bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Novel Multiple‐Ring Aromatic Spacer Based 2D Ruddlesden–Popper CsPbI3Solar Cell with Record Efficiency Beyond 16%
Authors: Yao Huanhuan , Li Zhizai , Shi Chang , Xu Youkui , Wang Qian , Li ZhenHua , Peng Guoqiang , Lei Yutian , Wang Haoxu , Ci Zhipeng , Jin Zhiwen 
Published: June 2022

AbstractTwo‐dimensional (2D) Ruddlesden–Popper (RP) CsPbI3perovskite possesses superior phase stability by introducing steric hindrance. However, due to the quantum and dielectric confinement effect, 2D structures usually exhibit large exciton binding energy, and the charge tunneling barrier across the organic interlayer is difficult to eliminate, resulting in poor charge transport and performance. Here, a multiple‐ring aromatic ammonium, 1‐naphthylamine (1‐NA) spacer is developed for 2D RP CsPbI3perovskite solar cell (PSC). Theoretical simulations and experimental characterizations demonstrate that the 2D RP CsPbI3perovskite using 1‐NA spacer with extended π‐conjugation lengths reduces the exciton binding energy and facilitates the efficient separation of excitons. In addition, its cations have a significant contribution to the conduction band, which can reduce the bandgap, promote electronic coupling between organic and inorganic layers, and improve interlayer charge transport. Importantly, the strong π–π conjugation of 1‐NA spacer can enhance intermolecular interactions and hydrogen bonding, and prepare high‐quality films with preferred vertical orientation, resulting in lower defect density, and directional charge transport. As a result, the (1‐NA)2(Cs)3Pb4I13PSC exhibits a record 16.62% performance with enhanced stability. This work provides an efficient approach to improve charge transport and device performance by developing multiple‐ring aromatic spacers.
Greenificated Molecularly Imprinted Materials for Advanced Applications
Authors: Ostovan Abbas , Arabi Maryam , Wang Yunqing , Li Jinhua , Li Bowei , Wang Xiaoyan , Chen Lingxin 
Published: June 2022

AbstractMolecular imprinting technology (MIT) produces artificial binding sites with precise complementarity to substrates and thereby is capable of exquisite molecular recognition. Over five decades of evolution, it is predicted that the resulting host imprinted materials will overtake natural receptors for research and application purposes, but in practice, this has not yet been realized due to the unsustainability of their life cycles (i.e., precursors, creation, use, recycling, and end‐of‐life). To address this issue, greenificated molecularly imprinted polymers (GMIPs) are a new class of plastic antibodies that have approached sustainability by following one or more of the greenification principles, while also demonstrating more far‐reaching applications compared to their natural counterparts. In this review, the most recent developments in the delicate design and advanced application of GMIPs in six fast‐growing and emerging fields are surveyed, namely biomedicine/therapy, catalysis, energy harvesting/storage, nanoparticle detection, gas sensing/adsorption, and environmental remediation. In addition, their distinct features are highlighted, and the optimal means to utilize these features for attaining incredibly far‐reaching applications are discussed. Importantly, the obscure technical challenges of the greenificated MIT are revealed, and conceivable solutions are offered. Lastly, several perspectives on future research directions are proposed.
Advances in Biodegradable Electronic Skin: Material Progress and Recent Applications in Sensing, Robotics, and Human–Machine Interfaces
Authors: Zarei Mohammad , Lee Giwon , Lee Seung Goo , Cho Kilwon 
Published: June 2022

AbstractThe rapid growth of the electronics industry and proliferation of electronic materials and telecommunications technologies has led to the release of a massive amount of untreated electronic waste (e‐waste) into the environment. Consequently, catastrophic environmental damage at the microbiome level and serious human health diseases threaten the natural fate of the planet. Currently, the demand for wearable electronics for applications in personalized medicine, electronic skins (e‐skins), and health monitoring is substantial and growing. Therefore, “green” characteristics such as biodegradability, self‐healing, and biocompatibility ensure the future application of wearable electronics and e‐skins in biomedical engineering and bioanalytical sciences. Leveraging the biodegradability, sustainability, and biocompatibility of natural materials will dramatically influence the fabrication of environmentally friendly e‐skins and wearable electronics. Here, the molecular and structural characteristics of biological skins and artificial e‐skins are discussed. The focus then turns to the biodegradable materials, including natural and synthetic‐polymer‐based materials, and their recent applications in the development of biodegradable e‐skin in wearable sensors, robotics, and human–machine interfaces (HMIs). Finally, the main challenges and outlook regarding the preparation and application of biodegradable e‐skins are critically discussed in a near‐future scenario, which is expected to lead to the next generation of biodegradable e‐skins.
High Thermal Conductivity 2D Materials: From Theory and Engineering to Applications
Authors: Wu Fan , Tian He , Shen Yang , Zhu Zheng‐Qiang , Liu Yanming , Hirtz Thomas , Wu Rui , Gou Guangyang , Qiao Yancong , Yang Yi , Xing Chao‐Yang , Zhang Gang , Ren Tian‐Ling 
Published: June 2022

AbstractTransistors are getting close to their physical limitation, and complex chip design technologies have made the hotspot problem more serious. Graphene and hBN, as representative 2D semi‐metal and dielectric materials, possess excellent thermal conductivities. Intrinsic 2D materials, 2D film materials, and 2D composite materials have been investigated, showing great potential for next‐generation thermal‐management materials. There are products that have already been commercialized based on graphene and hBN, but many companies seem to be sitting on the fence, and the obstacles toward implementation of these materials need to be specified. Here, high thermal conductivity 2D materials from theory and engineering to applications are reviewed, aiming to provide a comprehensive summary of the current state of the art of this field in order to give an overview and future prospects in application, manufacturing, and commercialization. From the theoretical perspective, the impact factors and development path of 2D materials for thermal dissipation and the engineering aspect of structural design are presented. The prospects and challenges are also tackled, expressing an objective view about future opportunities to build 2D‐based heat‐dissipation systems.
Ferroelectric BaTiO3 Based Multi‐Effects Coupled Materials and Devices
Authors: Qian Weiqi , Wu Heting , Yang Ya 
Published: June 2022

AbstractFerroelectric barium titanate (BaTiO3) with an intrinsic spontaneous polarization performs multiple remarkable properties. Recently, ferroelectric BaTiO3 based materials and devices are fabricated in multi‐effects coupled systems, such as self‐powered ultrasensitive sensing, energy harvesting, and electrochemical applications, which have gained growing interest with worldwide increasing researches. This review places a focus on current achievements in ferroelectric BaTiO3 based multi‐effects coupled materials and devices for capacitors, nanogenerators, sensors, electrochemistry, and other applications. First, the structure–activity relationship of BaTiO3 materials including various crystal structures and different morphologies is reported. It is interesting that multi‐effects coupled electronic devices and systems combining multiple properties have attached significant effort to realize enhanced performance contrasted to device applications with single effect. Finally, a brief understanding of opportunities and challenges for ferroelectric BaTiO3 based multi‐effects coupled materials and devices is given. The intention of this review is to encourage more effort in this nontoxic intelligent material, and impel more attention in pushing progress of this field in the future.
X‐ray Detectors With Ultrahigh Sensitivity Employing High Performance Transistors Based on a Fully Organic Small Molecule Semiconductor/Polymer Blend Active Layer
Authors: Tamayo Adrián , Fratelli Ilaria , Ciavatti Andrea , Martínez‐Domingo Carme , Branchini Paolo , Colantoni Elisabetta , De Rosa Stefania , Tortora Luca , Contillo Adriano , Santiago Raul , Bromley Stefan T. , Fraboni Beatrice , Mas‐Torrent Marta , Basiricò Laura 
Published: June 2022

AbstractThe implementation of organic semiconductor (OSC) materials in X‐ray detectors provides exciting new opportunities for developing a new generation of biocompatible devices with high potential for the fabrication of sensitive and low‐cost X‐ray imaging systems. Here, the fabrication of high performance organic field‐effect transistors (OFETs) based on blends of 1,4,8,11‐tetramethyl‐6,13‐triethylsilylethynyl pentacene (TMTES) with polystyrene is reported. The films are printed employing a low cost and high‐throughput deposition technique. The devices exhibit excellent electrical characteristics with a high mobility and low density of hole traps, which is ascribed to the favorable herringbone packing (different from most pentacene derivatives) and the vertical phase separation in the blend films. As a consequence, an exceptional high sensitivity of (4.10 ± 0.05) × 1010 µC Gy–1cm–3 for X‐ray detection is achieved, which is the highest reported so far for a direct X‐ray detector based on a tissue equivalent full organic active layer, and is higher than most perovskite film‐based X‐ray detectors. As a proof of concept to demonstrate the high potential of these devices, an X‐ray image with sub‐millimeter pixel size is recorded employing a 4‐pixel array. This work highlights the potential exploitation of high performance OFETs for future innovative large‐area and highly sensitive X‐ray detectors for medical dosimetry and diagnostic applications.
Beware the “loneliness gap”? Examining emerging inequalities and long‐term risks of loneliness and isolation emerging from COVID‐19
Authors: Patulny Roger , Bower Marlee 
Published: June 2022

AbstractEmerging evidence suggests COVID lockdowns have not only increased the social problem of loneliness but widened the ‘loneliness gap’ between the most and least lonely people. Qualitative investigation can reveal why this gap might have increased, for whom, and whether the loneliness gap will remain long term. Using multi‐wave qualitative survey data conducted during Australia’s 2020 lockdown period and beyond, we examine personal experiences of interaction transitioning out of lockdown. We find substantial and uneven impacts of COVID lasting well beyond lockdown. Participants reported heightened loneliness attributable to: physical isolation, health anxieties, ceased activities, reduced connection quality, and poor motivation. COVID also created new interactive difficulties for singles, those with physical and mental disabilities, their carers, and those with low social capital. There was also reported ‘pruning’ of social networks (i.e. reduced bridging, increased bonding social capital), and evidence that increased digital interaction did not substitute for lost physical contact. Younger people also experienced isolating COVID‐induced life disruptions (e.g. travel, university attendance etc). Findings suggest COVID has increased potential long‐term inequalities in loneliness, highlight the post COVID risks faced by vulnerable groups, and suggest caution in advocating digital solutions as a panacea for diminished physical interaction in the post‐pandemic world.
Radiotherapy‐Induced Cleavage of Quaternary Ammonium Groups Activates Prodrugs in Tumors
Authors: Guo Zhibin , Hong Hanyu , Zheng Yuedan , Wang Ziyang , Ding Zexuan , Fu Qunfeng , Liu Zhibo 
Published: June 2022

AbstractCleavage chemistry offers a new chance to activate chemotherapeutic prodrugs in a tumor‐selective manner, yet developing spatiotemporally controllable cleavage chemistry with deep tissue penetration is still a great challenge. Herein, we present a novel radiotherapy‐triggered cleavage chemistry that enables controlled drug release in tumors. Quaternary ammonium groups are identified as masking groups that can be efficiently removed by hydrated electrons (e−aq) from water radiolysis. The subsequently released tertiary amines can be anti‐cancer toxins or readily release functional molecules via 1,6‐elimination. This radiotherapy‐induced cleavage works successfully in living cells and tumor‐bearing mice, showing remarkable treatment efficacy when the mice are given carfilzomib prodrug and radiotherapy. This strategy provides a new perspective for combinational radiochemotherapy, which is the first‐line treatment for over 50 % of cancer patients.
Metal–Organic Frameworks with Low‐Valent Metal Nodes
Authors: Sikma R. Eric , Balto Krista P. , Figueroa Joshua S. , Cohen Seth M. 
Published: June 2022

AbstractMetal–organic frameworks (MOFs) are crystalline, 2‐ and 3‐dimensional coordination polymers formed by bonding interactions between metals and multitopic organic ligands. These are typically formed using hard Lewis basic organic ligands with high oxidation state metal ions. The use of low‐valent metals as structural elements in MOFs is far less common, despite the widespread use of such metals for catalysis, luminescence, and other applications. This Minireview focuses on recent advances in the field of low‐valent MOFs and offers a perspective on the future development of these materials.
Asymmetric Living Supramolecular Polymerization: Precise Fabrication of One‐Handed Helical Supramolecular Polymers
Authors: Wang Chao , Xu Lei , Zhou Li , Liu Na , Wu Zong‐Quan 
Published: June 2022

AbstractProgramming the organization of semiconducting polymers to form well‐defined nanoarchitectures is desirable for fabricating functional materials. In this work, semiconducting copolymers, poly(cholesterol allene)‐b‐poly(3‐hexylthiophene) (PCA‐b‐P3HT) containing helical PCA and poly(alkoxy allene)‐b‐poly(3‐hexylthiophene) (PAA‐b‐P3HT) containing achiral PAA segments, were prepared. Crystallization of P3HT and helicity of PCA drove PCA‐b‐P3HT self‐assemble into spherical nanoparticles that gradually transformed into one‐handed helical nanofibers. The chirality of PCA was transferred to the supramolecular architectures, induced high optical activity in P3HT. Interestingly, the chiral seed micelles of PCA‐b‐P3HT induced asymmetric copolymerization of achiral PAA‐b‐P3HT, which led to helical supramolecular block copolymers with defined helicity and controlled length. Remarkably, the supramolecular copolymers showed white‐light emission and circularly polarized luminescence.
A Plurizyme with Transaminase and Hydrolase Activity Catalyzes Cascade Reactions
Authors: Roda Sergi , Fernandez‐Lopez Laura , Benedens Marius , Bollinger Alexander , Thies Stephan , Schumacher Julia , Coscolín Cristina , Kazemi Masoud , Santiago Gerard , Gertzen Christoph G. W. , Gonzalez‐Alfonso Jose L. , Plou Francisco J. , Jaeger Karl‐Erich , Smits Sander H. J. , Ferrer Manuel , Guallar Víctor 
Published: June 2022

AbstractEngineering dual‐function single polypeptide catalysts with two abiotic or biotic catalytic entities (or combinations of both) supporting cascade reactions is becoming an important area of enzyme engineering and catalysis. Herein we present the development of a PluriZyme, TR2E2, with efficient native transaminase (kcat: 69.49±1.77 min−1) and artificial esterase (kcat: 3908–0.41 min−1) activities integrated into a single scaffold, and evaluate its utility in a cascade reaction. TR2E2 (pHopt: 8.0–9.5; Topt: 60–65 °C) efficiently converts methyl 3‐oxo‐4‐(2,4,5‐trifluorophenyl)butanoate into 3‐(R)‐amino‐4‐(2,4,5‐trifluorophenyl)butanoic acid, a crucial intermediate for the synthesis of antidiabetic drugs. The reaction proceeds through the conversion of the β‐keto ester into the β‐keto acid at the hydrolytic site and subsequently into the β‐amino acid (e.e. >99 %) at the transaminase site. The catalytic power of the TR2E2 PluriZyme was proven with a set of β‐keto esters, demonstrating the potential of such designs to address bioinspired cascade reactions.
Structure elucidation, DNA interaction, potential anticancer, molecular docking activities, and γ‐ray irradiation studies on novel mono‐ and binuclear Fe (II), Ni (II), Co (II), and Hg (II) Schiff base complexes
Authors: El-Boraey Hanaa A. , Abdel‐Qader Aya , Hussien Mostafa A. 
Published: June 2022

Bis Schiff base N,N–((1E,2E)‐ethane 1,2diylidene)bis(azanylylidene)di(isonicotinohydrazide) ligand L was reacted with Fe (III), Ni (II), Co (II), and Hg (II) chlorides to yield complexes (1–6). The structure of the synthesized ligand and metal complexes was well established by various spectroscopic techniques (Fourier‐transform infrared [FT‐IR], UV–Vis., and 1H NMR), mass spectrometry, elemental analysis (CHN) and physical studies (thermogravimetric analysis [TGA]/first derivative thermogravimetric analysis [DTG], powder X‐ray diffraction, molar conductance, and magnetic moment). Solid powder samples of the binuclear complexes (3 and 6) were irradiated at two different irradiation doses (150 and 200 kGy) to yield complexes (3F and 3F*) and (6F and 6F*), respectively. For the γ‐irradiated samples, FT‐IR, UV–Vis., and physical studies (TGA/DTG, X‐ray diffraction, molar conductance, and magnetic moment) were performed using the same methods as for the as‐prepared complexes. In addition, calf thymus ct‐DNA binding results monitored by agarose gel electrophoretic method indicated that the as‐prepared binuclear [Hg2LCl4(OH)2] complex (6) and its γ‐irradiated [Hg2LCl4(OH)2] complex (6F) have the ability to cleave ct‐DNA at a concentration of 30 and 70 μg/ml, respectively. Inhibitory activity against hepatocellular carcinoma cells (HepG‐2) and breast carcinoma cells (MCF‐7) of ligand and as‐prepared complexes (3, 6, and 6F) was evaluated. The results revealed that metal complexes exhibited enhanced activity in comparison to the free ligand, and the as‐prepared complex (6) shows an IC50 value of 5.7 ± 0.2 and 8.72 ± 0.6 μg/ml for the two cell lines, respectively. Docking process for the ligand and complexes (3) and (6) with liver cancer protein (ID: 4FM9) and breast cancer protein (ID: 1H7K) has been evaluated.
Performance of PEDOTOH/PEO‐based Supercapacitors in Agarose Gel Electrolyte
Authors: Wustoni Shofarul , Nikiforidis Georgios , Ohayon David , Inal Sahika , Indartono Yuli Setyo , Suendo Veinardi , Yuliarto Brian 
Published: June 2022

AbstractPoly(3,4‐ethylenedioxythiophene) (PEDOT) is a prime example of conducting polymer materials for supercapacitor electrodes that offer ease of processability and sophisticated chemical stability during operation and storage in aqueous environments. Yet, continuous improvement of its electrochemical capacitance and stability upon long cycles remains a major interest in the field, such as developing PEDOT‐based composites. This work evaluates the electrochemical performances of hydroxymethyl PEDOT (PEDOTOH) coupled with hydrogel additives, namely poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA), and polyethyleneimine (PEI), fabricated via a single‐step electrochemical polymerization method in an aqueous solution. The PEDOTOH/PEO composite exhibits the highest capacitance (195.2 F g−1) compared to pristine PEDOTOH (153.9 F g−1), PEDOTOH/PAA (129.9 F g−1), and PEDOTOH/PEI (142.3 F g−1) at a scan rate of 10 mV s−1. The PEDOTOH/PEO electrodes were then assembled into a symmetrical supercapacitor in an agarose gel. The type of supporting electrolytes and salt concentrations were further examined to identify the optimal agarose‐based gel electrolyte. The supercapacitors comprising 2 M agarose‐LiClO4 achieved a specific capacitance of 27.6 F g−1 at a current density of 2 A g−1, a capacitance retention of ∼94% after 10,000 charge/discharge cycles at 10.6 A g−1, delivering a maximum energy and power densities of 11.2 Wh kg−1 and 17.28 kW kg−1, respectively. The performance of the proposed supercapacitor outperformed several reported PEDOT‐based supercapacitors, including PEDOT/carbon fiber, PEDOT/CNT, and PEDOT/graphene composites. This study provides insights into the effect of incorporated hydrogel in the PEDOTOH network and the optimal conditions of agarose‐based gel electrolytes for high‐performance PEDOT‐based supercapacitor devices.
Whole exome analysis reveals the genomic profiling related to chemo‐resistance in Chinese population with limited‐disease small cell lung cancer
Authors: Yu Jiangyong , Zhao Shuangtao , Su Zhe , Song Chengli , Wu Lihong , Wang Jingbo , Bi Nan , Wang Lvhua 
Published: June 2022

AbstractPurposeThe mechanism of chemo‐resistance in small cell lung cancer (SCLC) is unclear. This study aims to explore the resistance‐related genomic profiles of residual tumors after neo‐adjuvant chemotherapy (NAC) in SCLC through the whole‐exome sequencing (WES).Experimental designA total of 416 limited diseases (LD) SCLC patients underwent surgery were retrospectively analyzed, of which 40 patients received NAC. Then we selected 29 patients undergoing NAC (n = 19) and chemotherapy naïve (CTN, n = 10) to perform WES sequence with formalin‐fixed paraffin‐embedded samples including tumor and paired para‐tumor.ResultsIn total, single nucleotide variation and mutation rate were similar between NAC and CTN groups. The mutation signatures were significantly discrepant between NAC and CTN groups, as well as among patients with partial response (PR), stable disease (SD), and progressive disease. There were more copy number variation deletions in NAC group compared with CTN group. The inactivation of TP53 and RB1 were the most significantly events in both NAC and CTN groups. RB1 nonsense mutations were recurrent in NAC group (9/19 vs. 0/9, 47.4% vs. 0%) with favorable survival, while the frame‐shift deletions were frequent in CTN group (3/9 vs. 3/19, 33.3% vs.15.8%). Integrated function enrichment revealed that the frequently mutant genes were involved in cell cycle, metabolic reprogramming, and oncogenic signaling pathways in NAC group, such as BTG2 pathway, glycolysis in senescence and P53 pathway. A total of 27 genes presented frequently mutant in NAC group and might played a positive role in drug resistance. Multiple genes including BRINP3, MYH6, ST18, and PCHD15, which were associated with prognosis, occurred mutant frequently in PR and SD groups.ConclusionResidual tumors after neo‐adjuvant therapy exhibited different mutation signature spectrum. Multiple genes including RB1 nonsense mutations, BRINP3, MYH6, ST18, and PCHD15 were with frequent mutation in residual tumors, which might participate chemo‐resistance and influenced the prognosis in patients with limited disease SCLC.
Ru(II)‐Catalyzed Hydroarylation of in situ Generated 3,3,3‐Trifluoro‐1‐propyne by C−H Bond Activation: A Facile and Practical Access to β‐Trifluoromethylstyrenes
Authors: Vuagnat Martin , Tognetti Vincent , Jubault Philippe , Besset Tatiana 
Published: June 2022

AbstractIn this study, a practical and straightforward synthesis of β‐(E)‐trifluoromethylstyrenes by ruthenium‐catalyzed C−H bond activation was developed. The readily available and inexpensive 2‐bromo‐3,3,3‐trifluoropropene (BTP), a non‐ozone depleting reagent, was used as a reservoir of 3,3,3‐trifluoropropyne. With this approach, the monofunctionalization of a panel of heteroarenes was possible in a safe and scalable manner (23 examples, up to 87 % yield). Mechanistic investigations and density functional theory (DFT) calculations were also conducted to get a better understanding of the mechanism of this transformation. These studies suggested that 1) a cyclometallated ruthenium complex enabled the transformation, 2) this complex exhibited high efficiency in this transformation compared to the commercially available [RuCl2(p‐cymene)]2 and 3) the mechanism proceeded through a bis‐cyclometallated ruthenium intermediate for the carboruthenation step.