bluuebunny/crossref_metadata_2025_split huggingface dataset:
One‐Pot Production of Vanillin from Capsaicinoids through a Retrosynthetic Enzyme Cascade
Authors: Kim Hong‐Gon , Jang Youngho , Shin Jong‐Shik 
Published: February 2024

AbstractVanillin is a key organoleptic component in vanilla, one of the most important natural flavors in the industry. The limited supply of natural vanilla, extracted from cured vanilla beans, elevates the commercial value of ‘natural’‐labeled vanillin, producible by microbial conversion of natural precursors such as ferulic acid, eugenol, isoeugenol, lignin, and glucose. However, cellular toxicity and undesirable overoxidation of vanillin remain challenges to the microbial methods. Here, we developed a one‐pot enzymatic conversion of capsaicinoids to vanillin by retracing the biosynthetic pathway found in Capsicum plants. The enzyme cascade consists of the hydrolysis of capsaicinoids by immobilized lipase B from Candida antarctica (CALB) and the oxidative deamination of the resulting vanillylamine by ω‐transaminase from Paracoccus denitrificans (PDTA). Process optimization of individual enzyme reactions was conducted on an analytical scale, enabling>95% reaction yield of vanillin from capsaicinoids in the one‐pot cascade reaction without undesirable accumulation of the oxidation byproduct and the inhibitory reaction intermediate, i. e., vanillic acid and vanillylamine, respectively. To verify practical applicability, we performed a preparative‐scale reaction starting with 1.75 g capsaicinoids and 2.75 g sodium pyruvate at 10 mg/mL CALB and 3 μM PDTA, leading to an 81% reaction yield and a 57% isolation yield. This study is, to the best of our knowledge, the first demonstration of one‐pot production of vanillin from capsaicinoids, which might pave the way for cost‐effective and sustainable access to natural‐labeled vanillin from a renewable feedstock readily available from Capsicum fruits.
Poly(Glutamic Acid‐Lysine) Hydrogels with Alternating Sequence Resist the Foreign Body Response in Rodents and Non‐Human Primates
Authors: Zhou Xianchi , Cao Wenzhong , Chen Yongcheng , Zhu Zihao , Chen Yifeng , Ni Yanwen , Liu Zuolong , Jia Fan , Lu Zhouyu , Ye Yang , Han Haijie , Yao Ke , Liu Weifeng , Wei Xinyue , Chen Shengfu , Wang Youxiang , Ji Jian , Zhang Peng 
Published: February 2024

AbstractThe foreign body response (FBR) to implanted biomaterials and biomedical devices can severely impede their functionality and even lead to failure. The discovery of effective anti‐FBR materials remains a formidable challenge. Inspire by the enrichment of glutamic acid (E) and lysine (K) residues on human protein surfaces, a class of zwitterionic polypeptide (ZIP) hydrogels with alternating E and K sequences to mitigate the FBR is prepared. When subcutaneously implanted, the ZIP hydrogels caused minimal inflammation after 2 weeks and no obvious collagen capsulation after 6 months in mice. Importantly, these hydrogels effectively resisted the FBR in non‐human primate models for at least 2 months. In addition, the enzymatic degradability of the gel can be controlled by adjusting the crosslinking degree or the optical isomerism of amino acid monomers. The long‐term FBR resistance and controlled degradability of ZIP hydrogels open up new possibilities for a broad range of biomedical applications.
Large‐Scale, Mechanically Robust, Solvent‐Resistant, and Antioxidant MXene‐Based Composites for Reliable Long‐Term Infrared Stealth
Authors: Guo Bi‐Fan , Wang Ye‐Jun , Cao Cheng‐Fei , Qu Zhang‐Hao , Song Jiang , Li Shi‐Neng , Gao Jie‐Feng , Song Pingan , Zhang Guo‐Dong , Shi Yong‐Qian , Tang Long‐Cheng 
Published: February 2024

AbstractMXene‐based thermal camouflage materials have gained increasing attention due to their low emissivity, however, the poor anti‐oxidation restricts their potential applications under complex environments. Various modification methods and strategies, e.g., the addition of antioxidant molecules and fillers have been developed to overcome this, but the realization of long‐term, reliable thermal camouflage using MXene network (coating) with excellent comprehensive performance remains a great challenge. Here, a MXene‐based hybrid network comodified with hyaluronic acid (HA) and hyperbranched polysiloxane (HSi) molecules is designed and fabricated. Notably, the presence of appreciated HA molecules restricts the oxidation of MXene sheets without altering infrared stealth performance, superior to other water‐soluble polymers; while the HSi molecules can act as efficient cross‐linking agents to generate strong interactions between MXene sheets and HA molecules. The optimized MXene/HA/HSi composites exhibit excellent mechanical flexibility (folded into crane structure), good water/solvent resistance, and long‐term stable thermal camouflage capability (with low infrared emissivity of ≈0.29). The long‐term thermal camouflage reliability (≈8 months) under various outdoor weathers and the scalable coating capability of the MXene‐coated textile enable them to disguise the IR signal of various targets in complex environments, indicating the great promise of achieved material for thermal camouflage, IR stealth, and counter surveillance.
Hydrogen Bond‐Mediated Self‐Shielded Moisture‐Responsive Structural Color for Time‐Temperature Indicating
Authors: Kou Donghui , Gao Lei , Lin Ruicheng , Zhang Shufen , Ma Wei 
Published: February 2024

AbstractEffective monitoring of the time‐temperature history of biological reagents, chemical drugs, and perishable foods during cold chain storage is crucial for ensuring their quality and efficacy. Time‐temperature indicators (TTIs) are developed to assess the cumulative impact of time and temperature on product quality. However, current indicators face challenges related to complex wrapping procedures, narrow tracking ranges, susceptibility to photobleaching, and pre‐use instability, hampering widespread use. Herein, the first moisture‐responsive 1D photonic crystal (1DPC) TTIs featuring robust structural colors, customizable time‐temperature ranges, and reliable renewability are demonstrated. The indicators exhibit distinct color‐changing responsiveness toward water vapor, which remains observable after prolonged storage at low temperatures. Significantly, the moisture responsiveness gradually diminishes at elevated temperatures over time due to ambient water‐induced hydrogen bond formation, effectively shielding the indicator from external stimuli. This property enables the naked‐eye inspection of product efficacy during cold chain storage. Additionally, the endowed flexibility of the TTI facilitates its easy attachment to targets, functioning as a convenient indicator label. Remarkably, the indicator can be stably stored for an extended period at room temperature before use, thereby showcasing substantial market potential.
Synergistic Integration of Nanogenerators and Solar Cells: Advanced Hybrid Structures and Applications
Authors: Hajra Sugato , Ali Amanat , Panda Swati , Song Heewoon , Rajaitha P. M. , Dubal Deepak , Borras Ana , In‐Na Pichaya , Vittayakorn Naratip , Vivekananthan Venkateswaran , Kim Hoe Joon , Divya Sivasubramani , Oh Tae Hwan 
Published: February 2024

AbstractThe rapid growth of global energy consumption and the increasing demand for sustainable and renewable energy sources have urged vast research into harnessing energy from various sources. Among them, the most promising approaches are nanogenerators (NGs) and solar cells (SCs), which independently offer innovative solutions for energy harvesting. This review paper presents a comprehensive analysis of the integration of NGs and SCs, exploring advanced hybrid structures and their diverse applications. First, an overview of the principles and working mechanisms of NGs and SCs is provided for seamless hybrid integrations. Then, various design strategies are discussed, such as piezoelectric and triboelectric NGs with different types of SCs. Finally, a wide range of applications are explored that benefit from the synergistic integration of NGs and SCs, including self‐powered electronics, wearable devices, environmental monitoring, and wireless sensor networks. The potential for these hybrid systems is highlighted to address real‐world energy needs and contribute to developing sustainable and self‐sufficient technologies. In conclusion, this review provides valuable insights into the state‐of‐the‐art developments in NGs and SCs integration, shedding light on advanced hybrid structures and their diverse applications.
Capturing mesoscale structures in computational fluid dynamics simulations of gas‐solid flows
Authors: Kumar Balivada Kusum , Ganesh Swathi , Goyal Himanshu 
Published: February 2024

AbstractMultiphase reactors' performance depends on the mesoscale structures formed due to multiphase hydrodynamics. Examples of mesoscale structures include gas bubbles in a fluidized bed and particle clusters in a riser. Experimental investigation of these mesoscale structures is challenging and expensive. To this end, computational fluid dynamics (CFD) simulations are extensively employed; however, post‐processing CFD data to capture mesoscale structures is challenging. This article develops a density‐based spatial clustering of applications with noise (DBSCAN)‐based methodology to capture and characterize mesoscale structures from multiphase CFD simulation data. DBSCAN is an unsupervised machine‐learning algorithm, which requires the value of two hyperparameters. A simple technique to calculate these hyperparameters is provided and the performance of DBSCAN is assessed on CFD‐DEM simulations of bubbling fluidized beds and particle clustering. We demonstrate the computational complexity of DBSCAN to be , lower than the existing techniques, by testing its scalability on highly resolved grids (up to 100 million grid points).
RET 634 germline/gonadal mosaicism generating a second pathogenic amino acid change in multiple endocrine neoplasia type 2A
Authors: Valente Flávia O. F. , Camacho Cléber P. , Lindsey Susan C. , Yang Ji H. , Kunii Ilda S. , Santos Roberto B. , Kizys Marina M. L. , Cerutti Janete M. , Dias‐da‐Silva Magnus R. , Maciel Rui M. B. 
Published: February 2024

AbstractGenetic testing for germline RET pathogenic variants, which cause the Multiple Endocrine Neoplasia Type 2 (MEN2) syndrome, has become crucial in managing patients with medullary thyroid carcinoma (MTC). Classically, RET heterozygous missense pathogenic variants are transmitted in a Mendelian autosomal dominant pattern, of which germline/gonadal mosaicism has never been reported. We report the novel occurrence of a MEN2A patient's family in which the siblings inherited three different RET 634 genotypes: wild type (p.Cys634), p.Cys634Gly or p.Cys634Arg heterozygous pathogenic variants. We hypothesized that germline/gonadal mosaicism, derived from an inherited + early somatic mutation in the mother or a double de novo mutation during maternal embryogenesis, led to this rare event in the RET gene. Exome analysis of the proband's deceased mother's paraffin‐embedded thyroid tissue confirmed the three nucleotides in the same 634 codon position. For the first time, we describe germline/gonadal mosaicism in RET, generating a second pathogenic amino acid change in the same codon causing MEN2A. Our finding shows that RET parental mosaicism, confirmed by somatic exome sequencing, might explain discrepant genotype cases in siblings with inherited cancers.
Fe, N‐Inducing Interfacial Electron Redistribution in NiCo Spinel on Biomass‐Derived Carbon for Bi‐functional Oxygen Conversion
Authors: Liu Yanyan , Zhou Limin , Liu Shuling , Li Shuqi , Zhou Jingjing , Li Xin , Chen Xiangmeng , Sun Kang , Li Baojun , Jiang Jianchun , Pang Huan 
Published: February 2024

AbstractHerein, an interfacial electron redistribution is proposed to boost the activity of carbon‐supported spinel NiCo2O4 catalyst toward oxygen conversion via Fe, N‐doping strategy. Fe‐doping into octahedron induces a redistribution of electrons between Co and Ni atoms on NiCo1.8Fe0.2O4@N‐carbon. The increased electron density of Co promotes the coordination of water to Co sites and further dissociation. The generation of proton from water improves the overall activity for the oxygen reduction reaction (ORR). The increased electron density of Ni facilitates the generation of oxygen vacancies. The Ni−VO−Fe structure accelerates the deprotonation of *OOH to improve the activity toward oxygen evolution reaction (OER). N‐doping modulates the electron density of carbon to form active sites for the adsorption and protonation of oxygen species. Fir wood‐derived carbon endows catalyst with an integral structure to enable outstanding electrocatalytic performance. The NiCo1.8Fe0.2O4@N‐carbon express high half‐wave potential up to 0.86 V in ORR and low overpotential of 270 mV at 10 mA cm−2 in OER. The zinc‐air batteries (ZABs) assembled with the as‐prepared catalyst achieve long‐term cycle stability (over 2000 cycles) with peak power density (180 mWcm−2). Fe, N‐doping strategy drives the catalysis of biomass‐derived carbon‐based catalysts to the highest level for the oxygen conversion in ZABs.
Reaktivität von Superbasischen Carbanionen erzeugt über Reduktiven Radikal‐Polaren Übergang im Kontext der Photoredoxkatalyse
Authors: Grotjahn Sascha , Graf Christina , Zelenka Jan , Pattanaik Aryaman , Müller Lea , Kutta Roger Jan , Rehbein Julia , Roithová Jana , Gschwind Ruth M. , Nuernberger Patrick , König Burkhard 
Published: February 2024

AbstractPhotokatalytische Reaktionen, die einen reduktiven radikal‐polaren Übergang (RRPCO) beinhalten, erzeugen Intermediate mit carbanionischer Reaktivität. Viele dieser postulierten Intermediate entsprechen hochreaktiven metallorganischen Verbindungen. Die Bedingungen für ihre Bildung werden im Allgemeinen jedoch von ihren isolierten metallorganischen Analoga nicht toleriert und häufig wird eine andere Reaktivität beobachtet. Unsere Untersuchungen zu ihrer Natur und Reaktivität unter den üblichen photokatalytischen Bedingungen zeigen auf, dass diese Intermediate in der Tat als freie, superbasische Carbanionen beschrieben werden können, die in der Lage sind, gängige polare Lösungsmittel wie Acetonitril und Dimethylsulfoxid zu deprotonieren, die normalerweise als inert gelten. Ihre Basizität, nicht nur gegenüber Lösungsmitteln, sondern auch gegenüber Elektrophilen wie Aldehyden, Ketonen und Estern, ist vergleichbar mit der Reaktivität von isolierten Carbanionen in der Gasphase. Zuvor erfolglose Reaktionen, von denen man annahm, dass sie aus mangelnder Reaktivität resultieren, lassen sich durch ihre hohe Reaktivität gegenüber dem Lösungsmittel und schwach aciden Protonen der Reaktionspartner erklären. Dies liefert eine intuitive Erklärung für das Verhalten von photokatalytisch erzeugten Carbanionen, die es ermöglicht, Reaktionsmechanismen zu verifizieren, bei denen ein RRPCO‐Schritt vermutet wird, und erlaubt eine Abschätzung des synthetischen Anwendungsbereiches.
The Ferroxidase Centre of Escherichia coli Bacterioferritin Plays a Key Role in the Reductive Mobilisation of the Mineral Iron Core
Authors: Bradley Justin M. , Bugg Zinnia , Sackey Aaren , Andrews Simon C. , Wilson Michael T. , Svistunenko Dimitri A. , Moore Geoffrey R. , Le Brun Nick E. 
Published: February 2024

AbstractFerritins are multimeric cage‐forming proteins that play a crucial role in cellular iron homeostasis. All H‐chain‐type ferritins harbour a diiron site, the ferroxidase centre, at the centre of a 4 α‐helical bundle, but bacterioferritins are unique in also binding 12 hemes per 24 meric assembly. The ferroxidase centre is known to be required for the rapid oxidation of Fe2+ during deposition of an immobilised ferric mineral core within the protein's hollow interior. In contrast, the heme of bacterioferritin is required for the efficient reduction of the mineral core during iron release, but has little effect on the rate of either oxidation or mineralisation of iron. Thus, the current view is that these two cofactors function in iron uptake and release, respectively, with no functional overlap. However, rapid electron transfer between the heme and ferroxidase centre of bacterioferritin from Escherichia coli was recently demonstrated, suggesting that the two cofactors may be functionally connected. Here we report absorbance and (magnetic) circular dichroism spectroscopies, together with in vitro assays of iron‐release kinetics, which demonstrate that the ferroxidase centre plays an important role in the reductive mobilisation of the bacterioferritin mineral core, which is dependent on the heme‐ferroxidase centre electron transfer pathway.
A Semi‐Automated, High‐Throughput Approach for the Synthesis and Identification of Highly Photo‐Cytotoxic Iridium Complexes
Authors: Kench Timothy , Rahardjo Arielle , Terrones Gianmarco G. , Bellamkonda Adinarayana , Maher Thomas E. , Storch Marko , Kulik Heather J. , Vilar Ramon 
Published: February 2024

AbstractThe discovery of new compounds with pharmacological properties is usually a lengthy, laborious and expensive process. Thus, there is increasing interest in developing workflows that allow for the rapid synthesis and evaluation of libraries of compounds with the aim of identifying leads for further drug development. Herein, we apply combinatorial synthesis to build a library of 90 iridium(III) complexes (81 of which are new) over two synthesise‐and‐test cycles, with the aim of identifying potential agents for photodynamic therapy. We demonstrate the power of this approach by identifying highly active complexes that are well‐tolerated in the dark but display very low nM phototoxicity against cancer cells. To build a detailed structure–activity relationship for this class of compounds we have used density functional theory (DFT) calculations to determine some key electronic parameters and study correlations with the experimental data. Finally, we present an optimised semi‐automated synthesise‐and‐test protocol to obtain multiplex data within 72 hours.
Study on mechanical, thermal and shape memory properties of polycarbonate/thermoplastic polyurethane blends
Authors: Tyagi Mukti , Rawat Rajkumar Singh , Tyagi Vinay Kumar , Talwar Meenu , Kumar Manmohan , Das Mukul , Roy Prasun 
Published: February 2024

AbstractThe objective of the study is preparation of shape memory blend of polycarbonate (PC) and thermoplastic polyurethane (TPU). Polycarbonate is blended with three types of TPUs and subsequently mechanical, thermal, morphological, and shape memory properties of the PC/TPU blends are studied. When TPU content in the blend is higher than 40% (by weight), the glass transition temperature related to PC is not shown in the differential scanning calorimetry thermogram, indicating loss of PC properties. The 60/40 optimized blend of PC/TPUs exhibits maximum increment of about 1100% in elongation and 43% decrement in tensile strength. The shape recovery of the optimized blend obtained by addition of 40% (by weight) of TPUs in PC polymer is found to be 65% and shape fixity is 97%. These results suggest that the blend of PC/TPU may be utilized for various applications where shape memory property is required including strategic applications.
Wettability alteration of oil‐wet carbonate rocks by chitosan derivatives for application in enhanced oil recovery II: High‐temperature and high‐pressure conditions—Core flooding tests
Authors: dos Santos Francisco Agatha Densy , Maia Kelly Cristina Bastos , de Almeida Cavadas Leandro , Eler Felipe Moreira , Grasseschi Daniel , Couto Paulo , Nascimento Regina Sandra Veiga 
Published: February 2024

AbstractBiopolymers, serving as Enhanced Oil Recovery (EOR) agents, are posing challenges and opportunities within the oil industry, particularly in demanding operational conditions. The assessment of trimethyl chitosan (TMC) and its hydrophobized derivative with myristoyl chloride (TMC‐C14) becomes crucial in these rigorous scenarios, presenting a significant challenge for polymer flooding. The study subjected TMC and TMC‐C14 to comprehensive evaluations as EOR agents, employing contact angle measurements, interfacial tension tests using the Drop Shape Analyzer (DSA), and core flood tests under conditions of 60°C, 1000 psi, and elevated salinity. Relative permeabilities were deduced from the results, while spontaneous imbibition tests provided insights into rock wettability. Amott cell tests underscored that both TMC and TMC‐C14 induced accelerated spontaneous oil production within a span of 30 days. Notably, TMC‐C14 exhibited superior interfacial activity compared to TMC, attributed to its hydrophobic segments. The impact on rock wettability was distinct: TMC shifted it towards water‐wet, while TMC‐C14 induced a neutral‐wet condition. This transformation was corroborated by contact angle measurements, imbibition tests, and relative permeability curves. Capillary forces, computed from DSA data and spontaneous imbibition tests, further validated the wettability‐altering tendencies of the chitosan derivatives on the rock. In core flooding tests and relative permeability curves, TMC demonstrated a notable improvement in the recovery factor (RF) compared to seawater. Specifically, RFTMC achieved 69%, surpassing RFbrine at 49%, affirming that the primary mechanism of action for chitosan derivatives lies in their ability to modify rock wettability. This study shows the potential of TMC and TMC‐C14 as effective EOR agents, shedding light on their interfacial activities, impact on rock wettability, and enhanced recovery factors in challenging operational conditions.
Chemical composition and biological activities of Cucurbita okeechobeensis extracts from its aerial parts, seeds, and fruit shells
Authors: Llorent‐Martínez Eulogio J. , Ruiz‐Medina Antonio , Terzic Milena , Sinan Kouadio Ibrahime , Koyuncu Ismail , Egi Kadir , Nilofar Nilofar , Zengin Gokhan 
Published: February 2024

AbstractThe Cucurbita genus has been widely used in traditional medicinal systems across different countries. In this study, we aimed to investigate the chemical composition, antioxidant properties, enzyme inhibitory, and cytotoxic effects of methanol and aqueous extracts obtained from the aerial parts, seeds, and fruit shells of Cucurbita okeechobeensis. Antioxidant properties were assessed using various chemical methods, including radical quenching (DPPH and ABTS), reducing power (CUPRAC and FRAP), metal chelation, and phosphomolybdenum assays. The extracts' enzyme inhibitory effects were tested against cholinesterase, amylase, glucosidase, and tyrosinase, whereas different cancer cell lines were used for the cytotoxicity study. The chemical composition, evaluated by HPLC‐ESI‐MSn, showed that the most abundant compounds were flavonoids (mainly quercetin glycosides) followed by phenolic acids (mostly caffeic acid derivatives). The aerial parts displayed stronger antioxidant ability than the seed and fruit shells, in agreement with the highest content in phytochemicals. In addition, the methanol extracts presented the highest bioactivity and content in phytochemicals; among them, the extract of the aerial part exhibited significant cytotoxic effects on cancer cell lines and induced apoptosis. Overall, our results suggest that C. okeechobeensis is a valuable source of bioactive compounds for the pharmaceutical and nutraceutical industries.