bluuebunny/crossref_metadata_2025 huggingface dataset:
A Semi‐Interpenetrating Poly(Ionic Liquid) Network‐Driven Low Hysteresis and Transparent Hydrogel as a Self‐Powered Multifunctional Sensor
Authors: Han Shaowei , Hu Yongkang , Wei Jia , Li Songwei , Yang Peipei , Mi Haoyang , Liu Chuntai , Shen Changyu
Published: May 2024

Conductive hydrogels are gaining significant attention as promising candidates for the fabrication materials for flexible electronics. Nevertheless, improving the tensile properties, hysteresis, durability, adhesion, and electrochemical properties of these hydrogels remains challenging. This work reports the development of a novel semi‐interpenetrating network poly(ionic liquid) hydrogel named PATV, via the in situ polymerization of acrylamide, N‐[Tris(hydroxymethyl)methyl] acrylamide, and 1‐vinyl‐3‐butylimidazolium tetrafluoroborate. The density functional theory calculations reveal that the poly(ionic liquid) in the hydrogel network acts as physical cross–linking points to construct hydrogen‐bond networks. Furthermore, the hydrogen‐bond networks dissipate energy efficiently and quickly, and thus stress concentration and hysteresis are avoided. The prepared hydrogel has a low hysteresis (9%), high tensile properties (900%), fast response (180 ms), high sensitivity (gauge factor = 10.4, pressure sensitivity = 0.14 kPa−1), and wide sensing range (tensile range: 1–600%, compression range: 0.1–20 kPa). A multifunctional sensor designed based on the designed hydrogel enables real‐time, rapid, and stable response‐ability for the detection of human movement, facial expression recognition, pronunciation, pulse, handwriting, and Morse code encryption. Furthermore, the assembled triboelectric nanogenerator displays an excellent energy harvesting capability, thus highlighting its potential application in self‐powered flexible wearable electronic devices.
Nitrogen‐Rich Carbon Dot‐Mediated n→π* Electronic Transition in Carbon Nitride for Superior Photocatalytic Hydrogen Peroxide Production
Authors: Guo Huazhang , Zhou Li , Huang Kai , Li Yongqiang , Hou Weidong , Liao Huange , Lian Cheng , Yang Siwei , Wu Deli , Lei Zhendong , Liu Zheng , Wang Liang
Published: May 2024

Solar‐driven synthesis of hydrogen peroxide (H2O2) through photocatalysis stands out as a promising avenue for sustainable energy generation, marked by environmental friendliness and industrial feasibility. However, the inherent limitations of carbon nitride (CN) in photocatalytic H2O2 production significantly impede their performance. Herein, a novel 0D/2D carbon dots‐modified CN nanosheet heterojunction (CDsMCN) is introduced, synthesized through a hydrothermal‐calcination tandem strategy induced by CDs derived from melamine. This innovative technique enhances the n→π* electronic transition in CDsMCN, accelerating the separation efficiency of electron‐hole pairs, boosting oxygen adsorption, and promoting a highly selective 2e− ORR. Comparative to pristine CN, CDs10MCN exhibited a remarkable tenfold increase in H2O2 production, reaching an impressive 1.48 mmol L−1. Furthermore, CDs10MCN demonstrates exceptional stability, maintaining its catalytic efficiency at the initial level over four consecutive cycles. The notable achievement of a molar selectivity of H2O2 ≈80% at an onset potential of 0.6 V (vs RHE) underscores its exceptional ability to produce the desired product selectively. Advanced in situ characterization together with DFT calculations revealed that the ultrathin CDs10MCN nanosheet heterojunction with enhanced n→π* electronic transition improves its optical properties, reduces bandgap, facilitates fast charge migration, and increases photocatalytic H2O2 performance, thereby serving as a promising candidate for advanced catalytic applications.
An Efficient Fiber Gel Dye‐Sensitized Solar Cell with Stable Interlaced Interfaces
Authors: Kang Xinyue , Song Jiatian , Liu Jiuzhou , Cao Siwei , Lin Zhengmeng , Jiang Hongyu , Yang Yiqing , Cheng Xiangran , Ai Yulu , Sun Xuemei , Zeng Kaiwen , Zhu Zhengfeng , Peng Huisheng
Published: May 2024

Fiber gel dye‐sensitized solar cells (FGDSCs) are recognized as an effective solution for high‐performance, durable and safe wearable power supply. However, poor and unstable interfaces between fiber electrodes and gel electrolytes are bottleneck problems that have restricted the photovoltaic performances of FGDSCs and their stabilities during deformations. Here, an FGDSC with stable interlaced interfaces is designed by incorporating polymerized gel electrolyte into the aligned channels in fiber electrodes and the gaps between photoanode and counter electrode in situ. The interlaced structure of gel electrolyte in FGDSC improves the interfacial stability and provided stable channels for rapid ion diffusions, offering efficient charge transports at interfaces. The resulting FGDSC thus produced a high power conversion efficiency of 7.95%, and it is further maintained by over 90% after bending for 5000 cycles. These FGDSCs can be integrated with fiber batteries as a self‐charging power system, demonstrating an effective power solution for wearables.
Novel Penetrated Nucleation Mechanism for Controlled Synthesis of 2D Materials on Metal Substrates
Authors: Xu Shaogang , He Changchun , Yan Feini , He Chao , Dong Xingxing , Yang Xiaobao , Xu Hu
Published: May 2024

2D materials have attracted considerable attention in the past decades for their unique properties, making the understanding of their nucleation process key to effective synthesis. Traditional explanations of thin‐film growth, focusing on the competition between atom interactions at the interface and within layers, often fall short of explaining real experimental results. Herein, a penetrated nucleation mechanism is proposed for 2D materials growth on metal substrates, taking into account the role of metal substrate atoms. This approach leads to a better understanding of how the surface shape evolves in two specific ways during growth in real experimental findings. Supported by detailed first‐principles simulations of boron on metal substrates and thermodynamic analyses of other studies involving metals and nonmetals, the above‐proposed mechanism is validated. Moreover, a broad strategy for growing large‐scale 2D materials on metal surfaces without creating undesired alloy layers is also presented, by adjusting the interfacial interactions by surface passivation, validated by existing experiments.
Facet‐Junction Induced Strong Metal Support Interaction for Enhanced Alkaline Hydrogen Evolution Reaction
Authors: Shen Wenqian , Fu Qiang , Tsang Chi Shing , Wong Lok Wing , Zheng Xiaodong , Zhao Jiong , Ly Thuc Hue
Published: May 2024

Strong metal‐support interaction (SMSI) plays a critical role in enhancing the catalytic performance of electrocatalysts. Currently, effective approaches to enhance the SMSI effect in supported electrocatalysts still need to be developed, and a comprehensive atomic‐level understanding of the underlying reaction mechanisms remains unclear. In this study, a novel facet‐junction strategy is proposed to enhance the SMSI between the loaded Ru atoms and the Co3O4 support. By modulating the ratio of exposed facet for (111)/(100) crystal plane in Co3O4, the hydrogen evolution reaction (HER) performance can be dramatically enhanced by 560% and can achieve a Pt‐like HER activity with the overpotential of 45 mV. Detailed analysis with atomic‐resolution integrated differential phase contrast (iDPC)‐scanning transmission electron microscopy (STEM), atomic‐resolution high angle annular dark field (HADDF)‐STEM, and electron energy loss spectroscopy (EELS) further proved that with proper (111)/(100) crystal plane ratio, the intensified charge distribution near the facet‐junction region would modify the electronic structure around the active sites. This work provides new insights to enhance the SMSI and will contribute to the rational design of highly efficient electrocatalysts for water splitting.
Preparation of NIR‐II Polymer Nanoprobe Through Twisted Intramolecular Charge Transfer and Förster Resonance Energy Transfer of NIR‐I Dye
Authors: Xia Bin , Ren Feng , Ma Xiaopeng , Yang Zheng‐Chuan , Jiang Zhi‐Lin , Fang Wei‐Wei , Wang Ning‐Wei , Hu Jin‐Long , Zhu Wei‐Duo , He Tao , Li Qing , Cao Bao‐Qiang , Li Zhen
Published: May 2024

Near‐infrared‐II (NIR‐II) fluorescence imaging is pivotal in biomedical research. Organic probes exhibit high potential in clinical translation, due to advantages such as precise structure design, low toxicity, and post‐modifications convenience. In related preparation, enhancement of NIR‐II tail emission from NIR‐I dyes is an efficient method. In particular, the promotion of twisted intramolecular charge transfer (TICT) of relevant NIR‐I dyes is a convenient protocol. However, present TICT‐type probes still show disadvantages in relatively low emission, large particle sizes, or limited choice of NIR‐I dyes, etc. Herein, the synthesis of stable small‐sized polymer NIR‐II fluoroprobes (e.g., 7.2 nm), integrating TICT and Förster resonance energy transfer process to synergistically enhance the NIR‐II emission is reported. Strong enhanced emissions can be obtained from various NIR‐I dyes and lanthanide elements (e.g., twelvefold at 1250 nm from Nd‐DTPA/IR‐808 sample). The fluorophore provides high‐resolution angiography, with high‐contrast imaging on middle cerebral artery occlusion model mice for distinguishing occlusion. The fluorophore can be rapidly excreted from the kidney (urine ≈65% within 4 h) in normal mice and exhibits long‐term renal retention on acute kidney injury mice, showing potential applications in the prognosis of kidney diseases. This development provides an effective strategy to design and synthesize effective NIR‐II fluoroprobes.
An Engineered Nanoplatform with Tropism Toward Irradiated Glioblastoma Augments Its Radioimmunotherapy Efficacy
Authors: Wang Zheng , Chen Fangman , Cao Yi , Zhang Fan , Sun Lina , Yang Chao , Xie Xiaochun , Wu Ziping , Sun Madi , Ma Fanshu , Shao Dan , Leong Kam W. , Pei Renjun
Published: May 2024

Combining radiotherapy with immune checkpoint blockade therapy offers a promising approach to treat glioblastoma multiforme (GBM), yet challenges such as limited effectiveness and immune‐related adverse events (irAEs) persist. These issues are largely due to the failure in targeting immunomodulators directly to the tumor microenvironment. To address this, a biomimetic nanoplatform that combines a genetically modified mesenchymal stem cell (MSC) membrane with a bioactive nanoparticle core for chemokine‐directed radioimmunotherapy of GBM is developed. The CC chemokine receptor 2 (CCR2)‐overexpressing MSC membrane acts as a tactical tentacle to achieve radiation‐induced tropism toward the abundant chemokine (CC motif) ligand 2 (CCL2) in irradiated gliomas. The nanoparticle core, comprising diselenide‐bridged mesoporous silica nanoparticles (MSNs) and PD‐L1 antibodies (αPD‐L1), enables X‐ray‐responsive drug release and radiosensitization. In two murine models with orthotopic GBM tumors, this nanoplatform reinvigorated immunogenic cell death, and augmented the efficacy and specificity of GBM radioimmunotherapy, with reduced occurrence of irAEs. This study suggests a promising radiation‐induced tropism strategy for targeted drug delivery, and presents a potent nanoplatform that enhances the efficacy and safety of radio‐immunotherapy.
Implication Logic Circuit Based on a Graphene Oxide Complementary Resistive Switching Device
Authors: Wang Lu , Zuo Ze , Zhang Xiafan , Wen Dianzhong
Published: May 2024

The logic circuit is the main component of an integrated circuit chip that dictates the operation and performance of the chip. The logic circuit based on a memristor can improve the integration and operation speed of the existing integrated circuit and reduce the chip size and the number of devices used by a single logic circuit. However, most of the research on logic circuits based on memristors has focused only on simulations, and research on the realization of logic circuits by hardware using actual memristors is limited. In this paper, a memristor based on graphene oxide with stable complementary resistive switching characteristics is fabricated, a logic circuit is built by using this device, and the logic functions of “IMP,” “AND,” and “NOR” are successfully realized. The complementary resistive switching device can alleviate the severe power loss caused by the memory separation of the von Neumann architecture. Moreover, its unique structure enables it to realize material logic independently without the use of multiple memristors and resistors, providing a new scheme for the physical realization of logic circuits. It also opens up a new path for integrated chips to break through von Neumann architecture.
Pd‐Catalyzed [3+6+3+6] Macrocyclizations of Aryl α‐Diazo‐β‐Ketoesters
Authors: Zhong Zhuang , de Aguirre Adiran , Besnard Céline , Poblador‐Bahamonde Amalia I. , Lacour Jérôme
Published: May 2024

Thanks to Pd(II)‐catalysis, an efficient synthesis of unsaturated macrocycles is achieved by [3+6+3+6] condensation of cyclic ethers with aryl α‐diazo‐β‐ketoesters. The presence of the electron‐rich aryl ester moieties forbids the use of dirhodium complexes as these diazo decomposition catalysts provoke unforeseen intermolecular Csp2−H insertion reactions that derail the targeted reactivity. However, with Pd(acac)2, using high concentration conditions (1 M), a variety of 18‐membered macrocycles (16 examples) is afforded with both aryl and alkyl diazo reagents. Catalyst selection for either electrophilic aromatic substitution (Rh) or ylide (Pd) pathways are explained by computational approaches.
Synthesis of Phthalazino[2,3‐a]cinnoline‐6,8,13(5H)‐triones via Ir(III)‐Catalyzed Dehydrogenative C−H/N−H Functionalization of N‐Aryl Phthalazinones
Authors: Zhang Chao , Zhang Ling‐Xi , Dong Lin
Published: May 2024

An Iridium(III)‐catalyzed C−H cyclization of N‐arylphthalazinones with α‐diazotized Meldrum's acid afforded tetracyclic phthalazine derivatives with a carbonyl group in 98% yield in only 30 min. The initial formation of tetracyclic phthalazine derivatives also provided access to a powerful building block. The utility of this method is emphasized by the synthetic transformation into a series of potentially bioactive derivatives.
Modeling self‐diffusion coefficients of ionic liquids using ePC‐SAFT and FVT combined with Einstein relation
Authors: Zuo Zhida , Lu Xiaohua , Ji Xiaoyan
Published: May 2024

The electrolyte perturbed‐chain statistical associating fluids theory (ePC‐SAFT) coupled with free volume theory (FVT) was combined with Einstein relation, that is, ePC‐SAFT‐FVT‐E, to describe self‐diffusion coefficients (SDCs) of ionic liquids (ILs). In modeling, ePC‐SAFT was used to calculate density, while FVT parameters, determined from viscosity data, were utilized to calculate the summation of ionic SDCs through the Einstein relation with one parameter. Two strategies were employed to determine this parameter: fitting experimental data for each IL or estimating a universal parameter from van der Waals volume. Comparative analysis reveals good agreement with experimental data, with average absolute relative deviations (ARDs) of 8.14% (strategy 1) and 10.29% (strategy 2). Subsequently, cationic and anionic SDCs were reliably determined from the summation of ionic SDCs, with average ARDs of 10.80% and 10.21%, respectively. This study indicates the ePC‐SAFT‐FVT‐E model, employing viscosity‐derived parameters and three universal parameters, reliably predicts SDCs of ILs in wide temperature and pressure ranges.
Unburdening care: Exploring modes of care through post‐productivist thought and Australian parliamentary inquiry representations
Authors: Khan Chabel
Published: May 2024

Research on care increasingly emphasises the “care‐less” or “uncaring” nature of state‐coordinated interventions imposed on marginalised communities. However, these perspectives tend to eliminate discussions about modes of care (Fox, Critical Social Policy, 15, 1995, 107) or the ways in which care is differentially experienced and performed. This paper argues for scholars to think multimodally about care, proposing a typology of four different modes of care: care‐as‐gift, ‐burden, ‐control and ‐cure. The paper makes a case for locating these modes of care within a post‐capitalist political horizon to respond to the demand to “unburden care.” That is, the political demand to provide the economic and social conditions that best enable caregiving and reduce gendered pressures on caregivers. The paper develops these arguments through the post‐productivist thought of Kathi Weeks (2011, The problem with work: feminism, marxism, antiwork politics, and postwork imaginaries. Durham, NC and London: Duke University Press) and a critical discursive examination of care representations made by submitters to two parliamentary inquiries into the Australian “pre‐employment” programme ParentsNext—a labour market activation programme that targets single‐parent caregivers “at risk of welfare dependency.” The paper contributes a critical and multimodal approach to better conceptualise competing framings of care's value and the ways in which the state can (un)burden caregiving.
Assessment of neurovascular uncoupling: APOE status is a key driver of early metabolic and vascular dysfunction
Authors: Onos Kristen D. , Lin Peter B. , Pandey Ravi S. , Persohn Scott A. , Burton Charles P. , Miner Ethan W. , Eldridge Kierra , Kanyinda Jonathan Nyandu , Foley Kate E. , Carter Gregory W. , Howell Gareth R. , Territo Paul R.
Published: May 2024

BACKGROUND

Alzheimer's disease (AD) is the most common cause of dementia worldwide, with apolipoprotein Eε4 (APOEε4) being the strongest genetic risk factor. Current clinical diagnostic imaging focuses on amyloid and tau; however, new methods are needed for earlier detection.

METHODS

PET imaging was used to assess metabolism‐perfusion in both sexes of aging C57BL/6J, and hAPOE mice, and were verified by transcriptomics, and immunopathology.

RESULTS

All hAPOE strains showed AD phenotype progression by 8 months, with females exhibiting the regional changes, which correlated with GO‐term enrichments for glucose metabolism, perfusion, and immunity. Uncoupling analysis revealed APOEε4/ε4 exhibited significant Type‐1 uncoupling (↓ glucose uptake, ↑ perfusion) at 8 and 12 months, while APOEε3/ε4 demonstrated Type‐2 uncoupling (↑ glucose uptake, ↓ perfusion), while immunopathology confirmed cell specific contributions.

DISCUSSION

This work highlights APOEε4 status in AD progression manifests as neurovascular uncoupling driven by immunological activation, and may serve as an early diagnostic biomarker.

Highlights

We developed a novel analytical method to analyze PET imaging of 18F‐FDG and 64Cu‐PTSM data in both sexes of aging C57BL/6J, and hAPOEε3/ε3, hAPOEε4/ε4, and hAPOEε3/ε4 mice to assess metabolism‐perfusion profiles termed neurovascular uncoupling.

This analysis revealed APOEε4/ε4 exhibited significant Type‐1 uncoupling (decreased glucose uptake, increased perfusion) at 8 and 12 months, while APOEε3/ε4 demonstrated significant Type‐2 uncoupling (increased glucose uptake, decreased perfusion) by 8 months which aligns with immunopathology and transcriptomic signatures.

This work highlights that there may be different mechanisms underlying age related changes in APOEε4/ε4 compared with APOEε3/ε4. We predict that these changes may be driven by immunological activation and response, and may serve as an early diagnostic biomarker.
Synthetic Sialosides Terminated with 8‐N‐Substituted Sialic Acid as Selective Substrates for Sialidases from Bacteria and Influenza Viruses
Authors: Mishra Bijoyananda , Yuan Yue , Yu Hai , Kang Hyeog , Gao Jin , Daniels Robert , Chen Xi
Published: May 2024

Sialosides containing C8‐modified sialic acids are challenging synthetic targets but potentially useful probes for diagnostic substrate profiling of sialidases and elucidating the binding specificity of sialic acid‐interacting proteins. Here, we demonstrate efficient chemoenzymatic methods for synthesizing para‐nitrophenol‐tagged α2–3‐ and α2–6‐linked sialyl galactosides containing C8‐acetamido, C8‐azido, or C8‐amino derivatized N‐acetylneuraminic acid (Neu5Ac). High‐throughput substrate specificity studies showed that the C8‐modification of sialic acid significantly changes its recognition by sialidases from humans, various bacteria, and different influenza A and B viruses. Sialosides carrying Neu5Ac with a C8‐azido modification were generally well tolerated by all the sialidases we tested, whereas sialosides containing C8‐acetamido‐modified Neu5Ac were only cleaved by selective bacterial sialidases. In contrast, sialosides with C8‐amino‐modified Neu5Ac were cleaved by a combination of selective bacterial and influenza A virus sialidases. These results indicate that sialosides terminated with a C8‐amino or C8‐acetamido‐modified sialic acid can be used with other sialosides for diagnostic profiling of disease‐causing sialidase‐producing pathogens.
ON–OFF Control of Marangoni Self‐propulsion via A Supra‐amphiphile Fuel and Switch
Authors: Zhu Guiqiang , Zhang Shu , Lu Guoxin , Peng Benwei , Lin Cuiling , Zhang Liqun , Shi Feng , Zhang Qian , Cheng Mengjiao
Published: May 2024

Marangoni self‐propulsion refers to motion of liquid or solid driven by a surface tension gradient, and has applications in soft robots/devices, cargo delivery, self‐assembly etc. However, two problems remain to be addressed for motion control (e.g., ON–OFF) with conventional surfactants as Marangoni fuel: (1) limited motion lifetime due to saturated interfacial adsorption of surfactants; (2) in‐ situ motion stop is difficult once Marangoni flows are triggered. Instead of covalent surfactants, supra‐amphiphiles with hydrophilic and hydrophobic parts linked noncovalently, hold promise to solve these problems owing to its dynamic and reversible surface activity responsively. Here, we propose a new concept of ‘supra‐amphiphile fuel and switch’ based on the facile synthesis of disodium‐4‐azobenzene‐amino‐1,3‐benzenedisulfonate (DABS) linked by a Schiff base, which has amphiphilicity for self‐propulsion, hydrolyzes timely to avoid saturated adsorption, and provides pH‐responsive control over ON‐OFF motion. The self‐propulsion lifetime is extended by 50‐fold with DABS and motion control is achieved. The mechanism is revealed with coupled interface chemistry involving two competitive processes of interfacial adsorption and hydrolysis of DABS based on both experiments and simulation. The concept of ‘supra‐amphiphile fuel and switch’ provides an active solution to prolong and control Marangoni self‐propulsive devices for the advance of intelligent material systems.
A Cytochrome P450 Enzyme Catalyses Oxetane Ring Formation in Paclitaxel Biosynthesis
Authors: Li Changkang , Yin Xinxin , Wang Shuai , Sui Songyang , Liu Jimei , Sun Xincheng , Di Jinming , Chen Ridao , Chen Dawei , Han Yaotian , Xie Kebo , Dai Jungui
Published: May 2024

Oxetane synthase (TmCYP1), a novel cytochrome P450 enzyme from Taxus×media cell cultures, has been functionally characterized to efficiently catalyse the formation of the oxetane ring in tetracyclic taxoids. Transient expression of TmCYP1 in Nicotiana benthamiana using 2α,5α,7β,9α,10β,13α‐hexaacetoxytaxa‐4(20),11(12)‐diene (1) as a substrate led to the production of a major oxetane derivative, 1β‐dehydroxybaccatin IV (1 a), and a minor 4β,20‐epoxide derivative, baccatin I (1 b). However, feeding the substrate decinnamoyltaxinine J (2), a 5‐deacetylated derivative of 1, yielded only 5α‐deacetylbaccatin I (2 b), a 4β,20‐epoxide. A possible reaction mechanism was proposed on the basis of substrate‐feeding, 2H and 18O isotope labelling experiments, and density functional theory calculations. This reaction could be an intramolecular oxidation‐acetoxyl rearrangement and the construction of the oxetane ring may occur through a concerted process; however, the 4β,20‐epoxide might be a shunt product. In this process, the C5‐O‐acetyl group in substrate is crucial for the oxetane ring formation but not for the 4(20)‐epoxy ring formation by TmCYP1. These findings provide a better understanding of the enzymatic formation of the oxetane ring in paclitaxel biosynthesis.
Isothiourea‐Catalysed Acylative Dynamic Kinetic Resolution of Tetra‐substituted Morpholinone and Benzoxazinone Lactols
Authors: Zhu Haoxiang , Manchado Alejandro , Omar Farah Abdikani , McKay Aidan P. , Cordes David B. , Cheong Paul Ha‐Yeon , Kasten Kevin , Smith Andrew D.
Published: May 2024

The development of methods to allow the selective acylative dynamic kinetic resolution (DKR) of tetra‐substituted lactols is a recognised synthetic challenge. In this manuscript, a highly enantioselective isothiourea‐catalysed acylative DKR of tetra‐substituted morpholinone and benzoxazinone‐derived lactols is reported. The scope and limitations of this methodology have been developed, with high enantioselectivity and good to excellent yields (up to 89 %, 99 : 1 er) observed across a broad range of substrate derivatives incorporating substitution at N(4) and C(2), di‐ and spirocyclic substitution at C(5) and C(6), as well as benzannulation (>35 examples in total). The DKR process is amenable to scale‐up on a 1 g laboratory scale. The factors leading to high selectivity in this DKR process have been probed through computation, with an N−C=O⋅⋅⋅isothiouronium interaction identified as key to producing ester products in highly enantioenriched form.
Recent Progress in Using Covalent Organic Frameworks to Stabilize Metal Anodes for Highly‐Efficient Rechargeable Batteries
Authors: Sun Jianlu , Kang Fangyuan , Yan Dongbo , Ding Tangjing , Wang Yulong , Zhou Xiaosi , Zhang Qichun
Published: May 2024

Alkali metals (e.g. Li, Na, and K) and multivalent metals (e.g. Zn, Mg, Ca, and Al) have become star anodes for developing high‐energy‐density rechargeable batteries due to their high theoretical capacity and excellent conductivity. However, the inevitable dendrites and unstable interfaces of metal anodes pose challenges to the safety and stability of batteries. To address these issues, covalent organic frameworks (COFs), as emerging materials, have been widely investigated due to their regular porous structure, flexible molecular design, and high specific surface area. In this minireview, we summarize the research progress of COFs in stabilizing metal anodes. First, we present the research origins of metal anodes and delve into their advantages and challenges as anodes based on the physical/chemical properties of alkali and multivalent metals. Then, special attention has been paid to the application of COFs in the host design of metal anodes, artificial solid electrolyte interfaces, electrolyte additives, solid‐state electrolytes, and separator modifications. Finally, a new perspective is provided for the research of metal anodes from the molecular design, pore modulation, and synthesis of COFs.
Properties of polylactic acid/gelatin/acetyl tributyl citrate blend materials
Authors: He Ruhui , Tao Yao , Luo Zhu , Yang Le , Liao Jingshun , Xu Mengxia , Yang Shenglong , Lin Yechun
Published: May 2024

The inherent brittleness and high cost of polylactic acid (PLA) hinder its further application. Developing low‐cost, flexible, and biodegradable gelatin (GEL)‐modified PLA is a way to broaden the application prospects of PLA applications. Acetyl tributyl citrate (ATBC) was added to overcome the process difficulty of PLA/GEL melt blending and toughening the blends. Maleic anhydride (MAH) grafted PLA (PLA‐g‐MAH) was prepared to improve the compatibility of the PLA/GEL/ATBC. Because of the interface, physical and chemical interaction induced by PLA‐g‐MAH, the compatibility among PLA, GEL, and ATBC was enhanced, which significantly improved the plasticizing efficiency of ATBC. Results showed that the elongation at break of the blends can be improved by 491%, 68 times higher than that of pristine PLA. Moreover, the modified blends did not break under the conditions of notch impact, which exhibited excellent toughness. The blends possessed a high degradation rate owing to the hydrophilic gelatin and PLA‐g‐MAH, significantly accelerated the degradation process of PLA. The prepared PLA/GEL/ATBC/PLA‐g‐MAH biomass blended plastics exhibited good comprehensive performance, with true sustainability and environmental friendliness.
Combination of NIR and UV‐LEDs enables physical and chemical drying of aqueous coating dispersions as new green technology
Authors: Appelhoff Lukas , Hornemann Nicolas , Schmidt Jochen , Krautz Anita , Strehmel Bernd
Published: May 2024

Heptamethine based cyanines, namely 1,3,‐trimethyl‐2‐(2‐2[2‐phenylsulfanyl‐3‐[2‐(1,3,3‐trimethyl‐1,3,3‐trithyl‐1,3‐dihydro‐indol‐2‐ylidene)‐ethylidene]cyclohex‐1‐enyl]vinyl)‐3H‐indolium chloride (S1) and 2‐[2‐(2‐chloro‐[2‐[1,1‐dimethyl‐7‐sulfo‐3‐(4‐sulfobutyl)‐1,3‐dihydro‐benzo[e]indol‐2‐ylidene]‐ethylidene]cyclopent‐1‐enyl]vinyl]‐1,1‐dimethyl‐7‐sulfo‐3‐(4‐sulfobutyl)‐1Hbenzo[e]indolium hydroxide, inner salt, triethylammonium salt (S2), efficiently result in physical drying of an aqueous dispersion comprising a polyurethane binder. S2 possesses a water solubility of 40 g/L. A high‐intensity near‐infrared‐LED emitting at 820 nm with an intensity of 1 W/cm2 served as light source. The cyanine converted the light absorbed into heat by internal conversion needing less drying time compared to conventional drying. Water content after film formation showed less then 1%. In the second step, ultraviolet (UV) exposure with a LED emitting at 395 nm resulted in formation of semi‐interpenetrating polymer networks by crosslinking of the multifunctional (meth)acrylate operating as reactive diluent. Ethyl phenyl(2,4,6‐trimethylbenzoyl)phosphinate‐L served as effective UV‐photoinitiator. Furthermore, the UV‐exposure together with Norrish Type I and Type II photoinitator systems results in a very efficient bleaching of the green physical dried film. This contribution shows for the first time a new photonic hybrid technique describing successful replacement of an oven‐based process by a photonic based step that generates heat needed for drying.
Assessing the spatial knowledge gaps of Odonata diversity and conservation in the South American Pampa
Authors: Pires Mateus , Martins Fernanda , del Palacio Alejandro , Muzón Javier , Vareira Luisa , Juen Leandro , Périco Eduardo
Published: May 2024

Anthropogenic activities highly threaten neotropical freshwater habitats. Aquatic insects are sensitive to environmental alterations and thus considered under great risk due to such pressures. However, large‐scale gaps regarding the knowledge of the distribution of aquatic insect species remain in the Neotropics, particularly in the South American temperate grasslands (Pampas), hindering the knowledge of hotspots of aquatic insect diversity and the prioritization of conservation areas destined to protect their populations.

Here, we review the current knowledge regarding the geographical distribution of Odonata species and use ecological niche models to estimate the areas with the highest potential richness of Odonata species in the Pampas. We also calculate a sampling effort index and interpolate it with maps of protected areas to identify the spatial knowledge gaps regarding their conservation in the region

Our compilation of Odonata species records retrieved 237 species for the Pampa. However, Odonata species were recorded in less than 2% of the Pampa. Our findings indicated a higher potential diversity of Odonata in northeastern Argentina, southern Uruguay and southern Brazil. Interpolations of sampling effort index and protected areas showed that 95% of the area potentially rich in Odonata species fall outside protected areas.

Our study highlights the shortfall regarding the knowledge of the distribution of Odonata diversity in non‐forest landscapes of the Neotropical region. It also shows that protected areas of the Pampa cover a minor area of the Odonata species range in the region.
Biochemical characterization of Bombyx mori Dicer‐2 that dices double‐stranded RNAs into 20‐nt small RNA
Authors: Tabara Midori , Harada Mayuko , Kuriyama Kazunori , Sakamoto Takuma , Takeda Atsushi , Fukuhara Toshiyuki , Tabunoki Hiroko
Published: May 2024

We detected enzymatic activity that generates 20‐nucleotide (nt) RNA from double‐stranded RNAs (dsRNAs) in crude extracts prepared from various silkworm (Bombyx mori) organs. The result using knocked‐down cultured cells indicated that this dicing activity originated from B. mori Dicer‐2 (BmDcr2). Biochemical analyses revealed that BmDcr2 preferentially cleaves 5′‐phosphorylated dsRNAs at the 20‐nt site—counted from the 5′‐phosphorylated end—and required ATP and magnesium ions for the dicing reaction. This is the first report of the biochemical characterization of Dicer‐2 in lepidopteran insects. This enzymatic property of BmDcr2 in vitro is consistent with the in vivo small interfering RNA profile in virus‐infected silkworm cells.
GOAT rs10096097 and CREB1 rs6740584 single nucleotide polymorphisms are associated with type 2 diabetes mellitus in Egyptians
Authors: Shahin Nancy N. , Shaker Olfat G. , Mahmoud Mohamed O.
Published: May 2024

Diabetes mellitus (DM) is a chronic disorder that affects nearly half a billion people around the world and causes millions of deaths annually. Treatment of diabetes or related complications represents an economic burden not only for developing countries but also for the developed ones. Hence, new efficient therapeutic and preventive strategies and screening tools are necessary. The current work aimed to assess the potential association of single nucleotide polymorphisms (SNPs) in ghrelin O‐acyltransferase (GOAT) rs10096097, cyclic adenosine monophosphate (cAMP) response element binding protein (CREB) rs6740584, and v‐maf musculoaponeurotic fibrosarcoma oncogene homolog A (MafA) rs62521874 genes with type 2 DM susceptibility in Egyptians. A total of 96 patients with type 2 DM along with 72 healthy individuals participated in this study. Genotyping was executed via real‐time polymerase chain reaction (PCR), and the serum protein levels of GOAT, CREB, and MafA were measured by enzyme‐linked immunosorbent assay (ELISA). Genotyping revealed a significant association of GOAT rs10096097 and CREB1 rs6740584 SNPs with type 2 diabetes risk, with significantly higher GOAT rs10096097 G allele and CREB1 rs6740584 T allele frequencies in diabetic patients than in controls. However, insignificant association was identified between the MafA rs62521874 SNP and diabetes in the examined sample of the Egyptian residents. Serum GOAT, CREB1, and MafA protein levels did not vary significantly between diabetic and control individuals. Yet, significant variation in serum GOAT and CREB1 levels was detected between CREB1 rs6740584 genotypes within the diabetic group, with CT and TT genotype carriers showing higher levels than AA genotype patients. GOAT rs10096097 and CREB1 rs6740584, but not MafA rs62521874, SNPs are associated with type 2 diabetes risk in the studied Egyptians.
In‐vitro and in‐silico investigations of SLC‐0111 hydrazinyl analogs as human carbonic anhydrase I, II, IX, and XII inhibitors
Authors: Sharma Vikas , Vats Lalit , Giovannuzzi Simone , Mohan Brij , Supuran Claudiu T. , Sharma Pawan K.
Published: May 2024

Two novel series of hydrazinyl‐based benzenesulfonamides 9a–j and 10a–j were designed and synthesized using SLC‐0111 as the lead molecule. The newly synthesized compounds were evaluated for their inhibitory activity against four different human carbonic anhydrase (hCA) isoforms I, II, IX, and XII. Both the series reported here were practically inactive against the off‐target isozyme hCA I. Notably, derivative 10a exhibited superior potency (Ki of 10.2 nM) than acetazolamide (AAZ) against the cytosolic isoform hCA II. The hCA IX and XII isoforms implicated in tumor progression were effectively inhibited with Kis in the low nanomolar range of 20.5–176.6 nM and 6.0–127.5 nM, respectively. Compound 9g emerged as the most potent and selective hCA IX and XII inhibitor with Ki of 20.5 nM and SI of 200.1, and Ki of 6.0 nM and SI of 683.7, respectively, over hCA I. Furthermore, six compounds (9a, 9h, 10a, 10g, 10i, and 10j) exhibited significant inhibition toward hCA IX (Kis = 27.0, 41.1, 27.4, 25.9, 40.7, and 30.8 nM) relative to AAZ and SLC‐0111 (Kis = 25.0 and 45.0 nM, respectively). These findings underscore the potential of these derivatives as potent and selective inhibitors of hCA IX and XII over the off‐target hCA I and II.
A hit expansion of 3‐benzamidopyrazine‐2‐carboxamide: Toward inhibitors of prolyl‐tRNA synthetase with antimycobacterial activity
Authors: Pallabothula Vinod Sukanth Kumar , Abdalrahman Nechirwan Taimur , Mori Matteo , Fekri Amir Hossein , Janďourek Ondřej , Konečná Klára , Paterová Pavla , Novák Martin , Dudášová‐Hatoková Paulína , Štěrbová‐Kovaříková Petra , Castellano Carlo , Meneghetti Fiorella , Villa Stefania , Kuneš Jiří , Juhás Martin , Zitko Jan
Published: May 2024

This study presents an exploration of the chemical space around derivatives of 3‐benzamidopyrazine‐2‐carboxamides, previously identified as potent antimycobacterial compounds with predicted binding to mycobacterial prolyl‐transfer RNA synthetase. New urea derivatives (Series‐1) were generally inactive, probably due to their preference for cis‐trans conformation (confirmed by density functional theory calculations and experimentally by nuclear overhauser effect spectroscopy NMR). Series‐2 (3‐benzamidopyrazine‐2‐carboxamides with disubstituted benzene ring) demonstrated that substituents larger than fluorine are not tolerated in the ortho position of the benzene ring. This series brought two new compounds (21: R = 2‐F, 4‐Cl and 22: R = 2‐F, 4‐Br) with in vitro activity against Mycobacterium tuberculosis H37Rv as well as multidrug‐resistant clinical isolates, with minimum inhibitory concentration ranging from 6.25 to 25 μg/mL. The lactone‐type derivatives 4H‐pyrazino[2,3‐d][1,3]oxazin‐4‐ones (Series‐3) were inactive, but solvent stability studies of compound 29 indicated that they might be developed to usable lactone prodrugs of inhibitors of mycobacterial aspartate decarboxylase (PanD).
Children with Hirschsprung's disease have high morbidity in the first 5 years of life
Authors: Damkjær Mads , Tan Joachim , Morris Joan K. , Loane Maria , Given Joanne , Cavero‐Carbonell Clara , Gissler Mika , Neville Amanda J. , Pierini Anna , Rissmann Anke , Tucker David , Garne Ester
Published: May 2024

Background

Hirschsprung's disease is a rare congenital anomaly of the colon with absence of the ganglionic nerve cells. The treatment of the anomaly is surgical.

Methods

This population‐based data‐linkage cohort study was part of the EUROlinkCAT project and investigated mortality and morbidity for the first 5 years of life for European children diagnosed with Hirschsprung's disease. Nine population‐based registries in five countries from the European surveillance of congenital anomalies network (EUROCAT) participated. Data on children born 1995–2014 and diagnosed with Hirschsprung's disease were linked to hospital databases. All analyses were adjusted for region and length of follow‐up, which differed by registry.

Results

The study included 680 children with Hirschsprung's disease. One‐year survival was 97.7% (95% CI: 96.4–98.7). Overall, 85% (82–87) had a code for a specified intestinal surgery within the first year increasing to 92% (90–94) before age 5 years. The median age at the first intestinal surgery up to 5 years was 28 days (11–46) and the median number of intestinal surgical procedures was 3.5 (3.1–3.9). Thirty days mortality after neonatal surgery (within 28 days after birth) was 0.9% (0.2–2.5) for children with a code for intestinal surgery within the first 28 days after birth and there were no deaths for children with a code for stoma surgery in the neonatal period.

Conclusion

Children with Hirschsprung's disease have a high morbidity in the first 5 years of life requiring more surgical procedures in addition to the initial surgery. Mortality after neonatal surgery is low.
Orange luminescence of α‐Al2O3 related to clusters consisting of F centers and divalent cations
Authors: Vigier Maxence , Massuyeau Florian , Fritsch Emmanuel
Published: May 2024

The orange luminescence of α‐Al2O3 under UV excitation is characterized by a 2.07‐eV orange broadband emission that has not yet been elucidated. This emission is present in natural and synthetic crystals and powders, as well as in Be‐treated samples. All orange‐luminescent materials have low Fe concentration (mostly <1000 ppm) with traces of divalent cations, mostly Mg, or Be in Be‐diffused material (dozens of ppm). Mg2+, Mn2+, and Be2+ cations substitute for trivalent Al. To accommodate the charge deficit, several defects are created, including oxygen vacancies also called F centers. Indeed, our excitation spectra revealed the presence of several different F centers (F, F+, and clustered F2, F2+, F22+) in those samples. However, the thermal stability and the measured luminescence lifetimes do not match with previously reported characteristics of isolated F centers. Based on our experiments, we suggest that a complex aggregate of two F centers (F22+) trapped at divalent cations is a major cause of this uncommon microsecond lifetime emission, even if a variety of other defects, including Cr3+, V3+, or interstitial Al3+, are present.
Association of patient socioeconomic status with outcomes after palliative treatment for disseminated cancer
Authors: Maduka Richard C. , Canavan Maureen E. , Walters Samantha L. , Ermer Theresa , Zhan Peter L. , Kaminski Michael F. , Li Andrew X. , Pichert Matthew D. , Salazar Michelle C. , Prsic Elizabeth H. , Boffa Daniel J.
Published: May 2024

Background

Palliative treatment has been associated with improved quality of life and survival for a wide variety of metastatic cancers. However, it is unclear whether the benefits of palliative treatment are uniformly experienced across the US cancer population. We evaluated patterns and outcomes of palliative treatment based on socioeconomic, sociodemographic and treating facility characteristics.

Methods

Patients diagnosed between 2008 and 2019 with Stage IV primary cancer of nine organ sites were analyzed in the National Cancer Database. The association between identified variables, and outcomes concerning the administration of palliative treatment were analyzed with multivariable logistic regression and Cox proportional hazard models.

Results

Overall 238,995 (23.6%) of Stage IV patients received palliative treatment, which increased over time for all cancers (from 20.7% in 2008 to 25.6% in 2019). Palliative treatment utilization differed significantly by region (West less than Northeast, OR: 0.55 [0.54–0.56], p < 0.001) and insurance payer status (uninsured greater than private insurance, OR: 1.35 [1.32–1.39], p < 0.001). Black race and Hispanic ethnicity were also associated with lower rates of palliative treatment compared to White and non‐Hispanics respectively (OR for Blacks: 0.91 [0.90–0.93], p < 0.001 and OR for Hispanics: 0.79 [0.77–0.81] p < 0.001).

Conclusions

There are important differences in the utilization of palliative treatment across different populations in the United States. A better understanding of variability in palliative treatment use and outcomes may identify opportunities to improve informed decision making and optimize quality of care at the end‐of‐life.
Xylarkarynone A and B: Two Bioactive Eremophilane Sesquiterpenes from Xylaria sp. HHY‐2
Authors: Zhu Li , Zhang Sheng‐Qi , Wang Yi‐Nong , Wang Jia‐Xin , Wang Cheng‐Yao , Cai Lan , Wen Zhao‐Fei , Deng Liang , Cai Le
Published: May 2024

A new compound xylarkarynone A (1), a first reported natural product compound xylarkarynone B (2) and eight known compounds (3‐10) were isolated from Xylaria sp. HHY‐2. Their structures were elucidated by spectroscopic methods, DP4+ probability analyses and electronic circular dichroism (ECD) calculations. The bioactivities of isolated compounds were assayed. Compound 1 exhibited obvious activity against A549 cells with an IC50 value of 6.12±0.28 μM. Additionally, compound 1 showed moderate antifungal activities against Plectosphaerella cucumerina and Aspergillus niger with minimum inhibitory concentrations (MICs) of both 16 μg/mL, which was at the same grade with positive control nystatin. Most compounds exhibited varying degrees of inhibitory activity against P. cucumerina, indicating that Xylaria sp. has potential as inhibitors against P. cucumerina.
The Development and Opportunities of Predictive Biotechnology
Authors: Nestl Bettina M. , Nebel Bernd A. , Resch Verena , Schürmann Martin , Tischler Dirk
Published: May 2024

Recent advances in bioeconomy allow a holistic view of existing and new process chains and enable novel production routines continuously advanced by academia and industry. All this progress benefits from a growing number of prediction tools that have found their way into the field. For example, automated genome annotations, tools for building model structures of proteins, and structural protein prediction methods such as AlphaFold2TM or RoseTTAFold have gained popularity in recent years. Recently, it has become apparent that more and more AI‐based tools are being developed and used for biocatalysis and biotechnology. This is an excellent opportunity for academia and industry to accelerate advancements in the field further. Biotechnology, as a rapidly growing interdisciplinary field, stands to benefit greatly from these developments.
Reprogramming Filamentous fd Viruses to Capture Copper Ions
Authors: Korkmaz Nuriye , Usman Muhammad , Kim Minyoung
Published: May 2024

C‐terminal truncated variants (A, VA, NVA, ANVA, FANVA and GFANVA) of our recently identified Cu(II) specific peptide “HGFANVA” were displayed on filamentous fd phages. Wild type fd‐tet and engineered virus variants were treated with 100 mM Cu(II) solution at a final phage concentration of 1011 vir/ml and 1012 vir/ml. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) imaging before Cu(II) exposure showed ≈6–8 nm thick filamentous virus layer formation. Cu(II) treatment resulted in aggregated bundle‐like assemblies with mineral deposition. HGFANVA phage formed aggregates with an excessive mineral coverage. As the virus concentration was 10‐fold decreased, nanowire‐like assemblies were observed for shorter peptide variants A, NVA and ANVA. Wild type fd phages did not show any mineral formation. Energy dispersive X‐ray spectroscopy (EDX) analyses revealed the presence of C and N peaks on phage organic material. Cu peak was only detected for engineered viruses. Metal ion binding of viruses was next investigated by enzyme‐linked immunosorbent assay (ELISA) analyses. Engineered viruses were able to bind Cu(II) forming mineralized intertwined structures although no His (H) unit was displayed. Such genetically reprogrammed virus based biological materials can be further applied for bioremediation studies to achieve a circular economy.
Inhibition of RNA Phosphodiester Backbone Cleavage in the Presence of Organic Cations of Different Sizes
Authors: Yoshioka Senri , Doi Asuka , Nakano Shu‐ichi
Published: May 2024

Living cells contain various types of organic cations that may interact with nucleic acids. In order to understand the nucleic acid–binding properties of organic cations of different sizes, we investigated the ability of simple organic cations to inhibit the RNA phosphodiester bond cleavage promoted by Mg2+, Pb2+, and RNA‐cleaving serum proteins. Kinetic analysis using chimeric DNA–RNA oligonucleotides showed that the cleavage at ribonucleotide sites was inhibited in the presence of monovalent cations comprising alkyl chains or benzene rings. The comparison of the cleavage rates in the presence of quaternary ammonium and phosphonium ions indicated that the steric hindrance effect of organic cations on their binding to the RNA backbone is significant when the cation size is larger than the phosphate–phosphate distance of a single‐stranded nucleic acid. The cleavage inhibition was also observed for ribonucleotides located in long loops but not in short loops of oligonucleotide structures, indicating less efficient binding of bulky cations to structurally constrained regions. These results reveal the unique nucleic acid–binding properties of bulky cations distinct from those of metal ions.