bluuebunny/crossref_metadata_2025_split huggingface dataset:
Selective RNA Processing and Stabilization are Multi‐Layer and Stoichiometric Regulators of Gene Expression in Escherichia coli
Authors: Liu Daixi , Lv Haibo , Wang Yafei , Chen Jinyu , Li Dexin , Huang Ranran 
Published: October 2023

AbstractSelective RNA processing and stabilization (SRPS) facilitates the differential expression of multiple genes in polycistronic operons. However, how the coordinated actions of SRPS‐related enzymes affect stoichiometric regulation remains unclear. In the present study, the first genome‐wide targetome analysis is reported of these enzymes in Escherichia coli, at a single‐nucleotide resolution. A strictly linear relationship is observed between the RNA pyrophosphohydrolase processing ratio and scores assigned to the first three nucleotides of the primary transcript. Stem‐loops associated with PNPase targetomes exhibit a folding free energy that is negatively correlated with the termination ratio of PNPase at the 3′ end. More than one‐tenth of the RNase E processing sites in the 5′‐untranslated regions（UTR） form different stem‐loops that affect ribosome‐binding and translation efficiency. The effectiveness of the SRPS elements is validated using a dual‐fluorescence reporter system. The findings highlight a multi‐layer and quantitative regulatory method for optimizing the stoichiometric expression of genes in bacteria and promoting the application of SRPS in synthetic biology.
Contrast Agent‐Free 3D Renal Ultrafast Doppler Imaging Reveals Vascular Dysfunction in Acute and Diabetic Kidney Diseases
Authors: Oh Donghyeon , Lee Donghyun , Heo Jinseok , Kweon Jooyoung , Yong Uijung , Jang Jinah , Ahn Yong Joo , Kim Chulhong 
Published: October 2023

AbstractTo combat the irreversible decline in renal function associated with kidney disease, it is essential to establish non‐invasive biomarkers for assessing renal microcirculation. However, the limited resolution and/or vascular sensitivity of existing diagnostic imaging techniques hinders the visualization of complex cortical vessels. Here, a 3D renal ultrafast Doppler (UFD) imaging system that uses a high ultrasound frequency (18 MHz) and ultrahigh frame rate (1 KHz per slice) to scan the entire volume of a rat's kidney in vivo is demonstrated. The system, which can visualize the full 3D renal vascular branching pyramid at a resolution of 167 µm without any contrast agent, is used to chronically and noninvasively monitor kidneys with acute kidney injury (AKI, 3 days) and diabetic kidney disease (DKD, 8 weeks). Multiparametric UFD analyses (e.g., vessel volume occupancy (VVO), fractional moving blood volume (FMBV), vessel number density (VND), and vessel tortuosity (VT)) describe rapid vascular rarefaction from AKI and long‐term vascular degeneration from DKD, while the renal pathogeneses are validated by in vitro blood serum testing and stained histopathology. This work demonstrates the potential of 3D renal UFD to offer valuable insights into assessing kidney perfusion levels for future research in diabetes and kidney transplantation.
Distinct Conformations of Mirabegron Determined by MicroED
Authors: Lin Jieye , Unge Johan , Gonen Tamir 
Published: October 2023

AbstractMirabegron, commonly known as “Myrbetriq”, has been widely prescribed as a medicine for overactive bladder syndrome for over a decade. However, the structure of the drug and what conformational changes it may undergo upon binding its receptor remain unknown. In this study, the authors employed microcrystal electron diffraction (MicroED) to reveal its elusive three‐dimensional (3D) structure. They find that the drug adopts two distinct conformational states (conformers) within the asymmetric unit. Analysis of hydrogen bonding and packing demonstrated that the hydrophilic groups are embedded within the crystal lattice, resulting in a hydrophobic surface and low water solubility. Structural comparison revealed the presence of trans‐ and cis‐ forms in conformers 1 and 2, respectively. Comparison of the structures of Mirabegron alone with that of the drug bound to its receptor, the beta 3 adrenergic receptor (β3AR) suggests that the drug undergoes major conformational change to fit in the receptor agonist binding site. This research highlights the efficacy of MicroED in determining the unknown and polymorphic structures of active pharmaceutical ingredients (APIs) directly from powders.
Discrimination of Hover Fly Species and Sexes by Wing Interference Signals
Authors: Li Meng , Runemark Anna , Hernandez Julio , Rota Jadranka , Bygebjerg Rune , Brydegaard Mikkel 
Published: October 2023

AbstractRemote automated surveillance of insect abundance and diversity is poised to revolutionize insect decline studies. The study reveals spectral analysis of thin‐film wing interference signals (WISs) can discriminate free‐flying insects beyond what can be accomplished by machine vision. Detectable by photonic sensors, WISs are robust indicators enabling species and sex identification. The first quantitative survey of insect wing thickness and modulation through shortwave‐infrared hyperspectral imaging of 600 wings from 30 hover fly species is presented. Fringy spectral reflectance of WIS can be explained by four optical parameters, including membrane thickness. Using a Naïve Bayes Classifier with five parameters that can be retrieved remotely, 91% is achieved accuracy in identification of species and sexes. WIS‐based surveillance is therefore a potent tool for remote insect identification and surveillance.
A Voltage‐Driven Transport Model to Identify Ion Migration as the Rate‐Limiting Step in Memristive Switching
Authors: Vazquez‐Arce Jorge Luis , Molina‐Reyes Joel , Contreras Oscar Edel , Tiznado Hugo 
Published: October 2023

AbstractThe physics behind the switching kinetics of memristors is gradually becoming clearer. The periods required for the onset of electromigration within memristors and the activation or deactivation of the low‐resistance state—referred to as the incubation and switching times—exhibit non‐linearity with applied voltage. This behavior prevails depending on the rate‐limiting step comprising nucleation and filament growth, electron transfer at the electrode/electrolyte interface, and ion migration through the electrolyte. Herein, a model is introduced for ion migration as the rate‐limiting step. This model analyses the incubation time and analytically correlates it with the electric field, diffusion coefficient, and temperature, facilitating the determination of threshold voltage and diffusivity from high to low resistance states for ion migration as the rate‐limiting step. By exploring parallel plate cells with Yttria‐Stabilized Zirconia (YSZ) of nanometer thickness, the application of the model is illustrated and the fundamental equations are applied to outstanding memristive cells in the literature. The applicability of this model to cells of various charge carriers is proposed, ranging from vacancies and electron transport to oxygen ions and metal cations, denoting its potential importance.
Regulating Phase Transition and Oxygen Redox to Achieve Stable High‐Voltage O3‐Type Cathode Materials for Sodium‐Ion Batteries
Authors: Zhang Kai , Xu Zhenming , Li Guodong , Luo Rui‐Jie , Ma Cui , Wang Yonggang , Zhou Yong‐Ning , Xia Yongyao 
Published: October 2023

AbstractO3‐type layered oxides are promising cathode materials for sodium‐ion batteries. However, unsatisfying cyclic stability hinders its practical application, mainly resulting from harmful phase transition and irreversible oxygen redox, especially in high‐voltage regions. Herein, a co‐doped strategy by incorporating Li+, Mg2+, Ca2+, and Sb5+ into the O3‐Na0.8Ni0.4Fe0.2Mn0.4O2 cathode materials is proposed. Both suppressing the undesired phase transition over 4.1 V (vs Na/Na+) and reducing the anisotropic strain are achieved with the novel Na0.8Ni0.3Fe0.2Mn0.3Li0.1Mg0.02Ca0.05Sb0.03O2 (LMCS NFM). Moreover, restricted but highly reversible oxygen redox is observed due to strong attraction from Sb5+ and special “Li–O‐vacancy” and “Mg–O‐vacancy” configurations. The strategy brings about excellent high‐voltage cyclic stability with a reversible capacity of 130 mAh g−1 and a capacity retention of 85% after 250 cycles at 4.2 V, and less thermal runaway risk and moisture sensitivity, increasing the probability of O3‐type oxide cathode practical applications.
Stabilitätsuntersuchungen an einem Pt@HGS‐Katalysator als Modellmaterial für Brennstoffzellenanwendungen: Die Rolle des lokalen pH‐Wertes
Authors: Gunnarson Alexander , Quast Thomas , Dieckhöfer Stefan , Pfänder Norbert , Schüth Ferdi , Schuhmann Wolfgang 
Published: October 2023

AbstractDie Erhöhung der Widerstandsfähigkeit von Katalysatoren gegen elektrochemische Degradation ist eine der wichtigsten Voraussetzungen für den breiteren Einsatz von Protonenaustausch‐Membran‐Brennstoffzellen (PEMFCs). Hier untersuchen wir die Degradation eines einzelnen Partikels eines hochstabilen Katalysators, Pt@HGS auf einer Nanoelektrode unter nicht‐limitierenden Massentransportbedingungen. Wir stellen fest, dass der Katalysator schneller degradiert als aufgrund früherer Ensemblemessungen erwartet wird. Auf Basis von Transmissionselektronenmikroskopie (TEM) an identischen Stellen nach elektrochemischer Belastung und Experimenten mit einer Katalysatorschicht auf einem TEM‐Träger schließen wir, dass lokal unterschiedliche pH‐Werte wahrscheinlich der Grund für diesen Stabilitätsunterschied sind. Letztendlich bietet diese Arbeit Einblicke in die tatsächlichen Bedingungen in einer PEMFC und wirft Fragen zur Anwendbarkeit von beschleunigten Belastungstests auf, die normalerweise zur Bewertung der Katalysatorstabilität durchgeführt werden, insbesondere wenn sie in Halbzellenaufbauten unter Inertgas durchgeführt werden.
Fluorogenic Photo‐Crosslinking of Glycan‐Binding Protein Recognition Using a Fluorinated Azido‐Coumarin Fucoside
Authors: Bousch Cécile , Vreulz Brandon , Kansal Kartikey , El‐Husseini Ali , Cecioni Samy 
Published: October 2023

AbstractGlycan recognition by glycan‐binding proteins is central to the biology of all living organisms. The efficient capture and characterization of relatively weak non‐covalent interactions remains an important challenge in various fields of research. Photoaffinity labeling strategies can create covalent bonds between interacting partners, and photoactive scaffolds such as benzophenone, diazirines and aryl azides have proved widely useful. Since their first introduction, relatively few improvements have been advanced and products of photoaffinity labeling remain difficult to detect. We report a fluorinated azido‐coumarin scaffold which enables photolabeling under fast and mild activation, and which can leave a fluorescent tag on crosslinked species. Coupling this scaffold to an α‐fucoside, we demonstrate fluorogenic photolabeling of glycan‐protein interactions over a wide range of affinities. We expect this strategy to be broadly applicable to other chromophores and we envision that such “fluoro‐crosslinkers” could become important tools for the traceable capture of non‐covalent binding events.
A Binary Silicon‐Centered Organoboron Catalyst with Superior Performance to That of Its Bifunctional Analogue
Authors: Xu Cheng‐Kai , Yang Guan‐Wen , Lu Chenjie , Wu Guang‐Peng 
Published: October 2023

AbstractThis work reported that a silicon‐centered alkyl borane/ammonium salt binary (two‐component) catalyst exhibits much higher activity than its bifunctional analogue (one‐component) for the ring‐opening polymerization of propylene oxide, showing 7.3 times the activity of its bifunctional analogue at a low catalyst loading of 0.01 mol %, and even 15.3 times the activity at an extremely low loading of 0.002 mol %. By using 19F NMR spectroscopy, control experiments, and theoretical calculation we discovered that the central silicon atom displays appropriate electron density and a larger intramolecular cavity, which is useful to co‐activate the monomer and to deliver propagating chains, thus leading to a better intramolecular synergic effect than its bifunctional analogue. A unique two‐pathway initiation mode was proposed to explain the unusual high activity of the binary catalytic system. This study breaks the traditional impression of the binary Lewis acid/nucleophilic catalyst with poor activity because of the increase in entropy.
Green Ether Electrolytes for Sustainable High‐voltage Potassium Ion Batteries
Authors: Ma Xuemei , Fu Hongwei , Shen Jingyi , Zhang Dianwei , Zhou Jiawan , Tong Chunyi , Rao Apparao M. , Zhou Jiang , Fan Ling , Lu Bingan 
Published: October 2023

AbstractEther‐based electrolytes are promising for secondary batteries due to their good compatibility with alkali metal anodes and high ionic conductivity. However, they suffer from poor oxidative stability and high toxicity, leading to severe electrolyte decomposition at high voltage and biosafety/environmental concerns when electrolyte leakage occurs. Here, we report a green ether solvent through a rational design of carbon‐chain regulation to elicit steric hindrance, such a structure significantly reducing the solvent‘s biotoxicity and tuning the solvation structure of electrolytes. Notably, our solvent design is versatile, and an anion‐dominated solvation structure is favored, facilitating a stable interphase formation on both the anode and cathode in potassium‐ion batteries. Remarkably, the green ether‐based electrolyte demonstrates excellent compatibility with K metal and graphite anode and a 4.2 V high‐voltage cathode (200 cycles with average Coulombic efficiency of 99.64 %). This work points to a promising path toward the molecular design of green ether‐based electrolytes for practical high‐voltage potassium‐ion batteries and other rechargeable batteries.
Subrutilane—A Hexacyclic Sesterterpene from Streptomyces subrutilus
Authors: Gu Binbin , Goldfuss Bernd , Schnakenburg Gregor , Dickschat Jeroen S. 
Published: October 2023

AbstractMining of a terpene synthase from Streptomyces subrutilus resulted in the identification of the hexacyclic sesterterpene subrutilane, besides eight pentacyclic side products. Subrutilane represents the first case of a saturated sesterterpene hydrocarbon. Its structure, including the absolute configuration, was unambiguously determined through X‐ray crystallographic analysis and stereoselective deuteration. The cyclisation mechanism to subrutilane and its side products was investigated in all detail by isotopic labelling experiments and DFT calculations. The subrutilane synthase (SrS) also converted (2Z)‐GFPP into one major product. Additional compounds were obtained from the substrate analogues (7R)‐6,7‐dihydro‐GFPP and (2Z,7R)‐6,7‐dihydro‐GFPP with blocked reactivity at the C6−C7 bond. Interestingly, the early steps of the cyclisation cascade with (2Z)‐GFPP and the saturated substrate analogues were analogous to those of GFPP, but then deviations from the natural cyclisation mode occur.
Polymeric organogel as an effective approach for eradication of heavy metal ions As, Pb, Cd, and Cr from the surface of groundwater through adsorption stratagem
Authors: Baruah Kankana , Dutta Riku , Doley Simanta , Sarma Bipul , Dolui Swapan Kumar 
Published: October 2023

AbstractExcess metal pollutant has affected and caused serious havoc in the lives of terrestrial as well as aquatic beings. The core of this work revolves around eradicating highly toxic heavy metal ions from underground water systems using a cost‐effective, high removal efficiency polymeric adsorbent capable of adsorbing and removing ionic metals whose backbone is composed of a bio‐degradable polymer, polyvinyl alcohol. The obtained adsorbent was characterized using FT‐IR, HNMR, and P‐XRD. Morphological studies were carried out using SEM. Detection and adsorption of metal ions were performed using SEM–EDX and AAS; wherein the adsorbent was found to remove nearly 80% of arsenic ions, 70.5% and 70.7% for lead and chromium ions while 60.7% for cadmium ions, respectively. Further, the kinetics of adsorption along with intraparticle diffusion studies were also performed to determine the mechanism alongside observing the isothermal influence of the sorbent. The adsorption capacity was seen to be highest in arsenic at around 570.42 mg g−1 thus acting as a potential and effective adsorbent for the removal of heavy metal ions from groundwater.
3D pollination biology using micro‐computed tomography and geometric morphometrics in Theobroma cacao
Authors: Wolcott Katherine A. , Stanley Edward L. , Gutierrez Osman A. , Wuchty Stefan , Whitlock Barbara Ann 
Published: October 2023

AbstractPremiseImaging technologies that capture three‐dimensional (3D) variation in floral morphology at micro‐ and nano‐resolutions are increasingly accessible. In herkogamous flowers, such as those of Theobroma cacao, structural barriers between anthers and stigmas represent bottlenecks that restrict pollinator size and access to reproductive organs. To study the unresolved pollination biology of cacao, we present a novel application of micro‐computed tomography (micro‐CT) using floral dimensions to quantify pollinator functional size limits.MethodsWe generated micro‐CT data sets from field‐collected flowers and museum specimens of potential pollinators. To compare floral variation, we used 3D Slicer to place landmarks on the surface models and performed a geometric morphometric (GMM) analysis using geomorph R. We identified the petal side door (an opening between the petal hoods and filament) as the main bottleneck for pollinator access. We compared its mean dimensions with proposed pollinators to identify viable candidates.ResultsWe identified three levels of likelihood for putative pollinators based on the number of morphological (body) dimensions that fit through the petal side door. We also found floral reward microstructures whose presence and location were previously unclear.DiscussionUsing micro‐CT and GMM to study the 3D pollination biology of cacao provides new evidence for predicting unknown pollinators. Incorporating geometry and floral rewards will strengthen plant–pollinator trait matching models for cacao and other species.
Methotrexate Safety and Efficacy in Combination Therapies in Patients With Early Rheumatoid Arthritis: A Post Hoc Analysis of a Randomized Controlled Trial
Authors: Lend Kristina , Koopman Frieda A. , Lampa Jon , Jansen Gerrit , Hetland Merete L. , Uhlig Till , Nordström Dan , Nurmohamed Michael , Gudbjornsson Bjorn , Rudin Anna , Østergaard Mikkel , Heiberg Marte S. , Sokka‐Isler Tuulikki , Hørslev‐Petersen Kim , Haavardsholm Espen A. , Grondal Gerdur , Twisk Jos W. R. , van Vollenhoven Ronald 
Published: October 2023

ObjectiveWe investigated methotrexate safety and the influence of dose on efficacy outcomes in combination with three different biologic treatments and with active conventional treatment (ACT) in early rheumatoid arthritis (RA).MethodsThis post hoc analysis included 812 treatment‐naïve patients with early RA who were randomized (1:1:1:1) in the NORD‐STAR trial to receive methotrexate in combination with ACT, certolizumab‐pegol, abatacept, or tocilizumab. Methotrexate safety, doses, and dose effects on Clinical Disease Activity Index (CDAI) remission were assessed after 24 weeks of treatment.ResultsCompared with ACT, the prevalence of methotrexate‐associated side effects was higher when methotrexate was combined with tocilizumab (hazard ratio [HR] 1.48, 95% confidence interval [CI] 1.20–1.84) but not with certolizumab‐pegol (HR 0.99, 95% CI 0.79–1.23) or with abatacept (HR 0.93, 95% CI 0.75–1.16). With ACT as the reference, the methotrexate dose was significantly lower when used in combination with tocilizumab (β −4.65, 95% CI −5.83 to −3.46; P < 0.001) or abatacept (β −1.15, 95% CI −2.27 to −0.03; P = 0.04), and it was numerically lower in combination with certolizumab‐pegol (β −1.07, 95% CI −2.21 to 0.07; P = 0.07). Methotrexate dose reductions were not associated with decreased CDAI remission rates within any of the treatment combinations.ConclusionMethotrexate was generally well tolerated in combination therapies, but adverse events were a limiting factor in receiving the target dose of 25 mg/wk, and these were more frequent in combination with tocilizumab versus ACT. On the other hand, methotrexate dose reductions were not associated with decreased CDAI remission rates within any of the four treatment combinations at 24 weeks.image
Catalyst‐ and Additive‐free, Regioselective 1,6‐Hydroarylation of para‐Quinone Methides with Anilines in HFIP
Authors: Zhu Longzhi , Ren Yining , Liu Xianping , Xu Shipan , Li Tao , Xu Weifeng , Li Zikang , Liu Yu , Xiong Biquan 
Published: October 2023

AbstractA simple and efficient method for the synthesis of diarylmethyl‐functionalized anilines through the hexafluoroisopropanol (HFIP)‐mediated regioselective 1,6‐hydroarylation reaction of para‐quinone methides (p‐QMs) with anilines under catalyst‐ and additive‐free conditions is reported. Various kinds of p‐QMs and amines (e. g. primary, secondary and tertiary amines) are well tolerated in this transformation without the pre‐protection of amino group, and the corresponding products could be generated with good to excellent yields and satisfactory regioselectivity under the optimized reaction conditions. In addition to adaptable amine compounds, indoles and their derivatives are also compatible with this reaction system. This transformation can be easily extended to a gram scale‐synthesis level to synthesize the target product. Furthermore, it is worth noting that some complex small aniline molecules with biological activity can be selectively modified using this method. The possible reaction mechanism is proposed through the step‐by‐step control experiments and DFT calculations, showing that the key process for achieving the regioselective 1,6‐hydroarylation of p‐QMs is the hydrogen bonding effect of HFIP to substrates.
Response surface methodology use in construction of polianiline‐coated carbon paste electrode–based biosensor: Modification and characterization
Authors: Yağız Esra , Ozyilmaz Gul , Ozyilmaz Ali Tuncay 
Published: October 2023

AbstractIn this study, the effect of amperometric glucose biosensor construction and using conditions on the current response was investigated in detail applying experimental design. Polyaniline (PANI) was synthesized on the carbon paste electrode (CPE) surface using the cyclic voltammetry technique in sodium oxalate (NaOx) electrolyte medium, and an amperometric biosensor was constructed by immobilizing glucose oxidase (GOD). Biosensor preparation (aniline, GOD and NaOx concentrations, and scan rate) and operating conditions (pH and applied potential) were optimized by Box–Behnken and optimal designs, respectively, via State Ease Design Expert 7.0.1.1 software. ANOVA analyses showed that among the biosensor preparation parameters, the NaOx concentration has the highest effect on the current measured in the presence of glucose, whereas in the optimization of pH and potential parameters applied in current measurement studies, it has been revealed that pH has a very high effect on the measured current. Several compounds, such as MWCNT, two different ionic liquids and two different organic molecules were added to carbon paste, and, among them, 2‐cyanoethylpyrrole (CPy) enhanced the efficacy highly, most probably due to its polymerization in the paste and increasing the electron transfer rate of the CPE. Sucrose‐ and lactose‐sensitive biosensors were also constructed by co‐immobilizing GOD with invertase (INV) or β‐galactosidase, respectively, onto modified CPE, and sensitivities to their substrates were shown by cyclic voltammetry and impedance analysis. CPy modification caused an increase in the current values, and also Imax/KM values increased approximately 11.8, 7.83, and 2.56 times for glucose‐, sucrose‐, and lactose‐sensitive CPEs, respectively.