bluuebunny/crossref_metadata_2025_split huggingface dataset:
Minisci‐Type Alkylation of N‐Heteroarenes by N‐(Acyloxy)phthalimide Esters Mediated by a Hantzsch Ester And Blue LED Light
Authors: Li Jiacheng , Siang Tan Suan , Kyne Sara Helen , Wai Hong Chan Philip 
Published: December 2021

AbstractA synthetic method that enables the Hantzsch ester‐mediated Minisci‐type C2‐alkylation of quinolines, isoquinolines and pyridines by N‐(acyloxy)phthalimide esters (NHPI) under blue LED (light emitting diode) light (456 nm) is described. Achieved under mild reaction conditions at room temperature, the metal‐free synthetic protocol was shown to be applicable to primary, secondary and tertiary NHPIs to give the alkylated N‐heterocyclic products in yields of 21–99%. On introducing a chiral phosphoric acid, an asymmetric version of the reaction was also realised and provided product enantiomeric excess (ee) values of 53–99%. The reaction mechanism was delineated to involve excitation of an electron‐donor acceptor (EDA) complex, formed from weak electrostatic interactions between the Hantzsch ester and NHPI, which generates the posited radical species of the redox active ester that undergoes addition to the N‐heterocycle.magnified image
Materials Characterization and Electrical Performance of Bilayer Structures for Enhanced Electrodeposition in Programmable Metallization Cells
Authors: Chamele Ninad , Balaban Mehmet B. , Patadia Arshey , Swain Smitha S. , Gonzalez‐Velo Yago , Roldan Manuel , Kozicki Michael 
Published: December 2021

AbstractLong channel lateral programmable metallization cell (PMC) devices, in which a metal electrodeposit is formed on a solid electrolyte between two coplanar electrodes several microns apart, have a variety of applications beyond standard microelectronics. Whereas fast electrodeposit growth over considerable distances can be achieved using high ion mobility chalcogenide electrolytes, the use of more foundry‐friendly materials, including copper‐doped transition metal oxides, leads to extremely low electrodeposit growth rates due to their low ion mobility and high resistivity. In this paper, a material system comprising a Cu2O/CuWO3bilayer formed by low temperature oxidation of Cu on WO3is examined. The Cu2O overlayer provides a low resistance parallel path for electrons, allowing electrodeposition to occur along the entire length of the device, thereby increasing the rate at which the electrodeposit fills the channel. A study of devices prepared under different conditions, resulting in different copper oxide thicknesses and copper concentrations in the layers, shows the influence of processing conditions on material composition, activation energy for current transport, electrodeposit morphology, and electrical characteristics. It is demonstrated that a very wide range of operating conditions is possible, including the bridging of 14 μm long channels in under 3 s using 2 V bias.
Introducing Water‐Network‐Assisted Proton Transfer for Boosted Electrocatalytic Hydrogen Evolution with Cobalt Corrole
Authors: Li Xialiang , Lv Bin , Zhang Xue‐Peng , Jin Xiaotong , Guo Kai , Zhou Dexia , Bian Hongtao , Zhang Wei , Apfel Ulf‐Peter , Cao Rui 
Published: December 2021

AbstractProton transfer is vital for many biological and chemical reactions. Hydrogen‐bonded water‐containing networks are often found in enzymes to assist proton transfer, but similar strategy has been rarely presented by synthetic catalysts. We herein report the Co corrole 1 with an appended crown ether unit and its boosted activity for the hydrogen evolution reaction (HER). Crystallographic and 1H NMR studies proved that the crown ether of 1 can grab water via hydrogen bonds. By using protic acids as proton sources, the HER activity of 1 was largely boosted with added water, while the activity of crown‐ether‐free analogues showed very small enhancement. Inhibition studies by adding 1) external 18‐crown‐6‐ether to extract water molecules and 2) potassium ion or N‐benzyl‐n‐butylamine to block the crown ether of 1 further confirmed its critical role in assisting proton transfer via grabbed water molecules. This work presents a synthetic example to boost HER through water‐containing networks.
Microfluidic Fabrication of Hierarchical‐Ordered ZIF‐L(Zn)@Ti3C2Tx Core–Sheath Fibers for High‐Performance Asymmetric Supercapacitors
Authors: Wu Guan , Sun Suya , Zhu Xiaolin , Ma Ziyang , Zhang Yuman , Bao Ningzhong 
Published: December 2021

AbstractWe report hierarchical‐ordered ZIF−L(Zn)@Ti3C2Tx MXene core–sheath fibers, in which a ZIF−L(Zn) nanowall array sheath is grown vertically on an anisotropic Ti3C2Tx core by Ti−O−Zn/Ti−F−Zn chemical bonds. Through highly efficient microfluidic assembly and microchannel reactions, ZIF−L(Zn)@Ti3C2Tx exhibits well‐developed micro‐/mesoporosity, ordered ionic pathways, fast interfacial electron conduction and large‐scale fabrication, significantly boosting charges dynamic transport and intercalation. The resultant ZIF−L(Zn)@Ti3C2Tx fiber presents large capacitance (1700 F cm−3) and outstanding rate performance in a 1 M H2SO4 electrolyte. Additionally, ZIF−L(Zn)@Ti3C2Tx fiber‐based solid‐state asymmetric supercapacitors deliver high energy density (19.0 mWh cm−3), excellent capacitance (854 F cm−3), large deformable/wearable capabilities and long‐time cyclic stability (20 000 cycles), which realize natural sunlight‐induced self‐powered applications to drive water level/earthquake alarm devices.
Implementation of Quantum Level Addressability and Geometric Phase Manipulation in Aligned Endohedral Fullerene Qudits
Authors: Zhou Shen , Yuan Jiayue , Wang Zi‐Yu , Ling Kun , Fu Peng‐Xiang , Fang Yu‐Hui , Wang Ye‐Xin , Liu Zheng , Porfyrakis Kyriakos , Briggs G. Andrew D. , Gao Song , Jiang Shang‐Da 
Published: December 2021

AbstractEndohedral nitrogen fullerenes have been proposed as building blocks for quantum information processing due to their long spin coherence time. However, addressability of the individual electron spin levels in such a multiplet system of 4S3/2 has never been achieved because of the molecular isotropy and transition degeneracy among the Zeeman levels. Herein, by molecular engineering, we lifted the degeneracy by zero‐field splitting effects and made the multiple transitions addressable by a liquid‐crystal‐assisted method. The endohedral nitrogen fullerene derivatives with rigid addends of spiro structure and large aspect ratios of regioselective bis‐addition improve the ordering of the spin ensemble. These samples empower endohedral‐fullerene‐based qudits, in which the transitions between the 4 electron spin levels were respectively addressed and coherently manipulated. The quantum geometric phase manipulation, which has long been proposed for the advantages in error tolerance and gating speed, was implemented in a pure electron spin system using molecules for the first time.
Aberrant post‐translational modifications in endosomal trafficking are potential therapeutic targets to avert therapy resistance in solid cancers
Authors: Onglao Winona , Khew‐Goodall Yeesim , Belle Leila , Lonic Ana 
Published: December 2021

AbstractDrugs targeting a single TK/RTK in the treatment of solid cancers has not had the same success seen in blood cancers. This is, in part, due to acquired resistance in solid cancers arising from a range of mechanisms including the upregulation of compensatory RTK signalling. Rather than attempting to inhibit individual compensatory RTK—requiring knowledge of which RTKs are upregulated in any given tumour—strategies to universally inhibit signalling from multiple RTKs may represent an effective alternative. Endosomal trafficking of RTKs is a common conduit that can regulate signalling from multiple RTKs simultaneously. As such, we posit that targeting endosomal trafficking—in particular, aberrant post‐translational modifications in cancers that contribute to dysregulated endosomal trafficking—could inhibit oncogenic signalling driven by multiple RTKs and pave the way for the development of a novel class of inhibitors that shift the trafficking of RTKs to inhibit tumour growth.
Metabolomic analysis of amino acids and organic acids in aging mouse eyes using gas chromatography–tandem mass spectrometry
Authors: Seo Chan , Park Sehoon , Kim Youngbae , Ji Moongi , Lee Hyeon‐Seong , Hwang Yun‐Ho , Choi Subin , Min Jeuk , Oh Song‐Jin , Yee Sung‐Tae , Lee Wonjae , Paik Man‐Jeong 
Published: December 2021

AbstractThis is a metabolomics study for monitoring altered amino acid (AA) and organic acid (OA) metabolism of in eyes from aging an mouse model at 8 and 18 weeks and 18 months. Simultaneous metabolic profiling analysis of OAs and AAs was performed as ethoxycarbonyl/methoxime/tert‐butyldimethylsilyl derivatives by gas chromatography–tandem mass spectrometry. A total of 42 metabolites—24 AAs and 18 OAs—were determined and their composition values were normalized to the corresponding mean values of 8‐week‐old mice as the control group. Then their normalized values were plotted as star graphs, which were distorted and readily distinguishable for each age‐related group. Among the 42 metabolites, 18 AAs and 11 OAs were age dependent and significantly different (p < 0.05). Principal component analysis and partial least squares discriminant analysis showed unclear separation between 8‐ and 18‐week‐old mice but clear separation between these and 18‐month‐old mice. In particular, the variable importance in projection scores of 4‐hydroxyproline, cis‐aconitic acid, glycine, isocitric acid, leucine, pipecolic acid and lysine from partial least‐squares–discriminant analysis were higher than 1.3. A heatmap for the classification and visualization of 42 metabolites showed differences in metabolite changes with aging. Altered AA and OA profiles were monitored, which may explain the metabolic disturbance of AA and OA. These findings are related to mitochondrial dysfunctions related to energy metabolism and the impaired antioxidant system in the aging eye. Therefore, the present metabolomics results of the association between physiological states and altered metabolism of AA and OA will be useful for understanding the aging eye and related diseases.
Resolvin D1‐loaded nanoliposomes promote M2 macrophage polarization and are effective in the treatment of osteoarthritis
Authors: Dravid Ameya A. , M. Dhanabalan Kaamini , Agarwal Smriti , Agarwal Rachit 
Published: December 2021

AbstractCurrent treatments for osteoarthritis (OA) offer symptomatic relief but do not prevent or halt the disease progression. Chronic low‐grade inflammation is considered a significant driver of OA. Specialized proresolution mediators are powerful agents of resolution but have a short in vivo half‐life. In this study, we have engineered a Resolvin D1 (RvD1)‐loaded nanoliposomal formulation (Lipo‐RvD1) that targets and resolves the OA‐associated inflammation. This formulation creates a depot of the RvD1 molecules that allows the controlled release of the molecule for up to 11 days in vitro. In surgically induced mice model of OA, only controlled‐release formulation of Lipo‐RvD1 was able to treat the progressing cartilage damage when administered a month after the surgery, while the free drug was unable to prevent cartilage damage. We found that Lipo‐RvD1 functions by damping the proinflammatory activity of synovial macrophages and recruiting a higher number of M2 macrophages at the site of inflammation. Our Lipo‐RvD1 formulation was able to target and suppress the formation of the osteophytes and showed analgesic effect, thus emphasizing its ability to treat clinical symptoms of OA. Such controlled‐release formulation of RvD1 could represent a patient‐compliant treatment for OA.
Comparative Performance of PETase as a Function of Reaction Conditions, Substrate Properties, and Product Accumulation
Authors: Erickson Erika , Shakespeare Thomas J. , Bratti Felicia , Buss Bonnie L. , Graham Rosie , Hawkins McKenzie A. , König Gerhard , Michener William E. , Miscall Joel , Ramirez Kelsey J. , Rorrer Nicholas A. , Zahn Michael , Pickford Andrew R. , McGeehan John E. , Beckham Gregg T. 
Published: December 2021

AbstractInvited for this month′s cover is the BOTTLE Consortium, featuring Gregg Beckham's laboratory from NREL and John McGeehan's laboratory from the University of Portsmouth. The cover image shows the application of poly(ethylene terephthalate) (PET) hydrolase enzymes on post‐consumer waste plastic, towards the development of an enzymatic PET recycling strategy. The Full Paper itself is available at 10.1002/cssc.202101932.
Nitrogen fertilization and high plant growing temperature increase herbivore performance
Authors: Raharivololoniaina Ange , Berweiler Svenja , Fischer Klaus 
Published: December 2021

AbstractGlobal environmental change exerts growing pressure on biodiversity. Anthropogenic climate and land use change are particularly important drivers of biodiversity loss. While their effects on biodiversity have been widely studied individually, interactions among them are poorly understood. Here, we investigate the effects of two common drivers of global change, increased temperature and nitrogen fertilization, on host‐plant quality and herbivore performance in the butterfly Lycaena tityrus. We show that butterfly performance was positively affected by plants grown at increased temperatures and nitrogen fertilization, the latter being in line with the nitrogen limitation hypothesis. Effects were largely consistent across treatments; that is, nitrogen deposition and temperature did not interact strongly to affect herbivore performance. Overall, females suffered more strongly than males from poor host‐plant quality. Our study demonstrates changes in host‐plant quality caused by variation in temperature and nitrogen availability, which induced indirect effects in an herbivore. Such indirect effects of global environmental change are an important source of variation and should be considered in order to reduce uncertainties with regard to the effects of global change on biodiversity.
Phospholipase activity of acyloxyacyl hydrolase induces IL‐22‐producing CD1a‐autoreactive T cells in individuals with psoriasis
Authors: Singh Randeep , Chen Yi‐Ling , Ng Soo Weei , Cain David , Etherington Rachel , Hardman Clare , Ogg Graham 
Published: December 2021

AbstractPsoriasis is a chronic inflammatory skin disease characterized by Th17 responses. Recent evidence has identified Langerhans cells to have a key role in disease pathogenesis, with constitutive high expression of CD1a and capacity to present lipid antigens to T cells. Phospholipase A2 enzymes generate neolipid antigens for recognition by CD1a‐reactive T cells; however, the broader enzymatic pathways of CD1a lipid ligand generation have not been thoroughly investigated. In this study, we used immunofluorescence of skin and ELISpot analyses of CD1a‐reactive T cells to investigate the role of the lipase acyloxyacyl hydrolase (AOAH) in CD1a ligand generation with relevance to the pathogenesis of psoriasis. We found that the PLA2 activity of rAOAH leads to the activation of circulating CD1a auto‐reactive T cells, leading to the production of IFN‐γ and IL‐22. Circulating AOAH‐responsive CD1a‐reactive T cells from patients with psoriasis showed elevated IL‐22 production. We observed that AOAH is highly expressed in psoriatic lesions compared to healthy skin. Overall, these data present a role for AOAH in generating antigens that activate circulating lipid‐specific CD1a‐restricted T cells and, thus, contribute to psoriatic inflammation. These findings suggest that inhibition of PLA2 activity of AOAH may have therapeutic potential for individuals with psoriasis.
A Macro‐Distinct Element Model (M‐DEM) for simulating in‐plane/out‐of‐plane interaction and combined failure mechanisms of unreinforced masonry structures
Authors: Malomo Daniele , DeJong Matthew J. 
Published: December 2021

AbstractIn the seismic analysis of unreinforced masonry (URM) structures, the modeling of out‐of‐plane (OOP) modes and their mechanical interaction with in‐plane (IP) loaded components are typically neglected when using simplified numerical methods. Although this may result in unconservative predictions, the high computational expense entailed by more refined approaches is often prohibitive for applied researchers and practitioners. To overcome these limitations, the demonstrated capabilities of a recently developed low‐cost Macro‐Distinct Element Model (M‐DEM) to simulate IP and OOP modes are extended in this work towards the modeling of IP/OOP interaction and combined failure mechanisms of URM assemblies. In the M‐DEM framework, shear and flexural damage are accounted for by zero‐thickness interface spring layers, whose layout is determined a priori as a function of the masonry texture, while crushing failure is modeled through homogenized finite element macro‐blocks. To adapt and validate this M‐DEM scheme to model IP/OOP interaction, past experiments on full‐scale C‐, U‐, and I‐shaped URM specimens tested under quasi‐static loading were simulated. The shake‐table response of a full‐scale C‐shaped URM assembly with openings was also numerically simulated up to collapse, representing a major improvement over previous macro‐element methods. After the comparison with experimental tests, a parametric investigation of the response of reference URM walls under combined IP/OOP actions was conducted, and the influence of previous IP damage on one‐ and two‐way OOP bending capacity is quantified. This aspect, despite being widely identified as of relevant interest, has only been marginally investigated in previous research, both experimentally and numerically.
Comparison of Species Sensitivity Distributions for Sediment-Associated Nonionic Organic Chemicals Through Equilibrium Partitioning Theory and Spiked-Sediment Toxicity Tests with Invertebrates
Authors: Hiki Kyoshiro , Iwasaki Yuichi , Watanabe Haruna , Yamamoto Hiroshi 
Published: December 2021

Abstract
Equilibrium partitioning (EqP) theory and spiked-sediment toxicity tests are useful methods to develop sediment quality benchmarks. However, neither approach has been directly compared based on species sensitivity distributions (SSDs) to date. In the present study, we compared SSDs for 10 nonionic hydrophobic chemicals (e.g., pyrethroid insecticides, other insecticides, and polycyclic aromatic hydrocarbons) based on 10–14-day spiked-sediment toxicity test data with those based on EqP theory using acute water-only tests. Because the exposure periods were different between the two tests, effective concentrations (i.e., median effective/lethal concentration) were corrected to compare SSDs. Accordingly, we found that hazardous concentrations for 50% and 5% of species (HC50 and HC5, respectively) differed by up to a factor of 100 and 129 between the two approaches, respectively. However, when five or more species were used for SSD estimation, their differences were reduced to a factor of 1.7 and 5.1 for HC50 and HC5, respectively, and the 95% confidence intervals of HC50 values overlapped considerably between the two approaches. These results suggest that when the number of test species is adequate, SSDs based on EqP theory and spiked-sediment tests are comparable in sediment risk assessments. Environ Toxicol Chem 2022;41:462–473. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Abstract
Species sensitivity distributions (SSDs) for nonionic organic chemicals were compared based on two approches: Equilibrium partitioning (EqP) theory and spiked-sediment toxicity tests.
Deep transfer learning of structural magnetic resonance imaging fused with blood parameters improves brain age prediction
Authors: Ren Bingyu , Wu Yingtong , Huang Liumei , Zhang Zhiguo , Huang Bingsheng , Zhang Huajie , Ma Jinting , Li Bing , Liu Xukun , Wu Guangyao , Zhang Jian , Shen Liming , Liu Qiong , Ni Jiazuan 
Published: December 2021

AbstractMachine learning has been applied to neuroimaging data for estimating brain age and capturing early cognitive impairment in neurodegenerative diseases. Blood parameters like neurofilament light chain are associated with aging. In order to improve brain age predictive accuracy, we constructed a model based on both brain structural magnetic resonance imaging (sMRI) and blood parameters. Healthy subjects (n = 93; 37 males; aged 50–85 years) were recruited. A deep learning network was firstly pretrained on a large set of MRI scans (n = 1,481; 659 males; aged 50–85 years) downloaded from multiple open‐source datasets, to provide weights on our recruited dataset. Evaluating the network on the recruited dataset resulted in mean absolute error (MAE) of 4.91 years and a high correlation (r = .67, p <.001) against chronological age. The sMRI data were then combined with five blood biochemical indicators including GLU, TG, TC, ApoA1 and ApoB, and 9 dementia‐associated biomarkers including ApoE genotype, HCY, NFL, TREM2, Aβ40, Aβ42, T‐tau, TIMP1, and VLDLR to construct a bilinear fusion model, which achieved a more accurate prediction of brain age (MAE, 3.96 years; r = .76, p <.001). Notably, the fusion model achieved better improvement in the group of older subjects (70–85 years). Extracted attention maps of the network showed that amygdala, pallidum, and olfactory were effective for age estimation. Mediation analysis further showed that brain structural features and blood parameters provided independent and significant impact. The constructed age prediction model may have promising potential in evaluation of brain health based on MRI and blood parameters.
RNA N6‐methyladenosine in nonocular and ocular disease
Authors: Wang Nan , Yao Fei , Liu Die , Jiang Haibo , Xia Xiaobo , Xiong Siqi 
Published: December 2021

AbstractN6‐methyladenosine (m6A), the sixth N methylation of adenylate (A) in RNA, is the most abundant transcriptome modification in eukaryotic messenger RNA (mRNAs). m6A modification exists in both coding mRNA and noncoding RNAs, and its functions are controlled by methyltransferase, demethylase, and m6A reading proteins. Methylation modification of m6A can regulate RNA cleavage, transport, stability, and expression. This review summarizes the enzymes involved in RNA m6A methylation and the commonly used detection methods. The role of m6A modification in physiological processes is described, and its impact on tumorigenesis, viral infection, and diabetes is further highlighted. Moreover, up‐to‐date knowledge of the implications of RNA m6A modification in ocular diseases such as uveal melanoma and diabetic retinopathy is introduced. Clarifying the mechanism of RNA m6A methylation will help elucidate the pathogenesis of various diseases, providing options for subsequent treatment.