bluuebunny/crossref_metadata_2025_split huggingface dataset:
Degradable Adhesives as Sustainable Alternatives to Acrylics via Ring‐Opening Radical Polymerization of Vinylcyclopropanes
Authors: Kim Daewhan , Yu Changhoon , Kwon Min Sang 
Published: February 2025

AbstractAcrylic pressure‐sensitive adhesives (PSAs) are loosely crosslinked polymer networks widely used across various industries. However, the network structure and inert nature of the acrylic polymer backbone present sustainability challenges. To address these issues, efforts are being made to incorporate degradable units into the polymer backbone. Yet, two key obstacles remain: i) the polymer does not degrade into sufficiently small fragments, and ii) the adhesive and viscoelastic properties are often inferior to those of conventional acrylic polymers. In this study, we developed a PSA utilizing vinylcyclopropane (VCP)‐based monomers and a VCP‐based crosslinker, achieving molecular‐level degradation while maintaining adhesive performance and viscoelastic properties comparable to traditional acrylic PSAs. Under optimized polymerization conditions, the polymer incorporates ozone‐labile double bonds into its backbone, enabling controlled molecular degradation without compromising its properties. By synthesizing and strategically combining various VCP‐based monomers, we developed PSAs with tailored adhesion and viscoelastic behavior on par with conventional acrylic PSAs. These advancements indicate that the degradable polymers and PSAs developed in this study are poised for practical application in the near future.
Helically Chiral Mixed‐Valence Systems Comprising N‐Heterotriangulenes: Stabilization of the Cationic Species by π‐Expansion
Authors: Borstelmann Jan , Zank Simon , Krug Marcel , Berger Georg , Fröhlich Nina , Glotz Gabriel , Gnannt Frederik , Schneider Lars , Rominger Frank , Deschler Felix , Clark Timothy , Gescheidt Georg , Guldi Dirk M. , Kivala Milan 
Published: February 2025

AbstractWe report the efficient stabilization of nitrogen‐centered radical cations in a dimeric N‐heterotriangulene bridged by a rigid π‐conjugated [5]helicene backbone (NTH). The rigid scaffold exhibits helical chirality, allowing the enantiomers to be separated and their chiroptical properties studied, including circular dichroism (CD) and circularly polarized luminescence (CPL). Successive oxidation towards the radical cation NTH⋅+ and dication NTH2+ reveals strong electronic communication between the two nitrogen‐centers, as demonstrated by X‐ray crystallography, electrochemistry, UV/Vis/nIR spectroscopy and electron paramagnetic resonance (EPR) spectroscopy. CD measurements of the enantiomerically pure cations reveal strong Cotton effects in the nIR region extending up to 2000 nm. Density functional theory confirms the observed enhanced electronic communication, classifying NTH⋅+ as a Robin‐Day Class III mixed‐valence charge‐transfer (MV–CT) system. NTH2+ exhibits a quinoidal structure with partial diradical character and open‐shell singlet ground state, as shown by variable temperature EPR measurements. Time‐resolved transient absorption spectroscopy shows the photo‐induced generation of NTH⋅+ in the presence of a suitable electron acceptor.
Capturing the Progressive Conformational Evolutions of Sterically‐Congested Dihydrophenazines via Crystallization
Authors: Chen Ziyu , Jin Xin , Shen Ruizi , Li Wen , Sun Lu , Su Jianhua , Qu Da‐Hui , Zhang Zhiyun , Tian He 
Published: February 2025

AbstractTo gain a deeper understanding of the sequential multistep excited‐state structural evolutions of N,N′‐diphenyl‐dihydrodibenzo[a,c]phenazine (DPAC) luminophores, we strategically freeze distinct conformations by crystallization, allowing to capture the progressive conformational transformations within a DPAC‐based framework by utilizing single‐crystal X‐ray diffractometry. Our focus lies in the innovative modification of DPAC via the synthesis of cyano (CN)‐substituted derivatives DPAC‐nCN (n=1–4, with n indicating the number of CN groups). The incorporation of electron‐withdrawing CN groups modulates electron delocalization and lowers energy barriers, facilitating access to conformational polymorphism within the crystals. Unlike the limited diversity observed in the crystallization behaviour of DPAC, the DPAC‐2CN to DPAC‐4CN derivatives exhibit distinct crystalline forms, with conformational diversity increasing in tandem with the number of CN substituents. Notably, the single DPAC‐4CN molecule features multi‐colored crystals transitioning from blue to red, with the folding angle of the polycyclic dihydrodibenzo[a,c]phenazine ring progressive varying from ~130° to ~172°. Additionally, DPAC‐4CN’s red crystals with high‐energy planar conformation (~172°) can experience a sudden jumping when subjected to stimuli. This study not only advances the understanding of conformational dynamics in dihydrophenazines but also paves a new way for the development of dynamic crystal materials.
Surface‐like NOx Reduction at an Atomically‐Precise Tricopper Cluster
Authors: Beamer Andrew W. , Buss Joshua A. 
Published: February 2025

AbstractThe combustion of nitrogen‐containing fuels and increasing use of nitrogen‐rich fertilizers is accumulating NOx pollutants in the environment. Copper is an attractive catalyst material for reductive NOx remediation, yet ambiguity persists regarding the elementary bond‐making and bond‐breaking steps occurring at the catalyst interface. Starting from a molecular tricuprous μ3‐oxo complex (1), an unusually reduced and highly reactive surface‐like cluster (2) has been prepared. Characterization data and electronic structure calculations are consistent with 2 featuring σ‐aromaticity that primes the tricopper core for two‐electron chemistry. Cluster 2 mediates catalytic reductive coupling of NO to N2, proceeding through N2O, via sequential oxygen atom transfer steps. Stoichiometric reduction of NO3− and NO2− is also disclosed, mapping the complete denitrification cycle at an atomically‐precise molecular cluster.
Synergistic Zn and MoS2 Tailored Co−N/C Environments Enabling Bifunctional ORR/OER Electrocatalysis for Advanced Li−O2 Batteries
Authors: Wang Zhiyang , Zhang Qi , Liu Wenhong , Luo Hao , Kong Xianghua , Yang Qingchun , Zhang Dawei , Yu Yan 
Published: February 2025

AbstractTo better adapt lithium‐oxygen batteries (LOBs) and overcome their sluggish oxygen reduction and evolution reactions (ORR/OER) kinetics, designing efficient bifunctional ORR/OER catalytic materials is essential. In this study, we successfully constructed a bifunctional ZnCo−N/C@MoS2 catalyst by tailoring the Co−N/C center with Zn incorporation and MoS2 encapsulation. Surprisingly, Zn atoms, which are typically considered to promote the Co atoms isolation, exhibit a promoting effect on the ORR performance of Co−N/C centers and enhance their stability under harsh conditions. Introducing MoS2 establishes Mo−N coupling centers, enhancing electron transfer and adjusting the charge density of Co active centers, thereby compensating OER activity limitation of ZnCo−N/C. In Li−O2 batteries, Zn and MoS2 synergistically optimize intermediate interactions and regulate LiO2 formation/decomposition, while Zn′s environmental adaptability and MoS2′s encapsulating protection jointly enhance operational stability. Results show that ZnCo−N/C@MoS2, serving as the oxygen electrode in Li−O2 batteries, achieves a low overpotential of 1.01 V, an ultra‐high specific capacity of 25,026 mAh g−1, and a long cycle life of 298 cycles. This work achieves bifunctionality in single‐atom catalysts through precise dual modulation of the catalytic environment, providing a novel strategy for the development of lithium‐oxygen batteries.
A Versatile Strategy to Transform Cationic Polymers for Efficient and Organ‐Selective mRNA Delivery
Authors: Lin Lixin , Su Kexin , Zhang Xinyue , Shi Lu , Yan Xinxin , Fu Qiuli , Yao Ke , Siegwart Daniel J. , Liu Shuai 
Published: February 2025

AbstractThe progress of mRNA therapeutics underscores the imperative demand for the development of targeted delivery systems. While cationic polymers hold promise as genetic vectors, their poor in vivo efficacy and numerous variants highlight the urgent need for a universal functionalization strategy to bolster their delivery capabilities. Here, we present a versatile strategy to transform low‐cost commercial cationic polymers into phospholipidated and alkylated polymers (PAPs), enabling efficient and organ‐selective mRNA delivery in vivo. This straightforward post‐functionalization method can be readily broadened to a diverse array of existing cationic polymers, enhancing their cellular uptake, endosomal escape, and mRNA release functionalities. Consequently, PAPs facilitate up to 30,500‐fold higher mRNA expression compared to their unmodified counterparts in vivo. Notably, the one‐component PAPs enable spleen‐specific mRNA delivery, with their vaccine application validated in a mouse melanoma model following intravenous administration. Better still, PAPs can synergize with different helper lipids to formulate four‐component lipid nanoparticles (LNPs), achieving respective lung‐ and liver‐specific mRNA delivery. Noteworthy is that these organ‐selective mRNA delivery systems significantly outperform previous polymer and LNP benchmarks. This transformation strategy for cationic polymers represents a generalized methodology to give highly effective mRNA carriers, highlighting substantial potential for clinical translation of mRNA therapies with organ‐targeting requirements.
Improving Light‐Responsive Efficiency of Type II Porous Liquid by Tailoring the Functionality of Host
Authors: Liu Yang , Jin Han‐Yan , Li Meng‐Meng , Zuo Mingrui , Kumar Dinker Manish , Kou Jiahui , Yan Juntao , Ding Lifeng , Sun Lin‐Bing 
Published: February 2025

AbstractLight‐responsive porous liquids (LPLs) attract significant attention for their controllable gas uptake under light irradiation, while their preparation has remained a great challenge. Here we report the fabrication of type II LPLs with enhanced light‐responsive efficiency by tailoring the host's functionality for the first time. The functionality of light‐responsive metal‐organic cage (MOC‐RL, constructed from dicopper and responsive ligands) is modified by introducing the second long‐chain alkyl ligand, producing MOC‐RL‐AL as a new host. A spatially hindered solvent based on polyethylene glycol, IL‐NTf2, is designed and can dissolve MOC‐RL‐AL due to the suitable interaction, creating a type II LPL (PL‐RL‐AL). Under light irradiation, the variation in propylene adsorption for PL‐RL‐AL increases by 58.0 % compared to PL‐RL. The enhanced light‐responsive efficiency is caused by easier control in accessibility of internal cavities within MOCs and increased number of external cavities between MOCs and IL‐NTf2. This makes PL‐RL‐AL the first LPL with the probability for propylene/propane separation.
Enhanced Cathode‐Electrolyte Interphase for Prolonged Cycling Stability of Aluminum‐Selenium Batteries Using Locally Concentrated Ionic Liquid Electrolytes
Authors: Xu Cheng , Diemant Thomas , Zhang Shuting , Liu Xu , Passerini Stefano 
Published: February 2025

AbstractAl−Se batteries (ASeBs) with high theoretical specific capacity and discharge voltage are promising energy storage devices. However, the detrimental shuttle effect occurring in conventional ionic liquid electrolytes (ILEs) challenges their development. Herein, a thicker cathode/electrolyte interphase (CEI) is constructed via employing locally concentrated IL electrolytes (LCILEs) to overcome these issues. It is demonstrated that LCILEs facilitate the incorporation of Emim+ into the electrode/electrolyte interphases, and, meanwhile, more Al−Cl species deposits are observed in the CEI. The formed CEI effectively prevents the dissolution of poly‐selenides, inhibiting their related parasitic reactions. These result in ASeBs, employing the LCILE, to deliver a specific discharge capacity of 218 mAh g−1 at 0.5 A g−1 after 100 cycles at 20 °C, while the cell using the neat ILE only maintains 38 mAh g−1 under the same conditions. Moreover, an Al−S cell operated in LCILEs reaches 578 mAh g−1 at 0.1 A g−1 after 150 cycles, which is also significantly better than 317 mAh g−1 in the neat ILE. This study provides an LCILE‐based strategy to reinforce the CEI in order to suppress the shuttle effect, realizing Al‐chalcogen batteries with better performance.
Improving Electrocatalytic CO2 Reduction over Iron Tetraphenylporphyrin with Triethanolamine as a CO2 Shuttle
Authors: Yin Zhiyuan , Zhang Mengchun , Long Yuchi , Lei Haitao , Li Xialiang , Zhang Xue‐Peng , Zhang Wei , Apfel Ulf‐Peter , Cao Rui 
Published: February 2025

AbstractDelivering CO2 molecules to catalyst sites is a vital step in the CO2 reduction reaction (CO2RR). Achievements have been made to develop efficient catalysts, but few efforts have been dedicated to improving CO2 delivering in solutions. Herein, we report on electrocatalytic CO2‐to‐CO conversion using Fe tetraphenylporphyrin (FeTPP) as a catalyst and triethanolamine as a CO2 shuttle. Compared to ethanol, the electrocatalytic CO2RR current with triethanolamine increases by more than three times. We show that triethanolamine can effectively capture a CO2 molecule to form a zwitterionic alkylcarbonate through the collaboration between its tripodal alcohol and amine units. This alkylcarbonate can release the bound CO2 molecule for activation at the Fe site upon its interaction with FeTPP. In addition to shuttling CO2, alkylcarbonates can also provide protons to assist the C−O bond cleavage. Therefore, this work is significant to demonstrate a new strategy to improve electrocatalytic CO2RR by shuttling CO2.
Crystallization Thermodynamics Regulation of 1.85 eV Wide‐Bandgap Perovskite for Efficient and Stable Perovskite‐Organic Tandem Photovoltaics
Authors: Xie Guanshui , Li Huan , Fang Jun , Wang Xin , Peng Haichen , Lin Dongxu , Huang Nuanshan , Gan Lin , Li Wenjia , Jiang Ruixuan , Bu Tongle , Huang Fuzhi , He Sisi , Qiu Longbin 
Published: February 2025

AbstractWide‐band gap perovskite with adjustable band gaps can be integrated with organic solar cells to form tandem solar cells (TSCs), thereby surpassing the Shockley–Queisser limit. However, increasing Br content to elevate the band gap above 1.8 eV complicates crystallization, leading to inferior film quality and defects due to the unmanageable evolution of intermediate phases. Surface passivation improves crystallization but hard to moderate the inhomogeneous component distributions and defects in the bulk phase. Here, we introduce a diammonium salt as an additive to regulate the homogeneity and crystallization of perovskite film, eliminating the low‐dimensional intermediate phase for orientated crystallization of 1.85 eV perovskite, resulting in efficient wide‐band gap perovskite solar cells with an impressive open‐circuit voltage (Voc) of 1.379 V and operational stability remaining 85 % of their initial efficiency after illumination for 1200 h. Furthermore, perovskite‐organic TSCs achieve a champion power conversion efficiency of 24.03 % and a high Voc of 2.108 V, one of the highest Voc for perovskite‐organic TSCs.
Benzoxazine/Micro‐Arc Oxidation High‐Temperature‐Resistant Composite Coating With Superior Corrosion Protection Performance on Magnesium Alloy
Authors: Zhu Hongxia , Cui Xuejun , Peng Sicheng , Qi Yuming , Xia Yiqing , Ren Qingchuan , Cheng Fei 
Published: February 2025

ABSTRACTIn this study, to seal the pores of a micro‐arc oxidation (MAO) coating, benzoxazine (BZ) is used to form a highly heat‐resistant MAO/BZ composite coating with excellent anti‐corrosion performance on a magnesium alloy. The as‐prepared BZ coating, which has a static water contact angle of 111.52° ± 2.6°, is bonded firmly to the MAO coating and can withstand a temperature of 300°C. The results of electrochemical tests indicate that the composite coating prepared by BZ with a concentration of 40% demonstrates a low corrosion current density of 9.01 × 10−12 A cm−2 in a 3.5 wt.% NaCl aqueous solution. Moreover, the composite coating exhibits an outstanding corrosion resistance after a neutral salt spray test for 82 days. Furthermore, it is concluded that an increased concentration of BZ can significantly increase the coating thickness with a dense curing crosslinking structure, which is a key factor in the corrosion protection of MAO coatings.
Parent Outcomes Following Participation in Cognitive Behavior Therapy for Autistic Children in a Community Setting: Parent Mental Health, Mindful Parenting, and Parenting Practices
Authors: Ibrahim Alaa T. , Lee Vivian , Vashi Nisha , Roudbarani Flora , Tablon Modica Paula , Pouyandeh Ava , Sellitto Teresa , Ameis Stephanie H. , Elkader Alex , Gray Kylie M. , Kerns Connor M. , Lai Meng‐Chuan , Lake Johanna , Thomson Kendra , Weiss Jonathan A. 
Published: February 2025

ABSTRACTParents of autistic children are at a higher risk for mental health problems, including anxiety, depression, and stress. Cognitive behavior therapy (CBT) that targets children's emotion regulation may have an indirect influence on parent outcomes, especially if they play a supporting role in their child's intervention. However, most CBT interventions have been carried out in highly controlled research settings and there are a few studies that examined parental outcomes after participating in autistic child‐focused CBT within a community setting. The current study examined parent outcomes (i.e., mental health problems, mindful parenting, and parenting practices) following a community‐based CBT program with concurrent parent involvement for autistic children, as well as associations between changes in parent and child outcomes (i.e., autism symptoms and emotion dysregulation). Participants included 77 parent–child dyads across seven community organizations in Ontario, Canada. Parents reported improved mindful parenting and positive parenting practices post‐intervention, and no significant changes in their mental health. Multiple mediation analyses revealed that positive changes in parent outcomes (i.e., mindful parenting and parenting practices) were associated with positive changes in child emotion regulation. These positive changes in parenting practices mediated the relationship between mindful parenting and child emotion regulation. Results suggest that participating in community‐based CBT is mutually beneficial for autistic children and their parents, particularly in improving parenting behaviors.
Brandschutz im mehrgeschossigen Holzbau – Stand der Technik
Authors: Engel Thomas , Rauch Michael , Werther Norman 
Published: February 2025

AbstractDer Beitrag thematisiert die brandschutztechnischen Herausforderungen und Fortschritte im mehrgeschossigen Holzbau, der als nachhaltiger Baustoff eine Schlüsselrolle in der Dekarbonisierung des Gebäudesektors einnimmt. Holz als brennbares Material kann durch gezielte Bemessung jegliche Feuerwiderstandsdauern erreichen. Entscheidende Faktoren für die Abbrandrate sind Holzart, Holzfeuchte und Brandszenarien, die die Dimensionierung der Querschnitte beeinflussen. Das Stufenmodell berücksichtigt variable Abbrandraten bei Brettsperrholz, bei dem Klebefugen und thermisches Verhalten eine entscheidende Rolle spielen. Brandschutzbekleidungen wie Gipsplatten erhöhen die Widerstandsfähigkeit von Holzbauteilen, indem sie die Entzündung und Verkohlung verzögern oder verhindern. Brandversuche verdeutlichen zudem die Bedeutung geschützter Holzoberflächen und zeigen, dass die zusätzliche strukturelle Brandlast durch ungeschützte oder nur anfänglich geschützte Holzoberflächen einen Einfluss auf die Branddynamik hat. Im Kontext von Realbrandversuchen bestätigt der Beitrag, dass handwerklich korrekt ausgeführte Bauteilanschlüsse und Elementfügungen den geforderten Feuerwiderstand gewährleisten. Die aktuellen Fortschritte flossen in Richtlinien wie die MHolzBauRL 2024 ein und schaffen eine geschlossene Nachweiskette für den Holzbau bis zur Hochhausgrenze.
Separation and Quantitative Estimation of Pharmacopeial Organic Impurities, Process‐Related Impurities, and Degradation Products of the Anti‐Schizophrenia Drug Clozapine in Pharmaceutical Formulations by Using Stability‐Indicating HPLC Method
Authors: Sharma Abhishek , Pedavenkatagari Narayana Reddy , Nagulancha Bhujanga Rao , Lakka Narasimha Swamy 
Published: February 2025

ABSTRACTClozapine is an antipsychotic medication primarily used to treat severe schizophrenia symptoms. This research aimed to develop and validate a reliable, rapid, and sensitive reverse‐phase high‐performance liquid chromatography (RP‐HPLC) method for measuring organic impurities in clozapine drug substances and products. The chromatographic separation was achieved using an Agilent Poroshell 120 EC‐C18 column with gradient elution, using mobile phases consisting of acetonitrile, methanol, pH 2.4 phosphate buffer, and ethanol. The method operated at a flow rate of 1.0 mL/min, with a 10‐μL injection volume, a column temperature of 35°C, and detection at 257 nm. Validation was performed according to ICH Q2(R2) guidelines and USP <1225> general chapter. The method demonstrated optimal resolution between adjacent peaks, with values greater than 1.5, and provided accurate estimations free from interference. Recovery and regression values ranged from 80.0% to 120.0%, with R2 values exceeding 0.9995. The quantification range spanned from the limit of quantification to 150% of the specification level. The stability‐indicating capability of the RP‐HPLC method was confirmed through forced degradation studies. This method has been successfully implemented in a quality control laboratory for real‐time analysis of clozapine drug substances and products.
Nonmotor Symptoms Differ Between Essential Tremor and Tremor‐Dominant Parkinson's Disease
Authors: Li Mingqiang , He Runcheng , Zhou Xun , Wang Yuzheng , Sun Qiying , Wang Chunyu , Zeng Sheng , Lei Lifang , Wu Heng , Yi Shanqing , Wen Jun , Xu Qian , Guo Jifeng , Tang Beisha ,   the China Essential Tremor Alliance
Published: February 2025

ABSTRACTBackgroundDistinguishing between essential tremor (ET) and tremor‐dominant Parkinson's disease (PD‐TD) can be challenging due to overlapping motor symptoms. This study aims to investigate the differences in nonmotor symptoms (NMS) between ET and PD‐TD patients to provide additional evidence for differentiating these two conditions.MethodsThis retrospective study included 1656 participants, comprising 558 PD‐TD patients, 584 ET patients, and 514 controls. ET patients were assessed using the Tremor Research Group Essential Tremor Rating Assessment Scale (TETRAS), while PD‐TD patients were evaluated based on the Unified Parkinson's Disease Rating Scale (UPDRS). All participants were assessed for NMS using the Nonmotor Symptoms Scale (NMSS).ResultsThe composite NMSS score for the PD‐TD group was significantly higher than that for the ET group and the control group (23.44 ± 20.20 vs. 12.60 ± 14.89 vs. 9.37 ± 12.44, p < 0.001). Compared to ET patients, PD‐TD patients had an increased risk of all NMS, especially in hyposmia (OR = 7.70, 95% CI: 5.11–11.62). The NMSS score, urinary symptoms, and hyposmia may play a role in differentiating ET from PD‐TD. The area under the curve (AUC) is 0.766 (95% CI: 0.739–0.793), with a sensitivity of 80.8% and specificity of 58.6%. When family history is included in the analysis, the AUC increases to 0.819 (95% CI: 0.795–0.843), with sensitivity improving to 82.4% and specificity to 68.2%.ConclusionsThe study reveals significant differences in NMS between ET and PD‐TD. Compared to patients with ET, those with PD‐TD exhibit more frequent and severe NMS. NMS and family history are helpful in differentiating between ET and PD‐TD.