Peptide‐Conjugated Silver Nanoparticles for the Colorimetric Detection of the Oncoprotein Mdm2 in Human Serum

Retout, Maurice; Gosselin, Bryan; Mattiuzzi, Alice; Ternad, Indiana; Jabin, Ivan; Bruylants, Gilles

doi:10.1002/cplu.202200043

Cited by 12 publications

(13 citation statements)

References 42 publications

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“…18 Only a few examples of nanoparticle aggregation-based assays in biological fluids have been reported. 19,20 Here, we show a novel process of reversible aggregation of AuNPs−citrate for alternative sensing strategies. Reversible aggregation of nanoparticles is challenging because, according to the Derjaguin−Landau−Verwey−Overbeek (DLVO) theory, 21 the particles can be trapped in deep energetic minima during the aggregation, thus transforming the aggregates into larger insoluble materials that can be only slightly dissociated by aggressive sonication; their optical properties cannot be recovered.…”

Section: ■ Introductionmentioning

confidence: 95%

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Di-Arginine Additives for Dissociation of Gold Nanoparticle Aggregates: A Matrix-Insensitive Approach with Applications in Protease Detection

Retout

Jin

Tsujimoto

et al. 2022

ACS Appl. Mater. Interfaces

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We report the reversible aggregation of gold nanoparticles (AuNPs) assemblies via a di-arginine peptide additive and thiolated PEGs (HS-PEGs). The AuNPs were first aggregated by attractive forces between the citrate-capped surface and the arginine side chains. We found that the HS-PEG thiol group has a higher affinity for the AuNP surface, thus leading to redispersion and colloidal stability. In turn, there was a robust and obvious color change due to on/off plasmonic coupling. The assemblies' dissociation was directly related to the HS-PEG structural properties such as their size or charge. As an example, HS-PEGs with a molecular weight below 1 kDa could dissociate 100% of the assemblies and restore the exact optical properties of the initial AuNP suspension (prior to the assembly). Surprisingly, the dissociation capacity of HS-PEGs was not affected by the composition of the operating medium and could be performed in complex matrices such as plasma, saliva, bile, urine, cell lysates, or even seawater. The high affinity of thiols for the gold surface encompasses by far the one of endogenous molecules and is thus favored. Moreover, starting with AuNPs already aggregated ensured the absence of a background signal as the dissociation of the assemblies was far from spontaneous. Remarkably, it was possible to dry the AuNP assemblies and solubilize them back with HS-PEGs, improving the colorimetric signal generation. We used this system for protease sensing in biological fluids. Trypsin was chosen as the model enzyme, and highly positively charged peptides were conjugated to HS-PEG molecules as cleavage substrates. The increase of positive charge of the HS-PEG−peptide conjugate quenched the dissociation capacity of the HS-PEG molecules, which could only be restored by the proteolytic cleavage. Picomolar limit of detection was obtained as well as the detection in saliva or urine.

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Section: ■ Introductionmentioning

confidence: 95%

“…Extreme dilution of the biological sample or extraction of the analyte from the matrix is thus often needed . Only a few examples of nanoparticle aggregation-based assays in biological fluids have been reported. , …”

Section: Introductionmentioning

confidence: 99%

Di-Arginine Additives for Dissociation of Gold Nanoparticle Aggregates: A Matrix-Insensitive Approach with Applications in Protease Detection

Retout

Jin

Tsujimoto

et al. 2022

ACS Appl. Mater. Interfaces

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View full text Add to dashboard Cite

show abstract

“…18 Only a few examples of nanoparticle aggregation-based assays in biological fluids have been reported. 19,20 Here, we show a novel process of reversible aggregation of AuNPs-citrate for alternative sensing strategies. Reversible aggregation of nanoparticles is challenging because, according to the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, 21 the particles can be trapped in a deep energetic minima during the aggregation, thus transforming the aggregates into larger insoluble materials that can be only slightly dissociated by aggressive sonication; their optical properties cannot be recovered.…”

Section: ■ Introductionmentioning

confidence: 97%

A di-arginine additive for dissociation of gold nanoparticle aggregates: A matrix-insensitive approach with applications in protease detection

Retout

Jin

Mantri

et al. 2022

Preprint

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We report the reversible aggregation of gold nanoparticle (AuNPs) assemblies via a di-arginine peptide additive and thiolated PEGs (HS-PEGs). The AuNPs were first aggregated by attractive forces between the citrate-capped surface and the arginine side chains. We found that HS-PEG thiol group has higher affinity for the AuNPs surface, thus leading to redisper-sion and colloidal stability. In turn, there was a robust and obvious color change due to on/off plasmonic coupling. The assemblies dissociation was directly related to the HS-PEG struc-tural properties such as their size or charge. As an example, HS-PEGs with a molecular weight below 1 kDa could dissociate 100% of the assemblies and restore the exact optical properties of the initial AuNPs suspension (prior to the assembly). Surprisingly, the dissocia-tion capacity of HS-PEGs was not affected by the composition of the operating medium and could be performed in complex matrices such as plasma, saliva, bile, urine, cell lysates or even sea water. The high affinity of thiols for the gold surface encompasses by far the one of endogenous molecules and is thus favorized. Moreover, starting with AuNPs already aggre-gated ensured the absence of background signal as the dissociation of the assemblies was far from spontaneous. Remarkably, it was possible to dry the AuNPs assemblies and to solubilize them back with HS-PEGs, improving the colorimetric signal generation. We used this system for protease sensing in biological fluid. Trypsin was chosen as model enzyme and highly positively charged peptides were conjugated to HS-PEG molecules as cleavage substrate. The increase of positive charge of the HS-PEG-peptide conjugate quenched the dissociation ca-pacity of the HS-PEG molecules which could only be restored by the proteolytic cleavage. Picomolar limit of detection was obtained as well as the detection in saliva or urine.

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“…In addition to having lower LODs than AuNPs in aggregation-based assays, AgNPs provide a larger color pallet because their plasmon band is tunable across the entire visible range . This aggregation-based approach has been used to detect proteins, , oligonucleotides, bacteria, and toxic metal ions …”

Section: Introductionmentioning

confidence: 99%

“…28 In addition to having lower LODs than AuNPs in aggregation-based assays, AgNPs provide a larger color pallet because their plasmon band is tunable across the entire visible range. 29 This aggregationbased approach has been used to detect proteins, 30,31 oligonucleotides, 32 bacteria, 33 and toxic metal ions. 34 Herein, we investigate how the optical properties of different gold−silver core−shell nanoparticles change when aggregated (crosslinked) and leverage that information to make a colorimetric enzyme sensor.…”

Section: ■ Introductionmentioning

confidence: 99%

Gold–Silver Core–Shell Nanoparticle Crosslinking Mediated by Protease Activity for Colorimetric Enzyme Detection

et al. 2022

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Plasmonic nanoparticles produce a localized surface plasmon resonance (LSPR) under optical excitation. The LSPR of nanoparticles can shift in response to changes in the local dielectric environment and produce a color change. This color change can be observed by the naked eye due to the exceptionally large extinction coefficients (10 8 −10 11 M −1 cm −1 ) of plasmonic nanoparticles. Herein, we investigate the optical shifts (i.e., color change) of three unique gold−silver core−shell nanoparticle structures in response to changes in their dielectric environment upon nanoparticle aggregation. Aggregation is induced by a cysteine-containing peptide that has a sulfhydryl near its N and C termini, which crosslinks nanoparticles. Furthermore, we demonstrate that adding proline spacers between the cysteines impacts the degree of aggregation and, ultimately, the color response. Using this information, we construct a colorimetric enzyme assay, where the signal produced from nanoparticle aggregation is modulated by proteolysis. The degree of aggregation and the resulting optical shift can be correlated with enzyme concentration with high linearity (R 2 = 0.998). Overall, this study explores the optical properties of gold−silver core−shell nanoparticles in a dispersed vs aggregated state and leverages that information to develop an enzyme sensor with a spectral LOD of 0.47 ± 0.09 nM.

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Peptide‐Conjugated Silver Nanoparticles for the Colorimetric Detection of the Oncoprotein Mdm2 in Human Serum

Cited by 12 publications

References 42 publications

Di-Arginine Additives for Dissociation of Gold Nanoparticle Aggregates: A Matrix-Insensitive Approach with Applications in Protease Detection

Di-Arginine Additives for Dissociation of Gold Nanoparticle Aggregates: A Matrix-Insensitive Approach with Applications in Protease Detection

A di-arginine additive for dissociation of gold nanoparticle aggregates: A matrix-insensitive approach with applications in protease detection

Gold–Silver Core–Shell Nanoparticle Crosslinking Mediated by Protease Activity for Colorimetric Enzyme Detection

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