FLASH-TYPE CHEMILUMINESCENCE SYSTEM BASED ON CUINS2@ZNS NANOMATERIAL

Abstract

A CuInS.sub.2@ZnS nanomaterial synthesized with thiosalicylic acid and sodium citrate as dual-stabilizers is taken as a chemiluminescent luminophore, and Tris buffer containing both N.sub.2H.sub.4.H.sub.2O and H.sub.2O.sub.2 is taken as the triggering solution; introducing the H.sub.2O.sub.2 into the triggering solution can bring out greatly enhanced CL emission and obviously shortened CL process, enable the CuInS.sub.2@ZnS nanomaterial with strong flash-type and near-infrared CL; the luminophore of CuInS.sub.2@ZnS nanomaterial is synthesized by a one-pot method; compared with acridinium ester (a classical flash-type chemiluminescent substance), the CuInS.sub.2@ZnS nanomaterial is simple in synthesis method, mild in conditions and short in the required time, the synthesized CuInS.sub.2@ZnS nanomaterial is not easy to decompose under light, and the CL waveband is in the near-infrared region.

Claims

1-10. (canceled)

11. A flash-type chemiluminescence (CL) liquid composition based on CuInS2/ZnS nanomaterial, wherein a CuInS2/ZnS nanomaterial as a chemiluminescent luminophore and a Tris buffer solution containing HYDRAZINE HYDRATE and H.sub.2O.sub.2 as the triggering solution form the flash-type CL liquid composition, wherein a concentration of the HYDRAZINE HYDRATE in the triggering solution is 5-30 mmol/L, wherein a concentration of the H.sub.2O.sub.2 in the triggering solution is above 0.01 mol/L, wherein a pH value of the triggering solution is 6-9.

12. The flash-type CL liquid composition based on a CuInS2/ZnS nanomaterial according to claim 11, wherein a concentration of the Tris in the triggering solution is 0.05-0.2 mol/L.

13. The flash-type CL liquid composition based on a CuInS2/ZnS nanomaterial according to claim 11, wherein a concentration of the N.sub.2H.sub.4.H.sub.2O in the triggering solution is 10-20 mmol/L.

14. The flash-type CL liquid composition based on a CuInS2/ZnS nanomaterial according to claim 11, wherein a concentration of the H.sub.2O.sub.2 in the triggering solution is 1-2 mol/L.

15. The flash-type CL liquid composition based on a CuInS2/ZnS nanomaterial according to claim 11, wherein a pH value of the triggering solution is 7-8.

16. The flash-type CL liquid composition based on a CuInS2/ZnS nanomaterial according to claim 11, wherein the chemiluminescent substance CuInS2/ZnS is centrifugally purified with isopropanol, dried to remove isopropanol and dissolved in water as much as one-tenth of an original volume of the chemiluminescent substance, then the triggering solution is added to excite the chemiluminescent substance, and a volume ratio of the triggering solution and the original solution is 1:1-5.

17. The flash-type CL liquid composition based on a CuInS2/ZnS nanomaterial according to claim 11, wherein a CL time of the flash-type CL liquid composition based on a CuInS2/ZnS nanomaterial is 1-10 s, and a CL radiation wavelength is 750-790 nm.

18. The flash-type CL liquid composition based on a CuInS2/ZnS nanomaterial according to claim 11, wherein the triggering solution is prepared according to the following steps: weighing Tris with a final concentration of 0.1 mol/L in 10 mL of deionized water, adding 0.05-0.2 mmol of HYDRAZINE HYDRATE, adjusting the pH value to 7-8 with HCl, and finally adding more than 5 mmol of H.sub.2O.sub.2 to obtain the triggering solution.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0037] FIG. 1 is a fluorescence spectrum and UV-vis absorption spectrum of the CuInS.sub.2/ZnS nanomaterial prepared in comparative example 1.

[0038] FIG. 2 is a CL spectrum of the CuInS.sub.2/ZnS nanomaterial and triggering solution-1 prepared in comparative example 1.

[0039] FIG. 3 is a CL intensity curve of the CuInS.sub.2/ZnS nanomaterial and triggering solution-1 prepared in comparative example 1.

[0040] FIG. 4 is an XRD pattern of the CuInS.sub.2/ZnS nanomaterial prepared in comparative example 1.

[0041] FIG. 5 is an XPS pattern of the CuInS.sub.2/ZnS nanomaterial prepared in comparative example 1.

[0042] FIG. 6 is a CL spectrum of the CuInS.sub.2/ZnS nanomaterial and an triggering solution-2 prepared in example 1.

[0043] FIG. 7 is a CL intensity curve of the CuInS.sub.2/ZnS nanomaterial and the triggering solution-2 prepared in example 1.

[0044] FIG. 8 is a comparison diagram of the CL intensities generated by the CuInS.sub.2/ZnS nanomaterial and corresponding triggering solutions prepared in examples 1, 2, 3, 4 and 5.

[0045] FIG. 9 is a comparison diagram of the CL intensities generated by the CuInS.sub.2/ZnS nanomaterial and corresponding triggering solutions prepared in examples 1, 6, 7, 8 and 9.

[0046] FIG. 10 is a comparison diagram of the CL intensities generated by the CuInS.sub.2/ZnS nanomaterial and corresponding triggering solutions prepared in examples 1, 10, 11 and 12.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0047] The present invention will be further described below through, but not limited to, embodiments.

[0048] The mass fraction of N.sub.2H.sub.4.H.sub.2O used in the embodiment of the present invention is 50%, and the mass fraction of H.sub.2O.sub.2 is 30%.

[0049] A PL (fluorescence) spectrum of the CuInS.sub.2/ZnS nanomaterial prepared in the embodiment was collected and obtained by an F-320 fluorescence spectrophotometer manufactured by Tianjin Gangdong Sci&Tech. Development Co., Ltd., and the triggering wavelength was 540 nm. The UV-vis absorption spectrum was collected and obtained by a TU-1901 UV-vis spectrophotometer manufactured by Beijing Purkinje General Instrument Co., Ltd. The CL spectrum was collected and obtained by a CCD grating spectrometer manufactured by Princeton Instruments. This instrument is composed of an Acton SP2300i monochrometer and a PyLoN400BReXcelon CCD detector, and the CL spectrum collection time is 10 s.

Comparative Example 1

[0050] A CuInS.sub.2/ZnS nanomaterial coated with double stabilizers of thiosalicylic acid and sodium citrate was synthesized by the following specific steps: [0051] (1) 0.024 g of thiosalicylic acid was weighed and added into a 100 mL three-neck flask, 10 mL of deionized water was added, the solution was stirred, the thiosalicylic acid was dissolved, and 30 mL of deionized water was added; [0052] (2) 800 μL of sodium citrate solution with a concentration of 0.04 mol/L, 2 mL of copper chloride solution with a concentration of 0.01 mol/L and 80 μL of indium trichloride solution with a concentration of 1 mol/L were added successively to step (1), and the mixed solution was stirred for the reaction for 5 min; [0053] (3) 124 μL of sodium sulfide solution with a concentration of 1 mol/L was added to step (2), and the mixed solution was heated to reflux at 95° C. for 45 min; and [0054] (4) 4 mL of zinc sulfide solution was added to step (3), the mixed solution was refluxed at 95° C. for 40 min to obtain the nanomaterial, and the nanomaterial was stored at 4° C.

[0055] The zinc sulfide solution was obtained from reaction between zinc acetate with a concentration of 0.04 mol/L and thiourea with a concentration of 0.04 mol/L, and the pH value was adjusted to 5.7-6.3. Then the CuInS.sub.2/ZnS nanomaterial was obtained.

[0056] The fluorescence spectrum and UV-vis absorption spectrum of the CuInS.sub.2/ZnS nanomaterial obtained are as shown in FIG. 1, wherein the solid line is a fluorescence spectrum curve, and the dotted line is a UV-vis spectrum curve. FIG. 1 shows that an ultraviolet absorption characteristic peak of the CuInS.sub.2/ZnS nanomaterial is at 500-540 nm, a fluorescence wavelength is at 650-680 nm, the Stokes shift is large, which is consistent with the characteristics of group I-III-VI quantum dots.

[0057] The XRD pattern of the CuInS.sub.2/ZnS nanomaterial is as shown in FIG. 4, the XPS pattern is as shown in FIG. 5.

[0058] An triggering solution-1 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 10 mL of deionized water, 10 μL of N.sub.2H.sub.4.H.sub.2O was added, and the pH value was adjusted to 7 with HCl.

[0059] 300 μL of CuInS.sub.2/ZnS nanomaterial was taken, placed in a centrifuge tube, centrifugally purified with isopropanol three times and rapidly dried by an air blower to remove isopropanol, the precipitate was dissolved in 30 μL of deionized water, the solution was taken out and placed in a sample cell, 300 μL of triggering solution-1 was rapidly injected, and a CL signal was collected.

[0060] The CL spectrum of the CuInS.sub.2/ZnS nanomaterial and the triggering solution-1 is as shown in FIG. 2. It can be known from FIG. 2 that the CL characteristic peak is at 780-820 nm.

[0061] The CL intensity curve of the CuInS.sub.2/ZnS nanomaterial and the triggering solution-1 is as shown in FIG. 3. It can be known from FIG. 3 that the CL intensity of the CL liquid composition containing 1 μmol of CuInS.sub.2/ZnS nanomaterial is 600-700, and the CL time is above 50 s.

Example 1

[0062] The preparation steps of the CuInS.sub.2/ZnS nanomaterial are the same as that in comparative example 1.

[0063] An triggering solution-2 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 8.5 mL of deionized water, 11.8 μL of N.sub.2H.sub.4.H.sub.2O was added, the pH value was adjusted to 7 with HCl, and 1.5 mL of H.sub.2O.sub.2 was added.

[0064] 1 μmol of CuInS.sub.2/ZnS nanomaterial was taken, placed in a centrifuge tube, centrifugally purified with isopropanol three times and rapidly dried by an air blower to remove isopropanol, the precipitate was dissolved in 30 μL of deionized water, the solution was taken out and placed in a sample cell, 300 μL of triggering solution-2 was rapidly injected, and a CL signal was collected.

Example 2

[0065] The steps are the same as those in example 1, and the difference lies in the triggering solution:

[0066] An triggering solution-3 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 8.5 mL of deionized water, 5.9 μL of N.sub.2H.sub.4.H.sub.2O was added, the pH value was adjusted to 7 with HCl, and 1.5 mL of H.sub.2O.sub.2 was added.

[0067] The CL spectrum of the CuInS.sub.2/ZnS nanomaterial and the triggering solution-2 in this example is as shown in FIG. 6. It can be known from FIG. 6 that the CL radiation wavelength of the CL liquid composition is in a near-infrared region, i.e., 750-790 nm.

[0068] The CL intensity curve of the CuInS.sub.2/ZnS nanomaterial and the triggering solution-2 in this embodiment is as shown in FIG. 7. It can be known from FIG. 7 that the CL intensity of the CL liquid composition containing 1 μmol of CuInS.sub.2/ZnS nanomaterial is above 500 k, which is more than 800 times as much as that of a liquid composition without H.sub.2O.sub.2, the CL time is 2-5 s, and the CL liquid composition belongs to a flash-type luminescence liquid composition.

Example 3

[0069] The steps are the same as those in example 1, and the difference lies in the triggering solution:

[0070] An triggering solution-4 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 8.5 mL of deionized water, 17.7 μL of N.sub.2H.sub.4.H.sub.2O was added, the pH value was adjusted to 7 with HCl, and 1.5 mL of H.sub.2O.sub.2 was added.

Example 4

[0071] The steps are the same as those in example 1, and the difference lies in the triggering solution:

[0072] An triggering solution-5 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 8.5 mL of deionized water, 23.6 μL of N.sub.2H.sub.4.H.sub.2O was added, the pH value was adjusted to 7 with HCl, and 1.5 mL of H.sub.2O.sub.2 was added.

Example 5

[0073] The steps are the same as those in example 1, and the difference lies in the triggering solution:

[0074] An triggering solution-6 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 8.5 mL of deionized water, 35.4 μL of N.sub.2H.sub.4.H.sub.2O was added, the pH value was adjusted to 7 with HCl, and 1.5 mL of H.sub.2O.sub.2 was added.

Example 6

[0075] The steps are the same as those in example 1, and the difference lies in the triggering solution:

[0076] An triggering solution-7 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 9.985 mL of deionized water, 11.8 μL of N.sub.2H.sub.4.H.sub.2O was added, the pH value was adjusted to 7 with HCl, and 0.015 mL of H.sub.2O.sub.2 was added.

Example 7

[0077] The steps are the same as those in example 1, and the difference lies in the triggering solution:

[0078] An triggering solution-8 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 9.85 mL of deionized water, 10.2 μL of N.sub.2H.sub.4.H.sub.2O was added, the pH value was adjusted to 7 with HCl, and 0.15 mL of H.sub.2O.sub.2 was added.

Example 8

[0079] The steps are the same as those in example 1, and the difference lies in the triggering solution:

[0080] An triggering solution-9 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 9.25 mL of deionized water, 10.9 μL of N.sub.2H.sub.4.H.sub.2O was added, the pH value was adjusted to 7 with HCl, and 0.75 mL of H.sub.2O.sub.2 was added.

Example 9

[0081] The steps are the same as those in example 1, and the difference lies in the triggering solution:

[0082] An triggering solution-10 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 7 mL of deionized water, 13.6 μL of N.sub.2H.sub.4.H.sub.2O was added, the pH value was adjusted to 7 with HCl, and 3 mL of H.sub.2O.sub.2 was added.

Example 10

[0083] The steps are the same as those in example 1, and the difference lies in the triggering solution:

[0084] An triggering solution-11 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 8.5 mL of deionized water, 11.8 μL of N.sub.2H.sub.4.H.sub.2O was added, the pH value was adjusted to 6 with HCl, and 1.5 mL of H.sub.2O.sub.2 was added.

Example 11

[0085] The steps are the same as those in example 1, and the difference lies in the triggering solution:

[0086] An triggering solution-12 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 8.5 mL of deionized water, 11.8 μL of N.sub.2H.sub.4.H.sub.2O was added, the pH value was adjusted to 8 with HCl, and 1.5 mL of H.sub.2O.sub.2 was added.

Example 12

[0087] The steps are the same as those in example 1, and the difference lies in the triggering solution:

[0088] An triggering solution-13 was prepared by the following specific steps: 0.1211 g of Tris was weighed and dissolved in 8.5 mL of deionized water, 11.8 μL of N.sub.2H.sub.4.H.sub.2O was added, the pH value was adjusted to 9 with HCl, and 1.5 mL of H.sub.2O.sub.2 was added.

Test Example 1

[0089] A comparison diagram of the CL intensities generated by the CuInS.sub.2/ZnS nanomaterial and corresponding triggering solutions prepared in examples 1, 2, 3, 4 and 5 is as shown in FIG. 8. It can be known from FIG. 9 that when a concentration of N.sub.2H.sub.4.H.sub.2O in the triggering solution is 10-20 mmol/L under the same conditions, the CL intensity is high, which is above 530 k.

Test Example 2

[0090] A comparison diagram of the CL intensities generated by the CuInS.sub.2/ZnS nanomaterial and corresponding triggering solutions prepared in examples 1, 6, 7, 8 and 9 is as shown in FIG. 9. It can be known from FIG. 10 that when a concentration of H.sub.2O.sub.2 in the triggering solution is 1-2 mol/L under the same conditions, the CL intensity is high, which is above 530 k.

Test Example 3

[0091] A comparison diagram of the CL intensities generated by the CuInS.sub.2/ZnS nanomaterial and corresponding triggering solutions prepared in examples 1, 10, 11 and 12 is as shown in FIG. 10. It can be known from FIG. 11 that when the pH value of the triggering solution is 7-8 under the same conditions, the CL intensity is high, which is above 450 k.