Monitoring spatial distribution of ethanol in microfluidic channels by using a thin layer of cholesteric liquid crystal

Monitoring spatial distribution of chemicals in microfluidic devices by using traditional sensors is a challenging task. In this paper, we report utilization of a thin layer of cholesteric liquid crystal for monitoring ethanol inside microfluidic channels. This thin layer can be either a polymer dispersed cholesteric liquid crystal (PDCLC) layer or a free cholesteric liquid crystal (CLC) layer separated from the microfluidic device by using a thin film of PDMS. They both show visible colorimetric responses to 4% of ethanol solution inside the microfluidic channels. Moreover, the spatial distribution of ethanol inside the microfluidic channel can be reflected as a color map on the CLC sensing layers. By using this device, we successfully detected ethanol produced from fermentation taking place inside the microfluidic channel. These microfluidic channels with embedded PDCLC or embedded CLC offer a new sensing solution for monitoring volatile organic compounds in microfluidic devices.     

Microfluidic sensing devices employing in situ-formed liquid crystal thin film for detection of biochemical interactions

Although biochemical sensing using liquid crystals (LC) has been demonstrated, relatively little attention has been paid towards the fabrication of in situ-formed LC sensing devices. Herein, we demonstrate a highly reproducible method to create uniform LC thin film on treated substrates, as needed, for LC sensing. We use shear forces generated by the laminar flow of aqueous liquid within a microfluidic channel to create LC thin films stabilized within microfabricated structures. The orientational response of the LC thin films to targeted analytes in aqueous phases was transduced and amplified by the optical birefringence of the LC thin films. The biochemical sensing capability of our sensing devices was demonstrated through experiments employing two chemical systems: dodecyl trimethylammonium bromide (DTAB) dissolved in an aqueous solution, and the hydrolysis of phospholipids by the enzyme phospholipase A(2) (PLA(2)).     

Electrical circuits from capillary flow driven evaporation deposition of carbon nanotube ink in non-porous V-grooves

Low cost pliable electronics portend the advancement of novel inexpensive microfluidic electrochemical devices. In the direct printing approach, the manner of deposition of conductive material from a liquid suspension to ensure electrical continuity is crucial. We describe here an approach in which V-groove networks that make up the path of circuitry are first scribed on non-porous inexpensive surfaces. Liquid drops of carbon nanotube ink are then placed on the surface adjacent to the V-grooves to enable wicking to produce the electrical circuit. This method essentially bypasses the need for inkjet printing. We investigate the basic efficacy of the conductive networks developed using this approach and demonstrate its use in generating electrically driven liquid flow of particles in a simple open capillary channel.     

Comparative study on different carbon nanotube materials in terms of transparent conductive coatings

We compared conductive transparent carbon nanotube coatings on glass substrates made of differently produced single-wall (SWNT), double-wall, and multiwall carbon nanotubes. The airbrushing approach and the vacuum filtration method were utilized for the fabrication of carbon nanotube films. The optoelectronic performance of the carbon nanotube film was found to strongly depend on many effects including the ratio of metallic-to-semiconducting tubes, dispersion, length, diameter, chirality, wall number, structural defects, and the properties of substrates. The electronic transportability and optical properties of the SWNT network can be significantly altered by chemical doping with thionyl chloride. Hall effect measurements revealed that all of these thin carbon nanotube films are of p-type probably due to the acid reflux-based purification and atmospheric impurities. The competition between variable-range hoping and fluctuation-assisted tunneling in the functionized carbon nanotube system could lead to a crossover behavior in the temperature dependence of the network resistance.     

Redox modulation of electroosmotic flow in a carbon nanotube membrane

Electroosmotic flow (EOF) is widely used to manipulate solutions in capillaries and microfluidic devices, and more recently in the nanotubes of a carbon nanotube membrane. In all of these applications it is important to control both the rate and direction of EOF through the system, independently of the electric field that drives EOF. For this reason, there has been considerable recent effort devoted to developing ways of modulating the rate and direction of EOF. We describe here a new method, and we use the carbon nanotube membrane (CNM) system to demonstrate this method. This new method entails coating the inside walls of the carbon nanotubes within the CNM with redox-active polymer films. The redox polymer, poly(vinylferrocene), can be reversibly electrochemically switched between an electrical neutral and a polycationic form. This provides a way for controlling both the magnitude and the sign of the surface charge on the nanotube walls, which in turn allows for control of both the rate and direction of EOF through the CNM.     

Effects of ionic surfactant adsorption on single-walled carbon nanotube thin film devices in aqueous solutions

Field-effect transistors were fabricated using high-density single-walled carbon nanotube (SWNT) thin films directly grown on suitable substrates. Such approach eliminated the variations of device behaviors in individual SWNT devices by utilizing a large number of SWNTs in each device. We have found that the behaviors of such devices are closely related to the surface charge densities around SWNTs in aqueous solutions. Adsorption of ionic surfactants on the surface could significantly modulate the device characteristics, which could be detected by measuring the conductance of the devices. The devices could be tuned to be sensitive to either anionic or cationic surfactants by tailoring the surface properties of SiO(2) substrates around SWNTs. This effect could be potentially used to design chemical and biological sensors.     

Electronically monitoring biological interactions with carbon nanotube field-effect transistors

The year 2008 marks the 10th anniversary of the carbon nanotube field-effect transistor (NTFET). In the past decade a vast amount of effort has been placed on the development of NTFET based sensors for the detection of both chemical and biological species. Towards this end, NTFETs show great promise because of their extreme environmental sensitivity, small size, and ultra-low power requirements. Despite the great progress NTFETs have shown in the field of biological sensing, debate still exists over the mechanistic origins underlying the electronic response of NTFET devices, specifically whether analyte species interact with the carbon nanotube conduction channel or if interaction with the NTFET electrodes actually triggers device response. In this tutorial review, we describe the fabrication of NTFET devices, and detail several reports that illustrate recent advances in biological detection using NTFET devices, while highlighting the suggested mechanisms explaining the device response to analyte species. In doing this we hope to show that NTFET technology has the potential for low-cost and portable bioanalytical platforms.     

Carbon nanotube transistors for biosensing applications

Electronic detection of biomolecules, although still in its early stages, is gradually emerging as an effective alternative to optical detection methods. We describe field effect transistor devices with carbon nanotube conducting channels that have been developed and used for biosensing and biodetection. Both transistors with single carbon nanotube conducting channels and devices with nanotube network conducting channels have been fabricated and their electronic characteristics examined. The devices readily respond to changes in the environment, and such effects have been examined using gas molecules and coatings with specific properties. Device operation in (conducting) buffer and in a dry environment--after buffer removal--is also discussed. Applications in the biosensing area are illustrated with three examples: the investigation of the interaction between devices and biomolecules, the electronic monitoring of biomolecular processes, and attempts to integrate cell membranes with active electronic devices.     

Directing and sensing changes in molecular conformation on individual carbon nanotube field effect transistors

This study explores how to populate the surface of the carbon nanotubes with functional molecules that can be toggled back-and-forth between different molecular conformations. The molecules synthesized for this study are tagged with a photoswitchable headgroup and a functional group which directs the assembly on the surface of the carbon nanotubes. Single-walled carbon nanotube field effect transistors switch between high and low conductance as the molecules are switched with light between open and closed conformations. These devices detect the photoswitching of approximately 104 molecules.     

Multifunctional chemical vapor sensors of aligned carbon nanotube and polymer composites

Partially coating perpendicularly aligned carbon nanotube arrays with an appropriate polymer thin film along their tube length provides a novel concept for developing new sensors of high sensitivity, good selectivity, and excellent environmental stability for the detection of a broad class of chemical vapors with low power consumption. The absorption and desorption of chemical vapors by the polymer matrix cause changes in the inter-tube distance and, hence, the surface resistance across the nanotube film. Simple measurements of the resistance change, therefore, constitute the nanotube-polymer chemical vapor sensors. These rationally designed, aligned carbon nanotube-polymer composite films are flexible and can be effectively integrated into many systems for a wide range of potential applications, including their use as multifunctional sensors for sensing chemical vapors, mechanical deformations, thermal and optical exposures.     

Thickness dependent sensing mechanism in sorted semi-conducting single walled nanotube based sensors

Single walled carbon nanotube (SWCNT) networks present outstanding potential for the development of SWCNT-based gas sensors. Due to the complexity of the transport properties of this material, the physical mechanisms at stake during exposure to gas are still under debate. Previously suggested mechanisms are charge transfer between gas molecules and SWCNT and Schottky barrier modulation. By comparing electrical measurements with an analytical model based on Schottky barrier modulation, we demonstrate that one mechanism or the other is predominant depending on the percolation of metallic carbon nanotubes. Below the metallic SWCNT percolation threshold, sensing is dominated by the modulation of the Schottky barrier, while above this threshold, it is only attributed to a charge transfer between SWCNT and gas molecules. Both mechanisms are discussed in terms of sensitivity and resolution leading to routes for the optimization of a gas sensor architecture based on highly enriched semiconducting carbon nanotube films.     

Drag on a nanotube in uniform liquid argon flow

In this work, nonequilibrium molecular dynamics (MD) simulations were performed to investigate uniform liquid argon flow past a carbon nanotube. In the simulation, nanotubes were modeled as rigid cylinders of carbon atoms. Both argon-argon and argon-carbon interactions were calculated based on Lennard-Jones potential. Simulated drag coefficients were compared with (i) published empirical equation which was based on experiments conducted with macroscale cylinders and (ii) finite element (FE) analyses based on Navier-Stokes equation for flow past a circular cylinder using the same dimensionless parameters used in MD simulations. Results show that classical continuum mechanics cannot be used to calculate drag on a nanotube. In slow flows, the drag coefficients on a single-walled nanotube calculated from MD simulations were larger than those from the empirical equation or FE analysis. The difference increased as the flow velocity decreased. For higher velocity flows, slippage on the surface of the nanotube was identified which resulted in lower drag coefficient from MD simulation. This explains why the drag coefficient from MD dropped faster than those from the empirical equation or FE simulation as the flow velocity increased. It was also found that the drag forces are almost equal for single- and double-walled nanotubes with the same outer diameter, implying that inner tubes do not interact with fluid molecules.     

碳纳米管薄膜晶体管中的接触电阻效应

利用不同功函数的金属作为接触电极,研究了网络状碳纳米管薄膜晶体管(CNT-TFT)的接触电阻效应。研究表明金属Pd与碳纳米管薄膜形成良好的欧姆接触, Au则形成近欧姆接触,这两种接触的器件的开态电流和迁移率较高。Ti和Al都与碳纳米管薄膜形成肖特基接触,且Al接触比Ti接触的势垒更高,接触电阻也更大,相应器件的开态电流和迁移率都较低。该结果表明对于CNT-TFT仍然可以通过接触来调控器件的性能,这对CNT-TFT的实用化进程具有重要的促进作用。     

Numerical and experimental investigation of ‘water fan’ effect due to electrohydrodynamic force in a microchamber

Electrohydrodynamics is commonly used in microfluidics to control and manipulate the fluid. Though there are studies on the rotation flow in suspended films, the thin film liquid is easily broken and cannot last long hence not applicable in specific applications. Here, we established a three‐dimensional microchamber embedded with two pairs of microelectrodes to investigate the rotational phenomenon of bulk of liquid which we called ‘water fan’ effect based on the electrohydrodynamics force. When proper voltages were applied on these microelectrodes, the tornado‐like rotation would be generated. Both the numerical and experimental results showed that the controllable and continuous rotation could be achieved in the microchamber. In addition, the concentration effect resulting from the rotation flow was also observed. The proposed method offers great promises in providing theoretical and practical guideline in microfluidic devices for mixing, separating, and cooling applications.     

Molecular beam-controlled nucleation and growth of vertically aligned single-wall carbon nanotube arrays

The main obstacle to widespread application of single-wall carbon nanotubes is the lack of reproducible synthesis methods of pure material. We describe a new growth method for single-wall carbon nanotubes that uses molecular beams of precursor gases that impinge on a heated substrate coated with a catalyst thin film. In this growth environment the gas and the substrate temperature are decoupled and carbon nanotube growth occurs by surface reactions without contribution from homogeneous gas-phase reactions. This controlled reaction environment revealed that SWCNT growth is a complex multicomponent reaction in which not just C, but also H, and O play a critical role. These experiments identified acetylene as a prolific direct building block for carbon network formation that is an order of magnitude more efficient than other small-molecule precursors. The molecular jet experiments show that with optimal catalyst particle size the incidence rate of acetylene molecules plays a critical role in the formation of single-wall carbon nanotubes and dense vertically aligned arrays in which they are the dominant component. The threshold for vertically aligned growth, the growth rate, the diameter, and the number of walls of the carbon nanotubes are systematically correlated with the acetylene incidence rate and the substrate temperature.     

Carbon nanotube detectors for microchip CE: comparative study of single-wall and multiwall carbon nanotube, and graphite powder films on glassy carbon, gold, and platinum electrode surfaces

The performance of microchip electrophoresis/electrochemistry system with carbon nanotube (CNT) film electrodes was studied. Electrocatalytic activities of different carbon materials (single-wall CNT (SWCNT), multiwall CNT (MWCNT), carbon powder) cast on different electrode substrates (glassy carbon (GC), gold, and platinum) were compared in a microfluidic setup and their performance as microchip electrochemical detectors was assessed. An MWCNT film on a GC electrode shows electrocatalytic effect toward oxidation of dopamine (E(1/2) shift of 0.09 V) and catechol (E(1/2) shift of 0.19 V) when compared to a bare GC electrode, while other CNT/carbon powder films on the GC electrode display negligible effects. Modification of a gold electrode by graphite powder results in a strong electrocatalytic effect toward oxidation of dopamine and catechol (E(1/2) shift of 0.14 and 0.11 V, respectively). A significant shift of the half-wave potentials to lower values also provide the MWCNT film (E(1/2) shift of 0.08 and 0.08 V for dopamine and catechol, respectively) and the SWCNT film (E(1/2) shift of 0.10 V for catechol) when compared to a bare gold electrode. A microfluidic device with a CNT film-modified detection electrode displays greatly improved separation resolution (R(s)) by a factor of two compared to a bare electrode, reflecting the electrocatalytic activity of CNT.     

Carbon nanotube based stationary phases for microchip chromatography

The objective of this article is to provide an overview and critical evaluation of the use of carbon nanotubes and related carbon-based nanomaterials for microchip chromatography. The unique properties of carbon nanotubes, such as a very high surface area and intriguing adsorptive behaviour, have already been demonstrated in more classical formats, for improved separation performance in gas and liquid chromatography, and for unique applications in solid phase extraction. Carbon nanotubes are now also entering the field of microfluidics, where there is a large potential to be able to provide integrated, tailor-made nanotube columns by means of catalytic growth of the nanotubes inside the fluidic channels. An evaluation of the different implementations of carbon nanotubes and related carbon-based nanomaterials for microfluidic chromatography devices is given in terms of separation performance and ease of fabrication.     

Dendron growth from vertically aligned single-walled carbon nanotube thin layer arrays for photovoltaic devices

Single-walled carbon nanotube arrays attached to conductive transparent electrodes have previously shown promise for use in photovoltaic devices, whilst still retaining light transmission. Here, chemical modification of these thin (<200 nm) arrays with PAMAM-type dendrons has been undertaken to enhance the photoresponse of these devices. The effect of modification on the electrode was measured by differential pulse voltammetry to detect the dendrons, and the effect on the nanotubes was measured by Raman spectroscopy. Solar simulator illumination of the cells was performed to measure the effect of the nanotube modification on the cell power, and determine the optimal modification. Electrochemical impedance spectroscopy was also used to investigate the equivalent electronic circuit elements of the cells. The optimal dendron modification occurred with the second generation (G-2.0), which gave a 70% increase in power over the unmodified nanotube array.     

Electrochemical properties of a fully integrated, singlewalled carbon nanotube coplanar three-electrode system on glass substrate

Fully integrated carbon nanotube-based three-electrode electrochemical systems were photolithographically prepared on glass substrates and electrochemically characterized. O₂ plasma treatment of the transferred single-walled carbon nanotube (SWCNT) film was voltammetrically optimized in terms of applied plasma power and the elapsed time. The patterned thin film Ag layer was chemically oxidized in an acidic solution for various dip times to form a chlorinated Ag layer. The Nernstian behavior of as-prepared and seven-day-aged Ag/AgCl thin-film electrodes was investigated for optimization, and the electrode's electrochemical attributes were compared to a commercial reference electrode. A quality control evaluation and a performance assessment of the fully integrated SWCNT-transferred sensing systems were performed using cyclic voltammetry. The proposed SWCNT-based three-electrode device exhibited clear electrochemistry under voltammetric conditions, and is therefore a candidate for use in all electrochemical biosensors.     

Apatite-forming ability of titanium compound nanotube thin films formed on a titanium metal plate in a simulated body fluid

We compared the apatite-forming ability of a sodium titanate nanotube thin film, an anatase-type titanium dioxide nanotube thin film, and a silver nanoparticle/silver titanate nanotube nanocomposite thin film, in simulated body fluid. The ability of the silver nanoparticle/silver titanate nanotube nanocomposite thin film is slightly higher than that of the anatase-type titanium dioxide nanotube thin film and significantly higher than that of the sodium titanate nanotube thin film. The high ability of the silver nanoparticle/silver titanate nanotube nanocomposite thin film is a newly observed phenomenon, which is probably due to the crystal structure of silver titanate – specifically, to the surface atomic arrangement, the large amount of Ti–OH formed on the nanotube surface, or both. The anatase-type titanium dioxide nanotube thin film and the silver nanoparticle/silver titanate nanotube nanocomposite thin film may have bright prospects for future use in implant materials such as artificial joints. The silver nanoparticle/silver titanate nanotube nanocomposite thin film is particularly promising for its antibacterial properties.