bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bioorthogonal Reaction‐Mediated Tumor‐Selective Delivery of CRISPR/Cas9 System for Dual‐Targeted Cancer Immunotherapy
Authors: Yang Jingjing , Yang Kaiyong , Du Shiyu , Luo Wen , Wang Chao , Liu Hongmei , Liu Kunguo , Zhang Zhibin , Gao Yanfeng , Han Xin , Song Yujun 
Published: July 2023

AbstractCRISPR system‐assisted immunotherapy is an attractive option in cancer therapy. However, its efficacy is still less than expected due to the limitations in delivering the CRISPR system to target cancer cells. Here, we report a new CRISPR/Cas9 tumor‐targeting delivery strategy based on bioorthogonal reactions for dual‐targeted cancer immunotherapy. First, selective in vivo metabolic labeling of cancer and activation of the cGAS‐STING pathway was achieved simultaneously through tumor microenvironment (TME)‐biodegradable hollow manganese dioxide (H‐MnO2) nano‐platform. Subsequently, CRISPR/Cas9 system‐loaded liposome was accumulated within the modified tumor tissue through in vivo click chemistry, resulting in the loss of protein tyrosine phosphatase N2 (PTPN2) and further sensitizing tumors to immunotherapy. Overall, our strategy provides a modular platform for precise gene editing in vivo and exhibits potent antitumor response by boosting innate and adaptive antitumor immunity.
Modulating Electronic Structures of Iron Clusters through Orbital Rehybridization by Adjacent Single Copper Sites for Efficient Oxygen Reduction
Authors: Qi Chunhong , Yang Haoyu , Sun Ziqi , Wang Haifeng , Xu Na , Zhu Guihua , Wang Lianjun , Jiang Wan , Yu Xiqian , Li Xiaopeng , Xiao Qi , Qiu Pengpeng , Luo Wei 
Published: July 2023

AbstractThe atom‐cluster interaction has recently been exploited as an effective way to increase the performance of metal‐nitrogen‐carbon catalysts for oxygen reduction reaction (ORR). However, the rational design of such catalysts and understanding their structure‐property correlations remain a great challenge. Herein, we demonstrate that the introduction of adjacent metal (M)−N4 single atoms (SAs) could significantly improve the ORR performance of a well‐screened Fe atomic cluster (AC) catalyst by combining density functional theory (DFT) calculations and experimental analysis. The DFT studies suggest that the Cu−N4 SAs act as a modulator to assist the O2 adsorption and cleavage of O−O bond on the Fe AC active center, as well as optimize the release of OH* intermediates to accelerate the whole ORR kinetic. The depositing of Fe AC with Cu−N4 SAs on nitrogen doped mesoporous carbon nanosheet are then constructed through a universal interfacial monomicelles assembly strategy. Consistent with theoretical predictions, the resultant catalyst exhibits an outstanding ORR performance with a half‐wave potential of 0.92 eV in alkali and 0.80 eV in acid, as well as a high power density of 214.8 mW cm−2 in zinc air battery. This work provides a novel strategy for precisely tuning the atomically dispersed poly‐metallic centers for electrocatalysis.
Visible‐Light‐Induced Control over Reversible Single‐Chain Nanoparticle Folding
Authors: Maag Patrick H. , Feist Florian , Truong Vinh X. , Frisch Hendrik , Roesky Peter W. , Barner‐Kowollik Christopher 
Published: July 2023

AbstractWe introduce a class of single‐chain nanoparticles (SCNPs) that respond to visible light (λmax=415 nm) with complete unfolding from their compact structure into linear chain analogues. The initial folding is achieved by a simple esterification reaction of the polymer backbone constituted of acrylic acid and polyethylene glycol carrying monomer units, introducing bimane moieties, which allow for the photochemical unfolding, reversing the ester‐bond formation. The compaction and the light driven unfolding proceed cleanly and are readily followed by size exclusion chromatography (SEC) and diffusion ordered NMR spectroscopy (DOSY), monitoring the change in the hydrodynamic radius (RH). Importantly, the folding reaction and the light‐induced unfolding are reversible, supported by the high conversion of the photo cleavage. As the unfolding reaction occurs in aqueous systems, the system holds promise for controlling the unfolding of SCNPs in biological environments.
Can Metal Cations Electrocatalyze Sulfur Redox Reaction and Suppress Polysulfide Shuttle?
Authors: Kumar Subramani , Swain Gitanjali , Krishnamoorthy Kothandam 
Published: July 2023

AbstractIn lithium‐sulfur (Li−S) batteries, sulfur undergoes various changes. It switches between cyclic structure and linear structure. The charge on the sulfur varies between a neutral state and a negative charge‐bearing state. Due to these changes, the sulfur/polysulfide dissolves in the battery electrolyte. Furthermore, the kinetics of the sulfur redox reaction is sluggish. Therefore, a material that can suppress sulfur/polysulfide dissolution and electrocatalyze sulfur redox reaction is needed. We hypothesize that the polysulfide dissolution can be suppressed if the host exhibits polyvalent electrostatic attraction. Polysulfide is a negative charge‐bearing molecule; hence the host must comprise multiple positive charges. Nickel cations with other heteroatoms have been explored as a host in Li−S batteries. The heteroatoms impart additional interactions. The easier way to circumvent the effect of heteroatoms is the addition of metal salts. However, metal salts can either exhibit monovalent or divalent attraction with polysulfides. Those interactions are weak and we must have polyvalent interaction. Towards this objective, we have designed and synthesized a material that comprises multiple divalent cations that is also devoid of heteroatoms. The Li−S batteries fabricated using the metal cation immobilized graphene showed a maximum specific capacity of 1022 mAh/g at 0.1 C rate. Among the metal cations, nickel cations showed better performance than cobalt cations. Thus, we demonstrate that metal cations immobilized on Graphene can efficiently electrocatalyze the sluggish sulfur redox reaction and suppress the polysulfide dissolution.
LiBF4 Induced Unique Surface Modification Enables Improved Electrochemical Performance of LiNi0.8Co0.1Mn0.1O2 Cathode
Authors: Zhou Xiaolin , Li Sihan , Feng Ze , Zhang Shan , Fan Xin , Wang Yan , Sun Dan , Li Huanhuan , Tang Yougen , Wang Haiyan , Li Jianfeng , Wei Jingchao 
Published: July 2023

AbstractLiNi0.8Co0.1Mn0.1O2 (NCM811) has been regarded as a potential cathode material for next‐generation lithium‐ion batteries. However, the electrochemical performance of this material is severely affected by structural deterioration and capacity degradation, and the residual lithium is one of the main culprits. Herein, we propose an effective strategy to design ultrathin coatings on the surface of NCM811 by using LiBF4 as the precursor. The homogeneous hybrid LiF‐Li2B4O7 coating layers can be obtained due to the reaction between LiBF4 and the residual lithium, which can not only effectively reduce the residual lithium, but also improve interfacial lithium‐ion diffusion kinetics and suppress side reactions. Accordingly, the LiBF4‐modified samples exhibited significantly improved electrochemical performance. The coated sample of NCM811@LBF‐0.7 delivers the 127.1 mAh g−1 discharge capacity with 69.8 % capacity retention even after 300 cycles at 1 C. While the pristine sample only shows 97.1 mAh g−1 and the capacity retention decreases to 31.0 %. This method provides a simple and effective strategy to extend the service life and safety characteristics of high‐energy‐density lithium‐ion batteries.
Characterization of tyrosine ammonia lyases from Flavobacterium johnsoniae and Herpetosiphon aurantiacus
Authors: Virklund Alexander , Jendresen Christian Bille , Nielsen Alex Toftgaard , Woodley John M. 
Published: July 2023

Abstractp‐Coumaric acid (pCA) can be produced via bioprocessing and is a promising chemical precursor to making organic thin film transistors. However, the required tyrosine ammonia lyase (TAL) enzyme generally has a low specific activity and suffers from competitive product inhibition. Here we characterized the purified TAL variants from Flavobacterium johnsoniae and Herpetosiphon aurantiacus in terms of their susceptibility to product inhibition and their activity and stability across pH and temperature via initial rate experiments. FjTAL was found to be more active than previously described and to have a relatively weak affinity for pCA, but modeling revealed that product inhibition would still be problematic at industrially relevant product concentrations, due to the low solubility of the substrate tyrosine. The activity of both variants increased with temperature when tested up to 45°C, but HaTAL1 was more stable at elevated temperature. FjTAL is a promising biocatalyst for pCA production, but enzyme or bioprocess engineering are required to stabilize FjTAL and reduce product inhibition.
A new dimension in medical education: Virtual reality in anatomy during COVID‐19 pandemic
Authors: Miltykh Ilia , Kafarov Edgar S. , Covantsev Serghei , Dadashev Ali S. , Skarlis Apostolos A. , Zenin Oleg K. 
Published: July 2023

AbstractVirtual reality technology has been increasingly used in the field of anatomy education, particularly in response to the COVID‐19 pandemic. Virtual reality in anatomy (VRA) allows the creation of immersive, three‐dimensional environments or experiences that can interact in a seemingly real or physical way. A comprehensive search of electronic databases was conducted to identify relevant studies. The search included studies published between 2020 and June 2023. The use of VRA education has been shown to be effective in improving students' understanding and retention of knowledge, as well as developing practical skills such as surgical techniques. VRA can allow students to visualize and interact with complex structures and systems in a way that is not possible with traditional methods. It can also provide a safe and ethical alternative to cadavers, which may be in short supply or have access restrictions. Additionally, VRA can be used to create customized learning experiences, allowing students to focus on specific areas of anatomy or to repeat certain exercises as needed. However, there are also limitations to the use of VRA education, including cost and the need for specialized equipment and training, as well as concerns about the realism and accuracy of VRA models. To fully utilize the potential of VRA education, it is important for educators to carefully consider the appropriate use of VR and to continuously evaluate its effectiveness. It is important for educators to carefully consider the appropriate use of VRA and to continuously evaluate its effectiveness to fully utilize its potential.
Two New Eudesmane‐Type Sesquiterpene from Clonostachys sp. Y6‐1and Their Cytotoxic Activity
Authors: Wang Mengru , Yang Run , Chen Yuansi , Ni Dongxuan , Bi Dewen , Li Qi , Huang Jiabi , Wang Hairong , Wang Weiguang , Li Hongliang , Xiao Weilie 
Published: July 2023

AbstractTwo undescribed eudesmane‐type sesquiterpenoids together with four known compounds were isolated from Clonostachys sp. Y6‐1 associated. Their chemical structures were unambiguously determined by NMR, mass spectrometry, and 13C‐NMR calculation as well as DP4+ probability analyses. The absolute configurations of compounds 1 and 2 were determined by ECD calculation and X‐ray single‐crystal diffraction methods. Furthermore, all isolates were evaluated for in vitro cytotoxic activities against MCF‐7, HCT‐116, MDA‐MB‐231, and SW620 cancer cells. Among them, bioactivity evaluation of compound 5 revealed that weak activity (IC50=66.55±0.82 μM) against SW620.
Severe arsenic poisoning due to Ayurvedic supplements
Authors: Hardin Jeremy , Seltzer Justin , Suhandynata Raymond , Spiegel Benjamin , Silver Robin , Thomas Diane , Galust Henrik , Friedman Nathan , Clark Richard , Momper Jeremiah 
Published: July 2023

Key Clinical MessagePatients that are taking Ayurvedic supplements have an increased risk of heavy metal toxicity. Lead, arsenic, and mercury are frequently identified in these supplements and can cause clinically significant toxicity. Clinicians should screen patients routinely for use of non‐pharmaceutical medications and supplements.
Co‐Catalyzed Hydrosilylation of Ketones under Base‐Free Conditions: A Convenient Route to Silyl Ethers or Secondary Alcohols
Authors: Stachowiak‐Dłużyńska Hanna , Hreczycho Grzegorz 
Published: July 2023

AbstractA cobalt‐catalyzed addition of hydrosilanes to unsaturated carbon‐oxygen bonds has been developed, relying on complexes featuring easily accessible and inexpensive PNP‐type pincer ligands. A wide range of heterocyclic, aliphatic, and aromatic ketones, including those containing both electron‐donating and electron‐withdrawing substituents, were transformed into silyl ethers or secondary alcohols with high yields. An important feature of this protocol is that silanes can act as both the substrates and activators, eliminating the need for external additives such as strong bases.
Lipase/H2SO4‐Cocatalyzed Dynamic Kinetic Resolution of Alcohols in Pickering Emulsion
Authors: Moon Jihoon , Kin Takusho , Mizuno Karin , Akai Shuji , Kanomata Kyohei 
Published: July 2023

AbstractThis study reports the first chemoenzymatic dynamic kinetic resolution (DKR) of racemic sec‐alcohols by simultaneously using immobilized lipase and aqueous sulfuric acid as catalysts for kinetic resolution and racemization, respectively. The nanoparticle‐stabilized phase separation in a Pickering emulsion enabled the use of these inherently incompatible catalysts in a single vessel. The racemization reaction in the aqueous sulfuric acid solution significantly suppressed the dehydrative side reactions that form alkenes and dimeric ethers, which are often observed in racemization using Brønsted/Lewis acids or oxovanadium compounds in organic solvents. The efficacy of the Pickering emulsion was confirmed by the significantly lower catalytic performance in DKR without emulsification. This method achieved high yields and high optical purities in the production of a wide range of sec‐alcohols.
A Numerical Simulation of Multiple‐Droplet Coalescence Characteristics under an Electric Field
Authors: Meng Min , Feng Silong 
Published: July 2023

AbstractA phase field method based on the Cahn‐Hilliard equation was used to establish a numerical model for the motion and coalescence of multiple droplets under an electric field. The influencing factors of the droplet coalescence rate, velocity field and pressure field distributions, and droplet cluster motion and coalescence were investigated. The observations showed that the dynamic behaviors of droplets under the action of the electric field can be characterized as not coming together, coalescence, and breakup after coalescence. High‐speed (low‐speed) and high‐pressure (low‐pressure) regions are generated inside the droplet or near the interface under the action of the electric field, and the size, number, and location of these regions change over time. The results of this study offer an essential guide for developing new electrostatic coalescers.
Catalytic Amination of Alcohols Using Diazo Compounds under Manganese Catalysis Through Hydrogenative N‐Alkylation Reaction
Authors: Babu Reshma , Sukanya Padhy Subarna , Kumar Rohit , Balaraman Ekambaram 
Published: July 2023

AbstractSustainable chemical production requires fundamentally new types of catalysts and catalytic technologies. The development of coherent and robust catalytic systems based on earth‐abundant transition metals is essential, but highly challenging. Herein, we systematically explored a general hydrogenative cleavage/N‐alkylation tandem of cyclic and acyclic diazo (N=N) compounds to value‐added amines under manganese catalysis. The reaction is catalyzed by a single‐site molecular manganese complex and proceeds via tandem dehydrogenation, transfer hydrogenation, and borrowing hydrogenation strategies. Interestingly, the reaction involves abundantly available renewable feedstocks, such as alcohols, that can act as (transfer)hydrogenating and alkylating agents. The synthetic application of our approach in large‐scale pharmaceutical synthesis and easy access to highly demanding N‐CH3/CD3 derivatives are also demonstrated. Kinetic studies show that the reaction rate depends on the concentration of alcohol and Mn‐catalyst and follows fractional orders. Several selective bond activation/formation reactions occur sequentially via amine–amide metal‐ligand cooperation.
Nachhaltige Kraftstoffe
Authors: Daschner Robert , Apfelbacher Andreas 
Published: July 2023

AbstractIm Projekt To‐Syn‐Fuel wurde ein vom Fraunhofer Institut Umsicht entwickeltes Verfahren zur Herstellung von Kraftstoffen aus Biomassereststoffen im Demonstrationsmaßstab umgesetzt. Während der Laufzeit wurden aus 500 t Klärschlamm mehr als 50.000 L biogenes Rohöl gewonnen.
Pflege von biobasierten Kühlschmierstoffen
Authors: Fuhrmann Philipp 
Published: July 2023

AbstractEine sorgfältige überwachung und Pflege von Kühlschmierstoffen zum Beispiel in Pumpen unerlässlich. Einen wichtigen Teil der Pflege stellt die Abtrennung fester Fremdstoffe dar. Eine exzellente Möglichkeit hierzu bietet die Dynamische Crossflow Filtration (DCF) mit keramischen Filterscheiben.
Alternating Copolymerization of Epoxides and Isothiocyanates to Diverse Functional Polythioimidocarbonates and Related Block Polymers†
Authors: Zhu Xiao‐Feng , Lu Xin‐Yu , Xu Cheng‐Kai , Fang Yu‐Bo , Yang Guan‐Wen , Li Wei , Wang Jingdai , Wu Guang‐Peng 
Published: July 2023

Comprehensive SummarySynthesis of diverse polythioimidocarbonates via ring‐opening copolymerization of epoxides and isothiocyanates catalyzed by organoboron catalyst was reported herein. Both aromatic and aliphatic isothiocyanates underwent successful copolymerization with terminal and internal epoxides, allowing for the precise tuning of the performance of the resultant copolymers over a broad range. The wide scope of available isothiocyanates and epoxides enables the direct construction of sulfur‐containing functional polymers featuring both high glass transition temperature and refractive index. Additionally, it was observed that aromatic isothiocyanates polymerize much faster than aliphatic ones, and the reactivity difference facilitated the one‐step synthesis of block polymers from mixed aromatic isothiocyanates, aliphatic isothiocyanates and epoxides due to the preferential incorporation of aromatic isothiocyanates over the aliphatic analogues during their alternating copolymerization with epoxides. The produced polythioimidocarbonates can be used as positive resists for electron beam lithography (sensitivity of 130 μC/cm2 and contrast of 1.53 for poly(CHO‐alt‐EITC)). Coupling with their high refractive index (1.58—1.68), polythioimidocarbonates might find functional applications in optics. These results render ring‐opening copolymerization of epoxides and isothiocyanates a facile route to enrich functional polymer library.
Trace cadmium determination in lake water matrix by flame atomic absorption spectrometry after manganese ferrite magnetic nanoparticles‐based dispersive solid phase extraction
Authors: Karaman Devrim Nur , Serbest Hakan , Kilinç Yağmur , Demirel Rabia , Bakırdere Sezgin 
Published: July 2023

AbstractIn this study, manganese ferrite magnetic nanoparticles‐based dispersive solid phase extraction (MF‐MNP‐DSPE) was developed for cadmium determination at trace level by flame atomic absorption spectrometry (FAAS). Manganese ferrite‐based magnetic nanoparticles were synthesized to be used as solid phase extraction sorbent. All the analytical conditions were optimized by univariate optimization approach to achieve high enrichment factors. Under the optimum conditions, limit of detection (LOD) and quantification (LOQ) values of the developed method were recorded as 1.3 and 4.3 µg L−1, respectively. Approximately 135‐fold improvement in the detection power by the MF‐MNP‐DSPE‐FAAS system was recorded over the traditional FAAS system based on LOD comparison. Recovery experiments were performed to test the applicability/accuracy of the developed method with lake water spiked at different concentrations. Percent recovery values were obtained between 87% and 112% by employing the matrix matching calibration strategy and this showed that the developed method is applicable for the determination of cadmium in lake water samples with high accuracy and precision.
Back in Person: Frontiers in Medicinal Chemistry 2023
Authors: Gehringer Matthias , Pape Felix , Méndez María , Barbie Philipp , Unzue Lopez Andrea , Lefranc Julien , Klingler Franca‐Maria , Hessler Gerhard , Langer Thierry , Diamanti Eleonora , Schiedel Matthias 
Published: July 2023

AbstractThe Frontiers in Medicinal Chemistry (FiMC) is the largest international Medicinal Chemistry conference in the German speaking area and took place from April 3rd to 5th 2023 in Vienna (Austria). Fortunately, after being cancelled in 2020 and two years (2021–2022) of entirely virtual meetings, due to the COVID‐19 pandemic, the FiMC could be held in a face‐to‐face format again. Organized by the Division of Medicinal Chemistry of the German Chemical Society (GDCh), the Division of Pharmaceutical and Medicinal Chemistry of the German Pharmaceutical Society (DPhG), together with the Division of Medicinal Chemistry of the Austrian Chemical Society (GÖCH), the Austrian Pharmaceutical Society (ÖPhG), and a local organization committee from the University of Vienna headed by Thierry Langer, the meeting brought together 260 participants from 21 countries. The program included 38 lectures by leading scientists from industry and academia as well as early career investigators. Moreover, 102 posters were presented in two highly interactive poster sessions.
Stability of Hill's spherical vortex
Authors: Choi Kyudong 
Published: July 2023

AbstractWe study stability of a spherical vortex introduced by M. Hill in 1894, which is an explicit solution of the three‐dimensional incompressible Euler equations. The flow is axi‐symmetric with no swirl, the vortex core is simply a ball sliding on the axis of symmetry with a constant speed, and the vorticity in the core is proportional to the distance from the symmetry axis. We use the variational setting introduced by A. Friedman and B. Turkington (Trans. Amer. Math. Soc., 1981), which produced a maximizer of the kinetic energy under constraints on vortex strength, impulse, and circulation. We match the set of maximizers with the Hill's vortex via the uniqueness result of C. Amick and L. Fraenkel (Arch. Rational Mech. Anal., 1986). The matching process is done by an approximation near exceptional points (so‐called metrical boundary points) of the vortex core. As a consequence, the stability up to a translation is obtained by using a concentrated compactness method.