bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Effect of Torsional Motion on Multiexciton Formation through Intramolecular Singlet Fission in Ferrocene‐Bridged Pentacene Dimers
Authors: Hayasaka Ryo , Sakai Hayato , Fuki Masaaki , Okamoto Tsubasa , Khan Ramsha , Higashi Masahiro , Tkachenko Nikolai V. , Kobori Yasuhiro , Hasobe Taku 
Published: January 2024

AbstractA series of ferrocene(Fc)‐bridged pentacene(Pc)‐dimers [Fc−Ph(2,n)−(Pc)2: n=number of phenylene spacers] were synthesized to examine the tortional motion effect of Fc‐terminated phenylene linkers on strongly coupled quintet multiexciton (5TT) formation through intramolecular singlet fission (ISF). Fc−Ph(2,4)−(Pc)2 has a relatively small electronic coupling and large conformational flexibility according to spectroscopic and theoretical analyses. Fc−Ph(2,4)−(Pc)2 exhibits a high‐yield 5TT together with quantitative singlet TT (1TT) generation through ISF. This demonstrates a much more efficient ISF than those of other less flexible Pc dimers. The activation entropy in 1TT spin conversion of Fc−Ph(2,4)−(Pc)2 is larger than those of the other systems due to the larger conformational flexibility associated with the torsional motion of the linkers. The torsional motion of linkers in 1TT is attributable to weakened metal‐ligand bonding in the Fc due to hybridization of the hole level of Pc to Fc in 1TT unpaired orbitals.
Photoinduced Decarboxylative Radical Phosphinylation
Authors: Cheng Yulu , Zhen Jingsen , Chai Linxiang , Wang Jian , Yin Junyue , Zhu Lin , Li Chaozhong 
Published: January 2024

AbstractReported herein is an unprecedented protocol for C(sp3)‐phosphinylation. With 1 mol % 4CzIPN (1,2,3,5‐tetrakis(carbazol‐9‐yl)‐4,6‐dicyanobenzene) as the catalyst, the visible light induced reaction of redox‐active esters of aliphatic carboxylic acids with dimethyl arylphosphonites or diethyl alkylphosphonites at room temperature provides the corresponding decarboxylative phosphinylation products in satisfactory yields. The protocol exhibits broad substrate scope and wide functional‐group compatibility, enabling the late‐stage modification of complex molecules and rapid synthesis of bioactive phosphinic acids such as glutamine synthetase phosphinothricin and a kynureninase inhibitor. A radical‐polar crossover mechanism involving the formation and subsequent oxidation of phosphoranyl radicals followed by nucleophilic demethylation (or deethylation) is proposed.
Hydrogenation of CO2 to Light Olefins over ZnZrOx/SSZ‐13
Authors: Chen Siyu , Wang Jiachen , Feng Zhendong , Jiang Yiming , Hu Hanwen , Qu Yuanzhi , Tang Shan , Li Zelong , Liu Jiaxu , Wang Jijie , Li Can 
Published: January 2024

AbstractConverting CO2 to olefins is an ideal route to achieve carbon neutrality. However, selective hydrogenation to light olefins, especially single‐component olefin, while reducing CH4 formation remains a great challenge. Herein, we developed ZnZrOx/SSZ‐13 tandem catalyst for the highly selective hydrogenation of CO2 to light olefins. This catalyst shows C2=−C4= and propylene selectivity up to 89.4 % and 52 %, respectively, while CH4 is suppressed down to 2 %, and there is no obvious deactivation. It is demonstrated that the isolated moderate Brønsted acid sites (BAS) of SSZ‐13 promotes the rapid conversion of intermediate species derived from ZnZrOx, thereby enhancing the kinetic coupling of the reactions and inhibit the formation of alkanes and improve the light olefins selectivity. Besides, the weaker BAS of SSZ‐13 promote the conversion of intermediates into aromatics with 4–6 methyl groups, which is conducive to the aromatics cycle. Accordingly, more propene can be obtained by elevating the Si/Al ratio of SSZ‐13. This provides an efficient strategy for CO2 hydrogenation to light olefins with high selectivity.
Stabilization of Acenes: “Geländer”‐Pentacenes
Authors: Ludwig Philipp , Rominger Frank , Freudenberg Jan , Bunz Uwe H. F. 
Published: January 2024

AbstractWe report soluble tetrakis‐biphenylyl substituted pentacenes comprised of sp2 carbons and synthesized from pentacene‐5,7,12,14‐tetraone. Intramolecular Yamamoto coupling of two tetrakis(chlorobiphenylyl)pentacenes yields helical, doubly wrapped pentacenes, in which the quaterphenylene units solubilize the pentacenes and shield their central anthracene units to an unprecedented degree. The criss‐cross‐bridged pentacenes resist (photo)oxidation, Diels–Alder reactions and are much less reactive than TIPS‐ethynylated pentacene. Extension of this concept might provide access to the larger acenes.
Intermediates in Mechanochemical Reactions
Authors: Ardila‐Fierro Karen J. , Hernández José G. 
Published: January 2024

AbstractMechanochemical reactions offer methodological and environmental advantages for chemical synthesis, constantly attracting attention within the scientific community. Besides unmistakable sustainability advantages, the conditions under which mechanochemical reactions occur, namely solventless conditions, sometimes facilitate the isolation of otherwise labile or inaccessible products. Despite these advantages, limited knowledge exists regarding the mechanisms of these reactions and the types of intermediates involved. Nevertheless, in an expanding number of cases, ex situ and in situ monitoring techniques have allowed for the observation, characterization, and isolation of reaction intermediates in mechanochemical transformations. In this Minireview, we present a series of examples in which reactive intermediates have been detected in mechanochemical reactions spanning organic, organometallic, inorganic, and materials chemistry. Many of these intermediates were stabilized by non‐covalent interactions, which played a pivotal role in guiding the chemical transformations. We believe that by uncovering and understanding such instances, the growing mechanochemistry community could find novel opportunities in catalysis and discover new mechanochemical reactions while achieving simplification in chemical reaction design.
Hygroscopic Solutes Enable Non‐van der Waals Electrolytes for Fire‐Tolerant Dual‐Air Batteries
Authors: Xia Huarong , Cao Shengkai , Lv Zhisheng , Wei Jiaqi , Yuan Song , Feng Xue , Chen Xiaodong 
Published: January 2024

AbstractThermal safety issues of batteries have hindered their large‐scale applications. Nonflammable electrolytes improved safety but solvent evaporation above 100 °C limited thermal tolerance, lacking reliability. Herein, fire‐tolerant metal‐air batteries were realized by introducing solute‐in‐air electrolytes whose hygroscopic solutes could spontaneously reabsorb the evaporated water solvent. Using Zn/CaCl2‐in‐air/carbon batteries as a proof‐of‐concept, they failed upon burning at 631.8 °C but self‐recovered then by reabsorbing water from the air at room temperature. Different from conventional aqueous electrolytes whose irreversible thermal transformation is determined by the boiling points of solvents, solute‐in‐air electrolytes make this transformation determined by the much higher decomposition temperature of solutes. It was found that stronger intramolecular bonds instead of intermolecular (van der Waals) interactions were strongly correlated to ultra‐high tolerance temperatures of our solute‐in‐air electrolytes, inspiring a concept of non‐van der Waals electrolytes. Our study would improve the understanding of the thermal properties of electrolytes, guide the design of solute‐in‐air electrolytes, and enhance battery safety.
DNA barcoding of the genus Gampsocleis (Orthoptera, Tettigoniidae) from China
Authors: Zhang Pu , Cai Yuting , Ma Lan , Chai Jinyan , Zhou Zhijun 
Published: January 2024

AbstractDNA barcoding is a useful addition to the traditional morphology‐based taxonomy. A ca. 650 bp fragment of the 5′ end of mitochondrial cytochrome c oxidase subunit I (hereafter COI‐5P) DNA barcoding was sued as a practical tool for Gampsocleis species identification. DNA barcodes from 889 specimens belonging to 8 putative Gampsocleis species was analyzed, including 687 newly generated DNA barcodes. These barcode sequences were clustered/grouped into Operational Taxonomic Units (OTUs) using the criteria of five algorithms, namely Barcode Index Number (BIN) System, Assemble Species by Automatic Partitioning (ASAP), a Java program uses an explicit, determinate algorithm to define Molecular Operational Taxonomic Unit (jMOTU), Generalized Mixed Yule Coalescent (GMYC), and Bayesian implementation of the Poisson Tree Processes model (bPTP). The Taxon ID Tree grouped sequences of morphospecies and almost all MOTUs in distinct nonoverlapping clusters. Both long‐ and short‐winged Gampsocleis species are reciprocally monophyletic in the Taxon ID Tree. In BOLD, 889 barcode sequences are assigned to 17 BINs. The algorithms ASAP, jMOTU, bPTP and GMYC clustered the barcode sequences into 6, 13, 10, and 23 MOTUs, respectively. BIN, ASAP, and bPTP algorithm placed three long‐winged species, G. sedakovii, G. sinensis and G. ussuriensis within the same MOTU. All species delimitation algorithms split two short‐winged species,G. fletcheri and G. gratiosa into at least two MOTUs each, except for ASAP algorithm. More detailed molecular and morphological integrative studies are required to clarify the status of these MOTUs in the future.
Alt‐health influencers and the threat of social media deplatforming
Authors: Zimdars Melissa 
Published: January 2024

AbstractThe threat of deplatforming as a content moderation strategy works to reduce harmful anti‐vaccine content and health mis/disinformation on particular social media platforms. However, through an analysis of alt‐health influencers, I show how the perpetual threat of being deplatformed allows them to strategically grow their audiences while funneling users to fringe platforms where the alt‐health influencers share anti‐vaccine and extremist content. Alt‐health influencers are thus able to “launder” their reputations and their content through mainstream social media platforms, acting in accordance with each platform's specific content moderation policies, while persuasively deploying “deep stories” and developing parasocial relationships across mainstream and fringe platforms, building an alt‐health influence network across platforms, and using threats of “censorship” on one platform to sell and legitimize their statuses as truth‐tellers and informational authorities on another. The threat of deplatforming aids in the spreading of health mis/disinformation across social media platforms, demonstrating the necessity of addressing well‐known alt‐health influencers who are detrimental to the health of the overall information ecosystem through decisive, consistent, and multi‐platform‐coordinated deplatforming.
Demand for live betting: An analysis using state‐space models
Authors: Ötting Marius , Michels Rouven , Langrock Roland , Deutscher Christian 
Published: January 2024

AbstractSports betting markets have grown very rapidly recently, with the total European gambling market worth 98.6 billion euro in 2019. Considering a high‐resolution (1 Hz) data set provided by a large European bookmaker, we investigate the demand for bet placements during matches and in particular the effect of news. Accounting for the general market activity level within a state‐space modelling framework, we analyse the market's response to events such as goals (i.e., major news). Our results indicate that markets strongly react to news, but other factors, such as the day of the week and the uncertainty of outcome, also affect the stakes placed. We thus provide insights into the behaviour of bettors during matches, which can be relevant for bookmakers, for example to predict future revenues, but also for more specialised tasks such as fraud detection.
[4]Helicenium Ion as Bipolar Redox Material for Symmetrical Fully Organic Pole‐less Redox Flow Battery
Authors: Moutet Jules , Mills David D. , Lozier Diego L. , Gianetti Thomas L. 
Published: January 2024

AbstractLong duration storage batteries such as Redox Flow Batteries (RFBs) are promising storage system to address the energy storage requirement that our society will require in the years to come. Recent effort has been focused on the development of metal free and high energy density system such as all‐organic non‐aqueous redox flow batteries (NAORFBs). However high‐voltage NAORFBs currently use distinct anolytes and catholytes, which are separated by a membrane sensitive to osmotic pressure, resulting in rapid capacity and energy density degradation over time. To address this issue, symmetric organic redox flow batteries (SORFBs) have been proposed as an elegant solution. We have introduced dimethoxyquinacridiniums (DMQA+) ions as efficient bipolar redox molecules (BRMs) in static H‐cell conditions. In this study, we present the first application of DMQA+ ions in a complete flow RFB prototype, showcasing their ability to operate with polarity reversal. Key kinetic properties were evaluated through cyclic voltammetry and DFT calculations. While coulombic and energy efficiency metrics were moderate, pegylated DMQA+ demonstrated impressive capacity retention of over 99.99 % and the capability to operate under polarity inversion, making it a highly attractive choice for grid‐scale, long‐lifespan energy storage applications.
Hyper‐production of porcine contagious pleuropneumonia subunit vaccine proteins in Escherichia coli by developing a bicistronic T7 expression system
Authors: Sun Manman , Gao Alex Xiong , Li An , Ledesma‐Amaro Rodrigo , Wang Peng , Chen Wenchao , Bai Zhonghu , Liu Xiuxia 
Published: January 2024

AbstractThe ApxII toxin and the outer membrane lipoprotein (Oml) of Actinobacillus pleuropneumoniae are important vaccine antigens against porcine contagious pleuropneumonia (PCP), a prevalent infectious disease affecting the swine industry worldwide. Previous studies have reported the recombinant expression of ApxII and Oml in Escherichia coli; however, their yields were not satisfactory. Here, we aimed to enhance the production of ApxII and Oml by constructing a bicistronic expression system based on the widely used T7 promoter. To create efficient T7 bicistronic expression cassettes, 16 different fore‐cistron sequences were introduced downstream of the T7 promoter. The expression of three vaccine antigens Oml1, Oml7, and ApxII in the four strongest bicistronic vectors were enhanced compared to the monocistronic control. Further optimization of the fermentation conditions in micro‐well plates (MWP) led to improved production. Finally, the production yields reached unprecedented levels of 2.43 g L−1 of Oml1, 2.59 g L−1 of Oml7, and 1.21 g L−1 of ApxII, in a 5 L bioreactor. These three antigens also demonstrated well‐protective immunity against A. pleuropneumoniae infection. In conclusion, this study establishes an efficient bicistronic T7 expression system that can be used to express recombinant proteins in E. coli and achieves the hyper‐production of PCP vaccine proteins.
A high catalytic efficiency and chemotolerant formate dehydrogenase from Bacillus simplex
Authors: Boonkumkrong Rattima , Chunthaboon Paweenapon , Munkajohnpong Pobthum , Watthaisong Pratchaya , Pimviriyakul Panu , Maenpuen Somchart , Chaiyen Pimchai , Tinikul Ruchanok 
Published: January 2024

AbstractNAD+‐dependent formate dehydrogenase (FDH) catalyzes the conversion of formate and NAD+ to produce carbon dioxide and NADH. The reaction is biotechnologically important because FDH is widely used for NADH regeneration in various enzymatic syntheses. However, major drawbacks of this versatile enzyme in industrial applications are its low activity, requiring its utilization in large amounts to achieve optimal process conditions. Here, FDH from Bacillus simplex (BsFDH) was characterized for its biochemical and catalytic properties in comparison to FDH from Pseudomonas sp. 101 (PsFDH), a commonly used FDH in various biocatalytic reactions. The data revealed that BsFDH possesses high formate oxidizing activity with a kcat value of 15.3 ± 1.9 s−1 at 25°C compared to 7.7 ± 1.0 s−1 for PsFDH. At the optimum temperature (60°C), BsFDH exhibited 6‐fold greater activity than PsFDH. The BsFDH displayed higher pH stability and a superior tolerance toward sodium azide and H2O2 inactivation, showing a 200‐fold higher Ki value for azide inhibition and remaining stable in the presence of 0.5% H2O2 compared to PsFDH. The application of BsFDH as a cofactor regeneration system for the detoxification of 4‐nitrophenol by the reaction of HadA, which produced a H2O2 byproduct was demonstrated. The biocatalytic cascades using BsFDH demonstrated a distinct superior conversion activity because the system tolerated H2O2 well. Altogether, the data showed that BsFDH is a robust enzyme suitable for future application in industrial biotechnology.
Development of an in‐line Raman analytical method for commercial‐scale CHO cell culture process monitoring: Influence of measurement channels and batch number on model performance
Authors: Yan Xu , Dong Xiaoxiao , Wan Yuxiang , Gao Dong , Chen Zhenhua , Zhang Ying , Zheng Zhilong , Chen Kaifeng , Jiao Jingyu , Sun Yan , He Zhuohong , Nie Lei , Fan Xiaohui , Wang Haibin , Qu Haibin 
Published: January 2024

AbstractThe mammalian cell culture process is a key step in commercial therapeutic protein production and needs to be monitored and controlled due to its complexity. Raman spectroscopy has been reported for cell culture process monitoring by analysis of many important parameters. However, studies on in‐line Raman monitoring of the cell culture process were mainly conducted on small or pilot scale. Developing in‐line Raman analytical methods for commercial‐scale cell culture process monitoring is more challenging. In this study, an in‐line Raman analytical method was developed for monitoring glucose, lactate, and viable cell density (VCD) in the Chinese hamster ovary (CHO) cell culture process during commercial production of biosimilar adalimumab (1500 L). The influence of different Raman measurement channels was considered to determine whether to merge data from different channels for model development. Raman calibration models were developed and optimized, with minimum root mean square error of prediction of 0.22 g L−1 for glucose in the range of 1.66–3.53 g L−1, 0.08 g L−1 for lactate in the range of 0.15–1.19 g L−1, 0.31 E6 cells mL−1 for VCD in the range of 0.96–5.68 E6 cells mL−1 on test sets. The developed analytical method can be used for cell culture process monitoring during manufacturing and meets the analytical purpose of this study. Further, the influence of the number of batches used for model calibration on model performance was also studied to determine how many batches are needed basically for method development. The proposed Raman analytical method development strategy and considerations will be useful for monitoring of similar bioprocesses.
First‐ and second‐generation integrated process for bioethanol production: Fermentation of molasses diluted with hemicellulose hydrolysate by recombinant Saccharomyces cerevisiae
Authors: de Oliveira Pereira Isabela , dos Santos Ângela A. , Guimarães Nick C. , Lima Cleilton S. , Zanella Eduardo , Matsushika Akinori , Rabelo Sarita C. , Stambuk Boris U. , Ienczak Jaciane L. 
Published: January 2024

AbstractThe integration of first‐ (1G) and second‐generation (2G) ethanol production by adding sugarcane juice or molasses to lignocellulosic hydrolysates offers the possibility to overcome the problem of inhibitors (acetic acid, furfural, hydroxymethylfurfural and phenolic compounds), and add nutrients (such as salts, sugars and nitrogen sources) to the fermentation medium, allowing the production of higher ethanol titers. In this work, an 1G2G production process was developed with hemicellulosic hydrolysate (HH) from a diluted sulfuric acid pretreatment of sugarcane bagasse and sugarcane molasses. The industrial Saccharomyces cerevisiae CAT‐1 was genetically modified for xylose consumption and used for co‐fermentation of sucrose, fructose, glucose, and xylose. The fed‐batch fermentation with high cell density that mimics an industrial fermentation was performed at bench scale fermenter, achieved high volumetric ethanol productivity of 1.59 g L−1 h−1, 0.39 g g−1 of ethanol yield, and 44.5 g L−1 ethanol titer, and shown that the yeast was able to consume all the sugars present in must simultaneously. With the results, it was possible to establish a mass balance for the global process: from pretreatment to the co‐fermentation of molasses and HH, and it was possible to establish an effective integrated process (1G2G) with sugarcane molasses and HH co‐fermentation employing a recombinant yeast.
Protein constraints in genome‐scale metabolic models: Data integration, parameter estimation, and prediction of metabolic phenotypes
Authors: Ferreira Maurício Alexander de Moura , Silveira Wendel Batista da , Nikoloski Zoran 
Published: January 2024

AbstractGenome‐scale metabolic models provide a valuable resource to study metabolism and cell physiology. These models are employed with approaches from the constraint‐based modeling framework to predict metabolic and physiological phenotypes. The prediction performance of genome‐scale metabolic models can be improved by including protein constraints. The resulting protein‐constrained models consider data on turnover numbers (kcat) and facilitate the integration of protein abundances. In this systematic review, we present and discuss the current state‐of‐the‐art regarding the estimation of kinetic parameters used in protein‐constrained models. We also highlight how data‐driven and constraint‐based approaches can aid the estimation of turnover numbers and their usage in improving predictions of cellular phenotypes. Finally, we identify standing challenges in protein‐constrained metabolic models and provide a perspective regarding future approaches to improve the predictive performance.
Green synthesis and bioefficacy screening of new insect growth regulators as eco‐friendly insecticides against the cotton mealybug Phenacoccus solenopsis
Authors: Bakry Moustafa M. S. , Abdelhamid Antar A. , Al‐Hoshani Nawal , El Hadi Mohamed Rania Ali , Gad Mohamed A. 
Published: January 2024

AbstractOvercoming or reducing the majority of difficulties caused by the use of common pesticides requires the use of developed, secure, unique and selective organic compounds. Due to their clear mechanism of action on pests and lower poisonousness towards vertebrates than conventional insecticides, juvenile hormone analogues as an example of insect growth regulators appear promising. Thus, a unique set of pure insect growth regulators has been synthesized. The structure of these synthesized compounds, which were related to the most well‐known insect growth regulator insecticides, was confirmed by elemental and contemporary spectroscopic investigations (IR, UV, 1H‐NMR, 13C NMR, and Dept 135 spectrum). Under laboratory conditions, the effectiveness of a chemically newly synthesized products was tested against the cotton mealybug, Phenacoccus solenopsis, and compared with Fenoxycarb as a reference insecticide. Compound 7 was discovered to be more effective than the other synthetic compounds, with LC50 values of 0.907 mg/L for adult female P. solenopsis and 0.377 mg/L for third instar nymphs. Furthermore, this results concluded that the adult female's stage of P. solenopsis was less sensitive to the checked treatments as matched to the third instar nymphs.