Adhesive Wearable Sensors for Electroencephalography from Hairy Scalp.

Electroencephalography has garnered interest for applications in mobile healthcare, human-machine interfaces, and Internet of Things. Conventional electroencephalography relies on wet and dry electrodes. Despite favorable interface impedance of wet electrodes and skin, the application of a large amount of gel at their interface with skin limits the electroencephalography spatial resolution, increases the risk of shorting between electrodes, and makes them unsuited for long-term mobile recording. In contrast, dry electrodes are better suited for long-term recordings but susceptible to motion artifacts. In addition, both wet and dry electrodes are non-adhesive to the hairy scalp and mechanical support, or chemical adhesives are used to hold them in place. Herein, a conical microstructure array (CMSA) based sensor made of carbon nanotube-polydimethylsiloxane composite is reported. The CMSA sensor is fabricated using the innovative, cost-effective, and scalable method of viscosity-controlled dip-pull process. The sensor adheres to the hairy scalp by generating negative pressure in its conical microstructures when it is pressed against scalp. Aided by the application of a trace amount of gel, CMSA sensor establishes good electrical contact with the skin, enabling its applications in mobile electroencephalography over extended periods. Notably, the signal quality of CMSA sensors is comparable to that of medical-grade wet gel electrodes.

Recent Advances in the Use of Surface-Enhanced Raman Scattering for Illicit Drug Detection.

The rapid increase in illicit drug use and its adverse health effects and socio-economic consequences have reached alarming proportions in recent years. Surface-enhanced Raman scattering (SERS) has emerged as a highly sensitive analytical tool for the detection of low dosages of drugs in liquid and solid samples. In the present article, we review the state-of-the-art use of SERS for chemical analysis of illicit drugs in aqueous and complex biological samples, including saliva, urine, and blood. We also include a review of the types of SERS substrates used for this purpose, pointing out recent advancements in substrate fabrication towards quantitative and qualitative detection of illicit drugs. Finally, we conclude by providing our perspective on the field of SERS-based drug detection, including presently faced challenges. Overall, our review provides evidence of the strong potential of SERS to establish itself as both a laboratory and in situ analytical method for fast and sensitive drug detection and identification.

Detection and quantification of toxicants in food and water using Ag-Au core-shell fractal SERS nanostructures and multivariate analysis.

Here we demonstrate a facile, two step formation of silver core - gold shell (Ag-Au) nanostructures using microelectrodes and assess their performance as surface-enhanced Raman scattering (SERS) substrates to detect and quantify toxicants. Ag nanostructures, serving as the scaffolds for the bimetallic structures, were grown first by using electrochemical deposition on the edges of microelectrodes functionalized with the alkanethiol, 11-mercaptoundecanoic acid. Subsequently, different concentrations of HAuCl4 were used to perform a galvanic reaction on the surfaces of the Ag nanostructures with aqueous droplets being placed on the microelectrodes for 10 min before the substrate was rinsed and dried. Lower HAuCl4 concentrations were found to better preserve the fractal morphology of the formed Ag-Au nanostructures, while higher concentrations resulted in Ag-Au fragments. The SERS enhancement factor for the Ag-Au nanostructures was estimated to have a max value of 6.51 x 105. Combining a data reduction technique with a linear classifier, both identification and quantification were demonstrated with 100% success. The toxicants thiram, thiabendazole, malachite green and biphenyl-4-thiol were all detected and identified at 1 ppm. Lastly, as a proof of concept, the Ag-Au nanostructures were transferred to a PDMS film resulting in a flexible SERS substrate capable of direct detection of thiram on an apple peel without any additional sample pre-treatment.

Cicada Wing Inspired Template-Stripped SERS Active 3D Metallic Nanostructures for the Detection of Toxic Substances.

This article introduces a bioinspired, cicada wing-like surface-enhanced Raman scattering (SERS) substrate based on template-stripped crossed surface relief grating (TS-CSRG). The substrate is polarization-independent, has tunable nanofeatures and can be fabricated in a cleanroom-free environment via holographic exposure followed by template-stripping using a UV-curable resin. The bioinspired nanostructures in the substrate are strategically designed to minimize the reflection of light for wavelengths shorter than their periodicity, promoting enhanced plasmonic regions for the Raman excitation wavelength at 632.8 nm over a large area. The grating pitch that enables an effective SERS signal is studied using Rhodamine 6G, with enhancement factors of the order of 1 × 104. Water contact angle measurements reveal that the TS-CSRGs are equally hydrophobic to cicada wings, providing them with potential self-cleaning and bactericidal properties. Finite-difference time-domain simulations are used to validate the nanofabrication parameters and to further confirm the polarization-independent electromagnetic field enhancement of the nanostructures. As a real-world application, label-free detection of melamine up to 1 ppm, the maximum concentration of the contaminant in food permitted by the World Health Organization, is demonstrated. The new bioinspired functional TS-CSRG SERS substrate holds great potential as a large-area, label-free SERS-active substrate for medical and biochemical sensing applications.

Developing an integrated microfluidic and miniaturized electrochemical biosensor for point of care determination of glucose in human plasma samples.

A cost-effective, point of care (POC) device based on highly oriented CNT arrays was developed as an electrochemical assay for real-time and sensitive detection of glucose in complex samples. A low-cost, microcontroller-based potentiostat consisting of Arduino Due and LMP9100-EVM was developed to perform electrochemical measurements such as cyclic voltammetry (CV) and amperometry. A syringe pump based on open-source electronics was designed to direct the flow through a microfluidic chip. Vertically aligned carbon nanotube (VACNT) sensor arrays, in combination with the miniature potentiostat and the syringe pumps, were utilized as a POC device for the rapid and accurate detection of glucose. The structure and morphology of samples were characterized by field emission scanning electron microscopy (FESEM) and attenuated total reflectance Fourier transform infrared spectrometry (ATR-FTIR). CV as well as electrochemical impedance spectroscopy (EIS) was performed to investigate the electrochemical behavior of the electrode with respect to different diffusion regimes. The mediator-less biosensor had a limit of detection of 23 µM and sensitivity of 1462 µA mM-1 cm-2 and 1050 µA mM-1 cm-2 at the linear range of 1.2-7.8 mM and 7.8-11.2 mM, respectively. The presence of other biological compounds such as uric acid (UA) and ascorbic acid (AA) did not interfere with the detection of glucose. Finally, the designed POC device was successfully applied for the determination of glucose in human blood plasma samples.

Screen-printed anion-exchange solid-phase extraction: A new strategy for point-of-care determination of angiotensin receptor blockers.

A miniaturized system of anion exchange solid phase extraction (SPE) based on a screen-printed electrode was developed as a point of care (POC) device for extraction and quantitative determination of anionic analytes. Nylon 6/polyaniline nanofibers were fabricated by electrospinning and in-situ oxidative polymerization techniques coated on a screen-printed working electrode and characterized by Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) methods. The effects of essential parameters such as desorption conditions, pH of the sample solution, adsorption voltage, adsorption time, and salt concentration on the performance of the method were investigated. To evaluate the performance of the system, angiotensin ΙΙ receptor antagonists, including valsartan, losartan, and irbesartan, were selected as model compounds and analyzed by HPLC/UV after extraction. The limits of detection and quantification were ranging between 0.4 and 0.9 µg L-1 and 1.3-3.0 µg L-1, respectively. The linear dynamic range for Losartan, Irbesartan, and Valsartan was 2-400, 4-1000, and 2-400 µg L-1, respectively, with R2 > 0.991. Finally, the method was applied for the determination of ARA-IIs in human blood plasma samples, and relative recoveries in the range of 89.0-107.8% with relative standard deviation (RSDs (≤8.9% were obtained.

Graphene Oxide Membranes for Isotopic Water Mixture Filtration: Preparation, Physicochemical Characterization, and Performance Assessment.

There is an increasing demand for nuclear reactors, driven by the global need for low CO2 producing energy sources. The use of light (H2O) or heavy water (D2O) in a nuclear reactor environment produces radioactive tritiated heavy (HTO, DTO) water as an inevitable contaminant. Considering the need for tritiated water removal and also the high commercial value of purified water isotopes, technologies that can efficiently separate isotopic mixtures of water in nuclear reactors are highly desirable. This study presents an experimental approach for producing graphene oxide (GO) membranes and assessing their performance in the filtration of isotopic water mixtures. Specifically, using D2O/H2O mixtures as model systems, we investigate the effect of physicochemical properties of GO, as well as membrane preparation conditions on membrane filtration efficiency. We find that membranes assembled using larger GO platelets of lower oxidation level generally exhibit higher deuterated water (HDO, D2O) rejection and filtrate flux. Moreover, membrane preparation conditions have a strong impact on the interlayer space between stacked GO nanoplatelets in the membrane, hence as a direct effect on filtration performance. Our experimental results also show a strong, nonmonotonic dependence of separation performance on operating temperature, as well as the existence of local temperature optima. Our work provides guidelines for simple and scalable preparation of GO membranes with very good mechanical stability, capable of achieving efficient separation of isotopic water.

Portable surface-enhanced Raman scattering analysis performed with microelectrode-templated silver nanodendrites.

Using a handheld Raman spectrometer, we demonstrate how silver nanodendritic substrates formed on microelectrode platforms can be used for ultrasensitive detection of target analytes, such as cocaine and melamine. The nanostructured substrates are formed through the electrochemical deposition of silver on electrically insulated silicon substrates with the aid of an alternating current (AC) signal applied to the microelectrodes. A nanostructure lateral growth rate of 8.90 ± 0.19 µm min-1 was achieved by implementing a semi-batch process that kept the reactant concentrations high during silver deposition. This facile process can be used with different microelectrode designs, thus allowing for customizable SERS substrates. Compared with a commercially available benchmark, our surface-enhanced Raman scattering (SERS) substrates were found to be at least twice more sensitive. Moreover, by applying multivariate analysis, specifically principal component analysis and linear classification models, the pesticide thiram was identified at 1 ppm with 100% accuracy in spiked apple juice without sample pre-processing. Our technique provides the means for combining microelectrode platforms with SERS for portable, point-of-care sensing applications.

Electrokinetically-Driven Assembly of Gold Colloids into Nanostructures for Surface-Enhanced Raman Scattering.

Surface-enhanced Raman scattering (SERS) enables the highly sensitive detection of (bio)chemical analytes in fluid samples; however, its application requires nanostructured gold/silver substrates, which presents a significant technical challenge. Here, we develop and apply a novel method for producing gold nanostructures for SERS application via the alternating current (AC) electrokinetic assembly of gold nanoparticles into two intricate and frequency-dependent structures: (1) nanowires, and (2) branched "nanotrees", that create extended sensing surfaces. We find that the growth of these nanostructures depends strongly on the parameters of the applied AC electric field (frequency and voltage) and ionic composition, specifically the electrical conductivity of the fluid. We demonstrate the sensing capabilities of these gold nanostructures via the chemical detection of rhodamine 6G, a Raman dye, and thiram, a toxic pesticide. Finally, we demonstrate how these SERS-active nanostructures can also be used as a concentration amplification device that can electrokinetically attract and specifically capture an analyte (here, streptavidin) onto the detection site.

Achieving high yield of graphene nanoplatelets in poloxamer-assisted ultrasonication of graphite in water.

The role of surfactant (Pluronic® F 127) concentration on the yield and morphological characteristics of graphene nanoplatelets (GNPs) produced from the sonication of aqueous graphene suspensions is investigated in this work. By employing a wide surfactant concentration range (0.1-15 wt%) and sonication power densities up to 420 W L-1 we identify two graphene exfoliation regimes: the first occurs at low sonication power densities (<340 W L-1) and produces GNPs with sizes 200-300 nm, aspect ratios between 70 and 100, and concentrations up 1 mg mL-1. In that regime, the surfactant concentration has no effect on the exfoliation results. In the second exfoliation regime (>340 W L-1), surfactant concentrations greater than 10 wt% produce dramatic increases in GNP yields, namely up to 3.0 mg mL-1, and overall larger GNPs (350-500 nm) with smaller aspect ratios (5-60). We attribute these changes to the onset of a more energy intensive mechanism, termed cleavage. Cleavage involves the separation of graphite clusters in sub-bulk multi-layered graphene entities, as opposed to exfoliation, which involves the separation of individual or few-layer GNPs. Choosing an exfoliation regime by tuning simple process parameters enables control over the yield, size and morphology of the produced GNPs.

Improving the Surface-Enhanced Raman Scattering Performance of Silver Nanodendritic Substrates with Sprayed-On Graphene-Based Coatings.

This study examines the improvements in surface-enhanced Raman scattering (SERS) performance achieved when silver nanodendritic structures are coated with various graphene-based materials, namely graphene oxide (GO), reduced graphene oxide (rGO), and graphene nanoplatelets (GNPs). The tests are performed on our unique SERS-active substrates, prepared on the surface of planar microelectrode chips using an electric field-guided Ag nanoparticle assembly process. The graphene-based materials are introduced into the substrate by means of an in-house spray-coating technique. The SERS enhancement effect of each coating is examined as a function of spray nozzle passes (N) and optimal values are identified for each coating type. The enhancements found for GO, rGO, and GNP (6⁻9 graphene layers thick) coatings are 2.3 (N = 25), 2.5 (N = 5), and 1.6 (N = 1), respectively. Additionally, in comparison with their uncoated counterparts, substrates coated with rGO (N = 5) are shown to enhance the intensity of the methamphetamine (5 ppb) spectrum in artificial saliva by approximately 3-fold. Overall, it can be concluded that the introduction of GO or rGO to the SERS substrate using spray-coating, a simple and also scalable method, can produce substantial SERS performance enhancement.

Direct Detection of Toxic Contaminants in Minimally Processed Food Products Using Dendritic Surface-Enhanced Raman Scattering Substrates.

We present a method for the surface-enhanced Raman scattering (SERS)-based detection of toxic contaminants in minimally processed liquid food products, through the use of a dendritic silver nanostructure, produced through electrokinetic assembly of nanoparticles from solution. The dendritic nanostructure is produced on the surface of a microelectrode chip, connected to an AC field with an imposed DC bias. We apply this chip for the detection of thiram, a toxic fruit pesticide, in apple juice, to a limit of detection of 115 ppb, with no sample preprocessing. We also apply the chip for the detection of melamine, a toxic contaminant/food additive, to a limit of detection of 1.5 ppm in milk and 105 ppb in infant formula. All the reported limits of detection are below the recommended safe limits in food products, rendering this technique useful as a screening method to identify liquid food with hazardous amounts of toxic contaminants.

Optimized inkjet-printed silver nanoparticle films: theoretical and experimental investigations.

We study the influence of inkjet printing scheme and sintering parameter on the electrical resistivity of multi-layer silver nanoparticle films. A central composite Design Of Experiments (DOE) is employed to maximize experimental efficiency and improve the statistical significance of parameter estimates. The resulting mathematical correlations allow to interpret the influence of the print and sintering parameters. Detailed inspection of the correlations reveals the existence of local extrema and indicates that a structured approach such as the DOE would be significantly more effective for fabricating films with a minimum of resistivity. Furthermore, we modify the well-known Fuchs-Sondheimer Mayadas-Shatzkes model to correlate the resistivity of a multi-layer nanoparticle film with the sintering temperature and time. The modified model uses literature data but one constant inferred from two experiments. After model adjustment, the resistivities of films fabricated with different parameters can be predicted with good accuracy. This validation tremendously increases applicability and relevance of the model.

In situ assembly of active surface-enhanced Raman scattering substrates via electric field-guided growth of dendritic nanoparticle structures.

Surface-enhanced Raman scattering (SERS) can provide ultrasensitive detection of chemical and biological analytes down to the level of a single molecule. The need for costly, nanostructured, noble-metal substrates, however, poses a major obstacle in the widespread application of the method. Here we present for the first time a novel type of metallic nanostructured substrates that, not only exhibit a remarkable SERS activity, but are also produced in a facile, cost-effective and nanofabrication-free manner. The substrates are formed through an electric field-guided assembly process of silver nanocolloids, which results in extended and interconnected dendritic nanoparticle structures with a high density of "hot spots". A unique and significant performance attribute of these nanostructures is their ability to also function as concentration amplification devices, thereby further enhancing their analyte detection efficiency. This major advantage against conventional SERS substrates is illustrated experimentally here with the concentration and detection of proteins from solution. Low limits of detection for illicit drugs, food contaminants and pesticides in relevant matrices are also demonstrated. The SERS-active dendrites are reusable and can be removed and replaced in a few minutes. The SERS substrates presented herein constitute a significant advance towards more effective and less expensive diagnostic tools.

Contact-Free Templating of 3-D Colloidal Structures Using Spatially Nonuniform AC Electric Fields.

The formation of ordered and regularly shaped structures of colloidal particles with the aid of spatially nonuniform electric fields is a modern research area of great interest. This work illustrates how alternating current (AC) electrokinetic effects (dielectrophoresis, electroosmosis) can serve as contact-free templates, inside which colloidal microspheres can assemble into a variety of shapes and sizes. We show how three-dimensional colloidal structures of square, circular, and diamond shape of many tens of micrometers in size can be reproducibly formed with a single set of quadrupolar microelectrodes. Numerical simulations performed help to explain the role of AC electroosmosis and AC dielectrophoresis on the shaping of these structures as a function of applied voltage and frequency. We also demonstrate how the templating repertoire is further enhanced with the simultaneous application of a second, individually controlled AC electric field, which enables a variety of asymmetric colloidal structures to be produced using the same set of quadrupolar microelectrodes. As the preservation of shape and size of such electric-field templated structures after medium evaporation still remains a big challenge, here we also report on a novel method that permits the stabilization and isolation of these particle assemblies through medium gelation and subsequent hydrogel removal with a UV/ozone treatment.

Accelerated detection of viral particles by combining AC electric field effects and micro-Raman spectroscopy.

A detection method that combines electric field-assisted virus capture on antibody-decorated surfaces with the "fingerprinting" capabilities of micro-Raman spectroscopy is demonstrated for the case of M13 virus in water. The proof-of-principle surface mapping of model bioparticles (protein coated polystyrene spheres) captured by an AC electric field between planar microelectrodes is presented with a methodology for analyzing the resulting spectra by comparing relative peak intensities. The same principle is applied to dielectrophoretically captured M13 phage particles whose presence is indirectly confirmed with micro-Raman spectroscopy using NeutrAvidin-Cy3 as a labeling molecule. It is concluded that the combination of electrokinetically driven virus sampling and micro-Raman based signal transduction provides a promising approach for time-efficient and in situ detection of viruses.

Correlation between the length reduction of carbon nanotubes and the electrical percolation threshold of melt compounded polyolefin composites.

The objectives of this work are to quantify the degree of multiwalled carbon nanotube (MWCNT) length reduction upon melt compounding and to demonstrate unambiguously that the length reduction is mainly responsible for the increase in electrical percolation threshold of the resulting composites. Polyolefin matrices of varying viscosities and different functional groups are melt compounded with MWCNTs. A simple method is developed to solubilize the polymer matrix and isolate the MWCNTs, enabling detailed imaging analysis. In spite of the perceived strength of the MWCNTs, the results demonstrate that the shear forces developed during melt mixing are sufficient to cause significant nanotube breakage and length reduction. Breakage is promoted when higher MWCNT contents are used, due to increased probability of particle collisions. Furthermore, the higher shear forces transmitted to the nanotubes in the presence of higher matrix viscosities and functional groups that promote interfacial interactions, shift the nanotube distribution toward smaller sizes. The length reduction of the MWCNTs causes significant increases in the percolation threshold, due to the loss of interconnectivity, which results in fewer conductive pathways. These findings are validated by comparing the experimental percolation threshold values with those predicted by the improved interparticle distance theoretical model.

A noncovalent compatibilization approach to improve the filler dispersion and properties of polyethylene/graphene composites.

Graphene was prepared by low temperature vacuum-assisted thermal exfoliation of graphite oxide. The resulting thermally reduced graphene oxide (TRGO) had a specific surface area of 586 m(2)/g and consisted of a mixture of single-layered and multilayered graphene. The TRGO was added to maleated linear low-density polyethylene LLDPE and to its derivatives with pyridine aromatic groups by melt compounding. The LLDPE/TRGO composites exhibited very low electrical percolation thresholds, between 0.5 and 0.9 vol %, depending on the matrix viscosity and the type of functional groups. The dispersion of the TRGO in the compatibilized composites was improved significantly, due to enhanced noncovalent interactions between the aromatic moieties grafted onto the polymer matrix and the filler. Better dispersion resulted in a slight increase in the rheological and electrical percolation thresholds, and to significant improvements in mechanical properties and thermal conductivity, compared to the noncompatibilized composites. The presence of high surface area nanoplatelets within the polymer also resulted in a substantially improved thermal stability. Compared to their counterparts containing multiwalled carbon nanotubes, LLDPE/TRGO composites had lower percolation thresholds. Therefore, lower amounts of TRGO were sufficient to impart electrical conductivity and modulus improvements, without compromising the ductility of the composites.

AC electrokinetic templating of colloidal particle assemblies: effect of electrohydrodynamic flows.

The use of spatially nonuniform electric fields for the contact-free colloidal particle assembly into ordered structures of various length scales is a research area of great interest. In the present work, numerical simulations are undertaken in order to advance our understanding of the physical mechanisms that govern this colloidal assembly process and their relation to the electric field characteristics and colloidal system properties. More specifically, the electric-field driven assembly of colloidal silica (d(p) = 0.32 and 2 µm) in DMSO, a near index matching fluid, is studied numerically over a range of voltages and concentration by means of a continuum thermodynamic approach. The equilibrium (u(f) = 0) and nonequilibrium (u(f) ≠ 0) cases were compared to determine whether fluid motion had an effect on the shape and size of assemblies. It was found that the nonequilibrium case was substantially different versus the equilibrium case, in both size and shape of the assembled structure. This dependence was related to the relative magnitudes of the electric-field driven convective motion of particles versus the fluid velocity. Fluid velocity magnitudes on the order of mm/s were predicted for 0.32 µm particles at 1% initial solids content, and the induced fluid velocity was found to be larger at the same voltage/initial volume fraction as the particle size decreased, owing to a larger contribution from entropic forces.

Morphology of fibroblasts grown on substrates formed by dielectrophoretically aligned carbon nanotubes.

Multiwall carbon nanotube templates formed on the surfaces of planar interdigitated microelectrode arrays by means of AC electric field-guided assembly are being explored as potential substrates for tissue engineering. The objective of the present study is to examine whether surface patterns of aligned multiwall carbon nanotubes can have an effect on cell growth, morphology, and alignment. Bovine fibroblasts grown on aligned carbon nanotubes for a period of 2 weeks were found to have raised bodies and pronounced cell extensions for anchoring themselves to the substrate similar to that of the cells found in native tissues. On the other hand, cells grown on various control surfaces had a flat, circular morphology. The cell cultures were visualized by means of SEM imaging and the resulting morphologies were statistically analyzed and compared.