CN105973472B - A kind of near-infrared fluorescent temperature sensing method and material - Google Patents
A kind of near-infrared fluorescent temperature sensing method and material Download PDFInfo
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- CN105973472B CN105973472B CN201610118230.7A CN201610118230A CN105973472B CN 105973472 B CN105973472 B CN 105973472B CN 201610118230 A CN201610118230 A CN 201610118230A CN 105973472 B CN105973472 B CN 105973472B
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Classifications
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- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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Abstract
The invention discloses a kind of near-infrared luminous temperature sensing method and its critical materials, with Yb3+Emission spectrum medium wavelength 900~970nm range fluorescence intensity and wavelength the fluorescence intensity of 900~985nm range ratio or its logarithm, or with Yb3+Emission spectrum in be located at two luminous zones near 945nm and 976nm fluorescence intensity parameter as measurement temperature of ratio or its logarithm.The method for sensing and material overcome the problem that temperature sensing is interfered by oxygen concentration in conventional fluorescent temperature sensor technology；On the other hand, rare earth luminescent material provided by the invention shows the unique characteristics of luminescence.Features described above makes temperature sensing method and material of the present invention show excellent near-infrared luminous temperature measurement accuracy and confidence level.
Description
Technical field
The present invention relates to temperature sensor technology, in particular to a kind of near-infrared fluorescent temperature sensing method and the realization sensing
The material of method.
Background technique
Temperature is one of the basic parameter of all kinds of science and technology.Compared with traditional contact type temperature sensor, shine temperature
Degree sensor have many advantages, such as the response time fastly, non-contact measurement mode, high spatial resolution high (R.J.Meier, et
Al., Chem.Soc.Rev.2013,42,7834), thus in such as live cell assays, aerodynamic studies, high voltage or strong
Electromagnetic environment monitor, coating research and development and food storage etc. have broad application prospects (M.Schaeferling, et
al.,Adv.Funct.Mater.2008,18,1399)。
Luminance temperature sensor is typically based on the luminosity of embedded photoluminescent material, such as emission wavelength position, luminous intensity
Or luminescent lifetime vary with temperature and the characteristic that changes carry out temperature sensing (G.Q.Yang, et al.,
Angew.Chem.Int.Ed.2011,50,8072).But other variables also have an impact to this kind of material emission property, especially
It is that the influence of oxygen concentration in system will lead to the significant decrease to temperature sensing accuracy, which greatly limits its application ranges
(O.S.Wolfbeis,et al.,Anal.Chem.2006,78,5094-5101).In order to reduce this influence, common practice
It is that luminescent material is embedded in inert material, such as choke macromolecule.However due to the diffusion of oxygen molecule or this kind of
The influence of dissolution in material, oxygen can not completely eliminate.Another method is to form temperature probe and oxygen probe
One combined probe, but this needs complicated iterative process to eliminate two kinds of parameters to the cross influence of probe, thus real
Now temperature is accurately measured.On the other hand, most of luminance temperature materials are to utilize ultraviolet or visible wavelength region light
Excitation or light emitting property, which greatly limits their detection depth and application in biological living analysis.Therefore, develop
It is a kind of with larger investigation depth, it can work near infrared wavelength region and the fluorescence temperature not interfered by oxygen detects
Method, and develop and can be used for the luminescent material haveing excellent performance of above-mentioned detection and be of great significance.
Trivalent ytterbium ion (Yb3+) fluorescence emission spectrum be located at 900~1100 nanometer ranges, have biggish wear to organism
Saturating depth, low damage and relatively narrow transmitting band to tissue, is highly suitable as near-infrared luminous biosensor.Especially
Yb3+Longer luminescent lifetime (> 10 μ s) is significantly larger than the autofluorescence (1~20ns) of biology, can be with using TIME RESOLVED TECHNIQUE
The background fluorescence bring in bioanalysis is effectively prevented to interfere.In addition, using two-photon technology to Yb3+Ionic complex into
Row sensitized luminescence is a kind of effective way that light excitation and launch wavelength are extended to near infrared region.Wong et al. (K.L.Wong,
Et al., J.Am.Chem.Soc.2011,133,20120) it reports a kind of single photon 430nm lower quantum yield is excited to can reach
2.5% luminous Yb3+Compound.This compound also has Yb reported at present3+Biggish two-photon excitation in compound
Action section (δ × Φ) is 9.2GM (1GM=10-50cm4s photon-1molecule-1)。
Summary of the invention
The object of the present invention is to provide used in a kind of not fluorescence temperature method for sensing and this method by oxygen interference
New sensing material.The present invention provides a kind of based on Yb3+Ion photoluminescence spectra, and the Fluorescence Ratio temperature that do not interfered by oxygen
Method for sensing is spent, this method contains Yb with ultraviolet light or the excitation of visible light or near infrared light3+Material emit Yb3+Ion
Characteristic fluorescence, with Yb3+Emission spectrum medium wavelength 900~970nm range fluorescence intensity and wavelength in 900~985nm range
Fluorescence intensity ratio or its logarithm as measurement temperature parameter；Or with Yb3+In luminescent spectrum, it is located at 945nm
With the ratio of the fluorescence intensity of two transmitting bands of 976nm or its logarithm as the parameter for measuring temperature.This method goes out people's will
Material ground has achieved the effect that the high-precision fluorescence temperature not interfered by oxygen measures.Invention also provides visible lights and close red
Outer photosensitizer Yb3+The excellent new material of luminescent properties.
Technical scheme is as follows:
A kind of fluorescence temperature method for sensing makes under ultraviolet light or the excitation of visible light or near infrared light containing Yb3+Hair
Luminescent material emits Yb3+The fluorescence of ion, with Yb3+Fluorescence intensity and wavelength of the emission spectrum medium wavelength in 900~970nm range
In the ratio of the fluorescence intensity of 900~985nm range or its logarithm as the parameter for measuring temperature, or with Yb3+Transmitting
The ratio or its logarithm that the fluorescence intensity of two luminous zones near 945nm and 976nm is located in spectrum are as measurement temperature
The parameter of degree, to realize that the high-precision temperature not interfered near infrared wavelength region and by oxygen detects.
Further, the measurement temperature is carried out according to following formula (1) or (2):
ln(I900-970/I900-985)=A (1/T)+B formula (1)
Or ln (I945/I976)=C (1/T)+D formula (2)
Wherein, T represents temperature；I900-970/I900-985For Yb3+Fluorescence of the emission spectrum medium wavelength in 900~970nm range
The ratio between the fluorescence intensity of intensity and wavelength in 900~985nm range；I945/I976For Yb3+945nm is located in emission spectrum
With the ratio of the fluorescence intensity of two luminous zones near 976nm；A, B, C, D are constant, can be obtained by measurement standard curve
?.
Above-mentioned fluorescence temperature method for sensing, it is described to contain Yb3+Luminescent material be in ultraviolet light or visible light or close red
Yb can be emitted under outer light excitation3+The Yb of the characteristic fluorescence of ion3+Ionic complex or the complex and host material form
Compound.Preferably, the complex used in the fluorescence temperature method for sensing has shown in formula I photosensitive of structure
Agent ligand:
In the Formulas I, R1、R2The alkyl for being 1~4 for carbon atom number, preferably ethyl；R3、R4Carbon atom number is 1~6
Alkyl, R5、R6、R7、R8The alkyl for being 1~4 for H or carbon atom number, preferably methyl or H.
It is further preferred that the complex has the structure as shown in Formula II:
Wherein, assistant ligand L can be selected from it is following shown in number be respectively hfa, pom, dbm, dnm, tta, hft, fod,
At least one of anion of bta, nta and nha.
It is further preferred that the complex uses tta for assistant ligand, there is the structure as shown in formula III
In general, the complex and host material composition compound in, the host material be organic polymer or
Inorganic oxide material.
The high-molecular organic material is preferably selected from polymethyl methacrylate, polystyrene and polycarbonate at least
It is a kind of.
The high-molecular organic material can also be selected from being constituted main chain with carbon-carbon bond and contains hydrophilic radical and hydrophobic simultaneously
The high-molecular compound of group；The hydrophobic grouping in alkyl, phenyl, aryl, ester group, carbonyl and ether at least one
Kind, the hydrophilic radical is selected from least one of carboxyl, hydroxyl, amide groups and poly- ethylene oxygroup.
Preferably, described that main chain and simultaneously the macromolecule chemical combination containing hydrophilic radical and hydrophobic grouping are constituted with carbon-carbon bond
Object is selected from methacrylic acid-methacrylate copolymer, EUDRAGIT L100, styrene-first
Base acrylic copolymer, acrylic acid and acrylic ester copolymers, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer
Object, styrene-maleic acid Arrcostab-maleic acid, phenylethylene-maleic anhydride-maleic acid isobutyl copolymer, benzene second
Alkene-maleic acid isobutyl-maleic acid, alkyl maleates-maleic acid, acrylamide-methacrylic acid
The copolymer and styrene-methacrylate-acrylic copolymer of ester copolymer, butyl maleate and methyl vinyl ether
At least one of；More preferable methacrylic acid-methacrylate copolymer, methacrylic acid-methyl methacrylate are total
Polymers, Styrene-methyl Acrylic Acid Copolymer, styrene-maleic acid copolymer, styrene-maleic acid Arrcostab-maleic acid are total
At least one of polymers and phenylethylene-maleic anhydride-maleic acid isobutyl copolymer.
The carbon-carbon bond constitutes the molecular weight of main chain and the high-molecular compound simultaneously containing hydrophilic radical and hydrophobic grouping
It is 1,500~200,000.
When the carbon-carbon bond constitutes main chain and high-molecular compound simultaneously containing hydrophilic radical and hydrophobic grouping contains carboxylic
When base, the quality of carboxylic group accounts for the 0.01%~40% of the gross mass of the high-molecular compound.
The host material and the Yb3+The mass ratio of complex is 0.5~10,00: 1.
Further, described to contain Yb3+Luminescent material be nanoparticle；Preferably, at the size of the nanoparticle
In 10~500 nanometer ranges.
Structure organic photosensitizer shown in formula I, the Yb containing structure photosensitizer shown in formula I3+Complex and such
The compound of complex and host material composition also belongs to protection scope of the present invention；
Preferably, the Yb containing structure photosensitizer shown in formula I3+Complex is that structure cooperates as shown in Formula II
Object.
Preferably, the composite material is formed for structure complex as described in Formula II with the host material compound
Object.
Present invention simultaneously provides organic photosensitizer shown in Formulas I and its Yb3+The synthetic method of complex.
Photosensitizer shown in Formulas I can be prepared by the following method:
The all alkylization reaction of amino on steps 1 and 2-amino-7- bromine fluorenes: 2- amino-7- bromine fluorenes (formula a) and R1COOH and
R2COOH reaction generates amide, then with NaBH4For reducing agent reducing amide, formula b compound is obtained；
No. 9 step 2, fluorenyl position alkylated reactions: make b compound that deprotonation occur with highly basic, then carried out with halogenated hydrocarbons
Alkylation, obtains formula c compound；
The aryl substitution reaction of step 3, fluorenyl bromine: lithium halogen occurs for formula c compound and organo-lithium compound (such as n-BuLi)
Exchange reaction, then electrophilic aryl addition reaction occurs with three polychlorostyrene piperazines, obtain formula d compound；
The electrophilic substitution reaction of step 4, chlorine piperazine: first reacting metal K and pyrazoles or derivatives thereof, generate respective negative from
Electrophilic substitution reaction occurs for son, then formula d compound and pyrazoles or derivatives thereof anion, generates compound of formula I.
In above-mentioned synthesis process, wherein R1、R2The alkyl for being 1~4 for carbon atom number, preferably ethyl；R3, R4Carbon atom
The alkyl that number is 1~6, R5、R6、R7、R8The alkyl for being 1~4 for H or carbon atom number, preferably methyl or H.
On the basis of the photosensitizer shown in Formulas I, make Formulas I photosensitizer and complex YbLm(m=3) complexation reaction occurs, obtains
To Yb shown in Formula II3+Complex:
In above-mentioned synthesis process, R1、R2The alkyl for being 1~4 for carbon atom number, preferably ethyl；R3, R4Carbon atom number is 1
~6 alkyl, R5、R6、R7、R8The alkyl for being 1~4 for H or carbon atom number, preferably methyl or H；L is assistant ligand, optional
At least from the above-mentioned shown number respectively anion of hfa, pom, dbm, dnm, tta, hft, fod, bta, nta and nha
It is a kind of.
The temperature detection method of offer of the invention, utilizes Yb3+Fluorescence of the luminous spectrum medium wavelength in 900~970nm range
The parameter of intensity and wavelength in the ratio between fluorescence intensity of 900~985nm range or its logarithm as measurement temperature, or with hair
The ratio or its logarithm that the fluorescence intensity of two transmitting bands near 945nm and 976nm is located in spectrum are as measurement temperature
The parameter of degree provides a kind of not by oxygen interference and with the fluorescence temperature method for sensing of excellent detection accuracy and investigation depth
(being better than 0.5K, embodiment 3), with completely new approach solve in fluorescence temperature sensing it is long-term since a difficulty always existing
Topic, i.e., there are larger interferences to fluorescence temperature detection result for oxygen concentration.The present inventor's studies have shown that above-mentioned detection method pair
In Yb3+Luminophor has generality (embodiment 4,5).In method for sensing of the invention, the measurement of temperature can be based on single
The fluorescence intensity ratio of the different wavelength range of the emission spectrum of rare earth compounding and carry out, this avoids components in compound
The problem of being unevenly distributed and leading to error.Our research is also shown that if using in the luminous spectrum, is located at
Parameter of the logarithm of the ratio of the fluorescence intensity of two transmitting bands near 945nm and 1010nm as measurement temperature, then oxygen
There is very big interference to the detection result of temperature, such as respectively in N2And O2The survey for the use of this parameter being 273K to temperature under atmosphere
Result difference 19K (embodiment 3) is measured, shows that temperature detection method tool proposed by the present invention has great advantage.
Structure provided by the invention organic photosensitizer shown in formula I is sensitized Yb with excellent long wave3+Luminescent properties,
In structure complex (R as shown in formula III1、R2For ethyl；R3, R4For butyl；R5=R6=R7=R8=methyl) in, it is close red
Outer two-photon is sensitized Yb3+Luminescent properties have been more than previously reported other Yb3+Complex (see embodiment 2).Usual organic RE is matched
The luminous intensity and quantum yield for closing object increase with temperature and are reduced, the organic rare-earth ligand of report different from the past, structure
The Yb as shown in formula III3+Complex (R1、R2For ethyl；R3, R4For butyl；R5=R6=R7=R8=methyl) and its and matrix
The Yb for the compound that material is formed3+Luminous intensity and fluorescence quantum yield increase with temperature and significantly increase (embodiment 3), these
Unexpected result showed that fluorescence temperature method for sensing of the invention and material have very high practical value, especially in work
Temperature sensing etc. has broad application prospects in body animal body, and luminescent nanoparticle provided by the invention is such answers
With having established excellent basis.
Detailed description of the invention
Fig. 1 is ultraviolet-visible absorption spectroscopy figure of the light-sensitive compound DFQZ in toluene solution in embodiment 1.
Fig. 2 is the Yb in embodiment 23+Complex Yb (tta)3The ultraviolet-visible absorption spectroscopy of the toluene solution of DFQZ.
Fig. 3 is Yb in embodiment 23+Complex Yb (tta)3Excitation spectrum (Detection wavelength of the DFQZ in toluene solution
For 976nm) and Yb3+Emission spectrum (excitation wavelength 480nm).
Fig. 4 is Yb in light-sensitive compound DFQZ in embodiment 1 and embodiment 23+Complex Yb (tta)3DFQZ is in toluene
Two photon absorption cross section and excitation wavelength relational graph in solution, concentration is 1 × 10-4mol L-1。
Fig. 5 is Yb in light-sensitive compound DFQZ in embodiment 1 and embodiment 23+Complex Yb (tta)3The toluene of DFQZ
The logarithm of the luminous intensity under the laser excitation of 810nm and 860nm and the logarithm of excitation light power density close respectively in solution
System's figure, concentration is 1 × 10-4mol L-1。
Fig. 6 is PMMA-Yb (tta) in embodiment 3 in 78-328K temperature range3DFQZ film is in a nitrogen atmosphere
Luminescent spectrum (excitation wavelength 450nm), the temperature that curve represents from the bottom to top in figure be successively 78K, 128K, 178K, 228K,
278K and 328K.
Fig. 7 is PMMA-Yb (tta) in embodiment 3 in 78-328K temperature range3DFQZ film respectively in nitrogen (a) and
The temperature that curve represents from the bottom to top in normalization luminescent spectrum (excitation wavelength 450nm) figure under oxygen (b) atmosphere is successively
It is 78K, 128K, 178K, 228K, 278K and 328K.
Fig. 8 is PMMA-Yb (tta) in embodiment 3 in 178-378K temperature range3DFQZ film ln under different atmosphere
(I900-970/I900-985) with the linear relationship chart of 1/T.
Fig. 9 is PMMA-Yb (tta) in embodiment 33DFQZ film in a nitrogen atmosphere differentiate by the temperature near 308K
Rate.
Figure 10 is PMMA-Yb (tta) in embodiment 3 in 178-378K temperature range3DFQZ film is under different atmosphere
ln(I945/I976) with the linear relationship chart of 1/T.
Figure 11 is PMMA-Yb (tta) in embodiment 3 in 178-378K temperature range3DFQZ film is under different atmosphere
ln(I945/I1010) with the linear relationship chart of 1/T.
Figure 12 Yb (tta) in embodiment 4 in 218-318K temperature range3·2H2The toluene solution of O is in a nitrogen atmosphere
Normalization luminescent spectrum (excitation wavelength 375nm, concentration be 1 × 10-4mol L-1), curve represents from the bottom to top in figure
Temperature is successively 218K, 238K, 258K, 278K, 298K and 318K.
Figure 13 is Yb (tta) in embodiment 4 in 218-318K temperature range3·2H2The toluene solution of O is in nitrogen atmosphere
Under ln (I900-965/I900-985) with the linear relationship chart of 1/T.
Figure 14 Yb (tta) in embodiment 5 in 178-318K temperature range3The toluene solution of dpbt is in a nitrogen atmosphere
Normalization luminescent spectrum (excitation wavelength 410nm, concentration be 1 × 10-4mol L-1), curve represents from the bottom to top in figure
Temperature is successively 178K, 198K, 218K, 238K, 258K, 278K, 298K and 318K.
Figure 15 is Yb (tta) in embodiment 5 in 178-318K temperature range3The toluene solution of dpbt is in nitrogen atmosphere
Under ln (I900-975/I900-985) with the linear relationship chart of 1/T.
Figure 16 K [Yb (Az) in embodiment 5 in 238-318K temperature range4] acetonitrile solution returning in a nitrogen atmosphere
One changes luminescent spectrum, and (excitation wavelength 400nm, concentration are 1 × 10-4mol L-1), the temperature that curve represents from the bottom to top in figure
It is successively 238K, 258K, 278K, 298K and 318K.
Figure 17 is the K [Yb (Az) in embodiment 5 in 258-318K temperature range4] acetonitrile solution in a nitrogen atmosphere
ln(I900-965/I900-990) with the linear relationship chart of 1/T.
Figure 18 is PMMA-Yb (tta) in embodiment 6 in 288-313K temperature range3DFQZ nanoparticle is in nitrogen
Normalization luminescent spectrum (excitation wavelength 450nm) under atmosphere, the temperature that curve represents from the bottom to top in figure be successively 288K,
293K, 298K, 303K, 308K and 313K；Illustration is temperature resolution of the nanoparticle near 308K.
Figure 19 is PMMA-Yb (tta) in embodiment 6 in 288-313K temperature range3DFQZ nanoparticle is in nitrogen
Ln (I under atmosphere900-970/I900-985) with the linear relationship chart of 1/T.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The reactant can be gotten from open business unless otherwise instructed.
Embodiment 1, synthesis sensitive ligand DFQZ (in Formulas I, R1、R2For ethyl；R3, R4For butyl；R5=R6=R7=R8=
Methyl)
In the present embodiment, DFQZ synthetic route, experiment condition and each step yield be as follows:
Specific steps are as follows:
1) synthesis of 2- (N, N diethyl) -7- bromine fluorenes (compound 2)
In 100ml round-bottomed flask, 2- amino -7- bromine fluorenes (compound 1) (1.0g, 3.8mmol) is taken to be dissolved in 60ml ice second
In acid.It places reaction liquid into ice-water bath, is slowly added to 1.6gNaBH4(42.7mmol), heating are warmed to room temperature reaction solution, then
It is slowly added to 1.6gNaBH4, reaction solution is heated to 85 DEG C and is maintained 40 minutes.It to fully reacting, is cooled to room temperature, NaOH is added
Aqueous solution is in neutrality system.Product is extracted three times with methylene chloride (20ml × 3), is merged organic phase and is done with anhydrous magnesium sulfate
Dry half an hour.It is filtered to remove desiccant, after solvent is removed under reduced pressure, using methylene chloride as eluant, eluent, silica gel is filler, column chromatography point
From purified product.Product is faint yellow solid, yield 95%.EI MS:m/z:315[M+].Anal.Calcd for C17H18BrN
C,64.57；H,5.74；N,4.43；Found:C,64.53；H,5.71；N,4.46.1H NMR(500MHz,CDCl3,TMS):
1.18-1.21 (t, J=7.0Hz, 6H), 3.39-3.43 (q, J=7.0Hz, 4H), 3.81 (s, 2H), 6.70-6.71 (d, J=
8.0Hz, 1H), 6.85 (s, 1H), 7.39-7.40 (d, J=8.0Hz, 1H), 7.43-7.44 (d, J=8.0Hz, 1H), 7.55-
7.56 (d, J=5.0Hz, 1H)
2) synthesis of the bromo- 9,9- di-n-butyl fluorenes (compound 3) of 2- (N, N diethyl) -7-
In 100ml branch mouth bottle, 0.71g 2- (N, N diethyl) -7- bromine fluorenes (compound 2) (2.2mmol) is dissolved in
In 50mlDMSO, under argon gas protection, 0.27g sodium hydrate solid powder is added.After reaction solution is cooled to 10 DEG C, protected in argon gas
It under shield, is added dropwise 0.57ml n-butyl iodide (0.92g, 5mmol), is stirred overnight at 90 DEG C.It is cooled to room temperature after reaction,
Reaction solution is poured into a large amount of water, product (3 × 15mL) is extracted with dichloromethane), merge organic phase and is done with anhydrous sodium sulfate
It is dry.It is filtered to remove desiccant, after solvent is removed under reduced pressure, methylene chloride is eluant, eluent, and silica gel is filler, column chromatography for separation purification
Product.Product is light gray solid, yield 90%.EI MS:m/z:427[M+].Anal.Calcd for C25H34NBr:C,
70.08；H,8.00；N,3.27；Found:C,69.89；H,8.17；N,3.21.1H NMR(400MHz,CDCl3,TMS):δ
(ppm) .0.63-0.65 (m, 4H), 0.68-0.71 (t, 6H), 1.05-1.13 (m, 4H), 1.18-1.21 (t, J=7.0Hz,
6H), 1.86-1.89 (t, J=7Hz, 4H), 3.29-3.43 (q, J=7Hz, 4H), 6.58-6.59 (d, J=8.4Hz, 1H),
6.64-6.66 (d J=8.5Hz, 1H), 7.35 (s, 1H), 7.36 (s, 1H), 7.37 (s, 1H), 7.46-7.48 (d, J=
8.5Hz,1H).
3) 2- (N, N diethyl) -7- (the chloro- 1,3,4- triazine -2- base of 4,6- bis-) -9,9- di-n-butyl fluorenes (compound 4)
Synthesis
Take bromo- 9,9- di-n-butyl fluorenes (compound 3) 1.2g (2.8mmol) of 2- (N, N diethyl) -7-, be dissolved in except
It in the tetrahydrofuran of water, after leading to argon gas deoxygenation, is placed in -78 DEG C of dry ice acetone bath, under protection of argon gas, is added with needle tubing injection
The hexane solution (1.6M, 4.5mmol) for entering 2.8ml n-BuLi, reacts under stiring after being slowly increased to room temperature to solution, then
Continue to be stirred to react 30min.The 0.8g (4.3mmol) three above-mentioned reaction solution being added in the dry ice acetone bath for being placed in -78 DEG C
It in the tetrahydrofuran solution of polychlorostyrene piperazine, is stirred to react after being slowly increased to room temperature to solution, is further continued for being stirred to react 60min.Decompression
After removing solvent, product is using methylene chloride as eluent, with silicagel column separating-purifying.Obtain 2- (N, N- dibutyl aniline -4-
Base) -4,6- two chloro- 1,3,5- triazine (compound 3) orange red grease.Yield is 35%.EI MS:m/z:468[M+],
Anal.Calcd for C26H30Cl2N4:C,66.52；H,6.44；N,11.93.Found:C,66.40；H,6.58,11.81.1H
NMR (400MHz, CDCl3, TMS): δ (ppm) .0.62-0.67 (m, 4H), 0.69-0.73 (t, J=7.2Hz, 6H), 1.06-
1.13 (m, 4H) 1.19-1.23 (t, J=7.0Hz, 6H), 1.87-1.91 (m, 4H), 3.40-3.45 (q, J=7.2Hz, 4H),
6.59-6.60 (d, J=2.4Hz, 1H), 6.65-6.68 (q, J=8.0Hz, 1H), 7.36 (s, 1H), 7.37 (s, 1H), 7.38
(s, 1H), 7.47-7.49 (d, J=10.0Hz, 1H)
4) 2- (N, N diethyl) -7- (4,6- bis- (3,5- dimethyl pyrazole -1- base) -1,3,4- triazine -2- base) -9,9-
The synthesis of di-n-butyl fluorenes (compound 5, DFQZ)
Under protection of argon gas, the metallic potassium 0.08g (2.07mmol) of fresh cut is added to the tetrahydrofuran through removing water process
In, add 3,5- dimethyl pyrazole 0.288g (3.0mmol), heating reflux reaction 3h, generate 3,5- dimethyl pyrazole bear from
Son.Above-mentioned reaction solution is placed in ice-water bath, under stiring, thereto be added 2- (N, N diethyl) -7- (4,6- bis- chloro- 1,3,
4- triazine -2- base) -9,9- di-n-butyl fluorenes (compound 4) 0.497g (1.0mmol), after stirring 1h at room temperature, at 80-85 DEG C
Oil bath in back flow reaction 12h.Solvent is removed under reduced pressure after reaction solution is cooling, with the mixed solvent of methylene chloride and ethyl acetate
(the two volume ratio is 3:1) is eluent, by crude product silicagel column separating-purifying.Gained crude product is mentioned through circulation HPLC separation again
It is pure, it is concentrated to get 2- (N, N diethyl) -7- (4,6- bis- (3,5- dimethyl pyrazole -1- base) -1,3,4- triazine -2- bases) -9,9-
The orange powder of di-n-butyl fluorenes (DFQZ).Yield is 30%.[M-H]+calc.:617.4080,Found:617.4070,
Anal.Calcd for C38H48N8:C,73.99；H,7.84；N,18.17Found:C,73.80；H,7.95；N,18.25.1H
NMR (400MHz, CDCl3, TMS): δ (ppm) .0.67-0.70 (t, 6H), 1.06-1.15 (m, 4H), 1.20-1.24 (t, J=
7.0Hz, 6H), 1.85-2.07 (m, 4H), 2.36 (s, 6H), 2.90 (s, 6H), 3.42-3.48 (q, J=7.0Hz, 4H), 6.11
(s, 2H), 6.92 (s, 1H), 6.68-6.90 (d, J=8.0Hz, 1H), 7.59-7.61 (d, J=8.8Hz, 1H), 7.62-7.64
(d, J=8.0Hz, 1H), 8.42 (s, 1H), 8.46-4.49 (q, J=8.0Hz, 1H)
Absorption spectrum of the DFQZ in toluene is as shown in Figure 1, at 293k, measure fluorescent quantum of the DFQZ in n-hexane
Yield is up to 0.95, and the fluorescence quantum yield in toluene is 0.83.
Embodiment 2, the photosensitive complex Yb (tta) of synthesis3DFQZ (in formula III, R1、R2For ethyl；R3, R4For butyl；R5
=R6=R7=R8=methyl)
Under agitation, by Yb (NO3)3·xH2The ethanol solution (15mL) of O (470.0mg, 1.0mmol) is added dropwise
Into the ethanol solution (15mL) of HTTA (666.6mg, 3.0mmol), and continue to stir at room temperature, while ammonium hydroxide is added dropwise, adjust
Solution ph is saved to neutrality.At 80-85 DEG C after heating reaction 3h, it is cooled to room temperature.It is spin-dried for ethyl alcohol, obtains light yellow solid,
After washing solid repeatedly with water, benzene, which is added, dissolves solid, with anhydrous CaCl2It is dry.After filtering off desiccant, vacuum distillation is removed
Solvent obtains light yellow oil, petroleum ether is added, heating, after filtering out insoluble matter, vacuum distillation removes petroleum ether, vacuum item
It is dry under part, obtain product Yb (tta)3·2H2The buff powder of O.Elemental analysis: YbC24H16O8F9S3Calcd.:C:
33.03,H:1.85；Found:C:33.63, H:1.83%；ESI-MS:m/z 859.9 [M+Na]+；Calcd.:
YbC24H12O6F9S3Na 859.6。
Under protection of argon gas, by 10mL Yb (tta)3·2H2The tetrahydrofuran solution of O (0.03mmol, 25.31mg) is added dropwise
Into the tetrahydrofuran solution of 10mL ligand DFQZ (0.03mmol, 18.48mg), stirring 30min is protected from light under room temperature.It will be above-mentioned anti-
After answering liquid that solvent is removed under reduced pressure, with a small amount of ether dissolution and it is filtered to remove insoluble matter, is added dropwise to the n-hexane as precipitating reagent, it will
The solid of precipitation is washed 2-3 times with n-hexane, dry, obtains product Yb (tta)3The orange powder of DFQZ.
Yb(tta)3The absorption spectrum of DFQZ is matched as shown in Fig. 2, from the figure, it can be seen that with after Yb (III) coordination
The absorption peak main peak of body DFQZ is located near 475nm, extends to compared to free ligand red shift 65nm, absorbing window
At 530nm.
Fig. 3 is complex Yb (tta)3Excitation and emission spectra (exciting light 480nm) of the DFQZ in toluene solution, by sending out
Penetrating spectrum can see, and Yb (III) is located near 980nm2F5/2→2F7/2Characteristic transition radiate peak and be located in 1000nm and
Two acromions near 1030nm.At 293k, Yb (tta) is measured3Photoluminescence quantum yield of the DFQZ in toluene is 2.3%.
DFQZ and Yb (tta)3DFQZ has extraordinary two-photon excitation luminous power, and Fig. 4 gives DFQZ and Yb
(tta)3The relational graph of two photon absorption cross section and excitation wavelength of the DFQZ in toluene solution, at 810nm, DFQZ's
Two photon absorption cross section reaches maximum value 851GM；At 860nm, Yb (tta)3The two photon absorption cross section of DFQZ reaches most
Big value 962GM, two-photon excitation action section (δ × Φ) is up to 22GM.Fig. 5 is DFQZ at 810nm, Yb (tta)3·DFQZ
Logarithm (log (P)) relational graph of the logarithm (log (I)) of luminous intensity and excitation light power density at 860nm, between the two
Meeting linear relationship, coefficient R > 0.9995 of linear fit well, the slope that fitting obtains straight line is to be approximately equal to 2,
Prove that luminescence process is the luminous process of a two-photon excitation.
Embodiment 3, preparation are based on PMMA-Yb (tta)3The temperature sensor of DFQZ
Under stiring by 1mg Yb (tta)3DFQZ is dissolved in the 10mL containing 9mg polymethyl methacrylate (PMMA)
In acetone soln, then gained mixed solution is added dropwise on 1.2cm × 1.7cm × 0.1cm quartz plate, 40 DEG C of vacuum drying
12h removes solvent, forms the PMMA-Yb (tta) that thickness is about 2.1 μm3DFQZ fluorescence temperature sensing membrane.
Fig. 6 is PMMA-Yb (tta) under nitrogen atmosphere3Luminescent spectrum of the DFQZ film at 78-328K.It is different from the past
The organic rare-earth ligand of report, as the temperature rises, PMMA-Yb (tta)3The fluorescence intensity of DFQZ film dramatically increases.
At the same time, temperature is increased to 328K by 78K, and photoluminescence quantum yield improves 5 times, is promoted to 1.0% by 0.2%.
Fig. 7 a) and b) be PMMA-Yb (tta) under nitrogen and oxygen atmosphere respectively3The normalization fluorescence of DFQZ film is sent out
Penetrate spectrum, it can be seen that the emission spectrum under different atmosphere within the scope of 900-985nm is quite similar, and oxygen is main
Influence the emission spectrum within the scope of 1000-1150nm.As can be seen from Figure 8, whether in nitrogen, oxygen or 20% oxygen
In the mixed atmosphere of 80% nitrogen, ln (I900-970/900-985) good linear relationship (R is presented to the 1/T reciprocal mapping of temperature2
=0.999), and oxygen concentration does not influence above-mentioned linear relationship, and for the detection resolution of temperature near 308K
Degree has reached 0.5K (Fig. 9).If being mapped with the natural logrithm of the intensity ratio at 945nm and 976nm to 1/T, also can get good
Linear relationship (Figure 10), and oxygen concentration does not also influence above-mentioned linear relationship.Should the experimental results showed that, the present invention provide
A kind of fluorescence temperature method for sensing not interfered by oxygen.
It should be noted that oxygen is for Yb3+Sensitized luminescence spectrum be not without influence, especially be greater than 985nm
Wave-length coverage, oxygen is to Yb3+Fluorescence spectrum interference is larger.If such as with the natural logrithm pair of intensity ratio at 945nm and 1010nm
1/T maps (Figure 11), although also can get linear relation, in the mixed of nitrogen, oxygen or 20% oxygen and 80% nitrogen
It closes the straight line that measures in atmosphere no longer to overlap, at this point, the difference of the temperature value measured in oxygen and nitrogen under 278K is
19K。
Embodiment 4, ultraviolet excitation Yb (tta)3·2H2O fluorescence temperature sensing
Yb(tta)3·2H2Ligand tta in O can be sensitized Yb under the ultraviolet excitation of 375nm3+It shines, toluene is molten
Normalization luminescent spectrum of the liquid within the scope of 218-318K is as shown in figure 12.With ln (I900-965/900-985) to the 1/T reciprocal of temperature
Mapping can get linear relationship (R as shown in fig. 13 that2=0.987).
Embodiment 5, excited by visible light Yb3+Complex fluorescent temperature sensing
Replace Yb (tta) using dpbt molecule (formula IV)3Sensitization ligand DFQZ in DFQZ, we, which synthesize, has obtained accordingly
Compound Yb (tta)3dpbt.Dpbt can be sensitized Yb under the excited by visible light of 410nm3+It shines, toluene solution is in 178-
Normalization luminescent spectrum within the scope of 318K is as shown in figure 14.With ln (I900-970/900-985) map to the 1/T reciprocal of temperature, it can
Obtain linear relationship (R as shown in figure 152=0.997).
Using ligand Az (Formula V) reported in the literature (S.Petoud, et al., Chem.Eur.J.2008,14,1264), close
At K [Yb (Az)4] compound (Formula IV), Az can be sensitized Yb under the excited by visible light of 410nm3+It shines, acetonitrile solution exists
Normalization luminescent spectrum within the scope of 258-318K is as shown in figure 16.With ln (I900-970/900-985) 1/T reciprocal of temperature is made
Figure, can get linear relationship (R as shown in figure 172=0.956)
Embodiment 6, preparation PMMA-Yb (tta)3DFQZ luminescent nanoparticle
It prepares Yb (tta)3(PMMA-co-MA, number are divided equally for DFQZ and Eudragit S100
Son amount is 36000, and the ratio of ester group and carboxyl is the acetone soln of 1:0.016) in copolymer, wherein Yb (tta)3DFQZ's
Concentration is 0.1g L-1, the concentration of PMMA-co-MA is 1g L-1.It is under room temperature and stirring condition, above-mentioned solution (2ml) is slow
It is added dropwise in 8ml deionized water, and continues stirring 30 minutes, obtain orange-yellow colloidal solution.Institute is removed under reduced pressure at 35 DEG C
The acetone in colloidal solution is obtained, the hydrosol is then heated to reflux 1h at 100 DEG C.The hydrosol after flowing back is in 50,000G
Lower centrifugation, collects gained precipitating, and ultrasound is scattered in precipitating again in 8ml deionized water, obtains with Yb (tta)3DFQZ is
Luminescent material, using PMMA-co-MA as the hydrosol of the nanoparticle of host material.Dynamic light scattering test shows prepared receive
The average grain diameter d of rice corpusclesavFor 51.2nm, particle diameter distribution is in the range of 35-70nm.
(the excitation as shown in figure 18 of normalization luminescent spectrum of the hydrosol of prepared nanoparticle within the scope of 288-313K
Wavelength: 450nm).With ln (I900-970/900-985) map to the 1/T reciprocal of temperature, it can get linear relationship as shown in figure 19
(R2=0.991).It is above-mentioned the experimental results showed that prepared nanoparticle can be used for the temperature sensing of biosystem.
Embodiment 7, PMMA-Yb (tta)3The preparation of DFQZ luminescent nanoparticle and temperature sensing property
By 1.0mg Yb (tta)3DFQZ and 10mg PMMA-co-MA is dissolved in 10mL acetone, utilizes reduced pressure induced
Microjet mixing method mix it with 100ml deionized water, actual conditions such as Chinese invention patent ZL 201110387910.6
Described in embodiment 2.Remaining acetone is removed under reduced pressure in obtained mixed liquor at 35 DEG C, is obtained with Yb (tta)3DFQZ is hair
Luminescent material, using PMMA-co-MA as the hydrosol of the nanoparticle of host material.Dynamic light scattering test shows prepared nanometer
The average grain diameter d of particleavFor 100nm, particle diameter distribution is in the range of 76-135nm.
(the excitation as shown in figure 18 of normalization luminescent spectrum of the hydrosol of prepared nanoparticle within the scope of 288-313K
Wavelength: 450nm).Data analysis shows, ln (I900-970/900-985) it with the 1/T reciprocal of temperature is linear relation, near 308K,
Prepared nanoparticle reaches 0.7K to the resolution ratio of temperature sensing.
Claims (16)
1. a kind of fluorescence temperature method for sensing makes under ultraviolet light or the excitation of visible light or near infrared light containing Yb3+Shine
Material emits Yb3+The fluorescence of ion, with Yb3+Emission spectrum medium wavelength 900~970nm range fluorescence intensity and wavelength
In the ratio of the fluorescence intensity of 900~985nm range or its logarithm as the parameter for measuring temperature, or with Yb3+Transmitting
The ratio that the fluorescence intensity of two luminous zones near 945nm and 976nm is located in spectrum or its logarithm are as measurement
The parameter of temperature, which is characterized in that described to contain Yb3+Luminescent material be to be excited in ultraviolet light or visible light or near infrared light
Under can emit Yb3+The Yb of the characteristic fluorescence of ion3+The compound of ionic complex or the complex and host material composition；
The photosensitizer ligand that the complex has structure shown in formula I:
In Formulas I, R1、R2The alkyl for being 1~4 for carbon atom number；R3、R4The alkyl that carbon atom number is 1~6, R5、R6、R7、
R8The alkyl for being 1~4 for H or carbon atom number.
2. fluorescence temperature method for sensing as described in claim 1, which is characterized in that measurement temperature is according to following formula (1)
Or (2) progress:
ln(I900-970/I900-985)=A (1/T)+B formula (1)
ln(I945/I976)=C (1/T)+D formula (2)
Wherein, T represents temperature；I900-970/I900-985For Yb3+Fluorescence intensity of the emission spectrum medium wavelength in 900~970nm range
With wavelength 900~985nm range the ratio between fluorescence intensity；I945/I976For Yb3+Be located in emission spectrum 945nm and
The ratio of the fluorescence intensity of two luminous zones near 976nm；A, B, C, D are constant.
3. fluorescence temperature method for sensing as described in claim 1, which is characterized in that the structure of the complex such as Formula II institute
Show:
Wherein: R1、R2The alkyl for being 1~4 for carbon atom number；R3、R4The alkyl that carbon atom number is 1~6, R5、R6、R7、R8For H or
The alkyl that carbon atom number is 1~4；L is assistant ligand.
4. fluorescence temperature method for sensing as claimed in claim 3, which is characterized in that the assistant ligand L is selected from lower column number
Respectively one of anion of hfa, pom, dbm, dnm, tta, hft, fod, bta, nta and nha or a variety of:
5. fluorescence temperature method for sensing as claimed in claim 4, which is characterized in that the complex has as shown in formula III
Structure:
6. fluorescence temperature method for sensing as described in claim 1, which is characterized in that the host material be organic polymer or
Inorganic oxide material.
7. fluorescence temperature method for sensing as claimed in claim 6, which is characterized in that the high-molecular organic material is selected from poly- first
At least one of base methyl acrylate, polystyrene and polycarbonate.
8. fluorescence temperature method for sensing as claimed in claim 6, which is characterized in that the high-molecular organic material be selected from
Carbon-carbon bond constitutes main chain and the simultaneously high-molecular compound containing hydrophilic radical and hydrophobic grouping；The wherein hydrophobic grouping choosing
From at least one of alkyl, phenyl, aryl, ester group, carbonyl and ether, the hydrophilic radical is selected from carboxyl, hydroxyl, amide
At least one of base and poly- ethylene oxygroup.
9. fluorescence temperature method for sensing as claimed in claim 8, which is characterized in that described to be constituted main chain and same with carbon-carbon bond
The high-molecular compound of Shi Hanyou hydrophilic radical and hydrophobic grouping is selected from methacrylic acid-methacrylate copolymer, methyl
Acryl acid-methyl methacrylate copolymer, Styrene-methyl Acrylic Acid Copolymer, acrylic acid and acrylic ester copolymers, benzene
Ethylene maleic acid copolymer, styrene-maleic anhydride copolymer, styrene-maleic acid Arrcostab-maleic acid, benzene second
Alkene-maleic anhydride-maleic acid isobutyl copolymer, styrene-maleic acid isobutyl-maleic acid, maleic acid alkane
Base ester-maleic acid, acrylamide-methacrylate copolymer, butyl maleate and methyl vinyl ether are total to
At least one of polymers and styrene-methacrylate-acrylic copolymer.
10. fluorescence temperature method for sensing as claimed in claim 8, which is characterized in that the carbon-carbon bond constitutes main chain and simultaneously
The molecular weight of high-molecular compound containing hydrophilic radical and hydrophobic grouping is 1,500~200,000.
11. fluorescence temperature method for sensing as described in claim 1, which is characterized in that the complex and host material form
Compound in, the host material and Yb3+The mass ratio of complex is 0.5~10,00: 1.
12. fluorescence temperature method for sensing as described in claim 1, which is characterized in that described to contain Yb3+Luminescent material be receive
Nanoparticle material.
13. a kind of photosensitizer, structure are shown in formula I:
In Formulas I, R1、R2The alkyl for being 1~4 for carbon atom number；R3、R4The alkyl that carbon atom number is 1~6, R5、R6、R7、R8For H or
The alkyl that carbon atom number is 1~4.
14. a kind of Yb3+Complex, structure is as shown in Formula II:
Wherein, R1、R2The alkyl for being 1~4 for carbon atom number, R3、R4The alkyl that carbon atom number is 1~6, R5、R6、R7、R8For H or
The alkyl that carbon atom number is 1~4, L is assistant ligand.
15. Yb as claimed in claim 143+Complex, which is characterized in that the assistant ligand L selected from lower column number distinguish
One of anion for hfa, pom, dbm, dnm, tta, hft, fod, bta, nta and nha is a variety of:
16. Yb as claimed in claim 143+Complex, structure is as shown in formula III:
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