare Beschreibung, wie sich torsionsflexible Moleküle im Verlauf der fortschreitenden Solvatation dynamisch an Wasser anpassen.
Cascaded *CO−*COH Intermediates on a Nonmetallic Plasmonic Photocatalyst for CO2‐to‐C2H6 with 90.6 % Selectivity
Authors: Ren Liteng , Yang Xiaonan , Sun Xin , Wang Yuling , Li Huiquan , Yuan Yupeng
Published: May 2024

Oxygen vacancies (OV) in nonmetallic plasmonic photocatalysts can decrease the energy barrier for CO2 reduction, boosting C1 intermediate production for potential C2 formation. However, their susceptibility to oxidation weakens C1 intermediate adsorption. Herein we proposed a “photoelectron injection” strategy to safeguard OV in W18O49 by creating a W18O49/ZIS (W/Z) plasmonic photocatalyst. Moreover, photoelectrons contribute to the local multi‐electron environment of W18O49, enhancing the intrinsic excitation of its hot electrons with extended lifetimes, as confirmed by in situ XPS and femtosecond transient absorption analysis. Density functional theory calculations revealed that W/Z with OV enhances CO2 adsorption, activating *CO production, while reducing the energy barrier for *COH production (0.054 eV) and subsequent *CO−*COH coupling (0.574 eV). Successive hydrogenation revealed that the free energy for *CH2CH2 hydrogenation (0.108 eV) was lower than that for *CH2CH2 desorption for C2H4 production (0.277 eV), favouring C2H6 production. Consequently, W/Z achieves an efficient C2H6 activity of 653.6 μmol g−1 h−1 under visible light, with an exceptionally high selectivity of 90.6 %. This work offers a new strategy for the rational design of plasmonic photocatalysts with high selectivity for C2+ products.
Oxidative Addition of E−H (E=C, N) Bonds to Transient Uranium(II) Centers
Authors: Fang Wei , Li Yafei , Zhang Tianze , Rajeshkumar Thayalan , del Rosal Iker , Zhao Yue , Wang Tianwei , Wang Shuao , Maron Laurent , Zhu Congqing
Published: May 2024

Two‐electron oxidative addition is one of the most important elementary reactions for d‐block transition metals but it is uncommon for f‐block elements. Here, we report the first examples of intermolecular oxidative addition of E−H (E=C, N) bonds to uranium(II) centers. The transient U(II) species was formed in‐situ by reducing a heterometallic cluster featuring U(IV)‐Pd(0) bonds with potassium‐graphite (KC8). Oxidative addition of C−H or N−H bonds to the U(II) centers was observed when this transient U(II) species was treated with benzene, carbazole or 1‐adamantylamine, respectively. The U(II) centers could also react with tetracene, biphenylene or N2O, leading to the formation of arene reduced U(IV) products and uranyl(VI) species via two‐ or four‐electron processes. This study demonstrates that the intermolecular two‐electron oxidative addition reactions are viable for actinide elements.
Unlocking the NIR‐II AIEgen for High Brightness through Intramolecular Electrostatic Locking
Authors: Wang Xinyuan , Yang Xueqin , Jiang Guanyu , Hu Zhubin , Liao Tao , Wang Guoxin , Zhang Xun , He Xinyuan , Zhang Jianyu , Zhang Jianquan , Cao Wuke , Zhang Kaizhen , Lam Jacky W. Y. , Sun Jianwei , Sun Haitao , Liang Yongye , Tang Ben Zhong
Published: May 2024

Fluorescent imaging and biosensing in the near‐infrared‐II (NIR‐II) window holds great promise for non‐invasive, radiation‐free, and rapid‐response clinical diagnosis. However, it's still challenging to develop bright NIR‐II fluorophores. In this study, we report a new strategy to enhance the brightness of NIR‐II aggregation‐induced emission (AIE) fluorophores through intramolecular electrostatic locking. By introducing sulfur atoms into the side chains of the thiophene bridge in TSEH molecule, the molecular motion of the conjugated backbone can be locked through intramolecular interactions between the sulfur and nitrogen atoms. This leads to enhanced NIR‐II fluorescent emission of TSEH in both solution and aggregation states. Notably, the encapsulated nanoparticles (NPs) of TSEH show enhanced brightness, which is 2.6‐fold higher than TEH NPs with alkyl side chains. The in vivo experiments reveal the feasibility of TSEH NPs in vascular and tumor imaging with a high signal‐to‐background ratio and precise resection for tiny tumors. In addition, polystyrene nanospheres encapsulated with TSEH are utilized for antigen detection in lateral flow assays, showing a signal‐to‐noise ratio 1.9‐fold higher than the TEH counterpart in detecting low‐concentration antigens. This work highlights the potential for developing bright NIR‐II fluorophores through intramolecular electrostatic locking and their potential applications in clinical diagnosis and biomedical research.
Photocatalytic activity of polyaniline‐potassium doped nickel oxide nanocomposites: A comprehensive investigation on multifaceted properties
Authors: Bhankhar Anupama , Saini Monika , Sehrawat Swati , Shukla Rajni
Published: May 2024

Polyaniline‐potassium doped nickel oxide nanocomposites (PANI/KNO) were efficiently synthesized via an in situ chemical oxidation method, meticulously confirmed by comprehensive x‐ray diffraction, Fourier transformation infrared spectroscopy, energy dispersive x‐ray spectroscopy, selected area electron diffraction, and x‐ray photoelectron spectroscopy analyses. The crystallite size and strain exhibited distinct behaviors, while field emission scanning electron microscopy revealed a blend of irregular spherical shapes and nanofibers, further confirmed by high resolution transmission electron microscopy. These composites exhibited significantly enhanced thermal stability, surpassing PANI by 1.39 times, and showcased a band gap exceeding 3 eV, along with multiple photoluminescence peaks at room temperature (RT). Moreover, their RT AC conductivity experienced a remarkable surge by 4.91 times compared to pure polyaniline. Jonscher's Power Law model and the Havriliak–Negami relaxation model are employed to elucidate the electrical properties of composite materials. The composites displayed nonDebye relaxation behavior with increased conductivity, as observed through impedance analysis, electrical modulus evaluation, and dielectric constant assessment. Additionally, evident superparamagnetic properties and multiple magnetic domains further contributed to their effectiveness. The PANI/KNO composite demonstrated photocatalytic efficiency, achieving over 90% degradation of methylene blue dye across four cycles, thus highlighting its superior photostability. Furthermore, investigations into its response to pH variations and scavenger activity underscored its immense potential for highly effective photocatalytic applications.
Enhancing the strength and toughness of polylactic acid through fused deposition modeling‐induced orientation and nucleation effects of attapulgite
Authors: Ni Yinxu , Gao Qingqing , Hao Zhilei , Liu Pei , Xu Kai , Fu Yan , Xu Gaojie , Zhu Liangzhu , Liu Fenghua
Published: May 2024

Simultaneously enhancing strength and toughness through simple and low‐cost methods has always been a challenge for polylactic acid (PLA) materials. In this context, natural attapulgite (ATT) nanorods were used as fillers combined with fused deposition modeling (FDM) to improve the strength and toughness of PLA. The printable PLA nanocomposite filaments filled with ATT nanorods were prepared by melting compounding and smoothly printed via a commercial FDM three‐dimensional (3D) printer. The influences of FDM process and ATT filling on the properties of PLA/ATT composite parts were evaluated through microstructure analysis, rheological, and mechanical tests. The results suggest that PLA/ATT composite parts manufactured by FDM exhibit superior mechanical properties, which can be attributed to the FDM induced orientation and nucleation effect of ATT nanorods. The tensile strength can reach 56 MPa with the addition of 2 wt% ATT at a nozzle temperature of 205°C, increasing by 24% compared to pure PLA. In addition, the fracture elongation of PLA/ATT parts printed by FDM has significantly increased to 26%, which is 924% higher than pure PLA. Furthermore, the filling of ATT significantly improves the storage modulus of composite parts. This work provides a new high‐strength, ultra tough, low‐cost, and printing stable PLA/ATT composite material and forming method, offering a promising avenue for the wider application of PLA and ATT in the future.
A systematic comparative description of extant turtle humeri, with comments on humerus disparity and evolution based on fossil comparisons
Authors: Hermanson Guilherme , Arnal Fernando A. M. , Szczygielski Tomasz , Evers Serjoscha W.
Published: May 2024

The humerus is central for locomotion in turtles as quadrupedal animals. Osteological variation across testudine clades remains poorly documented. Here, we systematically describe the humerus anatomy for all major extant turtle clades based on 38 species representing the phylogenetic and ecological diversity of crown turtles. Three Late Triassic species of shelled stem turtles (Testudindata) are included to establish the plesiomorphic humerus morphology. Our work is based on 3D models, establishing a publicly available digital database. Previously defined terms for anatomical sides of the humerus (e.g., dorsal, ventral) are often not aligned with the respective body sides in turtles and other quadrupedal animals with sprawling gait. We propose alternative anatomical directional terms to simplify communication: radial and ulnar (the sides articulating with the radius/ulna), capitular (the side bearing the humeral head), and intertubercular (opposite to capitular surface). Turtle humeri show low morphological variation with exceptions concentrated in locomotory specialists. We propose 15 discrete characters to summarize osteological variation for future phylogenetic studies. Disparity analyses comparing non‐shelled and shelled turtles indicate that the presence of the shell constrains humerus variation. Flippered aquatic turtles are released from this constraint and significantly increase overall disparity. Ontogenetic changes of turtle humeri are related to increased ossification and pronunciation of the proximal processes, the distal articulation areas, and the closure of the ectepicondylar groove to a foramen. Some turtle species retain juvenile features into adulthood and provide evidence for paedomorphic evolution. We review major changes of turtle humerus morphology throughout the evolution of its stem group.
Sustainable Synthesis through Catalyst‐Free Photoinduced Cascaded Bond Formation
Authors: Bhanja Rosalin , Kanti Bera Shyamal , Mal Prasenjit
Published: May 2024

The beginning of photochemical reactions revolutionized synthetic chemistry through sustainable practices. This review explores cutting‐edge developments in leveraging light‐induced processes for generating cascaded C−C and C‐hetero bonds without catalysts. Significantly, catalyst‐free photoinduced methodologies have garnered considerable attention, especially in the creation of varied heterocyclic frameworks for drug design and the synthesis of natural products. The article delves into underlying mechanisms, addresses limitations, and evaluates various methodologies, emphasizing the potential of photocatalyst and transition metal‐free photochemical reactions to enhance sustainability. Divided into two sections, it covers recent strides in C−C and C‐heteroatom and multiple C‐heteroatom bond formation reactions.
Is she still angry? Intact learning but no updating of facial expressions priors in autism
Authors: Twito Renana , Hadad Bat‐Sheva , Szpiro Sarit
Published: May 2024

Autistic people exhibit atypical use of prior information when processing simple perceptual stimuli; yet, it remains unclear whether and how these difficulties in using priors extend to complex social stimuli. Here, we compared autistic people without accompanying intellectual disability and nonautistic people in their ability to acquire an “emotional prior” of a facial expression and update this prior to a different facial expression of the same identity. Participants performed a two‐interval same/different discrimination task between two facial expressions. To study the acquisition of the prior, we examined how discrimination was modified by the contraction of the perceived facial expressions toward the average of presented stimuli (i.e., regression to the mean). At first, facial expressions surrounded one average emotional prior (mostly sad or angry), and then the average switched (to mostly angry or sad, accordingly). Autistic people exhibited challenges in facial discrimination, and yet acquired the first prior, demonstrating typical regression‐to‐the‐mean effects. However, unlike nonautistic people, autistic people did not update their perception to the second prior, suggesting they are less flexible in updating an acquired prior of emotional expressions. Our findings shed light on the perception of emotional expressions, one of the most pressing challenges in autism.
Baugruben im Grundwasser – Empfehlungen des Arbeitskreises „Baugruben“ (EAB)
Authors: Hettler Achim
Published: May 2024

Der Beitrag behandelt die Entwicklung der Sicherheitsnachweise bei Baugruben im Grundwasser von den Anfängen Ende der 1960er‐Jahre bis heute. Maßgebendes Regelwerk sind die Empfehlungen des Arbeitskreises „Baugruben“ (EAB), mittlerweile mit der 6. Auflage. Eingegangen wird nicht nur auf die EAB selbst, sondern auch auf die maßgebende Literatur.
Effects of educational disruption and changes in school context on children's mental health: Associations with school level disadvantage and individual bullying involvement
Authors: Badger Julia R. , Holst Carolina Guzman , Thompson Paul , Bowes Lucy , Hayes Rachel , Clarkson Susy , Hutchings Judy , Hastings Richard P.
Published: May 2024

Natural disasters happen across the world. The situations are different but the disruption to children's education and wellbeing is similar. This study focused on the school context changes caused by the COVID‐19 global disaster, and the impact of these changes on children's mental health. The aim was to better understand the associations between any mental health changes and children's school level of deprivation and pre‐disaster involvement in bullying. Cross‐sectional data were collected from 4316 children aged 6–11 years old, from 57 schools across England and Wales. Data were collected before the national lockdowns, early 2020, and 3–5 months after the final return to school, summer 2021, when schools were operating under a range of context restrictions. Child data included bullying involvement at school and health‐related quality of life; teacher data included reports of each child's internalising, externalising and prosocial behaviours. School‐level disadvantage was determined by the proportion of children in each school eligible to receive free school meals (an indicator of family disadvantage). The results showed that victims of bullying pre‐lockdown, and pupils from schools with a higher concentration of disadvantage, had significantly reduced externalising behaviours once back in the restricted school context. Victims had also increased their prosocial behaviours. It is possible that the restricted school context may have been a relief for the most vulnerable pupils. This study adds a new phase of understanding to the global disaster literature and the initial return to school when the environment is the same but the context has changed.
Clinical value of video oculomotor evaluation in the differential diagnosis of multiple system atrophy and Parkinson's disease
Authors: Zhou Dongxiao , Ma Qian , Huang Haiwei , Xu Xue
Published: May 2024

Background

Multiple system atrophy (MSA) is a neurodegenerative disease that progresses rapidly and has a poor prognosis. This study aimed to assess the value of video oculomotor evaluation (VOE) in the differential diagnosis of MSA and Parkinson's disease (PD).

Methods

In total, 28 patients with MSA, 31 patients with PD, and 30 age‐ and sex‐matched healthy controls (HC) were screened and included in this study. The evaluation consisted of a gaze‐holding test, smooth pursuit eye movement (SPEM), random saccade, and optokinetic nystagmus (OKN).

Results

The MSA and PD groups had more abnormalities and decreased SPEM gain than the HC group (64.29%, 35.48%, 10%, p < .001). The SPEM gain in the MSA group was significantly lower than that in the PD group at specific frequencies. Patients with MSA and PD showed prolonged latencies in all saccade directions compared with those with HC. However, the two diseases had no significant differences in the saccade parameters. The OKN gain gradually decreased from the HC to the PD and the MSA groups (p < .05). Compared with the PD group, the gain in the MSA group was further decreased in the OKN test at 30°/s (Left, p = .010; Right p = .016). Receiver operating characteristic curves showed that the combination of oculomotor parameters with age and course of disease could aid in the differential diagnosis of patients with MSA and PD, with a sensitivity of 89.29% and a specificity of 70.97%.

Conclusions

The combination of oculomotor parameters and clinical data may aid in the differential diagnosis of MSA and PD. Furthermore, VOE is vital in the identification of neurodegenerative diseases.
Investigation of the effectiveness of sound enrichment in the treatment of tinnitus due to hearing loss
Authors: Sendesen Eser , Turkyilmaz Didem
Published: May 2024

Objective

In previous animal studies, sound enhancement reduced tinnitus perception in cases associated with hearing loss. The aim of this study was to investigate the efficacy of sound enrichment therapy in tinnitus treatment by developing a protocol that includes criteria for psychoacoustic characteristics of tinnitus to determine whether the etiology is related to hearing loss.

Methods

A total of 96 patients with chronic tinnitus were included in the study. Fifty‐two patients in the study group and 44 patients in the placebo group considered residual inhibition (RI) outcomes and tinnitus pitches. Both groups received sound enrichment treatment with different spectrum contents. The tinnitus handicap inventory (THI), visual analog scale (VAS), minimum masking level (MML), and tinnitus loudness level (TLL) results were compared before and at 1, 3, and 6 months after treatment.

Results

There was a statistically significant difference between the groups in THI, VAS, MML, and TLL scores from the first month to all months after treatment (p < .01). For the study group, there was a statistically significant decrease in THI, VAS, MML, and TLL scores in the first month (p < .01). This decrease continued at a statistically significant level in the third month of posttreatment for THI (p < .05) and at all months for VAS‐1 (tinnitus severity) (p < .05) and VAS‐2 (tinnitus discomfort) (p < .05).

Conclusion

In clinical practice, after excluding other factors related to the tinnitus etiology, sound enrichment treatment can be effective in tinnitus cases where RI is positive and the tinnitus pitch is matched with a hearing loss between 45 and 55 dB HL in a relatively short period of 1 month.
Morphology of the dysplastic hip and the relationship with sex and acetabular version
Authors: Mechlenburg Inger , De Raedt Sepp , Achterberg Hakim C. , Stilling Maiken , Rømer Lone , Søballe Kjeld , de Bruijne Marleen
Published: May 2024

The dysplastic hip is characterized by incomplete coverage of the femoral head, resulting in increased risk of early osteoarthritis. The morphological variation of the hip joint is diverse and clear differences exist between females and males. The aim of this observational study was therefore to investigate the relationship between the morphology of the hip, sex, and hip dysplasia using a three‐dimensional model. Statistical shape models of the combined femur and pelvic bones were created from bilateral hips of 75 patients. Using manual angle measurements and regression analysis, the characteristic shape differences associated with sex and hip dysplasia were determined. The model showed clear differences associated with sex and hip dysplasia. We found that the acetabular anteversion in females was significantly higher (p < 0.0001) than in males while no significant difference in acetabular anteversion was found between normal and dysplastic hips (p = 0.11). The model showed that decreased acetabular anteversion resulted in the appearance of the cross‐over sign and the prominent ischial spine sign commonly associated with retroversion. Sex could be predicted with an area under the curve of 0.99 and hip dysplasia could be predicted with an area under the curve of ≥0.73. Our findings suggest that retroversion is a result of decreased anteversion of the acetabulum and is primarily associated with sex. This finding should be taken into account during the reorientation of the acetabulum in the surgical treatment of hip dysplasia.
Converting “cold” to “hot”: epigenetics strategies to improve immune therapy effect by regulating tumor‐associated immune suppressive cells
Authors: Tang Yijia , Cui Guangzu , Liu Haicong , Han Ying , Cai Changjing , Feng Ziyang , Shen Hong , Zeng Shan
Published: May 2024

Significant developments in cancer treatment have been made since the advent of immune therapies. However, there are still some patients with malignant tumors who do not benefit from immunotherapy. Tumors without immunogenicity are called “cold” tumors which are unresponsive to immunotherapy, and the opposite are “hot” tumors. Immune suppressive cells (ISCs) refer to cells which can inhibit the immune response such as tumor‐associated macrophages (TAMs), myeloid‐derived suppressor cells (MDSCs), regulatory T (Treg) cells and so on. The more ISCs infiltrated, the weaker the immunogenicity of the tumor, showing the characteristics of “cold” tumor. The dysfunction of ISCs in the tumor microenvironment (TME) may play essential roles in insensitive therapeutic reaction. Previous studies have found that epigenetic mechanisms play an important role in the regulation of ISCs. Regulating ISCs may be a new approach to transforming “cold” tumors into “hot” tumors. Here, we focused on the function of ISCs in the TME and discussed how epigenetics is involved in regulating ISCs. In addition, we summarized the mechanisms by which the epigenetic drugs convert immunotherapy‐insensitive tumors into immunotherapy‐sensitive tumors which would be an innovative tendency for future immunotherapy in “cold” tumor.