CN102812355A - Method for manufacturing thin layer chromatography plates - Google Patents

Abstract

A method for manufacturing a thin layer chromatography ("TLC") plate (100) is disclosed. The method includes forming a catalyst layer (104) disposed on a substrate that includes a first portion and at least a second portion, each of the first and at least a second portions exhibiting a selected non-linear configuration. The method also includes forming a layer of elongated nanostructures (e.g. carbon nanotubes), and at least partially coating the elongated nanostructures with a coating. The coating includes a stationary phase and/or precursor of a stationary phase for use in chromatography. The stationary phase is functionalized with hydroxyl groups by exposure to acidified water vapor or immersion in a concentrated acid liquid bath (e.g. HCI and methanol). At least a portion of the elongated nanostructures are removed after being coated.

Description

Method for Preparing Thin-Layer Chromatography Plates

Cross References to Related Applications

This application claims the benefit of US Provisional Application No. 61/339,095, entitled "Methods of Making Effective Thin Layer Chromatography Supports," filed February 26, 2010, the disclosure of which is hereby incorporated by reference in its entirety.

Background technique

Chromatography and solid phase extraction ("SPE") are common separation techniques employed in a variety of analytical chemistry and biochemical settings. Chromatography and SPE are commonly used for the separation, extraction and analysis of various components or fractions in a sample of interest. Chromatography and SPE can also be used for sample preparation, purification, concentration and cleanup.

Chromatography and SPE involve techniques for separating complex mixtures based on the differential affinities of sample components carried by the mobile phase through which the sample flows and the stationary phase through which the sample flows. In general, chromatography and SPE involve the use of stationary phases comprising sorbents packed in cartridges, columns, or disposed as thin layers on plates. Thin layer chromatography ("TLC") uses a stationary phase spread in a thin layer on a support or substrate plate. Commonly used stationary phases include silica-based absorbent materials.

Mobile phases are usually solvent-based liquids, although gas chromatography usually employs gaseous mobile phases. The composition of the liquid mobile phase can vary significantly depending on the various characteristics of the sample to be analyzed and the various components of the sample which it is desired to extract and/or analyze. For example, the pH and solvent properties of liquid mobile phases can vary significantly. Additionally, depending on the nature of the stationary phase employed, the composition of the liquid mobile phase may vary. During a given chromatography or SPE procedure, several different mobile phases are often employed.

A typical TLC plate is prepared by mixing a sorbent (which acts as a stationary phase) with a small amount of an inert binder and water. The mixture can be spread on a carrier sheet as a relatively viscous slurry. The resulting panels can then be dried and activated in an oven. The obtained stationary phase is bonded and fixed on a carrier sheet or other substrates through an adhesive. The presence of binders may lead to secondary interactions with the mobile phase and a decrease in separation efficiency.

Contents of the invention

Embodiments of the present invention relate to TLC plates, methods of using such TLC plates in chromatography, and related methods of preparation, wherein a plurality of elongated stationary phase structures are formed and immobilized without the use of a separate adhesive on the substrate. The absence of any binder prevents unwanted secondary interactions and improves separation efficiency.

In one embodiment, a method for preparing a TLC plate is disclosed. The method includes forming a layer of elongated nanostructures, and at least partially coating the elongated nanostructures with a coating. The coating includes a stationary phase and/or a stationary phase precursor for chromatography. In one embodiment, the elongated nanostructures can then be removed by heating in an oxidizing environment to burn off the elongated nanostructures. In one embodiment, the layer of elongated nanostructures includes a first portion grown on the first portion of the catalyst layer, and at least a second portion grown on at least a second portion of the catalyst layer, each portion exhibiting a selected non- linear structure.

In one embodiment, a TLC plate is disclosed. The TLC plate includes a substrate and a plurality of stationary phase structures extending longitudinally away from the substrate. At least a portion of the plurality of stationary phase structures exhibits an elongated geometry and is substantially free of carbon nanotubes ("CNTs") that serve as templates for forming the stationary phase structures thereon. In one embodiment, a plurality of stationary phase structures are arranged in a selected pattern on the substrate. The first and at least second portions of the plurality of stationary phase structures can each be arranged in a non-linear pattern, such as a zigzag pattern or other selected non-linear pattern. This non-linear pattern provides increased mechanical stability to the stationary phase structures, as individual stationary phase structures tend to at least partially entangle or contact each other, providing support relative to each other. Additionally, it has been found that the use of a zigzag or other non-linear pattern counteracts the tendency of material to peel off from the substrate during oxidation to form the stationary phase structure.

In one embodiment, a method of performing chromatography is disclosed. The method includes providing a TLC plate comprising a substrate and a plurality of stationary phase structures extending longitudinally away from the substrate. At least a portion of the plurality of stationary phase structures exhibits an elongated geometry. The method also includes applying the sample to be analyzed to the plurality of stationary phase structures of the TLC plate, and dragging the mobile phase through the plurality of stationary phase structures to which the sample is applied. The different components of the sample can be separated as the mobile phase, and the sample interacts with the TLC plate.

Any features of the disclosed embodiments may be used in combination with each other without limitation. Furthermore, other features and advantages of the present disclosure will become apparent to those of ordinary skill in the art by consideration of the following detailed description and accompanying drawings.

Description of drawings

Figure 1 is a schematic top plan view of an embodiment of a TLC plate intermediate structure comprising a substrate and a catalyst layer disposed on the substrate, wherein the catalyst layer exhibits a zigzag pattern;

Figure 2 is a schematic top plan view of another embodiment of a TLC plate intermediate structure similar to Figure 1, but with the catalyst layer showing an alternative zigzag pattern;

Figure 3 is a schematic top plan view of another embodiment of a TLC plate intermediate structure similar to Figure 1, but with catalyst layers exhibiting a substantially parallel spaced pattern;

Figure 4 is a schematic top plan view of another embodiment of a TLC plate intermediate structure similar to Figure 3, but with the catalyst layers exhibiting an alternative substantially parallel spaced pattern;

Figure 5 is a schematic top plan view of another embodiment of a TLC plate intermediate structure similar to Figure 1, but with the catalyst layer exhibiting a diamond pattern;

Figure 6 is a schematic top plan view of another embodiment of a TLC plate intermediate structure similar to Figure 5, but with the catalyst layer exhibiting an alternative diamond pattern;

Figure 7 is a schematic top plan view of another embodiment of a TLC plate intermediate structure similar to Figure 1, but with the catalyst layer showing a honeycomb pattern;

Figure 8 is a schematic top plan view of another embodiment of a TLC panel intermediate structure similar to Figure 7, but with the catalyst layer showing an alternative honeycomb pattern;

Figure 9 is a schematic top plan view of another embodiment of a TLC panel intermediate structure similar to Figure 7, but with the catalyst layer exhibiting an alternative honeycomb pattern;

10A is a cross-sectional view of the TLC plate intermediate structure of FIG. 1;

Figure 10B is a cross-sectional view of the TLC plate intermediate structure of Figure 10A with CNTs grown on the catalyst layer;

Figure 10C is a cross-sectional view of the TLC plate intermediate structure of Figure 10B in which CNTs have been at least partially coated with a coating;

Figure 10CC is an enlarged top plan view of one of the coated CNTs of Figure 10C;

Figure 10D is a cross-sectional view of the intermediate structure of the TLC plate of Figure 10C, wherein the CNTs have been burned off and the coating has been oxidized to form a stationary phase structure;

Figure 10DD is an enlarged top plan view similar to Figure 10CC, but with the CNTs burned away;

11A is a schematic top plan view of a TLC panel made from a TLC panel intermediate structure similar to that of FIG. 1;

11B is an enlarged top plan view of the TLC plate intermediate structure of FIG. 11A showing several high aspect ratio deposited stationary phase structures disposed on the TLC plate substrate;

Figures 12A and 12B present graphs depicting energy dispersive x-ray spectroscopy ("EDX") spectra of TLC plates before and after oxidation according to working examples of the present invention;

Figures 13A-13D present scanning electron microscope ("SEM") images of various nonlinear catalyst layer patterns formed on alumina substrates;

14A-14P present SEM images of TLC plates with different catalyst layer thicknesses and CNT and _SiO elongated nanostructures with different corresponding heights formed on the catalyst layer;

Figures 15A-15N present SEM images of silicon infiltrated CNTs and oxidized elongated nanostructures;

Figures 16A-16D present SEM and other images comparing the separation efficiency of various TLC plates;

Figure 17 shows various silicon-infiltrated CNT structures and images of the structure after oxidation;

Fig. 18A has provided the SEM image of the TLC plate of the _SiO of another kind of preparation with zigzag structure stationary phase structure;

Figure 18B shows the results of a TLC plate spotted with the CAMAG test mixture;

Figure 18C shows a comparison of commercially available TLC plates spotted with the CAMAG test mixture;

Figure 19 is a transmission electron microscope ("TEM") and a scanning transmission electron microscope ("STEM") image of a CNT core after infiltration to form a silicon shell, and electron energy loss spectroscopy ("EELS") correlation data; and

FIG. 20 is an SEM image of another prepared TLC plate with a zigzag structure.

Detailed ways

I． introduction

Embodiments of the present invention relate to TLC plates and related methods of preparation and use. The disclosed TLC plates can include multiple elongated stationary phase structures immobilized to a substrate without the use of a separate adhesive, thereby providing a highly porous structure suitable for chromatographic use. The absence of any binder prevents unwanted secondary interactions and improves separation efficiency.

II． Embodiments of methods of making TLC plates and TLC plate embodiments

In various embodiments, TLC plates can be prepared by forming a layer of elongated nanostructures on a substrate and then at least partially coating the layer with a coating comprising a stationary phase and/or a stationary phase precursor for chromatography. elongated nanostructures. Although CNTs are used as an example of a suitable elongated nanostructure in the description below, other elongated nanostructures, such as semiconductor nanowires with or without porous coating, metallic nanowires with or without porous coating, can also be used. wires, nanopillars formed by nanoimprint lithography, combinations of the foregoing nanostructures, or any other suitable nanostructures.

CNTs may generally be perpendicularly aligned with respect to each other, although adjacent CNTs may exhibit some contact and/or at least partial entanglement, which may provide increased mechanical stability to the entire CNT forest. The CNTs are coated with a stationary phase with a thickness smaller than the CNT spacing, which results in a porous medium through which separation is possible by means of chromatography. The CNT jungle is used as a framework on which the stationary phase can be coated and/or formed, resulting in a final structure that typically does not contain any binders used to bind the stationary phase to the substrate.

The substrate may include: a bottom layer, a backing layer disposed on the bottom layer, and a catalyst layer disposed on the backing layer to catalyze the growth of CNTs on the substrate. In general, the catalyst layer can be deposited on the backing layer by any suitable technique. The placement of the catalyst layer can be accomplished, for example, using photolithography, such as masking the catalyst layer and etching away the areas of the catalyst layer exposed through the mask. This photolithography method can be used to prepare catalyst layers with selected non-linear (eg zigzag) patterns. Other patterning methods can also be used, such as shadow masking with stencils during catalyst deposition or printing. In another embodiment, the catalyst layer can be applied so as to coat substantially the entire substrate.

The catalyst layer may comprise any suitable material _that catalyzes the growth of CNTs under appropriate growth conditions (eg, heating and exposure to process gases such as _H2 and carbonaceous gases such as _C2H4 ). Various transition metals may be suitable for use as catalyst layers. Suitable metals include, but are not limited to, iron, nickel, copper, cobalt, alloys of the foregoing, and combinations thereof.

The backing layer of the substrate provides support for the structure of the TLC panel. For example, the backing layer provides a support on which the catalyst layer may be deposited, and may also act as a diffusion barrier to help prevent chemical reactions between the catalyst layer and the underlying layer. Examples of backing layer materials may include, but are not limited to, silica (e.g. fused silica), alumina, low expansion high temperature borosilicate glass (e.g. Pyrex 7740 and/or Schott Borofloat glass), steel (e.g. stainless steel), silicon Wafer, nickel substrate or any other high temperature glass or other suitable material. In embodiments where the backing layer comprises a material other than alumina, the backing layer for CNT growth can be prepared by applying a thin layer of alumina over the non-alumina backing layer. The aluminum oxide layer may have a thickness of about 5-100 nm, more specifically about 10-50 nm, and most specifically about 20-40 nm (eg, about 30 nm).

A catalyst layer (eg iron) can be applied on the backing layer. The thickness of the catalyst layer may be about 0.1-15 nm, more specifically about 0.5-8 nm, and even more specifically about 0.5-5 nm (eg, about 2-3 nm). For example, the thickness of the catalyst layer can be about 0.5 nm, about 1 nm, about 2 nm, about 3 nm, about 4 nm, about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, about 10 nm, about 11 nm, about 12 nm, about 13 nm, About 14nm or about 15nm. Although specific catalyst layer thicknesses are described above, the inventors have further discovered that varying the thickness of the catalyst layer affects some or each of the diameter, density and height of CNTs grown under otherwise identical conditions. Thus, according to one embodiment, the catalyst layer thickness can be varied to vary one or more of the diameter, density, or height of the growing CNTs.

The catalyst layer may be applied in a selected non-linear or other pattern, or may be applied over substantially the entire surface of the backing layer. 1-9 illustrate various embodiments of catalyst layer patterns. For example, FIGS. 1 and 10A show a TLC plate intermediate structure 100 comprising a substrate 101 having a backing layer 102 disposed on a bottom layer 103 and a non-linear zigzag pattern formed on the backing layer 102. Catalyst layer 104, where dark lines represent patterned catalysts. In some embodiments, periodic cracks may be formed in some or all of the zigzag portions of the catalyst layer 104 to provide a more uniform average mobile phase flow rate to the eventually formed TLC plate. Figure 2 shows another embodiment of the zigzag pattern of the catalyst layer 104, where the dark lines represent the patterned catalyst. 3 and 4 each show a TLC plate intermediate structure 100 comprising a substrate 101 having a backing layer 102 disposed on a bottom layer 103 and formed in a substantially parallel pattern on the backing layer 102 according to another embodiment. Catalyst layer 104 on liner 102, where dark lines represent patterned catalyst. 5 and 6 each show a TLC plate intermediate structure 100 comprising a substrate 101 having a backing layer 102 disposed on a bottom layer 103 and formed in various repeating diamond patterns in various embodiments, according to various embodiments. The catalyst layer 104 on the backing layer 102, wherein the rhombus represents the catalyst. 7-9 each show a TLC panel intermediate structure 100 comprising a substrate 101 having a backing layer 102 disposed on a bottom layer 103 and formed in a different honeycomb pattern on the backing according to various embodiments. Catalyst layer 104 on layer 102. Figures 1 and 2 and 5-9 each show a non-linear catalyst pattern, whereas the patterns of Figures 3 and 4 show a generally linear catalyst pattern.

The catalyst layer 104 can be patterned to exhibit any desired spacing between adjacent portions of the patterned catalyst layer 104 . An example of the average bed spacing "S" is shown in Figure 1 . In one embodiment, the average bed spacing between adjacent portions of the patterned catalyst layer 104 is about 1-50 μm, more specifically about 3-20 μm, and most specifically about 5-15 μm (e.g., about 10 μm ). Those skilled in the art will appreciate that the catalyst layer 104 may be formed to have any desired pattern and/or spacing "S". In another embodiment, the catalyst layer 104 can be formed to cover substantially the entire backing layer 102 without any particular different pattern. In some embodiments, the catalyst layer 104 is spaced inward from the edge of the backing layer 102 such that CNT growth on the edge is substantially prevented. In some embodiments, spacing "S" may vary in one or both directions, eg, from zigzag portion to zigzag portion.

With the catalyst layer 104 formed on the backing layer 102, the TLC plate intermediate structure 100 can be placed on a suitable support (such as a quartz support) in a furnace and heated to about 600-900°C, more specifically about 650- 850°C and even more particularly a temperature in the range of about 700-800°C (eg about 750°C). Prior to CNT growth, the catalyst layer 104 may be annealed in an annealing process in which H _or other process gas is flowed through the catalyst layer 104 (e.g., within a fused silica tube) while the temperature is increased from ambient to the temperature at which CNT growth will occur. temperature. The flow rate of H ₂ may be about 300 cm ³ /min or other suitable flow rates.

A process gas (eg, H ₂ , ammonia, N _{2 ,} or combinations thereof) and a carbon-containing gas (eg, acetylene, ethylene, ethanol, methane, or combinations thereof) are introduced and flowed through the catalyst layer 104 . The carbon-containing gas stream may also contain an inert gas such as argon to control the growth rate of CNTs on or over the catalyst layer 104 . The flow ratio of process gas to carbon-containing gas (eg, ethylene) may be from about 0.5:1 to 1:1, more specifically from about 0.55:1 to 0.85:1, and even more specifically from about 0.6:1 to 0.8: 1.

Once the desired CNT growth height is reached, the flow of process gas and carbon-containing gas is turned off, with the furnace partially cooled, for example to between about 100-300°C, more specifically about 150-250°C and even more specifically At a temperature of about 175-225°C (eg, about 200°C), the furnace chamber may be purged with a flow of inert gas (eg, argon).

In one embodiment, in order to obtain higher aspect ratios of substrate width to CNT height, a "start/stop" approach can be employed. For example, the carbon-containing gas can be turned off during CNT growth, causing the CNTs to grow in multiple directions. This type of growth may be desirable in some embodiments, as it may result in more mechanically stable CNTs (eg, adjacent CNTs may be more likely to contact each other and/or at least partially entangle).

Figure 10B is a cross-sectional view of one embodiment of a structure similar to Figures 1 and 10A, in which CNTs 106 have been grown on and over catalyst layer 104. The CNTs 106 can be grown to extend longitudinally away from the substrate 101. For example, CNTs may extend substantially orthogonal (ie, perpendicular) to the respective surfaces of catalyst layer 104 and substrate 101 . The grown CNTs 106 can be single-walled or multi-walled, as desired. The grown CNT 106 can have an average diameter of about 3-20 nm, more particularly about 5-10 nm (e.g., about 8.5 nm), and about 10-2000 μm, about 10-1000 μm, about 10-500 μm, about 20-400 μm, about An average length of 20-200 μm, about 100-300 μm, about 10-100 μm, or about 20-200 μm. The grown CNTs 106 can exhibit an average aspect ratio (ie, the ratio of average length to average diameter) of about 10,000-2,000,000, such as about 10,000-1,000,000 or about 100,000-750,000.

The average length of CNT 106 growth can be selected based on the particular chromatographic application. For example, for ultra-thin layer chromatography ("UTLC"), the average length of CNT 106 can be about 10-100 μm, and for high-performance thin-layer chromatography ("HPTLC"), the average length of CNT 106 can be about 100-100 μm. 300 μm, and for preparative liquid chromatography (“PLC”), the average length of CNT 106 may be about 500-2000 μm.

Additional details on CNT 106 growth can be found in U.S. Patent Application Nos. 12/239,281 and 12/239,339, entitled "X-Ray Radiation Windows With Carbon Nanotube Frameworks." The above two applications claim priority from US Provisional Patent Application No. 60/995,881. US Patent Application Nos. 12/239,281 and 12/239,339 and US Provisional Patent Application No. 60/995,881 are hereby incorporated by reference in their entirety.

Although the CNTs 106 are described as being evenly spaced, the CNTs 106 can also be at least partially entangled with each other to form vertical CNT 106 walls. As previously described, at least partial entanglement and/or contact of CNTs 106 with each other helps to reduce, limit, or prevent vertical CNT 106 walls from bending out of plane. Furthermore, by patterning the catalyst layer 104 in a selected non-linear pattern, such as the pattern shown in FIG. The walls of the CNT 106 can be further stiffened to reduce, limit or prevent them from bending out of plane.

CNTs serve as a framework to be infiltrated by materials that can increase the mechanical stability of the overall structure and provide a stationary phase for chromatographic applications. Referring to FIG. 10C , after growth, the CNTs 106 may be infiltrated with one or more infiltrants (eg, precursor gases) to deposit a coating 108 on the CNTs 106 . Coating 108 includes a stationary phase and/or a stationary phase precursor. Examples of materials for coating 108 include, but are not limited to, elemental silicon (e.g., deposited from precursor _SiH gas), silicon dioxide, silicon nitride, elemental aluminum, alumina, elemental zirconium, zirconia (e.g., zirconia ), elemental titanium, titanium oxide, amorphous carbon, graphitic carbon, and combinations of the foregoing. Since the choice of coating 108 can alter the selectivity of the resulting TLC plate, the coating 108 used to prepare any given TLC plate can be selected based on the intended use of the TLC plate.

In one embodiment, infiltration of CNTs 106 may be accomplished using chemical vapor deposition, such as low pressure chemical vapor deposition ("LPCVD"), or other suitable deposition methods, such as atomic layer deposition ("ALD"). For example, the TLC plate intermediate structure shown in FIG. 10B can be placed in a furnace and heated to about 500-650° C., more specifically about 540-620° C. and even more specifically about 560-600° C. (e.g., about 580° C. )temperature. During infiltration, the osmotic pressure can be maintained at less than about 400 mTorr. For example, the osmotic pressure may be maintained at about 50-400 mTorr, more specifically about 100-300 mTorr, and even more specifically about 150-250 mTorr (eg, about 200 mTorr). Under these temperature and pressure conditions, the penetrant flows through the CNTs 106 such that a coating 108 is formed on the CNTs 106 (see FIG. 10C ). Processing time can affect the amount of coating material deposited. For example, the treatment time for infiltration may be about 0.5-10 hours, more specifically about 1-5 hours, and most specifically about 1-4 hours (eg, about 3 hours).

Amorphous carbon infiltration of CNT106 can be performed using a carbon source flowing through a fused silica tube at high temperature. For example ethylene can be mixed with argon at a flow rate of 200 cm ³ /min and flowed at a temperature of about 900° C., eg at a flow rate of 170 cm ³ /min. Due to the light absorbing properties of amorphous carbon, detection of analytes after separation may require post sample preparation. The process may include labeling the analyte with an oxidatively stable label, and removing carbon in a high temperature oxygen environment (eg, with an oxygen plasma). For example the developer may comprise silane in gas phase or in solution which will be applied to the TLC plate. In an oxidizing environment such as a furnace, plasma, or flame, the carbon is burned away, leaving behind a pattern of _SiO2 that will show where migration of the analyte occurs.

The CNT 106 can be infiltrated with elemental silicon by LPCVD, and then oxidized to form _SiO2 if needed or desired. Other deposition methods for SiO ₂ include direct SiO ₂ LPCVD, ALD, or by other CVD methods with SiH ₄ and O ₂ or SiH ₂ Cl ₂ and N ₂ O, or will be apparent to those skilled in the art from this disclosure. Other methods for CNT infiltration. The inventors performed LPCVD infiltration of CNTs with elemental silicon, followed by dry oxidation. The silicon infiltration method uses _SiH4 as the source of elemental silicon. Silicon infiltration was performed by flowing SiH ₄ at a flow rate of about 20 cm ³ /min at a temperature of about 530° C. and a pressure of about 160 mTorr for about 1-3 hours, depending on the desired film thickness (degree of infiltration). After silicon deposition, the material is placed in a furnace and processed to about 500-1000° C. for about 1-10 hours in air. This treatment converts elemental silicon to silica while also removing CNT106 by oxidizing them to CO and/or _CO , thereby leaving an elongated stationary phase structure made of silica without any appreciable amount CNT106 filled. Depending on the extent of the oxidation process, the elongated stationary phase structure may be a substantially solid nanowire without a hollow center in which the CNTs reside. This process produces a white and/or transparent _SiO2 material that can be used in chromatography. Silicon infiltration between and around the CNT wires can be nearly complete (eg, at least about 90%).

The CNT 106 can be infiltrated with a conformal coating of a selected material that has chromatographic capability or can be subsequently processed to achieve this capability instead using the ALD method. ALD can be used to infiltrate CNTs with _SiO2 . One such method may use _SiCl4 and water at a selected temperature. _SiCl4 was introduced into the chamber containing CNT106 and allowed to react for a predetermined time. After the self-limited chemisorption/physiosorption process is complete, water is introduced into the chamber, which reacts with the bound SiCl ₄ to make a conformal layer of SiO ₂ on the CNT 106 . Repeat this process until a predetermined _SiO2 film thickness is achieved. In other embodiments, CNTs 106 can be infiltrated using ALD-like methods. For example _SiCl4 is introduced, but excess _SiCl4 may or may not be completely removed by pumping before water is introduced. In turn, the excess water may or may not be completely removed before introducing _SiCl4 . As is appropriate for true ALD methods, SiO ₂ can be deposited faster by incomplete removal of excess reagents. This same strategy of incomplete material removal can be expected for other ALD chemistries that can be used to infiltrate CNTs 106 . Note also that a perfectly conformal coating of uniform thickness of CNT 106 may or may not be desired. The infiltration process can be designed to produce a coating of substantially non-uniform thickness in order to increase the surface area of the support.

10C is a cross-sectional view of the intermediate structure of the TLC plate shown in FIG. 10B in which CNTs 106 have been infiltrated with a penetrant such that a coating is deposited on the CNTs 106 to form a coating at least partially coating and extending along the periphery of each CNT 106. Layer 108. Where the penetrant is a silicon precursor gas such as silane, coating 108 may be silicon. However, as noted above, other precursor gases may be used so that coating 108 may be formed from aluminum or zirconium. Depending on the penetrant selected, the coating 108 may only at least partially or substantially coat the entire array of CNTs 106, or may also be coated in the middle of the backing layer 102 and the catalyst layer 104 between the CNTs 106, resulting in TLC plates bonded together. The coating 108 on each CNT 106 shown in FIG. 10C forms each high aspect ratio structure exhibiting an elongated annular geometry (e.g., substantially a hollow cylinder). The CNT 106 acts as a template around which the coating is deposited. In some embodiments, coating 108 may be porous or non-porous. The specific aspect ratio of the elongated structures made by coating 108 depends on the height of template CNT 106, deposition time, process temperature (e.g., temperature of infiltrant and CNT 106), or a combination of the foregoing process parameters. Figure 10CC is an enlarged top plan view of a single coated CNT 106 of Figure 10C. The plurality of elongated structures defined by the coating 108 coating each CNT 106 may have an average aspect ratio (i.e., the ratio of average length to average diameter) of about 10,000-2,000,000, such as about 10,000-1,000,000, or about 100,000- 750,000. The coating 108 coating the CNTs 106 may have an average radial thickness of about 10-100 nm, more specifically about 20-80 nm, and even more specifically about 25-40 nm (eg, about 30 nm). The average length of the elongated structures defined by the coating 108 can be substantially the same or similar to the template CNT 106.

Figure 19 shows TEM and STEM and EELS images of CNTs after coating with silicon to form a silicon shell. The analytical results indicated that no interdiffusion of carbon from the CNTs into the silicon coating was detected.

In some cases, the disordered growth of CNT 106 followed by infiltration and optional oxidation of coating 108 may pose a potential problem. During the oxidation process that converts silicon to silicon dioxide, the material undergoes volume expansion due to the addition of oxygen. Volume expansion causes material to detach from the backing, especially during longer, more complete oxidation times. Even if peeling does not appear to occur initially, the material can easily wrinkle and peel off as a result of slight bumps or touches due to swelling. One way to reduce, minimize, or eliminate delamination, flaking, or wrinkling of this material from the backing is by patterning the CNT growth catalyst (e.g., zigzag or otherwise non-linear) such that voids are built throughout the structure, thereby Volume expansion is allowed during the oxidation step. In addition, patterning of stationary phase media on a microscopic scale can improve separation efficiency. SEM images show how varying the thickness of the catalyst layer results in CNT growth of different heights. The SEM images are shown in Figures 14A-14P. Figures 14A-14P show the appearance of the infiltrated plate after the oxidation step in which the silicon is converted to silica and the CNTs 106 are removed. Note that the color change is indicative of a material change (i.e. dark for CNT, bright for _SiO2 ). SEM images of the patterned media before and after oxidation showed volume expansion during oxidation (see Figures 15A-15O).

The selected zigzag pattern may include any different angles greater than 0° and less than 180° between certain portions of the zigzag. A zigzag pattern such as that shown in FIGS. 1 , 2, 11A-11B, 18A and 20 may include an angle of about 90° between adjacent portions of the zigzag and zigzag of the pattern.

As noted above, the average bed spacing between adjacent portions of the patterned catalyst layer 104 may be about 1-50 μm, more specifically about 3-20 μm, and most specifically about 5-15 μm (eg, about 10 μm) . Infiltration with a penetrant after CNT 106 growth and/or growth of coating 108 around CNT 106 results in smaller spacing between adjacent elongated structures defined by coating 108 as CNT 106 grows laterally outward and toward each other . For example, the average spacing defined by coating 108 between adjacent elongated structures may be about 0.5-30 μm, more specifically about 2-10 μm, and most specifically about 4-8 μm. This spacing results in a bulk structure with a very high bulk porosity (ie the spacing between adjacent structures acts as pores through which the mobile phase and the sample carried by the mobile phase advance due to capillary action). When present, the porosity of any individual coating 108 (ie, as opposed to the bulk porosity created by the spacing between adjacent structures) also contributes to the overall porosity of the TLC plate.

In one embodiment, once the coating 108 has been deposited on the CNTs 106, the CNTs 106 may be partially or substantially completely removed. For example, the TLC plate intermediate structure shown in FIG. 10C can be placed in a furnace and heated (eg, to about 800-900° C., or about 850° C.) in the presence of an oxidizing atmosphere (eg, an oxygen atmosphere) to remove (eg, burn off ) substantially all of the CNTs 106, leaving only the coating 108 disposed on the backing layer 102 and the catalyst layer 104 of the TLC plate substrate 101. If the coating 108 is not a stationary phase, such an oxidation step may also serve to convert the coating 108 to a stationary phase by oxidizing the deposited coating 108 . For example, if coating 108 is silicon, aluminum, or zirconium, it may be oxidized to silicon oxide, aluminum oxide, or zirconium oxide, respectively. One embodiment of a method of removing CNTs 106 may include oxidation of coating 108 using a plasma of oxygen. Other methods for at least partially removing the CNTs 106 may include dissolving the CNTs 106, or removing them by any means.

Figure 10D is a cross-sectional view of the structure shown in Figure 10C, in which the CNTs 106 have been removed and the coating 108 has been oxidized to form a plurality of elongated stationary phase structures 108'. Figure 10DD is a top plan view of the stationary phase structure 108' after the CNTs 106 have been burned away. Figure 10D clearly shows the overall high aspect ratio configuration of the stationary phase structure 108'. Dimensions of the plurality of elongated stationary phase structures 108 ′ may be substantially the same or similar to the dimensions of the plurality of elongated structures defined by the coating 108 prior to oxidation. The oxidation process can be performed for at least about 5 hours, more specifically for at least about 10 hours, and most specifically for at least about 24 hours. The inventors have found that increased oxidation increases the separation efficiency achieved by oxidized stationary phases. In some embodiments, only a portion of coating 108 coating each CNT 106 is oxidized. In other embodiments, substantially all of the coating 108 coating each CNT 106 is oxidized.

Although elongated stationary phase structures 108' are depicted as hollow in FIGS. 10D and 10DD after CNT 106 removal, depending on the extent of the oxidation process, elongated stationary phase structures 108' may be substantially solid nanowires, Wherein the space previously occupied by CNT 106 is consumed or filled by oxide. In embodiments where the coating 108 is deposited by ALD or an ALD-like method (e.g., ALD deposition of silicon oxide), the resulting elongated stationary phase structure may be a hollow elongated cylinder where the CNTs 106 reside.

Removing the CNT 106 prior to use of the TLC plate prevents the CNT 106 from interfering with the separation of the mobile phase during use of the TLC plate (e.g. by secondary interactions). Additionally, this results in a white and/or transparent stationary phase; thus making evaluation of chromatographic results easier than if the stationary phase were black or brown. In embodiments where the coating 108 comprises amorphous carbon, the CNTs 106 may not be removed because both the coating 108 and the CNTs 106 contain carbon, thereby substantially eliminating any damage caused by the CNTs 106 present in the stationary phase formed during infiltration. Possibility of resulting secondary interactions.

In some embodiments, the stationary phase structure 108' comprises a white, off-white, transparent or or generally light colored material such that mobile phase compounds separated during use of the TLC plate are visible on the surface of the TLC plate after development. Silicon and/or silicon dioxide are examples of materials that provide such color contrast. In some embodiments, a fluorescent material (eg, ZnS) can be incorporated into a TLC plate to make a fluorescently active TLC plate. This can be done by depositing thin films on top of the chromatographic support or as a few monolayers below the chromatographic support. This can be done in liquid or gas phase. ALD as well as other CVD or liquid phase methods can be used to place inorganic species in or on chromatographic supports. For example, the fluorescent material may be at least partially coated and/or incorporated into the stationary phase structures 108', may at least partially coat the intermediate portion of the backing layer 102 between the stationary phase structures 108', or both.

Following oxidation and removal of the CNTs 106, in some embodiments, the TLC plate can be exposed to at least one acid to functionalize the stationary phase structure 108'. The TLC plate so formed can be placed in a furnace, for example, in the presence of HCl so that the HCl vapor places hydroxyl groups on the surface of the stationary phase structure 108' thereby functionalizing the stationary phase structure 108'. Additional chemical functionality and selectivity can be added to the stationary phase structure 108' by, for example, silylation with an alkyl moiety using any suitable gas phase chemistry. When the stationary phase structure 108 _' comprises silica (e.g., by oxidizing the _silicon coating ₁₀₈ ), the silica can be made Silicon functionalization.

In one embodiment, the stationary phase may be exposed to water vapor after the oxidation step and during cooling from the oxidation temperature to ambient temperature. Acidified water vapor can be used to hydroxylate the surface. This can be done, for example, by placing a TLC plate over a boiling HCl solution so that the solution vapor interacts with the stationary phase. The boiling solution may include methanol to aid in surface wetting. Other components that may be used include other strong acids (eg, nitric acid, HBr), organic acids (eg, acetic acid, formic acid, trifluoroacetic acid), or other suitable chemicals that can hydroxylate the surface. In one embodiment, the exposure may be for about 5 minutes, although shorter or longer times may be used. Silanol-containing surfaces can be silanized using a variety of silanes such as monochlorosilane, dichlorosilane, trichlorosilane, or combinations thereof. Examples of suitable silanes include alkylsilanes (e.g. octadecyltrichlorosilane, octadecyldimethylchlorosilane, perfluoroalkylsilane), aminosilanes, phenylsilanes, cyanosilanes, biphenylsilanes Silanes or combinations thereof. These silanes can be monofunctional (e.g. comprising one Si-Cl group, _one Si- _OCH3 group, one Si- _OCH2CH3 group or one Si-OC(O) _CH3 group) or polyfunctional silanes with surface reactive functional groups. Molecules such as octadecyldiisopropylchlorosilane, where the isopropyl group confers increased hydrolytic stability to silica TLC plates, are contemplated.

Exposure to acidified water vapor resulted in improved chromatographic performance of the material. Figures 16A-16D demonstrate how treatment with this acid affects the chromatographic capabilities of the material. The chemicals isolated in the images in Figures 16A-16D are Rhodamine 6G, Sunset Yellow FCF, and Sulforhodamine B. Rhodamine 6G was retained on the TLC plate to the greatest extent.

As mentioned, CNTs can be removed by wet or dry oxidation after infiltration. This method of CNT removal reduces the silanol ("SiOH") groups on the surface of the stationary phase structure 108', at least as far as the dry oxidation process is concerned. In order to increase the silanol groups on the surface of the stationary phase structure 108', the _SiO2 material of the stationary phase structure 108' may be subjected to an acidified water vapor treatment as described above. Additionally or alternatively, the _Si02 material of the stationary phase structure 108' may be subjected to a concentrated HCl acidic liquid bath for a predetermined period of time. For example a TLC plate can be immersed in an acid solution for a selected time. In one embodiment, the acid solution may contain 50:50 vol./vol. concentrated HCl and methanol, and the TLC plate may be heated therein to reflux temperature for several hours (eg, 4-20 hours). Methanol in the acid solution can aid in surface wetting. Other acids that can be used include those described elsewhere (eg, nitric acid, HBr, acetic acid, formic acid, trifluoroacetic acid, or combinations thereof). Exposure to HCl vapor or introduction of water vapor or acidified water vapor (including the acids described above or other suitable acids) into the oxidation chamber while cooling the material or at elevated temperature for a predetermined time increases the silica of the stationary phase structure 108'. The number of hydroxyl groups on the surface.

In one embodiment, TLC plates with enrichment zones can be prepared. This involves setting up regions with relatively low residence times where compounds are likely to be spotted. This allows the mobile phase to quickly carry the analytes through the region, and the analytes will then slow down as they reach the normal absorbent bed. This can be done by forming a pre-concentration zone with a low density stationary phase structure and/or selectively functionalizing this zone with chemicals that allow the analyte to reduce residence time.

In some embodiments, substrate 101 may be scribed or partially cut either before or after CNT 106 growth and/or coating of CNT 106. By scribing or cutting the substrate 101 , smaller TLC plates can be prepared by splitting larger TLC plates along the scribed/cut lines of the substrate 101 .

FIG. 11A is a top plan view of one embodiment of a TLC plate 100'. 11B is an enlarged view of a portion of a TLC plate 100' including a stationary phase structure 108' disposed between end 110 and end 112 of TLC plate 100'. TLC plates prepared according to the inventive methods disclosed herein provide a stationary phase which is attached to the substrate of the TLC plate without the use of any separate binder, such as typically calcium sulfate. The adhesive may affect the performance of the TLC plate due to secondary interactions caused by the adhesive. Not requiring any adhesives can result in a more efficient TLC plate while minimizing and/or preventing such secondary interactions.

The spacing of the stationary phase structures 108' is shown in FIGS. 11A and 11B, which is generally uniform. However, in some embodiments, the density of the stationary phase structures 108' may be different (eg, larger or smaller) at different locations on the TLC plate 100'. For example, the density of the stationary phase structure 108 ′ near end 110 may be different (eg, greater or less than) the density near end 112 . Alternatively, or in addition, the density of the stationary phase structure 108' varies with position, the composition of the stationary phase structure 108' may vary with position. As a non-limiting example, a portion of the stationary phase structure 108' may comprise zirconia, and another portion of the stationary phase structure 108' may comprise silica.

Furthermore, TLC plates prepared according to the inventive methods disclosed herein provide stationary phases with exceptionally high porosity. The high porosity and absence of binders can lead to increased efficiency of the TLC plate during use to analyze samples in the mobile phase. In one embodiment, a TLC plate formed according to the disclosed method is used to analyze sample material. In one embodiment, the sample to be analyzed is applied to the stationary phase structure 108' of the TLC plate 100' (eg, near the end 110). The mobile phase solvent or solvent mixture is then drawn along (eg, upwardly) the TLC plate 100' by capillary action (eg, by placing the TLC plate 100' in a container containing the solvent or solvent mixture). As the solvent or solvent mixture is drawn by capillary action along the TLC plate 100' towards the opposite end 112, the sample dissolves in the mobile phase and separation of the components in the sample is achieved because the different components of the sample move along the TLC plate 100' at different rates. TLC plate 100' rises. The high aspect ratio stationary phase structures 108' and the bulk porosity due to the spacing between each high aspect ratio stationary phase structure 108' allow the sample components to When 108', the components in the sample have excellent separation efficiency. The TLC plate 100' can also be used in HPTLC, where one or more of the application steps can be automated, thereby increasing the resolution achieved and allowing more accurate quantification.

III Working Example

The following working examples are for illustration purposes only and are not intended to limit the scope of the specification or the appended claims.

Example 1

Individual TLC plates were formed by applying a 30 nm layer of aluminum oxide on the backing layer. A 2-3nm iron catalyst film is deposited on the alumina layer and patterned by a photolithography process to form the TLC plate intermediate structure. The TLC plate intermediate structure was placed in a quartz support tube in a furnace and heated to about 750°C while flowing _H2 process gas through the quartz tube at a flow rate of about 500 standard ^cm3 /min. Once the furnace reached about ₇₅₀ °C, a flow of carbon-containing _C2H4 gas was started at a rate of about 700 standard ^cm3 /min. After the growth of CNTs was completed, the _H2 and _C2H4 gas flows were turned off, and _the quartz tube was purged with argon gas at a flow rate of about 350 standard ^cm3 /min while cooling the furnace to about 200 °C. The grown CNTs have a diameter of approximately 8.5 nm.

The grown CNTs are coated with silicon using LPCVD to deposit undoped polysilicon. The CNTs were placed in an LPCVD furnace and heated to about 580°C at a pressure of about 200 mTorr while flowing _SiH4 at a flow rate of about 20 standard ^cm3 /min for about 3 hours. The LPCVD method coated the CNT and alumina layers. After coating with silicon, the coated TLC plate intermediate structure is placed in a furnace and heated to about 850 °C and maintained at this temperature while being exposed to the atmosphere, thereby removing the CNTs and oxidizing the deposited silicon into silicon dioxide. Different oxidation samples were prepared in which the oxidation was carried out for about 5 hours, about 10 hours and about 24 hours. Experiments have shown that increasing the oxidation time increases the ability of analytes in the mobile phase to migrate through the silica/silica stationary phase.

Figures 12A and 12B show the EDX spectra of the panels before and after oxidation. Carbon is present prior to oxidation. A very small amount of carbon remains after oxidation. In addition, oxygen is chemically grafted onto the surface of silicon to form silicon dioxide.

Example 2-35

Individual TLC plates were formed by applying a 30 nm layer of alumina on the substrate. Afterwards, photoresist is applied, followed by photolithography and development. After development, the alumina layer and photoresist are then coated with a predetermined amount of catalyst material. In these examples, a 2, 4, 6 or 7 nm iron layer was deposited on top of the photoresist and aluminum oxide layers. After iron catalyst deposition, the substrate was placed in a bath of solvent acetone, which was used to remove photoresist and iron left on it, as seen in Figures 13A-13D. The TLC plate intermediate was then used for CNT growth by annealing the catalyst material by flowing 300 ^cm3 /min _H2 through a 1 inch fused silica tube while heating the furnace from ambient temperature to a temperature of 650-850°C. After annealing, CNTs were grown by flowing 100-1000 cm ³ /min ethylene mixed with 300 cm ³ /min H ₂ through a fused silica tube. Afterwards, cool the furnace while purging the fused silica tube with 380 cm ³ /min of argon to remove any remaining ethylene and hydrogen.

The CNTs are then infiltrated with elemental silicon by LPCVD and then oxidized to _SiO2 . The infiltration process used 20 cm ³ /min SiH ₄ at 530° C. and a pressure of 160 mTorr for about 1 hour. After silicon infiltration, the material is placed in a furnace in air and heated to about 500-1000° C. for about 1-10 hours to convert elemental silicon to silica and remove CNTs simultaneously. This process produces a white _SiO2 material suitable for chromatographic applications. Figure 17 depicts oxidized and non-oxidized examples of silicon infiltrated CNT TLC arrays thus formed. The silicon infiltrated CNTs are brown (darker), while the white plates are oxidized TLC plates. Figures 14A-14P show additional SEM images of these examples. Table I below provides information about each of these preparations.

Table I

Example picture Fe thickness Height of SiO2 _{nanostructures} 2 14A 7nm 105μm 3 14B 7nm 90μm 4 14C 7nm 80μm 5 14D 7nm 100μm 6 14E 6nm 100μm 7 14F 6nm 130μm 8 14G 6nm 140μm 9 14H 6nm 130μm 10 14I 4nm Warped board (height not measured) 11 14J 4nm 190μm 12 14K 4nm 165μm 13 14L 4nm 220μm 14 14M 2nm 145μm 15 14N 2nm 125μm 16 14O 2nm 142μm 17 14P 2nm 7μm

15A-15N are additional SEM images of fabricated examples. Each of Figures 15A-15N includes three rows of photographs. The first row of photographs shows silicon-infiltrated CNTs before oxidation. The second row of photographs represents the oxidized silicon nanostructure where silicon has been oxidized to _SiO2 . The third row of photos represents some additional views, where the first photo is a side view of the silicon nanostructure, the second photo is a side view of the _SiO2 nanostructure, and the third photo is an enlarged side view of the _SiO2 nanostructure . Table II below provides additional information on each of these preparations.

Table II

Example picture Fe thickness 18 15A 2nm 19 15B 2nm 20 15C 2nm twenty one 15D 2nm twenty two 15E 4nm twenty three 15F 4nm twenty four 15G 4nm 25 15H 6nm 26 15I 6nm 27 15J 6nm 28 15K 6nm 29 15L 7nm 30 15M 7nm 31 15N 7nm

16A-16D are SEM images of several prepared samples, and several prepared samples compared to commercially available TLC plates, conventionally processed TLC plates, and TLC plates treated with HCl vapor by placing the plates above 12M HCl for 5 minutes. Compare test results. Three different analytes - Rhodamine 6G, Sunset Yellow FCF and Sulforhodamine B - were used in the comparison test. Analytes were separated in the order listed above in a 9:1 dichloromethane:methanol solvent system. SEM images represent from left to right and top to bottom: (1) side view of the elongated nanostructure; (2) top view of the elongated nanostructure; (3) top plan view of the elongated nanostructure; and (4) elongated nanostructure. A zoomed-in view of a long nanostructure. Also shown (and labeled) is a comparative test of a commercially available TLC plate, a conventionally treated plate (i.e. the _SiO2 was not hydroxylated) and an HCl treated plate in which the _SiO2 was hydroxylated. As seen in the images, conventionally treated plates resulted in better analyte separation than commercially available TLC plates, and HCl treated plates resulted in better analyte separation than conventionally processed TLC plates. Table III below provides additional information about each of these examples.

Table III

Example picture Fe thickness 32 16A 4nm 33 16B 4nm 34 16C 4nm 35 16D 6nm

Example 36

The SEM image of Figure 18A shows a substantially continuous zigzag pattern of the formed _SiO2 stationary phase structure. To demonstrate the chromatographic capability of the TLC plate of Fig. 18A, a test solution produced by CAMAG (Muttenz, Switzerland) was used. As shown in Figure 18B, the TLC plate spotted with the CAMAG test mixture completely resolved all 5 analytes. The run distance was 45 mm with the toluene mobile phase. The _Rf values of the colored compounds are as follows: yellow: 0.933, red: 0.624, blue: 0.506, black: 0.32, purple: 0.231. This plate showed slightly different selectivity for the CAMAG test mixture compared to the commercial plate (Figure 18C). The R _f values of the colored compounds used in the commercial plates are as follows: Yellow: 0.260, Red: 0.136, Blue 0.120, Black: 0.098, Purple: 0.002. Additional test data comparing another similar micropreparative TLC plate according to an embodiment of the present invention to commercially available Merck TLC and HPTLC plates is shown in Table IV below. Micropreparative TLC plates according to embodiments of the present invention showed better separation efficiencies than commercially available Merck TLC and HPTLC plates, as evidenced by higher plate numbers.

Table IV

Figure 20 shows the SEM image of another substantially continuous zigzag pattern of _SiO2 stationary phase structure formed on a TLC plate.

The described embodiments can be used in different types of liquid or gas chromatography, such as high performance liquid chromatography ("HPLC"), ultra performance liquid chromatography ("UPLC"), microfluidic applications, pressurized liquid chromatography, microfluidic Or nanofluid chromatography, circular or reverse circular TLC and any other type of chromatography application. Different columns or separation media for HPLC, UPLC or microfluidic applications containing patterned or non-patterned permeated CNTs are within the scope of the present disclosure.

Although aspects and embodiments have been disclosed herein, other aspects and embodiments are also contemplated. The aspects and embodiments disclosed herein are for purposes of illustration and not limitation. Additionally, as used herein, including in the claims, the words "comprises," "has," and variations thereof (such as "comprising" and "comprising") are open-ended and distinct from the words "comprising" and variations ( eg "comprising") have the same meaning.

Claims (15)

1. method for preparing TLCP, said method comprises:

Formation is arranged on the catalyst layer on the base material, and said catalyst layer comprises first and second portion at least, said first and at least second portion demonstrate selected nonlinear organization separately;

Catalyst layer first and form elongated nanostructured layers at least on the second portion, wherein elongated nanostructured layers is included in first of growing in the first of catalyst layer and the second portion at least of on the second portion at least of catalyst layer, growing;

With coating at least part apply said elongated nanostructured, said coating comprises at least a of the stationary phase that is used for chromatogram or stationary phase precursor;

After part applied said elongated nanostructured at least with coating, part was removed said elongated nanostructured at least; With

Coating is immersed acidic liquid solution so that hydroxyl is attached on the said coating.

2. the method for claim 1, wherein said acidic liquid solution comprise and are selected from following acid: hydrochloric acid, nitric acid, hydrobromic acid, acetate, formic acid, trifluoroacetic acid and their combination.

3. the method for claim 1, wherein acidic liquid solution comprises the concentrated bath of HCl and the methyl alcohol of 50:50v/v.

4. like each described method of claim 1-3, the coating that wherein at least partly applies said elongated nanostructured has defined each slim-lined construction that extends longitudinally away from base material.

5. like each described method of claim 1-4, wherein said base material comprises the back sheet that catalyst layer is set on it, and said back sheet comprises at least a following material that is selected from: silicon dioxide, silicon, nickel aluminium oxide, borosilicate glass and steel.

6. like each described method of claim 1-5, wherein catalyst layer first and form elongated nanostructured layers on the second portion at least and comprise the carbon nano-tube layer.

7. like each described method of claim 1-6, wherein at least partly apply said elongated nanostructured and comprise that the formation coating is to comprise at least a following material that is selected from: silicon, silicon dioxide, silicon nitride, aluminium, aluminium oxide, titanium, titanium dioxide, zirconium and zirconia with coating.

8. method as claimed in claim 7, wherein form coating with comprise at least a be selected from silicon, silicon dioxide, silicon nitride, aluminium, aluminium oxide, titanium, titanium dioxide, zirconium and zirconic material comprise through low-pressure chemical vapor deposition with bleeding agent at least part permeate said elongated nanostructured.

9. like each described method of claim 1-8; Thereby wherein at least part remove said elongated nanostructured comprise oxidation at least the part coating that applies said elongated nanostructured form a plurality of stationary phase structures and the said elongated nanostructured of oxidation and make and be removed on said elongated nanostructured basically.

10. like each described method of claim 1-9, wherein said catalyst layer first and at least second portion all form the zigzag pattern.

11. method as claimed in claim 10, first and second parts of wherein said zigzag pattern relative to each other are about 90 °.

12. like each described method of claim 1-11, wherein at least a in stationary phase or the stationary phase precursor demonstrate about 10,000-2,000,000 average aspect ratio.

13. like each described method of claim 1-12, wherein at least a in stationary phase or the stationary phase precursor without adhesive attachment on base material.

14. like each described method of claim 1-13, wherein at least a part at least in stationary phase or the stationary phase precursor is tangled each other.

15. like each described method of claim 1-14, wherein at least a in stationary phase or the stationary phase precursor is in said first and demonstrate the equispaced of about 4-8 μ m at least between the second portion.

Images