bluuebunny/crossref_metadata_2025_split huggingface dataset:
Single‐Nucleus Transcriptome Profiling of Locally Advanced Cervical Squamous Cell Cancer Identifies Neural‐Like Progenitor Program Associated with the Efficacy of Radiotherapy
Authors: Zhang Lei , Ma Jun , Zhou Di , Zhou Junjun , Hu Bin , Ma Xiumei , Tang Jianming , Bai Yongrui , Chen Haiyan , Jing Ying 
Published: July 2023

AbstractRadiotherapy is the first‐line treatment for locally advanced cervical squamous cell cancer (CSCC). However, ≈50% of patients fail to respond to therapy and, in some cases, tumors progress after radical radiotherapy. Here, single‐nucleus RNA‐seq is performed to construct high‐resolution molecular landscapes of various cell types in CSCC before and during radiotherapy, to better understand radiotherapy related molecular responses within tumor microenvironment. The results show that expression levels of a neural‐like progenitor (NRP) program in tumor cells are significantly higher after radiotherapy and these are enriched in the tumors of nonresponding patients. The enrichment of the NRP program in malignant cells from the tumors of nonresponders in an independent cohort analyzed by bulk RNA‐seq is validated. In addition, an analysis of The Cancer Genome Atlas dataset shows that NRP expression is associated with poor prognosis in CSCC patients. In vitro experiments on the CSCC cell line demonstrate that downregulation of neuregulin 1 (NRG1), a key gene from NRP program, is associated with decreased cell growth and increased sensitivity to radiation. Immunohistochemistry staining in cohort 3 validated key genes, NRG1 and immediate early response 3 from immunomodulatory program, as radiosensitivity regulators. The findings reveal that the expression of NRP in CSCC can be used to predict the efficacy of radiotherapy.
Enantiopure Dinaphtho[2,3‐b:2,3‐f]thieno[3,2‐b]thiophenes: Reaching High Magnetoresistance Effect in OFETs
Authors: Volpi Martina , Jouclas Rémy , Liu Jie , Liu Guangfeng , Catalano Luca , McIntosh Nemo , Bardini Marco , Gatsios Christos , Modesti Federico , Turetta Nicholas , Beljonne David , Cornil Jérôme , Kennedy Alan R. , Koch Norbert , Erk Peter , Samorì Paolo , Schweicher Guillaume , Geerts Yves H. 
Published: July 2023

AbstractChiral molecules are known to behave as spin filters due to the chiral induced spin selectivity (CISS) effect. Chirality can be implemented in molecular semiconductors in order to study the role of the CISS effect in charge transport and to find new materials for spintronic applications. In this study, the design and synthesis of a new class of enantiopure chiral organic semiconductors based on the well‐known dinaphtho[2,3‐b:2,3‐f]thieno[3,2‐b]thiophene (DNTT) core functionalized with chiral alkyl side chains is presented. When introduced in an organic field‐effect transistor (OFET) with magnetic contacts, the two enantiomers, (R)‐DNTT and (S)‐DNTT, show an opposite behavior with respect to the relative direction of the magnetization of the contacts, oriented by an external magnetic field. Each enantiomer displays an unexpectedly high magnetoresistance over one preferred orientation of the spin current injected from the magnetic contacts. The result is the first reported OFET in which the current can be switched on and off upon inversion of the direction of the applied external magnetic field. This work contributes to the general understanding of the CISS effect and opens new avenues for the introduction of organic materials in spintronic devices.
[2+2+1+1] Cycloaddition for de novo Synthesis of Densely Functionalized Phenols
Authors: Wei Wei , Cheung Ka Key , Lin Ran , Kong Lam Cheung , Chan Ka Lok , Sung Herman H. Y. , Williams Ian D. , Tong Rongbiao , Lin Zhenyang , Jia Guochen 
Published: July 2023

AbstractA unique benzannulation strategy for regioselective de novo synthesis of densely functionalized phenols is described. Through metal‐mediated formal [2+2+1+1] cycloaddition of two different alkynes and two molecules of CO, a series of densely functionalized phenols were obtained. The benzannulation strategy allows efficient regioselective installation up to five different substituents on a phenol ring. The resulting phenols have a substitution pattern different from those obtained from Dötz and Danheiser benzannulations.
An Aptamer‐Functionalized DNA Circuit to Establish an Artificial Interaction between T Cells and Cancer Cells
Authors: Wang Zhimin , Zhang Yue , Wu Limei , Chen Jianghuai , Xie Sitao , He Jiaxuan , Zhang Qiang , Chen Hong , Chen Fengming , Liu Yue , Zhang Yutong , Zhuo Yuting , Wen Nachuan , Qiu Liping , Tan Weihong 
Published: July 2023

AbstractNongenetic strategies that enable control over the cell‐cell interaction network would be highly desired, particularly in T cell‐based cancer immunotherapy. In this work, we developed an aptamer‐functionalized DNA circuit to modulate the interaction between T cells and cancer cells. This DNA circuit was composed of recognition‐then‐triggering and aggregation‐then‐activation modules. Upon recognizing target cancer cells, the triggering strand was released to induce aggregation of immune receptors on the T cell surface, leading to an enhancement of T cell activity for effective cancer eradication. Our results demonstrated the feasibility of this DNA circuit for promoting target cancer cell‐directed stimulation of T cells, which, consequently, enhanced their killing effect on cancer cells. This DNA circuit, as a modular strategy to modulate intercellular interactions, could lead to a new paradigm for the development of nongenetic T cell‐based immunotherapy.
Bioelectrocatalytic Synthesis: Concepts and Applications
Authors: Boucher Dylan G. , Carroll Emily , Nguyen Zachary A. , Jadhav Rohit G. , Simoska Olja , Beaver Kevin , Minteer Shelley D. 
Published: July 2023

AbstractBioelectrocatalytic synthesis is the conversion of electrical energy into value‐added products using biocatalysts. These methods merge the specificity and selectivity of biocatalysis and energy‐related electrocatalysis to address challenges in the sustainable synthesis of pharmaceuticals, commodity chemicals, fuels, feedstocks and fertilizers. However, the specialized experimental setups and domain knowledge for bioelectrocatalysis pose a significant barrier to adoption. This review introduces key concepts of bioelectrosynthetic systems. We provide a tutorial on the methods of biocatalyst utilization, the setup of bioelectrosynthetic cells, and the analytical methods for assessing bioelectrocatalysts. Key applications of bioelectrosynthesis in ammonia production and small‐molecule synthesis are outlined for both enzymatic and microbial systems. This review serves as a necessary introduction and resource for the non‐specialist interested in bioelectrosynthetic research.
Base‐Modulated 1,3‐Regio‐ and Stereoselective Carboboration of Cyclohexenes
Authors: Kong Weiyu , Bao Yang , Lu Liguo , Han Zhipeng , Zhong Yifan , Zhang Ran , Li Yuqiang , Yin Guoyin 
Published: July 2023

AbstractWhile chain‐walking stimulates wide interest in both polymerization and organic synthesis, site‐ and stereoselective control of chain‐walking on rings is still a challenging task in the realm of organometallic catalysis. Inspired by a controllable chain‐walking on cyclohexane rings in olefin polymerization, we have developed a set of chain‐walking carboborations of cyclohexenes based on nickel catalysis. Different from the 1,4‐trans‐selectivity disclosed in polymer science, a high level of 1,3‐regio‐ and cis‐stereoselectivity is obtained in our reactions. Mechanistically, we discovery that the base affects the reduction ability of B2pin2 and different bases lead to different catalytic cycles and different regioselective products (1,2‐ Vs 1,3‐addition). This study provides a concise and modular method for the synthesis of 1,3‐disubstituted cyclohexylboron compounds. The incorporation of a readily modifiable boronate group greatly enhances the value of this method, the synthetic potential of which was highlighted by the synthesis of a series of high‐valued commercial chemicals and pharmaceutically interesting molecules.
MXene Fibers for Flexible and Wearable Electronics: Recent Progress and Future Perspectives
Authors: Li Fengchao , Zhao Shuiying , Wang Hongyan , Zhu Guang , Li Hongpeng 
Published: July 2023

AbstractWith the impetus of flexible electronics and micro‐nano fabrication technology, the human demand for flexible intelligent wearable devices is on an upsurge. In recent years, new functional fibers have undergone rapid development and emerged as an indispensable carrier of flexible wearable e‐textiles. However, to achieve their functional applications and durability, new functional fibers must possess good electrical and mechanical properties. As an emerging two‐dimensional material, MXenes have attracted immense attention for their high electrical conductivity, mechanical strength, specific surface area, adjustable surface properties, and exceptional processability. As such, MXenes have become an ideal candidate for the primary functional component of functional fibers. This paper presents a comprehensive review of research progress on MXene‐based fibers in the construction of flexible wearable electronic textiles. Firstly, we briefly outline the preparation methods of MXenes materials. Next, we summarize the processing types of MXene‐based fibers and highlight their performance parameters. Lastly, we summarize the primary application scenarios of MXene‐based fibers and anticipate the future development of flexible wearable e‐textiles.
Photo‐generated Charge Trapping in Phase Segregated Halide Perovskites – A Comprehensive Approach towards Efficient Photo‐Rechargeable Ion Capacitors
Authors: Kumar Tanuj , Kumar Ankush , Beniwal Shivang , Kumar Ramesh , Bag Monojit 
Published: July 2023

AbstractThe right balance between photo‐absorption and electronic‐ionic conductivity is needed for photo‐rechargeable bifunctional devices for off‐grid energy applications. Recently halide perovskites have been utilized for photo‐rechargeable supercapacitors, but the mechanism of photo‐capacitance enhancement is not known. Herein, we have fabricated mixed halide perovskites‐based photo‐rechargeable supercapacitors in two ways and examined the energy harvesting and storage capabilities of these devices. The porous electrode prepared from the mixed halide perovskites (CH3NH3PbBr2I) shows photo‐capacitance enhancement up to 15 F/g, while the electrode prepared from the blend of CH3NH3PbBr3 and CH3NH3PbI3 (2 : 1 by molar ratio) shows the photo‐capacitance diminution up to 12 F/g. Despite higher specific capacitance (~38 F/g in dark) in blend perovskites due to increased ion diffusion, the photo‐generated charge trapping at nanoscale phase segregation is responsible for the diminution in photo‐capacitance of these bifunctional devices, while a uniform mixing of halide ions in mixed halide perovskites nanocrystals leads to increased photo‐capacitance.
Teratogenesis and the epigenetic programming of congenital defects: Why paternal exposures matter
Authors: Golding Michael C. 
Published: July 2023

AbstractUntil recently, clinicians and researchers did not realize paternal exposures could impact child developmental outcomes. Indeed, although there is growing recognition that sperm carry a large amount of non‐genomic information and that paternal stressors influence the health of the next generation, toxicologists are only now beginning to explore the role paternal exposures have in dysgenesis and the incidence of congenital malformations. In this commentary, I will briefly summarize the few studies describing congenital malformations resulting from preconception paternal stressors, argue for the theoretical expansion of teratogenic perspectives into the male preconception period, and discuss some of the challenges in this newly emerging branch of toxicology. I argue that we must consider gametes the same as any other malleable precursor cell type and recognize that environmentally‐induced epigenetic changes acquired during the formation of the sperm and oocyte hold equal teratogenic potential as exposures during early development. Here, I propose the term epiteratogen to reference agents acting outside of pregnancy that, through epigenetic mechanisms, induce congenital malformations. Understanding the interactions between the environment, the essential epigenetic processes intrinsic to spermatogenesis, and their cumulative influences on embryo patterning is essential to addressing a significant blind spot in the field of developmental toxicology.
State‐space prior distribution for parameter of nonhomogeneous Poisson spatiotemporal models
Authors: Morales Fidel Ernesto Castro 
Published: July 2023

AbstractThis article proposes a new class of nonhomogeneous Poisson spatiotemporal model. In this approach, we use a state‐space model‐based prior distribution to handle the scale and shape parameters of the Weibull intensity function. The proposed prior distribution enables the inclusion of changes in the behavior of the intensity function over time. In defining the spatial correlation function of the model, we include anisotropy via spatial deformation. We estimate the model parameters from a Bayesian perspective, employ the Markov chain Monte Carlo approach, and validate this estimation procedure through a simulation exercise. Finally, the extreme rainfall in the southern semiarid region in northeastern Brazil is analyzed using the R10mm index. The proposed model showed better fit and prediction ability than did other nonhomogeneous Poisson spatiotemporal models available in the literature. This improvement in performance is mainly due to the flexibility of the intensity function that is achieved by allowing the incorporation, in time, of the climatic characteristics of this region.
Random forest and live single‐cell metabolomics reveal metabolic profiles of human macrophages upon polarization
Authors: Tang Huaqi , Ali Ahmed , Abdelazem Eman , Ottenhoff Tom H. M. , Heeren Ron M. A. , Mashaghi Alireza 
Published: July 2023

AbstractHuman macrophages are innate immune cells with diverse, functionally distinct phenotypes, namely, pro‐inflammatory M1 and anti‐inflammatory M2 macrophages. Both are involved in multiple physiological and pathological processes, including would healing, infection, and cancer. However, the metabolic differences between these phenotypes are largely unexplored at single‐cell resolution. To address this knowledge gap, an untargeted live single‐cell mass spectrometry‐based metabolomic profiling coupled with a machine‐learning data analysis approach was developed to investigate the metabolic profile of each phenotype at the single‐cell level. Results show that M1 and M2 macrophages have distinct metabolic profiles, with differential levels of fatty acyls, glycerophospholipids, and sterol lipids, which are important components of plasma membrane and involved in multiple biological processes. Furthermore, we could discern several putatively annotated molecules that contribute to inflammatory response of macrophages. The combination of random forest and live single‐cell metabolomics provided an in‐depth profile of the metabolome of primary human M1 and M2 macrophages at the single‐cell level for the first time, which will pave the way for future studies targeting the differentiation of other immune cells.
Sex differences in skeletal muscle fiber types: A meta‐analysis
Authors: Nuzzo James L. 
Published: July 2023

AbstractBiopsies have been acquired from living men and women to determine proportions of Type I (slow‐twitch) and II (fast‐twitch) skeletal muscle fibers since the 1970s. Sex differences have been assumed but the literature has not been submitted to meta‐analysis. Here, the aim was to generate effect sizes of sex differences in muscle fiber cross‐sectional areas, distribution percentages, and area percentages. Data from 2875 men and 2452 women, who participated in 110 studies, were analyzed. Myofibrillar adenosine triphosphatase histochemistry was used in 71.8% of studies to classify fibers as Type I, II, IIA, and/or IIX; immunohistochemistry, immunofluorescence, or sodium dodecyl sulfate‐polyacrylamide gel electrophoresis were used in 35.4% of studies to similarly classify myosin heavy chain (MHC) isoform content. Most studies involved biopsies from vastus lateralis (79.1%) in healthy individuals (92.7%) between 18 and 59 years old (80.9%). Men exhibited greater cross‐sectional areas for all fiber types (g = 0.40–1.68); greater distribution percentages for Type II, MHC II, IIA, IIX fibers (g = 0.26–0.34); greater area percentages for Type II, IIA, MHC IIA, IIX fibers (g = 0.39–0.93); greater Type II/I and Type IIA/I fiber area ratios (g = 0.63, 0.94). Women exhibited greater Type I and MHC I distribution percentages (g = −0.13, −0.44); greater Type I and MHC I area percentages (g = −0.53, −0.69); greater Type I/II fiber area ratios (g = −1.24). These data, which represent the largest repository of comparative muscle fiber type data from living men and women, can inform discussions about biological sex and its impact on pathologies and sports performance (e.g., explaining sex differences in muscle strength and muscle endurance).
A Single‐Site Mutation Tunes Fluorescence and Chromophorylation of an Orange Fluorescent Cyanobacteriochrome**
Authors: Janis Makena K. , Zou Wenping , Zastrow Melissa L. 
Published: July 2023

AbstractCyanobacteriochrome (CBCR) cGMP‐specific phosphodiesterase, adenylyl cyclase, and FhlA (GAF) domains bind bilin cofactors to confer sensory wavelengths important for various cyanobacterial photosensory processes. Many isolated GAF domains autocatalytically bind bilins, including the third GAF domain of CBCR Slr1393 from Synechocystis sp. PCC6803, which binds phycoerythrobilin (PEB) to yield a bright orange fluorescent protein. Compared to green fluorescent proteins, the smaller size and lack of an oxygen requirement for fluorescence make Slr1393g3 a promising platform for new genetically encoded fluorescent tools. Slr1393g3, however, shows low PEB binding efficiency (chromophorylation) at ~3 % compared to total Slr1393g3 expressed in E. coli. Here we used site‐directed mutagenesis and plasmid redesign methods to improve Slr1393g3‐PEB binding and demonstrate its utility as a fluorescent marker in live cells. Mutation at a single site, Trp496, tuned the emission over ~30 nm, likely by shifting autoisomerization of PEB to phycourobilin (PUB). Plasmid modifications for tuning relative expression of Slr1393g3 and PEB synthesis enzymes also improved chromophorylation and moving from a dual to single plasmid system facilitated exploration of a range of mutants via site saturation mutagenesis and sequence truncation. Collectively, the PEB/PUB chromophorylation was raised up to a total of 23 % with combined sequence truncation and W496H mutation.
Enhancing the Hydrodeoxygenation and Isomerization using Re Nanoparticles Decorated on Ni/SAPO‐11 Catalysts for Direct Production of Low‐Cold Flow Diesel from Triglycerides
Authors: Chuseang Jirawat , Itthibenchapong Vorranutch , Srifa Atthapon , Praikaew Wanichaya , Tuntithavornwat Soontorn , Rungtaweevoranit Bunyarat , Ratchahat Sakhon , Koo‐Amornpattana Wanida , Klysubun Wantana , Eiad‐ua Apiluck , Kiatkittipong Worapon , Assabumrungrat Suttichai 
Published: July 2023

AbstractThe novel bifunctional Ni−Re supported on bimodal SAPO‐11 catalyst was designed for an economically combined process of direct triglycerides hydro‐deoxygenation and isomerization into low‐cold flow diesel. The catalyst with a Ni to Re molar ratio of 1 : 0.12 exhibited superior performance for diesel production containing large fraction of iso‐alkanes in comparison to Ni and Re benchmarks. Comprehensive characterizations revealed that the detection of Ni and Re co‐existed with NiO and ReOx on SAPO‐11 after the reduction confirmed by XRD, XANES, and XPS analysis gave a large distribution of Lewis acid sites (>80 %) noticed by Pyridine‐DRIFTS measurement. Under investigations of WHSV, reaction temperature, and H2 pressure, the NiRe0.12 catalyst contributed a nearly theoretical 77.1 % liquid yield, accompanied by a 18.2 % jet‐range and 52.1 % diesel‐range yields with a classification for 46.8 % iso‐alkanes and 23.5 % normal alkanes yields; whereas, the cold‐flow properties of liquid product were in the ranges of winter diesel standard. It was remarkably noticed that the combination effects of Ni and nanosized Re species substantially improved the diesel production comprising iso‐alkanes components with proper catalyst lifetime and low carbon deposition attributing to the fabricated active metal species on bimodal SAPO‐11 features with large distribution of Lewis acidic sites.
Efficient Synthesis of Benzimidazole and Quinoline Derivatives Catalyzed by Functionalized Amidato Ruthenium Complexes in Water via Acceptorless Dehydrogenative Coupling Strategy
Authors: Liu Xin , Dong Wen‐Zhe , Liu Yining , Shao Wei‐Yu , Li Yang , Yu Xiaoqiang , Himeda Yuichiro , Wang Wan‐Hui , Bao Ming 
Published: July 2023

AbstractTransition‐metal‐catalyzed acceptorless dehydrogenative coupling (ADC) has emerged as a sustainable synthetic strategy for the construction of N‐heteroaromatics. Herein, a series of water‐soluble amidato Ru catalysts were designed, synthesized, and utilized in the selective synthesis of 2‐substituted benzimidazoles from the aromatic diamines and primary alcohols, as well as 2‐substituted quinolines from the substituted 2‐aminobenzyl alcohols and acetophenones via the ADC strategy in water. Catalyst 1 d bearing a strong electron‐donating hydroxyl group on the ligand exhibited the best catalytic activity. The catalytic system demonstrated remarkable efficiency and versatility, allowing for the application of over 40 substrates in two ADC reactions with good to high yields. Based on control experiments and density functional theory (DFT) calculations, a plausible mechanism was proposed, highlighting the significant role of functionalized amidato Ru complexes in catalyzing alcohol dehydrogenation via an outer‐sphere pathway.
Panchromatic Light‐Capturing Bis‐styryl BODIPY‐Perylenediimide Donor‐Acceptor Constructs: Occurrence of Sequential Energy Transfer Followed by Electron Transfer
Authors: Ileperuma Chamari V. , Garcés‐Garcés José , Shao Shuai , Fernández‐Lázaro Fernando , Sastre‐Santos Ángela , Karr Paul A. , D'Souza Francis 
Published: July 2023

AbstractTwo wide‐band‐capturing donor‐acceptor conjugates featuring bis‐styrylBODIPY and perylenediimide (PDI) have been newly synthesized, and the occurrence of ultrafast excitation transfer from the 1PDI* to BODIPY, and a subsequent electron transfer from the 1BODIPY* to PDI have been demonstrated. Optical absorption studies revealed panchromatic light capture but offered no evidence of ground‐state interactions between the donor and acceptor entities. Steady‐state fluorescence and excitation spectral recordings provided evidence of singlet‐singlet energy transfer in these dyads, and quenched fluorescence of bis‐styrylBODIPY emission in the dyads suggested additional photo‐events. The facile oxidation of bis‐styrylBODIPY and facile reduction of PDI, establishing their relative roles of electron donor and acceptor, were borne out by electrochemical studies. The electrostatic potential surfaces of the S1 and S2 states, derived from time‐dependent DFT calculations, supported excited charge transfer in these dyads. Spectro‐electrochemical studies on one‐electron‐oxidized and one‐electron‐reduced dyads and the monomeric precursor compounds were also performed in a thin‐layer optical cell under corresponding applied potentials. From this study, both bis‐styrylBODIPY⋅+ and PDI⋅− could be spectrally characterizes and were subsequently used in characterizing the electron‐transfer products. Finally, pump–probe spectral studies were performed in dichlorobenzene under selective PDI and bis‐styrylBODIPY excitation to secure energy and electron‐transfer evidence. The measured rate constants for energy transfer, kENT, were in the range of 1011 s−1, while the electron transfer rate constants, kET, were in the range of 1010 s−1, thus highlighting their potential use in solar energy harvesting and optoelectronic applications.