bluuebunny/crossref_metadata_2025 huggingface dataset:
Fabrication and Facile Surface Derivatization of Poly(ε‐caprolactone)‐Based Wound Dressing Materials Imparting Anti‐Infective, Excessive Biofluid Drainage, and Easy‐to‐Peel Characteristics
Authors: Mude Hemanjali , Tata Pranathi , Jamma Trinath , Ganesan Ramakrishnan , Ray Dutta Jayati
Published: March 2023

The rapid emergence of antimicrobial resistance warrants an antibiotic‐free approach to counter the bacterial threat in all possible applications of environmental and biomedical domains. In the context of smart wound dressing, besides imparting anti‐infective characteristics in a nonconventional fashion, it is also essential to imbibe multifunctional attributes like excessive biofluid drainage, easy‐to‐peel, optimal gas permeation, etc., for which appropriate material design is a prime requisite. In this work, poly(ε‐caprolactone) (PCL)− an FDA approved biocompatible polyester− is chosen for imparting antimicrobial properties by surface derivatization with molecularly‐dispersed ionic silver over quaternary ammonium moieties through a facile room temperate and organic solvent‐free approach. To render the other characteristics mentioned above, two different systems comprising PCL with varying porosity, namely, electrospun fibers and polyester‐coated cotton gauze, are developed. The dressing materials are thoroughly characterized and assessed for their structural, surface chemical, morphological, wettability, antibacterial, and peel strength properties as a function of surface derivatization steps. The bactericidal performance of the quaternary ammonium‐functionalized surfaces has enhanced manifold (≈7–10) after derivatizing with ionic silver. The in vivo efficacy study employing the dressing materials reveals ionic silver derivatized electrospun fibers as the most promising candidate, followed by cotton gauze‐coated with 5% PCL.
Sulfonic‐Pendent Vinylene‐Linked Covalent Organic Frameworks Enabling Benchmark Potential in Advanced Energy
Authors: Xu Ying , Yu Zhiwu , Zhang Qingyun , Luo Feng
Published: March 2023

Both proton exchange membrane fuel cells and uranium‐based nuclear techniques represent two green and advanced energies. However, both of them still face some intractable scientific and industrial problems. For the former, established proton‐conduction materials always suffer one or another defect such as low proton conductivity, high activation energy, bad durability, or just small‐scale product; while for the later, there still lacks available adsorbent to selectively recover of UO22+from concentrated nitric acid (>1 M) during the spent fuel reprocessing due to the deactivation of the adsorption site or the decomposition of adsorbent under such rigorous conditions. It is found that the above two issues can be well solved by the construction of sulfonic‐pendent vinylene‐linked covalent organic frameworks (COFs), since these COFs contain abundant sulfonic units for both intrinsic proton conduction and UO22+capture through strong coordination fixation and vinylene linkage that enhances the stability up to 12 M nitric acid (one of the best materials surviving in 12 M HNO3).
Evolution of the Ferroelectric Properties of AlScN Film by Electrical Cycling with an Inhomogeneous Field Distribution
Authors: Kim Kyung Do , Lee Yong Bin , Lee Suk Hyun , Lee In Soo , Ryoo Seung Kyu , Byun Seungyong , Lee Jae Hoon , Kim Hani , Park Hyeon Woo , Hwang Cheol Seong
Published: March 2023

This work investigates the evolution of the ferroelectric (FE) performance of the sputtered aluminum scandium nitride (AlScN) thin film, which has a high remanent polarization (Pr, > 100 µC cm−2) and coercive field (Ec, > 6 MV cm−1), with the electric field cycling. The work aims at elucidating the underlying origin of the severe fatigue behavior, even with a relatively small number of endurance cycles (<105). When cycled with a low electric field, an internal field is created by charges trapped between the FE layer and the interfacial dielectric layer (non‐FE). On the other hand, fatigue is observed when cycled with a high electric field cycling. This work proposes a new method to simulate a switching current utilizing an inhomogeneous field mechanism and the appropriate circuit model to assess the thickness change of the non‐FE layer. It is concluded that the thickened non‐FE layer after the field cycling results in fatigue.
Purely Electrical Controllable Spin–Orbit Torque‐Based Reconfigurable Physically Unclonable Functions
Authors: Zhao Xiaonan , Wang Xiujuan , Dong Yanan , Wang Wei , Bai Lihui , Chen Yanxue , Kang Shishou , Yan Shishen , Tian Yufeng
Published: March 2023

In the field of information hardware security, random variations obtained during device manufacturing process play a key role in generating unique and unclonable security keys. Existing physical unclonable functions (PUFs) utilizing these static randomnesses usually exhibit static challenge‐response pairs, which cannot be refreshed and limit their application prospects. Here, it is demonstrated that purely electrical controllable spin–orbit torque (SOT)‐based reconfigurable PUFs (rPUFs) can be realized in Pt/IrMn/Co/Ru/CoPt heterojunctions. By applying current pulses along two orthogonal directions, both the exchange bias between IrMn and Co and the SOT switching polarity (clockwise or counterclockwise) of perpendicularly magnetized CoPt can be reversibly controlled, which enables the realization of four rPUF states within a single device. By taking advantages of the sample growth and micro‐nanofabrication induced variations in the critical switching current density of SOT‐driven magnetization switching, the rPUF device with relatively good uniqueness and low bit error rate is achieved. Our work provides an approach to information hardware security and broadens the application of spintronics.
The Roles of Ni and Mn in the Thermal Stability of Lithium‐Rich Manganese‐Rich Oxide Cathode
Authors: Pan Hongyi , Jiao Sichen , Xue Zhichen , Zhang Jin , Xu Xilin , Gan Luyu , Li Quan , Liu Yijin , Yu Xiqian , Li Hong , Chen Liquan , Huang Xuejie
Published: March 2023

The pursuit of high‐energy‐density lithium‐ion batteries (LIBs) has brought extensive research on the high‐capacity lithium‐rich manganese‐rich oxide cathode (LRMO). However, practical applications of LRMO require a comprehensive understanding of its thermal stability, which determines the boundary for the safe use of LIBs. Here, systematic investigations of the thermal stability of LRMO are carried out by using in situ X‐ray diffraction and full‐field transmission X‐ray microscopy combined with X‐ray absorption near edge structure. The roles of Ni and Mn in affecting the thermal stability of LRMO are uncovered. It is surprising that Ni, despite being in the minority, acts as a key factor that governs the onset temperature of thermal decomposition. Unlike in lithium nickel‐cobalt‐manganese oxide cathodes where a higher content of Mn is believed to stabilize the structure with reduced heat release, in LRMO it causes more heat release which can be attributed to the lithium excess environment around Mn. In addition, it is revealed that the incomplete coverage of solid polymer electrolytes over the LRMO particle surface may lead to the deterioration of thermal stability. These findings provide mechanistic insights into the thermal behavior of LRMO cathodes for developing high‐capacity cathodes with improved safety, particularly, for future applications in solid‐state batteries.
24.96%‐Efficiency FACsPbI3 Perovskite Solar Cells Enabled by an Asymmetric 1,3‐Thiazole‐2,4‐Diammonium
Authors: Zhou Hui , Yang Lu , Duan Yuwei , Wu Meizi , Li Yong , Xu Dongfang , Zou Hong , Wang Jungang , Yang Shaomin , Liu Zhike
Published: March 2023

Surmounting complicated defects at the electron transport layer (ETL) and perovskite interface plays a non‐trivial role in improving efficiency and stability of perovskite solar cells (PSCs). Herein, an asymmetric interface modification strategy (AIMS) is developed to passivate the defects from both a SnO2 ETL and the perovskite buried surface via incorporating 1,3‐thiazole‐2,4‐diammonium (TDA) into the SnO2/perovskite interface. Detailed experimental and calculated results demonstrate that N3 (the nitrogen atom bonding to the imine) in the TDA preferentially cures the free hydroxyl (OH), oxygen vacancy (VO), and the Sn‐related defects on the SnO2 surface, while N1 (the nitrogen atom bonding to the vinyl) is more inclined to passivate the Pb2+ and I− related defects at the perovskite buried surface. As a result, the TDA‐modified FACsPbI3 PSC yields a champion power conversion efficiency (PCE) of 24.96% with a gratifying open‐circuit voltage (Voc) of 1.20 V. In addition, the optimized PSCs exhibit charming air‐operational stability with the unencapsulated device sustaining 97.04% of its initial PCE after storage in air conditions for 1400 h. The encapsulated device maintains 90.21% of its initial PCE after maximum power point tracking for 500 h.
Thermodynamic‐kinetic synergistic separation of CH4/N2 on a robust aluminum‐based metal‐organic framework
Authors: Zhang Feifei , Shang Hua , Zhai Bolun , Li Xiaomin , Zhang Yingying , Wang Xiaoqing , Li Jinping , Yang Jiangfeng
Published: March 2023

A robust aluminum‐based metal–organic framework (Al‐MOF) MIL‐120Al with 1D rhombic ultra‐microporous was reported. The nonpolar porous walls composed of para‐benzene rings with a comparable pore size to the kinetic diameter of methane allow it to exhibit a novel thermodynamic‐kinetic synergistic separation of CH4/N2 mixtures. The CH4 adsorption capacity was as high as 33.7 cm3/g (298 K, 1 bar), which is the highest uptake value among the Al‐MOFs reported to date. The diffusion rates of CH4 were faster than N2 in this structure as confirmed by time‐dependent kinetic adsorption profiles. Breakthrough experiments confirm that this MOF can completely separate the CH4/N2 mixture and the separation performance is not affected in the presence of H2O. Theoretical calculations reveal that pore centers with more energetically‐favorable binding sites for CH4 than N2. The results of pressure swing adsorption (PSA) simulations indicate that MIL‐120Al is a potential candidate for selective capture coal‐mine methane.
Validation of the prognostic significance of the 2022 European LeukemiaNet risk stratification system in intensive chemotherapy treated aged 18 to 65 years patients with de novo acute myeloid leukemia
Authors: Lo Min‐Yen , Tsai Xavier Cheng‐Hong , Lin Chien‐Chin , Tien Feng‐Ming , Kuo Yuan‐Yeh , Lee Wan‐Hsuan , Peng Yen‐Ling , Liu Ming‐Chih , Tseng Mei‐Hsuan , Hsu Cheng‐An , Chen Jui‐Che , Lin Liang‐In , Sun Hsun‐I , Chuang Yi‐Kuang , Ko Bor‐Sheng , Tang Jih‐Luh , Yao Ming , Chou Wen‐Chien , Hou Hsin‐An , Tien Hwei‐Fang
Published: March 2023

The European LeukemiaNet (ELN) recently proposed a revised recommendation for the diagnosis and management of acute myeloid leukemia (AML) in adults, recognized as ELN‐2022. However, validation in a large real‐world cohort remains lacking. In this study, we aimed to validate the prognostic relevance of the ELN‐2022 in a cohort of 809 de novo, non‐M3, younger (ages 18–65 years) AML patients receiving standard chemotherapy. The risk categories of 106 (13.1%) patients were reclassified from that determined using ELN‐2017 to that determined using ELN‐2022. The ELN‐2022 effectively helped distinguish patients as favorable, intermediate, and adverse risk groups in terms of remission rates and survival. Among patients who achieved first complete remission (CR1), allogeneic transplantation was beneficial for those in the intermediate risk group, but not for those in the favorable or adverse risk groups. We further refined the ELN‐2022 system by re‐categorizing AML patients with t(8;21)(q22;q22.1)/RUNX1::RUNX1T1 with KIThigh, JAK2 or FLT3‐ITDhigh mutations into the intermediate risk subset, AML patients with t(7;11)(p15;p15)/NUP98::HOXA9 and AML patients with co‐mutated DNMT3A and FLT3‐ITD into the adverse risk subsets, and AML patients with complex or monosomal karyotypes, inv (3)(q21.3q26.2) or t(3;3)(q21.3;q26.2)/GATA2,MECOM(EVI1) or TP53 mutation into the very adverse risk subset. The refined ELN‐2022 system performed effectively to distinguish patients as favorable, intermediate, adverse, and very adverse risk groups. In conclusion, the ELN‐2022 helped distinguish younger, intensively treated patients into three groups with distinct outcomes; the proposed refinement of ELN‐2022 may further improve risk stratification among AML patients. Prospective validation of the new predictive model is necessary.
Dissipating the fog: Cognitive trajectories and risk factors 1 year after COVID‐19 hospitalization
Authors: Gonçalves Natalia Gomes , Aliberti Márlon Juliano Romero , Bertola Laiss , Avelino‐Silva Thiago , Dias Murilo Bacchini , Apolinario Daniel , Busatto Geraldo , Forlenza Orestes , Nitrini Ricardo , Brucki Sonia Maria Dozzi , Brunoni Andre Russowsky , Vidal Kallene Summer Moreira , Jacob‐Filho Wilson , Suemoto Claudia Kimie ,   CO‐FRAIL Study Group, for the COVID HCFMUSP Study Group
Published: March 2023

Introduction

Cognitive impairment is common after severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) infection. However, associations between post‐hospital discharge risk factors and cognitive trajectories have not been explored.

Methods

A total of 1105 adults (mean age ± SD 64.9 ± 9.9 years, 44% women, 63% White) with severe coronavirus disease 2019 (COVID‐19) were evaluated for cognitive function 1 year after hospital discharge. Scores from cognitive tests were harmonized, and clusters of cognitive impairment were defined using sequential analysis.

Results

Three groups of cognitive trajectories were observed during the follow‐up: no cognitive impairment, initial short‐term cognitive impairment, and long‐term cognitive impairment. Predictors of cognitive decline after COVID‐19 were older age (β = −0.013, 95% CI = −0.023;−0.003), female sex (β = −0.230, 95% CI = −0.413;−0.047), previous dementia diagnosis or substantial memory complaints (β = −0.606, 95% CI = −0.877;−0.335), frailty before hospitalization (β = −0.191, 95% CI = −0.264;−0.119), higher platelet count (β = −0.101, 95% CI = −0.185;−0.018), and delirium (β = −0.483, 95% CI = −0.724;−0.244). Post‐discharge predictors included hospital readmissions and frailty.

Discussion

Cognitive impairment was common and the patterns of cognitive trajectories depended on sociodemographic, in‐hospital, and post‐hospitalization predictors.

Highlights

Cognitive impairment after coronavirus disease 2019 (COVID‐19) hospital discharge was associated with higher age, less education, delirium during hospitalization, a higher number of hospitalizations post discharge, and frailty before and after hospitalization.

Frequent cognitive evaluations for 12‐month post‐COVID‐19 hospitalization showed three possible cognitive trajectories: no cognitive impairment, initial short‐term impairment, and long‐term impairment.

This study highlights the importance of frequent cognitive testing to determine patterns of COVID‐19 cognitive impairment, given the high frequency of incident cognitive impairment 1 year after hospitalization.
Eine durchflusszytometrische Ultra‐Hochdurchsatz‐Durchmusterungsmethode für die Gelenkte Evolution von Oxidasen
Authors: Feng Lilin , Gao Liang , Besirlioglu Volkan , Essani Khalil , Wittwer Malte , Kurkina Tetiana , Ji Yu , Schwaneberg Ulrich
Published: March 2023

Oxidasen sind bedeutsam für die chemische und pharmazeutische Industrie, da sie hochselektive Oxidationen katalysieren. Allerdings müssen natürlich vorkommende Oxidasen für synthetische Anwendungen häufig mittels Gelenkter Evolution im Labor maßgeschneidert werden. Hierfür haben wir die breit anwendbare und robuste Durchmusterungs‐Plattform “FlOxi” entwickelt. FlOxi ist eine Durchflusszytometriemethode und nutzt Wasserstoffperoxid als Reaktionssnebenprodukt von in E. coli exprimierten Oxidasen, um Fe2+ zu Fe3+ zu oxidieren (Fenton‐Reaktion). Fe3+ vermittelt dabei die Immobilisierung von His6‐“markiertem” eGFP (eGFPHis) auf der E. coli‐Zelloberfläche, wodurch die Identifizierung von aktiven Oxidase‐Varianten mittels Durchflusszytometrie ermöglicht wird. FlOxi wurde mit zwei Oxidasen – einer Galaktose‐Oxidase (GalOx) und einer D‐Aminosäure‐Oxidase (D‐AAO) – validiert. Hierbei wurde in einer Gelenkten Evolutionsrunde eine GalOx‐Variante (T521A) mit einem 4.4‐fach niedrigeren Km‐Wert und eine D‐AAO‐Variante (L86M/G14/A48/T205) mit einem 4.2‐fach höheren kcat‐Wert aufgefunden. FlOxi kann universell für die Gelenkte Evolution von Wasserstoffperoxid‐produzierenden Oxidasen, auch für nicht‐fluoreszierende Substrate, eingesetzt werden.
Engineering a Self‐Grown TiO2/Ti‐MOF Heterojunction with Selectively Anchored High‐Density Pt Single‐Atomic Cocatalysts for Efficient Visible‐Light‐Driven Hydrogen Evolution
Authors: He Xiaoyu , Ding Yujia , Huang Zhennan , Liu Min , Chi Miaofang , Wu Zili , Segre Carlo U. , Song Chunshan , Wang Xiang , Guo Xinwen
Published: March 2023

A photocatalyst TiO2/Ti‐BPDC‐Pt is developed with a self‐grown TiO2/Ti‐metal–organic framework (MOF) heterojunction, i.e., TiO2/Ti‐BPDC, and selectively anchored high‐density Pt single‐atomic cocatalysts on Ti‐BPDC for photocatalytic hydrogen evolution. This intimate heterojunction, growing from the surface pyrolytic reconstruction of Ti‐BPDC, works in a direct Z‐scheme, efficiently separating electrons and holes. Pt is selectively anchored on Ti‐BPDC by ligands and is found in the form of single atoms with loading up to 1.8 wt %. The selective location of Pt is the electron‐enriched domain of the heterojunction, which further enhances the utilization of the separated electrons. This tailored TiO2/Ti‐BPDC‐Pt shows a significantly enhanced activity of 12.4 mmol g−1 h−1 compared to other TiO2‐ or MOF‐based catalysts. The structure‐activity relationship further proves the balance of two simultaneously exposed domains of heterojunctions is critical to fulfilling this kind of catalyst.
Solid‐Adsorbed Polymer‐Electrolyte Interphases for Stabilizing Metal Anodes in Aqueous Zn and Non‐Aqueous Li Batteries
Authors: Jin Shuo , Deng Yue , Chen Pengyu , Hong Shifeng , Garcia‐Mendez Regina , Sharma Arpita , Utomo Nyalaliska W. , Shao Yiqi , Yang Rong , Archer Lynden A.
Published: March 2023

Polymers are known to adsorb spontaneously from liquid solutions in contact with high‐energy substrates to form configurationally complex, but robust phases that often exhibit higher durability than might be expected from the individual physical bonds formed with the substrate. Rational control of the physical, chemical, and transport properties of such interphases has emerged as a fundamental opportunity for scientific and technological advances in energy storage technology but requires in‐depth understanding of the conformation states and electrochemical effect of the adsorbed polymers. Here, we analyze the interfacial adsorption of oligomeric polyethylene glycol (PEG) chains of moderate sizes dissolved in protic and aprotic liquid electrolytes and find that there is an optimum polymer molecular weight of approximately 400 Da at which the highest columbic efficiency is achieved for both Zn and Li deposition. These findings point to a simple, versatile approach for extending the lifetime of batteries.
Ir Nanoparticles Anchored on Metal‐Organic Frameworks for Efficient Overall Water Splitting under pH‐Universal Conditions
Authors: Yang Jun , Shen Yong , Sun Yamei , Xian Jiahui , Long Yanju , Li Guangqin
Published: March 2023

The construction of high‐activity and low‐cost electrocatalysts is critical for efficient hydrogen production by water electrolysis. Herein, we developed an advanced electrocatalyst by anchoring well‐dispersed Ir nanoparticles on nickel metal‐organic framework (MOF) Ni‐NDC (NDC: 2,6‐naphthalenedicarboxylic) nanosheets. Benefiting from the strong synergy between Ir and MOF through interfacial Ni−O−Ir bonds, the synthesized Ir@Ni‐NDC showed exceptional electrocatalytic performance for hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and overall water splitting in a wide pH range, superior to commercial benchmarks and most reported electrocatalysts. Theoretical calculations revealed that the charge redistribution of Ni−O−Ir bridge induced the optimization of H2O, OH* and H* adsorption, thus leading to the accelerated electrochemical kinetics for HER and OER. This work provides a new clue to exploit bifunctional electrocatalysts for pH‐universal overall water splitting.
Heterocyclic Chromophore Amphiphiles and their Supramolecular Polymerization
Authors: Đorđević Luka , Sai Hiroaki , Yang Yang , Sather Nicholas A. , Palmer Liam C. , Stupp Samuel I.
Published: March 2023

Supramolecular polymerization of π‐conjugated amphiphiles in water is an attractive approach to create functional nanostructures. Here, we report on the synthesis, optoelectronic and electrochemical properties, aqueous supramolecular polymerization, and conductivity of polycyclic aromatic dicarboximide amphiphiles. The chemical structure of the model perylene monoimide amphiphile was modified with heterocycles, essentially substituting one fused benzene ring with thiophene, pyridine or pyrrole rings. All the heterocycle‐containing monomers investigated underwent supramolecular polymerization in water. Large changes to the monomeric molecular dipole moments led to nanostructures with low electrical conductivity due to diminished interactions. Although the substitution of benzene with thiophene did not notably change the monomer dipole moment, it led to crystalline nanoribbons with 20‐fold higher electrical conductivity, due to enhanced dispersion interactions as a result of the presence of sulfur atoms.
A Flow Cytometry‐Based Ultrahigh‐Throughput Screening Method for Directed Evolution of Oxidases
Authors: Feng Lilin , Gao Liang , Besirlioglu Volkan , Essani Khalil , Wittwer Malte , Kurkina Tetiana , Ji Yu , Schwaneberg Ulrich
Published: March 2023

Oxidases are of interest to chemical and pharmaceutical industries because they catalyze highly selective oxidations. However, oxidases found in nature often need to be re‐engineered for synthetic applications. Herein, we developed a versatile and robust flow cytometry‐based screening platform “FlOxi” for directed oxidase evolution. FlOxi utilizes hydrogen peroxide produced by oxidases expressed in E. coli to oxidize Fe2+ to Fe3+ (Fenton reaction). Fe3+ mediates the immobilization of a His6‐tagged eGFP (eGFPHis) on the E. coli cell surface, ensuring the identification of beneficial oxidase variants by flow cytometry. FlOxi was validated with two oxidases—a galactose oxidase (GalOx) and a D‐amino acid oxidase (D‐AAO)—yielding a GalOx variant (T521A) with a 4.4‐fold lower Km value and a D‐AAO variant (L86M/G14/A48/T205) with a 4.2‐fold higher kcat than their wildtypes. Thus, FlOxi can be used for the evolution of hydrogen peroxide‐producing oxidases and applied for non‐fluorescent substrates.
Electronic Structure Manipulation of the Mott Insulator RuCl3 via Single‐Crystal to Single‐Crystal Topotactic Transformation
Authors: Lu Weiqun , Lee Hyungseok , Cha Joonil , Zhang Jian , Chung In
Published: March 2023

The core task for Mott insulators includes how rigid distributions of electrons evolve and how these induce exotic physical phenomena. However, it is highly challenging to chemically dope Mott insulators to tune properties. Herein, we report how to tailor electronic structures of the honeycomb Mott insulator RuCl3 employing a facile and reversible single‐crystal to single‐crystal intercalation process. The resulting product (NH4)0.5RuCl3⋅1.5 H2O forms a new hybrid superlattice of alternating RuCl3 monolayers with NH4+ and H2O molecules. Its manipulated electronic structure markedly shrinks the Mott–Hubbard gap from 1.2 to 0.7 eV. Its electrical conductivity increases by more than 103 folds. This arises from concurrently enhanced carrier concentration and mobility in contrary to the general physics rule of their inverse proportionality. We show topotactic and topochemical intercalation chemistry to control Mott insulators, escalating the prospect of discovering exotic physical phenomena.
Lewis Acid‐Mediated Radical Stabilization and Dynamic Covalent Bonding: Tunable, Reversible and Photocontrollable
Authors: Liu Min , Yang Xing , Sun Quanchun , Wang Tao , Pei Runbo , Yang Xingyu , Zhao Yue , Zhao Lili , Frenking Gernot , Wang Xinping
Published: March 2023

This work describes a strategy not only to isolate a dynamically stable radical with physical property tunability, but to efficiently regulate the radical dissociation with reversibility and photo controllability. The addition of Lewis acid B(C6F5)3 (BCF) into the solution of a radical σ‐dimer (1‐1) led to a stable radical (1⋅‐2B), which has been characterized by EPR spectroscopy, UV/Vis spectroscopy and single crystal X‐ray diffraction, in conjunction with theoretical calculation. The radical species is stabilized mainly by captodative effect, single electron transfer and steric effect. The absorption maximum of the radical can be tuned by using different Lewis acids. Dimer 1‐1 can be achieved back by addition of a stronger base into the solution of 1⋅‐2B, exhibiting a reversible process. By introducing a photo BCF generator, the dissociation of the dimer and the formation of the radical adduct become photocontrollable.
Phase Instability in van der Waals In2Se3 Determined by Surface Coordination
Authors: Yan Shanru , Xu Chao , Zhong Cenchen , Chen Yancong , Che Xiangli , Luo Xin , Zhu Ye
Published: March 2023

van der Waals In2Se3 has attracted significant attention for its room‐temperature 2D ferroelectricity/antiferroelectricity down to monolayer thickness. However, instability and potential degradation pathway in 2D In2Se3 have not yet been adequately addressed. Using a combination of experimental and theoretical approaches, we here unravel the phase instability in both α‐ and β′‐In2Se3 originating from the relatively unstable octahedral coordination. Together with the broken bonds at the edge steps, it leads to moisture‐facilitated oxidation of In2Se3 in air to form amorphous In2Se3−3xO3x layers and Se hemisphere particles. Both O2 and H2O are required for such surface oxidation, which can be further promoted by light illumination. In addition, the self‐passivation effect from the In2Se3−3xO3x layer can effectively limit such oxidation to only a few nanometer thickness. The achieved insight paves way for better understanding and optimizing 2D In2Se3 performance for device applications.
Asymmetric Synthesis of Vicinal Tetrasubstituted Diamines via Reductive Coupling of Ketimines Templated by Chiral Diborons
Authors: Zhou Mingkang , Lin Yaodong , Chen Xiao‐Xuan , Xu Guangqing , Chung Lung Wa , Tang Wenjun
Published: March 2023

We herein describe the chiral diboron‐templated asymmetric homocoupling of aryl alkyl ketimines, providing for the first time a series of chiral vicinal tetrasubstituted diamines with excellent ee values and good to high yields. The powerful and efficient diboron‐participated [3,3]‐sigmatropic rearrangement is successfully demonstrated by the homocoupling of a variety of ketimines thanks to the rational design and engineering of chiral diborons. Systematic DFT studies suggest that two chiral diborons adopt different conformational assembling strategies to couple the diboron template with ketimine substrates in their tight concerted transition states to ensure the excellent enantioselectivities. The synthetic value of chiral vicinal tetrasubstituted diamines is demonstrated by the asymmetric α‐bromination of aliphatic aldehydes by employing a chiral vicinal tetrasubstituted diamine‐based organocatalyst.
Unlocking a (Pseudo)‐Mechanically Interlocked Molecule with a Coronene “Shoehorn”
Authors: Ibáñez Susana , Świderek Katarzyna , Peris Eduardo
Published: March 2023

Mechanically interlocked molecules (MIMs) have gained increasing interest during the last decades, not only because of their aesthetic appeal, but also because their unique properties have allowed them to find applications in nanotechnology, catalysis, chemosensing and biomedicine. Herein we describe how a pyrene molecule with four octynyl substituents can be easily encapsulated within the cavity of a tetragold(I) rectangle‐like metallobox, by template formation of the metallo‐assembly in the presence of the guest. The resulting assembly behaves as a mechanically interlocked molecule (MIM), in which the four long limbs of the guest protrude from the entrances of the metallobox, thus locking the guest inside the cavity of the metallobox. The new assembly resembles a metallo‐suit[4]ane, given the number of protruding long limbs and the presence of the metal atoms in the host molecule. However, unlike normal MIMs, this molecule can release the tetra‐substituted pyrene guest by the addition of coronene, which can smoothly replace the guest in the cavity of the metallobox. Combined experimental and computational studies allowed the role of the coronene molecule in facilitating the release of the tetrasubstituted pyrene guest to be explained, through a process that we named “shoehorning”, as the coronene compresses the flexible limbs of the guest so that it can reduce its size to slide in and out the metallobox.
Thiazolylazopyrazoles as Nonsymmetric Bis‐Heteroaryl Azo Switches: High‐Yield Visible‐Light Photoisomerization and Increased Z‐Isomer Stability by o‐Carbonylation
Authors: Dang Tongtong , Dong Dongfang , Zhang Jiabin , He Yixin , Zhang Zhao‐Yang , Li Tao
Published: March 2023

Following the progress on mono‐heteroaryl azo switches (Het‐N=N‐Ph), a few bis‐heteroaryl azo switches (Het‐N=N‐Het) have been studied recently, whereas the nonsymmetric bis‐heteroaryl ones (Het1‐N=N‐Het2) that can combine the respective merits of each heterocycle, have received little attention. Here we report thiazolylazopyrazoles as nonsymmetric bis‐heteroaryl azo switches that combine the visible‐light switching character of the thiazole ring and the ease of o‐substitution of the pyrazole ring. Thiazolylazopyrazoles can achieve (near‐)quantitative visible‐light isomerization in both directions and long Z‐isomer thermal half‐lives of several days. In contrast to the drastically destabilizing effect of o‐methylation, o‐carbonylation of the pyrazole ring can remarkably stabilize Z isomers by inducing attractive intramolecular interactions (dispersion, C−H⋅⋅⋅N bond, and lone‐pair⋅⋅⋅π interaction). Our work highlights the importance of the rational combination of two heterocycles and suitable structural substitution in developing bis‐heteroaryl azo switches.
Non‐Redundant Roles of T Cell Costimulation Pathways in Inflammatory Arthritis Revealed by Dual Blockade of ICOS and CD28 with Acazicolcept (ALPN‐101)
Authors: Dillon Stacey R. , Evans Lawrence S. , Lewis Katherine E. , Debrot Susan , Blair Tiffany C. , Mudri Sherri , Kleist Kayla , Levin Steven D. , Bhandari Janhavi G. , Garrett Logan , Wolfson Martin F. , Holland Pamela M. , Rixon Mark W. , Peng Stanford L.
Published: March 2023

Objective

CD28 and inducible T cell costimulator (ICOS) appear to have nonredundant roles in T cell activation and adaptive immunity. We undertook this study to characterize in vitro and in vivo the therapeutic potential of acazicolcept (ALPN‐101), an Fc fusion protein of a human variant ICOS ligand (ICOSL) domain designed to inhibit both CD28 and ICOS costimulation, in inflammatory arthritis.

Methods

Acazicolcept was compared in vitro with inhibitors of either the CD28 or ICOS pathways (abatacept and belatacept [CTLA‐4Ig], prezalumab [anti‐ICOSL monoclonal antibody]) in receptor binding and signaling assays, and in a collagen‐induced arthritis (CIA) model. Acazicolcept was also compared in cytokine and gene expression assays of peripheral blood mononuclear cells (PBMCs) from healthy donors or rheumatoid arthritis (RA) or psoriatic arthritis (PsA) patients stimulated with artificial antigen‐presenting cells (APCs) expressing CD28 and ICOS ligands*.

Results

Acazicolcept bound CD28 and ICOS, prevented ligand binding, and inhibited human T cell functional interactions, matching or exceeding the activity of CD28 or ICOS costimulatory single‐pathway inhibitors tested individually or in combination. Acazicolcept administration significantly reduced disease in the CIA model and more potently than abatacept. Acazicolcept also inhibited proinflammatory cytokine production from stimulated PBMCs in cocultures with artificial APCs and demonstrated unique effects on gene expression distinct from those induced by abatacept, prezalumab, or a combination of both.

Conclusion

Both CD28 and ICOS signaling play critical roles in inflammatory arthritis. Therapeutic agents such as acazicolcept that coinhibit both ICOS and CD28 signaling may mitigate inflammation and/or disease progression in RA and PsA more effectively than inhibitors of either pathway alone.

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Reduction of Neutrophil Activation by Phosphodiesterase 4 Blockade in Behçet's Disease
Authors: Le Joncour Alexandre , Régnier Paul , Maciejewski‐Duval Anna , Charles Erwan , Barete Stéphane , Fouret Pierre , Rosenzwajg Michelle , Klatzmann David , Cacoub Patrice , Saadoun David
Published: March 2023

Objective

Behçet's disease (BD) is a systemic vasculitis with inflammatory lesions mediated by cytotoxic T cells and neutrophils. Apremilast, an orally available small‐molecule drug that selectively inhibits phosphodiesterase 4 (PDE4), has been recently approved for the treatment of BD. We aimed to investigate the effect of PDE4 inhibition on neutrophil activation in BD.

Methods

We studied surface markers and reactive oxygen species (ROS) production by flow cytometry, and neutrophil extracellular traps (NETs) production and molecular signature of neutrophils by transcriptome analysis before and after PDE4 inhibition.

Results

Activation surface markers (CD64, CD66b, CD11b, and CD11c), ROS production, and NETosis were up‐regulated in BD patient neutrophils compared to healthy donor neutrophils. Transcriptome analysis revealed 1,021 significantly dysregulated neutrophil genes between BD patients and healthy donors. Among dysregulated genes, we found a substantial enrichment for pathways linked to innate immunity, intracellular signaling, and chemotaxis in BD. Skin lesions of BD patients showed increased infiltration of neutrophils that colocalized with PDE4. Inhibition of PDE4 by apremilast strongly inhibited neutrophil surface activation markers as well as ROS production, NETosis, and genes and pathways related to innate immunity, intracellular signaling, and chemotaxis.

Conclusion

We highlight key biologic effects of apremilast on neutrophils in BD.
Anti–Neutrophil Extracellular Trap Antibodies in Antiphospholipid Antibody–Positive Patients: Results From the Antiphospholipid Syndrome Alliance for Clinical Trials and InternatiOnal Networking Clinical Database and Repository
Authors: Zuo Yu , Navaz Sherwin , Tsodikov Alex , Kmetova Katarina , Kluge Lyndsay , Ambati Amala , Hoy Claire K. , Yalavarthi Srilakshmi , de Andrade Danieli , Tektonidou Maria G. , Sciascia Savino , Pengo Vittorio , Ruiz‐Irastorza Guillermo , Belmont H. Michael , Gerosa Maria , Fortin Paul R. , de Jesus Guilherme Ramires , Branch D. Ware , Andreoli Laura , Rodriguez‐Almaraz Esther , Petri Michelle , Cervera Ricard , Willis Rohan , Karp David R. , Li Quan‐Zhen , Cohen Hannah , Bertolaccini Maria Laura , Erkan Doruk , Knight Jason S. ,   the Antiphospholipid Syndrome Alliance for Clinical Trials and InternatiOnal Networking
Published: March 2023

Objective

This study aimed to elucidate the presence, antigen specificities, and potential clinical associations of anti–neutrophil extracellular trap (anti‐NET) antibodies in a multinational cohort of antiphospholipid (aPL) antibody–positive patients who did not have lupus.

Methods

Anti‐NET IgG/IgM levels were measured in serum samples from 389 aPL‐positive patients; 308 patients met the classification criteria for antiphospholipid syndrome. Multivariate logistic regression with best variable model selection was used to determine clinical associations. For a subset of the patients (n = 214), we profiled autoantibodies using an autoantigen microarray platform.

Results

We found elevated levels of anti‐NET IgG and/or IgM in 45% of the aPL‐positive patients. High anti‐NET antibody levels are associated with more circulating myeloperoxidase (MPO)–DNA complexes, which are a biomarker of NETs. When considering clinical manifestations, positive anti‐NET IgG was associated with lesions affecting the white matter of the brain, even after adjusting for demographic variables and aPL profiles. Anti‐NET IgM tracked with complement consumption after controlling for aPL profiles; furthermore, patient serum samples containing high levels of anti‐NET IgM efficiently deposited complement C3d on NETs. As determined by autoantigen microarray, positive testing for anti‐NET IgG was significantly associated with several autoantibodies, including those recognizing citrullinated histones, heparan sulfate proteoglycan, laminin, MPO–DNA complexes, and nucleosomes. Anti‐NET IgM positivity was associated with autoantibodies targeting single‐stranded DNA, double‐stranded DNA, and proliferating cell nuclear antigen.

Conclusion

These data reveal high levels of anti‐NET antibodies in 45% of aPL‐positive patients, where they potentially activate the complement cascade. While anti‐NET IgM may especially recognize DNA in NETs, anti‐NET IgG species appear to be more likely to target NET‐associated protein antigens.
From invitation to destination: A systematic literature review of the use of picturebooks in inquiry‐based education
Authors: Oberman Rowan
Published: March 2023

Picturebooks offer powerful supports for teaching diverse content across different curriculum areas. Research and curriculum resources document their use in inquiry‐based education practices, particularly in relation to science and philosophy. There is, however, little theoretical analysis of this use or cross‐curricular comparisons. Applying a systematic literature review process, this paper examines existing empirical research on the use of picturebooks in formal inquiry‐based education contexts. The analysis considers the context in which the picturebooks were used, including curriculum context and class level, the role played by the picturebooks in the inquiries and the value ascribed to the use of picturebooks. The review proposes a framework for understanding and contrasting the varying roles played by picturebooks in inquiry‐based education approaches. This framework involves seven uses: invitations, provocations, mentors, models, resources, touchstones and destinations. Varying benefits are attributed to the use of picturebooks, including their practicality, inclusivity, complexity, aid to cognitive learning, emotional engagement and association with child readers. These benefits emphasise both the accessibility and the complexity of picturebooks. The review proposes that inquiry approaches should attend to picturebook form and content and the interdependency of the two. The review's analysis supports extended use of picturebooks across the curriculum, including in history, geography, citizenship and science education, as well as in interdisciplinary approaches.
Cell factory engineering: Challenges and opportunities for synthetic biology applications
Authors: Bachhav Bhagyashree , de Rossi Jacopo , Llanos Carlos D. , Segatori Laura
Published: March 2023

The production of high‐quality recombinant proteins is critical to maintaining a continuous supply of biopharmaceuticals, such as therapeutic antibodies. Engineering mammalian cell factories presents a number of limitations typically associated with the proteotoxic stress induced upon aberrant accumulation of off‐pathway protein folding intermediates, which eventually culminate in the induction of apoptosis. In this review, we will discuss advances in cell engineering and their applications at different hierarchical levels of control of the expression of recombinant proteins, from transcription and translational to posttranslational modifications and subcellular trafficking. We also highlight challenges and unique opportunities to apply modern synthetic biology tools to the design of programmable cell factories for improved biomanufacturing of therapeutic proteins.
pH‐Responsive and Reversible A‐Motif‐Based DNA Hydrogel: Synthesis and Biosensing Application**
Authors: Morya Vinod , Shukla Ashish Kumar , Ghoroi Chinmay , Bhatia Dhiraj
Published: March 2023

Functional DNA hydrogels with various motifs and functional groups require perfect sequence design to avoid cross‐bonding interference with themselves or other structural sequences. This work reports an A‐motif functional DNA hydrogel that does not require any sequence design. A‐motif DNA is a noncanonical parallel DNA duplex structure containing homopolymeric deoxyadenosines (poly‐dA) strands that undergo conformation changes from single strands at neutral pH to a parallel duplex DNA helix at acidic pH. Despite this and other advantages over other DNA motifs like no cross‐bonding interference with other structural sequences, the A‐motif has not been explored much. We successfully synthesized a DNA hydrogel by using an A‐motif as a reversible handle to polymerize a DNA three‐way junction. The A‐motif hydrogel was initially characterized by electrophoretic mobility shift assay, and dynamic light scattering, which showed the formation of higher‐order structures. Further, we used imaging techniques like atomic force microscopy and scanning electron microscope to validating its hydrogel like highly branched morphology. pH‐induced conformation transformation from monomers to gel is quick and reversible, and was analysed for multiple acid‐base cycles. The sol‐to‐gel transitions and gelation properties were further examined in rheological studies. The use of the A‐motif hydrogel in the visual detection of pathogenic target nucleic acid sequence was demonstrated for the first time in a capillary assay. Moreover, pH‐induced hydrogel formation was observed in situ as a layer over the mammalian cells. The proposed A‐motif DNA scaffold has enormous potential in designing stimuli‐responsive nanostructures that can be used for many biological applications.
Transvenous retrograde thoracic duct embolization for effective treatment of recurrent plastic bronchitis after fontan palliation
Authors: Haddad Raymond N. , Dautry Raphael , Bonnet Damien , Malekzadeh‐Milani Sophie
Published: March 2023

We report the case of a 5.5‐year‐old patient (16 kg/105 cm) who presented with plastic bronchitis (PB) refractory to conservative treatment 3 months after completion of Fontan palliation. Bi‐inguinal transnodal fluoroscopy‐guided lymphangiogram confirmed the chylous leak originating from the thoracic duct (TD) into the chest and did not opacify any central lymphatic vessel for direct transabdominal puncture. Retrograde transfemoral approach was adopted to catheterize the TD and selectively embolize its caudal portion using microcoils and liquid embolic adhesive. Recurrence of symptoms after 2 months indicated a redo catheterization to occlude the TD entirely using the same technique. The procedure was successful and the patient was discharged after 2 days with sustained clinical improvement at 24 months postoperative. In the context of refractory PB, end‐to‐end transvenous retrograde embolization of the TD appears to be an interesting alternative to more complex interventions such as transabdominal puncture, decompression, or surgical ligation of the TD.
Successful treatment with bortezomib for POEMS syndrome, overcoming complicated severe heart block
Authors: Nakamura Yuichi , Itoh Yoshihiro , Wakimoto Naoki , Kanno Ryu , Iida Shinichirou , Yamamoto Keiji
Published: March 2023

Cardiac bradyarrhythmia and conduction disorder may be rare, but recurrent adverse events caused by bortezomib. Here we report a case with POEMS syndrome presenting severe heart block after bortezomib plus dexamethasone therapy. After permanent pacemaker implantation, bortezomib was restarted and maintained, resulting in sustained complete response for POEMS syndrome.
Experimental Investigations of Heat Pipe Systems for Use in Electrical Engines
Authors: Margraf Hendrik , Lottis Marian , Deeb Mohammad , Luke Andrea
Published: March 2023

Mit dem Ziel die Effizienz elektrischer Arbeitskraftmaschinen durch ein innovatives Kühlsystem zu erhöhen, wird ein Wärmetransportsystem auf Basis von Wärmerohren entwickelt und analysiert. Die Leistungsfähigkeit des Systems bei Variation des Temperaturbereichs und des zugeführten Wärmestroms sowie der Einfluss der Rotation werden experimentell untersucht. Der Wärmewiderstand des Systems wird im Vergleich zu reiner Wärmeleitung um 98 % reduziert. Die Rotation des Systems hat keinen signifikanten Einfluss auf den Wärmewiderstand, der bis zum Erreichen der Leistungsgrenze konstant ist. Die Leistungsgrenze ist temperaturabhängig und stimmt annähernd mit der Kapillarkraftgrenze überein.
Untersuchung überlagerter Effekte von Druckverlust und Totvolumen durch Rekuperation am isobaren Expansionsmotor
Authors: Mügge Nils , Kronberg Alexander , Glushenkov Maxim , Kenig Eugeny Y.
Published: March 2023

Die Wirtschaftlichkeit von Wärmemotoren wird maßgeblich durch die Rückführung von Wärme in Rekuperatoren beeinflusst. Beim isobaren Expansionsmotor vom Bush‐Typ, einem Wärmemotor, der bereits mit Wärmequellen ab 60 °C betrieben werden kann, steigt der thermische Wirkungsgrad durch den Einsatz von Rekuperatoren signifikant. Gleichzeitig wirken sich das Fluidvolumen des Wärmeübertragers sowie der beim Betrieb auftretende Druckverlust negativ auf den thermischen Wirkungsrad aus. In dieser Arbeit wird der Zusammenhang von Totvolumen, Druckverlust und Wärmerückgewinnung untersucht und Empfehlungen für den Betrieb von Rekuperatoren am isobaren Expansionsmotor gegeben.
Phototheranostic Nanoagents for Imaging‐Guided Treatment of Oral Cancer†
Authors: Li Jisen , Zhang Yufan , Qu Jiafei , Gao Jing , Ding Dan , Shen Jing
Published: March 2023

Comprehensive Summary

Phototherapy showed almost a lack of drug resistance and, depending on the therapeutic effects of non‐invasive light‐stimulating photosensors. The side effects of phototherapy were greatly reduced compared to their traditional equivalents. Phototheranostic nanoagents had new properties in drug delivery, biocompatibility, targeting and response, in which traditional phototheranostic drugs can not possess. Recently, a large number of relevant studies have demonstrated that photodynamic therapy (PDT) in combination with other agents and image‐guided multifunctional photothermal therapy (PTT) were well suited for the treatment of oral cancer. Through the design of the nanoagents, researchers have discovered various applications for phototherapy, such as targeted release of co‐packaged drugs, multifunctional imaging for diagnosis and treatment combination, accurate targeting caused by nanocarriers, and synergistic chemotherapy with phototherapy. In this paper, we first reviewed the research related to phototheranostic nanoagents for image‐guided treatment of oral cancer. We tried to introduce the design concept and the treatment effect by three parts of components of phototheranostic nanoagents, categories of phototheranostic nanoagents and application of phototheranostic nanoagents. It also provided a reference for nanomaterial development and clinical applications in research of oral cancer treatment.