bluuebunny/crossref_metadata_2025_split huggingface dataset:
Being Smarter, Azobenzene‐Containing Biomaterial Showing Triple Stimuli‐Responsive Phase Change Property to Light, Humidity and Force at Room Temperature
Authors: Zhang Lei , Du Qianyao , Zhang Ziying , Chen Jia , Liu Yun , Luo Xiliang , Wang Zhen , Wu Zhongtao 
Published: October 2024

AbstractMultiple stimuli‐responsiveness is an attractive property that is studied in physical chemistry and materials chemistry. While, multiple stimuli‐responsive phase change in an isothermal way is rarely addressed for functional materials at room temperature. In this study, one azobenzene‐containing surfactant AZO is designed for the fabrication of triple stimuli‐responsive phase change biomaterial (Alg‐AZO) through the electrostatic complexation with natural alginate. Thanks to the photoisomerization ability, molecular flexibility and hydrophilicity of AZO, together with the tailoring effect of alginate on AZO, Alg‐AZO could perform reversible isothermal phase transition between liquid crystalline and isotropic liquid states under the stimuli of either light or humidity at room temperature. Furthermore, the humidity‐induced isotropic state can also fast transit to ordered state under shear force, owing to the π‐π interactions between planar trans‐AZO in Alg‐AZO material. With good biocompatibility, self‐healing property and in vivo wound healing promoting capacity that is promoted by light, humidity and force, Alg‐AZO would be suitable for working as a new smart biomaterial in biological and biomedical areas. This work provides a designing strategy for gaining multiple stimuli‐responsive smart materials based on biomacromolecules, and also opening a new opportunity for gaining self‐healing biomaterials capable of working in various conditions.
Durable Photo‐Pyroelectric Detection in a Diamine‐Constructed Lead‐Free Hybrid Perovskite Ferroelectric
Authors: Wang Yifei , Ye Huang , Wang Peng , Wu Ziyang , Guan Qianwen , Zhang Chengshu , Li Hang , Chen Shuang , Luo Junhua 
Published: October 2024

AbstractAs a subcategory of pyroelectric materials, hybrid perovskite ferroelectrics possess substantial pyroelectric properties and exceptional light absorption characteristics, demonstrating significant potential in the photo‐pyroelectric (PPE) detection field. Despite the significant advantages of hybrid perovskite ferroelectric materials for PPE detection, both the lead issue and the weak stability from van der Waals interactions in monoamines have hindered their further application. Here, 1D lead‐free ferroelectric (BDA)SbBr5 (1, where BDA is 1,4‐butanediammonium) is fabricated to achieve PPE detection. Compound 1 exhibits significant symmetry breaking attributed to the order–disorder transition of organic cations and octahedral distortions. Specifically, compound 1 enables broad‐spectrum PPE detection from UV to near‐infrared (377–980 nm) and further realizes switchable pyroelectric current after polarization. More importantly, the stability of the pyroelectric current is preserved without degradation over three months, attributed to the hydrogen bonding interactions of butanediamide. Further theoretical calculations of compound 1 reveal a more negative energy of formation than its monoamine homologs (BA)2SbBr5 (where BA is n‐butylammonium), which is evidence of its stability. These findings highlight 1 as a promising candidate for high‐stability and environmentally friendly PPE wide‐spectrum detection, representing a noteworthy advancement in the ferroelectric field.
Cu‐Atom Locations in Rocksalt SnTe Thermoelectric Alloy
Authors: Kawami Youichirou , Tran Xuan Quy , Yamamoto Tomokazu , Yoshioka Satoru , Murakami Yasukazu , Matsumura Syo , Nogita Kazuhiro , Zou Jin 
Published: October 2024

AbstractThe development of functional thermoelectric materials requires direct evidence of dopants’ locations to rationally design the electronic and phononic structure of the host matrix. In this study, Cs‐corrected scanning transmission electron microscopy and energy dispersive X‐ray spectroscopy is employed at the atomic scale to identify Cu atoms’ locations in a Cu‐doped SnTe thermoelectric alloy. It is revealed that Cu atoms in the rocksalt SnTe form solid solutions at both Sn and Te sites, contrary to their electronegativity order and the intentional Cu doping at Sn sites. Cu atoms are also located at the tetrahedral and crowdion sites of the face‐centred cubic structure, with varying degrees of correlations. Such high flexibility of Cu atoms in the rocksalt SnTe offers diverse phonon‐scattering mechanisms conducive to the ultra‐low lattice thermal conductivity of singly Cu‐doped SnTe. This study offers atomic‐scale insights for achieving more precise dopant engineering, leading to the accelerated development of functional thermoelectric materials.
Insight into Carrier and Phonon Transports of PbSnS2 Crystals
Authors: Zhan Shaoping , Bai Shulin , Qiu Yuting , Zheng Lei , Wang Sining , Zhu Yingcai , Tan Qing , Zhao Li‐Dong 
Published: October 2024

AbstractThe simultaneous optimization of n‐type and p‐type thermoelectric materials is advantageous to the practical application of the device. As an emerging thermoelectric material, PbSnS2 exhibits highly competitive thermoelectric properties due to its unique carrier and phonon transport characteristics. To promote the utilization of this low‐cost thermoelectric material, p‐type PbSnS2 crystals are synthesized and optimized through Na doping and Se alloying. The resulting thermoelectric transport properties differ significantly from those reported for n‐type crystals, prompting us to compare and analyze both n‐type (Cl‐doped) and p‐type (Na‐doped) PbSnS2 crystals from various perspectives. Cl doping is subject to weaker “Fermi pinning” and lower impurity ionization energy compared with Na doping, leading to higher doping efficiency. The different optimal performance directions in n‐type and p‐type crystals can be attributed to the distinct charge density distributions near the conduction band minimum (CBM) and the valence band maximum (VBM). Additionally, both n‐type and p‐type crystals exhibit ultralow lattice thermal conductivity due to the low symmetry of their twisted NaCl structure combined with the strong anharmonicity. This comprehensive analysis of PbSnS2 crystals provides a solid foundation for further performance optimization and device assembly, while also sheds light on the investigation of layered thermoelectric materials.
Lattice Boundary Enhancement on Thermoelectric Behaviors of Heavily Boron‐Doped Silicon for Energy Harvesting: Electrical versus Thermal Conductivity
Authors: Yu Tsai Shang , Tseng Po‐Hsien , Chen Chun Chi , Huang Cheng‐Ming , Yen Hung‐Wei , Chen Yi‐Sheng , Lin Kun‐Lin , Niu Ranming , Lai Yu‐Sheng , Ko Fu‐Hsiang 
Published: October 2024

AbstractGreen energy collection is crucial for achieving future net‐zero carbon emissions, with energy harvesting being a key solution. Silicon, a widely used p‐type semiconductor doped with boron ions, is prevalent in modern electronics. However, the impact of lattice boundaries from ion implantation doping on thermoelectric properties remains underexplored. A heavily boron‐doped silicon layer is used to enhance thermoelectric performance. The layers, formed on silicon, exhibit epitaxial crystal structures under all doping conditions using an ion implantation system. Transmission electron microscopy and atom probe tomography reveal that boron interstitial structures create boundaries in the silicon lattice. These boundaries effectively reduce the thermal conductivity of boron‐doped silicon compared to intrinsic silicon. At 372.76 K, the best power factor of the heavily boron‐doped silicon layer is 3.05 mW/m·K2, obtained at an implant dose of 1016 cm−2. This study demonstrates the raised electrical conductivity is induced by effectively substituting silicon with boron atoms, and the reduced thermal conductivity is caused by boron interstitial‐formed boundaries in silicon. These findings highlight the potential of heavily boron‐doped silicon in improving thermoelectric materials and advancing energy‐efficient technologies.
Spontaneous Formation of Solid Shell Polymeric Multicompartments at All‐Aqueous Interfaces
Authors: Perfeito Francisca G. , Vilabril Sara , Cerqueira Andreia , Oliveira Mariana B. , Mano João F. 
Published: October 2024

AbstractMulticompartmental capsules have demonstrated value in fields ranging from drug release, mimetics of artificial cells, to energy conversion and storage. However, the fabrication of devices with different compartments usually requires the use of toxic solvents, and/or the adaptation of technically demanding methods, including precision microfluidics and multistep processes. The spontaneous formation of multi‐core capsules resulting from polyelectrolyte complexation at the interface of a prototypic all‐aqueous two‐phase system is described here. The variation of polyelectrolyte concentration and complexation time are described as simple working parameters capable of driving the formation of compartments at different yields, as well as tailoring their morphology. The mild processing technology enables the encapsulation of animal cells, which are capable of invading capsule walls for specific processing conditions.
Surface Optimization of Noble‐Metal‐Free Conductive [Mn1/4Co1/2Ni1/4]O2 Nanosheets for Boosting Their Efficacy as Hybridization Matrices
Authors: Kwon Nam Hee , Kim Se‐Jun , Gu Tae‐Ha , Lee Jang Mee , Kim Myung Hwa , Paik Dooam , Jin Xiaoyan , Kim Hyungjun , Hwang Seong‐Ju 
Published: October 2024

AbstractConductive 2D nanosheets have evoked tremendous scientific efforts because of their high efficiency as hybridization matrices for improving diverse functionalities of nanostructured materials. To address the problems posed by previously reported conductive nanosheets like poorly‐interacting graphene and cost‐ineffective RuO2 nanosheets, economically feasible noble‐metal‐free conductive [MnxCo1−2xNix]O2 oxide nanosheets are synthesized with outstanding interfacial interaction capability. The surface‐optimized [Mn1/4Co1/2Ni1/4]O2 nanosheets outperformed RuO2/graphene nanosheets as hybridization matrices in exploring high‐performance visible‐light‐active (λ >420 nm) photocatalysts. The most efficient g‐C3N4–[Mn1/4Co1/2Ni1/4]O2 nanohybrid exhibited unusually high photocatalytic activity (NH4+ formation rate: 1.2 mmol g−1 h−1), i.e., one of the highest N2 reduction efficiencies. The outstanding hybridization effect of the defective [Mn1/4Co1/2Ni1/4]O2 nanosheets is attributed to the optimization of surface bonding character and electronic structure, allowing for improved interfacial coordination bonding with g‐C3N4 at the defect sites. Results from spectroscopic measurements and theoretical calculations reveal that hybridization helps optimize the bandgap energy, and improves charge separation, N2 adsorptivity, and surface reactivity. The universality of the [Mn1/4Co1/2Ni1/4]O2 nanosheet as versatile hybridization matrices is corroborated by the improvement in the electrocatalytic activity of hybridized Co−Fe‐LDH as well as the photocatalytic hydrogen production ability of hybridized CdS.
Orbital Current Boosting Magnetization Switching Efficiency in Metallic Superlattices
Authors: Wei Junwen , Xu Xinkai , Lin Zijin , Qu Yuanjing , Tang Xiaoli , Zhong Zhiyong , Zhang Huaiwu , Jin Lichuan 
Published: October 2024

AbstractOrbitronics is an emerging domain within spintronics, and it is characterized by a rapid development of methods for utilizing orbital current. Metals with strong spin‐orbit coupling have been effectively used to convert orbital current into orbital torque. This study introduces a metallic [W/Ti]3 superlattice that uses orbital current to significantly enhance the magnetization switching efficiency. The enhancement in torque efficiency is demonstrated via spin‐torque ferromagnetic resonance along with the extraction of damping‐like (ξDL) and field‐like spin‐orbit torque (SOT) efficiencies. ξDL for superlattices is more than 100 times higher than that for Pt. As a result, the critical switching current density of the superlattice becomes two orders of magnitude lower than that of Pt. This is primarily attributed to the orbital current generated by the orbital Rashba–Edelstein effect at the W/Ti interface. The thickness of Ti and W layers is modulated to develop a novel approach to utilize orbital current for augmenting SOT efficiency and magnetization switching efficiency in superlattices. The findings of this study provide a basis for developing low‐power‐consumption memory devices and memory with controllable critical current density in SOT‐magnetic random‐access memory applications.
Promoter Deletion Leading to Allele Specific Expression in a Genetically Unsolved Case of Primary Ciliary Dyskinesia
Authors: Beaman M. Makenzie , Yin Weining , Smith Amanda J. , Sears Patrick R. , Leigh Margaret W. , Ferkol Thomas W. , Kearney Brendan , Olivier Kenneth N. , Kimple Adam J. , Clarke Shannon , Huggins Erin , Nading Erica , Jung Seung‐Hye , Iyengar Apoorva K. , Zou Xue , Dang Hong , Barrera Alejandro , Majoros William H. , Rehder Catherine W. , Reddy Timothy E. , Ostrowski Lawrence E. , Allen Andrew S. , Knowles Michael R. , Zariwala Maimoona A. , Crawford Gregory E. 
Published: October 2024

ABSTRACTVariation in the non‐coding genome represents an understudied mechanism of disease and it remains challenging to predict if single nucleotide variants, small insertions and deletions, or structural variants in non‐coding genomic regions will be detrimental. Our approach using complementary RNA‐seq and targeted long‐read DNA sequencing can prioritize identification of non‐coding variants that lead to disease via alteration of gene splicing or expression. We have identified a patient with primary ciliary dyskinesia with a pathogenic coding variant on one allele of the SPAG1 gene, while the second allele appears normal by whole exome sequencing despite an autosomal recessive inheritance pattern. RNA sequencing revealed reduced SPAG1 transcript levels and exclusive allele specific expression of the known pathogenic allele, suggesting the presence of a non‐coding variant on the second allele that impacts transcription. Targeted long‐read DNA sequencing identified a heterozygous 3 kilobase deletion of the 5′ untranslated region of SPAG1, overlapping the promoter and first non‐coding exon. This non‐coding deletion was missed by whole exome sequencing and gene‐specific deletion/duplication analysis, highlighting the importance of investigating the non‐coding genome in patients with “missing” disease‐causing variation. This paradigm demonstrates the utility of both RNA and long‐read DNA sequencing in identifying pathogenic non‐coding variants in patients with unexplained genetic disease.
Rhodium‐Catalyzed Asymmetric Cyclopropanation of Indoles with N‐Triftosylhydrazones
Authors: He Caicai , Song Wei , Wei Dandan , Zhao Wei , Yu Qianfei , Tang Jiaqi , Ning Yongquan , Murali Karunanidhi , Sivaguru Paramasivam , de Ruiter Graham , Bi Xihe 
Published: October 2024

AbstractHerein we report a general rhodium‐catalyzed asymmetric intermolecular dearomative cyclopropanation of indoles using trifluoromethyl N‐triftosylhydrazones as carbene precursors. The reaction enables the rapid construction of diverse cyclopropane‐fused indolines bearing a trifluoromethylated quaternary stereocenter with high enantioselectivity (up to 99 % ee). This mild method exhibits broad substrate scope, tolerating various functional groups, and can even be utilized for the late‐stage diversification of complex bioactive molecules. DFT calculations suggest that the formation of a key zwitterionic intermediate is responsible for the chiral induction. Overall, this approach opens up new possibilities for asymmetric cyclopropanation of challenging aromatic heterocyclic compounds.
Regulating Non‐Equilibrium Solvation Structure in Locally Concentrated Ionic Liquid Electrolytes for Wide‐Temperature and High‐Voltage Lithium Metal Batteries
Authors: Tu Haifeng , Wang Zhicheng , Xue Jiangyan , Tang Zhiyong , Liu Yang , Liu Xiaofang , Liu Lingwang , Lu Suwan , Weng Shixiao , Gao Yiwen , Sun Guochao , Liu Zheng , Peng Keyang , Zhang Xin , Li Dejun , Wu Guangye , Liu Meinan , Hu Jianchen , Li Hong , Xu Jingjing , Wu Xiaodong 
Published: October 2024

AbstractThe development of high‐voltage lithium metal batteries (LMBs) encounters significant challenges due to aggressive electrode chemistry. Recently, locally concentrated ionic liquid electrolytes (LCILEs) have garnered attention for their exceptional stability with both Li anodes and high‐voltage cathodes. However, there remains a limited understanding of how diluents in LCILEs affect the thermodynamic stability of the solvation structure and transportation dynamics of Li+ ions. Herein, we propose a wide‐temperature LCILEs with 1,3‐dichloropropane (DCP13) diluent to construct a non‐equilibrium solvation structure under external electric field, wherein the DCP13 diluent enters the Li+ ion solvation sheath to enhance Li+ ion transport and suppress oxidative side reactions at high‐nickel cathode (LiNi0.9Co0.05Mn0.05O2, NCM90). Consequently, a Li/NCM90 cell utilizing this LCILE achieves a high capacity retention of 94 % after 240 cycles at 4.3 V, also operates stably at high cut‐off voltages from 4.4 V to 4.6 V and over a wide temperature range from −20 °C to 60 °C. Additionally, an Ah‐level pouch cell with this LCILE simultaneously achieves high‐energy‐density and stable cycling, manifesting the practical feasibility. This work redefines the role of diluents in LCILEs, providing inspiration for electrolyte design in developing high‐energy‐density batteries.
A General Hydrotrifluoromethylation of Unactivated Olefins Enabled by Voltage‐Gated Electrosynthesis
Authors: Alvarez Eva M. , Li Jinxiao , Malapit Christian A. 
Published: October 2024

AbstractHere we present the first successful hydrotrifluoromethylation of unactivated olefins under electrochemical conditions. Commercially available trifluoromethyl thianthrenium salt (TT+−CF3BF4−, Ep/2=−0.85 V vs Fc/Fc+) undergoes electrochemical reduction to generate CF3 radicals which add to olefins with exclusive chemoselectivity. The resulting carbon centered radical undergoes a second cathodic reduction, instead of a classical HAT process, to generate a carbanion that can be terminated by protonation from solvent. The use of MgBr2 (+0.20 V onset oxidation potential) plays a key role as an enabling sacrificial reductant for the reaction to operate in an undivided cell. Guided by cyclic voltammetry (CV) studies, fine‐tuning the solvent system, trifluoromethylating reagent's counteranion and careful selection of redox processes, this work led to the development of a voltage‐gated electrosynthesis by pairing two redox processes with a narrow potential difference (ΔE≈1.00 V) allowing the reaction to proceed with two important advances: (a) high reactivity and selectivity towards hydrotrifluoromethylation over undesired dibromination, and (b) an unprecedented functional group tolerance, including aniline, phenols, unprotected alcohol, epoxide, trialkyl amine, and several redox sensitive heterocycles.
Perylene‐Embedded Helical Nanographenes with Emission up to 1010 nm: Synthesis, Structures, and Chiroptical Properties
Authors: Huo Gui‐Fei , Xu Wei‐Tao , Hu Jinlian , Han Yi , Fan Wei , Wang Wei , Sun Zhe , Yang Hai‐Bo , Wu Jishan 
Published: October 2024

AbstractNear‐infrared (NIR) circularly polarized absorbing or emitting materials offer distinct advantages over their visible‐light counterparts and have attracted considerable interest across various fields. Materials exhibiting NIR chiroptical properties with high fluorescence quantum yields (ΦF) are particularly rare. In this study, we report the synthesis of a series of helical nanographenes (1, 2, 3, and 4), where perylene is fused with one to four hexa‐peri‐hexabenzocoronene (sub) units by a strategy involving Diels–Alder cycloaddition followed by a Scholl reaction. X‐ray crystallographic analysis confirmed their structures, revealing helicene moieties integrated into a highly contorted framework. Benefiting from a similar distribution pattern of frontier molecular orbitals to perylene and extended π‐conjugation, compounds 1–4 demonstrate respectable ΦF values of 31.9 %, 15.0 %, 13.7 %, and 6.5 %, respectively, with emission maxima reaching up to 1010 nm. Their enantiopure forms, isolated by preparative chiral HPLC, exhibit distinct circular dichroism signals and circularly polarized luminescence across a broad spectral range, extending from the ultraviolet to the NIR.
Photo‐Amplified Plasma Membrane Rupture by Membrane‐Anchoring NIR‐II Small Molecule Design for Improved Cancer Photoimmunotherapy
Authors: Chen Pengfei , Rong Jie , Chen Kai , Huang Tian , Shen Qingming , Sun Pengfei , Tang Weiwei , Fan Quli 
Published: October 2024

AbstractImmunotherapy is a promising cancer treatment method for eradicating tumor cells by enhancing the immune response. However, there are several major obstacles to conventional phototherapy‐mediated immune responses, including inadequate immunogenicity and immunosuppressive environment. Here, we present a novel photoimmunotherapy modality—the development of membrane‐anchoring small molecule inducing plasma membrane rupture (PMR) by NIR‐II photo‐stimulation, thus evoking cell necrotic death and enhancing antitumor immunotherapy. Our top‐performing membrane‐anchoring small molecule (CBT‐3) exhibits temperature‐tunable PMR efficiency, allowing rapid necrotic death in cancer cells at 50 μM dose by using exogenous NIR‐II light‐mediated mild photothermal effect (1064 nm, 0.6 W cm−2). Further evidence indicated that this gentle therapeutic approach activated inflammatory signaling pathways in cells, enhanced immunogenic cell death, and reshaped the immunosuppressive tumor microenvironment, ultimately promoting systemic antitumor immune responses in vivo. This study represents the first instance of utilizing NIR‐II photo‐amplified PMR effect based on membrane‐anchoring small molecule, providing a novel avenue for advancing cancer photoimmunotherapy.
Germylene Mediated Reductive C−C and C−N Coupling of an Isocyanide and its Device Application
Authors: Gour Kritika , Pramanik Debjit , Dash Soumya Ranjan , Shinde Dipak Dattatray , Venugopal Geethu , Vanka Kumar , Rath Arup K. , Sen Sakya S. 
Published: October 2024

AbstractWe have demonstrated a unique reductive coupling of 4‐iodophenyl isocyanide, facilitated by a perimidine‐based N‐heterocyclic germylene (NHGe), which yields a bis‐spirogerma compound featuring simultaneous C−C and C−N bond formation. This reaction, which leads to the oxidation of germanium from +2 to +4, represents a significant departure from previously documented isocyanide‐germylene interactions. The product exhibits extensive conjugation across its bicyclic C4Ge2N2 framework, conferring distinct photophysical properties, including prominent orange luminescence in both solution and solid states. The photophysical properties are supported by the TD‐DFT calculations confirming an n→π* transition. The potential application of this compound in optoelectronic devices, particularly as a hole transport layer in PbS quantum dot solar cells, is also explored, with promising preliminary results.