bluuebunny/crossref_metadata_2025_split huggingface dataset:
Silver‐Catalyzed Dearomative [2π+2σ] Cycloadditions of Indoles with Bicyclobutanes: Access to Indoline Fused Bicyclo[2.1.1]hexanes**
Authors: Tang Lei , Xiao Yuanjiu , Wu Feng , Zhou Jin‐Lan , Xu Tong‐Tong , Feng Jian‐Jun 
Published: October 2023

AbstractBicyclo[2.1.1]hexanes (BCHs) are becoming ever more important in drug design and development as bridged scaffolds that provide underexplored chemical space, but are difficult to access. Here a silver‐catalyzed dearomative [2π+2σ] cycloaddition strategy for the synthesis of indoline fused BCHs from N‐unprotected indoles and bicyclobutane precursors is described. The strain‐release dearomative cycloaddition operates under mild conditions, tolerating a wide range of functional groups. It is capable of forming BCHs with up to four contiguous quaternary carbon centers, achieving yields of up to 99 %. In addition, a scale‐up experiment and the synthetic transformations of the cycloadducts further highlighted the synthetic utility.
Gold‐Catalyzed 1,2‐Aryl Shift and Double Alkyne Benzannulation
Authors: Sanil Gana , Krzeszewski Maciej , Chaładaj Wojciech , Danikiewicz Witold , Knysh Iryna , Dobrzycki Łukasz , Staszewska‐Krajewska Olga , Cyrański Michał K. , Jacquemin Denis , Gryko Daniel T. 
Published: October 2023

AbstractThe tandem intramolecular hydroarylation of alkynes accompanied by a 1,2‐aryl shift is described. Harnessing the unique electron‐rich character of 1,4‐dihydropyrrolo[3,2‐b]pyrrole scaffold, we demonstrate that the hydroarylation of alkynes proceeds at the already occupied positions 2 and 5 leading to a 1,2‐aryl shift. Remarkably, the reaction proceeds only in the presence of cationic gold catalyst, and it leads to heretofore unknown π‐expanded, centrosymmetric pyrrolo[3,2‐b]pyrroles. The utility is verified in the preparation of 13 products that bear six conjugated rings. The observed compatibility with various functional groups allows for increased tunability with regard to the photophysical properties as well as providing sites for further functionalization. Computational studies of the reaction mechanism revealed that the formation of the six‐membered rings accompanied with a 1,2‐aryl shift is both kinetically and thermodynamically favourable over plausible formation of products containing 7‐membered rings. Steady‐state UV/Visible spectroscopy reveals that upon photoexcitation, the prepared S‐shaped N‐doped nanographenes undergo mostly radiative relaxation leading to large fluorescence quantum yields. Their optical properties are rationalized through time‐dependent density functional theory calculations. We anticipate that this chemistry will empower the creation of new materials with various functionalities.
Three‐Photon Infrared Stimulation of Endogenous Neuroreceptors in Vivo
Authors: Sortino Rosalba , Cunquero Marina , Castro‐Olvera Gustavo , Gelabert Ricard , Moreno Miquel , Riefolo Fabio , Matera Carlo , Fernàndez‐Castillo Noèlia , Agnetta Luca , Decker Michael , Lluch José M. , Hernando Jordi , Loza‐Alvarez Pablo , Gorostiza Pau 
Published: October 2023

AbstractTo interrogate neural circuits and crack their codes, in vivo brain activity imaging must be combined with spatiotemporally precise stimulation in three dimensions using genetic or pharmacological specificity. This challenge requires deep penetration and focusing as provided by infrared light and multiphoton excitation, and has promoted two‐photon photopharmacology and optogenetics. However, three‐photon brain stimulation in vivo remains to be demonstrated. We report the regulation of neuronal activity in zebrafish larvae by three‐photon excitation of a photoswitchable muscarinic agonist at 50 pM, a billion‐fold lower concentration than used for uncaging, and with mid‐infrared light of 1560 nm, the longest reported photoswitch wavelength. Robust, physiologically relevant photoresponses allow modulating brain activity in wild‐type animals with spatiotemporal and pharmacological precision. Computational calculations predict that azobenzene‐based ligands have high three‐photon absorption cross‐section and can be used directly with pulsed infrared light. The expansion of three‐photon pharmacology will deeply impact basic neurobiology and neuromodulation phototherapies.
Stereoselective Unsymmetrical 1,1‐Diborylation of Alkynes with a Neutral sp2−sp3 Diboron Reagent
Authors: Lou Xiangyu , Lin Jiaxin , Kwok Chun Yin , Lyu Hairong 
Published: October 2023

AbstractThe incorporation of two distinct boryl groups at the same carbon center in organic molecules has attracted growing research interest due to its potential for facilitating controlled, precise synthesis through stepwise dual carbon‐boron bond transformations. Here we report a method to access unsymmetrical 1,1‐diborylalkene (UDBA) stereoselectively via the reaction of readily available alkynes with a neutral sp2−sp3 diboron reagent (NHC)BH2‐Bpin (NHC=N‐heterocyclic carbene). Attributing to the chemically easily distinguishable nature of the sp2 and sp3 boryl moieties, controllable stepwise derivatization of the resultant UDBAs is realized. This process leads to various multifunctionalized olefins and organoborons, such as acylboranes, which are difficult to prepare by other methods.
Construction of High‐Density Binuclear Site Catalysts from Double Framework Interfaces at the Cooling Stage
Authors: Yang Shuai , Wei Yao , Li Xuewen , Mao Jianing , Mei Bingbao , Xu Qing , Li Xiaopeng , Jiang Zheng 
Published: October 2023

AbstractLow‐nuclear site catalysts with dual atoms have the potential for applications in energy and catalysis chemistry. Understanding the formation mechanism of dual metal sites is crucial for optimizing local structures and designing desired binuclear sites catalysts. In this study, we demonstrate for the first time the formation process of dual atoms through the pyrolysis of the interface of a double framework using Zn atoms in metal–organic frameworks and Co atoms in covalent organic frameworks. We unambiguously revealed that the cooling stage is the key point to form the binuclear sites by employing the in situ synchrotron radiation X‐ray absorption spectrum technique. The binuclear site catalysts show higher activity and selectivity than single dispersed atom catalysts for electrocatalytic oxygen reduction. This work guides us to synthesize and optimize the various binuclear sites for extensive catalytic applications.
Colorless, transparent, and shape memory polyurethane networks with high strength and recyclability
Authors: Ma Xiaojuan , Yue Huimin , Huang Miaoming , Huang Gaoshang , Yao Chenxin , Wu Yaohui , He Suqin , Liu Hao , Liu Wentao , Zhu Chengshen 
Published: October 2023

AbstractThe traditional thermoset polyurethanes (PUs) can be recycled through the dynamic carbamate bonds under specific conditions. However, there is limited research on the structural evolution and property changes of these PUs before and after recycling. Herein, we designed and fabricated a thermoset polyurethane network (PCU) using polyhexamethylene carbonate diol (PHMC‐diol) as soft segments, and isophorone diisocyanate (IPDI) and glycerol (GLY) as hard segments. Through careful formulation design, the PCU demonstrated colorless transparency (with up to 86% transmission), shape memory properties, and reprocessing capabilities, all achieved without introducing other dynamic covalent bonds. Furthermore, the PCU exhibited excellent mechanical properties, boasting a tensile strength of 59.2 ± 3.7 MPa and the elongation at break of 674.8 ± 37.3%. Of particular interest, the PCU samples displayed solid‐state plasticity and impressive shape memory performance, with shape fixity and recovery ratios exceeding 90%. Leveraging the combination of solid‐state plasticity and shape memory, the PCU samples demonstrated the ability to achieve arbitrary shape manipulations. Upon recycling, it was observed that the cross‐linking density of the PCU samples decreased, resulting in the formation of byproducts and subsequently leading to a reduction in tensile strength. Nonetheless, the PCU samples prepared in this study exhibit potential as thermadapt shape memory and recyclable materials.
Terahertz Probing of Anisotropic Conductivity and Morphology of CuMnAs Epitaxial Thin Films
Authors: Kubaščík Peter , Farkaš Andrej , Olejník Kamil , Troha Tinkara , Hývl Matěj , Krizek Filip , Joshi Deep Chandra , Ostatnický Tomáš , Jechumtál Jiří , Surýnek Miloš , Schmoranzerová Eva , Campion Richard P. , Zázvorka Jakub , Novák Vít , Kužel Petr , Jungwirth Tomáš , Němec Petr , Nádvorník Lukáš 
Published: October 2023

AbstractAntiferromagnetic CuMnAs thin films have attracted attention since the discovery of the manipulation of their magnetic structure via electrical, optical, and terahertz pulses, enabling convenient approaches for switching between magnetoresistive states of the film for information storage. However, the magnetic structure and, thus, the efficiency of the manipulation can be affected by the film morphology and growth defects. In this study, the properties of CuMnAs thin films are investigated by probing the asymmetrical growth‐related uniaxial anisotropy of electric conductivity by contact‐free terahertz transmission spectroscopy. It is shown that the terahertz measurements conveniently detect the conductivity anisotropy that is consistent with conventional DC Hall‐bar measurements. Moreover, the terahertz technique allows for considerably finer determination of anisotropy axes, and it is less sensitive to the local film degradation. Thanks to the averaging over a large detection area, the THz probing also allows an analysis of strongly non‐uniform thin films. Using scanning electron and near‐field terahertz microscopies, the observed anisotropic conductivity of CuMnAs is related to the elongation and orientation of growth defects, which both originate in the anisotropic growth of the films. In addition, control over the morphology of defects is demonstrated by using vicinal substrates.
Neural sensitivity to facial identity and facial expression discrimination in adults with autism
Authors: Van der Donck Stephanie , Hendriks Michelle , Vos Silke , Op de Beeck Hans , Boets Bart 
Published: October 2023

AbstractThe fluent processing of faces can be challenging for autistic individuals. Here, we assessed the neural sensitivity to rapid changes in subtle facial cues in 23 autistic men and 23 age and IQ matched non‐autistic (NA) controls using frequency‐tagging electroencephalography (EEG). In oddball paradigms examining the automatic and implicit discrimination of facial identity and facial expression, base rate images were presented at 6 Hz, periodically interleaved every fifth image with an oddball image (i.e. 1.2 Hz oddball frequency). These distinctive frequency tags for base rate and oddball stimuli allowed direct and objective quantification of the neural discrimination responses. We found no large differences in the neural sensitivity of participants in both groups, not for facial identity discrimination, nor for facial expression discrimination. Both groups also showed a clear face‐inversion effect, with reduced brain responses for inverted versus upright faces. Furthermore, sad faces generally elicited significantly lower neural amplitudes than angry, fearful and happy faces. The only minor group difference is the larger involvement of high‐level right‐hemisphere visual areas in NA men for facial expression processing. These findings are discussed from a developmental perspective, as they strikingly contrast with robust face processing deficits observed in autistic children using identical EEG paradigms.
Evaluation of the effect of designed PLGA‐arctiin nanoparticles modified with folic acid and chitosan on colon cancer cells
Authors: Alhadidi Mohammed Hussein Ajel , Tabrizi Masoud Homayouni , Ghobeh Maryam 
Published: October 2023

AbstractIn this study, we designed nanoparticles (NPs) based on polylactic acid glycolic acid modified with chitosan and folic acid to optimize the anti‐cancer, anti‐inflammatory, and antioxidant effects of arctiin (ARC), and we measured its effects on cancer cells, including colon cancer. NPs were synthesized using the W1/O/W2 double‐emulsion solvent evaporation method. Physicochemical characteristics of synthesized NPs (ARC‐PCF‐NPs), including average particle size, dispersity index (PDI), zeta potential (ZP), field emission scanning electron microscope figures, and encapsulation efficiency (EE), were evaluated. 2,2′‐Azino‐bis(3‐ethylbenzothiazoline‐6‐sulfonic acid) (ABTS), 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH), and ferric reducing antioxidant power (FRAP) methods were carried out to determine the antioxidant properties of NPs. 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl‐2H‐tetrazolium bromide assay was performed to investigate cytotoxicity effects on cancer cells and normal fibroblasts. Quantitative polymerase chain reaction was also performed on inflammatory and antioxidant genes. The obtained results indicated that the synthesized NPs have a size of 100 nm, a DPI of 0.36, a ZP of 26.30 mV, and EE was calculated at about 87.5%. The antioxidant influence of ARC‐PCF‐NPs was confirmed by inhibiting ABTS and DPPH free radicals and ferrous reduction in the FRAP method. Moreover, the reduction of inflammatory and antioxidant genes confirmed the anti‐inflammatory and antioxidant properties of NPs. These results indicate the modification of the surface of NPs in order to increase the bioavailability, stability, and effectiveness of medicinal compounds in therapeutic applications.
Metabolism of testosterone and progesterone by cytochrome P450 2C19 allelic variants
Authors: Takeji Shiori , Okada Mai , Hayashi Shu , Kanamaru Kengo , Uno Yuichi , Imaishi Hiromasa , Uno Tomohide 
Published: October 2023

AbstractCYP2C19 is a member of the human microsomal cytochrome P450 (CYP). Significant variation in CYP2C19 levels and activity can be attributed to polymorphisms in this gene. Wildtype CYP2C19 and 13 mutants (CYP2C19.1B, CYP2C19.5A, CYP2C19.5B, CYP2C19.6, CYP2C19.8, CYP2C19.9, CYP2C19.10, CYP2C19.11, CYP2C19.13, CYP2C19.16, CYP2C19.19, CYP2C19.23, CYP2C19.30, and CYP2C19.33) were coexpressed with NADPH‐cytochrome P450 reductase in Escherichia coli. Hydroxylase activity toward testosterone and progesterone was also examined. Ten CYP2C19 variants showed Soret peaks (450 nm) typical of P450 in the reduced CO‐difference spectra. CYP2C19.11 and CYP2C19.23 showed higher testosterone 11α, 16α‐/17‐ and progesterone 6β‐,21‐,16α‐/17α‐hydroxylase activities than CYP2C19.1B. CYP2C19.6, CYP2C19.16, CYP2C19.19, and CYP2C19.30 showed lower activity than CYP2C19.1B. CYP2C19.9, CYP2C19.10. CYP2C19.13, and CYP2C19.33 showed different hydroxylation activities than CYP2C19.1B. These results indicated that CYP2C19 variants have very different substrate specificities for testosterone and progesterone.
Coherent lives: Making sense of adoptees’ experiences in education through narrative identity
Authors: Brown Andrew , Shelton Katherine 
Published: October 2023

AbstractChildren adopted from care become part of a hidden, but no less vulnerable, group in the education system and may be overlooked for allocation of additional support and guidance. Adoption is a relatively unique experience and adds layers of complexity, difference and vulnerability to young people's lives that are poorly understood and under‐researched. Adopted adolescents face significant challenges in social, emotional and behavioural aspects of school life. An attainment gap persists throughout their educational career. Adoptees are strikingly absent from many conversations regarding care‐experienced young people yet their needs and challenges are comparable with those of their peers remaining in the care system. Assumptions are made about adoptees’ opportunity and capacity to recover, concealing challenges faced in adjusting to adoptive life, including education. The impact of adoptees’ early experiences could lead to complex identity formation processes during adolescence, with potential implications for education experience and performance. This paper explores the potential of applying a narrative adoptive identity perspective to answer questions about how adopted children and young people experience school as an adopted person, i.e. how does their lived experience as an adopted member of a school community impact on their engagement with school, schoolwork and peer networks? The concept of ‘communicative openness’ is used to illustrate the vital role the school community plays in enabling adopted children to transition into and thrive in school. Taking a narrative adoptive identity approach may enable teachers to better meet adoptees’ specific learning and teaching needs as dictated by their unique experiences and enhance opportunities for better educational progress.
Life detection in a universe of false positives
Authors: Smith Harrison B. , Mathis Cole 
Published: October 2023

AbstractAstrobiology aims to determine the distribution and diversity of life in the universe. But as the word “biosignature” suggests, what will be detected is not life itself, but an observation implicating living systems. Our limited access to other worlds suggests this observation is more likely to reflect out‐of‐equilibrium gasses than a writhing octopus. Yet, anything short of a writhing octopus will raise skepticism about what has been detected. Resolving that skepticism requires a theory to delineate processes due to life and those due to abiotic mechanisms. This poses an existential question for life detection: How do astrobiologists plan to detect life on exoplanets via features shared between non‐living and living systems? We argue that you cannot without an underlying theory of life. We illustrate this by analyzing the hypothetical detection of an “Earth 2.0” exoplanet. Without a theory of life, we argue the community should focus on identifying unambiguous features of life via four areas: examining life on Earth, building life in the lab, probing the solar system, and searching for technosignatures. Ultimately, we ask, what exactly do astrobiologists hope to learn by searching for life?
Expression and application of aflatoxin degrading enzyme gene in Pichia pastoris
Authors: Li Li , Mei Mengning , Wang Jun , Huang Jiang , Zong Xuyan , Wang Xiangyu 
Published: October 2023

AbstractIn this study, three aflatoxin degrading enzyme genes, tv‐adtz, arm‐adtz and cu‐adtz, were heterologously expressed in Pichia pastoris. The protein expression of the enzyme solution was detected by sodium dodecyl sulfate polyacrylamide gel electrophoresis, and the results showed that specific protein bands were detected and the target genes were successfully integrated into Pichia pastoris. The enzyme activities and detoxification efficiency of TV‐ADTZ, Arm‐ADTZ and Cu‐ADTZ crude enzyme solutions were detected, and the highest enzyme activities were up to 3.57, 4.30, and 2.41 U mL−1, and the highest degradation rates were up to 45.58%, 60.0% and 34.21%, respectively. Arm‐ADTZ with the best degradation effect was selected and designed for detoxification application experiments to test its detoxification efficiency of AFB1 in aqueous phase and in the process of moldy ground corn and preparation of DDGS, respectively, and the degradation rates reached 78.94%, 56.48%, and 24.31% after 24 h of reaction, respectively. Thus, it can be seen that the aflatoxin‐degrading enzyme gene was successfully integrated into Pichia pastoris and secreted for expression, and the expressed product could effectively degrade AFB1.
A low‐cost cure for CUREs: An undergraduate microbiology course engaging students in authentic research using publicly available datasets
Authors: Avramovska Ognenka , Rokop Megan E. 
Published: October 2023

AbstractUndergraduate research experiences are key to preparing STEM students for a range of careers and graduate programs, and to impacting retention in STEM. Providing undergraduate research experiences can be challenging for institutions due to the high cost associated with equipment and reagents, lab space, and research mentors. In this study, we present an upper‐level microbiology seminar course that does not require these resources, as each student chooses and performs their own research project using data obtained from publicly available datasets. The faculty member provides hands‐on instruction and regular feedback to mentor the cohort of students through all stages of their research projects, from honing a research question, to choosing a dataset, to data analysis and visualization. Students build science communication skills through each writing a scientific paper, and creating and presenting a scientific poster. These papers and presentations, along with results from student pre‐ and post‐surveys, demonstrate that students built research and communication skills, while also building their confidence and interest in science careers. To access this research experience, students only need to register for this course; no application or selection is required, and no prior research experience is expected. The use of publicly available data makes this course a low‐cost way to integrate authentic research projects into the college curriculum, and can be adapted to courses in any discipline. Such “low‐cost CUREs” (course‐based undergraduate research experiences) can be used to build capacity for undergraduate research experiences that are so crucial to preparing students for opportunities in and beyond college.
Integrated UHPLC–QE/MS, transcriptomics and network pharmacology reveal the mechanisms via which Liang‐Yan‐Yi‐Zhen‐San promotes the browning of white adipose tissue
Authors: Yao Dong , Xing Bo , Li Xiang , Xu Zi‐Hua , Liu Qian , Liu Xin , Wu Qiong , Cui Ya‐Ling , Fan Ying , Zhao Qing‐Chun 
Published: October 2023

AbstractWe have previously shown that Liang‐Yan‐Yi‐Zhen‐San (LYYZS), an ancient Chinese herbal formula, can promote the browning of white adipose tissue. In this study, we sought to determine which active ingredients of LYYZS mediated its effects on the browning of white adipose tissue. Employing ultra‐high performance liquid chromatography–Q‐Exactive HF mass spectrometry, a total of 52 LYYZS ingredients were identified. On this basis, 1,560 ingredient‐related targets of LYYZS were screened using the HERB databases. Meanwhile, RNA sequencing analysis of the inguinal white adipose tissue of mice produced a total of 3148 genes that were significantly differentially expressed following LYYZS treatment and differentially expressed genes regarded as browning‐related targets. Through the network pharmacological analysis, a total of 136 intersection targets were obtained and an ingredient–target–pathway network was established. According to network pharmacology analysis, 10 ingredients containing trans‐cinnamaldehyde, genistein, daidzein, calycosin, arginine, coumarin, oleic acid, isoleucine, palmitic acid and tyrosine were regarded as active ingredients of browning of white adipose tissue. Integrated evaluation using chemical analysis, transcriptomics and network pharmacology provides an efficient strategy for discovering the active ingredients involved in how LYYZS promotes the browning of white adipose tissue.