Sequential pH‐Dependent Adsorption of Ionic Amphiphilic Diblock Copolymer Micelles and Choline Oxidase Onto Conductive Substrates: Toward the Design of Biosensors

Sigolaeva, Larisa V.; Günther, Ulrike; Pergushov, Dmitry V.; Gladyr, Snezhana Yu.; Kurochkin, Ilya N.; Schacher, Felix H.

doi:10.1002/mabi.201300580

Cited by 31 publications

(30 citation statements)

References 62 publications

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“…It is worth noting that the degree of protonation of the PDMAEMA block of 25 – 30% at physiological pH of 7.4 (see potentiometric titration curves given in the Figure S4 ) was sufficient for the strong multipoint anchoring of DNA. This corresponds to the results we already reported for the pH-dependent interaction of similar diblock copolymers deposited onto solid surfaces with enzymes and proteins [ 35 , 40 , 42 ].…”

Section: Resultssupporting

confidence: 91%

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Rational Design of Amphiphilic Diblock Copolymer/MWCNT Surface Modifiers and Their Application for Direct Electrochemical Sensing of DNA

et al. 2020

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We demonstrate the application of amphiphilic ionic poly(n-butylmethacrylate)-block- poly(2-(dimethylamino)ethyl methacrylate) diblock copolymers (PnBMA40-b-PDMAEMA40, PnBMA40-b-PDMAEMA120, PnBMA70-b-PDMAEMA120) for dispersing multiwalled carbon nanotubes (MWCNTs) in aqueous media, a subsequent efficient surface modification of screen-printed electrodes (SPEs), and the application of the modified SPEs for DNA electrochemistry. Stable and fine aqueous dispersions of MWCNTs were obtained with PnBMAx-b-PDMAEMAy diblock copolymers, regardless of the structure of the copolymer and the amount of MWCNTs in the dispersions. The effect of the diblock copolymer structure was important when the dispersions of MWCNTs were deposited as modifying layers on surfaces of SPEs, resulting in considerable increases of the electroactive surface areas and great acceleration of the electron transfer rate. The SPE/(PnBMAx-b-PDMAEMAy + MWCNT) constructs were further exploited for direct electrochemical oxidation of the guanine (G) and adenine (A) residues in a model salmon sperm double-stranded DNA (dsDNA). Two well-defined irreversible oxidation peaks were observed at about +600 and +900 mV, corresponding to the electrochemical oxidation of G and A residues, respectively. A multi-parametric optimization of dsDNA electrochemistry enables one to get the limits of detection (LOD) as low as 5 μg/mL (0.25 μM) and 1 μg/mL (0.05 μM) for G and A residues, respectively. The achieved sensitivity of DNA assay enables quantification of the A and G residues of dsDNA in the presence of human serum and DNA in isolated human leukocytes.

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Section: Resultssupporting

confidence: 91%

“…The typical appearance of the micelles is shown in Figure S3 . The solution behavior of P n BMA x - b -PDMAEMA y diblock copolymers is in good agreement with former published data for similar diblock copolymers [ 40 ].…”

Section: Resultssupporting

confidence: 90%

Rational Design of Amphiphilic Diblock Copolymer/MWCNT Surface Modifiers and Their Application for Direct Electrochemical Sensing of DNA

et al. 2020

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“…This graphite-based surface is characterized by high roughness due to the presence of 3–10 μm graphite flakes, with the roughness within one flake being 86 ± 2 nm [6,12]. The high hydrophobicity of this surface results in a hard wettability, confirmed by the high value of the static contact angle of 133.3° ± 0.8°, to which a high roughness makes an additional contribution [5,6]. The initial graphite surface was additionally premodified with MnO 2 nanoparticles to impart the surface sensitivity to hydrogen peroxide (see Experimental Part, and the Scheme 2 therein).…”

Section: Resultsmentioning

confidence: 99%

“…Recently, we have shown that the surface modification of conductive substrates by functional polymers via their simple adsorption under the right conditions allows for the subsequent efficient binding of biomolecules, where the polymer layer acts as peculiar ‘glue’ keeping such bioactive species firmly at the interface [5,6]. With the help of this approach, easily-preparable enzymatic biosensor setups were constructed and applied for electrochemical detection of choline [5,6,7,8], phenol [5,9,10], blood esterases [9,11], and organophosphates [12].…”

Section: Introductionmentioning

confidence: 99%

Surface Functionalization by Stimuli-Sensitive Microgels for Effective Enzyme Uptake and Rational Design of Biosensor Setups

et al. 2018

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We highlight microgel/enzyme thin films that were deposited onto solid interfaces via two sequential steps, the adsorption of temperature- and pH-sensitive microgels, followed by their complexation with the enzyme choline oxidase, ChO. Two kinds of functional (ionic) microgels were compared in this work in regard to their adsorptive behavior and interaction with ChO, that is, poly(N-isopropylacrylamide-co-N-(3-aminopropyl)methacrylamide), P(NIPAM-co-APMA), bearing primary amino groups, and poly(N-isopropylacrylamide-co-N-[3-(dimethylamino) propyl]methacrylamide), P(NIPAM-co-DMAPMA), bearing tertiary amino groups. The stimuli-sensitive properties of the microgels in the solution were characterized by potentiometric titration, dynamic light scattering (DLS), and laser microelectrophoresis. The peculiarities of the adsorptive behavior of both the microgels and the specific character of their interaction with ChO were revealed by a combination of surface characterization techniques. The surface charge was characterized by electrokinetic analysis (EKA) for the initial graphite surface and the same one after the subsequent deposition of the microgels and the enzyme under different adsorption regimes. The masses of wet microgel and microgel/enzyme films were determined by quartz crystal microbalance with dissipation monitoring (QCM-D) upon the subsequent deposition of the components under the same adsorption conditions, on a surface of gold-coated quartz crystals. Finally, the enzymatic responses of the microgel/enzyme films deposited on graphite electrodes to choline were tested amperometrically. The presence of functional primary amino groups in the P(NIPAM-co-APMA) microgel enables a covalent enzyme-to-microgel coupling via glutar aldehyde cross-linking, thereby resulting in a considerable improvement of the biosensor operational stability.

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“…Polymer membrane based biosensors have been applied in fluids, as detecting surfaces, and in the form of immobilized nanoreactors on functionalized surfaces (Turner, 2013). For example, micelles of poly (n-butylmethacrylate)-block-poly (N,N-dimethylaminoethyl methacrylate) (PnBMA- b -PDMAEMA), and choline oxidase were used to obtain bilayer films on conductive surfaces at different pH-values (Sigolaeva et al, 2014). Sequential electrostatic adsorption of diblock copolymer micelles combined with the additional possibility of crosslinking enzymes within such films produced highly active and stable biosensor coatings.…”

Section: Present and Future Perspectives On Biomedical Applicationsmentioning

confidence: 99%

Biomolecules Turn Self-Assembling Amphiphilic Block Co-polymer Platforms Into Biomimetic Interfaces

et al. 2019

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Biological membranes constitute an interface between cells and their surroundings and form distinct compartments within the cell. They also host a variety of biomolecules that carry out vital functions including selective transport, signal transduction and cell-cell communication. Due to the vast complexity and versatility of the different membranes, there is a critical need for simplified and specific model membrane platforms to explore the behaviors of individual biomolecules while preserving their intrinsic function. Information obtained from model membrane platforms should make invaluable contributions to current and emerging technologies in biotechnology, nanotechnology and medicine. Amphiphilic block co-polymers are ideal building blocks to create model membrane platforms with enhanced stability and robustness. They form various supramolecular assemblies, ranging from three-dimensional structures (e.g., micelles, nanoparticles, or vesicles) in aqueous solution to planar polymer membranes on solid supports (e.g., polymer cushioned/tethered membranes,) and membrane-like polymer brushes. Furthermore, polymer micelles and polymersomes can also be immobilized on solid supports to take advantage of a wide range of surface sensitive analytical tools. In this review article, we focus on self-assembled amphiphilic block copolymer platforms that are hosting biomolecules. We present different strategies for harnessing polymer platforms with biomolecules either by integrating proteins or peptides into assemblies or by attaching proteins or DNA to their surface. We will discuss how to obtain synthetic structures on solid supports and their characterization using different surface sensitive analytical tools. Finally, we highlight present and future perspectives of polymer micelles and polymersomes for biomedical applications and those of solid-supported polymer membranes for biosensing.

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Sequential pH‐Dependent Adsorption of Ionic Amphiphilic Diblock Copolymer Micelles and Choline Oxidase Onto Conductive Substrates: Toward the Design of Biosensors

Cited by 31 publications

References 62 publications

Rational Design of Amphiphilic Diblock Copolymer/MWCNT Surface Modifiers and Their Application for Direct Electrochemical Sensing of DNA

Rational Design of Amphiphilic Diblock Copolymer/MWCNT Surface Modifiers and Their Application for Direct Electrochemical Sensing of DNA

Surface Functionalization by Stimuli-Sensitive Microgels for Effective Enzyme Uptake and Rational Design of Biosensor Setups

Biomolecules Turn Self-Assembling Amphiphilic Block Co-polymer Platforms Into Biomimetic Interfaces

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