Chiral ionic liquids as stationary phases in gas chromatography

Recently, it has been found that room-temperature ionic liquids can be used as stable, unusual selectivity stationary phases. They show "dual nature" properties, in that they separate nonpolar compounds as if they are nonpolar stationary phases and separate polar compounds as if they are polar stationary phases. Extending ionic liquids to the realm of chiral separations can be done in two ways: (1) a chiral selector can be dissolved in an achiral ionic liquid, or (2) the ionic liquid itself can be chiral. There is a single precedent for the first approach, but nothing has been reported for the second approach. In this work, we present the first enantiomeric separations using chiral ionic liquid stationary phases in gas chromatography. Compounds that have been separated using these ionic liquid chiral selectors include alcohols, diols, sulfoxides, epoxides, and acetylated amines. Because of the synthetic nature of these chiral selectors, the configuration of the stereogenic center can be controlled and altered for mechanistic studies and reversing enantiomeric retention.     

Peptide-mediated formation of single-wall carbon nanotube composites

The formation of silica- and titania-coated single-wall carbon nanotubes (SWNTs) using a mutlifunctional peptide to both suspend SWNTs and direct the precipitation of silica and titania at room temperature is demonstrated.     

Charge noise in liquid-gated single-wall carbon nanotube transistors

The noise properties of single-walled carbon nanotube transistors (SWNT-FETs) are essential for the performance of electronic circuits and sensors. Here, we investigate the mechanism responsible for the low-frequency noise in liquid-gated SWNT-FETs and its scaling with the length of the nanotube channel down to the nanometer scale. We show that the gate dependence of the noise amplitude provides strong evidence for a recently proposed charge-noise model. We find that the power of the charge noise scales as the inverse of the channel length of the SWNT-FET. Our measurements also show that surprisingly the ionic strength of the surrounding electrolyte has a minimal effect on the noise magnitude in SWNT-FETs.     

High-performance single-wall carbon nanotube transparent conductive films

A single-wall carbon nanotube(SWCNT) has superior optical,electrical,and mechanical properties due to its unique structure and is therefore expected to be able to form flexible high-performance transparent conductive films(TCFs).However,the optoelectronic performance of these films needs to be improved to meet the requirements of many devices.The electrical resistivity of SWCNTTCFs is mainly determined by the intrinsic resistivity of individual SWCNTs and their junction resistance in networks.We analyze these key factors and focus on the optimization of SWCNTs and their networks,which include the diameter,length,crystallinity and electrical type of the SWCNTs,and the bundle size and interconnects in networks,as well as chemical doping and microgrid design.We conclude that isolated/small-bundle,heavily doped metallic or semiconducting SWCNTs with a large diameter,long length and high crystallinity are necessary to fabricate high-performance SWCNTTCFs.A simple,controllable way to construct macroscopic SWCNT networks with Y-type connections,welded junctions or microgrid design is important in achieving a low resistivity.Finally,some insights into the key challenges in the manufacture and use of SWCNT TCFs and their prospects are presented,hoping to shed light on promoting the practical application of SWCNT TCFs in future flexible and stretchable optoelectronics.     

Electroluminescence from single-wall carbon nanotube network transistors

The electroluminescence (EL) properties from single-wall carbon nanotube network field-effect transistors (NNFETs) and small bundle carbon nanotube field effect transistors (CNFETs) are studied using spectroscopy and imaging in the near-infrared (NIR). At room temperature, NNFETs produce broad (approximately 180 meV) and structured NIR spectra, while they are narrower (approximately 80 meV) for CNFETs. EL emission from NNFETs is located in the vicinity of the minority carrier injecting contact (drain) and the spectrum of the emission is red shifted with respect to the corresponding absorption spectrum. A phenomenological model based on a Fermi-Dirac distribution of carriers in the nanotube network reproduces the spectral features observed. This work supports bipolar (electron-hole) current recombination as the main mechanism of emission and highlights the drastic influence of carrier distribution on the optoelectronic properties of carbon nanotube films.     

A triple quantum dot in a single-wall carbon nanotube

A top-gated single-wall carbon nanotube is used to define three coupled quantum dots in series between two electrodes. The additional electron number on each quantum dot is controlled by top-gate voltages allowing for current measurements of single, double, and triple quantum dot stability diagrams. Simulations using a capacitor model including tunnel coupling between neighboring dots captures the observed behavior with good agreement. Furthermore, anticrossings between indirectly coupled levels and higher order cotunneling are discussed.     

Structure of semidilute single-wall carbon nanotube suspensions and gels

The microscopic network structure of surfactant-stabilized single-wall carbon nanotubes (SWNTs) in water was investigated as a function of SWNT concentration in the semidilute (overlapping) regime using small-angle neutron scattering (SANS). Most of the samples exhibit rigid rod behavior (i.e., Q(-1) intensity variation) at large scattering wavevector, Q, and a crossover to network behavior (i.e., approximately Q(-2) intensity variation) at low Q. The mesh size, xi, of the network was determined from the crossover of rigid rod to network behavior in the SANS intensity profile and was found to decrease with increasing SWNT concentration. When the dispersion quality of these associating rigid rods was degraded, only approximately Q(-2) intensity variation was observed at both high and low Q. Small-angle X-ray scattering measurements of the same stable dispersions were relatively insensitive to network structure because of poor contrast between SWNTs and surfactant.     

Design criteria for transparent single-wall carbon nanotube thin-film transistors

A study based on two-dimensional percolation theory yielding quantitative parameters for optimum connectivity of transparent single-wall carbon nanotube (SWNT) thin films is reported. Optimum SWNT concentration in the filtrated solution was found to be 0.1 mg/L with a volume of 30 mL. Such parameters lead to SWNT fractions in the films of approximately Phi = 1.8 x 10(-3), much below the metallic percolation threshold, which is found to be approximately PhiC = 5.5 x 10(-3). Therefore, the performance of transparent carbon nanotube thin-film transistors is limited by the metallic SWNTs, even below their percolation threshold. We show how this effect is related to hopping or tunneling between neighboring metallic tubes.     

Immobilized ionic liquids as high-selectivity/high-temperature/high-stability gas chromatography stationary phases

Ionic liquids (ILs) are a class of nonmolecular solvents in which the cation/anion combination can be easily tuned to provide desired chemical and physical properties. When used as stationary phases in gas-liquid chromatography, ionic liquids exhibit dual nature retention selectivity. That is, they are able to separate polar molecules such as a polar stationary phase and nonpolar molecules such as a nonpolar stationary phase. However, issues such as optimization of the wetting ability of the ionic liquid on fused-silica capillaries, the maximum operating temperatures of the stationary phases, and nonuniform film thickness on the wall of the capillary at high temperatures have limited their use in gas chromatography. As described in this paper, these limitations are overcome by cross-linking a new class of ionic liquid monomers by free radical reactions to provide a more durable and robust stationary phase. By lightly cross-linking the ionic liquid stationary phase using a small amount of free radical initiator, high-efficiency capillary columns were produced that are able to endure high temperatures with little column bleed. Two types of cross-linked IL stationary phases are developed. A partially cross-linked stationary phase allows for high-efficiency separations up to temperatures of approximately 280 degrees C. However, by creating a more highly cross-linked stationary phase of geminal dicationic ILs, exclusively, an increase in efficiency is observed at high temperatures allowing for its use over 350 degrees C. In addition, through the use of solvation thermodynamics and interaction parameters, it was shown that the cross-linking/immobilization of the ionic liquid does not affect the selectivity of the stationary phase thereby preserving its dual nature retention behavior.     

Air-stable room-temperature photodetector based on large-diameter small-bundle single-wall carbon nanotube films

1.Introduction Photodetectors are of great importance for a variety of industrial and scientific applications, such as in spectroscopy, solar energy harvesting, thermo-therapy, military detection, and a variety of biochemical sensors[1-5].Nowadays, relatively mature light detectors are mainly based on semiconducting materials including GaN, InGaAs and HgCdTe[6,7], and their light detection capability can reach 1011 Jones.However, most devices need to be cooled down to low working temperatures to achieve a high performance.In addition, these materials are usually not stable under strong illumination and not flexible[8,9], which greatly restricts the application range of fabricated photodetectors, especially in flexible and wearable devices.Therefore, the development of flexible, air-stable, room-temperature photodetectors is highly desired.     

High-stability ionic liquids. A new class of stationary phases for gas chromatography

Room-temperature ionic liquids are a class of non-molecular ionic solvents with low melting points. Their properties have the potential to be especially useful as stationary phases in gas-liquid chromatography (GLC). A series of common ionic liquids were evaluated as GLC stationary phases. It was found that many of these ionic liquids suffer from low thermal stability and possess unfavorable retention behavior for some classes of molecules. Two new ionic liquids were engineered and synthesized to overcome these drawbacks. The two new ionic liquids (1-benzyl-3-methylimidazolium trifluoromethanesulfonate and 1-(4-methoxyphenyl)-3-methylimidazolium trifluoromethanesulfonate) are based on "bulky" imidazolium cations with trifluoromethanesulfonate anions. Their solvation characteristics were evaluated using the Abraham solvation parameter model and correlations made between the structure of the cation and the degree to which the ionic liquids retain certain analytes. The new ionic liquids have good thermal stability up to 260 degrees C, provide symmetrical peak shapes, and because of their broad range of solvation-type interactions, exhibit dual-nature selectivity behavior. In addition, the ionic liquid stationary phases provided different retention behavior for many analytes compared to a commercial methylphenyl polysiloxane GLC stationary phase. This difference in selectivity is due to the unique solvation characteristics of the ionic liquids and makes them very useful as dualnature GLC stationary phases.     

Voltage-induced dependence of Raman-active modes in single-wall carbon nanotube thin films

We report on electrical Raman measurements in transparent and conducting single-wall carbon nanotube (SWNT) thin films. Application of external voltage results in downshifts of the D and G modes and in reduction of their intensity. The intensities of the radial breathing modes increase with external electric field related to the application of the external voltage in metallic SWNTs, while decreasing in semiconducting SWNTs. A model explaining the phenomenon in terms of both direct and indirect (Joule heating) effects of the field is proposed. Our work rules out the elimination of large amounts of metallic SWNTs in thin film transistors using high field pulses. Our results support the existence of Kohn anomalies in the Raman-active optical branches of metallic graphitic materials.     

Temperature dependence of electron-to-lattice energy transfer in single-wall carbon nanotube bundles

The electron-phonon coupling strength in single-wall carbon nanotube (SWNT) bundles has been studied directly in the time domain by femtosecond time-resolved photoelectron spectroscopy. We have measured the dependence of H(Te, Tl), the rate of energy transfer between the electronic system and the lattice as a function of electron and lattice temperatures Te and Tl. The experiments are consistent with a T5 dependence of H on the electron and lattice temperatures, respectively. The results can be related to the e-ph mass enhancement parameter lambda. The experimentally obtained value of for lambda/[symbol: see text] D2, where [symbol: see text] D is the Debye temperature, suggests that e-ph scattering times at the Fermi level of SWNT bundles can be exceptionally long, exceeding 1.5 ps at room temperature.     

Thermal conductance and thermopower of an individual single-wall carbon nanotube

We have observed experimentally that the thermal conductance of a 2.76-microm-long individual suspended single-wall carbon nanotube (SWCNT) was very close to the calculated ballistic thermal conductance of a 1-nm-diameter SWCNT without showing signatures of phonon-phonon Umklapp scattering for temperatures between 110 and 300 K. Although the observed thermopower of the SWCNT can be attributed to a linear diffusion contribution and a constant phonon drag effect, there could be an additional contact effect.     

Polar-liquid, derivatized cyclodextrin stationary phases for the capillary gas chromatography separation of enantiomers

A new class of hydrophilic, relatively polar liquid, cyclodextrin (CD) derivatives have been used as highly selective chiral stationary phases (CSPs) for capillary gas chromatography (GC). Several possible requirements for liquidity in CD derivatives are discussed. O-(S)-2-Hydroxypropyl derivatives of alpha-, beta-, and gamma-cyclodextrins were synthesized, exclusively characterized, permethylated, and evaluated for enantioselectivity. Seventy pairs of enantiomers were resolved. They represent a wide variety of structural types and classes of compounds including chiral alkyl amines, amino alcohols, epoxides, pyrans, furans, sugars, diols, esters, ketones, bicyclic compounds, alcohols, and so on. Many of these compounds were not aromatic and cannot be resolved on any known liquid chromatographic CSP. Often, these enantiomers had far less functionality than required for LC separation. General properties of these CSPs as well as possible insights into the separation mechanism are discussed.     

High-performance, static-coated silicon microfabricated columns for gas chromatography

A procedure is described for the preparation of high-performance etched silicon columns for gas chromatography. Rectangular channels, 150 mum wide by 240 mum deep are fabricated in silicon substrates by gas-phase reactive ion etching. A 0.1-0.2-mum-thick film of dimethyl polysiloxane stationary phase is deposited on the channel walls by filling the channel with a dilute solution in 1:1 n-pentane and dichloromethane and pumping away the solvent. A thermally activated cross-linking agent is used for in situ cross-linking. A 3-m-long microfabricated column generated approximately 12 500 theoretical plates at optimal operating conditions using air as carrier gas. A kinetic model for the efficiency of rectangular cross-section columns is used to evaluate column performance. Results indicate an additional source of gas-phase dispersion beyond longitudinal diffusion and nonequilibrium effects, probably resulting from numerous turns in the gas flow path through the channel. The columns are thermally stable to at least 180 degrees C using air carrier gas. Temperature programming is demonstrated for the boiling point range from n-C5 to n-C12. A 3.0-m-long column heated at 10 degrees C/min obtains a peak capacity of over 100 peaks with a resolution of 1.18 and a separation time of approximately 500 s. With a 0.25-m-long column heated at 30 degrees C/min, a peak capacity of 28 peaks is obtained with a separation time of 150 s. Applications are shown for the analysis of air-phase petroleum hydrocarbons and the high-speed analysis of chemical warfare agent and explosive markers.     

Molecular design of strong single-wall carbon nanotube/polyelectrolyte multilayer composites

The mechanical failure of hybrid materials made from polymers and single-wall carbon nanotubes (SWNT) is primarily attributed to poor matrix-SWNT connectivity and severe phase segregation. Both problems can be successfully mitigated when the SWNT composite is made following the protocol of layer-by-layer assembly. This deposition technique prevents phase segregation of the polymer/SWNT binary system, and after subsequent crosslinking, the nanometre-scale uniform composite with SWNT loading as high as 50 wt% can be obtained. The free-standing SWNT/polyelectrolyte membranes delaminated from the substrate were found to be exceptionally strong with a tensile strength approaching that of hard ceramics. Because of the lightweight nature of SWNT composites, the prepared free-standing membranes can serve as components for a variety of long-lifetime devices.     

Thermal conductance of an individual single-wall carbon nanotube above room temperature

The thermal properties of a suspended metallic single-wall carbon nanotube (SWNT) are extracted from its high-bias (I-V) electrical characteristics over the 300-800 K temperature range, achieved by Joule self-heating. The thermal conductance is approximately 2.4 nW/K, and the thermal conductivity is nearly 3500 Wm(-1)K(-1) at room temperature for a SWNT of length 2.6 mum and diameter 1.7 nm. A subtle decrease in thermal conductivity steeper than 1/T is observed at the upper end of the temperature range, which is attributed to second-order three-phonon scattering between two acoustic modes and one optical mode. We discuss sources of uncertainty and propose a simple analytical model for the SWNT thermal conductivity including length and temperature dependence.