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1.
J Phys Chem Lett ; 10(21): 6910-6914, 2019 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-31638400

RESUMO

The electrochemical properties of gas molecules are of great interest for both fundamental and applied research. In this study, we introduce a novel concept to systematically alter the electrochemical behavior and, in particular, the redox potential of neutral gas molecules. The concept is based on the use of an ion-binding agent, or "ionophore", to bind and stabilize the ionic electrochemical reaction product. We demonstrate that the ionophore-assisted electrochemical oxidation of hydrogen in a room-temperature ionic liquid electrolyte is shifted by almost 1 V toward more negative potentials in comparison to an ionophore-free electrolyte. The altered electrochemical response in the presence of the ionophore not only yields insights into the reaction mechanism but also can be used to determine the diffusion coefficient of the ionophore species. This ionophore-modulated electrochemistry of neutral gas molecules opens up new avenues for the development of highly selective electrochemical sensors.

2.
J Phys Chem B ; 123(34): 7436-7444, 2019 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-31379167

RESUMO

Protein electrochemistry studies at a polarized interface between two immiscible electrolyte solutions (ITIES) indicate that the detection mechanism of a protein at the interface involves a combination of protein-anion complexation and interfacial adsorption processes. A detailed characterization of the protein-facilitated mechanism of ion transfer at the ITIES will allow the development of new label-free biomolecular detection tools. Molecular dynamics simulations were performed to describe the mechanism of transfer of the hydrophobic anion tetraphenylborate (TPB-) from a 1,2-dichloroethane (organic) phase to an aqueous phase mediated by lysozyme as a model protein under the action of an external electric field. The anion migrated to the protein at the interface and formed multiple contacts. The side chains of positively charged Lys and Arg residues formed electrostatic interactions with the anion. Nonpolar residues like Trp, Met, and Val formed hydrophobic contacts with the anion as it moved along the protein surface. During this process, lysozyme adopted multiple, partially unfolded conformations at the interface, all involving various anion-protein complexes with small free-energy barriers between them. The general mechanism of protein-facilitated ion transfer at a polarized liquid-liquid interface thus likely involves the movement of a hydrophobic anion along the protein surface through a combination of electrostatic and hydrophobic interactions.

3.
Langmuir ; 35(17): 5821-5829, 2019 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-30955327

RESUMO

The electroadsorption of proteins at aqueous-organic interfaces offers the possibility to examine protein structural rearrangements upon interaction with lipophilic phases, without modifying the bulk protein or relying on a solid support. The aqueous-organic interface has already provided a simple means of electrochemical protein detection, often involving adsorption and ion complexation; however, little is yet known about the protein structure at these electrified interfaces. This work focuses on the interaction between proteins and an electrified aqueous-organic interface via controlled protein electroadsorption. Four proteins known to be electroactive at such interfaces were studied: lysozyme, myoglobin, cytochrome c, and hemoglobin. Following controlled protein electroadsorption onto the interface, ex situ structural characterization of the proteins by FTIR spectroscopy was undertaken, focusing on secondary structural traits within the amide I band. The structural variations observed included unfolding to form aggregated antiparallel ß-sheets, where the rearrangement was specifically dependent on the interaction with the organic phase. This was supported by MALDI ToF MS measurements, which showed the formation of protein-anion complexes for three of these proteins, and molecular dynamic simulations, which modeled the structure of lysozyme at an aqueous-organic interface. On the basis of these findings, the modulation of protein secondary structure by interfacial electrochemistry opens up unique prospects to selectively modify proteins.

4.
Anal Chem ; 90(17): 10256-10262, 2018 09 04.
Artigo em Inglês | MEDLINE | ID: mdl-30073829

RESUMO

The electrochemical behavior and detection of sulfated carbohydrates were investigated at an array of microinterfaces between two immiscible electrolyte solutions where the organic phase was gelled. It was found that the electrochemical signal was dependent on the organic phase electrolyte cation. Cyclic voltammetry (CV) of sucrose octasulfate (SOS) with bis(triphenylphosphoranylidene)ammonium BTPPA+ as the organic phase cation did not provide a response to a 10 µM SOS concentration. However, when the organic phase cation was tetradodecylammonium TDDA+, a distinct peak was present in the CV at ca. -0.47 V, indicative of a desorption process following adsorption during the preceding scan. This detection peak shifted to ca. -0.28 V when tridodecylmethylammonium TDMA+ was the organic phase cation, indicating an increased binding strength between this alkylammonium cation and SOS. By combining electroadsorption with TDMA+ as the organic phase electrolyte cation, detection limits of 0.064 µM SOS in 10 mM LiCl and 0.16 µM in a synthetic urine aqueous phase were achieved. The detection limit was improved to 0.036 µM SOS (10 mM LiCl) when the electroadsorption time was increased to 180 s, indicating the analytical capability for the detection of SOS and related sugars by ion-transfer adsorptive stripping voltammetry.

5.
Faraday Discuss ; 210(0): 113-130, 2018 10 01.
Artigo em Inglês | MEDLINE | ID: mdl-29974089

RESUMO

The investigation of electrochemical processes at the interface of two immiscible electrolyte solutions (ITIES) is of great interest for sensing applications, and serves as a surrogate to the study of biological transport phenomena, e.g. ion channels. Alongside e-beam lithography, focused ion beam (FIB) milling is an attractive method to prototype and fabricate nanopore arrays that support nanoITIES. Within this contribution, we explore the capability of FIB/scanning electron microscopy (SEM) tomography to visualize the actual pore structure and interfaces at silica-modified nanoporous membranes. The nanopores were also characterized by atomic force microscopy (AFM) using ultra-sharp AFM probes to determine the pore diameter, and using scanning transmission electron microscopy (STEM) and energy dispersive X-ray (EDX) spectroscopy, providing additional information on the elemental composition of deposits within the pores. Si-rich particles could be identified within the pores as well as at the orifice that had faced the organic electrolyte solution during electrochemical deposition. The prospects of the used techniques for investigating the interface at or within FIB-milled nanopores will be discussed.

6.
Anal Chem ; 90(15): 8727-8731, 2018 08 07.
Artigo em Inglês | MEDLINE | ID: mdl-30016079

RESUMO

While ion transfer studies were shown to be a promising method for fundamental electrochemistry, pharmacokinetic studies, and sensing, they suffer from inherent instability of the interface formed between the organic and aqueous phases. This limits to some extent the range of solvents which can be used and confines these studies to the laboratory. We propose here the use of paper, which has revolutionized the way we think of miniaturized analytical devices during the past decade, as a perfect substrate for ion transfer studies across the liquid-liquid interface. We describe the design of a simple three-phase electrode paper-based setup for redox-driven transfer of anions from an aqueous to an organic phase. Electrochemical measurements of seven different anions and concentration dependence studies are in good agreement with the results obtained with traditional setups. Additionally, we show the applicability and limitations of such setups to the analysis of anion mixtures.

7.
Anal Chem ; 90(14): 8470-8477, 2018 07 17.
Artigo em Inglês | MEDLINE | ID: mdl-29893124

RESUMO

The electrochemical behavior of a synthetic oligonucleotide, thrombin-binding aptamer (TBA, 15-mer), was explored at a liquid-organogel microinterface array. TBA did not display any response when only background electrolytes were present in both phases. On the basis of literature reports that surfactants can influence nucleic acid detection, the response in the presence of cetyltrimethylammonium (CTA+) was examined. With both TBA and CTA+ in the aqueous phase, the transfer current for CTA+ was diminished, signifying the interaction of CTA+ with TBA. Experiments with CTA+ spiked into the organic phase revealed a sharp current peak, consistent with the interfacial formation of a CTA+-TBA complex. However, use of CTA+ as the organic phase electrolyte cation, as the salt with tetrakis(4-chlorophenyl)borate, greatly improved the response to TBA. In this case, a distinctive peak response (at ca. -0.25 V) was attributed to the transfer of CTA+ across the soft interface to complex with aqueous phase TBA. Employing this process as a detection step enabled a detection limit of 0.11 µM TBA (by cyclic voltammetry). Furthermore, the presence of magnesium cations at physiological concentration resulted in the disappearance of the TBA response because of Mg2+-induced folding of TBA. Also, the current response of TBA was decreased by the addition of thrombin, indicating TBA interacted with this binding partner. Finally, the interfacial surfactant-aptamer interaction was explored in a synthetic urine matrix that afforded a detection limit of 0.29 µM TBA. These results suggest that aptamer-binding interactions can be monitored by electrochemistry at aqueous-organic interfaces and open up a new possibility for detection in aptamer-binding assays.

8.
Artigo em Inglês | MEDLINE | ID: mdl-29572033

RESUMO

The beta amyloid protein (Aß) plays a central role in Alzheimer's disease (AD) pathogenesis and its interaction with cell membranes in known to promote mutually disruptive structural perturbations that contribute to amyloid deposition and neurodegeneration in the brain. In addition to protein aggregation at the membrane interface and disruption of membrane integrity, growing reports demonstrate an important role for the membrane in modulating Aß production and uptake into cells. The aim of this review is to highlight and summarize recent literature that have contributed insight into the implications of altered membrane composition on amyloid precursor protein (APP) proteolysis, production of Aß, its internalization in to cells via permeabilization and receptor mediated uptake. Here, we also review the various membrane model systems and experimental tools used for probing Aß-membrane interactions to investigate the key mechanistic aspects underlying the accumulation and toxicity of Aß in AD.

9.
Analyst ; 142(17): 3194-3202, 2017 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-28758647

RESUMO

Fucoidans are sulfated polysaccharides mostly derived from algae and used in a number of applications (e.g. nutrition, cosmetics, pharmaceuticals and biomaterials). In this study, the electrochemical behaviour of fucoidans extracted from two algal species (Undaria pinnatifida and Fucus vesiculosus) was assessed using voltammetry at an array of micro-interfaces formed between two immiscible electrolyte solutions (µITIES) in which the organic electrolyte phase was gelled. Cyclic voltammetry revealed an adsorption process when scanning to negative potentials, followed by a desorption peak at ca. -0.50 V on the reverse scan, indicating the electroactivity of both fucoidans. U. pinnatifida fucoidan showed a more intense voltammetric signal compared to F. vesiculosus fucoidan. In addition, use of tridodecylmethylammonium (TDMA+) or tetradodecylammonium (TDDA+) as the organic phase electrolyte cation provided improved detection of both fucoidans relative to the use of bis(triphenylphosphoranylidene)ammonium (BTPPA+) cation. Application of adsorptive stripping voltammetry provided a linear response of current with fucoidan concentration in the range 2-20 µg mL-1 for U. pinnatifida fucoidan (with TDMA+) and 10-100 µg mL-1 for F. vesiculosus fucoidan (with TDDA+). The combination of TDMA+ in the organic phase and adsorptive pre-concentration for 180 s afforded a detection limit of 1.8 µg mL-1 fucoidan (U. pinnatifida) in aqueous phase of 10 mM NaOH and 2.3 µg mL-1 in synthetic urine (pH adjusted). These investigations demonstrate the electroactivity of fucoidans at the µITIES array and provide scope for their detection at low µg mL-1 concentrations using this approach.

10.
Macromol Rapid Commun ; 38(2)2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27859900

RESUMO

(Co)Polymers containing pentafluorophenylacetylene (F5 PA) have been prepared for the first time mediated by [Rh(nbd)Cl]2 /NEt3 to give materials with properties typical of poly(phenylacetylene)s prepared with this catalyst/co-catalyst combination. It is demonstrated that the F5 PA repeat units in these new (co)polymers serve as convenient reactive species for post-polymerization modification with thiols via para-fluoro aromatic nucleophilic substitution reactions to give an entirely new family of novel thioether-functional polyene materials accompanied by absorption maxima shifts of up to 130 nm. Finally, the electrochemical properties of these new fluorinated polyene materials are briefly examined and the distinct difference in behavior of the F5 PA homopolymer versus polyphenylacetylene, copolymers, and functional derivatives is highlighted.


Assuntos
Técnicas Eletroquímicas , Hidrocarbonetos Fluorados/química , Hidrocarbonetos Fluorados/síntese química , Polienos/química , Polienos/síntese química , Estrutura Molecular , Polimerização
11.
Anal Chem ; 88(23): 11302-11305, 2016 12 06.
Artigo em Inglês | MEDLINE | ID: mdl-27934107

RESUMO

A label-free electrochemical strategy for the detection of a cancer biomarker, prostate specific membrane antigen (PSMA), at picomolar concentrations without the use of antibodies, was investigated. The approach is based on the assisted ion transfer of protons, generated by a series of enzymatic reactions, at an array of microinterfaces between two immiscible electrolyte solutions (µ-ITIES). This nonredox electrochemical approach based on biocatalysis-coupled proton transfer at the µ-ITIES array opens a new way to detect the prostate cancer biomarker, with detection capability achieved at concentrations below those indicative of disease presence. The strategy is expected to contribute to cancer diagnostics, recurrence monitoring, and therapeutic treatment efficacy.


Assuntos
Antígenos de Superfície/análise , Biocatálise , Biomarcadores Tumorais/análise , Técnicas Eletroquímicas , Glutamato Carboxipeptidase II/análise , Neoplasias da Próstata/enzimologia , Géis/química , Humanos , Masculino , Neoplasias da Próstata/diagnóstico por imagem
12.
Anal Chem ; 88(13): 6689-95, 2016 07 05.
Artigo em Inglês | MEDLINE | ID: mdl-27264360

RESUMO

The direct experimental characterization of diffusion processes at nanoscale remains a challenge that could help elucidate processes in biology, medicine and technology. In this report, two experimental approaches were employed to visualize ion diffusion profiles at the orifices of nanopores (radius (ra) of 86 ± 6 nm) in array format: (1) electrochemically assisted formation of silica deposits based on surfactant ion transfer across nanointerfaces between two immiscible electrolyte solutions (nanoITIES); (2) combined atomic force - scanning electrochemical microscopy (AFM-SECM) imaging of topography and redox species diffusion through the nanopores. The nature of the diffusion zones formed around the pores is directly related to the interpore distance within the array. Nanopore arrays with different ratios of pore center-to-center separation (rc) to pore radius (ra) were fabricated by focused ion beam (FIB) milling of silicon nitride (SiN) membranes, with 100 pores in a hexagonal arrangement. The ion diffusion profiles determined by the two visualization methods indicated the formation of overlapped or independent diffusion profiles at nanopore arrays with rc/ra ratios of 21 ± 2 and 91 ± 7, respectively. In particular, the silica deposition method resulted in formation of a single deposit encompassing the complete array with closer nanopore arrangement, whereas individual silica deposits were formed around each nanopore within the more widely spaced array. The methods reveal direct experimental evidence of diffusion zones at nanopore arrays and provide practical illustration that the pore-pore separation within such arrays has a significant impact on diffusional transport as the pore size is reduced to the nanoscale. These approaches to nanoscale diffusion zone visualization open up possibilities for better understanding of molecular transport processes within miniaturized systems.


Assuntos
Técnicas Eletroquímicas , Nanoporos , Difusão , Membranas Artificiais , Análise em Microsséries , Microscopia de Força Atômica , Compostos de Silício/química , Dióxido de Silício/química
13.
Anal Chem ; 88(10): 5104-11, 2016 05 17.
Artigo em Inglês | MEDLINE | ID: mdl-27063949

RESUMO

The demonstration of prolonged amperometric detection of oxygen in room-temperature ionic liquids (RTILs) was achieved by the use of mechanical polishing to activate platinum screen-printed electrodes (Pt-SPEs). The RTILs studied were 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) and N-butyl-N-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide ([C4mpyrr][NTf2]). It was found that voltammetry on polished Pt-SPEs exhibited less deterioration (in terms of voltammogram shapes, stability of peak currents, and appearance of contaminant peaks) from long-term consecutive cycling under 100% vol oxygen flow in both RTILs. The detection capability of these RTIL/Pt-SPE systems, initially subjected to long-term consecutive voltammetric cycling, was also investigated by cyclic voltammetry (CV) and long-term chronoamperometry (LTCA). Current versus concentration plots were linear on both unpolished and polished electrodes for 10-100% vol O2 (using CV) and 0.1-5% vol O2 (using LTCA). However, sensitivities and limits of detection (LODs) from CV were found to improve significantly on polished electrodes compared to unpolished electrodes, particularly in [C2mim][NTf2], but also moderately in [C4mpyrr][NTf2]. The lowest LODs (of ca. 0.1% vol O2) were found on polished SPEs using LTCA, with the most stable responses observed in [C4mpyrr][NTf2]. Calibration graphs could not be obtained on unpolished electrodes in both RTILs using LTCA. The results show that polishing markedly improves the analytical performances of Pt-SPEs for oxygen sensing in RTILs. The reusability of such disposable Pt-SPEs, after the surfaces had been experimentally fouled, was also demonstrated through the use of polishing. Mechanical polishing of Pt-SPE devices offers a viable approach to performance improvement for amperometric gas sensing.

14.
Annu Rev Anal Chem (Palo Alto Calif) ; 9(1): 145-61, 2016 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-27049634

RESUMO

Ion transfer at the interface between immiscible electrolyte solutions offers many benefits to analytical chemistry, including the ability to detect nonredox active ionized analytes, to detect ions whose redox electrochemistry is accompanied by complications, and to separate ions based on electrocontrolled partition. Nanoscale miniaturization of such interfaces brings the benefits of enhanced mass transport, which in turn leads to improved analytical performance in areas such as sensitivity and limits of detection. This review discusses the development of such nanoscale interfaces between immiscible liquids and examines the analytical advances that have been made to date, including prospects for trace detection of ion concentrations.

15.
J Phys Chem B ; 120(12): 3100-12, 2016 Mar 31.
Artigo em Inglês | MEDLINE | ID: mdl-26950406

RESUMO

The adsorption of proteins at the interface between two immiscible electrolyte solutions has been found to be key to their bioelectroactivity at such interfaces. Combined with interfacial complexation of organic phase anions by cationic proteins, this adsorption process may be exploited to achieve nanomolar protein detection. In this study, replica exchange molecular dynamics simulations have been performed to elucidate for the first time the molecular mechanism of adsorption and subsequent unfolding of hen egg white lysozyme at low pH at a polarized 1,2-dichloroethane/water interface. The unfolding of lysozyme was observed to occur as soon as it reaches the organic-aqueous interface, which resulted in a number of distinct orientations at the interface. In all cases, lysozyme interacted with the organic phase through regions rich in nonpolar amino acids, such that the side chains are directed toward the organic phase, whereas charged and polar residues were oriented toward the aqueous phase. By contrast, as expected, lysozyme in neat water at low pH does not exhibit significant structural changes. These findings demonstrate the key influence of the organic phase upon adsorption of lysozyme under the influence of an electric field, which results in the unfolding of its structure.


Assuntos
Dicloretos de Etileno/química , Muramidase/química , Desdobramento de Proteína , Adsorção , Concentração de Íons de Hidrogênio , Simulação de Dinâmica Molecular , Muramidase/metabolismo , Propriedades de Superfície , Água/química
16.
Anal Chem ; 88(5): 2596-604, 2016 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-26853853

RESUMO

Arrays of microscale interfaces between two immiscible electrolyte solutions (µITIES) were formed using glass membranes perforated with microscale pores by laser ablation. Square arrays of 100 micropores in 130 µm thick borosilicate glass coverslips were functionalized with trichloro(1H,1H,2H,2H-perfluorooctyl)silane on one side, to render the surface hydrophobic and support the formation of aqueous-organic liquid-liquid microinterfaces. The pores show a conical shape, with larger radii at the laser entry side (26.5 µm) than at the laser exit side (11.5 µm). The modified surfaces were characterized by contact angle measurements and X-ray photoelectron spectroscopy. The organic phase was placed on the hydrophobic side of the membrane, enabling the array of µITIES to be located at either the wider or narrower pore mouth. The electrochemical behavior of the µITIES arrays were investigated by tetrapropylammonium ion transfer across water-1,6-dichlorohexane interfaces together with finite element computational simulations. The data suggest that the smallest microinterfaces (formed on the laser exit side) were located at the mouth of the pore in hemispherical geometry, while the larger microinterfaces (formed on the laser entry side) were flatter in shape but exhibited more instability due to the significant roughness of the glass around the pore mouths. The glass membrane-supported µITIES arrays presented here provide a new platform for chemical and biochemical sensing systems.

17.
Angew Chem Int Ed Engl ; 54(49): 14903-6, 2015 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-26489692

RESUMO

At the water-trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate ([P14,6,6,6][FAP]) ionic liquid interface, the unusual electrochemical transfer behavior of protons (H(+)) and deuterium ions (D(+)) was identified. Alkali metal cations (such as Li(+), Na(+), K(+)) did not undergo this transfer. H(+)/D(+) transfers were assisted by the hydrophobic counter anion of the ionic liquid, [FAP](-), resulting in the formation of a mixed capacitive layer from the filling of the latent voids within the anisotropic ionic liquid structure. This phenomenon could impact areas such as proton-coupled electron transfers, fuel cells, and hydrogen storage where ionic liquids are used as aprotic solvents.

18.
Anal Chim Acta ; 893: 34-40, 2015 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-26398420

RESUMO

Ion transfer at aqueous-organogel interfaces enables the non-redox detection of ions and ionisable species by voltammetry. In this study, a non-thermal method for preparation of an organogel was employed and used for the detection of hen-egg-white-lysozyme (HEWL) via adsorptive stripping voltammetry at an array of aqueous-organogel microinterfaces. Tetrahydrofuran solvent casting was employed to prepare the organogel mixture, hence removing the need for heating of the solution to be gelled, as used in previous studies. Cyclic voltammetry of HEWL at the microinterface array revealed a broad adsorption process on the forward scan, at positive applied potentials, followed by a desorption peak at ca. 0.68 V, indicating the detection of HEWL in this region. Application of an adsorption step, where a constant optimized potential of 0.95 V was applied, followed by voltammetric detection provided for a linear response range of 0.02-0.84 µM and a detection limit of 0.030 µM for 300 s adsorption. The detection limit was further improved by utilizing differential pulse stripping voltammetry, resulting in detection limits of 0.017 µM, 0.014 µM, and 0.010 µM for adsorptive pre-concentration times of 60, 120 and 300 s, respectively, in unstirred solutions. These results are an improvement over other methods for the detection of HEWL at aqueous-organic interfaces and offers a basis for the label-free detection of protein.


Assuntos
Técnicas Eletroquímicas , Ensaios Enzimáticos/métodos , Géis/química , Muramidase/análise , Solventes/química , Adsorção , Animais , Galinhas , Eletrodos , Oxirredução , Água/química
19.
Anal Chem ; 87(11): 5486-90, 2015 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-25962586

RESUMO

In this work, independent radial diffusion at arrayed nanointerfaces between two immiscible electrolyte solutions (nanoITIES) was achieved. The arrays were formed at nanopores fabricated by focused ion beam milling of silicon nitride (SiN) membranes, enabling the reproducible and systematic design of five arrays with different ratios of pore center-to-center distance (rc) to pore radius (ra). Voltammetry across water-1,6-dichlorohexane nanoITIES formed at these arrays was examined by the interfacial transfer of tetrapropylammonium ions. The diffusion-limited ion-transfer current increased with the ratio rc/ra, reaching a plateau for rc/ra ≥ 56, which was equivalent to the theoretical current for radial diffusion to an array of independent nanoITIES. As a result, mass transport to the nanoITIES arrays was greatly enhanced due to the decreased overlap of diffusion zones at adjacent nanoITIES, allowing each interface in the array to behave independently. When the rc/ra ratio increased from 13 to 56, the analytical performance parameters of sensitivity and limit of detection were improved from 0.50 (±0.02) A M(-1) to 0.76 (±0.02) A M(-1) and from 0.101 (±0.003) µM to 0.072 (±0.002) µM, respectively. These results provide an experimental basis for the design of arrayed nanointerfaces for electrochemical sensing.

20.
Anal Chem ; 87(8): 4487-94, 2015 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-25815423

RESUMO

In this work, the ion-transfer voltammetric detection of the protonated ß-blocker propranolol was explored at arrays of nanoscale interfaces between two immiscible electrolyte solutions (ITIES). Silicon nitride nanoporous membranes with 400 pores in a hexagonal arrangement, with either 50 or 17 nm radius pores, were used to form regular arrays of nanoITIES. It was found that the aqueous-to-organic ion-transfer current continuously increased steadily rather than reaching a limiting current plateau after the ion-transfer wave; the slope of this limiting current region was concentration dependent and associated with the high ion flux at the nanointerfaces. Electrochemical data were examined in terms of an independent nanointerface approach and an equivalent microdisc approach, supported by finite element simulation. In comparison to the larger interface configuration (50 nm radius), the array of 17 nm radius nanoITIES exhibited a 6.5-times higher current density for propranolol detection due to the enhanced ion flux arising from the convergent diffusion to smaller electrochemical interfaces. Both nanoITIES arrays achieved the equivalent limits of detection, 0.8 µM, using cyclic voltammetry. Additionally, the effect of scan rate on the charging and faradaic currents at these nanoITIES arrays, as well as their stability over time, was investigated. The results demonstrate that arrays of nanoscale liquid-liquid interfaces can be applied to study electrochemical drug transfer, and provide the basis for the development of miniaturized and integrated detection platforms for drug analysis.


Assuntos
Técnicas Eletroquímicas , Nanopartículas/química , Propranolol/análise , Compostos de Silício/química , Eletrólitos/química , Íons/química , Tamanho da Partícula , Porosidade , Soluções , Propriedades de Superfície
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