bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractStrong 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

AbstractThe 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

AbstractThe 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

AbstractRestrained 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

AbstractOne 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

AbstractFour 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

AbstractThe 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

AbstractSolid‐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

AbstractThe 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

AbstractCarinata 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

AbstractIn 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.
Preparation, Structural Analysis and Antioxidant Activity of Polysaccharides and Their Derivatives from Pueraria lobata
Authors: Fan Yumin , Huang Gangliang 
Published: March 2023

AbstractPueraria 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

AbstractPsoralens 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

AbstractCarbon 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

AbstractInk 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

AbstractCarbon 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

AbstractThe 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.
Controlled Shell and Kernel Modifications of Atomically Precise Pd/Ag Superatomic Nanoclusters
Authors: Ni Yu‐Rong , Pillay Michael N. , Chiu Tzu‐Hao , Wu Ying‐Yann , Kahlal Samia , Saillard Jean‐Yves , Liu C. W. 
Published: March 2023

AbstractThe first 8‐electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg19(dtp)12] (dtp=S2P(OiPr)2−) 1 and [PdHAg20(dtp)12]+ 2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of trifluoroacetic acid, resulting in the formation of 2 in 55 % yield. Further modification of the shell results in the formation of [PdAg21(dtp)12]+ 3 via an internal redox reaction, with the system retaining an 8‐electron superatomic configuration. The interstitial hydride in 1 and 2 contributes its 1s1 electron to the superatomic electron count and occupies a PdAg3 tetrahedron. The distributions of isomers corresponding to different dispositions of the outer capping Ag atoms are investigated by multinuclear VT NMR spectroscopy. The emissive state of 3 has a lifetime of 200 μs (λex=448; λem=842), while 1 and 2 are non‐emissive. The catalytic reduction of 4‐nitrophenol is demonstrated with 1–3 at room temperature.