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Anion-capped metallohost allows extremely slow guest uptake and on-demand acceleration of guest exchange.

ABSTRACT: The switching of molecular recognition selectivity is important for tuning molecular functions based on host-guest binding. While the switching processes in artificial functional molecules are usually driven by changes of the thermodynamic stabilities, non-equilibrium phenomena also play an important role in biological systems. Thus, here we designed a host-guest system utilizing a non-equilibrium kinetically trapped state for on-demand and time-programmable control of molecular functions. We synthesized a bis(saloph) macrocyclic cobalt(III) metallohost 1(OTf)2, which has anion caps at both sides of the cation-binding site. The anion caps effectively retard the guest uptake/release so that we can easily make a non-equilibrium kinetically trapped state. Indeed, we can obtain a long-lived kinetically trapped state {[1·K]3++La3+} prior to the formation of the thermodynamically more stable state {[1·La]5++K+}. The guest exchange to the more stable state from this kinetically trapped state is significantly accelerated by exchange of TfO- anion caps by AcO- in an on-demand manner.

SUBMITTER: Sakata Y

PROVIDER: S-EPMC5510176 | biostudies-literature | 2017 Jul

REPOSITORIES: biostudies-literature

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Anion-capped metallohost allows extremely slow guest uptake and on-demand acceleration of guest exchange.

Sakata Yoko Y Murata Chiho C Akine Shigehisa S

Nature communications 20170712

The switching of molecular recognition selectivity is important for tuning molecular functions based on host-guest binding. While the switching processes in artificial functional molecules are usually driven by changes of the thermodynamic stabilities, non-equilibrium phenomena also play an important role in biological systems. Thus, here we designed a host-guest system utilizing a non-equilibrium kinetically trapped state for on-demand and time-programmable control of molecular functions. We sy ...[more]

PMID: 28699635

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Project description:This Review provides an overview of the emerging concepts of catalysts, membranes, and membrane electrode assemblies (MEAs) for water electrolyzers with anion-exchange membranes (AEMs), also known as zero-gap alkaline water electrolyzers. Much of the recent progress is due to improvements in materials chemistry, MEA designs, and optimized operation conditions. Research on anion-exchange polymers (AEPs) has focused on the cationic head/backbone/side-chain structures and key properties such as ionic conductivity and alkaline stability. Several approaches, such as cross-linking, microphase, and organic/inorganic composites, have been proposed to improve the anion-exchange performance and the chemical and mechanical stability of AEMs. Numerous AEMs now exceed values of 0.1 S/cm (at 60-80 °C), although the stability specifically at temperatures exceeding 60 °C needs further enhancement. The oxygen evolution reaction (OER) is still a limiting factor. An analysis of thin-layer OER data suggests that NiFe-type catalysts have the highest activity. There is debate on the active-site mechanism of the NiFe catalysts, and their long-term stability needs to be understood. Addition of Co to NiFe increases the conductivity of these catalysts. The same analysis for the hydrogen evolution reaction (HER) shows carbon-supported Pt to be dominating, although PtNi alloys and clusters of Ni(OH)2 on Pt show competitive activities. Recent advances in forming and embedding well-dispersed Ru nanoparticles on functionalized high-surface-area carbon supports show promising HER activities. However, the stability of these catalysts under actual AEMWE operating conditions needs to be proven. The field is advancing rapidly but could benefit through the adaptation of new in situ techniques, standardized evaluation protocols for AEMWE conditions, and innovative catalyst-structure designs. Nevertheless, single AEM water electrolyzer cells have been operated for several thousand hours at temperatures and current densities as high as 60 °C and 1 A/cm2, respectively.

Dataset Information

Anion-capped metallohost allows extremely slow guest uptake and on-demand acceleration of guest exchange.

Publications

Anion-capped metallohost allows extremely slow guest uptake and on-demand acceleration of guest exchange.

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