bluuebunny/crossref_metadata_2025 huggingface dataset:
Acoustic Crystallization of 2D Colloidal Crystals
Authors: Menath Johannes , Mohammadi Reza , Grauer Jens Christian , Deters Claudius , Böhm Maike , Liebchen Benno , Janssen Liesbeth M. C. , Löwen Hartmut , Vogel Nicolas
Published: October 2022

2D colloidal crystallization provides a simple strategy to produce defined nanostructure arrays over macroscopic areas. Regularity and long‐range order of such crystals is essential to ensure functionality, but difficult to achieve in self‐assembling systems. Here, a simple loudspeaker setup for the acoustic crystallization of 2D colloidal crystals (ACDC) of polystyrene, microgels, and core–shell particles at liquid interfaces is introduced. This setup anneals an interfacial colloidal monolayer and affords an increase in average grain size by almost two orders of magnitude. The order is characterized via the structural color of the colloidal crystal, the acoustic annealing process is optimized via the frequency and the amplitude of the applied sound wave, and its efficiency is rationalized via the surface coverage‐dependent interactions within the interfacial colloidal monolayer. Computer simulations show that multiple rearrangement mechanisms at different length scales, from the local motion around voids to grain boundary movements via consecutive particle rotations around common centers, collude to remove defects. The experimentally simple ACDC process, paired with the demonstrated applicability toward complex particle systems, provides access to highly defined nanostructure arrays for a wide range of research communities.
Braiding Lateral Morphotropic Grain Boundaries in Homogenetic Oxides
Authors: Chen Shengru , Zhang Qinghua , Rong Dongke , Xu Yue , Zhang Jinfeng , Pei Fangfang , Bai He , Shang Yan‐Xing , Lin Shan , Jin Qiao , Hong Haitao , Wang Can , Yan Wensheng , Guo Haizhong , Zhu Tao , Gu Lin , Gong Yu , Li Qian , Wang Lingfei , Liu Gang‐Qin , Jin Kui‐juan , Guo Er‐Jia
Published: October 2022

Interfaces formed by correlated oxides offer a critical avenue for discovering emergent phenomena and quantum states. However, the fabrication of oxide interfaces with variable crystallographic orientations and strain states integrated along a film plane is extremely challenging by conventional layer‐by‐layer stacking or self‐assembling. Here, the creation of morphotropic grain boundaries (GBs) in laterally interconnected cobaltite homostructures is reported. Single‐crystalline substrates and suspended ultrathin freestanding membranes provide independent templates for coherent epitaxy and constraint on the growth orientation, resulting in seamless and atomically sharp GBs. Electronic states and magnetic behavior in hybrid structures are laterally modulated and isolated by GBs, enabling artificially engineered functionalities in the planar matrix. This work offers a simple and scalable method for fabricating unprecedented innovative interfaces through controlled synthesis routes as well as providing a platform for exploring potential applications in neuromorphics, solid‐state batteries, and catalysis.
Mesoporous PdN Alloy Nanocubes for Efficient Electrochemical Nitrate Reduction to Ammonia
Authors: Sun Lizhi , Liu Ben
Published: October 2022

Developing highly active and selective electrocatalysts for electrochemical nitrate reduction reaction (NITRR) is very important for synthesizing recyclable ammonia (NH3) in an economic and environmentally friendly manner. Despite some encouraging progress, their activity and selectivity have been remarkably slower than expected. In this manuscript, mesoporous palladium‐nonmetal (meso‐PdX) nanocubes (NCs) are reported as a new series of highly efficient electrocatalysts for selective nitrate reduction reaction (NITRR) electrocatalysis to NH3. The samples feature uniformly alloyed compositions and highly penetrated mesopores with abundant highly active sites and optimized electronic structures. The best meso‐PdN NCs hold an outstanding NITRR activity and selectivity with a remarkable NH3 Faradaic efficiency of 96.1% and a yield rate of 3760 µg h−1 mg−1, suppressing the state‐of‐the‐art electrocatalysts. Meanwhile, meso‐PdN NCs are electrocatalytically stable, retaining well the activity and selectivity of NO3−‐to‐NH3 electrocatalysis for more than 20 cycles. Detailed mechanism studies ascribe the superior performance to combined compositional and structural synergies of meso‐PdN NCs that not only promote the adsorption (reactivity) of NO3− and the desorption of NH3 but also increase the retention time of key intermediates for the deeper NITRR electrocatalysis to NH3 through an eight‐electron pathway.
Dynamic Sustainable Polyimide Film Combining Hardness with Softness via a “Mimosa‐Like” Bionic Strategy
Authors: Wan Baoquan , Yang Xing , Dong Xiaodi , Zheng Ming‐Sheng , Zhao Quanliang , Zhang Hongkuan , Chen George , Zha Jun‐Wei
Published: October 2022

Dielectric polyimides (PIs) are ubiquitous as insulation in electrical power systems and electronic devices. Generally, dynamic polyimide is required to solve irreversible failure processes of electrical or mechanical damage, for example, under high temperature, pressure, and field strength. The challenge lies in the design of the molecular structure of rigid polyimide to achieve dynamic reversibility. Herein, a low‐molecular‐weight polyimide gene unit is designed to crosslink with polyimide ligase to prepare the smart film. Interestingly, due to the variability of gene unit and ligase combinations, the polyimide films combining hardness with softness are designed into three forms via a “Mimosa‐like” bionic strategy to adapt to different application scenarios. Meanwhile, the films have good degradation efficiency, excellent recyclability, and can be self‐healable, which makes them reuse. Clearly, the films can be used in the preparation of ultrafast sensors with a response time ≈0.15 s and the application of corona‐resistant films with 100% recovery. Furthermore, the construction of polyimide and carbon‐fiber‐reinforced composites (CFRCs) has been verified to apply to the worse environment. Nicely, the composites have the property of multiple cycles and the non‐destructive recycle rate of carbon fiber (CF) is as high as 100%. The design idea of preparing high‐strength dynamic polyimide by crosslinking simple polyimide gene unit with ligase could provide a good foundation and a clear case for the sustainable development of electrical and electronic polyimides, from the perspective of Mimosa bionics.
Controlled Fabrication of Carbon Nanotube Microspheres from Emulsion Templates: Exploring the Dynamics of Solvent Loss and Nanoparticle Assembly
Authors: Sanders Kate A. , De Volder Michael F. L.
Published: October 2022

The use of emulsions as templates for nanomaterial assembly is a versatile method to create controlled microstructures. However, production rates are often low, particularly where the droplet phase solvent must be removed to achieve consolidation. Here, the emulsion templated fabrication of microparticles from multi‐walled carbon nanotubes (CNTs) is studied. As an exemplar primary nanoparticle for microparticle assembly, CNTs present particular challenges due to their strong inter‐particle interactions and limited dispersion in solvents. Nevertheless, small batches of CNT microparticles have demonstrated promising performances in energy storage, environmental remediation, and sensing due to their controlled structures. Improving CNT microparticle production through emulsion processing is therefore interesting to promote these real‐world applications. In this work, it is shown that the slow rate of CNT microparticle formation from water‐in‐oil emulsions is due to spontaneous emulsification. Then methanol‐in‐oil emulsions are tested, which rapidly form fragile CNT capsules. Using mixtures of methanol and water, a faster rate of solvent loss can be balanced alongside nanoparticle assembly; CNT microparticle formation is up to twice as fast using 40% methanol compared to aqueous dispersions. In addition to facilitating faster CNT microparticle production, these findings offer more broadly applicable insights into the mechanisms of solvent transport in emulsions.
Soft Underwater Swimming Robots Based on Artificial Muscle
Authors: Wang Ruiqian , Zhang Chuang , Zhang Yiwei , Tan Wenjun , Chen Wenyuan , Liu Lianqing
Published: October 2022

With the increasing requirements of underwater missions and the rapid development of soft robotics technologies, soft underwater swimming robots have become a hot topic of research due to their low noise, high flexibility, and high environmental adaptability. In the past 10 years, research into soft underwater robots based on artificial muscle actuation has made considerable progress. Herein, a comprehensive survey on recent advances in soft underwater swimming robots based on different actuation methods is reviewed systematically, including pressure actuation, intelligent material actuation, and biomaterial actuation. First, for each type of actuation, the actuating principle, structural design, and swimming performance of soft underwater robots are introduced in detail. Then, according to the different swimming modes of underwater organisms, the aforementioned soft underwater robots are classified and compared. The results show that for different swimming tasks and application scenarios, the robot needs to realize the optimal design by reasonably selecting the actuating method and the swimming mode. This review summarizes the advanced information and critical technology in designing high‐performance soft underwater robots in the aspect of structural design, actuating methods, and swimming modes and offers an insightful outlook for the future development of soft robots.
On‐Chip Light–Atom Interactions: Physics and Applications
Authors: Wang Weiyi , Xu Yuting , Chai Zhen
Published: October 2022

The large volumes induced by complex free‐space optical paths pose a challenge to quantum precision measurement and optical communication in traditional optics. Meanwhile, on‐chip integration is an important requirement for quantum technology. To simplify complicated optical systems, the development of miniaturized and integrated devices with a variety of structures, such as optical waveguide, microcavity, photonic crystal, and metasurface, has attracted increasing attention. Herein, on‐chip light–atom interactions affected by these nanostructures from the aspects of recent advancement in their physics and applications are reviewed. In recent years, different nanostructures are used to realize the functions of macro‐optical systems. The structural characteristics, interaction mechanisms, and main achievements in terms of the applications of the corresponding devices are demonstrated and compared. Finally, the research trends and challenges as well as the scope for future work are discussed.
Toward a Deeper Understanding of Gut Microbiome in Depression: The Promise of Clinical Applicability
Authors: Liu Lanxiang , Wang Haiyang , Zhang Hanping , Chen Xueyi , Zhang Yangdong , Wu Ji , Zhao Libo , Wang Dongfang , Pu Juncai , Ji Ping , Xie Peng
Published: October 2022

The emergence of the coronavirus disease 2019 pandemic has dramatically increased the global prevalence of depression. Unfortunately, antidepressant drugs benefit only a small minority of patients. Thus, there is an urgent need to develop new interventions. Accumulating evidence supports a causal relationship between gut microbiota dysbiosis and depression. To advance microbiota‐based diagnostics and therapeutics of depression, a comprehensive overview of microbial alterations in depression is presented to identify effector microbial biomarkers. This procedure generated 215 bacterial taxa from humans and 312 from animal models. Compared to controls, depression shows significant differences in β‐diversity, but no changes in microbial richness and diversity. Additionally, species‐specific microbial changes are identified like increased Eggerthella in humans and decreased Acetatifactor in rodent models. Moreover, a disrupted microbiome balance and functional changes, characterized by an enrichment of pro‐inflammatory bacteria (e.g., Desulfovibrio and Escherichia/Shigella) and depletion of anti‐inflammatory butyrate‐producing bacteria (e.g., Bifidobacterium and Faecalibacterium) are consistently shared across species. Confounding effects of geographical region, depression type, and intestinal segments are also investigated. Ultimately, a total of 178 species and subspecies probiotics are identified to alleviate the depressive phenotypes. Current findings provide a foundation for developing microbiota‐based diagnostics and therapeutics and advancing microbiota‐oriented precision medicine for depression.
Charge generation in organic solar cells: Journey toward 20% power conversion efficiency
Authors: Tamai Yasunari
Published: October 2022

The power conversion efficiencies of organic solar cells (OSCs) have routinely lagged far behind those of their inorganic counterparts. However, owing to the enormous contributions of many researchers, the power conversion efficiencies of OSCs have rapidly improved and now exceed 19%. The charge generation mechanisms in OSCs have been heavily debated during this period while acquiring valuable knowledge. This review highlights fundamental and cutting‐edge research that rationalizes why OSCs can generate photocurrent so efficiently. In particular, a photophysicist's views on exciton diffusion to donor:acceptor interfaces, charge transfer at the donor:acceptor interface, and long‐range spatial dissociation of charge transfer states are discussed. Although a general consensus in this area has not been reached yet, recent time‐resolved spectroscopic measurements provide important photophysical insights that can help achieving a better understanding of the charge generation mechanism in OSCs. Based on these observations, future research directions for realizing further improvements in OSC performance are discussed.
Multi‐rate observer design and optimal control to maximize productivity of an industry‐scale fermentation process
Authors: Shah Parth , Sheriff M. Ziyan , Bangi Mohammed Saad Faizan , Kravaris Costas , Kwon Joseph Sang‐Il , Botre Chiranjivi , Hirota Junichi
Published: October 2022

Chemical industries focus primarily on profitable operations, resulting in growing attention and advances in the field of digital twins and optimal control algorithms. However, most industries still struggle due to a lack of physical sensors, infrequent measurements, and asynchronous sampling. Thus, in this work, we have designed a multi‐rate state observer for state estimation from plant measurements and developed a model predictive controller (MPC) that maximized the profitability of an industry‐scale fermentation process (fermenter volume < 378,500 L). Additionally, as the fermentation process is complex due to the use of microorganisms, which cannot be accurately captured using a first‐principles model, we utilize a previously developed hybrid model in the proposed MPC formulation. The MPC uses a GAMS‐MATLAB framework to determine the optimal input profiles while considering practical process constraints. It is shown using multiple datasets, that the MPC can increase productivity while also decreasing the plant operating cost.
An Artificial Neuron with a Leaky Fin‐Shaped Field‐Effect Transistor for a Highly Scalable Capacitive Neural Network
Authors: Han Joon-Kyu , Yu Ji-Man , Kim Do-Wan , Choi Yang-Kyu
Published: October 2022

A capacitive neural network with a capacitive crossbar array that can replace a traditional resistive crossbar array can drastically lower static power consumption during reading operations because a capacitor consumes only dynamic power. Herein, a leaky fin‐shaped field‐effect transistor (L‐FinFET) neuron is fabricated and then applied for use in a highly scalable capacitive neural network with leaky integrate‐and‐fire (LIF) operations that are attributed to a leaky charge trap layer in a gate stack. An additional circuit such as a voltage‐to‐current converter (V–I converter) is no longer required when the L‐FinFET is applied to the capacitive neural network, as the L‐FinFET can directly accept a voltage signal from capacitive synapses. Furthermore, a reset circuit is not necessary given the ability to spontaneously restore to the initial state owing to the leaky charge trap layer. A highly scalable capacitive neural network is realizable due to the size‐reduction ability of the L‐FinFET and the simplified circuit. Finally, an entirely hardware‐based capacitive neural network with the L‐FinFET is demonstrated for the recognition of a simple pattern.
An Artificial Thermal Nociceptor Based on Xanthan Gum‐Gated Synaptic Transistors to Emulate Human Thermal Nociception
Authors: Li Fang Zhou , Liu Hong Rui , Guo Jian Miao , Zhou Xin Yi , Liu Ke Kang , Liang Lin Zi , Pei Xin Yi , Zhou Fei Chi , Huang Feng , Wang Hong , Liu Yang Hui
Published: October 2022

Nociceptors are kinds of sensory neurons that send warning information to the central nervous system in response to noxious stimuli. Thermal nociception happens as the thermal stimulus exceeds 45 °C as this temperature is perceived to be potentially harmful. Simulating this function is of great significance to developing bioinspired electronic skins and humanoid robots, which thus creates more demands for electronic devices that can simulate thermal nociception. Herein, an artificial thermal nociceptor (ATN) is fabricated by integrating a temperature sensor and a synaptic transistor, which can simulate the thermal pain threshold of the human body and operates in a very similar way as the transient receptor potential vanilloid 1 (TRPV1). For this ATN, the function of temperature sensing is realized by a graphite–polydimethylsiloxane (Gr–PDMS) composite temperature sensor, and the synaptic functions, as well as nociceptor features, are emulated through a synaptic transistor using xanthan gum polysaccharide electrolyte as gate dielectric, providing energy‐efficient building blocks for brain‐inspired computation systems. In a word, the ATN proposed can help to open a new avenue and provides more possibilities in the design of artificial sensory systems with the functions of temperature perception and thermal feedback.
Methodological correlates of variability in the prevalence of posttraumatic stress disorder in high‐risk occupational groups: A systematic review and meta‐regression
Authors: White Nicole , Wagner Shannon L. , Corneil Wayne , Fraess‐Phillips Alex , Krutop Elyssa , Fyfe Trina , Matthews Lynda R. , Randall Christine , Regehr Cheryl , White Marc , Alden Lynn E. , Buys Nicholas , Carey Mary G.
Published: October 2022

Background

Although numerous studies have reported on PTSD prevalence in high‐risk occupational samples, previous meta‐analytic work has been severely limited by the extreme variability in prevalence outcomes.

Methods

The present systematic review and meta‐regression examined methodological sources of variability in PTSD outcomes across the literature on high‐risk personnel with a specific focus on measurement tool selection.

Results

The pooled global prevalence of PTSD in high‐risk personnel was 12.1% [6.5%, 23.5%], and was similar to estimates obtained in other meta‐analytic work. However, meta‐regression revealed that PTSD prevalence differed significantly as a function of measurement tool selection, study inclusion criteria related to previous traumatic exposure, sample size, and study quality. PTSD prevalence estimates also differed significantly by occupational group and over time, as has also been reported in previous work, though exploratory examination of trends in measurement selection across these factors suggests that measurement strategy may partially explain some of these previously reported differences.

Conclusions

Our results highlight a pressing need to better understand the role of measurement strategies and other methodological choices in characterizing variable prevalence outcomes. Understanding the role of methodological variance will be critical for work attempting to reliably characterize prevalence as well as risk and protective factors for PTSD.
Regioselective, Greener Protocol for the Synthesis of N‐Heterocyclic Compounds Catalyzed by Recyclable CuO NPs Coated with Ionic Liquid (CuO[HN222][Al2Cl7]
Authors: Kumar Parveen , Tomar Vijesh , Joshi Raj Kumar , Nemiwal Meena
Published: October 2022

The identification of purine‐derived ligands for a diversity of nucleotide‐dependent enzymes has assisted in enlightenment in interest in the synthesis of purine derivatives in recent decades. The research work discloses the synthesis of CuO NPs coated with ionic liquid (triethylammonium chloride (HN222) & aluminium chloride) as a novel and powerful nanocatalyst (CuO[HN222][Al2Cl7]) as well as the exploration of its activity in the synthesis of N‐arylnucleobase and N‐aryl heterocyclic derivatives by C−N cross‐coupling reaction between adenine, imidazole, and benzimidazole compounds with aryl boronic acids in greener solvent at room temperature. This practical approach produced the products with good to excellent yields in acceptable reaction time (3 h). The nanocatalyst was characterized by Brunauer‐Emmett‐Teller (BET), Energy‐dispersive X‐ray spectroscopy (EDS), Fourier‐transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), Powder X‐ray diffraction (P‐XRD), and X‐ray photoelectron spectroscopy (XPS). Additional eco‐friendly aspects of this nanocatalyst include strong catalytic activity, ease of recovery of nanocatalyst from the reaction mixture via filtration, and recyclability upto five times without significant performance loss.
Two‐Dimensional Excitonic Networks Directed by DNA Templates as an Efficient Model Light‐Harvesting and Energy Transfer System
Authors: Zhou Xu , Satyabola Deeksha , Liu Hao , Jiang Shuoxing , Qi Xiaodong , Yu Lu , Lin Su , Liu Yan , Woodbury Neal W. , Yan Hao
Published: October 2022

Photosynthetic organisms organize discrete light‐harvesting complexes into large‐scale networks to facilitate efficient light collection and utilization. Inspired by nature, herein, synthetic DNA templates were used to direct the formation of dye aggregates with a cyanine dye, K21, into discrete branched photonic complexes, and two‐dimensional (2D) excitonic networks. The DNA templates ranged from four‐arm DNA tiles, ≈10 nm in each arm, to 2D wireframe DNA origami nanostructures with different geometries and varying dimensions up to 100×100 nm. These DNA‐templated dye aggregates presented strongly coupled spectral features and delocalized exciton characteristics, enabling efficient photon collection and energy transfer. Compared to the discrete branched photonic systems templated on individual DNA tiles, the interconnected excitonic networks showed approximately a 2‐fold increase in energy transfer efficiency. This bottom‐up assembly strategy paves the way to create 2D excitonic systems with complex geometries and engineered energy pathways.
CAPturAM, eine chemo‐enzymatische Strategie zur selektiven Detektion von physiologischen CAPAM‐Targets
Authors: Muthmann Nils , Albers Marvin , Rentmeister Andrea
Published: October 2022

Modifizierte Nukleotide beeinflussen eukaryontische mRNAs in allen Bereichen ihres Lebenszyklus und tragen zur Regulierung der Genexpression auf Transkriptions‐ und Translationsebene bei. An der 5′‐Kappe kommt Adenosin als erstes transkribiertes Nukleotid häufig als N6‐Methyl‐2′‐O‐methyladenosin (m6Am) vor. Dieser Modifikationstyp tritt gewebespezifisch und reversibel auf, was auf eine regulatorische Funktion hindeutet. CAPAM wurde als Methyltransferase identifiziert, die für die Bildung von m6Am verantwortlich ist, doch erweist sich die direkte Identifizierung ihrer Zieltranskripte als schwierig, da Antikörper nicht zwischen internem N6‐Methyladenosin (m6A) und m6Am unterscheiden können. Hier stellen wir CAPturAM vor, einen antikörperfreien chemisch‐biologischen Ansatz zur direkten Anreicherung und Detektion physiologischer CAPAM‐Targets. Wir nutzen die Promiskuität von CAPAM aus, um Propargylgruppen gezielt an seine Targets zu transferieren. Die anschließende Funktionalisierung ermöglicht die Anreicherung dieser Target‐RNAs. Unter Verwendung von Wildtyp‐ und CAPAM−/−‐Zellen wurde CAPturAM erfolgreich eingesetzt, um CAPAM‐Targets zu bestätigen oder zu widerlegen, was die gegenwärtige Überprüfung und Identifizierung von CAPAM‐Targets erleichtert.
The Single‐Component Flavin Reductase/Flavin‐Dependent Halogenase AetF is a Versatile Catalyst for Selective Bromination and Iodination of Arenes and Olefins**
Authors: Jiang Yuhua , Snodgrass Harrison M. , Zubi Yasmine S. , Roof Caitlin V. , Guan Yanfei , Mondal Dibyendu , Honeycutt Nicholas H. , Lee Johnny W. , Lewis Russell D. , Martinez Carlos A. , Lewis Jared C.
Published: October 2022

Flavin‐dependent halogenases (FDHs) natively catalyze selective halogenation of electron rich aromatic and enolate groups. Nearly all FDHs reported to date require a separate flavin reductase to supply them with FADH2, which complicates biocatalysis applications. In this study, we establish that the single component flavin reductase/flavin dependent halogenase AetF catalyzes halogenation of a diverse set of substrates using a commercially available glucose dehydrogenase to drive its halogenase activity. High site selectivity, activity on relatively unactivated substrates, and high enantioselectivity for atroposelective bromination and bromolactonization was demonstrated. Site‐selective iodination and enantioselective cycloiodoetherification was also possible using AetF. The substrate and reaction scope of AetF suggest that it has the potential to greatly improve the utility of biocatalytic halogenation.
Thiazole Imide‐Based All‐Acceptor Homopolymer with Branched Ethylene Glycol Side Chains for Organic Thermoelectrics
Authors: Shi Yongqiang , Li Jianfeng , Sun Hengda , Li Yongchun , Wang Yimei , Wu Ziang , Jeong Sang Young , Woo Han Young , Fabiano Simone , Guo Xugang
Published: October 2022

n‐Type semiconducting polymers with high thermoelectric performance remain challenging due to the scarcity of molecular design strategy, limiting their applications in organic thermoelectric (OTE) devices. Herein, we provide a new approach to enhance the OTE performance of n‐doped polymers by introducing acceptor‐acceptor (A‐A) type backbone bearing branched ethylene glycol (EG) side chains. When doped with 4‐(2,3‐dihydro‐1,3‐dimethyl‐1H‐benzimidazol‐2‐yl)‐N,N‐dimethylbenzenamine (N‐DMBI), the A‐A homopolymer PDTzTI‐TEG exhibits n‐type electrical conductivity (σ) up to 34 S cm−1and power factor value of 15.7 μW m−1 K−2. The OTE performance of PDTzTI‐TEG is far greater than that of homopolymer PBTI‐TEG (σ=0.27 S cm−1), indicating that introducing electron‐deficient thiazole units in the backbone further improves the n‐doping efficiency. These results demonstrate that developing A‐A type polymers with EG side chains is an effective strategy to enhance n‐type OTE performance.
A Photoresponsive Battery Based on a Redox‐Coupled Covalent‐Organic‐Framework Hybrid Photoelectrochemical Cathode
Authors: Wang Wei , Zhang Xiang , Lin Jing , Zhu Lei , Zhou Enbo , Feng Yangyang , Yuan Daqiang , Wang Yaobing
Published: October 2022

Photoresponsive batteries promise flexible and low‐cost solar‐to‐electrochemical energy storage (SES), but suffer from a limited SES efficiency due to rapid charge recombination and sluggish redox. Here, we present a porous‐shell/core hybrid of covalent organic framework@carbon nanotube. This hybrid ensures long‐lived separated charges (τave=3.0 ns) by an electron transfer relay starting from the donor‐acceptor molecules to the nanoscale heterojunction. These charges are further allowed to drive high‐rate redox of −C=O/−C−O− and −C−N/−C=N+ with facile kinetics. Equipped with this photoelectrochemical cathode, a photoresponsive aqueous battery shows a 5‐fold enhancement in SES efficiency (1.1 % at 1 sun) over their counterparts. It is unveiled that the electron relay favors the formation of electron‐enriching −C−O− and hole‐enriching −C=N+ groups responsible for photoelectrochemical Zn2+ and OTf− storage cascade; and further, the general photo coupled ions transfer (PCIT) process is proposed. This work presents an inspiring photoelectrochemical cathode design and theoretical insight for photoresponsive batteries.
Stimuli‐Responsive RNA‐Cleaving DNAzyme for Biomedical Application
Authors: Wang Siyuan , Liu Yaqi , Shang Jinhua , Wang Huimin , Yang Changying , Liu Xiaoqing , Wang Fuan
Published: October 2022

DNAzymes are synthetic deoxynucleotide oligomers with catalytic properties selected through in vitro systematic evolution of ligands by exponential enrichment (SELEX) technique. RNA‐cleaving DNAzymes have attracted increasing attentions in bioanalysis and biomedical applications due to their simple synthesis and modification, stable structure, and high catalytic activity. Especially, their different modes of activity regulation enable their extensive theranostic development. This review introduces the in vitro selection of DNAzymes and some typical ones, followed by the description of various stimuli‐responsive regulation strategies on DNAzyme activity, including metal ion cofactors, small molecules, protease, light, and heat. Then the recent advances of DNAzyme‐based biosensors, therapeutic applications, cell‐cell interaction regulation, and logic operation are summarized. At last, the current challenges and possible development of DNAzyme‐based biosensors are discussed.
V2O5 as a versatile electrode material for postlithium energy storage systems
Authors: Fu Qiang , Zhao Hainan , Sarapulova Angelina , Dsoke Sonia
Published: October 2022

Postlithium batteries have received intense attention as an alternative for large‐scale electric energy storage systems due to their rich resources and low cost. Vanadium pentoxide (V2O5) is very promising as a host material because of its rich structure, high capacity, easy preparation, and adequate safety. V2O5 has several modifications, including α‐, β‐, δ‐, γ‐, ζ‐, and ε‐V2O5, as well as hydrate V2O5 (V2O5·nH2O). In this mini‐review, we comprehensively summarize the crystal structure of polymorphs V2O5 materials, their relationships, and their applications in postlithium batteries, including monovalent (Na+, K+), multivalent‐ion (Mg2+, Ca2+, Zn2+, Al3+), and nonmetallic (H+, NH4+)‐based batteries. Finally, general strategies are reviewed to improve the performance of V2O5.
Bioevaluation of synthetic pyridones as dual inhibitors of α‐amylase and α‐glucosidase enzymes and potential antioxidants
Authors: Saleem Faiza , Khan Khalid Mohammed , Ullah Nisar , Özil Musa , Baltaş Nimet , Hameed Shehryar , Salar Uzma , Wadood Abdul , Rehman Ashfaq Ur , Kumar Mukesh , Taha Muhammad , Haider Syed Moazzam
Published: October 2022

Herein, a library of novel pyridone derivatives 1–34 was designed, synthesized, and evaluated for α‐amylase and α‐glucosidase inhibitory as well as antioxidant activities. Pyridone derivatives 1–34 were synthesized via a one‐pot multi‐component reaction of variously substituted aromatic aldehydes, acetophenone, ethyl cyanoacetate, and ammonium acetate in absolute ethanol. Synthetic compounds 1–34 were structurally characterized by different spectroscopic techniques. Most of the tested compounds showed more promising inhibition potential than the standard acarbose (IC50 = 14.87 ± 0.16 µM) but compounds 13 and 12 were found to be the most potent compounds with IC50 values of 9.20 ± 0.14 µM and 3.05 ± 0.18 µM against α‐amylase and α‐glucosidase enzymes, respectively. Compounds 1–34 also displayed moderate antioxidant potential in the range of IC50 = 96.50 ± 0.45 to 189.98 ± 1.00 µM in comparison to the control butylated hydroxytoluene (BHT) (IC50 = 66.50 ± 0.36 µM), in DPPH radical scavenging activities. Additionally, all synthetic derivatives were subjected to a molecular docking study to investigate the interaction details of compounds 1–34 (ligands) with the active site of enzymes (receptors). These results indicate that the newly synthesized pyridone class may serve as promising lead candidates for controlling diabetes mellitus and as antioxidants.
Autoreactive Plasmablasts After B Cell Depletion With Rituximab and Relapses in Antineutrophil Cytoplasmic Antibody–Associated Vasculitis
Authors: Berti Alvise , Hillion Sophie , Konig Maximilian F. , Moura Marta Casal , Hummel Amber M. , Carmona Eva , Peikert Tobias , Fervenza Fernando C. , Kallenberg Cees G.M. , Langford Carol A. , Merkel Peter A. , Monach Paul A. , Seo Philip , Spiera Robert F. , Brunetta Paul , St. Clair E. William , Harris Kristina M. , Stone John H. , Grandi Guido , Pers Jacques‐Olivier , Specks Ulrich , Cornec Divi
Published: October 2022

Objective

Autoreactive B cells are responsible for antineutrophil cytoplasmic antibody (ANCA) production in ANCA‐associated vasculitis (AAV). Rituximab (RTX) depletes circulating B cells, including autoreactive B cells. We aimed to evaluate changes and associations with relapse of the circulating autoreactive B cell pool following therapeutic B cell depletion in AAV.

Methods

Sequential flow cytometry was performed on 148 samples of peripheral blood mononuclear cells from 23 patients with proteinase 3 (PR3)–ANCA–positive AAV who were treated with RTX for remission induction and monitored after stopping therapy during long‐term follow‐up in a prospective clinical trial. PR3 was used as a ligand to target autoreactive PR3‐specific (PR3+) B cells. B cell recurrence was considered as the first blood sample with ≥10 B cells/μl after RTX treatment.

Results

At B cell recurrence, PR3+ B cell frequency among B cells was higher than baseline (P < 0.01). Within both PR3+ and total B cells, frequencies of transitional and naive subsets were higher at B cell recurrence than at baseline, while memory subsets were lower (P < 0.001 for all comparisons). At B cell recurrence, frequencies of B cells and subsets did not differ between patients who experienced relapse and patients who remained in remission. In contrast, the plasmablast frequency within the PR3+ B cell pool was higher in patients who experienced relapse and associated with a shorter time to relapse. Frequencies of PR3+ plasmablasts higher than baseline were more likely to be found in patients who experienced relapse within the following 12 months compared to those in sustained remission (P < 0.05).

Conclusion

The composition of the autoreactive B cell pool varies significantly following RTX treatment in AAV, and early plasmablast enrichment within the autoreactive pool is associated with future relapses.
Osseous topography in biologically driven flap design in minimally invasive regenerative therapy: A classification proposal
Authors: Velasquez‐Plata Diego
Published: October 2022

Minimally invasive periodontal regenerative surgical procedures are a paradigm shift that demands a unique approach encompassing specialized armamentarium, magnification tools, knowledge of handling properties of biomaterials, and specific flap designs. Biologically driven flap design is dictated by optimal soft and hard tissue handling, flap perfusion, and wound stability, all in the pursuit of primary intention healing. The unique architecture of the infrabony defect is a determining factor on incision tracing, boundaries of flap extension, and biomaterial selection. The purpose of this article is to propose a flap design classification based on the osseous topography of infrabony defects during biologically driven minimally invasive surgical periodontal regenerative therapy.
Enzymatic Generation of Double‐Modified AdoMet Analogues and Their Application in Cascade Reactions with Different Methyltransferases
Authors: Erguven Mehmet , Cornelissen Nicolas V. , Peters Aileen , Karaca Ezgi , Rentmeister Andrea
Published: October 2022

Methyltransferases (MTases) have become an important tool for site‐specific alkylation and biomolecular labelling. In biocatalytic cascades with methionine adenosyltransferases (MATs), transfer of functional moieties has been realized starting from methionine analogues and ATP. However, the widespread use ofS‐adenosyl‐l‐methionine (AdoMet) and the abundance of MTases accepting sulfonium centre modifications limit selective modification in mixtures. AdoMet analogues with additional modifications at the nucleoside moiety bear potential for acceptance by specific MTases. Here, we explored the generation of double‐modified AdoMets by an engineeredMethanocaldococcus jannaschiiMAT (PC‐MjMAT), using 19 ATP analogues in combination with two methionine analogues. This substrate screening was extended to cascade reactions and to MTase competition assays. Our results show that MTase targeting selectivity can be improved by using bulky substituents at the N6of adenine. The facile access to >10 new AdoMet analogues provides the groundwork for developing MAT‐MTase cascades for orthogonal biomolecular labelling.
Engineering Liganded Gold Nanoclusters as Efficient Theranostic Agents for Cancer Applications
Authors: Bonačić‐Koutecký Vlasta , Le Guével Xavier , Antoine Rodolphe
Published: October 2022

Luminescent gold nanoclusters are rapidly gaining attention as efficient theranostic targets for imaging and therapeutics. Indeed, their ease of synthesis, their tunable optical properties and tumor targeting make them potential candidates for sensitive diagnosis and efficacious therapeutic applications. This concept highlights the key components for designing gold nanoclusters as efficient theranostics focusing on application in the field of oncology.
Synthetic Studies with Bacitracin A and Preparation of Analogues Containing Alternative Zinc Binding Groups
Authors: Buijs Ned , Vlaming Halana C. , van Haren Matthijs J. , Martin Nathaniel I.
Published: October 2022

The growing threat of drug‐resistant bacteria is a global concern, highlighting the urgent need for new antibiotics and antibacterial strategies. In this light, practical synthetic access to natural product antibiotics can provide important structure‐activity insights while also opening avenues for the development of novel analogues with improved properties. To this end, we report an optimised synthetic route for the preparation of the clinically used macrocyclic peptide antibiotic bacitracin. Our combined solid‐ and solution‐phase approach addresses the problematic, and previously unreported, formation of undesired epimers associated with the stereochemically fragile N‐terminal thiazoline moiety. A number of bacitracin analogues were also prepared wherein the thiazoline motif was replaced by other known zinc‐binding moieties and their antibacterial activities evaluated.
Toluene Removal By A Sequential Adsorption‐Thermal Catalytic Process On Ag/Hopcalite
Authors: Sonar Shilpa , Giraudon Jean‐Marc , Lamonier Jean‐François , Morent Rino , De Geyter Nathalie , Löfberg Axel
Published: October 2022

Hopcalite supported Ag (wt.%: 0.5; 1; 2; 10)‐containing materials were prepared by wet impregnation followed by calcination at 400 °C for adsorption‐thermal catalytic oxidation of toluene. Based on breakthrough experiments, the duration of the adsorption step was set around 38 min to minimize toluene loss at the outlet of the reactor (<3 mol% of the amount of toluene adsorbed) allowing to determine a dynamic useful adsorption capacity for toluene. Thermal oxidation was performed in a He : O2 (75 : 25) gaseous mixture from 20 °C to 250 °C (90 min) to assess the catalytic properties of the bifunctional materials throughout on‐line monitoring of unreacted toluene and CO2 during the temperature programmed reaction. Hop‐0.5 Ag exhibited the best performance with a CO2 yield of 98.9 %. Excellent redox properties and minimization of thermal effects were invoked to enhance total oxidation of toluene. Additionally, these bifunctional materials showed good stability under cycling conditions.
Harnessing Keto‐Enol Tautomerism to Modulate β‐Ketoenamine‐based Covalent Organic Frameworks for Visible‐Light‐Driven CO2 Reduction
Authors: Ai Lvye , Li Wanrong , Wang Qian , Cui Fuzhi , Jiang Guofang
Published: October 2022

Covalent organic frameworks (COFs) have attracted extensive attention as promising photocatalysts for CO2 reduction. However, there are few reports on the relationship between keto‐enol tautomerism and COFs photocatalyst activity. Three different β‐ketoenamine‐based COFs were prepared by varying the proportion of hydroxyl units in the aldehyde precursor, in which only the HCOF‐2 shows the structural features of the reversible keto‐enol tautomerism. Through density functional theory (DFT) calculations and experiments, the effects of keto‐enol tautomerism on the light absorption intensity, band position, band gap, and carrier separation of these COFs were investigated. The reversible keto‐enol tautomerism contributes to narrowing the band gap and promoting the light absorption capacity. In addition, the reversible keto‐enol tautomerism leads to molecular polarization, which promotes the separation and transmission of carriers within the material. As a result, HCOF‐2 exhibits optimal photocatalytic activity, yielding 309 and 96 μmol g−1 of CO and CH4 respectively within 10 h. This work provides an explanation of the relationship between keto‐enol tautomerism and photocatalytic activity.
Improved Performance of a Europium‐based Metal‐Organic Framework for Cyanosilylation of Demanding Ketones
Authors: Pérez Juana M. , Echenique‐Errandonea Estitxu , Rojas Sara , Choquesillo‐Lazarte Duane , Seco José M. , López‐Vargas Mireya E. , Rodríguez‐Diéguez Antonio , Fernández Ignacio
Published: October 2022

Solvothermally promoted assembly of the multifunctional 3‐amino‐4‐hydroxybenzoic acid ligand with the corresponding Eu salt gives rise to the formation of a porous metal‐organic framework with the general formula {[Eu5L6(OH)3(H2O)3] ⋅ 5DMF}n (1) that has been tested as heterogeneous catalyst for the cyanosilylation of a broad scope of ketones in solvent‐free conditions, using the lowest catalyst loading of 0.5 mol% ever reported, and exhibiting no leak and high recyclability.
Constrained Geometry ansa‐Half‐Sandwich Complexes of Magnesium – Versatile s‐Block Catalysts
Authors: Wirtz Lisa , Ghulam Kinza Yasmin , Morgenstern Bernd , Schäfer André
Published: October 2022

The synthesis, characterization and catalytic application of a series of constrained geometry ansa‐half‐sandwich complexes of magnesium is reported. These versatile s‐block catalysts were applied in different dehydrocoupling and hydroelementation reactions, demonstrating a broad applicability with particularly remarkable performance in dehydrocoupling reactions.
Hybrid Technique for Removal of Arsenic from Drinking Water
Authors: Sarkar Soumi , Hazra Soumendu , Chakraborty Kaushik , Nayak Ananya , Saha Prabirkumar
Published: October 2022

Amalgamation of a supported liquid membrane (SLM) and electrocoagulation are carried out to remove As(III) and As(V) from drinking water to achieve a high treatment efficiency. The process is based on uphill transport of arsenic ions against their concentration gradients across phases and has the advantage of simultaneous extraction and recovery followed by electrocoagulation of arsenic. The aim of the process is selective separation of arsenic from drinking water and to reduce its concentration below 10 ppb. An iron‐arsenic precipitate is obtained by using an iron anode and the said precipitate is a value‐added saleable product. Various adsorption isotherms are evaluated to understand the removal mechanism of arsenic by the formation of iron‐arsenic precipitates. The Freundlich isotherm and Dubinin‐Radushkevich model are found to fit well with the adsorption data of the removal of arsenic ions.
Preorganized Polyaromatic Soft Terdentate Hosts for the Capture of [Ln(β‐diketonate)3] Guests in Solution
Authors: Naseri Soroush , Mirzakhani Mohsen , Besnard Céline , Guénée Laure , Briant Liza , Nozary Homayoun , Piguet Claude
Published: October 2022

The concept of preorganization is famous in coordination chemistry for having transformed flexible bidentate 2,2’‐bipyridine scaffolds into rigid 1,10‐phenanthroline platforms. The resulting boosted affinities for d‐block cations has successfully paved the way for the design of a wealth of functional complexes, devices and materials for analysis and optics. Its extension toward terdentate homologues adapted for the selective complexation of f‐block cations with larger coordination numbers remains more overlooked. The resulting rigidification of 2,6‐bis(1‐methyl‐1H‐benzo[d]imidazol‐2‐yl)pyridine ligands (L1–L7) produces the highly preorganized and extended polyaromatic benzo[4′,5′]imidazo[1′,2′ : 1,2]pyrido[3,4‐b]benzo[4,5]imidazo[1,2‐h][1,7]naphthyridines (L8–L11) receptors, which offer some novel and rare opportunities for efficiently complexing trivalent lanthanides with polyaromatic soft terimine ligands. The crystal structures of the stable heteroleptic [LkLn(hfac)3] adducts (Lk=L1,L8,L9; Ln=La, Eu, Gd, Er, Yb, Y; H‐hfac=1,1,1,5,5,5‐hexafluoropentane‐2,4‐dione) show a drastic decrease in the Ln−N bond valences upon replacement of the flexible ligandL1with its preorganized counterpartsL8andL9. This points to a limited match between the preorganized cavity and the entering [Ln(hfac)3] lanthanide containers. However, thermodynamic studies conducted in dichloromethane reach the opposite conclusion, with an improved affinity, by up to three orders of magnitude for catching Ln(hfac)3whenL1is replaced by the preorganizedL8–L9receptors. The key to the enigma lies in the removal of the energy penalty which accompanies the formation of flexible [L1Ln(hfac)3] complexes in solution. This driving force overcomes the poor match between the preorganized terdentate N∩N∩N cavity inL8andL9and the size of trivalent lanthanides. As planned, the rigid, planar and extended π‐conjugated system found inL8andL9shifts the ligand‐centered absorption bands by about 5000 cm−1toward lower energies, a crucial point if these stable [L8Ln(hfac)3] and [L9Ln(hfac)3] platforms have to be considered for the visible sensitization of luminescent lanthanides in metallopolymers.
Particle Technology in the Formulation and Fabrication of Thermal Energy Storage Materials
Authors: Jiang Zhu , Li Xinyi , Jin Yi , Zhang Xiaosong , Tong Lige , Wang Li , Ding Yulong
Published: October 2022

This article reviews the state of the art of the formulation and fabrication of sensible, latent, and thermochemical thermal energy storage (TES) materials with special focus on the role of particle technology in enhancing the performance of these materials. Molten salt‐based sensible TES materials have been intensively studied, particularly the use of doped nanoparticles for enhancing specific heat capacity and thermal conductivity. For latent TES, the inclusion of property enhancers is among the most effective approaches to address the low thermal conductivity and supercooling issues of phase change materials (PCMs), whereas the encapsulation of PCMs and structurally stabilized composite PCMs are the favorable methods to address leakage and chemical incompatibility challenges. Thermochemical TES materials are often incorporated with an inert or an active host matrix for structural stabilization.
New efficient logarithmic estimators using multi‐auxiliary information under ranked set sampling
Authors: Bhushan Shashi , Kumar Anoop
Published: October 2022

This article proposes a new efficient logarithmic class of estimators for estimating the population mean in the case of multi‐auxiliary information using ranked set sampling. The bias and mean square error of the proposed estimators are reported up to the first order of approximation. It is demonstrated analytically and numerically that the proposed estimators are always better than their competitors. We accomplished an empirical study using some real populations and a simulation study using some artificially generated populations to support the analytical comparisons between the proposed estimators and their competitors.