CN102721681B

CN102721681B - Carbon dioxide chemical fluorescent sensor material on basis of amidine/guanidine group and preparation detection method thereof

Info

Publication number: CN102721681B
Application number: CN201210180027.4A
Authority: CN
Inventors: 王耀; 田彤; 江雷
Original assignee: Beihang University
Current assignee: Beihang University
Priority date: 2012-06-01
Filing date: 2012-06-01
Publication date: 2014-09-17
Anticipated expiration: 2032-06-01
Also published as: CN102721681A

Abstract

The invention discloses a carbon dioxide chemical fluorescent sensor material on the basis of an amidine/guanidine group and a preparation detection method thereof. The chemical fluorescent sensor material consists of a fluorescent substance and a matrix substance; the matrix substance is formed by a liquid organism or a liquid organic mixture comprising the amidine group and/or the guanidine group and a liquid organism or a liquid organic mixture comprising a hydroxyl group and/or an amidogen group, or the matrix substance is a liquid organism comprising the amidine group and/or the guanidine group and the hydroxyl group and/or the amidogen group; the ratio of amounts of substances of the amidine group and/or the guanidine group to the hydroxyl group and/or the amidogen group in the matrix substance meets 1:10 to 10:1; and the chemical fluorescent sensor material comprises 0.5mg/mL to 4mg/mL of fluorescent substance. The raw materials for preparing the chemical fluorescent sensor material are simple, convenient and cheap; the chemical fluorescent sensor material is environmental-friendly; in the using process of the chemical fluorescent sensor material, other residual energy cannot be consumed; and the chemical fluorescent sensor material has simple and convenient testing process and a visual and visible result.

Description

A kind of carbon dioxide chemistry fluorescent optical sensor material and preparation detection method thereof based on amidine/guanidine radicals

Technical field

The invention belongs to Intelligent Measurement Material Field, particularly a kind of carbon dioxide chemistry fluorescent optical sensor material and preparation detection method thereof based on amidine/guanidine radicals.

Background technology

Stimuli responsive material is the one in intellectual material, has people also referred to as environment-responsive material, it be a class under environmental stimuli, can there is the material of respective change in some physics of self or chemical property.Environmental stimuli comprises light, heat, acidity, solvent, ionic strength, Electric and magnetic fields etc.In the time that these stimulus signals occur, material will be made response under environmental stimuli, i.e. himself character, as phase, shape, surface energy, reaction rate, viscosity, film infiltration rate or recognition performance, surface wettability etc. can change thereupon.And above everything, all to come from stimuli responsive molecule under environmental stimuli, molecular structure changes, and has directly caused the variation of molecule at aspects such as amphipathic, dissolubility, molecular conformations, thereby has caused the physicochemical property of material itself to have greatly changed.That is to say, environmental stimuli impels material molecule or micromechanism that predetermined response occurs, thereby makes its specific macro property that corresponding variation occur thereupon.

Along with developing rapidly of modern industry, a large amount of natural burned and consumption containing carbon resource, makes unprecedented CO ₂be discharged in atmosphere, cause greenhouse effect constantly to aggravate.CO ₂as causing one of principal element of greenhouse effect, reducing its discharge is the task of top priority, has caused the extensive concern of global all circles, simultaneously CO ₂sensor is more and more subject to people's attention, for example, in fields such as occupational health, publilc health and social welfares.We need to detect CO in the environment such as mine, sewer, well, tunnel and space capsule ₂the content of gas, because too high CO ₂concentration can be brought great threat to people's life security.Volcanic gas generally comprises the CO of 10～40% concentration ₂, therefore detect the CO in the gas that volcano, hot spring, seabed chimney etc. discharge ₂concentration can help our look-ahead volcanic explosion, earthquake and tsunami.Many anthropogenic discharges' gas is such as vehicle exhaust, industrial gaseous waste etc. contain a large amount of CO equally ₂, in much artificial gas (flue gas, biogas etc.), can sneak into the carbon dioxide of high concentration, sometimes even can be up to 50%.Therefore realize the quantitative test to carbon dioxide content, safeguarding human life's property safety, ensure the safety in production in industrial process, and be significant above controlling greenhouse gas emission.

Galvanochemistry (EC) and infrared spectrum (IR) method are generally used for carbon dioxide and detect.EC sensor is usually operated at high temperature (300～800 ° of C), and this not only can consume a large amount of energy, and is not suitable for existing the place of inflammable explosive article.Simultaneously infrared sensor, not only bulky but also fake expensively, the interference of CO gas is also a stubborn problem simultaneously because CO gas usually with CO ₂mix, and its infrared absorption spectrum and CO ₂similar, this can cause very large interference to detecting.In addition no matter be EC or infrared spectrum CO, ₂detecting device is all vulnerable to the interference of water.Gas chromatograph-mass spectrometer (GCMS) also can be used for detecting CO ₂but this process is expensive and consuming time.Field effect transistor based on carbon nano-tube and inorganic semiconductor also have CO ₂the application prospect detecting, but need complicated equipment and trace routine.

Summary of the invention

For problems of the prior art, the invention provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals and preparation method thereof, the environmental facies of this chemiluminescence sensor material own are to close friend, and in use can not consume other unnecessary energy.Prepare this chemiluminescence sensor material starting material used easy, cheap, major part can have been bought from the market, or can be synthetic by simple method, with low cost.

The present invention proposes a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, described fluorescent material is the luminous quasi-molecule of aggregation inducing, the serve as reasons liquid state organics that contains amidino groups and/or guanidine radicals or liquid organic mixture, the liquid state organics that contains hydroxyl and/or amido or liquid organic mixture of described base matter forms, or is the liquid state organics containing amidino groups and/or guanidine radicals, hydroxyl and/or amido; And in base matter, the ratio of the amount of substance of amidino groups and/or guanidine radicals, hydroxyl and/or amido meets 1:10～10:1; The addition of fluorescent material meets the fluorescent material that contains 0.5mg～4mg/mL in overall chemiluminescence sensor material.

The present invention also proposes a kind of preparation detection method of the carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, specifically comprises following step:

Step 1: prepare base matter:

Described base matter is by the liquid state organics that contains amidino groups and/or guanidine radicals or liquid organic mixture, the liquid state organics that contains hydroxyl and/or amido or liquid organic mixture form, base matter also can be for containing amidino groups and/or guanidine radicals, the liquid state organics of hydroxyl and/or amido, when base matter the serve as reasons liquid state organics or the liquid organic mixture that contain amidino groups and/or guanidine radicals, when the liquid state organics that contains hydroxyl and/or amido or liquid organic mixture form, according to amidino groups and/or guanidine radicals, the ratio that the ratio of the amount of substance of hydroxyl and/or amido is 1:10～10:1 is prepared base matter, when base matter is for containing amidino groups and/or guanidine radicals, when the liquid state organics of hydroxyl and/or amido, select to meet amidino groups and/or guanidine radicals on synthetic strand, the liquid state organics that the ratio of the amount of substance of hydroxyl and/or amido is 1:10～10:1,

Step 2: add analytically pure fluorescent material in the base matter preparing, the addition of fluorescent material meets the fluorescent material that contains 0.5mg～4mg/mL in overall chemiluminescence sensor material, add after fluorescent material, mix, and sample is carried out to ultrasonic processing;

Step 3: under normal temperature, be 99.999% CO to constantly passing into purity in the chemiluminescence sensor material making ₂gas, the flow that passes into gas is 0.1～5mL/s, measures its fluorescence emission spectrum under fluorescence emission spectrometer, obtains CO ₂pass into the typical curve of volume-maximum fluorescence spectral intensity, this curve is quantitatively detected to CO in mixed gas as typical curve ₂volume fraction;

Step 4: under normal temperature, pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow that passes into gas is 0.1～5mL/s, measures its fluorescence emission spectrum under fluorescence emission spectrometer, records this and passes into the fluorescence emission spectral intensity under gas volume;

Step 5: by the CO obtaining in the fluorescence emission spectral intensity of measuring under fluorescence emission spectrometer in step 4 and step 3 ₂the typical curve that passes into volume-maximum fluorescence spectral intensity is compared, and draws CO in the mixed gas passing in step 4 ₂the volume fraction of gas.

The invention has the advantages that:

(1) the invention provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals and preparation method thereof, prepare this chemiluminescence sensor material starting material used easy, cheap, major part can have been bought from the market, or can be synthetic by simple method, with low cost.

(2) the invention provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals and preparation method thereof, the environmental facies of this chemiluminescence sensor material own are to close friend, and in use can not consume other unnecessary energy.

(3) the invention provides a kind of CO based on amidine/guanidine radicals ₂chemiluminescence sensor material and preparation method thereof, can overcome CO in the past ₂fluorescent optical sensor costliness, complexity, be subject to the impact of CO gas and water, this material can not be subject to the impact of CO gas, and to the larger tolerance of having of water.

(4) the invention provides a kind of CO based on amidine/guanidine radicals ₂chemiluminescence sensor material and preparation method thereof, the simple testing process of this fluorescent optical sensor material, and visual result.

(5) the invention provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals and preparation method thereof, this chemiluminescence sensor test CO ₂time simple to operate, quick, measuring method is quantitative, and anti-interference (as the interference of anti-CO and water), test phenomenon be macroscopic, simplify greatly CO ₂testing process, applied range.

Brief description of the drawings

Fig. 1-A～Fig. 1-F: the molecular structural formula of fluorescent material in the present invention;

Fig. 2-A～Fig. 2-I: the molecular structural formula that contains the liquid state organics of guanidine radicals in the present invention;

Fig. 3-A～Fig. 3-B: the molecular structural formula that contains the liquid state organics of amidino groups and hydroxyl in the present invention;

Fig. 3-C: the molecular structural formula that contains the liquid state organics of guanidine radicals and hydroxyl in the present invention;

Fig. 4-A: the synthetic route chart that contains the liquid state organics of amidino groups and hydroxyl in Fig. 3-A;

Fig. 4-B: the synthetic route chart that contains the liquid state organics of amidino groups and hydroxyl in Fig. 3-B;

Fig. 4-C: the synthetic route chart that contains the liquid state organics of guanidine radicals and hydroxyl in Fig. 3-C;

In Fig. 5: embodiment 1, the carbon dioxide chemistry fluorescent optical sensor material of preparation is at different CO ₂fluorescence emission spectrum under intake;

In Fig. 6: embodiment 1, the carbon dioxide chemistry fluorescent optical sensor material of preparation is at different CO ₂the maximum fluorescence emission spectral intensity of correspondence under intake;

In Fig. 7: embodiment 1, the carbon dioxide chemistry fluorescent optical sensor material of preparation is passing into CO ₂front photo in kind;

In Fig. 8: embodiment 1, the carbon dioxide chemistry fluorescent optical sensor material of preparation is passing into CO ₂after photo in kind.

Embodiment

Below in conjunction with drawings and Examples, the present invention is described in further detail.

The invention provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, described fluorescent material is the luminous quasi-molecule of aggregation inducing (AIE), as shown in Fig. 1-A～Fig. 1-F, be preferably tetraphenyl ethene (TPE), 1, 1, 2, 3, 4, 5-six benzene-1 hydrogen-Siloles, 9-diphenyl methylene-4, 9-dihydro-1 hydrogen-fluorenes or 1, 2, 3, 4-tetraphenyl-1, 3-cyclo-octadiene etc., the formation of described base matter is divided into following several situation: (1) is by the liquid state organics that contains amidino groups and/or guanidine radicals or liquid organic mixture, the liquid state organics that contains hydroxyl and/or amido or liquid organic mixture form, (2) base matter can be also the liquid state organics containing amidino groups and/or guanidine radicals, hydroxyl and/or amine amido.

The ratio of the amidino groups in described chemiluminescence sensor material and/or the amount of substance of guanidine radicals, hydroxyl and/or amido meets 1:10～10:1.The addition of fluorescent material (analyzing pure) meets the fluorescent material that contains 0.5mg～4mg/mL in overall chemiluminescence sensor material.Owing to being necessary for liquid restriction under amidino groups and guanidine radicals synthetic method and synthetic rear normal temperature, so for liquefied mixture, the liquid state organics that simultaneously contains amidino groups and guanidine radicals is extremely difficult to realize, therefore the liquid state organics that contains amidino groups and/or guanidine radicals described in the present invention or liquid organic mixture only comprise the liquid state organics of amidino groups, the liquid state organics that contains guanidine radicals, three kinds of situations of organic mixture that the liquid state organics that contains amidino groups and the liquid state organics that contains guanidine radicals form, when select the liquid state organics that contains amidino groups and the liquid state organics that contains guanidine radicals to form organic mixture time, the summation of the amount of substance of amidino groups and guanidine radicals meets the proportion requirement of 1:10～10:1, amidino groups and guanidine radicals are each other without concrete proportion requirement.The described liquid state organics that contains hydroxyl and/or amido or liquid organic mixture specifically comprise following several situation: the organic mixture that the liquid state organics (liquid alcohols) that contains hydroxyl, the liquid state organics that contains amido, the liquid state organics that contains amido and hydroxyl, the liquid state organics (liquid alcohols) that contains hydroxyl and the liquid state organics that contains amido form.In the time of organic mixture both of these case that the liquid state organics of selecting to contain amido and hydroxyl, the liquid state organics (liquid alcohols) that contains hydroxyl and the liquid state organics that contains amido form, both amount of substances of hydroxyl and/or amido also only need meet overall ratio and require, be the proportion requirement that the summation of the amount of substance of institute's hydroxyl and two kinds of groups of amido meets 1:10～10:1, hydroxyl and amido are each other without concrete proportion requirement.

The described liquid state organics that contains hydroxyl is the one in alcohols material, specifically be preferably methyl alcohol, ethanol, n-propanol, normal butyl alcohol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, isopropyl alcohol, isobutyl alcohol, isoamylol, secondary butanols, tertiary butyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, phenmethylol, benzhydrol, triphenylcarbinol, ethylene glycol, 1, ammediol or 1, under the normal temperature such as 2,3-glycerine, be liquid alcohol.The described liquid state organics that contains amido is for meeting R-NH ₂all kinds of normal temperature under be the one in liquid aminated compounds.The potpourri that the liquid state organics that the organic mixture that the described liquid state organics that contains hydroxyl liquid state organics and contain amido forms is specially the above-mentioned liquid state organics that contains hydroxyl and contains amido forms, blending ratio each other does not limit.Containing the liquid state organics that hydroxyl and amido form is amine alcohol compound, is preferably that when 5-amido-1-amylalcohol is representative, to contain under amido and hydroxyl and normal temperature be liquid amine alcohol compound.The liquid state organics that contains amidino groups is the organism that contains amidino groups group on strand, as shown in Fig. 2-A～Fig. 2-I.The liquid state organics that contains guanidine radicals is the organism that contains guanidino group on strand, the organic mixture that the liquid state organics that contains amidino groups and the liquid state organics that contains guanidine radicals form is the above-mentioned organism that contains amidino groups group and the organic potpourri that contains guanidino group, and the proportional range that is mixed with each other does not limit.

Described base matter is while containing the liquid state organics of amidino groups and/or guanidine radicals, hydroxyl and/or amido, specifically be divided into containing the liquid state organics of amidino groups and hydroxyl, containing two kinds of situations of liquid state organics of guanidine radicals and hydroxyl, containing the molecular structural formula of the liquid state organics of amidino groups and hydroxyl as shown in Fig. 3-A and Fig. 3-B, wherein the building-up process of the liquid state organics containing amidino groups and hydroxyl shown in Fig. 3-A is as shown in Fig. 4-A, and wherein the building-up process of the liquid state organics containing amidino groups and hydroxyl shown in Fig. 3-B is as shown in Fig. 4-B; Containing the molecular structural formula of the liquid state organics of guanidine radicals and hydroxyl, as shown in Fig. 3-C, its building-up process is as shown in Fig. 4-C.Because during for the synthetic liquid state organics containing amidino groups and/or guanidine radicals, hydroxyl and/or amido, be only easier to realize at synthetic above-mentioned two situations time ratio, and be difficult to realization for the liquid state organics of other several situations synthetic.

Described amidino groups structural formula is designated as A, and described guanidine radicals structural formula is designated as B;

Described structural formula A is expressed as

Described structural formula B is expressed as

In the chemiluminescence sensor material proposing in the present invention, pass into CO ₂after gas, all can there is significant variation in the character such as the viscosity of the solution of this chemiluminescence sensor material, polarity, dissolubility, by low viscous nonionic liquid, there is themopositive reaction and generate full-bodied ionic liquid in solution, and can be worth to detect CO by the change that characterizes viscosity ₂content.

The preparation detection method of a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals that the present invention proposes, specifically comprises following step:

Step 1: prepare base matter:

Described base matter is made up of the liquid state organics that contains amidino groups and/or guanidine radicals or liquid organic mixture, the liquid state organics that contains hydroxyl and/or amido or liquid organic mixture, and base matter can be also the liquid state organics containing amidino groups and/or guanidine radicals, hydroxyl and/or amido.When base matter is served as reasons the liquid state organics that contains amidino groups and/or guanidine radicals or liquid organic mixture, the liquid state organics that contains hydroxyl and/or amido or liquid organic mixture while forming, the ratio that is 1:10～10:1 according to the ratio of the amount of substance of amidino groups and/or guanidine radicals, hydroxyl and/or amido is prepared base matter, and concrete proportioning when practical application will be chosen best proportioning according to test.When base matter is while containing the liquid state organics of amidino groups and/or guanidine radicals, hydroxyl and/or amido, because this type organic individual molecule contains amidino groups and/or guanidine radicals, hydroxyl and/or amido simultaneously, the liquid state organics that the ratio of selecting to meet on synthetic strand the amount of substance of amidino groups and/or guanidine radicals, hydroxyl and/or amido is 1:10～10:1.

Step 2: add analytically pure fluorescent material in the base matter preparing, this fluorescent material is the luminous quasi-molecule of aggregation inducing (AIE), the addition of fluorescent material meets the fluorescent material that contains 0.5mg/mL～4mg/mL in overall chemiluminescence sensor material, add after fluorescent material, mix, and sample is carried out to ultrasonic processing more than 10min, fluorescent material is better dissolved.

Step 3: under normal temperature (20～25 DEG C), the CO that is 99.999% to the purity that passes into different volumes (amount) in the chemiluminescence sensor material making ₂gas, passing into flow velocity is 0.1～5mL/s, passes into after gas 5～10s, leaves standstill 3min, measures its fluorescence emission spectrum, and then continue to pass into CO under fluorescence emission spectrometer ₂after gas 5～10s, then leave standstill 3min, measure its fluorescence emission spectrum under fluorescence emission spectrometer, order is carried out successively, finally, along with passing into the prolongation (as pass into the gas cumulative time be 5～600s) of time, obtains passing into the CO under flow at gas with various ₂pass into the typical curve of volume-maximum fluorescence emission spectral intensity, this curve is quantitatively detected to CO in mixed gas as typical curve ₂volume fraction.

Step 4: under normal temperature (20～25 DEG C), pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow that passes into gas is 0.1～5mL/s, consistent with the gas flow in step 3, passes into (after 5～600s) after mixed gas certain hour, records this and pass into the fluorescence emission spectral intensity of chemiluminescence sensor material under the time.

Step 5: by the CO obtaining in the fluorescence emission spectral intensity of measuring under fluorescence emission spectrometer in step 4 and step 3 ₂the typical curve that passes into volume-maximum fluorescence emission spectral intensity is compared, and draws CO in the mixed gas passing in step 4 ₂the volume fraction of gas.

embodiment 1

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, specifically selects tetraphenyl ethene, and molecular structural formula is as shown in Fig. 1-A.Base matter is by liquid amine alcohol compound 5-amido-1 amylalcohol, 1 that contains amido and hydroxyl, and 8-diaza-bicyclo [5.4.0] 11-7-alkene (DBU) forms, and the molecular structural formula of 1,8-diaza-bicyclo [5.4.0], 11-7-alkene (DBU) is as shown in Fig. 2-A.Wherein in the summation of the amount of substance of amido and two kinds of groups of hydroxyl and DBU, the ratio of the amount of substance of amidino groups is 1:1, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 3mg/mL.Selected DBU molecule is very special, with the mixed solution of alcohols or amine in, in the situation that atomic water gaging exists, just can generate a large amount of precipitations with water, thus the naked-eye observation of impact to fluorescence, and base matter is selected 5-amido-1 amylalcohol, in the time having water to exist, the white precipitate that water and DBU molecule generate has good dissolubility in this ion liquid system, thereby can not generate a large amount of white precipitates, can not exert an influence to the observation of fluorescence.

The preparation detection method of a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals that the present embodiment proposes, specifically comprises following step:

Step 1: prepare base matter:

Analytically pure 5-amido-1 amylalcohol is mixed with analytically pure DBU, and in the amount of substance summation that meets amido and hydroxyl in the amylalcohol of 5-amido-1 and DBU, the ratio of the amount of substance of amidino groups is 1:1.

Step 2: add analytically pure tetraphenyl ethene in the base matter preparing, addition meets the tetraphenyl ethene that contains 3mg/mL in overall chemiluminescence sensor material, after adding tetraphenyl ethene, mix, then carry out ultrasonic processing more than 10min, tetraphenyl ethene is better dissolved.

Step 3: under normal temperature (20 DEG C), the CO that is 99.999% to the purity that passes into different volumes (amount) in the chemiluminescence sensor material making ₂gas, passing into flow velocity is 4mL/s, passes into after gas 5s, leaves standstill 3min, measures its fluorescence emission spectrum, and then continue to pass into CO under fluorescence emission spectrometer ₂after gas 5s, then leave standstill 3min, measure its fluorescence emission spectrum under fluorescence emission spectrometer, order is carried out successively, and final is 400s along with passing into the prolongation of time until pass into gas time cumulation, obtains passing into the CO under gas flow at this ₂pass into the typical curve of volume-maximum fluorescence spectral intensity, this curve is quantitatively detected to CO in mixed gas as typical curve ₂content.

Step 4: under normal temperature (20 DEG C), pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow that passes into gas is 4mL/s, after the time that passes into mixed gas is 400s, records this and pass into the fluorescence emission spectral intensity of chemiluminescence sensor material under the time.

In the present embodiment, passing into CO ₂before gas, the pattern of this carbon dioxide chemistry fluorescent optical sensor material as shown in Figure 7, is passing into CO ₂after gas, this fluorescent optical sensor material pattern as shown in Figure 8.In this embodiment, the fluorescence emission spectral intensity of measuring under fluorescence emission spectrometer in step 4 is 120, by itself and CO ₂the typical curve that passes into volume-maximum fluorescence spectral intensity is compared, the pure CO in known this gas to be measured ₂gas volume is 1160mL, so can obtain CO in the mixed gas passing in step 4 ₂the volume fraction of gas is 72.5%.

embodiment 2(the liquid state organics that contains amidino groups mixes with alcohols liquid state organics)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, selection analysis pure 1,1,2,3,4,5-, six benzene-1 hydrogen-Siloles, molecular structural formula is as shown in Fig. 1-B.Base matter is by analytically pure n-propanol, analytically pure composition, structural representation as shown in Fig. 2-B.Wherein in n-propanol the amount of substance of hydroxyl with containing amidino groups molecule in the ratio of amidino groups amount of substance be 1:1, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 4mg/mL.

Step 1: prepare base matter:

By analytically pure n-propanol and analytically pure amidino compounds mix, and meet amount of substance and the amidino compounds of hydroxyl in n-propanol the ratio of the amount of substance of middle amidino groups is 1:1.

Step 2: add analytically pure tetraphenyl ethene in the base matter preparing, addition meets the tetraphenyl ethene that contains 4mg/mL in overall chemiluminescence sensor material, add after tetraphenyl ethene, mix, and sample is carried out to ultrasonic processing more than 10min, fluorescent material is better dissolved.

Step 3: under normal temperature (20 DEG C), the CO that is 99.999% to the purity that passes into different volumes (amount) in the chemiluminescence sensor material making ₂gas, passing into flow velocity is 2mL/s, passes into after gas 10s, leaves standstill 3min, measures its fluorescence emission spectrum, and then continue to pass into CO under fluorescence emission spectrometer ₂after gas 10s, then leave standstill 3min, measure its fluorescence emission spectrum under fluorescence emission spectrometer, order is carried out successively, and final is 400s along with passing into the prolongation of time until pass into gas time cumulation, obtains passing into the CO under gas flow at this ₂pass into the typical curve of volume-maximum fluorescence spectral intensity, this curve is quantitatively detected to CO in mixed gas as typical curve ₂content.

Step 4: under normal temperature (20 DEG C), pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow velocity that passes into gas is 2mL/s, after the time that passes into mixed gas is 400s, records this and pass into the fluorescent emission intensity of chemiluminescence sensor material under the time.

embodiment 3(amidino compounds mixes with amine)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, be specially analytically pure 1,2,3,4-tetraphenyl-1,3-cyclo-octadiene, molecular structural formula is as shown in Fig. 1-F.Base matter is by analytically pure n-propylamine, analytically pure shown in composition, molecular structural formula as shown in Fig. 2-B.Wherein the summation of the amount of substance of amido and two kinds of groups of hydroxyl with containing amidino groups molecule in the ratio of amidino groups amount of substance be 1:1, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 2mg/mL.

Step 1: prepare base matter:

Analytically pure n-propylamine is mixed with analytically pure amidino compounds, and the ratio that meets the amount of substance of amidino groups in the amount of substance of amido in n-propylamine and amidino compounds is 1:1.

Step 2: add analytically pure tetraphenyl ethene in the base matter preparing, addition meets the tetraphenyl ethene that contains 2mg/mL in overall chemiluminescence sensor material, add after tetraphenyl ethene, mix, and sample is carried out to ultrasonic processing more than 10min, fluorescent material is better dissolved.

Step 3: under normal temperature (20 DEG C), the CO that is 99.999% to the purity that passes into different volumes (amount) in the chemiluminescence sensor material making ₂gas, passing into flow velocity is 0.1mL/s, passes into after gas 5s, leaves standstill 3min, measures its fluorescence emission spectrum, and then continue to pass into CO under fluorescence emission spectrometer ₂after gas 5s, then leave standstill 3min, measure its fluorescence emission spectrum under fluorescence emission spectrometer, order is carried out successively, and final is 600s along with passing into the prolongation of time until pass into gas time cumulation, obtains passing into the CO under gas flow at this ₂pass into the typical curve of volume-maximum fluorescence spectral intensity, this curve is quantitatively detected to CO in mixed gas as typical curve ₂content.

Step 4: under normal temperature (25 DEG C), pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow that passes into gas is 1mL/s, after the time that passes into mixed gas is 600s, records this and pass into the fluorescent emission intensity of chemiluminescence sensor material under the time.

embodiment 4(amidino compounds mixes with amine alcohols)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, be specially 9-diphenyl methylene-4,9-dihydro-1 hydrogen-fluorenes, molecular structural formula is as shown in Fig. 1-C.Base matter is by analytically pure 5-amido-1 amylalcohol, analytically pure shown in composition (Fig. 2-B).The wherein summation of the amount of substance of amido and two kinds of groups of hydroxyl and the liquid state organics that contains amidino groups in the amylalcohol of 5-amido-1 the ratio of the amount of substance of middle amidino groups is 1:1, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 3mg/mL.

Step 1: prepare base matter:

Analytically pure 5-amido-1 amylalcohol is mixed with analytically pure amidino compounds (Fig. 2-B), and to meet the ratio that amido in the amylalcohol of 5-amido-1 adds the amount of substance of amidino groups in the amount of substance of hydroxyl and amidino compounds be 1:1.

Step 2: add analytically pure tetraphenyl ethene in the base matter preparing, addition meets the tetraphenyl ethene that contains 3mg/mL in overall chemiluminescence sensor material, add after tetraphenyl ethene, mix, and sample is carried out to ultrasonic processing more than 10min, fluorescent material is better dissolved.

Step 3: under normal temperature (20 DEG C), the CO that is 99.999% to the purity that passes into different volumes (amount) in the chemiluminescence sensor material making ₂gas, passing into flow velocity is 3mL/s, passes into after gas 5s, leaves standstill 3min, measures its fluorescence emission spectrum, and then continue to pass into CO under fluorescence emission spectrometer ₂after gas 5s, then leave standstill 3min, measure its fluorescence emission spectrum under fluorescence emission spectrometer, order is carried out successively, and final is 500s along with passing into the prolongation of time until pass into gas time cumulation, obtains passing into the CO under gas flow at this ₂pass into the typical curve of volume-maximum fluorescence spectral intensity, this curve is quantitatively detected to CO in mixed gas as typical curve ₂content.

Step 4: under normal temperature (20 DEG C), pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow that passes into gas is 3mL/s, after the time that passes into mixed gas is 500s, records this and pass into the fluorescent emission intensity of chemiluminescence sensor material under the time.

embodiment 5(amidino compounds mixes with amine, alcohols)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, is specially analytically pure tetraphenyl ethene, and molecular structural formula is as shown in Fig. 1-A.Base matter is by analytically pure n-propanol, analytically pure n-propylamine, analytically pure shown in composition (Fig. 2-B).The wherein summation of the amount of substance of amido and two kinds of groups of hydroxyl and the liquid state organics that contains amidino groups in n-propanol, n-propylamine potpourri the ratio of the amount of substance of middle amidino groups is 1:1, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 0.5mg/mL.

Step 1: prepare base matter:

By analytically pure n-propanol, analytically pure n-propylamine and the analytically pure liquid state organics containing amidino groups mix, wherein in n-propanol, n-propylamine potpourri, in the summation of the amount of substance of amido and two kinds of groups of hydroxyl and amidino compounds, the ratio of the amount of substance of amidino groups is 1:1.

Step 2: add analytically pure tetraphenyl ethene in the base matter preparing, addition meets the fluorescent material that contains 0.5mg/mL in overall chemiluminescence sensor material, add after fluorescent material, mix, and sample is carried out to ultrasonic processing more than 10min, fluorescent material is better dissolved.

Step 3: under normal temperature (20 DEG C), the CO that is 99.999% to the purity that passes into different volumes (amount) in the chemiluminescence sensor material making ₂gas, passing into flow velocity is 5mL/s, passes into after gas 7s, leaves standstill 3min, measures its fluorescence emission spectrum, and then continue to pass into CO under fluorescence emission spectrometer ₂after gas 7s, then leave standstill 3min, measure its fluorescence emission spectrum under fluorescence emission spectrometer, order is carried out successively, and final is 400s along with passing into the prolongation of time until pass into gas time cumulation, obtains passing into the CO under gas flow at this ₂pass into the typical curve of volume-maximum fluorescence spectral intensity, this curve is quantitatively detected to CO in mixed gas as typical curve ₂content.

Step 4: under normal temperature (20 DEG C), pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow that passes into gas is 5mL/s, after the time that passes into mixed gas is 400s, records this and pass into the fluorescent emission intensity of chemiluminescence sensor material under the time.

embodiment 6(guanidine compound mixes with amine)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, is specially analytically pure tetraphenyl ethene, and molecular structural formula is as shown in Fig. 1-A.Base matter is by analytically pure n-propylamine, analytically pure shown in composition, molecular structural formula as shown in Fig. 2-E.Wherein in n-propylamine the amount of substance of amido and with the ratio of the amount of substance containing guanidine radicals in the liquid state organics of guanidine radicals be 1:1, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 4mg/mL.

Step 1: prepare base matter:

Analytically pure n-propylamine is mixed with analytically pure guanidine compound, and meet the amount of substance of amido in n-propylamine and with guanidine compound in the ratio of amount of substance of guanidine radicals be 1:1.

Step 4: under normal temperature (20 DEG C), pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow that passes into gas is 4mL/s, after the time that passes into mixed gas is 400s, records this and pass into the fluorescent emission intensity of chemiluminescence sensor material under the time.

embodiment 7(guanidine compound mixes with alcohols)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, is specially analytically pure tetraphenyl ethene, and molecular structural formula is as shown in Fig. 1-A.Base matter is by analytically pure n-propanol, analytically pure composition shown in (Fig. 2-E).The wherein amount of hydroxylated material and the liquid state organics that contains guanidine radicals in n-propanol the ratio of the amount of substance of middle guanidine radicals is 1:2, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 1mg/mL.

Step 1: prepare base matter:

By analytically pure n-propanol and analytically pure mix, and meet the amount of hydroxylated material in n-propanol and contain guanidine radicals liquid state organics the ratio of the amount of substance of middle guanidine radicals is 1:2.

Step 2: add analytically pure tetraphenyl ethene in the base matter preparing, addition meets the tetraphenyl ethene that contains 1mg/mL in overall chemiluminescence sensor material, add after tetraphenyl ethene, mix, and sample is carried out to ultrasonic processing more than 10min, fluorescent material is better dissolved.

Step 3: under normal temperature (20 DEG C), the CO that is 99.999% to the purity that passes into different volumes (amount) in the chemiluminescence sensor material making ₂gas, passing into flow velocity is 1mL/s, passes into after gas 5s, leaves standstill 3min, measures its fluorescence emission spectrum, and then continue to pass into CO under fluorescence emission spectrometer ₂after gas 5s, then leave standstill 3min, measure its fluorescence emission spectrum under fluorescence emission spectrometer, order is carried out successively, and final is 400s along with passing into the prolongation of time until pass into gas time cumulation, obtains passing into the CO under gas flow at this ₂pass into the typical curve of volume-maximum fluorescence spectral intensity, this curve is quantitatively detected to CO in mixed gas as typical curve ₂content.

Step 4: under normal temperature (20 DEG C), pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow that passes into gas is 1mL/s, after the time that passes into mixed gas is 400s, records this and pass into the fluorescent emission intensity of chemiluminescence sensor material under the time.

embodiment 8(guanidine compound mixes with amine alcohols)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, is specially analytically pure tetraphenyl ethene, and molecular structural formula is as shown in Fig. 1-A.Base matter is by analytically pure 5-amido-1 amylalcohol, analytically pure composition shown in (Fig. 2-E).Wherein in the amylalcohol of 5-amido-1 amount of substance of amido and two kinds of groups of hydroxyl always with the liquid state organics that contains guanidine radicals in the ratio of amount of substance of guanidine radicals be 1:3, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 4mg/mL.

Step 1: prepare base matter:

By analytically pure 5-amido-1 amylalcohol and analytically pure mix, and in the summation that meets the amount of substance of amido and two kinds of groups of hydroxyl in the amylalcohol of 5-amido-1 and guanidine compound, the ratio of the amount of substance of guanidine radicals is 1:3.

Step 2: add analytically pure tetraphenyl ethene in the base matter preparing, addition meets the fluorescent material that contains 4mg/mL in overall chemiluminescence sensor material, add after fluorescent material, mix, and sample is carried out to ultrasonic processing more than 10min, fluorescent material is better dissolved.

Step 3: under normal temperature (20 DEG C), constantly pass into CO in the chemiluminescence sensor material making ₂gas (purity is 99.999%), the flow that passes into gas is 4mL/s, passes into after gas 5s, leaves standstill 3min, measures its fluorescence emission spectrum, and then continue to pass into CO under fluorescence emission spectrometer ₂after gas 5s, then leave standstill 3min, measure its fluorescence emission spectrum under fluorescence emission spectrometer, order is carried out successively, and final is 400s along with passing into the prolongation of time until pass into gas time cumulation, obtains passing into the CO under gas flow at this ₂pass into the typical curve of volume-maximum fluorescence spectral intensity, this curve is quantitatively detected to CO in mixed gas as typical curve ₂content.

Step 4: under normal temperature (20 DEG C), the CO that is 99.999% to the purity that passes into different volumes (amount) in the chemiluminescence sensor material making ₂gas, passing into flow velocity is 4mL/s, after the time that passes into mixed gas is 400s, records this and pass into the fluorescent emission intensity of chemiluminescence sensor material under the time.

embodiment 9(guanidine compound mixes with amine, alcohols)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, is specially tetraphenyl ethene, and molecular structural formula is as shown in Fig. 1-A.Base matter is by analytically pure n-propanol, analytically pure n-propylamine, analytically pure composition shown in (Fig. 2-E).The wherein summation of the amount of substance of amido and two kinds of groups of hydroxyl and the liquid state organics that contains guanidine radicals in n-propanol and n-propylamine in the ratio of guanidine radicals amount of substance be 3:1, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 3mg/mL.

Step 1: prepare base matter:

By analytically pure n-propanol, n-propylamine and analytically pure mix, wherein the summation of the amount of substance of amido and two kinds of groups of hydroxyl and the liquid state organics that contains guanidine radicals in n-propanol, n-propylamine the ratio of the amount of substance of middle guanidine radicals is 3:1.

embodiment 10(amidino compounds, guanidine compound mix with alcohols)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, is specially tetraphenyl ethene, and molecular structural formula is as shown in Fig. 1-A.Base matter is by analytically pure n-propanol, analytically pure (Fig. 2-B), analytically pure composition shown in (Fig. 2-E).Wherein in n-propanol the amount of substance of hydroxyl and with the ratio of middle amidino groups and guanidine radicals amount of substance summation is 1:1, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 3mg/mL.

Step 1: prepare base matter:

By analytically pure n-propanol and analytically pure (Fig. 2-B), mix (Fig. 2-E), and the amount of substance that meets hydroxyl in n-propanol with in potpourri, to add the ratio of the amount of guanidine radicals be 1:1 to amidino groups.

Step 2: add analytically pure tetraphenyl ethene in the base matter preparing, addition meets the tetraphenyl ethene that contains 3mg/mL in overall chemiluminescence sensor material, add after tetraphenyl ethene, mix, and sample is carried out to ultrasonic processing more than 10min, tetraphenyl ethene is better dissolved.

Step 3: under normal temperature (20 DEG C), the CO that is 99.999% to the purity that passes into different volumes (amount) in the chemiluminescence sensor material making ₂gas, passing into flow velocity is 4mL/s, passes into after gas 5s, leaves standstill 3min, measures its fluorescence emission spectrum, and then continue to pass into CO under fluorescence emission spectrometer ₂after gas 5s, then leave standstill 3min, measure its fluorescence emission spectrum under fluorescence emission spectrometer, order is carried out successively, and final is 300s along with passing into the prolongation of time until pass into gas time cumulation, obtains passing into the CO under gas flow at this ₂pass into the typical curve of volume-maximum fluorescence spectral intensity, this curve is quantitatively detected to CO in mixed gas as typical curve ₂content.

Step 4: under normal temperature (20 DEG C), pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow that passes into gas is 4mL/s, after the time that passes into mixed gas is 300s, records this and pass into the fluorescent emission intensity of chemiluminescence sensor material under the time.

embodiment 11(amidino compounds, guanidine compound mix with amine)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, is specially analytically pure tetraphenyl ethene, and molecular structural formula is as shown in Fig. 1-A.Base matter is by analytically pure n-propylamine, analytically pure (Fig. 2-B), analytically pure composition shown in (Fig. 2-E).Wherein in n-propylamine the amount of substance of amido and with the ratio of middle amidino groups and guanidine radicals amount of substance summation is 1:2, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 3mg/mL.

Step 1: prepare base matter:

By analytically pure n-propylamine and analytically pure analytically pure mix, and meet the amount of substance of amido in n-propylamine and with middle amidino groups is 1:2 with the ratio of guanidine radicals amount of substance summation.

Step 2: add analytically pure tetraphenyl ethene in the base matter preparing, addition meets the fluorescent material that contains 3mg/mL in overall chemiluminescence sensor material, add after fluorescent material, mix, and sample is carried out to ultrasonic processing more than 10min, fluorescent material is better dissolved.

embodiment 12(amidino compounds, guanidine compound mix with amine alcohols)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, is specially tetraphenyl ethene, and molecular structural formula is as shown in Fig. 1-A.Base matter by 5-amido-1 amylalcohol, (Fig. 2-B), composition shown in (Fig. 2-E).The ratio that wherein in the amylalcohol of 5-amido-1, in the summation of the amount of substance of amido and two kinds of groups of hydroxyl and amidino compounds, guanidine compound potpourri, amidino groups adds the amount of guanidine radicals is 3:1, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 3mg/mL.

Step 1: prepare base matter:

Analytically pure 5-amido-1 amylalcohol is mixed with analytically pure amidino compounds (Fig. 2-B), guanidine compound (Fig. 2-E), and meet amido in the amylalcohol of 5-amido-1 add the amount of substance of hydroxyl and with amidino compounds, guanidine compound potpourri in the amidino groups ratio that adds guanidine radicals amount of substance be 3:1.

Step 4: under normal temperature (20 DEG C), pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow that passes into gas is after time that 4mL/s passes into mixed gas being 400s, records this and pass into the fluorescent emission intensity of chemiluminescence sensor material under the time.

Step 5: by the CO obtaining in the fluorescence emission spectral intensity of measuring under fluorescence emission spectrometer in step 4 and step 3 ₂the typical curve that passes into volume-maximum fluorescence spectral intensity is compared, and draws CO in the mixed gas passing in step 4 ₂the volume 1,2,3 of gas, 4-tetraphenyl-1,3-cyclo-octadiene mark.

embodiment 13(amidino compounds, guanidine compound mix with amine, alcohols)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, is specially tetraphenyl ethene, and molecular structural formula is as shown in Fig. 1-A.Base matter is by analytically pure n-propanol, analytically pure n-propylamine, analytically pure (Fig. 2-B), analytically pure composition shown in (Fig. 2-E).Wherein in n-propanol and n-propylamine the summation of the amount of substance of contained amido and two kinds of groups of hydroxyl with in the ratio of summation of amount of substance of contained amidino groups and guanidine radicals be 2:1, and the addition of tetraphenyl ethene to meet the volumetric concentration that tetraphenyl ethene accounts for overall sensor material be 3mg/mL.

Step 1: prepare base matter:

By analytically pure n-propanol, n-propylamine mix with analytically pure amidino compounds, guanidine compound, the ratio that wherein in n-propanol, n-propylamine potpourri, in the summation of the amount of substance of amido and two kinds of groups of hydroxyl and amidino compounds, guanidine compound potpourri, amidino groups adds the amount of guanidine radicals is 2:1.

embodiment 14(contains the system of amidino groups or guanidine radicals and hydroxyl simultaneously)

The present embodiment provides a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, this chemiluminescence sensor material is made up of fluorescent material and base matter, fluorescent material is the luminous quasi-molecule of aggregation inducing, is specially analytically pure tetraphenyl ethene, and molecular structural formula is as shown in Fig. 1-A.Base matter is analytically pure (Fig. 3-A).Wherein to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 2mg/mL to the addition of fluorescent material.

Step 1: prepare base matter:

The base matter of getting certain volume is analytically pure

Step 3: under normal temperature (20 DEG C), the CO that is 99.999% to the purity that passes into different volumes (amount) in the chemiluminescence sensor material making ₂gas, passing into flow velocity is 3mL/s, passes into after gas 10s, leaves standstill 3min, measures its fluorescence emission spectrum, and then continue to pass into CO under fluorescence emission spectrometer ₂after gas 10s, then leave standstill 3min, measure its fluorescence emission spectrum under fluorescence emission spectrometer, order is carried out successively, and final is 400s along with passing into the prolongation of time until pass into gas time cumulation, obtains passing into the CO under gas flow at this ₂pass into the typical curve of volume-maximum fluorescence spectral intensity, this curve is quantitatively detected to CO in mixed gas as typical curve ₂content.

Step 4: under normal temperature (20 DEG C), pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow that passes into gas is 3mL/s, after the time that passes into mixed gas is 400s, records this and pass into the fluorescent emission intensity of chemiluminescence sensor material under the time.

embodiment 15(the liquid state organics that contains amidino groups mixes with alcohols liquid state organics)

Composition and the embodiment's 2 of the carbon dioxide chemistry fluorescent optical sensor material that the present embodiment proposes is basic identical, and difference is only, in the carbon dioxide chemistry fluorescent optical sensor material of the present embodiment in n-propanol the amount of substance of hydroxyl with contain amidino groups molecule in the ratio of amidino groups amount of substance be 1:5, all the other contents are identical with embodiment 2.

embodiment 16(amidino compounds mixes with amine)

The CO that the present embodiment proposes ₂the composition of chemiluminescence sensor material and embodiment's 3 is basic identical, and difference is only, in the carbon dioxide chemistry fluorescent optical sensor material of the present embodiment the summation of the amount of substance of amido and two kinds of groups of hydroxyl with containing amidino groups molecule in the ratio of amidino groups amount of substance be 5:1, all the other contents are identical with embodiment 3.

embodiment 17(amidino compounds mixes with amine alcohols)

The composition of the carbon dioxide chemistry fluorescent optical sensor material that the present embodiment proposes and embodiment's 4 is basic identical, difference is only, the summation of the amount of substance of amido and two kinds of groups of hydroxyl and liquid state organics containing amidino groups in the amylalcohol of 5-amido-1 in the carbon dioxide chemistry fluorescent optical sensor material of the present embodiment the ratio of the amount of substance of middle amidino groups is 1:8, and all the other contents are identical with embodiment 4.

embodiment 19(amidino compounds mixes with amine, alcohols)

The composition of the carbon dioxide chemistry fluorescent optical sensor material that the present embodiment proposes and embodiment's 5 is basic identical, difference is only, the summation of the amount of substance of amido and two kinds of groups of hydroxyl and liquid state organics containing amidino groups in n-propanol, n-propylamine potpourri in the carbon dioxide chemistry fluorescent optical sensor material of the present embodiment the ratio of the amount of substance of middle amidino groups is 8:1, and all the other contents are identical with embodiment 5.

Real executing routine 20(amidino compounds mixes with amine, alcohols)

The composition of the carbon dioxide chemistry fluorescent optical sensor material that the present embodiment proposes and embodiment's 5 is basic identical, difference is only, the summation of the amount of substance of amido and two kinds of groups of hydroxyl and liquid state organics containing amidino groups in n-propanol, n-propylamine potpourri in the carbon dioxide chemistry fluorescent optical sensor material of the present embodiment the ratio of the amount of substance of middle amidino groups is 10:1, and all the other contents are identical with embodiment 5.

embodiment 21(amidino compounds mixes with amine, alcohols)

The composition of the carbon dioxide chemistry fluorescent optical sensor material that the present embodiment proposes and embodiment's 5 is basic identical, difference is only, the summation of the amount of substance of amido and two kinds of groups of hydroxyl and liquid state organics containing amidino groups in n-propanol, n-propylamine potpourri in the carbon dioxide chemistry fluorescent optical sensor material of the present embodiment the ratio of the amount of substance of middle amidino groups is 1:10, and all the other contents are identical with embodiment 5.

Claims

1. the carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, it is characterized in that: this chemiluminescence sensor material is made up of fluorescent material and base matter, described fluorescent material is the luminous quasi-molecule of aggregation inducing, the serve as reasons liquid state organics that contains amidino groups and/or guanidine radicals or liquid organic mixture, the liquid state organics that contains hydroxyl and/or amido or liquid organic mixture of described base matter forms, or is the liquid state organics containing amidino groups and/or guanidine radicals, hydroxyl and/or amido; And in base matter, the ratio of the amount of substance of amidino groups and/or guanidine radicals, hydroxyl and/or amido meets 1:10～10:1; The addition of fluorescent material meets the fluorescent material that contains 0.5mg～4mg/mL in overall chemiluminescence sensor material; The luminous quasi-molecule of described aggregation inducing is tetraphenyl ethene, 1,1,2,3,4,5-six benzene-1 hydrogen-Siloles, 9-diphenyl methylene-4,9-dihydro-1 hydrogen-fluorenes or 1,2,3,4-tetraphenyl-1,3-cyclo-octadiene; The described liquid state organics that contains hydroxyl and/or amido or liquid organic mixture comprise: the organic mixture that the liquid state organics that contains hydroxyl, the liquid state organics that contains amido, the liquid state organics that contains amido and hydroxyl, the liquid state organics that contains hydroxyl and the liquid state organics that contains amido form; The described liquid state organics that contains hydroxyl is methyl alcohol, ethanol, n-propanol, normal butyl alcohol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, isopropyl alcohol, isobutyl alcohol, isoamylol, secondary butanols, tertiary butyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, phenmethylol, benzhydrol, triphenylcarbinol, ethylene glycol, 1, ammediol or 1,2,3-glycerine; The described liquid state organics that contains amido is for meeting R-NH ₂all kinds of normal temperature under be the one in liquid aminated compounds.

2. a kind of carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals according to claim 1, is characterized in that: the described liquid state organics that contains amidino groups and/or guanidine radicals or liquid organic mixture comprise the organic mixture that the liquid state organics of amidino groups, the liquid state organics that contains guanidine radicals, the liquid state organics that contains amidino groups and the liquid state organics that contains guanidine radicals form.

3. a preparation detection method for the carbon dioxide chemistry fluorescent optical sensor material based on amidine/guanidine radicals, is characterized in that: specifically comprise following step:

Step 1: prepare base matter:

Described base matter is by liquid amine alcohol compound 5-amido-1 amylalcohol, 1 that contains amido and hydroxyl, 8-diaza-bicyclo [5.4.0] 11-7-alkene is DBU composition, wherein in the summation of the amount of substance of amido and two kinds of groups of hydroxyl and DBU, the ratio of the amount of substance of amidino groups is 1:1, and the addition of fluorescent material to meet the volumetric concentration that fluorescent material accounts for overall sensor material be 3mg/mL; Described fluorescent material is tetraphenyl ethene;

Step 2: add analytically pure fluorescent material in the base matter preparing, add after fluorescent material, mix, and sample is carried out to ultrasonic processing;

Step 3: under normal temperature, be 99.999% CO to constantly passing into purity in the chemiluminescence sensor material making ₂gas, the flow velocity that passes into gas is 0.1～5mL/s, measures its fluorescence emission spectrum under fluorescence emission spectrometer, obtains CO ₂pass into the typical curve of volume-maximum fluorescence emission spectral intensity, this curve is quantitatively detected to CO in mixed gas as typical curve ₂volume fraction;

Step 4: under normal temperature, pass into and need to detect CO in the fluorescent material of preserving to the sealing that records typical curve ₂the mixed gas of content, the flow velocity that passes into gas is 0.1～5mL/s, measures its fluorescence emission spectrum under fluorescence emission spectrometer, records this and passes into the fluorescence emission spectral intensity under gas volume;