Gold nanoparticles modified electrodes for biosensors

Biomolecules are chemical compounds found in living organisms which are the building blocks of life and perform important functions. Fluctuation from the normal concentration of these biomolecules in living system leads to several disorders. Thus the exact determination of them in human fluids is essential in the clinical point of view. High performance liquid chromatography, flow injection analysis, capillary electrophoresis, fluorimetry, spectrophotometry, electrochemical and chemiluminescence techniques were usually used for the determination of biologically important molecules. Among these techniques, electrochemical determination of biomolecules has several advantages over other methods viz., simplicity, selectivity and sensitivity. In the past two decades, electrodes modified with polymer films, self-assembled monolayers containing different functional groups and carbon paste have been used as electrochemical sensors. But in recent years, nanomaterials based electrochemical sensors play an important role in the improvement of public health because of its rapid detection, high sensitivity and specificity in clinical diagnostics. To date gold nanoparticles (AuNPs) have received arousing attention mainly due to their fascinating electronic and optical properties as a consequence of their reduced dimensions. These unique properties of AuNPs make them as an ideal candidate for the immobilization of enzymes for biosensing. Further, the electrochemical properties of AuNPs reveal that they exhibit interesting properties by enhancing the electrode conductivity, facilitating electron transfer and improving the detection limit of biomolecules. In this chapter, we summarized the different strategies used for the attachment of AuNPs on electrode surfaces and highlighted the electrochemical determination of glucose, ascorbic acid (AA), uric acid (UA) and dopamine derivatives using the AuNPs modified electrodes.

Electrocatalytic oxidation of ascorbic acid using a single layer of gold nanoparticles immobilized on 1,6-hexanedithiol modified gold electrode

This paper describes the electrocatalytic oxidation of ascorbic acid (AA) in phosphate buffer solution by the immobilized citrate capped gold nanoparticles (AuNPs) on 1,6-hexanedithiol (HDT) modified Au electrode. X-ray photoelectron spectrum (XPS) of HDT suggests that it forms a monolayer on Au surface through one of the two single bondSH groups and the other single bondSH group is pointing away from the electrode surface. The free single bondSH groups of HDT were used to covalently attach colloidal AuNPs. The covalent attachment of AuNPs on HDT monolayer was confirmed from the observed characteristic carboxylate ion stretching modes of citrate attached with AuNPs in the infra-red reflection absorption spectrum (IRRAS) in addition to a higher reductive desorption charges obtained for AuNPs immobilized on HDT modified Au (Au/HDT/AuNPs) electrode in 0.1 M KOH when compared to HDT modified Au (Au/HDT) electrode. The electron transfer reaction of [Fe(CN)6]4−/3− was markedly hindered at the HDT modified Au (Au/HDT) electrode while it was restored with a peak separation of 74 mV after the immobilization of AuNPs on Au/HDT (Au/HDT/AuNPs) electrode indicating a good electronic communication between the immobilized AuNPs and the underlying bulk Au electrode through a HDT monolayer. The Cottrell slope obtained from the potential-step chronoamperometric measurements for the reduction of ferricyanide at Au/HDT/AuNPs was higher than that of bare Au electrode indicating the increased effective surface area of AuNPs modified electrode. The Au/HDT/AuNPs electrode exhibits excellent electrocatalytic activity towards the oxidation of ascorbic acid (AA) by enhancing the oxidation peak current to more than two times with a 210 mV negative shift in the oxidation potential when compared to a bare Au electrode. The standard heterogeneous electron transfer rate constant (ks) calculated for AA oxidation at Au/HDT/AuNPs electrode was 5.4 × 10−3 cm s−1. The oxidation peak of AA at Au/HDT/AuNPs electrode was highly stable upon repeated potential cycling. Linear calibration plot was obtained for AA over the concentration range of 1–110 μM with a correlation coefficient of 0.9950. The detection limit of AA was found to be 1 μM. The common physiological interferents such as glucose, oxalate ions and urea do not show any interference within the detection limit of AA. The selectivity of the AuNPs modified electrode was illustrated by the determination of AA in the presence of uric acid.

CORR Insights® : loss of cement-bone interlock in retrieved tibial components from total knee arthroplasties

Most surgeons cement the tibial component in total knee replacement surgery. Mid-term registry data from a number of countries, including those from the United Kingdom and Australia, support the excellent survivorship of cemented tibial components. In spite of this success, results can always be improved, and cementing technique can play a role. Cementing technique on the tibia is not standardized, and surgeons still differ about the best ways to deliver cement into the cancellous bone of the upper tibia. Questions remain regarding whether to use a gun or a syringe to inject the cement into the cancellous bone of the tibial plateau . The ideal cement penetration into the tibial plateau is debated, though most reports suggest that 4 mm to 10 mm is ideal. Thicker mantles are thought to be dangerous due to the risk of bone necrosis, but there is little in the literature to support this contention...

A new study on binder performance and formulation modification of anti-corrosive primer based on ethyl silicate resin

Zinc-rich ethyl silicate coatings are quite successful in protecting steel against corrosion under severe exposing conditions. In spite of providing excellent cathodic protection to steel structure after film curing, two-component zinc-rich ethyl silicate coatings have some limitations, one of which is inadequate shelf life as a result of in-can binder gelation. In this work, the preparation steps of ethyl silicate such as pre-hydrolysis, dehydration and organometallic reactions were surveyed and herein an approach towards understanding the cause and effect relationship of the use of ingredients is presented. The effects of water and catalytic acid dosages on gel time under accelerated conditions and the effect of alcoholic solvent order on the rate of the hydrolysis and dehydration reactions were studied via Karl-Fischer test determining the water content of hydrolysate. A thriving optimization in shelf life without any loss in physical–mechanical characteristics of the final film (e.g. hardness, adhesion, solvent and salt spray resistance) was obtained.

Nanoscale texture on glass and titanium substrates by physical vapor deposition process

The aim of the paper is to give a feasibility study on the material deposition of Nanoscale textured morphology of titanium and titanium oxide layers on titanium and glass substrates. As a recent development in nanoscale deposition, Physical Vapor Deposition (PVD) based DC magnetron sputtering has been the choice for the deposition process. The nanoscale morphology and surface roughness of the samples have been characterized using Atomic Force Microscope (AFM). The surface roughnesses obtained from AFM have been compared using surface profiler. From the results we can say that the roughness values are dependent on the surface roughness of the substrate. The glass substrate was relatively smoother than the titanium plate and hence lower layer roughness was obtained. From AFM a unique nano-pattern of a boomerang shaped titanium oxide layer on glass substrate have been obtained. The boomerang shaped nano-scale pattern was found to be smaller when the layer was deposited at higher sputtering power. This indicated that the morphology of the deposited titanium oxide layer has been influenced by the sputtering power.

Equilibrium and column studies of iron exchange with strong acid cation resin

The exchange of iron species from iron (III) chloride solutions with a strong acid cation resin has been investigated in relation to a variety of water and wastewater applications. A detailed equilibrium isotherm analysis was conducted wherein models such as Langmuir Vageler, Competitive Langmuir, Freundlich, Temkin, Dubinin Astakhov, Sips and Brouers-Sotolongo were applied to the experimental data. An important conclusion was that both the bottle-point method and solution normality used to generate the ion exchange equilibrium information influenced which sorption model fitted the isotherm profiles optimally. Invariably, the calculated value for the maximum loading of iron on strong acid cation resin was substantially higher than the value of 47.1 g/kg of resin which would occur if one Fe3+ ion exchanged for three “H+” sites on the resin surface. Consequently, it was suggested that above pH 1, various iron complexes sorbed to the resin in a manner which required less than 3 sites per iron moiety. Column trials suggested that the iron loading was 86.6 g/kg of resin when 1342 mg/L Fe (III) ions in water were flowed at 31.7 bed volumes per hour. Regeneration with 5 to 10 % HCl solutions reclaimed approximately 90 % of exchange sites.

An examination of isotherm generation : impact of bottle-point method upon potassium ion exchange with strong acid cation resin

This paper relates to the importance of impact of the chosen bottle-point method when conducting ion exchange equilibria experiments. As an illustration, potassium ion exchange with strong acid cation resin was investigated due to its relevance to the treatment of various industrial effluents and groundwater. The “constant mass” bottle-point method was shown to be problematic in that depending upon the resin mass used the equilibrium isotherm profiles were different. Indeed, application of common equilibrium isotherm models revealed that the optimal fit could be with either the Freundlich or Temkin equations, depending upon the conditions employed. It could be inferred that the resin surface was heterogeneous in character, but precise conclusions regarding the variation in the heat of sorption were not possible. Estimation of the maximum potassium loading was also inconsistent when employing the “constant mass” method. The “constant concentration” bottle-point method illustrated that the Freundlich model was a good representation of the exchange process. The isotherms recorded were relatively consistent when compared to the “constant mass” approach. Unification of all the equilibrium isotherm data acquired was achieved by use of the Langmuir Vageler expression. The maximum loading of potassium ions was predicted to be at least 116.5 g/kg resin.

A modified Density-Based Scanning Algorithm with Noise for spatial travel pattern analysis from Smart Card AFC data

Smart Card Automated Fare Collection (AFC) data has been extensively exploited to understand passenger behavior, passenger segment, trip purpose and improve transit planning through spatial travel pattern analysis. The literature has been evolving from simple to more sophisticated methods such as from aggregated to individual travel pattern analysis, and from stop-to-stop to flexible stop aggregation. However, the issue of high computing complexity has limited these methods in practical applications. This paper proposes a new algorithm named Weighted Stop Density Based Scanning Algorithm with Noise (WS-DBSCAN) based on the classical Density Based Scanning Algorithm with Noise (DBSCAN) algorithm to detect and update the daily changes in travel pattern. WS-DBSCAN converts the classical quadratic computation complexity DBSCAN to a problem of sub-quadratic complexity. The numerical experiment using the real AFC data in South East Queensland, Australia shows that the algorithm costs only 0.45% in computation time compared to the classical DBSCAN, but provides the same clustering results.

Removal of herbicides from aqueous solutions by modified forms of montmorillonite

This investigation for the removal of agricultural pollutants, imazaquin and atrazine was conducted using montmorillonite (MMT) exchanged with organic cations through ion exchange. The study found that the adsorption of the herbicides was affected by the degree of organic cation saturations, the size of organic cations and the different natures of the herbicides. The modified clays intercalated with the larger surfactant molecules at the higher concentrations tended to enhance the adsorption of imazaquin and atrazine. In particular, the organoclays were highly efficient for the removal of imazaquin while the adsorption of atrazine was minimal due to the different hydrophobicities. Both imazaquin and atrazine were influenced by the changes of pH. The amphoteric imazaquin exists as an anion at the pH 5–7 and the anionic imazaquin was protonated to a neutral and further a cationic form when the pH is lower. The weak base, atrazine was also protonated at lower pH values. The anionic imazaquin had a strong affinity to the organoclays on the external surface as well as in the interlayer space of the MMT through electrostatic and hydrophobic interactions. In this study, the electrostatic interaction can be the primary mechanism involved during the adsorption process. This study also investigated a comparative adsorption for the imazaquin and atrazine and the lower adsorption of atrazine was enhanced and this phenomenon was due to the synergetic effect. This work highlights a potential mechanism for the removal of specific persistence herbicides from the environment.

Removal characteristics of ammonium nitrogen from wastewater by modified Ca-bentonites

A modified inorganic bentonite (Na/Al) based on purified Ca-bentonite was prepared through exchanging Al and Na ions in the interlayer space of Ca-bentonite. The structural properties of purified and modified bentonites were characterized by XRD and SEM analysis. Batch experiments were performed for the adsorption of ammonium nitrogen and different experimental conditions were studied in order to investigate the optimum adsorption conditions. Comparative experiments were also carried out for natural Ca-bentonite (RB), unmodified purified bentonite (PB) and modified purified bentonite (MB). Through the thermodynamic analysis, the ammonium nitrogen adsorption process can be spontaneous, the standard heat was −41.46kJmol −1 , and the adsorption process based on ion exchange adsorption. The ammonium nitrogen adsorption capacity of MB (46.904mg/g) was improved compared to raw bentonite (RB) (26.631mg/g), which was among the highest values of ammonium nitrogen adsorption compared with other adsorbents according to the literatures. The described process provides a potential pathway for the removal of ammonium nitrogen at low concentrations encountered in most natural waters.

Thermogravimetric analysis of tetradecyltrimethylammonium bromide-modified beidellites

The surfaces of natural beidellite clay were modified with cationic surfactant, tetradecyltrimethylammonium bromide, at different concentrations. The organo-beidellites were analysed using thermogravimetric analysis which shows four thermal oxidation/decomposition steps. The first step of mass loss is observed from room temperature to 130 °C due to the dehydration of adsorbed water. The second step of mass loss between 130 and 400 °C is attributed to the oxidation step of the intercalated organic surfactant with the formation of charcoal. The third mass loss happens between 400 and 500 °C which is assigned to the loss of hydroxyl groups on the edge of clays and the further oxidation step of charcoal. The fourth step is ascribed to the loss of structural OH units as well as the final oxidation/decomposition step of charcoal which takes place between 500 and 700 °C. Thermogravimetric analysis has proven to be a useful tool for estimating loaded surfactant amount.

Graphene-oxide-modified β-tricalcium phosphate bioceramics stimulate in vitro and in vivo osteogenesis

Graphene oxide (GO) has attracted much interest for applications in bone tissue engineering; however, until now the interaction between GO and stem cells, and the in vivo bone-forming ability of GO has not been explored. The aim of this study was to produce a GO-modified β-tricalcium phosphate (β-TCP-GRA) biceramics and then explore the material’s osteogenic capacity in vitro and in vivo, as well as unravel some of the molecular mechanisms behind this. β-TCP-GRA disks and scaffolds were successfully prepared by a simple GO/water suspension soaking method in combination with heat treatment. These scaffolds were found to significantly enhance the proliferation, alkaline phosphatase activity and osteogenic gene expression of human bone marrow stromal cells (hBMSCs), when compared to β-TCP without GO modification (controls). Activation of the Wnt/β-catenin signaling pathway in hBMSCs appears to be the mechanism behind this osteogenic induction by β-TCP-GRA. β-TCP-GRA scaffolds led to an increased rate of in vivo new bone formation compared to β-TCP controls, indicative of the stimulatory effect of GO on in vivo osteogenesis, making GO modification of β-TCP a very promising method for applications in bone tissue engineering, in particular for the regeneration of large bone defects.