Composition for detecting acidic compound

Abstract

A composition for detecting an acidic compound and a method using the same are discloses herein. In some embodiments, the method includes contacting a composition comprising a metal-organic hybrid structure formed by coordinate bond between a compound represented by the following Chemical Formula 1 or a salt thereof and a metal ion, with an acidic compound to be detected, wherein the composition is in the form of a metallogel prior to contact with the acidic compound, and detecting the acidic compound based on the transition of the composition from the form of a metallogel to a liquid phase. In some embodiments, detection of the acidic compound can be visually confirmed by phase transformation of the composition from a metallogel to a liquid phase.

Claims

1. A method of detecting an acidic compound, comprising: contacting a composition comprising a metal-organic hybrid structure formed by coordinate bond between a compound represented by the following Chemical Formula 1 or a salt thereof and a metal ion, with an acidic compound to be detected, wherein the composition is in the form of a metallogel prior to contact with the acidic compound; and detecting the acidic compound based on the transition of the composition from the form of a metallogel to a liquid phase: ##STR00006## in Chemical Formula 1, each R is independently -R.sub.1, —NH—CO-R.sub.2, or —NH-R.sub.2, each R.sub.1 is independently —OH, C.sub.6-60 aryl, C.sub.1-10 alkyl, or an amino acid residue, and R.sub.2 is C.sub.1-10 alkyl, C.sub.6-60 aryl, or C.sub.4-60 heteroaryl containing any one of N, O, and S.

2. The method according to claim 1, wherein each R.sub.1 is independently —OH, phenyl, naphthyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, or an amino acid residue selected from the group consisting of alanine, cysteine, aspartic acid, glutamic acid, phenylalanine, histidine, isoleucine, lysine, leucine, methionine, asparagine, pyrrolysine, glutamine, arginine, serine, threonine, selenocysteine, valine, tryptophan, and tyrosine.

3. The method according to claim 1, wherein R.sub.2 is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, hexyl, octyl, phenyl, naphthyl, or pyridinyl.

4. The method according to claim 1, wherein the compound represented by Chemical Formula 1 are compounds represented by the following Chemical Formulas 1-1 to 1-5: ##STR00007## ##STR00008##

5. The method according to claim 1, wherein the metal of the metal ion is Period 1 transition metal, Period 2 transition metal, Period 3 transition metal, or lanthanide metal.

6. The method according to claim 1, wherein the metal of the metal ion is Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, Ir, Pt, Au, Tb, Eu, or Yb.

7. The method according to claim 1, wherein the acidic compound is a liquid or a gas.

8. The method according to claim 1, wherein the acidic compound is hydrogen chloride, hydrogen fluoride, hydrogen bromide, trifluoroacetic acid, acetic acid, nitrogen oxide, nitric acid, sulfur oxide or sulfuric acid.

9. The method according to claim 1, wherein the composition further comprises: a solvent, wherein the solvent is trapped between spaces in the metal-organic hybrid structure.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 schematically shows a network structure of metal-organic frameworks of the present invention.

(2) FIG. 2 shows a state in which the composition for detecting an acidic compound of the present invention is mounted in a cylinder.

(3) FIG. 3 is a graph showing the time (seconds) required for the metal-organic hybrid structure of the present invention to change to a liquid.

(4) FIG. 4 shows a state in which cobalt metallogel changes to a liquid with time by weight percentage in Experimental Example of the present invention.

(5) FIG. 5 shows a state in which copper metallogel changes to a liquid with time by weight percentage in Experimental Example of the present invention.

(6) FIG. 6 shows a state in which zinc metallogel changes to a liquid with time by weight percentage in Experimental Example of the present invention.

(7) FIG. 7 shows the results of expressing the degelation process of zinc metallogel by trifluoroacetic acid in units of time.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(8) Hereinafter, preferred examples will be presented to facilitate understanding of the present invention. However, these examples are provided for a better understanding of the present invention only, and are not intended to limit the scope of the invention.

Preparation Example: Preparation of tetraoxime biphenyl diol

(9) ##STR00005##

(10) (Step 1)

(11) HMTA (hexamethylenetetramine, 7.530 g, 53.70 mmol) was added into a dried round-bottom flask. The flask was purged with argon, and TFA (trifluoroacetic acid, 50 mL) was added. After completely dissolving HMTA, biphenyl-4,4′-diol (1.000 g, 5.370 mmol) was rapidly added. After confirming that the mixture turned to an orange color, the mixture was heated at 120° C. for 7 days. The product was dark red, and it was poured into 4N HCl (100 mL) to isolate the yellow precipitate. The precipitate was recrystallized with hot DMSO to obtain 2.460 g of yellow microcrystals (yield: 65.1%).

(12) (Step 2)

(13) The compound (0.296 g, 1.000 mmol) prepared in step 1 and NH.sub.2OH—HCl (0.420 g, 6.0 mmol) were added into a reactor. After adding water (7 mL), the mixture was heated to 80° C. Methanol was added dropwise until the mixture became transparent. After tightly sealing the reactor, the mixture was heated to 100° C. for 1 hour. After cooling to room temperature, water was added to induce precipitation. The solid material was isolated by filtration, and washed with water to obtain a light yellow product (powder, 0.360 g).

(14) .sup.1H NMR (300 MHz, DMSO-d) δ 11.60 (s, 4H), 10.88 (s, 2H), 8.45 (s, 4H), 7.83 (s, s)

Examples 1-1 to 1-4

1) Example 1-1

(15) The compound (tetraoxime biphenol, 25 mg) prepared in the previous Preparation Example was dissolved in DMF (0.88 mL). Then, triethylamine (0.02 mL) was added dropwise and mixed to prepare a solution A. In addition, Co(OAc).sub.2.4H.sub.2O (35 mg) was dissolved in DMF (3.53 mL) to prepare a solution B. The solution A (0.1 mL) and the solution B (0.4 mL) were mixed to prepare a metallogel, which was then sonicated for 1 minute to increase the strength of the metallogel. The metallogel thus prepared was named “Cobalt metallogel 2 wt %”.

2) Examples 1-2 to 1-4

(16) A metallogel was prepared in the same manner as in Example 1-1, except that the amount of DMF used was controlled as shown in Table 1 below during the preparation of the solutions A and B,

(17) TABLE-US-00001 TABLE 1 Amount of DMF Amount of DMF used during used during preparation of preparation of solution A solution B Example 1-1 Cobalt metallogel 0.88 mL 3.53 mL 2 wt % Example 1-2 Cobalt metallogel 0.43 mL 1.73 mL 4 wt % Example 1-3 Cobalt metallogel 0.28 mL 1.13 mL 6 wt % Example 1-4 Cobalt metallogel 0.21 mL 0.83 mL 8 wt %

Examples 2-1 to 2-4

1) Example 2-1

(18) The compound (tetraoxime biphenol, 25 mg) prepared in the previous Preparation Example was dissolved in DMF (1.09 mL). Then, triethylamine (0.02 mL) was added dropwise and mixed to prepare a solution A. In addition, Cu(acac).sub.2 (55 mg) was dissolved in DMF (4.36 mL) to prepare a solution B. The solution A (0.1 mL) and the solution B (0.4 mL) were mixed to prepare a metallogel, which was then sonicated for 1 minute to increase the strength of the metallogel. The metallogel thus prepared was named “Cobalt metallogel 2 wt %”.

2) Examples 2-2 to 2-4

(19) A metallogel was prepared in the same manner as in Example 2-1, except that the amount of DMF used was controlled as shown in Table 2 below during the preparation of the solutions A and B,

(20) TABLE-US-00002 TABLE 2 Amount of DMF Amount of DMF used during used during preparation of preparation of solution A solution B Example 2-1 Copper metallogel 1.09 mL 4.36 mL 2 wt % Example 2-2 Copper metallogel 0.53 mL 2.14 mL 4 wt % Example 2-3 Copper metallogel 0.35 mL 1.39 mL 6 wt % Example 2-4 Copper metallogel 0.26 mL 1.02 mL 8 wt %

Examples 3-1 to 3-4

1) Example 3-1

(21) The compound (tetraoxime biphenol, 25 mg) prepared in the previous Preparation Example was dissolved in DMF (1.04 mL). Then, triethylamine (0.02 mL) was added dropwise and mixed to prepare a solution A. In addition, Zn(acac).sub.2.Math.H.sub.2O (50 mg) was dissolved in DMF (4.15 mL) to prepare a solution B. The solution A (0.1 mL) and the solution B (0.4 mL) were mixed to prepare a metallogel, which was then sonicated for 1 minute to increase the strength of the metallogel. The metallogel thus prepared was named “Zinc metallogel 2 wt %”.

2) Examples 3-2 to 3-4

(22) A metallogel was prepared in the same manner as in Example 3-1, except that the amount of DMF used was controlled as shown in Table 3 below during the preparation of the solutions A and B,

(23) TABLE-US-00003 TABLE 3 Amount of DMF Amount of DMF used during used during preparation of preparation of solution A solution B Example 3-1 Zinc metallogel 1.04 mL 4.15 mL 2 wt % Example 3-2 Zinc metallogel 0.51 mL 2.03 mL 4 wt % Example 3-3 Zinc metallogel 0.33 mL 1.33 mL 6 wt % Example 3-4 Zinc metallogel 0.24 mL 0.98 mL 8 wt %

Experimental Example

(24) As shown in FIG. 2, a fixed volume of the metallogel of Examples previously prepared was placed inside the cylinder. After an o-ring was attached and the system was isolated from the outside by using a clamp, hydrogen chloride gas was flowed into the cylinder at a constant flow rate and flow rate. Then, the time (second) was measured while observing the degelation state of metallogel. The time required for complete degelation of metallogel is shown in Table 4 below. This graph (FIG. 3) and the image observed based on a fixed time interval are shown in FIGS. 4 to 6.

(25) TABLE-US-00004 TABLE 4 2 wt % 4 wt % 6 wt % 8 wt % Copper metallogel 128 s 210 s 310 s 397 s Cobalt metallogel —  88 s 100 s 124 s Zinc metallogel 107 s 125 s 166 s 225 s

(26) As described above, it was confirmed that hydrogen chloride gas could be detected within a short time, and the metallogel exhibited a time difference according to the metal and weight % thereof. Therefore, it can be confirmed that the above-mentioned characteristics can be used to control the detection of the acidic compound and its sensitivity.

Experimental Example 2

(27) As shown in FIG. 2, 4 wt % of Zinc metallogel (1.2 mL) of Example 3-2 previously prepared was placed inside the cylinder. An o-ring was attached to one end of the cylinder and connected to an oil bubbler to check the internal pressure of the cylinder. The other end of the cylinder was connected with a round bottom flask containing trifluoroacetic acid and a tygon tube. Nitrogen was poured into a round bottom flask so that the trifluoroacetic acid vapor passed through the cylinder, and the degelation process of metallogel was recorded by digital imaging and captured at a fixed time interval (20 seconds) and shown in FIG. 7.