bluuebunny/crossref_metadata_2025 huggingface dataset:
Tranexamic Acid in Patients Undergoing Liver Resection
Authors: Karanicolas Paul J. , Lin Yulia , McCluskey Stuart A. , Tarshis Jordan , Thorpe Kevin E. , Wei Alice , Dixon Elijah , Porter Geoff , Chaudhury Prosanto , Nanji Sulaiman , Ruo Leyo , Tsang Melanie E. , Skaro Anton , Eeson Gareth , Cleary Sean , Moulton Carol-Anne , Ball Chad G. , Hallet Julie , Coburn Natalie , Serrano Pablo E. , Jayaraman Shiva , Law Calvin , Tandan Ved , Sapisochin Gonzalo , Nagorney David , Quan Douglas , Smoot Rory , Gallinger Steven , Metrakos Peter , Reichman Trevor W. , Jalink Diederick , Bennett Sean , Sutherland Francis , Solano Edward , Molinari Michele , Tang Ephraim S. , Warner Susanne G. , Bathe Oliver F. , Barkun Jeffrey , Kendrick Michael L. , Truty Mark , Roke Rachel , Xu Grace , Lafreniere-Roula Myriam , Guyatt Gordon ,   HPB CONCEPT Team
Published: August 2024

Importance

Tranexamic acid reduces bleeding and blood transfusion in many types of surgery, but its effect in patients undergoing liver resection for a cancer-related indication remains unclear.

Objective

To determine whether tranexamic acid reduces red blood cell transfusion within 7 days of liver resection.

Design, Setting, and Participants

Multicenter randomized clinical trial of tranexamic acid vs placebo conducted from December 1, 2014, to November 8, 2022, at 10 hepatopancreaticobiliary sites in Canada and 1 site in the United States, with 90-day follow-up. Participants, clinicians, and data collectors were blinded to allocation. A volunteer sample of 1384 patients undergoing liver resection for a cancer-related indication met eligibility criteria and consented to randomization.

Interventions

Tranexamic acid (1-g bolus followed by 1-g infusion over 8 hours; n = 619) or matching placebo (n = 626) beginning at induction of anesthesia.

Main Outcomes and Measures

The primary outcome was receipt of red blood cell transfusion within 7 days of surgery.

Results

The primary analysis included 1245 participants (mean age, 63.2 years; 39.8% female; 56.1% with a diagnosis of colorectal liver metastases). Perioperative characteristics were similar between groups. Red blood cell transfusion occurred in 16.3% of participants (n = 101) in the tranexamic acid group and 14.5% (n = 91) in the placebo group (odds ratio, 1.15 [95% CI, 0.84-1.56]; P = .38; absolute difference, 2% [95% CI, −2% to 6%]). Measured intraoperative blood loss (tranexamic acid, 817.3 mL; placebo, 836.7 mL; P = .75) and total estimated blood loss over 7 days (tranexamic acid, 1504.0 mL; placebo, 1551.2 mL; P = .38) were similar between groups. Participants receiving tranexamic acid experienced significantly more complications compared with placebo (odds ratio, 1.28 [95% CI, 1.02-1.60]; P = .03), with no significant difference in venous thromboembolism (odds ratio, 1.68 [95% CI, 0.95-3.07]; P = .08).

Conclusions and Relevance

Among patients undergoing liver resection for a cancer-related indication, tranexamic acid did not reduce bleeding or blood transfusion but increased perioperative complications.

Trial Registration

ClinicalTrials.gov Identifier: NCT02261415
Florida’s Red Flag Gun Law and Firearm and Nonfirearm Homicide and Suicide Rates
Authors: Gimbrone Catherine , Rudolph Kara E.
Published: August 2024

This study estimates the association between Florida’s red flag law enactment and firearm and nonfirearm homicide and suicide rates.
Screening and Supplementation for Iron Deficiency and Iron Deficiency Anemia During Pregnancy
Authors:   US Preventive Services Task Force, Nicholson Wanda K. , Silverstein Michael , Wong John B. , Chelmow David , Coker Tumaini Rucker , Davis Esa M. , Jaén Carlos Roberto , Krousel-Wood Marie , Lee Sei , Li Li , Rao Goutham , Ruiz John M. , Stevermer James , Tsevat Joel , Underwood Sandra Millon , Wiehe Sarah
Published: August 2024

Importance

Iron deficiency is the leading cause of anemia during pregnancy. According to survey data from 1999 to 2006, overall estimated prevalence of iron deficiency during pregnancy is near 18% and increases across the 3 trimesters of pregnancy (from 6.9% to 14.3% to 28.4%). An estimated 5% of pregnant persons have iron deficiency anemia.

Objective

The US Preventive Services Task Force (USPSTF) commissioned a systematic review to evaluate the evidence on the benefits and harms of screening and supplementation for iron deficiency with and without anemia on maternal and infant health outcomes in asymptomatic pregnant persons.

Population

Asymptomatic pregnant adolescents and adults.

Evidence Assessment

The USPSTF concludes that the current evidence is insufficient, and the balance of benefits and harms of screening for iron deficiency and iron deficiency anemia in asymptomatic pregnant persons on maternal and infant health outcomes cannot be determined. The USPSTF also concludes that the current evidence is insufficient, and the balance of benefits and harms of iron supplementation in asymptomatic pregnant persons on maternal and infant health outcomes cannot be determined.

Recommendation

The USPSTF concludes that the current evidence is insufficient to assess the balance of benefits and harms of screening for iron deficiency and iron deficiency anemia in pregnant persons to prevent adverse maternal and infant health outcomes. (I statement) The USPSTF concludes that the current evidence is insufficient to assess the balance of benefits and harms of routine supplementation for iron deficiency and iron deficiency anemia in pregnant persons to prevent adverse maternal and infant health outcomes. (I statement)
Axial Impact Performances of Composite Aluminum Foam Tubes
Authors: Wang Jiacheng , Xu Xinpei , Zhang Zan , Zhang Zichen , Xia Xingchuan , Qiu Zixuan , Cui Lipeng , Ding Jian , Liu Yongchang
Published: August 2024

An improved melt foaming method is employed to fabricate composite aluminum foam tubes (CAFTs) with varying diameter ratios, achieving metallurgical bonding between the aluminum foam and aluminum tubes. Based on the structural characteristics of aluminum foam‐filled tubes and traditional numerical formula for calculating the energy absorption properties of metal foams, a new calculation formula is proposed to accurately evaluate energy absorption performance of CAFTs under axial load, enabling more precise numerical calculation of total energy absorption. Furthermore, drop weight impact tests and finite element simulations are conducted to investigate the axial impact performance and deformation mechanism of CAFTs. The influence of diameter ratio on crashworthiness and energy absorption performance is also analyzed. As the diameter ratios decrease, both the impact resistance and total energy absorption of CAFTs increase, while the degree of tube damage gradually decreases. Moreover, finite element simulation results demonstrate that metallurgical combination between aluminum foam and aluminum tubes effectively transfers stress to thin‐walled tubes with better load‐bearing performance, preventing concentrated collapse of aluminum foam core. Additionally, the presence of aluminum foam provides robust restraint against deformation or rupture in thin‐walled tubes.
Microstructure and Mechanical Properties Evolution of W@WC/Fe Core–Shell Bar‐Reinforced Iron Matrix Composites: Effect of In‐situ Solid Diffusion Time
Authors: Bai Haiqiang , Wang Lei , Kang Ling , Liu Jianbo , Zhuang Weijun , Zhong Lisheng , Wan Zengli , Xu Yunhua
Published: August 2024

To improve the strength and toughness of conventional particle‐reinforced iron matrix composites, W@WC/Fe core–shell bar‐reinforced iron matrix composites (CBIMCs) are synthesized by casting and in‐situ solid‐phase diffusion method. These composites, which have an architecture similar to concrete, consist of a core of residual W bar and a shell of gradient‐structured WC‐Fe layer. The effect of in‐situ solid diffusion time on the evolution of microstructure and mechanical properties of the composites is investigated. It is observed that for in‐situ solid diffusion times ranging from 3 to 24 h, the reinforcement in the composites remained as W@WC/Fe core–shell bars. As the solid diffusion time increased, the diameter of the W core gradually decreased, and the thickness of the WC‐Fe shell layer increased. At a solid diffusion time of 30 h, the reinforcement transitioned to the WC‐Fe composite bar. Additionally, with longer solid diffusion times, the WC particles transformed from a triangular prism shape to a truncated octahedron. The composite prepared at 18 h exhibits the highest ultimate compression strength and strain, reaching values of 1100 ± 18 MPa and 35.5 ± 1.3%, respectively. This excellent ultimate compression strength is mainly due to the WC particles, which enhanced load transfer strengthening and dislocation strengthening. Moreover, the metal W core and iron matrix effectively hinder microcrack propagation, thus contributing to the enhanced toughness of the composite.
Revealing Enhanced Optoelectronic Performance of Sb2Se3‐Based Self‐Sustaining Heterostructures with Bi2Se3 and ZnSe: A Dual Polarity Photo Response
Authors: Kumar Kapil , Sharma Prince , Verma Sahil , Saini Saurabh K. , Kumar Tailor Naveen , Husale Sudhir , Singh Rajiv K. , Satapathi Soumitra , Achanta Venu Gopal , Kumar Mahesh
Published: August 2024

Through precise band engineering, Van der Waals heterostructures integration holds great promise for advancing high‐performance optoelectronic devices, especially photodetectors. This study presents self‐sustaining, dual‐polarity, high photo‐responsive heterostrutures (HS) photodetectors based on Sb2Se3, specifically Bi2Se3/Sb2Se3 and ZnSe/Sb2Se3. The Bi2Se3 (ZnSe) layer functions as a channel in a reconfigurable HS phototransistor configuration. These HS devices demonstrate a negative photoconductive response with bias‐modulated polarity switching of the photocurrent. The Bi2Se3/Sb2Se3 device exhibits a responsivity switch from −4 mA W−1 to 0.14 A W−1, while the ZnSe/Sb2Se3 device shows a substantially enhanced responsivity switch from ‐400 mA W−1 to 12 A W−1. This negative photo response results from a photoinduced carrier trapping mechanism at the interface of the channel layer and photosensitizer material. The bias modulation enables the switching from negative to positive responsivity. A comprehensive investigation of photoconductivity modulation provides a deeper understanding of the impact of the photogating effect and trap states under applied bias conditions. Ultrafast transient spectroscopy supports these findings, offering insights into the dynamics of charge carrier relaxation mechanisms and the trapping of photoexcited carriers in defect states, crucial for explaining the dual polarity photo response. These devices present significant advantages for switchable light imaging, optical communication, memory devices, convolution processing, and logic circuits.
In situ Ligand‐Managed SnO2 Electron Transport Layer for High‐Efficiency and Stable Perovskite Solar Cells
Authors: Sun Yulu , Xu Ruoyao , Yang Lin , Dai Jinfei , Zhu Xinyi , Cao Xiangrong , Li Peizhou , Tang Hebing , Liu Tao , Mo Daolei , Wang Yunxuan , Li Jingrui , Yuan Fang , Jiao Bo , Wu Zhaoxin , Dong Hua
Published: August 2024

Tin oxide (SnO2) with high conductivity and excellent photostability has been considered as one of the most promising materials for efficient electron transport layer (ETL) in perovskite solar cells (PSCs). Among them, SnO2 nanoparticles (NPs) dispersions have been extensively utilized due to their facile film formation. However, the inherent defects and agglomeration issues of SnO2 NPs, as well as the limited tunability and instability of the post‐treatment process for surface/interface engineering strategy, still hinder its further applications. Herein, a ligand‐management strategy implemented during the in situ synthesis of NPs that can effectively achieve uniform modification of NPs is proposed. During the synthesis of SnO2 NPs, the grafting reaction between diethyl 2‐chloromalonate (DCMA) and the surface of SnO2 NPs is completed. Compared with the post‐treatment process, this intrinsic DCMA‐passivated SnO2 (DCMA‐SnO2) effectively reduces the trap state density at the interface between perovskite and ETL while enhancing surface chemical stability. Consequently, PSCs based on DCMA‐SnO2 achieve a champion PCE of 25.39% for small cells (active area of 0.0655 cm2) and 20.61% for solar modules (active area of 23.25 cm2), demonstrating excellent shelf‐life/light soaking stability (advanced level of ISOS stability protocols). This ligand‐management strategy exhibits significant application potential in preparing high‐efficiency large‐area PSCs.
The Reinforced Separation of Intractable Gas Mixtures by Using Porous Adsorbents
Authors: Ke Quanli , Xiong Feng , Fang Guonan , Chen Jing , Niu Xiaopo , Pan Pengyun , Cui Guokai , Xing Huabin , Lu Hanfeng
Published: August 2024

This review focuses on the mechanism and driving force in the intractable gas separation using porous adsorbents. A variety of intractable mixtures have been discussed, including air separation, carbon capture, and hydrocarbon purification. Moreover, the separation systems are categorized according to distinctly biased modes depending on the minor differences in the kinetic diameter, dipole/quadruple moment, and polarizability of the adsorbates, or sorted by the varied separation occasions (e.g., CO2 capture from flue gas or air) and driving forces (thermodynamic and kinetic separation, molecular sieving). Each section highlights the functionalization strategies for porous materials, like synthesis condition optimization and organic group modifications for porous carbon materials, cation exchange and heteroatom doping for zeolites, and metal node‐organic ligand adjustments for MOFs. These functionalization strategies are subsequently associated with enhanced adsorption performances (capacity, selectivity, structural/thermal stability, moisture resistance, etc.) toward the analog gas mixtures. Finally, this review also discusses future challenges and prospects for using porous materials in intractable gas separation. Therein, the combination of theoretical calculation with the synthesis condition and adsorption parameters optimization of porous adsorbents may have great potential, given its fast targeting of candidate adsorbents and deeper insights into the adsorption forces in the confined pores and cages.
Zinc‐Mediated Carbamoyl Amination of Alkylidenecyclopropane‐Tethered Carbamoyl Chlorides: Synthesis of Functionalized 2‐Quinolones
Authors: Deng Jing‐Tong , Lang Ming , Peng Jin‐Bao
Published: August 2024

The transition metal catalyzed cyclization of alkene‐tethered carbamoyl chloride has emerged as a tool to construct oxindoles bearing quaternary centers. Most of these reactions proceed via carbometalation‐initiated 5‐exo‐trig cyclization followed by nucleophilic trapping of the resulting σ alkyl‐metal species to achieve diverse functionalized oxindoles. The 6‐endo‐trig type cyclization of alkene‐tethered carbamoyl chloride has been rarely reported. Herein, a zinc‐mediated carbamoyl amination of alkylidenecyclopropane‐tethered carbamoyl chlorides with anilines for the synthesis of functionalized 2‐quinolones was developed. A range of different substituted 2‐quinolones were prepared in 65–89% yield from alkylidenecyclopropane‐tethered carbamoyl chlorides and aniline derivatives using a Zn/TMSCl system.
Meis1 Targets Protein Tyrosine Phosphatase Receptor J in Fibroblast to Retard Chronic Kidney Disease Progression
Authors: Bai Mi , Xu Shuang , Jiang Mingzhu , Guo Yuxian , Hu Dandan , He Jia , Wang Ting , Zhang Yu , Guo Yan , Zhang Yue , Huang Songming , Jia Zhanjun , Zhang Aihua
Published: August 2024

Renal fibrosis is a common pathological feature of chronic kidney disease (CKD) with the proliferation and activation of myofibroblasts being definite effectors and drivers. Here, increased expression of Meis1 (myeloid ecotropic viral integration site 1) is observed, predominantly in the nucleus of the kidney of CKD patients and mice, and negatively correlates with serum creatinine. Fibroblast‐specific knock‐in of Meis1 inhibits myofibroblast activation and attenuates renal fibrosis and kidney dysfunction in CKD models. Overexpression of Meis1 in NRK‐49F cells suppresses the pro‐fibrotic response induced by transforming growth factor‐β1 but accelerates by its knockdown. Mechanistically, Meis1 targets protein tyrosine phosphatase receptor J (Ptprj) to block renal fibrosis by inhibiting the proliferation and activation of fibroblasts. Finally, a new activator of Ptprj is identified through computer‐aided virtual screening, which has the effect of alleviating renal fibrosis. Collectively, these results illustrate that the Meis1/Ptprj axis has therapeutic potential for clinically treating CKD.
CRISPR Screening and Comparative LC‐MS Analysis Identify Genes Mediating Efficacy of Delamanid and Pretomanid against Mycobacterium tuberculosis
Authors: Yan Mei‐Yi , Li Haifeng , Qu Yun‐Mo , Li Si‐Shang , Zheng Dandan , Guo Xiao‐Peng , Wu Zhaojun , Lu Jie , Pang Yu , Li Weimin , Yang Jian , Zhan Lingjun , Sun Yi‐Cheng
Published: August 2024

Tuberculosis (TB), the leading cause of death from bacterial infections worldwide, results from infection with Mycobacterium tuberculosis (Mtb). The antitubercular agents delamanid (DLM) and pretomanid (PMD) are nitroimidazole prodrugs that require activation by an enzyme intrinsic to Mtb; however, the mechanism(s) of action and the associated metabolic pathways are largely unclear. Profiling of the chemical‐genetic interactions of PMD and DLM in Mtb using combined CRISPR screening reveals that the mutation of rv2073c increases susceptibility of Mtb to these nitroimidazole drugs both in vitro and in infected mice, whereas mutation of rv0078 increases drug resistance. Further assays show that Rv2073c might confer intrinsic resistance to DLM/PMD by interfering with inhibition of the drug target, decaprenylphophoryl‐2‐keto‐b‐D‐erythro‐pentose reductase (DprE2), by active nicotinamide adenine dinucleotide (NAD) adducts. Characterization of the metabolic pathways of DLM/PMD in Mtb using a combination of chemical genetics and comparative liquid chromatography‐mass spectrometry (LC‐MS) analysis of DLM/PMD metabolites reveals that Rv0077c, which is negatively regulated by Rv0078, mediates drug resistance by metabolizing activated DLM/PMD. These results might guide development of new nitroimidazole prodrugs and new regimens for TB treatment.
Trapped in Endosome PEGylated Ultra‐Small Iron Oxide Nanoparticles Enable Extraordinarily High MR Imaging Contrast for Hepatocellular Carcinomas
Authors: Zhou Dandan , Shan Shanshan , Chen Lei , Li Cang , Wang Hongzhao , Lu Kuan , Ge Jianxian , Wang Ning , Afshari Mohammad Javad , Zhang Yaqin , Zeng Jianfeng , Gao Mingyuan
Published: August 2024

The early diagnosis of hepatocellular carcinomas (HCCs) remains challenging in the clinic. Primovist‐enhanced magnetic resonance imaging (MRI) aids HCC diagnosis but loses sensitivity for tumors <2 cm. Therefore, developing advanced MRI contrast agents is imperative for improving the diagnostic accuracy of HCCs in very‐early‐stage. To address this challenge, PEGylated ultra‐small iron oxide nanoparticles (PUSIONPs) are synthesized and employed as liver‐specific T1 MRI contrast agents. Intravenous delivery produces simultaneous hyperintense HCC and hypointense hepatic parenchyma signals on T1 imaging, creating an extraordinarily high tumor‐to‐liver contrast. Systematic studies uncover PUSIONP distribution in hepatic parenchyma, HCC lesions at the organ, tissue, cellular, and subcellular levels, revealing endosomal confinement of PUSIONP without aggregation. By mimicking such situations, the dependency of relaxometric properties on local PUSIONP concentration is investigated, emphasizing the key role of different endosomal concentrations in liver and tumor cells for high tumor‐to‐liver contrast and clear tumor boundaries. These findings offer exceptional imaging capabilities for early HCC diagnosis, potentially benefiting real HCC patients.
Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [FeV(Cor)(NAd)]
Authors: You Tingjie , Shing Ka‐Pan , Wu Liangliang , Wu Kai , Wang Hua‐Hua , Liu Yungen , Du Lili , Liang Runhui , Phillips David Lee , Chang Xiao‐Yong , Huang Jie‐Sheng , Che Chi‐Ming
Published: August 2024

As nitrogen analogues of iron‐oxo species, high‐valent iron‐imido species have attracted great interest in the past decades. FeV‐alkylimido species are generally considered to be key reaction intermediates in Fe(III)‐catalyzed C(sp3)─H bond aminations of alkyl azides but remain underexplored. Here, it is reported that iron‐corrole (Cor) complexes can catalyze a wide range of intramolecular C─H amination reactions of alkyl azides to afford a variety of 5‐, 6‐ and 7‐membered N‐heterocycles, including alkaloids and natural product derivatives, with up to 3880 turnover numbers (TONs) and excellent diastereoselectivity (>99:1 d.r.). Mechanistic studies including density functional theory (DFT) calculations and intermolecular hydrogen atom abstraction (HAA) reactions reveal key reactive FeV‐alkylimido intermediates. The [FeV(Cor)(NAd)] (Ad = adamantyl) complex is independently prepared and characterized through electron paramagnetic resonance (EPR), resonance Raman (rR) measurement, and X‐ray photoelectron spectroscopy (XPS). This complex is reactive toward HAA reactions with kinetic isotope effects (KIEs) similar to [Fe(Cor)]‐catalyzed intramolecular C─H amination of alkyl azides.
Asymmetric Structural Engineering of Hot‐Exciton Emitters Achieving a Breakthrough in Non‐Doped BT.2020 Blue OLEDs with a Record 9.5% External Quantum Efficiency
Authors: Ma Bingzhu , Zhang Baijun , Zhang Han , Huang Yu , Liu Lu , Wang Baoling , Yang Dezhi , Ma Dongge , Tang Ben Zhong , Wang Zhiming
Published: August 2024

High‐efficiency non‐doped deep‐blue organic light‐emitting diodes (OLEDs) meeting the standard of BT.2020 color gamut is desired but rarely reported. Herein, an asymmetric structural engineering based on crossed long‐short axis (CLSA) strategy is developed to obtain three new deep‐blue emitters (BICZ, PHDPYCZ, and PHPYCZ) with a hot‐exciton characteristic. Compared to 2BuCz‐CNCz featuring a symmetric single hole‐transport framework, these asymmetric emitters with the introduction of different electron‐transport units show the enhancement of photoluminescence efficiency and improvement of bipolar charge transport capacity. Further combined with high radiative exciton utilization efficiency and light outcoupling efficiency, the non‐doped OLED based on PHPYCZ exhibits the best performance with an excellent current efficiency of 3.49%, a record‐high maximum external quantum efficiency of 9.5%, and a CIE y coordinate of 0.049 approaching the BT.2020 blue point. The breakthrough obtained in this work can inspire the molecular design of deep‐blue emitters for high‐performance non‐doped BT.2020 blue OLEDs.
Programmable Analog Circuits with Neuromorphic Nanostructured Platinum Films
Authors: Radice Stefano , Profumo Filippo , Borghi Francesca , Falqui Andrea , Milani Paolo
Published: August 2024

Self‐assembled nanoparticle or nanowire networks have recently come under the spotlight as systems able to emulate brain‐like data processing performances by exploiting the memristive character and the wiring of the junctions connecting the nanostructured network building blocks. Recently it is demonstrated that nanostructured Au films, fabricated by the assembling of gold clusters produced in the gas phase, have non‐linear and non‐local electric conduction properties caused by the extremely high density of grain boundaries and the resulting complex arrangement of nanojunctions. These observations suggest that nanostructured metallic films can be explored and exploited as a novel class of neuromorphic systems for unconventional electronic devices. Here it is reported that nanostructured cluster‐assembled Pt films show resistive switching activity, negative differential resistance, and reversible memory effects. These properties allow the use of nanostructured Pt films in programmable analog circuits, such as gain amplifiers and relaxation oscillators with fast response.
Manipulating Multivalent Anion Intercalation for High‐Energy Aqueous Zn–Graphite Dual‐Ion Batteries
Authors: Zheng Ying , Xie Xiaolin , Ueno Hiroshi , Deng Ting , Zheng Weitao
Published: August 2024

Anion intercalation in graphite is deemed as a promising electrode chemistry in aqueous energy storage systems due to its high onset potential. Given the limited space in graphite, multivalent anions are favorable to achieve high specific capacity. However, relevant studies are scarce so that fundamental understandings of multivalent anion intercalation remain unclear. Herein, the intercalation behaviors of ClO4−, SO42−, and PO43− in graphite are systematically investigated. High capacity and interaction between anion and graphite are proved to be contradictory as the electric charge increases. As a result, ClO4− and SO42− intercalation exhibits promising performance in primitive graphite, while PO43− intercalation is much restricted due to the intensified electronic interaction. Two Zn–graphite dual‐ion batteries based on ClO4− and SO42− intercalations display high voltages of 1.85 V, and specific energies of 106 and 112 Wh kg−1. This work provides fundamental understandings of multivalent anion intercalation and guidance to fabricate aqueous batteries (ABs) with high energy density.
Zwitterionic Nanoconfined Proton‐Sieve: Charged Casing for Accelerating Proton Conduction
Authors: Zou Wenwu , Jiang Guoxing , Li Baotao , Zhang Weifeng , Wang Liming , Cui Zhiming , Song Huiyu , Liang Zhenxing , Du Li
Published: August 2024

Since specifying the structure during operation tends to be challenging for intrinsically proton‐conducting polymers, it becomes increasingly essential to establish a well‐defined migration path in order to predict the proton conductivity. Zwitterion covalent organic frameworks (ziCOFs) provide a platform in crystal frameworks to investigate the proton transfer mechanism, considering their specific charged channel walls, deprotonation surface, and host–guest interactions. Here, a zwitterion nanoconfined proton‐sieves (ziNPS) with “charged casing” channel of charged pathways is proposed to demonstrate theoretically the effectiveness of proton conduction. Density functional theory and molecular dynamic simulation results show that the ziNPS with different anion groups all achieve a shorter hydrogen bond to increase the dense “hydronium‐water” domain, creating a channel of hydrogen bond networks to provide a long‐range pathway for the proton to migrate. As expected, the proton conductivity test by electrochemical impedance spectroscopy demonstrates the aforementioned concept as well. This research presents a fresh view of the ion conduction mechanism originating from localized zwitterionic units, which can apply to the fabrication of COF‐based proton conductors.
Plasmagestützter Prozess mit Einzelatom‐Katalysatoren zur Nachhaltigen Umwandlung von Kunststoffabfällen
Authors: Yu Xiao , Rao Zhiqiang , Chen Guoxing , Yang Yuantao , Yoon Songhak , Liu Lina , Huang Zeai , Widenmeyer Marc , Guo Heng , Homm Gert , Kunz Ulrike , Liu Xingmin , Ionescu Emanuel , Molina‐Luna Leopoldo , Tu Xin , Zhou Ying , Weidenkaff Anke
Published: August 2024

Die stetig steigende Menge an Kunststoffabfällen erfordert effektive Lösungen zur Bewältigung dieser Herausforderung. In dieser Studie stellen wir eine neuartige plasmagestützte Strategie zur schnellen Zersetzung verschiedener Plastikabfälle, einschließlich Mischungen, in hochwertige Kohlenstoffnanomaterialien und Wasserstoff vor. Die H2‐Ausbeute und die H2‐Selektivität, die durch die katalysatorfreien plasmagestützten Prozesse erzielt wurden, sind 14,2‐ bzw. 5,9‐mal höher als bisher unter ähnlichen Bedingungen mit konventioneller thermischer Pyrolyse erreicht wurde. Bemerkenswert ist, dass dieser katalysatorfreie Plasmaprozess einen signifikant höheren Energieertrag an H2 (gH2/kWh) im Vergleich zu anderen Pyrolyseprozessen liefert. Durch die Kopplung von Plasmapyrolyse mit thermischer Katalyse durch den Einsatz von atomar dispergierten Katalysatoren 1 Gew.‐ % M/CeO2 (M=Fe, Co und Ni) kann die Wasserstoffproduktion weiter gesteigert werden. Insbesondere der 1 Gew.– %Co/CeO2 Katalysator zeigte eine hervorragende katalytische Leistung über 10 Zyklen der Kunststoffabfallzersetzung hinweg und erreichte die höchste H2‐Ausbeute von 46,7 mmol/gplastic (entsprechend 64,4 % der theoretischen H2‐Ausbeute) und nahezu 100 % Wasserstoffatom‐Rückgewinnungseffizienz im 7. Zyklus. Atomar dispergiertes Fe auf der CeO2‐Oberfläche (1 Gew.– % Fe/CeO2) konnte im integrierten plasma‐thermischen Katalyseprozess eine H2‐Ausbeute erzielen wie sie sonst nur mit deutlich höheren Beladungen von Fe‐Partikeln auf der CeO2‐Oberfläche (10 Gew.– % Fe/CeO2) erreicht wird. Daher wurde demonstriert, dass Einzelatom‐Katalysatoren einen vielversprechenden Weg für ein kostengünstiges und effizientes chemisches Kunststoffrecycling darstellen. Durch eine Kombination aus Experiment und Modellierung haben wir ein tiefgehendes Verständnis der katalytischen Mechanismen der untersuchten Einzelatom‐Katalysatoren im entwickelten plasmagestützten Prozess erzielt. Dieser innovative und unkomplizierte Ansatz bietet eine vielversprechende und schnelle Strategie zur kontinuierlichen Umwandlung verschiedener Kunststoffabfallströme, einschließlich gemischter und kontaminierter Quellen, in hochwertige Produkte, die eine Kreislaufwirtschaft für Kunststoffe unterstützen.
High Performance Memristors Based on Imine‐Linked Covalent Organic Frameworks Obtained Using a Protonation Modification Strategy
Authors: Che Qian , Li Chenyu , Chen Zhihui , Yang Shuai , Zhang Weifeng , Yu Gui
Published: August 2024

Imine‐linked covalent organic frameworks (COFs) are garnering substantial interest in resistive random‐access memory, attributed to their superior crystallinity, excellent chemical and thermal stability, and modifiable molecular structures. However, the development of high‐performance COF‐based memristors impeded by challenges such as low conjugation degree of imine bonds and poor electron delocalization ability. Herein, we report a protonation strategy to modify the imine bonds of donor‐acceptor (D‐A) type COFs. This modification significantly enhances the electron delocalization capability of imine bonds, lowers the energy barriers for electron injection from electrodes, and stabilizes the conductive charge transfer state, thus markedly improving device performance. The protonated COF‐BTT‐BPy and COF‐BTT‐TAPT thin films‐based memristors show remarkable device performance with a high ON/OFF current ratio of 105, a low driving voltage, and outstanding endurance exceeding 600 and 1300 cycles, respectively, which is nearly twice the durability of analogous non‐protonated COFs‐based memristors. Notably, the protonated COF‐BTT‐TAPT‐based memristor exhibit the highest number of cycles reported at present. This work not only unprecedentedly enhances the performance of COF‐based memristors, but also provides a universal and promising approach for the molecular design and potential application of D‐A type imine‐linked COFs.
Enantio‐ und regiokonvergente, nickelkatalysierte Veretherung von Phenolen durch Allylierung zur Darstellung chiraler C(sp3)−O‐Allylarylether
Authors: Brösamlen Daniel , Neb Daniel , Oestreich Martin
Published: August 2024

Es wird eine enantio‐ und regiokonvergente Allylierung von Phenolen unter Nickelkatalyse mit einem α‐/γ‐Regioisomerengemisch racemischer silylierter/germylierter Allylchloride beschrieben. Die Silyl‐/Germylgruppe steuert die Regioselektivität, und die Umwandlung liefert enantiomerenangereicherte unsymmetrische 1,3‐disubstituierte Allylarylether mit ausgezeichneter Regiokontrolle in guten Ausbeuten und mit hervorragenden Enantioselektivitäten. Bemerkenswerterweise wird keine nickelvermittelte C−O‐Bindungsaktivierung bei Raumtemperatur beobachtet. Der synthetische Wert dieser hochfunktionalisierten, siliciumhaltigen Bausteine wird in einer Reihe chemoselektiver Umwandlungen aufgezeigt, einschließlich einer [3,3]‐sigmatropen Umlagerung zur Herstellung eines α‐chiralen Silans.
Steering the Selectivity of CORR from Acetate to Ethanol via Tailoring the Thermodynamic Activity of Water
Authors: Liu Jia , Zhang Bao , Chen Derong , Peng Ouwen , Ma Haibin , Xi Shibo , Wu Chao , Hu Qikun , Zhang Kun , Feng Junyuan , Ping Loh Kian
Published: August 2024

The electrochemical conversion of carbon monoxide (CO) into oxygenated C2+ products at high rates and selectivity offers a promising approach for the two‐step conversion of carbon dioxide (CO2). However, a major drawback of the CO electrochemical reduction in alkaline electrolyte is the preference for the acetate pathway over the more valuable ethanol pathway. Recent research has shed light on the significant impact of thermodynamic water activity on the electrochemical CO2 reduction reaction pathways, but less is understood for the electrochemical reduction of CO. In this study, we investigated how the water activity at the electrified interface can be enhanced to adjust the selectivity between acetate and ethanol. We employed an ionomer modifier to lower the local concentration of alkali ions (via Donnan exclusion), successfully enhancing ethanol production while suppressing acetate formation. We observed a remarkable improvement in the Faradaic efficiency of ethanol and alcohol (i. e. ethanol, propanol etc), which reached 42.5 % and 55.1 %, respectively, at a current density of 700 mA cm−2. The partial current densities of ethanol and alcohol reached 698 and 942 mA cm−2 at 2000 mA cm−2. Furthermore, we achieved a 3.7‐fold increase in the ethanol/acetate ratio, providing clear evidence of our successful modulation of product selectivity.
Intermolecular Anionic Mixed‐Valence and π‐Dimer Complexes of ortho‐Pentannulated Bisazacoronene Diimide
Authors: David Arthur H. G. , Roger Maxime , Alévêque Olivier , Melnychenko Heorhii , Le Bras Laura , Allain Magali , Gapin Adèle , Canevet David , Ségut Olivier , Levillain Eric , Goujon Antoine
Published: August 2024

This study reports the serendipitous discovery of intermolecular anionic mixed‐valence (MV) and π‐dimer species in ortho‐pentannulated BisAzaCoroneneDiimides (BACDs) during their electrochemical reduction in a non‐aqueous solvent. A library of nitrogen‐containing extended PDIs was synthesized via an aza‐benzannulation reaction followed by a Pd‐catalysed ortho‐pentannulation reaction. Ortho‐pentannulated BACDs revealed strong aggregation abilities in solution. Concentration‐dependent UV/Vis absorption spectra, variable temperature 1H NMR experiments, and atomic force microscopy coupled to molecular dynamics support their self‐assembly into columnar aggregates. Cyclic voltammetry experiments in dichloromethane reveal prominent splitting of the first reduction wave, attributed to the formation of unprecedented intermolecular anionic MV and π‐dimers in organic solvent. These species were thoroughly characterized by real‐time spectroelectrochemistry, electrochemical simulations and theoretical calculations. Remarkably, this work underscores the tuneable nature of AzaBenzannulatedPerylene Diimides (AzaBPDIs) and BACDs, emphasizing their potential as a promising scaffold for designing supramolecular materials with long‐range radical anion delocalization. The observation of this phenomenon provides insights into the fundamental behaviour of supramolecular organic semiconductors, thereby paving the way for the development of novel electronic devices and electron‐deficient materials.
Strain‐Induced Structural Rearrangement Towards a White‐Light‐Emitting Adamantane‐Type Cluster Dimer
Authors: Wang Jie , Rojas‐Leon Iran , Rinn Niklas , Guggolz Lukas , Ziese Ferdinand , Sanna Simone , Rosemann Nils W. , Dehnen Stefanie
Published: August 2024

Group 14/16 adamantane‐type hybrid clusters of the type [(RT)4E6] (T=group 14 element, E=group 16 element, R=organic group) have been reported to emit white‐light when irradiated in an amorphous state with a continuous‐wave (CW) infrared laser diode. This effect is enhanced if the cluster core is varied from a binary to a more complex composition. To further explore this phenomenon, we synthesized clusters with a multinary R/R’‐T/T’‐E/E’ composition, including isolobal replacement of E with CH2, in [(2‐NpSi){CH2Sn(S)Ph}3] (1, Np=naphthyl). When expanding one of the CH2 moieties to a C2H4 group, thus generating a R/R’‐T/T’‐E/E’/E’’ cluster composition, we unexpectedly observed a dimerization of the initially formed, yet non‐isolable adamantane‐like cluster [(2‐NpSi){CH2Sn(S)Ph}2{C2H4Sn(S)Ph}] (2) to [(2‐NpSi){CH2Sn(S)Ph}2{C2H4Sn(S)Ph}]2 (3), exhibiting a heretofore unprecedented cluster architecture. Both monomeric 1 and dimeric 3, show white‐light emission as thin films. The nonlinear optical response of the compounds was also modelled with DFT methods.
Collective Asymmetric Synthesis of Thiosilvatins
Authors: Liu Jian , Ekberg Robin , Koning Nicolas R. , Strand Daniel
Published: August 2024

Thiosilvatins are a family of biologically active sulfenylated diketopiperazine natural products. The first members were reported over 40 years ago, but total synthesis of a thiosilvatin has remained elusive. Here, we describe the first, collective, synthesis of the parent epidithiodiketopiperazine (−)‐dithiosilvatin and ten related thiosilvatins. Several of the targets are structurally revised. A catalytic asymmetric sulfenylation of triketopiperazines efficiently controls absolute configuration at the thioaminal units. Further synthetic highlights include a diastereoconvergent installation of the requisite cis‐orientation of the sulfur atoms and a tandem epidisulfide formation/O‐prenylation under mild Mitsunobu conditions. The described methods for late‐stage diversification of sensitive bis(methylthio)diketopiperazines offer a blueprint for systematically exploring this interesting 3D‐pharmacophore in stereochemically pure form.
Hofmann Clathrates: A “Blue Box” Approach to Modulate Spin‐Crossover Properties
Authors: Getzner Livia , Vendier Laure , Molnár Gábor , Rotaru Aurelian , Cobo Saioa , Bousseksou Azzedine
Published: August 2024

Hofmann coordination polymers (CPs) with cationic ligands provide an innovative strategy for recognizing π‐electron‐rich aromatic molecules – similar to the “little blue box”. In this study, we demonstrate that hydroquinone molecules can be incorporated into these coordination polymers when redox‐active bipyridinium derivatives are used as axial ligands. The insertion leads to a significant structural modification, resulting in a shift of the spin transition by 150 K and an approximate 23 % increase in volume, caused by the strong donor‐acceptor π‐π stacking interaction formed between the ligands and the guest molecule. These findings have been confirmed through temperature‐dependent single crystal X‐ray diffraction, magnetic measurements and optical reflectivity measurements.
Hydrogen Bonding Chemistry in Aqueous Ammonium Ion Batteries
Authors: Zhou Mengmeng , Huang Xinjun , Li Hui , Duan Xiaoguang , Zhao Qin , Ma Tianyi
Published: August 2024

Aqueous ammonium ion batteries (AIBs) pose the advantages of high safety, low cost, and high efficiency, capturing substantial research interest. The intrinsic chemical properties of NH4+ promote the formation of hydrogen bonds with other constituents in AIBs, critically influencing the processes of NH4+ transfer, storage, and diffusion. This review delves into the pivotal role of hydrogen bonding chemistry in AIBs. Firstly, the principles of hydrogen bond are elucidated as the dominant chemical interaction governing NH4+ dynamics in AIBs. Subsequently, a detailed analysis is conducted on the impacts of hydrogen bonds in both electrolytes and electrode materials. Furthermore, the practical applications of hydrogen bonding chemistry within the context of AIBs are assessed. Finally, strategic insights and future research directions are proposed to harness hydrogen bonding effects for optimizing AIB performance. This review aims to define the mechanisms and impacts of hydrogen bonds in AIBs, providing robust strategies to enhance electrochemical performance, deepen the understanding of energy storage mechanisms, and guide the future advancement of AIBs technology.
Eggshell bio‐filler integration in jute/banana fiber‐reinforced epoxy hybrid composites: Fabrication and characterization
Authors: Dev Barshan , Rahman Md Ashikur , Khan Ayub Nabi , Siddique Abu Bakr , Alam Md Rubel , Rahman Md Zillur
Published: August 2024

The use of waste‐based bio‐fillers in composite manufacturing has increased in recent years due to their sustainable and biodegradable characteristics. The current study fabricates jute/banana (JB) fiber‐reinforced epoxy composites incorporating waste‐derived eggshell (ES) bio‐filler and investigates the effect of ES bio‐filler on the mechanical, morphological, and water absorption properties of the composites. JB fibers (1:1) and varying ES filler contents (5, 10, 15, and 20 wt%) were used to manufacture the composites using the hand lay‐up technique. Their tensile, flexural, and impact properties, microstructure, chemical compositions, and water absorption are then examined. It is found that the composite composed of 15 wt% ES exhibits better tensile and flexural properties with a tensile modulus and strength of 4.42 GPa and 95.27 MPa, and a flexural modulus and strength of 3.96 GPa and 117.47 MPa, respectively, whereas the composite filled with 5 wt% ES shows a maximum impact strength of 46.83 kJ/m2 and drops with increasing bio‐fillers. Scanning electron microscopy reveals that composite failures occur due to jute and banana fiber fractures, filler–fiber‐matrix debonding, fiber pullout, and ES filler agglomeration. Moreover, water absorption reduces as the ES content rises, and the 20 wt% ES filler‐based composite shows a minimum water absorption of 7.67% after 240 h. This study provides some insights to promote the usage of ES bio‐filler in natural fiber composites to improve their mechanical and water absorption properties and their potential applications in the internal structures of automobiles, aircraft, and construction.
Enhanced Type 1 Interferon Signature in Axial Spondyloarthritis Patients Unresponsive to Secukinumab Treatment
Authors: Pacheco Addison , Maguire Sinead , Qaiyum Zoya , Tang Michael , Bridger Adam , Lim Melissa , Tavasolian Fataneh , Yau Enoch , Crome Sarah Q. , Haroon Nigil , Inman Robert D.
Published: August 2024

Objective

Axial spondyloarthritis (axSpA) is an inflammatory disease in which overactive interleukin (IL)‐17A–producing cells are implicated in a central role. Therapeutically, biologics that target IL‐17A, such as secukinumab, have demonstrated improved clinical outcomes. Despite this translational success, there is a gap in understanding why some patients with axSpA do not respond to IL‐17A–blocking therapy. Our study aims to discriminate immune profiles between secukinumab responders (SEC‐R) and nonresponders (SEC‐NR).

Methods

Peripheral blood mononuclear cells were collected from 30 patients with axSpA before and 24 weeks after secukinumab treatment. Frequency of CD4+ subsets were compared between SEC‐R and SEC‐NR using flow cytometry. Mature CD45RO+CD45RA‐CD4+ T cells were fluorescent‐activated cell sorting sorted, and RNA was measured using NanoString analysis.

Results

SEC‐NR had an increased frequency of IL‐17A–producing RORγt+CD4+ T cells compared to healthy controls before secukinumab treatment (P < 0.01). SEC‐NR had a significant increase of CXCR3+ CD4+ T cells before secukinumab treatment compared to SEC‐R (P < 0.01). Differentially expressed gene analysis revealed up‐regulation of type 1 interferon (IFN)‐regulated genes in SEC‐NR patients compared to SEC‐R patients after receiving the biologic. SEC‐R patients had an up‐regulated cytotoxic CD4+ T cell gene signature before receiving secukinumab treatment compared to SEC‐NR patients.

Conclusion

The increased frequency of IL‐17A–producing cells in SEC‐NR patients suggests a larger inflammatory burden than SEC‐R patients. With treatment, SEC‐NR patients have a more pronounced type 1 IFN signature than SEC‐R patients, suggesting a mechanism contributing to this larger inflammatory burden. The results point toward more immune heterogeneity in axSpA than has been recognized and highlights the need for precision therapeutics in this disease.

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Efficient Synthesis and Iodine‐Functionalization of Pyrazoles via KIO3/PhSeSePh System under Acidic Conditions
Authors: Peglow Thiago J. , Thomaz João Pedro S. S. C. , Nobre Patrick C. , Scimmi Cecilia , Santi Claudio , Nascimento Vanessa
Published: August 2024

This manuscript reports a novel method for the direct iodination of the C‐4 pyrazole ring generated in situ by the reaction of 1,1,3,3‐tetramethoxypropane and various hydrazines. In this approach, potassium iodate (KIO3) is used as the iodinating agent and (PhSe)2 is used as catalysts under acidic conditions. This protocol provides a convenient method for the efficient synthesis of 4‐iodo‐1‐aryl‐1H‐pyrazoles, valuable intermediates for several different coupling reactions.
Evaluating the quality characteristics of intermediate wheatgrass grown in the Canadian prairies
Authors: Ferguson Mackenzie , Valsalan Anashwar , Cattani Douglas , Malalgoda Maneka
Published: August 2024

Background and Objectives

Intermediate wheatgrass (IWG) is an underutilized perennial grain in the Canadian market with excellent nutritional and environmental benefits. The aim of this study was to assess the impact of the growing environment on the physiochemical and functional properties of IWG grown in three different growing locations in the Canadian prairies. IWG flours were compared between growing locations and years as well as alongside Canada Western Red Spring Wheat whole meal (CWRS‐WM) and refined flour.

Findings

The proximate composition of IWG flours between years and growing locations had significant (p < .05) differences for protein, fiber, and ash content but showed little difference for starch content. Owing to differences in proximate composition, variances in mixing parameters, starch pasting properties, and protein profiles were observed. Overall IWG performed poorly in a bread system at 100% incorporation largely due to its lack of high molecular weight glutenin.

Conclusion

Understanding the impacts that growing location and year have on the proximate composition and therefore working parameters will aid in the development of new wheat products fortified with IWG. These products will contribute to a more resilient and diverse food system, that will provide nutrient‐dense food options for consumers.

Significance and Novelty

There is very limited research on IWG grown in the Canadian prairies, and this study is among the first studies focused on characterizing IWG grown in Canada.
Genital rash: A manifestation of metastatic Crohn's disease
Authors: Chetwood John David , Arzivian Arteen , Shin Joo‐Shik , Tamilarasan Aravind Gokul
Published: August 2024

Key Clinical Message

Metastatic Crohn's disease is the rarest cutaneous manifestation of Crohn's disease, it presents as cutaneous lesions in areas that are anatomically non‐contiguous with the gastrointestinal tract. It requires a high index of suspicion for diagnosis which is confirmed on histopathology. Infliximab can be an effective treatment.