bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ligand‐Controlled Stereoselective Synthesis of 2‐Deoxy‐β‐C‐glycosides by Cobalt Catalysis
Authors: Liu Bingxue , Liu Deguang , Rong Xianle , Lu Xi , Fu Yao , Liu Qiang 
Published: March 2023

Abstract2‐Deoxy‐β‐C‐glycosides represent an important class of carbohydrates that are present in many bioactive molecules. However, owing to the lack of substituents at the C2 position, the stereoselective synthesis of 2‐deoxy‐β‐C‐glycosides is highly challenging. Herein, we report a ligand‐controlled stereoselective C‐alkyl glycosylation reaction to access 2‐deoxy‐β‐C‐alkyl glycosides from readily available glycals and alkyl halides. This method exhibits broad substrate scope and excellent diastereoselectivity under very mild conditions. In addition, unprecedented stereodivergent synthesis of 2‐deoxy‐C‐ribofuranosides is achieved using different chiral bisoxazoline ligands. Mechanistic studies suggest that hydrometallation of the glycal with the bisoxazoline‐ligated Co−H species may be the turnover‐limiting and stereodetermining step of this transformation.
Mobile Molecules: Reactivity Profiling Guides Faster Movement on a Cysteine Track
Authors: Bo Zonghua , Lim Zhong Hui , Duarte Fernanda , Bayley Hagan , Qing Yujia 
Published: March 2023

AbstractWe previously reported a molecular hopper, which makes sub‐nanometer steps by thiol‐disulfide interchange along a track with cysteine footholds within a protein nanopore. Here we optimize the hopping rate (ca. 0.1 s−1 in the previous work) with a view towards rapid enzymeless biopolymer characterization during translocation within nanopores. We first took a single‐molecule approach to obtain the reactivity profiles of individual footholds. The pKa values of cysteine thiols within a pore ranged from 9.17 to 9.85, and the pH‐independent rate constants of the thiolates with a small‐molecule disulfide varied by up to 20‐fold. Through site‐specific mutagenesis and a pH increase from 8.5 to 9.5, the overall hopping rate of a DNA cargo along a five‐cysteine track was accelerated 4‐fold, and the rate‐limiting step 21‐fold.
Asymmetric C1 Extension of Aldehydes through Biocatalytic Cascades for Stereodivergent Synthesis of Mandelic Acids
Authors: Liu Yanqiong , Fu Zunyun , Dong Haihong , Zhang Jingxuan , Mao Yingle , Zheng Mingyue , Liao Cangsong 
Published: March 2023

AbstractThe development of mild, efficient, and enantioselective methods for preparing chiral building blocks from simple, renewable carbon units has been a long‐term goal of the sustainable chemical industry. Mandelate derivatives are valuable pharmaceutical intermediates and chiral resolving agents, but their manufacture relies heavily on highly toxic cyanide. Herein, we report (S)‐4‐hydroxymandelate synthase (HmaS)‐centered biocatalytic cascades for the synthesis of mandelates from benzaldehydes and glycine. We show that HmaS can be engineered to perform R‐selective hydroxylation by single‐point mutation, empowering the stereodivergent synthesis of both (S)‐ and (R)‐mandelate derivatives. These biocatalytic cascades enabled the production of various mandelate derivatives with high atom economy as well as excellent yields (up to 98 %) and ee values (up to >99 %). This methodology offers an effective cyanide‐free technology for greener and sustainable production of mandelate derivatives.
Synthesis and Photophysical Properties of Monometallic C^C* Platinum(II) Formamidinate Complexes using Sterically Demanding Ligands
Authors: Wurl Felix , Stipurin Sergej , Kollar Joshua Immanuel , Strassner Thomas 
Published: March 2023

AbstractA novel class of cyclometalated platinum(II) complexes—previously considered to be inaccessible—was synthesized by an improved synthetic route utilizing ligands predicted by density functional theory calculations. Based on a concise quantum chemical screening three model ligands with varying steric demand were chosen and a series of six photoluminescent C^C* cyclometalated platinum(II) formamidinate complexes was obtained. The least sterically demanding ligand led to a bimetallic complex in two isomeric forms, which could be separated and confirmed by the corresponding solid‐state structures. Sterically more hindered amidinate ligands gave the monometallic complexes supporting the theoretical predictions. The monometallic complexes show a significant hypsochromic shift of the emission wavelength, explained by the loss of the metal‐metal interactions. Depending on the cyclometalating ligand quantum yields up to 87 % with short decay times were found for this new class of phosphorescent green‐blue to pure blue platinum(II) emitters.
The upper extremity regional anaesthesia trifecta: three upper extremity nerve blocks for awake upper‐limb surgery in a patient with a history of contralateral pneumonectomy*
Authors: Le D. T. , McNulty L. , Krakowski J. C. 
Published: March 2023

SummaryWhile regional anaesthesia plays a pivotal role in the perioperative management of patients undergoing upper extremity surgery, its utility can be limited by the risk of hemi‐diaphragmatic paresis. Furthermore, each approach to blocking the brachial plexus has associated limitations that may result in incomplete upper extremity anaesthesia. We describe the combination of three upper extremity nerve blocks to achieve surgical anaesthesia of the whole arm for a patient who had previously undergone a contralateral pneumonectomy. On this occasion, she required upper arm lipectomy and arteriovenous fistula formation. Adequate blockade was achieved with no significant perioperative complications. This case demonstrates the potential of this approach for patients with respiratory compromise undergoing upper limb procedures.
Underlying mechanisms that ensure actomyosin‐mediated directional remodeling of cell–cell contacts for multicellular movement
Authors: Uechi Hiroyuki , Kuranaga Erina 
Published: March 2023

AbstractActomyosin (actin‐myosin II complex)‐mediated contractile forces are central to the generation of multifaceted uni‐ and multi‐cellular material properties and dynamics such as cell division, migration, and tissue morphogenesis. In the present article, we summarize our recent researches addressing molecular mechanisms that ensure actomyosin‐mediated directional cell–cell junction remodeling, either shortening or extension, driving cell rearrangement for epithelial morphogenesis. Genetic perturbation clarified two points concerning cell–cell junction remodeling: an inhibitory mechanism against negative feedback in which actomyosin contractile forces, which are well known to induce cell–cell junction shortening, can concomitantly alter actin dynamics, oppositely leading to perturbation of the shortening; and tricellular junctions as a point that organizes extension of new cell–cell junctions after shortening. These findings highlight the notion that cells develop underpinning mechanisms to transform the multi‐tasking property of actomyosin contractile forces into specific and proper cellular dynamics in space and time.
Bioinspired multicolour carbon dots: comprehensive cytotoxicity, phytotoxicity, and bioimaging in animal cells and plants
Authors: Assariha Sara , Alvandi Nikta , Rouhani Shohre , Esfandiari Neda 
Published: March 2023

AbstractDuring the past decades, carbon dots (CDs) as a kind of nanoparticles with interesting fluorescence properties have retained their place as one of the best bioimaging agents, although their effects on plants have been rarely studied. In this study, we synthesized two kinds of concentration‐dependent multicolour CDs using two solvent approaches, phosphate‐buffered saline (PBS) and ethanol 20%. We confirmed the nature of the CDs through Fourier transform infrared spectroscopy, atomic force microscopy, dynamic light scattering, zeta potential, X‐ray powder diffraction, and high‐resolution transmission electron microscopy. Afterwards, the cytotoxicity, phytotoxicity, and bioimaging of animal cells and plants using both synthesized CDs were examined. Eventually, PBS‐based CDs were recommended during this study as an efficient bioimaging agent for animal cells and plants because of the appealing features of this CD, such as a small size range of less than 10 nm, surface charge with an average of −24 mV, a high quantum yield of 35.82%, the higher fluorescence intensity of ~400 a.u. for blue fluorescence light and 250 a.u. for green fluorescence light. Other features showing the superiority of PBS‐based CDs include high photostability, low phytotoxicity (p ≤ 0.05 and p ≤ 0.01) and above all, there was no significant cytotoxicity at the concentration range of 500–7.81 μg/ml.
Zinc silicate phosphor: Insights of X‐ray induced and temperature enabled luminescence
Authors: Diana P. , Saravanakumar Subramanian , Sivaganesh D. , Sivakumar V. , Li Yang , Sebastian S. , Kim Ji‐Man , Karthick Kannan Padmanathan , Sangeetha L. , Praneeth Vijayendran K. K. 
Published: March 2023

AbstractThe present investigation deals with the effect of calcination temperature on the structural and thermoluminescent (TL) properties of Zn2SiO4 materials. For this study, Zn2SiO4 was prepared via a simple hydrothermal route and calcinated at temperatures from 700°C to 1100°C in an air atmosphere. TL data of all Zn2SiO4 samples showed two peaks at around 240°C and 330°C due to the formation of the luminescence centre during X‐ray irradiation. More interestingly, the Zn2SiO4 sample calcinated at 900°C exhibited a shift in the TL peak (282°C and 354°C) with an optimal TL intensity attributed to its good crystallinity with a well‐defined hexagonal plate‐like morphology. X‐ray‐irradiated Zn2SiO4 samples calcinated at 900°C exhibited a high‐temperature TL glow curve peak, suggesting that the present material could be used for high‐temperature dosimetry applications.
The investigation on the hypercoagulability of hepatocellular carcinoma‐related cerebral infarction with thromboelastography
Authors: Cen Gengyu , Song Yiting , Chen Shijian , Liu Liuyu , Wang Jun , Zhang Jian , Li Jing , Li Guohui , Li Haihua , Liang Hongbin , Liang Zhijian 
Published: March 2023

AbstractAimTo investigate the hypercoagulability of hepatocellular carcinoma (HCC)‐related cerebral infarction (HCRCI) with thromboelastography (TEG).MethodsA multicenter prospective study was conducted in HCRCI patients, HCC patients without cerebral infarction, and acute cerebral infarction (ACI) patients without HCC between January 2016 and December 2019. TEG parameters and laboratory and clinical data were collected and compared among the three groups. To confirm the independent risk factors of HCRCI, multivariate analyses were conducted. Receiver operating characteristic (ROC) curves were utilized to evaluate the area under the curve (AUC) plotted by each independent risk factor.ResultsThere were 38 patients recruited in the HCRCI group, and 152 patients were recruited to the HCC group and the ACI group. The levels of plasma neutrophil count, D‐dimer, α‐fetoprotein (AFP), carcinoembryonic antigen, and maximum amplitude (MA)—a parameter of TEG—were significantly higher in the HCRCI group than HCC and ACI groups. Multivariate logistic regression analysis showed that increased neutrophile count, D‐dimer, AFP, and MA were independently associated with HCRCI. ROC curve analysis showed first that AUC of MA for HCRCI was .875, which was larger than the other risk factors, and second that the optimal cutoff value for MA was 61.35, with a sensitivity of 89.50% and specificity of 66.40%.ConclusionIt was suggested that TEG disclosed that the pathogenesis of HCRIC is exactly related to the hypercoagulability. And with a cutoff value of MA equaling to 61.35, TEG facilitates clinicians to identify HCC patients at high risk of HCRIC.
Screening and Inhibition Mechanism of Xanthine Oxidase Inhibitors in Ethanolic Extracts of Chimonanthus salicifolius Hu Leaves
Authors: Meng Wenya , Lin Suyun , Ouyang Kehui , Chen Lingli , Zhang Ying , Wang Wenjun 
Published: March 2023

AbstractThis study aimed to evaluate the inhibition of the ethanol elutions of Chimonanthus salicifolius Hu leaves (CsHL) against xanthine oxidase (XO). The results of XO inhibition assay and enzymatic superoxide free radical scavenging assay in vitro showed that 70 % ethanol eluate (EE) had the best inhibitory effect and followed by 40 % EE. High performance liquid chromatograph analysis showed that quercetin and kaempferol were the potential active components of XO inhibition. The inhibition mechanism of quercetin and kaempferol on XO was investigated by kinetic analysis and fluorescence quenching titration assay. The molecular simulation further revealed that quercetin and kaempferol bind to XO mainly by hydrogen bonding and van der Waals, blocking the entry of substrates and leading to the inhibition of XO. In conclusion, the CsHL have inhibitory effects on XO activity, which provides a theoretical basis for relieving or preventing hyperuricemia and gout as a natural food or medicinal plant in the future.
Chemical Profile and Cytotoxicity Evaluation of Aerial Parts of Marrubium vulgare L. From Different Locations in Turkey
Authors: Demiroz Akbulut Tugce , Aydin Kose Fadime , Demirci Betul , Baykan Sura 
Published: March 2023

AbstractMarrubium vulgare L. (Lamiaceae) is used for respiratory and gastrointestinal system disorders in folk medicine. According to European Pharmacopoeia criteria, standardization of the plant is defined by its marrubiin content. In present study, phenolics, marrubiin and essential oil compositions of M. vulgare from different locations in Turkey were analyzed quantitatively by UPLC, GC and GC/MS. Besides, their cytotoxic potentials were evaluated.In the samples, forsythoside B (77–400 mg/100 g dw), arenarioside (forsythoside F) (0–241 mg/100 g dw), verbascoside (acteoside) (171–416 mg/100 g dw) and apigenin‐7‐O‐glucoside (0–17 mg/100 g dw) were determined in different ranges. Marrubiin contents (0.58–1.46 %) of some samples were two times higher than European Pharmacopoeia standards (0.7 %). β‐Caryophyllene (7.24–20.34 %), (Z)‐β‐farnesene (1.58–34.85 %), germacrene D (9.8–13.37 %), bicyclogermacrene (1.71–8.63 %) and β‐bisabolene (0–16.68 %) were detected as major compounds in essential oils. The sample from the west of Aegean Region showed cytotoxicity against human neuroblastoma (SH‐SY5Y) cell lines (IC50: 59.80 μg/mL) although it has no effect on non‐cancerous NIH‐3T3cell lines.This is the first report on phenolic profiles of M. vulgare populations from Turkey. Their potential as marrubiin source for pharmaceutical industry should be considered.
Practical evaluation of prelithiation strategies for next‐generation lithium‐ion batteries
Authors: Chen Shiming , Wang Zhen , Zhang Meng , Shi Xiaoze , Wang Lu , An Weifeng , Li Zikun , Pan Feng , Yang Luyi 
Published: March 2023

AbstractWith the increasing market demand for high‐performance lithium‐ion batteries with high‐capacity electrode materials, reducing the irreversible capacity loss in the initial cycle and compensating for the active lithium loss during the cycling process are critical challenges. In recent years, various prelithiation strategies have been developed to overcome these issues. Since these approaches are carried out under a wide range of conditions, it is essential to evaluate their suitability for large‐scale commercial applications. In this review, these strategies are categorized based on different battery assembling stages that they are implemented in, including active material synthesis, the slurry mixing process, electrode pretreatment, and battery fabrication. Furthermore, their advantages and disadvantages in commercial production are discussed from the perspective of thermodynamics and kinetics. This review aims to provide guidance for the future development of prelithiation strategies toward commercialization, which will potentially promote the practical application of next‐generation high‐energy‐density lithium‐ion batteries.
A Multiresponsive Calix[6]arene Pseudorotaxane Empowered by Fluorophoric Dansyl Groups
Authors: Andreoni Leonardo , Beneventi Giovanni Mariano , Giovanardi Gabriele , Cera Gianpiero , Credi Alberto , Arduini Arturo , Secchi Andrea , Silvi Serena 
Published: March 2023

AbstractWe report the synthesis and characterization, by means of NMR and UV‐visible spectroscopy and electrochemical techniques, of a dansyl calix[6]arene derivative and of its pseudorotaxane complex with a bipyridinium‐based axle. This novel macrocycle shows remarkable complexation ability, in analogy with parent compounds, while the dansyl moieties impart valuable features to the system. Indeed, these units: i) signal the state of the system by fluorescence; ii) can be reversibly protonated, enabling the modulation of the complexation abilities of the macrocycle; iii) participate in photoinduced electron transfer processes, which may be exploited to tune the stability of the supramolecular complex. Therefore, in this multiresponsive pseudorotaxane, the threading and de‐threading motions of the molecular components can be modulated either by protonation of the calixarene host or by reduction of the bipyridinium guest, which can be accomplished both by electrochemical reduction and via photoinduced electron transfer. Overall, three orthogonal and reversible stimuli can be used to induce molecular movements of the pseudorotaxane components.
CD109‐regulated mechanical properties of endothelial cells
Authors: Starodubtseva Maria N. , Liu Ju , Nadyrov Eldar A. , Shkliarava Nastassia M. , Sadouskaya Alena U. , Starodubtsev Ivan E. , Achinovich Sergey L. , Meng Xianli , Zinovkin Dmitry A. , Pranjol Md Zahidul Islam 
Published: March 2023

AbstractCD109 antigen on the endothelial cell surface plays an important role in vascular pathology. The aim of the work was to investigate the effect of the immobilization of CD109 antigen with specific antibodies on nanomechanical properties of human umbilical endothelial cells (HUVECs) using atomic force microscopy in quantitative nanomechanical property mapping mode (PeakForce QNM). Anti‐CD109 antibodies induced significant stiffening of the cell surface Me(LQ; UQ): in 1.45(1.07;2.29) times with respect to control cells for fixed cells and in 4.9(3.6;5.9) times with respect to control cells for living cells, and changes in the spatial distribution of cell surface mechanical properties. The changes in the HUVEC's mechanical properties were accompanied by the activation of the TGF‐/Smad2/3 signaling pathway and reorganization of the vimentin and actin cytoskeletal elements. Our findings show that blocking CD109 antigen using anti‐CD109 antibodies leads in HUVECs to the processes similar to that occur after cell TGF‐β‐signaling activation. Therefore, we suggest that CD109 antigen may be involved in regulating the mechanical behavior of endothelial cells.
δ13C values of urinary 19‐norandrosterone in antidoping samples and potential for adverse findings from boar offal consumption
Authors: Nair Vinod S. , Howa John D. , Morrison Matthew S. , Beggs Lacey , Campbell Thane , Fedoruk Matthew , Ahrens Brian , Eichner Daniel 
Published: March 2023

Abstract19‐Norandrosterone (19NA) is the preferred urinary target compound to identify doping with nandrolone or related 19‐norsteroids. At concentrations between 2.5 and 15 ng/mL, isotope ratio mass spectrometry (IRMS) is required to establish exogenous origin of urinary 19NA. An absolute difference of 3‰ between urinary 19NA and an endogenous reference compound (ERC) constitutes a finding for exogenous origin of 19NA. Over the last 3 years, 77 samples containing urinary 19NA between 2.5 and 15 ng/mL were analyzed at our laboratory. The measured δ13C values for 19NA ranged from −29.5‰ to −16.8‰. In comparison, the δ13C values for the corresponding urinary ERCs ranged from −22.4‰ to −16.2‰. Due to the considerable overlap in values between the target compound and the natural range of urinary ERCs, it can be challenging to distinguish between endogenous and exogenous origins of urinary 19NA. In addition, it is well known that consumption of offal from non‐castrated pigs can produce 19NA in urine. To determine whether this could cause a positive IRMS finding under the current IRMS positivity criteria, meat from non‐castrated boars fed a mixture of corn and soy was consumed by 13 volunteers. Two volunteers produced 19NA findings above 2.5 ng/mL, and the measured isotope values, while inconsistent with documented 19‐norsteroid preparations, did meet IRMS positivity criteria. However, these increases in 19NA urinary concentrations were short‐lived due to rapid elimination. Timely follow‐up collections may help support a claim for dietary exposure when low urinary concentrations of 19NA with pseudo‐endogenous isotope values are observed.
The origin of cultivated mangosteen (Garcinia mangostana L. var. mangostana): Critical assessments and an evolutionary‐ecological perspective
Authors: Yao T. L. , Nazre M. , McKey D. , Jalonen R. , Duminil J. 
Published: March 2023

AbstractMangosteen (Garcinia mangostana var. mangostana) is a popular tropical fruit, yet many aspects of its biology and evolutionary history are little known. Its origin remains contentious, although recent findings suggest G. mangostana L. var. malaccensis (Hook. f.) Nazre (synonym: G. malaccensis Hook. f.) as the sole progenitor. We review hypotheses on the origin of mangosteen and clarify points that have been affected by errors of fact and interpretation. The narrow focus and lack of detail in published results make their interpretation difficult. When possible, we support our interpretations with field observations and examination of herbarium specimens. We outline the main biological traits (e.g., dioecy, facultative apomixis, and polyploidy) of mangosteen and its wild relatives to infer traits that might have evolved during domestication of mangosteen. We find no clear indication that apomixis and polyploidy evolved during domestication. Polyploidy is known in the wild relatives, but apomixis has not yet been demonstrated. Also, we propose a testable new evolutionary‐ecological framework that we call “Forest‐Dusun Interface” to infer processes in the origin of mangosteen. Dusun (Malay) refers to subsistence orchards in this context. Lastly, we propose future studies to address identified knowledge gaps.
Synthesis of Phosphate Esters by Using Diphenyl Ditelluride as Organocatalyst
Authors: Goulart Helen A. , Araujo Daniela R. , Iarocz Lucas E. B. , Pizzi Bruna R. , Barcellos Thiago , Silva Márcio S. , Perin Gelson 
Published: March 2023

AbstractWe report a protocol for the synthesis of new dialkyl(1‐(organolthio)naphthalen‐2‐yl)phosphates and derivatives via a dehydrogenative phosphorylation reaction between functionalized naphthols and H‐phosphonates. Diphenyl ditelluride was employed as an organocatalyst and sonochemistry as an alternative energy source. The reaction conditions were defined through a factorial design approach, and the best condition provided the synthesis of dialkyl(1‐(organolthio)naphthalen‐2‐yl)phosphates in yields that varied from 51–98 % under ultrasound irradiation after 2 h of sonication. The synthetic protocol was also effective for phenol and thiophenol starting materials. All products were characterized by state‐of‐the‐art spectroscopic and spectrometric techniques.
Polystyrene‐Supported Aminocatalyst Derived from Diarylprolinol for Asymmetric α‐Amination of Aldehydes
Authors: Kumar Rohtash , Singh Suraj , Mehta Ronak , Appayee Chandrakumar 
Published: March 2023

AbstractA new class of polystyrene‐supported aminocatalysts with a triazole linker from diphenyl prolinol were developed. Their catalytic activity was tested in the asymmetric α‐amination of aldehydes. The substrate scope of this catalysis was studied under the optimized reaction conditions. The reusability of the polystyrene‐supported aminocatalyst was demonstrated up to four cycles. Based on the reaction results, a reaction mechanism was proposed for the asymmetric α‐amination of aldehydes.