A fluorescent double-network-structured hybrid nanogel as embeddable nanoglucometer for intracellular glucometry

Fan, Jiao Rong; Jiang, Xiran; Hu, Yumei; Shi, Yan; Ding, Li; Wu, Weitai

doi:10.1039/c2bm00162d

Cited by 24 publications

(59 citation statements)

References 65 publications

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“…52,53 This is further confirmed by the result of additional experiments that the τ value upon adding [ammonia] s = 30.0 ppm is nearly independent of the concentration of ARM microgels in the range 5-90 µg/mL (Fig. 6b).…”

Section: Volume Phase Transitionsupporting

confidence: 67%

Synthesis and characterization of ammonia-responsive polymer microgels

et al. 2015

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aWe report a type of polymer microgels that undergo rapid, reversible, and highly sensitive volume phase transitions upon varying ammonia concentrations in milieu. Such an ammonia-responsive microgel is made by tethering of a phenoxazinium, N-(5-(3-azidopropylamino)-9H-benzo[a]-phenoxazin-9-ylidene)-N-methylmethanaminium chloride, to the network chains of poly(N-isopropylacrylamide-co-propargyl acrylate) via copper(I)-catalyzed azide-alkene cycloaddition. Tethering of the ammonia-recognizable phenoxazinium onto polymer network chains makes the microgels responsive to ammonia. While a fast (<0.1 s) and stable shrinkage of the microgels can be reached upon adding ammonia over a clinically relevant range (0.25−2.9 ppm), the microgels can convert the elevated concentrations of the solution-/gas-phase ammonia into enhanced photoluminescence signals, which make the microgels different from the phenoxazinium or its analogs reported in previous arts that exhibit ammonia-induced quenching in photoluminescence. With the microgels as probes, the detection limit was ca. 7.3×10 -2 and 3.9 ppb, respectively, for the solution-and the gas-phase ammonia. These features enable "turn-on" photoluminescence detection of ammonia in breath.

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Section: Volume Phase Transitionsupporting

confidence: 67%

Synthesis and characterization of ammonia-responsive polymer microgels

et al. 2015

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“…So far, a variety of optical markers have been explored to prepare the boronic acid-based hybrid nanogels for continuous glucose sensors, including fluorescent organic dyes, semiconductor QDs, and noble metal nanoparticles (NPs). [12][13][14][15][16][17][18][19][20] However, these optical markers have potential problems for practical applications. For example, organic dyes are concerned with poor photostability and potential toxicity, semiconductor QDs are associated with the inherent heavy metal toxicity, and noble metal materials involve high cost.…”

Section: Introductionmentioning

confidence: 98%

Immobilization of Carbon Dots in Molecularly Imprinted Microgels for Optical Sensing of Glucose at Physiological pH

Wang

Velado

et al. 2015

ACS Appl. Mater. Interfaces

124

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Nanosized carbon dots (CDs) are emerging as superior fluorophores for biosensing and a bioimaging agent with excellent photostability, chemical inertness, and marginal cytotoxicity. This paper reports a facile one-pot strategy to immobilize the biocompatible and fluorescent CDs (∼6 nm) into the glucose-imprinted poly(N-isopropylacrylamide-acrylamide-vinylphenylboronic acid) [poly(NIPAM-AAm-VPBA)] copolymer microgels for continuous optical glucose detection. The CDs designed with surface hydroxyl/carboxyl groups can form complexes with the AAm comonomers via hydrogen bonds and, thus, can be easily immobilized into the gel network during the polymerization reaction. The resultant glucose-imprinted hybrid microgels can reversibly swell and shrink in response to the variation of surrounding glucose concentration and correspondingly quench and recover the fluorescence signals of the embedded CDs, converting biochemical signals to optical signals. The highly imprinted hybrid microgels demonstrate much higher sensitivity and selectivity for glucose detection than the nonimprinted hybrid microgels over a clinically relevant range of 0-30 mM at physiological pH and benefited from the synergistic effects of the glucose molecular contour and the geometrical constraint of the binding sites dictated by the glucose imprinting process. The highly stable immobilization of CDs in the gel networks provides the hybrid microgels with excellent optical signal reproducibility after five repeated cycles of addition and dialysis removal of glucose in the bathing medium. In addition, the hybrid microgels show no effect on the cell viability in the tested concentration range of 25-100 μg/mL. The glucose-imprinted poly(NIPAM-AAm-VPBA)-CDs hybrid microgels demonstrate a great promise for a new glucose sensor that can continuously monitor glucose level change.

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“…In the early works, glucose oxidase and lectin were popular and already proved significant interests, but those natural receptors have severe disadvantages including the potential instability during use or sterilization. 17,[21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] A key issue for pPBA microgels concerns the tailoring of the glucose-responsive volume phase transition behavior of those microgels to meet the criteria of respective applications. 18 This has led to considerable interest in developing glucose-responsive polymer gels based on poly(phenylboronic acid) (pPBA).…”

Section: Introductionmentioning

confidence: 99%

“…It is well known that the binding of glucose to form the glucoseboronate complex (charged), 39 more stable than the glucoseboronic acid complex (uncharged), 40 can increase the ionization degree on the microgels and builds up a Donnan potential; the complexation can also change the polymer-solvent affinity (at neutral state, PBA has a hydrophobic character, but becomes more hydrophilic upon complexation). [21][22][23][24][25] However, it should be noted that those pPBA (micro)gels reported previously [7][8][9][10]13,[21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38]41,43 can only undergo a fixed type (swelling and/or shrinking) of glucose-responsive volume phase transition behavior. In this respect, most pPBA microgels that undergo this complexation will swell when glucose concentration increases.…”

Section: Introductionmentioning

confidence: 99%

Switchable glucose-responsive volume phase transition behavior of poly(phenylboronic acid) microgels

et al. 2015

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aWe develop a class of poly(phenylboronic acid) microgels, which are made of 3-aminophenylboronic acid covalently bonded onto oligo(ethylene glycol)-based polymers, to demonstrate the feasibility of on-site tailoring on the glucoseresponsive volume phase transition behavior of poly(phenylboronic acid) gels. Different from the poly(phenylboronic acid) gels reported previously that typically undergo a fixed type (swelling and/or shrinking) of glucose-responsive volume phase transition behavior, the presented microgels can display switchable behaviors upon adding glucose: shrinking (at temperature ≤29.0 o C), unresponsive (29.0-33.0 o C), and swelling (≥33.0 o C). The underlying mechanism for such an on-site tailoring is possibly associated with a competition of glucose-induced increase in the Donnan potential (favoring swelling; due to the formation of glucose-boronates or glucose-bis-boronates) and additional cross-links (favoring shrinking; due to the formation of glucose-bis-boronates) at a particular temperature. Accompanied by this on-site tailoring, the photoluminescence of the microgels can be tuned from "turn-off" (e.g., at 25.0 o C) to "turn-on" (e.g., at 37.0 o C) upon adding glucose, which may provide a functional basis for biosensors for prospective biomedical applications.

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A fluorescent double-network-structured hybrid nanogel as embeddable nanoglucometer for intracellular glucometry

Cited by 24 publications

References 65 publications

Synthesis and characterization of ammonia-responsive polymer microgels

Synthesis and characterization of ammonia-responsive polymer microgels

Immobilization of Carbon Dots in Molecularly Imprinted Microgels for Optical Sensing of Glucose at Physiological pH

Switchable glucose-responsive volume phase transition behavior of poly(phenylboronic acid) microgels

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