CN106083935A - Ruthenium (II) the diimine reactivity fluorescence indicator of silicone-containing base and synthetic method thereof and the application in oxygen sensitive fluorescent screen - Google Patents
Ruthenium (II) the diimine reactivity fluorescence indicator of silicone-containing base and synthetic method thereof and the application in oxygen sensitive fluorescent screen Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
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- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Abstract
The invention discloses ruthenium (II) the diimine reactivity fluorescence indicator of a kind of silicone-containing base and synthetic method thereof and the application in oxygen sensitive fluorescent screen.γ isocyanates propyl group alkoxy silane is reacted by the present invention with 5 amino o-phenanthrolines or ruthenium (II) diimine three ligand complex containing 5 amino o-phenanthrolines, ruthenium (II) the diimine three ligand complex reactivity fluorescence indicator of synthesis silicone-containing, and through the hydrolysis of siloxy group and condensation, it is bonded with siliceous hydroxylcontaining materials surface chemistry, chemistry is fixed on substrate surface, forms stable oxygen sensitive fluorescent screen.Oxygen sensitive fluorescent screen prepared by the inventive method can effectively solve the problem that fluorescence indicator is run off by water extraction, improves the service life of fluorescent film.
Description
Technical field
The invention belongs to analytical chemistry and sensor field, be specifically related to ruthenium (the II)-diimine of a kind of silicone-containing base
Reactive fluorescence indicator and synthetic method thereof and the application in oxygen sensitive fluorescent screen.
Background technology
The oxygen molecule being dissolved in water body is referred to as dissolved oxygen.Dissolved oxygen mostlys come from the oxygen in air and water plant light
The oxygen that cooperation produces, and some biologies, microorganism and the reducing substances in water body can consume the oxygen in water body.Therefore,
Dissolved oxygen is affected by many factors such as air pressure, water temperature, sunshine, aquatic organism activities, and its content changes over.Dissolved oxygen is to aquatic
Greatly, when dissolved oxygen is less than 7mg/L, the activity of some oxygen consumptions biologies can be remarkably decreased in thing impact;At dissolved oxygen less than 4mg/L
Time, some Fish can death by suffocation;When dissolved oxygen tends to 0, some Anaerobes meeting amount reproduction, produce and pollute, destroy water
Matter.The detection of dissolved oxygen is the most particularly significant to fields such as environmental monitoring, sewage disposal, aquaculture, biochemical reactions, it is desirable to have fast
Measuring method fast, sensitive, efficient, reliable and technology.
At present, the measuring method of dissolved oxygen mainly has iodimetric titration, electrochemical process and Fluorimetric Quenching Method.Iodimetric titration is a kind of biography
The dissolved oxygen detection method of system, it is to react with the dissolved oxygen in water body with the bivalent manganese of excess in the basic conditions, generates four
Valency manganese compound precipitates, and is fixed by dissolved oxygen.Then adding sulphuric acid makes tetravalent manganese precipitate dissolve, and reacts with potassium iodide, is reduced to
Bivalent manganese, obtains the iodine of equivalent, the iodine finally generated with sodium thiosulfate titration, extrapolates tetravalent manganese precipitation
Molal quantity and the dissolved oxygen content of water body.Its analytical procedure is loaded down with trivial details, operation requires height, the detection cycle is long, it is impossible to realize dissolved oxygen
On-line measurement.Electrochemical process is that dissolved oxygen passes through semipermeable membrane, with electrolyte, oxidation-reduction reaction occurs at electrode, impact
Electrode current, compares with reference electrode, tries to achieve dissolved oxygen content.Electrochemical process measuring speed is fast, but electrolyte participates in aoxidizing-anding also
Former reaction, semipermeable membrane can aging regression, electrolyte and semipermeable membrane need often to change, instrument must regular calibration, be not suitable for
Line monitoring and high-frequency measurement.Fluorimetric Quenching Method is can to occur with the fluorescence molecule being in excited state based on dissolved molecular oxygen
Collision, shifts excitation energy, makes the fluorescent emission of fluorescence molecule reduce, i.e. fluorescent quenching.Fluorescence intensity and fluorescence lifetime and dissolving
Oxygen content negative correlation, can try to achieve the content of dissolved oxygen in water body by measuring fluorescence intensity or fluorescence lifetime.Fluorimetric Quenching Method has
There are not oxygen consumption, the advantage such as accuracy of detection is high, capacity of resisting disturbance is strong, easy to use, it may be achieved the real-time monitoring of dissolved oxygen, become
The main stream approach of Dissolved Oxygen in Water detection.
The key element of fluorescent quenching dissolved oxygen sensor is oxygen sensitive fluorescent screen, and it is by fluorescence indicator and loads with indicator
Base material constitute.Conventional fluorescence indicator is three ligand complexes of ruthenium (II) and diimine.Its molecular structure rigidity is big, altogether
Yoke degree is high, and central atom is low toward the electron transition energy barrier of part, and available blue light is as excitation source, fluorescence emission spectrum peak
Wavelength, at 570-620nm, has that photochemical stability is good, visible absorption coefficient is big, fluorescence quantum efficiency is high, Stokes displacement
The advantages such as big and fluorescence lifetime length, are widely used in fluorescent quenching dissolved oxygen sensor.The method loading with fluorescence indicator is main
There are physically trapping method, Electrostatic Absorption method and chemical bonding.Physically trapping method is to be dissolved in together with polymer by fluorescence indicator
Organic solvent, by solvent flashing hardened coating film, is embedded in fluorescence indicator among thin polymer film;Or by fluorescence indicator
It is mixed into prepolymer, crosslinking curing film forming, fluorescence indicator is embedded among crosslinking polymer thin film.Investment immobilizing indicator
Filmogen used mainly has polyacrylamide, polyacrylate, polyvinyl alcohol, polrvinyl chloride (PVC), cellulose, silicon rubber
Its filmogen such as glue.It is slow that the greatest weakness of investment is in response to speed;Secondly, it is phase interaction between fluorescence indicator with base material
With weak, in use such as factors such as solvent, temperature, solution, pH, fluorescence indicator can be made because of a variety of causes to run off.
Electrostatic Absorption method is to be adsorbed on base material by fluorescent indicator molecule by electrostatic interaction.It is mainly charged group
The fixing fluorescence indicator with opposite charges of base material.For example with ion exchange resin (or ion exchange membrane) fixing band electric charge
Or there is the fluorescence indicator of highly polar substituent group.In practice more is cation exchange resin fixing band positive charge
Rhodamine class reagent, anion exchange resin fixing band sulfonic group or the fluorescence indicator of carboxyl.Electrostatic Absorption method is deposited equally
At fluorescence indicator losing issue, and the charged group on base material easily has an effect with solvent.
Chemical bonding is to be directly or indirectly bonded on base material by chemical bond by reactivity fluorescence indicator, forms oxygen
Sensitive fluorescent screen.Chemical bond is firm, it is not easy to fracture, it is possible to resolve the problem that fluorescent film fluorescence indicator runs off;Fluorescence refers to simultaneously
Showing that agent directly contacts with measured liquid, response speed is greatly improved.Chemical bonding it is crucial that fluorescence indicator have can be with
The functional group of substrate surface reaction.The fluorescence indicator of synthesis there is no reactive functional groups in early days, and market responds activity
Ruthenium (II)-diimine class fluorescence indicator is little.Synthetic reaction ruthenium (II)-diimine class fluorescence indicator, passes through chemical bond
It is fixed to substrate surface, the loss of fluorescence indicator in oxygen sensitive fluorescent screen can be alleviated, improve the use longevity of oxygen sensitive fluorescent screen
Life.
Summary of the invention
It is an object of the invention to solve the problem that general oxygen sensitive fluorescent screen fluorescence indicator runs off.General oxygen sensitivity is glimmering
Light film is to be fixed in the substrate by fluorescence indicator by physical absorption or physically trapping mostly, and fluorescence indicator is easily extracted by water
Take loss.Synthetic reaction fluorescence indicator, makes indicator be fixed on base material by chemical bond, it is possible to resolve oxygen sensitive fluorescent screen
Fluorescence indicator by water extraction run off problem.
The outer-shell electron of divalent ruthenium cation is configured as 4s24p64d6, after hydridization, have 6 unoccupied orbitals, 12 can be accommodated and join
Position electronics, with three diimide ligand complexations, can form three ligand complexes of tool fluorescence activity.Ruthenium (II) and the three of diimine
Ligand complex can generate through two-step method, i.e. raw with diimide ligand complexation with two ligand complexes of diimine by ruthenium (II)
Become, it is possible to generated with diimine one step complexation by ruthenium ion.
The chemism of NCO is high, can be with the active hydrogen generation additive reaction of amine.Containing primary amine or secondary amine two are sub-
Amine ligand contains active hydrogen, can be with NCO addition.5-amino-o-phenanthroline is the diimine ligand of common band primary amine groups
Body, both can be with ruthenium ion complexation, it is possible to NCO addition.γ-isocyanates propyl trialkoxy silane is with three
Alkoxyl, can react with 5-amino-o-phenanthroline, on this diimide ligand introduce siloxane group, it is possible to containing 5-amino-
The ruthenium (II) of o-phenanthroline-diimine three ligand complex reaction, directly refers at ruthenium (II)-diimine three ligand complex fluorescence
Show introducing siloxane group in agent.
The present invention is achieved through the following technical solutions:
The ruthenium (II) of silicone-containing base-diimine reactivity fluorescence indicator, at least 1 of a silicone-containing base, 10-is adjacent
The synthesis of the ruthenium (II) of phenanthroline ligand-diimine three ligand reaction fluorescence indicator, can pass through γ-isocyanates propyl group three
Alkoxy silane synthesizes with 5-amino-o-phenanthroline ligand reaction.Silica on ruthenium (II)-diimine three ligand complex
Groups is easy to hydrolysis in acid condition, can form siliconoxygen bond with the surface base material condensation containing silicone hydroxyl, thus by ruthenium
(II)-diimine three ligand complex fluorescence indicator is fixed to substrate surface, forms the oxygen sensitive fluorescent screen that chemistry is fixing.
The 1,10-phenanthroline derivatives that diimine is silicone-containing base of described silicone-containing base;Described silicone-containing
The 1,10-phenanthroline derivatives of base is reacted with 5-amido-1,10-o-phenanthroline by γ-isocyanates propyl group alkoxy silane
Generate.
The synthetic method of the ruthenium (II) of a kind of silicone-containing base-diimine reactivity fluorescence indicator, comprises the steps:
1) by γ-isocyanates propyl trialkoxy silane and ruthenium (the II)-diimine three containing 5-amido-1,10-o-phenanthroline
Ligand complex is dissolved in dry organic solvent respectively;
2) by two kinds of solution mixing post-heating of step 1) gained to 40-600C, stirring reaction 1-3 hour, obtain crude product;
3) crude product rotary distillation is concentrated, vacuum drying, obtain solid product;
4) the solid product ether being dried is cleaned, filters, vacuum drying, obtain the ruthenium (II)-two of refined silicone-containing base
Imine reaction fluorescence indicator.
In said method, amido-1 Han 5-in step 1), the ruthenium (II) of 10-o-phenanthroline-diimine three ligand complex
It is 1:1.1-1:1.3 with the mol ratio of γ-isocyanates propyl trialkoxy silane, to improve ruthenium (II)-diimine three part
The utilization rate of complex.
In said method, the diimine in described ruthenium (II)-diimine three ligand complex is 4,7-diphenyl-1,10-
O-phenanthroline, 1,10-o-phenanthroline or 2,2'-bipyridyl and their derivant.Preferably, described ruthenium (II)-diimine three
Diimine in ligand complex is 4,7-diphenyl-1,10-o-phenanthroline, 1,10-o-phenanthroline or 2,2'-bipyridyl;Its
In 4,7-diphenyl-1, the conjugated degree of 10-o-phenanthroline is big, and part rigidity is high, and absorbing wavelength is longer, should be first-selected.It spreads out
Biology also should make three ligand complex absorption spectrum Einstein shifts be primary.
In said method, organic solvent tetrahydrofuran, dichloromethane, chloroform, ether all use molecular sieve drying.Water pair
Siloxy group and isocyanates are the most active, and molecular sieve drying removes the minor amount of water in solvent, on the one hand avoid siloxy group
Hydrolytic crosslinking, on the other hand reduces the loss of isocyanates.Ether is limited to the dissolubility of ruthenium (II)-diimine complex, and
Preferable to propyl group alkoxy silane dissolubility, volatility is high, makees cleanout fluid with ether and can improve cleaning efficiency.
In said method, in balance ruthenium (II)-diimine three ligand complex, the anion of divalent ruthenium (II) positive charge is
One or more ions in chloride ion, perchlorate and hexafluorophosphoricacid acid ions.
In said method, the alkoxyl first-selection methoxyl group in γ-isocyanates propyl trialkoxy silane and ethyoxyl.Silicon
Alkoxyl in oxygen alkane is short and small, and hydrolysing activity is high, and the reactivity of fluorescence indicator is the highest.Because reactivity is high, to wait body
Long-pending ethanol and water as solvent, can ensure the dissolubility of ruthenium (the II)-diimine reactivity fluorescence indicator of silicone-containing base,
The fast hydrolyzing of siloxy group can be ensured again.
The ruthenium (II) of a kind of silicone-containing base prepared by above-described preparation method-diimine reactivity fluorescence instruction
Agent, described reactive fluorescence indicator is three ligand complexes of ruthenium (II) and diimine, in three diimide ligands at least one
Individual diimide ligand is the diimine of silicone-containing base;The diimine of described silicone-containing base is by the siloxanes containing NCO
Generation is reacted with the diimine of amino-contained.
The ruthenium (II) of described a kind of silicone-containing base-diimine reactivity fluorescence indicator is in oxygen sensitive fluorescent screen
Application, i.e. prepares a kind of oxygen sensitive fluorescent screen measuring dissolved oxygen, and the fluorescence indicator constituting fluorescent film is silicone-containing base
Ruthenium (II)-diimine three ligand complex;The substrate surface constituting fluorescent film need to have silicone hydroxyl, can be processed by surface and make base material
With silicone hydroxyl;Reactive ruthenium (II)-diimine fluorescence indicator passes through hydrolysis and the condensation of siloxanes, with the silicon of substrate surface
Hydroxyl forms siliconoxygen bond, makes the oxygen sensitive fluorescent screen that chemistry is fixing.
Described siloxanes is to complete with infusion process with the condensation reaction of base material, and this method is to prepare the simplest of coating at base material
Method.Ruthenium (II)-diimine reactivity fluorescence indicator is dissolved in the alcohol-water solution of acidity, be made into mass concentration be 0.2% ~
The reactive fluorescence indicator solution of 0.8%, is warming up to 50-70oC hydrolyzes, then base material immerses reactive fluorescence indicator solution
Absorption fluorescence indicator soaks 20-60min, 70-80 after taking-upoC heat drying 1-3 hour, the condensation completing silicone hydroxyl is anti-
Should, obtain the oxygen sensitive fluorescent screen of chemical fixing fluorescence indicator.
Preferably, hydrolysis temperature is 70oC。
Compared with prior art, present invention have the advantage that and technique effect:
The present invention, compared with the oxygen sensitive fluorescent screen being generally used for DO determination, has fluorescence indicator and not easily runs off, and uses
The advantage of life-span length.
Accompanying drawing explanation
Fig. 1 is reactive fluorescence indicator [Ru (dpp)2(phen-Si)] Cl2Molecular structure.
Fig. 2 is the response curve of chemistry fixed oxygen sensitive fluorescent screen.
Fig. 3 is the response curve of physically trapping oxygen sensitive fluorescent screen.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited only to below embodiment.
Code name in literary composition:
Dpp:4,7-diphenyl-1,10-o-phenanthroline
Phen:1,10-o-phenanthroline
phen-NH2: 5-amino-o-phenanthroline
ITPS: isocyanates propyl-triethoxysilicane
[Ru(dpp)3]Cl2: three (4,7-diphenyl-1,10-o-phenanthroline) ruthenium (II) dichloride
[Ru(dpp)2(phen-NH2)]Cl2: two (4,7-diphenyl-1,10-o-phenanthroline) 5-amido-phenanthroline ruthenium (II)
Dichloride
[Ru(dpp)2(phen-Si)] Cl2: two (4,7-diphenyl-1,10-o-phenanthroline) siloxanes-5-amide-neighbour's phenanthrene is coughed up
Quinoline ruthenium (II) dichloride
Embodiment 1
The synthesis of fluorescence indicator:
By 200 mg 5-amino-o-phenanthroline (phen-NH2) and 835 mg Ru (dpp)2Cl2It is dissolved in 10ml dehydrated alcohol, will
Solution is transferred to 25ml there-necked flask, is warming up to 70 DEG C, the hydroxylammonium chloride salt ethanol solution 1ml of dropping 1mol/L, back flow reaction
16h.With the acetone of volume ratio 4:1 after gained crude product is spin-dried for: ethanol solution dissolves, crystallize in refrigerator freezing, divide after filtration
Not with frozen water, cold washing with acetone 3 times, be vacuum dried two (4,7-diphenyl-1,10-o-phenanthroline) 5-amido-neighbour's phenanthrene is coughed up
Quinoline ruthenium (II) dichloride { [Ru (dpp)2(phen-NH2)]Cl2Fluorescence indicator.
With 4A molecular sieve drying dichloromethane, oxolane and ether, the Ru that 150mg (0.15mmol) is synthesized
(dpp)2(phen-NH2)]Cl2Fluorescence indicator is dissolved in 20ml dichloromethane;By 48mg (0.195mmol) γ-Carbimide.
Ester propyl-triethoxysilicane (IPTS) is dissolved in 10ml oxolane, by Ru (dpp)2(phen-NH2)]Cl2Solution and IPTS
Solution is transferred in 100ml there-necked flask, adds 5ml oxolane, is warming up to 60oC is stirred at reflux reaction 1 hour, obtains and slightly produces
Thing.Reactant liquor rotary distillation is concentrated, vacuum dried solid product.Clean with ether and filter, vacuum drying, obtain refined
The ruthenium (II) of silicone-containing base-diimine reactivity fluorescence indicator [Ru (dpp)2(phen-Si)] Cl2, molecular structure such as figure
Shown in 1.
Glass surface treatment:
Microscope slide is immersed 35oThe fluorine-containing glass etching liquid 30min of C, cleans with deionized water;Immerse 35oThe 10wt% of C
NaOH solution 15min, cleans with deionized water;Immerse the 30 wt% hydrogen peroxide that volume ratio is 3:7 and the dense sulfur of 98 wt% of 70 DEG C
60min in the mixed liquor of acid, cleans with deionized water, dries up with nitrogen, obtain the microscope slide of surface coarsening and hydroxylation.
Fluorescence indicator is fixed:
In 100ml beaker, add 10ml deionized water and 10ml ethanol, with hydrochloric acid, the pH value of alcohol-water mixed solution is adjusted to
4, by the ruthenium (II) of 0.1g silicone-containing base-diimine reactivity fluorescence indicator [Ru (dpp)2(phen-Si)] Cl2Add
In alcohol-water mixed solvent, it is made into the fluorescence indicator solution that mass concentration is 0.5%.Fluorescence indicator solution is heated to
70oC, immerses 30min in fluorescence indicator solution, 80 after taking-up by the microscope slide of hydroxylationoC oven drying 2 hours, treats diaphragm
Clean with ethanol and deionized water after cooling, dry up with nitrogen, obtain the load glass of chemical fixing ruthenium (II)-diimine fluorescence indicator
Sheet.
Embodiment 2
The synthesis of fluorescence indicator:
By 200 mg 5-amino-o-phenanthroline (phen-NH2) and 835 mg Ru (dpp)2Cl2It is dissolved in 10ml dehydrated alcohol, will
Solution is transferred to 25ml there-necked flask, is warming up to 70 DEG C, the hydroxylammonium chloride salt ethanol solution 1ml of dropping 1mol/L, back flow reaction
16h.With the acetone of volume ratio 4:1 after gained crude product is spin-dried for: ethanol solution dissolves, crystallize in refrigerator freezing, divide after filtration
Not with frozen water, cold washing with acetone 3 times, be vacuum dried two (4,7-diphenyl-1,10-o-phenanthroline) 5-amido-neighbour's phenanthrene is coughed up
Quinoline ruthenium (II) dichloride { [Ru (dpp)2(phen-NH2)]Cl2Fluorescence indicator.
With 4A molecular sieve drying dichloromethane, oxolane and ether, the Ru that 150mg (0.15mmol) is synthesized
(dpp)2(phen-NH2)]Cl2Fluorescence indicator is dissolved in 20ml dichloromethane;By 35mg (0.17mmol) γ-isocyanates
Propyl trimethoxy silicane (IPTS) is dissolved in 10ml oxolane, by Ru (dpp)2(phen-NH2)]Cl2Solution and IPTS are molten
Liquid is transferred in 100ml there-necked flask, adds 5ml oxolane, is warming up to 45oC stirring reaction 3 hours, obtains crude product.Will be anti-
Liquid rotary distillation is answered to concentrate, vacuum dried solid product.Clean with ether and filter, vacuum drying, obtain refined containing silica
The ruthenium (II) of alkyl-diimine reactivity fluorescence indicator [Ru (dpp)2(phen-Si)] Cl2。
Glass surface treatment:
Microscope slide is immersed 35oThe fluorine-containing glass etching liquid 30min of C, cleans with deionized water;Immerse 35oThe 10wt% of C
NaOH solution 15min, cleans with deionized water;Immerse the 30 wt% hydrogen peroxide that volume ratio is 3:7 and the dense sulfur of 98 wt% of 70 DEG C
60min in the mixed liquor of acid, cleans with deionized water, dries up with nitrogen, obtain the microscope slide of surface coarsening and hydroxylation.
Fluorescence indicator is fixed:
In 100ml beaker, add 10ml deionized water and 10ml ethanol, with hydrochloric acid, the pH value of alcohol-water mixed solution is adjusted to
4, by the ruthenium (II) of 0.1g silicone-containing base-diimine reactivity fluorescence indicator [Ru (dpp)2(phen-Si)] Cl2Add
In alcohol-water mixed solvent, it is made into the fluorescence indicator solution that mass concentration is 0.8%.Fluorescence indicator solution is heated to
50oC, immerses 60min in fluorescence indicator solution, 70 after taking-up by the microscope slide of hydroxylationoC oven drying 3 hours, treats diaphragm
Clean with ethanol and deionized water after cooling, dry up with nitrogen, obtain the load glass of chemical fixing ruthenium (II)-diimine fluorescence indicator
Sheet.
Comparative example 1:
5.5g ethanol and 6g water being added four-hole bottle, drips 0.5 ml hydrochloric acid, regulation pH value to 4, is warming up to 60 DEG C, adds 7.4g
Dimethyldiethoxysilane, continues stirring hydrolysis 10min, is then added dropwise over 10.4g tetraethyl orthosilicate, continue reaction 2hr,
Synthesis R/Si is than the modified silicasol alcohol-water solution being 1.Take 2ml modified silicasol alcohol-water solution, add 2mg tri-(4,7-bis-
Phenyl-1,10-phenanthroline ruthenium (II) dichloride [Ru (dpp)3]Cl2Fluorescence indicator, by Ludox/[Ru (dpp)3]Cl2
Solution is coated on hydroxylation slide surface, treats that solvent evaporates into coating surface drying, in 70oC curing oven 3 hours, obtains modified silicon and coagulates
Glue cladding [Ru (dpp)3]Cl2Oxygen sensitive fluorescent screen.
The oxygen sensitive fluorescent screen of preparation is immersed in the hot water of 50 DEG C, measure the glimmering light intensity of fluorescent film with soak time
Change.Table 1 is the oxygen sensitive fluorescent screen fluorescence output change with the water logging time.Fig. 2 and Fig. 3 is respectively embodiment 1 sensitive fluorescence
Film and comparative example 1 sensitive fluorescent screen round robin curve from air to anaerobic water.
Table 1
The oxygen sensitive fluorescent screen that embodiment 1 chemistry is fixed is 50oSoaking one month in C hot water, fluorescence intensity declines about 8%, soaks
During by two month, fluorescence intensity is dropped by less than again 1%, is basically stable near the 91% of initial fluorescence output.
The oxygen sensitive fluorescent screen that embodiment 2 chemistry is fixed is 50oSoaking one month in C hot water, fluorescence intensity declines close
8%, when being dipped into two month, fluorescence intensity is dropped by less than again 1%, is basically stable near the 92% of initial fluorescence output.
And the oxygen sensitive fluorescent screen of comparative example 1 physically trapping is 50oSoaking one month in C hot water, fluorescence intensity declines near
50%, when being dipped into two month, fluorescence intensity declines again 21%, the 41.6% of fluorescence output only former output.
Embodiment 1 chemistry fixed oxygen sensitive fluorescent screen output from air to anaerobic water increases to 0.13mV from 0.09mV,
Response time is 30 seconds, and the output of comparative example 1 physically trapping fluorescent film increases to 0.65mV from 0.45mV, and response time is 5
Minute.Chemistry fixed oxygen sensitive fluorescent screen has more preferable response speed and stability than physically trapping oxygen sensitive fluorescent screen.
Claims (10)
1. the synthetic method of the ruthenium (II) of a silicone-containing base-diimine reactivity fluorescence indicator, it is characterised in that tool
Body comprises the steps:
1) γ-isocyanates propyl group alkoxy silane and ruthenium (the II)-diimine three containing 5-amido-1,10-o-phenanthroline are joined
Body complex is dissolved in organic solvent respectively;
2) by two kinds of solution mixing post-heating of step 1) gained to 40-600C, stirring reaction 1-3 hour, obtain crude product;
3) crude product rotary distillation is concentrated, vacuum drying, obtain solid product;
4) the solid product ether being dried is cleaned filtration, vacuum drying, obtain the ruthenium (II)-two of refined silicone-containing base
Imine reaction fluorescence indicator.
Synthetic method the most according to claim 1, it is characterised in that γ described in step 1)-isocyanates propyl group alkoxyl
Silane is the one in γ-isocyanates propyl trimethoxy silicane and γ-isocyanates propyl-triethoxysilicane.
Synthetic method the most according to claim 1, it is characterised in that amido-1 Han 5-described in step 1), 10-o-phenanthroline
Ruthenium (II)-diimine three ligand complex in diimine be that 4,7-diphenyl-1,10-o-phenanthroline, 1,10-neighbour's phenanthrene are coughed up
Quinoline, 2,2'-bipyridyl or their derivant.
Synthetic method the most according to claim 1, it is characterised in that amido-1 Han 5-described in step 1), 10-o-phenanthroline
The mol ratio of ruthenium (II)-diimine three ligand complex and γ-isocyanates propyl group alkoxy silane be 1:1.1-1:1.3.
Synthetic method the most according to claim 1, it is characterised in that organic solvent described in step 1) is molecular sieve drying
More than one in oxolane, dichloromethane and chloroform.
Synthetic method the most according to claim 1, it is characterised in that amido-1 Han 5-described in step 1), 10-o-phenanthroline
Ruthenium (II)-diimine three ligand complex in balance divalent ruthenium (II) positive charge anion be chloride ion, perchlorate from
Son and hexafluorophosphoricacid acid ions in more than one.
7. ruthenium (the II)-diimine of a kind of silicone-containing base prepared by the preparation method described in any one of claim 1-6 is anti-
Answering property fluorescence indicator, it is characterised in that described reactive fluorescence indicator is three ligand complexes of ruthenium (II) and diimine,
In three diimide ligands, at least one diimide ligand is the diimine of silicone-containing base;The diimine of described silicone-containing base
Generation is reacted by the diimine of the siloxanes containing NCO with amino-contained.
8. the ruthenium (II) of a kind of silicone-containing base described in claim 7-diimine reactivity fluorescence indicator is glimmering in oxygen sensitivity
Application in light film, it is characterised in that concrete applying step is to be referred to by the ruthenium (II) of silicone-containing base-diimine reactivity fluorescence
Showing agent solution, by hydrolysis and the condensation reaction of siloxy group, be chemically bonded to the substrate surface containing silicone hydroxyl, preparation chemistry is solid
Determine the oxygen sensitive fluorescent screen of fluorescence indicator.
Ruthenium (the II)-diimine reactivity fluorescence indicator of a kind of silicone-containing base the most according to claim 8 is quick at oxygen
Application in sense fluorescent film, it is characterised in that the ruthenium (II) of described silicone-containing base-diimine reactivity fluorescence indicator solution
For the acid solution of equal-volume ethanol Yu water, mass concentration is 0.2-0.8%.
Ruthenium (the II)-diimine reactivity fluorescence indicator of a kind of silicone-containing base the most according to claim 8 is quick at oxygen
Application in sense fluorescent film, it is characterised in that described in be chemically bonded to the substrate surface containing silicone hydroxyl be by the base containing silicone hydroxyl
Material is placed in 50-70oAfter the ruthenium (II) of the silicone-containing base of C-diimine reactivity fluorescence indicator solution soaks 20-60min,
In 70-80oC is dried 1-3 hour.
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CN107389640A (en) * | 2017-07-27 | 2017-11-24 | 中国科学院合肥物质科学研究院 | Two dot product fraction fluorescence lifetime rapid detection systems |
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CN114921241A (en) * | 2022-04-14 | 2022-08-19 | 新疆农业大学 | Preparation method and application of manganese-containing complex cellulose-based fluorescent functional material |
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