Electrically-active nanoporous membranes are prepared by coating the surface of anodized alumina with electroactive polymers using vapor phase polymerization with four combinations of conjugated polymers and doping ions: poly(3,4-ethylenedioxythiophone) and polypyrrole, FeCl3 and FeTs3. The permeability of the polymer-coated membranes is measured as a function of the applied electric potential. A reversible three-fold increase is found in molecular flux of a neutral dye for membranes in oxidized state compared to that in the reduced state. After analyzing various factors that may affect the molecular transport through these membranes, it is concluded that the observed behavior results mostly from swelling/deswelling of the polymers and from the confinement of the polymers inside the nanopores.
A ternary composite supercapacitor electrode consisting of phosphomolybdic acid (HMA), a renewable biopolymer, lignin, and polypyrrole was synthesized by a simple one-step simultaneous electrochemical deposition and characterized by electrochemical methods. It was found that the addition of HMA increased the specific capacitance of the polypyrrole-lignin composite from 477 to 682 F g(-1) ( at a discharge current of 1 A g(-1)) and also significantly improved the charge storage capacity from 6(to 128 mA h g(-1).
A highly-sensitive glucose biosensor amenable to ultra-miniaturisation was fabricated by immobilisation of glucose oxidase (GOx), onto a poly(2,6-diaminopyridine)/multi-walled carbon nanotube/glassy carbon electrode (poly(2,6-DP)/MWNT/GCE). Cyclic voltammetry was used for both the electrochemical synthesis of poly-(2,6-DP) on the surface of a MWNT-modified GC electrode, and characterisation of the polymers deposited on the GC electrode. The synergistic effect of the high active surface area of both the conducting polymer, i.e., poly-(2,6-DP) and MWNT gave rise to a remarkable improvement in the electrocatalytic properties of the biosensor. The transfer coefficient (alpha), heterogeneous electron transfer rate constant and Michaelis-Menten constant were calculated to be 0.6, 4 s(-1) and 0.20 mM at pH 7.4, respectively. The GOx/poly(2,6-DP)/MWNT/GC bioelectrode exhibited two linear responses to glucose in the concentration ranging from 0.42 mu M to 8.0 mM with a correlation coefficient of 0.95, sensitivity of 52.0 mu AmM-1 cm(-2), repeatability of 1.6% and long-term stability, which could make it a promising bioelectrode for precise detection of glucose in the biological samples. (C) 2013 Elsevier B.V. All rights reserved.
A highly-sensitive glucose biosensor amenable to ultraminiaturisation was fabricated by immobilization of glucose oxidase (wGOX), onto a poly(2,6-diaminopyridine)/multi-walled carbon nanotube/glassy carbon electrode (poly(2,6-DP)/MWCNT/GCE). Cyclic voltammetry was used for both the electrochemical synthesis of poly-(2,6-DP) on the surface of a MWCNT-modified GC electrode, and characterization of the polymers deposited on the GC electrode. The synergistic effect of the high active surface area of both the conducting-polymer, i.e., poly-(2,6-DP) and MWCNT gave rise to a remarkable improvement in the electrocatalytic properties of the biosensor. The transfer coefficient (alpha), heterogeneous electron transfer rate constant and Michaelis-Menten constant were calculated to be 0.6, 4 s-1 and 0.22 mM at pH 7.4, respectively. The GOx/poly(2,6-DP)/MWCNT/GC bioelectrode exhibited two linear responses to glucose in the concentration ranging from 0.42 mu M to 8.0 mM with a correlation coefficient of 0.95, sensitivity of 52.0 mu AmM-1 cm-2, repeatability of 1.6% and long-term stability, which could make it a promising bioelectrode for precise detection of glucose in the biological samples. (C) 2016 Elsevier B.V. All rights reserved.
In this paper, a simple and sensitive approach for human epidermal growth factor receptor 2 (HER2) detection is presented, using antibody-functionalised magnetic beads coupled to screen-printed cells. The immunoassay is based on a sandwich format in which a primary monoclonal antibody anti-HER2 is coupled to protein A modified magnetic beads. The modified beads are then used to capture the protein from the sample solution and a sandwich assay is performed by adding a secondary monoclonal antibody anti-HER2 labelled with biotin. The enzyme alkaline phosphatase (AP) conjugated with streptavidin and its substrate (1-naphthyl-phosphate) are then used for the electrochemical detection by differential pulse voltammetry (DPV). The experimental conditions for the immunoassay were optimised. The performance of the assay in terms of sensitivity, reproducibility and selectivity has been studied in buffer and serum samples from hospital patients.
Rapid development in technology and society has generated diverse developments in many fields including biosensors in healthcare application. Here, the design of integrated biosensor comprises mass sensing (Quartz Crystal Microbalance) and electrochemistry sensing (Electrochemical Impedance Spectroscopy, EIS and Cyclic Voltammetry, CV) will be presented. The integrated sensor system is developed based on the innovative use of the top electrode of a quartz crystal microbalance (QCM) resonator as a working electrode for the electrochemistry technique. Integration of QCM with the electrochemistry technique is realized by fabricating a semicircular counter electrode near the upper electrode on the same side of the quartz crystal. CV and EIS measurement was conducted using finite element modeling, COMSOL (TM) 5.2 with the probe marker of 1 mmol L-1 of [Fe(CN)(6)](3-/4-). CV test was done to study the effect between increasing scan rate and peak current (anodic and cathodic) in observing the reversible electrochemical process. This observation is crucial in ensuring the electrochemical processes follow the Randles-Sevcik equation in characterizing the platform changes behavior. Later, EIS test was performed in order to measure the radius of the semicircle which reflects the charge transfer resistance (R-CT) of the redox marker. To show the effectiveness of this sensor, gold immobilization surface was electrochemically simulated and reported. Thus, an ultra-sensitive biosensor that capable to produce multi-analysis in the detection of biological targets in terms of electrochemical change of electrode interfaces, which is the crucial step towards the engineering of advanced bioelectronics.
Transmission Mueller-matrix spectroscopic ellipsometry is applied to the cuticle of the beetle Cetonia aurata in the spectral range 300-1000 nm. The cuticle is optically reciprocal and exhibits circular Bragg filter features for green light. By using differential decomposition of the Mueller matrix, the circular and linear birefringence as well as dichroism of the beetle cuticle are quantified. A maximum value of structural optical activity of 560 degrees/mm is found. (C) 2016 Optical Society of America
Regeneration is a key goal in the design of immunosensors. In this study, we report the temperature-regulated interaction of N-isopropylacrylamide (PNIPAAm) functionalised cardiac troponin T (cTnT) with anti-cTnT. Covalently bonded PNIPAAm on an anti-cTnT bioelectrode showed on/off-switchability, regeneration capacity and temperature triggered sensitivity for cTnT. Above the lower critical solution temperature (LCST), PNIPAAm provides a liphophilic microenvironment with specific volume reduction at the bioelectrode surface, making available binding space for cTnT, and facilitating analyte recognition. Computational studies provide details about the structural changes occurring at the electrode above and below the LCST. Furthermore, free energies associated with the binding of cTnT with PNIPAAm at 25 (Delta G(coil)=-6.0 Kcal/mole) and 37 degrees C (Delta G(globular)=-41.0 kcal/mole) were calculated to elucidate the interaction and stability of the antigen-antibody complex. The responsiveness of such assemblies opens the way for miniaturised, smart immuno-technologies with built-in programmable interactions of antigen-antibody upon receiving stimuli.
Regeneration of immunosensors is a longstanding challenge. We have developed a re-usable troponin-T (TnT) immunoassay based on localised surface plasmon resonance (LSPR) at gold nanorods (GNR). Thermosensitive poly(N-isopropylacrylamide) (PNIPAAM) was functionalised with anti-TnT to control the affinity interaction with TnT. The LSPR was extremely sensitive to the dielectric constant of the surrounding medium as modulated by antigen binding after 20 min incubation at 37 degrees C. Computational modelling incorporating molecular docking, molecular dynamics and free energy calculations was used to elucidate the interactions between the various subsystems namely, IgG-antibody (c. f., anti-TnT), PNIPAAM and/or TnT. This study demonstrates a remarkable temperature dependent immuno-interaction due to changes in the PNIPAAM secondary structures, i.e., globular and coil, at above or below the lower critical solution temperature (LCST). A series of concentrations of TnT were measured by correlating the lambda(LSPR) shift with relative changes in extinction intensity at the distinct plasmonic maximum (i. e., 832 nm). The magnitude of the red shift in lambda(LSPR) was nearly linear with increasing concentration of TnT, over the range 7.6 x 10(-15) to 9.1 x 10(-4) g/mL. The LSPR based nano-immunoassay could be simply regenerated by switching the polymer conformation and creating a gradient of microenvironments between the two states with a modest change in temperature.
Alteration in expression of miRNAs has been correlated with different cancer types, tumour stage and response to treatments. In this context, a structurally responsive oligonucleotide-based electrochemical impedimetric biosensor has been developed for the simple and sensitive detection of miRNA-21. A highly specific biotinylated DNA/LNA molecular beacon (MB) probe was conjugated with gold nanoparticles (AuNPs) to create an integrated, dual function bio-label (biotin-MB-AuNPs) for both biorecognition and signal generation. In the presence of target miRNA-21, hybridisation takes place resulting in the "activation" of the biotin-MB; this event makes the biotin group, which was previously "protected" by the steric hindrance of the MB stem-loop structure, accessible. The activated biotin-MB-AuNPs/miRNA complexes become available for capture, via supramolecular interaction, onto a nentravidin-modified electrode for electrochemical transduction. The binding event results in a decrease of the charge transfer resistance at the working electrode/electrolyte interface. The biosensor responded linearly in the range 1-1000 pM of miRNA-21, with a limit of detection of 0.3 pM, good reproducibility (Relative Standard deviation (RSD) =3.3%) and high selectivity over other miRNAs (i.e. miRNA221 and miRNA-205) sequences. Detection of miRNA-21 in spiked serum samples at clinically relevant levels (low pM range) was also demonstrated, thus illustrating the potential of the biosensor for point-of-care clinical applications. The proposed biosensor design, based on the combination of a neutravidin transducing surface and the dual-function biotin-MB-AuNPs bio-label, provides a simple and robust approach for detection of short-length nucleic acid targets, such as miRNAs.
The extremely specialised anatomical function of citrate inside the prostate, make it one of the preferred biomarkers for early stage detection of prostate cancer. However, current detection methods are seriously limited due to the very low citrate concentrations that need to be measured in order to follow disease progression. In the present work, we report a novel citrate-selective-sensor based on iron (III) phthalocyanine chloride-C-monoamido-Poly-n-Butyl Acrylate (Fe(III)MAPcC1 P n BA) modified gold -electrodes for the electrochemical determination and estimation of the pathophysiological range of citrate. The newly synthesised ionophore has been structurally characterised using Fourier transform infrared (FTIR) and UV-vis spectroscopy. Contact angle measurements and atomic force microscopy (AFM) have been used to investigate the adhesion and morphological properties of the membrane. The developed citrate-selective-electrodes had a Nernstian sensitivity of-19.34 +/- 0.83 mV/decade with a detection limit of about 9 x 10-6M and a linear range from 4 x 10(-5)M to 10(-1) M, which covered the pathologically important clinical range. Electrochemical impedance spectroscopy (EIS) showed very high sensitivity with a lower Limit of detection 1.7 x 10(-9) M and linear detection range (10(-8)-10(-1) M), which is very important not only for the early-stage diagnosis and screening procedures, but also in mapping the stage of the cancer too. (C) 2016 Elsevier B.V. All rights reserved.
Fast and accurate detection of microorganisms is of key importance in clinical analysis and in food and water quality monitoring. Salmonella typhimurium is responsible for about a third of all cases of food borne diseases and consequently, its fast detection is of great importance for ensuring the safety of foodstuffs. We report the development of a label-free impedimetric aptamer-based biosensor for S. typhimurium detection. The aptamer biosensor was fabricated by grafting a diazonium-supporting layer onto screen printed carbon electrodes (SPEs), via electrochemical or chemical approaches, followed by chemical immobilisation of aminated-aptamer. FTIR-ATR, contact angle and electrochemical measurements were used to monitor the fabrication process. Results showed that electrochemical immobilisation of the diazonium-grafting layer allowed the formation of a denser aptamer layer, which resulted in higher sensitivity. The developed aptamer-biosensor responded linearly, on a logarithm scale, over the concentration range 1 x 10(1) to 1 x 10(8) CFU mL(-1), with a limit of quantification (LOQ) of 1 x 10(1) CFU mL(-1) and a limit of detection (LOD) of 6 CFU mL(-1). Selectivity studies showed that the aptamer biosensor could discriminate S. typhimurium from 6 other model bacteria strains. Finally, recovery studies demonstrated its suitability for the detection of S. typhimurium in spiked (1 x 10(2), 1 x 10(4) and 1 x 10(6) CFU mL(-1)) apple juice samples. (C) 2016 Elsevier B.V. All rights reserved.
Glucose-6-phosphateplays an important role in carbohydrate metabolism of all living organisms.Compared to the conventional analytical methods available for estimation of glucose-6-phosphate,the biosensors having relative simplicity, specificity, low-cost and fastresponse time are a promising alternative. We have reported a glucose-6-phosphatesensor based on screen-printed electrode utilizing Prussian blue nanoparticlesand enzymes, glucose-6-phosphate dehydrogenase and glutathione reductase. The Prussianblue nanoparticles acted as a mediator enhancing the rate of electrochemical responses.The Fourier transforminfrared spectroscopy and energy-dispersiveX-ray spectroscopy study confirmed the formation of Prussian blue, whereas, the atomic forced microscopy revealed that Prussian bluenanoparticles were about 25-30 nm in diameter. To obtainmaximum amperometric response, optimization studies were conducted for pH,enzyme and cofactor loading. The proposed glucose-6-phosphate biosensor showed goodstability, rapid response time and broad linear response in the range of 0.01-1.25mM and detection limit of 6.3 mM. The biosensor also worked well for serum samples and exhibitedexcellent anti-interference ability.
Field effect devices based on catalytic metal-oxide-silicon carbide (MOSiC) structures can be used as high temperature gas sensors. The devices are sensitive to hydrocarbons and hydrogen and can be operated up to at least 900 degrees C, which make them suitable for several combustion applications, Simulated and real exhaust gases from a car engine have been studied at sensor temperatures from 200 to 650 degrees C, and it was round that the sensor signal is high for excess hydrocarbon and low for excess oxygen. The response time is less than 100 ms and only a small degradation of the devices was observed after several days of operation. The devices also react to changes of the gas composition In the fuel-rich and fuel-lean region. The devices show an interesting temperature dependence in the fuel rich region.
Despite several types of fluorescent sensing molecules have been proposed and examined to signal Hg2+ ion binding, the development of fluorescence-based devices for in-field Hg2+ detection and screening in environmental and industrial samples is still a challenging task. Herein, we report the synthesis and characterization of three new coumarin-based fluorescent chemosensors featuring mixed thia/aza macrocyclic framework as receptors units, that is, ligands L1-L3. These probes revealed an OFF-ON selective response to the presence of Hg2+ ions in MeCN/H2O 4:1 (v/v), which allowed imaging of this metal ion in Cos-7 cells in vitro. Once included in silica core-polyethylene glycol (PEG) shell nanoparticles or supported on polyvinyl chloride (PVC)-based polymeric membranes, ligands L1-L3 can also selectively sense Hg2+ ions in pure water. In particular we have developed an optical sensing array tacking advantage of the fluorescent properties of ligand L3 and based on the computer screen photo assisted technique (CSPT). In the device ligand L3 is dispersed into PVC membranes and it quantitatively responds to Hg2+ ions in natural water samples.
Biosensor technology not only holds great promise for the healthcare market but it is also expected to have significant impacts in other areas such as environmental and food analysis. Between the different biosensor formats nucleic acid-based biosensors are gaining increasingly importance allowing the specific identification of DNA/RNA fragments and, more recently, the detection of biological or chemical species. Direct identification of DNA/RNA fragments, via hybridisation assays (genosensors), has been shown to be a very powerful tool for the detection of pathogens in environment and food, in food contamination analysis and food allergens monitoring. Recently the discovery of aptamers, synthetic receptors based on short functional DNA/RNA chains, has opened new opportunities for oligonucleotide based biosensors and more specifically in the detection of biological and/or chemical species, such as proteins and pollutants. In this paper an overview of the most recent advances in the development and applications of nucleic acid-based biosensors for environmental and food safety/quality application will be presented with special emphasis on electrochemical and optical hybridisation genosensors and aptasensors.
Low density DNA arrays are of growing interest in the field of fast clinical/environmental analysis; for example in clinical analysis these can find application in areas as early diagnosis of genetic diseases or as support in the diagnosis of genetically associated diseases.
Coeliac disease, a small intestinal inflammation triggered by the intake of gluten, has been shown to affect only genetically predisposed individuals. Relation between Coeliac disease and two Human Leukocyte Antigens (HLA) genes, DQ2 and DQ8, has been reported, with almost 100% of the affected patients carrying at least one of them.
In this seminar the development of a low density electrochemical genosensor array for medium resolution typing of Coeliac disease associated HLA genes, is presented.
The proposed array was based on an enzymatic sandwich assay format performed at a photolitographically fabricated electrode array.
The optimisation of different aspects as surface chemistry, assay conditions, probe's design and single stranded DNA generation, together with real sample analysis will be present.
Mobile diagnostics for healthcare, food safety and environmental monitoring, demand a new generation of inexpensive sensing systems suitable for production in high volume. Herein we report on the development of a new disposable electrochemical instrument exploiting the latest advances in printed electronics and printed biosensors. The current system is manufactured under ambient conditions with all interconnections printed; electrochemical measurements and data elaboration are realized by the integration onto the platform of two chips: a MICROCHIP-PIC24F16KA101 and a Texas Instruments LMP91000. A PEDOT.PSS vertical electrochromic display (VECD) is also incorporated into the system to visualize the data. A printed Enfucell 3V manganese dioxide battery was used to deliver the required power. Finally, in order to demonstrate the utility of the system, screen-printed sensors for the detection of glucose were added and the performance of the overall system was evaluated.
The possibility of introducing a computationally assisted method to study aptamer-protein interaction was evaluated with the aim of streamlining the screening and selection of new aptamers. Starting from information on the 15-mer (5-GGTTGGTGTGGTTGG-3 thrombin binding aptamer (TBA), a library of mutated DNA sequences (994 elements) was generated and screened using shapegauss a shape-based scoring function from openeye software to generate computationally derived binding scores. The TBA and three other mutated oligonucleotides, selected on the basis of their binding score (best, medium, worst), were incorporated into surface plasmon resonance (SPR) biosensors. By reducing the ionic strength (binding buffer, 50 mMTrisHC1pH 7.4, 140 mM NaCl, 1 mM MgCl(2), diluted 1:50) in order to match the simulated condition, the analytical performances of the four oligonucleotide sequences were compared using signal amplitude, sensitivity (slope), linearity (R(2)) and reproducibility (CVav %). The experimental results were in agreement with the simulation findings.
Conducting polymers have been widely explored for many different purposes including sensing. In thisthesis the conducive properties of pyrrole and the carbohydrate binding properties of boronic acid iscombined to make a reagent-free detector for carbohydrates. The polymer is manufactured in form ofparticles in the μm scale to create a porous film which has a high surface to volume ratio.The material was characterised and the binding properties were evaluated for galactose and glucose.Proof of binding was found via both electrochemical methods and QCM-D. A correlation between R2 value and concentration of substrate was found which enables measurement of concentration of carbohydratesin unknown samples.
In this work, the first example of a hierarchically structured hollow silica system is reported without any chemical modification to the enzyme involved in the process. The leaching of the physically adsorbed enzyme is substantially restrained in comparison to pure hollow silica supports. The hierarchical architecture is composed of the ordered hollow silica spheres with a shell-in-shell structure. This rationally integrated architecture, which serves as the host for glucose oxidase immobilization, displays many significant advantages, including increases in mechanical stability, enzyme loading, and bioactivity, and a decrease in enzyme leaching compared to existing pure hollow silica matrices. This facilitates further multifarious applications for enhanced enzyme immobilization, biosensors, and biocatalysis.
A highly efficient nanoreactor that contains silver nanoparticles in hollow silica spheres and an interpolymer network as a gate-keeper has been developed following a facile procedure. The fast "signal-triggered switch of the smart network results in a high reactivity and a high response rate, yielding improved potential for many practical applications.
The application of pyrrole-substituted porphyrin electropolymers for simultaneous optical and electrochemical analysis of red-ox active analytes, namely diazo-conjugated dyes of Sudan family, is presented. Sudan colorants are widely used in many fields, but accurate screening of their consumption is required due to their high toxicity. The inherent electrochemical activity of Sudan dyes, as far as their intense coloration, makes possible to find the appropriate conditions of hybrid optical and electrochemical porphyrin electropolymer based sensor array system application. This approach allowed a significant increase in the chemical information, improving the analytical system performance in terms of selectivity and sensitivity, and permitted the fast and simple monitoring of Sudan dye analytes.
In this work simple microcontact printed gold-wafers were used to make a lectin panel for investigation and separation of different meat juices from fresh meat of cattle, chicken, pig, cod, turkey and lamb. Seven different lectins were thus attached to gold surfaces using the streptavidin-biotin method. Lectins recognize and bind specifically to carbohydrate structures present on different proteins. The bio-recognition was evaluated with null ellipsometry and the data obtained was related to an internal standard of lactoferrin. The data was evaluated with multivariate data analysis techniques to identify possible separation or grouping of data. Scanning ellipsometry was used for visualization of the binding pattern of the lectins and the meat juice proteins. The 2-dimensional images obtained could be used to visualize the protein distribution, furthermore, to exclude anomalies. The results showed that the different meat juices could be separated from each other. Using a simple model based on an artificial neuronal net, it was also possible to classify meat juices from the mammals investigated.
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A self-polishing voltammetric sensor was recently developed and has been applied to samples of urea, milk and sewage water. The polishing device continuously grinds a platinum ring electrode, offering a reproducible and clean electrode surface. Principal component analysis (PCA) and partial least squares (PLS) techniques were applied to interpret the data and to build prediction models. In an evaluation of samples with different urea concentrations, the grinding step allows for repeatable measurements, similar to those after electrochemical cleaning. Furthermore, for the determination of sewage water concentrations in drinking water and for the evaluation of different fat contents in milk samples, the polishing eliminates sensor drift produced by electrode fouling. The results show that the application of a self-polishing unit offers a promising tool for electrochemical studies of difficult analytes and complex media. (C) 2014 Elsevier B.V. All rights reserved.
Point-of-care (POC) diagnostics brings tests nearer to the site of patient care. The turnaround time is short, and minimal manual interference enables quick clinical management decisions. Growth in POC diagnostics is being continuously fueled by the global burden of cardiovascular and infectious diseases. Early diagnosis and rapid initiation of treatment are crucial in the management of such patients. This review provides the rationale for the use of POC tests in acute coronary syndrome, heart failure, human immunodeficiency virus, and tuberculosis. We also consider emerging technologies that are based on advanced nanomaterials and microfluidics, improved assay sensitivity, miniaturization in device design, reduced costs, and high-throughput multiplex detection, all of which may shape the future development of POC diagnostics.
We have demonstrated an entirely new concept of a wearable theranostic device in the form of a contact lens (theranostic lens) with a dual-functional hybrid surface to modulate and detect a pathogenic attack, using a the corneal HSV serotype-1 (HSV-1) model. The theranostic lenses were constructed using a facile layer-by-layer surface engineering technique, keeping the theranostic lenses with good surface wettability, optically transparency, and nontoxic toward human corneal epithelial cells. The theranostic lenses were used to capture and concentrate inflammatory cytokines such as interleukin-1 alpha (IL-1 alpha), which is upregulated during HSV-1 reactivation, for sensitive, noninvasive diagnostics. The theranostic lens also incorporated an antiviral coating to serve as a first line of defense to protect patients against disease. Our strategy tackles major problems in tear diagnostics that are mainly associated with the sampling of a relatively small volume of fluid and the low concentration of biomarkers. The theranostic lenses show effective anti-HSV-1 activity and good analytical performance for the detection of IL-1a, with a limit of detection of 1.43 pg mL(-1) and a wide linear range covering the clinically relevant region. This work offers a new paradigm for wearable noninvasive healthcare devices combining diagnosis and protection against disease, while supporting patient compliance. We believe that this approach holds immense promise as a next-generation point-of-care and decentralized diagnostic/theranostic platform for a range of biomarkers.
The length scale for nanomaterial is small enough to be invisible and presume innocence for the initial avoidance of the toxicity issues. Again it was beyond the understanding of the time frame when nanotechnology just blooms that a length scale itself might be an important toxic parameter apart from its materialistic properties. We present this report to address the fundamental issues and questions related to the nanotoxicity issues from laboratory to the land of applications. We emphasize about the basic nanoscale materials that are regularly being used by the scientific community and the nanotechnology based materials that has already in the market or will come soon.
This paper presents an equivalent electric circuit model that describes adsorption-desorption processes occurring on bio and chemical sensor surfaces under the Langmuir hypothesis and considers the following practical case: the pressure or concentration of the particles in the test chamber is not perturbed by these processes and keeps its initial value, as in the cases of relatively high pressure or concentration values with zero molecular flow, or in the presence of a molecular flow at any pressure or concentration value. It is also pointed out that the equivalent circuit for Langmuir adsorption is similar to the circuit proposed for enzymatic reactions. Even if this work essentially covers theoretic aspects, a way is suggested for the possible experimental determination of both adsorption-desorption parameters and adsorption-desorption site density. (C) 2016 Elsevier B.V. All rights reserved.
Since almost every fifth patient treated in hospital care develops pressure ulcers, early identification of risk is important. A non-invasive method for the elucidation of endogenous biomarkers related to pressure ulcers could be an excellent tool for this purpose. We therefore found it of interest to determine if there is a difference in the emissions of volatiles from compressed and uncompressed tissue. The ultimate goal is to find a non-invasive method to obtain an early warning for the risk of developing pressure ulcers for bed-ridden persons. Chemical analysis of the emissions, collected in compresses, was made with gas-chromatography – mass spectrometry and with a chemical sensor array, the so called electronic nose. It was found that the emissions from healthy and hospitalized persons differed significantly irrespective of the site. Within each group there was a clear difference between the compressed and uncompressed site. Peaks that could be certainly deemed as markers of the compression were, however, not identified. Nonetheless, different compounds connected to the application of local mechanical pressure were found. The results obtained with GC-MS reveal the complexity of VOC composition, thus an array of non-selective chemical sensors seems to be a suitable choice for the analysis of skin emission from compressed tissues; it may represent a practical instrument for bed side diagnostics. Results show that the adopted electronic noses are likely sensitive to the total amount of the emission rather than to its composition. The development of a gas sensor-based device requires then the design of sensor receptors adequate to detect the VOCs bouquet typical of pressure. This preliminary experiment evidences the necessity of studies where each given person is followed for a long time in a ward in order to detect the insurgence of specific VOCs pattern changes signalling the occurrence of ulcers.
The computer screen photo-assisted techniques (CSPT) have been developed during the last 10 years through an extensive collaboration between University of Rome "Tor Vergata" and Linkoping University in Sweden. CSPT has thus evolved into a concept we now call computer screen assisted digital photography, yielding detailed information about the interaction between color indicators and (volatile) analytes. In the present paper, we give a brief summary of the CSPT concept and its connection to digital photography. We concentrate, however, on the most recent results, which were obtained by using most of the degrees of freedom offered by a computer screen as a light source and a digital (web) camera as a detector. Thus, we describe in detail recent experiments on cotton yarns impregnated with color indicators for volatile organic molecules. The interaction between the color indicators and molecules, like trimethylamine, was investigated by CSPT in high dynamic imaging together with a background noise limiting algorithm. It is shown that the simultaneous use of the last two additions to the CSPT concept considerably enhances the chemical sensing ability of CSPT. It is concluded that the collaboration between Rome and Linkoping has generated a useful platform for further developments of chemical analysis with a ubiquitous instrumentation, a (computer) screen and a web camera. This technique is aimed at facilitating the assembly of opto-chemical sensors with evident benefits in the reduction of cost of sensor systems and in an increased integrability with the existent telecommunication infrastructures.
High sensitivity and cross-selectivity are mandatory properties for sensor arrays. Although metalloporphyrins and pH indicators are among the most common and appropriate choices for the preparation of optical sensor arrays, the sensitivity spectrum of these dyes is limited to those analytes able to induce an optical response. To extend the receptive field of optical sensors, we explore the design of composite materials, where the molecular interaction among the subunits enriches their sensing working mechanisms. We demonstrate that blends of single metalloporphyrins and pH indicators, tested with a transduction apparatus based on ubiquitous and easily available hardware, can be endowed with sensing properties wider than those of single constituents, enabling the recognition of a broad range of volatiles.
Natural olfaction suggests that numerous replicas of small sensors can achieve large sensitivity. This concept of sensor redundancy can be exploited by use of optical chemical sensors whose use of image sensors enables the simultaneous measurement of several spatially distributed indicators. Digital image sensors split the framed scene into hundreds of thousands of pixels each corresponding to a portion of the sensing layer. The signal from each pixel can be regarded as an independent sensor, which leads to a highly redundant sensor array. Such redundancy can eventually be exploited to increase the signal-to-noise ratio. In this paper we report an algorithm for reduction of the noise of pixel signals. For this purpose, the algorithm processes the output of groups of pixels whose signals share the same time behavior, as is the case for signals related to the same indicator. To define these groups of pixels, unsupervised clustering, based on classification of the indicator colors, is proposed here. This approach to signal processing is tested in experiments on the chemical sensitivity of replicas of eight indicators spotted on to a plastic substrate. Results show that the groups of pixels can be defined independently of the geometrical arrangement of the sensing spots, and substantial improvement of the signal-to-noise ratio is obtained, enabling the detection of volatile compounds at any location on the distributed sensing layer.
The hydrogen sensitivity of palladium-silicon dioxidesilicon (Pd-MOS) structures was demonstrated about 25 years ago. One of the most interesting features of the Pd-MOS device as a hydrogen sensor is its very large dynamic pressure range. Such devices are now used in several practical applications and in commercially available equipment, both as single sensors and in sensor arrays. We recall that the hydrogen sensitivity of the device occurs due to a hydrogen induced polarization at the Pd-SiO2 interface as schematically shown in Figure 1. During the years, several types of devices have been developed, both with insulators other than silicon dioxide and catalytic metals other than palladium. Furthermore, it has been demonstrated that sensors with thin, discontinuous catalytic metals can detect molecules, like ammonia, which are not detected by sensors with thick continuous palladium gates. 1-3 Although several insulators have been used in hydrogen sensitive Pd-insulator-semiconductor
Existing actuators in robotics are noisy, rigid and not very lifelike in their movements. There is a need for actuators in especially limb prosthetics and exoskeletons that are silent, softly moving and preferably operating on low currents. One such solution is the conducting polymers.
Textiles are well researched and there is a wide variety of patterning. Even more important is their reproducibility and how easily they are mass-produced.
This thesis work combines conducting polymers with textiles to achieve linear textile actuators. The textiles are coated with the conducting polymer Polypyrrole which has the property of volume change, when a voltage is applied and there is a reservoir of ions accessible. The volume change, expansion and contraction, results in a linear actuation. The force and strain are measured while changing different parameters and the results are evaluated in this thesis.
In this study, cryogel-based molecularly imprinted composite cartridges were designed for the rapid, efficient, and selective preconcentration of benzo[a]pyrene (BaP) from water samples. First, a BaP-imprinted poly(2-hydroxyethyl methacrylate-N-methacryloyl-(L)-phenylalanine) composite cartridge was synthesized under semi-frozen conditions and characterized by scanning electron microscopy, elemental analysis, Fourier transform infrared spectroscopy, and swelling tests. After the optimization of preconcentration parameters, i.e., pH and initial BaP concentration, the selectivity and preconcentration efficiency, and reusability of these cartridges were also evaluated. In selectivity experiments, BaP imprinted composite cartridge exhibited binding capacities 3.09, 9.52, 8.87, and 8.77-fold higher than that of the non-imprinted composite cartridge in the presence of competitors, such as benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), indeno[1,2,3-cd]pyrene (lcdP), and 1-naphthol, respectively. The method detection limit (MDL), relative standard deviation (RSD) and preconcentration efficiency (PE) of the synthesized composite cartridge were calculated as 24.86 mu g/L, 1.60%, and 349,6%, respectively. (C) 2016 Elsevier B.V. All rights reserved.
A novel strategy for site-specific and covalent attachment of proteins has been developed, intended for robust and controllable immobilization of histidine (His)-tagged ligands in protein microarrays. The method is termed chelation assisted photoimmobilization (CAP) and was demonstrated using human IgG-Fc modified with C-terminal hexahistidines (His-IgGFc) as the ligand and protein A as the analyte. Alkanethiols terminated with either nitrilotriacetic acid (NTA), benzophenone (BP); or oligo(ethylene glycol) were synthesized and mixed self-assembled monolayers (SAMs) were prepared on gold and thoroughly characterized by infrared reflection absorption spectroscopy (IRAS), ellipsometry, and contact angle goniometry. In the process of CAP, NTA chelates Ni2+ and the complex coordinates the His-tagged ligand in an oriented assembly. The ligand is then photoimmobilized via BP, which forms covalent bonds upon UV light activation. In the development of affinity biosensors and protein microarrays, site-specific attachment of ligands in a fashion where analyte binding sites are available is often preferred to random coupling. Analyte binding performance of ligands immobilized either by CAP or by standard amine coupling was characterized by surface plasmon resonance in combination with IRAS. The relative analyte response with randomly coupled ligand was 2.5 times higher than when site-specific attachment was used. This is a reminder that also when immobilizing ligands via residues far from the binding site, there are many other factors influencing availability and activity. Still, CAP provides a valuable expansion of protein immobilization techniques since it offers attractive microarraying possibilities amenable to applications within proteomics.
Pulsed voltammetry has been applied to drinking water monitoring. This non-selective technique facilitates detection of several different threats to the drinking water. A multivariate algorithm shows that anomaly detection is possible with a minimum of false alarms. Multivariate analysis can also be used to classify different types of substances added to the drinking water. Low concentrations of sewage water contaminating the drinking water can be detected. A network of such sensors is envisaged to facilitate real-time and on-line monitoring of drinking water distribution networks.
A simple electrostatic model of the adsorbate–adsorbateinteraction of hydrogen atoms at a Pd–SiO 2 interface is presented. The model predicts a hydrogen adsorption isotherm of the Temkin type. It is found that, in practice, an upper limit for the hydrogen response of a Pd-metal-oxide-semiconductor device exists. The value (in V) is equal to the difference of the initial heats of adsorption (in eV) of the interface and the Pd bulk, respectively. Furthermore, a corresponding maximum hydrogen concentration, at the interface, of 1×10 18 m −2 is predicted. The predictions are in good agreement with previously observed experimental data.
A method for diesel detection in surface water in the low ppb range is presented. Even though standard commercial metal oxide gas sensors with detection limits in the ppm range are used, extraction of volatile compounds from the water enables a detection limit of about 2 ppb diesel in the water. The technique can be used for surface water monitoring. The standard technique of ultraviolet fluorescence detection has an interference problem with humic substances. This is not a problem with the suggested technique. Results from lab measurements as well as field tests at a water utility in the Stockholm region in Sweden are presented. (C) 2016 Published by Elsevier Ltd.
Some recent results from the scanning force microscopy activity at our laboratory are presented. A brief description of attractive mode force microscopy is followed by a discussion of the following examples: O2/H2-induced morphology changes in thin palladium films, structure of spin cast polysulfone films, fibrinogen adsorption on hydrophobic SiO2, and force measurements on hydrophobic/hydrophilic substrates.
The structure of thin Pd films evaporated onto planar SiO2 substrates changes dramatically during oxygen/hydrogen exposures in ultrahigh vacuum. In this work we have used an atomic force microscope(AFM), operated in the attractive mode, to obtain the three‐dimensional morphology of the Pd surface for different film thicknesses and treatments, and compared the data with transmission electron microscopy(TEM) micrographs. During restructuring, a 100‐Å film changes from being a smooth continuous film with cracks into metal clusters dispersed on the SiO2 support. In the 5‐Å case the metal films are already well dispersed as fabricated. Here the gas exposure instead results in a clustering effect resulting in larger particles. The AFM gives results which are consistent with TEM micrographs but also gives additional information on metal particle shape which can lead to a further understanding of the restructuring process.
Polypyrrole (PPy) is a conducting polymer that enables controlled drug release upon electrical stimulation. We characterized the biocompatibility of PPy with human primary osteoblasts, and the effect of dopants. We investigated the biocompatibility of PPy comprising various dopants, i.e. p-toluene sulfonate (PPy-pTS), chondroitin sulfate (PPy-CS), or dodecylbenzenesulfonate (PPy-DBS), with human primary osteoblasts. PPy-DBS showed the roughest appearance of all surfaces tested, and its wettability was similar to the gold-coated control. The average number of attached cells was 45% higher on PPy-DBS than on PPyCS or PPy-pTS, although gene expression of the proliferation marker Ki-67 was similar in osteoblasts on all surfaces tested. Osteoblasts seeded on PPy-DBS or gold showed similar vinculin attachment points, vinculin area per cell area, actin filament structure, and Ferets diameter, while cells seeded on PPY-CS or PPY-pTS showed disturbed focal adhesions and were enlarged with disorganized actin filaments. Osteoblasts grown on PPy-DBS or gold showed enhanced alkaline phosphatase activity and osteocalcin gene expression, but reduced osteopontin gene expression compared to cells grown on PPy-pTS and PPy-CS. In conclusion, PPy doped with DBS showed excellent biocompatibility, which resulted in maintaining focal adhesions, cell morphology, cell number, alkaline phosphatase activity, and osteocalcin gene expression. Taken together, conducting polymers doped with DBS are well tolerated by osteoblasts. Our results could provide a basis for the development of novel orthopedic or dental implants with controlled release of antibiotics and pharmaceutics that fight infections or focally enhance bone formation in a tightly controlled manner.
Trilayer polypyrrole microactuators that can operate in air have previously been developed. They consist of two outer layers ofthe electroactive polymer polypyrrole (PPy) and one inner layer of a porous poly(vinylidene flouride) (PVDF) membranecontaining a liquid electrolyte. The two outer layers of PPy are each connected with gold electrodes and separated by the porousPVDF membrane. This microtool is fabricated by bottom-up microfabrication However, porous PVDF layer is not compatible with bottom upmicrofabrication and highly swollen SPE suffers from gold electrode delamination. Hence, in this MSc project/thesis a novelmethod of flexible electrode fabrication with conducting polymers was developed by soft lithography and drop-on-demandprinting. The gold electrodes were replaced by patterned vapor phase polymerized (VPP) poly(3,4-ethylenedioxythiophene) (PEDOT)electrodes due to its high electrical conductivity and versatile process ability. The replacement of the stiff gold electrodes byflexible and stretchable PEDOT allowed high volume change of the material and motions. The PEDOT electrodes werefabricated by patterning the oxidant iron tosylate using microcontact printing and drop-on-demand printing. Moreover, thePVDF membrane has been replaced by a nitrile butadiene rubber/poly(ethylene oxide) semi-interpenetrating polymer network(IPN) to increase ion conductivity and strechability and hence actuator performance.