A novel method of fabricating a nanopore based on a glass tube for single-molecule detection

A novel nanopore fabrication method is reported by thermally pulling a glass tube in a two step process. The principle is based on the physical footprint of the phase change of the paraffin sealed inside the glass tube to form a nanocavity in the broken terminal during the second step of the pulling process. A nanopore with minimum diameter of 40?nm is fabricated after rubbing the terminal to make the channel through it. IgG molecules are used to test whether the nanopore can discriminate biomolecules. A transient current change from increasing to decreasing was observed when IgG molecules passed through the nanopore in pure water, suggesting that the IgG has a Y-shaped structure. This is in agreement with the known IgG structure. Experiments also uncovered that the train pulse signals due to the translocation of the biomolecules are sensitive to salt solutions. It was found that the negative amplitude of the pulse signal can be screened while the IgG molecules are mixed with a low KCL concentration solution. When changing from low to high salt concentrations we observed an inversion of the peak orientation. This is attributed to the competing conductance contribution to the ionic currents from the charges carried by the IgG molecules themselves and the exclusive ions blocked by the IgG molecules, suggesting that the salt ions in the solution may hide the true biomolecule structure.     

Simultaneous alternating and direct current readout of protein ion channel blocking events using glass nanopore membranes

Alternating current (ac) phase-sensitive detection is used to measure the conductance of the ion channel alpha-hemolysin (alphaHL), while simultaneously applying a direct current (dc) bias to electrostatically control the binding affinity and kinetics of charged molecules within the protein lumen. Ion channel conductance was recorded while applying a 10-20 mV rms, 1-2 kHz bias across a single alphaHL protein inserted in a 1,2-diphytanoyl-sn-glycero-3-phosphocholine lipid bilayer that is suspended across the orifice (100-500 nm radius) of a glass nanopore membrane. Step changes in the ac ion channel conductance with a temporal response (t(10-90)) of 1.5 ms and noise amplitude of approximately 2 pA were obtained using a low-noise potentiostat and a lock-in amplifier. These conditions were used to monitor the reversible and stochastic binding of heptakis-(6-O-sulfo)-beta-cyclodextrin and a nine base pair DNA hairpin molecule to the ion channel. Alternating current methodology allows the binding kinetics and affinity between the protein ion channel and analyte to be investigated as a function of the dc bias, including ion channel conductance measurements in the absence of a dc bias.     

Silica nanoparticles with enlarged nanopore size for the loading and release of biological proteins

Silica nanoparticles (SNs) with a nanoporous structure are attractive for the delivery of biomolecules. This study developed a SNs-based protein delivery system with nanopore sizes large enough to uptake protein molecules. The use of trioctylmethylammonium bromide (TOMAB) as an auxiliary chemical facilitated a dramatic increase in pore size from 2.6 nm to 17.4 nm. The surface was highly negatively-charged with a zeta potential of approximately ? 35 at pH 7. Positively-charged protein cytochrome C was encapsulated effectively within the large pore spaces of the SNs, with a protein loading capacity of almost 2-fold increase due to the pore size increase. The loaded protein exhibited sustained release for approximately one week with an initial burst in a day, suggesting the SNs tailored with enlarged nanopores should be useful for the delivery of large protein molecules for tissue regeneration.     

A facile method for fabricating TiO2@mesoporous carbon and three-layered nanocomposites

Herein, we report a new and facile method for fabricating TiO(2)@mesoporous carbon hybrid materials. Uniform polydopamine (PDA) layers were coated onto the surface of titanate nanotubes (TNTs) and TiO(2) nanorods (TNDs) through the spontaneous adhesion and self-polymerization of dopamine during the dipping process. Core-shell mesoporous carbon nanotubes with TiO(2) nanorods or nanoparticles encapsulated inside (TiO(2)@MC) were then obtained by transforming PDA layers into carbonaceous ones through calcination in nitrogen at 800 °C. The thickness of the mesoporous carbon layers is tens of nanometers and can be controlled by adjusting the coated PDA layers through the self-polymerization reaction time. In addition, three-layered nanocomposites of TiO(2)@MC@MO (MO, metal oxide) can be readily prepared by utilizing PDA layers in TNTs@PDA or TNDs@PDA to adsorb the metal ions, followed by the calcination process.     

Carbon nanofiber electrodes and controlled nanogaps for scanning electrochemical microscopy experiments

The electrochemical behavior of electrodes made by sealing carbon nanofibers in glass or with electrophoretic paint has been studied by scanning electrochemical microscopy (SECM). Because of their small electroactive surface area, conical geometry with a low aspect ratio and high overpotential for proton and oxygen reduction, carbon nanofiber (CNF) electrodes are promising candidates for producing electrode nanogaps, imaging with high spatial resolution and for the electrodeposition of single metal nanoparticles (e.g., Pt, Pd) for studies as electrocatalysts. By using the feedback mode of the SECM, a CNF tip can produce a gap that is smaller than 20 nm from a platinum disk. Similarly, the SECM used in a tip-collection substrate-generation mode, which subsequently shows a feedback interaction at short distances, makes it possible to detect a single CNF by another CNF and then to form a nanometer gap between the two electrodes. This approach was used to image vertically aligned CNF arrays. This method is useful in the detection in a homogeneous solution of short-lifetime intermediates, which can be electrochemically generated at one electrode and collected at the second at distances that are equivalent to a nanosecond time scale.     

Novel guidelines for the development of pM-selective glass electrodes from oxide glasses

There have been no guidelines for developing pM-selective (M = alkali metal ions) glass membrane electrodes. One of the key points for developing pM-selective glasses is to make glasses not responsive to changes in pH, since pM-measurements can be disturbed by the pH of the solution. As hydrogen-bonded protons in glasses are mobile and their mobility is thought to be responsible for pH-sensitivity, glasses for pM-selective electrodes should contain no hydrogen-bonded protons and no non-bridging oxygen. In this paper, guidelines for developing pH-selective glasses are proposed by using pNa-selective glasses in the Na₂O–Al₂O₃–SiO₂ system as examples. This revised version was published online in November 2006 with corrections to the Cover Date.     

A novel method for fabricating the surface-enhanced Raman scattering substrates and its enhanced properties

We have got large area surface-enhanced Raman scattering (SERS) substrates with uniform high enhancement factors by the so-called moulage method for the first time. A silver film (99.99%) with several millimeters thickness was thermally evaporated on the porous anodic alumina templates and the SERS substrate was got after moving off the templates. Surface-enhanced Raman scattering spectra of pyridine (0.01 Mol/L) were measured under 632.8 nm excitation. The experimental enhancement factors were more than 10(5) and S/N(p-p) around 100 was obtained. We have compared the SERS spectra of pyridine collected from different locations on the same SERS substrate and different substrates, which illustrate the well uniform enhance properties and the reproducibility of this method, respectively. The comparison of the SERS spectra, obtained from the SERS substrates and Ag film evaporated directly on glass slide, have proved that the electromagnetic coupling between two adjacent nanoparticles was important to the SERS effect. We also used rhodamine 6G as the probe molecules and found that the different molecules were very sensitive to the morphology of the SERS substrates.     

制冷机用稀土磁性材料及其形状尺寸与加工

在概述了近年来制冷技术中应用较多的稀土磁性材料的基础上,介绍了这些材料在应用过程中形状与尺寸的确定思路和方法以及所采用的加工工艺。     

SoI--gel modification of pH electrode glass membranes for sensing anions and metal ions

To obtain glass membrane electrodes selective for anions and metal ions, pH electrode glass membranes were modified by a sol-gel method using a quaternary ammonium salt and a bis(crown ether). A chloride ion-sensing glass membrane was designed, in which a pH electrode glass membrane was modified chemically by an alkoxysilyl quaternary ammonium chloride. X-ray photoelectron spectroscopy confirmed the chemical bonding of the quaternary ammonium moiety to the starting glass surface, which afforded the first example of glass-based "anion"-sensing membranes. A neutral carrier-type sodium ion-selective glass membrane was also fabricated which encapsulates a bis(12-crown-4) derivative in its sol-gel-derived surface. Both sol-gel-modified anion and metal ion-selective glass electrodes exhibited high sensitivity to their ion activity changes. The present sol-gel modification paves the way for designing glass-based ion sensors with tailor-made ion selectivities toward anions as well as cations.     

The displacive compensation of porosity (DCP) method for fabricating dense, shaped, high-ceramic-bearing bodies at modest temperatures

A novel process is introduced for the fabrication of dense, shaped ceramic/metal composites of high ceramic content: the Displacive Compensation of Porosity (DCP) method. In this process, a metallic liquid is allowed to infiltrate and undergo a displacement reaction with a porous oxide preform. Unlike other displacement-reaction-based processes (e.g., the C⁴, RMP, and AAA processes), a larger volume of oxide is generated than is consumed, so that composites with relatively high ceramic contents can be fabricated. Bar- and disk-shaped MgO/Mg-Al composites were produced by the infiltration and reaction of molten Mg with porous Al₂O₃ preforms at 1000 °C. By varying the relative density of the preforms (from 53.3 to 71.0% of theoretical), the magnesia content of the final composites could be adjusted from 70.4 to 85.6 vol %. Because the increase in oxide volume associated with the conversion of alumina into magnesia was accommodated by the prior pore volume of the preforms, the composites retained the shapes and dimensions (to within a few percent) of the starting preforms. The MgO/Mg-Al composites were lightweight (2.94–3.30 g/cm³), dense (97.7–99.0% of theoretical), and resistant to hydration. Bar-shaped MgO/Mg-Al composites exhibited average flexural strength and indentation toughness values of 244 MPa and 5.4 MPa · m^1/2, respectively.     

Control of thickness uniformity and grain size in graphene films for transparent conductive electrodes

Large-scale and transferable graphene films grown on metal substrates by chemical vapor deposition (CVD) still hold great promise for future nanotechnology. To realize the promise, one of the key issues is to further improve the quality of graphene, e.g., uniform thickness, large grain size, and low defects. Here we grow graphene films on Cu foils by CVD at ambient pressure, and study the graphene nucleation and growth processes under different concentrations of carbon precursor. On the basis of the results, we develop a two-step ambient pressure CVD process to synthesize continuous single-layer graphene films with large grain size (up to hundreds of square micrometers). Scanning electron microscopy and Raman spectroscopy characterizations confirm the film thickness and uniformity. The transferred graphene films on cover glass slips show high electrical conductivity and high optical transmittance that make them suitable as transparent conductive electrodes. The growth mechanism of CVD graphene on Cu is also discussed, and a growth model has been proposed. Our results provide important guidance toward the synthesis of high quality uniform graphene films, and could offer a great driving force for graphene based applications.     

Novel counter electrodes based on NiP-plated glass and Ti plate substrate for dye-sensitized solar cells

Novel counter electrodes based on NiP-plated glass and Ti plate substrate were prepared by thermal decomposition of H₂PtCl₆. Their properties and application in dye-sensitized solar cells were investigated. Platinized Ti plate electrode (Pt/TP electrode) and platinized NiP-plated glass electrode (Pt/NiP electrode) exhibited the same electrochemical activity for triiodide reduction as platinized fluorine-dope tin oxide (FTO) conducting glass electrode (Pt/FTO electrode). However, Pt/NiP electrode and Pt/TP electrode have the advantage over the Pt/FTO electrode in increasing the light reflectance and reducing the sheet resistance, which resulted to improve the light harvest efficiency and the fill factor of the dye-sensitized solar cells effectively. Examination of the anodic dissolution indicated the good stability of the Pt/NiP electrode and Pt/TP electrode in the electrolyte containing iodide/triiodide.     

Biocompatibility and Biodegradation of novel PHB porous substrates with controlled multi-pore size by emulsion templates method

PHB porous substrates were prepared based on the mono-membrane fabricated by emulsion templates method. The key factors of the method affecting the pore size and porosity of the PHB porous substrates were studied. The surface of PHB porous substrates were investigated by scanning electron microscope (SEM), which showed the even pore size and regular arranged pore. The transect of the PHB porous substrates prepared using the templates method was good. Moreover, the effects of variation of surfactant content (P%) and water content (R) on the pore size and porosity of PHB films were discussed. Preliminary studies showed that when P% is less than 20%, the pore size made by emulsion templates ranged from 5 μm to 30 μm with the value of P increasing. As P% is up to 20%. It was interesting to see that the porous substrates had muti-pore size distribution, i.e., median pore sizes were about 5 μm and inside the wall of pore, there existed numerous micro-pores size can be controlled from 100 nm to 500 nm only by adjusting the parameter R of the microemulsion. The cell-compatibility was evaluated via Chinese Hamster Lung (CHL) fibroblast cultivation in vitro. The Cells were cultured on both the mono-pore size membrane prepared by emulsion templates and the multi-pore size membrane prepared by microemulsion templates. It can be seen that the cells cultured on multi-pore size membrane stretched their morphology and proliferated better than that of mono-pore size membrane. These results indicated that the multi-pore size membrane had better cell-compatibility and was more suitable for tissue engineering. The degradation experiment indicated that the degradation of PHB porous substrates were accelerated by enzyme in vitro and the porous configuration was favorable to its degradation.     

Fabrication of submicrometer-sized gold electrodes of controlled geometry for scanning electrochemical-atomic force microscopy

A method for fabricating submicrometer-sized gold electrodes of conical or spherical geometry is described. By generating an electric arc between an etched gold microwire and a tungsten counter electrode, the very end of the gold microwire can be melted and given an overall spherical or conical shape a few hundred nanometers in size. The whole wire is subsequently insulated via the cathodic deposition of electrophoretic paint. By applying a high-voltage pulse to the microwire, the film covering its very end can then be selectively removed, thus exposing a submicrometer-sized electrode surface of predefined geometry. The selective exposure of the preformed end of the microwire is demonstrated by cyclic voltammetry, scanning electron microscopy, and metal electrodeposition experiments. The electrophoretic paint coating provides a low-capacitance, robust insulating film allowing exploration of a very wide potential window in aqueous solution. The submicrometer-sized electrodes can easily be turned into probes suitable for combined scanning electrochemical-atomic force microscopy by bending and flattening the gold microwire so that the tip is borne by a flexible enough arm. The good agreement between theoretical and experimental scanning electrochemical microscopy approach curves thus obtained confirms that only the very end of the tip, of predefined geometry, is exposed to the solution.     

Fabrication of porous alumina ceramics having cell windows with controlled size by PMMA template method

Highly porous alumina compacts have been prepared by filling alumina slurry into opening of a specially designed template block prepared by cross-linked (cl-) polymethylmethacrylate (PMMA) microspheres (mean particle size: 98.6 μm) under reduced pressure, followed by firing to remove the template and then sintering at 1600 °C. The template blocks were prepared by utilizing cl-PMMA and acetone solution dissolving noncrosslinked (Ncl-) PMMA as an adhesive to make partial connection among the cl-PMMA microspheres. Furthermore, the effects of the addition of other chemicals (two types of triblockcopolymers and a nonionic surfactant) to the Ncl-PMMA adhesive solution were tested to improve the wettability of the solution to cl-PMMA and then to control the cell windows among the cl-PMMA-originated cells after the firing. By employing the template block, prepared with the adhesive solution containing an appropriate amount of triblockcopolymer, a highly porous alumina compact having an open porosity of 77.2%, a mean cell window diameter of 28.8 μm, and strong alumina skeleton could be fabricated.     

Influence of controlled particle size on pore size distribution and mechanical resistance of agarose beads for bioadsorption application

ABSTRACT

In this work the influence of fabrication conditions (ion strength, surfactant utilization) on the macro- (particle size distribution, PSD) and microscopic [pore size distribution (PoSD), specific surface area] structure of agarose beads was investigated. The main purpose was achieving uniform sized and porous beads with improved mechanical strength for bioseparation and chromatography applications. Therefore, PSD, PoSD, mechanical resistance, and flux through packed bed of the fabricated beads (4, 6, and 8% wt/wt) were analyzed. Based on porosimetry results, it was found that increasing ion concentration or presence of surfactant (the key variable for narrowing PSD) decreases the span value of PSD (p-value <0.05); thus, leading to a more uniform distribution. Moreover, as a result of controlling PSD, the PoSD changes from micro- to meso- and macropores in higher ion charged solutions. Furthermore, the obtained PoSD affects mechanical resistance of the prepared microspheres either as single beads or packed in a column. Mesoporous 6%-agarose beads showed the highest flux due to elevated mechanical resistance and elastic characteristic. Mesoporous 4%-beads showed the highest elasticity, and thus lower flux through column. These results demonstrate that manipulation of both macro- and microscopic characteristics of the beads should be commensurate with the intended application i.e., bioadsorption chromatography.