pH Oscillator Stretched in Space but Frozen in Time

Hermans, Thomas M.; Stewart, Philip; Grzybowski, Bartosz A.

doi:10.1021/jz502711c

Cited by 7 publications

(6 citation statements)

References 35 publications

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“…Localized illumination was applied to a Today increased interest is focused on dynamic, non-equilibrium material properties varying with time: a life inspired nanoscale machinery (1)(2)(3)(4). It involves needs for effective energy conversion with the focus on oscillation reactions (5), chemical networking (6), autocatalytic (7) and autoamplification (8) reactions, mimicking living systems (9), using cell metabolic biomolecules (10) and ions, e.g. proton gradients (11).…”

Section: Significancementioning

confidence: 99%

Light-Induced Proton Pumping with a Semiconductor: Vision for Photoproton Lateral Separation and Robust Manipulation

Maltanava

Poznyak

Andreeva

et al. 2017

ACS Appl. Mater. Interfaces

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Energy-transfer reactions are the key for living open systems, biological chemical networking, and the development of life-inspired nanoscale machineries. It is a challenge to find simple reliable synthetic chemical networks providing a localization of the time-dependent flux of matter. In this paper, we look to photocatalytic reaction on TiO from different angles, focusing on proton generation and introducing a reliable, minimal-reagent-consuming, stable inorganic light-promoted proton pump. Localized illumination was applied to a TiO surface in solution for reversible spatially controlled "inorganic photoproton" isometric cycling, the lateral separation of water-splitting reactions. The proton flux is pumped during the irradiation of the surface of TiO and dynamically maintained at the irradiated surface area in the absence of any membrane or predetermined material structure. Moreover, we spatially predetermine a transient acidic pH value on the TiO surface in the irradiated area with the feedback-driven generation of a base as deactivator. Importantly we describe how to effectively monitor the spatial localization of the process by the in situ scanning ion-selective electrode technique (SIET) measurements for pH and the scanning vibrating electrode technique (SVET) for local photoelectrochemical studies without additional pH-sensitive dye markers. This work shows the great potential for time- and space-resolved water-splitting reactions for following the investigation of pH-stimulated processes in open systems with their flexible localization on a surface.

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Section: Significancementioning

confidence: 99%

Light-Induced Proton Pumping with a Semiconductor: Vision for Photoproton Lateral Separation and Robust Manipulation

Maltanava

Poznyak

Andreeva

et al. 2017

ACS Appl. Mater. Interfaces

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“…The controlled structuring of liquids, in space and time, is a new frontier in soft matter science and engineering with profound implications for next-generation catalysis, 1−3 energy conversion, 4 additive manufacturing, 5 and nonequilibrium chemical systems. 6 An emerging and versatile strategy to structure a liquid within another involves the spontaneous assembly of nanoparticle surfactants (NP-surfactants) into a monolayer at the liquid/liquid interface. NP-surfactant monolayers form at the interface between two immiscible liquids when colloidal nanomaterials in one phase are held at the interface by polymers dissolved in the second phase, provided the polymer is modified with at least one functional group that is attracted to complementary functionality on the surface of the colloid; this process is concomitant with an overall reduction in the interfacial energy.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Self-Regulated Nanoparticle Assembly at Liquid/Liquid Interfaces: A Route to Adaptive Structuring of Liquids

et al. 2017

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The controlled structuring of liquids into arbitrary shapes can be achieved in biphasic liquid media using the interfacial assemblies of nanoparticle surfactants (NP-surfactants), that consist of a polar nanoparticle "head group" bound to one or more hydrophobic polymer "tails". The nonequilibrium shapes of the suspended liquid phase can be rendered permanent by the jamming of the NP-surfactants formed and assembled at the interface between the liquids as the system attempts to minimize the interfacial area between the liquids. While critical to the structuring process, little is known of the dynamic mechanical properties of the NP-surfactant monolayer at the interface as it is dictated by the characteristics of the component, including NP size and concentration and the molecular weight and concentration of polymers bound to the NPs. Here we provide the first comprehensive understanding of the dynamic mechanical character of two-dimensional NP-surfactant assemblies at liquid/liquid interfaces. Our results indicate that the dynamics of NP-polymer interactions are self-regulated across multiple time scales and are associated with specific mesoscale interactions between self-similar and cross-complementary components. Furthermore, the mechanical properties of the NP-surfactant monolayer are tunable over a broad range and deterministic on the basis of those component inputs. This control is key to tailoring the functional attributes of the reconfigurable structured liquids to suit specific applications.

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“…Some chemical systems, being far from equilibrium, show nonlinear kinetic behaviors, such as periodic oscillations [1] , chaos [2] , wave propagation and pattern formation [3] . Among such nonlinear systems, periodic chemical oscillation not only exhibits the unique kinetic behaviors but it has also been used as unique tools in the analytical field.…”

mentioning

confidence: 99%

“…But the method has difficulty in distinguishing isomers because the ion fragments come from two isomers may have the same mass-to-charge ratio and similar distribution. By coupling the high separation efficiency of gas chromatograph (GC) with high sensitivity of mass (1, In this paper, an accomplishment for identification of two position isomers (1,3-CHD and 1,4-CHD) was achieved by using a Briggs−Rauscher oscillating reaction. The concentrations of 1,3-CHD and 1,4-CHD that can be distinguished is over the range from 9.0×10 -4 to 8.0×10 -3 M. Compared with our previous application of using BR reaction for quantitative measurement of analytes [12][13][14][15][16][17] , this electrochemical technonogy involving a BR reactor provieds a new rapid qualitative method in identification of two isomers (1,3-CHD and 1,4-CHD) with simpler equipment.…”

mentioning

confidence: 99%

An Application of Chemical Oscillation: Distinguishing Two Isomers between Cyclohexane-1,3-dione and 1,4-cyclohexanedione

Chen

et al. 2016

Electrochimica Acta

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In the analytical field, previous applications of chemical oscillation focused on quantitative analysis. We report in this paper a novel qualitative method electrochemically distinguishing two positional isomers by utilizing their perturbation effects on a catalyzed Briggs-Rauscher (BR) oscillation. The catalyst in the system is a macrocyclic nickel (Ⅱ) complex NiL(ClO 4 ) 2 , where the ligand L in the complex is 5,7,7,12,14,14-hexemethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene. The experimental results indicated that addition of cyclohexane-1,3-dione (1,3-CHD) or 1,4-cyclohexanedione (1,4-CHD) could affect the profiles of potentiometric oscillations, but their changes in the profiles are greatly different. When 1,3-CHD was injected into the oscillating system, there was an initial spiking of the oscillations, accompanying by quenching of oscillations before the regeneration of oscillations.While 1,4-CHD was injected into the dynamic mixture, the oscillatory system responded to the perturbation with only slight decrease followed by a sharp increase in the potential, before it resumed to its normal oscillation state. The perturbation of 1,3-CHD involves inhibition time, whereas the perturbation of 1,4-CHD does not.Hence these two positional isomers could be distinguished by using their different perturbation effects on a BR dynamic system in the range of 9.0×10 -4 to 8.0×10 -3 M.Our assumption is that, perturbation of 1,3-CHD on the oscillating system involves a radical oxidization process to produce carboxylic acid, whereas perturbation of  Corresponding author. 2 1,4-CHD assumes idiodation and elimination steps to form 1,4-benzoquinone. Such different perturbation mechanisms are responsible for the difference in potentiometric oscillation profiles change. This hypothesis was confirmed by products analysis by FTIR and UV spectra.

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pH Oscillator Stretched in Space but Frozen in Time

Cited by 7 publications

References 35 publications

Light-Induced Proton Pumping with a Semiconductor: Vision for Photoproton Lateral Separation and Robust Manipulation

Light-Induced Proton Pumping with a Semiconductor: Vision for Photoproton Lateral Separation and Robust Manipulation

Self-Regulated Nanoparticle Assembly at Liquid/Liquid Interfaces: A Route to Adaptive Structuring of Liquids

An Application of Chemical Oscillation: Distinguishing Two Isomers between Cyclohexane-1,3-dione and 1,4-cyclohexanedione

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