Xueling Feng

Redox active gels: synthesis, structures and applications

Recent years have brought significant advances and developments in the area of redox-responsive polymers. This review outlines major developments that focused on the incorporation of redox responsive components that are covalently attached as pending or crosslinking groups along a polymer backbone. Among the major contestants, ferrocenes, conjugated polymers, tetrathiafulvalene, transition metal ions and disulfide bonds represent major contributions in this field. The unique technological feature of these responsive gels capable of redox stimuli controlled and reversible changes is the ability to tune their shapes, color, solubility, or display sol-to-gel transitions.

Breathing Pores on Command: Redox‐Responsive Spongy Membranes from Poly(ferrocenylsilane)s

Redox-responsive porous membranes can be readily formed by electrostatic complexation between redox active poly(ferrocenylsilane) PFS-based poly(ionic liquid)s and organic acids. Redox-induced changes on this membrane demonstrated reversible switching between more open and more closed porous structures. By taking advantage of the structure changes in the oxidized and reduced states, the porous membrane exhibits reversible permeability control and shows great potential in gated filtration, catalysis, and controlled release.

Electrografting of Stimuli-Responsive, Redox Active Organometallic Polymers to Gold from Ionic Liquids

Robust, dense, redox active organometallic poly(ferrocenylsilane) (PFS) grafted films were formed within 5 min by cathodic reduction of Au substrates, immersed in a solution of imidazolium-functionalized PFS chains in the ionic liquid 1-ethyl-3-methylimidazolium ethyl sulfate. The electrografted polymer films were employed as an electrochemical sensor, exhibiting high sensitivity, stability, and reproducibility.

Poly(N-isopropylacrylamide)–poly(ferrocenylsilane) dual-responsive hydrogels: synthesis, characterization and antimicrobial applications

Novel hydrogels composed of thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) and redox-responsive poly(ferrocenylsilane) (PFS) macromolecules were formed by photopolymerization. PFS chains bearing acrylate side groups were copolymerized with NIPAM and N,N′-methylenebisacrylamide in tetrahydrofuran in a predetermined ratio under ultraviolet light-emitting diode (UV-LED) irradiation at a wavelength of 365 nm, in the presence of a photoinitiator. Crosslinking occurred smoothly, providing homogeneous hydrogels. The equilibrium swelling ratio, rheology and morphology of these hybrid PNIPAM–PFS-based hydrogels were investigated. The thermo-responsive properties of the hydrogels were studied as a function of the PFS oxidation state. In situ fabrication of silver nanoparticles inside the hydrogel network via reduction of silver nitrate by the PFS chains led to hydrogel composites. These composites showed strong antimicrobial activity while maintaining a high biocompatibility with cells

Covalent layer-by-layer assembly of redox-active polymer multilayers.

Poly(ferrocenyl(3-bromopropyl)methylsilane) and poly(ethylene imine) are employed in a layer-by-layer deposition process to form covalently connected, redox-active multilayer thin films by means of an amine alkylation reaction. The stepwise buildup of these multilayers on silicon, ITO, and quartz substrates was monitored by UV-vis absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR), static contact angle measurements, surface plasmon resonance (SPR), atomic force microscopy, ellipsometry, and cyclic voltammetry, which provide evidence for a linear increase in multilayer thickness with the number of deposited bilayers. Upon oxidation and reduction, these covalently interconnected layers do not disassemble, in contrast to poly(ferrocenylsilane) (PFS) layers featuring similar backbone structures that are held together by electrostatic forces. The PFS/PEI multilayers are effective for the electrochemical sensing of ascorbic acid and hydrogen peroxide and show improved sensing performance at higher bilayer numbers. These covalently linked layers are readily derivatized further and can therefore be regarded as a versatile platform for creating robust, tailorable, redox-active interfaces with applications in sensing and biofuel cells.

Electrochemical sensing by surface-immobilized poly(ferrocenylsilane) grafts

Chemically modified electrodes, decorated with covalently tethered poly(ferrocenylsilane) – PFS chains, are fabricated. Robust, relatively dense redox-active films with a height of around 10 nm are successfully formed by reaction of poly(ferrocenyl(3-iodopropyl)methylsilane) with amine-terminated monolayers on silicon or gold surfaces. The electrochemical properties of the surface-immobilized PFS chains are studied using cyclic voltammetry (CV) and differential pulse voltammetry (DPV), both in aqueous and organic media. Information on the properties of these films as a function of redox state is gained using quantitative adherence measurements between the films and AFM tips. An ascorbic acid electrochemical sensor based on these surface-anchored PFS chains, exhibiting a high sensitivity and stability, was fabricated. The PFS layers described are easily derivatized, thus forming a platform for creating highly tailorable redox-active interfaces.

Highly Swellable, Dual-Responsive Hydrogels Based on PNIPAM and Redox Active Poly(ferrocenylsilane) Poly(ionic liquid)s: Synthesis, Structure, and Properties

Highly swellable, dual-responsive hydrogels, consisting of thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) and redox-responsive poly(ferrocenylsilane) (PFS) based poly(ionic liquid)s (PILs) are formed by photo-polymerization. PFS chains bearing cross-linkable vinylimidazolium (VIm) side groups are copolymerized with NIPAM in aqueous solutions under ultraviolet light (λ = 365 nm) in the presence of a photoinitiator. The PFS-PILs serve as a macro-cross-linker and also provide redox responsiveness. The swelling ratio, morphology, and lower critical solution temperature (LCST) of the hydrogels are studied as a function of the PNIPAM/PFS ratio. The value of the LCST is dependent on the choice of the counterion of the PIL and the PNIPAM/PFS ratio. The hydrogel is employed as a reducing environment for the in situ fabrication of gold nanoparticles (AuNPs), forming AuNP-hydrogel composites. The localized surface plasmon resonance peak of the as-synthesized Au nanoparticles inside the hydrogel could be tuned by altering the temperature.

Organometallic polymers for electrode decoration in sensing applications

Macromolecules containing metals combine the processing advantages of polymers with the functionality offered by the metal centers. This review outlines the progress and recent developments in the area of electrochemical chemo/biosensors that are based on organometallic polymers. We focus on materials in which the metal centers provide function, allowing these materials to be used in electrochemical sensing applications based on various transduction mechanisms. Examples of chemo/biosensors featuring organometallic polymers that possess Fe, Os, Co and Ru are discussed.

Hydrogels with a Memory: Dual-Responsive, Organometallic Poly(ionic liquid)s with Hysteretic Volume-Phase Transition

We report on the synthesis and structure–property relations of a novel, dual-responsive organometallic poly(ionic liquid) (PIL), consisting of a poly(ferrocenylsilane) backbone of alternating redox-active, silane-bridged ferrocene units and tetraalkylphosphonium sulfonate moieties in the side groups. This PIL is redox responsive due to the presence of ferrocene in the backbone and also exhibits a lower critical solution temperature (LCST)-type thermal responsive behavior. The LCST phase transition originates from the interaction between water molecules and the ionic substituents and shows a concentration-dependent, tunable transition temperature in aqueous solution. The PIL’s LCST-type transition temperature can also be influenced by varying the redox state of ferrocene in the polymer main chain. As the polymer can be readily cross-linked and is easily converted into hydrogels, it represents a new dual-responsive materials platform. Interestingly, the as-formed hydrogels display an unusual, strongly hysteretic volume-phase transition indicating useful thermal memory properties. By employing the dispersing abilities of this cationic PIL, CNT-hydrogel composites were successfully prepared. These hybrid conductive composite hydrogels showed bi-stable states and tunable resistance in heating–cooling cycles.

Highly Sensitive, Label-Free Detection of 2,4-Dichlorophenoxyacetic Acid Using an Optofluidic Chip

A highly sensitive approach for rapid and label-free detection of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) using an optofluidic chip is demonstrated. The optofluidic chip is prepared by covalent immobilization of 2,4-D-bovine serum albumin (2,4-D-BSA) conjugate to an integrated microring resonator. Subsequent detection of 2,4-D carried out in a competitive immunoreaction format enables selective detection of 2,4-D in different types of water samples, including bottled, tap, and lake water, at a limit of detection (LOD) of 4.5 pg/mL and in a quantitative range of 15-105 pg/mL. The microring resonator-based optofluidic chip is reusable with ultrahigh sensitivity that offers real-time and on-site detection of low-molecular-weight targets for potential applications in food safety and environmental monitoring.