Functionalised bimodal periodic mesoporous organosilicates (PMOS) and method for producing same using pseudomorphic transformation

Abstract

The invention relates to a method for producing functionalised bimodal periodic mesoporous organosilicates (PMOs) by means of pseudomorphic transformation, to functionalised bimodal periodic mesoporous organosilicates (PMOs) that comprise at least one organosilicate and at least one functional component, and to the use of the PMO as a filter material, adsorption means, sensor material or carrier material for pharmaceutical products, insecticides or pesticides.

Claims

1. Functionalised bimodal periodic mesoporous organosilicates (PMOs) comprising at least one organosilicate and at least one functional component, wherein the functionalised bimodal PMOs have primary pores and secondary pores, wherein the secondary pores branch off from the primary pores, wherein the primary pores are pores with a larger pore diameter, also called transport pores, and the secondary pores are pores with a smaller pore diameter, also called reaction pores, wherein the primary pores are mesopores or macropores with an average pore diameter of 30 nm to 200 nm, wherein the secondary pores are hexagonal or cubic mesopores with an average pore diameter of 2 nm to 50 nm, wherein the functionalised bimodal PMOs have a specific surface area of at least 500 m.sup.2/g.

2. The functionalised bimodal PMOs according to claim 1, wherein the macroscopic shape of the PMOs is a membrane, a fibre, a cube, a sphere, a cylinder, a tube or granules.

3. The functionalised bimodal PMOs according to claim 1, wherein 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.

4. The functionalised bimodal PMOs according to claim 3, wherein the macroscopic shape of the PMOs is a membrane, a fibre, a cube, a sphere, a cylinder, a tube or granules.

5. An optical sensor comprising the functionalised bimodal PMOs according to claim 1.

6. An optical sensor comprising the functionalised bimodal PMOs according to claim 2.

7. An optical sensor comprising the functionalised bimodal PMOs according to claim 3.

8. An optical sensor comprising the functionalised bimodal PMOs according to claim 4.

9. A method comprising qualitatively or quantitatively detecting an analyte in a sample using the optical sensor according to claim 5, for the quantification of the oxygen partial pressure (pO.sub.2), the dissolved oxygen (DO), the carbon dioxide partial pressure (pCO.sub.2), the pH, pressure and/or temperature of a sample.

10. A method comprising using the functionalised bimodal PMOs according to claim 1 as a filter material, adsorption means, sensor material or carrier material for a pharmaceutical product, insecticide or pesticide.

11. A filter material, adsorption means, sensor material or carrier material for a pharmaceutical product, insecticide or pesticide, having applied thereon a coating comprising the functionalised bimodal PMOs according to claim 1.

12. A method comprising qualitatively or quantitatively detecting an analyte in a sample using the optical sensor according to claim 6, for the quantification of the oxygen partial pressure (pO.sub.2), the dissolved oxygen (DO), the carbon dioxide partial pressure (pCO.sub.2), the pH, pressure and/or temperature of a sample.

13. A method comprising using the functionalised bimodal PMOs according to claim 2 as a filter material, adsorption means, sensor material or carrier material for a pharmaceutical product, insecticide or pesticide.

14. A method comprising using the functionalised bimodal PMOs according to claim 2 as a coating for a filter material, adsorption means, sensor material or carrier material for a pharmaceutical product, insecticide or pesticide.

15. A method comprising qualitatively or quantitatively detecting an analyte in a sample using the optical sensor according to claim 7, for the quantification of the oxygen partial pressure (pO.sub.2), the dissolved oxygen (DO), the carbon dioxide partial pressure (pCO.sub.2), the pH, pressure and/or temperature of a sample.

16. A method comprising using the functionalised bimodal PMOs according to claim 3 as a filter material, adsorption means, sensor material or carrier material for a pharmaceutical product, insecticide or pesticide.

17. A method comprising applying a coating on a filter material, adsorption means, sensor material or carrier material for a pharmaceutical product, insecticide or pesticide, wherein the coating comprises the functionalised bimodal PMOs according to claim 1.

18. A method comprising qualitatively or quantitatively detecting an analyte in a sample using the optical sensor according to claim 8, for the quantification of the oxygen partial pressure (pO.sub.2), the dissolved oxygen (DO), the carbon dioxide partial pressure (pCO.sub.2), the pH, pressure and/or temperature of a sample.

19. A method comprising using the functionalised bimodal PMOs according to claim 4 as a filter material, adsorption means, sensor material or carrier material for a pharmaceutical product, insecticide or pesticide.

20. A method comprising applying a coating on a filter material, adsorption means, sensor material or carrier material for a pharmaceutical product, insecticide or pesticide, wherein the coating comprises the functionalised bimodal PMOs according to claim 3.

Description

(1) The invention will be explained in detail in the following with reference to some embodiments and accompanying drawings. The embodiments are intended to describe the invention without limiting it.

(2) In the drawings:

(3) FIG. 1 shows (A) the nitrogen isotherm and (B) the pore radius distribution of PMOs functionalised with platinum(II) 5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)porphyrin (PtTFPP).

(4) FIG. 2 shows the thermogravimetry/differential thermal analysis of PMOs functionalised with platinum(II) 5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)porphyrin (PtTFPP).

(5) FIG. 3 shows the .sup.29Si cross-polarisation magic-angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectra of (A) PMOs without a functional component and (B) PMOs functionalised with PtTFPP.

(6) FIG. 4 shows the .sup.13C cross-polarisation magic-angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectra of (A) PMOs functionalised with (3-aminopropyl)triethoxysilane (APTES) and hexafluorobenzene with a contact time of 2 ms, (B) PMOs functionalised with APTES and hexafluorobenzene with a contact time of 500 μs, and (C) PMOs functionalised with APTES.

(7) FIG. 5 shows the .sup.13C cross-polarisation magic-angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectra of (A) PMOs functionalised with N-(6-aminohexyl)aminopropyltrimethoxysilane (AHAPTMS) and hexafluorobenzene with a contact time of 2 ms, (B) PMOs functionalised with AHAPTMS and hexafluorobenzene with a contact time of 500 μs, and (C) PMOs functionalised with AHAPTMS.

(8) FIG. 6 shows (A) the phase shift and (B) the Stern-Volmer plot of PMOs functionalised with PtTFPP in the oxygen concentration range of 0 to 20.95 vol. %.

(9) FIG. 7 shows the XRD diffractogram of PMO with PtTFPP

(10) 1 g of starting material is mixed with a mixture of functional component and 1:4 (m %) organosilane/toluene, shaken until homogeneous and left closed for a certain time at room temperature. Drying takes place overnight at 120° C. The sample is then mixed with the structure-directing agent and reacted for 1 to 7 d at the appropriate temperature. This is followed by extraction with methanolic hydrochloric acid. The sample is washed neutral with distilled water and dried at 120° C. overnight.

(11) TABLE-US-00001 TABLE 1 Parameters used to produce functionalised bimodal PMOs with the addition of the functional component after step a). Starting material e.g. porous glass as membranes, granules, spheres, cylinders, wafers with partially porous regions Organosilane e.g. bis(trimethoxysilylethyl)benzene Functional component e.g. platinum(II) 5,10,15,20-tetrakis-(2,3,4,5,6- pentafluorophenyl)porphyrin (PtTFPP) or 8-hydroxypyrene-1,3,6- trisulfonic acid (HPTS) Functional component e.g. 0.5 percent by mass per 1 g of concentration Starting material Structure-directing agent CTMAOH or coblock polymer P123 Pseudomorphic 1 to 7 d transformation duration Reaction temperature e.g. 120° C.

(12) 1 g of starting material is shaken with a functional group in a suitable solvent (volume=triple the pore volume of the starting material) for 1 hour at room temperature. Drying takes place overnight at a certain temperature.

(13) TABLE-US-00002 TABLE 2 Parameters used to bind a functional group after step a). Starting material e.g. porous glass as membranes, granules, spheres, cylinders, wafers Functional group e.g. 3-mercaptopropyltrimethoxysilane, 3- (anchor molecule) aminopropyltriethoxysilane, N-(6- aminohexyl)aminopropyltrimethoxysilane Functional group e.g. 7.5 percent by mass concentration Solvent e.g. ethanol, acetone, toluene, water, mixtures of different solvents Drying temperature e.g. 90° C.

(14) A certain concentration of functional component is dissolved in 1 ml of solvent and catalyst. The mixture is added to 1 g of starting material, shaken until homogeneous and reacted for one hour at 75° C. Drying takes place overnight at a suitable temperature. This is followed by washing three times with a suitable solvent and washing once with another solvent at room temperature. Drying takes place overnight at the appropriate temperature. Subsequent PMO production: 1 g of sample is mixed with a mixture of 1:4 organosilane/toluene, shaken until homogeneous and left closed for a certain time at room temperature. Drying takes place overnight at 120° C. The sample is then mixed with the structure-directing agent and reacted for 1 to 7 d at the appropriate temperature. This is followed by extraction with methanolic hydrochloric acid. The sample is washed neutral with distilled water and dried at 120° C. overnight.

(15) TABLE-US-00003 TABLE 3 Parameters used to bind a functional component. Starting material e.g. modified porous glass as membranes, granules, spheres, cylinders, wafers with partially porous modified regions Functional component e.g. platinum(II) 5,10,15,20-tetrakis- (2,3,4,5,6-pentafluorophenyl)porphyrin (PtTFPP) or 8-hydroxypyrene-1,3,6- trisulfonic acid (HPTS) Functional component e.g. 0.75 percent by mass per 1 g concentration Starting material Solvent e.g. dimethylformamide, toluene, ethanol Catalyst Triethylamine 20 μl with 1 g of starting material or hydrochloric acid Drying temperature e.g. 120° C. Organosilane e.g. bis(trimethoxysilylethyl)benzene Structure-directing agent CTMAOH or coblock polymer P123 Pseudomorphic 1 to 7 d transformation duration Reaction temperature e.g. 120° C.

(16) The sample was measured with a Quantachrome Autosorb iQ device at −196° C. Activation took place at 150° C. The PMO PtTFPP sample is a PMO produced from CPG spheres with starting pores of 120 nm in size. Bis(trimethoxysilylethyl)benzol was used as the organosilane and PtTFPP as the functional component.

(17) TABLE-US-00004 TABLE 5 Results for nitrogen low-temperature adsorption of the PMOs functionalised with PtTFPP. Pore volume Mesopore volume BET-OF Sample Loading [cm.sup.3/g] [cm.sup.3/g] [m.sup.2/g] PMOs 20% 0.9 0.7 852 functionalised by mass with PtTFPP

(18) FIG. 1 shows (A) the nitrogen isotherm and (B) the pore radius distribution of PMOs functionalised with platinum(II) 5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)porphyrin (PtTFPP). The nitrogen isotherm corresponds to a sorption isotherm type IVb. There was a stepwise adsorption, typical for mesoporous materials, the increase at p≈0.95 indicates that starting pores are still present. The pore radius distribution confirms that pores with a diameter of 4 nm and starting pores (120 nm) are present.

(19) Type IVb isotherm according to IUPAC, without hysteresis, is typical for mesoporous materials and shows pore diameters from 3 according to BJH and 4.1 according to DFT.

(20) Thermogravimetry is the determination of the loss of mass of a substance in a temperature interval of RT-800° C. For this purpose, the sample is continuously heated at 10 K/min in a constant air flow (50 ml/min). If reactions such as dehydration, oxidation or decomposition occur with temperature increase, the mass of the sample is reduced. This change in mass is measured as a function of temperature or time. The loss of mass can be continuous or stepwise.

(21) The measurements were carried out on the LINSEIS STA PT1600 from Linseis. The PMO PtTFPP sample used is a PMO produced from CPG spheres with starting pores of the size 120 nm. Bis(trimethoxysilylethyl)benzene was used as the organosilane and PtTFPP as the functional component.

(22) FIG. 2 shows the thermogravimetry/differential thermal analysis of PMOs functionalised with platinum(II) 5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)porphyrin (PtTFPP). Thermogravimetry shows a loss of mass at 100° C. due to physisorbed water, a loss of mass at 420° C. due to the decomposition of organometallic complexes, a loss of mass at 500 to 650° C. due to phenyl groups incorporated in the silica network and a total loss of mass (200 to 800° C.) of 9% (m/m).

(23) The .sup.29Si CP-MAS NMR measurement was carried out using Bruker Avance 750, rotation frequency 7 kHz, repeat time 3 s and with a contact time of 5 ms.

(24) The PMO PtTFPP sample used is a PMO produced from CPG spheres with starting pores of the size 120 nm. Bis(trimethoxysilylethyl)benzene was used as the organosilane and PtTFPP as the functional component. The PMO reference sample is a PMO produced from CPG spheres with starting pores of the size 120 nm. Bis(trimethoxysilylethyl)benzene was used as the organosilane.

(25) FIG. 3 shows the .sup.29Si cross-polarisation magic-angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectra of (A) PMOs without a functional component and (B) PMOs functionalised with PtTFPP. From the signals and their intensities (Table 6), it can be clearly seen that the direct input of the PtTFPP dye does not lead to any change in the silicate network. The dye does not affect the formation of the periodic mesoporous system and there is no bonding between the PMO and the dye. It can be assumed that the dye is encapsulated and adsorbed in the PMO network.

(26) TABLE-US-00005 TABLE 6 Shifts and intensities of the .sup.29Si CP-MAS NMR signals. Sample T.sup.2 T.sup.3 Q.sup.2 Q.sup.3 Q.sup.4 PMOs −56.16 −66.81 −91.35 −100.72 −110.61 functionalised ppm ppm ppm ppm ppm with PtTFPP 3.63% 13.38% 10.94% 58.81% 13.23%

(27) The .sup.13C CP-MAS NMR measurement was carried out using Bruker Avance 750, rotation frequency 10 kHz, repeat time 3 s.

(28) In order to demonstrate the bonding of the functional component PtTFPP, a model compound is used, which is very similar to the binding molecule in the porphyrin complex of PtTFPP, hexafluorobenzene. The PG APTES sample used are CPG spheres with starting pores of the size 120 nm modified with 3-aminopropyltriethoxyilane. The PG APTES hexafluorobenzene sample are CPG spheres with starting pores of the size 120 nm modified with 3-aminopropyltriethoxyilane and subsequent bonding of hexafluorobenzene to APTES.

(29) FIG. 4 shows the .sup.13C cross-polarisation magic-angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectra of (A) CPG modified with (3-aminopropyl)triethoxysilane (APTES) and hexafluorobenzene with a contact time of 2 ms, (B) CPG modified with APTES and hexafluorobenzene with a contact time of 500 μs, and (C) CPG modified with APTES with a contact time of 500 μs.

(30) The CP-MAS NMR measurement was carried out using Bruker Avance 750, rotation frequency 10 kHz, repeat time 3 s.

(31) The .sup.13C CP-MAS NMR spectra show that a covalent bond exists between APTES and hexafluorobenzene (Table 7 and Table 8). The signal of C3 at 45.3 ppm decreases and the signal of C—NH-benzene (C′3) at 48.3 ppm is clearly identifiable, as well as the benzene signals (aromatic range) 124 and 138 ppm in the aromatic range of 120 to 145 ppm. The C—NH—C signal (aromatic range) at 116 ppm cannot be identified due to insufficient concentration or contact time. The peak at 124 ppm shows that there is a change in hexafluorobenzene. It is no longer highly symmetrical. Adsorption or no bonding would be expressed in a signal with a shift of 138 ppm (resolution in solid-state NMR too low to split the peak into two signals). It can therefore be assumed that the formation of a second aromatic signal describes a bond between APTES and hexafluorobenzene.

(32) Hexafluorobenzene is highly symmetrical and gives two signals in the liquid .sup.13C NMR (without fluorine decoupling) with the shifts of δ=137 and 139 ppm.

(3-Aminopropyl)triethoxysilane (APTES) (Reference)

(33) ##STR00001##

(34) TABLE-US-00006 TABLE 7 Shifts and intensities of the APTES .sup.13C CP-MA NMR signals. Shift δ Shift δ Intensity [ppm] theory [ppm] [%] C1 14.5 10.7 32.4 C2 27.1 25.2 35.6 C3 45.3 43.7 32

(3-Aminopropyl)triethoxysilane (APTES) and hexafluorobenzene (Reference)

(35) ##STR00002##

(36) TABLE-US-00007 TABLE 8 Shifts and intensities of the APTES-hexafluorobenzene .sup.13C CP-MAS NMR signals. Shift δ Shift δ Intensity [ppm] theory [ppm] [%] C1 14.8 9.5 28.6 C2 24.5 23.6 30.3 C3 45.3 43.0 14.7 C′3 48.3 47.9 14.2 Aromatic region 116.3 — — Aromatic region 131-143 123.8 . . . 137.2 4.4 . . . 7.8

(37) FIG. 5 shows .sup.13C cross-polarisation magic-angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectra of (A) CPG modified with N-(6-aminohexyl)aminopropyltrimethoxysilane (AHAPTMS) and hexafluorobenzene with a contact time of 2 ms, (B) CPG modified with AHAPTMS and hexafluorobenzene with a contact time of 500 μs, and (C) CPG modified with AHAPTMS with a contact time of 500 μs.

(38) The signal of C—NH.sub.2 at 41.6 ppm (theory 42.1 ppm) decreases due to the addition of hexafluorobenzene. The signal of C—NH benzene at 45.4 ppm (theory 45.1 ppm) is clearly identifiable and shows that a covalent bond exists between APTES and hexafluorobenzene.

(39) The CP-MAS NMR measurement was carried out with Bruker Avance 750, rotation frequency 10 kHz, repeat time 3 s.

N-(6-aminohexyl)aminopropyltrimethoxysilane (AHAPTMS) Theory

(40) ##STR00003##

N-(6-aminohexyl)aminopropyltrimethoxysilane (AHAPTMS) and hexafluorobenzene (Theory)

(41) ##STR00004##

(42) Detection of the incorporation of the functional component into the PMO

(43) The functionalised bimodal PMOs were rinsed thoroughly with toluene. There was no leaching effect, which confirmed the incorporation of the functional component into the network.

(44) Oxygen measurement and determination of the Stern-Volmer constant

(45) The oxygen measurement was carried out from 0 vol. % to 20.95 vol. % oxygen to nitrogen (FIG. 6).

(46) FIG. 6 shows (A) the phase shift and (B) the Stern-Volmer plot of PMOs functionalised with PtTFPP in the oxygen concentration range of 0 to 20.95 vol. %. The Stern-Volmer equation describes the dependence of the intensity of the fluorescence of a fluorescent dye on the concentration of substances that quench the fluorescence, e.g. oxygen. The Stern-Volmer plot shows a linear course and the Stern-Volmer constant K.sub.sv was determined to be 0.0244.

(47) FIG. 7 shows a diffractogram of the functionalised bimodal PMOs. This has the reflections 100, 110 and 200, which are typical for hexagonal pore structure with pseudo-crystalline walls.

CITED NON-PATENT LITERATURE

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