bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electron‐Phonon Coupling Suppression by Enhanced Lattice Rigidity in 2D Perovskite Single Crystals for High‐Performance X‐Ray Detection
Authors: Zhang Bobo , Zheng Tao , You Jiaxue , Ma Chuang , Liu Yucheng , Zhang Lu , Xi Jun , Dong Guohua , Liu Ming , Liu Shengzhong (Frank) 
Published: December 2022

Abstract2D Dion−Jacobson (DJ) perovskite single crystals (PSCs) usually demonstrate better X‐ray detection performance than Ruddlesden‐Popper (RP) PSCs. However, the mechanism of the improved performance is still elusive. Here, by the aid of strong interactions between dimethylbiguanide (DGA) and PbI2, a novel DJ‐perovskitoid (DGA)PbI4 is designed. From the comparison of (DGA)PbI4 to other 2D PSCs, it is discovered that the tiniest lattice distortion and increased hydrogen bonds in the atom‐scaled analysis strengthen lattice rigidity and weaken electron‐phonon coupling to suppress disordered scattering of carriers, resulting in significantly improved carrier transport and stability. Therefore, high carrier mobility (78.1 cm2 V−1 s−1) and a pronounced sensitivity of 4869.0 µC Gyair−1cm−2 are achieved using (DGA)PbI4, which are the best in 2D Pb‐based PSC devices to date. Finally, the (DGA)PbI4 devices exhibit good spatial resolution in X‐ray imaging and excellent long‐term stability to work as a promising candidate for medical diagnostics and nondestructive determination.
Improvement of the Photoelectrochemical Stability of Cu2O Photocathode by PhCCCu Grafting
Authors: Zhang Wen , Bai Yadi , Tian Meng , Liu Ya‐Ge , Hou Jiawei , Li Chengbo , Jiang Hai‐Ying , Tang Junwang 
Published: December 2022

AbstractAs one of the most efficient photocathodes, Cu2O has attracted substantial attention because of its theoretically high solar‐to‐hydrogen (STH) efficiency. However, its applications in photoelectrochemical (PEC) fields are severely restricted by the poor stability derived from serious photocorrosion. In this work, high‐quality phenylethynyl copper (PhCCCu) are successfully self‐assembled on the surface of Cu2O photocathode by a novel photothermal method to improve its photostability. With the protection of the PhCCCu layer, 85% of the initial photocurrent density can be remained, while only 28% of initial photocurrent density is left on bare Cu2O photocathode prepared on a copper foam (CF) substrate. The significantly improved photostability of Cu2O photocathode by the PhCCCu protective layer is attributed to its strong hydrophobicity, which can efficiently inhibit the corrosion of Cu2O by the aqueous electrolyte solution due to its special crystal structure. Based on the obtained PhCCCu/Cu2O photocathode, a two‐photoelectrode cell with excellent stability (>5 h) has also been successfully constructed for water splitting without the need of an electric bias.
A Multimodal Study on the Unique Sensing Behavior of a Guest@Metal‐Organic Framework Material for the Detection of Volatile Acetone
Authors: Möslein Annika F. , Gutiérrez Mario , Titov Kirill , Donà Lorenzo , Civalleri Bartolomeo , Frogley Mark D. , Cinque Gianfelice , Rudić Svemir , Tan Jin‐Chong 
Published: December 2022

AbstractOwing to their unique functionalities and tailorable properties that are unattainable in conventional materials, metal‐organic frameworks (MOFs) have emerged as candidate materials for next‐generation chemical sensors and optoelectronics. For instance, the ZnQ@OX‐1 composite material, comprising a light‐emitting guest encapsulated in the pores of the OX‐1 framework, affords excellent sensing performance: a visible color change upon exposure to volatile acetone. In this work, a multimodal study on the exceptional vapochromism of this composite material using high‐resolution spectroscopy techniques based on inelastic neutron scattering and synchrotron radiation is presented, supported by density functional theory calculations. While FTIR spectroscopy in the far‐IR and mid‐IR regions reveals the underlying interactions between ZnQ, OX‐1, and acetone, the limit of detection at 50 ppm is determined through in situ gas dosing experiments using fluorescence spectroscopy. In addition, in situ gas dosing on the single crystal level is achieved with near‐field infrared nanospectroscopy.
Thru‐Hole Epitaxy: A Highway for Controllable and Transferable Epitaxial Growth
Authors: Jang Dongsoo , Ahn Chulwoo , Lee Youngjun , Lee Seungjun , Lee Hyunkyu , Kim Donghoi , Kim Yongsun , Park Ji‐Yong , Kwon Young‐Kyun , Choi Jaewu , Kim Chinkyo 
Published: December 2022

AbstractControllable growth and facile transferability of a crystalline film with desired characteristics, acquired by tuning composition and crystallographic orientation, become highly demanded for advanced flexible devices. Here the desired crystallographic orientations and facile transferability of a crystalline film can be achieved by “thru‐hole epitaxy” in a straightforward and undemanding manner with no limitation on the layer number and polarity of a 2D space layer and the surface characteristics. The crystallographic alignment can be established by the connectedness of the grown material to the substrate through a small net cross‐sectional area of thru‐holes, which also allows the straightforward detachment of the grown material. Thru‐hole epitaxy can be adopted for the realization of advanced flexible devices on large scale with desired crystallographic orientation and facile transferability.
Formation of Monolayer Charge Density Waves and Anomalous Edge Doping in Na Doped Bulk VSe2
Authors: Chazarin Ulysse , Lezoualc'h Mahé , Chou Jyh‐Ping , Pai Woei Wu , Karn Abhishek , Sankar Raman , Chacon Cyril C. , Girard Yann , Repain Vincent , Bellec Amandine , Rousset Sylvie , Smogunov Alexander , Dappe Yannick J. , Lagoute Jérôme 
Published: December 2022

AbstractAlkali atom doping is an efficient way to induce charge transfer and Fermi level tuning in layered materials through intercalation. However, there is a general lack of microscopic understanding of the effect of doping inhomogeneity in geometric and electronic aspects. Here, we report surface doping of a bulk VSe2 crystal by sodium. Na atoms form intercalated subsurface islands that modify the electronic phase of the top layer of VSe2. In addition to n‐doping, the charge density wave of the intercalated VSe2 surface layer changes from the (4 × 4) bulk phase to the () known in monolayer phase of VSe2. Surprisingly, an electronic state at the edges of Na‐intercalated area shift anomalously upward in energy as detected by scanning tunneling spectroscopy. This is explained by a local gating effect resulting from local dipoles at the edges. The study illustrates a clear example of intercalation effect that should be general in alkali‐intercalated bulk layered materials.
Hybrid Image Graphene Polaritons with Extremely Confined Mode and Field Enhancement in the Terahertz Regime
Authors: Huang Chia‐Chien 
Published: December 2022

AbstractGuiding terahertz waves below the diffraction limit of light typically excite graphene plasmons (GPs). However, the mode confinements of conventional GPs using graphene–dielectric interfaces are limited. To further squeeze the optical mode sizes, a graphene–dielectric–metal (GDM) configuration supporting an image graphene plasmon (IGP) has been reported recently through the plasmon interactions in a graphene sheet and its mirror image inside a metal with out‐of‐phase charge oscillations. This study proposes a waveguide structure consisting of a cylindrical dielectric wire over a GDM to achieve an ultraconfined mode area by coupling a dielectric waveguide and an IGP mode. Furthermore, this work examines the dependence of waveguide dimensions and material properties on the mode characteristics of the proposed hybrid IGP (HIGP). This HIGP achieves plasmon wavelengths 20 times shorter and normalized propagation lengths twice longer than GPs, accompanying a mode size of 3 × 10−8A0, where A0 is the diffraction‐limited mode area. Moreover, the simple structure makes the HIGP easy to be verified experimentally. This work demonstrates that the HIGP delivering strong light–matter interactions at extremely compact dimensions can be exploited for building highly integrated, enhanced nonlinear, high‐resolution sensing and imaging THz devices.
Synthesis of Functionalized 3‐(1H‐Isochromen)‐chromones via Ag2O‐Catalyzed Cascade Cyclization Reaction of o‐Hydroxyarylenaminones with o‐Alkynylbenzaldehydes
Authors: Zhang Mingshuai , Liu Zhuoyuan , Chen Longkun , Liu Donghan , Sun Yulin , Chai Zhangmengjie , Chen Xue‐Bing , Yu Fuchao 
Published: December 2022

AbstractA silver‐catalyzed protocol for the synthesis of 3‐(1H‐isochromen)‐chromones is described. The method involves an initial 6‐endo‐dig cyclization of o‐alkynylbenzaldehydes and domino C−H alkylation and chromone annulation of the o‐hydroxyarylenaminones, which enables the installation of 1H‐isochromen and chromone in a single structure. This synthetic strategy is advantageous for the excellent regioselectivity, step economy, concise one‐pot methodology, gram‐scale synthesis, as well as high bond‐forming efficiency.magnified image
Facile and Efficient SynthesisofFluorene and Indenoarene Carboxylates from Biaryldiazoacetates via BlueLight‐promoted Intramolecular CarbeneC−H Insertion
Authors: Zeng Tong‐Tong , Zhang Hao‐Yuan , Xie Zhen‐Biao , Dong Ying‐Ying , Gong Shan‐Shan , Sun Qi 
Published: December 2022

AbstractInspired by the recent discovery that aryldiazoacetates could be excited with visible light to generate carbenes in a mild and catalyst‐free manner, we tested the possibility to induce the cyclization of fluorenes from biaryldiazoacetate precursors simply by visible light irradiation at ambient temperature. The experimental results showed that 455 nm blue light is most effective on the synthesis of a diversity of fluorenes and indenoarenes in excellent yields. Analysis of UV absorbance and electronic transition properties of biaryldiazoacetates revealed that their absorbance peaks in the blue light region are due to the n–π* transition of diazo group. Their small ϵ420 nm values well explains the fact that only when exposed to intense blue light could biaryldiazoaetates be excited to generate carbenes. Theoretical calculations and kinetic isotopic effect (KIE) study illustrated that the fluorene cyclization proceeds via the intramolecular carbene C−H insertion pathway rather than the cyclopropanation pathway. In addition, a furan ring‐opening mechanism for the unexpected formation of an indene‐based unsaturated aldehyde was also proposed based on the calculated potential energy surfaces of three plausible reaction pathways.
Cytochrome P450 Catalyzes Benzene Ring Formation in the Biosynthesis of Trialkyl‐Substituted Aromatic Polyketides
Authors: Yang Yu Meng , Zhao Er Juan , Wei Wanqing , Xu Zi Fei , Shi Jing , Wu Xuan , Zhang Bo , Igarashi Yasuhiro , Jiao Rui Hua , Liang Yong , Tan Ren Xiang , Ge Hui Ming 
Published: December 2022

AbstractLorneic acid and related natural products are characterized by a trialkyl‐substituted benzene ring. The formation of the aromatic core in the middle of the polyketide chain is unusual. We characterized a cytochrome P450 enzyme that can catalyze the hallmark benzene ring formation from an acyclic polyene substrate through genetic and biochemical analysis. Using this P450 as a beacon for genome mining, we obtained 12 homologous type I polyketide synthase (PKS) gene clusters, among which two gene clusters are activated and able to produce trialkyl‐substituted aromatic polyketides. Quantum chemical calculations were performed to elucidate the plausible mechanism for P450‐catalyzed benzene ring formation. Our work expands our knowledge of the catalytic diversity of cytochrome P450.
An Engineered OmpG Nanopore with Displayed Peptide Motifs for Single‐Molecule Multiplex Protein Detection
Authors: Foster Joshua C. , Pham Bach , Pham Ryan , Kim Minji , Moore Matthew D. , Chen Min 
Published: December 2022

AbstractMolecular detection via nanopore, achieved by monitoring changes in ionic current arising from analyte interaction with the sensor pore, is a promising technology for multiplex sensing development. Outer Membrane Protein G (OmpG), a monomeric porin possessing seven functionalizable loops, has been reported as an effective sensing platform for selective protein detection. Using flow cytometry to screen unfavorable constructs, we identified two OmpG nanopores with unique peptide motifs displayed in either loop 3 or 6, which also exhibited distinct analyte signals in single‐channel current recordings. We exploited these motif‐displaying loops concurrently to facilitate single‐molecule multiplex protein detection in a mixture. We additionally report a strategy to increase sensor sensitivity via avidity motif display. These sensing schemes may be expanded to more sophisticated designs utilizing additional loops to increase multiplicity and sensitivity.
DNA‐Encoded Libraries: Towards Harnessing their Full Power with Darwinian Evolution
Authors: Dockerill Millicent , Winssinger Nicolas 
Published: December 2022

AbstractDNA‐encoded library (DEL) technologies are transforming the drug discovery process, enabling the identification of ligands at unprecedented speed and scale. DEL makes use of libraries that are orders of magnitude larger than traditional high‐throughput screens. While a DNA tag alludes to a genotype–phenotype connection that is exploitable for molecular evolution, most of the work in the field is performed with libraries where the tag serves as an amplifiable barcode but does not allow “translation” into the synthetic product it is linked to. In this Review, we cover technologies that enable the “translation” of the genetic tag into synthetic molecules, both biochemically and chemically, and explore how it can be used to harness Darwinian evolutionary pressure.
Giant Water Uptake Enabled Ultrahigh Proton Conductivity of Graphdiyne Oxide
Authors: Li Weiqi , Xu Cong , Xiong Tianyi , Jiang Yanan , Ma Wenjie , Yu Ping , Mao Lanqun 
Published: December 2022

AbstractProton conductors have attracted great attention in various fields, especially in energy production. Here, we find that graphdiyne oxide (GDYO), derived from graphdiyne (GDY), features the highest proton conductivity of 0.54 S cm−1 (100 % RH, 348 K) among the oxidized carbon allotropes reported so far. The sp‐ and sp2‐co‐hybridized carbon skeleton of GDY enables GDYO with the giant water uptake, which is 2.4 times larger than that of graphene oxide (GO), resulting in ultrahigh proton conductivity by increasing the proton concentration and proton conduction pathways. This ultrahigh proton conductivity of GDYO is further proved in a methanol fuel cell by using GDYO membrane as proton exchange membrane. The GDYO membrane enables the cell with higher open circuit voltage, larger power density and lower methanol permeability, compared with commercial Nafion 117. Moreover, the GDYO membrane bears high ion exchange capacity, good acidic stability and low swelling ratio.
Stabilizing Cobalt‐free Li‐rich Layered Oxide Cathodes through Oxygen Lattice Regulation by Two‐phase Ru Doping
Authors: Fan Yameng , Olsson Emilia , Liang Gemeng , Wang Zhijie , D'Angelo Anita M. , Johannessen Bernt , Thomsen Lars , Cowie Bruce , Li Jingxi , Zhang Fangli , Zhao Yunlong , Pang Wei Kong , Cai Qiong , Guo Zaiping 
Published: December 2022

AbstractThe application of Li‐rich layered oxides is hindered by their dramatic capacity and voltage decay on cycling. This work comprehensively studies the mechanistic behaviour of cobalt‐free Li1.2Ni0.2Mn0.6O2 and demonstrates the positive impact of two‐phase Ru doping. A mechanistic transition from the monoclinic to the hexagonal behaviour is found for the structural evolution of Li1.2Ni0.2Mn0.6O2, and the improvement mechanism of Ru doping is understood using the combination of in operando and post‐mortem synchrotron analyses. The two‐phase Ru doping improves the structural reversibility in the first cycle and restrains structural degradation during cycling by stabilizing oxygen (O2−) redox and reducing Mn reduction, thus enabling high structural stability, an extraordinarily stable voltage (decay rate <0.45 mV per cycle), and a high capacity‐retention rate during long‐term cycling. The understanding of the structure‐function relationship of Li1.2Ni0.2Mn0.6O2 sheds light on the selective doping strategy and rational materials design for better‐performance Li‐rich layered oxides.
Synthesis of N‐Glycosides by Silver‐Assisted Gold Catalysis
Authors: Chakraborty Saptashwa , Mishra Bijoyananda , Kumar Das Pratim , Pasari Sandip , Hotha Srinivas 
Published: December 2022

AbstractThe synthesis of N‐glycosides from stable glycosyl donors in a catalytic fashion is still challenging, though they exist ubiquitously in DNA, RNA, glycoproteins, and other biological molecules. Herein, silver‐assisted gold‐catalyzed activation of alkynyl glycosyl carbonate donors is shown to be a versatile approach for the synthesis of purine and pyrimidine nucleosides, asparagine glycosides and quinolin‐2‐one N‐glycosides. Thus synthesized nucleosides were subjected to the oxidation–reduction sequence for the conversion of Ribf‐ into Araf‐ nucleosides, giving access to nucleosides that are otherwise difficult to synthesize. Furthermore, the protocol is demonstrated to be suitable for the synthesis of 2’‐modified nucleosides in a facile manner. Direct attachment of an asparagine‐containing dipeptide to the glucopyranose and subsequent extrapolation to afford the dipeptide disaccharide unit of chloroviruses is yet another facet of this endeavor.
Up/Down Tuning of Poly(ionic liquid)s in Aqueous Two‐Phase Systems
Authors: Tang Yuntao , Zhang Yige , Chen Xi , Xie Xiaowen , Zhou Ning , Dai Zhifeng , Xiong Yubing 
Published: December 2022

AbstractThermally induced reversible up/down migration of poly(ionic liquid)s (PILs) in aqueous two‐phase systems (ATPSs) was achieved for the first time in this study. Novel ATPSs were fabricated using azobenzene (Azo)‐ and benzyl (Bn)‐modified PILs, and their upper and lower phases could be easily tuned using the grafting degree (GD) of the Azo and Bn groups. Bn‐PIL with higher GDBn could go up into the upper phase and Azo‐PIL come down to the lower phase when the temperature increased (>65 °C); this behavior was reversed at lower temperatures. Moreover, a reversible two‐phase/single‐phase transition was realized under UV irradiation. Experimental and simulation results revealed that the difference in the hydration capacity between Bn‐PIL and Azo‐PIL accounted for their unique phase‐separation behavior. A versatile platform for fabricating ATPSs with tunable stimuli‐responsive behavior can be realized based on our findings, which can broaden their applications in the fields of smart separation systems and functional material development.
Synthesis of Fibrous Phosphorus Micropillar Arrays with Pyro‐Phototronic Effects
Authors: Zhang Shuai , Ma Shufang , Cao Ben , Zhuang Qiandong , Xu Yang , Wang Jiahui , Zhang Xishuo , Nan Xiaoye , Hao Xiaodong , Xu Bingshe 
Published: December 2022

AbstractThe bottom‐up preparation of two‐dimensional material micro‐nano structures at scale facilitates the realisation of integrated applications in optoelectronic devices. Fibrous Phosphorus (FP), an allotrope of black phosphorus (BP), is one of the most promising candidate materials in the field of optoelectronics with its unique crystal structure and properties.[1] However, to date, there are no bottom‐up micro‐nano structure preparation methods for crystalline phosphorus allotropes.[1c, 2] Herein, we present the bottom‐up preparation of fibrous phosphorus micropillar (FP‐MP) arrays via a low‐pressure gas‐phase transport (LP‐CVT) method that controls the directional phase transition from amorphous red phosphorus (ARP) to FP. In addition, self‐powered photodetectors (PD) of FP‐MP arrays with pyro‐phototronic effects achieved detection beyond the band gap limit. Our results provide a new approach for bottom‐up preparation of other crystalline allotropes of phosphorus.
Synthesis of water‐soluble protoporphyrin IX polymers and their photodynamic application
Authors: Shi Jiahao , Lu Zhengnan , Pan Yan , Sheng Yang , Sun Yixin , Deng Linhong , Bradley Mark , Zhou Le , Zhang Rong 
Published: December 2022

AbstractProtoporphyrin IX (PpIX) is a photosensitizer used in photodynamic therapy, however, its poor aqueous solubility always presents challenges and limits its application. To solve these problems water‐soluble derivatives of PpIX were synthesized by esterification with polyethylene glycol, and polymerization of the PpIX diol with hexamethylene diisocyanate to form a water‐soluble polyurethane. The polyurethane PpIX derivatives were characterized and showed high levels of singlet oxygen generation. The photodynamic antibacterial activity of the PpIX derivatives were explored on Escherichia coli, Staphylococcus aureus and methicillin‐resistant Staphylococcus aureus indicated that 100% antibacterial killing was achieved with a concentration of 40 μM upon 405 nm irradiation for 5 min. The polyurethane showed high biocompatibility in the dark with a variety of cell lines, but when exposed to 405 nm light (for 5 min) cytotoxic singlet oxygen was generated, resulting in cell death. Importantly, this was also possible with 635 nm illumination. In summary this novel protoporphyrin polyurethane overcomes the issues of solubility, and offers enhanced killing (singlet oxygen) generation with the potential to be used in photodynamic therapy for both antibacterial and anticancer treatment.
Incorporating free‐flowing rivers into global biodiversity targets: Prioritization and targeted interventions to maintain ecological integrity
Authors: Petersen Chantel R. , van Deventer Heidi , Smith‐Adao Lindie B. , Nel Jeanne L. 
Published: December 2022

Abstract

Free‐flowing rivers (FFRs) are important surrogates for freshwater biodiversity as there are increasingly fewer rivers that reflect intact habitat and species diversity from source to sea. The status and changes in the ecological condition or protection of FFRs is not explicitly reported on in global biodiversity targets. Indices are proposed for reporting such changes to the Sustainable Development Goals (SDGs) 6 and 15, Aichi Target 11, and the post‐2020 global biodiversity framework.
FFRs were identified at a countrywide scale in South Africa for protection, planning, monitoring, and assessing changes in their ecological condition and protection status. They were selected and prioritized using criteria co‐produced with national, provincial, and local river managers and policy makers. Given the high competition for water resources and the unlikely possibility for strictly protecting all FFRs, a subset of FFRs, termed ‘flagship FFRs’, was identified.
Methods for reporting changes in the protection levels of prioritized FFRs at a countrywide scale were developed, which included indices of FFRs related to global targets: the loss of the extent of FFRs in a natural and largely natural ecological condition for SDG 6; changes in the connectivity of FFRs included in the post‐2020 global biodiversity framework targets; and changes in protection levels of FFRs for Aichi Target 11 and SDG 15.1.2.
Flagship FFRs attracted targeted management initiatives and thus maintained their connectivity and ecological condition. This was not true when all FFRs were considered; in the broader set of FFRs, longitudinal fragmentation increased and ecological condition declined from 2011 to 2018.
Considering the increasing pressures rivers are likely to experience from human and climate change impacts, particularly in semi‐arid to temperate environments, urgent prioritization and monitoring of FFRs is called for so that a targeted set of protection and management strategies can be applied.