Layer by layer deposition of zirconium oxide onto silicon

Zirconium oxide films have been produced by sequential adsorption of diluted zirconium alkoxide solutions onto a silicon wafer. After 100 deposition cycles, the film thickness increases quasi linearly with the alkoxide concentration. However, the film density decreases. Analysis of these results demonstrates that the amount of zirconium grafted at each cycle follows a Freundlich-type adsorption law, characterizing a disordered adsorption with condensation between adsorbates. Although an average monolayer can be adsorbed at each cycle, it is not dense. The resulting films are highly homogeneous and remain amorphous up to 600 °C. Despite of the low film density, the static dielectric constant measured at 1 kHz in capacitance-voltage geometry is around 15 for the films heat-treated at 300 °C in air as compared to 22 for the bulk ZrO₂.     

Layer by layer deposition of hydroxyapatite onto the collagen matrix

Layer by layer (LbL) deposition is a useful method for deposition of many inorganic (including metals, oxides and phosphates) and organic (including polymers and proteins) components on a large range of substrates. The LbL deposition of hydroxyapatite (HA) onto a collagen matrix involves HA synthesis on the collagen matrix starting from electrically charged precursors such as Ca²⁺ and PO₄³⁻ at a proper pH to precipitate the desired calcium phosphate.The LbL deposition process was continuously monitored in order to study the amount of HA deposited in each layer. The deposition of the first layers of HA was concluded to be highly influenced by the collagen matrix. When the collagen matrix is crosslinked with glutaraldehyde, the matrix structure is not modified during the deposition, and the porosity will decrease with the number of layers until saturation is reached. Following pore saturation, HA will be only deposited onto the mineralized collagen matrix surface. The obtained composite materials were characterized by XRD, SEM, DTA-TG and FTIR.     

Amperometric glucose microelectrodes prepared through immobilization of glucose oxidase in redox hydrogels.

Glucose microelectrodes have been formed with glucose oxidase immobilized in poly[(vinylpyridine)Os(bipyridine)2Cl] derivative-based redox hydrogels on beveled carbon-fiber microdisk (7 microns diameter) electrodes. In the resulting microelectrode, the steady-state glucose electrooxidation current density is 0.3 mA cm-2 and the sensitivity is 20 mA cm-2 M-1. The current density and sensitivity are 10 times higher than in macroelectrodes made with the same hydrogel. Furthermore, the current is less affected by a change in the partial pressure of oxygen. The higher current density and lower oxygen sensitivity point to the efficient collection of electrons through their diffusion in the redox hydrogel to the electrode surface. These results contrast with those observed for enzyme electrodes based on diffusing mediators, where loss of the enzyme-reduced mediator by radial diffusion to the solution decreases the current densities of microelectrodes relative to similar macroelectrodes.     

Molecular dynamics study of dipalmitoylphosphatidylcholine lipid layer self-assembly onto a single-walled carbon nanotube

Single-walled carbon nanotubes (SWNTs) are possible nano-injectors and delivery vehicles of molecular probes and drugs into cells. In order to explore the interaction between lipid membranes and carbon nanotubes, we investigate the binding mechanism of dipalmitoylphosphatidylcholine (DPPC) with SWNTs by molecular dynamics. In low concentration range simulations, the DPPC molecules form a supramolecular two-layered cylindrical structure wrapped around the carbon nanotube surface. The hydrophobic part of DPPC is adsorbed on the surface of the nanotube, and the hydrophilic top is oriented towards the aqueous phase. For higher concentration ranges, the DPPC molecules are found to form a supramolecular multi-layered structure wrapped around the carbon nanotube surface. At the saturation point a membrane-like structure is self-assembled with a width of 41.4 Å, which is slightly larger than the width of a cell membrane. Our study sheds light on the existing conflicting simulation data on adsorption of single-chained phospholipids.      

壳聚糖凝胶材料固定葡萄糖氧化酶制电极的研究

以壳聚糖为载体研究凝胶法固定葡萄糖氧化酶制电极。试验研究了载体壳聚糖的降解性；交联剂戊二醛的浓度、用量；电极的载酶量等固定化条件对所组建的传感器性能的影响。通过影响规律的分析、优化固定化条件的研究，找出了根据壳聚糖溶液粘度适当调整交联剂成二醛的用量和铂丝在酶膜母液中浸涂时间，克服壳聚糖的降解性对酶电极性能的影响，建立了制备性能相近的GOD传感器的方法。     

Layer-by-layer self-assembly of glucose oxidase and Os(Bpy)2CIPyCH2NH-poly(allylamine) bioelectrode

The uptake of glucose oxidase (GOx) onto a polycationic redox polymer (PAA-Os)-modified surface, by adsorption from dilute aqueous GOx solutions, was followed by the quartz crystal microbalance (QCM) and shows double exponential kinetics. The electrochemistry of the layer-by-layer-deposited redox-active polymer was followed by cyclic voltammetry in glucose-free solutions, and the enzyme catalysis mediated by the redox polymer was studied in beta-D-glucose-containing solutions. AFM studies of the different layers showed the existence of large two dimension enzyme aggregates on the osmium polymer for 1 microM GOx and less aggregation for 50 nM GOx solutions. When the short alkanethiol, 2,2'-diaminoethyldisulfide was preadsorbed onto gold, a monoexponential adsorption law was observed, and single GOx enzyme molecules could be seen on the surface where the enzyme was adsorbed from 50 nM GOx in water.     

DNA as a support for glucose oxidase immobilization at Prussian blue-modified glassy carbon electrode in biosensor preparation

An amperometric glucose biosensor has been developed using DNA as a matrix of Glucose oxidase (GOx) at Prussian-blue (PB)-modified glassy carbon (GC) electrode. GC electrode was chemically modified by the PB. GOx was immobilized together with DNA at the working area of the PB-modified electrode by placing a drop of the mixture of DNA and GOx. The response of the biosensor for glucose was evaluated amperometrically. Upon immobilization of glucose oxidase with DNA, the biosensor showed rapid response toward the glucose. On the other hand, no significant response was obtained in the absence of DNA. Experimental conditions influencing the biosensor performance were optimized and assessed. This biosensor offered an excellent electrochemical response for glucose concentration in micro mol level with high sensitivity and selectivity and short response time. The levels of the relative standard deviation (RSDs), (<4%) for the entire analyses reflected a highly reproducible sensor performance. Through the use of optimized conditions, a linear relationship between current and glucose concentration was obtained up to 4 x 10(-4) M. In addition, this biosensor showed high reproducibility and stability.     

Electrodeposition of chitosan-glucose oxidase biocomposite onto Pt-Pb nanoparticles modified stainless steel needle electrode for amperometric glucose biosensor

A glucose biosensor was fabricated by electrodepositing chitosan (CS)-glucose oxidase(GOD) biocomposite onto the stainless steel needle electrode (SSN electrode) modified by Pt–Pb nanoparticles (Pt–Pb/SSN electrode). Firstly, Pt–Pb nanoparticles were deposited onto the SSN electrode and then CS-GOD biocomposite was co-electrodeposited onto the Pt–Pb/SSN electrode in a mixed solution containing p-benzoquinone (p-BQ), CS and GOD. The electrochemical results showed that the Pt–Pb nanoparticles can accelerate the electron transfer and improve the effective surface area of the SSN electrode. As a result, the detection range of the proposed biosensor was from 0.03 to 9 mM with a current sensitivity of 0.4485 μA/mM and a response time of 15 s. The Michaelis constant value was calculated to be 4.9837 mM. The cell test results indicated that the electrodes have a low cytotoxicity. This work provided a suitable technology for the fabrication of the needle-type glucose biosensor.     

Amperometric glucose sensor based on enhanced catalytic reduction of oxygen using glucose oxidase adsorbed onto core-shell Fe3O4@silica@Au magnetic nanoparticles

Monodisperse Fe₃O₄ magnetic nanoparticles (NPs) were prepared under facile solvothermal conditions and successively functionalized with silica and Au to form core/shell Fe₃O₄@silica@Au NPs. Furthermore, the samples were used as matrix to construct a glucose sensor based on glucose oxidase (GOD). The immobilized GOD retained its bioactivity with high protein load of 3.92 × 10^? 9 mol·cm^? 2, and exhibited a surface-controlled quasi-reversible redox reaction, with a fast heterogeneous electron transfer rate of 7.98 ± 0.6 s^? 1. The glucose biosensor showed a broad linear range up to 3.97 mM with high sensitivity of 62.45 μA·mM^? 1 cm^? 2 and fast response (less than 5 s).     

Electrochemical behavior of polyphenol oxidase immobilized in self-assembled structures layer by layer with cationic polyallylamine

We report here a novel bioelectrode based on self-assembled multilayers of polyphenol oxidase intercalated with cationic polyallylamine built up on a thiol-modified gold surface. We use an immobilization strategy previously described by Hodak J. et al. (Langmuir 1997, 13, 2708-2716) Quartz crystal microbalance with electroacustic impedance experiments were carried out to follow quantitatively the multilayer film formation. The response of the self-assembly polyphenol oxidase-polyallylamine electrodes toward different metabolically related catecholamines was studied, to evaluate enzyme kinetics. For the analyzed compounds, only dopamine and its metabolite Dopac gave catalytic currents at applied potential close to 0 V. These responses were proportional to the number of polyphenol oxidase-immobilized layers and were also controlled by the enzymatic reaction. The combination of microgravimetric and electrochemical techniques allowed us to determine the kinetic enzymatic constants, showing that the decomposition rate for the enzyme-substrate complex is slower than the enzymatic reoxidation step.     

Applications of polymers for biomolecule immobilization in electrochemical biosensors

Polymers are becoming inseparable from biomolecule immobilization strategies and biosensor platforms. Their original role as electrical insulators has been progressively substituted by their electrical conductive abilities, which opens a new and broad scope of applications. In addition, recent advances in diagnostic chips and microfluidic systems, together with the requirements of mass-production technologies, have raised the need to replace glass by polymeric materials, which are more suitable for production through simple manufacturing processes. Conducting polymers (CPs), in particular, are especially amenable for electrochemical biosensor development for providing biomolecule immobilization and for rapid electron transfer. It is expected that the combination of known polymer substrates, but also new transducing and biocompatible interfaces, with nanobiotechnological structures, like nanoparticles, carbon nanotubes (CNTs) and nanoengineered ‘smart’ polymers, may generate composites with new and interesting properties, providing higher sensitivity and stability of the immobilized molecules, thus constituting the basis for new and improved analytical devices for biomedical and other applications. This review covers the state-of-the-art and main novelties about the use of polymers for immobilization of biomolecules in electrochemical biosensor platforms.     

Covalent immobilization of DNA onto functionalized mica for atomic force microscopy

The immobilization of DNA on the self-assembled monolayer of 3-aminopropyltrimethoxysilane (APTES) on mica wafer functionalized with glutaraldehyde (GA) by chemical bonding was studied by atomic force microscopy (AFM). The DNA used for our investigation was amplified by polymerase chain reaction, and primers were labeled with a -NH2 group at their 5' terminus. The surfaces were analyzed by X-ray photoelectron spectroscopy (XPS) and AFM. Results from XPS and AFM showed that the mica with the APTES and activated with GA can be formed, and the flatness of the mica can be adapted for AFM images. We found that the modified surface was capable of binding DNA molecules so that it withstood a thorough rinsing with a solution of sodium dodecylsulfate. Covalent binding between the aldehyde-terminated membrane and -NH2 groups at both ends of double-stranded DNA resulted in immobilization and straightening of the DNA.     

Effect of linoleic-acid modified carboxymethyl chitosan on bromelain immobilization onto self-assembled nanoparticles

Hydrogel nanoparticles could be prepared by using linoleic acid (LA) modified carboxymethyl chitosan (CMCS) after sonication. Bromelain could be loaded onto nanoparticles of LA-CMCS. Factors affecting the activity of the immobilized enzyme, including temperature, storage etc., were investigated in this study. The results showed that the stability of bromelain for heat and storage was improved after immobilization on nanoparticles. The Michaelis constant (K _m) of the immobilized enzyme was smaller than that of free enzyme, indicating that the immobilization could promote the stability of the enzyme and strengthen the affinity of the enzyme for the substrate.     

Effect of linoleic-acid modified carboxymethyl chitosan on bromelain immobilization onto self-assembled nanoparticles

Hydrogel nanoparticles could be prepared by using linoleic acid (LA) modified carboxymethyl chitosan (CMCS) after sonication. Bromelain could be loaded onto nanoparticles of LA-CMCS. Factors affecting the activity of the immobil     

Grafting of buckminsterfullerene onto polythiophene: novel intramolecular donor-acceptor polymers

Conjugated polymer-fullerene composites have shown efficient photoinduced charge transfer. The attachment of a fullerene moiety to the conducting polymer backbone is expected to lead to materials with more intimate association of the donor/acceptor sites. Two approaches to the attachment of fullerenes onto polythiophene derivatives have been explored. In the first case, fullerene has been bonded to a bithiophene derivative which can be electropolymerized. In the second, solvent processable polythiophene copolymers were prepared and functionalized with fullerene. Both these systems exhibit electrochemical and optoelectrochemical properties for fullerene and the conducting polymer.     

Rapid pattern transfer of biomimetic surface structures onto thermoplastic polymers

Biomimetic surface structures have profound influences on the development of many emerging devices and systems. In this study, a sequential approach involving sputtering, electroforming and embossing for transferring biological surface structures to thermoplastic polymers were investigated and developed. The surface structure on dung beetles (Phanaeus vindex) was used as a case study. A nickel pattern was fabricated by directly sputtering and electroforming the biological surface of the beetle. The resulting nickel structure was used as an embossing master for rapid feature transfer onto ABS substrates. The replicated surface patterns on the polymer were found to be comparable with those on the dung beetle. Contact angle measurements showed that the originally hydrophilic surface is rendered hydrophobic with the addition of the biomimetic topography.     

Study of bi-enzyme immobilization onto layered double hydroxides nanomaterials for histamine biosensor application

In this work, we present the development of a hybrid biomembrane based on the immobilization of diamine oxidase (DAO) into LDH thin films for histamine detection. The LDHs preselected as host matrixes are: hydrotalcites (Mg2Al(CO3)0.5(OH)6), lowaite (Mg4Fe(OH)10Cl) and hydrocalumite (Ca2Al(OH)6Cl). The immobilized probes were characterized by atomic force microscopy (AFM) and attenuated total reflection infrared spectroscopy (IR-ATR mode). The analysis of these results shows that the immobilization of DAO occurs with all type of selected LDH and is stable after a 7 day-immersion in phosphate buffer solution. The LDH incorporating magnesium or calcium divalent cations present high-quality surface topology for DAO immobilization and the ability to keep the enzyme in a well conformation for biogenic amines catabolism and histamine detection.