Unraveling the Nano-Bio Interface Interactions of a Lipase Adsorbed on Gold Nanoparticles under Laser Excitation.

The complex nature and structure of biomolecules and nanoparticles and their interactions make it challenging to achieve a deeper understanding of the dynamics at the nano-bio interface of enzymes and plasmonic nanoparticles subjected to light excitation. In this study, circular dichroism (CD) and Raman spectroscopic experiments and molecular dynamics (MD) simulations were used to investigate the potential changes at the nano-bio interface upon plasmonic excitation. Our data showed that photothermal and thermal heating induced distinct changes in the secondary structure of a model nanobioconjugate composed of lipase fromCandida antarcticafraction B (CALB) and gold nanoparticles (AuNPs). The use of a green laser led to a substantial decrease in the α-helix content of the lipase from 66% to 13% and an increase in the ß-sheet content from 5% to 31% compared to the initial conformation of the nanobioconjugate. In contrast, the differences under similar thermal heating conditions were only 55% and 11%, respectively. This study revealed important differences related to the enzyme secondary structure, enzyme-nanoparticle interactions, and the stability of the enzyme catalytic triad (Ser105-Asp187-His224), influenced by the instantaneous local temperature increase generated from photothermal heating compared to the slower rate of thermal heating of the bulk. These results provide valuable insights into the interactions between biomolecules and plasmonic nanoparticles induced by photothermal heating, advancing plasmonic biocatalysis and related fields.

Superior Electrocatalysis Delivered by a Directional Electron Transfer Cascade in Hierarchical CoNi/Ru@C.

Exploiting directional electron transfer cascades could lead to high-performance electrocatalysts for processes such as the hydrogen evolution reaction, but realising such systems is difficult. Herein, a hierarchical confined material (CoNi/Ru@C) is presented, which provides a suitable spatial junction to enable directional electron transfer, giving superior hydrogen evolution in alkaline water/seawater.

Hierarchically fractal Co with highly exposed active facets and directed electron-transfer effect.

Hierarchically fractal Co with highly exposed active (002) facets, possessing a higher work function and more moderate hydrogen adsorption free energy, has been synthesized via a template-free self-assembly method for the directed electron-transfer design of HER catalysts. It shows a great improvement in the HER activity in comparison with that of nanostructured Co.

Mechanochemical Strategies for the Preparation of SiO2-Supported AgAu Nanoalloy Catalysts.

Silver-gold nanoalloys were prepared from their metal salts precursors through bottom-up mechanochemical synthesis, using one-pot or galvanic replacement reaction strategies. The nanostructures were prepared over amorphous SiO2 as an inert supporting material, facilitating their stabilization without the use of any stabilizing agent. The nanomaterials were extensively characterized, confirming the formation of the bimetallic nanostructures. The nanoalloys were tested as catalysts in the hydrogenation of 2-nitroaniline and exhibited up to 4-fold the rate constant and up to 37% increased conversion compared to the respective single metal nanoparticles. Our approach is advantageous to produce nanoparticles with clean surfaces with available catalytic sites, directly in the solid-state and in an environmentally friendly manner.

Stimuli-Responsive Regulation of Biocatalysis through Metallic Nanoparticle Interaction.

The remote control of biocatalytic processes in an extracellular medium is an exciting idea to deliver innovative solutions in the biocatalysis field. With this purpose, metallic nanoparticles (NPs) are great candidates, as their inherent thermal, electric, magnetic, and plasmonic properties can readily be manipulated upon external stimuli. Exploring the unique NP properties beyond an anchoring platform for enzymes brings up the opportunity to extend the efficiency of biocatalysts and modulate their activity through triggered events. In this review, we discuss a set of external stimuli, such as light, electricity, magnetism, and temperature, as tools for the regulation of nanobiocatalysis, including the challenges and perspectives regarding their use. In addition, we elaborate on the use of combined stimuli that create a more refined framework in terms of a multiresponsive system. Finally, we envision this review might instigate researchers in this field of study with a set of promising opportunities in the near future.

Electrical Stimulation and Conductive Polymers as a Powerful Toolbox for Tailoring Cell Behaviour in vitro.

Electrical stimulation (ES) is a well-known method for guiding the behaviour of nerve cells in in vitro systems based on the response of these cells to an electric field. From this perspective, understanding how the electrochemical stimulus can be tuned for the design of a desired cell response is of great importance. Most biomedical studies propose the application of an electrical potential to cell culture arrays while examining the cell response regarding viability, morphology, and gene expression. Conversely, various studies failed to evaluate how the fine physicochemical properties of the materials used for cell culture influence the observed behaviours. Among the various materials used for culturing cells under ES, conductive polymers (CPs) are widely used either in pristine form or in addition to other polymers. CPs themselves do not possess the optimal surface for cell compatibility because of their hydrophobic nature, which leads to poor protein adhesion and, hence, poor bioactivity. Therefore, understanding how to tailor the chemical properties on the material surface will determine the obtention of improved ES platforms. Moreover, the structure of the material, either in a thin film or in porous electrospun scaffolds, also affects the biochemical response and needs to be considered. In this review, we examine how materials based on CPs influence cell behaviour under ES, and we compile the various ES setups and physicochemical properties that affect cell behaviour. This review concerns the culture of various cell types, such as neurons, fibroblasts, osteoblasts, and Schwann cells, and it also covers studies on stem cells prone to ES. To understand the mechanistic behaviour of these devices, we also examine studies presenting a more detailed biomolecular level of interaction. This review aims to guide the design of future ES setups regarding the influence of material properties and electrochemical conditions on the behaviour of in vitro cell studies.

Porous Graphene Oxide Films Prepared via the Breath-Figure Method: A Simple Strategy for Switching Access of Redox Species to an Electrode Surface.

Porous materials can be modified with physical barriers to control the transport of ions and molecules through channels via an external stimulus. Such capability has brought attention toward drug delivery, separation methods, nanofluidics, and point-of-care devices. In this context, gated platforms on which access to an electrode surface of species in solution can be reversibly hindered/unhindered on demand are appearing as promising materials for sensing and microfluidic switches. The preparation of a reversible gated device usually requires mesoporous materials, nanopores, or molecularly imprinted polymers. Here, we show how the breath-figure method assembly of graphene oxide can be used as a simple strategy to produce gated electrochemical materials. This was achieved by forming an organized porous thin film of graphene oxide onto an ITO surface. Localized brushes of thermoresponsive poly(N-isopropylacrylamide) were then grown to specific sites of the porous film by in situ reversible addition-fragmentation chain-transfer polymerization. The gating mechanism relies on the polymeric chains to expand and contract depending on the thermal stimulus, thus modulating the accessibility of redox species inside the pores. The resulting platform was shown to reversibly hinder or facilitate the electron transfer of solution redox species by modulating temperature from the room value to 45 °C or vice versa.

High-resolution light-activated electrochemistry on amorphous silicon-based photoelectrodes.

Light-activated electrochemistry (LAE) consists of employing a focused light beam to illuminate a semiconducting area and make it electrochemically active. Here, we show how to reduce the electrochemical spatial resolution to submicron by exploiting the short lateral diffusion of charge carriers in amorphous silicon to improve the resolution of LAE by 60 times.

Spatially localized electrodeposition of multiple metals via light-activated electrochemistry for surface enhanced Raman spectroscopy applications.

Light can be used to address electrochemical reactions on a monolithic semiconducting electrode with spatial and temporal resolution. Herein, such principle was used for the electrodeposition of Au, Ag and Cu nanoparticles on a unique silicon-based electrode. The parallel nature of the process granted manufacturing speed and platforms were applied to discriminate molecules via multi-wavelength and multivariate Raman analysis.

Electrochemical quartz crystal microbalance with dissipation investigation of fibronectin adsorption dynamics driven by electrical stimulation onto a conducting and partially biodegradable copolymer.

Functional surface coatings are a key option for biomedical applications, from polymeric supports for tissue engineering to smart matrices for controlled drug delivery. Therefore, the synthesis of new materials for biological applications and developments is promising. Hence, biocompatible and stimuli-responsive polymers are interesting materials, especially when they present conductive properties. PEDOT-co-PDLLA graft copolymer exhibits physicochemical and mechanical characteristics required for biomedical purposes, associated with electroactive, biocompatible, and partially biodegradable properties. Herein, the study of fibronectin (FN) adsorption onto PEDOT-co-PDLLA carried out by an electrochemical quartz crystal microbalance with dissipation is reported. The amount of FN adsorbed onto PEDOT-co-PDLLA was higher than that adsorbed onto the Au surface, with a significant increase when electrical stimulation was applied (either at +0.5 or -0.125 V). Additionally, FN binds to the copolymer interface in an unfolded conformation, which can promote better NIH-3T3 fibroblast cell adhesion and later cell development.

The effect of nanoscale surface electrical properties of partially biodegradable PEDOT-co-PDLLA conducting polymers on protein adhesion investigated by atomic force microscopy.

This study used atomic force microscopy (AFM) to elucidate the interaction of fibronectin (FN) on a conducting and partially biodegradable copolymer of poly(3,4-ethylenedioxythiophene) and poly(d,l-lactic acid) (PEDOT-co-PDLLA) in three different proportions (1:05, 1:25 and 1:50). The copolymers with higher PEDOT:PDLLA content ratios (1:05 and 1:25) had higher surface roughness, water contact angle, with current and conductivity occurring at discrete large grain structures on the surface. In contrast, the lower PEDOT:PDLLA content ratio (1:50) did not show high conductivity grains but showed homogenous surface conductivity across the entire surface. Using FN-functionalized AFM probes, force measurements showed that the copolymers with higher PEDOT content (1:05 and 1:25) had significantly lower adhesion forces (~0.2-0.3 nN), while the copolymer with the lower content of PEDOT (1:50) had stronger FN interactions with significantly higher adhesion forces of 1 nN. By correlating the spatially distributed electrical surfaces with FN interactions, we observed that the synthesis of 1:50 PEDOT:PDLLA produced more uniformly doped polymer films that facilitated FN adsorption through favorable interactions with accessible sulfate dopants. Importantly, these findings are correlated with previous studies showing increased stem cell migration and differentiation on 1:50 PEDOT:PDLLA surfaces compared with surfaces with 1:05 and 1:25 PEDOT:PDLLA ratios.

Novel Conducting and Biodegradable Copolymers with Noncytotoxic Properties toward Embryonic Stem Cells.

Electroactive biomaterials that are easily processed as scaffolds with good biocompatibility for tissue regeneration are difficult to design. Herein, the synthesis and characterization of a variety of novel electroactive, biodegradable biomaterials based on poly(3,4-ethylenedioxythiphene) copolymerized with poly(d,l lactic acid) (PEDOT-co-PDLLA) are presented. These copolymers were obtained using (2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol (EDOT-OH) as an initiator in a lactide ring-opening polymerization reaction, resulting in EDOT-PDLLA macromonomer. Conducting PEDOT-co-PDLLA copolymers (in three different proportions) were achieved by chemical copolymerization with 3,4-ethylenedioxythiophene (EDOT) monomers and persulfate oxidant. The PEDOT-co-PDLLA copolymers were structurally characterized by 1H NMR and Fourier transform infrared spectroscopy. Cyclic voltammetry confirmed the electroactive character of the materials, and conductivity measurements were performed via electrochemical impedance spectroscopy. In vitro biodegradability was evaluated using proteinase K over 35 days, showing 29-46% (w/w) biodegradation. Noncytotoxicity was assessed by adhesion, migration, and proliferation assays using embryonic stem cells (E14.tg2a); excellent neuronal differentiation was observed. These novel electroactive and biodegradable PEDOT-co-PDLLA copolymers present surface chemistry and charge density properties that make them potentially useful as scaffold materials in different fields of applications, especially for neuronal tissue engineering.

Kinetics, Assembling, and Conformation Control of L-Cysteine Adsorption on Pt Investigated by in situ FTIR Spectroscopy and QCM-D.

A quartz crystal microbalance method with dissipation (QCM-D) and attenuated total reflection Fourier-transform infrared (ATR-FTIRS) spectroscopy were used to study the adsorption of L-cysteine (L-Cys) on Pt. Through QCM-D, it was possible to verify that the viscoelastic properties of the adsorbed species play an important role in the adsorption, rendering Sauerbrey's equation inapplicable. The modelling of QCM-D data exposed two different processes for the adsorption reaction. The first one had an activation time and is fast, whereas the second is slow. These processes were also resolved by ATR-FTIRS and identified to be water and anion adsorption preceded by L-Cys adsorption. Both techniques reveal that the degree of surface coverage is pH dependent. Spectroscopic data indicate that the conformation of L-Cys(ads) changes with pH and that the structures do not fully agree with those proposed in literature for other metallic surfaces. The assembling of the adsorbed monolayer appeared to be very fast, and it was not possible to determine or quantify this kinetics. The conformation is also controlled by applied potential, and the anion adsorption and interfacial water depends on the conformation of the adsorbed molecules.

One pot biocatalytic synthesis of a biodegradable electroactive macromonomer based on 3,4-ethylenedioxytiophene and poly(l-lactic acid).

A novel electroactive macromonomer based on poly(l-lactic acid) (PLLA) with (3,4-ethylenedioxythiophene) (EDOT) functional end groups, was prepared by a traditional approach of organometallic polymerization with stannous octanoate [Sn(oct2)] and enzymatic polymerization using immobilized Candida antarctica Lipase B (CAL-B) and Amano lipase Pseudomonas cepacia(PS-IM), as catalysts. In the synthetic strategy, (2,3-dihydrothieno[3,4-b] dioxin-2-yl)methanol (EDOT-OH) was used to initiate the ring opening polymerization of lactide to yield PLLA with EDOT end group. All macromonomers (EDOT-PLLA) were characterized by 1H and 13C RMN, MALDI-TOF, GPC and EDX. Moreover, ICP-OES analysis showed the presence of Sn traces in the material synthesized by the traditional approach, but that pathway led to macromonomers with higher molecular weight while the enzymatic route led to completely metal-free macromonomers with medium and lower molecular weights. Also, electrochemical and chemical polymerization of EDOT-PLLA were tested showing that it is possible to prepare degradable conducting polymers based on poly(3,4-ethylenedioxythiphene) (PEDOT). The biocatalytic synthesis is a very promising and environmental friendly pathway for the preparation of biodegradable materials for short time applications.

Electrochromic properties of a metallo-supramolecular polymer derived from tetra(2-pyridyl-1,4-pyrazine) ligands integrated in thin multilayer films.

The electrochromic behavior of iron complexes derived from tetra-2-pyridyl-1,4-pyrazine (TPPZ) and a hexacyanoferrate species in polyelectrolytic multilayer adsorbed films is described for the first time. This complex macromolecule was deposited onto indium-tin oxide (ITO) substrates via self-assembly, and the morphology of the modified electrodes was studied using atomic force microscopy (AFM), which indicated that the hybrid film containing the polyelectrolyte multilayer and the iron complex was highly homogeneous and was approximately 50 nm thick. The modified electrodes exhibited excellent electrochromic behavior with both intense and persistent coloration as well as a chromatic contrast of approximately 70%. In addition, this system achieved high electrochromic efficiency (over 70 cm(2) C(-1) at 630 nm) and a response time that could be measured in milliseconds. The electrode was cycled more than 10(3) times, indicating excellent stability.

Synthesis and characterization of stable Co and Cd doped nickel hydroxide nanoparticles for electrochemical applications.

The present paper describes the physical-chemical characterization and electrochemical behavior of a new nanomaterial formed by the addition of cadmium and cobalt atoms into the structure of nickel hydroxide nanoparticles, these ones synthesized by an easy sonochemical method. Particles of about 5 nm diameter were obtained and characterized by high resolution transmission electron microscopy (HRTEM), X-ray diffraction and Raman spectroscopy. Different nickel hydroxide nanoparticles were immobilized onto transparent conducting substrates by using electrostatic layer-by-layer providing thin films at the nanoscale and the electrochemical behavior was investigated. The formation of a mixed hydroxide was corroborated by observation of very interesting properties as redox potential shifting to less positive potentials and high stability when submitted to long electrochemical cycling or high times of ultrasonic synthesis, suggesting practical applications.

On the stabilization of conducting pernigraniline salt by the synthesis and oxidation of polyaniline in hydrophobic ionic liquids.

The electrochemical polymerization of aniline in a hydrophobic room-temperature ionic liquid and the spectroelectrochemical characterization of the formed film are presented. The polymerization occurs without the presence of acid in 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide (BMMITFSI), leading to a very stable electroactive material where no degradation was observed even at high applied potentials. Both in situ UV-Vis and Raman spectroscopic studies provided evidence for the stabilization of pernigraniline salt at high oxidation potentials and that this polyaniline state is the conducting form, as was corroborated by in situ resistance measurements. These data are indicative that low conductivity is not an intrinsic property of pernigraniline salt and this point must be reconsidered.

Mixed Ni/Co hydroxide nanoparticles synthesized by sonochemical method.

Nickel hydroxide nanoparticles with different amounts of cobalt atoms in the structure forming a unique material, were synthesized by using ultrasonic radiation. The particles of 5 nm diameter were prepared and characterized by X-Ray diffraction, Raman and Infrared spectroscopies, and thermogravimetry. The incorporation of cobalt leads to distinct crystalline planes, showing an opened and disarranged structure, indicating the stabilization of the alpha-Ni(OH)2 phase.

Design of molecular wires based on supramolecular structures for application in glucose biosensors.

In the present work, the synthesis and the spectroelectrochemical characterization of a novel iron compound derived of tetra-2-pyridyl-1,4-pyrazine (TPPZ) with hexacyanoferrate species forming a very stable supramolecular complex in the presence of polypyrrole (PPY) matrix, is described. The hybrid material has shown excellent catalytic activity towards H(2)O(2) detection that makes it suitable for being used as redox mediator in a glucose biosensor. The hybrid FeTPPZFeCN/PPY film presents satisfactory detection limits and high sensitivity for H(2)O(2) in the presence of K(+) or Na(+) ions. For the glucose biosensor, a linear range up to 1.1 mmoll(-1) of glucose was observed with no interferences. In this case, the sensitivities obtained were 7.88 and 5.90 microAmmol(-1)lcm(-2) in phosphate buffer or NaCl solutions, respectively. The good sensitivity is related to the presence of a high-dimensional structure based on polypyridine type ligands providing an "electron antennae effect" facilitating electron tunneling between the protein and the electrode.

Polypyrrole/copper hexacyanoferrate hybrid as redox mediator for glucose biosensors.

A copper containing Prussian Blue analogue was incorporated into a conducting polypyrrole film. The modified electrode was synthesized through an electrochemical two-step methodology leading to very stable and homogeneous hybrid films. These electrodes were proved to show excellent catalytic properties towards H(2)O(2) detection, with a performance higher than those observed for Prussian Blue and other analogues. Electrochemical impedance spectroscopy experiments demonstrated that the excellent performance of these hybrid films is strongly related to the electronic conductivity of the polymeric matrix that is wiring the copper hexacyanoferrate sites. A glucose biosensor was built-up by the immobilization of glucose oxidase; the sensitivity obtained being higher than other biosensors reported in the literature even in Na(+) containing electrolytes.