bluuebunny/crossref_metadata_2025 huggingface dataset:
Split‐Type Magnetic Soft Tactile Sensor with 3D Force Decoupling
Authors: Dai Huangzhe , Zhang Chengqian , Pan Chengfeng , Hu Hao , Ji Kaipeng , Sun Haonan , Lyu Chenxin , Tang Daofan , Li Tiefeng , Fu Jianzhong , Zhao Peng
Published: November 2023

Tactile sensory organs for sensing 3D force, such as human skin and fish lateral lines, are indispensable for organisms. With their sensory properties enhanced by layered structures, typical sensory organs can achieve excellent perception as well as protection under frequent mechanical contact. Here, inspired by these layered structures, a split‐type magnetic soft tactile sensor with wireless 3D force sensing and a high accuracy (1.33%) fabricated by developing a centripetal magnetization arrangement and theoretical decoupling model is introduced. The 3D force decoupling capability enables it to achieve a perception close to that of human skin in multiple dimensions without complex calibration. Benefiting from the 3D force decoupling capability and split design with a long effective distance (>20 mm), several sensors are assembled in air and water to achieve delicate robotic operation and water flow‐based navigation with an offset <1.03%, illustrating the extensive potential of magnetic tactile sensors in flexible electronics, human‒machine interactions, and bionic robots.
Asymmetric Cross Couplings of Trifluoromethyl Radical to Vinylarenes with N‐Hydroxy‐oxazinediones and Subsequent Aerobic Oxidative Homocoupling of 2‐Naphthols Catalysed by Chiral Vanadyl Complexes
Authors: Chen Chien‐Tien , Hung Shiang‐Fu , Tsai Bang‐You , Chen Tsung‐Cheng , Lein Chien‐I , Tseng Pin‐Xuan , Chang Yu‐Chang , Chuang Chin‐Wei , Agarwal Rachit , Hsu Chan‐Wei , Shimizu Yuto , Fujii Ryoma , Mori Seiji
Published: November 2023

Asymmetric three‐component, 1,2‐aminoxy‐trifluoromethylation of styrenes with N‐hydroxy‐1,3‐benz/naphthoxazine‐2,4‐diones (i. e., N‐OH‐(B/Np)OxzOn) catalysed by chiral vanadyl complexes derived from N‐salicylidene‐L‐t‐leucinate were explored. Among 14 different solvents and 13 different catalysts screened, the best reaction scenarios were in 2‐propanol with 3‐(2,5‐dimethyl)phenyl‐5‐bromo (DMP), or 3‐t‐butyl‐5‐bromo substituted catalysts that led to the corresponding complementary (R)‐ and (S)‐products with potential biological activities in 45–91% yields and up to 85 and 75% ee, respectively. Further optimisation with the DMP catalyst led to the best combination of 3‐halo/3,5‐dihalo‐styrenes with 6‐/7‐Br−N−OH‐(B/Np)OxzOn as the trapping agents. The corresponding eight different products were isolated in 52–75% yields with ees in a range of 88–93% (R). Based on Density Functional Theory (DFT) calculations with conformational searches, the origin of enantiocontrol and the working mechanism were proposed by resorting to a bidentate‐chelation between the amide or carbamate C=O group and N−OH group in the trapping agent to the vanadyl center followed by asymmetric benzylic radical trapping in an SH2 fashion. Subsequent Fragment Molecular Orbital (FMO)/Pair Interaction Energy Decomposition Analysis (PIEDA) calculations with the DMP catalyst were carried out to rationalize the extent of asymmetric induction. One representative product derived from p‐methyl‐styrene and NpOxzOn was hydrolyzed in basic MeOH with decarboxylation to unmask its carbamate moiety. The resulting chiral (R)‐N‐benzoxy‐3‐hydroxy‐2‐naphthamide was subjected to aerobic, oxidative homo‐coupling catalysed by the DMP catalyst in CCl4. The corresponding 2,2‐binaphthol product was isolated in 90% (brsm) yield with nearly complete diastereo‐control at the created (M)‐axial chirality, allowing for sequential, bi‐functional asymmetric cross‐coupling applications.
Total Synthesis of the Myrioneuron Alkaloid (−)‐Schoberine B and Its Enantiomer (+)‐Schoberine B
Authors: Calbó Arnau , Griera Rosa , Bosch Joan , Amat Mercedes
Published: November 2023

A dynamic kinetic asymmetric transformation, involving the generation of four stereogenic centers with a well‐defined configuration, occurs in the cyclocondensation of diastereomeric mixtures of 2‐oxocyclohexanepropionic acid racemates 6 with (1S,2R)‐cis‐aminoindanol: two major tetracyclic lactams, 7 a and 7 b, that differ in the configuration of the four stereocenters on the decahydroquinoline moiety were obtained. From the above lactams, the removal of the chiral auxiliary, the introduction of a 2‐piperidone ring, and the closure of the diazine ring complete the first enantioselective total synthesis of the Myrioneuron alkaloid (−)‐schoberine B and its enantiomer (+)‐schoberine B.
Mechanistic Insights on the Enantioselective (4+3) Cycloaddition Between Oxyallylcations and Furans Catalyzed by BINOL‐Based Phosphoramides
Authors: Pedrón Manuel , Villar Laura , Uria Uxue , Prieto Liher , Tejero Tomas , Merino Pedro , Vicario Jose L.
Published: November 2023

The mechanism of the enantioselective (4+3) cycloaddition between furan derivatives and oxyallylcations, which are generated from the corresponding oxiranes through in situ oxidation of allenamides, has been studied using DFT methods. The research has revealed that, under acid‐catalysis by a chiral non‐racemic phosphoramide, the epoxide ring‐opening proceeds without any energy barrier, while the rate‐limiting step is the electrophilic attack of the intermediate enaminium ion on the furan ring. The reaction exhibits low energy barriers when dealing with furan derivatives unsubstituted at C2 and C5. Calculations predict the formation of an achiral regioisomer for 2‐substituted furans, a prediction that has been experimentally confirmed. Additionally, the calculations accurately predict the reaction with substituted allenamides.
Rh‐Catalyzed Cycloaddition of C60 with Enynes: Unveiling the Mechanistic Pathway
Authors: Castanyer Cristina , Artigas Albert , Insa‐Carreras Nil , Solà Miquel , Pla‐Quintana Anna , Roglans Anna
Published: November 2023

In this study we present a method for functionalizing C60 through a Rh‐catalyzed cyclization reaction with 1,6‐enynes, resulting in the formation of a fused bicyclic structure. Additionally, fullerene derivatives are further functionalized through regioselective photooxygenation reactions. Our DFT calculations reveal two distinct reaction pathways: one involving rhodium‐catalyzed cycloisomerization of the enyne followed by Diels‐Alder with C60, and the other featuring a rhodium‐catalyzed [2+2+2] cycloaddition of enyne and C60 followed by isomerization. Surprisingly, both pathways exhibit nearly identical energy barriers. However, experimental tests indicate that the predominant pathway varies depending on the substitution motifs of the substrates.
Biomass‐Derived Carbon Materials for the Adsorption of Organic Pollutants
Authors: Qiu Shuxian , Li Qiaoling , Li Xiaoying , Ma Jingxing , Wu Liqing , Xie Xiangjuan , Wu Lixia , Askari Saeed , Dewangan Nikita , Ashok Jangam , Gao Xingyuan , Kawi Sibudjing
Published: November 2023

With the development of economy and increasing environmental awareness, how to effectively remove organic pollutants in wastewater is a research hotspot. Adsorption is one of the effective methods, and the adsorption material is the key factor to determine the efficiency. In this review, biomass‐derived carbon materials as adsorbents of organic pollutants and the adsorption mechanism are discussed in depth. The effects of carbonization and activation on the morphology and structure of carbon materials; the modification strategies of carbon adsorbents, the adsorption performance of biomass‐derived carbon materials for organic pollutants are described and illustrated; the future work of the biomass‐derived carbon materials is proposed.
Structural and Physicochemical Properties of Carbon Doped Boron Nitride Fullerenes: Effect of Doping Level and Atomic Arrangement
Authors: Escobedo‐Morales Alejandro , Salazar‐Villanueva Martín , Guatemala‐Vera Hiram , Pedraza‐Chan María S. , Camacho‐García José H. , Chigo‐Anota Ernesto
Published: November 2023

The effect of carbon doping on the structural and physicochemical properties of B12N12‐xCx [4, 6]‐fullerenes (0 ≤ x ≤ 6) (BNFs) is studied in the frame of the density functional theory. All non‐symmetry related isomers are modeled. Although carbon doping reduces the cohesive energy of the BNFs, most of them remain stable. It is found that the location of carbon atoms in the lowest‐energy isomers follows a definite sequence as the doping level increases. The results indicate that substitutional carbon lowers the gap energy and chemical hardness of BNFs, but it increases their electronegativity and electrophilicity index. Particularly, carbon doping makes BNFs more susceptible to nucleophilic attacks. Additionally, the charge redistribution and structural asymmetry generated by carbon doping endows BNFs with polar character. A dipole alignment parameter is introduced to elucidate some correlation between the atomic arrangement and the polarity of the systems. While carbon doping enhances the capability of BNFs to interact with other chemical species, possible toxicity concerns are highlighted. Finally, possible fingerprints to identify successful carbon doping through infrared and UV–vis spectroscopy are proposed.
Pan‐Cancer Single‐Nucleus Total RNA Sequencing Using snHH‐Seq
Authors: Chen Haide , Fang Xiunan , Shao Jikai , Zhang Qi , Xu Liwei , Chen Jiaye , Mei Yuqing , Jiang Mengmeng , Wang Yuting , Li Zhouyang , Chen Zihang , Chen Yang , Yu Chengxuan , Ma Lifeng , Zhang Peijing , Zhang Tianyu , Liao Yuan , Lv Yuexiao , Wang Xueyi , Yang Lei , Fu Yuting , Chen Daobao , Jiang Liming , Yan Feng , Lu Wei , Chen Gao , Shen Huahao , Wang Jingjing , Wang Changchun , Liang Tingbo , Han Xiaoping , Wang Yongcheng , Guo Guoji
Published: November 2023

Tumor heterogeneity and its drivers impair tumor progression and cancer therapy. Single‐cell RNA sequencing is used to investigate the heterogeneity of tumor ecosystems. However, most methods of scRNA‐seq amplify the termini of polyadenylated transcripts, making it challenging to perform total RNA analysis and somatic mutation analysis.Therefore, a high‐throughput and high‐sensitivity method called snHH‐seq is developed, which combines random primers and a preindex strategy in the droplet microfluidic platform. This innovative method allows for the detection of total RNA in single nuclei from clinically frozen samples. A robust pipeline to facilitate the analysis of full‐length RNA‐seq data is also established. snHH‐seq is applied to more than 730 000 single nuclei from 32 patients with various tumor types. The pan‐cancer study enables it to comprehensively profile data on the tumor transcriptome, including expression levels, mutations, splicing patterns, clone dynamics, etc. New malignant cell subclusters and exploring their specific function across cancers are identified. Furthermore, the malignant status of epithelial cells is investigated among different cancer types with respect to mutation and splicing patterns. The ability to detect full‐length RNA at the single‐nucleus level provides a powerful tool for studying complex biological systems and has broad implications for understanding tumor pathology.
Reliable Accessibility of Intermediate Polarization States in Textured Ferroelectric Al0.66Sc0.34N Thin Film
Authors: Lee Tae Yoon , Song Myeong Seop , Cho Jung Woo , Choi In Hyeok , An Chihwan , Lee Jong Seok , Chae Seung Chul
Published: November 2023

Ferroelectric materials are promising candidates for neuromorphic computing synaptic devices due to the nonvolatile multiplicity of spontaneous polarization. To ensure a sufficient memory window, ferroelectric materials with a large coercivity are urgently required for practical applications in highly scaled multi‐bit memory devices. Herein, a remarkable reliability of intermediate ferroelectric polarization states is demonstrated in a textured Al0.66Sc0.34N thin film with a coercive field of 2.4 MV cm−1. Al0.66Sc0.34N thin films are prepared at 300 °C on Pt (111)/Ti/SiO2/Si substrates using a radio frequency reactive sputtering method. Al0.66Sc0.34N thin films exhibit viable ferroelectricity with a large remanent polarization value of >100 µC cm−2. Through the conventional current–voltage characteristics, polarization switching kinetics, and temperature dependence of coercivity, the reproducibility of multiple polarization states with apparent accuracy is attributed to a small critical volume (3.7 × 10−28 m3) and a large activation energy (3.3 × 1027 eV m−3) for nucleation of the ferroelectric domain. This study demonstrates the potential of ferroelectric Al1‐xScxN for synaptic weight elements in neural network hardware.
Value‐Added Aqueous Metal‐Redox Bicatalyst Batteries
Authors: Wang Hao‐Yu , Ren Jin‐Tao , Sun Ming‐Lei , Tian Wen‐Wen , Feng Yi , Yuan Zhong‐Yong
Published: November 2023

The development and utilization of electrochemical energy conversion and storage devices can maximize intermittent renewable energy and balance environmental issues. Aqueous metal‐redox bicatalyst batteries, incorporating value‐added electro‐reduction reactions during discharge process at the cathode, are considered a particularly attractive alternative for simultaneous electricity generation and valuable chemical production. In this review, for the first time, a holistic and subtle description of value‐added metal‐redox bicatalyst batteries is made, focusing on recent efforts to optimize the energy conversion/chemical production‐involved cathodic discharging reactions, including CO2 reduction reaction (CO2RR), nitrogen reduction reaction (NRR), nitric oxide reduction reaction (NORR), nitrate reduction reaction (NO3−RR), nitrite reduction reaction (NO2−RR), hydrogen evolution reaction (HER), and acetylene reduction reaction (ARR). A macroscopic understanding of design principles in terms of anodes, cathodes, and reaction parameters is provided. Some mechanism explorations, feasibility analyses, technoeconomic assessments, device combinations, and associated comparisons are involved to deepen the understanding of different systems and evaluate their application prospects. Perspectives on and opportunities for future research directions are also outlined.
Numerical investigation of oil droplet detachment from wall surface by a microbubble using ternary phase‐field model
Authors: Yuhara Yuki , Shirzadi Mohammadreza , Fukasawa Tomonori , Fukui Kunihiro , Ishigami Toru
Published: November 2023

In this study, we investigated the detachment of an oil droplet from a wall surface by microbubbles (MBs) using the numerical simulation of a gas–liquid–liquid three‐phase flow based on a phase‐field model. A single MB was collided with an oil droplet adhered to a wall surface to determine whether the droplet would detach from the wall. It was confirmed that the oil droplet detached from the wall when the interfacial tension between the water and oil or between the bubble and oil was low. To clarify the mechanism, we theoretically calculated the balance of interfacial tension at the three‐fluid contact line. The lower the interfacial tension between the water and oil and between the bubble and oil, the smaller the contact angle of the oil droplet on the bubble. This increased wettability was the driving force that caused the oil droplet to detach from the wall surface.
Defining curative endpoints for sickle cell disease in the era of gene therapy and gene editing
Authors: Locatelli Franco , Corbacioglu Selim , Hobbs William , Frangoul Haydar , Walters Mark C.
Published: November 2023

A growing number of gene therapy‐ and gene editing‐based treatments for patients with sickle cell disease (SCD) are entering clinical trials. These treatments, designed to target the underlying cause of SCD, have the potential to provide functional cures, which until now were possible only through allogeneic hematopoietic stem cell transplant. However, as these novel approaches advance from early‐ to late‐stage clinical trials, it is essential to identify physiologically and clinically relevant endpoints that can demonstrate the achievement of a functional cure for SCD. Here, we present an overview of the pathophysiology of SCD and current treatment options, review ongoing SCD clinical trials using gene therapy or gene editing approaches, and identify the most relevant endpoints for demonstrating the attainment of a functional cure for SCD.
Influence of COVID‐19 on the emergence of stone‐tool use behavior in a population of common long‐tailed macaques (Macaca fascicularis fascicularis) in Thailand
Authors: Muhammad Raza , Kaikaew Titiporn , Panjan Suchada , Meesawat Suthirote , Thabthimthong Wipaporn , Payungporn Sunchai , Apipattarachaiwong Jirawat , Kanthaswamy Sreetharan , Hamada Yuzuru , Luncz Lydia V. , Malaivijitnond Suchinda
Published: November 2023

Stone tool use is a rare behavior across nonhuman primates. Here we report the first population of common long‐tailed macaques (Macaca fascicularis fascicularis) who customarily used stone tools to open rock oysters (Saccostrea forskali) on a small island along the Thai Gulf in Koh Ped (KPE), eastern Thailand. We observed this population several times during the past 10 years, but no stone‐tool use behavior was observed until our survey during the coronavirus disease 2019 (COVID‐19) pandemic in July 2022. KPE is located in Pattaya City, a hotspot for tourism in Thailand. Tourists in this area frequently provided large amounts of food for the monkeys on KPE. During the COVID‐19 curfew, however, tourists were not allowed to access the island, and monkeys began to face food scarcity. During this time, we observed stone‐tool use behavior for the first time on KPE. Based on our observations, the first tool manipulation was similar to stone throwing (a known precursor of stone tool use). From our observations in March 2023, we found 17 subadult/adult animals performing the behavior, 15 of 17 were males and mostly solitary while performing the behavior. The M. f. fascicularis subspecies was confirmed by distribution, morphological characteristics, and mtDNA and SRY gene sequences. Taken together, we proposed that the stone tool use behavior in the KPE common long‐tailed macaques emerged due to the COVID‐19 food scarcity. Since traveling is no longer restricted many tourists have started coming back to the island, and there is a high risk for this stone tool‐use behavior to disappear within this population of long‐tailed macaques.
The High Potential of ε‐Poly‐l‐Lysine for the Development of Antimicrobial Biomaterials
Authors: Lebaudy Eloïse , Guilbaud-Chéreau Chloé , Frisch Benoit , Vrana Nihal Engin , Lavalle Philippe
Published: November 2023

ε‐poly‐l‐lysine (ε‐PLL) is a natural polypeptide/polycation originating from bacteria. Thanks to its antifungal and antibacterial properties, it is the subject of extensive research in the food and medical industries. ε‐PLL is also used to develop biomaterials in a broad range of applications, such as drug delivery, wound healing, or antimicrobial coatings. Indeed, loading ε‐PLL inside nanoparticles, functionalizing implant surfaces with ε‐PLL, or developing hydrogels based on reactions between ε‐PLL and other polymers can improve the materials properties, leading to biocompatible, antibacterial, and antifungal systems. These characteristics are necessary not only for the development of biomaterials, for their integrity in a biological environment, but also for improving the performances of medical devices. Moreover, ε‐PLL can be used as an alternative to antibiotics as its mechanism of action reduces the bacterial resistance risk compared with antibiotics. Finally, “smart” systems using ε‐PLL may be developed, with controllable material degradation or drug delivery via pH or temperature variations. This review sought to gather the latest research on the development of antimicrobial biomaterials based on the ε‐PLL polypeptide.
Automated Structural Activity Screening of β‐Diketonate Assemblies with High‐Throughput Ion Mobility‐Mass Spectrometry
Authors: Williams Oscar H. Lloyd , Rusli Olivia , Ezzedinloo Lida , Dodgen Tyren M. , Clegg Jack K. , Rijs Nicole J.
Published: November 2023

Embracing complexity in design, metallo‐supramolecular self‐assembly presents an opportunity for fabricating materials of economic significance. The array of accessible supramolecules is alluring, along with favourable energy requirements. Implementation is hampered by an inability to efficiently characterise complex mixtures. The stoichiometry, size, shape, guest binding properties and reactivity of individual components and combinations thereof are inherently challenging to resolve. A large combinatorial library of four transition metals (Fe, Cu, Ni and Zn), and six β‐diketonate ligands at different molar ratios and pH was robotically prepared and directly analysed over multiple timepoints with electrospray ionisation travelling wave ion mobility‐mass spectrometry. The dataset was parsed for self‐assembling activity without first attempting to structurally assign individual species. Self‐assembling systems were readily categorised without manual data‐handling, allowing efficient screening of self‐assembly activity. This workflow clarifies solution phase supramolecular assembly processes without manual, bottom‐up processing. The complex behaviour of the self‐assembling systems was reduced to simpler qualities, which could be automatically processed.
Integrated Conversion of Lignocellulosic Biomass to Bio‐Based Amphiphiles using a Functionalization‐Defunctionalization Approach
Authors: Sun Songlan , De Angelis Gaia , Bertella Stefania , Jones Marie J. , Dick Graham R. , Amstad Esther , Luterbacher Jeremy S.
Published: November 2023

Concerns over the sustainability and end‐of‐life properties of fossil‐derived surfactants have driven interest in bio‐based alternatives. Lignocellulosic biomass with its polar functional groups is an obvious feedstock for surfactant production but its use is limited by process complexity and low yield. Here, we present a simple two‐step approach to prepare bio‐based amphiphiles directly from hemicellulose and lignin at high yields (29 % w/w based on the total raw biomass and >80 % w/w of these two fractions). Acetal functionalization of xylan and lignin with fatty aldehydes during fractionation introduced hydrophobic segments and subsequent defunctionalization by hydrogenolysis of the xylose derivatives or acidic hydrolysis of the lignin derivatives produced amphiphiles. The resulting biodegradable xylose acetals and/or ethers, and lignin‐based amphiphilic polymers both largely retained their original natural structures, but exhibited competitive or superior surface activity in water/oil systems compared to common bio‐based surfactants.
Polymer Modification Strategy to Modulate Reaction Microenvironment for Enhanced CO2 Electroreduction to Ethylene
Authors: Deng Ting , Jia Shuaiqiang , Chen Chunjun , Jiao Jiapeng , Chen Xiao , Xue Cheng , Xia Wei , Xing Xueqing , Zhu Qinggong , Wu Haihong , He Mingyuan , Han Buxing
Published: November 2023

Modulation of the microenvironment on the electrode surface is one of the effective means to improve the efficiency of electrocatalytic carbon dioxide reduction (eCO2RR). To achieve high conversion rates, the phase boundary at the electrode surface should be finely controlled to overcome the limitation of CO2 solubility in the aqueous electrolyte. Herein, we developed a simple and efficient method to structure electrocatalyst with a superhydrophobic surface microenvironment by one‐step co‐electrodeposition of Cu and polytetrafluoroethylene (PTFE) on carbon paper. The super‐hydrophobic Cu‐based electrode displayed a high ethylene (C2H4) selectivity with a Faraday efficiency (FE) of 67.3 % at −1.25 V vs. reversible hydrogen electrode (RHE) in an H‐type cell, which is 2.5 times higher than a regular Cu electrode without PTFE. By using PTFE as a surface modifier, the activity of eCO2RR is enhanced and water (proton) adsorption is inhibited. This strategy has the potential to be applied to other gas‐conversion electrocatalysts.
Corner Engineering: Tailoring Enzymes for Enhanced Resistance and Thermostability in Deep Eutectic Solvents
Authors: Wang Xinyue , Sheng Yijie , Cui Haiyang , Qiao Jie , Song Yibo , Li Xiujuan , Huang He
Published: November 2023

Deep eutectic solvents (DESs), heralded for their synthesis simplicity, economic viability, and reduced volatility and flammability, have found increasing application in biocatalysis. However, challenges persist due to a frequent diminution in enzyme activity and stability. Herein, we developed a general protein engineering strategy, termed corner engineering, to acquire DES‐resistant and thermostable enzymes via precise tailoring of the transition region in enzyme structure. Employing Bacillus subtilis lipase A (BSLA) as a model, we delineated the engineering process, yielding five multi‐DESs resistant variants with highly improved thermostability, such as K88E/N89 K exhibited up to a 10.0‐fold catalytic efficiency (kcat/KM) increase in 30 % (v/v) choline chloride (ChCl): acetamide and 4.1‐fold in 95 % (v/v) ChCl: ethylene glycol accompanying 6.7‐fold thermal resistance improvement than wild type at ≈50 °C. The generality of the optimized approach was validated by two extra industrial enzymes, endo‐β‐1,4‐glucanase PvCel5A (used for biofuel production) and esterase Bs2Est (used for plastics degradation). The molecular investigations revealed that increased water molecules at substrate binding cleft and finetuned helix formation at the corner region are two dominant determinants governing elevated resistance and thermostability. This study, coupling corner engineering with obtained molecular insights, illuminates enzyme‐DES interaction patterns and fosters the rational design of more DES‐resistant and thermostable enzymes in biocatalysis and biotransformation.
Vitamin B12‐Photocatalyzed Cyclopropanation of Electron‐Deficient Alkenes Using Dichloromethane as the Methylene Source**
Authors: Teye‐Kau John Hayford G. , Ayodele Mayokun J. , Pitre Spencer P.
Published: November 2023

The cyclopropyl group is of great importance in medicinal chemistry, as it can be leveraged to influence a range of pharmaceutical properties in drug molecules. This report describes a Vitamin B12‐photocatalyzed approach for the cyclopropanation of electron‐deficient alkenes using dichloromethane (CH2Cl2) as the methylene source. The reaction proceeds in good to excellent yields under mild conditions, has excellent functional group compatibility, and is highly chemoselective. The scope could also be extended to the preparation of D2‐cyclopropyl and methyl‐substituted cyclopropyl adducts starting from CD2Cl2 and 1,1‐dichloroethane, respectively.
Au‐Modified Carbon Electrodes Produced by Laser Scribing for Electrochemical Analysis of Probiotic Activity
Authors: Gongoni Juliana L. M. , Chumanov George , Paixão Thiago R. L. C. , Garcia Carlos D.
Published: November 2023

A simple and fast (<15 min), two‐step laser scribing of cardboard substrates is described as a method for fabricating carbon electrodes modified with metallic nanoparticles. The first scribing step patterned a cardboard substrate (promoting the formation of porous carbon electrodes). The second step was included to produce metallic nanoparticles via a chemical reduction process of cations from an aqueous solution. For these experiments, the effects of copper, silver, nickel, cobalt, zinc, and gold were evaluated considering their effect on the electrical properties and the composition of the carbon materials produced. These experiments revealed that, despite significant changes in resistance (from 138±7 Ω for plain electrodes to just 53±3 Ω for Au‐modified electrodes), only marginal changes were observed in the morphology or composition of the material produced (IG/ID ranged from 1.2±0.3 for the plain cardboard to 1.8±0.3 for the cobalt‐modified electrodes). To demonstrate the applicability of the proposed strategy, Au‐modified electrodes were assembled into electrochemical sensors and applied to measure the metabolic activity of live microorganisms in various commercial samples, requiring only 100 μL of sample and 10 min of incubation time.
Challenges posed by hijacked journals in Scopus
Authors: Abalkina Anna
Published: November 2023

This study presents and explains the phenomenon of indexjacking, which involves the systematic infiltration of hijacked journals into international indexing databases, with Scopus being one of the most infiltrated among these databases. Through an analysis of known lists of hijacked journals, the study identified at least 67 hijacked journals that have penetrated Scopus since 2013. Of these, 33 journals indexed unauthorized content in Scopus and 23 compromised the homepage link in the journal's profile, while 11 did both. As of September 2023, 41 hijacked journals are still compromising the data of legitimate journals in Scopus. The presence of hijacked journals in Scopus is a challenge for scientific integrity due to the legitimization of unreliable papers that have not undergone peer review and compromises the quality of the Scopus database. The presence of hijacked journals in Scopus has far‐reaching effects. Papers published in these journals may be cited, and unauthorized content from these journals in Scopus is thus imported into other databases, including ORCID and the WHO COVID‐19 Research Database. This poses a particular challenge for research evaluation in those countries, where cloned versions of approved journals may be used to acquire publications and verifying their authenticity can be difficult.
Excellence in Acrylation – Scope and Limitation of Glucosyl Imidazolium‐coated Novozym 435 Catalyzed (Meth)acryl Ester Synthesis
Authors: Lehmann Paul , Jopp Stefan
Published: November 2023

The incorporation of carbohydrate based ionic liquids as a support for Novozym 435 was previously studied by the authors for the acrylation of n‐butanol as the target substrate, which was used as the foundation for the design of experiments. The combination of carbohydrate based ionic liquids and Novozym 435 remains a key aspect of this work. Building upon this, the reaction parameters were optimized for the Novozym catalyst. Substrate screening was performed to explore the scope and limitations of room temperature acrylation reactions. Herein, different alcohols and reaction conditions were screened extensively for the different acrylate products with yields of up to 99.9 % determined via gas chromatography (GC). Standard straight chain alcohols, 2‐functionalized ethanol derivatives with electron donating and withdrawing groups, and more sterically challenging substrates were investigated over a broad concentration region. To further underline the applicability of the modified biocatalyst, two alcohols were converted with methacrylic acid. The presented method offers a greener pathway for acrylate synthesis, which eliminates the need for high reaction temperatures, strongly acidic catalysts and/or polymerization inhibitors as used in non‐biocatalytic acrylate synthesis.
Radiofrequency dielectric spectroscopy study: Effects of pH, hydrogen bond donors and acceptors on the attachment of spectrin skeleton to the lipid membrane of erythrocytes
Authors: Ivanov Ivan T. , Paarvanova Boyana K.
Published: November 2023

Band 3 protein and glycophorin C are the two major integral proteins of the lipid membrane of human red blood cells (RBCs). They are attached from below to a network of elastic filamentous spectrin, the third major RBC membrane protein. The binding properties of the attachments to spectrin affect the shape and deformability of RBCs. We addressed band 3 and glycophorin C attachments to spectrin by measuring the strength of two recently discovered radiofrequency dielectric relaxations, βsp (1.4 MHz) and γ1sp (9 MHz), that are observable as changes in the complex admittance of RBCs in medium. In medium at pH 5.2, and also in media with protic substances (formamide, methylformamide, or urea), the βsp relaxation became inhibited that is attributable to detachment of glycophorin C from spectrin. In medium at pH 9.2, we observed inhibition of γ1sp relaxation attributable to detachment of band 3 from spectrin, as also was seen in media with aprotic substances difluoropyridine, dimethylsolfoxide, dimethylformamide, acetone, sodium tetrakis(4‐fluorophenyl)borate), chlorpromazine, thioridazine and trifluopiperazine. The viscogenic cosolvents (glycerol, ethylene glycol, or i‐erythritol) inhibited both the βsp and γ1sp relaxations and significantly lowered their characteristic frequencies. Our observations indicate that the glycophorin C attachment to spectrin has nucleophilic centers whose saturation disconnects this attachment and inhibits the βsp relaxation, whereas at band 3‐spectrin attachment site, it is the saturation of electrophilic centers that weakens this attachment and inhibits the γ1sp relaxation.
Brain organoids: A revolutionary tool for modeling neurological disorders and development of therapeutics
Authors: Acharya Prabha , Choi Na Young , Shrestha Sunil , Jeong Sehoon , Lee Moo‐Yeal
Published: November 2023

Brain organoids are self‐organized, three‐dimensional (3D) aggregates derived from pluripotent stem cells that have cell types and cellular architectures resembling those of the developing human brain. The current understanding of human brain developmental processes and neurological disorders has advanced significantly with the introduction of this in vitro model. Brain organoids serve as a translational link between two‐dimensional (2D) cultures and in vivo models which imitate the neural tube formation at the early and late stages and the differentiation of neuroepithelium with whole‐brain regionalization. In addition, the generation of region‐specific brain organoids made it possible to investigate the pathogenic and etiological aspects of acquired and inherited brain disease along with drug discovery and drug toxicity testing. In this review article, we first summarize an overview of the existing methods and platforms used for generating brain organoids and their limitations and then discuss the recent advancement in brain organoid technology. In addition, we discuss how brain organoids have been used to model aspects of neurodevelopmental and neurodegenerative diseases, including autism spectrum disorder (ASD), Rett syndrome, Zika virus‐related microcephaly, Alzheimer's disease (AD), Parkinson's disease (PD), and Huntington's disease (HD).
An integrated liver, hippocampus and serum metabolomics based on UPLC–Q‐TOF–MS revealed the therapeutical mechanism of Ziziphi Spinosae Semen in p‐chlorophenylalanine‐induced insomnia rats
Authors: Chu Yingxin , Zhang Yinjie , Liu Jiaxing , Du Chenhui , Yan Yan
Published: November 2023

Ziziphi Spinosae Semen (ZSS), a well‐known herbal medicine for treating insomnia, is popular in not only China but also in Europe, India and Iran. However, its underlying mechanisms remain unclear. In this work, taking the targeted organs of insomnia, the liver and hippocampus, as the objects, a combination metabolomics based on ultra‐high performance liquid chromatography coupled with quadrupole time‐of‐flight mass spectrometry (UPLC–Q‐TOF–MS) was established to illustrate the abnormality of metabolic characteristics of the liver, hippocampus and serum of p‐chlorophenylalanine (PCPA)‐induced insomnia rats and to demonstrate the mechanism of ZSS in treating insomnia. The results showed that ZSS could restore the brain cell morphology, decrease the degree of hepatocyte necrosis and regulate the disturbance of neurotransmitters and hormones in insomnia rats. In terms of metabolomics, a total of 33 liver metabolites, 25 hippocampal metabolites and 18 serum metabolites were finally selected as the potential biomarkers and an important pathway of phenylalanine, tyrosine and tryptophan biosynthesis was common in three tissues in PCPA rats. Meanwhile, ZSS significantly reversed the levels of 23 liver metabolites, 15 hippocampal metabolites and 5 serum metabolites. The present study demonstrates the actions of ZSS in treating insomnia by enhancing both cerebral and hepatic functions.
How emotions and green altruism explain consumer purchase intention toward circular economy products: A multi‐group analysis on willingness to be environmentally friendly
Authors: Chao Cheng‐Min , Yu Tai‐Kuei
Published: November 2023

Circular economy products are one of the solutions that can help solve the current environmental crisis and consequently achieve environmental sustainability. The theory of planned behavior (TPB) is the most important social psychological theory to explain individual purchasing behavior. However, the theory lacks a consideration of emotions, green altruism, and other factors. In order to address the research gap, this study proposes and tests a new theoretical model that incorporates variables such as emotions, green altruism, and the willingness to be environmentally friendly (WEF) into its extended model based on the TPB framework, in order to investigate the determinants that have an effect on Taiwanese consumers' purchase intention toward circular economy products. This study also uses multi‐group analysis (MGA) to analyze the moderating effects of WEF on its new theoretical model. It collected data from 387 Taiwanese consumers and analyzed the data using partial least squares (PLS). The research results showed (1) emotions, attitudes, green altruism, and perceived behavior control have a positive effect on consumer purchase intention toward circular economy products; (2) emotions have a positive effect on attitudes, green altruism, subjective norms, and perceived behavior control; and (3) groups with different levels of WEF have significant differences on consumer purchase intention toward circular economy products, in terms of emotions, attitudes, and green altruism. The results of this study can provide a reference for manufacturers and public policy makers to understand how consumers' emotions and green altruism can affect the decision‐making process to making purchase of circular economy products.
An automated high inoculation density fed‐batch bioreactor, enabled through N‐1 perfusion, accommodates clonal diversity and doubles titers
Authors: Olin Mikayla , Wolnick Nicolas , Crittenden Hunter , Quach Anthony , Russell Brian , Hendrick Shannon , Armstrong Julia , Webster Thaddaeus , Hadley Brian , Dickson Marissa , Hodgkins Jessica , Busa Kevin , Connolly Roger , Downey Brandon
Published: November 2023

An important consideration for biopharmaceutical processes is the cost of goods (CoGs) of biotherapeutics manufacturing. CoGs can be reduced by dramatically increasing the productivity of the bioreactor process. In this study, we demonstrate that an intensified process which couples a perfused N‐1 seed reactor and a fully automated high inoculation density (HID) N stage reactor substantially increases the bioreactor productivity as compared to a low inoculation density (LID) control fed‐batch process. A panel of six CHOK1SV GS‐KO® CHO cell lines expressing three different monoclonal antibodies was evaluated in this intensified process, achieving an average 85% titer increase and 132% space–time yield (STY) increase was demonstrated when comparing the 12‐day HID process to a 15‐day LID control process. These productivity increases were enabled by automated nutrient feeding in both the N‐1 and N stage bioreactors using in‐line process analytical technologies (PAT) and feedback control. The N‐1 bioreactor utilized in‐line capacitance to automatically feed the bioreactor based on a capacitance‐specific perfusion rate (CapSPR). The N‐stage bioreactor utilized in‐line Raman spectroscopy to estimate real‐time concentrations of glucose, phenylalanine, and methionine, which are held to target set points using automatic feed additions. These automated feeding methodologies were shown to be generalizable across six cell lines with diverse feed requirements. We show this new process can accommodate clonal diversity and reproducibly achieve substantial titer uplifts compared to traditional cell culture processes, thereby establishing a baseline technology platform upon which further increases bioreactor productivity and CoGs reduction can be achieved.
Prediction of attributable mortality in pediatric patients with cancer admitted to the intensive care unit for suspected infection: A comprehensive evaluation of risk scores
Authors: Rubnitz Zachary , Sun Yilun , Agulnik Asya , Merritt Pamela , Allison Kim , Ferrolino Jose , Dallas Ronald , Tang Li , Wolf Joshua
Published: November 2023

Objective

To evaluate the performance of existing sepsis scores for prediction of adverse outcomes in children with cancer admitted to the ICU with suspected sepsis.

Design

Retrospective chart review using data available at 1, 6, 12, and 24 h after ICU admission to calculate the Pediatric Risk of Mortality 3 (PRISM‐3), Pediatric Sequential Organ Failure Assessment (pSOFA), Paediatric Logistic Organ Dysfunction 2 (PELOD‐2), and Quick Pediatric Sequential Organ Failure Assessment (qSOFA) scores.

Area under the receiver operator characteristic curve (AUROC) was used to evaluate performance for prediction of attributable mortality. Sensitivity analyses included recalculation of scores using worst preceding values for each variable, excluding hematologic parameters, and prediction of alternative outcomes.

Setting

St. Jude Children's Research Hospital, a pediatric comprehensive cancer center in the USA.

Patients

Pediatric patients (<25 years of age) receiving conventional therapy for cancer admitted to the ICU with suspected sepsis between 2013 and 2019.

Results

Of 207 included episodes of suspected sepsis, attributable mortality was 16 (7.7%) and all evaluated sepsis scores performed poorly (maximal AUROC of 0.73 for qSOFA at 1 and 24 h). Sensitivity analyses did not identify an alternative approach that significantly improved prediction.

Conclusions

Currently available sepsis scores perform poorly for prediction of attributable mortality in children with cancer who present to ICU with suspected sepsis. More research is needed to identify reliable predictors of adverse outcomes in this population.
Ningalins, Pyrrole‐Bearing Metabolites Isolated from Didemnum spp. Synthesis and MDR‐Reversion Activity in Cancer Therapy
Authors: Segura‐Quezada Luis A. , Hernández‐Velázquez Edson D. , Corrales‐Escobosa Alma R. , de León‐Solis Claudia , Solorio‐Alvarado César R.
Published: November 2023

Multi‐Drug Resistance (MDR) is one of the most frequent problems observed in the course of cancer chemotherapy. Cells under treatment, tend to develop survival mechanisms to drug‐action thus generating drug‐resistance. One of the most important mechanism to get it is the over expression of P‐gp glycoprotein, which acts as an efflux‐pump releasing the drug outside of the cancer cell. A strategy for a succesfull treatment consists in the co‐administration of one compound that acts against P‐gp and another which acts against the cell during chemotherapy. Ningalins are pyrrole‐containing naturally occurring compounds isolated mainly from the marine tunicate Didemnum spp and also they are some of the top reversing agents in MDR treatment acting on P‐gp. Considering the relevance displayed for some of these isolated alkaloids or their core as a drug for co‐administration in cancer therapy, all the total synthesis described to date for the members of ningalins family are reviewed herein.
Inhibition of mitochondria induces apoptosis and reduces telomere length and activity in acute myeloid leukemia stem cells
Authors: Valipour Behnaz , Davari Sahar , Farahzadi Raheleh , Pourrasol Shahram , Mehran Niloofar , Dizaji Asl Khadijeh , Altaha Seyed Mansour , Hojjati Zahra , Nozad Charoudeh Hojjatollah
Published: November 2023

Acute myeloid leukemia (AML) is a highly lethal hematological malignancy in adults and children. Abnormal proliferation of leukemia stem cells (LSC) with CD34+ and CD38− phenotypes are the main clinical features of AML. Patients with AML face drug resistance and treatment failure due to a default in stem and progenitor cells. Therefore, defining LSC properties is necessary for targeting leukemia‐initiating cells. Mitochondrial mass and activity increase in AML initiating cells compared with normal stem cells. This idea has offered the inhibition of the mitochondrial translation machinery to reduce the number of leukemia‐initiating cells in patients with AML Tigecycline is an FDA‐approved microbial antibiotic that inhibits oxidative phosphorylation in mitochondria, resulting in the suppression of leukemia cell proliferation with little toxicity to normal cells. Thus, the present study was conducted to evaluate whether LSC is influenced by mitochondrial inhibition. We measured the IC50 of tigecycline in KG‐1a AML cell lines. KG‐1a AML cell lines were separated into CD34+ and CD34− cells by MACS. In the following, these cells were treated with 20 µM (IC50) tigecycline. The expression of Annexin/PI, Caspase 3, apoptotic genes (BCL2, BCLX, BAX, BAD, and P53) and proteins (P53, BAX, BCL2 and Caspase 9) was evaluated in CD34+, CD34− and KG‐1a AML cells. In addition, the telomere length and expression of hTERT were evaluated in this study. The results indicated that BCl2 (gene and protein) and BCLX gene dramatically decreased. In addition, BAD, BAX, and P53 gene and protein expression significantly increased in CD34+ AML cells compared to CD34− AML cells. The results also suggested that tigecycline induced intrinsic (Cleaved‐caspase 9/Pro‐Caspase 9 ratio) and p53‐mediated apoptosis. Furthermore, hTERT gene expression and telomere length decreased in the tigecycline‐treated groups. Taken together, our findings indicate that inhibition of mitochondrial activity with tigecycline can induce apoptosis in cancer stem cells and can be used as a novel method for cancer therapy.
Diverting Ni‐Catalyzed Direct Benzylic C−H Hydroxylation towards Trifluoroethoxylation
Authors: Bushmin Dmitry S. , Samsonenko Denis G. , Talsi Evgenii P. , Lyakin Oleg Y. , Bryliakov Konstantin P.
Published: November 2023

Nickel(II) complexes with the simple N4 donor aminopyridine ligands BPMEN (N,N′‐dimethyl‐N,N′‐bis(2‐pyridylmethyl)‐1,2‐diaminoethane) and TPA (tris(2‐pyridylmethyl)amine) have been demonstrated to perform as efficient catalysts for the regioselective oxygenation of benzylic C−H groups with m‐chloroperoxybenzoic acid under mild conditions (at 20 °C), typically ensuring >90 % substrate conversions within 1 h at 1 mol % catalyst loadings. Unprecedentedly, replacing the commonly used mixed reaction solvent CH3CN/CH2Cl2 with 2,2,2‐trifluoroethanol diverts the selectivity of the above Ni‐based catalyst systems from hydroxylation/ketonization to trifluoroalkoxylation, with the formation of 1‐phenylalkyl 2,2,2‐trifluoroethyl ethers. The use of 2,2,2‐trifluoroethanol ensures high substrate conversion values (up to 97 %), as well as high selectivity for the ether formation (up to 92 %). Preliminary discussion of the reaction mechanism is given based on the catalytic and literature data.