Functionalized bimodal Periodic Mesoporous Organosilicates (PMOs) and methods of making the same using pseudomorphic transformations
阅读说明：本技术 官能化双峰周期性介孔有机硅酸盐(pmo)及使用赝晶转变制造其的方法 (Functionalized bimodal Periodic Mesoporous Organosilicates (PMOs) and methods of making the same using pseudomorphic transformations ) 是由 萨斯基亚·齐哈尔 马提亚斯·劳 马丁·莫尔扬 于 2018-11-26 设计创作，主要内容包括：本发明涉及一种通过赝晶转变制造官能化双峰周期性介孔有机硅酸盐(PMO)的方法；涉及包含至少一种有机硅酸盐和至少一种官能组分的官能化双峰周期性介孔有机硅酸盐(PMO)；以及涉及所述PMO作为过滤材料、吸附介质、传感器材料或用于医药产品、杀虫剂或农药的载体材料的用途。(The present invention relates to a method for making functionalized bimodal Periodic Mesoporous Organosilicates (PMOs) by pseudomorphic transformation; to functionalized bimodal Periodic Mesoporous Organosilicates (PMOs) comprising at least one organosilicate and at least one functional component; and to the use of said PMO as a filter material, an adsorption medium, a sensor material or a carrier material for pharmaceutical products, pesticides or pesticides.)
1. A method of making a functionalized bimodal Periodic Mesoporous Organosilicate (PMO) by pseudomorphic transformation, the method comprising the steps of:
a) providing a monomodal mesoporous or macroporous glass,
b) adding at least one polysilylated organosilane and a solvent,
c) drying and crosslinking the at least one polysilylated organosilane on the surface of the unimodal mesoporous or macroporous glass,
d) adding at least one structure directing agent and performing pseudomorphic transformation,
e) the structure-directing agent is extracted from the mixture,
wherein at least one functional component is added after step a) and/or after step e),
wherein the macroscopic shape of the mesoporous or macroporous glass remains unchanged during steps b) to e).
2. The method of claim 1, wherein the at least one functional component is selected from the group consisting of a functional group, a dye, an enzyme, a protein, an antibody, a nucleic acid, a virus, and a noble metal cluster.
3. The method according to claim 1 or 2, characterized in that at least one functional group is added after step a) or after step e) and is covalently bonded to at least one further functional component.
4. The method according to any one of claims 1 to 3, wherein the structure directing agent is selected from ionic surfactants or non-ionic surfactants.
5. The method according to any one of claims 1 to 4, characterized in that the end-capping is performed after steps a) to e).
6. A functionalized bimodal Periodic Mesoporous Organosilicate (PMO) comprising at least one organosilicate and at least one functional component,
wherein the functionalized bimodal PMO has primary pores and secondary pores, wherein the primary pores are meso-or macropores having an average pore diameter of 30nm to 200nm,
wherein the secondary pores are hexagonal or cubic mesopores having an average pore diameter of 2nm to 50nm,
wherein the functionalized bimodal PMO has at least 500m2Specific surface area in g.
7. A functionalized bimodal PMO according to claim 6, wherein said functional component is selected from a functional group, a dye, an enzyme, a protein, an antibody, a nucleic acid, a virus or a noble metal cluster.
8. The functionalized bimodal PMO according to claim 6 or 7, characterized in that the macroscopic shape of the PMO is a membrane, a fiber, a cube, a sphere, a cylinder, a tube or a particle.
9. An optical sensor comprising a functionalized bimodal PMO according to any one of claims 6 to 8.
10. Use of the optical sensor according to claim 9 for qualitative or quantitative detection of an analyte in a sample, for quantification of the partial pressure of oxygen (pO) of a sample2) Dissolved Oxygen (DO), partial pressure of carbon dioxide (pCO)2) pH, pressure and/or temperature.
11. Use of the functionalized bimodal PMO according to any one of claims 6 to 8 as a filter material, an adsorption medium, a sensor material or a carrier material for a pharmaceutical product, an insecticide or a pesticide.
12. Use of the functionalized bimodal PMO according to any one of claims 6 to 8 as a coating for a filter material, an adsorption medium, a sensor material or a carrier material for a pharmaceutical product, an insecticide or a pesticide.
Technical Field
The present invention relates to a method for producing functionalized bimodal Periodic Mesoporous Organosilicates (PMOs) by pseudomorphic transformation, to functionalized bimodal Periodic Mesoporous Organosilicates (PMOs) comprising at least one organosilicate and at least one functional component selected from the group consisting of functional groups, dyes, enzymes and antibodies, and to the use of said PMOs as filter materials, adsorption media, sensor materials or as carrier materials for pharmaceutical products, insecticides or pesticides.
Background
Porous materials, in particular porous glasses with properties such as chemical, thermal and mechanical resistance and a multiplicity of geometries, have a wide range of potential applications. They are composed of 96-98% SiO2A composition and having a unimodal pore structure structured as a spongy three-dimensional network [ F. Janowski, W. Heyer,
They are classified into microporous materials (< 2nm), mesoporous materials (2nm to 50nm) and macroporous materials (> 50nm) according to pore size.
Using sol-gel method and pseudomorphic transformation, specific surface area exceeding 1000m can be manufactured2(g), narrow pore distribution and high long-range order degree.
Yanagisawa et al describe the use of alkyltrimethylammonium surfactants to make mesoporous silica materials with uniform pore diameters from sodium silicalite layered silicates,wherein about 900m is obtained2Specific surface area/g and pore radius distribution of 2nm to 5nm (Yanagisawa et al, 1990).
In 1992, Mobil Oil Company developed the so-called M41S silicate phase, which is a periodic mesoporous silica material (Kresge et al, 1992, Beck et al, 1992). Typical representatives are the Mobil composition of matter number 41 (MCM-41) and the Mobil composition of matter number 48 (MCM-48). Disadvantageously, these inorganic compounds have a hydrophilic surface and thus hydrophobicity can only be ensured by the organofunctional inorganic anchoring group.
Silicate precursors such as tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), or tetraisopropyl orthosilicate (TPOS) are used in sol-gel processes.
Organosilicates can be made from silicate precursors using a sol-gel process. Shea et al and Loyt et al describe the use of sol-gel methods to make organosilicate xerogels and aerogels from bis-and poly-silylated organosilanes (Shea et al, 1992, Loyt et al, 1995, Shea et al, 2001). Inagaki et al and Melde et al describe for the first time the condensation reaction of bis-silylated organosilanes with the addition of a structure directing agent (e.g., a surfactant) to a Periodic Mesoporous Organosilicate (PMO). (Inagaki et al, 1999, Melde et al, 1999, Asefa et al, 1999) wherein bridged polysilsesquioxanes having organic residues are arranged in a framework having a periodic hexagonal arrangement of pores.
Other possibilities for making mesoporous organosilicates are the application of organic groups after their preparation to pure inorganic mesoporous silicate materials (grafting), wherein surface silanol groups are reacted with organofunctional alkoxysilanes, chlorosilanes, silazanes, and cocondensation in which silicate precursors such as TEOS are reacted with alkoxysilanes, chlorosilanes and structure directing agents (Hoffmann et al, 2006). The reaction with organic molecules may lead to a decrease in porosity due to possible pore closure.
The periodic mesoporous organosilicate is formed using an internal templating method.
In known methods of making mesoporous organosilicates, clogging or bottleneck reduction of pores and uneven distribution on the surface can be disadvantageous. The macroscopic shape is not freely selectable.
In general, sol-gel chemistry results in the formation of cracks and shrinkage processes during manufacturing, since it is a liquid phase chemistry and thus difficult to pre-adjust the macroscopic shape.
Disclosure of Invention
It is therefore an object of the present invention to provide a method of making bimodal porous materials in which the pore size, geometry and functionalization can be varied.
It is also an object of the present invention to provide functionalized porous materials that are dimensionally stable.
According to the present invention, said object is achieved by a process for the production of a functionalized bimodal Periodic Mesoporous Organosilicate (PMO) having preferably a hexagonal or cubic arrangement of pores by pseudomorphic transformation according to the present invention, comprising the steps of:
a) providing a monomodal mesoporous or macroporous glass,
b) adding at least one polysilylated organosilane and a solvent,
c) drying and crosslinking the at least one polysilylated organosilane on the surface of the unimodal mesoporous or macroporous glass,
d) adding at least one structure directing agent and performing pseudomorphic transformation,
e) the structure-directing agent is extracted from the mixture,
wherein at least one functional component is added after step a) and/or after step e),
wherein the macroscopic shape of the mesoporous or macroporous glass remains unchanged during steps b) to e).
According to the invention, "functionalized" is understood to mean modified with at least one functional component. According to the invention, "unimodal" is understood to mean the presence of a pore system. According to the invention, "bimodal" is understood to mean that two pore systems are present. By pore system is understood a cavity system in materials or coatings, which is distinguished by their pore diameter. The bimodal pore system preferably has a hierarchical structure, i.e. secondary pores branch off from primary pores. According to the invention, primary pores are understood to be pores with a larger pore diameter, also referred to as transport pores, while secondary pores are understood to be pores with a smaller pore diameter, also referred to as reaction pores.
According to the invention, the pore system comprises pores selected from the group consisting of mesopores and macropores. Mesoporous is understood to be a pore having a pore diameter of 2nm to 50 nm. Macropores are understood to be pores having a pore diameter of at least 50nm, preferably greater than 50 nm.
According to the invention, Periodic Mesoporous Organosilicates (PMOs) are understood to be organosilicates having at least one system of at least partially ordered mesopores and a narrow pore radius distribution.
Pseudomorphic transformation according to the present invention is understood to be the conversion of porous silicates into ordered mesoporous silicates using internal template synthesis, so-called micelle templated silica, wherein the initial pore system, i.e. the pore system of the porous silicate, is converted into an ordered mesoporous pore system before the pseudomorphic transformation, the macroscopic shape of the porous silicate being preserved. The self-organization of the structure directing agent during pseudomorphic transformations creates an ordered pore system. The partial pseudomorphic transformation after step d) results in the formation of a bimodal pore system comprising primary pores and secondary pores.
According to the invention, glass is understood to be an amorphous porous solid containing silica.
In one embodiment, the mesoporous or macroporous glass is selected from the group consisting of quartz glass, alkali borosilicate glass, porous silicates, such as VYCOR glass, Controlled Pore Glass (CPG), silica gel, MTS material (MTS ═ micelle templated silica), TRISOPOR, silica sol-gel material and biogenic silica, such as rice husk ash.
Controlled Pore Glass (CPG) is understood to be a porous silicate which is produced from alkali borosilicate glass by heat treatment, phase separation into a silicate phase and a borate phase and extraction of the borate phase.
VYCOR glass is understood to be porous glass or quartz glass produced using the VYCOR method.
According to the invention, at least one polysilylated organosilane is added in step b).
According to the invention, at least one functional component is added after step a) or after step e) or after step a) and after step e). The functional components are bound by adsorption or covalent bonding. Functional components are understood to be groups or molecular residues having reactivity, color intensity, luminescence intensity, enzymatic activity or antigen-binding properties.
In another embodiment, the at least one functional component is selected from a functional group, a dye, an enzyme, a protein, an antibody, a nucleic acid, a virus, or a noble metal cluster.
Functional groups are to be understood as meaning molecules which decisively determine the material properties, in particular the hydrophobicity and/or the reaction behavior of the PMO. In one embodiment, the functional group is selected from substituted alkoxysilanes, preferably 3' -glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, trimethoxy (2-phenylethyl) silane; substituted chlorosilanes, substituted silanes, diepoxides, substituted Polydimethylsiloxanes (PDMS), preferably hydroxy polydimethylsiloxanes (OH-PDMS); substituted silazanes, preferably Hexamethyldisilazane (HDMS); boranes, substituted alkoxy titanium compounds, disilanes, alkoxides, alcohols, acids, bases, ionic liquids, isocyanates, or quaternary ammonium compounds.
In one embodiment, the functional group comprises an anchor molecule. Anchor molecules are understood to be linker molecules and spacers. The anchoring molecule advantageously acts as a spacer.
In one embodiment, the functional component is covalently bonded to the anchoring molecule.
In another embodiment, the dye is selected from the group consisting of an oxygen sensitive dye, a carbon dioxide sensitive dye, a pH sensitive dye, a temperature sensitive dye, a pressure sensitive dye, a nitroxide sensitive dye, an amino sensitive dye, and/or a peroxyester sensitive dye.
In one embodiment, the oxygen-sensitive dye is selected from luminescent dyes, preferably from metalloporphyrins, metallophenanthrolines or metallobipyridines, particularly preferably from palladium porphyrins, palladium phenanthrolines or palladium bipyridines, platinum porphyrins, platinum phenanthrolines or platinum bipyridines, or ruthenium porphyrins, ruthenium phenanthrolines or ruthenium bipyridines.
Luminescent dyes are to be understood as meaning substances which, after being supplied with energy, emit light in the visible, UV or IR spectral range.
In one embodiment, the carbon dioxide sensitive dye is selected from luminescent dyes, preferably from ruthenium porphyrins, ruthenium phenanthrolines or ruthenium bipyridines; aza-BODIPY dyes, particularly preferably aza-BODIPY phenol red; triphenylmethane dyes, particularly preferably bromothymol blue, bromophenol blue or cresol red; fluorescein or Fluorescein Isothiocyanate (FITC), pyrene dyes, particularly preferably fluorescein; or an azo dye.
In one embodiment, the pH sensitive dye is selected from luminescent dyes, preferably aza-BODIPY dyes, particularly preferably aza-BODIPY phenol red; triphenylmethane dyes, particularly preferably bromothymol blue, bromophenol blue or cresol red; a xanthene dye, preferably rhodamine, fluorescein or Fluorescein Isothiocyanate (FITC); pyrene dyes, particularly preferably fluorescein; or an azo dye.
Liu and Sullivan disclose temperature-sensitive dyes and pressure-sensitive dyes (Liu and Sullivan, 2005). The temperature-sensitive dye and the pressure-sensitive dye are preferably selected from luminescent dyes. The temperature-sensitive dyes are particularly preferably selected from pyronines, very particularly preferably from rhodamines; metal perylenes, metal bipyridines, metal phenanthrolines, preferably tris (1, 10-phenanthroline) ruthenium (II) dichloride; or europium (III) thiophenecarboxyltrifluoroacetate. The pressure-sensitive dyes are particularly preferably selected from the group consisting of metalloporphyrins, metalloperylenes, metallophenanthrolines, preferably tris (1, 10-phenanthroline) ruthenium (II) dichloride or metal bipyridines.
In one embodiment, the nitroxide sensitive dye is selected from metal oxides, preferably ZnO, SnO2Or V2O5. In another embodiment, the dye is selected from nitro-sensitive dyes. By "nitro-sensitive dyes" it is understood dyes which are sensitive to nitro compounds, such as trinitrotoluene (TNT) or Dinitrotoluene (DNT). In one embodiment, the nitro-sensitive dye is selected from metalloporphyrins.
In one embodiment, the amino-sensitive dye is selected from metal oxides, preferably ZnO, SnO2Or V2O5。
In one embodiment, the peroxoate-sensitive dye is selected from luminescent dyes, preferably from metalloporphyrins.
Enzymes are biomolecules that can act as catalysts to accelerate chemical reactions. Most enzymes are proteins. However, the term also encompasses catalytically active RNA (ribozymes). In one embodiment, the enzyme is selected from an oxidoreductase or hydrolase; the enzyme is preferably selected from acetylcholinesterase or aldehyde dehydrogenase.
Proteins are biomolecules consisting of amino acid residues via peptide bonds. The term encompasses both peptides having at least two amino acid residues and macromolecules, which may have several thousand amino acid residues and may also consist of a plurality of polypeptide chains as subunits. In one embodiment, the protein is selected from globular proteins and fibrous proteins, such as globulins and keratins.
The term "antibody" within the meaning of the present invention covers all antibodies or antibody fragments capable of specifically binding to an antigen. Recombinant antibodies are antibodies produced by means of genetically modified organisms. The term "antibody" encompasses intact monoclonal antibodies and epitope-binding fragments thereof. Herein, epitope-binding fragments (also referred to herein as antibody fragments) comprise those portions of an antibody that are capable of binding an antigen. Antibody fragments within the meaning of the present invention include Fab, Fab ', F (ab')2Fd, single chain variable fragment (scFv), single chain antibody, disulfide-linked variable fragment (sdFv) and light chain variable region-containing (V)L) Or heavy chain variable region (V)H) A fragment of (a). The antibody fragment contains a first region (C) selected from the group consisting of a hinge region and a constant region, either alone or in combinationH1) A second region (C)H2) And a third region (C)H3) Other combinations of regions.
Furthermore, the term antibody encompasses recombinantly produced antibodies, such as diabodies, triabodies, and tetrabodies. The term "antibody" also encompasses chimeric antibodies in which different portions of the antibody are derived from different species, such as antibodies having murine variable regions combined with human constant regions. In one embodiment, the antibody is selected from an immunoglobulin, preferably immunoglobulin a, immunoglobulin D, immunoglobulin E, immunoglobulin G, immunoglobulin M, immunoglobulin W or immunoglobulin Y. In one embodiment, the antibody is labeled, preferably with a fluorescent dye, more particularly preferably with fluorescein isothiocyanate, tetramethyl rhodamine isocyanate or fluorescein.
The term nucleic acid within the meaning of the present specification encompasses deoxyribonucleic acid (DNA), ribonucleic acid (RNA) and Peptide Nucleic Acid (PNA), as well as all modifications derived from these basic structures, such as phosphorothioate, phosphoramidate, O-methyl derivatives and Locked Nucleic Acid (LNA). The nucleic acid may be single-stranded, double-stranded, or a mixture thereof. In one embodiment, the nucleic acids are composed of different nucleotides.
Viruses are to be understood as meaning, in particular, infectious particles which, by transmission, spread outside the cell as virus particles and propagate as viruses in suitable host cells. However, in the present specification, the term also encompasses attenuated (attenuated) or recombinant viruses which are non-infectious or only capable of propagation under certain circumstances (e.g. in specific packaging cells). In one embodiment, the virus is selected from viruses used for water, water analysis, for example.
Noble metal clusters are understood to be compounds in which at least three noble metal atoms are bonded via metal-metal bonds. In one embodiment, the noble metal cluster is selected from a silver cluster or a gold cluster.
In a preferred embodiment, the at least one functional component is a luminescent dye and a noble metal cluster. Advantageously, the noble metal cluster enhances the luminescence of the luminescent dye.
In an embodiment of the process according to the invention, at least one functional component is added after step a) or after step a) and after step e) or only after step e).
In the case of temperature-sensitive functional components such as viruses, nucleic acids and proteins, enzymes and antibodies, and temperature-sensitive dyes, the addition is preferably carried out after step e).
In another embodiment of the method according to the invention, a functional group is added after step a), followed by the addition of another functional component selected from the group consisting of a dye, an enzyme, a protein, an antibody, a nucleic acid, a virus or a noble metal cluster.
In another embodiment of the process according to the invention, a functional group selected from hydrophobic functional groups, preferably organofunctional trialkoxysilanes, is added after step a), followed by the addition of another hydrophobic functional component. Advantageously, the functional component not only remains adsorbed, but also remains covalently bonded in the system through a covalent bond.
In another embodiment of the process according to the invention, a functional group is added after step a), followed by the addition of another functional component, wherein the functional group is covalently bonded to the other functional component. According to the invention, functional groups and other functional components are incorporated into the PMO.
Multisilylated organosilanes are understood to be organically bridged alkoxysilanes, organically bridged alkylhydroxysilanes or organically bridged alkylchlorosilanes. In one embodiment, the at least one polysilylated organosilane is selected from the group consisting of a disilane, a trisilane, a tetrasilane, and a polysilane, wherein a disilane is understood to be an organobridging silane having two silyl groups, a trisilane is understood to be an organobridging silane having three silyl groups, a tetrasilane is understood to be an organobridging silane having four silyl groups, and a polysilane is understood to be an organobridging silane having a plurality of silyl groups, wherein "having a plurality of silyl groups" is understood to be at least 5.
In one embodiment, the at least one polysilylated organosilane is selected from unsubstituted or substituted disilanes, preferably from unsubstituted or substituted, saturated or unsaturated, linear or cyclic bis (trimethoxysilyl) or bis (triethoxysilyl) C1 to C12 hydrocarbon compounds, particularly preferably bis (trimethoxysilylmethyl) benzene, bis (trimethoxysilylethyl) benzene, bis (triethoxysilylethyl) biphenyl, 1, 2-bis (trimethoxysilyl) ethane or bis [3- (trimethoxysilyl) propyl ] amine.
The C1 to C12 hydrocarbon compounds are understood to be hydrocarbon compounds having 1 to 12 carbon atoms.
In another embodiment, the at least one polysilylated organosilane is selected from unsubstituted or substituted trisilanes or tetrasilanes, preferably from unsubstituted or substituted, saturated or unsaturated, linear or cyclic tri (trimethoxysilyl), tri (triethoxysilyl), tetra (trimethoxysilyl) or tetra (triethoxysilyl) C1 to C12 hydrocarbon compounds, most particularly preferably from 1,3, 5-tri (triethoxysilyl) benzene, 1,3, 5-tri (triethoxysilyl) cyclohexane or tetra (triethoxysilylethyl) -silane.
Solvents are understood to be inorganic or organic liquids which are capable of bringing solids or liquids into solution physically. A prerequisite for suitability as a solvent is that neither the solvent nor the dissolved substance undergo a chemical change during the dissolution process. In another embodiment of the process according to the invention, the solvent is selected from organic solvents, preferably acetone, ethanol, methanol and/or toluene.
In another embodiment of the process according to the invention, in step c) the at least one polysilylated organosilane is dried and crosslinked on the surface of the monomodal mesoporous or macroporous glass at a temperature of 60 ℃ to 170 ℃, preferably at a temperature of at least the boiling point of the solvent and at most the boiling point of the polysilylated organosilane for 12 to 24 hours. The functional component and the at least one polysilylated organosilane are adsorbed and/or covalently bonded to the surface of the unimodal mesoporous or macroporous glass.
Surfaces are understood to be inner pore surfaces and outer pore surfaces.
In a preferred embodiment of the method according to the invention, in step c) the at least one polysilylated organosilane is dried and crosslinked on the surface of the monomodal mesoporous or macroporous glass for 18 hours.
In another embodiment of the process according to the invention, the structure directing agent in step d) is selected from ionic surfactants or non-ionic surfactants, preferably from ionic surfactants, more particularly preferably from the hydroxides of quaternary alkylammonium compounds.
In another embodiment of the process according to the invention, the ionic surfactant is prepared from the bromide and chloride salts of C6 to C18 alkyltrimethylammonium compounds or the bromide and chloride salts of alkylpyridinium compounds by means of an anion exchanger, preferably from cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), octadecyltrimethylammonium bromide (OTAB) or octadecyltrimethylammonium chloride (OTAC).
In another embodiment of the method according to the invention, the non-ionic surfactant is selected from triblock copolymers, preferably poloxamers or poly (ethylene oxide) -poly (DL-lactic-co-glycolic acid) -poly (ethylene oxide) (EO)16(L28G3)EO16)。
Poloxamers are understood to be block copolymers of Ethylene Oxide (EO) and Propylene Oxide (PO) or of Ethylene Oxide (EO) and Butylene Oxide (BO).
In a preferred embodiment of the process according to the invention, the nonionic surfactant is selected from P-123 (EO)20PO70EO20)、F-127(EO106PO70EO106) And B50-6600 (EO)39BO47EO39)。
By selecting the structure directing agent in step d), the pore diameter of the secondary pore system of the PMO can advantageously be adjusted in the range of 2nm to 50 nm.
In one embodiment of the method according to the invention, the pseudomorphic transformation in step d) is performed at a pH of at least 12.
In one embodiment of the method according to the invention, the pseudomorphic transformation in step d) is performed for 1 to 7 days, preferably 3 days.
In another embodiment of the method according to the invention, the pseudomorphic transformation is performed at a temperature of 100 ℃ to 130 ℃.
In another embodiment of the process according to the invention, the end-capping is carried out after steps a) to e). Blocked is understood to mean that the terminal silanol groups are replaced in particular by non-reactive groups, such as alkyl groups or alkylsilyl groups.
In one embodiment of the process according to the invention, the end-capping replaces the silanol groups with trimethylsilyl groups.
In one embodiment of the method according to the invention, the end-caps close the pores. In one embodiment of the method according to the invention, the pores are closed after steps a) to e), wherein after step a) at least one temperature-sensitive dye and/or pressure-sensitive dye is added.
In one embodiment, the secondary pores are blocked by the addition of a basic aminoorganoalkoxysilane, preferably (3-aminopropyl) triethoxysilane (APTES). Due to the closed pores, there is advantageously no interaction between at least one functional component, preferably a temperature-sensitive dye or a pressure-sensitive dye, and the environment.
The method according to the invention advantageously produces periodic mesoporous materials with a bimodal pore system, wherein a narrow pore radius distribution is achieved. The PMO is also advantageously fabricated while maintaining a macroscopic shape. By selecting the structure directing agent, the pore size of the secondary pores can also be advantageously varied, and by selecting the functional component, the functionalization can be varied, wherein the process according to the invention leads to a homogeneous distribution of the functional component in the PMO. It is further advantageous to have flexibility in the choice of starting material geometry and size of the transport apertures.
Furthermore, the object is solved by a functionalized bimodal periodic mesoporous organic acid salt (PMO) comprising at least one organosilicate and at least one functional component, wherein the functionalized bimodal PMO has a primary pore and a secondary pore, wherein the primary pore is a mesopore or macropore with an average pore diameter of 30nm to 200nm, preferably a macropore with a diameter in the range of 60nm to 200nm, wherein the secondary pore is a mesopore with an average pore diameter of 2nm to 50nm, preferably a diameter in the range of 2nm to 30nm, more preferably in the range of 2nm to 20nm, wherein the functionalized bimodal PMO has at least 500m of at least2Specific surface area in g.
According to the invention, a specific surface is understood to be the entire surface contained in the sample, also between the particles and within the pores. The specific surface area is preferably determined by nitrogen cryosorption (according to BET DIN-ISO 9277).
In another embodiment, the functionalized bimodal PMO according to the present invention has a 500m2G to 1200m2Specific surface area in g. In a preferred embodiment, the functionalized bimodal PMO according to the present invention has a particle size of 800m2G to 1000m2Specific surface area in g.
In one embodiment, the functionalized bimodal PMO according to the present invention has at most 10%, preferably at most 5%, particularly preferably at most 1% closed pores.
The proportion of open porosity can be determined by helium density measurement according to DIN 1936.
In one embodiment of the functionalized bimodal PMO according to the present invention, the periodic mesoporous organosilicate has a hexagonal or cubic microstructure. The main component is SiO2In SiO2With integrated organic bridges in the network. The PMO preferably has a proportion of SiO of more than 70%2。
In another embodiment, the macroscopic shape of the functionalized bimodal PMO is a film, fiber, cube, sphere, cylinder, tube, or particle.
Advantageously, the functionalized bimodal PMO according to the present invention is dimensionally stable. Dimensionally stable is understood to mean that there is no shrinkage and no crack formation. Furthermore, advantageously, the bimodal PMO according to the invention has a pore system with a narrow pore radius distribution and a homogeneous distribution of the functional component in the PMO.
Another aspect of the invention relates to an optical sensor comprising a functionalized bimodal PMO according to the invention.
In one embodiment, the optical sensor comprising the functionalized bimodal PMO according to the present invention is designed for qualitative and/or quantitative detection of an analyte in a sample, preferably the oxygen partial pressure, the proportion of dissolved oxygen or the carbon dioxide partial pressure of the sample, or for quantification of the pH, pressure or temperature of the sample.
Another aspect of the invention relates toAnd an optical sensor for qualitative and/or quantitative detection of an analyte in a sample for quantification of the partial pressure of oxygen (pO)2) Dissolved Oxygen (DO), partial pressure of carbon dioxide (pCO)2) And pH, use for quantifying pH, pressure and/or temperature of a sample.
Another aspect of the present invention relates to the use of the functionalized bimodal PMO according to the present invention as a filter material, as an adsorption medium, as a sensor material or as a carrier material for pharmaceutical products, pesticides or pesticides, preferably as a sensor material.
In one embodiment, the functionalized bimodal PMO according to the present invention is used as a coating for a filter material, a coating for an adsorption medium, a coating for a sensor material or a coating for a carrier material for a pharmaceutical product, an insecticide or a pesticide, preferably as a coating for a sensor material.
It is also advantageous to combine the features of the above-described embodiments and the claims in order to realize the invention.
The invention will be explained in detail below with reference to some embodiments and the accompanying drawings. These embodiments are intended to illustrate the invention and not to limit the invention.
Drawings
FIG. 1 shows (A) nitrogen isotherms and (B) pore radius distributions of PMOs functionalized with 5,10,15, 20-tetrakis- (2,3,4,5, 6-pentafluorophenyl) porphyrin platinum (II) (PtTFPP).
FIG. 2 shows the thermogravimetric/differential thermal analysis of PMO functionalized with 5,10,15, 20-tetrakis- (2,3,4,5, 6-pentafluorophenyl) porphyrin platinum (II) (PtTFPP).
FIG. 3 shows (A) PMO without functional component29Si cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy and (B) of PMO functionalized with PtTFPP29Si cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectra.
FIG. 4 shows (A) PMO functionalized with (3-aminopropyl) triethoxysilane (APTES) and hexafluorobenzene13C-cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy with a contact time of 2ms, (B) of PMO functionalized with APTES and hexafluorobenzene13C-Cross-polarized magic Angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) Spectroscopy, when in contactWith a spacing of 500. mu.s, and (C) PMO functionalized with APTES13C-Cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy.
FIG. 5 shows (A) PMO functionalized with N- (6-aminohexyl) aminopropyltrimethoxysilane (AHAPTMS) and hexafluorobenzene13C-Cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) Spectroscopy with a contact time of 2ms, (B) of PMO functionalized with AHAPTMS and hexafluorobenzene13C cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy with a contact time of 500. mu.s, and (C) of PMO functionalized with AHAPTMS13C-Cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy.
Fig. 6 shows (a) phase shift and (B) Stern-Volmer plots of PMO functionalized with PtTFPP over an oxygen concentration range of 0 to 20.95 vol%.
Figure 7 shows the XRD diffractogram of PMO with PtTFPP.
Detailed Description
1g of starting material was mixed with a mixture of functional component and 1:4 (m%) organosilane/toluene, shaken until homogeneous and left closed at room temperature for a certain time. Drying was carried out at 120 ℃ overnight. The sample is then mixed with the structure directing agent and reacted at an appropriate temperature for 1 to 7 days. Then extracting with hydrochloric acid methanol solution. The sample was washed to neutrality with distilled water and dried at 120 ℃ overnight.
Table 1 parameters for making functionalized bimodal PMOs with addition of functional component after step a).
1g of starting material together with functional groups was shaken in a suitable solvent (volume three times the pore volume of the starting material) for 1 hour at room temperature. Drying at a certain temperature overnight.
Table 2 parameters for binding functional groups after step a).
A concentration of the functional component was dissolved in 1ml of solvent and catalyst. The mixture was added to 1g of the starting material, shaken until homogeneous, and reacted at 75 ℃ for 1 hour. Dry overnight at the appropriate temperature. Then washed three times with a suitable solvent and once with another solvent at room temperature.
Dried at the appropriate temperature overnight. Subsequent PMO fabrication: 1g of the sample was mixed with a 1:4 organosilane/toluene mixture, shaken until homogeneous, and kept sealed for a certain time at room temperature. Drying was carried out at 120 ℃ overnight. The sample is then mixed with the structure directing agent and reacted at an appropriate temperature for 1 to 7 days. Then extracting with hydrochloric acid methanol solution. The sample was washed to neutrality with distilled water and dried at 120 ℃ overnight.
Table 3 parameters for binding functional components.
The samples were measured at-196 ℃ using a Quantachrome Autosorb iQ device. Activation was carried out at 150 ℃. The PMO PtTFPP sample was PMO made from CPG spheres with a starting pore size of 120 nm. Bis (trimethoxysilylethyl) benzene was used as the organosilane, and PtTFPP was used as the functional component.
Table 5 nitrogen cryosorption results of PMO functionalized with PtTFPP.
FIG. 1 shows (A) nitrogen isotherms and (B) pore radius distributions of PMOs functionalized with 5,10,15, 20-tetrakis- (2,3,4,5, 6-pentafluorophenyl) porphyrin platinum (II) (PtTFPP). The nitrogen isotherm corresponds to the IVb adsorption isotherm. There is a typical stepwise adsorption for mesoporous materials, and an increase at p ≈ 0.95 indicates that the starting pores are still present. The pore radius distribution confirmed the presence of pores with a diameter of 4nm and starting pores (120 nm).
According to the IVb-type isotherm of IUPAC, there is no hysteresis, typical for mesoporous materials, and pore diameters of 3 according to BJH and 4.1 according to DFT are shown.
Thermogravimetric analysis is the determination of mass loss of a substance in the temperature interval RT-800 ℃. For this purpose, the sample was heated continuously at 10K/min in a constant air flow (50 ml/min). If a reaction such as dehydration, oxidation or decomposition occurs with an increase in temperature, the mass of the sample decreases. This change in quality is measured as a function of temperature or time. The mass loss may be continuous or gradual.
Measurements were performed on LINSEIS STA PT1600 from Linses. The PMO PtTFPP samples used were PMO made from CPG spheres with starting pores of size 120 nm. Bis (trimethoxysilylethyl) benzene was used as the organosilane, and PtTFPP was used as the functional component.
FIG. 2 shows the thermogravimetric/differential thermal analysis of PMO functionalized with 5,10,15, 20-tetrakis- (2,3,4,5, 6-pentafluorophenyl) porphyrin platinum (II) (PtTFPP). Thermogravimetric analysis showed mass loss at 100 ℃ due to physically adsorbed water, mass loss at 420 ℃ due to decomposition of organometallic complex, mass loss at 500 ℃ to 650 ℃ due to phenyl group incorporated in silica network and total mass loss of 9% (m/m) (200 ℃ to 800 ℃).
29Si CP-MAS NMR measurements were performed using Bruker Avance 750, a spin frequency of 7kHz, a repetition time of 3 seconds and a contact time of 5 ms.
The PMO PtTFPP samples used were PMO made from CPG spheres with starting pores of size 120 nm. Bis (trimethoxysilylethyl) benzene was used as the organosilane, and PtTFPP was used as the functional component. The PMO reference sample was PMO made from CPG spheres with starting pores of size 120 nm. Bis (trimethoxysilylethyl) benzene was used as organosilane.
FIG. 3 shows (A) PMO without functional component29Si cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy and (B) of PMO functionalized with PtTFPP29Si cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectra. From the signals and their intensities (Table 6) it is clearIt is seen that direct input of the PtTFPP dye does not result in any change in the silicate network. The dye does not affect the formation of the periodic mesoporous system and there is no bond between the PMO and the dye. It can be assumed that the dye is encapsulated and adsorbed in the PMO network.
TABLE 629Shift and intensity of Si CP-MAS NMR signal.
13C CP-MAS NMR measurements were performed using Bruker Avance 750, a spin frequency of 10kHz, with a repetition time of 3 seconds.
To demonstrate the bonding of the functional component PtTFPP, a model compound was used, which is very similar to the binding molecule hexafluorobenzene in the porphyrin complex of PtTFPP. The PG APTES sample used was a CPG sphere modified with 3-aminopropyltriethoxysilane having an initial pore size of 120 nm. The PG APTES hexafluorobenzene sample was a CPG sphere with a starting pore size of 120nm modified with 3-aminopropyltriethoxysilane, followed by bonding of hexafluorobenzene to APTES.
FIG. 4 shows (A) CPG modified with (3-aminopropyl) triethoxysilane (APTES) and hexafluorobenzene13C-cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy with a contact time of 2ms, and (B) modification of CPG with APTES and hexafluorobenzene13C-cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy with a contact time of 500. mu.s, and (C) of CPG modified with APTES13C-Cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy with a contact time of 500. mu.s.
CP-MAS NMR measurements were performed using Bruker Avance 750, rotating at a frequency of 10kHz, with a repetition time of 3 seconds.
13C CP-MAS NMR spectra showed the presence of a covalent bond between APTES and hexafluorobenzene (tables 7 and 8). The signal at 45.3ppm of C3 decreased and the signal at 48.3ppm of C-NH-benzene (C'3) was clearly identifiable, and the signals for benzene in the range of 120ppm to 145ppm aromatics (aromatics range) 124ppm and 138ppm were also clearly identifiable. The C-NH-C signal at 116ppm could not be recognized due to insufficient concentration or contact time(aromatic range). The peak at 124ppm shows a change in hexafluorobenzene. It is no longer highly symmetrical. Adsorption or lack of bonding will be indicated in the signal with 138ppm shift (resolution in solid state NMR too low to split the peak into two signals). It can therefore be assumed that the formation of the second aromatic signal describes the bond between APTES and hexafluorobenzene.
Hexafluorobenzene is highly symmetrical and is in liquid form13Two signals are given in C NMR (no fluorine decoupling), with shifts of 137ppm and 139 ppm.
(3-aminopropyl) triethoxysilane (APTES) (reference):
TABLE 7 APTES13Shift and intensity of the C CP-MA NMR signal.
(3-aminopropyl) triethoxysilane (APTES) and hexafluorobenzene (ref):
TABLE 8 APTES-hexafluorobenzene13Shift and intensity of C CP-MAS NMR signals.
FIG. 5 shows the preparation of (A) CPG modified with N- (6-aminohexyl) aminopropyltrimethoxysilane (AHAPTMS) and hexafluorobenzene13C-cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy with a contact time of 2ms, and (B) modification of CPG with AHAPTMS and hexafluorobenzene13C cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy with a contact time of 500. mu.s, and (C) of CPG modified with AHAPTMS13C-Cross-polarized magic angle spin (CP-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy with a contact time of 500. mu.s.
C-NH at 41.6ppm (theoretical 42.1ppm)2The signal of (a) is reduced by the addition of hexafluorobenzene. The signal for C-NH benzene at 45.4ppm (theoretical 45.1ppm) was clearly identifiable and indicated the presence of a covalent bond between APTES and hexafluorobenzene.
CP-MAS NMR measurements were performed using Bruker Avance 750, rotating at a frequency of 10kHz, with a repetition time of 3 seconds.
Theory of N- (6-aminohexyl) aminopropyltrimethoxysilane (AHAPTMS):
n- (6-aminohexyl) aminopropyltrimethoxysilane (AHAPTMS) and hexafluorobenzene (theory):
detection of functional component incorporation into PMO
The functionalized bimodal PMO was rinsed thoroughly with toluene. There was no leaching effect, confirming the incorporation of the functional component into the network.
Oxygen measurement and determination of Stern-Walmer constant
Oxygen measurements were made from 0 to 20.95 volume% oxygen to nitrogen (figure 6).
Fig. 6 shows (a) phase shift and (B) Stern-Volmer plots of PMO functionalized with PtTFPP over an oxygen concentration range of 0 to 20.95 vol%. The Steen-Walmer equation describes the dependence of the fluorescence intensity of a fluorescent dye on the concentration of a substance that quenches fluorescence, such as oxygen. Stern-Walmer plots show a linear process and the Stern-Walmer constant KSVWas determined to be 0.0244.
Figure 7 shows the diffraction pattern of the functionalized bimodal PMO. With
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