Interfaces to connect thin-layer chromatography with electrospray ionization mass spectrometry

This study has developed two interfaces to connect small-size thin-layer chromatography (TLC) with electrospray ionization mass spectrometry (ES-MS) for the continuous analysis of organic mixtures. The interfaces are (1) two bound optical fibers inserted into the C18-bonded particles at the exit of a small TLC channel and (2) a small commercial TLC strip with a sharpened tip. A reservoir continuously supplied a makeup solution to the tip of the TLC channel. The high voltage required for electrospray ionization was introduced into the makeup solution or mobile phase through a Pt wire, and electrospray was generated at the tip of the bonded optical fibers and at the sharp end of the TLC strip. Since small-size TLC channels were used, the elution time was short and less than 0.2 microL of the sample solution and 200 microL of the eluting solvent were required. Organic mixtures were separated successfully and detected on-line using the TLC/ES-MS techniques.     

Sheathless capillary electrophoresis/electrospray ionization mass spectrometry using a pulled bare fused-silica capillary as the electrospray emitter

It has always been assumed that electrical contact at the capillary outlet is a necessary requirement when coupling capillary electrophoresis (CE) with electrospray ionization mass spectrometry (ESI-MS). In this study, we used a pulled bare-capillary tip as the ESI emitter, but neither was it coated with any electrically conductive materials nor was a high external voltage applied on its outlet. In this paper, we demonstrate that this straightforward approach may be used to generate multiply charged ions of proteins and peptides through electrospray ionization. Our results indicate that peptides and proteins, including bradykinin, cytochrome c, myoglobin, and tryptic digest products that elute from a pulled bare-capillary tip can be detected directly by ESI-MS using the tapered bare-capillary interface. Thus, we have demonstrated that CE and ESI-MS may be combined successfully without the need to modify the outlet of the capillary tip with an electrically contacting material.     

Flow fractionation of microparticles under a dielectrophoretic field in a quadrupole electrode capillary.

A technique of fractionation for microparticles was proposed that utilized a unique combination of a dielectrophoretic (DEP) field generated by a quadrupole electrode and a laminar flow in a capillary of 82.5 microm in radius. The fabricated capillary possessed four platinum wires in its inside wall as a quadrupole electrode. In a nonuniform electric field generated by the quadrupole electrode, microparticles, such as polystyrene and carbon, in water experienced DEP forces in the radial direction. When a sample solution was pumped in, an ideal laminar flow perpendicular to the DEP force was formed inside the capillary. The microparticles dynamically migrated by the DEP force across the laminar flow while they were carried by the flow. A theoretical model taking the DEP force and the laminar flow pattern into account predicted the elution profiles of the single microparticles quantitatively. The elution times of the microparticles depended on the dielectric properties and the sizes of the microparticles, as well as the voltage and frequency of the applied alternating current.     

Subattomole-Sensitivity Microchip Nanoelectrospray Source with Time-of-Flight Mass Spectrometry Detection

A microfabricated microfluidic device coupled with a nanospray tip for electrospray ionization of dilute solutions is described. The device has been interfaced with a time-of-flight mass spectrometer and evaluated for sensitive, high-speed detection of peptides and proteins. The electrospray voltage was applied through the microchip to the nanospray capillary that was attached at the end of a microfabricated channel. Fluid delivery rates were 20-30 nL min(-)(1) through the hybridized structure without any pressure assistance. On-line microchip electrophoresis has been demonstrated and the effect of the capillary-chip junction on band broadening examined. Full mass spectra are acquired within 10-20 ms at 50-100 spectra s(-)(1) storage rates. Detection of subattomole levels of sample from a 100 nM solution is demonstrated for infusion experiments.     

Hydrogen sensing properties of dielectrophoretically assembled SnO2 nanoparticles on CMOS-compatible micro-hotplates

We fabricated nanoparticle-based gas through in situ ac dielectrophoretical assembling of drop-coated SnO(2) nanoparticles to bridge the gap between electrodes with high aspect ratio. While the conventional dielectrophoresis (DEP) adopts a microfluidic system for continuous flow of the solution during the process, we just drop-coated a small amount of solution onto the electrodes and executed in situ DEP for a very short time. This is a very simple, cost-effective, time-saving, and highly reproducible process. We fixed the duration time and applied voltage for the DEP at 1 s and 1 V respectively and changed the frequencies from 1 up to 500 kHz. I-V characteristics of the samples were checked and it was found that DEP samples fabricated at 1 s, 1 V and 150 kHz conditions showed considerably higher connectivity of the nanoparticles. This can be attributed to the excellent step coverage achieved by ac DEP under those conditions. The devices drop-coated and dielectrophoretically assembled at other ac frequency conditions showed poor connectivity. Hydrogen gas sensing properties of the sensors fabricated under 1 s, 1 V and 150 kHz conditions were checked by flowing through 160 ppm H(2). The sensitivity reaches a maximum value of ~ 700% at 350 °C. The response time is ~ 200 s at 350 °C.     

Synthesis and morphology analysis of electrospun copper nanowires

We report the fabrication of copper nanowires (NWs) using electrospinning technique. This processing technique was used successfully to synthesize copper NWs with various morphologies using a precursor composed of copper acetate salt and poly(vinyl) alcohol. The obtained NWs were characterized through high resolution scanning electron microscopy and atomic force microscopy and it was found that their morphology is sensitive to the applied voltage and solution flow rate. Their diameter decreased with increasing voltage and increasing flow rate. Moreover, at higher flow rate and lower voltage, the roughness of NWs became more pronounced. In addition, further improvement in NW morphology may be obtained with appropriate heat treatment. These copper NWs with varying morphologies and microstructures have potential applications in different engineering domains such as electronics, optoelectronics, and catalysis.     

Frequency dependence of alternating current electrospray ionization mass spectrometry

The novel effects resulting from the entrainment of low mobility ions during alternating current (ac) electrospray ionization are examined through mass spectrometry and voltage/current measurements. Curious phenomena such as pH modulation at high frequencies (>150 kHz) of an applied ac electric field are revealed and explained using simple mechanistic arguments. Current measurements are utilized to supplement these observations, and a simplified one-dimensional transient diffusion model for charge transport is used to arrive at a scaling law that provides better insight into the ac electrospray ionization process. Moreover, because of the different pathway for ion formation in comparison to direct current (dc) electrospray, ac electrospray (at frequencies >250 kHz) is shown to reduce the effects of ionization suppression in a mixture of two molecules with different surface activities.     

Two opposite growth modes of carbon nanofibers prepared by catalytic decomposition of acetylene at low temperature

Helical carbon fibers were synthesized by the catalytic decomposition of acetylene as carbon source at low temperature of 240–260 °C with two nanocopper catalysts prepared by the hydrogen-arc plasma method and thermal decomposition of copper tartrate. Two growth modes for helical carbon fibers were obtained. One is mirror-symmetric growth mode, and the other is asymmetric growth mode. In the two growth modes, there were always only two helical fibers in regular shapes that were grown over a single copper nanoparticle. The two helical fibers had identical coil diameter, coil length, fiber diameter, cycle number, tight coil pitch, and cross section. In mirror-symmetric growth mode, the two helical fibers had absolutely opposite helical senses. The catalyst particle size was less than 50 nm and the coil diameter was <100 nm. Whereas in asymmetric growth mode, the two helical fibers had absolutely identical helical senses. The catalyst particle size was larger than 200 nm and their coil diameters reached 1 μm. The catalyst particle size had considerable effect on the growth mode for helical carbon fibers.     

Formation of thick dielectrophoretic carbon nanotube fibers

The aim of this work was to study the formation process of dielectrophoretic (DEP) carbon nanotube fibers (CNT-fibers) and characterize the fiber properties relevant to their technological applications. The fiber diameter was shown to increase when applied voltage was increased (up to 350 V(pp)) and when retraction speed was decreased (down from 400 μm s(-1)) in accordance with theoretical expectations. This paper represents the first demonstration of the formation of thick DEP CNT-fibers (up to ～ ?0.4 mm). This is an intriguing result, as it expands the diversity of possible applications of the fibers and facilitates their characterization by analytical methods that require large quantities of the material. The performance of these thick fibers was as follows: a density of ～ 0.35 g cm(-3), a tensile strength of ～ 15 MPa, a Young's modulus of ～ 1 GPa, and an electrical resistivity of ～ 70 mΩ cm.     

Increasing the sensitivity of liquid introduction mass spectrometry by combining electrospray ionization and solvent assisted inlet ionization

Combining electrospray ionization (ESI) and solvent assisted inlet ionization (SAII) provides higher ion abundances over a wide range of concentrations for peptides and proteins than either ESI or SAII. In this method, a voltage is applied to a union connector linking tubing from a solvent delivery device and the fused silica capillary, used with SAII, inserted into a heated inlet tube of an Orbitrap Exactive mass spectrometer (MS). The union can be metal or polymeric and the voltage can be applied directly or contactless. Solution flow rates from less than a 1 μL min(-1) to over 100 μL min(-1) can be accommodated. It appears that the voltage is only necessary to provide charge separation in solution, and the hot MS inlet tube and the high velocity of gas through the tube linking atmospheric pressure and vacuum provides droplet formation. As little as 100 V produces an increase in ion abundance for certain compounds using this method relative to no voltage. Interestingly, the total ion current observed with SAII and this electrosprayed inlet ionization (ESII) method are very similar for weak acid solutions, but with voltage on, the ion abundance for peptides and proteins increase as much as 100-fold relative to other compounds in the solution being analyzed. Thus, switching between SAII (voltage off) and ESII (voltage on) provides a more complete picture of the solution contents than either method alone.     

聚-DL/L-丙交酯(30DL/70L)纳米纤维的电纺研究

对生物可吸收聚-DL/L-丙交酯(30DL/70L)体系进行了静电纺丝.研究了聚-DL/L-丙交酯(30DL/70L)的浓度,加料速度,电压,喷头与接收体之间的距离等因素对纤维形态的影响,制备出纳米纤维膜,并用扫描电镜(SEM)等对纤维膜进行表征.结果表明,电纺溶液浓度和溶剂对纤维直径影响比较明显,减小电纺溶液浓度和采用复合溶剂CHCl3/DMF可得到更细的纳米纤维;一定范围内适当的增加电压、减小距离和减小加料速度有利于减小纤维直径.在聚-DL/L-丙交酯(30DL/70L)浓度为5g/100mL溶剂、加料速度1mL/h、喷头与接收体之间的距离6cm、电压15kV电纺条件下,可制备直径50nm左右的聚-DL/L-丙交酯(30DL/70L)纳米纤维膜.     

Activated carbon nanofibers derived from coconut shell charcoal for dye removal application

Activated carbon nanofibers (ACNF) have been successfully prepared using an electrospinning method with coconut shell charcoal (CSC) as a carbon source and poly(vinyl alcohol) (PVA) as a spinning polymer agent. The high voltage of 10 kV was applied for the electrospinning system. The positive electrode of the high voltage power supply was connected to the needle tip, and the grounded electrode was connected to the metallic collector wrapped with an aluminum foil. The dry fibers in the form of a fibrous mat were collected in the aluminum foil. The average pore diameters of the generated fibers for all variables ranging from 2.23 to 3.73 nm corresponding to mesoporous carbon nanofibers. The total pore volumes were ranging from 0.50 to 0.92 cm³/g. IACNF-60 had the largest surface area of 1,277 m²/g obtained from the use of PVA 12 w/v %, 60 wt% CSC, and the use of iodine treatment before thermal stabilization, carbonization, and activation stages. Methylene blue solution was used as a model for the dye adsorption capacity that followed the Langmuir adsorption model. IACNF-60 also indicated the highest theoretical maximum monolayer adsorption capacity in the amount of 166.7 mg/g. Furthermore, the methylene blue removal ability of IACNF-60 for the third cycle was maintained relatively constant at 96%.     

A one-step process to engineer superhydrophobic copper surfaces

Superhydrophobic surfaces are conventionally prepared employing two steps: roughening a surface and lowering their surface energy. In the present work, a direct voltage (DC) is applied between two copper plates immersed in a dilute ethanolic stearic acid solution. The surface of the anodic copper electrode transforms to superhydrophobic due to a reaction between copper and stearic acid solution. The fabrication process of superhydrophobic copper surfaces is simplified in just one-step. The surface of the anodic copper is found to be covered with flower-like low surface energy copper stearate films providing the water contact angle of 153 ± 2° with the roll-off properties.     

Separation of latex spheres using dielectrophoresis and fluid flow

The authors present a method for separation of two latex spheres populations using dielectrophoresis (DEP) and the fluid drag force. Microelectrodes of a suitable layout are used to trap one population of spheres, while the other one is dragged away from the electrodes by the generated fluid flow. The finite difference method is implemented in C++ to calculate the potential distribution by solving Laplace's equation. From the potential distribution, the DEP force on particles is calculated. The drag force on particles due to the liquid motion is calculated from the observed fluid velocity. The experimental results are shown to be in good agreement with the numerical solution.     

Fabricated Wavy Micro/Nanofiber via Auxiliary Electrodes in Near-Field Electrospinning

Wavy fibers fabricated by electrohydrodynamic jet printing (E-J-P) have been used in many applications, such as sensors, electromechanical systems, stretchable electronics products, and flexible displays. Auxiliary electrodes (A-E) were initially used to control the deposited morphology of the wavy fibers in this study. A polyethylene oxide solution was electrospun with an applied voltage of 1 kV and an alternating current power (ACP) supplied to A-E. The experimental results show that the amplitude can be controlled by the voltage of the ACP, and the generated frequency of the wavy fiber is the same as the frequency of the ACP.     

Electrodeposition of exfoliated graphite nanoplatelets onto carbon fibers and properties of their epoxy composites

Exfoliated graphite nanoplatelet (xGnP)/copper (Cu) coated carbon fibers were fabricated by electrophoretic deposition under different applied voltages. The electrical and mechanical properties of individual fibers and composites made from these fibers and epoxy resin were investigated. The electrical resistivity of xGnP/Cu coated single carbon fiber is lower than that of the uncoated control sample and decreases with increase in the applied voltage. The xGnP and metallic Cu were simultaneously deposited on the carbon fiber surface as a result of the electrochemical cell configuration. The interfacial shear strength decreases with applied voltage up to 30 V but increases with applied voltage of over 30 V. The interfacial shear strength for the coated samples except the 50 V treated sample is lower than that of control sample. The flexural strength and modulus of xGnP/Cu coated carbon/epoxy composites is higher than those of control sample due to the reinforcing effect of xGnP/Cu coated on the carbon fibers.     

Electric field and tip geometry effects on dielectrophoretic growth of carbon nanotube nanofibrils on scanning probes

Single-wall carbon nanotube (SWNT) nanofibrils were assembled onto a variety of conductive scanning probes including atomic force microscope (AFM) tips and scanning tunnelling microscope (STM) needles using positive dielectrophoresis (DEP). The magnitude of the applied electric field was varied in the range of 1-20?V to investigate its effect on the dimensions of the assembled SWNT nanofibrils. Both length and diameter grew asymptotically as voltage increased from 5 to 18?V. Below 4?V, stable attachment of SWNT nanofibrils could not be achieved due to the relatively weak DEP force versus Brownian motion. At voltages of 20?V and higher, low quality nanofibrils resulted from incorporating large amounts of impurities. For intermediate voltages, optimal nanofibrils were achieved, though pivotal to this assembly is the wetting behaviour upon tip immersion in the SWNT suspension drop. This process was monitored in situ to correlate wetting angle and probe geometry (cone angles and tip height), revealing that probes with narrow cone angles and long shanks are optimal. It is proposed that this results from less wetting of the probe apex, and therefore reduces capillary forces and especially force transients during the nanofibril drawing process. Relatively rigid probes (force constant ≥2?N?m(-1)) exhibited no perceivable cantilever bending upon wetting and de-wetting, resulting in the most stable process control.     

Design and numerical investigation of a circular microchannel for particle/cell separation using dielectrophoresis

Precisely separating particles/cells with different sizes and physical properties has been an interest for point-of-care diagnostics and personalized treatment. Dielectrophoresis (DEP) is widely known as a powerful and non-invasive technique to separate particles and cells. This paper presents a comprehensive numerical investigation of particle/cell separation in circular microchannels using DEP. First, the geometrical parameters of the circular microchannel affecting DEP force are determined by performing an analytical solution. Then, by developing a solver in OpenFOAM, the effect of these parameters on particles deflection is investigated. According to the results, two different circular microchannels are presented to investigate the continuous separation of bio-particles (based on their physical properties) and polystyrene particles (based on their size). The results showed that a minimum voltage of 7, 9, and 12 V is required to achieve 100 % purity and separation efficiency for separating red blood cells from MDA-MB-231 cancer cells at the flow rate of 0.5, 1.0, and 1.5 µl/min, respectively. Also, the efficient separation of 5 and 10 µm polystyrene particles at the flow rate of 0.1 µl/min is possible only at the voltage of 9 V. The results of this numerical study can be useful for the fabrication of an optimal microdevice for the continuous DEP separation of particles and cells.     

Electrostatic potential in a bent piezoelectric nanowire. The fundamental theory of nanogenerator and nanopiezotronics

We have applied the perturbation theory for calculating the piezoelectric potential distribution in a nanowire (NW) as pushed by a lateral force at the tip. The analytical solution given under the first-order approximation produces a result that is within 6% from the full numerically calculated result using the finite element method. The calculation shows that the piezoelectric potential in the NW almost does not depend on the z-coordinate along the NW unless very close to the two ends, meaning that the NW can be approximately taken as a "parallel plated capacitor". This is entirely consistent to the model established for nanopiezotronics, in which the potential drop across the nanowire serves as the gate voltage for the piezoelectric field effect transistor. The maximum potential at the surface of the NW is directly proportional to the lateral displacement of the NW and inversely proportional to the cube of its length-to-diameter aspect ratio. The magnitude of piezoelectric potential for a NW of diameter 50 nm and length 600 nm is approximately 0.3 V. This voltage is much larger than the thermal voltage ( approximately 25 mV) and is high enough to drive the metal-semiconductor Schottky diode at the interface between atomic force microscope tip and the ZnO NW, as assumed in our original mechanism for the nanogenerators.     

Continuous sorting of microparticles using dielectrophoresis

Sorting of particles such as cells is a critical process for many biomedical applications, and it is challenging to integrate it into an analytical microdevice. We report an effective and flexible dielectrophoresis (DEP)-based microfluidic device for continuous sorting of multiple particles in a microchannel. The particle sorter is composed of two components-a DEP focusing unit and a Movable DEP Trap (MDT). The trap is formed by an array of microelectrodes at the bottom of the channel and a transparent electrode plate placed at the top. The location of the trap is dependent on the configuration of voltages on the array and therefore is addressable. Flowing particles are first directed and focused into a single particle stream by the focusing unit. The streamed particles are then sorted into different fractions using the movable trap by rapidly switching the applied voltage. The performance of the sorter is demonstrated by successfully sorting microparticles in a continuous flow. The proposed DEP-based microfluidic sorter can be implemented in applications such as sample preparation and cell sorting for subsequent analytical processing, where sorting of particles is needed.