KR101502696B1 - Biogenic porous silica immobilized structure, method for preparing the same, and use thereof - Google Patents

Abstract

The present invention relates to a structure in which a porous silica based on a biomolecule is immobilized, a method for producing the porous structure, and a use thereof, and relates to a biomolecule derived from a biomolecule- The porous structure of the porous scaffolds has a large surface area, which facilitates the bonding of catalysts, biomolecules, and the like, and can be utilized in the fields of catalysis, biosensors, drug delivery systems, and semiconductors.

Description

TECHNICAL FIELD [0001] The present invention relates to a porous silica-immobilized structure,

TECHNICAL FIELD The present invention relates to a structure in which porous silica originating from a biological material is immobilized, a method for producing the same, and uses thereof.

The frustule is made up of amorphous SiO ₂ except for the organic matter of the diatom. Applications of diatomic devices include targeting micro-carriers for drug delivery (Losic D et < RTI ID = 0.0 > al . K Nanosci Nanotechnol . 2006; 6: 982-989.], Biosensors for antibody arrays [Stefano L et al . Acta biomaterialia . 2008; 4: 126-130 .; Stefano L et al . Biosens Bioelectron . 2009; 24: 1580-1584 .; Townley HE et al . Adv Funct Mater 2008; 18: 369-374 .; Gale DK et al . Advanced functional materials. 2009; 19: 926-933.], A sensitive gas detector [Michael R et al . Angew . Chem . Int . Ed. 2007; 46: 5724-5727 .; Lettieri S et al . Adv func mater , 2008; 18: 1257-1264.], separation process [Losic D et al . K Nanosci Nanotechnol . Solar cells, battery electrodes, electroluminescent display devices (Jeffryes et al., 2006; 6: 982-989), photocatalysts and photovoltaic applications, al . J. Mater . Res . 2008; 23 (12): 3255-3262 .; Jeffryes C et al . Energy environment science , 2011; 4: 3930-3941.]. Techniques for joining the scrim pieces onto the substrate surface have been developed in order to manufacture the technique and apparatus for modifying the surface of the scrim piece.

In order to produce a diatom-based device, the technique of joining the gypsum pieces onto the material surface serving as a substrate is considered to be very important. Examples of frustule bonding technology include (1) a hot melt adhesive (hereinafter referred to as " hot melt adhesive ") on a glass substrate using the floating property of a convex shape of a scaly piece derived from the genus Coscinodiscus sp. film, HMA), followed by floating array of scrap pieces on the water droplets formed on the HMA, followed by water evaporation to fix them in a monolayer [Wang Y et al . Biochemical and biophysical research communications . 2012; 420: 1-5.), (2) amylopropyltriethoxysilane (APES) was used to modify the mica substrate, a phyllosilicate mineral group, , A technique of allowing diatoms to be easily adhered onto the modified surface by incubation and then baking and fixing at 400 ° C for 2 hours [Umemura K et al . J Biol Physics , 2008; 34: 189-196.), (3) a technique in which diatoms are treated with hydrogen peroxide to separate the scrap pieces and then deposited on a silicon wafer by spin coating at 700 rpm for 30 seconds [Lee DH et al . Journal of materials chemistry . 2008; 18: 3633-3635.), (4) the surfaces were activated by treating 0.8-1.2% hydrofluoric acid (HF) on the surface of the glass substrate and the sculptured pieces, and then the scrim pieces were subjected to a flexible corrosion- And then baked at 80 ° C for 3 hours under the condition of 0.4-0.6 MPa to form and fix Si-O-Si bonds [Zhang D et al . J micomech microeng, 2012; 22:. 35021-35029 ], (5) positive charges poly (allyl amine hydrochloride (positively charged poly (allylamine hydrochloride) (PHA)) disc-shaped koseuki nodi kusu Wilde resiyi (Coscinodiscus using wailesii) of (~ 200㎛) technology for fixing on the glass substrate surface [W Wang, J Am Chem Soc , 2009; 131: 4178-4179.].

 Wang Y et al. Biochemical and biophysical research communications. 2012; 420: 1-5  Umemura K et al. J Biol Phys, 2008; 34: 189-196  Lee DH et al. Journal of materials chemistry. 2008; 18: 3633-3635  Zhang D et al. J micomech microeng, 2012; 22: 35021-35029  Wang W, J Am Chem Soc, 2009; 131: 4178-4179

An object of the present invention is to provide a structure in which a streamlined sculpture is fixed on a substrate surface using a cationic binder layer, a method for producing the same, and a use thereof.

According to an aspect of the present invention, A binder layer formed on one surface of the substrate and containing a cationic compound; And a layer of frustules with streamlined shape structure uniformly formed on the binder layer.

The present invention also relates to a method of forming a thin film, comprising: forming a cationic binder layer on a substrate surface; And forming a layer of frustules with streamlined shape structure in the cationic binder layer.

The present invention provides a product selected from a catalyst, a biosensor, a drug delivery system, or a semiconductor comprising the structure according to the present invention.

The present invention can provide a surface area required for catalysts and biomolecules in a very simple and economical manner by fixing a streamlined piece of silica having a porous structure, which is a silica-derived silica, to the surface of a substrate using a cationic binder.

Such a structure can be usefully used for a catalyst, a biosensor, a drug delivery system, or a semiconductor.

FIG. 1 is a comparative representation of a demand vector force according to the shape of a scraper to be fixed to the surface of a substrate. FIG. 1 (a) shows a streamlined sculpture, and FIG.
FIG. 2 shows the structure of the present invention, (a) a structure forming process, and (b) a structure.
Figure 3 is a schematic representation of the process of making the structure of the present invention, wherein (a) is a pretreatment process of silica glass, and (b) is a streamlined slag monolayer formation process.
Figure 4 shows the X-ray diffraction spectrum for streamline sculpted particles.
Figure 5 is a graphical representation of surface potential analysis results of streamlined slabs under various conditions.
FIG. 6 is a photograph showing the wettability profile of a streamlined sliced monolayer formed on the binder layer according to the concentration of the cationic compound. (A) 100 μl of 0.1% PLL, 200 μl of (b) Results.
7 shows the contact angle of a streamlined sliced monolayer formed in the binder layer according to the concentration of the cationic compound.
Fig. 8 shows chemical compositional analysis results of the structure of the present invention.
Fig. 9 is a graph showing FE-SEM photographs showing the streamlined slices fixed on the binder layer by concentration of the cationic compound, 200 쨉 l of (a) / (f) of 0.1% PLL, (b) (a) - (e): 100, (f) - (j), 300 μl of (c) : × 500 magnification).
Figure 10 shows the number of fixed streamlined slices per silica glass surface area (230 占 퐉 x 230 占 퐉).

Hereinafter, the configuration of the present invention will be described in detail.

The present invention relates to a substrate; A binder layer formed on one surface of the substrate and containing a cationic compound; And a layer comprising frustules with streamlined shape structure uniformly formed on the binder layer.

In order to provide a surface having a high surface area required for a catalyst, biomolecule, etc., the structure of the present invention uses a scaly piece of silica originating from a three-dimensional porous organism, and is composed of a substrate having a negative charge and SiO ₂ , And is characterized in that a streamlined scrap is uniformly fixed as a single layer on a substrate through chemical bonding by connecting the scrap pieces with a binder having a positive charge.

In the structure of the present invention, the rectangular sculpture can be represented by the points where the fixed point on the substrate surface is the surface and the surface, or the points where the surface and the line meet (see Fig. 1b), and the streamlined sculpture is fixed only to the substrate surface Because of the presence of points, the force required for fixation may be greater than for rectangular pieces (see FIG. 1A). Thus, the chemical bonding of the cationic binder and the streamlined scrap can make the streamlined scrap piece fixed on the substrate uniformly.

The substrate can be used without limitation as long as it is a substrate having a negative charge or a surface modified to have a negative charge. Examples of the substrate include soda glass, lime glass, silica glass, ceramic materials, fused silica, borosilicate glass, An alumosilicate glass, or a lead borate glass, or the like.

The binder layer may be a cationic compound having a positive electric charge, which connects a substrate having a negative charge and a streamlined slice having a negative electric charge. For example, a compound represented by the following formula (1) (poly (ethylene glycol) bis (3-aminopropyl) terminated [PEG-NH ₃ ⁺ ]) or polyarylamine hydrochloride (poly allylamine hydrochloride, etc. may be used alone or in combination of two or more:

[Chemical Formula 1]

In the above formula (1), n represents 1000 to 2000.

The compound of Formula 1 includes an amine group and can bind negatively charged materials and can have a molecular weight of 150,000 to 300,000.

The streamlined scrap may be any streamlined scrap derived from an organism without limitation, such as Caloneis schroederi , Navicula , and the like.

The streamlined sculpture may be separated from attached diatoms using methods known in the art or may be purchased commercially.

The streamlined sculpture may have a major axis length of 10 to 30 占 퐉 and a minor axis length of 3 to 8 占 퐉, but is not particularly limited thereto.

The present invention also relates to a method of forming a thin film, comprising: forming a cationic binder layer on a substrate surface; And forming a layer of frustules with streamlined shape structure in the cationic binder layer.

The substrate may be made of a material having a negative charge, or a material having a surface-modified material having a negative charge. Preferably, silica glass can be used.

The substrate may undergo a pretreatment process for surface activation before forming the cationic binder layer on one side.

The pretreatment process of the substrate is not particularly limited, but can be performed through the process of FIG. First, the silica glass is cut to an appropriate size, washed to remove foreign substances, and ultrasonicated under a surfactant for ceramic cleaning. The ultrasonic treatment can be carried out at 20 to 90 ° C for 1 to 5 hours, but can be appropriately adjusted depending on the type of the substrate. The ultrasonic treated silica glass is washed and then immersed in an acid solution to activate the surface. After washing with distilled water, it is dehydrated and dried.

The pretreated substrate is coated with a cationic compound and then dried to form a cationic binder layer.

The drying process may be blow dry, but is not particularly limited thereto.

The kind of the cationic compound is as described above.

Next, a solution containing a streamlined slice is deposited on the cationic binder layer, and then a streamlined sliced monolayer is formed through a condensation process, a sol-gel process, ionic bonding, or the like .

The solution containing the streamlined scaly pieces may be water or a solution in which streamlined scrap pieces are dispersed in an organic solvent, and preferably, streamlined scrap pieces are dispersed in water or ethanol.

Through the above steps, a monolayer having uniformly fixed streamlined slices is formed on the cationic binder layer to form the structure of the present invention.

According to one embodiment of the present invention, as the concentration of the cationic compound increases, the number of fixed streams of the streamy scrapings increases. Also, as the concentration of the cationic compound increases, the contact angle of the streamlined diatomaceous strata increases, and the wettability tends to decrease.

The method of the present invention can easily and economically fix three-dimensional porous silica originating from a living body uniformly on a substrate and maximize the surface area of the surface, thus facilitating the fixation of catalysts and biomolecules.

Accordingly, the present invention provides a product selected from a catalyst comprising the structure, a biosensor, a drug delivery system, or a semiconductor.

Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.

Example 1 Production of Streamlined Silica Glass Fixed Silica Glass

Figure 2 illustrates one embodiment of the structure of the present invention, in which silica glass is used as the substrate, and as a streamlined sculpture, Caloneis < RTI ID = 0.0 > Schroederi- derived long-axis length of about 20 μm was used.

The surface of the silica glass was pretreated (Fig. 3A). First, prepared silica glass (manufactured by Marienfeld, LOT 22320) was cut into a size of 1 cm x 3 cm, washed with flowing water to remove foreign substances present on the surface, and then ultrasonically cleaned with a ceramic washing detergent 50 C < / RTI > for 1 hour. The silica glass was then washed with a third-order distilled water (DDW) using a squeeze bottle, immersed in 0.5 M HCl, and treated for 20 minutes to activate the silica glass surface. After surface activation, it was immersed in 20 mL of DDW solution for about 1 minute for silica glass wash. Washing was done 3 times in total, and fresh DDW was used for each washing step. After washing, the silica glass was dehydrated with 94% ethanol and N ₂ 0.0 > (blow dry). ≪ / RTI >

(L-lysine) as a binder between the silica glass and the streamlined slabs to form a streamlined sliced monolayer on the silica glass surface (Fig. 3b) And then dried. After the drying process, streamlined slabs dispersed in a solvent of 94% ethanol were deposited and fixed through a condensation process, and unbonded streamlined slabs were washed with a sufficient amount of DDW using a squeeze bottle. After washing, dehydrated with 94% ethanol and blow dried with N ₂ gas.

≪ Experimental Example 1 > Crystallinity analysis of streamlined slabs

The crystallinity of streamlined specimens was analyzed using x-ray diffraction (XRD) (D8 Discover, Bruker, Germany). Cu was used as the cation source. The wavelength was 1.5406, scan type 2, the scan range was 15 ~ 80 °, the scan step was 0.02, and the scan rate was 0.5 sec / step.

As shown in Fig. 4, the streamlined sculpture shows poor overall crystalline structure. As a result, it was judged that the crystals of the streamlined slices were amorphous.

<Experimental Example 2> Surface potential analysis of a streamlined slab

In order to select the binder used for fixing the streamlined scrap, we measured the surface potential change along the interface between the solution and the streamlined scrap. Surface potential changes were analyzed using the zeta potential (Zen 3600, Malvern, England) method. For this purpose, streamline scrap nanoparticles were mixed with a streamlined slab of poly (L-lysine) and polyethylene glycol bis (3-aminopropyl) terminated [PEG-NH ^{3 +} ] solution with DDW, ethanol, NaCl, After the particles were dispersed, the scattered wavelength of the particles was measured using an argon (Ar) laser, and an electric field was applied to measure the zeta potential energy.

Zeta potential value by sample number Name of sample Zeta potential (mV) One Streamlined slabs dispersed in water -57.73 2 Streamlined slabs dispersed in ethanol -5.48 3 Streamlined slabs dispersed in 0.3 M NaCl -18.47 4 Streamlined slabs coated with 0.03% PLL dispersed in water 58.6 5 Streamlined slabs coated with PEG-NH ₃ ⁺ (2 wt% in NaCl) dispersed in water 0.36

As shown in Table 1, the untreated streamlined slabs were measured in solvents such as DDW, ethanol, and 0.3M NaCl, and the zeta potential of the streamlined slabs in all the solvents showed negative charge. In addition, the environmental friendliness of the polymer poly (L- lysine) and polyethylene glycol bis (3-aminopropyl) when coated with federated terminated [PEG-NH ^{3 +]} in figures streamlined pieces, poly compared to PEG-NH3 ⁺ (L- Lysine) was found to have a much higher positive charge. Poly (L-lysine) was used to immobilize streamlined scrims on the silica glass surface, since it may be more effective to utilize poly (L-lysine) with a relatively strong positive charge because silica glass has a strong negative charge.

5 is a graph showing the results of the zeta potential measurement of Table 1.

<Experimental Example 3> Wettability analysis of streamlined sculptured surface

And the method of analyzing the degree of hydrophilicity of the surface by the surface characteristic analysis method is mainly utilized. Therefore, a tensiometer (Phoenix-300, SEO, Korea) was used to analyze the effect of the streamlined scrap on the silica surface. The hydrophilic change of the surface was measured by a goniometer when a monolayer was formed using 3 mg of streamlined sculpture after binding to a silica glass surface at a concentration of 0.1% of poly (L-lysine). The contact angle of water droplets was measured by dropping one drop of DDW with a tensiometer syringe on the silica glass surface fixed to the streamlined scrap. The contact angle was measured as the mean value of the left angle and the right angle between the surface and the water droplets formed on the surface.

FIG. 6 shows the results of photographing the shape of water droplets on a streamlined sliced monolayer formed according to the concentration of poly (L-lysine). As shown in FIG. 6, a sample of 100 μL of poly (L-lysine) had a contact angle of 30.33 °, (L-lysine) was found to be 34.16 ° in the case of the sample using 300 μl of poly (L-lysine). It can be seen that as the concentration of poly (L-lysine) bound to the silica glass surface increases, the degree of wetting decreases finely. The contact angle measured according to the sample is shown in Fig.

Experimental Example 4 X-ray photoelectron spectroscopy (XPS) analysis of the chemical composition of the streamlined sculptured monolayer surface

XPS is a precision analytical instrument for analyzing the chemical bonding state of outermost layers from the outermost surface of the surface to tens of nanometers. Through the analysis using XPS, we could obtain information about the chemical composition of the streamlined diatomaceous strata fixed on the silica glass surface. For this, the pass energy of X-ray source wide scan (XPS) (Thermo VG, UK) was measured under monochromatic Al-K condition of 50eV and step size of 1.0eV, pass energy of narrow scan was 20eV, step size was measured at 0.1 eV. Only the flood gun was used except the ion etching gun, and the vacuum was measured at 2 × 10 ^-9 mB. The XPS spectrum was calibrated based on the binding energy of C 1 s of aliphatic hydrocarbons of 285 eV. The sample was prepared by binding 600 μl of 0.1% poly (L-lysine) to the surface of silica glass, followed by fixing 3 mg of streamlined scrap.

FIG. 8 shows an XPS spectroscopic scan, and the atomic percentage values of the elements constituting the fixed streamlined slab monolayer are shown in Table 2. The peaks of C and N elements are attributed to poly (L-lysine), and Si is derived from silica glass and streamlined slabs. In the case of O, poly (L-lysine), silica glass, and streamlined sculpture are common elements.

XPS atomic ratio of the structure Element type Atomic ratio% C 1s 44.75 O1s 30.46 N 1s 5.75 Si 2p 19.03

<Experimental Example 5> Analysis of the surface morphology of a streamlined type sculptured fixed layer using field emission scanning electron microscopy (FE-SEM)

(JSM-6700F, JEOL, Japan & England) was used to determine the effect on the surface morphology of the silica glass for the fixed layer of streamlined sculptured particles after the streamlined scrap was fixed on the silica glass surface. Respectively. The FE-SEM analysis was performed by coating a streamlined scrap on a silica glass surface with Pt for 10 minutes before observation. FIG. 9 shows the results of FE-SEM observation of the degree of streamlined slices fixed on the silica glass surface according to the concentration at which the same concentration of poly (L-lysine) solution was applied. The poly (L- Lysine) was used as a 0.1% solution. The upper part of FIG. 9 is a result of observation at a magnification of 100 times, and the lower photographs are a result of observation at a magnification of 500 times. Samples observed at 100 times magnification are approximately the observed surface area in the range of about 1 mm ² .

As shown in FIG. 9, it was found that the streamlined scrap particles were fixed in a fairly homogeneous manner. As can be seen from the photographs observed at the lower 500-fold magnification, as the amount of poly (L-lysine) increases, the number of streamlined slices increases. In FIG. 9, the number of streamlined slices per surface area of (230 μm × 230 μm) was found to be about 84 (a), 108 (b), 125 (d) As shown in FIG.

Claims (10)

Board;
A binder layer formed on one surface of the substrate and containing a cationic compound; And
And a layer of frustules with streamlined shape structure formed uniformly over the binder layer.
The method according to claim 1,
The substrate may be a soda glass, a lime glass, a silica glass, a ceramic, a fused silica, a borosilicate glass, an alumosilicate glass, or a lead borate glass.
The method according to claim 1,
The cationic compound is a compound represented by the following formula (1), a poly (ethylene glycol) bis (3-aminopropyl) terminated [PEG-NH ₃ ⁺ ] and a polyallylamine hydro- &Lt; RTI ID = 0.0 &gt; poly (allylamine &lt; / RTI &gt; hydrochloride)
[Chemical Formula 1]

In the above formula (1), n represents 1000 to 2000.
delete The method according to claim 1,
The streamlined sculpture is called Caloneis schroederi ) or Navicula .
Forming a cationic binder layer on the substrate surface; And
And forming a layer of frustules with streamlined shape structure in the cationic binder layer.
The method according to claim 6,
Further comprising pretreating the substrate for surface activation prior to forming the cationic binder layer.
The method according to claim 6,
The cationic binder layer comprises a cationic compound represented by the following formula (1), polyethylene glycol bis (3-aminopropyl) terminated [PEG-NH ₃ ⁺ ] and poly Wherein at least one selected from the group consisting of poly (allylamine hydrochloride) is applied to a substrate, followed by drying to form a structure,
[Chemical Formula 1]

In the above formula (1), n represents 1000 to 2000.
The method according to claim 6,
Wherein the streamlined diatomaceous stratum is formed by a condensation process, a sol-gel process or ionic bonding after depositing a solution containing a streamlined sculpture on a binder layer.
A product selected from a catalyst, a biosensor, a drug delivery system, or a semiconductor comprising the structure according to claim 1.

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