bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Systematic Study of Methyl Carbodithioate Esters as Effective Gold Contact Groups for Single‐Molecule Electronics
Authors: Ward Jonathan S. , Vezzoli Andrea , Wells Charlie , Bailey Steven , Jarvis Samuel P. , Lambert Colin J. , Robertson Craig , Nichols Richard J. , Higgins Simon J. 
Published: May 2024

AbstractThere are several binding groups used within molecular electronics for anchoring molecules to metal electrodes (e.g., R−SMe, R−NH2, R−CS2−, R−S−). However, some anchoring groups that bind strongly to electrodes have poor/unknown stability, some have weak electrode coupling, while for some their binding motifs are not well defined. Further binding groups are required to aid molecular design and to achieve a suitable balance in performance across a range of properties. We present an in‐depth investigation into the use of carbodithioate esters as contact groups for single‐molecule conductance measurements, using scanning tunnelling microscopy break junction measurements (STM‐BJ) and detailed surface spectroscopic analysis. We demonstrate that the methyl carbodithioate ester acts as an effective contact for gold electrodes in STM‐BJ measurements. Surface enhanced Raman measurements demonstrate that the C=S functionality remains intact when adsorbed on to gold nanoparticles. A gold(I) complex was also synthesised showing a stable C=S→AuI interaction from the ester. Comparison with a benzyl thiomethyl ether demonstrates that the C=S moiety significantly contributes to charge transport in single‐molecule junctions. The overall performance of the CS2Me group demonstrates it should be used more extensively and has strong potential for the fabrication of larger area devices with long‐term stability.
Cu1−Fe Dual Sites for Superior Neutral Ammonia Electrosynthesis from Nitrate
Authors: Zhou Biao , Yu Linghao , Zhang Weixing , Liu Xupeng , Zhang Hao , Cheng Jundi , Chen Ziyue , Zhang Hao , Li Meiqi , Shi Yanbiao , Jia Falong , Huang Yi , Zhang Lizhi , Ai Zhihui 
Published: May 2024

AbstractThe electrochemical nitrate reduction reaction (NO3RR) is able to convert nitrate (NO3−) into reusable ammonia (NH3), offering a green treatment and resource utilization strategy of nitrate wastewater and ammonia synthesis. The conversion of NO3− to NH3 undergoes water dissociation to generate active hydrogen atoms and nitrogen‐containing intermediates hydrogenation tandemly. The two relay processes compete for the same active sites, especially under pH‐neutral condition, resulting in the suboptimal efficiency and selectivity in the electrosynthesis of NH3 from NO3−. Herein, we constructed a Cu1‐Fe dual‐site catalyst by anchoring Cu single atoms on amorphous iron oxide shell of nanoscale zero‐valent iron (nZVI) for the electrochemical NO3RR, achieving an impressive NO3− removal efficiency of 94.8 % and NH3 selectivity of 99.2 % under neutral pH and nitrate concentration of 50 mg L−1 NO3−−N conditions, greatly surpassing the performance of nZVI counterpart. This superior performance can be attributed to the synergistic effect of enhanced NO3− adsorption on Fe sites and strengthened water activation on single‐atom Cu sites, decreasing the energy barrier for the rate‐determining step of *NO‐to‐*NOH. This work develops a novel strategy of fabricating dual‐site catalysts to enhance the electrosynthesis of NH3 from NO3−, and presents an environmentally sustainable approach for neutral nitrate wastewater treatment.
Site‐Selective Distal C(sp3)−H Bromination of Aliphatic Amines as a Gateway for Forging Nitrogen‐Containing sp3 Architectures
Authors: Chen Jinhong , Tan Clarence , Rodrigalvarez Jesus , Zhang Shuai , Martin Ruben 
Published: May 2024

AbstractHerein, we disclose a new strategy that rapidly and reliably incorporates bromine atoms at distal, secondary C(sp3)−H sites in aliphatic amines with an excellent and predictable site‐selectivity pattern. The resulting halogenated building blocks serve as versatile linchpins to enable a series of carbon‐carbon and carbon‐heteroatom bond‐formations at remote C(sp3) sites, thus offering a new modular and unified platform that expediates the access to advanced sp3 architectures possessing valuable nitrogen‐containing saturated heterocycles of interest in medicinal chemistry settings.
A Hybrid Orbitrap‐Nanoelectromechanical Systems Approach for the Analysis of Individual, Intact Proteins in Real Time
Authors: Neumann Adam P. , Sage Eric , Boll Dmitri , Reinhardt‐Szyba Maria , Fon Warren , Masselon Christophe , Hentz Sébastien , Sader John E. , Makarov Alexander , Roukes Michael L. 
Published: May 2024

AbstractNanoelectromechanical systems (NEMS)‐based mass spectrometry (MS) is an emerging technique that enables determination of the mass of individual adsorbed particles by driving nanomechanical devices at resonance and monitoring the real‐time changes in their resonance frequencies induced by each single molecule adsorption event. We incorporate NEMS into an Orbitrap mass spectrometer and report our progress towards leveraging the single‐molecule capabilities of the NEMS to enhance the dynamic range of conventional MS instrumentation and to offer new capabilities for performing deep proteomic analysis of clinically relevant samples. We use the hybrid instrument to deliver E. coli GroEL molecules (801 kDa) to the NEMS devices in their native, intact state. Custom ion optics are used to focus the beam down to 40 μm diameter with a maximum flux of 25 molecules/second. The mass spectrum obtained with NEMS‐MS shows good agreement with the known mass of GroEL.
A Cyclometalated Ruthenium(II) Complex Induces Oncosis for Synergistic Activation of Innate and Adaptive Immunity
Authors: Feng Tao , Tang Zixin , Shu Jun , Wu Xianbo , Jiang Hui , Chen Zhuoli , Chen Yu , Ji Liangnian , Chao Hui 
Published: May 2024

AbstractAn optimal cancer chemotherapy regimen should effectively address the drug resistance of tumors while eliciting antitumor‐immune responses. Research has shown that non‐apoptotic cell death, such as pyroptosis and ferroptosis, can enhance the immune response. Despite this, there has been limited investigation and reporting on the mechanisms of oncosis and its correlation with immune response. Herein, we designed and synthesized a Ru(II) complex that targeted the nucleus and mitochondria to induce cell oncosis. Briefly, the Ru(II) complex disrupts the nucleus and mitochondria DNA, which active polyADP‐ribose polymerase 1, accompanied by ATP consumption and porimin activation. Concurrently, mitochondrial damage and endoplasmic reticulum stress result in the release of Ca2+ ions and increased expression of Calpain 1. Subsequently, specific pore proteins porimin and Calpain 1 promote cristae destruction or vacuolation, ultimately leading to cell membrane rupture. The analysis of RNA sequencing demonstrates that the Ru(II) complex can initiate the oncosis‐associated pathway and activate both innate and adaptive immunity. In vivo experiments have confirmed that oncosis promotes dendritic cell maturation and awakens adaptive cytotoxic T lymphocytes but also activates the innate immune by inducing the polarization of macrophages towards an M1 phenotype.
Unraveling the Unique Strong Metal‐Support Interaction in Titanium Dioxide Supported Platinum Clusters for the Hydrogen Evolution Reaction
Authors: Luo Zhouxin , Han Xiao , Ma Zhentao , Zhang Bingxing , Zheng Xusheng , Liu Yongfeng , Gao Mingxia , Zhao Guoqiang , Lin Yue , Pan Hongge , Sun Wenping 
Published: May 2024

AbstractStrong metal‐support interaction (SMSI) is crucial to modulating the nature of metal species, yet the SMSI behaviors of sub‐nanometer metal clusters remain unknown due to the difficulties in constructing SMSI at cluster scale. Herein, we achieve the successful construction of the SMSI between Pt clusters and amorphous TiO2 nanosheets by vacuum annealing, which requires a relatively low temperature that avoids the aggregation of small clusters. In situ scanning transmission electron microscopy observation is employed to explore the SMSI behaviors, and the results reveal the dynamic rearrangement of Pt atoms upon annealing for the first time. The originally disordered Pt atoms become ordered as the crystallizing of the amorphous TiO2 support, forming an epitaxial interface between Pt and TiO2. Such a SMSI state can remain stable in oxidation environment even at 400 °C. Further investigations prove that the electron transfer from TiO2 to Pt occupies the Pt 5d orbitals, which is responsible for the disappeared CO adsorption ability of Pt/TiO2 after forming SMSI. This work not only opens a new avenue for constructing SMSI at cluster scale but also provides in‐depth understanding on the unique SMSI behavior, which would stimulate the development of supported metal clusters for catalysis applications.
Photoinitiated Transient Self‐Assembly in a Catalytically Driven Chemical Reaction Cycle
Authors: Valera Jorge S. , López‐Acosta Álvaro , Hermans Thomas M. 
Published: May 2024

AbstractChemically fueled chemical reaction networks (CRNs) are essential in controlling dissipative self‐assembly. A key challenge in the field is to store chemical fuel‐precursors or “pre‐fuels” in the system that are converted into activating or deactivating fuels in a catalytically controlled CRN. In addition, real‐time control over catalysis in a CRN by light is highly desirable, but so far not yet achieved. Here we show a catalytically driven CRN that is photoinitiated with 450 nm light, producing activated monomers that go on to perform transient self‐assembly. Monomer activation proceeds via photoredox catalysis, converting the monomer alcohol groups into the corresponding aldehydes that self‐assemble into large supramolecular fibers. Monomer deactivation is achieved by organometallic catalysis that relies on pre‐fuel hydrolysis to release formate (i.e. the deactivating fuel). Additionally, irradiation with 305 nm light accelerates the release of formate by photo‐uncaging the pre‐fuel, leading to a factor of ca. 2 faster deactivation of the monomer. Overall, we show transient self‐assembly upon visible light photoactivation, and tunable life‐times by ultraviolet light.
Enhanced Electron Delocalization Induced by Ferromagnetic Sulfur doped C3N4 Triggers Selective H2O2 Production
Authors: Xu Siran , Yu Yue , Zhang Xiaoyu , Xue Dongping , Wei Yifan , Xia Huicong , Zhang Fuxiang , Zhang Jia‐Nan 
Published: May 2024

AbstractFor the 2D metal‐free carbon catalysts, the atomic coplanar architecture enables a large number of pz orbitals to overlap laterally, thus forming π‐electron delocalization, and the delocalization degree of the central atom dominates the catalytic activity. Herein, designing sulfur‐doped defect‐rich graphitic carbon nitride (S‐Nv‐C3N4) materials as a model, we propose a strategy to promote localized electron polarization by enhancing the ferromagnetism of ultra‐thin 2D carbon nitride nanosheets. The introduction of sulfur (S) further promotes localized ferromagnetic coupling, thereby inducing long‐range ferromagnetic ordering and accelerating the electron interface transport. Meanwhile, the hybridization of sulfur atoms breaks the symmetry and integrity of the unit structure, promotes electron enrichment and stimulating electron delocalization at the active site. This optimization enhances the *OOH desorption, providing a favorable kinetic pathway for the production of hydrogen peroxide (H2O2). Consequently, S‐Nv‐C3N4 exhibits high selectivity (>95 %) and achieves a superb H2O2 production rate, approaching 4374.8 ppm during continuous electrolysis over 300 hour. According to theoretical calculation and in situ spectroscopy, the ortho‐S configuration can provide ferromagnetic perturbation in carbon active centers, leading to the electron delocalization, which optimizes the OOH* adsorption during the catalytic process.
High anticancer activity in short response time exhibited by a new azobenzene derivative and its copper complex
Authors: Dev Samrat , Mitra Debarpan , Sinha Chittaranjan , Das Gaurav , Murmu Nabendu , Maity Amit Ranjan , Pandey Souvik 
Published: May 2024

o‐Aminoazotoluene (OAT), capable of photoisomerization, and o‐vanillin, a potent comutagen, have been used to synthesize a new ligand, HL, [C6H4(CH3)N=NC6H3(CH3)N=CHC6H3(OH)(OCH3)], which, upon complexation with copper(II), results in a new copper(II) complex‐Cu(L)2, [Cu{C6H4(CH3)N=NC6H3(CH3)N=CHC6H3(OCH3)O}2]. Both HL and Cu(L)2 have been characterized by single‐crystal X‐ray diffraction measurements along with other analytical techniques, for example, IR spectroscopy, NMR spectroscopy, UV–Vis spectroscopy, elemental analysis and mass spectrometry. These compounds were tested with different in vitro anticancer assay as well as with in silico studies. A comparative study has been demonstrated on anticancer activity of HL and Cu(L)2 with the ligand HAZ, {C6H5N=NC6H4N=CHC6H3(OH)(OCH3)} and its Cu‐complex, [Cu(AZ)2, Cu{C6H5N=NC6H4N=CHC6H3(OCH3)O}2]. The sensing properties of HAZ, along with the synthesis and structural properties of both HAZ and Cu(AZ)2, have been reported by our group earlier. Cytotoxicity measurements on MCF7 cell lines show that Cu(L)2 and Cu(AZ)2 have higher anticancer activity than their corresponding ligands. The apoptotic effect of Cu‐complex was studied through nuclear fragmentation assay and AO/EB dual‐staining assay on MCF7 cell line. The IC50 value of Cu(L)2 in 0.01% DMSO/water after 24‐h treatment was found 4.2 μM, which is one of the lowest values with this response time compared to the other analogous anticancer compounds. Finally, we have evaluated the expression of hERα protein with respect to Cu‐complexes, and it was observed that Cu(L)2 caused more down‐regulation of hERα as compared to Cu(AZ)2.
Tough bilayer thermo‐responsive hydrogel actuator reinforced by Fe3+ complexation
Authors: Tian Shilin , Wang Ziquan , Wang Xusheng , Yang Feng , Shi Hongqi , Wen Huimin , Shen Tianyu , Zhu Zhenkun , Wang Yangxin , Zhao Huaixia 
Published: May 2024

AbstractHydrogel actuators usually suffer from the poor mechanical property, which hinders their wide applications. In this study, we propose a tough bilayer hydrogel actuator that can respond quickly to temperature. The hydrogels are composed of poly(N‐isopropylacylamide) (PNIPAM) layer and poly(acrylamide‐co‐acrylic acid) (P(AAm‐co‐AAc)) layer strengthened through Fe3+ complexation with carboxyl groups. By optimizing the PNIPAM content, the resulting bilayer hydrogel P(NIPAM0.9/AAm‐co‐AAc)‐Fe3+ exhibits fast and large‐amplitude bending and recovery in response to temperature. It also shows excellent mechanical properties with a tensile strength of 2.54 MPa, tensile modulus of 3.7 MPa, and toughness of 9.4 MJ/m3, respectively. Besides, the multiple noncovalent interactions within the hydrogels, including Fe+‐mediated coordination and hydrogen bonds, can serve as dynamic but stable associations, leading to a good self‐healing ability. The bilayer hydrogel is further made into a gripper that can effectively and sensitively respond to temperature to capture and release an object, showing its potential application in artificial intelligent devices.
Pure Green Ag–In–Ga–S/Ga–S Quantum Dot Light‐Emitting Diodes with Electron Transport Materials Exhibiting Enhanced Luminescence Properties
Authors: Motomura Genichi , Ohisa Satoru , Uematsu Taro , Kuwabata Susumu , Kameyama Tatsuya , Torimoto Tsukasa , Fujisaki Yoshihide 
Published: May 2024

AbstractQuantum dots (QDs) are essential luminescent materials with applications in wide‐color‐gamut displays requiring exceptional color reproducibility. Multinary semiconductor QDs composed of groups I, III and VI elements are expected to serve as eco‐friendly materials to replace conventional QDs owing to the potential narrow spectral widths and tunable bandgaps of the former. Although optimized Ag–In–Ga–S/Ga–S core/shell QDs (AIGS QDs) have exhibited vibrant green emissions, electroluminescence from QD‐based light‐emitting diodes (QLEDs) incorporating these AIGS QDs is reduced as a consequence of the effects of defect sites. The present work therefore examines the incorporation of electron transport materials (ETMs) into AIGS QD emitting layers. A device incorporating emitting layers composed of AIGS QDs and 2,4,6‐tris(3‐(3‐pyridyl)phenyl)‐1,3,5‐triazine (TmPPyTz), with the latter acting as a highly conductive ETM, exhibits a low driving voltage and high efficiency. Furthermore, the addition of two ETMs — TmPPyTz and tris(2,4,6‐trimethyl‐3‐(pyridin‐3‐yl)phenyl)borane — is found to provide enhanced luminescence properties because these materials are deposited in the emitting layer in different forms and hence has varying effects in terms of improving conductivity and charge balance. The resulting QLEDs have a sharp spectral width of 30 nm, suggesting a level of color purity suitable for wide‐color‐gamut displays.
Unlocking the therapeutic potential of TRPV3: Insights into thermosensation, channel modulation, and skin homeostasis involving TRPV3
Authors: Lei Jing , Tominaga Makoto 
Published: May 2024

AbstractRecent insights reveal the significant role of TRPV3 in warmth sensation. A novel finding elucidated how thermosensation is affected by TRPV3 membrane abundance that is modulated by the transmembrane protein TMEM79. TRPV3 is a warmth‐sensitive ion channel predominantly expressed in epithelial cells, particularly skin keratinocytes. Multiple studies investigated the roles of TRPV3 in cutaneous physiology and pathophysiology. TRPV3 activation by innocuous warm temperatures in keratinocytes highlights its significance in temperature sensation, but whether TRPV3 directly contributes to warmth sensations in vivo remains controversial. This review explores the electrophysiological and structural properties of TRPV3 and how modulators affect its intricate regulatory mechanisms. Moreover, we discuss the multifaceted involvement of TRPV3 in skin physiology and pathology, including barrier formation, hair growth, inflammation, and itching. Finally, we examine the potential of TRPV3 as a therapeutic target for skin diseases and highlight its diverse role in maintaining skin homeostasis.
The use of bioluminescent enzyme bioassay for the analysis of human saliva: Advantages and disadvantages
Authors: Kolenchukova Oksana A. , Dedora Anastasia O. , Stepanova Lyudmila V. , Kravchuk Vlada U. , Kratasyuk Valentina A. 
Published: May 2024

AbstractThe purpose of the work was to find optimal conditions for bioluminescent enzymatic analysis of saliva (based on the use of NADH:FMN oxidoreductase + luciferase) and then to determine the biological effect of using bioluminescence assay of saliva to study the physiological state of the body under normal and pathological conditions. The saliva of snowboarders and students were studied in the “rest–training” model. The saliva of patients diagnosed with acute pharyngitis was examined in the “sick–healthy” model. Bioluminescence assay was performed with a lyophilized and immobilized bi‐enzyme system using cuvette, plate, and portable luminometers. The concentrations of secretory immunoglobulin A (sIgA) and cortisol were determined by enzyme immunoassay, and the total protein content was measured by spectrophotometric method. The activity of the bioluminescent system enzymes increased as the amount and volume of saliva in the sample was decreased. The cuvette and plate luminometers were sensitive to changes in the luminescence intensity in saliva assay. Luminescence intensity correlated with the concentrations of sIgA and cortisol. The integrated bioluminescent index for saliva was reduced in the “rest–training” model and increased in the “sick–healthy” model. Thus, the non‐invasive bioluminescent saliva analysis may be a promising tool for assessing the health of the population.
A carbon dot‐based time‐dependent color‐changing room temperature phosphorescent material with facile synthesis
Authors: Zhang Le , Bian Zhentao , Hu Guangzhou 
Published: May 2024

AbstractCarbon dots have attracted widespread attention due to their excellent optical properties and so on and are therefore used in various fields such as anti‐counterfeiting. There are many reports on carbon dot‐based room‐temperature phosphorescent materials, but there are still fewer reports on carbon dot‐based room‐temperature phosphorescent materials with time‐dependent color‐changing properties. In this work, a time‐dependent color‐changing carbon dot‐based room‐temperature phosphorescent material with the ability to change from green to blue was successfully prepared by a simple one‐pot heating method using hydroxyurea as the only raw material. In this process, hydroxyurea is used as both a carbon and nitrogen source, and in the process of material formation, hydroxyurea also partially forms cyanuric acid as a matrix to make the carbon dots uniformly dispersed in it. By blending the ratio of the dual emission centers of the carbon dots themselves, the final effect of time‐dependent color‐changing is achieved by taking advantage of the intensity changes and color differences of each emission center. The present work provides new ideas for the preparation of time‐dependent color‐changing carbon dot‐based room‐temperature phosphorescent materials.
Clinical relevance of somatic mutations in Chinese lung adenocarcinoma and their prognostic implications for survival
Authors: Li Tongxin , Liu Jie , Zhou Yu , Huang Shengyuan , Wang Dong , Chen Jianrong , Fu Yong , He Ping 
Published: May 2024

AbstractBackgroundTo comprehensively elucidate the genomic and mutational features of lung cancer cases, and lung adenocarcinoma (LUAD), it is imperative to conduct ongoing investigations into the genomic landscape. In this study, we aim to analyze the somatic mutation profile and assessed the significance of these informative genes utilizing a retrospective LUAD cohort.MethodsA total of 247 Chinese samples were analyzed to exhibit the tumor somatic genomic alterations in patients with LUAD. The Cox regression analysis was employed to identify prognosis‐related genes and establish a predictive model for stratifying patients with LUAD.ResultsIn the Dianjiang People's Hospital (DPH) cohort, the top five frequent mutated genes were (Epidermal growth factor receptor) EGFR (68%), TP53 (30%), RBM10 (13%), LRP1B (9%), and KRAS (9%). Of which, EGFR is a mostly altered driver gene, and most mutation sites are located in tyrosine kinase regions. Oncogene pathway alteration and mutation signature analysis demonstrated the RTK‐RAS pathway alteration, and smoking was the main carcinogenic factor of the DPH cohort. Furthermore, we identified 34 driver genes in the DPH cohort, including EGFR (68%), TP53 (30.4%), RBM10 (12.6%), KRAS (8.5%), LRP1B (8.5%), and so on, and 45 Clinical Characteristic‐Related Genes (CCRGs) were found to closely related to the clinical high‐risk factors. We developed a Multiple Parameter Gene Mutation (MPGM) risk model by integrating critical genes and oncogenic pathway alterations in LUAD patients from the DPH cohort. Based on publicly available LUAD datasets, we identified five genes, including BRCA2, Anaplastic lymphoma kinase (ALK), BRAF, EGFR, and Platelet‐Derived Growth Factor Receptor Alpha (PDGFRA), according to the multivariable Cox regression analysis. The MPGM‐low group showed significantly better overall survival (OS) compared to the MPGM‐high group (p < 0.0001, area under the curve (AUC) = 0.754). The robust performance was validated in 55 LUAD patients from the DPH cohort and another LUAD dataset. Immune characteristics analysis revealed a higher proportion of primarily DCs and mononuclear cells in the MPGM‐low risk group, while the MPGM‐high risk group showed lower immune cells and higher tumor cell infiltration.ConclusionThis study provides a comprehensive genomic landscape of Chinese LUAD patients and develops an MPGM risk model for LUAD prognosis stratification. Further follow‐up will be performed for the patients in the DPH cohort consistently to explore the resistance and prognosis genetic features.