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RSC Adv
2021 Feb 17;1114:8134-8141. doi: 10.1039/d0ra07608b.
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Photoluminescent sea urchin-shaped carbon-nanobranched polymers as nanoprobes for the selective and sensitive assay of hypochlorite.
Zhang X
,
Qu J
,
Ding SN
.
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This work reports donor-acceptor type sea urchin-like carbon nanobranched polymers (SUCNPs). As a novel carbon-based nanomaterial, SUCNPs were effectively synthesized for the first time through a facile and economical solvothermal approach employing uric acid and l-cysteine as nitrogen/sulfur sources. The nitrogen-rich structure of the heterocylic aromatic polymer led to a blue fluorescence at the excitation/emission maxima of 350/436 nm with robust photostability. SUNCPs showed highly selective ability towards hypochlorite (ClO-) against other relevant interfering substances. Upon exposure to a growing concentration of ClO-, SUCNPs fluorescence presented a gradual rise with a remarkable blue shift by virtue of the inhibition of photoinduced charge transfer (PCT) process. A linear relationship was established between the fluorescence intensity ratio (I 401 nm/I 436 nm) and the ClO- concentration in the range of 0.1-200 μM. The detection limit was as low as 30 nM (3σ/k). The "turn-on" type nanoprobe was further used in real samples and paper-based analytical chips efficiently, implying its application in a sophisticated and convenient platform.
Fig. 1. Effects of the mass ratio of the precursors (A and B) and reaction time (C) on the FL emission intensity of the SUCNPs (I436 nm), λex = 350 nm, slit width = 2 nm. The measurements were conducted in triplicate, and each RSD was lower than 5.81%. DLS curves of the SUCNPs at different reaction stages: 1 h (D), 3 h (E) and 4.5 h (F).
Fig. 2. Characterization of the SUCNPs. (A) TEM, (B) EDS, (C) element contents of C, N, O, S, (D) XRD, (E) FTIR and (F) Raman spectra.
Scheme 1. Schematic of the synthesis process of the SUCNPs and the mechanism of fluorescent detection of ClO− by the SUCNPs.
Fig. 3. XPS C 1s (A), N 1s (B), O 1s (C) and S 2p (D) spectra of the SUCNPs.
Fig. 4. (A) The normalized UV-vis absorption (a) and FL emission spectra ((b) λex = 350 nm) of the SUCNPs. Inset: photographs under daylight and 350 nm UV light. (B) FL emission spectra of aqueous solutions of SUCNPs with various excitation wavelengths. The slit widths were 2 nm.
Fig. 5. (A) FL emission spectra of SUCNPs with increasing concentrations of ClO− anions, λex = 350 nm, slit width = 2 nm. Inset: photographs of SUCNPs solution and SUCNP solution with the addition of ClO− under UV light (365 nm). (B) Plots of I401 nm/I436 nmversus ClO− concentration. Inset: the linear relationship. Error bars are shown for the standard derivation of three tests, and each RSD is lower than 5.13%.
Fig. 6. (A) FL decay and (B) FL lifetimes of the SUCNPs with or without ClO− (650 μM). (C) S 2p and (D) O 1s XPS spectra of SUCNPs–ClO−.
Fig. 7. Selectivity of the SUCNPs for ClO− over other species. The measurements were conducted in triplicate, and each RSD was lower than 4.8%.
Fig. 8. Photographs of the SUCNPs test paper before (A) and after (B) exposure to the ClO− anions (100 μM) under UV light excitation (λex = 365 nm).
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