bluuebunny/crossref_metadata_2025 huggingface dataset:
Exploiting Atomic Control to Show When Atoms Become Molecules
Authors: Kranz Ludwik , Osika Edyta N. , Monir Serajum , Hsueh Yu‐Ling , Fricke Lukas , Hile Samuel J. , Chung Yousun , Keizer Joris G. , Rahman Rajib , Simmons Michelle Y.
Published: November 2023

Precision‐placed atom qubits in silicon offer a unique means to confine electrons and control their spins with extreme accuracy, which can be leveraged to construct powerful quantum computers. To date atom qubits in silicon have been successfully realized using electrons hosted either on a single phosphorus atom or on a multi‐donor quantum dot. Here, a novel molecular regime is explored in which electrons are bound to two donor dots separated by ≈8 nm in a natural silicon substrate. The molecular state, provided by these spatially separated donors, is used to study with exquisite precision the impact of confinement potential on the electronic and spin properties of qubits. Unique spin filling measurements, performed on up to five electrons, confirm how electrons are shared between both sites of the molecule, forming hybridized molecular states. The precise atomic locations of the donor atoms in the silicon lattice are determined by combining the experimental electron spin resonance spectra and the state‐of‐the‐art atomistic modeling of multi‐electron wave‐functions in presence of realistic electric fields. The donor molecule studied in this work exhibits excellent qubit properties and addresses the impact that the confinement potential has, at the atomic scale, on the desired properties of electron spin qubits.
Penta‐Coordinated Y Sites Modulated Single Bi Sites for Promoted Selectivity of Electrochemical CO2 Reduction
Authors: Liang Zhong , Song Lianpeng , Jiang Yong , Liu Jincheng , Zhang Yabin , Zhang Qian , Yan Chun‐Hua , Du Yaping
Published: November 2023

Atomically dispersed catalysts with two active sites have attracted attention in recent years. The two different sites may act synergistically in catalytic reactions or one site as active site and another regulates it. In this work, rare earth (RE)‐based single‐atom combo catalyst BiY/CN (with Y penta‐coordinated) is synthesized and characterized carefully for electrochemical reduction of CO2 to formic acid for the first time. The state of active Bi and Y species in the prepared catalyst is proved by the extended X‐ray absorption fine structure spectra and aberration‐corrected high‐angle annular dark field scanning transmission electron microscopy. The comprehensive experimental results and density functional theory calculations show Y sites covered by hydroxyls not only avoid being poisoned by *HCO2 at working conditions, but also serve as a spectator to affect the charge state of Bi sites, promoting performance by facilitating the transformation of *HCO2 intermediate to HCOOH. This work provides a new perspective on RE elements in electrocatalytic carbon dioxide reactions in future studies.
Recent Advances on NIR‐II Light‐Enhanced Chemodynamic Therapy
Authors: Wu Gui‐long , Tan Xiaofeng , Yang Qinglai
Published: November 2023

Chemodynamic therapy (CDT) is a particular oncological therapeutic strategy by generates the highly toxic hydroxyl radical (•OH) from the dismutation of endogenous hydrogen peroxide (H2O2) via Fenton or Fenton‐like reactions. However, single CDT therapies have been limited by unsatisfactory efficacy. Enhanced chemodynamic therapy (ECDT) triggered by near‐infrared (NIR) is a novel therapeutic modality based on light energy to improve the efficiency of Fenton or Fenton‐like reactions. However, the limited penetration and imaging capability of the visible (400–650 nm) and traditional NIR‐I region (650–900 nm) light‐amplified CDT restrict the prospects for its clinical application. Combined with the high penetration/high precision imaging characteristics of the second near‐infrared (NIR‐II,) nanoplatform, it is expected to kill deep tumors efficiently while imaging the treatment process in real‐time, and more notably, the NIR‐II region radiation with wavelengths above 1000 nm can minimize the irradiation damage to normal tissues. Such NIR‐II ECDT nanoplatforms have greatly improved the effectiveness of CDT therapy and demonstrated extraordinary potential for clinical applications. Accordingly, various strategies have been explored in the past years to improve the efficiency of NIR‐II Enhanced CDT. In this review, the mechanisms and strategies used to improve the performance of NIR‐II‐enhanced CDT are outlined.
UV‐Curing Assisted Direct Ink Writing of Dense, Crack‐Free, and High‐Performance Zirconia‐Based Composites With Aligned Alumina Platelets
Authors: Li Maoyin , Huang Shuigen , Willems Evita , Soete Jeroen , Inokoshi Masanao , Van Meerbeek Bart , Vleugels Jef , Zhang Fei
Published: November 2023

Additive manufacturing (AM) of high‐performance structural ceramic components with comparative strength and toughness as conventionally manufactured ceramics remains challenging. Here, a UV‐curing approach is integrated in direct ink writing (DIW), taking advantage from DIW to enable an easy use of high solid‐loading pastes and multi‐layered materials with compositional changes; while, avoiding drying problems. UV‐curable opaque zirconia‐based slurries with a solid loading of 51 vol% are developed to fabricate dense and crack‐free alumina‐toughened zirconia (ATZ) containing 3 wt% alumina platelets. Importantly, a non‐reactive diluent is added to relieve polymerization‐induced internal stresses, avoid subsequent warping and cracking, and facilitate the de‐binding. For the first time, UV‐curing assisted DIW‐printed ceramic after sintering reveals even better mechanical properties than that processed by a conventional pressing. This is attributed to the aligned alumina platelets, enhancing crack deflection and improving the fracture toughness from 6.8 ± 0.3 MPa m0.5 (compacted) to 7.4 ± 0.3 MPa m0.5 (DIW). The four‐point bending strength of the DIW ATZ (1009 ± 93 MPa) is also higher than that of the conventionally manufactured equivalent (861 ± 68 MPa). Besides homogeneous ceramic, laminate structures are demonstrated. This work provides a valuable hybrid approach to additively manufacture tough and strong ceramic components.
High‐Quality Hybrid Perovskite Thin Films by Post‐Treatment Technologies in Photovoltaic Applications
Authors: Li Mingguang , Zhu Zheng , Wang Zhizhi , Pan Wenjing , Cao Xinxiu , Wu Guangbao , Chen Runfeng
Published: November 2023

Incredible progress in photovoltaic devices based on hybrid perovskite materials has been made in the past few decades, and a record‐certified power conversion efficiency (PCE) of over 26% has been achieved in single‐junction perovskite solar cells (PSCs). In the fabrication of high‐efficiency PSCs, the postprocessing procedures toward perovskites are essential for designing high‐quality perovskite thin films; developing efficient and reliable post‐treatment techniques is very important to promote the progress of PSCs. Here, recent post‐treatment technological reforms toward perovskite thin films are summarized, and the principal functions of the post‐treatment strategies on the design of high‐quality perovskite films have been thoroughly analyzed by dividing into two categories in this review: thermal annealing (TA)‐related technique and TA‐free technique. The latest research progress of the above two types of post‐treatment techniques is summarized and discussed, focusing on the optimization of postprocessing conditions, the regulation of perovskite qualities, and the enhancement of device performance. Finally, an outlook of the prospect trends and future challenges for the fabrication of the perovskite layer and the production of highly efficient PSCs is given.
1D Insertion Chains Induced Small‐Polaron Collapse in MoS2 2D Layers Toward Fast‐Charging Sodium‐Ion Batteries
Authors: Lv Zhuoran , Zhao Chendong , Xie Miao , Cai Mingzhi , Peng Baixin , Ren Dayong , Fang Yuqiang , Dong Wujie , Zhao Wei , Lin Tianquan , Lv Ximeng , Zheng Gengfeng , Huang Fuqiang
Published: November 2023

Molybdenum disulfide (MoS2) with high theoretical capacity is viewed as a promising anode for sodium‐ion batteries but suffers from inferior rate capability owing to the polaron‐induced slow charge transfer. Herein, a polaron collapse strategy induced by electron‐rich insertions is proposed to effectively solve the above issue. Specifically, 1D [MoS] chains are inserted into MoS2 to break the symmetry states of 2D layers and induce small‐polaron collapse to gain fast charge transfer so that the as‐obtained thermodynamically stable Mo2S3 shows metallic behavior with 107 times larger electrical conductivity than that of MoS2. Theoretical calculations demonstrate that Mo2S3 owns highly delocalized anions, which substantially reduce the interactions of Na−S to efficiently accelerate Na+ diffusion, endowing Mo2S3 lower energy barrier (0.38 vs 0.65 eV of MoS2). The novel Mo2S3 anode exhibits a high capacity of 510 mAh g−1 at 0.5 C and a superior high‐rate stability of 217 mAh g−1 at 40 C over 15 000 cycles. Further in situ and ex situ characterizations reveal the in‐depth reversible redox chemistry in Mo2S3. The proposed polaron collapse strategy for intrinsically facilitating charge transfer can be conducive to electrode design for fast‐charging batteries.
Trisulfide Bond‐Mediated Molecular Phototheranostic Platform for “Activatable” NIR‐II Imaging‐Guided Enhanced Gas/Chemo‐Hypothermal Photothermal Therapy
Authors: Wu Gui‐long , Liu Fen , Li Na , Fu Qian , Wang Cheng‐kun , Yang Sha , Xiao Hao , Tang Li , Wang Feirong , Zhou Wei , Wang Wenjie , Kang Qiang , Li Zelong , Lin Nanyun , Wu Yinyin , Chen Guodong , Tan Xiaofeng , Yang Qinglai
Published: November 2023

Tumor microenvironment (TME)‐triggered phototheranostic platform offers a feasible strategy to improve cancer diagnosis accuracy and minimize treatment side effects. Developing a stable and biocompatible molecular phototheranostic platform for TME‐activated second near‐infrared (NIR‐II) fluorescence imaging‐guided multimodal cascade therapy is a promising strategy for creating desirable anticancer agents. Herein, a new NIR‐II fluorescence imaging‐guided activatable molecular phototheranostic platform (IR‐FEP‐RGD‐S‐S‐S‐Fc) is presented for actively targeted tumor imaging and hydrogen sulfide (H2S) gas‐enhanced chemodynamic‐hypothermal photothermal combined therapy (CDT/HPTT). It is revealed for the first time that the coupling distance between IR‐FE and ferrocene is proportional to the photoinduced electron transfer (PET), and the aqueous environment is favorable for PET generation. The part of Cyclic‐RGDfK (cRGDfk) peptides can target the tumor and benefit the endocytosis of nanoparticles. The high‐concentration glutathione (GSH) in the TME will separate the fluorescence molecule and ferrocene by the GSH‐sensitive trisulfide bond, realizing light‐up NIR‐II fluorescence imaging and a cascade of trimodal synergistic CDT/HPTT/gas therapy (GT). In addition, the accumulation of hydroxyl radicals (•OH) and down‐regulation of glutathione peroxidase 4 (GPX4) can produce excessive harmful lipid hydroperoxides, ultimately leading to ferroptosis.
Smart Dual‐Exsolved Self‐Assembled Anode Enables Efficient and Robust Methane‐Fueled Solid Oxide Fuel Cells
Authors: Hu Feng , Chen Kongfa , Ling Yihan , Huang Yonglong , Zhao Sunce , Wang Sijiao , Gui Liangqi , He Beibei , Zhao Ling
Published: November 2023

Perovskite oxides have emerged as alternative anode materials for hydrocarbon‐fueled solid oxide fuel cells (SOFCs). Nevertheless, the sluggish kinetics for hydrocarbon conversion hinder their commercial applications. Herein, a novel dual‐exsolved self‐assembled anode for CH4‐fueled SOFCs is developed. The designed Ru@Ru‐Sr2Fe1.5Mo0.5O6‐δ(SFM)/Ru‐Gd0.1Ce0.9O2‐δ(GDC) anode exhibits a unique hierarchical structure of nano‐heterointerfaces exsolved on submicron skeletons. As a result, the Ru@Ru‐SFM/Ru‐GDC anode‐based single cell achieves high peak power densities of 1.03 and 0.63 W cm−2 at 800 °C under humidified H2 and CH4, surpassing most reported perovskite‐based anodes. Moreover, this anode demonstrates negligible degradation over 200 h in humidified CH4, indicating high resistance to carbon deposition. Density functional theory calculations reveal that the created metal‐oxide heterointerfaces of Ru@Ru‐SFM and Ru@Ru‐GDC have higher intrinsic activities for CH4 conversion compared to pristine SFM. These findings highlight a viable design of the dual‐exsolved self‐assembled anode for efficient and robust hydrocarbon‐fueled SOFCs.
Palladium‐Catalyzed α‐Selective Halogenation of Triptycene Using Sulfur Directing Group
Authors: Ueno Keisuke , Nishii Yuji , Hirano Koji , Miura Masahiro
Published: November 2023

Functionalized triptycene derivatives have attracted significant research interest because of their potential applications in many research fields. Although the conventional Diels‐Alder reaction of anthracenes with benzynes has been a versatile synthetic tool for functionalized triptycenes, it is hardly possible to control the product regioselectivity. In this report, we demonstrate the selective synthesis of 1,8,13‐trisubstituted triptycenes by Pd‐catalyzed α‐bromination. As for the directing group, SMe group was the most effective to facilitate the halogenation of the proximal three benzene rings. The obtained product was further derivatized through allylation and Rh‐catalyzed hydroboration reactions.
Capturing Doublet Intermediate Emitters by Chemically Crosslinking Confinement towards Spatiotemporal Encryption
Authors: Li Haomin , Lei Huanyu , Ma Shudeng , Song Tianfu , Li Yan , Yu Haifeng
Published: November 2023

Photoluminescence is one of the most meticulous ways to manipulate light energy. Typical photoluminescent emitters are mostly stable substances with a pure photophysical process of spontaneous photon‐emission from their excited states. Intermediate emitters are elusive attributing to their synchronous energy transfer process including photophysical and incomplete photochemical pathways. An intermediate emitter containing radicals is more difficult to be observed due to its inherent chemical reactivity. Here, these challenges are overcome by spontaneously formed space limitations in polymer crosslinking networks meanwhile chemically active intermediates are captured. These doublet intermediates exhibit unique long‐wavelength emissions under chemically crosslinking confinement conditions, and their luminous mechanism provides a novel perspective for designing intermediate emitters with liquid‐crystal character and photoresponsive features towards spatiotemporal encryption, promising for the detection of photochemical reactions and the development of fascinating luminescent systems.
Nickel‐Catalyzed Asymmetric Propargyl‐Aryl Cross‐Electrophile Coupling
Authors: Ding Linlin , Zhao Yue , Lu Hongjian , Shi Zhuangzhi , Wang Minyan
Published: November 2023

Performing asymmetric cross‐coupling reactions between propargylic electrophiles and aryl nucleophiles is a well‐established method to build enantioenriched benzylic alkynes. Here, a catalytic enantioselective propargyl‐aryl cross‐coupling between two electrophiles was achieved for the first time in a stereoconvergent manner. Propargylic chlorides were treated with aryl iodides as well as heteroaryl iodides in the presence of a chiral nickel complex, and manganese metal was used as a stoichiometric reductant, allowing for the construction of a propargyl C‐aryl bond under mild conditions. An alternative dual nickel/photoredox catalytic protocol was also developed for this cross‐electrophile coupling in the absence of a metal reductant. The potential utility of this conversion is demonstrated in the facile construction of stereoenriched bioactive molecule derivatives and medicinal compounds based on the diversity of acetylenic chemistry. Detailed experimental studies have revealed the key mechanistic features of this transformation.
One‐Dimensionally Arranged Quantum‐Dot Superstructures Guided by a Supramolecular Polymer Template
Authors: Yamauchi Mitsuaki , Nakatsukasa Kanako , Kubo Naoki , Yamada Hiroko , Masuo Sadahiro
Published: November 2023

Colloidal quantum dots (QDs) exhibit important photophysical properties, such as long‐range energy diffusion, miniband formation, and collective photoluminescence, when aggregated into well‐defined superstructures, such as three‐dimensional (3D) and two‐dimensional (2D) superlattices. However, the construction of one‐dimensional (1D) QD superstructures, which have a simpler arrangement, is challenging; therefore, the photophysical properties of 1D‐arranged QDs have not been studied previously. Herein, we report a versatile strategy to obtain 1D‐arranged QDs using a supramolecular polymer (SP) template. The SP is composed of self‐assembling cholesterol derivatives containing two amide groups for hydrogen bonding and a carboxyl group as an adhesion moiety on the QDs. Upon mixing the SP and dispersed QDs in low‐polarity solvents, the QDs self‐adhered to the SP and self‐arranged into 1D superstructures through van der Waals interactions between the surface organic ligands of the QDs, as confirmed by transmission electron microscopy. Furthermore, we revealed efficient photoinduced fluorescence resonance energy transfer between the 1D‐arranged QDs by an in‐depth analysis of the emission spectra and decay curves.
Self‐Assembly of an [M8L24]16+ Intertwined Cube and a Giant [M12L16]24+ Orthobicupola
Authors: Baby Sainaba Arppitha , Venkateswarulu Mangili , Bhandari Pallab , Clegg Jack K. , Sarathi Mukherjee Partha
Published: November 2023

Through coordination‐driven self‐assembly, aesthetically captivating structures can be formed by tuning the length or flexibility of various components. The self‐assembly of an elongated rigid terphenyl‐based tetra‐pyridyl ligand (L1) with a cis‐Pd(II) acceptor produces an [M12L16]24+ triangular orthobicupola structure (1). When flexibility is introduced into the ligand by the incorporation of a ‐CH2‐ group between the dipyridylamine and terphenyl rings in the ligand (L2), anunique [M8L24]16+ water‐soluble ‘intertwined cubic structure’ (2) results. The inherent flexibility of ligand L2 might be the key factor behind the formation of the thermodynamically stable and ′intertwined cubic structure′ in this scenario. This research showcases the ability to design and fabricate novel, topologically distinctive molecular structures by a straightforward and efficient approach.
Room‐Temperature Salt Template Synthesis of Nitrogen‐Doped 3D Porous Carbon for Fast Metal‐Ion Storage
Authors: Chen Bochao , Qi Zijia , Chen Biao , Liu Xin , Li Huan , Han Xiaopeng , Zhou Guangmin , Hu Wenbin , Zhao Naiqin , He Chunnian
Published: November 2023

The water‐soluble salt‐template technique holds great promise for fabricating 3D porous materials. However, an equipment‐free and pore‐size controllable synthetic approach employing salt‐template precursors at room temperature has remained unexplored. Herein, we introduce a green room‐temperature antisolvent precipitation strategy for creating salt‐template self‐assembly precursors to universally produce 3D porous materials with controllable pore size. Through a combination of theoretical simulations and advanced characterization techniques, we unveil the antisolvent precipitation mechanism and provide guidelines for selecting raw materials and controlling the size of precipitated salt. Following the calcination and washing steps, we achieve large‐scale and universal production of 3D porous materials and the recycling of the salt templates and antisolvents. The optimized nitrogen‐doped 3D porous carbon (N‐3DPC) materials demonstrate distinctive structural benefits, facilitating a high capacity for potassium‐ion storage along with exceptional reversibility. This is further supported by in situ electrochemical impedance spectra, in situ Raman spectroscopy, and theoretical calculations. The anode shows a high rate capacity of 181 mAh g−1 at 4 A g−1 in the full cell. This study addresses the knowledge gap concerning the room‐temperature synthesis of salt‐template self‐assembly precursors for the large‐scale production of porous materials, thereby expanding their potential applications for electrochemical energy conversion and storage.
Multiplying Oxygen Permeability of a Ruddlesden‐Popper Oxide by Orientation Control via Magnets
Authors: Zhao Zhijun , Chen Guoxing , Escobar Cano Giamper , Kißling Patrick A. , Stölting Oliver , Breidenstein Bernd , Polarz Sebastian , Bigall Nadja C. , Weidenkaff Anke , Feldhoff Armin
Published: November 2023

Ruddlesden‐Popper‐type oxides exhibit remarkable chemical stability in comparison to perovskite oxides. However, they display lower oxygen permeability. We present an approach to overcome this trade‐off by leveraging the anisotropic properties of Nd2NiO4+δ. Its (a,b)‐plane, having oxygen diffusion coefficient and surface exchange coefficient several orders of magnitude higher than its c‐axis, can be aligned perpendicular to the gradient of oxygen partial pressure by a magnetic field (0.81 T). A stable and high oxygen flux of 1.40 mL min−1 cm−2 was achieved for at least 120 h at 1223 K by a textured asymmetric disk membrane with 1.0 mm thickness under the pure CO2 sweeping. Its excellent operational stability was also verified even at 1023 K in pure CO2. These findings highlight the significant enhancement in oxygen permeation membrane performance achievable by adjusting the grain orientation. Consequently, Nd2NiO4+δ emerges as a promising candidate for industrial applications in air separation, syngas production, and CO2 capture under harsh conditions.
Diphosphine Ligand‐Enabled Nickel‐Catalyzed Chelate‐Assisted Inner‐Selective Migratory Hydroarylation of Alkenes
Authors: He Hua‐Dong , Chitrakar Ravi , Cao Zhi‐Wei , Wang Dao‐Ming , She Li‐Qin , Zhao Peng‐Gang , Wu Yichen , Xu Yuan‐Qing , Cao Zhong‐Yan , Wang Peng
Published: November 2023

The precise control of the regioselectivity in the transition metal‐catalyzed migratory hydrofunctionalization of alkenes remains a big challenge. With a transient ketimine directing group, the nickel‐catalyzed migratory β‐selective hydroarylation and hydroalkenylation of alkenyl ketones has been realized with aryl boronic acids using alkyl halide as the mild hydride source for the first time. The key to this success is the use of a diphosphine ligand, which is capable of the generation of a Ni(II)‐H species in the presence of alkyl bromide, and enabling the efficient migratory insertion of alkene into Ni(II)‐H species and the sequent rapid chain walking process. The present approach diminishes organosilanes reductant, tolerates a wide array of complex functionalities with excellent regioselective control. Moreover, this catalytic system could also be applied to the migratory hydroarylation of alkenyl azahetereoarenes, thus providing a general approach for the preparation of 1,2‐aryl heteroaryl motifs with wide potential applications in pharmaceutical discovery.
Converting Waste Plastic to Liquid Organic Hydrogen Carriers
Authors: Soltani Mahdokht , Rorrer Julie E.
Published: November 2023

The accumulation of waste plastics in landfills and the environment, as well as the contribution of plastics manufacturing to global warming, call for the development of new technologies that would enable circularity for synthetic polymers. Thus far, emerging approaches for chemical recycling of plastics have largely focused on producing fuels, lubricants, and/or monomers. In a recent study, Junde Wei and colleagues demonstrated a new catalytic system capable of converting oxygen‐containing aromatic plastic waste into liquid organic hydrogen carriers (LOHCs), which can be used for hydrogen storage. The authors utilized Ru−ReOx/SiO2 materials with zeolite HZSM‐5 as a co‐catalyst for the direct hydrodeoxygenation (HDO) of oxygen‐containing aromatic plastic wastes that yield cycloalkanes as LOHCs with a theoretical hydrogen capacity of ≈5.74 wt % under mild reaction conditions. Subsequent efficiency and stability tests of cycloalkane dehydrogenation over Pt/Al2O3 validated that the HDO products can serve as LOHCs to generate H2 gas. Overall, their approach not only opens doors to alleviating the severe burden of plastic waste globally, but also offers a way to generate clean energy and ease the challenges associated with hydrogen storage and transportation.
Dormancy and double‐activation strategy for construction of high‐performance mixed‐matrix membranes
Authors: Li Shuo , Han Wei‐Yao , Wang Zhao‐Xu , Sun Yu‐Jie , Zheng Zilong , Yin Ming‐Jie , Liu Shaomin , An Quan‐Fu
Published: November 2023

Mixed‐matrix membranes (MMMs) have the potential for energy‐efficient gas separation by matching the superior mass transfer and anti‐plasticization properties of the fillers with processability and scaling up features of the polymers. However, construction of high‐performance MMMs has been prohibited due to low filler‐loading and the existence of interfacial defects. Here, high MOF‐loaded, i.e., 55 wt %, MMMs are developed by a ‘dormancy and double‐activation’ (DDA) strategy. High MOF precursor concentration suppresses crystallization in the membrane casting solution, realizing molecular level mixing of all components. Then, the polymeric matrix was formed with uniform encapsulation of MOF nutrients. Subsequently, double‐activation was employed to induce MOF crystallization: the alkali promotes MOFs nucleation to harvest small porous nanocrystals while excessive ligands activate the metal ions to enhance the MOFs conversion. As such, quasi‐semi‐continuous mass transfer channels can be formed in the MMMs by the connected MOFs nanocrystals to boost the gas permeability. The optimized MMM shows significantly ameliorated CO2 permeability, i.e., 2841 Barrer, five‐fold enhancement compared with pristine polymer membrane, with a good CO2/N2 selectivity of 36. Besides, the nanosized MOFs intensify their interaction with polymer chains, endowing the MMMs with good anti‐plasticization behaviour and stability, which advances practical application of MMMs in carbon capture.
(3+2) Annulation of 4‐Acetoxy Allenoate with Aldimine Enabled by AgF‐Assisted P(III)/P(V) Catalysis
Authors: Qian Jinlong , Zhou Lijin , Peng Rouxuan , Tong Xiaofeng
Published: November 2023

A phosphine‐catalyzed (3+2) annulation of 4‐acetoxy allenoate and aldimine with the assistance of AgF is described. The success of this reaction hinges on the metathesis between the enolate‐phosphonium zwitterion and AgF, leading to a key intermediate comprising of silver enolate and a fluorophosphorane P(V)‐moiety. The former is able to undergo a Mannich reaction with aldimine, whereas the latter initiates a cascade sequence of AcO‐elimination/aza‐addition, thus furnishing the P(III)/P(V) catalysis. By taking advantage of the silver enolate, a preliminary attempt at an asymmetric variant was conducted with the combination of an achiral phosphine catalyst and a chiral bis(oxazolinyl)pyridine ligand (PyBox), giving moderate enantioselectivity.
Fully Aromatic Self‐Assembled Hole‐Selective Layer toward Efficient Inverted Wide‐Bandgap Perovskite Solar Cells with Ultraviolet Resistance
Authors: Li Chi , Zhang Zilong , Zhang Huifeng , Yan Wenlong , Li Yuheng , Liang Lusheng , Yu Wei , Yu Xuteng , Wang Yao , Yang Ye , Nazeeruddin Mohammad Khaja , Gao Peng
Published: November 2023

Ultraviolet‐induced degradation has emerged as a critical stability concern impeding the widespread adoption of perovskite solar cells (PSCs), particularly in the context of phase‐unstable wide‐band gap perovskite films. This study introduces a novel approach by employing a fully aromatic carbazole‐based self‐assembled monolayer, denoted as (4‐(3,6‐dimethoxy‐9H‐carbazol‐9‐yl)phenyl)phosphonic acid (MeO‐PhPACz), as a hole‐selective layer (HSL) in inverted wide‐band gap PSCs. Incorporating a conjugated linker plays a pivotal role in promoting the formation of a dense and highly ordered HSL on substrates, facilitating subsequent perovskite interfacial interactions, and fostering the growth of uniform perovskite films. The high‐quality film could effectively suppress interfacial non‐radiative recombination, improving hole extraction/transport efficiency. Through these advancements, the optimized wide‐band gap PSCs, featuring a band gap of 1.68 eV, attain an impressive power conversion efficiency (PCE) of 21.10 %. Remarkably, MeO‐PhPACz demonstrates inherent UV resistance and heightened UV absorption capabilities, substantially improving UV resistance for the targeted PSCs. This characteristic holds significance for the feasibility of large‐scale outdoor applications.
Multi‐d Electron Synergy in LaNi1‐xCoxRu Intermetallics Boosts Electrocatalytic Hydrogen Evolution
Authors: Shen Shijie , Zhang Huanhuan , Song Kai , Wang Zongpeng , Shang Tongtong , Gao Ang , Zhang Qinghua , Gu Lin , Zhong Wenwu
Published: November 2023

Despite the fact that d‐band center theory links the d electron structure of transition metals to their catalytic activity, it is yet unknown how the synergistic effect of multi‐d electrons impacts catalytic performance. Herein, novel LaNi1‐xCoxRu intermetallics containing 5d, 4d, and 3d electrons were prepared. In these compounds, the 5d orbital of La transfers electrons to the 4d orbital of Ru, which provides adsorption sites for H*. The 3d orbitals of Ni and Co interact with the 5d and 4d orbitals to generate an anisotropic electron distribution, which facilitates the adsorption and desorption of OH*. The synergistic effect of multi‐d electrons ensures efficient catalytic activity. The optimized LaNi0.5Co0.5Ru has an overpotential of 43mV at 10 mA cm−2 for alkaline electrocatalytic hydrogen evolution reaction. Beyond offering a variety of new electrocatalysts, this work reveals the multi‐d electron synergy in promoting catalytic reaction.
Achieving the High Capacity and High Stability of Li‐Rich Oxide Cathode in Garnet‐Based Solid‐State Battery
Authors: Chen Butian , Zhang Jicheng , Wong Deniz , Wang Tenghui , Li Taiguang , Liu Chong , Sun Limei , Liu Xiangfeng
Published: November 2023

Solid‐state batteries (SSBs) based on Li‐rich Mn‐based oxide (LRMO) cathodes attract much attention because of their high energy density as well as high safety. But their development was seriously hindered by the interfacial instability and inferior electrochemical performance. Herein, we design a three‐dimensional foam‐structured GaN−Li composite anode and successfully construct a high‐performance SSB based on Co‐free Li1.2Ni0.2Mn0.6O2 cathode and Li6.5La3Zr1.5Ta0.5O12 (LLZTO) solid electrolyte. The interfacial resistance is considerably reduced to only 1.53 Ω cm2 and the assembled Li symmetric cell is stably cycled more than 10,000 h at 0.1–0.2 mA cm−2. The full battery shows a high initial capacity of 245 mAh g−1 at 0.1 C and does not show any capacity degradation after 200 cycles at 0.2 C (≈100 %). The voltage decay is well suppressed and it is significantly decreased from 2.96 mV/cycle to only 0.66 mV/cycle. The SSB also shows a very high rate capability (≈170 mAh g−1 at 1 C) comparable to a liquid electrolyte‐based battery. Moreover, the oxygen anion redox (OAR) reversibility of LRMO in SSB is much higher than that in liquid electrolyte‐based cells. This study offers a distinct strategy for constructing high‐performance LRMO‐based SSBs and sheds light on the development and application of high‐energy density SSBs.
A Pyrene‐Fused Dimerized Acceptor for Ternary Organic Solar Cells with 19% Efficiency and High Thermal Stability
Authors: Liu Xucong , Zhang Zhou , Wang Chao , Zhang Cuifen , Liang Shijie , Fang Haisheng , Wang Bo , Tang Zheng , Xiao Chengyi , Li Weiwei
Published: November 2023

A pyrene‐fused dimerized electron acceptor has been successfully synthesized and subsequently incorporated as the third component in ternary organic solar cells (OSCs). Diverging from the traditional dimerized acceptors with a linear configuration, this novel electron acceptor displays a distinctive “butterfly‐like” structure, comprising two Y‐acceptors as wings fused with a pyrene‐based backbone. The extended π‐conjugated backbone and the electron‐donating nature of pyrene enable the new acceptor to show low solubility, elevated glass transition temperature (Tg), and low‐lying frontier energy levels. Consequently, the new dimerized acceptor seamlessly integrates as the third component into ternary OSCs, enhancing electron transporting properties, reducing non‐radiative voltage loss, and elevating open‐circuit voltage. These merits have enabled the ternary OSCs to show an exceptional efficiency of 19.07%, a marked improvement compared to the 17.6% attained in binary OSCs. More importantly, the high Tg exhibited by the pyrene‐fused electron acceptor helps to stabilize the morphology of the photoactive layer thermal‐treated at 70 °C, retaining 88.7% efficiency over 600 hours. For comparison, binary OSCs experience a decline to 73.7% efficiency after the same duration. These results indicate that the “butterfly‐like” design and the incorporation of a pyrene unit is a promising strategy in the development of dimerized electron acceptors for OSCs.
Modulating Skeletons of Covalent Organic Framework for High‐Efficiency Gold Recovery
Authors: Liu Minghao , Jiang Di , Fu Yubin , Zheng Chen George , Bi Shuai , Ding Xuesong , He Jun , Han Bao‐Hang , Xu Qing , Zeng Gaofeng
Published: November 2023

Covalent organic frameworks (COFs) have attracted considerable attention as adsorbents for capturing and separating gold from electronic wastes. To enhance the binding capture efficiency, constructing hydrogen‐bond nanotraps along the pore walls was one of the most widely adopted approaches. However, the development of absorbing skeletons was ignored due to the weak binding ability of the gold salts (Au). Herein, we demonstrated skeleton engineering to construct highly efficiently absorbs for Au capture. The strong electronic donating feature of diarylamine units enhanced the electronic density of binding sites (imine‐linkage) and thus resulted in high capacities over 1750 mg g−1 for all three COFs. Moreover, the absorbing performance was further improved via the ionization of diarylamine units. The ionic COF achieved 90 % of the maximal adsorption capacity, 1.63 times of that from the charge‐neutral COF within ten minutes, and showed remarkable uptakes of 1834 mg g−1, exceptional selectivity (97.45 %) and cycling stability. The theoretical calculation revealed the binding sites altering from imine bonds to ionic amine sites after ionization of the frameworks, which enabled to bind the AuCl4− via coulomb force and contributed to enhanced absorbing kinetics. This work inspires us to design molecular/ionic capture based on COFs.
Novel nitrogen‐rich anchored nickel (II) phthalocyanine with composite of multiwalled carbon nanotubes on modified glassy carbon electrode: Sensitive and selective electrocatalytic activity of nitrite
Authors: Mounesh  , Reddy K. R. Venugopala , Pandith Anup , Eldesoky Gaber E. , Nagaraja Bhari Mallanna
Published: November 2023

This work describes the synthesis of novel nickel tetra substituted 6‐bromobenzothiazole carboxamide nickel (II) phthalocyanine (NiTBBTCAPc) and confirmed by spectroscopic‐microscopic methods and as well as electrochemical analysis. The electrochemical oxidation of nitrite was studied on NiTBBTCAPc‐multiwalled carbon nanotube (MWCNTs)/glassy carbon electrode (GCE) due to its better electron transferring ability than bare GCE and NiTBBTCAPc/GCE. As there is acceleration in surface area of GCE by multiwalled carbon nanotubes, a cyclic voltammetry (CV), differential pulse voltammetry (DPV), and amperometric techniques utilized for nitrite sensor were developed. The sensor exhibited a fast response towards nitrite with a detection limit of 3.012 nM and a linear concentration range of 50–900 nM by the CV method. The fabricated sensor shows excellent electrocatalytic activity compared with the modified electrode with Pc with a composite of MWCNTs towards oxidation of nitrite. The NiTBBTCAPc‐MWCNTs/GCE shows good repeatability, stability, and high selectivity even in the presence of excess ascorbic acid (AA), dopamine (DA), uric acid (UA), paracetamol (PA), glucose, Pb (II), Cd (II), Ca (II), and Mg (II). Finally, for usage in practical applications, the modified electrode was employed to achieve quantitative detection of nitrite in drinking water and cabbage vegetable samples, respectively.
Amino Acids Fueling Fibroblast‐Like Synoviocyte Activation and Arthritis By Regulating Chemokine Expression and Leukocyte Migration
Authors: Karonitsch Thomas , Saferding Victoria , Kieler Markus , von Dalwigk Karolina , Tosevska Anela , Heller Gerwin , Dellinger Mirjam , Niederreiter Birgit , Kartnig Felix , Steiner Carl W. , Georgel Philippe , Kiener Hans P. , Smolen Josef S. , Korb‐Pap Adelheid , Bonelli Michael , Aletaha Daniel , Blüml Stephan
Published: November 2023

Objective

We analyzed the impact of amino acid (AA) availability on the inflammatory response in arthritis.

Methods

We stimulated rheumatoid arthritis (RA) fibroblast‐like synoviocytes (FLSs) with tumor necrosis factor (TNF) in the presence or absence of proteinogenic AAs and measured their response by QuantSeq 3′ messenger RNA sequencing, quantitative polymerase chain reaction, and enzyme‐linked immunosorbent assay. Signal transduction events were determined by Western blot. We performed K/BxN serum transfer arthritis in mice receiving a normal and a low‐protein diet and analyzed arthritis clinically and histologically.

Results

Deprivation of AAs decreased the expression of a specific subset of genes, including the chemokines CXCL10, CCL2, and CCL5 in TNF‐stimulated FLSs. Mechanistically, the presence of AAs was required for the TNF‐induced activation of an interferon regulatory factor 1 (IRF1)‐STAT1 signaling circuit that drives the expression of chemotactic factors. The expression of IRF1 and the IRF1‐dependent gene set in FLSs was highly correlated with the presence of inflammatory cells in human RA, emphasizing the important role of this AA‐dependent pathway in inflammatory cell recruitment to the synovial tissue. Finally, we show that mice receiving a low‐protein diet expressed less IRF1 in the inflamed synovium and consequently developed reduced clinical and histologic signs of arthritis.

Conclusion

AA deprivation reduces the severity of arthritis by suppressing the expression of IRF1‐STAT1–driven chemokines, which are crucial for leukocyte recruitment to the arthritic joint. Overall, our study provides novel insights into critical determinants of inflammatory arthritis and may pave the way for dietary intervention trials in RA.

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Utilisation and impact of predict prostate on decision‐making among clinicians and patients in a specialist tertiary referral centre: A retrospective cohort study
Authors: Pandiaraja Madhumitha , Pryle Isolde , West Leah , Gardner Lucy , Shallcross Olivia , Tay June , Shah Nimish , Gnanapragasam Vincent , Lamb Benjamin W.
Published: November 2023

Background

Patients with intermediate‐risk prostate cancer are faced with the decision of whether to undergo radical treatment. Decision‐making aids, such as Predict Prostate, can empower both clinicians and patients to make treatment decisions with personalised information, but their impact on multi‐disciplinary team (MDT) decision‐making and uptake of radical treatment remains unknown.

Objective

The objective of this study is to assess the utilisation and utility of Predict Prostate in informing treatment decisions for patients with intermediate‐risk prostate cancer.

Patients and Methods

A retrospective cohort study was conducted in Cambridge University Hospitals (CUH) of patients referred to the prostate cancer specialist multi‐disciplinary team (pcSMDT) and robotic prostatectomy clinic (ROPD) between September 2019 and August 2021 for consideration of radical prostatectomy (RARP). Data on patient characteristics, use of PredictProstate and management decisions were collected from the Epic electronic medical record (EMR) of 839 patients, of whom 386 had intermediate‐risk prostate cancer.

Results

The use of Predict Prostate at the pcSMDT increased in the second half of the study period (34.5% vs. 23.8%, p < 0.001). The use of Predict Prostate was associated with an increased likelihood of attending ROPD for men with CPG2 prostate cancer (OR = 2.155, 95% CI = 1.158–4.013, p = 0.015) but a reduced likelihood of proceeding with RARP for men with CPG2 (OR = 0.397, 95% CI = 0.209–0.753, p = 0.005) and CPG3 (OR = 0.305, 95% CI = 0.108–0.861, p = 0.025) prostate cancer.

Conclusion

Our study showed that the use of Predict Prostate for patients with intermediate‐risk prostate cancer is associated with increased attendance at specialist surgical clinic and a reduced chance of undergoing radical prostate surgery.
Reconstruction of tracheal window‐shape defect by 3D printed polycaprolatone scaffold coated with Silk Fibroin Methacryloyl
Authors: Shan Yibo , Shen Zhiming , Lu Yi , Zhu Jianwei , Sun Fei , Chen Wenxuan , Yuan Lei , Shi Hongcan
Published: November 2023

In this study, we aimed to utilize autologous tracheal epithelia and BMSCs as the seeding cells, utilize PCL coated with SilMA as the hybrid scaffold to carry the cells and KGN, which can selectively stimulate chondrogenic differentiation of BMSCs. This hybrid tracheal substitution was carried out to repair the tracheal partial window‐shape defect. Firstly, SilMA with the concentration of 10%, 15% and 20% was prepared, and the experiment of swelling and degradation was performed. With the increase of the concentration, the swelling ratio of SilMA decreased, and the degradation progress slowed down. Upon the result of CCK‐8 test and HE staining of 3D co‐culture, the SilMA with concentration of 20% was selected. Next, SilMA and the cells attached to SilMA were characterized by SEM. Furthermore, in vitro cytotoxicity test shows that 20% SilMA has good cytocompatibility. The hybrid scaffold was then made by PCL coated with 20% SilMA. The mechanical test shows this hybrid scaffold has better biomechanical properties than native trachea. In vivo tracheal defect repair assays were conducted to evaluate the effect of the hybrid substitution. H&E staining, IHC staining and IF staining showed that this hybrid substitution ensured the viability, proliferation and migration of epithelium. However, it is sad that the results of chondrogenesis were not obvious. This study is expected to provide new strategies for the fields of tracheal replacement therapy needing mechanical properties and epithelization.
Pharmacological Activities of Rhododendron afghanicum; an Endemic Species of Khyber Pakhtunkhwa, Pakistan
Authors: Alam Khan , Ahmad Nadeem , Ahmad Imran , Nafees Muhammad
Published: November 2023

Majority of different kinds of metabolites having therapeutic characteristics are thought to be stored in medicinal plants. So, the present study was aimed to explore the crude extract of leaves and stem of R. afghanicum for phytochemical screening and various pharmacological activities. Toxicological studies at 100 mg/kg showed 60 % mortality where its safe dose level was 90 mg/kg. Phytochemical screening revealed the presence of alkaloids, glycosides, flavonoids and tannins in both extracts. Bacterial strains were susceptible to (RLEt) and (RLM) crude extracts except Staphylococcus aureus. RSM showed maximum anti‐inflammatory activity (20.16 %) followed by RSEt (20.14 %) where lowest activity was displayed by RLEt (18.46 %). Phytotoxic activity showed a substantial dose‐dependent phyto‐inhibition of Lemna minor. An outstanding cytotoxic potential was displayed with LD50 values of 9.46 and 13.03 μg/ml in both stem extracts. RLEt demonstrated a dose‐dependent pain relief at 30, 60 and 90 mg/kg which was 31 %, 40 % and 52 % respectively. A considerable spasmolytic action was observed by the shrinkage of jejunum muscle in albino mice. RLEt at 1000 ppm showed (17 mm) and RLM at 1000 ppm showed (16 mm) zone of inhibition against Aspergillus niger. These findings support and corroborate the traditional applications of R. afghanicum for treating digestive, analgesic and inflammatory ailments.
The effect of (neo)adjuvant chemotherapy on long‐term survival outcomes in patients with invasive lobular breast cancer treated with endocrine therapy: A retrospective cohort study
Authors: Öztekin Selin , Hooning Maartje J. , van Deurzen Carolien H. M. , Dietvorst Anne‐Marie H. P. , Drooger Jan C. , Kitzen Jos J. E. M. , Martens John W. M. , van der Padt‐Pruijsten Annemieke , Vastbinder Mijntje B. , Zuetenhorst Hanneke , Heemskerk‐Gerritsen Bernadette A. M. , Jager Agnes
Published: November 2023

Background

Despite histological and molecular differences between invasive lobular carcinoma (ILC) and invasive carcinoma of no special type, according to national treatment guidelines no distinction is made regarding the use of (neo)adjuvant chemotherapy. Studies on the long‐term outcome of chemotherapy in patients with ILC are scarce and show inconclusive results.

Methods

All patients with estrogen receptor (ER)–positive, human epidermal growth factor receptor 2 (HER2)–negative ILC with an indication for chemotherapy treated with adjuvant endocrine therapy were selected from the Erasmus Medical Center Breast Cancer database. Cox proportional hazards models were used to estimate the effect of chemotherapy on recurrence‐free survival (RFS), breast cancer–specific survival (BCSS), and overall survival (OS).

Results

A total of 520 patients were selected, of whom 379 were treated with chemotherapy and 141 were not. Patients in the chemotherapy group were younger (51 vs. 61 years old; p < .001), had a higher T status (T3+, 33% vs. 14%; p < .001), and more often had lymph node involvement (80% vs. 49%; p < .001) in comparison to the no‐chemotherapy group. After adjusting for confounders, chemotherapy treatment was not associated with better RFS (hazard ratio [HR], 1.20; 95% confidence interval [CI], 0.63–2.31), BCSS (HR, 1.24; 95% CI, 0.60–2.58), or OS (HR, 0.97; 95% CI, 0.56–1.66). This was also reflected by adjusted Cox survival curves in the chemotherapy versus no‐chemotherapy group for RFS (75% vs. 79%), BCSS (80% vs. 84%), and OS (72% vs. 71%).

Conclusions

Chemotherapy is not associated with improved RFS, BCSS, or OS for patients with ER+/HER2− ILC treated with adjuvant endocrine therapy and with an indication for chemotherapy.
An IQ Consortium Perspective on Best Practices for Bioanalytical and Immunogenicity Assessment Aspects of CAR‐T and TCR‐T Cellular Therapies Development
Authors: Gokemeijer Jochem , Balasubramanian Nanda , Ogasawara Ken , Grudzinska‐Goebel Joanna , Upreti Vijay V. , Mody Hardik , Kasar Siddha , Vepachedu Venkata R. , Xu Weifeng , Gupta Swati , Tarcsa Edit , Dodge Robert , Herr Kate , Yang Tong‐Yuan , Tourdot Sophie , Jawa Vibha
Published: November 2023

CAR‐T therapies have shown remarkable efficacy against hematological malignancies in the clinic over the last decade and new studies indicate that progress is being made to use these novel therapies to target solid tumors as well as treat autoimmune disease. Innovation in the field, including TCR‐T, allogeneic or “off the shelf” CAR‐T, and autoantigen/armored CAR‐Ts are likely to increase the efficacy and applications of these therapies. The unique aspects of these cell‐based therapeutics; patient‐derived cells, intracellular expression, in vivo expansion, and phenotypic changes provide unique bioanalytical challenges to develop pharmacokinetic and immunogenicity assessments. The International Consortium for Innovation and Quality in Pharmaceutical Development (IQ) Translational and ADME Sciences Leadership Group (TALG) has brought together a group of industry experts to discuss and consider these challenges. In this white paper, we present the IQ consortium perspective on the best practices and considerations for bioanalytical and immunogenicity aspects toward the optimal development of CAR‐T and TCR‐T cell therapies.