bluuebunny/crossref_metadata_2025 huggingface dataset:
Highly Conductive MXene/PEDOT:PSS‐Integrated Poly(N‐Isopropylacrylamide) Hydrogels for Bioinspired Somatosensory Soft Actuators
Authors: Xue Pan , Valenzuela Cristian , Ma Shaoshuai , Zhang Xuan , Ma Jiazhe , Chen Yuanhao , Xu Xinhua , Wang Ling
Published: March 2023

Sophisticated sensing and actuation capabilities of many living organisms in nature have inspired scientists to develop biomimetic somatosensory soft robots. Herein, the design and fabrication of homogeneous and highly conductive hydrogels for bioinspired somatosensory soft actuators are reported. The conductive hydrogels are synthesized by in situ copolymerization of conductive surface‐functionalized MXene/Poly(3,4‐ethylenedioxythiophene)/poly(styrenesulfonate) ink with thermoresponsive poly(N‐isopropylacrylamide) hydrogels. The resulting hydrogels are found to exhibit high conductivity (11.76 S m−1), strain sensitivity (GF of 9.93), broad working strain range (≈560% strain), and high stability after over 300 loading–unloading cycles at 100% strain. Importantly, shape‐programmable somatosensory hydrogel actuators with rapid response, light‐driven remote control, and self‐sensing capability are developed by chemically integrating the conductive hydrogels with a structurally colored polymer. As the proof‐of‐concept illustration, structurally colored hydrogel actuators are applied for devising light‐driven programmable shape‐morphing of an artificial octopus, an artificial fish, and a soft gripper that can simultaneously monitor their own motions via real‐time resistance variation. This work is expected to offer new insights into the design of advanced somatosensory materials with self‐sensing and actuation capabilities, and pave an avenue for the development of soft‐matter‐based self‐regulatory intelligence via built‐in feedback control that is of paramount significance for intelligent soft robotics and automated machines.
When Polymorphism in Metal–Organic Frameworks Enables Water Sorption Profile Tunability for Enhancing Heat Allocation and Water Harvesting Performance
Authors: Matemb Ma Ntep Tobie J. , Wahiduzzaman Mohammad , Laurenz Eric , Cornu Ieuan , Mouchaham Georges , Dovgaliuk Iurii , Nandi Shyamapada , Knop Klaus , Jansen Christian , Nouar Farid , Florian Pierre , Füldner Gerrit , Maurin Guillaume , Janiak Christoph , Serre Christian
Published: March 2023

The development of thermally driven water‐sorption‐based technologies relies on high‐performing water vapor adsorbents. Here, polymorphism in Al–metal–organic frameworks is disclosed as a new strategy to tune the hydrophilicity of MOFs. This involves the formation of MOFs built from chains of either trans‐ or cis‐ µ‐OH‐connected corner‐sharing AlO4(OH)2 octahedra. Specifically, [Al(OH)(muc)] or MIP‐211, is made of trans, trans‐muconate linkers, and cis‐µ‐OH‐connected corner‐sharing AlO4(OH)2 octahedra giving a 3D network with sinusoidal channels. The polymorph MIL‐53‐muc has a tiny change in the chain structure that results in a shift of the step position of the water isotherm from P/P0 ≈ 0.5 in MIL‐53‐muc, to P/P0 ≈ 0.3 in MIP‐211. Solid‐state NMR and Grand Canonical Monte Carlo reveal that the adsorption occurs initially between two hydroxyl groups of the chains, favored by the cis‐positioning in MIP‐211, resulting in a more hydrophilic behavior. Finally, theoretical evaluations show that MIP‐211 would allow achieving a coefficient of performance for cooling (COPc) of 0.63 with an ultralow driving temperature of 60 °C, outperforming benchmark sorbents for small temperature lifts. Combined with its high stability, easy regeneration, huge water uptake capacity, green synthesis, MIP‐211 is among the best adsorbents for adsorption‐driven air conditioning and water harvesting from the air.
Determining the Electronic Structure and Thermoelectric Properties of MoS2/MoSe2 Type‐I Heterojunction by DFT and the Landauer Approach
Authors: López‐Galán Oscar A. , Perez Israel , Nogan John , Ramos Manuel
Published: March 2023

The electronic structure and thermoelectric properties of MoX2 (X = S, Se) Van der Waals heterojunctions are reported, with the intention of motivating the design of electronic devices using such materials. Calculations indicate the proposed heterojunctions are thermodynamically stable and present a band gap reduction from 1.8 eV to 0.8 eV. The latter effect is highly related to interactions between metallic d‐character orbitals and chalcogen p‐character orbitals. The theoretical approach allows to predict a transition from semiconducting to semi‐metallic behavior. The band alignment indicates a type‐I heterojunction and band offsets of 0.2 eV. Transport properties show clear n‐type nature and a high Seebeck coefficient at 300 K, along with conductivity values (σ/τ) in the order of 1020. Lastly, using the Landauer approach and ballistic transport, the proposed heterojunctions can be modeled as a channel material for a typical one‐gate transistor configuration predicting subthreshold values of ≈60 mV dec−1 and field–effect mobilities of ≈160 cm−2 V−1 s−1.
Nonlinear Chiral Metasurfaces Based on the Optical Kerr Effect
Authors: Kang Lei , Wu Yuhao , Werner Douglas H.
Published: March 2023

Chiral nanostructures have immense potential for complete polarization control of light. Given the intrinsic 3D structure of circularly polarized light, nanoarchitectures with structural chirality in 3D space are usually required to achieve “full” chiroptical response. On the other hand, due to the lack of available active materials at optical wavelengths, examples of chiral photonic devices that can be tuned in an active manner remain rare. Here, based on the large Kerr nonlinearities of silicon, the nonlinear chiroptical response from a planar Si metasurface supporting high quality (Q)‐factor guided mode resonances (GMRs) at near‐infrared wavelengths, are numerically demonstrated. In the linear regime, the optical anisotropy of the C2‐symmetric structure associated with the observed GMRs leads to a pair of chiral resonance modes, enabling pronounced cross‐polarization transmission circular dichroism and a strong handedness‐dependent field enhancement effect. Owing to the nonlinear Kerr effect, such Si metasurfaces are seen to exhibit prominent chiral‐selective optical nonlinearity. Importantly, a pronounced co‐polarization transmission circular dichroism is observed, suggesting that the circularly polarized waves in the nonlinear regime possess asymmetric Jones matrices. Dielectric chiral metasurfaces with Kerr nonlinearities can be utilized to facilitate polarization‐state modulators with simple planar structures.
Ultra‐Broadband, Tunable, and Transparent Microwave Meta‐Absorber Using ITO and Water Substrate
Authors: Ge Jiahao , Zhang Yaqiang , Li Haonan , Dong Hongxing , Zhang Long
Published: March 2023

Integrating broadband absorption, dynamic tunability, and high optical transparency into a single microwave absorber remains a crucial challenge. Here, an ultra‐broadband, tunable, and transparent microwave meta‐absorber comprising double‐layer indium tin oxide resonant patterns and a water‐based substrate is theoretically presented and experimentally demonstrated. Experimental measurements indicate that the designed meta‐absorber can achieve over 90% absorption in an ultra‐broadband frequency range of 12.49–98.21 GHz with a relative bandwidth of 154.9%, while the average optical transmittance is 60.49%. In addition, a multiple reflections interference model is employed to elucidate the physical mechanisms of the ultra‐broadband absorber. Furthermore, its absorption performance can be reversibly switched between ultra‐broadband and dual‐broadband by altering the water substrate thickness. These peculiar properties make the proposed meta‐absorber more favorable for practical applications in modern stealth materials and optical windows.
Angular Superoscillatory Metalens Empowers Single‐Shot Measurement of OAM Modes with Finer Intervals
Authors: Zhang Runzhe , Guo Yinghui , Li Xiaoyin , He Qiong , Zhang Qi , Zhang Fei , Xu Mingfeng , Wang Maoyu , Pu Mingbo , Luo Xiangang
Published: March 2023

Distinct from conventional optical lenses suffering from the diffraction limit, the superoscillatory lens offers an alternative approach to realize far‐field sub‐diffraction focusing and find significant applications in both microscopy and telescopy. During the past few years, planar micro/nanostructures are unitized to precisely manipulate the optical fields through a standard lens to realize a superoscillatory field along the radial direction of the pupil. Here, an angular superoscillatory metalens (ASOM) is demonstrated by combining the superoscillatory phase and angular metalens phase in a single metasurface. To the best of the authors’ knowledge, this is the first work that focuses on the angular superoscillatory phenomenon. As a proof‐of‐concept application demo, this study shows the ASOM can map the received orbital angular modes (OAMs) into focusing patterns at the focal plane with different azimuth angles. Therefore, the OAM spectrum incorporating multiple modes can be determined with a single‐shot measurement according to the precalibrated mapping relationship. This study shows that the OAM resolution is scaled up about 3.2 times compared with a normal angular metalens, thanks to the shrinkage of the focal patterns. This approach may push the development of integrated and high‐dimensional optical and quantum systems.
Visible‐Light‐Driven Multicomponent Radical Cascade Versatile Alkylation of Quinoxalinones Enabled by Electron Donor Acceptor Complex in Water
Authors: Sun Bin , Tang Xiao‐Li , Zhuang Xiaohui , Ling Lan , Huang Panyi , Wang Jiayang , Jin Can
Published: March 2023

An operationally simple aqueous phase three‐component photochemical strategy for the alkylation of quinoxalin‐2(1H)‐ones with diethyl α‐bromomalonate and unactivated alkenes in the absence of both photoredox catalysts and additive has been developed. This reaction is driven by the photochemical activity of electron donor‐acceptor (EDA) complexes formed by quinoxalin‐2(1H)‐ones and diethyl α‐bromomalonate. Irradiation with visible light triggered single‐electron transfer (SET) from the quinoxalin‐2(1H)‐ones to the diethyl α‐bromomalonate, inducing the formation of the corresponding alkyl radical and the subsequent radical tandem reaction. It provides an efficient way to construct alkylated quinoxalinones from simple small molecules.

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Chemical Sensors Based on Graphene and 2D Graphene Analogs
Authors: Lee Chung Won , Eom Tae Hoon , Cho Sung Hwan , Jang Ho Won
Published: March 2023

The outbreak of the global pandemic has aroused significant attention from the public for healthy living environments. From this point of view, chemical sensors are crucial since these devices or actuators have diverse applications, such as environmental monitoring, food safety, industry, and healthcare. The development of chemical sensors may substitute human senses and precisely identify unspecified substances or discriminate materials accurately. For the implementation of chemical sensors utilized in daily life, there are requirements such as portability, low cost, low power consumption, high selectivity, and sensitivity. The most adequate materials are 2D materials that exactly agree with the described conditions. 2D materials have been studied for sensor applications owing to their unique material characteristics specialized for detecting particular substances. High surface to volume ratio or numerous reaction sites are representative physical properties of 2D materials. Furthermore, high carrier mobility is a typical feature of these substances appropriate for manufacturing advanced chemical sensors. Herein, the history and recent advances of 2D material‐based chemical sensors along with a description of perspectives and future challenges are introduced. This review provides a guideline for preparing chemical sensors based on 2D materials as next‐generation sensing devices.
Ionic Liquids: Momentous Tools in Transdermal Delivery of Biomacromolecules
Authors: Li Lisha , Tai Zongguang , Wu Xiying , Wu Junchao , Zhang Tingrui , Chen Zhongjian , Zhu Quangang
Published: March 2023

Transdermal drug delivery is a promising strategy characterized by minor fluctuations in blood concentrations, few adverse effects, convenience, and excellent patient compliance, especially for biomacromolecules. Conversely, traditional delivery methods are limited by their poor penetration abilities and complex preparation and application techniques. However, some inherent properties of biomacromolecules, such as large sizes, complex structure, and poor stability, can affect their ability to overcome skin barriers and reach deeper layers. Ionic liquids (ILs) are organic salts composed of asymmetric cations and anions in liquid form below 100 °C. ILs provide excellent protection for biomacromolecules and can facilitate their passage through the stratum corneum to cells for therapeutic effects. Therefore, they represent one of the most promising approaches to promoting transdermal penetration. Here, the barriers to effective transdermal delivery, including skin properties and the stability and biocompatibility of IL‐based biomacromolecule formulations, are highlighted and the current status of IL‐based biomacromolecule formulations are focused on, the tremendous advantages of using ILs based on current challenges in transdermal drug delivery are discussed, and light is shed on several ILs frequently used in the delivery of biomacromolecules.
Band Structure Engineering of MXenes for Low‐Loss Visible Epsilon‐Near‐Zero Properties by First‐Principles Calculation
Authors: Xu Bo , Xiang Hui , Wei Lai , Yin Jiang , Huang Yineng
Published: March 2023

Epsilon‐near‐zero (ENZ) photonics, which exhibit extraordinary capabilities in terms of controlling light–matter interactions, have been attracting increased interest in recent years. However, several challenges still lie ahead, such as large optical loss and the rarity of ENZ candidates, especially in the visible range. Here, by first‐principles calculations, this work proposes dozens of MXenes with promising plasmonic properties that could be potential ENZ candidates with very low loss in the visible range by band structure engineering. Because of the special electronic structures of these MXenes, they all possess quite large screened plasmonic frequencies: , but less than the interband transition onsets, which cause the ENZ properties in these MXenes to appear in the visible range with very low loss (ε2 less than 0.2) by eliminating the interband transition loss at the ENZ frequencies. Furthermore, it is also demonstrated that the ENZ properties in MXenes, including the ENZ frequency and loss, can be effectively tuned upon surface modifications, such as −Cl and −OH. These outstanding ENZ properties, including tunablity and low‐loss, make these MXenes great for potential applications in ENZ photonics, especially in the visible‐light range.
Ameliorating Properties of Perovskite and Perovskite–Silicon Tandem Solar Cells via Mesoporous Antireflection Coating Model
Authors: Wang Weijian , Yu Gang , Mao Lebao , Attique Sanam , Si Zhiwei , Yang Qing , Zhang Yongqiang , Huang Guiqiu , Zhang Haiyan , Yan Ximing , Wang Shengfu , Zhang Xiuhua
Published: March 2023

It is anticipated that perovskite solar cells (PSCs) will overtake other products in the market for next‐generation photovoltaics. The optical loss, however, continues to be a flaw that restricts the photocurrent (Jph) of PSCs. Mesoporous antireflection coatings (ARCs), both monolayer and multilayer, are designed using a combination of the finite element method and equivalent medium theory, and ARCs models are merged with PSCs. In the current work, mesoporous ARCs are made, the optical performance of the device is evaluated using optical modeling, and then the ARCs are integrated into solar cells. The simulation results show that the Jph of planar inverted PSCs can increase to 24.00 mA cm−2 when the front surface of PSCs adopts mesoporous ARC (via parameter optimization and sensible arrangement and combination). An increase of 0.98 mA cm−2 in Jph of PSCs is observed in comparison with flat ARC (23.02 mA cm−2). The strong light transmission and low reflection properties of the mesoporous ARCs are confirmed by the optimized solution. It is important to note that the first fusion of mesoporous and multilayer ARC offers a fresh approach to the development of perovskite and perovskite/silicon tandem solar cells with extremely high efficiency.
All‐in‐One Sensing System for Online Vibration Monitoring via IR Wireless Communication as Driven by High‐Power TENG
Authors: Wu Han , Wang Zihan , Zhu Boyu , Wang Hanqing , Lu Chengyue , Kang Meicun , Kang Shenglin , Ding Wenbo , Yang Lijun , Liao Ruijin , Wang Jiyu , Wang Zhong Lin
Published: March 2023

Abnormal vibration is a direct response to the mechanical defects of electrical equipment, and requires reliable vibration sensing for health condition evaluation in the associated system. The triboelectric nanogenerator (TENG) triggered by random vibration to generate electrical energy/signal while giving feedback on the vibration state, paving a promising way towards self‐powered sensors. Here, an all‐in‐one sensing system configured with a vibration sensor demonstrates instantaneous discharge boosted TENG and IR wireless communication for vibration state online monitoring. The sandwich‐structured TENG combined with mechanical switches can release the co‐accumulated charges from dual triboelectric layers to yield giant instantaneous output power of 616 W, which is 106 times higher than that of the continuous discharge. Moreover, an IR LED as a transmitter driven by the TENG can form an all‐in‐one vibration sensor enabling wireless communication, where the sensor can be further integrated with repeaters and phones to establish a wireless vibration online monitoring system for vibration state visualization. This work presents a novel idea to implement high‐power TENG with IR communication integration for in situ vibration online monitoring. Such a strategy is potentially available for distributed sensor construction towards abnormal signal monitoring that reflects the operating state of equipment.
Progress and Perspectives for Solar‐Driven Water Electrolysis to Produce Green Hydrogen
Authors: Zhao Hui , Yuan Zhong‐Yong
Published: March 2023

Solar‐driven water electrolysis has been considered to be a promising route to produce green hydrogen, because the conventional water electrolysis system is not completely renewable as it requires power from nonrenewable fossil fuel sources. This review emphasizes the strategies for solar‐driven water electrolysis, including the construction of photovoltaic (PV)‐water electrolyzer systems, PV‐rechargeable energy storage device‐water electrolyzer systems with solar energy as the sole input energy, and photoelectrochemical water splitting systems. The basic discussions of the above strategies for solar‐driven water electrolysis are first presented. Meanwhile, replacing the oxygen evolution reaction with the electrooxidation of organic compounds can effectively improve the efficiency of water splitting. Also, solar‐driven seawater electrolysis greatly broadens the practical applications due to the abundant reserves of seawater. Recent years have witnessed great development in the field of solar‐driven water electrolysis. The recent research development in the area is subsequently reviewed. Finally, perspectives on the existing challenges along with some opportunities for the further development of solar‐driven water electrolysis are provided.
Synthesis of 1,2,4‐Triazoles and 1,3,4‐Thiadiazinones by [3+2] and [3+3] Domino Annulation Reactions of Nitrile Imines with Succinimide and Thiazolidine‐2,4‐dione
Authors: Krishna Chilaka Sai , Prasad Chinthapally Krishna , Kumar Soda Anil , Kumar Chellu Ramesh , Kurva Srinivas , Babu Nanubolu Jagadeesh , Madabhushi Sridhar
Published: March 2023

Herein; we report protocols for the synthesis of 1,2,4‐triazoles and 1,3,4‐ thiadiazinones by [3+2] and [3+3] domino annulation reactions of nitrile imines with succinimide and thiazolidine‐2,4‐dione, respectively, using a base (1.5 equivalents) and alcohol as a solvent. In these reactions, notably, alcohol serves not only as a solvent but also as a reactant participating in the formation of ester functionality in products. These methodologies provide metal‐free and direct approaches to the synthesis of 1,2,4‐triazoles and 1,3,4‐thiadiazinones under mild conditions with a wide substrate scope and high yields.
Association between ambient temperature and chronic rhinosinusitis
Authors: Du Runming , Jiao Wangteng , Ma Junxiong , Zhou Qinfeng , Liang Zhi‐Sheng , Sun Shengzhi , Ahmed Omar G. , Rowan Nicholas R. , Pinto Jayant M. , Ramanathan Murugappan , Zhang Zhenyu
Published: March 2023

Background

Chronic exposure to particulate matter air pollution (PM2.5) is associated with chronic rhinosinusitis (CRS). Elevated ambient temperature may increase PM2.5 levels and thereby exacerbate sinonasal symptoms. This study investigates the association between high ambient temperature and the risk of CRS diagnosis.

Methods

Patients with CRS were diagnosed at Johns Hopkins hospitals from May to October 2013–2022, and controls were matched patients without CRS meanwhile. A total of 4752 patients (2376 cases and 2376 controls) were identified with a mean (SD) age of 51.8 (16.8) years. The effect of maximum ambient temperature on symptoms was estimated with a distributed lag nonlinear model (DLNM). Extreme heat was defined as 35.0°C (95th percentile of the maximum temperature distribution). Conditional logistic regression models estimated the association between extreme heat and the risk of CRS diagnosis.

Results

Exposure to extreme heat was associated with increased odds of exacerbation of CRS symptoms (odds ratio [OR] 1.11, 95% confidence interval [CI] 1.03–1.19). The cumulative effect of extreme heat during 0–21 lag days was significant (OR 2.37, 95% CI 1.60–3.50) compared with the minimum morbidity temperature (MMT) at 25.3°C. Associations were more pronounced among young and middle‐aged patients and patients with abnormal weight.

Conclusions

We found that short‐term exposure to high ambient temperature is associated with increased CRS diagnosis, suggesting a cascading effect of meteorological phenomena. These results highlight climate change's potentially deleterious health effects on upper airway diseases, which could have a significant public health impact.
Real‐World Outcomes of Endovascular Thrombectomy for Basilar Artery Occlusion: Results of the BArONIS Study
Authors: Dicpinigaitis Alis J. , Dick‐Godfrey Rosalind , Gellerson Olivia , Shapiro Steven D. , Kamal Haris , Ghozy Sherief , Kaur Gurmeen , Desai Shashvat M. , Ortega‐Gutierrez Santiago , Yaghi Shadi , Altschul David J. , Jadhav Ashutosh P. , Hassan Ameer E. , Nguyen Thanh N. , Brook Allan L. , Mayer Stephan A. , Jovin Tudor G. , Nogueira Raul G. , Gandhi Chirag D. , Al‐Mufti Fawaz
Published: March 2023

Objective

To evaluate clinical outcomes of endovascular thrombectomy (EVT) for acute basilar artery occlusion (BAO) using population‐level data from the United States.

Methods

Weighted discharge data from the National Inpatient Sample were queried to identify adult patients with acute BAO during the period of 2015 to 2019 treated with EVT or medical management only. Complex samples statistical methods and propensity‐score adjustment using inverse probability of treatment weighting (IPTW) were performed to assess clinical endpoints.

Results

Among 3,950 BAO patients identified, 1,425 (36.1%) were treated with EVT [mean age 66.7 years, median National Institute of Health Stroke Scale (NIHSS) score 22]. On unadjusted analysis, 155 (10.9%) EVT patients achieved favorable functional outcomes (discharge disposition to home without services), while 515 (36.1%) experienced in‐hospital mortality, and 20 (1.4%) developed symptomatic intracranial hemorrhage (sICH). Following propensity‐score adjustment by IPTW accounting for age, stroke severity, and comorbidity burden, EVT was independently associated with favorable functional outcome [adjusted odds ratio (aOR) 1.25, 95% confidence interval (CI) 1.07, 1.46; p = 0.004], but not with in‐hospital mortality or sICH. In an IPTW‐adjusted sub‐group analysis of patients with NIHSS scores >20, EVT was associated with both favorable functional outcome (discharge disposition to home or to acute rehabilitation) (aOR 1.55, 95% CI 1.24, 1.94; p < 0.001) and decreased mortality (aOR 0.78, 95% CI 0.69, 0.89; p < 0.001), but not with sICH.

Interpretation

This retrospective population‐based analysis using a large national registry provides real‐world evidence of a potential benefit of EVT in acute BAO patients. ANN NEUROL 2023;94:55–60
Suppressive Strong Metal‐Support Interactions on Ruthenium/TiO2 Promote Light‐Driven Photothermal CO2 Reduction with Methane
Authors: Li Qiang , Wang Huiling , Zhang Meng , Li Guanghui , Chen Jing , Jia Hongpeng
Published: March 2023

Strong metal‐support interactions (SMSI) have gained great attention in the heterogeneous catalysis field, but its negative role in regulating light‐induced electron transfer is rarely explored. Herein, we describe how SMSI significantly restrains the activity of Ru/TiO2 in light‐driven CO2 reduction by CH4 due to the photo‐induced transfer of electrons from TiO2 to Ru. In contrast, on suppression of SMSI Ru/TiO2−H2 achieves a 46‐fold CO2 conversion rate compared to Ru/TiO2. For Ru/TiO2−H2, a considerable number of photo‐excited hot electrons from Ru nanoparticles (NPs) migrate to oxygen vacancies (OVs) and facilitate CO2 activation under illumination, simultaneously rendering Ruδ+ electron deficient and better able to accelerate CH4 decomposition. Consequently, photothermal catalysis over Ru/TiO2−H2 lowers the activation energy and overcomes the limitations of a purely thermal system. This work offers a novel strategy for designing efficient photothermal catalysts by regulating two‐phase interactions.
Enantioselective Synthesis of Dihydropyrazoles by Palladium/Xu‐Phos‐Catalyzed Alleneamination of β,γ‐Unsaturated Hydrazones with Propargylic Acetates
Authors: Zhang Shuting , Wu Shuaijie , Wang Qiang , Xu Shiji , Han Ying , Yan Chao‐Guo , Zhang Junliang , Wang Lei
Published: March 2023

The palladium‐catalyzed asymmetric carboamination reaction is one of the most significant transformations in organic chemistry. Herein, we report the first palladium‐catalyzed asymmetric alleneamination of β,γ‐unsaturated hydrazones with propargylic acetates. This protocol enables the efficient installation of various multisubstituted allene groups onto dihydropyrazoles in good yields with excellent enantioselectivities. The chiral sulfinamide phosphine ligand Xu‐5 exhibits highly efficient stereoselective control in this protocol. The salient features of this reaction include the readily available starting materials, a broad substrate scope, an easy scale‐up, mild reaction conditions and versatile transformations.
Photosystem II Inspired NiFe‐Based Electrocatalysts for Efficient Water Oxidation via Second Coordination Sphere Effect
Authors: Liu Ming , Li Na , Wang Xuemin , Zhao Jia , Zhong Di‐Chang , Li Wei , Bu Xian‐He
Published: March 2023

The mismatched fast‐electron‐slow‐proton process in the electrocatalytic oxygen evolution reaction (OER) severely restricts the catalytic efficiency. To overcome these issues, accelerating the proton transfer and elucidating the kinetic mechanism are highly sought after. Herein, inspired by photosystem II, we develop a family of OER electrocatalysts with FeO6/NiO6 units and carboxylate anions (TA2−) in the first and second coordination sphere, respectively. Benefiting from the synergistic effect of the metal units and TA2−, the optimized catalyst delivers superior activity with a low overpotential of 270 mV at 200 mA cm−2 and excellent cycling stability over 300 h. A proton‐transfer‐promotion mechanism is proposed by in situ Raman, catalytic tests, and theoretical calculations. The TA2− (proton acceptor) can mediate proton transfer pathways by preferentially accepting protons, which optimizes the O−H adsorption/activation process and reduces the kinetic barrier for O−O bond formation.
Methane Photooxidation with Nearly 100 % Selectivity Towards Oxygenates: Proton Rebound Ensures the Regeneration of Methanol
Authors: Cao Yuehan , Yu Wang , Han Chunqiu , Yang Yuantao , Rao Zhiqiang , Guo Rui , Dong Fan , Zhang Ruiyang , Zhou Ying
Published: March 2023

Restrained by uncontrollable dehydrogenation process, the target products of methane direct conversion would suffer from an inevitable overoxidation, which is deemed as one of the most challenging issues in catalysis. Herein, based on the concept of a hydrogen bonding trap, we proposed a novel concept to modulate the methane conversion pathway to hinder the overoxidation of target products. Taking boron nitride as a proof‐of‐concept model, for the first time it is found that the designed N−H bonds can work as a hydrogen bonding trap to attract electrons. Benefitting from this property, the N−H bonds on the BN surface rather than C−H bonds in formaldehyde prefer to cleave, greatly suppressing the continuous dehydrogenation process. More importantly, formaldehyde will combine with the released protons, which leads to a proton rebound process to regenerate methanol. As a result, BN shows a high methane conversion rate (8.5 %) and nearly 100 % product selectivity to oxygenates under atmospheric pressure.
An Iron‐Catalyzed Protein Desulfurization Method Reminiscent of Aquatic Chemistry
Authors: Desmet Rémi , Boidin‐Wichlacz Céline , Mhidia Reda , Tasiemski Aurélie , Agouridas Vangelis , Melnyk Oleg
Published: March 2023

One pillar of protein chemical synthesis based on the application of ligation chemistries to cysteine is the group of reactions enabling the selective desulfurization of cysteine residues into alanines. Modern desulfurization reactions use a phosphine as a sink for sulfur under activation conditions involving the generation of sulfur‐centered radicals. Here we show that cysteine desulfurization by a phosphine can be effected efficiently by micromolar concentrations of iron under aerobic conditions in hydrogen carbonate buffer, that is using conditions that are reminiscent of iron‐catalyzed oxidation phenomena occurring in natural waters. Therefore, our work shows that chemical processes taking place in aquatic systems can be adapted to a chemical reactor for triggering a complex chemoselective transformation at the protein level, while minimizing the resort to harmful chemicals.
Pyrene‐Based Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production
Authors: Sun Jiamin , Sekhar Jena Himanshu , Krishnaraj Chidharth , Singh Rawat Kuber , Abednatanzi Sara , Chakraborty Jeet , Laemont Andreas , Liu Wanlu , Chen Hui , Liu Ying‐Ya , Leus Karen , Vrielinck Henk , Van Speybroeck Veronique , Van Der Voort Pascal
Published: March 2023

Four highly porous covalent organic frameworks (COFs) containing pyrene units were prepared and explored for photocatalytic H2O2 production. The experimental studies are complemented by density functional theory calculations, proving that the pyrene unit is more active for H2O2 production than the bipyridine and (diarylamino)benzene units reported previously. H2O2 decomposition experiments verified that the distribution of pyrene units over a large surface area of COFs plays an important role in catalytic performance. The Py‐Py‐COF though contains more pyrene units than other COFs which induces a high H2O2 decomposition due to a dense concentration of pyrene in close proximity over a limited surface area. Therefore, a two‐phase reaction system (water‐benzyl alcohol) was employed to inhibit H2O2 decomposition. This is the first report on applying pyrene‐based COFs in a two‐phase system for photocatalytic H2O2 generation.
Reversible Li Plating on Graphite Anodes through Electrolyte Engineering for Fast‐Charging Batteries
Authors: Yue Xinyang , Zhang Jing , Dong Yongteng , Chen Yuanmao , Shi Zhangqin , Xu Xuejiao , Li Xunlu , Liang Zheng
Published: March 2023

The difficulties to identify the rate‐limiting step cause the lithium (Li) plating hard to be completely avoided on graphite anodes during fast charging. Therefore, Li plating regulation and morphology control are proposed to address this issue. Specifically, a Li plating‐reversible graphite anode is achieved via a localized high‐concentration electrolyte (LHCE) to successfully regulate the Li plating with high reversibility over high‐rate cycling. The evolution of solid electrolyte interphase (SEI) before and after Li plating is deeply investigated to explore the interaction between the lithiation behavior and electrochemical interface polarization. Under the fact that Li plating contributes 40 % of total lithiation capacity, the stable LiF‐rich SEI renders the anode a higher average Coulombic efficiency (99.9 %) throughout 240 cycles and a 99.95 % reversibility of Li plating. Consequently, a self‐made 1.2‐Ah LiNi0.5Mn0.3Co0.2O2 | graphite pouch cell delivers a competitive retention of 84.4 % even at 7.2 A (6 C) after 150 cycles. This work creates an ingenious bridge between the graphite anode and Li plating, for realizing the high‐performance fast‐charging batteries.
Determining the Role of Ion Transport Throughput in Solid‐State Lithium Batteries
Authors: Yang Ke , Zhao Liang , An Xufei , Chen Likun , Ma Jiabin , Mi Jinshuo , He Yan‐Bing
Published: March 2023

Solid‐state lithium metal batteries (SSLMBs) are promising candidates for high‐energy‐density energy storage devices. However, there still lacks an evaluation criterion to estimate real research status and compare overall performance of the developed SSLMBs. Herein, we propose a comprehensive descriptor, Li+ transport throughput (
), to estimate actual conditions and output performance of the SSLMBs. The
is defined as molar number of Li+ passing through unit area of electrode/electrolyte interface in an hour (mol m−2 h−1) during cycling of battery, which is a quantizable value after taking complex aspects including cycle rate, electrode areal capacity and polarization into account. On this basis, we evaluate the
of liquid, quasi‐solid‐state and solid‐state batteries, and highlight three key aspects to achieve high value of
via building highly efficient cross‐phase, cross‐gap and cross‐interface ion transport in the solid‐state battery systems. We believe that the new concept of
provides milestone guidelines towards large‐scale commercialization of SSLMBs.
Systematic investigation on the effect of processing procedures on the performance of oil‐resistant thermoplastic vulcanizates based on HNBR/TPEE
Authors: Cui Ziwen , Wei Liping , Liu Yingjun , Du Aihua
Published: March 2023

The unique “sea‐island” phase of thermoplastic vulcanizates (TPVs) dictates an inseparable correlation between micro‐morphology and properties, the studies on the processing procedures in dynamic vulcanization are of great significance for the preparation of TPVs with desirable performance. Herein, a new type of oil‐resistant TPV with superior stretchability, low hardness, and high elasticity has been successfully fabricated based on hydrogenated acrylonitrile butadiene rubber (HNBR) and thermoplastic polyester elastomer (TPEE). The effect of processing procedures on the phase morphology, rubber network strength, mechanical properties, rheological performance, thermal stability, and oil resistance of HNBR/TPEE TPV was systematically investigated. In the masterbatch procedure, the homogeneous dispersion of the cross‐linking agent in the rubber phase contributes to stronger rubber networks and effectively reduces HNBR particle size. TPV prepared by masterbatch procedure exhibits a more comprehensive performance with improved mechanical properties, better rheological performance, enhanced thermal stability and oil resistance. In contrast, excessive dispersion of peroxide in the plastic phase during the pre‐compound procedure is demonstrated to the degradation of TPEE, resulting in large‐sized defective domains, while the deterioration of the rubber network leads to the inferior performance of TPV. This study provides new insights into the selection of the optimal procedure for preparing oil‐resistant TPVs.
Designing a GIS‐based supply chain for producing carinata‐based sustainable aviation fuel in Georgia, USA
Authors: Ullah Kazi Masel , Masum Farhad Hossain , Field John L. , Dwivedi Puneet
Published: March 2023

Carinata is a potential crop for sustainable aviation fuel (SAF) production in the southern USA. However, as a novel crop, the cost‐effectiveness and environmental feasibility of carinata feedstock are unknown, and there are questions about the optimal supply chain configuration for carinata‐based SAF production. This study aims to design a supply chain model for carinata‐based SAF production by optimizing the location of farms and facilities (e.g. storage units, crushing mills, biorefineries) for a minimum transportation cost under a set of supply and demand conditions. An integrated mixed‐integer linear programming (MILP) model was combined with geographical information system (GIS) analysis to design a spatially explicit supply chain configuration. The GIS‐based network analysis considered all of the counties in Georgia to set the candidate locations of carinata farms and facilities, and determined minimum cost and emission routes between those counties and the airport using existing transportation networks and modes (e.g. road, rail and pipeline). The MILP model determined the final selection of the farms and the number of facilities and their locations over those minimum‐cost routes. With this supply chain configuration, the minimum price of SAF was $0.92 L−1, which is $0.44 higher than conventional aviation fuel (CAF). The associated carbon intensity of SAF was estimated at 940.7 g CO2e L−1, a reduction of 66% relative to the carbon intensity of equivalent CAF. The study found that a carbon tax (or subsidy) of $230.48 t CO2e−1 would be needed to overcome the cost differential with CAF and promote carinata‐based SAF in Georgia.
General histological woes: Encore. Tissues, please
Authors: Neumann Paul E. , Neumann Eve E.
Published: March 2023

In a previous essay, we wrote about the shortcomings of the four basic tissue dogma of histology ‐ miscellaneous tissues lumped under the ill‐fitting name “connective tissues” and the existence of human tissues that are not recognized as subtypes of any of the four “basic types”. A provisional reclassification of human tissues was constructed to improve the precision and completeness of the tissue taxonomy. Here, we address criticisms from a recent paper that claims that the four basic tissue dogma is more useful than that revised classification in medical education and in clinical practice. Some of the criticism appears to arise from the common misconception of a tissue as simply an array of similar cells.
New OCR letter addresses pregnancy discrimination
Authors: Lyerly Eric
Published: March 2023

There has been a recent trend at the federal level to strengthen protections for pregnant women. In January 2023, U.S. Congress passed a spending package that included two pieces of legislation concerning pregnant workers and new mothers. The Pregnant Workers Fairness Act requires employers to provide reasonable accommodations to employees affected by pregnancy, child birth, or related conditions. The Providing Urgent Maternal Protections (PUMP) for Nursing Mothers Act provides protections for new mothers who need to pump breastmilk for a nursing child.
Preparation, Structural Analysis and Antioxidant Activity of Polysaccharides and Their Derivatives from Pueraria lobata
Authors: Fan Yumin , Huang Gangliang
Published: March 2023

Pueraria lobata polysaccharides (PLPs) were obtained by hot water extraction using Pueraria lobata as raw material. Structural analysis revealed that PLPs may have a repetitive backbone units of →4) ‐α‐D‐Glcp (1→4‐α‐D‐Glcp (1→. Phosphorylated Pueraria lobata polysaccharides (P‐PLPs), carboxymethylated Pueraria lobata polysaccharides (CM‐PLPs) and acetylated Pueraria lobata polysaccharides (Ac‐PLPs) were obtained by chemical modifications of PLPs, respectively. The physicochemical properties and antioxidant activities of these four Pueraria lobata polysaccharides were studied in comparison. In particular, the clearance rate of P‐PLPs exceeded 80 %, and was expected to achieve the same effect as Vc. The results showed that the effects of different chemical modifications on the antioxidant activity of PLPs varied greatly.
Unique Crosslinking Properties of Psoralen‐Conjugated Oligonucleotides Developed by Novel Psoralen N‐Hydroxysuccinimide Esters
Authors: Nakao Juki , Mikame Yu , Eshima Honoka , Yamamoto Tsuyoshi , Dohno Chikara , Wada Takehiko , Yamayoshi Asako
Published: March 2023

Psoralens and their derivatives, such as trioxsalen, have unique crosslinking features to DNA. However, psoralen monomers do not have sequence‐specific crosslinking ability with the target DNA. With the development of psoralen‐conjugated oligonucleotides (Ps‐Oligos), sequence‐specific crosslinking with target DNA has become achievable, thereby expanding the application of psoralen‐conjugated molecules in gene transcription inhibition, gene knockout, and targeted recombination by genome editing. In this study, we developed two novel psoralen N‐hydroxysuccinimide (NHS) esters that allow the introduction of psoralens into any amino‐modified oligonucleotides. Quantitative evaluation of the photo‐crosslinking efficiencies of the Ps‐Oligos to target single‐stranded DNAs revealed that the crosslinking selectivity to 5‐mC is the unique feature of trioxsalen. We found that the introduction of an oligonucleotide via a linker at the C‐5 position of psoralen can promote favorable crosslinking to target double‐stranded DNA. We believe our findings are essential information for the development of Ps‐Oligos as novel gene regulation tools.
Voltammetric Sensor Based on Waste‐Derived Carbon Nanodots for Enhanced Detection of Nitrobenzene
Authors: Bressi Viviana , Chiarotto Isabella , Ferlazzo Angelo , Celesti Consuelo , Michenzi Cinzia , Len Thomas , Iannazzo Daniela , Neri Giovanni , Espro Claudia
Published: March 2023

Carbon dots (CDs) samples were synthesized from orange peel waste (OPW) via a simple and eco‐friendly hydrothermal carbonization (HTC) and electrochemical (EC) bottom‐up synthesis integrated approach. The comprehensive chemical‐physical characterization of CDs samples, carried out by various techniques such as TEM, EDX, XRD, FT‐IR, underlined their morphological and microstructural features. The CDs exhibited attractive electrochemical properties, and thus an electrochemical sensor by modifying a screen printed carbon electrode (CDs/SPCE) for the detection of nitrobenzene (NB) in water was developed. Electroanalytical performances of CDs/SPCE sensor using differential pulse voltammetry (DPV) demonstrated its high sensitivity (9.36 μA μM−1 cm−2) towards NB in a wide linear dynamic range (0.1–2000 μM) and a low limit of detection (LOD=13 nM). The electrochemical sensor also shown high selectivity, long‐term stability, and repeatability. This paper might open the way to a new synergistic HTC‐EC approach for the synthesis of CDs from waste biomass material and their advanced application in highly efficient electrochemical sensors.
Ink source prediction and assessment based on direct analysis in real‐time mass spectrometry via the likelihood ratio
Authors: Chen Xiaohong , Yang Xu , Zhang Jing‐wei , Tang Hao , Zhang Qing‐hua , Wang Ya‐chen , Jiang Zi‐feng , Liu Yan‐ling
Published: March 2023

Ink classification is the ability to distinguish unknown inks into different groups, and ink source prediction is the ability to predict the manufacturer or model of an unknown ink. These are regular tasks in forensic analysis. The latter is more challenging than the former, as ink source prediction has expanded beyond ink classification. In this work, we reported on an approach to predict the source of black inks based on direct analysis in real time mass spectrometry and assess the strength of black ink source prediction conclusion via the likelihood ratio, using a dataset that included 39 inks from three manufacturers with a high market share. Most of these inks contain similar or identical chemical components. Dimensionality reduction based on the principal component analysis and unified manifold approximation and projection algorithms was implemented, and subsequently, the distribution plots illustrated the variations between and within the inks. Unified manifold approximation and projection showed significant priority in avoiding overcrowding of cluster representation versus principal component analysis, with results as high as 99.83% for the prediction of the ink source using 41,432 spectra data (70% data for training and 30% data for testing) after dimensionality reduction. A likelihood ratio was used to evaluate the strength of ink evidence, and the pool‐adjacent‐violators algorithm and logistic algorithms were used to calibrate the likelihood ratio. The results showed that the pool‐adjacent‐violators algorithm and logistic algorithms both had an excellent equal error rate of 0.004 but slightly different results in the rates of misleading evidence in favor of the prosecutor's hypothesis, rates of misleading evidence in favor of the defense's hypothesis, log likelihood ratio costs after calibration ( ), and minimum log likelihood ratio costs ( ). A blind test validated the robustness of the methods.
Imidazole linker‐induced covalent triazine framework–ZIF hybrids for confined hollow carbon super‐heterostructures toward a long‐life supercapacitor
Authors: Vadiyar Madagonda M. , Kim Ji‐Young , Bae Jee‐Hwan , Nam Kyung‐Wan
Published: March 2023

Carbon super‐heterostructures with high nitrogen contents from the covalent hybrid precursors of covalent triazine frameworks (CTFs) and zeolitic imidazolic frameworks (ZIFs) are scarcely explored because of CTF's ordered structure and toxic superacid that dissolves or destabilizes the metal nodes. To solve this problem, herein, we report a straightforward two‐step pathway for the covalent hybridization of disordered CTF (d–CTF)–ZIF composites via preincorporation of an imidazole (IM) linker into ordered CTFs, followed by the imidazole‐site‐specific covalent growth of ZIFs. Direct carbonization of these synthesized d–CTF−IM−ZIF hybrids results in unique hollow carbon super‐heterostructures with ultrahigh nitrogen content (>18.6%), high specific surface area (1663 m2 g−1), and beneficial trace metal (Co/Zn NPs) contents for promoting the redox pseudocapacitance. As proof of concept, the obtained carbon super‐heterostructure (Co–Zn–NCSNH–800) is used as a positive electrode in an asymmetric supercapacitor, demonstrating a remarkable energy density of 61 Wh kg−1 and extraordinary cyclic stability of 97% retention after 30,000 cycles at the cell level. Our presynthetic modifications of CTF and their covalent hybridization with ZIF crystals pave the way toward new design strategies for synthesizing functional porous carbon materials for promising energy applications.
Elemental Magnesium as an Early Transition Metal Substitute: From Pentafulvene Coordination to Deprotonation of Amines
Authors: de Graaff Simon , Schmidtmann Marc , Beckhaus Rüdiger
Published: March 2023

The reaction of magnesium turnings and 6,6‐di‐para‐tolylpentafulvene was investigated. Under mild conditions, the magnesium dissolves, forming the MgII complex 1 with a π‐η5 : σ‐κ1 coordinating ligand of the dimerized pentafulvene, analyzed by NMR and XRD investigations. As a magnesium pentafulvene complex was a possible intermediate, amines were employed as intercepting agents. Thereby, the amines were formally deprotonated by elemental magnesium, yielding the first examples of Cp'Mg(THF)2NR2 complexes. This reaction competes with the formation of 1 and a consecutive formal [1,5]‐H‐shift forming an ansa‐magnesocene. Employing amines with low basicity gave quantitative conversion to the amide complexes.