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CuInS2/ZnS 纳米晶
JOURNAL OF RARE EARTHS · 2017 · IF 2.429

Gd3+ doped CuInS2/ZnS nanocrystals with high quantum yield for bimodal fluorescence/magnetic resonance imaging

Caiyan YU,Tongtong XUAN,Sunqi LOU,Xiaoxiao LIU,Guohai LIAN,Huili LI

Recently, CuInS 2 /ZnS nanocrystals (CISZ NCs) have been widely used in many fields due to their excellent properties, such as tunable photoluminescence (PL) spectra, broad absorption, and non-toxicity. In order to expand the application of CISZ NCs, Gd 3+ was introduced into the host serving as paramagnetic modules to achieve magnetic resonance imaging (MRI) enhancement. MRI probes could provide high-resolution anatomical information. The derived Gd-Cu-In-S/ZnS nanocrystals (GCISZNCs) exhibited the strong orange photoluminescence with a quantum yield of 57.6% and significantly high longitudinal relaxivity ( r 1 =20.4 mmol/s) in comparison with commercial Magnevist (Gd-DTPA, r 1 =4.5 mmol/s). Effective enhancement of MRI and improved longitudinal relaxivity as well as lower cytotoxicity mode GCISZ NCs an ideal MRI probe, suggesting its potential and significance in practical biological and clinic applications in the future.

研究领域: 生物医学工程 · 材料科学 · 医学影像学
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ANALYTICAL CHEMISTRY · 2021 · IF 6.986

Hydrazine Hydrate and Dissolved Oxygen-Triggered Near-Infrared Chemiluminescence from CuInS2@ZnS Nanocrystals for Bioassays

Zhipeng Li,Xunxun Deng,Shuo Wu,Shuangtian Dong,Guizheng Zou

The overwhelming majority of commercially available chemiluminescence (CL) assays are conducted in the eye-visible region. Herein, a near-infrared (NIR) aqueous CL strategy was proposed with CuInS2@ZnS nanocrystals (CIS@ZnS NCs) as emitters. Hydrazine hydrate (N2H4·H2O) could inject electrons into the conduction band of the CIS@ZnS NCs and simultaneously transformed to the intermediate radical N2H3•. N2H3• reduced dissolved oxygen (O2) to O2–•, while the O2–• could inject holes into the valence band of the CIS@ZnS NCs. The recombination of electrons and holes at Cu+ defects in CIS@ZnS NCs eventually yielded efficient NIR CL at around 824.1 nm, which is the longest waveband for NCs CL to the best of our knowledge. The NIR CL could be conveniently performed in the neutral aqueous medium (pH 7.0) with a quantum yield of 0.0155 Einstein/mol and was successfully employed for constructing a signal-off CL biosensor with ascorbic acid as the analyte as well as a signal-on CL biosensor for determining ascorbate oxidase, which indicates that this NIR CL system has a promising potential for bioassays in diverse ways.

研究领域: 分析化学 · 生物医学工程
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ANALYTICAL CHEMISTRY · 2019 · IF 6.35

Promising Electrochemiluminescence from CuInS2/ZnS Nanocrystals/Hydrazine via Internal Cu(I)/Cu(II) Couple Cycling

Li Fu,Bin Zhang,Xiaoyan Long,Kena Fu,Xuwen Gao,Guizheng Zou

Screening a novel electrochemiluminescence (ECL) system is crucial to ECL evolution. Herein, an efficient ECL system with less interference and environmental concern under physiological condition is developed via a unique internal Cu(I)/Cu(II) couple cycling amplified strategy by employing the glutathione- and citrate-capped copper indium sulfide (CIS)/ZnS nanocrystals (NCs) as electrochemiluminophore and N2H4·H2O as co-reactant. CIS/ZnS NCs can be electrochemically injected with valence band (VB) hole at 0.46 and 0.87 V (vs Ag/AgCl), and then achieve the same hole-injected states by relocalizing VB holes with the Cu(I) species inside of CIS/ZnS NCs to form internal Cu(II) defects, while each N2H4·H2O molecule can be successively oxidized to two more reducing species N2H3• and N2H2 around 0.10 V, and inject conduction band (CB) electron onto CIS/ZnS NCs for triple times. The internal Cu(I)/Cu(II) couple cycling involved radiative-charge recombination between these VB hole and CB electron eventually enables two efficient near-infrared ECL processes (around 731 nm) at 0.55 and 0.87 V, in which each single nanocrystal may participate in multiple ECL reaction cycles to produce multiple photons for amplified ECL, similar to the tris(bipyridyl)ruthenium(III) based ECL system. The low-triggering-potential ECL process at 0.55 V can be utilized to selectively determine Cu(II) with a wide linear range from 10 and 1500 nM and a limit of detection of 5 nM (S/N = 3). This work presents a NCs engineering and co-reactant selecting combined strategy for further ECL evolution.

研究领域: 分析化学 · 纳米技术 · 电化学 · 材料科学
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ANALYTICAL CHEMISTRY · 2022 · IF 8.008

Glow and Flash Adjustable Chemiluminescence with Tunable Waveband from the Same CuInS2@ZnS Nanocrystal Luminophore

Shuangtian Dong,Dongyang Wang,Xuwen Gao,Li Fu,Jingna Jia,Yuqi Xu,Bin Zhang,Guizheng Zou

All commercial chemiluminescence (CL) assays are conducted with either glow or flash CL of eye-visible waveband from chemical luminophores. Herein, glow and flash, as well as waveband adjustable CL from the same nanoparticle luminophore of thiol-capped CuInS2@ZnS nanocrystals (CIS@ZnS-Thiol), are proposed via extensively exploiting the differed redox nature of CL triggering reagents. Taking thiosalicylic acid (TSA) as the model thiol-capping agent, the electron-injection-initiated charge transfer between CIS@ZnS-TSA and reductant can bring out efficient glow CL while the hole-injection-initiated charge transfer between CIS@ZnS-TSA and oxidant can give off obvious flash CL under optimum conditions. The maximum emission wavelength for CL of CIS@ZnS-TSA is adjustable from 730 nm to 823 nm via employing different triggering agents. Promisingly, the coexistent reductant of N2H4·H2O and oxidant of H2O2 can be employed as dual triggering reagents to trigger eye-visible and highly efficient flash CL from CIS@ZnS-TSA. The maximum emission intensity for flash CL of CIS@ZnS-TSA/N2H4–H2O2 is 101-fold greater than the glow CL of CIS@ZnS-TSA/N2H4 and 22-fold greater than the flash CL of CIS@ZnS-TSA/H2O2, respectively. The flash CL from CIS@ZnS-TSA/N2H4–H2O2 is qualified for highly sensitive and selective CL immunoassay in a commercialized typical procedure with the entire operating process manually terminated within 35 min.

研究领域: 纳米技术 · 分析化学 · 生物医学工程
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ANALYTICAL CHEMISTRY · 2022 · IF 8.008

Spectrum-Resolved Electrochemiluminescence to Multiplex the Immunoassay and DNA Probe Assay

Xuwen Gao,Xiancheng Liu,Ying Zeng,Qingqing Zhang,Bin Zhang,Guizheng Zou

The investigation on electrochemiluminescence (ECL) multiplexing bioassays mainly focuses on simultaneously detecting either proteins or nucleic acids. To overcome the limitation of a short waveband for spectrum-resolved ECL multiplexing bioassays, herein, a highly monochromatic (FWHM <40 nm) and bandgap-engineered ECL luminophore, that is, mercaptopropionic acid-capped and Zn2+-mediated aggregation-induced emission (AIE) assembly of Au nanocrystals (NCs) (Zn2+-AIE-AuNCs), of strong emission and the maximum emission wavelength at 485 nm is developed. The highly monochromatic and bandgap-engineered ECL (485 nm) of Zn2+-AIE-AuNCs can multiplex with the single-waveband and surface-defect-involved ECL (775 nm) of dual-stabilizer-capped CuInS2@ZnS NCs (CIS@ZnS-NCs), enabling a spectrum-resolved ECL multiplexing strategy with different NCs luminophores of a similar particle size as tags. This ECL multiplexing strategy can be utilized to simultaneously detect antigen and DNA probe together without any additional signal amplification procedure and obvious spectroscopic cross-talk, in which the highly monochromatic ECL from Zn2+-AIE-AuNCs is utilized to dynamically determine human carcinoembryonic antigen from 1 pg/mL to 50 ng/mL with a limit of detection (LOD) of 0.3 pg/mL, while the single-waveband ECL from CIS@ZnS-NCs is employed to linearly detect wild-type p53 from 1 pM to 50 nM with a LOD of 0.5 pM. The ECL immunoassay of the proposed strategy is free from the interference of the synchronously conducted DNA probe assay and vice versa, which would open an avenue to couple the immunoassay and DNA probe assay together for clinical colon and breast cancer identification.

研究领域: 分析化学 · 生物医学工程 · 纳米技术 · 临床诊断
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