bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractRuO2 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

AbstractHeavy‐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

AbstractThe 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

AbstractChirality, 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

AbstractThe 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

AbstractBuried 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

AbstractDue 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

AbstractIn 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

AbstractA 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

AbstractAn 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

AbstractAll‐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

AbstractObjectiveThe 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.MethodsA 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.ResultsThere 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).ConclusionLp(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

AbstractPurposeThis 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.MethodsData 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.ResultsAnalyses 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.ConclusionThe 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

AbstractBackgroundAdolescents 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.ObjectiveThis 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.MethodsSemi‐structured interviews were conducted with adolescents and young adults who experienced negative events during their treatment.ResultsFollowing 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.ConclusionWhile 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.
Social class and conspicuous brand logo in gift choice
Authors: Lee Jaehoon , Haderlie Todd C. , Miyazaki Anthony D. , Lee Yuri 
Published: January 2024

AbstractWhile conspicuous consumption may be more prevalent for consumers identified as lower (vs. higher) social class, little is known about when and why they prefer conspicuousness in their consumption activities. Drawing from the conceptual perspectives of class‐based norms and self‐protection, we demonstrate the differential effects of social class on preferences for conspicuous logos and the possible explanations underlying the effects. To this end, we employ gift‐giving contexts and identify gift recipients (self‐recipient vs. other‐recipient) as an important boundary condition. Across four studies, lower‐ (vs. higher‐) social‐class consumers exhibit stronger preferences for conspicuous logos, particularly when choosing a gift for others. This effect occurs because lower‐ (vs. higher‐) social‐class consumers have a stronger desire to fit in with others and gain social status. These findings shed light on when and why lower‐social‐class consumers prefer conspicuous logos.