3D Dense Encapsulated Architecture of 2D Bi Nanosheets Enabling Potassium-Ion Storage with Superior Volumetric and Areal Capacities.

2D alloy-based anodes show promise in potassium-ion batteries (PIBs). Nevertheless, their low tap density and huge volume expansion cause insufficient volumetric capacity and cycling stability. Herein, a 3D highly dense encapsulated architecture of 2D-Bi nanosheets (HD-Bi@G) with conducive elastic networks and 3D compact encapsulation structure of 2D nano-sheets are developed. As expected, HD-Bi@G anode exhibits a considerable volumetric capacity of 1032.2 mAh cm-3 , stable long-life span with 75% retention after 2000 cycles, superior rate capability of 271.0 mAh g-1 at 104 C, and high areal capacity of 7.94 mAh cm-2 (loading: 24.2 mg cm-2 ) in PIBs. The superior volumetric and areal performance mechanisms are revealed through systematic kinetic investigations, ex situ characterization techniques, and theorical calculation. The 3D high-conductivity elastic network with dense encapsulated 2D-Bi architecture effectively relieves the volume expansion and pulverization of Bi nanosheets, maintains internal 2D structure with fast kinetics, and overcome sluggish ionic/electronic diffusion obstacle of ultra-thick, dense electrodes. The uniquely encapsulated 2D-nanosheet structure greatly reduces K+ diffusion energy barrier and accelerates K+ diffusion kinetics. These findings validate a feasible approach to fabricate 3D dense encapsulated architectures of 2D-alloy nanosheets with conductive elastic networks, enabling the design of ultra-thick, dense electrodes for high-volumetric-energy-density energy storage.

Novel Ultra-Stable 2D SbBi Alloy Structure with Precise Regulation Ratio Enables Long-Stable Potassium/Lithium-Ion Storage.

The inferior cycling stabilities or low capacities of 2D Sb or Bi limit their applications in high-capacity and long-stability potassium/lithium-ion batteries (PIBs/LIBs). Therefore, integrating the synergy of high-capacity Sb and high-stability Bi to fabricate 2D binary alloys is an intriguing and challenging endeavor. Herein, a series of novel 2D binary SbBi alloys with different atomic ratios are fabricated using a simple one-step co-replacement method. Among these fabricated alloys, the 2D-Sb0.6 Bi0.4 anode exhibits high-capacity and ultra-stable potassium and lithium storage performance. Particularly, the 2D-Sb0.6 Bi0.4 anode has a high-stability capacity of 381.1 mAh g-1 after 500 cycles at 0.2 A g-1 (≈87.8% retention) and an ultra-long-cycling stability of 1000 cycles (0.037% decay per cycle) at 1.0 A g-1 in PIBs. Besides, the superior lithium and potassium storage mechanism is revealed by kinetic analysis, in-situ/ex-situ characterization techniques, and theoretical calculations. This mainly originates from the ultra-stable structure and synergistic interaction within the 2D-binary alloy, which significantly alleviates the volume expansion, enhances K+ adsorption energy, and decreases the K+ diffusion energy barrier compared to individual 2D-Bi or 2D-Sb. This study verifies a new scalable design strategy for creating 2D binary (even ternary) alloys, offering valuable insights into their fundamental mechanisms in rechargeable batteries.

Synergistically Accelerating Adsorption-Electrocataysis of Sulfur Species via Interfacial Built-In Electric Field of SnS2 -MXene Mott-Schottky Heterojunction in Li-S Batteries.

Developing efficient heterojunction electrocatalysts and uncovering their atomic-level interfacial mechanism in promoting sulfur-species adsorption-electrocatalysis are interesting yet challenging in lithium-sulfur batteries (LSBs). Here, multifunctional SnS2 -MXene Mott-Schottky heterojunctions with interfacial built-in electric field (BIEF) are developed, as a model to decipher their BIEF effect for accelerating synergistic adsorption-electrocatalysis of bidirectional sulfur conversion. Theoretical and experimental analysis confirm that because Ti atoms in MXene easily lost electrons, whereas S atoms in SnS2 easily gain electrons, and under Mott-Schottky influence, SnS2 -MXene heterojunction forms the spontaneous BIEF, leading to the electronic flow from MXene to SnS2 , so SnS2 surface easily bonds with more lithium polysulfides. Moreover, the hetero-interface quickly propels abundant Li+ /electron transfer, so greatly lowering Li2 S nucleation/decomposition barrier, promoting bidirectional sulfur conversion. Therefore, S/SnS2 -MXene cathode displays a high reversible capacity (1,188.5 mAh g-1 at 0.2 C) and a stable long-life span with 500 cycles (≈82.7% retention at 1.0 C). Importantly, the thick sulfur cathode (sulfur loading: 8.0 mg cm-2 ) presents a large areal capacity of 7.35 mAh cm-2 at lean electrolyte of 5.0 µL mgs -1 . This work verifies the substantive mechanism that how BIEF optimizes the catalytic performance of heterojunctions and provides an effective strategy for deigning efficient bidirectional Li-S catalysts in LSBs.

Unraveling the Atomic-Level Manipulation Mechanism of Li2 S Redox Kinetics via Electron-Donor Doping for Designing High-Volumetric-Energy-Density, Lean-Electrolyte Lithium-Sulfur Batteries.

Designing dense thick sulfur cathodes to gain high-volumetric/areal-capacity lithium-sulfur batteries (LSBs) in lean electrolytes is extremely desired. Nevertheless, the severe Li2 S clogging and unclear mechanism seriously hinder its development. Herein, an integrated strategy is developed to manipulate Li2 S redox kinetics of CoP/MXene catalyst via electron-donor Cu doping. Meanwhile a dense S/Cu0.1 Co0.9 P/MXene cathode (density = 1.95 g cm-3 ) is constructed, which presents a large volumetric capacity of 1664 Ah L-1 (routine electrolyte) and a high areal capacity of ≈8.3 mAh cm-2 (lean electrolyte of 5.0 µL mgs -1 ) at 0.1 C. Systematical thermodynamics, kinetics, and theoretical simulation confirm that electron-donor Cu doping induces the charge accumulation of Co atoms to form more chemical bonding with polysulfides, whereas weakens CoS bonding energy and generates abundant lattice vacancies and active sites to facilitate the diffusion and catalysis of polysulfides/Li2 S on electrocatalyst surface, thereby decreasing the diffusion energy barrier and activation energy of Li2 S nucleation and dissolution, boosting Li2 S redox kinetics, and inhibiting shuttling in the dense thick sulfur cathode. This work deeply understands the atomic-level manipulation mechanism of Li2 S redox kinetics and provides dependable principles for designing high-volumetric-energy-density, lean-electrolyte LSBs through integrating bidirectional electro-catalysts with manipulated Li2 S redox and dense-sulfur engineering.

Green and Scalable Template-Free Strategy to Fabricate Honeycomb-Like Interconnected Porous Micro-Sized Layered Sb for High-Performance Potassium Storage.

The tremendous volume change and severe pulverization of micro-sized Sb anode generate no stable capacity in potassium-ion batteries (PIBs). The honeycomb-like porous structure provides free spaces to accommodate its volume expansion and offers efficient ion transport, yet complex synthesis and low yield limits its large-scale application. Here, a green, scalable template-free method for designing a 3D honeycomb-like interconnected porous micro-sized Sb (porous-Sb) is proposed. Its honeycomb-like porous formation mechanism is also verified. Under hydrothermal conditions, Sb reacts with water and dissolved oxygen in water, undergoing non-homogeneous and continuous corrosion at grain boundaries, and producing soluble H2 Sb2 O6 (H2 O), which regulates the porous structure of Sb by controlling reaction time. Benefiting from its porous structure and micron size, porous-Sb anode displays large gravimetric and volumetric capacities with 655.5 mAh g-1 and 2,001.9 mAh cm-3 at 0.05 A g-1 and superior rate performance of 441.9 mAh g-1 at 2.0 A g-1 in PIBs. Furthermore, ex situ characterization and kinetic analysis uncover the small volume expansion and fast K+ reaction kinetics of porous Sb during potassiation/depotassiation, originating from its large electrolyte contact area and internal expansion mechanism. It verifies a green, scalable template-free strategy to construct honeycomb-like porous metals for energy storage and conversion.

Ru/Rh Cation Doping and Oxygen-Vacancy Engineering of FeOOH Nanoarrays@Ti3 C2 Tx MXene Heterojunction for Highly Efficient and Stable Electrocatalytic Oxygen Evolution.

Oxyhydroxides hold promise as highly-efficient non-noble electrocatalysts for the oxygen evolution reaction (OER), but their poor conductivity and structural instability greatly impede their progress. Herein, the authors develop a cation-doping and oxygenvacancy engineering strategy to fabricate Ru/Rh-doped FeOOH nanoarrays with abundant oxygen-vacancies in situ grown on Ti3 C2 Tx MXene (Ru/Rh-FeOOH@Ti3 C2 Tx ) as highly-efficient OER electrocatalysts. Benefiting from Ru/Rh-cation regulation, oxygenvacancy engineering, and heterojunction synergy between MXene and modulated FeOOH, the optimized Rh/Ru-FeOOH@Ti3 C2 Tx electrocatalysts exhibit excellent OER activities and remarkable stabilities with 100 h. Particularly, 3%Rh-FeOOH@Ti3 C2 Tx electrocatalyst only needs a 223 mV overpotential at 10 mA cm-2 and 306 mV to reach 100 mA cm-2 , which is superior to commercial IrO2 catalyst and most reported oxyhydroxide-based electrocatalysts. Further, systematically theoretical caculation, kinetics, thermodynamics, and microstructural analysis verify that the integration of Ru/Rh-cation doping and oxygen vacancy obviously enhances the intrinsic conductivity and lattice defects of FeOOH and expose more active sites, thereby decreasing the adsorption/desorption energy barrier and activation energy, and improving the specific activity and catalytic kinetics of electrocatalysts, whereas in situ hybridization with MXene strengthens the structural stability. This work clearly confirms that cationdoping and oxygen-vacancy engineering offers a joint strategy for the electronic structure modulation and design of highly-efficient inexpensive OER electrocatalysts.

Integrating Dually Encapsulated Si Architecture and Dense Structural Engineering for Ultrahigh Volumetric and Areal Capacity of Lithium Storage.

High-theoretical-capacity silicon anodes hold promise in lithium-ion batteries (LIBs). Nevertheless, their huge volume expansion (∼300%) and poor conductivity show the need for the simultaneous introduction of low-density conductive carbon and nanosized Si to conquer the above issues, yet they result in low volumetric performance. Herein, we develop an integration strategy of a dually encapsulated Si structure and dense structural engineering to fabricate a three-dimensional (3D) highly dense Ti3C2Tx MXene and graphene dual-encapsulated Si monolith architecture (HD-Si@Ti3C2Tx@G). Because of its high density (1.6 g cm-3), high conductivity (151 S m-1), and 3D dense dual-encapsulated Si architecture, the resultant HD-Si@Ti3C2Tx@G monolith anode displays an ultrahigh volumetric capacity of 5206 mAh cm-3 (gravimetric capacity: 2892 mAh g-1) at 0.1 A g-1 and a superior long lifespan of 800 cycles at 1.0 A g-1. Notably, the thick and dense monolithic anode presents a large areal capacity of 17.9 mAh cm-2. In-situ TEM and ex-situ SEM techniques, and systematic kinetics and structural stability analysis during cycling demonstrate that such superior volumetric and areal performances stem from its dual-encapsulated Si architecture by the 3D conductive and elastic networks of MXene and graphene, which can provide fast electron and ion transfer, effective volume buffer, and good electrolyte permeability even with a thick electrode, whereas the dense structure results in a large volumetric performance. This work offers a simple and feasible strategy to greatly improve the volumetric and areal capacity of alloy-based anodes for large-scale applications via integrating a dual-encapsulated strategy and dense-structure engineering.

Oxygen Vacancy and Core-Shell Heterojunction Engineering of Anemone-Like CoP@CoOOH Bifunctional Electrocatalyst for Efficient Overall Water Splitting.

Constructing cost-efficient and robust bifunctional electrocatalysts for both neutral and alkaline water splitting is highly desired, but still affords a great challenge, due to sluggish hydrogen/oxygen evolution reaction (HER/OER) kinetics. Herein, an in situ integration engineering strategy of oxygen-vacancy and core-shell heterojunction to fabricate an anemone-like CoP@CoOOH core-shell heterojunction with rich oxygen-vacancies supported on carbon paper (CoP@CoOOH/CP), is described. Benefiting from the synergy of CoP core and oxygen-vacancy-rich CoOOH shell, the as-obtained CoP@CoOOH/CP catalyst displays low overpotentials at 10 mA cm-2 for HER (89.6 mV/81.7 mV) and OER (318 mV/200 mV) in neutral and alkaline media, respectively. Notably, a two-electrode electrolyzer, using CoP@CoOOH/CP as bifunctional catalyst to achieve 10 mA cm-2 , only needs low-cell voltages in neutral (1.65 V) and alkaline (1.52 V) electrolyte. Besides, systematically experimental and theoretical results reveal that the core-shell heterojunction efficiently accelerates the catalytic kinetics and strengthens the structural stability, while rich oxygen-vacancies efficiently decrease the kinetic barrier and activation energy, and reduce the energy barrier of the rate-determining-step for OER intermediates, thus intrinsically boosting OER performance. This work clearly demonstrates that oxygen-vacancy and core-shell heterojunction engineering provide an effective strategy to design highly-efficient non-precious, bi-functional electrocatalysts for pH-universal water splitting.

Honeycomb-like biomass carbon with planted CoNi3 alloys to form hierarchical composites for high-performance supercapacitors.

It is a significant challenge to combine a large pseudocapacitive material with conductive honeycomb-like carbon frameworks for long-term stable supercapacitors. Herein, hierarchical composite materials are manufactured by using biomass carbon, ZIF-67, and a mild pore former (Ni(CH3COO)2) to generate alloy-type CoNi3 nanoparticles planted into conductive honeycomb-like carbon frameworks (C@ZIF-67-T). Meanwhile, the effect of carbonization temperature on the honeycomb-like pore size and the structure of composite materials is systematically investigated. As the honeycomb-like carbon skeleton structure guarantees good ionic and electronic conductivities and a large contact area, whereas the alloy nanoparticles provide a rich redox reaction for Faradaic capacitance. Therefore, the as-obtained C@ZIF-67-600 electrode presents a remarkable specific capacitance of 1044.8 F · g-1 at 1.0 A · g-1 and an ultra-long cycling stability with 30,000 cycles at 5.0 A · g-1 in a three-electrode system. In addition, the assembled C@ZIF-67-600//activated carbon asymmetrical supercapacitor exhibit a high specific capacitance of 274.4F · g-1 at 1.0 A · g-1 and a long-term stable lifespan with a capacitance retention of 87% after 20,000 cycles at 5.0 A · g-1. Besides, the asymmetrical supercapacitor also presents a maximum energy density of 85.13 Wh · kg-1 at a power density of 750 W · kg-1. Such superior electrochemical performance demonstrate that the designed electrode material provides a promising energy storage application.

Ultrahigh-Volumetric-Energy-Density Lithium-Sulfur Batteries with Lean Electrolyte Enabled by Cobalt-Doped MoSe2/Ti3C2Tx MXene Bifunctional Catalyst.

It is a significant challenge to design a dense high-sulfur-loaded cathode and meanwhile to acquire fast sulfur redox kinetics and suppress the heavy shuttling in the lean electrolyte, thus to acquire a high volumetric energy density without sacrificing gravimetric performance for realistic Li-S batteries (LSBs). Herein, we develop a cation-doping strategy to tailor the electronic structure and catalytic activity of MoSe2 that in situ hybridized with conductive Ti3C2Tx MXene, thus obtaining a Co-MoSe2/MXene bifunctional catalyst as a high-efficient sulfur host. Combining a smart design of the dense sulfur structure, the as-fabricated highly dense S/Co-MoSe2/MXene monolith cathode (density: 1.88 g cm-3, conductivity: 230 S m-1) achieves a high reversible specific capacity of 1454 mAh g-1 and an ultrahigh volumetric energy density of 3659 Wh L-1 at a routine electrolyte and a high areal capacity of ∼8.0 mAh cm-2 under an extremely lean electrolyte of 3.5 µL mgs-1 at 0.1 C. Experimental and DFT theoretical results uncover that introducing Co element into the MoSe2 plane can form a shorter Co-Se bond, impel the Mo 3d band to approach the Fermi level, and provide strong interactions between polysulfides and Co-MoSe2, thereby enhancing its intrinsic electronic conductivity and catalytic activity for fast redox kinetics and uniform Li2S nucleation in a dense high-sulfur-loaded cathode. This deep work provides a good strategy for constructing high-volumetric-energy-density, high-areal-capacity LSBs with lean electrolytes.

Green, Template-Less Synthesis of Honeycomb-like Porous Micron-Sized Red Phosphorus for High-Performance Lithium Storage.

Large-volume-expansion-induced material pulverization severely limits the electrochemical performance of high-capacity red phosphorus (RP) in alkali-ion batteries. Honeycomb-like porous materials can effectively solve the issues due to their abundant interconnected pore structures. Nevertheless, it is difficult and greatly challenging to fabricate a honeycomb-like porous RP that has not yet been fabricated via chemical synthesis. Herein, we successfully fabricate a honeycomb-like porous micron-sized red phosphorus (HPRP) with a controlled pore structure via a large-scale green and template-less hydrothermal strategy. It is demonstrated that dissolved oxygen in the solution can accelerate the destruction of P9 cages of RP, thus forming abundant active defects with a faster reaction rate, so the fast corrosion forms the honeycomb-like porous structure. Owing to the free volume, interconnected porous structure, and strong robustness, the optimized HPRP-36 can mitigate drastic volume variation and prevent pulverization during cycling resulting in tiny particle-level outward expansion, demonstrated by in situ TEM and ex situ SEM analysis. Thus, the HPRP-36 anode delivers a large reversible capacity (2587.4 mAh g-1 at 0.05 A g-1) and long-cycling stability with over 500 cycles (∼81.9% capacity retention at 0.5 A g-1) in lithium-ion batteries. This generally scalable, green strategy and deep insights provide a good entry point in designing honeycomb-like porous micron-sized materials for high-performance electrochemical energy storage and conversion.

Targeted graphene oxide for drug delivery as a therapeutic nanoplatform against Parkinson's disease.

There has been an exponential increase in the rate of incidence of Parkinson's disease (PD) with aging in the global population. PD, the second most common neurodegenerative disorder, results from damaged dopamine neurons in the substantia nigra pars compacta (SNpc), along with the deposition of abnormal α-synuclein (α-Syn), and the progressive degeneration of neurons in striatal regions. Despite extensive investigations to understand the pathophysiology of PD to develop effective therapies to restrict its progression, there is currently no cure for PD. Puerarin (Pue) is a natural compound with remarkable anti-PD properties. However, its poor pharmacological properties, including poor water solubility, inadequate bioavailability, and incomplete penetration of the blood-brain barrier (BBB) have restricted its use for the treatment of PD. Nevertheless, advancements in nanotechnology have revealed the potential advantages of targeted drug delivery into the brain to treat PD. Here, we used Pue-loaded graphene oxide (GO) nanosheets, which have an excellent drug-loading ability, modifiable surface functional groups, and good biocompatibility. Then, Pue was transported across the BBB into the brain using lactoferrin (Lf) as the targeting ligand, which could bind to the vascular endothelial receptor on the BBB. In vivo and in vitro results indicated that this multifunctional brain targeted drug delivery system (Lf-GO-Pue) was an effective and safe therapy for PD.

Ultrahigh and Durable Volumetric Lithium/Sodium Storage Enabled by a Highly Dense Graphene-Encapsulated Nitrogen-Doped Carbon@Sn Compact Monolith.

Tin-based composites hold promise as anodes for high-capacity lithium/sodium-ion batteries (LIBs/SIBs); however, it is necessary to use carbon coated nanosized tin to solve the issues related to large volume changes during electrochemical cycling, thus leading to the low volumetric capacity for tin-based composites due to their low packing density. Herein, we design a highly dense graphene-encapsulated nitrogen-doped carbon@Sn (HD N-C@Sn/G) compact monolith with Sn nanoparticles double-encapsulated by N-C and graphene, which exhibits a high density of 2.6 g cm-3 and a high conductivity of 212 S m-1. The as-obtained HD N-C@Sn/G monolith anode exhibits ultrahigh and durable volumetric lithium/sodium storage. Specifically, it delivers a high volumetric capacity of 2692 mAh cm-3 after 100 cycles at 0.1 A g-1 and an ultralong cycling stability exceeding 1500 cycles at 1.0 A g-1 with only 0.019% capacity decay per cycle in lithium-ion batteries. Besides, in situ TEM and ex situ SEM have revealed that the unique double-encapsulated structure effectively mitigates drastic volume variation of the tin nanoparticles during electrode cycling. Furthermore, the full cell using HD N-C@Sn/G as an anode and LiCoO2 as a cathode displays a superior cycling stability. This work provides a new avenue and deep insight into the design of high-volumetric-capacity alloy-based anodes with ultralong cycle life.

Transparent and Self-Supporting Graphene Films with Wrinkled- Graphene-Wall-Assembled Opening Polyhedron Building Blocks for High Performance Flexible/Transparent Supercapacitors.

Improving mass loading while maintaining high transparency and large surface area in one self-supporting graphene film is still a challenge. Unfortunately, all of these factors are absolutely essential for enhancing the energy storage performance of transparent supercapacitors for practical applications. To solve the above bottleneck problem, we produce a novel self-supporting flexible and transparent graphene film (STF-GF) with wrinkled-wall-assembled opened-hollow polyhedron building units. Taking advantage of the microscopic morphology, the STF-GF exhibits improved mass loading with high transmittance (70.2% at 550 nm), a large surface area (1105.6 m2/g), and good electrochemical performance: high energy (552.3 µWh/cm3), power densities (561.9 mW/cm3), a superlong cycle life, and good cycling stability (the capacitance retention is ∼94.8% after 20,000 cycles).

Nitrogen-Doped Carbon-Encapsulated SnO2@Sn Nanoparticles Uniformly Grafted on Three-Dimensional Graphene-like Networks as Anode for High-Performance Lithium-Ion Batteries.

A peculiar nanostructure consisting of nitrogen-doped, carbon-encapsulated (N-C) SnO2@Sn nanoparticles grafted on three-dimensional (3D) graphene-like networks (designated as N-C@SnO2@Sn/3D-GNs) has been fabricated via a low-cost and scalable method, namely an in situ hydrolysis of Sn salts and immobilization of SnO2 nanoparticles on the surface of 3D-GNs, followed by an in situ polymerization of dopamine on the surface of the SnO2/3D-GNs, and finally a carbonization. In the composites, three-layer core-shell N-C@SnO2@Sn nanoparticles were uniformly grafted onto the surfaces of 3D-GNs, which promotes highly efficient insertion/extraction of Li(+). In addition, the outermost N-C layer with graphene-like structure of the N-C@SnO2@Sn nanoparticles can effectively buffer the large volume changes, enhance electronic conductivity, and prevent SnO2/Sn aggregation and pulverization during discharge/charge. The middle SnO2 layer can be changed into active Sn and nano-Li2O during discharge, as described by SnO2 + Li(+) → Sn + Li2O, whereas the thus-formed nano-Li2O can provide a facile environment for the alloying process and facilitate good cycling behavior, so as to further improve the cycling performance of the composite. The inner Sn layer with large theoretical capacity can guarantee high lithium storage in the composite. The 3D-GNs, with high electrical conductivity (1.50 × 10(3) S m(-1)), large surface area (1143 m(2) g(-1)), and high mechanical flexibility, tightly pin the core-shell structure of the N-C@SnO2@Sn nanoparticles and thus lead to remarkably enhanced electrical conductivity and structural integrity of the overall electrode. Consequently, this novel hybrid anode exhibits highly stable capacity of up to 901 mAh g(-1), with ∼89.3% capacity retention after 200 cycles at 0.1 A g(-1) and superior high rate performance, as well as a long lifetime of 500 cycles with 84.0% retention at 1.0 A g(-1). Importantly, this unique hybrid design is expected to be extended to other alloy-type anode materials such as silicon, germanium, etc.

Simultaneous formation of ultrahigh surface area and three-dimensional hierarchical porous graphene-like networks for fast and highly stable supercapacitors.

A new one-step ion-exchange/activation combination method using a metal-ion exchanged resin as a carbon precursor is used to prepare a ultrahigh surface area and three-dimensional hierarchical porous graphene-like networks for fast and highly stable supercapacitors.

Immobilization of enzymes at high load/activity by aqueous electrodeposition of enzyme-tethered chitosan for highly sensitive amperometric biosensing.

Electrodeposition has been so widely used to immobilize biomacromolecules, and it is always an important topic to increase the load and activity of the immobilized biomacromolecules. We report here on a new, simple and rather universal method for the highly efficient immobilization of enzymes by aqueous electrodeposition of enzyme-tethered chitosan (CS) for sensitive amperometric biosensing. Glucose oxidase (GOx) is chosen here to examine the proposed protocol in detail. GOx was crosslinked to CS with low-concentration glutaraldehyde (GA, 0.080 wt%), and the electroreduction of added H(2)O(2) increased the electrode-surface pH and triggered the electrodeposition of a GOx-GA-CS composite film. The GOx-GA-CS electrodeposition was monitored by an electrochemical quartz crystal microbalance and is theoretically discussed based on an electrogenerated base-to-acid titration model. The prepared first-generation enzyme electrode (CS-GA-GOx/Pt(nano)/Au) exhibits a current sensitivity as high as 102 microA mM(-1) cm(-2) at 0.70 V vs SCE, being 13 times that of the CS-GOx/Pt(nano)/Au prepared similarly but without the GOx-CS precrosslinking. UV-vis spectrophotometric determination of the GOx remains in the supernatant liquids after pH-induced CS precipitation suggested a high enzyme load in the GOx-GA-CS film, and amperometric measurements suggested a negligible decrease in the enzymatic activity of GOx after its reaction with the low-concentration GA. Also, the proposed protocol works well for the precrosslinking manner of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide/N-hydroxysulfosuccinimide activation, the water-electroreduction-triggered CS electrodeposition, the second-generation biosensing mode, a 5.0-microm-radius Pt ultramicroelectrode, and immobilization of alkaline phosphatase for phenyl phosphate biosensing. The proposed protocol of pretethering the target biomacromolecules to the electrodeposition precusor for immobilization of the biomacromolecule at high load/activity is recommended for wide applications.

Polymeric bionanocomposite cast thin films with in situ laccase-catalyzed polymerization of dopamine for biosensing and biofuel cell applications.

We report here on the facile preparation of polymer-enzyme-multiwalled carbon nanotubes (MWCNTs) cast films accompanying in situ laccase (Lac)-catalyzed polymerization for electrochemical biosensing and biofuel cell applications. Lac-catalyzed polymerization of dopamine (DA) as a new substrate was examined in detail by UV-vis spectroscopy, cyclic voltammetry, quartz crystal microbalance, and scanning electron microscopy. Casting the aqueous mixture of DA, Lac and MWCNTs on a glassy carbon electrode (GCE) yielded a robust polydopamine (PDA)-Lac-MWCNTs/GCE that can sense hydroquinone with 643 microA mM(-1) cm(-2) sensitivity and 20-nM detection limit (S/N = 3). The DA substrate yielded the best biosensing performance, as compared with aniline, o-phenylenediamine, or o-aminophenol as the substrate for similar Lac-catalyzed polymerization. Casting the aqueous mixture of DA, glucose oxidase (GOx), Lac, and MWCNTs on a Pt electrode yielded a robust PDA-GOx-Lac-MWCNTs/Pt electrode that exhibits glucose-detection sensitivity of 68.6 microA mM(-1) cm(-2). In addition, 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) was also coimmobilized to yield a PDA-Lac-MWCNTs-ABTS/GCE that can effectively catalyze the reduction of O(2), and it was successfully used as the biocathode of a membraneless glucose/O(2) biofuel cell (BFC) in pH 5.0 Britton-Robinson buffer. The proposed biomacromolecule-immobilization platform based on enzyme-catalyzed polymerization may be useful for preparing many other multifunctional polymeric bionanocomposites for wide applications.