bluuebunny/crossref_metadata_2025 huggingface dataset:
Infliximab in neurosarcoidosis: a systematic review and meta‐analysis
Authors: Chaiyanarm Siwakorn , Satiraphan Piraya , Apiraksattaykul Natnasak , Jitprapaikulsan Jiraporn , Owattanapanich Weerapat , Rungjirajittranon Tarinee , Nanthasi Witsarut
Published: December 2023

Objectives

To evaluate the clinical outcomes and relapse rates in neurosarcoidosis patients administered infliximab.

Methods

A systematic review was conducted using the MEDLINE, EMBASE, SCOPUS, and Cochrane Library databases. The search included studies from their inception to March 2023. We included case‐series studies with at least 10 neurosarcoidosis patients undergoing any treatment type. Studies were also required to report at least one of the following outcomes: response rate, overall survival rate, or relapse rate. This study adhered to the Preferred Reporting Items for Systematic Reviews and Meta‐Analyses guidelines. A random‐effects model facilitated the analysis of proportional treatment outcomes. Study quality was evaluated using the modified Newcastle–Ottawa quality assessment scale, while a funnel plot helped detect any publication bias.

Results

Seven studies comprising 237 patients with neurosarcoidosis were included in the analysis. Of these patients, 184 (77.6%) received treatment with infliximab. The pooled proportion of patients showing clinical improvement after infliximab treatment was 0.74 (95% CI 0.64–0.84, I2 = 49.73%). Relapse rates, derived from four studies, stood at 0.38 (95% CI 0.22–0.55, I2 = 56.92%). Most studies reported successful tapering or cessation of corticosteroid dosage in patients receiving infliximab. Adverse effects were reported in 52 (29.4%) patients, of which 39 out of 54 events (72.2%) were linked to infections.

Interpretation

Infliximab demonstrated potential improvement in clinical outcomes for patients with refractory neurosarcoidosis and showed potential for reducing the dosage of concurrent corticosteroids. However, a degree of relapse was observed, with infections being the primary concern for adverse events.
A Novel Approach for Rapid Material Library Generation Using Laser‐Remelting
Authors: Gaag Tobias , Heidowitzsch Maximilian , Galgon Florian , Körner Carolin , Zenk Christopher H.
Published: December 2023

Cost‐ and time‐demanding trial‐and‐error methods have been the historical route for alloy development. A combinatorial approach can significantly simplify and accelerate the development process by characterization of composition dependent properties on material libraries, which are specimens or sets of specimens that map out a certain composition space, often employing composition profiles. Herein, a promising production method for such a material library is proposed: laser‐remelting of stacked blocks of different compositions is evaluated for its suitability to produce material libraries, using the ternary CrCoNi system for a proof‐of‐concept. The composition profiles of the successfully created CrCoNi material library were measured by electron probe micro analysis. The intermixing has a length of about 2.5 mm. An analytical model describing the intermixing process is proposed and shows value in the estimation of the intermixing length after the first melting step. The comparison of the experimental microstructure observations from this work and from literature shows mostly good agreement with some deviations related to microsegregation and finite quenching cooling rates, which is supported by thermodynamic calculations regarding phase stability. In the single‐phase region, the mechanical properties as measured via microhardness indentation are discussed as potential candidates for model validation.
Single Metal Atoms Anchored on N‐Doped Holey Graphene as Efficient Dual‐Active‐Component Catalysts for Nitroarene Reduction
Authors: Hu Hanyu , Liu Pei , Cao Sufeng , You Liming , Zhang Ning , Xi Jiangbo , Guo Sheng , Zhou Kun
Published: December 2023

Developing efficient catalysts for facilitating organic synthesis processes is a popular but challenging topic in modern chemical industries. A combination of active metals and an active support structure is, in theory, an effective strategy for boosting catalytic activity but such combinations have been rarely explored. Herein, a strategy for fabricating highly efficient dual‐active‐component catalysts (DACCs) is presented by anchoring single‐atom metals (M1; e.g., Pd1, Ni1, Co1, and Zn1) or double‐atomic metals (e.g., Pd1‐Co1, Pd1‐Ru1, and Pd1‐Ni1) on nitrogen‐doped holey graphene (NHG). Among the resultant DACCs, Pd1/NHG, which combines atomically dispersed metal species and an active NHG carbocatalyst, has been shown to display enhanced catalytic performance toward nitroarene reduction . In particular, its catalytic efficiency in reducing 4‐nitrophenol corresponds to a turnover frequency of 2.0 min−1, which is 97 times higher than the benchmark set by commercial Pd/C catalysts (5.0 wt.%), and vastly superior to those of its counterparts (e.g., NHG carbocatalyst and NHG supported Pd clusters. Notably, four intermediates and two active components (i.e., NHG and single‐atom Pd) in the nitroarene reduction process have been identified. This study presents an effective and versatile synthetic strategy to prepare DACCs through the combination of metallic catalysts and a carbocatalyst substrate.
Printed Electronic Devices and Systems for Interfacing with Single Cells up to Organoids
Authors: Saghafi Mahsa K. , Vasantham Srivatsan K. , Hussain Navid , Mathew George , Colombo Federico , Schamberger Barbara , Pohl Eric , Marques Gabriel Cadilha , Breitung Ben , Tanaka Motomu , Bastmeyer Martin , Selhuber‐Unkel Christine , Schepers Ute , Hirtz Michael , Aghassi‐Hagmann Jasmin
Published: December 2023

The field of bioelectronics with the aim to contact cells, cell clusters, biological tissues and organoids has become a vast enterprise. Currently, it is mainly relying on classical micro‐ and nanofabrication methods to build devices and systems. Very recently the field is highly pushed by the development of novel printable organic, inorganic and biomaterials as well as advanced digital printing technologies such as laser and inkjet printing employed in this endeavor. Recent advantages in alternative additive manufacturing and 3D printing methods enable interesting new routes, in particular for applications requiring the incorporation of delicate biomaterials or creation of 3D scaffold structures that show a high potential for bioelectronics and building of hybrid bio‐/inorganic devices. Here the current state of printed 2D and 3D electronic structures and related lithography techniques for the interfacing of electronic devices with biological systems are reviewed. The focus lies on in vitro applications for interfacing single cell, cell clusters, and organoids. Challenges and future prospects are discussed for all‐printed hybrid bio/electronic systems targeting biomedical research, diagnostics, and health monitoring.
Screening Therapeutic Effects of MSC‐EVs to Acute Lung Injury Model on A Chip
Authors: Chen Weiwei , Zhu Yujuan , Liu Rui , Kong Bin , Xia Nan , Zhao Yuanjin , Sun Lingyun
Published: December 2023

Acute lung injury (ALI) is a lethal disease with high mortality rate, and its physiologically relevant models that could mimic human disease processes are urgently needed to study pathophysiology and predict drug efficacy. Here, this work presents a novel lipopolysaccharide (LPS) based ALI model on a microfluidic chip that reconstitutes an air–liquid interface lined by human alveolar epithelium and microvascular endothelium for screening the therapeutic effects of mesenchymal stem cells (MSC) derived extracellular vesicles (MSC‐EVs) to the biomimetic ALI. The air–liquid interface is established by coculture of alveolar epithelium and microvascular endothelium on the opposite sides of the porous membrane. The functionalized architecture is characterized by integrate cell layers and suitable permeability. Using this biomimetic microsystem, LPS based ALI model is established, which exhibits the disrupted alveolar‐capillary barrier, reduced transepithelial/transendothelial electrical resistance (TEER), and impaired expression of junction proteins. As a reliable disease model, this work examines the effects of MSC‐EVs, and the data indicate the therapeutic potential of EVs for severe ALI. MSC‐EVs can alleviate barrier disruption by restoring both the epithelial and endothelial barrier integrity. They hope this study can become a unique approach to study human pathophysiology of ALI and advance drug development.
Novel Ultra‐Stable 2D SbBi Alloy Structure with Precise Regulation Ratio Enables Long‐Stable Potassium/Lithium‐Ion Storage
Authors: Liu Xi , Wang Xinying , Zhou Yiru , Wang Bingchun , Zhao Ligong , Zheng He , Wang Jianbo , Liu Junhao , Liu Jun , Li Yunyong
Published: December 2023

The inferior cycling stabilities or low capacities of 2D Sb or Bi limit their applications in high‐capacity and long‐stability potassium/lithium‐ion batteries (PIBs/LIBs). Therefore, integrating the synergy of high‐capacity Sb and high‐stability Bi to fabricate 2D binary alloys is an intriguing and challenging endeavor. Herein, a series of novel 2D binary SbBi alloys with different atomic ratios are fabricated using a simple one‐step co‐replacement method. Among these fabricated alloys, the 2D‐Sb0.6Bi0.4 anode exhibits high‐capacity and ultra‐stable potassium and lithium storage performance. Particularly, the 2D‐Sb0.6Bi0.4 anode has a high‐stability capacity of 381.1 mAh g−1 after 500 cycles at 0.2 A g−1 (≈87.8% retention) and an ultra‐long‐cycling stability of 1000 cycles (0.037% decay per cycle) at 1.0 A g−1 in PIBs. Besides, the superior lithium and potassium storage mechanism is revealed by kinetic analysis, in‐situ/ex‐situ characterization techniques, and theoretical calculations. This mainly originates from the ultra‐stable structure and synergistic interaction within the 2D‐binary alloy, which significantly alleviates the volume expansion, enhances K+ adsorption energy, and decreases the K+ diffusion energy barrier compared to individual 2D‐Bi or 2D‐Sb. This study verifies a new scalable design strategy for creating 2D binary (even ternary) alloys, offering valuable insights into their fundamental mechanisms in rechargeable batteries.
Progress in Research and Application of Modified Silk Fibroin Fibers
Authors: Chai Shanshan , Wu Hong , Peng Xingjian , Tan Zifang , Cao Hanlin , Wei Liang , Mao Xue , Zhang Zhenfang , Zhou Fenglei , Zhang Qingling , Sun Runjun , Liu Chengkun
Published: December 2023

Silk fibroin (SF) is a biodegradable protein and possesses superior skin‐friendliness, biocompatibility, low immunogenicity, and non‐toxicity. However, SF has a series of drawbacks. For example, the application of SF in water filtration is limited by its inadequate ability to adsorb heavy metal ions. It is not inherently antibacterial, making SF ineffective as a filter to eliminate airborne bacteria. SF without conductivity is not suitable for use in sensors and triboelectric nanogenerators. In tissue engineering, deficient mechanical and anti‐inflammatory properties also have an influence on the rate of wound recovery. While physical and chemical modifications will improve its application properties as well as broaden its application areas. This review describes the modification of SF by filling, blending, structural adjustment, post treatment, crosslinking, grafting, and in situ polymerization to provide it with other functional properties. Modified SF fibers prepared by various methods (e.g., wet/dry/microfluidic spinning, electrospinning) are discussed, and they can be used in water/air filtration, chemical/pressure/strain sensors, triboelectric nanogenerators, artificial skin, wound dressings, and tissue scaffolds. Finally, the development trend of the modified SF fibers is prospected. This review has a reference significance on how to use modified SF fibers to improve filtration efficiency, sensor performance, and wound recovery.
Strongly Luminescent Tetradentate Palladium(II)‐TADF Emitters. Blue TADF And TADF‐Sensitized OLEDs with External Quantum Efficiencies Over 23%
Authors: Sit Man‐Ki , Tong Glenna So Ming , Lam Tsz‐Lung , Cheng Gang , Hung Faan‐Fung , So Kwok‐Ming , Du Lili , Choy Kin‐On , Low Kam‐Hung , Che Chi‐Ming
Published: December 2023

Due to the low‐lying Pd(4d)‐orbitals, luminescent palladium(II) complexes usually show 3IL phosphorescence (IL = intraligand) with excited state lifetimes in the range of hundreds of microseconds, which limits their application in blue organic light‐emitting diodes (OLEDs). Here, a molecular design strategy for the development of strongly luminescent Pd(II)‐based thermally activated delayed fluorescence (TADF) emitters with fast radiative decay rate constants and reverse intersystem crossing rate (kRISC) constants is presented. The synthesized tetradentate [Pd(N*C*C^N)] TADF emitters show sky‐blue to yellow (λmax = 484–565 nm) emission with excited state lifetimes in the range of 0.9−8.7 µs and high photoluminescence quantum yield of up to 77% in CH2Cl2 solution. In 5 wt.% 2,8‐bis(diphenylphosphoryl)dibenzo[b,d]furan (PPF) thin films, these [Pd(N*C*C^N)] TADF complexes display blue to sky‐blue (476−496 nm) emission with quantum yields close to unity. Variable‐temperature emission lifetime measurements, femtosecond time‐resolved spectroscopy, and density functional theory (DFT) and time‐dependent DFT (TDDFT) calculations together reveal ultrafast kRISC rate constants of these [Pd(N*C*C^N)] TADF emitters. Using these Pd(II)‐TADF emitters as dopants, sky‐blue TADF and blue TADF‐sensitized OLEDs with small efficiency roll‐offs achieved high maximum external quantum efficiencies (EQEs) of 24.8% and 23.1%, respectively.
Quantum Sensing and Light Guiding with Fluorescent Nanodiamond‐Doped PVA Fibers
Authors: Styles Roy , Candini Andrea , Guarino Vincenzo , Robertson Islay , Singh Priya , Cruz‐Maya Iriczalli , Benfenati Valentina , Abraham Amanda N. , Abe Hiroshi , Ohshima Takeshi , Broadway David A. , Greentree Andrew D. , Gibson Brant C. , Ambrosio Luigi , Tetienne Jean‐Philippe , Reineck Philipp
Published: December 2023

Fluorescent nanodiamonds (FNDs) containing quantum defects enable the optical measurement of electromagnetic fields and temperature and are among the most developed nanoscale quantum sensors today. Yet, for many applications in biomedicine and beyond, FNDs must be integrated into biocompatible substrates that preserve FND sensitivity and bring FNDs within nanoscale distance of their sensing target. At the same time, the high excitation light intensity required for most quantum sensing protocols remains a major challenge for applications in biomedicine. Here, it is shown that FNDs embedded in polyvinyl‐alcohol (PVA) fibers are a powerful 3D platform for nanoscale quantum sensing via light guiding. First, it is demonstrated that biocompatible PVA fibers can guide light to excite FNDs >10 µm from the excitation beam. Using this light‐guiding‐enabled excitation, optically detected magnetic resonance (ODMR) and T1 spin relaxometry measurements are performed using the nitrogen‐vacancy (NV) center in FNDs. Through ODMR thermometry, it is shown that light‐guiding‐enabled excitation mitigates light‐induced heating. Finally, the quantum sensing capability of the platform is established by detecting paramagnetic gadolinium in a dry and aqueous environment using T1 relaxometry of the NV center in FNDs. These results pave the way for light‐guiding‐enabled optical quantum sensing in biomedicine using nanodiamond‐doped biosubstrates.
Hybrid Active–Passive Control of an Unconventional Smart Window Based on Dye‐Doped Dual‐Frequency Liquid Crystal
Authors: Sung Guan-Fu , Lee Wei
Published: December 2023

The allure of dual‐frequency liquid crystal (DFLC) stems from its unique feature of the switchable and revertible sign of dielectric anisotropy. In addition to the common frequency‐modulation method, this study focuses on manipulating the dielectric anisotropy in DFLC through change in temperature. Herein, the hybrid control of a dichroic‐dye‐doped DFLC smart window is proposed, which offers a passive‐control function by reacting to the temperature and automatically switching to one of the three distinct transmission levels: the transparent, variably gray (tinted or translucent), and opaque states. In contrast to conventional, passively controlled smart windows that typically exhibit a gray or opaque state at high temperatures and become transparent at low temperatures, the suggested smart window thermally operates in the opposite manner, presenting a unique characteristic that holds significant potential for a wide range of applications. This thermally reverse‐mode smart window allows one to actively control the degree of transparency by applied voltage at various frequencies as well. A parameter termed the “crossover temperature” is introduced as an indicator of the potency for the change in dielectric anisotropy of the DFLC by temperature. The operation scheme of the hybrid electrical‐and‐thermal control for the proposed vertically aligned dye‐doped DFLC smart window is summarized.
High‐Efficiency Pancharatnam–Berry Metasurface‐Based Surface Plasma Coupler
Authors: Zhu Rongrong , Liu Dan , Lu Huan , Peng Liang , Cai Tong , Zheng Bin
Published: December 2023

To excite surface plasmon polaritons (SPPs) in an ultrathin way, metasurface‐based SPP couplers are widely used for converting propagating waves into driven waves bounded on their surfaces. Among them, the Pancharatnam–Berry (PB) metasurface coupler has a strong ability to control spin‐polarized waves, but is still limited by its coupling efficiency. Herein, a PB metasurface‐based SPP coupler that can support efficient circular‐polarization conversion with both the transverse magnetic and transverse electric modes of the SPP is proposed. The coupler is composed of an upper transmissive PB gradient metasurface and a lower eigenmode board to transform a circularly polarized plane wave into left‐handed circularly polarized and right‐handed circularly polarized surface waves that propagate in opposite directions. In the experimental results, it is indicated that the directionality factor of the tested SPP coupler is 28.6. The proposed PB metasurface coupler may pave the way for future integrated optical devices with high efficiency and excellent polarization‐split properties.
AR‐Enabled Persistent Human–Machine Interfaces via a Scalable Soft Electrode Array
Authors: Kim Hodam , Cha Ho‐Seung , Kim Minseon , Lee Yoon Jae , Yi Hoon , Lee Sung Hoon , Ira Soltis , Kim Hojoong , Im Chang‐Hwan , Yeo Woon‐Hong
Published: December 2023

Augmented reality (AR) is a computer graphics technique that creates a seamless interface between the real and virtual worlds. AR usage rapidly spreads across diverse areas, such as healthcare, education, and entertainment. Despite its immense potential, AR interface controls rely on an external joystick, a smartphone, or a fixed camera system susceptible to lighting. Here, an AR‐integrated soft wearable electronic system that detects the gestures of a subject for more intuitive, accurate, and direct control of external systems is introduced. Specifically, a soft, all‐in‐one wearable device includes a scalable electrode array and integrated wireless system to measure electromyograms for real‐time continuous recognition of hand gestures. An advanced machine learning algorithm embedded in the system enables the classification of ten different classes with an accuracy of 96.08%. Compared to the conventional rigid wearables, the multi‐channel soft wearable system offers an enhanced signal‐to‐noise ratio and consistency over multiple uses due to skin conformality. The demonstration of the AR‐integrated soft wearable system for drone control captures the potential of the platform technology to offer numerous human–machine interface opportunities for users to interact remotely with external hardware and software.
Low Onset‐Potential Z‐Scheme Ta3N5‐based Photoanode with Enhanced Light Harvesting and Charge Transport
Authors: Kwon Hee Ryeong , Yang Jin Wook , Choi Sungkyun , Cheon Woo Seok , Im In Hyuk , Kim Younhwa , Park Jungwon , Lee Gwan‐Hyoung , Jang Ho Won
Published: December 2023

Simultaneous enhancement of light harvesting and charge transport in photoelectrochemical (PEC) systems is a major challenge to achieving high solar‐to‐hydrogen efficiency. Here, a Ta3N5‐Si Z‐scheme system is constructed to facilitate charge transport pathways from generation to catalysis, taking advantage of the exquisite bandgap and band position of Ta3N5. The tailored Ta3N5‐Si junction with an NbNx electron mediator effectively establishes a Z‐scheme charge transport and enhances the driving force for water oxidation, reducing the onset potential by an increment in photovoltage. Moreover, the nitrogen‐doped CoFeOx co‐catalyst boosts hole dynamics and kinetics at the surface level, resulting in improved hole extraction for water oxidation catalysis. The synergy between the above strategies cooperatively expedites the charge separation and transport in a Ta3N5 photoanode, which decreases the photocurrent onset potential from 0.69 to 0.27 V versus the reversible hydrogen electrode, a reduction of 420 mV. This result represents one of the lowest onset potentials observed for Ta3N5‐based photoanodes. A systematic approach to enhancing photovoltage and photocurrent expands the design concept of metal nitride‐based PEC devices.
Towards bespoke optimizations of energy efficiency in HPC environments
Authors: Tracey Robert , Elisseev Vadim , Smyrnakis Michalis , Hoang Lan , Fellows Mark , Ackers Michael , Laughton Andrew , Hill Stephen , Folkes Phillip , Whittle John
Published: December 2023

We present bespoke energy efficiency optimizations in high performance computing (HPC) environments using holistic approach to data collection, analysis and proactive management of resources and workloads. Our solution has three major components: (i) platform for collecting, storing and processing data from multiple sources across hardware and software stacks, (ii) collections of regression machine learning (ML) algorithms for making workloads classifications and energy usage predictions, (iii) agent‐based decision‐making framework for delivering control decisions to middle‐ware and infrastructure thus supporting real time or near real energy efficiency optimizations. We will provide some concrete examples of using our proposed approach in HPC environment.
Age at cardiovascular disease onset, dementia risk, and the role of lifestyle factors
Authors: van Gennip April C. E. , van Sloten Thomas T. , Fayosse Aurore , Sabia Séverine , Singh‐Manoux Archana
Published: December 2023

INTRODUCTION

We first examined the role of age at cardiovascular disease (CVD) onset for incident dementia, and then examined whether lifestyle factors at guideline‐recommended levels in individuals with CVD mitigates dementia risk.

METHODS

We used population‐based data (Whitehall II: n = 10,308/baseline 1985–1988/examinations every 4–5 years). Lifestyle factors (non‐smoking, body mass index [BMI], physical activity, diet) were extracted post‐CVD.

RESULTS

Over a median of 31.6 years, 3275 (32.1%) developed CVD. At age 70, risk of dementia was higher in individuals with CVD onset before (hazard ratio [HR] of incident dementia for participants with CVD before age 60, using participants without CVD at age 70 as the reference: 1.56, 95% confidence interal [CI] 1.18–2.08) but not after 60 years. In participants with CVD, a greater number of lifestyle factors at recommended levels post‐CVD was associated with a lower dementia risk (per lifestyle factor at recommended level HR: 0.73, 95% CI 0.59–0.92).

DISCUSSION

Our results suggest that early onset CVD is associated with a higher dementia risk at older ages. In those with CVD, the dementia risk was lower if lifestyle factors are at recommended levels following CVD diagnosis.

Highlights

CVD in midlife but not in late life is associated with a higher risk of dementia.

Dementia risk in CVD patients is lower if their lifestyle factors are at recommended levels.

These findings provide evidence to promote CVD prevention in midlife or earlier.

Study findings also show the importance of a healthy lifestyle in those with CVD.
Predicting clinical progression trajectories of early Alzheimer's disease patients
Authors: Devanarayan Viswanath , Ye Yuanqing , Charil Arnaud , Andreozzi Erica , Sachdev Pallavi , Llano Daniel A. , Tian Lu , Zhu Liang , Hampel Harald , Kramer Lynn , Dhadda Shobha , Irizarry Michael ,   for the Alzheimer's Disease Neuroimaging Initiative (ADNI)
Published: December 2023

BACKGROUND

Models for forecasting individual clinical progression trajectories in early Alzheimer's disease (AD) are needed for optimizing clinical studies and patient monitoring.

METHODS

Prediction models were constructed using a clinical trial training cohort (TC; n = 934) via a gradient boosting algorithm and then evaluated in two validation cohorts (VC 1, n = 235; VC 2, n = 421). Model inputs included baseline clinical features (cognitive function assessments, APOE ε4 status, and demographics) and brain magnetic resonance imaging (MRI) measures.

RESULTS

The model using clinical features achieved R2 of 0.21 and 0.31 for predicting 2‐year cognitive decline in VC 1 and VC 2, respectively. Adding MRI features improved the R2 to 0.29 in VC 1, which employed the same preprocessing pipeline as the TC. Utilizing these model‐based predictions for clinical trial enrichment reduced the required sample size by 20% to 49%.

DISCUSSION

Our validated prediction models enable baseline prediction of clinical progression trajectories in early AD, benefiting clinical trial enrichment and various applications.
Direct Decarboxylation of Trifluoroacetates Enabled by Iron Photocatalysis**
Authors: Fernández‐García Sara , Chantzakou Veronika O. , Juliá‐Hernández Francisco
Published: December 2023

Trifluoroacetates are the most abundant and accessible sources of trifluoromethyl groups, which are key components in pharmaceuticals and agrochemicals. The generation of trifluoromethyl reactive radicals from trifluoroacetates requires their decarboxylation, which is hampered by their high oxidation potential. This constitutes a major challenge for redox‐based methods, because of the need to pair the redox potentials with trifluoroacetate. Here we report a strategy based on iron photocatalysis to promote the direct photodecarboxylation of trifluoroacetates that displays reactivity features that escape from redox limitations. Our synthetic design has enabled the use of trifluoroacetates for the trifluoromethylation of more easily oxidizable organic substrates, offering new opportunities for late‐stage derivatization campaigns using chemical feedstocks, Earth‐abundant catalysts, and visible‐light.
Chemical Engineering of Artificial Transcription Factors by Orthogonal Palladium(II)‐Mediated S‐Arylation Reactions
Authors: Lin Xiaoxi , Harel Omer , Jbara Muhammad
Published: December 2023

Site‐selective functionalization strategies are in high demand to prepare well‐defined homogeneous proteins for basic research and biomedical applications. In this regard, cysteine‐based reactions have enabled a broad set of transformations to produce modified proteins for various applications. However, these approaches were mainly employed to modify a single reactive site with a specific transformation. Achieving site selectivity or multiple transformations, essential for preparing complex biomolecules, remains challenging. Herein we demonstrate the power of combining palladium(II)‐mediated C−S bond formation and C−S bond cleavage reactions to selectively edit desired cysteine sites in complex and uniquely modified proteins. We developed an orthogonal palladium(II) strategy for rapid and effective diversification of multiple cysteine sites (3–6 residues) with various transformations. Importantly, we employed our approach to prepare 10 complex analogues, including modified, stapled, and multimeric proteins on a milligram scale. Furthermore, we also synthesized a focused library of stabilized artificial transcription factors that displayed enhanced stability and potent DNA binding activity. Our approach enables rapid and effective protein editing and opens new avenues to engineer new biomolecules for fundamental research and therapeutic applications.
Quantitative Construction of Boronic‐Ester Linkages in Covalent Organic Frameworks for the Carbon Dioxide Reduction
Authors: Yang Xiubei , Li Xuewen , Liu Minghao , Yang Shuai , Xu Qing , Zeng Gaofeng
Published: December 2023

Covalent organic frameworks (COFs) have been utilized for catalyzing the reduction of carbon dioxide (CO2RR) due to their atomic metal centers and controllable pore channels, which are facilitated by different covalent bonds. However, the exploration of boron‐based linkages in these catalytic COFs has been limited owing to potential instability. Herein, we present the construction of boronic ester‐linked COFs through nucleophilic substitution reactions in order to catalyze the CO2RR. The inclusion of abundant fluorine atoms within the frameworks enhances their hydrophobicity and subsequently improves water tolerance and chemical stability of COFs. The content of boron atoms in the COF linkages was carefully controlled, with COFs featuring a higher density of boron atoms exhibiting increased electronic conductivity, enhanced reductive ability, and stronger binding affinity towards CO2. Consequently, these COFs demonstrate improved activity and selectivity. The optimized COFs achieve the highest activity, achieving a turnover frequency of 1695.3 h−1 and a CO selectivity of 95.0 % at −0.9 V. Operando synchrotron radiation measurements confirm the stability of Co (II) atoms as catalytically active sites. By successfully constructing boronic ester‐linked COFs, we not only address potential instability concerns but also achieve exceptional catalytic performance for CO2RR.
Li6E5Li6: Tetrel Sandwich Complexes with 10‐π‐Electrons
Authors: Inostroza Diego , Leyva‐Parra Luis , Pino‐Rios Ricardo , Solar‐Encinas José , Vásquez‐Espinal Alejandro , Pan Sudip , Merino Gabriel , Yañez Osvaldo , Tiznado William
Published: December 2023

When (4n +2) π‐electrons are located in single planar ring, it conventionally qualifies as aromatic. According Hückel's rule, systems possessing ten π‐electrons should be aromatic. Herein we report a series of D5h Li6E5Li6 sandwich structures, representing the first global minima featuring ten π‐electrons E510− ring (E=Si−Pb). However, these π‐electrons localize as five π‐lone‐pairs rather than delocalized orbitals. The high symmetry structure achieved is a direct consequence of σ‐aromaticity, particularly favored in elements from Si to Pb, resulting in a pronounced diatropic ring current flow that contributes to the enhanced stability of these systems.
Using Machine Learning to Predict the Antibacterial Activity of Ruthenium Complexes**
Authors: Orsi Markus , Shing Loh Boon , Weng Cheng , Ang Wee Han , Frei Angelo
Published: December 2023

Rising antimicrobial resistance (AMR) and lack of innovation in the antibiotic pipeline necessitate novel approaches to discovering new drugs. Metal complexes have proven to be promising antimicrobial compounds, but the number of studied compounds is still low compared to the millions of organic molecules investigated so far. Lately, machine learning (ML) has emerged as a valuable tool for guiding the design of small organic molecules, potentially even in low‐data scenarios. For the first time, we extend the application of ML to the discovery of metal‐based medicines. Utilising 288 modularly synthesized ruthenium arene Schiff‐base complexes and their antibacterial properties, a series of ML models were trained. The models perform well and are used to predict the activity of 54 new compounds. These displayed a 5.7x higher hit‐rate (53.7 %) against methicillin‐resistant Staphylococcus aureus (MRSA) compared to the original library (9.4 %), demonstrating that ML can be applied to improve the success‐rates in the search of new metalloantibiotics. This work paves the way for more ambitious applications of ML in the field of metal‐based drug discovery.
Confinement of p‐Xylene in the Pores of a Bilanthanide Metal–Organic Framework for Highly Selective Recognition
Authors: Wang Mengmeng , Han Zongsu , Wang Kunyu , Zhao Bin , Sun Tiankai , Wu Yuewei , Cheng Peng , Shi Wei
Published: December 2023

The rapid and accurate sensing of p‐xylene, an essential raw material with a multi‐billion‐dollar market, in xylene mixture is of great significance in industry; however, the highly similar molecular structures, energy levels, and spectral characteristics of xylene isomers make the selective recognition extremely challenging. Metal–organic frameworks (MOFs) exhibiting tailorable pores and potential binding sites provide prospects for xylene sensing but a comprehensive understanding of the pore effect is still elusive, primarily due to the intricacies involved in the sensing process. Herein, we reported a robust bilanthanide MOF NKU‐999‐EuTb with precisely engineered pores to accommodate p‐xylene, of which the binding sites were confirmed by single crystal X‐ray diffraction and dynamic magnetic susceptibilities. NKU‐999‐EuTb exhibits high‐performance in selective recognition for p‐xylene towards its isomers. Through a systematical study, it was revealed that absorbing p‐xylene into the pores governs the sensing performance. This work provides insights for developing advanced sensing materials for complex isomers.
Prospects in the application of a frontally curable epoxy resin for cured‐in‐place‐pipe rehabilitation
Authors: Malik Muhammad Salman , Wolfahrt Markus , Domínguez Pardo Juan J. , Bublitz Dirk , Schlögl Sandra
Published: December 2023

Photocurable acrylates and vinyl esters are among the most commonly used resins in cured‐in‐place‐pipe (CIPP) rehabilitation technology, as they impart excellent thermomechanical properties in composite pipes. In the quest for achieving a higher energy efficiency of the photo‐curing process in CIPP, the frontal polymerization technique is a viable alternative that requires a lower irradiation dosage coupled with exceptionally high curing speeds and depths. Herein, for the first time, we report the application of frontal polymerization in the rehabilitation of underground pipes using a newly developed frontally curable epoxy‐based resin (Trelleborg Self‐Curing*). The neat resin is characterized for degree of cure, glass transition temperature, and mechanical properties via FTIR, DMA, and tensile tests, respectively. In a comprehensive way, the properties are benchmarked against commercially available acrylate (Trelleborg Light Cure*) and vinyl ester (Trelleborg Rapid Cure*) resins to evaluate their applicability for CIPP. The results show a higher glass transition temperature and final monomer conversion for the frontally cured resin, which cures significantly faster than the reference resins under the same irradiation conditions. In proof‐of‐concept trials, the newly developed resin successfully cures polymeric liners in a PVC host pipe with 100% water tightness and without losing its structural integrity. Results from ring stiffness tests for cured composite pipes additionally show that liners cured with Trelleborg Self‐Curing* resin pass the minimum required Young's modulus for non‐pressure drainage pipes as per ASTM F1216. Thus, frontally curable epoxy‐based resins are a promising and competitive alternative to acrylates and vinyl esters in CIPP.
Comb‐shaped block poly(arylene ether sulfone ketone)s for anion exchange membranes
Authors: Lai Ao Nan , Li Shu Chun , Zheng Pei Zhi , Zhou Shu Feng , Wu Shi Jie
Published: December 2023

A well‐designed architecture is presented here to construct high‐performance anion exchange membranes (AEMs). A series of quaternized fluorene‐containing block poly(arylene ether sulfone ketone)s (QFPESK‐m‐n) is synthesized as the main chains, and grafted with comb‐shaped C8 long alkyl chains for the AEMs. By varying the hydrophilic segment’ length, there has been a significant change in the microstructure as well as phase separation morphology of the membranes, as confirmed by atomic force microscopy. Hence the as‐prepared AEMs with moderate ion exchange capacities (IECs) show enhanced hydroxide conductivities in the range of 28.8―94.7 mS⋅cm−1 from 30 to 80°C. Furthermore, based on the block backbones and hydrophobic comb‐shaped alkyl chains, the AEMs show low‐level swelling ratios of 4.3% to 9.2% at 30°C and from 6.2% to 13.2% at 80°C, and superior ratios of conductivity to swelling. In addition, the QFPESK‐m‐n AEMs also depict acceptable mechanical properties, good thermal stability and an optimizable alkaline stability.
Tropical Atlantic rainfall drives bias in extratropical seasonal forecasts
Authors: Collier T. , Kettleborough J. , Scaife A. A. , Hermanson L. , Davis P.
Published: December 2023

We investigate the impact of seasonal forecast biases in the Tropical Atlantic on the North Atlantic. The analysis uses a novel ensemble‐based method to estimate the impact of tropical rainfall bias on forecasts of the Extratropical North Atlantic. The inter‐ensemble spread of the forecast model is used to estimate the impact of the bias in Tropical Atlantic rainfall on the North Atlantic by selecting model members that happen to produce forecast anomalies that most closely resemble the tropical rainfall bias and using these as a proxy for the model error. The Tropical Atlantic rainfall bias impacts Rossby wave sources over the Subtropical Atlantic and there is a clear Rossby wave pattern originating from this area which is comparable to the mean bias in hindcasts. We argue that Tropical Atlantic rainfall errors explain a significant amount of the bias in seasonal forecasts over the Extratropical North Atlantic.
Lithium Fluoride Embedded Prelithiated Graphite Interface Layer Enables Stable All‐solid‐state Lithium Ion Batteries
Authors: Zhang Nini , Guo Dingcheng , Su Qili , Deng Shungui , Lu Yong , Li Zhe , Liu Haijing , Yao Xiayin
Published: December 2023

All‐solid‐state rechargeable batteries are regarded as one of the most promising next‐generation energy storage devices, while their cycling stability is still a great challenge due to the nonuniform lithium ion transportation and the loss of active lithium during cycling. Herein, a LiF embedded prelithiated graphite interface layer is designed and inserted between Li6PS5Cl solid electrolyte layer and graphite anode layer. The presence of LiF, C−F bonds and prelithiated graphite in this unique interface layer can facilitate uniform lithium ion migration and compensate the loss of active lithium, thus significantly improving the cyclic performances of both monopolar and bipolar all‐solid‐state lithium ion batteries. After 100 cycles at 0.1 C, the capacity retention increases from 58 % to 78.5 % for the monopolar LiNi0.5Co0.2Mn0.3O2|Li6PS5Cl|LiF@2.5 %Li@G|graphite all‐solid‐state lithium ion battery. Besides, the bipolar all‐solid‐state lithium ion batteries show a high discharge plateau of ~7.6 V with a capacity retention of 60.2 % after 190 cycles at 0.1 C. This work demonstrates the effectiveness of LiF embedded prelithiated graphite interface layer for improving the electrochemical performances of all‐solid‐state lithium ion batteries.
Hierarchical Representation of Measurement Data, Metrological Uncertainty and Metadata for Calibrated Battery Tests
Authors: Moradpour Amin , Kasper Manuel , Moertelmaier Manuel , R‐Smith Nawfal Al‐Zubaidi , Kienberger Ferry
Published: December 2023

We present an interoperable hierarchical data representation for battery tests, leading to improved scalability of data transmission and enhanced data accessibility and comprehensibility for both human interpretation and machine processing. The hierarchical data format includes the raw trace electrical measurement data, the metrological calibration and uncertainty data, the metadata such as experimental settings, instruments and software versions, as well as post‐processed data such as electrochemical model fit parameters. This data representation allows repetition of the battery test under the exact same conditions such that identical results are achieved within defined error bounds. This is in line with the general F. A. I. R. data approach and provides repeatability and traceability in the battery value chain. As an application of the hierarchical data representation, we show the classification of cells as pass/fail being performed with quantitative confidence levels. We demonstrate the complete workflow of establishing the hierarchical data structure for electrochemical impedance spectroscopy (EIS), starting from metrological traceability of the calibration and uncertainty analysis towards the storage of the structured data as a single integrated file that preserves the hierarchical data format. The structured data file is provided in JSON format in the Zenodo repository, as well as the program scripts to generate and read the JSON EIS files.
Direct ammonia oxidation (Dirammox) is favored over cell growth in Alcaligenes ammonioxydans HO‐1 to deal with the toxicity of ammonium
Authors: Lv Jun‐Lu , Min Di , Cheng Zhou‐Hua , Zhang Jia‐Xin , Li Wen‐Wei , Mu Yang , Liu Shuang‐Jiang , Liu Dong‐Feng
Published: December 2023

Bacteria capable of direct ammonia oxidation (Dirammox) play important roles in global nitrogen cycling and nutrient removal from wastewater. Dirammox process, NH3 → NH2OH → N2, first defined in Alcaligenes ammonioxydans HO‐1 and encoded by dnf gene cluster, has been found to widely exist in aquatic environments. However, because of multidrug resistance in Alcaligenes species, the key genes involved in the Dirammox pathway and the interaction between Dirammox process and the physiological state of Alcaligenes species remain unclear. In this work, ammonia removal via the redistribution of nitrogen between Dirammox and microbial growth in A. ammonioxydans HO‐1, a model organism of Alcaligenes species, was investigated. The dnfA, dnfB, dnfC, and dnfR genes were found to play important roles in the Dirammox process in A. ammonioxydans HO‐1, while dnfH, dnfG, and dnfD were not essential genes. Furthermore, an unexpected redistribution phenomenon for nitrogen between Dirammox and cell growth for ammonia removal in HO‐1 was revealed. After the disruption of the Dirammox in HO‐1, more consumed NH4+ was recovered as biomass‐N via rapid metabolic response and upregulated expression of genes associated with ammonia transport and assimilation, tricarboxylic acid cycle, sulfur metabolism, ribosome synthesis, and other molecular functions. These findings deepen our understanding of the molecular mechanisms for Dirammox process in the genus Alcaligenes and provide useful information about the application of Alcaligenes species for ammonia‐rich wastewater treatment.
Chemical Profile and Biological Activities Of Piper mikanianum (Kunth) Steud Essential Oil for Development and Improvement of Oral Rinse
Authors: Alencar Araujo Maia Philippe , Dantas Pereira Ana Paula , de Oliveira Braz Ana Valéria , Carvalho Rodrigues Mariana , de Lima Silva Jussara , Pereira Lucetti Elaine Cristina , Martins de Lima João Paulo , da Silva Luiz Everson , do Amaral Wanderlei , Quefi Blasco , Andrade Rebelo Ricardo , Melo Coutinho Henrique Douglas , Ferreira Matias Edinardo Fagner
Published: December 2023

Introduction: Studies prove that the use of medicinal plants is a custom carried out by man since ancient times, the evolution of the pharmaceutical industry makes more people consume more natural products. Currently, we can observe that mouthwashes containing natural compounds have shown a growth in demand in the markets and in the professional community. Objective: The present study aims to carry out the chemical characterization and microbiological potential of Piper mikanianum (Kunth) Steud essential oil (EOPm), providing data that allows the development of a low‐cost mouthwash formulation aimed at vulnerable communities. Methods: The evaluation of the antibacterial activity and modulator of bacterial resistance was performed by the microdilution method to determine the minimum inhibitory concentration (MIC). The chemical components were characterized by gas chromatography coupled to mass spectrometry, identified 28 constituents, in which Safrole Phenylpropanoid is the major compound, representing 72.6 % of the total composition, followed by α‐pinene (10.7 %), Limonene (2 %), β‐caryophyllene (2 %), E‐nerolidol (1.9 %), spathulenol (1.3 %) and camphene (1.1 %). Results: The EOPm showed a MIC minimum inhibitory concentration≥1024 μg/mL for all bacterial strains used in the tests. When the EOPm modulating activity combined with chlorhexidine, mouthwash, ampicillin, gentamicin and penicillin G was evaluated against bacterial resistance, the oil showed significant synergistic activity, reducing the MIC of the products tested in combination, in percentage between 20.6 % to 98 .4 %. Conclusions: We recommend the expansion of tests with greater variation of EOPm concentration combinations and the products used in this study, as well as toxicity evaluation and in vivo tests, seeking the development of a possible low‐cost mouthwash formulation accessible to the most vulnerable population.
In Vitro and In Silico Antioxidant Activity and Molecular Characterization of Bauhinia ungulata L. Essential Oil
Authors: Nunes de Andrade Medeiros Sandra Regina , Conrado Bezerra Iverson , José da Silva Artur , Leal Pedroza Lucas Aleixo , Gomes Martins Regildo Max , Moniz Ana Maria Henrique , Gonçalves Reis de Melo Ana Cristina , Souza Paiva Weslley , Gubert Priscila , Alves de Melo Filho Antonio
Published: December 2023

Bauhinia ungulata is an antioxidant medicinal plant that has been manipuled in Brazil to lower glycemic index as well is for alternative treatment for diabetes. Therefore, the present hearch has aimed to investigates the antioxidant effects of the essential oil of Bauhinia ungulata L. (EOBU) collected in Amazon region better specified in Boa Vista, Roraima, Brazil, located in the Amazon region. Gas chromatography had been used to characterize the components, and antioxidant assays such as DPPH, TAC, reducing power, Fe2+ chelation, and total phenols had also been performed. The major constituents had molecularly anchored with the human catalase (CAT) enzyme, and maltol has showed as a positive control. Among the 25 revealed components, the main ones have been α‐bisabolol (27.2 %), β‐Caryophyllene (12.5 %) and Epi‐γ‐eudesmol (13.6 %). The EOBU has comproved a TAC value of 618.79 mg of ascorbic acid equivalent, free radical scavenging capacity (DPPH) around 53.7 % and 65.27 %, Fe2+ chelation capacity of 161±6 and 126.7±39.6, for 0.1 mg.mL−1 and 0.5 mg.mL−1, respectively. The power around the EOBU has appeared percentages equals to 28.66 %, 44.6 %, and 77.03 % in the concentrations tested. As well as, 96.5 % of total phenols. The compounds α‐bisabolol (−5.7±0.4 Kcal.mol−1) and β‐caryophyllene (−6.1±0.5 Kcal.mol−1) have showed good interaction with CAT compared to Maltol (−4.4±0.4 Kcal.mol−1). The present work has demonstrated that EOBU functions as a potent antioxidant, capable of scavenging free radicals and reducing oxidative stress damage.