GLASS CONTAINER COATED INTERNALLY WITH A METAL-ORGANIC FRAMEWORK

Abstract

The present invention relates to a device consisting of a glass container, the inner walls of which have been modified after successive activation, silanisation and amidation reactions to house a porous crystalline coating. Said coating, which has the atomic sequence SiOR-M-MOF, is covalently bonded to the inner wall of the container in an inverted radial manner, where R may be A) Si(CH.sub.2).sub.3NHCH(O)(C.sub.6H.sub.4)COO; B) Si(CH.sub.2).sub.nNHCH(O)(CH.sub.2).sub.2(C.sub.2HN.sub.3)(CH.sub.2).sub.n(C.sub.6H.sub.4)COO; C) Si(CH.sub.2).sub.nOCH.sub.2CH(OH)CH.sub.2NH(CH.sub.2).sub.n(C.sub.6H.sub.4)COO; D) Si(CH.sub.2).sub.nS(CH.sub.2).sub.2(CH.sub.2).sub.n(C.sub.6H.sub.4)COO, and M is a metal dependent on the type of MOF. The container can be used for the extraction and pre-concentration of analytes present in samples of different natures, from environmental to biological. The invention also relates to the use thereof for dosing medicines or for colouring or flavouring beverages.

Claims

1. A glass container comprising: an inner wall, and a coating of formula SiOR-M-MOF covalently bonded to the inner wall in an inverted radial manner, where MOF is a metal-organic framework, where M is a metal dependent on a type of the MOF, and where R is an intermediate compound selected from the group consisting of: A) Si(CH.sub.2).sub.3NHCH(O)(C.sub.6H.sub.4)COO; B) Si(CH.sub.2).sub.nNHCH(O)(CH.sub.2).sub.2(C.sub.2HN.sub.3)(CH.sub.2).sub.n(C.sub.6H.sub.4)COO; C) Si(CH.sub.2).sub.nOCH.sub.2CH(OH)CH.sub.2NH(CH.sub.2).sub.n(C.sub.6H.sub.4)COO; D) Si(CH.sub.2).sub.nS(CH.sub.2).sub.2(CH.sub.2).sub.n(C.sub.6H.sub.4)COO, with an n which can take values between 0 and 6.

2. The glass container according to claim 1, where the M is selected from the group consisting of Zr, Ti, Al, Cr, Fe, Mn, Co, Ni, Cu, Zn, Mg, Ca, Sc, and Sr.

3. The glass container according to claim 2, where the MOF is selected from the group consisting of UiO-66(Zr), UiO-66(Zr)NH.sub.2, UiO-66(Zr)NO.sub.2, MIL-101(Fe), MIL-101(Fe)NH.sub.2, MIL-100(Cr), CIM-80(Al), PCN-250(Fe.sub.2Co), PCN-250(Fe), UiO-67, HKUST-1, DUT-52, DUT-67, or modifications thereof with a terminal amino group or a terminal azido group.

4. A method of manufacturing a glass container including an inner wall and a coating of formula SiOR-M-MOF covalently bonded to the inner wall in an inverted radial manner, where MOF is a metal-organic framework, where M is a metal dependent on a type of the MOF, and where R is an intermediate compound selected from the group consisting of: Si(CH.sub.2).sub.3NHCH(O)(C.sub.6H.sub.4)COO; B) Si(CH.sub.2).sub.nNHCH(O)(CH.sub.2).sub.2(C.sub.2HN.sub.3)(CH.sub.2).sub.n(C.sub.6H.sub.4)COO; C) Si(CH.sub.2).sub.nOCH.sub.2CH(OH)CH.sub.2NH(CH.sub.2).sub.n(C.sub.6H.sub.4)COO; D) Si(CH.sub.2).sub.nS(CH.sub.2).sub.2(CH.sub.2).sub.n(C.sub.6H.sub.4)COO, with an n which can take values between 0 and 6, the method comprising chemically modifying a surface of the inner wall after successive activation, silanisation and amidation reactions or after a click chemistry reaction.

5. A thin film microextraction (TFME) device for preconcentrating a sample in analytical chemistry, the TFME device comprising: a glass body having an inner wall, and a coating of formula SiOR-M-MOF covalently bonded to the inner wall in an inverted radial manner, where MOF is a metal-organic framework, where M is a metal dependent on a type of the MOF, and where R is an intermediate compound selected from the group consisting of: Si(CH.sub.2).sub.3NHCH(O)(C.sub.6H.sub.4)COO; B) Si(CH.sub.2).sub.nNHCH(O)(CH.sub.2).sub.2(C.sub.2HN.sub.3)(CH.sub.2).sub.n(C.sub.6H.sub.4)COO; C) Si(CH.sub.2).sub.nOCH.sub.2CH(OH)CH.sub.2NH(CH.sub.2).sub.n(C.sub.6H.sub.4)COO; D) Si(CH.sub.2).sub.nS(CH.sub.2).sub.2(CH.sub.2).sub.n(C.sub.6H.sub.4)COO, with an n which can take values between 0 and 6.

6. (canceled)

7. (canceled)

8. The manufacturing method of claim 4, where the M is selected from the group consisting of Zr, Ti, Al, Cr, Fe, Mn, Co, Ni, Cu, Zn, Mg, Ca, Sc, and Sr.

9. The manufacturing method of claim 8, where the MOF is selected from the group consisting of UiO-66(Zr), UiO-66(Zr)NH2, UiO-66(Zr)NO2, MIL-101(Fe), MIL-101(Fe)NH2, MIL-100(Cr), CIM-80(Al), PCN-250(Fe2Co), PCN-250(Fe), UiO-67, HKUST-1, DUT-52, DUT-67, or modifications thereof with a terminal amino group or a terminal azido group.

10. The TFME device of claim 5, where the M is selected from the group consisting of Zr, Ti, Al, Cr, Fe, Mn, Co, Ni, Cu, Zn, Mg, Ca, Sc, and Sr.

11. The TFME device of claim 10, where the MOF is selected from the group consisting of UiO-66(Zr), UiO-66(Zr)NH2, UiO-66(Zr)NO2, MIL-101(Fe), MIL-101(Fe)NH2, MIL-100(Cr), CIM-80(Al), PCN-250(Fe2Co), PCN-250(Fe), UiO-67, HKUST-1, DUT-52, DUT-67, or modifications thereof with a terminal amino group or a terminal azido group.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figures are included for the purpose of clarifying the most representative parts of this invention. The examples shown below are merely illustrative, but in no case limit the invention:

[0038] FIG. 1 shows general diagram of the device. I=screw cap, II=headspace not coated, III=inner wall coated with MOF.

[0039] FIG. 2 shows a representative diagram of the chemical reactions for the first and last embodiments of the invention. Step 1: surface activation, step 2: silanisation reaction with terminal amino groups, step 3: reaction to form the amide and to expose terminal carboxylic groups, step 4: solvothermal MOF growth.

[0040] FIG. 3 shows a representative diagram of the second embodiment of the invention.

[0041] Step 1: surface activation, step 2: silanisation reaction with terminal amino groups, step 3: reaction to form an amide and to expose terminal alkyne groups on the surface, step 4: alkyne-azide click reaction using MOFs with terminal azide groups.

[0042] FIG. 4 shows a representative diagram of the third embodiment of the invention. Step 1: surface activation, step 2: silanisation reaction with terminal epoxide groups, step 3: epoxide opening reaction using MOFs with terminal amino groups.

[0043] FIG. 5 shows a scanning electron microscopy (SEM) image of the cross-section of a glass container coated with MOF MIL-101(Fe).

[0044] FIG. 6 shows the extraction efficiency of the device with the MOF MIL-101(Fe) coating manufactured according to the first embodiment of the invention using: carbamazepine (a), 4-cumylphenol (b), benzophenone-3 (c), triclosan (d), 4-tert-octilphenol (e), 4-octilphenol (f), chrysene (g), and indeno[1,2,3-cd]pyrene (h).

[0045] FIG. 7 shows the extraction efficiency of the device with the MOF UiO-66(Zr) coating manufactured following the method described in the fourth embodiment using: carbamazepine (a), 4-cumylphenol (b), benzophenone-3 (c), triclosan (d), 4-tert-octilphenol (e), 4-octilphenol (f), chrysene (g), and indeno[1,2,3-cd]pyrene (h).

EMBODIMENT OF THE INVENTION

[0046] Some illustrative examples that, however, in no way seek to limit this invention are described below.

[0047] In a first embodiment of the invention, the stationary phase having an inverted radial atomic sequence, container SiOSi(CH.sub.2).sub.3NHC(O)(C.sub.6H.sub.4)COOFe-MOF, is obtained by means of four main steps: 1) silica surface activation with an alkaline solution, 2) silanisation reaction to generate terminal 3-aminopropyl groups, 3) amidation reaction to generate terminal carboxyl groups, and 4) MOF MIL-101(Fe) growth by means of solvothermal synthesis (FIG. 2).

[0048] The method performed inside the glass container is described below:

[0049] 1. Container activation is performed by adding a 1 M aqueous NaOH solution for 24 hours at 25 C., and after appropriate washing with water, a second 1 M HCl solution is added for 30 minutes at 25 C.

[0050] 2. Container glass silanisation is performed by adding 3-aminopropyltriethoxysilane (APTES) that is left to act for 24 hours at 60 C.

[0051] 3. The amidation reaction to produce terminal carboxyl groups is carried out by adding to the container, in an inert atmosphere, a triethylamine solution in tetrahydrofuran (THF) and then another 0.04 M terephthaloyl chloride solution in THF. The container is closed and kept at 60 C. for 24 hours until the reaction occurs completely.

[0052] 4. Finally, the incorporation of MOF MIL-101(Fe) is performed by adding a solution in dimethylformamide of 0.1 M iron (III) chloride and 0.05 M terephthalic acid to the container. The container is closed and kept at 110 C. for 20 hours until the MOF has grown on the inner surface of the container.

[0053] The container thus prepared has a uniform MOF layer of about 5 m on the inner surface of the container (FIG. 5). Before starting to use said container, it is convenient to perform washing with dimethylformamide and with ethanol/acetone, and to perform low-pressure heating on the open container to remove possible DMF residues or reagents that remain trapped in the pores of the material.

[0054] In a second embodiment of the invention, the stationary phase having an inverted radial atomic sequence, container SiOSi(CH.sub.2).sub.3NHC(O)(CH.sub.2).sub.2(C.sub.2N.sub.3H)(CH.sub.2).sub.3(C.sub.6H.sub.4)COOZr-MOF, is obtained by means of four steps: 1) silica surface activation with an alkaline solution, 2) silanisation reaction to generate terminal 3-aminopropyl groups, 3) amidation reaction to generate terminal alkyne groups, 4) post-synthetic modification of the MOF for incorporating terminal azide groups and alkyne-azide cycloaddition reaction for anchoring the MOF (FIG. 3).

[0055] The method performed inside the glass container is described below:

[0056] 1. Container activation is performed by adding a 1 M aqueous NaOH solution for 24 hours at 25 C., and after appropriate washing with water, a second 1 M HCl solution is added for 30 minutes at 25 C.

[0057] 2. Container glass silanisation is performed by adding 3-aminopropyltriethoxysilane (APTES) that is left to act for 24 hours at 60 C.

[0058] 3. The amidation reaction to produce terminal alkyne groups is carried out by adding in the container an aqueous N-hydroxysuccinimide solution (0.002 M), 1-ethyl-3(3-dimethylaminopropyl)carbodiimide (0.124 M), and 4-pentinoic acid (0.071 M). The container is closed and kept at 25 C. for 24 hours until the reaction occurs completely.

[0059] 4. Post-synthetic modification of MOF UiO-66 is performed by submerging same in a DMF solution containing 4-azidopropylbenzoic acid for 24 hours.

[0060] 5. The alkyne-azide cycloaddition reaction is performed by adding an aqueous solution of CuSO.sub.4 5H.sub.2O (0.06 M) and sodium ascorbate (0.12 M) and then a dispersion of MOF UiO-66 in water and acetonitrile (50:50, v/v). The container is closed and the reaction is left to occur at 25 C. for 24 hours.

[0061] The container thus prepared has a uniform MOF layer of about 0.5 m on the inner surface of the container. Before starting to use said container, it is convenient to perform washing with ethanol/acetone, and to perform heating at reduced pressure on the open container to remove possible solvent residues or reagents that remain trapped in the pores of the MOF.

[0062] In a third embodiment of the invention (FIG. 4), the stationary phase having an inverted radial atomic sequence, container SiOSi(CH.sub.2).sub.3OCH.sub.2CH(OH)CH.sub.2NH(CH.sub.2).sub.2(C.sub.6H.sub.4)COOZr-MOF, is obtained by means of three steps: 1) silica surface activation with an alkaline solution, 2) silanisation reaction to generate terminal 3-glycidyloxypropyl groups, 3) post-synthetic modification of the MOF for surface functionalisation with terminal amino groups and ring opening reaction of the epoxide groups for anchoring the MOF.

[0063] The method performed inside the glass container is described below:

[0064] 1. Container activation is performed by adding a 1 M aqueous NaOH solution for 24 hours at 25 C., and after appropriate washing with water, a second 1 M HCl solution is added for 30 minutes at 25 C.

[0065] 2. Container glass silanisation is performed by adding 3-glycidyloxypropyltrimethoxysilane (GLYMO) that is left to act for 24 hours at 60 C.

[0066] 3. Post-synthetic modification of the MOF is performed by submerging same in a DMF solution containing 4-aminopropylbenzoic acid for 24 hours.

[0067] 4. The ring opening reaction of the epoxide groups is carried out by adding a dispersion in dimethylformamide (DMF) of MOF UiO-66(Zr) functionalised with amino groups. The container is closed and kept at 100 C. for 24 hours until the reaction occurs completely.

[0068] The container thus prepared has a uniform MOF layer of about 0.5 m on the inner surface of the container. Before starting to use said container, it is convenient to perform washing with ethanol/acetone, and to perform heating at reduced pressure on the open container to remove possible solvent residues or reagents that remain trapped in the pores of the MOF.

[0069] In a last embodiment of the invention (FIG. 2), the stationary phase having a radial atomic sequence, container SiOSi(CH.sub.2).sub.3NHC(O)(C.sub.6H.sub.4)COOZr-MOF, is obtained by means of four steps: 1) silica surface activation with an alkaline solution, 2) silanisation reaction to generate terminal 3-aminopropyl groups, 3) amidation reaction to generate terminal carboxyl groups, and 4) MOF UiO-66(Zr) growth by means of solvothermal synthesis. The method performed inside the glass container is described below:

[0070] 1. Container activation is performed by adding a 1 M aqueous NaOH solution for 24 hours at 25 C., and after appropriate washing with water, a second 1 M HCl solution is added for 30 minutes at 25 C.

[0071] 2. Container glass silanisation is performed by adding 3-aminopropylsilane (APTES) that is left to act for 24 hours at 60 C.

[0072] 3. The amidation reaction to produce terminal carboxyl groups is carried out by adding to the container, in an inert atmosphere, a triethylamine solution in tetrahydrofuran (THF) and then another 0.04 M terephthaloyl chloride solution in THF. The container is closed and kept at 60 C. for 24 hours until the reaction occurs completely.

[0073] 4. Finally, the incorporation of MOF UiO-66(Zr) is performed by adding a solution in dimethylformamide of 0.02 M zirconium(IV) chloride and 0.02 M terephthalic acid to the container. The container is closed and kept at 120 C. for 24 hours until the MOF has grown on the inner surface of the container.

[0074] The container thus prepared has a uniform MOF layer of about 1 m on the inner surface of the container. Before starting to use said container, it is convenient to perform washing with dimethylformamide and with ethanol/acetone, and to perform low-pressure heating on the open container to remove possible DMF residues or reagents that remain trapped in the pores of the material.

[0075] FIGS. 6 and 7 show the results obtained for extraction efficiency using the devices of the first and last embodiments of the invention for the analytical determination of eight organic compounds of different natures (PAHs, phenols, a drug, a disinfectant, and a solar panel) at a concentration of 10 ppb in 10 mL of water. The process is very simple, the sample is added to the vial, a time of extraction by means of stirring of 5 minutes is used, and after extraction, the supernatant is discarded, 500 L of acetonitrile are added to the vial and the desorption step occurs for 5 minutes under vortex stirring. Centrifugation was not required in the entire microextraction method, which ensures the simplicity of the device in the daily use thereof.