共查询到20条相似文献,搜索用时 31 毫秒
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Liu Y Song Y Rockenbauer A Sun J Hemann C Villamena FA Zweier JL 《The Journal of organic chemistry》2011,76(10):3853-3860
Measurement of thiol concentrations is of great importance for characterizing their critical role in normal metabolism and disease. Low-frequency electron paramagnetic resonance (EPR) spectroscopy and imaging, coupled with the use of exogenous paramagnetic probes, have been indispensable techniques for the in vivo measurement of various physiological parameters owing to the specificity, noninvasiveness and good depth of magnetic field penetration in animal tissues. However, in vivo detection of thiol levels by EPR spectroscopy and imaging is limited due to the need for improved probes. We report the first synthesis of trityl radical-conjugated disulfide biradicals (TSSN and TSST) as paramagnetic thiol probes. The use of trityl radicals in the construction of these biradicals greatly facilitates thiol measurement by EPR spectroscopy since trityls have extraordinary stability in living tissues with a single narrow EPR line that enables high sensitivity and resolution for in vivo EPR spectroscopy and imaging. Both biradicals exhibit broad characteristic EPR spectra at room temperature because of their intramolecular spin-spin interaction. Reaction of these biradicals with thiol compounds such as glutathione (GSH) and cysteine results in the formation of trityl monoradicals which exhibit high spectral sensitivity to oxygen. The moderately slow reaction between the biradicals and GSH (k(2) ~ 0.3 M(-1) s(-1) for TSSN and 0.2 M(-1) s(-1) for TSST) allows for in vivo measurement of GSH concentration without altering the redox environment in biological systems. The GSH concentration in rat liver was determined to be 3.49 ± 0.14 mM by TSSN and 3.67 ± 0.24 mM by TSST, consistent with the value (3.71 ± 0.09 mM) determined by the Ellman's reagent. Thus, these trityl-based thiol probes exhibit unique properties enabling measurement of thiols in biological systems and should be of great value for monitoring redox metabolism. 相似文献
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快速增长的对安全能源的需求,促使科研工作者不断探索高能量密度的可充锂离子电池(LIBs)。发展原位表征技术能更好地研究电池工作中的锂离子镶嵌机制和电池失效因素。固体核磁共振(NMR)能有效的测试短程化学环境:通过对~1H、~(6,7)Li、~(11)B、~(13)C、~(17)O、~(19)F、~(23)Na和~(31)P等同位素来探测电池材料的微观结构。除了魔角旋转(MAS)高分辨NMR谱图研究电池材料的精细结构之外,核磁共振还能无损地捕获、研究电池材料在充放电循环中的演化。因此,原位核磁共振NMR及成像(MRI)可拓展到电池充放电循环中的锂离子的动态演化以及锂离子浓度的时空分布信息。互为补充地,电子顺磁共振(EPR)及成像(EPRI)能有效地跟踪和捕获电极过渡金属、阴氧离子(O_2~(n-))的氧化还原过程。这些实时捕获的动态信息能更好地指导电极材料的构效、微观设计和电池组装的改进,最终获得优异的电化学性能。 相似文献
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用于疾病诊断的Gd~Ⅲ/量子点多模态成像探针的构建 总被引:2,自引:0,他引:2
结合核磁共振成像(MRI)和荧光成像技术,以钆离子、近红外低毒量子点、二氧化硅和聚丙烯酸(PAA)等为原料,采用一系列纳米载体自组装技术,构建出MRI弛豫率/荧光效率高和生物相容性好的GdⅢ/量子点多模态纳米探针.结果表明,与未螯合GdⅢ的量子点纳米探针相比,GdⅢ/量子点多模态纳米探针具有更高的弛豫率;t1-加权MRI成像也证实了GdⅢ/量子点多模态纳米探针具有很好的阳性造影功效. 相似文献
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Haitao Wu Vincent Coble Olga Vasalatiy Rolf E. Swenson Murali C. Krishna James B. Mitchell 《Tetrahedron letters》2014
Nitroxides can ameliorate the toxic effects of radiation during cancer therapy. Nitroxides are paramagnetic and can be used in magnetic resonance imaging (MRI) and electron paramagnetic resonance imaging (EPRI) to monitor in vivo oxidative stress status. Compound 5 (3-(N-piperidinemethyl)-2,2,5,5-tetramethyl-1-oxy-3-pyrroline) was found to be the most effective nitroxide radioprotector. An efficient synthesis for this promising radioprotector was developed. 相似文献
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Imaging brain tumor by dendrimer-based optical/paramagnetic nanoprobe across the blood-brain barrier
Yan H Wang J Yi P Lei H Zhan C Xie C Feng L Qian J Zhu J Lu W Li C 《Chemical communications (Cambridge, England)》2011,47(28):8130-8132
A multimodal optical/paramagnetic nanoprobe, Den-Angio, was developed and demonstrated a capability to circumvent the blood brain barrier (BBB) and visualize brain tumors with high sensitivity in vivo. Den-Angio holds promise to pre-operatively localize brain tumors and make image-guided tumor resection possible during surgery. 相似文献
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Xu S Chen S Zhang M Shen T 《Journal of photochemistry and photobiology. B, Biology》2003,72(1-3):61-67
Two phenmethylamino hypocrellin B derivatives are novel photodynamic agents synthesized by a mild reaction between hypocrellin B and phenmethylamine. The red absorption of the photosensitizers is enlarged distinctly and the peri-hydroxylated perylenequinone structure of the parent HB is preserved. 9,10-diphenyl-anthracene (DPA) bleaching and electron paramagnetic resonance (EPR) spin trapping techniques were used to study the photodynamic activities of the phenmethylamino hypocrellin B derivatives in the presence of oxygen. Singlet oxygen (1O2) and superoxide anion radical (O2*-) generated in the process of illumination of the phenmethylamino hypocrellin B in aerobic solution were observed. The photodamage of PMAHBs to MGC803 cancer cells was investigated in vitro. The results in vitro reveal that the phenmethylamino hypocrellin B derivatives show a much less significant decrease in cytotoxicity than that of their parent HB. It exhibits higher selectivity of light-orientation, which can decrease the damage to normal tissues by irradiating the tumor tissues, and so increases the drug safety. 相似文献
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Dr. Michael Harris Dr. Silvanose Biju Prof. Tatjana N. Parac-Vogt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(61):13838-13847
Contrast agents for magnetic resonance imaging have historically been based on paramagnetic metal complexes, particularly Gd3+ chelates, which tend to lose their contrast enhancement ability with increasing magnetic field strength. Emerging high-field MRI applications require the development of novel contrast agents that exhibit high relaxation enhancement as a function of magnetic field strength. Paramagnetic ions such as Dy3+, Tb3+ or Ho3+ incorporated into supramolecular or inorganic nano-architectures represent promising platforms for the development of high field MRI contrast agents. Furthermore, such platforms allow facile inclusion of multiple imaging modalities, therapeutic loading, and targeting vectors. This Minireview examines the application of contrast agents for high-field MRI, which range from single molecules to nanoparticles. Approaches to create multimodal agents by combining high-field MRI contrast properties with another imaging modality are also discussed. 相似文献
9.
Dawid Janasik Dr. Tomasz Krawczyk 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(5):e202102556
Magnetic resonance imaging (MRI) is one of the most powerful imaging tools today, capable of displaying superior soft-tissue contrast. This review discusses developments in the field of 19F MRI multimodal probes in combination with optical fluorescence imaging (OFI), 1H MRI, chemical exchange saturation transfer (CEST) MRI, ultrasonography (USG), X-ray computed tomography (CT), single photon emission tomography (SPECT), positron emission tomography (PET), and photoacoustic imaging (PAI). In each case, multimodal 19F MRI probes compensate for the deficiency of individual techniques and offer improved sensitivity or accuracy of detection over unimodal counterparts. Strategies for designing 19F MRI multimodal probes are described with respect to their structure, physicochemical properties, biocompatibility, and the quality of images. 相似文献
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Xueting Pan Weiwei Wang Zhijun Huang Shuang Liu Juan Guo Fengrong Zhang Hongjun Yuan Xin Li Fengyong Liu Huiyu Liu 《Angewandte Chemie (International ed. in English)》2020,59(32):13557-13561
The high reactive oxygen species (ROS) generation ability and simple construction of sonosensitizer systems remain challenging in sonodynamic therapy against the hypoxic tumor. In this work, we rationally prepared MOF‐derived double‐layer hollow manganese silicate nanoparticle (DHMS) with highly effective ROS yield under ultrasound irradiation for multimodal imaging‐guided sonodynamic therapy (SDT). The presence of Mn in DHMS increased ROS generation efficiency because it could be oxidized by holes to improve the electron–hole separation. Moreover, DHMS could produce oxygen in the tumor microenvironment, which helps overcome the hypoxia of the solid tumor and thus enhance the treatment efficiency. In vivo experiments demonstrated efficient tumor inhibition in DHMS‐mediated SDT guided by ultrasound and magnetic resonance imaging. This work presents a MOF‐derived nanoparticle with sonosensitive and oxygen generating ability, which provides a promising strategy for tumor hypoxia in SDT. 相似文献
11.
Owing to its excellent biological properties, peptide has been widely used in the design of nanoprobes capable of enhancing tumor imaging signals. In recent years, a number of peptide-based nanoprobes with strong loading capacity and great biocompatibility have been developed for precision tumor imaging by coupling peptide motifs with different imaging agents. It is worth noting that, compared with "always on" mode, the use of stimulus-mediated in situ activatable mode to design and control the self-assembly or nanostructure transformation of peptide-based nanoprobes in vivo can achieve the significant improvement of imaging efficiency. Herein, we summarize the recent progress of in situ activatable peptide-based nanoprobes for tumor imaging in diverse imaging modes, including magnetic resonance imaging(MRI), fluorescence imaging(FI), photoacoustic imaging(PAI), radionuclide imaging(RI) and multimodal imaging. Finally, we briefly prospect the challenges and potential development directions of this field. 相似文献
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Dr. Xueting Pan Dr. Weiwei Wang Dr. Zhijun Huang Shuang Liu Juan Guo Fengrong Zhang Hongjun Yuan Xin Li Prof. Fengyong Liu Prof. Huiyu Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13659-13663
The high reactive oxygen species (ROS) generation ability and simple construction of sonosensitizer systems remain challenging in sonodynamic therapy against the hypoxic tumor. In this work, we rationally prepared MOF-derived double-layer hollow manganese silicate nanoparticle (DHMS) with highly effective ROS yield under ultrasound irradiation for multimodal imaging-guided sonodynamic therapy (SDT). The presence of Mn in DHMS increased ROS generation efficiency because it could be oxidized by holes to improve the electron–hole separation. Moreover, DHMS could produce oxygen in the tumor microenvironment, which helps overcome the hypoxia of the solid tumor and thus enhance the treatment efficiency. In vivo experiments demonstrated efficient tumor inhibition in DHMS-mediated SDT guided by ultrasound and magnetic resonance imaging. This work presents a MOF-derived nanoparticle with sonosensitive and oxygen generating ability, which provides a promising strategy for tumor hypoxia in SDT. 相似文献
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Qunying Jiang Min Pan Jialing Hu Junlin Sun Lei Fan Zhiqiao Zou Jianshuang Wei Xiaoquan Yang Xiaoqing Liu 《Chemical science》2021,12(1):148
Many cancer treatments including photodynamic therapy (PDT) utilize reactive oxygen species (ROS) to kill tumor cells. However, elevated antioxidant defense systems in cancer cells result in resistance to the therapy involving ROS. Here we describe a highly effective phototherapy through regulation of redox homeostasis with a biocompatible and versatile nanotherapeutic to inhibit tumor growth and metastasis. We systematically explore and exploit methylene blue adsorbed polydopamine nanoparticles as a targeted and precise nanocarrier, oxidative stress amplifier, photodynamic/photothermal agent, and multimodal probe for fluorescence, photothermal and photoacoustic imaging to enhance anti-tumor efficacy. Remarkably, following the glutathione-stimulated photosensitizer release to generate exogenous ROS, polydopamine eliminates the endogenous ROS scavenging system through depleting the primary antioxidant, thus amplifying the phototherapy and effectively suppressing tumor growth in vitro and in vivo. Furthermore, this approach enables a robust inhibition against breast cancer metastasis, as oxidative stress is a vital impediment to distant metastasis in tumor cells. Innovative, safe and effective nanotherapeutics via regulation of redox balance may provide a clinically relevant approach for cancer treatment.Amplified oxidative stress achieved by modulating redox homeostasis with PDA–MB for highly effective synergistic phototherapy to inhibit primary tumors and metastases. 相似文献
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Enzymatically Shifting Nitroxides for EPR Spectroscopy and Overhauser‐Enhanced Magnetic Resonance Imaging
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Prof. Gérard Audran Lionel Bosco Dr. Paul Brémond Prof. Jean‐Michel Franconi Neha Koonjoo Prof. Sylvain R. A. Marque Philippe Massot Dr. Philippe Mellet Dr. Elodie Parzy Prof. Eric Thiaudière 《Angewandte Chemie (International ed. in English)》2015,54(45):13379-13384
In vivo investigations of enzymatic processes using non‐invasive approaches are a long‐lasting challenge. Recently, we showed that Overhauser‐enhanced MRI is suitable to such a purpose. A β‐phosphorylated nitroxide substrate prototype exhibiting keto–enol equilibrium upon enzymatic activity has been prepared. Upon enzymatic hydrolysis, a large variation of the phosphorus hyperfine coupling constant (ΔaP=4 G) was observed. The enzymatic activities of several enzymes were conveniently monitored by electronic paramagnetic resonance (EPR). Using a 0.2 T MRI machine, in vitro and in vivo OMRI experiments were successfully performed, affording a 1200 % enhanced MRI signal in vitro, and a 600 % enhanced signal in vivo. These results highlight the enhanced imaging potential of these nitroxides upon specific enzymatic substrate‐to‐product conversion. 相似文献
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Supramolecular Phthalocyanine Assemblies for Improved Photoacoustic Imaging and Photothermal Therapy
Xingshu Li Eun‐Yeong Park Youngnam Kang Nahyun Kwon Mengyao Yang Seunghyun Lee Won Jong Kim Chulhong Kim Juyoung Yoon 《Angewandte Chemie (International ed. in English)》2020,59(22):8630-8634
Phototheranostic nanoplatforms are of particular interest for cancer diagnosis and imaging‐guided therapy. Herein, we develop a supramolecular approach to fabricate a nanostructured phototheranostic agent through the direct self‐assembly of two water‐soluble phthalocyanine derivatives, PcS4 and PcN4. The nature of the molecular recognition between PcS4 and PcN4 facilitates the formation of nanostructure (PcS4‐PcN4) and consequently enables the fabrication of PcS4‐PcN4 with completely quenched fluorescence and reduced singlet oxygen generation, leading to the high photoacoustic and photothermal activity of PcS4‐PcN4. In vivo evaluations suggest that PcS4‐PcN4 could not only efficiently visualize a tumor with high contrast through whole‐body photoacoustic imaging but also enable excellent photothermal therapy for cancer. 相似文献
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Dr. Pascal Kadjane Prof. Dr. Carlos Platas‐Iglesias Dr. Philipp Boehm‐Sturm Dr. Vincent Truffault Dr. Gisela E. Hagberg Prof. Dr. Mathias Hoehn Prof. Dr. Nikos K. Logothetis Priv.‐Doz. Dr. Goran Angelovski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7351-7362
Responsive or smart magnetic resonance imaging (MRI) contrast agents are molecular sensors that alter the MRI signal upon changes in a particular parameter in their microenvironment. Consequently, they could be exploited for visualization of various biochemical events that take place at molecular and cellular levels. In this study, a set of dual‐frequency calcium‐responsive MRI agents are reported. These are paramagnetic, fluorine‐containing complexes that produce remarkably high MRI signal changes at the 1H and 19F frequencies at varying Ca2+ concentrations. The nature of the processes triggered by Ca2+ was revealed, allowing a better understanding of these complex systems and their further improvement. The findings indicate that these double‐frequency tracers hold great promise for development of novel functional MRI methods. 相似文献
17.
SimLabel: a graphical user interface to simulate continuous wave EPR spectra from site‐directed spin labeling experiments
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E. Etienne N. Le Breton M. Martinho E. Mileo V. Belle 《Magnetic resonance in chemistry : MRC》2017,55(8):714-719
Site‐directed spin labeling (SDSL) combined with continuous wave electron paramagnetic resonance (cw EPR) spectroscopy is a powerful technique to reveal, at the residue level, structural transitions in proteins. SDSL‐EPR is based on the selective grafting of a paramagnetic label on the protein under study, followed by cw EPR analysis. To extract valuable quantitative information from SDSL‐EPR spectra and thus give reliable interpretation on biological system dynamics, numerical simulations of the spectra are required. Such spectral simulations can be carried out by coding in MATLAB using functions from the EasySpin toolbox. For non‐expert users of MATLAB, this could be a complex task or even impede the use of such simulation tool. We developed a graphical user interface called SimLabel dedicated to run cw EPR spectra simulations particularly coming from SDSL‐EPR experiments. Simlabel provides an intuitive way to visualize, simulate, and fit such cw EPR spectra. An example of SDSL‐EPR spectra simulation concerning the study of an intrinsically disordered region undergoing a local induced folding is described and discussed. We believe that this new tool will help the users to rapidly obtain reliable simulated spectra and hence facilitate the interpretation of their results. Copyright © 2017 John Wiley & Sons, Ltd. 相似文献
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A Multifunctional Nanomicelle for Real‐Time Targeted Imaging and Precise Near‐Infrared Cancer Therapy
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Jiangwei Tian Dr. Lin Ding Prof. Huangxian Ju Dr. Yongchao Yang Xilan Li Prof. Zhen Shen Dr. Zhi Zhu Prof. Jun‐Sheng Yu Prof. Chaoyong James Yang 《Angewandte Chemie (International ed. in English)》2014,53(36):9544-9549
Simultaneous targeted cancer imaging, therapy and real‐time therapeutic monitoring can prevent over‐ or undertreatment. This work describes the design of a multifunctional nanomicelle for recognition and precise near‐infrared (NIR) cancer therapy. The nanomicelle encapsulates a new pH‐activatable fluorescent probe and a robust NIR photosensitizer, R16FP, and is functionalized with a newly screened cancer‐specific aptamer for targeting viable cancer cells. The fluorescent probe can light up the lysosomes for real‐time imaging. Upon NIR irradiation, R16FP‐mediated generation of reactive oxygen species causes lysosomal destruction and subsequently trigger lysosomal cell death. Meanwhile the fluorescent probe can reflect the cellular status and in situ visualize the treatment process. This protocol can provide molecular information for precise therapy and therapeutic monitoring. 相似文献
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Molecular imaging has rapidly developed to answer the need of image contrast in medical diagnostic imaging to go beyond morphological information to include functional differences in imaged tissues at the cellular and molecular levels. Vibrational (infrared (IR) and Raman) imaging has rapidly emerged among the molecular imaging modalities available, due to its label-free combination of high spatial resolution with chemical specificity. This article presents the physical basis of vibrational spectroscopy and imaging, followed by illustration of their preclinical in vitro applications in body fluids and cells, ex vivo tissues and in vivo small animals and ending with a brief discussion of their clinical translation. After comparing the advantages and disadvantages of IR/Raman imaging with the other main modalities, such as magnetic resonance imaging (MRI), computed tomography (CT), positron emission tomography/single-photon emission-computed tomography (PET/SPECT), ultrasound (US) and photoacoustic imaging (PAI), the design of multimodal probes combining vibrational imaging with other modalities is discussed, illustrated by some preclinical proof-of-concept examples. 相似文献
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Jiamei Han Dr. Guohai Liang Prof. Da Xing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8353-8362
Accurate diagnosis of tumor characteristics, including its location and boundary, is of immense value to subsequent therapy. Activatable magnetic resonance imaging (MRI) contrast agents that respond to tumor-specific microenvironments, such as the redox state, pH, and enzyme activity, enable better mapping of tumor tissue. However, the practical application of most reported activatable agents is hampered by problems including potential toxicity, inefficient elimination, and slow activation. In this study, we developed a zwitterionic iron complex (Fe-ZDS) as a positive MRI contrast agent for tumor-specific imaging. Fe-ZDS could dissociate in weakly acidic solution rapidly, accompanied by clear longitudinal relaxivity (r1) enhancement, which enabled the complex to act as a pH-sensitive contrast agent for tumor-specific MR imaging. In vivo experiments showed that Fe-ZDS rapidly enhanced the tumor-to-normal contrast ratio by >40 %, which assisted in distinguishing the tumor boundary. Furthermore, Fe-ZDS circulated freely in the bloodstream and was excreted relatively safely via kidneys owing to its zwitterionic nature. Therefore, Fe-ZDS is an ideal candidate for a tumor-specific MRI contrast agent and holds considerable potential for clinical translation. 相似文献