bluuebunny/crossref_metadata_2025 huggingface dataset:
Nano‐ and Micro‐Platforms in Therapeutic Proteins Delivery for Cancer Therapy: Materials and Strategies
Authors: Han Huijie , Santos Hélder A.
Published: September 2024

Proteins have emerged as promising therapeutics in oncology due to their great specificity. Many treatment strategies are developed based on protein biologics, such as immunotherapy, starvation therapy, and pro‐apoptosis therapy, while some protein biologics have entered the clinics. However, clinical translation is severely impeded by instability, short circulation time, poor transmembrane transportation, and immunogenicity. Micro‐ and nano‐particles‐based drug delivery platforms are designed to solve those problems and enhance protein therapeutic efficacy. This review first summarizes the different types of therapeutic proteins in clinical and research stages, highlighting their administration limitations. Next, various types of micro‐ and nano‐particles are described to demonstrate how they can overcome those limitations. The potential of micro‐ and nano‐particles are then explored to enhance the therapeutic efficacy of proteins by combinational therapies. Finally, the challenges and future directions of protein biologics carriers are discussed for optimized protein delivery.
Photoinduced Radical Borylation of Robust Carbon–Heteroatom Bonds
Authors: Tian Ya‐Ming , Pu Xiang , Sánchez Alejandro Heredero , Silva Wagner , Gschwind Ruth M. , König Burkhard
Published: September 2024

Photoinduced borylation has emerged as a valuable strategy for synthesizing arylboronic esters. However, photochemical transformations involving inert bonds such as C(sp2)−F bonds are still challenging. Herein, we report a straightforward and operationally simple method for the activation of various inert carbon–heteroatom bonds, enabling the synthesis of diverse arylboronic esters without the need for transition metals or catalysts. Mechanistic investigations reveal that the deprotonation of DMSO plays a pivotal role in the reaction, and the excited DMSO anion can undergo electron transfer to the aryl substrates activated by anionic sp2–sp3 diboron compounds, i. e., [FB2pin2]−, thereby facilitating the cleavage of carbon–heteroatom bonds. The reaction allows the conversion of diverse Caryl–hetero bonds in batch and flow reactors into the corresponding arylboronic esters. The products can be used in a subsequent Suzuki‐Miyaura cross‐coupling without isolation.
A Pneumatic Flexible Linear Actuator Inspired by Snake Swallowing
Authors: Qi Yuyan , Shao Jiaqi , Zhao Yongjian , Niu Tong , Yang Yi , Zhong Songyi , Xie Shaorong , Lin Yangqiao , Yang Yang
Published: September 2024

Soft robots spark a revolution in human–machine interaction. However, developing high‐performance soft actuators remains challenging due to trade‐offs among output force, driving distance, control precision, safety, and compliance. Here, addressing the lack of long‐distance, high‐precision flexible linear actuators, an innovative pneumatic flexible linear actuator (PFLA) is introduced, inspired by the smooth and controlled process observed in snakes ingesting sizable food, such as eggs. This PFLA combines a soft tube, emulating the snake's body cavity, with a pneumatically driven piston. Through the joint modulation of moving resistance and driving force by pneumatic pressure, the PFLA exhibits exceptional motion control capabilities, including self‐holding without pressure supply, smooth low‐speed motion (down to 0.004 m s–1), high‐speed motion (up to 5.6 m s–1) with low air pressure demand, and a self‐protection mechanism. Highlighting its adaptability and versatility, the PFLA finds applications in various settings, including a wearable assistive devices, a manipulator capable of precise path tracking and positioning, and rapid transportation in diverse environments for pipeline inspection and firefighting. This PFLA combines biomimetic principles with sophisticated fluidic actuation to achieve long‐distance, flexible, precise, and safe actuation, offering a more adaptive solution for force/motion transmission, particularly in challenging environments.
Enhancing Cardioprotection Through Neutrophil‐Mediated Delivery of 18β‐Glycyrrhetinic Acid in Myocardial Ischemia/Reperfusion Injury
Authors: Han Dongjian , Wang Fuhang , Jiang Qingjiao , Qiao Zhentao , Zhuang Yuansong , An Quanxu , Li Yuhang , Tang Yazhe , Li Chenyao , Shen Deliang
Published: September 2024

Myocardial ischemia/reperfusion injury (MI/RI) generates reactive oxygen species (ROS) and initiates inflammatory responses. Traditional therapies targeting specific cytokines or ROS often prove inadequate. An innovative drug delivery system (DDS) is developed using neutrophil decoys (NDs) that encapsulate 18β‐glycyrrhetinic acid (GA) within a hydrolyzable oxalate polymer (HOP) and neutrophil membrane vesicles (NMVs). These NDs are responsive to hydrogen peroxide (H2O2), enabling controlled GA release. Additionally, NDs adsorb inflammatory factors, thereby reducing inflammation. They exhibit enhanced adhesion to inflamed endothelial cells (ECs) and improved penetration. Once internalized by cardiomyocytes through clathrin‐mediated endocytosis, NDs protect against ROS‐induced damage and inhibit HMGB1 translocation. In vivo studies show that NDs preferentially accumulate in injured myocardium, reducing infarct size, mitigating adverse remodeling, and enhancing cardiac function, all while maintaining favorable biosafety profiles. This neutrophil‐based system offers a promising targeted therapy for MI/RI by addressing both inflammation and ROS, holding potential for future clinical applications.
Highly Selective Solar CO2 Conversion into Formic Acid in Nickel‐Perylene‐C3N4 Semiconductor Photocatalyst
Authors: Yang Long , Sivasankaran Ramesh Poonchi , Song Mee Kyung , Pawar Amol Uttam , Lee Don Keun , Kang Young Soo
Published: September 2024

Photocatalytic (PC) CO2 reduction reaction (CO2RR) into value‐added oxygenated products is one of the most promising ways of solving climate warming change and energy crisis simultaneously. To reach higher selectivity and productivity of fuel products, it still remains great challenge in controlling both simultaneous sequential multi‐electron/proton shuttling through different transporting pathway, which determines the intermediates and final products. Consequently, a multifunctional nickel‐perylene‐carbon nitride nanosheet (NS‐P‐g‐C3N4‐Ni) are constructed rationally to strengthen the electron and proton transfer via different pathway at the same time through molecule‐level carbon backbone with excellent conductivity/charge capacity and proton transport via pendant functional group of ‐NH2 from water oxidation sites of Ni metal cluster on perylene skeleton. CO2 adsorption is enhanced and reduction energy is reduced by the complexation of N‐atom site of NS‐P‐g‐C3N4‐Ni and adjustment of co‐planarity, optimizing conduction band and band gap with energy controllable techniques. In situ FT‐IR/Raman/EPR spectra identified and verified the transformation of active intermediates (*CO2•−, *COOH and H*COO−) adsorbed on the NS‐P‐g‐C3N4‐Ni by complexation and highly selective production of formic acid (60%) is achieved. This work sheds light on the construction of effective well‐structured sites in photocatalytic CO2 reduction to produce value‐added products with higher selectivity and productivity.
Cathode‐Free Aqueous Micro‐battery for an All‐in‐One Wearable System with Ultralong Stability
Authors: Huang Tao , Gao Bowen , Li Mingfeng , Zhou Xin , He Wenbin , Yan Jinfeng , Luo Xiao , Lai Wei , Li Jian , Luo Shijun , Yue Yang , Ma Yanan , Gao Yihua
Published: September 2024

Constructing an all‐in‐one wearable electronic system integrated with an energy‐harvesting, an energy‐storing, and a working unit can fundamentally solve the problems of sustainable energy supply, miniaturization, and lightweight for further commercialization. Here, an all‐in‐one wearable system consisting of solar cell, cathode‐free zinc ion micro‐battery (ZIMB) and piezoresistive pressure sensor is proposed, achieving an ultralong and stable power supply. Under the action of photocurrent, this integrated system is stimulated to in situ generate MnO2 on the initial cathode‐free substrate, meanwhile converts into chemical energy for powering the sensor, which eliminates prepreparation and treatment of the cathode for energy storage units. The facial cathode‐free ZIMB combining the all‐in‐one design enhances matching degree between different units and improves the integration. The working mechanism of the cathode‐free ZIMB is analyzed systematically through multiple ex situ characterizations and density functional theory (DFT) simulation. And the integrated sensing system illuminating for 12.0 h realizes the ultralong energy supply of the pressure sensor up to 150 000 cycles. As a concept, the integrated wearable electronic is used to detect human physiological signals, showcasing potential applications in activity monitoring, intelligent robotics, human–computer interaction, and other related fields.
Swelling the d/p‐Band Center Difference Induced by Heterostructure Self‐Optimization Engineering for Enhanced Water Oxidation
Authors: Wang Xuemin , Liu Ming , Li Na , Li Zhigang , Zhang Cui , Liu Shuangxi
Published: September 2024

Monitoring the dynamic behavior of active species and modulating their electronic architecture are crucial for the development of efficient catalysts. Here, a 3D ordered multi‐level porous Ni2P/CeO2 heterojunction catalyst with a “self‐optimization effect” is strategically synthesized for efficient oxygen evolution reaction (OER). This catalyst exhibits a low overpotential of 235 mV at 20 mA cm−2 in 1.0 m KOH. During the OER process, the heterojunction catalyst specifically undergoes a unique phase transition involving the leaching of the P element, which triggers the formation of the PO43−‐NiOOH/CeO2 catalyst with PO43− adsorbed on the surface of the reconstructed product NiOOH/CeO2. Density functional theory calculations reveal that the CeO2 and adsorbed‐PO43− in the self‐optimized structure are essential and minor factors for enhancing catalytic activity, respectively. They collaborate to promote the redistribution of electron density in surface Ni and O, increasing the d/p‐band center difference. This phenomenon results in optimized adsorption/desorption of the key intermediates such as *OOH and improved catalytic performance. Overall, this research highlights the potential of d/p‐band modulation for the rational design of cost‐effective and high‐efficiency electrocatalysts.
A New Ocular Phenotype Combining Juvenile Glaucoma and Doyne Honeycomb Retinal Dystrophy (Malattia Leventinese) due to a Novel EFEMP1 Pathogenic Variant
Authors: Chacon‐Camacho Oscar F. , Ordaz‐Robles Thania , Cid‐García Marion A. , Yepes‐Rodríguez Olivia , Arce‐González Rocio , Martínez‐Aguilar Alan , Zenteno Juan Carlos
Published: September 2024

Doyne honeycomb retinal dystrophy (DHRD), also termed malattia leventinese (MLVT), is a dominantly inherited ocular disease characterized by the progressive accumulation of macular and peripapillary drusenoid material beneath the retinal pigment epithelium in the Bruch membrane. In all affected individuals genetically characterized to date, DHRD/MLVT is caused by a single heterozygous p.Arg345Trp missense variant in the EGF‐containing fibulin‐like extracellular matrix protein 1, EFEMP1. Recently, pathogenic variants in the EFEMP1 gene have also been demonstrated in several families with juvenile or adult‐onset hereditary isolated glaucoma. Here, we describe a family featuring a unique phenotype of juvenile glaucoma and DHRD/MLVT caused by a novel EFEMP1 variant. Our results expand both the ocular phenotype associated with EFEMP1 variants and the molecular spectrum causing DHRD by describing the first non‐p.Arg345Trp EFEMP1 pathogenic allele.
Assessing adequacy of surgical extent in CRSwNP: The Completion of Surgery Index
Authors: Workman Alan D. , Kuppusamy Krithika , Lerner David K. , Bosso John V. , Douglas Jennifer E. , Kohanski Michael A. , Adappa Nithin D. , Palmer James N.
Published: September 2024

Background

Endoscopic sinus surgery (ESS) maximized for topical steroid irrigations is highly effective for polyp disease. As extent and completeness of ESS varies widely by situation and practitioner, it is important to understand when revision surgery is appropriate, particularly in the era of biologic treatments.

Methods

A Completion of Surgery Index (CoSI) was developed to assess operative changes in polyp patients using pre‐ and postoperative computed tomography scans. The CoSI was then applied and tested in a cohort of consecutive chronic rhinosinusitis with nasal polyps (CRSwNP) patients, and examined within the context of quality‐of‐life improvements.

Results

The CoSI assesses surgical extent on a scale of 0–100, with 100 representing the highest possible degree of surgical completeness. Among 100 consecutive CRSwNP patients undergoing ESS in 2021 with postoperative topical steroid irrigations, including 75 revision surgeries, SNOT‐22 scores improved at 6 months postoperatively, with durable and consistent improvement at 24 months (p < 0.001). Preoperative CoSI scores in revision surgery patients were 49.4 ± 26.0, improving to 91.0 ± 8.1 postoperatively. SNOT‐22 scores for primary ESS patients and patients with a preoperative CoSI score of less than 70 improved by 26.4 and 28.1 points, respectively, in contrast to patients with a preoperative CoSI of 70 or greater (14.1 points, p = 0.029).

Conclusions

It is important to define extent of surgery in CRSwNP to stratify postsurgical patients based on likelihood to benefit from revision surgery or alternative medications. The CoSI can be utilized to identify patients who are likely to improve significantly with revision surgical intervention.
Age‐related differences in olfactory training outcomes: A prospective cohort study
Authors: Lawrence Amelia S. , Veach Jodi , Alapati Rahul , Virgen Celina G. , Wright Robert , Materia Frank , Villwock Jennifer A.
Published: September 2024

Introduction

While olfactory function decreases with age, it is unknown how age affects olfactory training (OT) efficacy. This study compared OT in two cohorts of subjects: aged ≤50 (younger cohort) and aged 51+ (older cohort) with olfactory dysfunction (OD) primarily from COVID‐19 infection.

Methods

Subjects with OD primarily secondary to COVID‐19 infection were prospectively recruited and enrolled into an OT registry. Baseline data were collected and they were provided with a training kit and asked to complete OT at home twice daily for 6 months. Participants were asked to follow‐up at 3 and 6 months during training for olfactory testing and quality‐of‐life surveys (Sino‐Nasal Outcomes Test‐22 [SNOT‐22] and Questionnaire of Olfactory Disorders Negative Statements [QoD‐NS]).

Results

Fifty‐six participants completed OT (younger cohort: n = 26, older cohort: n = 30). There were no significant differences between cohorts’ Affordable Rapid Olfactory Measurement Array (AROMA), QoD‐NS, or SNOT‐22 scores at any time point. Both cohorts showed significant AROMA score improvement of more than 16 points from baseline to 3 months (younger cohort: p = 0.001; older cohort: p = 0.008). The younger cohort had significant improvements in QoD‐NS (p = 0.008) and SNOT‐22 (p = 0.042) between baseline and 3 months while the older cohort improved from 3 to 6 months (QoD‐NS: p = 0.027, SNOT‐22: p = 0.049).

Conclusion

Both cohorts demonstrated similar significant improvement in olfactory function after 3 months of OT. The timeline of subjective improvement was different between cohorts, with younger patients experiencing earlier improvement.
Redox Activity and Potentials of Bidentate N‐Ligands Commonly Applied in Nickel‐Catalyzed Cross‐Coupling Reactions
Authors: Dawson Gregory A. , Seith Maria C. , Neary Michelle C. , Diao Tianning
Published: September 2024

Bidentate N‐ligands are paramount to recent advances in nickel‐catalyzed cross‐coupling reactions. Through comprehensive organometallic, spectroscopic, and computational studies on bi‐oxazoline and imidazoline ligands, we reveal that a square planar geometry enables redox activity of these ligands in stabilizing nickel radical species. This finding contrasts with the prior assumption that bi‐oxazoline lacks redox activity due to strong mesomeric donation. Moreover, we conducted systematic cyclic voltammetry (CV) analyses of bidentate pyridyl, oxazoline, and imidazoline nitrogen ligands, along with their corresponding nickel complexes. Complexation with nickel shifts the reduction potentials to a more positive region and narrows the differences in redox potentials among the ligands. Additionally, various ligands led to different degrees of bromide dissociation from singly reduced (L)Ni(Ar)(Br) complexes, reflecting varying reactivity in the subsequent activation of alkyl halides, a crucial step in cross‐electrophile coupling. These insights highlight the significant electronic effects of ligands on the stability of metalloradical species and their redox potentials, which interplay with coordination geometry. Quantifying the electron‐donating, π‐accepting properties of these ligands, as well as their effect on catalyst speciation, provides crucial benchmarks for controlling catalytic activity and enhancing catalyst stability.
α,β‐Dehydrogenation Adjacent to Sulfur‐ and Phosphorus‐ Containing Compounds
Authors: Sun Yang , Newhouse Timothy
Published: September 2024

Here, we report a robust nickel‐catalyzed α,β‐dehydrogenation process designed for substrates that contain electron‐withdrawing sulfur and phosphorus groups. Leveraging the formation of organozinc intermediates and the utilization of a mild oxidant, allyl methyl carbonate, this methodology exhibits remarkable efficiency and outstanding diastereoselectivities across a diverse array of substrates, achieving E : Z ratios exceeding 20 : 1. Investigation through deuterium incorporation studies and an analysis of the reaction sequence leading to the formation of the dehydrogenative allylation side product, provide useful insights into reaction optimization.
Heterogeneous Nucleation Regulation Amends Unfavorable Crystallization Orientation and Defect Features of Antimony Selenosulfide Film for High‐Efficient Planar Solar Cells
Authors: Ren Donglou , Li Chen , Xiong Jun , Liang Weizheng , Cathelinaud Michel , Zhang Xianghua , Chen Shuo , Li Zhiqiang , Pan Daocheng , Liang Guangxing , Zou Bingsuo
Published: September 2024

Antimony selenosulfide (Sb2(S,Se)3) has obtained widespread concern for photovoltaic applications as a light absorber due to superior photoelectric features. Accordingly, various deposition technologies have been developed in recent years, especially hydrothermal deposition method, which has achieved a great success. However, device performances are limited with severe carrier recombination, relating to the quality of absorber and interfaces. Herein, bulk and interface defects are simultaneously suppressed by regulating heterogeneous nucleation kinetics with barium dibromide (BaBr2) introduction. In details, the Br adsorbs and dopes on the polar planes of cadmium sulfide (CdS) buffer layer, promoting the exposure of nonpolar planes of CdS, which facilitates the favorable growth of [hk1]‐Sb2(S,Se)3 films possessing superior crystallinity and small interface defects. Additionally, the Se/S ratio is increased due to the replacement of Se by Br, causing a downshift of the Fermi levels with a benign band alignment and a shallow‐level defect. Moreover, Ba2+ is located at grain boundaries by coordination with S and Se ions, passivating grain boundary defects. Consequently, the efficiency is increased from 7.70 % to 10.12 %. This work opens an avenue towards regulating the heterogeneous nucleation kinetics of Sb2(S,Se)3 film deposited via hydrothermal deposition approach to optimize its crystalline orientation and defect features.
Intrinsic Activity Identification of Noble Metal Single‐Sites for Electrocatalytic Chlorine Evolution
Authors: Quan Li , Zhao Xin , Yang Li‐Ming , You Bo , Xia Bao Yu
Published: September 2024

Single‐atom catalysts with maximal atom‐utilization have emerged as promising alternatives for chlorine evolution reaction (CER) toward valuable Cl2 production. However, understanding their intrinsic CER activity has so far been plagued due to the lack of well‐defined atomic structure controlling. Herein, we prepare and identify a series of atomically dispersed noble metals (e.g., Pt, Ir, Ru) in nitrogen‐doped nanocarbons (M1−N−C) with an identical M−N4 moiety, which allows objective activity evaluation. Electrochemical experiments, operando Raman spectroscopy, and quasi‐in situ electron paramagnetic resonance spectroscopy analyses collectively reveal that all the three M1−N−C proceed the CER via a direct Cl‐mediated Vomer‐Heyrovský mechanism with reactivity following the trend of Pt1−N−C>Ir1−N−C>Ru1−N−C. Density functional theory (DFT) calculations reveal that this activity trend is governed by the binding strength of Cl*−Cl intermediate (ΔGCl*−Cl) on M−N4 sites (Pt<Ir<Ru) featuring distinct d‐band centers, providing a reliable thermodynamic descriptor for rational design of single metal sites toward Cl2 electrosynthesis.
Synthesis of Non‐canonical Tryptophan Variants via Rh‐catalyzed C−H Functionalization of Anilines
Authors: Huang Jonathan Z. , Ying Vanessa Y. , Seyedsayamdost Mohammad R.
Published: September 2024

Tryptophan and its non‐canonical variants play critical roles in pharmaceutical molecules and various enzymes. Facile access to this privileged class of amino acids from readily available building blocks remains a long‐standing challenge. Here, we report a regioselective synthesis of non‐canonical tryptophans bearing C4−C7 substituents via Rh‐catalyzed annulation between structurally diverse tert‐butyloxycarbonyl (Boc)‐protected anilines and alkynyl chlorides readily prepared from amino acid building blocks. This transformation harnesses Boc‐directed C−H metalation and demetalation to afford a wide range of C2‐unsubstituted indole products in a redox‐neutral fashion. This umpolung approach compared to the classic Larock indole synthesis offers a novel mechanism for heteroarene annulation and will be useful for the synthesis of natural products and drug molecules containing non‐canonical tryptophan residues in a highly regioselective manner.
Zincophilic Sites Enriched Hydrogen‐Bonded Organic Framework as Multifunctional Regulating Interfacial Layers for Stable Zinc Metal Batteries
Authors: Ding Jie , He Jiajing , Chen Ling , Sun Yi , Xu Yi , Lv Li‐Ping , Wang Yong
Published: September 2024

To construct an efficient regulating layer for Zn anodes that can simultaneously address the issues of dendritic growth and side reactions is highly demanded for stable zinc metal batteries (ZMBs). Herein, we fabricate a hydrogen‐bonded organic framework (HOF) enriched with zincophilic sites as a multifunctional layer to regulate Zn anodes with controlled spatial ion flux and stable interfacial chemistry (MA‐BTA@Zn). The framework with abundant H‐bonds helps capture H2O and remove the solvated shells on [Zn(H2O)6]2+, leading to suppressed side reactions. The HOF layer also helps form electrolyte‐philic surfaces and expose Zn (002) crystal planes which benefit for rapid conduction and uniform deposition of Zn2+, and weakened sides reactions. Additionally, the electrochemically active zincophilic sites (C=O, −NH2 and triazine groups) favor the targeted guidance and penetration of Zn2+ and provide advantageous sites for uniform Zn deposition. High Young's modulus of the HOF layer further contributes to a high interfacial flexibility and stability against Zn plating‐associated stress. The MA‐BTA@Zn symmetric cells thereby obtain a substantially extended battery life over 1000 h at 4 mA cm−2. The MA‐BTA@Zn||Cu half‐cell demonstrates a highly reversible Zn stripping/plating process over 1500 cycles with impressive average Coulombic efficiency (CE) of 99.5 % at 10 mA cm−2.
A Tandem Catalysis for Isoindolinone Synthesis over Single‐Atom Pd/TiO2 Catalyst
Authors: Xie Jin , Cheng Jianian , Peng Junbao , Zhang Jieyun , Wu Xiaojing , Zhang Ruihui , Li Zelong , Li Can
Published: September 2024

Developing an efficient strategy to replace the conventional synthesis method for producing isoindolinone (IIO) scaffold, a crucial structural motif for constructing pharmaceutical molecules, remains to be a great challenge. Herein, a single‐atom Pd/TiO2 tandem catalysis has been developed for the IIO scaffold synthesis by using readily available phthalic anhydride (PA), ammonia, and H2. The single‐atom Pd/TiO2 catalyst demonstrates superior catalytic performance, achieving a PA conversion of 99 %, an IIO selectivity of 91 %, and a turnover frequency (TOF) up to 4807 h−1. This exceptional performance can be attributed to the tandem catalysis between TiO2 support and single‐atom Pd. The TiO2 efficiently catalyzes the conversion of PA with ammonia to form phthalimide (PAM), subsequently transformed into IIO over TiO2 through the reaction of PAM with NH3 and the spillover hydrogen species derived from single‐atom Pd. Notably, NH3 functions not only as a reactant but also as a promoter to accelerate the reduction of amides combined with the Pd/TiO2 catalyst. This tandem catalysis of a single‐atom Pd/TiO2 catalyst provides a promising strategy for the synthesis of the crucial IIO platform molecules.
A Urease‐Based pH Photoswitch: A General Route to Light‐to‐pH Transduction
Authors: Ivanov Nikita M. , Slivkov Alexandar I. , Huck Wilhelm T. S.
Published: September 2024

New approaches for the integration of chemical and physical stimuli to control the dynamics of artificial enzymatic reaction networks (ERNs) are needed. Here, we present a general approach to convert a light stimulus into a time‐programmed pH response. We developed and characterized a panel of photoswitchable inhibitors of urease. Urease activity, now regulated by light via the photoinhibitors, leads to an increase in pH upon hydrolysis of urea into ammonia. Careful choice of characteristics of light, and concentrations of enzyme, substrate, and photoinhibitor, allowed us to control the timing of the pH transition. Furthermore, as all enzymes have an activity–pH profile, the urease photoinhibitor system can be used to regulate the activities of other enzymes in small reaction networks.
Reduction Polymerization of CO2 with Phenylene Silanes Catalyzed by Single Component B(C6F5)3
Authors: He Wenhao , Li Bingwen , Li Yuxuan , Liu Xinli , Cui Dongmei
Published: September 2024

CO2 is an abundant C1 resource but a green‐house gas and chemically inert. Thus, its utilization has been a promising but challenging project. Herein, we report the unprecedented polymerization of CO2 and C6H4(SiMe2H)2 using B(C6F5)3 alone under mild conditions to give poly(silphenylene siloxane) accompanied by releasing CH4. The copolymerization can be extended to comonomers of phenylene silanes bearing functional groups. Moreover, it combines with Piers‐Rubinsztajn reaction to establish a tandem polymerization system to achieve super thermal resistant poly(siloxane‐co‐silphenylene siloxane)s. Density functional theory reveals that B(C6F5)3 is activated by silanes to form free HB(C6F5)2, which is the true active species for CO2 reducing to borylformate, the rate controlling step of the polymerization procedure. The subsequent multiple reductions of borylformate to CH4 and the step‐growth to poly(silphenylene siloxane)s can be fulfilled by both B(C6F5)3 and HB(C6F5)2, and the former shows a slightly higher activity. This work opens a new avenue of utilizing CO2 to fabricate polysiloxanes that is unable to access using current manners.
Cobalt‐Potassium Synergistic Modification Effects on Fe‐Based Catalysts for CO2 Hydrogenation to Low‐Carbon Olefins
Authors: Jia Yi Jing , Tao Jin Quan , Liu Hao Ran , Huang Wen Bin , Yao Rongpeng , Niu Miaomiao , Li Rongrong , Wei Qiang , Zhou Ya Song
Published: September 2024

To enhance the CO2 hydrogenation activity and low‐carbon olefin selectivity of Fe‐based catalysts, a strategy involving the use of metal promoters to modulate the structure of active metal centers in catalyst preparation was proposed. The incipient wetness impregnation method was used to introduce modifying agents K and/or Co into the Fe/Al2O3 catalyst. Characterization techniques such as XRD, BET, SEM, HRTEM, H2‐TPR, XPS, CO2‐TPD, NH3‐TPD, and TG were employed to investigate the effects of the modifying agents on the dispersion, reducibility, electronic properties, and acid–base properties of active metal species. Furthermore, the influence of K and Co modification on the CO2 hydrogenation activity and low‐carbon olefin selectivity of Fe/Al2O3 catalysts was explored. The results revealed that the introduction of K generated more basic sites and electron‐rich active metal centers in the catalyst, facilitating the adsorption and activation of CO2, while suppressing the hydrogenation of olefins and the formation of methane, thus improving the selectivity towards low‐carbon olefins. Co promoter facilitated the dispersion of Fe species, exposing more active sites and enhancing the FTS reaction activity, leading to more CO being converted into C2+ hydrocarbon products. Under the synergistic effect of K and Co, the CO2 conversion activity of the Fe‐based catalyst significantly increased, achieving a CO2 conversion rate of 37%, while the selectivity towards C2‐C4= increased to 31.9%.
Repurposing antiparasitic N,N′‐aliphatic diamine derivatives as promising antimycobacterial agents
Authors: Recio‐Balsells Alejandro I. , Carlucci Renzo , Giovannuzzi Simone , Carta Fabrizio , Supuran Claudiu T. , Tekwani Babu L. , Morbidoni Héctor R. , Labadie Guillermo R.
Published: September 2024

In previous studies, we demonstrated the potent activity of a library of 25 N,N′‐disubstituted diamines (NNDDA) toward Trypanosomatid and Apicomplexa parasites. Considering the structure similarity between this collection and SQ109, an antituberculosis compound, and its compelling antiparasitic properties, we aimed to repurpose this library for tuberculosis treatment. We assayed this collection against Mycobacterium tuberculosis H37Rv and M. avium, obtaining several compounds with MIC values below 10 µM. The most active analogs were also evaluated against M. smegmatis, a non‐pathogenic species, and the non‐tuberculosis mycobacteria M. abscessus, M. kansasii, and M. fortuitum. 3c stands out as the lead mycobacterial compound of the collection, with potent activity against M. tuberculosis (minimal inhibitory concentration [MIC] = 3.4 µM) and moderate activity against M. smegmatis, M. kansasii, and M. fortuitum (all with MIC values of 26.8 µM). To unravel the mechanism of action, we employed the web‐based platform Polypharmacology Browser 2 (PPB2), obtaining carbonic anhydrases as potential drug targets. Nevertheless, none of the compounds displayed experimental inhibition. In summary, our study confirms the validity of the repurposing approach and underscores the antimycobacterial potential of NNDDA compounds, especially the analog 3c, setting a stepping stone for further studies.
Understanding the Role of Type I Interferons in Cutaneous Lupus and Dermatomyositis: Toward Better Therapeutics
Authors: Hile Grace A. , Werth Victoria P.
Published: September 2024

A 29‐year‐old female presented to a rheumatology‐dermatology clinic with a pruritic rash that began 6 months prior, after a viral illness. She had previously been diagnosed with eczema and treated with antihistamines and topical steroids without improvement. She also noted fatigue, hair loss, and severe scalp pruritus. Physical examination was notable for violaceous periorbital edema, scaly erythematous papules on the metacarpophalangeal joints of bilateral hands, dilated capillaries of the proximal nail folds, scaly plaques on bilateral elbows, and excoriated erythematous plaques on upper chest, back and hips. The patient reported no muscle weakness, and strength testing and creatinine phosphokinase were normal. Magnetic resonance imaging of the thigh showed no evidence of inflammation or edema. Antibody testing was negative. A diagnosis of clinically amyopathic dermatomyositis was made. Computed tomography scans of the chest, abdomen and pelvis, colonoscopy, and mammogram showed no evidence of cancer. The patient was initiated on methotrexate. Her cutaneous manifestations persisted with debilitating intractable pruritus, and thus, she was transitioned to mycophenolate mofetil, again with minimal improvement. Intravenous immunoglobulin was not approved by insurance given the lack of muscle involvement in her disease. This patient's case highlights a common clinical scenario in rheumatology and dermatology and raises several important issues related to the immunologic underpinnings of cutaneous lupus erythematosus (CLE) and dermatomyositis (DM): What is the role of type I interferon (IFN) in triggering skin disease in CLE and DM? What is the role of IFN in the pathogenesis of skin inflammation in CLE and DM? Can we apply what we know about IFN‐targeted therapeutics in CLE and DM to develop better treatments for skin disease?
Metal Halide Perovskites for Photocatalysis: Performance and Mechanistic Studies
Authors: Thanetchaiyakup Adisak , Sadek Mansour , Bati Gabor , Xiao Yonghao , Wang Xingyu , Yang Jingcheng , Liu Zhenpeng , Wang Shun‐Yi , Soo Han Sen
Published: September 2024

Metal halide perovskites, both lead‐based and lead‐free variants, have emerged as highly versatile materials with widespread applications across various fields, including photovoltaics, optoelectronics, and photocatalysis. This review provides a succinct overview of the recent advancements in the utilization of lead and lead‐free halide perovskites specifically in photocatalysis. We explore the diverse range of photocatalytic reactions enabled by metal halide perovskites, including organic transformations, carbon dioxide reduction, pollutant degradation, and hydrogen production. We highlight key developments, mechanistic insights, and challenges in the field, offering our perspectives on the future research directions and potential applications. By summarizing recent findings from the literature, this review aims to provide a timely resource for researchers interested in harnessing the full potential of metal halide perovskites for sustainable and efficient photocatalytic processes.
MnO Modified Porous Carbon with Improved Adsorption Capability and Promoted Redox Kinetics in Lithium‐Sulfur Batteries
Authors: Liang Chen , Xue Jiangyan , Wang Zhongkai , Xu Jingjing , Wu Xiaodong
Published: September 2024

Lithium‐sulfur (Li−S) batteries are recognized as one of the most promising next‐generation battery systems. However, the severe shuttle effect poses a crucial challenge for its large scale application. Herein, through simple freeze‐drying and subsequently annealing, the MnO was utilized to modify porous carbon and thereby form stable bond order toward lithium polysulfides (LiPSs), thus inhibiting the shuttle effect. Besides, the MnO nanoparticles can increase the reaction sites, accelerate the kinetic conversion of LiPSs, facilitate the formation and decomposition of Li2S during discharging and charging. Benefit from the merits of MnO mentioned above together with the physical confinement derived from porous carbon, the Li−S battery assembled with S@MnO−C cathode delivers excellent performance both in rate capacity and long‐cycling, with a high capacity of 555 mAh g−1 after 200 cycles at 0.3 C. This work broadens the potential and enlightens the strategy for designing efficient cathodes toward Li−S sulfur batteries.
Climate transition risk and enterprise default probability
Authors: Sun Haibo , He Shuguang , Cheng Nan , Liu Zhonglu
Published: September 2024

Preventing and controlling the risk of enterprise default is an important way to maintain financial stability. When mitigating and adapting to climate change, it is important to study whether climate transition risk affects the probability of enterprise default. This article systematically analyzes data for Chinese‐listed companies from 2000 to 2019 and finds that climate transition risk significantly increases enterprise default probability (EDF). In addition, pilot carbon emission trading schemes and national carbon emission trading increase this effect. Financing constraints and profitability act as transmission channels; the transmission path, in turn, is influenced by the enterprise environment, social, and governance (ESG) factors and executive compensation. Excellent enterprise ESG performance can lower the positive impact of climate transition risk on EDF. However, higher executive compensation has the opposite effect: high compensation is associated with higher risk. When considering different business types, climate transition risk is more likely to increase the default probability of small assets or non‐state‐owned enterprises. This study helps describe the internal relationship between climate transition risk and EDF, and provides insights to better prevent and address the problem of enterprise debt default caused by climate transition risk.
Synthetic Strategies Towards the Generation of Penicillin‐Containing Hybrids in the Search for Anticancer Activity
Authors: Martiren Nadia L. , Bajicoff Sofia , Bellizzi Yanina , Blank Viviana C. , Roguin Leonor P. , Cornier Patricia G. , Mata Ernesto G. , Delpiccolo Carina M. L.
Published: September 2024

An extended library of hybrids that combined a penicillin derivative with a peptoid moiety was designed and synthetized using either a solid‐phase or a mixed solid‐phase/solution‐phase strategy. The library was further evaluated for antiproliferative activity. While none of the different synthesized compounds showed significant cytotoxicity against a normal cell line, tumor cell results drew several conclusions, when comparing with our reference, the highly active triazolylpeptidyl penicillin derivative, TAF7f. Thus, when the 1,2,3‐triazole group was exchanged by its “retro‐inverse” analogue, no change was noted in the activity of the hybrids; however, better performance was generally obtained if the triazole is replaced by a glycine moiety. Additionally, the absence of hydrogen bond donor groups decreased the compounds activity, which could explain that, in general, this set of derivatives were less active than their peptide‐containing analogues. From this study, is indisputable that, regardless of the type of chain (peptide, peptoid or mixture) attached to penicillin, an isobutyl side chain placed in the position closest to penicillin and a benzyl in the next position are determinant for the activity.
The new rehabilitation definition for research purposes could improve rehabilitation description in Cochrane Systematic Reviews
Authors: Battel Irene , Arienti Chiara , Levack William , Kiekens Carlotte , Negrini Stefano
Published: September 2024

Introduction

In 2022, Cochrane Rehabilitation developed a new definition of rehabilitation for research purposes with 80 global stakeholders, aiming to support and improve the production and reporting of primary and evidence‐synthesis rehabilitation studies.

Objective

To compare how Cochrane Systematic Review (CSR) authors describe rehabilitation interventions against criteria derived from the new rehabilitation definition.

To assess limitations or gaps in the rehabilitation definition.

Methods

We analysed a sample of 124 randomly selected CSRs tagged in the Cochrane Rehabilitation database. We converted the Cochrane Rehabilitation definition for research purposes into a set of 13 criteria grouped according to the four PICO elements and searched for the corresponding key elements in each CSR. We verified if and where in the review these elements were present. Two reviewers rated each CSR, resolving disagreements with a third author when needed. We analysed the findings using descriptive statistics.

Results

Eight (6.5%) of 124 CSRs met all rehabilitation definition criteria. These were CSRs that investigated the effects of complex rehabilitation interventions. Three (2.4%) CSRs did not meet any PICO elements. Overall, the “Intervention‐General” element and disability criterion had the highest prevalence of absent and unclear reporting, while the “Intervention‐Specific” and “Outcome” elements were most frequently reported, albeit not in the “Description of the intervention” section of the review.

Discussion

This study showed that the key elements of the new rehabilitation definition are almost always reported in publications identified as rehabilitation reviews but not always consistently or clearly. The disability criterion was frequently unreported, given that the main aim of rehabilitation is reducing disability. Also, the main elements of rehabilitation were frequently not reported. We did not find important gaps in the new definition. All elements of the new definition should be considered when writing review protocols and designing strategies and tools on rehabilitation topics.
Bridging With Low‐Molecular‐Weight Heparin Versus Antiplatelet Therapy in Patients Undergoing Noncardiac Surgery After Percutaneous Coronary Intervention: A Comprehensive Review
Authors: Iqbal Syed Javaid , Baloch Zulfiqar Qutrio , Malik Jahanzeb , Bhimani Nikeeta , Mehmoodi Amin , Gupta Vishal
Published: September 2024

Background

This review article discussed the use of bridging therapy with low‐molecular‐weight heparin (LMWH) in patients who undergo noncardiac surgery (NCS) after percutaneous coronary intervention (PCI).

Hypotheses

Patients who undergo PCI are at an increased risk of thrombotic events due to their underlying cardiovascular disease. However, many of these patients may require NCS at some point in their lives, which poses a significant challenge for clinicians as they balance the risk of thrombotic events against the risk of bleeding associated with antithrombotic therapy.

Results

This review evaluates the current evidence on the use of bridging therapy with LMWH in patients undergoing NCS after PCI, focusing on outcomes related to the efficacy and safety of antithrombotic therapy. The article also discusses the limitations of the current evidence and highlights areas where further research is needed to optimize the management of antithrombotic therapy in this patient population.

Conclusion

The goal of this review was to provide clinicians with a comprehensive summary of the available evidence to guide clinical decision‐making and improve patient outcomes.
Size and Morphology Dependent Activity of Cu Clusters for CO2 Activation and Reduction: A First Principles Investigation
Authors: Amin Seerat , Krishnamurty Sailaja , Ahmad Dar Manzoor , Joshi Krati
Published: September 2024

Various Cu‐based materials in diverse forms have been investigated as efficient catalysts for electrochemical reduction of CO2; however, they suffer from issues such as higher over potential and poor selectivity. The activity and selectivity of CO2 electro reduction have been shown to change significantly when the surface morphology (steps, kinks, and edges) of these catalysts is altered. In light of this, size and morphology dependent activity of selected copper clusters, Cun (n=2–20) have been evaluated for the activation and reduction of CO2 molecule. The phase‐space of these copper clusters is rich in conformations of distinct morphologies starting from planar, 2D geometries to prolate‐shaped geometries and also high‐symmetry structures. The binding efficiency and the activation of CO2 are highest for medium sized clusters (n=9–17) with prolate‐morphologies as compared to small or larger sized CunCO2 clusters that are existing mainly as planar (triangular, tetragonal etc.) or highly‐symmetric geometries (icosahedron, capped‐icosahedron etc.), respectively. The best performing (prolate‐shaped) CunCO2 conformations are quite fluxional and also they are thermally stable, as demonstrated by the molecular dynamics simulations. Furthermore, on these CunCO2 conformations, the step‐by‐step hydrogenation pathways of CO2 to produce value‐added products like methanol, formic acid, and methane are exceptionally favorable and energy‐efficient.
Life Cycle of LiFePO4 Batteries: Production, Recycling, and Market Trends
Authors: Rostami Hossein , Valio Johanna , Tynjälä Pekka , Lassi Ulla , Suominen Pekka
Published: September 2024

Significant attention has focused on olivine‐structured LiFePO4 (LFP) as a promising cathode active material (CAM) for lithium‐ion batteries. This iron‐based compound offers advantages over commonly used Co and Ni due to its lower toxicity abundance, and cost‐effectiveness. Despite its current commercial use in energy storage technology, there remains a need for cost‐effective production methods to create electrochemically active LiFePO4. Consequently, there is ongoing interest in developing innovative approaches for LiFePO4 production. While LFP batteries exhibit significant thermal stability, cycling performance, and environmental benefits, their growing adoption has increased battery disposal rates. Improper disposal practices for waste LFP batteries result in environmental degradation and the depletion of valuable resources. This review comprehensively examines diverse synthesis approaches for generating LFP powders, encompassing conventional methodologies alongside novel procedures. Furthermore, it conducts an in‐depth assessment of the methodologies employed in recycling waste LFP batteries. Moreover, it emphasizes the importance of LFP cathode recycling and investigates pretreatment techniques to enhance understanding. Additionally, it provides valuable insights into the recycling process of used LFP batteries, aiming to raise awareness regarding the market for retired LFP batteries and advocate for the enduring sustainability of lithium‐ion batteries.
Fluorene vs. Spirobifluorene: Effect of the π‐System on TADF Properties
Authors: Silies Tim , Doltsinis Nikos L. , Daniliuc Constantin G. , Rizzo Fabio
Published: September 2024

There are many options to design a molecular structure that could result in thermally activated delayed fluorescence (TADF). One promising strategy is to use the donor‐π‐acceptor motive where an electron‐donating unit is linked to an electron‐acceptor via an aryl moiety like phenyl. While this approach is widely used and well understood, the performance of the chromophores can be limited by different energy loss pathways, e. g. internal conversion, or by π‐stacking. To circumvent these problems rigid structures with sterically demanding substituents are applied. In this work, we designed two TADF emitters based on phenothiazine and nitrile linked via spiro‐9,9’‐bi[fluorene] or 9,9‐dimethylfluorene and compared the effect of the linker on the physical properties of the dyes. This work emphasizes the importance of careful design of conjugated spacer for efficient TADF emitters.