bluuebunny/crossref_metadata_2025_split huggingface dataset:
Recent Developments of Nanodiamond Quantum Sensors for Biological Applications
Authors: Wu Yingke , Weil Tanja 
Published: March 2022

AbstractMeasuring certain quantities at the nanoscale is often limited to strict conditions such as low temperature or vacuum. However, the recently developed nanodiamond (ND) quantum sensing technology shows great promise for ultrasensitive diagnosis and probing subcellular parameters at ambient conditions. Atom defects (i.e., N, Si) within the ND lattice provide stable emissions and sometimes spin‐dependent photoluminescence. These unique properties endow ND quantum sensors with the capacity to detect local temperature, magnetic fields, electric fields, or strain. In this review, some of the recent, most exciting developments in the preparation and application of ND sensors to solve current challenges in biology and medicine including ultrasensitive detection of virions and local sensing of pH, radical species, magnetic fields, temperature, and rotational movements, are discussed.
Large‐Scale Synthesis of Spinel NixMn3‐xO4 Solid Solution Immobilized with Iridium Single Atoms for Efficient Alkaline Seawater Electrolysis
Authors: Wen Ning , Xia Yuguo , Wang Haihua , Zhang Dongpeng , Wang Haimei , Wang Xiang , Jiao Xiuling , Chen Dairong 
Published: March 2022

AbstractSeawater electrolysis not only affords a promising approach to produce clean hydrogen fuel but also alleviates the bottleneck of freshwater feeds. Here, a novel strategy for large‐scale preparing spinel NixMn3‐xO4 solid solution immobilized with iridium single‐atoms (Ir‐SAs) is developed by the sol–gel method. Benefitting from the surface‐exposed Ir‐SAs, Ir1/Ni1.6Mn1.4O4 reveals boosted oxygen evolution reaction (OER) performance, achieving overpotentials of 330 and 350 mV at current densities of 100 and 200 mA cm–2 in alkaline seawater. Moreover, only a cell voltage of 1.50 V is required to reach 500 mA cm–2 with assembled Ir1/Ni1.6Mn1.4O4‖Pt/C electrode pair under the industrial operating condition. The experimental characterizations and theoretical calculations highlight the effect of Ir‐SAs on improving the intrinsic OER activity and facilitating surface charge transfer kinetics, and evidence the energetically stabilized *OOH and the destabilized chloride ion adsorption in Ir1/Ni1.6Mn1.4O4. This work demonstrates an effective method to produce efficient alkaline seawater electrocatalyst massively.
Challenges and Opportunities for Renewable Ammonia Production via Plasmon‐Assisted Photocatalysis
Authors: Puértolas Begoña , Comesaña‐Hermo Miguel , Besteiro Lucas V. , Vázquez‐González Margarita , Correa‐Duarte Miguel A. 
Published: March 2022

AbstractDespite its severe operating conditions, associated energy consumption, and environmental concerns, the manufacture of nitrogen‐rich fertilizers still relies heavily on producing ammonia in centralized chemical plants via the Haber–Bosch process. A distributed and more sustainable scheme considers the on‐site production of carbon‐neutral fertilizers at ambient conditions in photocatalytic reactors powered by sunlight. Among the different strategies proposed to boost the nitrogen reduction ability of conventional catalysts, the incorporation of plasmonic nanomaterials is gaining widespread interest owing to their unique optical tunability and their potential to improve the efficiency and selectivity of many chemical transformations. This Perspective examines the state‐of‐the‐art for the nitrogen reduction reaction via plasmon‐driven photocatalysis and discusses design principles for advancing it. The different physical mechanisms underlying the operation of plasmonic materials in a catalytic setting, and the dimensions along which the catalysts can be tuned to harness them are detailed. Paths to overcome current frontiers in the field, including design strategies of plasmonic photocatalysts, the development of complementary characterization techniques, the standardization of the reaction conditions and ammonia quantification methods, and the possibilities offered by theoretical methods to drive material discovery, identifying fundamental bottlenecks, and proposing directions for the advancement of this emerging field are outlined.
Multimodal Imaging‐Guided Photothermal Immunotherapy Based on a Versatile NIR‐II Aggregation‐Induced Emission Luminogen
Authors: Yan Dingyuan , Wang Miao , Wu Qian , Niu Niu , Li Meng , Song Ruixiang , Rao Jie , Kang Miaomiao , Zhang Zhijun , Zhou Feifan , Wang Dong , Tang Ben Zhong 
Published: March 2022

AbstractSynergistic photothermal immunotherapy has captured great attention owing to the mutually strengthening therapeutic outcomes towards both original tumors and abscopal tumors. Herein, a versatile theranostic agent displaying aggregation‐induced emission, namely TPA‐BT‐DPTQ, was designed and prepared based on benzo[c]thiophene unit as a building block; it can be used for simultaneous fluorescence imaging (FLI) in the second near‐infrared (NIR‐II) window, photoacoustic imaging (PAI), photothermal imaging (PTI), and thermal eradication of tumors. Further experiments validate that photothermal therapy (PTT) mediated by TPA‐BT‐DPTQ nanoparticles not only destroys the primary tumor but also enhances immunogenicity for further suppressing the growth of tumors at distant sites. Furthermore, PTT combining a programmed death‐ligand 1 (PD‐L1) antibody prevents the metastasis and recurrence of cancer by potentiating the effect of immunotherapy.
Enantio‐, Diastereo‐ and Regioselective Synthesis of Chiral Cyclic and Acyclic gem‐Difluoromethylenes by Palladium‐Catalyzed [4+2] Cycloaddition
Authors: Uno Hiroto , Kawai Koki , Araki Taichi , Shiro Motoo , Shibata Norio 
Published: March 2022

Abstractgem‐Difluoromethylene moieties are attractive in medicinal chemistry due to their ability to mimic other more ubiquitous functional groups. Thus, effective asymmetric methods for their construction are highly desirable, especially for the industrial production of chiral drugs. Using a Pd‐catalyzed asymmetric [4+2] cycloaddition between substituted‐2‐alkylidenetrimethylene carbonates and gem‐difluoroalkyl ketones, we were able to easily access chiral 1,3‐dioxanes that contain a tetrasubstituted difluoroalkyl stereogenic center in cyclic and acyclic skeletons. A novel phosphoramidite ligand, which contains a bulky 1,1‐dinaphthylmethanamino moiety, was developed to provide the products in high yield with excellent enantio‐, diastereo‐, and regioselectivity. Strikingly, the gem‐difluoro substitution pattern promotes the reaction, and pentafluoroethylketone, an α,α‐difluorinated β‐ketoester, and a β‐ketosulfone are suitable substrates for this method.
Extended Conjugation Attenuates the Quenching of Aggregation‐Induced Emitters by Photocyclization Pathways
Authors: Turley Andrew T. , Saha Promeet K. , Danos Andrew , Bismillah Aisha N. , Monkman Andrew P. , Yufit Dmitry S. , Curchod Basile F. E. , Etherington Marc K. , McGonigal Paul R. 
Published: March 2022

AbstractHerein, we expose how the antagonistic relationship between solid‐state luminescence and photocyclization of oligoaryl alkene chromophores is modulated by the conjugation length of their alkenyl backbones. Heptaaryl cycloheptatriene molecular rotors exhibit aggregation‐induced emission characteristics. We show that their emission is turned off upon breaking the conjugation of the cycloheptatriene by epoxide formation. While this modification is deleterious to photoluminescence, it enables formation of extended polycyclic frameworks by Mallory reactions. We exploit this dichotomy (i) to manipulate emission properties in a controlled manner and (ii) as a synthetic tool to link together pairs of phenyl rings in a specific sequence. This method to alter the tendency of oligoaryl alkenes to undergo photocyclization can inform the design of solid‐state emitters that avoid this quenching mechanism, while also allowing selective cyclization in syntheses of polycyclic aromatic hydrocarbons.
Copper‐Catalyzed Monooxygenation of Phenols: Evidence for a Mononuclear Reaction Mechanism
Authors: Schneider Rebecca , Engesser Tobias A. , Näther Christian , Krossing Ingo , Tuczek Felix 
Published: March 2022

AbstractThe CuI salts [Cu(CH3CN)4]PF and [Cu(oDFB)2]PF with the very weakly coordinating anion Al(OC(CF3)3)4− (PF) as well as [Cu(NEt3)2]PF comprising the unique, linear bis‐triethylamine complex [Cu(NEt3)2]+ were synthesized and examined as catalysts for the conversion of monophenols to o‐quinones. The activities of these CuI salts towards monooxygenation of 2,4‐di‐tert‐butylphenol (DTBP‐H) were compared to those of [Cu(CH3CN)4]X salts with “classic” anions (BF4−, OTf−, PF6−), revealing an anion effect on the activity of the catalyst and a ligand effect on the reaction rate. The reaction is drastically accelerated by employing CuII‐semiquinone complexes as catalysts, indicating that formation of a CuII complex precedes the actual catalytic cycle. This result and other experimental observations show that with these systems the oxygenation of monophenols does not follow a dinuclear, but a mononuclear pathway analogous to that of topaquinone cofactor biosynthesis in amine oxidase.
Bioassay‐Guided Isolation of Nematicidal Artemisinic Acid and Dihydroartemisinic Acid from Artemisia annua L. and Evaluation of Their Activity against Meloidogyne incognita
Authors: Wang Delong , Li Min , Yuan Chunxia , Fang Yali , Zhang Zhijia 
Published: March 2022

AbstractThe extract of Artemisia annua L. has been shown to possess the nematicidal activity but the potent constituents were unclear. Herein, two nematicidal sesquiterpenoid acids artemisinic acid (ArA) and dihydroartemisinic acid (DHArA) were isolated from the methanol extract of the aerial parts of A. annua L. by the bioassay‐guided isolation method using Meloidogyne incognita second stage juveniles (J2s) as the screening target. The in vitro activity, control efficacy in the pot experiment, and toxic effects of these two natural compounds against M. incognita were evaluated. The in vitro results showed that the EC50/48h values of ArA and DHArA were 0.37 mM and 0.76 mM against J2s, respectively. In the pot experiment, ArA and DHArA at the dose of 5 mg (a.i.)/pot could achieve the same level of control efficacy compared with avermectins at 2 mg (a.i.)/pot. Microscopic observations indicated the obvious toxic symptoms of J2s after ArA‐ and DHArA‐treatment, including the shrinking body, imperfect body wall, and undiscerning organs. The physiological and biochemical studies, together with the toxic symptoms, revealed that ArA and DHArA had great impacts on the membrane system of J2s. Additionally, ArA occurring the α, β‐unsaturated carbonyl was demonstrated to be reactive with glutathione (GSH) and cause the decrease of GSH content in J2s. Taken together, the present study suggests that ArA and DHArA or ArA‐ and DHArA‐based extracts of A. annua L. have a substantial potential to be used as botanical agents for integrated disease management programs against root‐knot nematodes in crop protection.
A Catalytic Strategy for Selective Production of 5‐Formylfuran‐2‐carboxylic Acid and Furan‐2,5‐dicarboxylic Acid
Authors: Wiesfeld Jan J. , Asakawa Miyuki , Aoshima Takayuki , Fukuoka Atsushi , Hensen Emiel J. M. , Nakajima Kiyotaka 
Published: March 2022

AbstractA novel catalytic strategy involving protective chemistry is presented for the selective production of 5‐formylfuran‐2‐carboxylic acid (FFCA) and furan‐2,5‐dicarboxylic acid (FDCA) from concentrated 5‐hydroxymethylfurfural (HMF) solutions. By protecting the reactive formyl group of HMF by acetalization with 1,3‐propanediol (PDO), degradation and premature oxidation of HMF is suppressed. A hydroxyapatite‐supported Au catalyst can selectively oxidize HMF‐acetal in a 10 wt % solution to FFCA‐acetal in 94 % yield in 2 hours at 373 K under 0.5 MPa of O2. Deprotection of FFCA‐acetal by mineral acids affords FFCA in 98 % yield and recovers nearly all PDO. FFCA in a 20 wt % solution can be oxidized to FDCA in 95 % yield under similar reaction conditions. The presented chemistry contributes to the development of novel manufacturing routes of prospective biobased monomer precursors using protecting agents.
Electrochemical Pretreatment of Solid‐Electrolyte Interphase Formation for Enhanced Li4Ti5O12 Anode Performance in a Molten Li−Ca Binary Salt Hydrate Electrolyte
Authors: Kondou Shinji , Watanabe Yoshifumi , Dokko Kaoru , Watanabe Masayoshi , Ueno Kazuhide 
Published: March 2022

AbstractWater‐in‐salt electrolytes have been widely explored because of their expanded electrochemical stability (>3.0 V). However, the instability of solid‐electrolyte interphase (SEI) in aqueous electrolytes leads to their reductive decomposition on the negative electrodes of low‐potential anode materials. Here, we demonstrate significant improvement in the cycle performance of a Li4Ti5O12 electrode using a Li−Ca binary salt hydrate (LCH) electrolyte in combination with an optimized electrochemical pretreatment process. Compared with a hydrate‐melt electrolyte, the LCH electrolyte provided less water‐soluble Ca‐based SEI components, and careful pretreatment process enabled the formation of a thicker SEI layer on the Li4Ti5O12 electrode. Protected with the hardly soluble, thick SEI layer, the Li4Ti5O12 electrode effectively mitigated unfavorable side reactions and achieved 95.5 % capacity retention over 50 cycles. These results offer insight into a promising route for stable SEI layer formation for the practical use of low‐potential anode materials in aqueous rechargeable lithium‐ion batteries.
EczemaPred: A computational framework for personalised prediction of eczema severity dynamics
Authors: Hurault Guillem , Stalder Jean François , Mery Sophie , Delarue Alain , Saint Aroman Markéta , Josse Gwendal , Tanaka Reiko J. 
Published: March 2022

AbstractBackgroundAtopic dermatitis (AD) is a chronic inflammatory skin disease leading to substantial quality of life impairment with heterogeneous treatment responses. People with AD would benefit from personalised treatment strategies, whose design requires predicting how AD severity evolves for each individual.ObjectiveThis study aims to develop a computational framework for personalised prediction of AD severity dynamics.MethodsWe introduced EczemaPred, a computational framework to predict patient‐dependent dynamic evolution of AD severity using Bayesian state‐space models that describe latent dynamics of AD severity items and how they are measured. We used EczemaPred to predict the dynamic evolution of validated patient‐oriented scoring atopic dermatitis (PO‐SCORAD) by combining predictions from the models for the nine severity items of PO‐SCORAD (six intensity signs, extent of eczema, and two subjective symptoms). We validated this approach using longitudinal data from two independent studies: a published clinical study in which PO‐SCORAD was measured twice weekly for 347 AD patients over 17 weeks, and another one in which PO‐SCORAD was recorded daily by 16 AD patients for 12 weeks.ResultsEczemaPred achieved good performance for personalised predictions of PO‐SCORAD and its severity items daily to weekly. EczemaPred outperformed standard time‐series forecasting models such as a mixed effect autoregressive model. The uncertainty in predicting PO‐SCORAD was mainly attributed to that in predicting intensity signs (75% of the overall uncertainty).ConclusionsEczemaPred serves as a computational framework to make a personalised prediction of AD severity dynamics relevant to clinical practice. EczemaPred is available as an R package.
Aramid Nanofibers Aerogel‐filled Wood‐based Carbon Material for Flexible Solid Supercapacitors
Authors: Niu Qingyuan , Zhang Hui , Gao Kezheng , Tang Qiheng , Sun Xiankai , Zhao Shuyan , Wang Lizhen 
Published: March 2022

AbstractDelignified wood‐based carbon material is a potential cost‐effective and environmentally‐friendly flexible electrode material. However, the abundant intertubular cavities not only endow excellent flexibility, but also inevitably deteriorate the conductivity, integrity and areal density of the delignified wood‐based flexible carbon material, which is not conducive to improve the energy storage performance. In this work, an aramid nanofiber‐based carbon aerogel was filled in the intertubular cavities via a series of processes, including filled by virtue of the unidirectional capillary forces, gelation, freeze‐drying and carbonization. The filled carbon aerogel can significantly increase the conductivity and the sheet resistance is as low as about 28±5 Ω sq−1. The filled carbon aerogel does not deteriorate its excellent energy storage behavior derived from the unique low‐tortuosity and open slender tubular microstructure. The filled carbon aerogel can improve the space utilization of the delignified wood‐based carbon. The areal specific capacitance has been increased from 20.8 to 51.9 mF cm−2 at a current density of 50 μA cm−2. The area specific capacitance still remains at 33.9 mF cm−2 when the current density increased to 1000 μA cm−2. The aramid nanofibers aerogel‐filled wood‐based carbon flexible interdigitated solid supercapacitors also exhibit excellent flexibility and folding endurance.
Treating hidradenitis suppurativa in special populations: Pregnancy, lactation, and comorbid conditions
Authors: Aldana Isabella , Sanyi Adaugo A. , Mayo Tiffany T. 
Published: March 2022

AbstractIntroductionHidradenitis suppurativa (HS) is an inflammatory cutaneous condition of chronic and debilitating nature. Management of HS includes pharmacological or surgical interventions, and new emerging therapies continue to provide new avenues for treatment. There are treatment options, however, that may be contraindicated in special populations of patients.MethodsA literature search was conducted utilizing PubMed and MEDLINE (Medical Subject Headings [MeSH]) for the terms “hidradenitis suppurativa” and “acne inversa”. All review articles, randomized controlled studies, open‐label extension studies, and conference abstracts published up to August 2021 were included. References of identified articles were searched for additional articles.ResultsHere, we present an in‐depth review of HS, with a focus on treatment of HS in special populations including those who are pregnant, lactating, or suffering with a comorbid condition such as inflammatory bowel disease or cancer, in hopes of providing further insight into management of this debilitating disease while seeking clinically safe approaches.ConclusionIdentifying appropriate treatment regimens specific to each aforementioned special population may provide clinicians a more streamlined way to manage patients and the opportunity to improve upon the overall quality of life of patients with HS.chronic and debilitating nature.
Spatial and temporal variations in salt marsh microorganisms of the Wadden Sea
Authors: Rinke Maria , Maraun Mark , Scheu Stefan 
Published: March 2022

AbstractSalt marshes exist at the interface of the marine and the terrestrial system. Shore height differences and associated variations in inundation frequency result in altered abiotic conditions, plant communities, and resource input into the belowground system. These factors result in three unique zones, the upper salt marsh (USM), the lower salt marsh (LSM), and the pioneer zone (PZ). Marine detritus, such as micro‐ and macroalgae, is typically flushed into the PZ daily, with storm surges moving both salt marsh detritus and marine detritus into higher salt marsh zones. Microbial assemblages are essential for the decomposition of organic matter and have been shown to sensitively respond to changes in abiotic conditions such as oxygen supply and salinity. However, temporal and spatial dynamics of microbial communities of Wadden Sea salt marshes received little attention. We investigated the dynamics of soil microbial communities across horizontal (USM, LSM, and PZ), vertical (0–5 and 5–10‐cm sediment depth), and temporal (spring, summer, and autumn) scales in the Wadden Sea salt marsh of the European North Atlantic coast using phospholipid fatty acid (PLFA) analysis. Our results show strong spatial dynamics both among salt marsh zones and between sediment depths, but temporal dynamics to be only minor. Despite varying in space and time, PLFA markers indicated that bacteria generally were the dominant microbial group across salt marsh zones and seasons, however, their dominance was most pronounced in the USM, whereas fungal biomass peaked in the LSM and algal biomass in the PZ. Only algal markers and the stress marker monounsaturated to saturated fatty acid ratio responded to seasonality. Overall, therefore, the results indicate remarkable temporal stability of salt marsh microbial communities despite strong variability in abiotic factors.
Designing and leading collaborative urban climate governance: Comparative experiences of co‐creation from Copenhagen and Oslo
Authors: Hofstad Hege , Sørensen Eva , Torfing Jacob , Vedeld Trond 
Published: March 2022

AbstractThis article has a twofold aim. First, inspired by collaborative governance theory, the article develops an analytical framework built around three ideal co‐creation strategies utilized by city governments for building capacity and addressing urban climate solutions. Second, this co‐creation framework is applied to a comparative case study of climate governance in two climate‐ambitious Scandinavian cities, Copenhagen and Oslo, to illustrate the role of co‐creation as an approach and tool for urban climate governance. The comparative analysis reveals how the two cities navigate differently within a polycentric ecosystem of actors depending on a variety of contextual factors and whether climate responses are geared mainly towards assembling and aligning public, private business or citizen actors, respectively, for collaborative efforts. The findings suggest that both cities combine two ideal co‐creation strategies, a whole of government strategy with an externally focused stakeholder strategy, while neither of the cities has adopted a full‐fledged externally focused civil society co‐creation strategy. The findings have implications for co‐creation theory and urban climate leadership. In both cities, the benefits of co‐creation are found to depend on support from both conducive institutional design and new forms of public leadership. Over time, leadership has started to congeal into a distinctive type of co‐creational leadership based on both hands‐on and hands‐off tools and instruments in climate responses. The findings suggest that a co‐creation approach benefits the debate on citizen participation in climate governance as it brings a nuanced understanding of the multiple roles that citizens can play in relation to both public and private services and business actors; as residents, consumers, climate agents, as well as voters with rights and responsibilities who can provide the city leadership with legitimacy but also oppose climate action.