bluuebunny/crossref_metadata_2025_split huggingface dataset:
Multiple twinning of diamond synthesized by acetylene flame
Authors: Son Sam Ick , Chung Su Jin 
Published: August 2004

Abstract
The relation between the domains and domain boundaries of multiple twins of diamond were investigated by the electron back scatter diffraction (EBSD) method and high resolution transmission electron microscopy (HRTEM). Multiple twinned diamonds have two types of icosahedral morphologies. One is an almost perfect icosahedron in which all of the faces are {111} faces. The other is a hollow icosahedron similar to one of the Kepler-Poinsot polyhedrons. The indented negative trigonal faces are formed from the {100} faces of a cube. It was confirmed that the convex edges of the twinned icosahedron corresponded to the Σ3 boundaries, whereas the concave edges were assigned to the Σ9 twin boundary by means of the EBSD analysis.
It was confirmed from the HRTEM image that a series of dislocations compensate for the mismatching angle which occurs after five successive twinning.
Crystal and molecular structures of two triorganophosphinegold(I) 2-amino-cyclopent-1-ene-1-carbodithioates
Authors: Ho Soo Yei , Tiekink Edward R. T. 
Published: August 2004

Abstract
The molecular structures of Ph3PAu · (S2CC5H6NH2-2) and (4-MeOC6H4)3PAu(S2CC5H6NH2-2) · CH2Cl2 display the expected linear S-Au-P coordination geometries. The hydrogen-bonding functionality in the 1,1-dithiolate ligands, i.e., —NH2 groups, allows for the formation of hydrogen-bonded, i.e., N—H…S, mediated chains in the respective crystal structures.
Field‐Free Switching of Magnetization in Oxide Superlattice by Engineering the Interfacial Reconstruction
Authors: Zheng Dongxing , Fang Yue‐Wen , Wen Yan , Song Kepeng , Li Yan , Fang Bin , Zhang Chenhui , Chen Aitian , Liu Chen , Algaidi Hanin , Tang Meng , Ma Yinchang , Li Peng , Zhang Xixiang 
Published: February 2024

AbstractSpin‐orbit torque resulting from non‐magnetic materials with strong spin‐orbit coupling enables electrically controlled magnetization switching, offering potential applications in ultralow‐power memory and logic devices. However, such switching of perpendicular magnetization usually requires an in‐plane magnetic field along the applied current direction, which limits its use. To address this challenge, an all‐oxide superlattice is designed and fabricated that show both the perpendicular magneto‐crystalline anisotropy and in‐plane magnetic anisotropies induced by interfacial engineering. The results demonstrate that the coexistence of perpendicular and in plane magnetic anisotropy breaks the symmetry and thus enables the pure electrical switching of perpendicular magnetization.
Machine Learning in Soft Matter: From Simulations to Experiments
Authors: Zhang Kaihua , Gong Xiangrui , Jiang Ying 
Published: February 2024

AbstractSoft matter with diverse functionalities that are easily designable has fascinated tremendous research interests in the past several decades. Nevertheless, the inherent confluence of time and length scale ubiquitous in soft matter immensely complicates the elucidation of the structure–property relationship and thereby severely impedes the function exploration of soft materials. Recently, the emergent machine learning (ML) techniques open new paradigms in property prediction and molecular design of functional materials, due to their extraordinarily distinguished performance in the aspect of trend identity and pattern extraction from data, and objective optimization by accelerating the guided search in high‐dimensional spaces. This review exclusively focuses on the current state‐of‐the‐art progress in the development of ML techniques applied in the realms of soft matter, ranging from coarse‐grained simulations to theoretical prediction on the structural formation and macroscopic properties, as well as the optimization and algorithm‐aided design in experiments. Finally, an outlook on the challenges and opportunities for this rapidly evolving field is discussed.
Rational Design of Janus Metal Atomic‐Site Catalysts for Efficient Polysulfide Conversion and Alkali Metal Deposition: Advances and Prospects
Authors: Dai Guangfu , Li Shouzhe , Shi Menglin , Sun Lingxin , Jiang Ying , Hui Kwun Nam , Ye Zhengqing 
Published: February 2024

AbstractAlthough metal–sulfur batteries (M–S batteries, M = Li, Na, K) are promising next‐generation energy‐storage devices because of ultrahigh theoretical energy density, low cost, and environmentally friendliness, their practical applications are significantly hindered by the shuttle effect of polysulfides and growth of alkali metal dendrites. These issues can be mitigated by using Janus metal atomic‐site catalysts, which possess the maximum atom utilization efficiency (≈100%), adjustable electronic structures, and tailorable catalytic sites, thereby effectively improving the electrochemical performance of M–S batteries. In this review, the recent progress and development of Janus metal atomic‐sites on the properties, synthesis, and characterizations are reviewed. Then, the recent advances in Janus metal atomic‐site catalysts intended for accelerating polysulfide conversion and regulating alkali metal deposition, briefly introducing the working principles of the Janus metal atomic‐site catalysts in M–S batteries, are systematically summarized. Furthermore, a high emphasis is placed on effective regulation strategies for the rational design of Janus metal atomic‐site catalysts in M–S batteries. Finally, the current challenges and future research directions are also presented to develop high‐efficiency Janus metal atomic‐site catalysts for high‐energy M–S batteries.
Mn‐Based Artificial Mitochondrial Complex “VI” Acts as an Electron and Free Radical Conversion Factory to Suppress Macrophage Inflammatory Response
Authors: Ren Mingxing , Zhou Chongjing , Li Xinyi , Zhang Yining , Li Meng , Song Haoyue , Liu Fengyi , Chen Tao , Xu Xinxin , Yang Sheng 
Published: February 2024

AbstractDisturbance in the mitochondrial electron transport chain (ETC) is a key factor in the emerging discovery of immune cell activation in inflammatory diseases, yet specific regulation of ETC homeostasis is extremely challenging. In this paper, a mitochondrial complex biomimetic nanozyme (MCBN), which plays the role of an artificial “VI” complex and acts as an electron and free radical conversion factory to regulate ETC homeostasis is creatively developed. MCBN is composed of bovine serum albumin (BSA), polyethylene glycol (PEG), and triphenylphosphine (TPP) hierarchically encapsulating MnO2 polycrystalline particles. It has nanoscale size and biological properties like natural complexes. In vivo and in vitro experiments confirm that MCBN can target the mitochondrial complexes of inflammatory macrophages, absorb excess electrons in ETC, and convert the electrons to decompose H2O2. By reducing the ROS and ATP bursts and converting existing free radicals, inhibiting NLRP3 inflammatory vesicle activation and NF‐κB signaling pathway, MCBN effectively suppresses macrophage M1 activation and inflammatory factor secretion. It also demonstrates good inflammation control and significantly alleviates alveolar bone loss in a mouse model of ligation‐induced periodontitis. This is the first nanozyme that mimics the mitochondrial complex and regulates ETC, demonstrating the potential application of MCBN in immune diseases.
Molecular Motor‐Driven Light‐Controlled Logic‐Gated K+ Channel for Cancer Cell Apoptosis
Authors: Li Cong , Wu Yaqi , Zhu Yihang , Yan Jing , Liu Shengda , Xu Jiayun , Fa Shixin , Yan Tengfei , Zhu Dingcheng , Yan Yi , Liu Junqiu 
Published: February 2024

AbstractDeveloping artificial ion transport systems, which process complicated information and step‐wise regulate properties, is essential for deeply comprehending the subtle dynamic behaviors of natural channel proteins (NCPs). Here a photo‐controlled logic‐gated K+ channel based on single‐chain random heteropolymers containing molecular motors, exhibiting multi‐core processor‐like properties to step‐wise control ion transport is reported. Designed with oxygen, deoxygenation, and different wavelengths of light as input signals, complicated logical circuits comprising “YES”, “AND”, “OR” and “NOT” gate components are established. Implementing these logical circuits with K+ transport efficiencies as output signals, multiple state transitions including “ON”, “Partially OFF” and “Totally OFF” in liposomes and cancer cells are realized, further causing step‐wise anticancer treatments. Dramatic K+ efflux in the “ON” state (decrease by 50% within 7 min) significantly induces cancer cell apoptosis. This integrated logic‐gated strategy will be expanded toward understanding the delicate mechanism underlying NCPs and treating cancer or other diseases is expected.
Sensitive Thermochromic Behavior of InSeI, a Highly Anisotropic and Tubular 1D van der Waals Crystal
Authors: Cordova Dmitri Leo Mesoza , Zhou Yinong , Milligan Griffin M. , Cheng Leo , Kerr Tyler , Ziller Joseph , Wu Ruqian , Arguilla Maxx Q. 
Published: February 2024

AbstractThermochromism, the change in color of a material with temperature, is the fundamental basis of optical thermometry. A longstanding challenge in realizing sensitive optical thermometers for widespread use is identifying materials with pronounced thermometric optical performance in the visible range. Herein, it is demonstrated that single crystals of indium selenium iodide (InSeI), a 1D van der Waals (vdW) solid consisting of weakly bound helical chains, exhibit considerable visible range thermochromism. A strong temperature‐dependent optical band edge absorption shift ranging from 450 to 530 nm (2.8 to 2.3 eV) over a 380 K temperature range with an experimental (dEg/dT)max value extracted to be 1.26 × 10−3 eV K−1 is shown. This value lies appreciably above most dense conventional semiconductors in the visible range and is comparable to soft lattice solids. The authors further seek to understand the origin of this unusually sensitive thermochromic behavior and find that it arises from strong electron–phonon interactions and anharmonic phonons that significantly broaden band edges and lower the Eg with increasing temperature. The identification of structural signatures resulting in sensitive thermochromism in 1D vdW crystals opens avenues in discovering low‐dimensional solids with strong temperature‐dependent optical responses across broad spectral windows, dimensionalities, and size regimes.
Multi‐Functional Spirobifluorene Phosphonate Based Exciplex Interface Enables Voc Reaching 95% of Theoretical Limit for Perovskite Solar Cells
Authors: Hu Xinyu , Shen Ni , Zhang Dezhong , Wu Yanjie , Shang Rui , Wang Lixiang , Qin Chuanjiang 
Published: February 2024

AbstractMetal halide perovskite solar cells (PSCs) show significant advancements in power conversion efficiency (PCE). However, the open‐circuit voltage (VOC) of PSCs is limited by interfacial factors such as defect‐induced recombination, energy band mismatch, and non‐intimate interface contact. Here, an exciplex interface is first developed based on the strategically designed and synthesized two spirobifluorene phosphonate molecules to mitigate VOC loss in PSCs. The exciplex interface constructed by the intimate contact between the multi‐functional molecules and hole transport layer takes the roles to promote the hole extraction by donor–acceptor interaction, passivate coordination‐unsaturated Pb2+ defects by equipped phosphonate groups, and optimize the energy level alignment. As a result, a record VOC of 1.26 V with a perovskite bandgap of 1.61 eV is achieved, representing over 95% of theoretical limit. This advancement leads to an increase in PCE from 21.29% to 24.12% and improved stability. The exciplex interface paves the way for addressing the long‐standing challenge of VOC loss and promotes the wider application of PSCs.
Manual preference, performance, and dexterity for bimanual grass‐feeding behavior in wild geladas (Theropithecus gelada)
Authors: Truppa Valentina , Gamba Marco , Togliatto Roberta , Caselli Marta , Zanoli Anna , Palagi Elisabetta , Norscia Ivan 
Published: February 2024

AbstractWe assessed whether wild geladas, highly specialized terrestrial grass eaters, are lateralized for bimanual grass‐plucking behavior. According to the literature, we expected that complex motor movements in grass feeding would favor the emergence of a population‐level hand bias in these primates. In addition, we described geladas' manual behavior based on systematic observations of several individuals. Our study group included 28 individuals belonging to a population of free‐ranging geladas frequenting the Kundi plateau, Ethiopia. We filmed monkeys while feeding on grass, and hand preference and performance were coded. Geladas performed more plucking movements per second with their left hand (LH) compared to the right one and preferred their LH both to start and finish collection bouts. Also, the rhythmic movements of each hand had a significant tendency toward isochrony. Finally, geladas used forceful pad‐to‐pad precision grips, in‐hand movements, and compound grips to pluck and collect grass blades, considered the most advanced manual skills in primate species. The LH's leading role suggests an advantage of the right hemisphere in regulating geladas' bimanual grass‐feeding behavior. The tactile input from the hands and/or rhythmic hand movements might contribute to explaining this pattern of laterality. Our findings highlighted the importance of adopting multiple laterality measures to investigate manual laterality. Moreover, the need to speed up the execution time of manual foraging might be a further important factor in studying the evolution of manual laterality and dexterity in primates.
Biodegradable Monometallic Aluminum as a Biotuner for Tumor Pyroptosis
Authors: Liang Yuan , Lei Pengpeng , An Ran , Du Pengye , Liu Shuyu , Wei Yi , Zhang Hongjie 
Published: February 2024

AbstractPyroptosis is an effective anti‐tumor strategy. However, monometallic pyroptosis biotuners have not been explored until now. Here, we discover for the first time that biodegradable monometallic Al can act as a pyroptosis biotuner for tumor therapy. pH‐sensitive Al nanoparticles (Al@P) are obtained by equipping polyethylene glycol‐b‐(poly(methyl methacrylate)‐co‐poly(4‐vinylpyridine), which can exert their effect at the tumor site without affecting normal cells. The H2 and Al3+ release by Al@P in the acidic environment of tumors disrupts the redox balance and ionic homeostasis in tumor cells, thus generating large amounts of reactive oxygen species (ROS), leading to caspase‐1 activation, gasdermin D cleavage, and IL‐1β/LDH release, which induces canonical pyroptotic death. Meanwhile, the prodrug Doxorubicin (Pro‐DOX) is successfully loaded onto Al@P (Al@P‐P) and can be activated by ROS to release DOX in the tumor cells, thus further improving the tumor‐killing efficiency. Ultimately, Al@P‐P is degradable and exhibits efficient tumor inhibition.
Adaptisorption of Nonporous Polymer Crystals
Authors: Shan Tianyu , Chen Liya , Xiao Ding , Xiao Xuedong , Wang Jiao , Chen Xuan , Guo Qing‐Hui , Li Guangfeng , Stoddart J. Fraser , Huang Feihe 
Published: February 2024

AbstractAlthough our knowledge and understanding of adsorptions in natural and artificial systems has increased dramatically during the past century, adsorption associated with nonporous polymers remains something of a mystery, hampering applications. Here we demonstrate a model system for adaptisorption of nonporous polymers, wherein dative B−N bonds and host‐guest binding units act as the kinetic and thermodynamic components, respectively. The coupling of these two components enables nonporous polymer crystals to adsorb molecules from solution and undergo recrystallization as thermodynamically favored crystals. Adaptisorption of nonporous polymer crystals not only extends the types of adsorption in which the sorbate molecules are integrated in a precise and orderly manner in the sorbent systems, but also provides a facile and accurate approach to the construction of polymeric materials with precise architectures and integrated functions.
On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales Topologies
Authors: Biswas Kalyan , Chen Qifan , Obermann Sebastian , Ma Ji , Soler‐Polo Diego , Melidonie Jason , Barragán Ana , Sánchez‐Grande Ana , Lauwaet Koen , Gallego José M. , Miranda Rodolfo , Écija David , Jelínek Pavel , Feng Xinliang , Urgel José I. 
Published: February 2024

AbstractThe incorporation of non‐benzenoid motifs in graphene nanostructures significantly impacts their properties, making them attractive for applications in carbon‐based electronics. However, understanding how specific non‐benzenoid structures influence their properties remains limited, and further investigations are needed to fully comprehend their implications. Here, we report an on‐surface synthetic strategy toward fabricating non‐benzenoid nanographenes containing different combinations of pentagonal and heptagonal rings. Their structure and electronic properties were investigated via scanning tunneling microscopy and spectroscopy, complemented by computational investigations. After thermal activation of the precursor P on the Au(111) surface, we detected two major nanographene products. Nanographene Aa−a embeds two azulene units formed through oxidative ring‐closure of methyl substituents, while Aa−s contains one azulene unit and one Stone‐Wales defect, formed by the combination of oxidative ring‐closure and skeletal ring‐rearrangement reactions. Aa−a exhibits an antiferromagnetic ground state with the highest magnetic exchange coupling reported up to date for a non‐benzenoid containing nanographene, coexisting with side‐products with closed shell configurations resulted from the combination of ring‐closure and ring‐rearragement reactions (Ba−a, Ba−s, Bs‐a and Bs−s). Our results provide insights into the single gold atom assisted synthesis of novel NGs containing non‐benzenoid motifs and their tailored electronic/magnetic properties.
Piezofluorochromism in Hierarchical Porous π‐stacked Supermolecular Spring Frameworks from Aromatic Chiral Cages
Authors: Cui Dongxu , Bai Fuquan , Zhang Long , Li Wei , Zhang Yuxiao , Wang Kai , Wu Min , Sun Chunyi , Zang Hongying , Zou Bo , Wang Xinlong , Su Zhongmin 
Published: February 2024

AbstractPiezochromic materials that exhibit pressure‐dependent luminescence variations are attracting interest with wide potential applications in mechanical sensors, anticounterfeiting and storage devices. Crystalline porous materials (CPMs) have been widely studied in piezochromism for highly tunable luminescence. Nevertheless, reversible and high‐contrast emission response with a wide pressure range is still challenging. Herein, the first example of hierarchical porous cage‐based πOF (Cage‐πOF‐1) with spring structure was synthesized by using aromatic chiral cages as building blocks. Its elastic properties evaluated based on the bulk modulus (9.5 GPa) is softer than most reported CPMs and the collapse point (20.0 GPa) significantly exceeds ever reported CPMs. As smart materials, Cage‐πOF‐1 displays linear pressure‐dependent emission and achieves a high‐contrast emission difference up to 154 nm. Pressure‐responsive limit is up to 16 GPa, outperforming the CPMs reported so far. Dedicated experiments and density functional theory (DFT) calculations illustrate that π–π interactions‐dominated controllable structural shrinkage and porous‐spring‐structure‐mediated elasticity is responsible for the outstanding piezofluorochromism.
Unusual Electronic Structures of an Electron Transfer Series of [Cr(μ‐η1 : η1‐N2)Cr]0/1+/2+
Authors: Wang Gao‐Xiang , Shan Chunxiao , Chen Wang , Wu Botao , Zhang Peng , Wei Junnian , Xi Zhenfeng , Ye Shengfa 
Published: February 2024

AbstractIn dinitrogen (N2) fixation chemistry, bimetallic end‐on bridging N2 complexes M(μ‐η1 : η1‐N2)M can split N2 into terminal nitrides and hence attract great attention. To date, only 4d and 5d transition complexes, but none of 3d counterparts, could realize such a transformation. Likewise, complexes {[Cp*Cr(dmpe)]2(μ‐N2)}0/1+/2+ (1–3) are incapable to cleave N2, in contrast to their Mo congeners. Remarkably, cross this series the N−N bond length of the N2 ligand and the N−N stretching frequency exhibit unprecedented nonmonotonic variations, and complexes 1 and 2 in both solid and solution states display rare thermally activated ligand‐mediated two‐center spin transitions, distinct from discrete dinuclear spin crossovers. In‐depth analyses using wave function based ab initio calculations reveal that the Cr‐N2‐Cr bonding in complexes 1–3 is distinguished by strong multireference character and cannot be described by solely one electron configuration or Lewis structure, and that all intriguing spectroscopic observations originate in their sophisticate multireference electronic structures. More critical is that such multireference bonding of complexes 1–3 is at least a key factor that contributes to their kinetic inertness toward N2 splitting. The mechanistic understanding is then used to rationalize the disparate reactivity of related 3d M(μ‐η1 : η1‐N2)M complexes compared to their 4d and 5d analogs.
Bimetallic Synergy Enables Silole Insertion into THF and the Synthesis of Erbium Single‐Molecule Magnets
Authors: De Siddhartha , Mondal Arpan , Giblin Sean R. , Layfield Richard A. 
Published: February 2024

AbstractThe potassium silole K2[SiC4‐2,5‐(SiMe3)2‐3,4‐Ph2] reacts with [M(η8‐COT)(THF)4][BPh4] (M=Er, Y; COT=cyclo‐octatetraenyl) in THF to give products that feature unprecedented insertion of the nucleophilic silicon centre into a carbon‐oxygen bond of THF. The structure of the major product, [(μ‐η8 : η8‐COT)M(μ‐L1)K]∞ (1M), consists of polymeric chains of sandwich complexes, where the spiro‐bicyclic silapyran ligand [C4H8OSiC4(SiMe3)2Ph2]2− (L1) coordinates to potassium via the oxygen. The minor product [(μ‐η8 : η8‐COT)M(μ‐L1)K(THF)]2 (2M) features coordination of the silapyran to the rare‐earth metal. In forming 1M and 2M, silole insertion into THF only occurs in the presence of potassium and the rare‐earth metal, highlighting the importance of bimetallic synergy. The lower nucleophilicity of germanium(II) leads to contrasting reactivity of the potassium germole K2[GeC4‐2,5‐(SiMe3)2‐3,4‐Me2] towards [M(η8‐COT)(THF)4][BPh4], with intact transfer of the germole occurring to give the coordination polymers [{η5‐GeC4(SiMe3)2Me2}M(η8‐COT)K]∞ (3M). Despite the differences in reactivity induced by the group 14 heteroatom, the single‐molecule magnet properties of 1Er, 2Er and 3Er are similar, with thermally activated relaxation occurring via the first‐excited Kramers doublet, subject to effective energy barriers of 122, 80 and 91 cm−1, respectively. Compound 1Er is also analysed by high‐frequency dynamic magnetic susceptibility measurements up to 106 Hz.