bluuebunny/crossref_metadata_2025 huggingface dataset:
Impact of Various Land Use Systems on Nitrogen Dynamics: A Review
Authors: Biradar Sayali , Thakare Ritu , Kamble B. M.
Published: January 2024

Rapid and unregulated conversion of agricultural fields into non-agricultural lands is becoming a major concern in many countries. The shortage of cultivable lands will make it harder to achieve ever-increasing food demands in upcoming years. Assessing land use-induced changes in soil nitrogen is essential for addressing agroecosystem transformation and sustainable land productivity issues. Numerous studies have shown that land use pattern has a significant effect on nitrogen storage and turnover along with varied degrees of mineralization rate and nitrogen forms present. The content of nitrogen fraction can be used as an indicator of the rate of mineralization and eventually microbial richness of soils. As per the study, it is observed that inorganic nitrogen fractions constitute hardly 1-2% of total nitrogen, whereas organic nitrogen takes up almost 98-99% of total nitrogen that is majorly sourced from organic residues in soils. The exchangeable NO3-N and exchangeable NH3-N are majorly plant-utilizable, easily mineralized forms whereas only amino acid-N has been proved to be directly utilizable organic nitrogen form. Even today large number of producers are dependent on synthetic nitrogen sources for crop production. Improving nitrogen use efficiency by reducing the natural losses and improving the inherent mineralization rate of organic nitrogen might help lower fertilizer dependency and so the cost of production.  In this paper, soil inorganic and organic nitrogen contents, types, and its contribution to plant production are reviewed to explore the exact role of nitrogen forms as influenced under different land use systems.
Image Based Authentication Using Zero-Knowledge Protocol
Authors: V. Samyadevi , S. Anguraj , G. Singaravel , S. Suganya
Published: January 2024

Numerous well-known Internet applications have been introduced as a result of technological advancements. E-banking, or mobile banking, is one such vital program that significantly affects our contemporary lives. Although banks urge customers to interact online, citing it as a secure method, the truth reveals serious risks involved. The ongoing expansion of mobile banking applications raises concerns about security and drives up the expense of putting strong security measures in place for banks and clients alike. This study explores potential compromises via methods like Trojan horses, botnets, and phishing as it dives into the weaknesses of mobile banking systems. Although multifactor authentication solutions are available to verify the authenticity of clients, their transaction-level focus exposes browsers and smart phones to man-in-the-middle attacks. This work recognizes the urgent need for improved security for mobile banking and offers a novel approach to authentication. The main focus is on a hybrid one-time password solution that combines SHA 256-bit encryption with random OTP. The suggested approach seeks to strengthen security at the transaction and authentication levels by integrating picture verification into the authentication procedure.
Practical Guide to Education Program Evaluation Research
Authors: de Moya Marc , Haukoos Jason S. , Itani Kamal M. F.
Published: January 2024

This Guide to Statistics and Methods describes common methods for building evidence of validity for a program within health professional education and provides a framework for program evaluation.
Selective Laser Sintering versus Multi Jet Fusion: A Comprehensive Comparison Study Based on the Properties of Glass Beads‐Reinforced Polyamide 12
Authors: Lupone Federico , Padovano Elisa , Lambertini Vito Guido , Sampieri Roberta , Casamento Francesco , Zecchi Silvia , Badini Claudio
Published: January 2024

Selective laser sintering (SLS) and multi jet fusion (MJF) are the most widespread powder bed fusion additive manufacturing techniques for fabricating polymeric parts since they offer great design flexibility, productivity, and geometrical accuracy. However, these technologies differ in the thermal energy source used to melt the powders as well as the innovative use of printing agents featured in the latter one to promote material consolidation and to avoid thermal bleeding at the part contours. The use of a single powder made of glass beads‐reinforced polyamide 12 (PA12/GB) for the fabrication of MJF and SLS samples makes possible a systematic comparison of the printed parts properties. A thoughtful analysis of the microstructure and mechanical properties of the samples reveals differences and peculiarities between the two technologies. SLS exhibits lower porosity and higher mechanical performances when the parts are printed along the build plane thanks to the powerful heating ensured by the laser. In contrast, MJF samples show higher mechanical isotropy with great flexural and tensile behavior for vertically oriented parts. The role of glass beads in the material behavior is defined by their mechanical properties, meaning higher rigidity and lower strength compared to neat PA12, and fracture mechanism.
Low‐Roughness 3D‐Printed Surfaces by Ironing for the Integration with Printed Electronics
Authors: Neuhaus Benno , Idris Mohamad Kannan , Naderi Paria , El‐Hajj Yoland , Grau Gerd
Published: January 2024

The roughness of 3D‐printed surfaces poses a challenge when integrating fused filament fabrication (FFF) printing with printed electronics, leading to inconsistencies and breaks in the circuit traces. To improve the surface roughness, an ironing toolpath is proposed. The ironing toolpath involves the hot nozzle going over the printed surface with finer line spacing, remelting the surface to fill gaps, and creating a smooth finish. For further optimization, various ironing parameters are investigated including flow, speed, line spacing, and temperature. A wide range of materials is tested, including commonly used low‐temperature filaments (polylactic acid, polyethylene terephthalate, acrylonitrile butadiene styrene) and high‐temperature filaments (polysulfone, polyetherimide, polyether ether ketone) suitable for integration with printed electronics and medical applications. To collect the extensive datasets, an automated measurement system is deployed. With this method, surface roughness reductions of up to 96.6% are achieved and significant trends are identified. Lastly, the integration of 3D printing with electronics is demonstrated by printing a high‐resolution strain gauge structure on top of an ironed surface and embedding it into fully printed tweezers which can be used in medical robotics. The insights on ironing extend beyond electronics and can also be valuable in other areas where low surface roughness of FFF‐printed parts is required.
High Speed Dual‐Band Photodetector for Dual‐Channel Optical Communications in Wavelength Division Multiplexing and Security Enhancement
Authors: Wang Zhaoming , Gao Yu , Li Yibin , Yan Hao , Kang Feiyu , Shen Yang , Zhang Xiao‐Ping , Wei Guodan , Fu Hongyan
Published: January 2024

The forthcoming wireless networks must integrate to a high density of end‐user devices while ensuring a superior quality of service. It is imperative to devise solutions that reduce the density of wireless access points and associated costs, while simultaneously ensuring security and privacy throughout propagation. Herein, a novel dual‐band photodetector with high selective responsivities in distinct visible and near‐infrared (NIR) band is developed as an optical signal receiver. The receiver has an unprecedented fast switch speed > 500 kHz between different operation modes. Leveraging this fast switch speed, a high‐speed Multiple‐Input‐Single‐Output (MISO) system is developed, fusing spectrum resources from visible to infrared bands. The system achieves a data rate of 600 Kbps in the visible channel and 500 Kbps in the NIR channel, with a sum rate of 1.1 Mbps. This is the highest single‐channel data rate and sum rate among reported dual‐band photodetectors. Additionally, two previously overlooked mechanisms, the Subtraction and Addition modes, are studied in detail. The four operation modes are developed to establish a novel physical encryption method in terms of arithmetic relation. The dual‐channel coupled link can support a data rate of 200 Kbps, significantly enhancing communication security.
A Freeze‐Resistant, Highly Stretchable and Biocompatible Organohydrogel for Non‐Delayed Wearable Sensing at Ultralow‐Temperatures
Authors: Huang Xinxin , Zheng Zhihao , Wang Haiqi , Xu Weipeng , Wu Ming , Wang Minyan , Chen Canwen , Wan Lu , Du Ruichun , Zhu Tangsong , Huang Zhiyi , Wang Xiaoliang , Wang Xiaofeng , Zhang Qiuhong , Jia Xudong
Published: January 2024

Wearable electronics based on conductive hydrogels (CHs) easily suffer from prolonged response times, reduced wearing comfort, shortened service lives, and impaired signal accuracy in cold environments, because conventional CHs tend to freeze at subzero temperatures and lose their flexibility, adhesion, transparency, and conductivity, which will limit their applications in extreme environments. Inspired by the way psychrotolerant creatures and superabsorbent materials interfere with the hydrogen bonding networks of water, a freeze‐resistant conductive organohydrogel (COH) is facilely fabricated. The synergy effect between charged polar terminal groups and a binary solvent system of water–ethylene glycol weakens the hydrogen bonding between water molecules and endows the COH with remarkable freezing tolerance (−78 °C). Additionally, the obtained COH is ultra‐stretchable (≈6185%), tough (9.2 MJ m−3), highly transparent (≈99%), self‐adhesive (10.2–27.8 kPa), and biocompatible. This versatile COH is assembled into a strain sensor and a well‐designed bracelet electrocardiogram sensor. Benefiting from the exceptional low‐temperature tolerance of the prepared COH, these devices exhibit fast response with delay‐free signals even at −40 °C. Overall, this work proposes a strategy to develop multifunctional COHs for supporting human health in cold environments.
Asymmetric Charge Distribution of Active Centers in Small Molecule Quinone Cathode Boosts High‐Energy and High‐Rate Aqueous Zinc‐Organic Batteries
Authors: Li Cuicui , Hu Liang , Ren Xiuyun , Lin Lu , Zhan Changzhen , Weng Qingsong , Sun Xiaoqi , Yu Xiaoliang
Published: January 2024

Small molecule quinone compounds are attractive cathode materials for rechargeable aqueous zinc‐organic batteries (AZOBs) because of their structural diversity and low‐cost merits. Among them, nonpolar quinones are dominant given the relatively low solubilities in aqueous electrolytes. However, their poor electronic conductivity and accumulated Coulombic repulsion lead to underutilized active sites and sluggish redox kinetics. Here, polar 2,6‐dimethoxy‐1,4‐benzoquinone (m‐DMBQ) works as an advanced AZOB cathode with unexpectedly superior performance over the nonpolar isomer of 2,5‐dimethoxy‐1,4‐benzoquinone (p‐DMBQ). The asymmetric charge distribution of active centers in the p−π conjugated backbone of m‐DMBQ induces reduced bandgap with improved electronic conductivity and redox activity, thus achieving a high specific capacity of 312 mAh g−1 approaching the theoretical limit. Additionally, the lowest unoccupied molecular orbital energy level is lowered for an increased average discharge voltage of 0.88 V. Characterizations and computational studies revealed boosted competitiveness of H+ relative to Zn2+ for significantly enhanced charge transfer kinetics and reversibility. As a result, the as‐fabricated AZOB achieves a high energy density of 275 Wh kg−1 based on m‐DMBQ along with high‐rate capability and long‐term cycling stability. This work provides a new molecular engineering strategy through regulating charge distribution symmetry for boosting charge storage in organic cathodes.
Accelerating Hydrogen Desorption of Nickel Molybdenum Cathode via Copper Modulation for Pure‐Water‐Fed Hydroxide Exchange Membrane Electrolyzer
Authors: Yang Shengxiong , Zhang Zheye , Oliveira Alexandra M. , Xi Shibo , Zhiani Mohammad , Zhang Jian , Tu Zhengkai , Xiao Fei , Wang Shuai , Yan Yushan , Xiao Junwu
Published: January 2024

The more sluggish kinetics of hydrogen evolution catalysts in base as compare to that in acid to some degree restricts hydrogen production performance of hydroxide exchange membrane electrolyzers, especially when using earth‐abundant catalysts. Here a ternary nickel–copper–molybdenum hydrogen evolution catalyst is reported that exhibits ≈5 times higher turnover frequency than without copper doping. The X‐ray absorption near‐edge structure and valence band spectrum demonstrate that the light doping of copper into nickel–molybdenum alloy modulates the electronic structure and downshifts the d‐band center, resulting in accelerated hydrogen desorption, as consolidated by H2 temperature programmed desorption and theoretical calculation. An electrolyzer employing this cathode catalyst and a nickel–iron anode, gives a current density of 1.7 A cm−2 at 2.0 V with a pure‐water feed through the anode, which outperforms the 2025 target proposed by the United States Department of Energy, and even is operated continuously for over 1000 h with a decay rate of as low as 0.5 mV h−1. Post‐mortem analysis discloses that hydroxide exchange ionomer migration is one of the key factors affecting long‐term durability. This work demonstrates the feasibility of a low‐cost, water‐fed hydroxide exchange membrane electrolyzer achieving industrial‐level performance and lifetime.
Memristor‐Based Neuromorphic Chips
Authors: Duan Xuegang , Cao Zelin , Gao Kaikai , Yan Wentao , Sun Siyu , Zhou Guangdong , Wu Zhenhua , Ren Fenggang , Sun Bai
Published: January 2024

In the era of information, characterized by an exponential growth in data volume and an escalating level of data abstraction, there has been a substantial focus on brain‐like chips, which are known for their robust processing power and energy‐efficient operation. Memristors are widely acknowledged as the optimal electronic devices for the realization of neuromorphic computing, due to their innate ability to emulate the interconnection and information transfer processes witnessed among neurons. This review paper focuses on memristor‐based neuromorphic chips, which provide an extensive description of the working principle and characteristic features of memristors, along with their applications in the realm of neuromorphic chips. Subsequently, a thorough discussion of the memristor array, which serves as the pivotal component of the neuromorphic chip, as well as an examination of the present mainstream neural networks, is delved. Furthermore, the design of the neuromorphic chip is categorized into three crucial sections, including synapse‐neuron cores, networks on chip (NoC), and neural network design. Finally, the key performance metrics of the chip is highlighted, as well as the key metrics related to the memristor devices are employed to realize both the synaptic and neuronal components.
Wearable Sensors for Breath Monitoring Based on Water‐Based Hexagonal Boron Nitride Inks Made with Supramolecular Functionalization
Authors: Chen Liming , Hu Kui , Lu Mingyang , Chen Ziqi , Chen Xiwen , Zhou Tianqi , Liu Xuqing , Yin Wuliang , Casiraghi Cinzia , Song Xiuju
Published: January 2024

Wearable humidity sensors are attracting strong attention as they allow for real‐time and continuous monitoring of important physiological information by enabling activity tracking as well as air quality assessment. Amongst 2Dimensional (2D) materials, graphene oxide (GO) is very attractive for humidity sensing due to its tuneable surface chemistry, high surface area, processability in water, and easy integration onto flexible substrates. However, strong hysteresis, low sensitivity, and cross‐sensitivity issues limit the use of GO in practical applications, where continuous monitoring is preferred. Herein, a wearable and wireless impedance‐based humidity sensor made with pyrene‐functionalized hexagonal boron nitride (h‐BN) nanosheets is demonstrated. The device shows enhanced sensitivity towards relative humidity (RH) (>1010 Ohms/%RH in the range from 5% to 100% RH), fast response (0.1 ms), no appreciable hysteresis, and no cross‐sensitivity with temperature in the range of 25–60 °C. The h‐BN‐based sensor is able to monitor the whole breathing cycle process of exhaling and inhaling, hence enabling to record in real‐time the subtlest changes of respiratory signals associated with different daily activities as well as various symptoms of flu, without requiring any direct contact with the individual.
Molecular Engineering of a Spider Silk and Mussel Foot Hybrid Protein Gives a Strong and Tough Biomimetic Adhesive
Authors: Yin Yin , Roas‐Escalona Nelmary , Linder Markus B.
Published: January 2024

High performance bio‐based materials are an important part of future sustainable technology, and engineered proteins provide excellent possibilities as functional polymers. Adhesives are widely needed for composite materials and biomimetic structures. In biological adhesives, two features have emerged as especially interesting—the role of coacervation and the presence of 3,4‐dihydroxyphenylalanine (DOPA). To study these, protein engineering is used to construct a hybrid silk‐mussel foot protein (mfp) adhesive. Tyr residues in the purified mfp are oxidized to DOPA and an encoded SpyCatcher‐Tag system allowed easy click‐chemistry to couple silk and mfp and to study the parts separately. The combined silk‐mfp protein have a strong tendency to coacervate. DOPA affected the properties of coacervates and increased adhesion by several ways of measuring. In lap shear testing, the combined mfp‐silk protein is superior to any of the components studied separately. Coacervation is suggested to contribute to the adhesion of silk‐mfp, and shows several features suggested to lead to the strength and toughness of natural adhesives. In the lap shear system, coacervation have a stronger overall effect on adhesion than the presence of DOPA. The results show that protein design provides a route toward high performance biosynthetic polymers and future sustainable materials.
Self‐Destructible Electromagnetic Interference Shielding Films
Authors: Zhou Yang , Pan Yamin , Liu Chuntai , Shen Changyu , Liu Xianhu
Published: January 2024

In response to the increasing utilization of communication technology, there is a growing need for electromagnetic interference (EMI) shielding materials to adapt to diverse application scenarios. In this study, the self‐destructible EMI shielding films (SEFs) that possess the unique capability to reduce conductivity and shielding efficiency through temperature elevation are introduced. The SEFs effectively fulfill the requirement of triggering EMI shielding failure under specific conditions, which can be achieved by simply spraying a mixture of thermally expandable microspheres (TEMs), conductive fillers, and resin substrates. The segregated structures resulting from the incorporation of TEMs confer exceptional electrical conductivity and superior EMI shielding performance at low conductive filler content. When the ambient temperature surpasses the glass transition temperature of the TEM shell, the thermally expandable characteristics cause a disruption in the conductive path of the SEFs, leading to a significant decline in shielding effectiveness. Additionally, the SEFs exhibit outstanding Joule heating effects (90 °C) at low voltage (1.5 V) within a brief time frame (10 s). Importantly, when employed as Joule heaters, the SEFs possess an intrinsic safety mechanism that automatically ceases operation in the event of circuit overload, thus minimizing any potential risks.
Antioxidant Activity via Free Radical Scavenging of Pitavastatin and Its Hydroxylated Derivatives: A Quantum Chemical Attempt Aiming to Assist Drug Development
Authors: Bâldea Ioan
Published: January 2024

Although experiments have long provided empirical evidence that statins can suppress various oxidation pathways, theoretical attempts to quantify the antioxidant activity of statins (read, atorvastatin ATV, the only one studied so far) are not published until last year. Extensive results reported here for pitavastatin (PVT) and derivatives include the thermodynamic antioxidant descriptors (bond dissociation enthalpy [BDE], adiabatic ionization potential [IP], proton dissociation enthalpy [PDE], proton affinity [PA], and electron transfer enthalpy [ETE]) related to the three antioxidant mechanisms (hydrogen atom transfer [HAT], stepwise electron transfer proton transfer [SETPT], sequential proton loss electron transfer [SPLET]). The particular emphasis is on the PVT's hydroxylated derivatives wherein a hydroxy group replaces a hydrogen atom either on the quinoline core (Q‐hydroxylated metabolites) or on the fluorophenyl ring (F‐hydroxylated metabolites). The calculations indicate that both the Q‐ and F‐hydroxylated derivatives possess antioxidant properties superior to the parent PVT molecule. Given the fact that, to the best of the knowledge, no experimental data for the antioxidant potency of PVT and its hydroxylated derivatives exist, this is a theoretical prediction for the validation of which it is aimed hereby to stimulate companion experimental in vivo and in vitro investigations and inspire pharmacologists in further drug developments.
OR11H1 Missense Variant Confers the Susceptibility to Vogt‒Koyanagi‒Harada Disease by Mediating Gadd45g Expression
Authors: Li Xingran , Wang Guoqing , Wang Xiaotang , Li Wanqian , Li Na , Liu Xianyang , Fan Wei , He Siyuan , Han Yue , Su Guannan , Cao Qingfeng , Yang Peizeng , Hou Shengping
Published: January 2024

Vogt‒Koyanagi‒Harada (VKH) disease is a severe autoimmune disease. Herein, whole‐exome sequencing (WES) study are performed on 2,573 controls and 229 VKH patients with follow‐up next‐generation sequencing (NGS) in a collection of 2,380 controls and 2,278 VKH patients. A rare c.188T>C (p Val63Ala) variant in the olfactory receptor 11H1 (OR11H1) gene is found to be significantly associated with VKH disease (rs71235604, Pcombined = 7.83 × 10−30, odds ratio = 3.12). Functional study showes that OR11H1‐A63 significantly increased inflammatory factors production and exacerbated barrier function damage. Further studies using RNA‐sequencing find that OR11H1‐A63 markedly increased growth arrest and DNA‐damage‐inducible gamma (GADD45G) expression. Moreover, OR11H1‐A63 activates the MAPK and NF‐κB pathways, and accelerates inflammatory cascades. In addition, inhibiting GADD45G alleviates inflammatory factor secretion, likely due to the regulatory effect of GADD45G on the MAPK and NF‐κB pathways. Collectively, this study suggests that the OR11H1‐A63 missense mutation may increase susceptibility to VKH disease in a GADD45G‐dependent manner.
Novel molecular mechanism in Malan syndrome uncovered through genome sequencing reanalysis, exon‐level Array, and RNA sequencing
Authors: Zhao Jian , Longo Nicola , Lewis Robert G. , Nicholas Thomas J. , Boyden Steven E. , Andrews Ashley , Larson Austin ,   Undiagnosed Diseases Network, Bayrak‐Toydemir Pinar , Botto Lorenzo D. , Mao Rong
Published: January 2024

The NFIX gene encodes a DNA‐binding protein belonging to the nuclear factor one (NFI) family of transcription factors. Pathogenic variants of NFIX are associated with two autosomal dominant Mendelian disorders, Malan syndrome (MIM 614753) and Marshall–Smith syndrome (MIM 602535), which are clinically distinct due to different disease‐causing mechanisms. NFIX variants associated with Malan syndrome are missense variants mostly located in exon 2 encoding the N‐terminal DNA binding and dimerization domain or are protein‐truncating variants that trigger nonsense‐mediated mRNA decay (NMD) resulting in NFIX haploinsufficiency. NFIX variants associated with Marshall–Smith syndrome are protein‐truncating and are clustered between exons 6 and 10, including a recurrent Alu‐mediated deletion of exons 6 and 7, which can escape NMD. The more severe phenotype of Marshall–Smith syndrome is likely due to a dominant‐negative effect of these protein‐truncating variants that escape NMD. Here, we report a child with clinical features of Malan syndrome who has a de novo NFIX intragenic duplication. Using genome sequencing, exon‐level microarray analysis, and RNA sequencing, we show that this duplication encompasses exons 6 and 7 and leads to NFIX haploinsufficiency. To our knowledge, this is the first reported case of Malan Syndrome caused by an intragenic NFIX duplication.
Accessing Functionalized Furans from Reacting Enynones and Enynals through Furyl Metal Carbenes
Authors: Cho Ho‐Jun , Kim Ju Hyun
Published: January 2024

Enynones and enynals represent donor‐type carbene precursors that efficiently form furyl metal carbenes via a catalytic intramolecular 5‐exo‐dig cyclization and rearrangement cascade, in a 100 % atom‐economical manner, using various metals. These furyl metal carbenes have been successfully utilized in numerous carbene reactions, including metal carbene X−H insertion, cyclopropanations, metathesis, and cross‐coupling, demonstrating a broad reaction scope and efficiency in constructing highly functionalized furans. Recent years have witnessed significant advancements in transformations involving furyl metal carbenes, especially in asymmetric carbene insertion reactions, domino reactions involving zwitterionic intermediates, various rearrangement strategies, and their application in synthesizing functional materials and drug candidates. In this review, we summarize recent progress in furyl metal carbene reactions generated from enynones and enynals, focusing on the synthesis of highly functionalized furans.
Strain‐modulated Ru‐O Covalency in Ru‐Sn Oxide Enabling Efficient and Stable Water Oxidation in Acidic Solution
Authors: Xu Yiming , Mao Zhixian , Zhang Jifang , Ji Jiapeng , Zou Yu , Dong Mengyang , Fu Bo , Hu Mengqing , Zhang Kaidi , Chen Ziyao , Chen Shan , Yin Huajie , Liu Porun , Zhao Huijun
Published: January 2024

RuO2 is one of the benchmark electrocatalysts used as the anode material in proton exchange membrane water electrolyser. However, its long‐term stability is compromised due to the participation of lattice oxygen and metal dissolution during oxygen evolution reaction (OER). In this work, weakened covalency of Ru−O bond was tailored by introducing tensile strain to RuO6 octahedrons in a binary Ru−Sn oxide matrix, prohibiting the participation of lattice oxygen and the dissolution of Ru, thereby significantly improving the long‐term stability. Moreover, the tensile strain also optimized the adsorption energy of intermediates and boosted the OER activity. Remarkably, the RuSnOx electrocatalyst exhibited excellent OER activity in 0.1 M HClO4 and required merely 184 mV overpotential at a current density of 10 mA cm−2. Moreover, it delivered a current density of 10 mA cm−2 for at least 150 h with negligible potential increase. This work exemplifies an effective strategy for engineering Ru‐based catalysts with extraordinary performance toward water splitting.
Dicarboxylic Acid‐Assisted Surface Oxide Removal and Passivation of Indium Antimonide Colloidal Quantum Dots for Short‐Wave Infrared Photodetectors
Authors: Zhang Yangning , Xia Pan , Rehl Benjamin , Parmar Darshan H. , Choi Dongsun , Imran Muhammad , Chen Yiqing , Liu Yanjiang , Vafaie Maral , Li Chongwen , Atan Ozan , Pina Joao M. , Paritmongkol Watcharaphol , Levina Larissa , Voznyy Oleksandr , Hoogland Sjoerd , Sargent Edward H.
Published: January 2024

Heavy‐metal‐free III–V colloidal quantum dots (CQDs) are promising materials for solution‐processed short‐wave infrared (SWIR) photodetectors. Recent progress in the synthesis of indium antimonide (InSb) CQDs with sizes smaller than the Bohr exciton radius enables quantum‐size effect tuning of the band gap. However, it has been challenging to achieve uniform InSb CQDs with band gaps below 0.9 eV, as well as to control the surface chemistry of these large‐diameter CQDs. This has, to date, limited the development of InSb CQD photodetectors that are sensitive to
1400 nm light. Here we adopt solvent engineering to facilitate a diffusion‐limited growth regime, leading to uniform CQDs with a band gap of 0.89 eV. We then develop a CQD surface reconstruction strategy that employs a dicarboxylic acid to selectively remove the native In/Sb oxides, and enables a carboxylate‐halide co‐passivation with the subsequent halide ligand exchange. We find that this strategy reduces trap density by half compared to controls, and enables electronic coupling among CQDs. Photodetectors made using the tailored CQDs achieve an external quantum efficiency of 25 % at 1400 nm, the highest among III–V CQD photodetectors in this spectral region.
Negative Lattice Expansion in an O3‐Type Transition‐Metal Oxide Cathode for Highly Stable Sodium‐Ion Batteries
Authors: Zhang Tong , Ren Meng , Huang Yaohui , Li Fei , Hua Weibo , Indris Sylvio , Li Fujun
Published: January 2024

The sodium extraction/insertion in layered transition‐metal oxide (TMO) cathode materials are typically accompanied by slab sliding and lattice changes, leading to microstructure destruction and capacity decay. Herein, negative lattice expansion is observed in an O3 type Ni‐based layered cathode of Na0.9Ni0.32Zn0.08Fe0.1Mn0.3Ti0.2O2 upon Na+ extraction. It is attributed to the weak Zn2+−O2− orbital hybridization and increased electron density of the surrounding oxygen for reinforced interlayer O−O repulsive force. This enables gliding of TMO slabs for the intergrowth phase transition of P3→OP2 to alleviate lattice strain with moderate lattice shrinkage, which exhibits general interslab spacings and volume changes as low as 2.4 % and 1.9 %, respectively. The strong Ti−O bonds accommodate the internal distortion of TMO6 octahedra due to the flexibility of TiO6 octahedra during cycling. These endow a high specific capacity of 144.9 mAh g−1 and excellent cycling performance of pouch‐type sodium‐ion batteries with 93 % capacity retention after 3600 cycles.
Spontaneous Symmetry Breaking of Achiral Molecules Leading to the Formation of Homochiral Superstructures that Exhibit Mechanoluminescence
Authors: Liu Zheng‐Fei , Ye Xin‐Yi , Chen Lihua , Niu Li‐Ya , Jin Wei Jun , Zhang Shaodong , Yang Qing‐Zheng
Published: January 2024

Chirality, with its intrinsic symmetry‐breaking feature, is frequently utilized in the creation of acentric crystalline functional materials that exhibit intriguing optoelectronic properties. On the other hand, the development of chiral crystals from achiral molecules offers a solution that bypasses the need for enantiopure motifs, presenting a promising alternative and thereby expanding the possibilities of the self‐assembly toolkit. Nevertheless, the rational design of achiral molecules that prefer spontaneous symmetry breaking during crystallization has so far been obscure. In this study, we present a series of six achiral molecules, demonstrating that when these conformationally flexible molecules adopt a cis‐conformation and engage in multiple non‐covalent interactions along a helical path, they collectively self‐assemble into chiral superstructures consisting of single‐handed supramolecular columns. When these homochiral supramolecular columns align in parallel, they form polar crystals that exhibit intense luminescence upon grinding or scraping. We therefore demonstrate our molecular design strategy could significantly increase the likelihood of symmetry breaking in achiral molecular synthons during self‐assembly, offering a facile access to novel chiral crystalline materials with unique optoelectronic properties.
Step‐growth Polymerization of Aziridines with Elemental Sulfur: Easy Access to Linear Polysulfides and Their Use as Recyclable Adhesives
Authors: Huang Huishan , Zheng Shuojia , Luo Jiye , Gao Liang , Fang Yanxiong , Zhang Zhen , Dong Jinxiang , Hadjichristidis Nikos
Published: January 2024

The bulk radical polymerization of bis(aziridine) with molten elemental sulfur resulted in brittle, cross‐linked polymers. However, when the bis(aziridine) was treated with elemental sulfur in the presence of an organobase, the ring‐opening reaction of aziridine with oligosulfide anions occurred, leading to the formation of linear polymers by step‐growth polymerization. These newly synthesized polymers possess repeating units containing a sulfonamide or amide functional moiety and oligosulfide bonds with an average sulfur segment of about two. A small molecular model reaction confirmed the nucleophilic addition reaction of elemental sulfur to aziridine. It was verified that S−S dynamic bond exchange takes place in the presence of an organic base within the linear chains. The mixture of the synthesized polysulfides with pyridine exhibits exceptional adhesive properties when applied to steel, and aluminum substrates. Notably, these prepared adhesives displayed good reusability due to the dynamic S−S exchange and complete recyclability due to their solution processability. This elemental sulfur‐involved polymerization approach represents an innovative method for the synthesis of advanced sulfur‐containing polymers, demonstrating the potential for various applications in adhesives and beyond.
Electronically Manipulated Molecular Strategy Enabling Highly Efficient Tin Perovskite Photovoltaics
Authors: Teng Tian‐Yu , Su Zhen‐Huang , Hu Fan , Chen Chun‐Hao , Chen Jing , Wang Kai‐Li , Xue Di , Gao Xing‐Yu , Wang Zhao‐Kui
Published: January 2024

Buried interface modification can effectively improve the compatibility between interfaces. Given the distinct interface selections in perovskite solar cells (PSCs), the applicability of a singular modification material remains limited. Consequently, in response to this challenge, we devised a tailored molecular strategy based on the electronic effects of specific functional groups. Therefore, we prepared three distinct silane coupling agents, and due to the varying inductive effects of these functional groups, the electronic distribution and molecular dipole moments of the coupling agents are correspondingly altered. Among them, trimethoxy (3,3,3‐trifluoropropyl)‐silane (F3‐TMOS), which possesses electron‐withdrawing groups, generates a molecular dipole moment directed toward the hole transport layer (HTL). This approach changes the work function of the HTL, optimizes the energy level alignment, reduces the open‐circuit voltage loss, and facilitates carrier transport. Furthermore, through the buffering effect of the coupling agent, the interface strain and lattice distortion caused by annealing the perovskite are reduced, enhancing the stability of the tin‐based perovskite. Encouragingly, tin PSCs treated with F3‐TMOS achieved a champion efficiency of 14.67 %. This strategy provides an expedient avenue for the design of buried interface modification materials, enabling precise molecular adjustments in accordance with distinct interfacial contexts to ameliorate mismatched energetics and enhance carrier dynamics.
CsPbBr3 Quantum Dots Promoted Depolymerization of Oxidized Lignin via Photocatalytic Semi‐Hydrogenation/Reduction Strategy
Authors: Jiang Huating , Liu Minxia , Lian Xiao , Zhu Mingxiang , Zhang Fang
Published: January 2024

Due to the demanding depolymerization conditions and limited catalytic efficiency, enhancing lignin valorization remains challenging. Therefore, lowering the bond dissociation energy (BDE) has emerged as a viable strategy for achieving mild yet highly effective cleavage of bonds. In this study, a photocatalytic semi‐hydrogenation/reduction strategy utilizing CsPbBr3 quantum dots (CPB‐QDs) and Hantzsch ester (HEH2) as a synergistic catalytic system was introduced to reduce the BDE of Cβ−O−Ar, achieving effective cleavage of the Cβ−O−Ar bond. This strategy offers a wide substrate scope encompassing various β‐O‐4 model lignin dimers, preoxidized β‐O‐4 polymers, and native oxidized lignin, resulting in the production of corresponding ketones and phenols. Notably, this approach attained a turnover frequency (TOF) that is 17 times higher than that of the reported Ir‐catalytic system in the photocatalytic depolymerization of the lignin model dimers. It has been observed via meticulous experimentation that HEH2 can be activated by CPB‐QDs via single electron transfer (SET), generating HEH2⋅+ as a hydrogen donor while also serving as a hole quencher. Moreover, HEH2⋅+ readily forms an active transition state with the substrates via hydrogen bonding. Subsequently, the proton‐coupled electron transfer (PCET) from HEH2⋅+ to the carbonyl group of the substrate generates a Cα⋅ intermediate.
A viscoelastic–viscoplastic modeling approach for amorphous polymers in vacuum forming simulation
Authors: Schwär Florian , Kauffmann Axel
Published: January 2024

In this study, the simulation of a vacuum forming process employing a micromechanical inspired viscoelastic–viscoplastic model is investigated. In the vacuum forming process, a plastic sheet is heated above the glass transition temperature and subsequently forced into a mold by applying a vacuum. The model consists of a generalized Maxwell model combined with an dissipative element in series. Each Maxwell element incorporates a hyperelastic element in series with a viscous element based on a hyperbolical law. While the generalized Maxwell model considers the relaxation due to molecular alignment, the additional viscous element is a modification based on the approach of Bergström and thus considers molecular chain reptation. The model is designed with the aim to converge to the generalized linear Maxwell model in the limit of small deformation. Furthermore, the viscous modeling is temperature activated and follows the Williams–Landel–Ferry approach in the limit of linear viscoelasticity. To simulate rheological standard experiments, a physical‐network‐based implementation into Simscape is presented. To validate the performance of the model in thermoforming, it is implemented into Fortran programming language for finite element simulation with Abaqus/Explicit. It can be shown that the simulation is able to predict the thickness in high correlation with experimental results.
Construction of silicone with quaternized hydantoin‐based N‐chloramines on cotton with aid of supercritical interpenetration for antibacterial synergism
Authors: Chen Yong , Suo Fangyu , Pei Chuanzheng , Wang Yunzhe , Sun Rongxin , Wang Xinran , Wang Ning , Zhao Qian , Wu Tao
Published: January 2024

A silicone carrying combined functionalities of different mechanisms and physiochemical properties is synthesized as a strategy for faster and broader bacterial eliminations. Briefly, ring‐opening alcoholysis of succinic anhydride with 2‐dimethylaminoethanol and subsequent esterification of the alcoholysis product with 5‐(4‐hydroxyphenyl)imidazolidine‐2,4‐dione produced a structure with one tertiary amine and two hydantoinyl NH bonds. The tertiary amine was quaternized with 3‐chloro‐1‐propanol whose OH was then alcoholyzed with SiH of poly(methylhydrosiloxane). The polymeric product was interpenetrated into cotton at 30 MPa and 50°C in supercritical CO2 and treated with tert‐butyl hypochlorite to chlorinate its hydantoinyl NH bonds, forming a 78 nm biocidal layer of silicone with quaternized hydantoin‐based N‐chloramines. Antibacterial tests showed that the quaternary ammonium salt and two hydantoin‐based N‐chloramines act synergistically due to their complementary features, killing both Staphylococcus aureus and Escherichia coli much more efficiently than each functionality. More importantly, the ratio of N‐chloramine to quaternary ammonium salt of 2:1 herein also provided higher efficacy than a reported counterpart with a 1:1 ratio. Biocidability of the modified cotton had promising stability and rechargeability, which indicates that supercritical interpenetration produced a durable interfacial layer without the necessity of chemical bonding.
Measuring the speed of gravity at short distances: Sensitivity estimate
Authors: Frajuca Carlos , da Silva Bortoli Fabio , Garcia Natan Vanelli , Magalhaes Nadja Simao
Published: January 2024

An experimental set up was proposed to determine the speed of gravitational signals traveling in air or in some other medium. It involves two vibrating masses—the emitters, which will be the sources of periodic tidal gravitational signals—and one sapphire‐made mass that will act as a detector, positioned between the two emitters. The detector is planned to be suspended in vacuum and cooled down to 4.2 K, and its vibrational amplitude should be measured by a microwave signal (with ultra‐low phase‐noise) that is expected to resonate with the whispering gallery modes inside the detector. The mechanical and electrical quality factors of sapphire are quite high, yielding a very narrow detection band that reduces the detector sensitivity while amplifying the phase difference of the emitters' signals. The frequencies of the normal modes of the detector were previously determined using a finite element program. In this work, these frequencies are applied to the calculation of a first estimate of the sensitivity of the experiment.
Influence of Electrode Structuring Techniques on the Performance of All‐Solid‐State Batteries
Authors: Clausnitzer Moritz , Danner Timo , Prifling Benedikt , Neumann Matthias , Schmidt Volker , Latz Arnulf
Published: January 2024

All‐solid‐state batteries (ASSBs) offer a promising route to safer batteries with superior energy density compared to conventional Li‐ion batteries (LIBs). However, the design of the composite cathode and optimization of the underlying microstructure is one of the aspects requiring intensive research. Achieving both high energy and power density remains challenging due to limitations in ionic conductivity and active material loading. Using structure‐resolved simulations, we investigate the potential of perforated and layered electrode designs to enhance ASSB performance. Design strategies showing significant performance increase in LIBs are evaluated regarding their application to ASSBs. Composite cathodes with solid electrolyte channels in the structure do not significantly increase cell performance compared to unstructured electrodes. However, the design with a two‐layer cathode proves promising. The layered structure effectively balances improved ionic transport due to increased solid electrolyte fraction at the separator side and substantial active material loading through increased active material fraction at the current collector side of the cathode. Our research highlights key challenges in ASSB development and provides a clear direction for future studies in the field.
The value of Lp(a) and TG/HDLC in peripheral blood to assess the stability of carotid plaque in patients with ischemic stroke
Authors: Tian Yanan , Lu Lei , Zhang Yazhao , Wei Jianhui
Published: January 2024

Objective

The objective of this study was to investigate the relationship between lipoprotein (a) (Lp(a)), triglyceride/high‐density lipoprotein cholesterol (TG/HDL‐C), and the stability of carotid atherosclerotic plaque in patients with acute ischemic stroke.

Methods

A total of 142 patients with acute ischemic stroke were selected and divided into group A (59 cases of stable plaque formation) and group B (83 cases of unstable plaque formation) according to the characteristics of carotid artery plaque formation detected by carotid color Doppler ultrasound. The serum Lp(a), lipid metabolism indexes, peripheral blood routine indexes, and related serum inflammatory factors indexes were compared between the two groups. Receiver operating characteristic curve and multivariate logistic regression model were used to analyze the relationship between each index and the formation of carotid unstable plaque.

Results

There were no significant differences in serum total cholesterol (TC), HDL‐C, and low‐density lipoprotein cholesterol (LDL‐C) between groups A and B (p > .05). The values of Lp(a), TG, and TG/HDL‐C in group B were higher than those in group A, and the differences were statistically significant (p < .05). There were no significant differences in serum TC, HDL‐C, and LDL‐C between groups A and B (p > .05). The values of Lp(a), TG, and TG/HDL‐C in group B were higher than those in group A, and the differences were statistically significant (p < .05). The values of HBA1C, Lp‐PLA2, CRP, CysC, Hcy, TNF‐α, neutrophils, and NLR in group B were higher than those in group A, and the differences were statistically significant (p < .05). There was no significant difference in FPG, systolic blood pressure, diastolic blood pressure, Hb, white blood cells, platelets, and lymphocytes between groups A and B (p > .05). The results of logistic regression model showed that the increase of Lp(a), TG/HDL‐C, HBA1C, Lp‐PLA2, CRP, CysC, Hcy, and NLR could increase the risk of carotid artery unstable plaque in patients with ischemic stroke (p < .05).

Conclusion

Lp(a) and TG/HDL‐C have certain value in evaluating the stability of carotid atherosclerotic plaque in patients with acute ischemic stroke, and the increased levels of LP (a) and TG/HDL‐C will significantly increase the risk of carotid unstable plaque in patients.
The psychometric properties and treatment outcomes associated with two measures of youth therapeutic alliance using naturalistic data
Authors: Mahon Daryl , Minami Takuya , Brown (G. S.) Jeb
Published: January 2024

Purpose

This is the second of two articles that examine the psychometric properties and treatment outcomes associated with two measures of the therapeutic alliance in naturalistic routine settings.

Methods

Data were taken from the ACORN database for youth, and, where available, parent/carer, attending for psychotherapy treatment in naturalistic settings (N = 12,573). The sample, the largest to date, included only those completing both an alliance measure and an outcome measure at every session. Two sets of three different alliance items are used across the two populations in routine practice.

Results

Analyses revealed that the alliance explained no more than 3% of the variance in outcomes. Alliance measures exhibit ceiling effects, and as such, drawing conclusions about correlations with outcomes can be difficult. Any drop in alliance score as rated by both youth and parent/carer is predictive of outcomes, with parent/carer ratings being marginally more predictive. Where the alliance is rated as better by youth or parent/carer in comparison with ratings as worse, effect sizes are up to 50% better for the youth.

Conclusion

The therapeutic alliance remains an important non‐specific treatment component; however, measures of the alliance have ceiling effects. Both youth and their parent/carer can provide important feedback to the therapist, and any drop in alliance is predictive of clinically meaningful change. As such, therapists should monitor the alliance with both youth and parent/carer. Implications for practice, training and research are considered.
Hindering events in psychotherapy with adolescents: A retrospective investigation of patients' recollection
Authors: Calabrò Alessia , Cassera Luisa , Aschieri Filippo
Published: January 2024

Background

Adolescents often drop out of psychotherapy, with research indicating that almost half of adolescents abandon therapy prematurely. Authors have recommended that, in order to increase engagement and prevent dropout, it is important for clinicians to manage and maintain the therapeutic setting and the relationship.

Objective

This study was designed to investigate the impact of events that hinder the therapeutic alliance in psychotherapy with adolescents, with attention to the adolescents' experiences of these events, how such events were managed within the therapeutic relationship and consequences for the course of treatment.

Methods

Semi‐structured interviews were conducted with adolescents and young adults who experienced negative events during their treatment.

Results

Following a structured thematic analysis, four main domains of hindering events were identified: (a) the nature of problems; (b) subjective experience; (c) response to the events; and (d) consequences of these events.

Conclusion

While there were some similarities between hindering events in adult psychotherapy and that undertaken with adolescents, findings indicate that working with adolescents presents specific challenges associated with limited independence that is typical of this stage of life, and this has implications for clinical practice.