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Prismanes have been attracting interest for nearly 50 years because of their geometric symmetry, highly strained structures, and unique applications due to their high carbon densities and bulky structures. Although [3]-, [4]-, and [5]-prismanes have been synthesised, [6]-prismanes and their derivatives remain elusive. Herein, fluorine chemistry, molecular mechanics, molecular orbital package, and density functional theory calculations were used to design and implement the photoisomerisation of octafluoro[2.2]paracyclophane (selected based on the good overlap of its lowest unoccupied molecular orbitals and short distance between the benzene rings) into octafluoro-[6]-prismane. Specifically, a dilute solution of the above precursor in CH3CN/H2O/dimethyl sulfoxide (DMSO) (2:1:8, v/v/v) solution was irradiated with ultraviolet light, with the formation of the desired product confirmed through the use of nuclear magnetic resonance spectroscopy and gas chromatography-mass spectrometry. The product was thermally stable in solution but not under work-up conditions, which complicated the further analysis and single-crystal preparation. The key criteria for successful photoisomerisation were the presence of fluorine substituents in the cyclophane structure and DMSO in the solvent system. A more stable derivative design requires the isolation of prismane products. The proposed fluorination-based synthetic strategy is applicable to developing novel high-strain molecules/materials with three-dimensional skeletons.
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Hypersensitivity reactions are an adverse effect of anticancer drug therapy. Prophylactic administration of antiallergic drugs and steroids is recommended when administering drugs associated with a high hypersensitivity reaction incidence. First-generation antihistamines are generally used in this setting. These medications, however, induce drowsiness and sedation due to their inhibitory effects on the central nervous system. They are contraindicated in patients with angle-closure glaucoma and prostatic hyperplasia. Second-generation antihistamines are used as alternative drugs for such cases in our hospital. This study investigated the use of second-generation antihistamines at our hospital and examined their efficacy and safety. A total of 7 second-generation antihistamines were used at our hospital. Approximately 90% of the target patients were shifted from first-generation antihistamines to bilastine or desloratadine. The most frequent reasons for changing to second- generation antihistamines were drowsiness(32.3%)and car driving(24.2%). No central inhibitory side effects were observed upon consumption of second-generation antihistamines. Only 2 patients(3.2%)developed hypersensitivity reactions after changing to second-generation antihistamines. Our findings suggest that second-generation antihistamines are effective in preventing hypersensitivity reactions. These medications may be used in patients who have concerns regarding the central inhibitory side effects of first-generation antihistamines or their potential to exacerbate comorbidities. Their use can help improve the safety of anticancer drug therapy.
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Antineoplásicos , Hipersensibilidade a Drogas , Antagonistas dos Receptores Histamínicos , Humanos , Idoso , Estudos Retrospectivos , Masculino , Antineoplásicos/efeitos adversos , Antineoplásicos/uso terapêutico , Pessoa de Meia-Idade , Feminino , Hipersensibilidade a Drogas/prevenção & controle , Hipersensibilidade a Drogas/etiologia , Antagonistas dos Receptores Histamínicos/uso terapêutico , Neoplasias/tratamento farmacológico , Idoso de 80 Anos ou mais , AdultoRESUMO
Electron transfers in multinuclear metal complexes are the origin of their unique functionalities both in natural and artificial systems. However, electron transfers in multinuclear metal complexes are generally complicated, and predicting and controlling these electron transfers is extremely difficult. Herein, we report the precise manipulation of the electron transfers in multinuclear metal complexes. The development of a rational synthetic strategy afforded a series of pentanuclear metal complexes which composed of metal ions and 3,5-bis(2-pyridyl)pyrazole (Hbpp) as a platform to probe the phenomena. Electrochemical and spectroscopic investigations clarified overall picture of the electron transfers in the pentanuclear complexes. In addition, unique electron transfer behaviors, in which the reduction of a metal center occurs during the oxidation of the overall complex, were identified. We also elucidated the two dominant factors that determine the manner of the electron transfers. Our results provide comprehensive guidelines for interpreting the complicated electron transfers in multinuclear metal complexes.
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BACKGROUND: Ectopic fat is fat that accumulates in or around specific organs or compartments of the body including myocardium. The clinical features of type 2 diabetes patients with high fat accumulation in the myocardium remain unknown. Moreover, little is known about the influence of myocardial fat accumulation in type 2 diabetes on coronary artery disease and cardiac dysfunction. We aimed to clarify the clinical features, including cardiac functions, of type 2 diabetes patients with myocardial fat accumulation. METHODS: We retrospectively enrolled type 2 diabetes patients who underwent ECG-gated coronary computed tomography angiography (CCTA) and abdominal computed tomography (CT) scan examinations within 1 year of CCTA from January 2000 to March 2021. High fat accumulation in the myocardium was defined as the low mean myocardial CT value of three regions of interest, and the associations between CT values and clinical characteristics or cardiac functions were assessed. RESULTS: In total, 124 patients were enrolled (72 males and 52 females). The mean age was 66.6 years, the mean BMI was 26.2 kg/m2, the mean ejection fraction (EF) was 67.6%, and the mean myocardial CT value was 47.7 Hounsfield unit. A significant positive correlation was found between myocardial CT value and EF (r = 0.3644, p = 0.0004). The multiple regression analyses also showed that myocardial CT value was independently associated with EF (estimate, 0.304; 95% confidence interval (CI) 0.092 to 0.517; p = 0.0056). Myocardial CT value showed significant negative correlations with BMI, visceral fat area and subcutaneous fat area (r = - 0.1923, - 0.2654, and -0.3569, respectively, p < 0.05). In patients who were ≥ 65 years or female, myocardial CT value showed significant positive correlations with not only EF (r = 0.3542 and 0.4085, respectively, p < 0.01) but also early lateral annular tissue Doppler velocity (Lat e') (r = 0.5148 and 0.5361, respectively, p < 0.05). The multiple regression analyses showed that myocardial CT value was independently associated with EF and Lat e' in these subgroups (p < 0.05). CONCLUSIONS: Patients with type 2 diabetes, especially in elderly or female patients, who had more myocardial fat had more severe left ventricular systolic and diastolic dysfunctions. Reducing myocardial fat accumulation may be a therapeutic target for type 2 diabetes patients.
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Doença da Artéria Coronariana , Diabetes Mellitus Tipo 2 , Idoso , Masculino , Humanos , Feminino , Diabetes Mellitus Tipo 2/complicações , Diabetes Mellitus Tipo 2/diagnóstico , Diabetes Mellitus Tipo 2/epidemiologia , Estudos Retrospectivos , Miocárdio , Coração , Doença da Artéria Coronariana/diagnóstico por imagemRESUMO
In this study, we successfully synthesized the double perovskite oxide Cd2FeReO6 by using a high-temperature and high-pressure method. The crystal structure was confirmed to belong to the P21/n space group, exhibiting approximately 68% ordering of Fe3+ and Re5+ ions at the perovskite B-site with the remaining regions showing antisite disorder. The measured Curie temperature of Cd2FeReO6 was 460 K, slightly lower than expected but still significantly above room temperature. Remarkably, Cd2FeReO6 displayed a remarkable low-field butterfly type tunneling magnetoresistance of -23% (-37% between the lowest and the largest values) at 5 K and 90 kOe, the highest among the A2FeReO6 (A = Ca, Sr, Pb, Ba) family. First-principles calculations provided insight into the origin of this observed magnetoresistance behavior, revealing Cd2FeReO6's half-metallic ferrimagnetic nature. This research extends our understanding of the double perovskite family and emphasizes its potential significance in the domains of spintronics and materials science. The exploration of differing magnetoresistance behaviors between Cd2FeReO6 and Ca2FeReO6, along with the influence of antisite disorder in Cd2FeReO6, opens intriguing avenues for further research.
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Although the oxidation of water is efficiently catalysed by the oxygen-evolving complex in photosystem II (refs 1 and 2), it remains one of the main bottlenecks when aiming for synthetic chemical fuel production powered by sunlight or electricity. Consequently, the development of active and stable water oxidation catalysts is crucial, with heterogeneous systems considered more suitable for practical use and their homogeneous counterparts more suitable for targeted, molecular-level design guided by mechanistic understanding. Research into the mechanism of water oxidation has resulted in a range of synthetic molecular catalysts, yet there remains much interest in systems that use abundant, inexpensive and environmentally benign metals such as iron (the most abundant transition metal in the Earth's crust and found in natural and synthetic oxidation catalysts). Water oxidation catalysts based on mononuclear iron complexes have been explored, but they often deactivate rapidly and exhibit relatively low activities. Here we report a pentanuclear iron complex that efficiently and robustly catalyses water oxidation with a turnover frequency of 1,900 per second, which is about three orders of magnitude larger than that of other iron-based catalysts. Electrochemical analysis confirms the redox flexibility of the system, characterized by six different oxidation states between Fe(II)5 and Fe(III)5; the Fe(III)5 state is active for oxidizing water. Quantum chemistry calculations indicate that the presence of adjacent active sites facilitates O-O bond formation with a reaction barrier of less than ten kilocalories per mole. Although the need for a high overpotential and the inability to operate in water-rich solutions limit the practicality of the present system, our findings clearly indicate that efficient water oxidation catalysts based on iron complexes can be created by ensuring that the system has redox flexibility and contains adjacent water-activation sites.
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Three-dimensional hierarchical morphologies widely exist in natural and biomimetic materials, which impart preferential functions including liquid and mass transport, energy conversion, and signal transmission for various applications. While notable progress has been made in the design and manufacturing of various hierarchical materials, the state-of-the-art approaches suffer from limited materials selection, high costs, as well as low processing throughput. Herein, by harnessing the configurable elastic crack engineering-controlled formation and configuration of cracks in elastic materials-an effect normally avoided in various industrial processes, we report the development of a facile and powerful technique that enables the faithful transfer of arbitrary hierarchical structures with broad material compatibility and structural and functional integrity. Our work paves the way for the cost-effective, large-scale production of a variety of flexible, inexpensive, and transparent 3D hierarchical and biomimetic materials.
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Invited for the cover of this issue are Ryuta Ishikawa and Satoshi Kawata at Fukuoka University and co-workers at Osaka University, Tohoku University, and Kumamoto University, Japan, collaborating within the research project "SOFT CRYSTALS". The image depicts the thermally induced simultaneous switching of magnetism and electrical conductivity in a two-dimensional supramolecular architecture composed of dinuclear FeII spin-crossover complexes and partially charged 7,7',8,8'-tetracyano-p-quinodimethanide radicals. 10.1002/chem.201903934.
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The reaction of Fe(OAc)2 and Hbpypz with neutral TCNQ results in the formation of [Fe2 (bpypz)2 (TCNQ)2 ](TCNQ)2 (1), in which Hbpypz=3,5-bis(2-pyridyl)pyrazole and TCNQ=7,7',8,8'-tetracyano-p-quinodimethane. Crystal packing of 1 with uncoordinated TCNQ and π-π stacking of bpypz- ligands produces an extended two-dimensional supramolecular coordination assembly. Temperature dependence of the dc magnetic susceptibility and heat capacity measurements indicate that 1 undergoes an abrupt spin crossover (SCO) with thermal spin transition temperatures of 339 and 337â K for the heating and cooling modes, respectively, resulting in a thermal hysteresis of 2â K. Remarkably, the temperature dependence of dc electrical transport exhibits a transition that coincides with thermal SCO, demonstrating the thermally induced magnetic and electrical bistability of 1, strongly correlating magnetism with electrical conductivity. This outstanding feature leads to thermally induced simultaneous switching of magnetism and electrical conductivity and a magnetoresistance effect.
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Plasmonic Ag nano-assemblies moving in a living cell were employed to visualize the spatiotemporal change of intracellular pH by surface-enhanced Raman scattering. Ag nano-assemblies were functionalized with 4-mercaptobenzoic acid (p-MBA) to monitor the variation of the surrounding pH. SERS spectra from the functionalized nano-assemblies that were transported in a cell were recorded to estimate the local pH on the pathways travelled by the nano-assemblies. 3D nanoparticle tracking and SERS measurements were simultaneously performed to trace the pH dynamics with a spatial accuracy of several tens of nanometers and a temporal resolution of 200 ms, which are sufficient to reveal pH changes associated with intracellular transportation. The pH trajectory of the functionalized nanoparticle can be used to visualize the dynamic change of the chemical environment caused by organelle interactions, such as endosomal trafficking and lysosomal fusion. This breakthrough creates a new paradigm for intracellular analysis using SERS and reveals new capability for rapid use of SERS in biological analysis.
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Ouro , Nanopartículas Metálicas , Concentração de Íons de Hidrogênio , Análise Espectral RamanRESUMO
Intracellular pH is one of the key factors for understanding various biological processes in biological cells. Plasmonic gold and silver nanoparticles (NPs) have been extensively studied for surface-enhanced Raman scattering (SERS) applications for pH sensing as a local pH probe in a living cell. However, the SERS performance of NPs depends on material, size, and shape, which can be controlled by chemical synthesis. Here, we synthesized 18 types of gold and silver NPs with different morphologies such as sphere, rod, flower, star, core/shell, hollow, octahedra, core/satellites, and chainlike aggregates, and quantitatively compared their SERS performance for pH sensing. The SERS intensity from the most commonly utilized SERS probe molecule ( para-mercaptobenzoic acid, p-MBA) for pH sensing was measured at the single nanoparticle level under the same measurement parameters such as low laser power (0.5 mW/µm2), short integration time (100 ms) at wavelengths of 405, 488, 532, 584, 676, and 785 nm. In our measurement, the Ag chain, Ag core/satellites, Ag@Au core/satellites, and Au core/satellites nanoassemblies showed efficient pH sensing at the single particle level. By using p-MBA-conjugated Au@Ag core/satellites, we performed time-lapse pH measurements during apoptosis of HeLa cells. These experimental results confirmed that the pH measurement using p-MBA-conjugated Au@Ag core/satellites can be applied for long-term measurements of intracellular pH during cellular events.
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Host-guest materials based on coordination polymers (CPs) are currently emerging as potential candidates for battery applications. In this context, we describe the preparation of three-dimensional network structures containing BF4 anions and water molecules in the one-dimensional (1D) channels via hydrothermal reactions between Cu(BF4)2 and 4,4'-bipyridine or 1,2-di-4-pyridylethylene. A systematic characterization of the obtained CPs using single-crystal X-ray diffraction, X-ray absorption fine structure, and an electrochemical test was performed. The results showed that the BF4 anions were electrochemically reduced to BF3 in the cavities of the CPs, with concomitant elimination of a leaving fluoride at room temperature. Using this electrochemical property, a prototype battery, in which the CPs act as the anode and graphite as the cathode, was demonstrated. The cell exhibited a practical discharge potential of â¼1.5 V. This constitutes the first demonstration of CPs showing electrochemical B-F bond activation in the 1D channels and rocking-chair-type fluoride insertion and extraction by changes in the electric potential.
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Raman scattering microscopy is becoming one of the hot topics in analytical microscopy as a tool for analyzing advanced nanomaterials, such as biomolecules in a live cell for the study of cellular dynamics, semiconductor devices for characterizing strain distribution and contamination, and nanocarbons and nano-2D materials. In this paper, we review the recent progress in the development of Raman scattering microscopy from the viewpoint of spatial resolution and scattering efficiency. To overcome the extremely small cross section of Raman scattering, we discuss three approaches for the enhancement of scattering efficiency and show that the scattering enhancement synergistically increases the spatial resolution. We discuss the mechanisms of tip-enhanced Raman scattering, deep-UV resonant Raman scattering, and coherent nonlinear Raman scattering for micro- and nanoscope applications. The combinations of these three approaches are also shown as nanometer-resolution Raman scattering microscopy. The critical issues of the structures, materials, and reproducibility of tips and three-dimensionality for TERS; photodegradation for resonant Raman scattering; and laser availability for coherent nonlinear Raman scattering are also discussed.
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An analytical technique operating at the nanoscale must be flexible regarding variable experimental conditions while ideally also being highly specific, extremely sensitive, and spatially confined. In this respect, tip-enhanced Raman scattering (TERS) has been demonstrated to be ideally suited to, e.g., elucidating chemical reaction mechanisms, determining the distribution of components and identifying and localizing specific molecular structures at the nanometre scale. TERS combines the specificity of Raman spectroscopy with the high spatial resolution of scanning probe microscopies by utilizing plasmonic nanostructures to confine the incident electromagnetic field and increase it by many orders of magnitude. Consequently, molecular structure information in the optical near field that is inaccessible to other optical microscopy methods can be obtained. In this general review, the development of this still-young technique, from early experiments to recent achievements concerning inorganic, organic, and biological materials, is addressed. Accordingly, the technical developments necessary for stable and reliable AFM- and STM-based TERS experiments, together with the specific properties of the instruments under different conditions, are reviewed. The review also highlights selected experiments illustrating the capabilities of this emerging technique, the number of users of which has steadily increased since its inception in 2000. Finally, an assessment of the frontiers and new concepts of TERS, which aim towards rendering it a general and widely applicable technique that combines the highest possible lateral resolution and extreme sensitivity, is provided.
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We demonstrated resolution improvement in two-photon excitation microscopy by combining saturated excitation (SAX) of fluorescence and pupil manipulation. We theoretically estimated the resolution improvement and the sidelobe effect in the point spread function with various pupil designs and found that the combination of SAX and core-ring illumination can effectively enhance the spatial resolution in 3D and suppress sidelobe artifacts. The experimental demonstration shows that the proposed technique is effective for observation with a depth of 100 µm in a tissue phantom and can be applied to 3D observations of tissue samples with higher spatial resolution than conventional two-photon excitation microscopy.
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Iluminação , Microscopia de Fluorescência/métodos , Fótons , Corantes Fluorescentes/química , Células HeLa , Humanos , Imagens de FantasmasRESUMO
Identification of small-molecule-binding sites in protein is important for drug discovery and analysis of protein function. Modified amino-acid residue(s) can be identified by proteolytic cleavage followed by liquid chromatography-mass spectrometry (LC-MS), but this is often hindered by the complexity of the peptide mixtures. We have developed alkyne-tag Raman screening (ATRaS) for identifying binding sites. In ATRaS, small molecules are tagged with alkyne and form covalent bond with proteins. After proteolysis and HPLC, fractions containing the labeled peptides with alkyne tags are detected by means of surface-enhanced Raman scattering (SERS) using silver nanoparticles and sent to MS/MS to identify the binding site. The use of SERS realizes high sensitivity (detection limit: â¼100 femtomole) and reproducibility in the peptide screening. By using an automated ATRaS system, we successfully identified the inhibitor-binding site in cysteine protease cathepsin B, a potential drug target and prognostic marker for tumor metastasis. We further showed that the ATRaS system works for complex mixtures of trypsin-digested cell lysate. The ATRaS technology, which provides high molecular selectivity to LC-MS analysis, has potential to contribute in various research fields, such as drug discovery, proteomics, metabolomics and chemical biology.
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We provide an overview of Fano resonance and plasmon induced transparency (PIT) as well as on plasmons coupling in planar structures, and we discuss their application in sensing and enhanced spectroscopy. Metal-insulator-metal (MIM) structures, which are known to support symmetric and anti-symmetric surface plasmon polaritons (SPPs) arising from the coupling between two SPPs at the metal-insulator interfaces, exhibit anticrossing behavior of the dispersion relations arising from the coupling of the symmetric SPP and the metal/air SPP. Multilayer structures, formed by a metal film and a high-index dielectric waveguide (WG), separated by a low-index dielectric spacer layer, give narrow resonances of PIT and Fano line shapes. An optimized Fano structure shows a giant field intensity enhancement value of 106 in air at the surface of the high-index dielectric WG. The calculated field enhancement factor and the figure of merit for the sensitivity of the Fano structure in air can be 104 times as large as those of the conventional surface plasmon resonance and WG sensors.
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We previously showed that bisarylbutadiyne (BADY), which has a conjugated diyne structure, exhibits an intense peak in the cellular Raman-silent region. Here, we synthesized a mitochondria-selective Raman probe by linking bisphenylbutadiyne with triphenylphosphonium, a well-known mitochondrial targeting moiety. This probe, named MitoBADY, has a Raman peak 27 times more intense than that of 5-ethynyl-2'-deoxyuridine. Raman microscopy using submicromolar extracellular probe concentrations successfully visualized mitochondria in living cells. A full Raman spectrum is acquired at each pixel of the scanned sample, and we showed that simultaneous Raman imaging of MitoBADY and endogenous cellular biomolecules can be achieved in a single scan. MitoBADY should be useful for the study of mitochondrial dynamics.
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Alcinos/química , Mitocôndrias/química , Análise Espectral Raman , Desoxiuridina/análogos & derivados , Desoxiuridina/química , Desoxiuridina/metabolismo , Células HeLa , Humanos , Microscopia de Fluorescência , Mitocôndrias/metabolismoRESUMO
We demonstrate dynamic surface-enhanced Raman scattering (SERS) imaging with 3 dimensional mapping in a living cell by combining a confocal Raman spectrometer and dual-focus dark-field microscopy. Gold nanoparticles acting as a probe traveling through the living cell, are tracked by dual-focus dark-field imaging, with position feedback to the confocal Raman spectrometer in order to record evolving SERS signals from the same gold nanoparticle moving through the cell. Simultaneous detection of motion and the SERS spectrum enables the visualization of the SERS pathways. Observation of how the SERS spectra change in space and time during biological functions or by changes of the molecular environment provides exciting opportunities for understanding the molecular basis of the cell dynamics.
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Imageamento Tridimensional/métodos , Nanopartículas Metálicas/química , Transdução de Sinais , Análise Espectral Raman/métodos , Transporte Biológico , Rastreamento de Células , Citoplasma/química , Ouro/química , Humanos , Ressonância de Plasmônio de SuperfícieRESUMO
Local temperature of a nanoscale volume is precisely determined by tip-enhanced terahertz Raman spectroscopy in the low temperature range of several tens of degrees. Heat generated by the tip-enhanced electric field is directly transferred to single-walled carbon nanotubes by heat conduction and radiation at the nanoscale. This heating modulates the intensity ratio of anti-Stokes/Stokes Raman scattering of the radial breathing mode of the carbon nanotube based on the Boltzmann distribution at elevated temperatures. Owing to the low-energy feature of the radial breathing mode, the local temperature of the probing volume has been successfully extracted with high sensitivity. The dependence of the temperature rise underneath the tip apex on the incident power coincides with the analytical results calculated by finite element method based on the tip enhancement effect and the consequent steady-state temperature via Joule heat generation. The results show that the local temperature at the nanoscale can be controlled in the low temperature range simply by the incident laser power while exhibiting a sufficiently high tip enhancement effect as an analytical tool for thermally sensitive materials (e.g., proteins, DNA). Graphical Abstract Tip-enhanced THz Raman spectroscopy detects the low frequency Raman mode both in Stokes and anti-Stokes shifts, which precisely reflects the local temperature of the sample volume.