bluuebunny/crossref_metadata_2025_split huggingface dataset:
Designing Salen‐Based Porous Organic Polymers for Enhanced Electrolytic Water Splitting into Oxygen
Authors: Pal Hiranmoy , Karmakar Arun , Sadhukhan Arnab , Koner Kalipada , Karak Shayan , Sharma Rahul Kumar , Ghosh Manasi , Dey Krishna Kishor , Pathak Biswarup , Kundu Subrata , Banerjee Rahul 
Published: August 2024

AbstractThe development of electricity‐driven oxygen evolution reaction (OER) is a potent solution for energy storage applications. In recent years, there is a surge in interest in designing transition metal‐based catalysts with stable linkages, presenting an efficient alternative to noble metal‐based electrocatalysts. Transition metal complexes linked by salen ligands garner considerable attention due to their capacity to chelate and stabilize metal ions. This work presents a novel approach by strategically incorporating the metal–salen core into a porous organic polymer (POP) backbone, thereby fabricating a highly effective electrocatalyst for oxygen evolution. The judicious selection of metal–salen active sites, coupled with the intramolecular free volume (IMFV) of the triptycene core and the high specific surface area of the salen–POPs, result in superior OER activity. By precisely tuning the structure through variation of the transition metal in the salen unit, deep insights are gained into their electrocatalytic behavior. Notably, the most efficient catalyst, Ni‐DHDA‐TAT, exhibits an impressively low overpotential (η10) of ≈ 270 mV at a current density of 10 mA cm−2 for OER (in 1 m KOH). Further, Ni‐DHDA‐TAT retains its activity even after 50 h of chronoamperometry and 1000 cyclic voltammetry cycles with negligible degradation in its initial performance.
Adaptive No‐Tip Distribution of Rich Charge‐Density‐Clusters Guiding Confinement Deposition with Repair Function toward Highly Reversible Zinc Anode
Authors: Hu Xiaomeng , He Zhongqian , Zhao Qiwen , Zhou Jie , Wang Changding , Huang Shaozhen , Zhou Gang , Xu Bingang , Wang Bin , Chen Libao , Chen Yuejiao 
Published: August 2024

AbstractThe plating/stripping behavior of Zn ions on the Zn anode, driven by an electric field, is a key process in determining the performance of aqueous zinc ion batteries (AZIBs). Process‐induced unevenness of commercial Zn foils results in poor reversibility of Zn anodes. Herein, a self‐healing dynamic anode/electrolyte interface is constructed by incorporating hydroxyl‐rich alcohols with high charge density and zincophilicity into the original electrolyte. These alcohols selectively anchor on electron‐poor sites in the charging state, inducing domain‐limited deposition of Zn2+ to achieve a dense, uniform, and flat deposition state. As a result, a durable Zn anode with excellent electrochemical reversibility can be realized in practical cycling (average Coulombic efficiency of 99.5%). Even under deep plating/stripping conditions (5 mA cm−2 and 5mAh cm−2), the modified electrolyte exhibits a remarkable repair effect on corroded Zn anodes that have been cycled in base electrolyte, extending the lifespan to over 1,020 h. This represents a 15.6‐fold enhancement in lifespan compared to recycling in the base electrolyte. This strategy for electrolyte additive directly influences the design of ultra‐long‐life AZIBs and provides concrete concepts for the recovery of zinc anodes.
Achieving Ultrahigh Transparency and Superior Mechanical Properties in Flexible Polyimide Nanofoams Through CO2 Foaming for Thermal Insulation
Authors: Li Xin'ao , Zong Yumeng , Li Wenjuan , Qian Jin , Qiang Zhe , Ye Changhuai , Zhu Meifang 
Published: August 2024

AbstractTransparent polymer nanofoams offer significant potential for thermal insulation, particularly for energy‐saving windows, where both transparency and low thermal conductivity are crucial. However, grand challenges remain in preparing polymer nanofoam monoliths with pore sizes smaller than 40 nm to achieve high optical transparency via minimized light scattering. Herein, the preparation of highly transparent nanofoam monoliths based on fluorinated polyimide (FPI) using CO2 foaming is reported for the first time. The high CO2 absorption capacity and robust melt strength of the FPI matrix significantly promote bubble nucleation while minimizing cell coalescence during CO2 foaming process, resulting in ultra‐small pore sizes down to sub‐10 nm. These FPI nanofoams, with a thickness of ≈0.2 mm, can exhibit high optical transmittance (>85% in the wavelength range of 500–700 nm) and low haze (≈18%), which is unprecedented for polymer foams prepared using foaming methods. Furthermore, these FPI nanofoams demonstrate superior mechanical and thermal insulation properties compared to micron‐sized FPI foams and maintain remarkable mechanical flexibility and structural stability even under harsh conditions, including extreme temperatures and water exposure. Transparent nanofoams prepared using a scalable CO2 foaming method can serve as the next‐generation thermal insulation materials, with broad potential applications in energy‐efficient buildings, and aerospace.
Unraveling the Role of Spacer Cations: Toward Constructing Ideal Dion–Jacobson Halide Perovskites
Authors: Lai Zhengxun , Shen Yi , Jiang Bei , Zhang Yuxuan , Meng You , Yin Di , Gao Boxiang , Wang Weijun , Xie Pengshan , Yan Yan , Yip SenPo , Liao Lei , Ho Johnny C. 
Published: August 2024

AbstractDion–Jacobson‐type 2D halide perovskites (DJPs) present an ideal alternative to their 3D counterparts due to their superior stability and exceptional optoelectronic properties. Despite the numerous DJPs proposed in recent years, the impact of different spacer cations on DJPs remains unclear. This understanding is crucial for researchers to select suitable materials and is an urgent requirement for the development of higher‐performance DJPs‐based devices. In this study, the influence of the chain‐like spacer cations with varying branch chains and chain lengths is thoroughly examined using both theoretical and experimental methods. The findings reveal that spacer cations with high polarity components along the main chain direction enhance the stability and photoelectric properties of DJPs. Additionally, it is found that the chain length of the spacer cation plays a critical role. Chain lengths that are too long or too short can detrimentally affect the photoelectric performance and stability of DJPs. These insights will guide researchers in selecting suitable spacer cations and in innovating new types of DJPs.
Tuning the Electronic and Electrochemical Properties of 3D Porous Laser‐Induced Graphene by Electrochemically Induced Deposition of Polyoxovanadate Nanoclusters for Flexible Supercapacitors
Authors: Arya Nikhil , Dinda Sirshendu , Diemant Thomas , Wang Ke , Fichtner Maximilian , Anjass Montaha 
Published: August 2024

AbstractThe advancement of microelectronic devices mandates the development of flexible energy storage systems to enable the fabrication of miniaturized and wearable electronics. Herein, a sustainable approach is demonstrated for tuning the electronic and electrochemical properties of hierarchically porous laser‐induced graphene (LIG) substrates. The methodology entails the electrochemical deposition of polyoxovanadate nanoclusters (K5(CH3CN)3[V12O32Cl] (= K5{V12}) onto the highly porous LIG matrix. The comprehensive characterization is integrated through micro‐Raman spectroscopy and in‐depth X‐ray photoelectron spectroscopy to elucidate the deposition mechanism and electronic properties of the fabricated electrode. The results indicate a significant correlation between the orientation of the deposited clusters and the non‐crystalline regions of the LIG structure. Additionally, the cluster deposition results in a reduction of grain boundary defects in the nano‐graphite lattice of LIG. The optimized electrode exhibits enhanced areal capacitance (CA) of 125 mF cm−2 at a current density of 0.1 mA cm−2, representing a fivefold improvement compared to the undoped LIG substrate. Furthermore, as a proof of concept, a flexible solid‐state symmetrical supercapacitor device, fabricated with a PVA‐H2SO4 gel electrolyte, demonstrates an areal capacitance of 24.92 mF cm−2 at current density of 0.1 mA cm−2 and exhibits exceptional cycling stability, enduring up to 5000 consecutive galvanostatic charge‐discharge cycles.
Lignosulfonate‐Derived Conducting Organohydrogel as Anisotrpic Bioadhesive for Motion‐Artifact‐Free Epidermal Bioelectronics
Authors: Shen Jinlai , Cai Minkun , Li Gang , Guo Chuan Fei , Qiu Xueqing , Qian Yong 
Published: August 2024

AbstractGel‐based adhesives show promising prospects in epidermal bioelectronics because of their potential applications in physiological signal collection and electrical stimulation. An ideal epidermal adhesive should exhibit robust adhesion for lamination and poor adhesion for easy peeling, in addition to strain‐insensitivity in electrical properties for motion‐artifact‐free physiological signal collection. Here, lignosulfonate‐derived organohydrogel adhesives with anisotropic and tunable adhesion, together with unprecedented strain‐insensitivity are synthesized. The organohydrogel exhibits a high interfacial toughness of 728 J m−2 on fresh porcine skin, while the adhesion can be screened by covering a denatured silk fibroin. An anisotropic adhesive with an adhesion heterogeneity is designed, showing a 14.2‐fold difference in adhesion strength along two different directions for on‐demand attachment and removal. The adhesive can transform into a highly porous structure, which has only a 3% resistance increase at 100% strain. The strain‐insensitivity of the adhesive lies in the strong interaction of ions and the 3D porous structure, which enables motion‐artifact‐free and high‐quality electrophysiological signal collection within the strain range of the human skin. The lignosulfonate‐derived on‐demand organohydrogel adhesive is expected to be used in epidermal bioelectronics, human‐machine interaction, metaverse, and beyond.
PAFerroptosis Combined with Metabolic Disturbance of Mito by p52‐ZER6 for Enhanced Cancer Immunotherapy induced by Nano‐Bacilliform‐Enzyme
Authors: Xi Zi‐yue , Fan Chuan‐yong , Zhu Shuang , Nie Gan‐yu , Xi Xin‐ran , Jiang Ying‐ying , Zhou Yao , Mei Yi‐hua , Xu Lu 
Published: August 2024

AbstractThe confused gene expressions and molecular mechanisms for mitochondrial dysfunction of traditional nanoenzymes is a challenge for tumor therapy. Herein, a nano‐bacilliform‐enzyme obtains the ability to inhibit p52‐ZER6 signal pathway, regulate the genes related to mitochondrial metabolism, and possess the GOx/CAT/POD‐like property. NBE acquires catalytic activity from the electronic energy transition. The tannin of NBE as a mitochondrial (Mito)‐targeting guide overloads MitoROS, and then metabolic disorder and lipid peroxidation of Mito membrane occurs, thus leading to a novel death pathway called PAFerroptosis (pyroptosis, apoptosis, and Ferroptosis). Simultaneously, in order to refrain from mitophagy, hydroxychloroquine is mixed with NBE to form a combo with strength pyroptosis. As a result, NBE/combo improves the PAFerroptosis obviously by activation of CD8+T cells and inactivation of MDSC cells, up‐regulating expression of caspase‐3 signal pathway, intercepting DHODH pathway to arrive excellent antitumor effect (93%). Therefore, this study establishes a rational nanoenzyme for mitochondrial dysfunction without mitophagy for effective antitumor therapy.
Encapsulation of Prussian Blue Analogues with Conductive Polymers for High‐Performance Ammonium‐Ion Storage
Authors: Liu Qiang , Zhang Dongzhi , Yang Yunting , Gu Yalan , Liang Zhenyan , Chen Wenshu , Wu Yuping , Hu Linfeng 
Published: August 2024

AbstractMultivalent manganese‐based Prussian blue analogues (Mn‐PBA) possess multi‐electron transfer characteristics and exhibit unique properties for achieving high energy density in ammonium ion batteries (AIBs). However, the irreversible structural collapse and sluggish ionic diffusion kinetics result in inferior rate capability and undesirable lifespan. Herein, guided by theoretical calculations, a series of ultrafine Mn‐PBA@ conductive polymers core–shell composites through an in situ polymerization and encapsulation strategy are synthesized to solve the above existing issues for Mn‐PBA. Among various designed conductive polymers (including the poly‐pyrrole (ppy), polyaniline, and poly(3,4‐ethylenedioxythiophene)) coated on Mn‐PBA, the Mn‐PBA@ppy shows the strongest adsorption for ammonium ions and the highest manganese atom removal energy barrier. Acting as the cathode of AIBs, the designed Mn‐PBA@ppy exhibits a remarkable high capacity of 72 mAh g−1, a super‐stable discharge platform of 0.81 V, and excellent cycling stability of 94% retention for over 300 cycles (0.1 A g−1) with an ultrahigh NH4+ diffusion coefficient of ≈1.38 × 10−8 cm−2 s−1. This work offers an in situ polymer encapsulation approach to simultaneously enhance the ammonium ion diffusion kinetics and structural stability. More importantly, this organic/inorganic interfacial design can promote the development of cathode materials with rapid diffusion kinetics and excellent cyclic stability.
Recurrent carotid paragangliomas in a syndromic patient with a heterozygous missense variant in DNA Methyltransferase 3 Alpha
Authors: German Ryan J. , Vuocolo Blake , Vossaert Liesbeth , Saba Lisa , Fletcher Robin , Tedder Matthew L. , Sadikovic Bekim , Kerkhof Jennifer , Wangler Michael , Bacino Carlos A. ,   The Texome Project
Published: August 2024

AbstractWe report a 40‐year‐old African American female with a novel variant in exon 8 of DNA methyltransferase 3 alpha (DNMT3A), (NM_022552.4: c.905G>C, p.G302A) who presented with a history of recurrent carotid paragangliomas, mediastinal mass, intellectual disability, dysarthria, cholelithiasis, diabetes mellitus, hypertension, and dysmorphic features. We interpret this novel variant as likely pathogenic and causative for the patient's syndromic features of Heyn–Sproul–Jackson syndrome. Heyn–Sproul–Jackson syndrome is a condition caused by gain‐of‐function genetic changes in DNMT3A. Paragangliomas have also been observed in non‐syndromic patients with genetic alterations in DNMT3A. We describe a patient with clinical features of Heyn–Sproul–Jackson syndrome such as intellectual disability, dysarthria, brachydactyly, and lack of brain MRI findings to add evidence to associate paragangliomas with DNMT3A and draw particular attention to the potential involvement of the proline‐tryptophan‐tryptophan‐proline domain of DNMT3A.
Nickel‐Catalyzed Reductive Protocol to Access Silacyclobutanes with Unprecedented Functional Group Tolerance
Authors: Yang Ling‐yun , Qin Ying , Zhao Zhihan , Zhao Dongbing 
Published: August 2024

AbstractWhile significant progress has been made in the area of transition metal‐catalyzed ring‐opening and formal cycloaddition reactions of 1,1‐disubstituted silacyclobutanes (SCBs), synthesizing these SCBs—particularly those bearing additional functional groups—continues to present synthetic challenges. In this context, we present a novel Ni‐catalyzed reductive coupling reaction that combines 1‐chloro‐substituted silacyclobutanes with aryl or vinyl halides and pseudohalides, thereby obviating the need for organometallic reagents. This method facilitates the generation of 1,1‐disubstituted silacyclobutanes with a remarkable tolerance for various functional groups. This approach serves as a complementary and more step‐economical alternative to the commonly used yet moisture‐ and air‐sensitive nucleophilic substitution reactions involving Grignard or lithium reagents. Our initial mechanistic studies indicate that this reaction is initiated by oxidative cleavage of the Si−Cl bond in 1‐chlorosilacyclobutanes, which represents a distinct mechanism from the previously documented reductive coupling processes involving carbon electrophiles and chlorosilanes.
Non‐Equilibrium Dissipative Assembly with Switchable Biological Functions
Authors: Zhao Peng , Zhao Yuanfeng , Lu Yan , Xu Linjie , Li Bohan , Zhao Yingshuai , Zhou Wei , Yan Pu , Wang Youfu , Cao Kecheng , Zheng Yijun 
Published: August 2024

AbstractNatural dissipative assembly (DSA) often exhibit energy‐driven shifts in natural functions. However, creating man‐made DSA that can mimic such biological activities transformation remains relatively rare. Herein, we introduce a cytomembrane‐like dissipative assembly system based on chiral supramolecules. This system employs benzoyl cysteine in an out of equilibrium manner, enabling the shifts in biofunctions while minimizing material use. Specifically, aroyl‐cystine derivatives primarily assemble into stable M‐helix nanofibers under equilibrium conditions. These nanofibers enhance fibroblast adhesion and proliferation through stereospecific interactions with chiral cellular membranes. Upon the addition of chemical fuels, these functional nanofibers temporarily transform into non‐equilibrium nanospheres, facilitating efficient drug delivery. Subsequently, these nanospheres revert to their original nanofiber state, effectively recycling the drug. The programmable function‐shifting ability of this DSA establishes it as a novel, fuel‐driven drug delivery vehicle. And the bioactive DSA not only addresses a gap in synthetic DSAs within biological applications but also sets the stage for innovative designs of ′living′ materials.
Structure‐Based Design of Bicyclic Helical Peptides That Target the Oncogene β‐Catenin
Authors: Yeste‐Vázquez Alejandro , Paulussen Felix M. , Wendt Mathias , Klintrot Rasmus , Schulte Clemens , Wallraven Kerstin , van Gijzel Lieke , Simeonov Boris , van der Gaag Maurice , Gerber Alan , Maric Hans M. , Hennig Sven , Grossmann Tom N. 
Published: August 2024

AbstractThe inhibition of intracellular protein‐protein interactions is challenging, in particular, when involved interfaces lack pronounced cavities. The transcriptional co‐activator protein and oncogene β‐catenin is a prime example of such a challenging target. Despite extensive targeting efforts, available high‐affinity binders comprise only large molecular weight inhibitors. This hampers the further development of therapeutically useful compounds. Herein, we report the design of a considerably smaller peptidomimetic scaffold derived from the α‐helical β‐catenin‐binding motif of Axin. Sequence maturation and bicyclization provided a stitched peptide with an unprecedented crosslink architecture. The binding mode and site were confirmed by a crystal structure. Further derivatization yielded a β‐catenin inhibitor with single‐digit micromolar activity in a cell‐based assay. This study sheds light on how to design helix mimetics with reduced molecular weight thereby improving their biological activity.
Molybdenum Disulfide Induced Phase Control Synthesis of Multi‐dimensional Co3S4‐MoS2 Heteronanostructures via Cation Exchange
Authors: He Yu‐Qing , Xu Hou‐Ming , Zhang Jian‐Ding , Zheng Dong , Zhang Gang , Fan Xu‐Zhuo , Ou‐Yang He , Liu Yu‐Qing , Lv An‐Chen , Zhao Jia‐Wei , Shi Cheng‐Wu , Han Shi‐Kui 
Published: August 2024

AbstractPhase control over cation exchange (CE) reactions has emerged as an important approach for the synthesis of nanomaterials (NMs), enabling precise determination of their reactivity and properties. Although factors such as crystal structure and morphology have been studied for the phase engineering of CE reactions in NMs, there remains a lack of systematic investigation to reveal the impact for the factors in heterogeneous materials. Herein, we report a molybdenum disulfide induced phase control method for synthesizing multidimensional Co3S4‐MoS2 heteronanostructures (HNs) via cation exchange. MoS2 in parent Cu1.94S‐MoS2 HNs are proved to affect the thermodynamics and kinetics of CE reactions, and facilitate the formation of Co3S4‐MoS2 HNs with controlled phase. This MoS2 induced phase control method can be extended to other parent HNs with multiple dimensions, which shows its diversity. Further, theoretical calculations demonstrate that Co3S4 (111)/MoS2 (001) exhibits a higher adhesion work, providing further evidence that MoS2 enables phase control in the HNs CE reactions, inducing the generation of novel Co3S4‐MoS2 HNs. As a proof‐of‐concept application for crystal phase‐ and dimensionality‐dependent of cobalt sulfide based HNs, the obtained Co3S4‐MoS2 heteronanoplates (HNPls) show remarkable performance in hydrogen evolution reactions (HER) under alkaline media. This synthetic methodology provides a unique design strategy to control the crystal structure and fills the gap in the study of heterogeneous materials on CE reaction over phase engineering that are otherwise inaccessible.
Oscillating Structural Transformations in the Electrochemical Synthesis of Graphene Oxide from Graphite
Authors: Gurzęda Bartosz , Jeżowski Paweł , Boulanger Nicolas , Talyzin Alexandr V. 
Published: August 2024

AbstractElectrochemical synthesis of graphene oxide (GO) is known to occur with potential oscillations, but the structural changes underlying these oscillations have remained unclear. In situ time‐resolved synchrotron radiation X‐ray diffraction demonstrates that the electrochemical synthesis of GO in aqueous H2SO4 can be described as an oscillating reaction. The transformation from graphite to GO proceeds through periodic structural oscillations that correlate with potential cycles. Stage‐1 graphite intercalation compound (GIC) is found only at the peak of the potential cycle, but not at the bottom of the cycle. Stage‐1 GIC is formed in the first half‐cycle from stage‐2 GIC and then transforms into “pristine graphite oxide” (PGO) on the lower side of the potential cycle, after which the cycle restarts with the formation of a new portion of stage‐1 GIC. Water‐washing results in the transformation of PGO into water‐swollen GO with d(001) ~11 Å. These periodic structural changes can be considered a new type of oscillating reaction. The presented results provide broad insights into the oscillating structural changes occurring during the anodic graphite oxidation in aqueous H2SO4 and allow to update of the mechanism of GO electrochemical formation.
Recognition and order of multiple sidechains by metal–organic framework enhances the separation of hexane isomers
Authors: Markad Datta , Kershaw Cook Laurence J. , Pétuya Rémi , Yan Yong , Gilford Oliver , Verma Ajay , Mali Bhupendra P. , Robertson Craig M. , Berry Neil G. , Darling George R. , Dyer Matthew S. , Antypov Dmytro , Katsoulidis Alexandros P. , Rosseinsky Matthew J. 
Published: August 2024

AbstractPorous materials perform molecular sorting, separation and transformation by interaction between their framework structures and the substrates. Proteins also interact with molecules to effect chemical transformations, but rely on the precise sequence of the amino acid building units along a common polypeptide backbone to maximise their performance. Design strategies that positionally order sidechains over a defined porous framework to diversify the internal surface chemistry would enhance control of substrate processing. Here we show that different sidechains can be ordered over a metal–organic framework through recognition of their distinct chemistries during synthesis. The sidechains are recognised because each one forces the common building unit that defines the backbone of the framework into a different conformation in order to form the extended structure. The resulting sidechain ordering affords hexane isomer separation performance superior to that of the same framework decorated only with sidechains of a single kind. The separated molecules adopt distinct arrangements within the resulting modified pore geometry, reflecting their strongly differentiated environments precisely created by the ordered sidechains. The development of frameworks that recognize and order multiple sidechain functionality by conformational control offers tailoring of the internal surfaces within families of porous materials to direct interactions at the molecular level.