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Nature Communications · 2022 ·Vol. 13 ·期 1 ·1-11 · IF 17.694

Assembly-induced spin transfer and distance-dependent spin coupling in atomically precise AgCu nanoclusters

Xia Nan,Xing Jianpei,Peng Di,Ji Shiyu,Zha Jun,Yan Nan,Su Yan,Jiang Xue,Zeng Zhi,Zhao Jijun,Wu Zhikun

Nanoparticle assembly paves the way for unanticipated properties and applications from the nanoscale to the macroscopic world. However, the study of such material systems is greatly inhibited due to the obscure compositions and structures of nanoparticles (especially the surface structures). The assembly of atomically precise nanoparticles is challenging, and such an assembly of nanoparticles with metal core sizes strictly larger than 1 nm has not been achieved yet. Here, we introduced an on-site synthesis-and-assembly strategy, and successfully obtained a straight-chain assembly structure consisting of Ag 77 Cu 22 (CHT) 48 (CHT: cyclohexanethiolate) nanoparticles with two nanoparticles separated by one S atom, as revealed by mass spectrometry and single crystal X-ray crystallography. Although Ag 77 Cu 22 (CHT) 48 bears one unpaired shell-closing electron, the magnetic moment is found to be mainly localized at the S linker with magnetic isotropy, and the sulfur radicals were experimentally verified and found to be unstable after disassembly, demonstrating assembly-induced spin transfer. Besides, spin nanoparticles are found to couple and lose their paramagnetism at sufficiently short inter-nanoparticle distance, namely, the spin coupling depends on the inter-nanoparticle distance. However, it is not found that the spin coupling leads to the nanoparticle growth.

研究领域: 材料科学 · 化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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Nanoscale · 2017 ·Vol. 9 ·期 47 ·18845-18854 · IF 7.367

Copper inter-nanoclusters distance-modulated chromism of self-assembly induced emission

Lin Ai,Zhaoyu Liu,Ding Zhou,Jiale Liu,Haoyang Zou,Zhennan Wu,Yi Liu,Hao Zhang,Bai Yang

Metal nanoclusters (NCs) have attracted broad attention for their molecular-like electronic structures and unique emission properties, but the difficulty in controlling emission color greatly limits their application in illumination and display. In this work, we demonstrate the capability to control the self-assembly induced emission (SAIE) of Cu NCs by modulating the inter-NC distance in the self-assembly materials, which is capable of tuning the emission color from green to red. The inter-NC distance is mainly modulated by controlling the experimental variables during the NC self-assembly, such as the species of the solvents and ligands, duration of assembly, temperature, and so forth. These experimental variables influence the balance of inter-NC weak interactions, thus altering the distance of as-assembled NCs. The variation of the inter-NC distance greatly influences the photo-physical behavior of Cu NCs, and in particular the ligand-to-Cu–Cu charge transfer, permitting the tuning of the emission color. As the Cu NCs self-assembly materials exhibit strong, stable, and color-tunable SAIE, they are employed as the color conversion materials for fabricating white light-emitting diodes.

CAS / MDL: 112-55-0
研究领域: 材料科学 · 光学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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MICROCHIMICA ACTA · 2020 ·Vol. 187 ·期 3 ·1-9 · IF 6.232

Highly selective fluorimetric and colorimetric sensing of mercury(II) by exploiting the self-assembly-induced emission of 4-chlorothiophenol capped copper nanoclusters

Wang Hai-Bo,Bai Hong-Yu,Wang Ya-Shu,Gan Tian,Liu Yan-Ming

A highly stable copper nanoclusters (CuNC) carrying 4-chlorothiophenol as a protective ligand is described. They display self-assembly-induced emission with excitation/emission maxima at 330/605 nm even in neutral or alkaline aqueous environment. The fluorescence of these CuNC is quenched by Hg(II). Quenching is mainly ascribed to the formation of a complex formed via Hg-S bonding between the Hg(II) ions and the ligand. This destroys the ordered architectures of the assembled CuNC. The assay enables Hg(II) to be determined with good sensitivity and a linear response ranging from 1 to 500 nM Hg(II) with a 0.3 nM limit of detection. In addition, the method was implemented in a test strip (which undergoes a color change from red to blue) that can be used for visual determination of Hg(II) in complex environmental water samples. Novel and highly selective fluorimetric and colorimetric methods have been designed for mercury(II) ions determination based on stable self-assembly-induced emission of copper nanoclusters.

研究领域: 分析化学 · 环境科学 · 材料科学
✓ 已验证 DOI 高影响因子
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ACS Applied Materials & Interfaces · 2017 · IF 7.504

Engineering the Self-Assembly Induced Emission of Cu Nanoclusters by Au(I) Doping

Jiale Liu,Zhennan Wu,Ye Tian,Yanchun Li,Lin Ai,Tingting Li,Haoyang Zou,Yi Liu,Xindong Zhang,Hao Zhang,Bai Yang

Aggregation-induced emission (AIE) and self-assembly induced emission (SAIE) effects have been employed to tune the emission properties of metal nanoclusters (NCs). However, it is still not possible to further enhance the photoluminescence quantum yields (PLQYs) and control the emission colors of the NCs using AIE and SAIE. On the basis of our recent work studying the contribution of Cu(I) defects in the SAIE of Cu NCs, in this article, Au(I) was doped into Cu NC self-assembled nanosheets (NSASs) to construct a more stable Au(I)-centered state. As a result, the PLQYs, emission stability, and tunability of emission colors of the Cu NSASs were significantly improved. Detailed studies reveal that the doped Au(I) induces a Au(I)–Cu(I) metallophilic interaction, which leads to a ligand-to-Cu–Au charge transfer, which facilitates the relaxation of excited electrons via a radiative pathway, thereby enhancing the emission intensity. The charge transfer from Cu to Au lowers the energy, thus leading to the red-shift of PL emission. Au(I) is likely doped into the Cu NSASs rather than in individual NCs, because 0.3% Au doping is enough to alter the emission properties. By mixing Au(I)-doped Cu NSASs with different emission colors (due to different Au doping percentages) as color conversion materials on commercially available 365 nm GaN chips, a white light-emitting diode prototype is fabricated.

CAS / MDL: 2923-18-4 2966-50-9
研究领域: 材料科学 · 纳米技术 · 光学工程
✓ 已验证 产品关联 DOI PubMed 高影响因子
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SENSORS AND ACTUATORS B-CHEMICAL · 2020 · IF 7.1

Tuning the hydrophobicity of pyridinium-based probes to realize the mitochondria-targeted photodynamic therapy and mitophagy tracking

Yuyang Zhang,Lianke Wang,Qingpeng Rao,Yingcui Bu,Tianren Xu,Xiaojiao Zhu,Jie Zhang,Yupeng Tian,Hongping Zhou

Targeting mitochondria and dynamically tracking mitophagy are profoundly important in the field of photodynamic therapy (PDT) which relies on the photosensitizers (PSs) under light irradiation. While simultaneously realizing the effective reactive oxygen species (ROS) generation, accurately mitochondrial targeting, and dynamic tracking in a single PS still is a challenging issue. In this context, a series of pyridinium-based cationic fluorogens with aggregation induced emission (AIE) has been developed for this issue. The hydrophobicity of these fluorogens can be finely tuned by modulating the length of the alkyl chains on pyridinium unit. The well-tuned hydrophobicity of TL8C with C 8 -alkyl chain gives rise to the specifically mitochondrial targeting capability of TL8C based on the appropriate synergistic effect of hydrophobic and electrostatic interaction. Meanwhile, TL8C can produce ROS in high efficiency. The excellent mitochondrial targeting and the effective ROS generation allow TL8C for the specifically mitochondria-targeted PDT as well as the real time monitoring of mitophagy.

CAS / MDL: 307554-62-7
研究领域: 生物化学 · 分子生物学 · 医学 · 细胞生物学
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Small · 2022 ·Vol. 18 ·期 27 ·2201826 · IF 15.153

Color-Tunable Fluorescent Hierarchical Nanoassemblies with Concentration-Encoded Emission

Jia Kong,Wenxin Li,Shixuan Zhao,Jiaxing Zhang,Tianli Yue,Yuefei Wang,Yinqiang Xia,Zhonghong Li

Cephalopods possess a dynamic coloration behavior to change their iridescence due to the concentration-induced optical properties of chromatophores and hierarchical assembly of reflectin. However, cephalopods rarely have iridescence in the darkfield. It would be interesting to develop color-tunable fluorescent hierarchical nanoassemblies with concentration-encoded emission. Herein, to construct the bioavailable fluorophore with dynamic coloration properties, a histidine-rich peptide is designed, which can self-assemble into hierarchical nanoassemblies stabilized by hydrogen bonds and π–π stacking interactions. The peptidyl nanoassemblies emit fluorescent iridescence, encompassing the blue to orange region due to the assembly-induced emission. The fluorescence of histidine-rich peptides is color-tunable and reversible, which can be dynamically controlled in a concentration-encoded mode. Due to the coloration ability of histidine-rich peptides, fluorescent polychromatic human cells are developed, highlighting its potential role as a fluorescent candidate for future applications such as bioimaging, implantable light-emitting diodes, and photochromic camouflage.

研究领域: 材料科学 · 生物材料 · 生物医学工程 · 纳米技术 · 光学
✓ 已验证 DOI PubMed 高影响因子
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Nature Communications · 2022 ·Vol. 13 ·期 1 ·1-13 · IF 17.694

A bioactivated in vivo assembly nanotechnology fabricated NIR probe for small pancreatic tumor intraoperative imaging

Ren Han,Zeng Xiang-Zhong,Zhao Xiao-Xiao,Hou Da-yong,Yao Haodong,Yaseen Muhammad,Zhao Lina,Xu Wan-hai,Wang Hao,Li Li-Li

Real-time imaging of the tumour boundary is important during surgery to ensure that sufficient tumour tissue has been removed. However, the current fluorescence probes for bioimaging suffer from poor tumour specificity and narrow application of the imaging window used. Here, we report a bioactivated in vivo assembly (BIVA) nanotechnology, demonstrating a general optical probe with enhanced tumour accumulation and prolonged imaging window. The BIVA probe exhibits active targeting and assembly induced retention effect, which improves selectivity to tumours. The surface specific nanofiber assembly on the tumour surface increases the accumulation of probe at the boundary of the tumor. The blood circulation time of the BIVA probe is prolonged by 110 min compared to idocyanine green. The assembly induced metabolic stability broaden the difference between the tumor and background, obtaining a delayed imaging window between 8–96 h with better signal-to-background contrast (>9 folds). The fabricated BIVA probe permits precise imaging of small sized (<2 mm) orthotopic pancreatic tumors in vivo. The high specificity and sensitivity of the BIVA probe may further benefit the intraoperative imaging in a clinical setting.

研究领域: 生物医学工程 · 纳米技术 · 癌症成像 · 外科肿瘤学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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MATERIALS & DESIGN · 2022 · IF 9.417

Natural small molecule self-assembled hydrogel inhibited tumor growth and lung metastasis of 4T1 breast cancer by regulating the CXCL1/2-S100A8/9 axis

Yuqin Yang,Desheng Cai,Yisong Shu,Zhihua Yuan,Wenmin Pi,Yaozhi Zhang,Jihui Lu,Jingyi Jiao,Xuehao Cheng,Feifei Li,Penglong Wang,Haimin Lei

It is crucial to inhibit tumor growth and distant metastasis for breast cancer (BC) therapy. However, the treatment primarily dependent on surgery, chemotherapy, and radiotherapy is far from satisfactory. It had been demonstrated that the CXCL1/2-S100A8/9 axis played an essential role in BC therapy. Therefore, we constructed a natural product hydrogel for BC therapy by blocking CXCL1 signaling. The GK-GA (phytochemicals of Genkwa Flos -glycyrrhizic acid) hydrogel was designed in a one-step “green” approach. The pharmacodynamics study showed GK-GA exhibited significant anti-tumor and anti-lung metastasis activities, resulting in the inhibition rate of tumor growth (IRG) over 90 % at 6.25 mg·kg −1 , and did not display any obvious toxicity. In addition, the potent antitumor efficiency was also attributed to aggregation/assembly-induced retention (AIR) property. RNA sequencing analysis revealed the gene expression was significantly down-regulated in the GK-GA group, which were BCL2, CASP3, CXCL1, CXCL2, CXCR2, S100A8, S100A9, and confirmed further by western blot (WB). Our findings indicated natural product GK-GA hydrogel inhibited tumor growth and lung metastasis via the BCL2-CASP3 mitochondrial apoptosis pathway as well as the CXCL1/2-S100A8/9 pathway. This study provides inspiration for the fabrication of new excipients-free nano-dispersion in a one-step, no‐carrier‐added, organic solvent-free, “green” approach, particularly for small molecular antitumor agents.

CAS / MDL: 25316-40-9
研究领域: 肿瘤学 · 药学 · 分子生物学 · 癌症治疗
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ANALYTICAL CHEMISTRY · 2023 · IF 7.4

Quantitative Ratiometric Biosensors Based on Fluorescent Ferrocene-Modified Histidine Dipeptide Nanoassemblies

Jia Kong,Shixuan Zhao,Xue Han,Wenxin Li,Jiaxing Zhang,Yuefei Wang,Xihui Shen,Yinqiang Xia,Zhonghong Li

Fluorescent proteins (FPs) provide a ratiometric readout for quantitative assessment of the destination of internalized biomolecules. FP-inspired peptide nanostructures that can compete with FPs in their capacity are the most preferred building blocks for the synthesis of fluorescent soft matter. However, realizing a ratiometric emission from a single peptide fluorophore remains exclusive since multicolor emission is a rare property in peptide nanostructures. Here, we describe a bioinspired peptidyl platform for ratiometric intracellular quantitation by employing a single ferrocene-modified histidine dipeptide. The intensiometric ratio of green to blue fluorescence correlates linearly with the concentration of the peptide by three orders of magnitude. The ratiometric fluorescence of the peptide is an assembly-induced emission originating from hydrogen bonds and aromatic interactions. Additionally, modular design enables ferrocene-modified histidine dipeptides to use as a general platform for the construction of intricate peptides that retain the ratiometric fluorescent properties. The ratiometric peptide technique promises flexibility in the design of a wide spectrum of stoichiometric biosensors for quantitatively understanding the trafficking and subcellular fate of biomolecules.

研究领域: 生物化学 · 纳米技术 · 分子生物学 · 生物物理学 · 分析化学
✓ 已验证 DOI PubMed 高影响因子
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