Polymer crystallization-driven, periodic patterning on carbon nanotubes

We report herein a unique means to periodically pattern polymeric materials on individual carbon nanotubes (CNTs) using a controlled polymer crystallization method. One-dimensional (1D) CNTs were periodically decorated with polymer lamellar crystals, resulting in nano-hybrid shish-kebab (NHSK) structures. The periodicity of the polymer lamellae varies from 20 to 150 nm. The kebabs are approximately 5-10 nm thick (along CNT direction) with a lateral size of approximately 20 nm to micrometers, which can be readily controlled by varying crystallization conditions. Both polyethylene and Nylon 66 were successfully decorated on single-walled carbon nanotubes (SWNTs), multiwalled carbon nanotubes (MWNTs), as well as vapor grown carbon nanofibers (CNFs). The formation mechanism was attributed to "size-dependent soft epitaxy". Because NHSK formation conditions depend on CNT structures, it further provides a unique opportunity for CNT separation. The reported method opens a gateway to periodically patterning polymers and different functional groups on individual CNTs in an ordered and controlled manner, an attractive research field that is yet to be explored.     

An automated electrokinetic continuous sample introduction system for microfluidic chip-based capillary electrophoresis

An automated and continuous sample introduction system for microfluidic chip-based capillary electrophoresis (CE) was developed in this work. An efficient world-to-chip interface for chip-based CE separation was produced by horizontally connecting a Z-shaped fused silica capillary sampling probe to the sample loading channel of a crossed-channel chip. The sample presentation system was composed of an array of bottom-slotted sample vials filled alternately with samples and working electrolyte, horizontally positioned on a programmable linearly moving platform. On moving the array from one vial to the next, and scanning the probe, which was fixed with a platinum electrode on its tip, through the slots of the vials, a series of samples, each followed by a flow of working electrolyte was continuously introduced electrokinetically from the off-chip vials into the sample loading channel of the chip. The performance of the system was demonstrated in the separation and determination of FITC-labeled arginine and phenylalanine with LIF detection, by continuously introducing a train of different samples. Employing 4.5 kV sampling voltage (1000 V cm(-1) field strength) for 30 s and 1.8 kV separation voltage (400 V cm(-1) field strength) for 70 s, throughputs of 36 h(-1) were achieved with <1.0% carryover and 4.6, 3.2 and 4.0% RSD for arginine, FITC and phenylalanine, respectively (n = 11). Net sample consumption was only 240 nL for each sample.     

Field Emission Properties of Multi-walled Carbon Nanotubes Grown on Silicon Nanoporous Pillar Array

"Multi-walled carbon nanotubes (CNTs) were grown on a silicon nanoporous pillar array (Si-NPA) by thermal chemical vapor deposition. Surface morphologies and microstructure of the resultant were studied by a field emission scanning electron microscope, Raman spectrum, transmission electron microscope, and highresolution transmission electron microscopy. The composition of samples was determined by energy dispersive X-ray spectroscopy (EDS). The results showed that a great deal of CNTs, with diameter in the range of 20-70 nm, incorporated with Si-NPA and a large scale nest array of CNTs/Si-NPA (NACNT/Si-NPA) was formed. EDS analysis showed that the composition of carbon nanotubes was carbon. Field emission measurements showed that a current density of 5 mA/cm2 was obtained at an electric field of 4.26 V/1m, with a turn-on field of 1.3 V/1m. The enhancement factor calculated according to the Fowler-Nordheim theory was ?11,000. This excellent field emission performance is attributed to the unique structure and morphology of NACNT/Si-NPA, especially the formation of a nest-shaped carbon nanotube array. A schematic drawing that illustrates the experimental configuration is given. These results indicate that NACNT/Si-NPA might be an ideal candidate cathode for potential applications in flat panel displays."     

Hierarchical structures of carbon nanotubes and arrays of chromium-capped silicon nanopillars: formation and electrical properties

The formation of stochastically oriented carbon-nanotube networks on top of an array of free-standing chromium-capped silicon nanopillars is reported. The combination of nanosphere lithography and chemical vapor deposition enables the construction of nanostructures that exhibit a hierarchical sequence of structural sizes. Metallic chromium serves as an etching mask for Si-pillar formation and as a nucleation site for the formation of carbon nanotubes through the chemical vapor deposition of ethene, ethanol, and methane, respectively, thereby bridging individual pillars from top to top. Iron and cobalt were applied onto the chromium caps as catalysts for CNT growth and the influence of different carbon sources and different gas-flow rates were investigated. The carbon nanotubes were structurally characterized and their DC electrical properties were studied by in situ local- and ex situ macroscopic measurements, both of which reveal their semiconductor properties. This process demonstrates how carbon nanotubes can be integrated into Si-based semiconductors and, thus, this process may be used to form high-surface-area sensors or new porous catalyst supports with enhanced gas-permeation properties.     

Analytical temperature rising elution fractionation of different polyethylene types using a column filled with carbon nanotubes

A high temperature gel permeation chromatograph (GPC) was coupled with a gas chromatograph (GC) oven to obtain an analytical temperature rising elution fractionation (TREF) system with evaporative light scattering detection. On this instrument, a new column partially filled with pristine carbon nanotubes (CNT) was tested by evaluating the elution profiles in function of temperature (thermograms) of different polyethylene (PE) types. By comparing these thermograms with those obtained with a traditional TREF column filled with metallic wires, the adsorption of polymer chains on the pristine CNT was clearly evidenced. The thermograms given by the column filled with CNT are similar with those provided by literature when chromatographic columns filled with porous graphitic carbon are used for this application, usually described as high temperature thermal gradient interaction chromatography (HT-TGIC).     

Fast supercritical fluid chromatography hydrocarbon group-type separations of diesel fuels using packed and monolithic columns

Two approaches for decreasing diesel hydrocarbon group-type separation times by normal phase supercritical fluid chromatography (SFC) are compared. Short (10-15 cm) columns with small 3 microm diameter packing are compared with monolithic Chromolith bare silica columns under high carbon dioxide flow rates approaching 5 ml min(-1). Elution times are reduced up to 13-fold on a 10 cm Chromolith column and 7-fold on the short packed columns compared with conventional length columns run at typical flow rates. Short packed columns, with their higher surface area and retention characteristics, offer higher resolutions compared with Chromolith columns. Diesel samples are separated into saturates, mono-, di-, tri-, and polyaromatics in as little as 2 min on a 10 cm packed silica column. Diesel group-type results on a 15 cm titania-silica coupled column compare favorably with results from longer columns.     

An amperometric glucose biosensor based on glucose oxidase immobilized in electropolymerized poly(o-aminophenol) and carbon nanotubes composite film on a gold electrode.

An amperometric glucose biosensor is developed that is based on immobilization of glucose oxidase (GOD) in a composite film of poly(o-aminophenol) (POAP) and carbon nanotubes (CNT), which are electrochemically co-polymerized at a gold (Au) electrode. Because of the high surface per volume ratio and excellent electrical conductivity of CNT, the biosensor based on an Au/POAP/CNT/GOD electrode has lower detection limit (0.01 mM), larger maximum response current (0.24 mA cm(-2)) and higher sensitivity (11.4 mA M(-1) cm(-2)) than the values of the biosensor based on an Au/POAP/GOD electrode. Additionally, the biosensor shows fast response time, large response current, and good anti-interferent ability for ascorbic acid, uric acid and acetaminophen. Good reproducibility and stability of the biosensor are also observed.     

Cyclodextrin-modified monolithic columns for resolving dansyl amino acid enantiomers and positional isomers by capillary electrochromatography

We describe beta- and gamma-cyclodextrins (beta- and gamma-CD)-modified monolithic columns prepared by sol-gel process and chemical modifications. The monolithic silica column was fabricated inside a fused-silica capillary with 100 microm inner diameter by sol-gel process. The monolithic silica matrix was chemically modified chiral selectors of beta- or gamma-CDs with a spacer of 3-glycidoxypropyltrimethoxysilane by on-column reactions. Gamma-CD-modified monolithic column has successfully been applied for the separation of dansyl amino acid enantiomers. Beta-CD-modified monolithic column has been used for the separation of the positional isomers of o-, m-, and p-cresols and the enantioseparation of racemates of benzoin and several dansyl amino acids by capillary electrochromatography, respectively. For the separation of neutral positional isomers, a positive electric field was applied. However, for the separation of negatively charged analytes, a negative electric field was applied at the inlet of column. The separation efficiency of 5.0 x 10(4) theoretical plates/m for dansyl-L-threonine was obtained at electric field strength of -300 V/cm in the mobile phase of 50 mM 2-(N-morpholino)ethanesulfonic acid (MES)-Tris/methanol (70/30) buffer at pH 7.0. L-enantiomers were eluted as the first peak. Scanning electron micrograph showed that monolithic columns have the morphology of continuous skeleton and large through-pores.     

Hierarchical Structures of Carbon Nanotubes and Arrays of Chromium‐Capped Silicon Nanopillars: Formation and Electrical Properties

The formation of stochastically oriented carbon‐nanotube networks on top of an array of free‐standing chromium‐capped silicon nanopillars is reported. The combination of nanosphere lithography and chemical vapor deposition enables the construction of nanostructures that exhibit a hierarchical sequence of structural sizes. Metallic chromium serves as an etching mask for Si‐pillar formation and as a nucleation site for the formation of carbon nanotubes through the chemical vapor deposition of ethene, ethanol, and methane, respectively, thereby bridging individual pillars from top to top. Iron and cobalt were applied onto the chromium caps as catalysts for CNT growth and the influence of different carbon sources and different gas‐flow rates were investigated. The carbon nanotubes were structurally characterized and their DC electrical properties were studied by in situ local‐ and ex situ macroscopic measurements, both of which reveal their semiconductor properties. This process demonstrates how carbon nanotubes can be integrated into Si‐based semiconductors and, thus, this process may be used to form high‐surface‐area sensors or new porous catalyst supports with enhanced gas‐permeation properties.     

High surface area carbon aerogels as porous substrates for direct growth of carbon nanotubes

Novel carbon composites are fabricated through catalyzed CVD growth of carbon nanotubes directly on the inner surfaces of monolithic carbon aerogel (CA) substrates. Uniform CNT yield is obtained throughout the internal pore volume of CA monoliths with macroscopic dimensions. These composites possess large surface areas (>1000 m(2) g(-1)) and exhibit enhanced electrical conductivity following CNT growth.     

The influence and utility of varying field strength for the separation of tryptic peptides by ion mobility-mass spectrometry

The influence of field strength on the separation of tryptic peptides by drift tube-based ion mobility-mass spectrometry is reported. Operating the ion mobility drift tube at elevated field strengths (expressed in V cm(-1) torr(-1)) reduces separation times and increases ion transmission efficiencies. Several accounts in the literature suggest that performing ion mobility separation at elevated field strength can change the selectivity of ion separation. To evaluate the field strength dependant selectivity of ion mobility separation, we examined a data set of 65 singly charged tryptic peptide ion signals (mass range 500-2500 m/z) at six different field strengths and four different drift gas compositions (He, N2, Ar, and CH4). Our results clearly illustrate that changing the field strength from low field (15 V cm(-1) torr(-1)) to high field (66 V cm(-1) torr(-1)) does not significantly alter the selectivity or peak capacity of IM-MS. The implications of these results are discussed in the context of separation methodologies that rely on the field strength dependence of ion mobility for separation selectivity, e.g., high-field asymmetric ion mobility spectrometry (FAIMS).     

层层组装构筑聚电解质/碳纳米管导电黏附膜

首先将聚烯丙基胺盐酸盐与碳纳米管制成复合物(PAH-CNT), 再通过层层组装技术构筑了聚丙烯酸和碳纳米管混合物(PAA-CNT)与PAH-CNT多层复合膜(PAH-CNT/PAA-CNT). PAH-CNT/PAA-CNT多层复合膜同时具有导电和黏附性能. 在玻璃和ITO基片上沉积的PAH-CNT/PAA-CNT多层复合膜的最大拉伸剪切强度接近7 MPa, 即1 cm²的黏附膜可以承受约70 kg的重物. 碳纳米管的引入使PAH-CNT/PAA-CNT多层复合膜具有更好的导电性.     

A new method of quantification of pipemidic-acid by capillary zone electrophoresis with end-column amperometric detection

Capillary zone electrophoresis was employed for the determination of pipemidic acid using an end-column amperometric detection with a carbon fiber microdisk array electrode, at a constant potential of -1.10 V vs. saturated calomel electrode. The optimum conditions of separation and detection were 1.2 x 10(-4) mol/LNaOAc - 8.8 x 10(-4) mol/ LHOAc for the buffer solution, 20 kV for the separation voltage, 5 kV and 10 s for the injection voltage and the injection time. The limit of detection was 1.05 x 10(-7) mol/L or 189 amol (S/N=3). The relative standard deviation was 0.31% for the migration time and 2.0% for the electrophoretic peak current. The method was applied to determining pipemidic acid in human serum.     

Separation of carbon nanotubes by frit inlet asymmetrical flow field-flow fractionation

Flow field-flow fractionation (flow FFF), a separation technique for particles and macromolecules, has been used to separate carbon nanotubes (CNT). The carbon nanotube ropes that were purified from a raw carbon nanotube mixture by acidic reflux followed by cross-flow filtration using a hollow fiber module were cut into shorter lengths by sonication under a concentrated acid mixture. The cut carbon nanotubes were separated by using a modified flow FFF channel system, frit inlet asymmetrical flow FFF (FI AFIFFF) channel, which was useful in the continuous flow operation during injection and separation. Carbon nanotubes, before and after the cutting process, were clearly distinguished by their retention profiles. The narrow volume fractions of CNT collected during flow FFF runs were confirmed by field emission scanning electron microscopy and Raman spectroscopy. Experimentally, it was found that retention of carbon nanotubes in flow FFF was dependent on the use of surfactant for CNT dispersion and for the carrier solution in flow FFF. In this work, the use of flow FFF for the size differentiation of carbon nanotubes in the process of preparation or purification was demonstrated.     

Electrochemical biosensors based on redox carbon nanotubes prepared by noncovalent functionalization with 1,10-phenanthroline-5,6-dione

To improve the electrocatalytic activities of carbon nanotubes (CNT) towards the oxidation of nicotinamide adenine dinucleotide (NADH), we derive them with a redox mediator, 1,10-phenanthroline-5,6-dione (PD), by the noncovalent functionalization method. The redox carbon nanotubes (PD/CNT/GC) show excellent electrocatalytic activities towards the oxidation of NADH (catalytic reaction rate constant, k(h) = 7.26 × 10(3) M(-1) s(-1)), so the determination of NADH can be achieved with a high sensitivity of 8.77 μA mM(-1) under the potential of 0.0 V with minimal interference. We also develop an amperometric ethanol biosensor by integration of alcohol dehydrogenase (ADH) within the redox carbon nanotubes (PD/CNT/GC). The ethanol biosensor exhibits a wide linear range up to 7 mM with a lower detection limit of 0.30 mM as well as a high sensitivity of 10.85 nA mM(-1).     

Enhancement of Electrochemical Capacitance of Carbon Nanotubes by Polythionine Modification

Thionine molecules have been electropolymerized onto different types of carbon nanotubes (CNT) using a cyclic voltammetry scanning technology, including multi‐walled carbon nanotubes, single‐walled carbon nanotubes and aligned carbon nanotubes. Results indicate that such prepared nanocomposites have combined the intrinsic faradic capacitance of polythionine with the double layer capacitance of polythionine‐CNT, and thus the polythionine modification obviously enhanced the CNT capacitance. Especially the carboxyl group modified multi‐walled carbon nanotubes, which have made their nanotube tips opened, allowed much more electropolymerization cycles and then obtained a most significant increment in capacitance than the other three ones.     

A vertically aligned carbon nanotube-based impedance sensing biosensor for rapid and high sensitive detection of cancer cells

A novel vertically aligned carbon nanotube based electrical cell impedance sensing biosensor (CNT-ECIS) was demonstrated for the first time as a more rapid, sensitive and specific device for the detection of cancer cells. This biosensor is based on the fast entrapment of cancer cells on vertically aligned carbon nanotube arrays and leads to mechanical and electrical interactions between CNT tips and entrapped cell membranes, changing the impedance of the biosensor. CNT-ECIS was fabricated through a photolithography process on Ni/SiO(2)/Si layers. Carbon nanotube arrays have been grown on 9 nm thick patterned Ni microelectrodes by DC-PECVD. SW48 colon cancer cells were passed over the surface of CNT covered electrodes to be specifically entrapped on elastic nanotube beams. CNT arrays act as both adhesive and conductive agents and impedance changes occurred as fast as 30 s (for whole entrapment and signaling processes). CNT-ECIS detected the cancer cells with the concentration as low as 4000 cells cm(-2) on its surface and a sensitivity of 1.7 × 10(-3)Ω cm(2). Time and cell efficiency factor (TEF and CEF) parameters were defined which describe the sensor's rapidness and resolution, respectively. TEF and CEF of CNT-ECIS were much higher than other cell based electrical biosensors which are compared in this paper.     

Microfabricated porous glass channels for electrokinetic separation devices

Electrically insulated porous SiO2 channels for electrokinetic separation devices were fabricated based on a mask-less etching process for creation of high aspect ratio needles in silicon. The silicon needles are converted to SiO2 by oxidation and integrated within the interior of a fluidic channel network. The channels are about 5 microm high with a pore size of 0.5+/-0.2 microm. An electrophoretic separation of a mixture of fluorescein and 5-carboxyfluorescein using epi-fluorescence detection was performed to verify proper electrokinetic transport in the porous channels. The plate height was about 170,000 m-1 for a field strength of 170 V cm-1. In the near future, it is intended to extend the fabrication scheme to include an array of porous pillars for capillary electrochromatography experiments.     

Electrophoretic separation of aniline derivatives using fused silica capillaries coated with acid treated single-walled carbon nanotubes

This paper reports on a new strategy for coating fused silica capillaries based on the ionic adsorption of acid treated single-walled carbon nanotubes (SWCNTs) on a poly(diallydimethylammonium chloride)-modified fused silica surface. The coated capillaries were used to demonstrate their performance for baseline separation of a mixture of seven nitrogen-containing aromatic compounds compared to capillary zone electrophoresis. This combined layer formed a coating material that could be useful for improvement of the selectivity of the solutes in an electrical field. We reasoned that the interaction of the solutes and the modified capillary wall occurred mainly via ionic interactions with the charged moieties of CNTs. The single-walled CNT modified capillaries were very stable and could be used for over 200 repeated analyses without compromising its analytical performance.     

Surfactant-directed polypyrrole/CNT nanocables: synthesis, characterization, and enhanced electrical properties.

We describe here a new approach to the synthesis of size-controllable polypyrrole/carbon nanotube (CNT) nanocables by in situ chemical oxidative polymerization directed by the cationic surfactant cetyltrimethylammonium bromide (CTAB) or the nonionic surfactant polyethylene glycol mono-p-nonylphenyl ether (Opi-10). When carbon nanotubes are dispersed in a solution containing a certain concentration of CTAB or Opi-10, the surfactant molecules are adsorbed and arranged regularly on the CNT surfaces. On addition of pyrrole, some of the monomer is adsorbed at the surface of CNTs and/or wedged between the arranged CTAB or Opi-10 molecules. When ammonium persulfate (APS) is added, pyrrole is polymerized in situ at the surfaces of the CNTs (core layer) and ultimately forms the outer shell of the nanocables. Such polypyrrole/CNT nanocables show enhanced electrical properties; a negative temperature coefficient of resistance at 77-300 K and a negative magnetoresistance at 10-200 K were observed.