CN107936946A - Fluorescence method distinguishes the preparation and application of the organic fluorescence sensor array of a few class explosives - Google Patents
Fluorescence method distinguishes the preparation and application of the organic fluorescence sensor array of a few class explosives Download PDFInfo
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Abstract
The present invention relates to fluorescence sense array that can five class explosives be detected with differentiation being made of several fluorescent sensing materials and its preparation method and application, the fluorescence sense array interacts what the nano material that self assembly obtains formed by carbazole derivates by several by π π.Composition material in the fluorescence sense array of the present invention is organic fluorescence sensing material, has typical P-type material feature and good stability of photoluminescence, and the fluorescence sense array of these materials composition has explosive distinguishes effect well.
Description
Technical field
The invention belongs to the fluorescence sense array of organic semiconductor fluorescent nano material composition, more particularly to based on carbazole point
Design, synthesis, assembling sensor array and the fluorescence response variation according to sensor array of several p-type semiconductor materials of son
Selectivity distinguishes a few class explosives.
Background technology
All there is very big threat to personal safety, national security, natural environment in explosive.Therefore researcher is quick-fried
Substantial amounts of work has been done in terms of the detection research of fried thing, if while explosive is detected, explosive can have been distinguished,
This is significant in anti-terrorism.Conventional explosive can substantially be divided into following a few classes：Nitroparaffin hydro carbons (DMNB), nitryl aromatic
Compound (DNT, TNT), nitro amine (RDX), nitro esters (PETN), black powder (S), peroxide (TATP) etc..Mesh
The preceding method for explosive detection differentiation is fewer.And sensor array is as a kind of widely used differentiation means, such side
Method is assembled into sensor array, such as colorimetric sensing array using a few class materials, organic in volatility plus aided analysis method
Thing, Toxic differentiation etc. have been achieved for larger progress.Therefore sensor array can also be used as one kind to distinguish well
The means of explosive.
It is based on Fluorometric assay explosive that fluorescence sense array, which distinguishes explosive,.Fluorometric assay distinguishes explosive
Main principle is that with explosive different degrees of physics chemical action occurs for several fluorescence molecule materials for forming sensor array
And different change in fluorescence signals is produced, then signal Analysis reaches differentiation purpose.First, have not per a kind of explosive molecule
Same chemical property.Such as nitryl aromatic class explosive (DNT, TNT), this kind of molecular vapor pressure is higher, and volatility is relatively preferable；
Nitro electron-withdrawing power on aromatic rings is strong, reduces the LUMO energy of molecule, and the particularity of aromatic rings, such explosive
It is strong with fluorescence molecule combination power, therefore this kind of explosive easily detects, and studies also to compare more.And nitro amine (RDX) and
Nitro esters (PETN) explosive vapors force down, and volatility is poor, and these molecule electron donations are poor, relatively difficult inspection
Survey.And detected in S and peroxide explosive molecule because acomia color group also seems difficult.Therefore, utilization sensing as few as possible
Array, the target of multiclass explosive is distinguished with simple analysis, it appears particularly difficult with regard to that can reach.
At present, the explosive category that the array differentiating method in existing report can be distinguished is less, and more is no more than three classes.
And these sensor arrays composition is complicated, and cost is high, needs to use cumbersome analysis method during differentiation.This obvious nothing
Method meets actual demand.Realize that simple sensor array distinguishes multiclass explosive, this is filled with scientific research person challenge.
The content of the invention
An object of the present invention is to provide can be to the progress high sensitivity fluoroscopic examination differentiation of a few class explosives by several
The sensor array that kind organic fluorescence sensing material is assembled into.
The second object of the present invention, which is to provide, to be assembled into and can carry out high sensitivity fluoroscopic examination differentiation to a few class explosives
Sensor array several organic fluorescence sensing materials preparation method.
The third object of the present invention be to provide can to a few class explosives have high sensitivity fluoroscopic examination distinguish by several
The application for the sensor array that class organic fluorescence sensing material is assembled into.
The purpose of core of the present invention is to prepare that the glimmering of high sensitivity fluoroscopic examination differentiation can be carried out to a few class explosives
Light sensing array, this sensor array are composed of several different organic fluorescence sensing materials.The present invention's is combined into sensing
The different materials of array are a series of p-type organic fluorescence sensing materials based on carbazole molecules, each in these types of material
Kind material is the structure for synthesizing the carbazole derivates with different side chains by varying carbazole molecules side chain and its degree of polymerization
Thing, obtains several one-dimensional organic semiconductor nanowires or nanobelt by the method for self assembly, by manufacture craft, prepares i.e.
The present invention's can carry out a few class explosives being assembled by several organic fluorescence sensing materials for high sensitivity fluoroscopic examination differentiation
Into sensor array.The material of sensor array is combined into the present invention, i.e. several the nano wires or nanobelt of molecule assembling compare table
Area is larger, has the features such as surface pore is more, is conducive to be detected suction of the explosive steam in nano wire or nanometer belt surface
It is attached diffusion and preferably interact, produce different fluorescence responses due to the different surfaces physicochemical properties of material, array
In response of a few class materials to every a kind of explosive be distinctive, therefore a kind of identification marking of similar fingerprint can be formed,
Therefore explosive can be distinguished.It is several with different substituents group side chain carbazole molecules in sensor array in the present invention
The organic fluorescence sensing material that derivative self-assembled obtains has different patterns, i.e. nanobelt and nano wire, to different explosions
Thing produces different fluorescence responses, during as a sensor array, can reach differentiation effect according to different fluorescence responses.Therefore originally
The fluorescence sense array of invention can be as the organic fluorescence sensor array that a few class explosives are detected with differentiation.
The present invention is achieved by following technical solution：
The fluorescence sense array that a kind of machine fluorescent sensing material is assembled into, wherein the fluorescence sense array is by two or more
Can to a few class explosives carry out fluorescence monitoring differentiation organic fluorescence sensing material be arranged in order composition, each is described organic
Fluorescent material is to be obtained as the carbazole derivates as described in formula (I) by π-π interaction self assemblies：
In the formula (I),
R' is identical or different, is independently from each other-(CH2)x’-R5-R6, wherein, x ' is 0,1 or 2, R5For arlydene or
Halo arlydene, R6For H ,-COOR7、-COR7、C2-6Alkynyl, C ≡ N or C3-6Alkyl, R7For H, C1-4Alkyl；
N is the integer of 3-40；
R is selected from C1-10Straight or branched alkyl ,-(CH2)x-R1-O-R2、-(CH2)y-R 1-R3Or-(CH2)z-R4,
Wherein, x 0,1 or 2, y 0,1 or the integer that 2, z are 1-9, R1For arlydene or halo arlydene, R2For C1-10
Straight or branched alkyl, R3For-H ,-CHF2、-CF3、C1-10Straight or branched alkyl, C3-10Cycloalkyl, by CHF2Or
CF3Substituted C1-10Straight or branched alkyl, C3-10Cycloalkyl, by CHF2Or CF3Substituted C3-10Cycloalkyl, R4For-
CHF2、-CF3。
Preferably, fluorescence sense array of the present invention is arranged in order as the organic fluorescence sensing material described in 2~6 kinds
Composition.
According to the present invention, the organic fluorescence materials length in the fluorescence sense array is adjustable, between two neighboring material
Away from adjustable.
According to the present invention, in the fluorescence sense array, the length of every kind of organic fluorescence sensing material is 3mm-20mm, can
Adjust, be preferably 8-10mm；The spacing of two neighboring material is 5mm-50mm, adjustable, is preferably 15-20mm.
It is further preferred that R' is identical or different ,-(CH is independently from each other2)x’-R5-R6, x ' is 0 or 1；R5For halogen
For arlydene (wherein halogen is selected from fluorine, chlorine or bromine), such as halophenylene, arlydene, such as phenylene or naphthylene；R6For
C≡CH、C≡C-CH3Or C ≡ N；
It is further preferred that R ' is identical or different ,-(CH is independently from each other2)x’-R5-R6, x ' is 0 or 1；R6For-
COOR7、-COR7；R7For methyl or ethyl；
It is further preferred that R' is identical or different, the one kind being independently from each other in following eight kinds of groups：
Wherein, upside is connection site.
Preferably, R is selected from C3-10Straight or branched alkyl, (CH2)x-R1-O-R2、-(CH2)y-R1-R3Or-(CH2)z-
R4,
Wherein, x 0,1 or 2, y 0,1 or the integer that 2, z are 2-6, R1For phenylene or naphthylene or halophenylene,
R2For C1-10Straight or branched alkyl, R3For-H ,-CF3、C1-10Straight or branched alkyl or CF3Substituted C1-10Straight chain
Or branched alkyl, R4For-CF3。
Preferably, R is selected from C3-10Branched alkyl, the branched alkyl is asymmetric alkyl.
It is further preferred that the one kind of R in following radicals：
In above-mentioned group, the upside of structural formula is connection site.
Fluorescence sense array according to the present invention, each material in the organic fluorescence sensing material is by one kind
The organic semiconductor nanowires or nanometer that carbazole derivates as described in the formula (I) are obtained by π-π interaction self assemblies
Band.
Further, each material in the organic fluorescence sensing material is by the organic semiconductor nanometer
The perforated membrane with net structure that line or nanobelt self assembly are knitted to form.
The present invention also provides the preparation method of fluorescence sense array, it is characterised in that described method includes following steps：
(1) carbazole derivates shown in the formula (I) with specific functional groups are synthesized,
Wherein each substituent is as defined above；
(2) in the mixed liquor of good solvent and poor solvent, obtained by way of self assembly described several organic glimmering
Light sensing material,
(3) diverse location that will be assembled obtained several fluorescent materials and be applied to respectively on the inside of same glass tube, obtains described
Sensor array.
According to the present invention, in step (1)：
When preparing the carbazole derivates of n=3 in formula (I), the step (1) specifically includes：
Compound shown in (1a) formula (II) and RX ' react, and compound shown in formula (III) is made；
X in formula (II) and formula (III) is identical or different, is independently from each other halogen (such as Br, I)；X ' in RX '
Selected from halogen (such as Br, I)；The same formula of definition (I) of formula (III) and the R in RX '；
Compound shown in (1b) formula (III) and R ' B (OH)2Compound shown in formula (IV) is made in reaction；
Formula (IV) and R ' B (OH)2In, the same formula of definition (I) of R '；In formula (IV), the same formula of definition (III) of R and X；
Compound shown in formula (V) is made with bis (pinacolato) diboron reaction in compound shown in (1c) formula (III)；
In formula (V), the same formula of definition (I) of R；
Compound shown in (1d) formula (IV) reacts to obtain carbazole derivates shown in formula (I) with compound shown in formula (V), wherein
N=3；Wherein, the molar ratio of compound shown in formula (IV) and compound shown in formula (V) is 2.1:1~2.5:1 (is, for example, 2.2:
1)；
When preparing 3 in formula (I)<During the carbazole derivates of n≤40, the step (1) specifically includes：
Compound shown in (1a) formula (II) and RX ' react, and compound shown in formula (III) is made；
X in formula (II) and formula (III) is identical or different, is independently from each other halogen (such as Br, I)；X ' in RX '
Selected from halogen (such as Br, I)；The same formula of definition (I) of formula (III) and the R in RX '；
Compound shown in (1a ') formula (II ') and RX ' react, and compound shown in formula (III ') is made；
X in formula (II ') and formula (III ') is identical or different, is independently from each other halogen (such as Br, I)；In RX '
X ' is selected from halogen (such as Br, I)；The same formula of definition (I) of formula (III ') and the R in RX '；M is the integer of 2-38；
Compound shown in (1b) formula (III) and R ' B (OH)2Compound shown in formula (IV) is made in reaction；
Formula (IV) and R ' B (OH)2In, the same formula of definition (I) of R '；In formula (IV), the same formula of definition (III) of R and X；
Compound shown in formula (V ') is made with bis (pinacolato) diboron reaction in compound shown in (1c ') formula (III ')；
In formula (V '), the same formula of definition (I) of R, m is the integer of 2-38；
Compound shown in (1d ') formula (IV) reacts to obtain carbazole derivates shown in formula (I) with compound shown in formula (V '), its
In 3<n≤40；Wherein, the molar ratio of compound shown in formula (IV) and compound shown in formula (V ') is 2.1:1~2.5:1 (such as
For 2.2:1).
Preferably, the step (2) includes：Click shown in the formula (I) with different specific functional groups that step (1) is obtained
Zole derivatives are dissolved in good solvent, then add poor solvent, are stood, and the carbazole derivates shown in the formula (I) pass through certainly
The suspension of organic fluorescence sensing material described in assembling mode；
Preferably, the step (2) further comprises：The suspension of several organic fluorescence sensing materials is stood
Afterwards, take out positioned at the organic fluorescence sensing material for preparing container bottom, be again placed in shaking up scattered in poor solvent and wash repeatedly
Wash, obtain the organic fluorescence sensing material；
Preferably, the volume ratio (ml of the good solvent and poor solvent:Ml it is) 1:3~1:10；
Preferably, the good solvent is selected from chloralkane and C2-5Esters, are, for example, dichloromethane, chloroform, 1,2- dichloros
Ethane, ethyl acetate or methyl acetate；
Preferably, the poor solvent is alcohol organic solvent or cycloalkane, is, for example, methanol, ethanol or hexamethylene.
Preferably, the step (3) includes：By the suspension of the organic fluorescence sensing material obtained in step (2) successively
Same glass tube is injected, after waiting solvent volatilization dry, remembers the organic fluorescence sensor array.
Fluorescence sense array of the present invention is the netted knot formed by several organic semiconductor nanowires or nanobelt
The porous film material composition of structure, these materials have high-specific surface area, different to the fluorescence response of different explosives, according to fluorescence
Response can be detected differentiation to a few class explosives by analysis.
The present invention also provides application of the fluorescence sense array in a few class explosives are distinguished, wherein the fluorescence sense
This row is made of several organic fluorescence sensing materials.
According to the present invention, the fluorescence sense array can carry out a few class explosives rapid fluorescence detection differentiation.
According to the present invention, the fluorescence sense array can be used for distinguishing solid explosive detection.
Application according to the present invention, the fluorescence sense array can be used for distinguishing the trace detection of a few class explosives, institute
The trace stated is ng or secondary ng ranks.
In the present invention, the fluorescence sense array is contacted with trace explosive (explosive is preferably solid) steam
When, because each fluorescent material has different substitution functional group pendants and different patterns, possess different surface things
Physicochemical property, it may occur that various forms of fluorescence change, by analyzing the signal of these change in fluorescence, available for reality to several
The detection of class explosive is distinguished.
Obtained different sensing materials are spin-coated in quartz glass plate pipe, by the way that explosive is placed in heating gun, are led to
Cross and different temperature is set to improve the vapour concentration of explosive, when different explosive steam is from having different substitution functional groups
During the organic fluorescence sensing material contact of side chain, multi-form change can occur for the fluorescence of the difference fluorescent sensing material, lead to
Analysis change in fluorescence signal is crossed so as to achieve the purpose that to distinguish a few class explosive detections.
A few class explosives are selected from hexogen (RDX), trinitrotoluene (TNT), dinitrotoluene (DNT) (DNT) Ji Wusi
Alcohol tetranitrate (PETN), ammonium nitrate (AN), black powder (S), nitromethane (NM) and 2,3- dinitro -2,3- dimethylbutanes
(DMNB)。
The main body of the composition material of the fluorescence sense array of the present invention is a kind of typical P-type semiconductor fluorescence sense material
Material.Substitution functional group and the degree of polymerization of main body, the organic fluorescence after several designs so formed have been modified in present invention design
When the high-temperature steam of sensing material and the explosive containing nitro interacts, it may occur that different degrees of electronics transfer or strong and weak
Different physical absorptions, causes various forms of change in fluorescence of several organic fluorescence sensing materials, the fluorescence response of material 1
Q1 is named as, the fluorescence response of material 2 is named as Q2, and the fluorescence response of material N is named as QN.What is be achieved in that is various forms of
Change in fluorescence array is different and distinctive to every a kind of explosive.It is so this by several different organic fluorescence sensing materials
The sensor array of composition can carry out a few class explosives rapid fluorescence detection and distinguish.
It should be noted that a few class explosives of the present invention, distinguish according to classification, in a kind of explosive
One or more explosives may be contained.
Beneficial effects of the present invention：
The organic fluorescence sensing material that the present invention uses is obtained by carbazole derivates by the π-π self assemblies that interact, and is led to
The specific substitution functional group pendant in modification main body and the degree of polymerization are crossed, various forms of fluorescence change to different explosives can be formed
Change, the present invention by assembling by several this kind of organic fluorescence sensing materials with different change in fluorescence by forming sensing battle array
Row, form to the distinctive change in fluorescence array of each explosive, and realize and carry out fluorescence differentiation to a few class explosives.
The sensor array of the present invention can carry out detection zone point at ng grades to a few class explosives, and high sensitivity is distinguished in detection,
And the composition of sensor array and operation are easier.By design, further this sensor array can be made can be quick-fried to several classes
Fried thing is used for quickly detecting the portable equipment of differentiation, and in society, this is the work being of great significance, tool for application and service
There are far-reaching application and development prospect.
Present invention also offers the simple efficiently preparation side of several organic fluorescence sensing materials in the sensor array
Method, the synthetic route of the method is simple, and easy to prepare on a large scale, nanowire growth method is simple and quick.
Brief description of the drawings
Fig. 1 fluorescence sense array structure schematic diagrames of the present invention.
The R of Fig. 2 embodiment of the present invention 1 is normal octane, and n is the nuclear magnetic data spectrogram of 3 carbazole derivates.
The R of Fig. 3 embodiment of the present invention 1 is normal octane, and n is the mass spectrometric data figure of 3 carbazole derivates.
The R of Fig. 4 embodiment of the present invention 2 is benzyl, and n is the nuclear magnetic data spectrogram of 3 carbazole derivates.
The R of Fig. 5 embodiment of the present invention 1 is normal octane, and what the carbazole derivates that n is 3 were constructed has hypersensitive fluorescence
The SEM image of the organic semiconductor nanowires of response.
The R of Fig. 6 embodiment of the present invention 1 is normal octane, and what the carbazole derivates that n is 3 were constructed has hypersensitive fluorescence
The perforated membrane for the net structure that the organic semiconductor nanowires self assembly of response is knitted to form and the R of the embodiment of the present invention 2 are different
Butyl, the braiding of the organic semiconductor nanowires self assembly with hypersensitive fluorescence response that the carbazole derivates that n is 3 are constructed
Detection fluorescence curve figure of the sensor array of the perforated membrane composition of the net structure of formation to TNT.1.1<Q2/Q1<2.
The R of Fig. 7 embodiment of the present invention 1 is normal octane, and what the carbazole derivates that n is 3 were constructed has hypersensitive fluorescence
The perforated membrane for the net structure that the organic semiconductor nanowires self assembly of response is knitted to form and the R of the embodiment of the present invention 2 are different
Butyl, the braiding of the organic semiconductor nanowires self assembly with hypersensitive fluorescence response that the carbazole derivates that n is 3 are constructed
Detection fluorescence curve figure of the sensor array of the perforated membrane composition of the net structure of formation to DNT.1.1<Q2/Q1<2.
The R of Fig. 8 embodiment of the present invention 1 is normal octane, and what the carbazole derivates that n is 3 were constructed has hypersensitive fluorescence
The perforated membrane for the net structure that the organic semiconductor nanowires self assembly of response is knitted to form and the R of the embodiment of the present invention 2 are different
Butyl, the braiding of the organic semiconductor nanowires self assembly with hypersensitive fluorescence response that the carbazole derivates that n is 3 are constructed
Detection fluorescence curve figure of the sensor array of the perforated membrane composition of the net structure of formation to S.2.1<Q2/Q1<4.5.
The R of Fig. 9 embodiment of the present invention 1 is normal octane, and what the carbazole derivates that n is 3 were constructed has hypersensitive fluorescence
The perforated membrane for the net structure that the organic semiconductor nanowires self assembly of response is knitted to form and the R of the embodiment of the present invention 2 are different
Butyl, the braiding of the organic semiconductor nanowires self assembly with hypersensitive fluorescence response that the carbazole derivates that n is 3 are constructed
Detection fluorescence curve figure of the sensor array of the perforated membrane composition of the net structure of formation to RDX.2.1<Q1/Q2<4.0.
The R of Figure 10 embodiment of the present invention 1 is normal octane, and the carbazole derivates that n is 3 are constructed glimmering with hypersensitive
The perforated membrane for the net structure that the organic semiconductor nanowires self assembly of photoresponse is knitted to form and the R of the embodiment of the present invention 2 are
Isobutyl group, the organic semiconductor nanowires self assembly with hypersensitive fluorescence response that the carbazole derivates that n is 3 are constructed are compiled
Knit detection fluorescence curve figure of the sensor array of the perforated membrane composition for the net structure to be formed to PETN.2.1<Q1/Q2<4.0.
The R of Figure 11 embodiment of the present invention 1 is normal octane, and the carbazole derivates that n is 3 are constructed glimmering with hypersensitive
The perforated membrane for the net structure that the organic semiconductor nanowires self assembly of photoresponse is knitted to form and the R of the embodiment of the present invention 2 are
Isobutyl group, the organic semiconductor nanowires self assembly with hypersensitive fluorescence response that the carbazole derivates that n is 3 are constructed are compiled
Knit detection fluorescence curve figure of the sensor array of the perforated membrane composition for the net structure to be formed to DMNB.Fluorescence response is by near
100% recovery.
The R of Figure 12 embodiment of the present invention 1 is normal octane, and the carbazole derivates that n is 3 are constructed glimmering with hypersensitive
The perforated membrane for the net structure that the organic semiconductor nanowires self assembly of photoresponse is knitted to form and the R of the embodiment of the present invention 2 are
Isobutyl group, the organic semiconductor nanowires self assembly with hypersensitive fluorescence response that the carbazole derivates that n is 3 are constructed are compiled
Knit detection fluorescence curve figure of the sensor array of the perforated membrane composition for the net structure to be formed to AN.1.1<Q1/Q2<2.0.
The R of Figure 13 embodiment of the present invention 1 is normal octane, and the carbazole derivates that n is 3 are constructed glimmering with hypersensitive
The perforated membrane for the net structure that the organic semiconductor nanowires self assembly of photoresponse is knitted to form rings the fluorescence of four class explosives
Q1 should be named as, the R of the embodiment of the present invention 2 is isobutyl group, and what the carbazole derivates that n is 3 were constructed has hypersensitive fluorescence
The sensor array of the perforated membrane composition for the net structure that the organic semiconductor nanowires self assembly of response is knitted to form is quick-fried to four classes
The fluorescence response of fried thing is named as Q2, and figure is done according to Q1/Q2 and Q2/Q1.
The R of Figure 14 embodiment of the present invention 1 is normal octane, and the carbazole derivates that n is 3 are constructed glimmering with hypersensitive
The perforated membrane for the net structure that the organic semiconductor nanowires self assembly of photoresponse is knitted to form and the R of the embodiment of the present invention 2 are
Isobutyl group, the organic semiconductor nanowires self assembly with hypersensitive fluorescence response that the carbazole derivates that n is 3 are constructed are compiled
Knit detection fluorescence curve figure of the sensor array of the perforated membrane composition for the net structure to be formed to NM.Fluorescence response is by nearly 100%
Recovery.
Embodiment
As it was previously stated, the invention discloses can carry out the organic glimmering of high sensitivity fluoroscopic examination differentiation to a few class explosives
The preparation method of light sensing material, in a preferred embodiment of the present invention, the carbazole for preparing n=3 in formula (I) derive
Thing, the step (1) specifically include：
Compound shown in (1a) formula (II) and RX ' react, and compound shown in formula (III) is made；
X in formula (II) and formula (III) is identical or different, is independently from each other halogen (such as Br, I)；X ' in RX '
Selected from halogen (such as Br, I)；The same formula of definition (I) of formula (III) and the R in RX '；
Compound shown in (1b) formula (III) and R ' B (OH)2Compound shown in formula (IV) is made in reaction；
Formula (IV) and R ' B (OH)2In, the same formula of definition (I) of R '；In formula (IV), the same formula of definition (III) of R and X；
Compound shown in formula (V) is made with bis (pinacolato) diboron reaction in compound shown in (1c) formula (III)；
In formula (V), the same formula of definition (I) of R；
Compound shown in (1d) formula (IV) reacts to obtain carbazole derivates shown in formula (I) with compound shown in formula (V), wherein
N=3；Wherein, the molar ratio of compound shown in formula (IV) and compound shown in formula (V) is 2.1:1~2.5:1 (is, for example, 2.2:
1)。
In another preferred embodiment of the present invention, prepare 3 in formula (I)<The carbazole derivates of n≤40, the step
Suddenly (1) specifically includes：
Compound shown in (1a) formula (II) and RX ' react, and compound shown in formula (III) is made；
X in formula (II) and formula (III) is identical or different, is independently from each other halogen (such as Br, I)；X ' in RX '
Selected from halogen (such as Br, I)；The same formula of definition (I) of formula (III) and the R in RX '；
Compound shown in (1a ') formula (II ') and RX ' react, and compound shown in formula (III ') is made；
X in formula (II ') and formula (III ') is identical or different, is independently from each other halogen (such as Br, I)；In RX '
X ' is selected from halogen (such as Br, I)；The same formula of definition (I) of formula (III ') and the R in RX '；M is the integer of 2-38；
Compound shown in (1b) formula (III) and R ' B (OH)2Compound shown in formula (IV) is made in reaction；
Formula (IV) and R ' B (OH)2In, the same formula of definition (I) of R '；In formula (IV), the same formula of definition (III) of R and X；
Compound shown in formula (V ') is made with bis (pinacolato) diboron reaction in compound shown in (1c ') formula (III ')；
In formula (V '), the same formula of definition (I) of R, m is the integer of 2-38；
Compound shown in (1d ') formula (IV) reacts to obtain carbazole derivates shown in formula (I) with compound shown in formula (V '), its
In 3<n≤40；Wherein, the molar ratio of compound shown in formula (IV) and compound shown in formula (V ') is 2.1:1~2.5:1 (such as
For 2.2:1).
In above-mentioned steps (1a) or (1a '), the reaction carries out in a solvent.The solvent for can dissolve formula (II) or
The organic solvent of compound shown in formula (II '), is, for example, amides compound, can specifically be selected from N, N- dimethyl-formamidines.
In above-mentioned steps (1a) or (1a '), the reaction carries out at a temperature of -10~10 DEG C, it is preferable that -5~5 DEG C.
In above-mentioned steps (1a), the reaction carries out under the action of catalyst.The catalyst is, for example, sodium hydride.Formula
(II) compound shown in and the equivalent proportion of catalyst are 1:1.1~1:1.3, it is preferably 1:1.2.
In above-mentioned steps (1a '), the reaction carries out under the action of catalyst.The catalyst is, for example, sodium hydride.
Compound shown in formula (II ') and the equivalent proportion of catalyst are 1:(m+0.1)~1:(m+0.3), it is preferably 1:(m+0.2), m 2-
38 integer.
In above-mentioned steps (1a), the equivalent proportion of formula (II) compound and RX ' are 1.1.2~1:1.5, it is preferably 1:1.3.
In above-mentioned steps (1a '), the equivalent proportion of formula (II ') compound and RX ' are 1:(m+0.2)~1:(m+0.5), preferably
For 1:(m+0.3), m is the integer of 2-38.
In a preferable technical solution, the carbazole derivates of n=3 in formula (I) are prepared, the step (1a) is specific
For：2, the 7- dibromo carbazoles of 1 equivalent are dissolved in N, the solution that concentration is 1g/30ml is configured in N- dimethyl-formamidines, will be upper
State solution to be placed in 0 DEG C of ice bath, be slowly added to the sodium hydride solid of 1.2 equivalents, after persistently stirring half an hour, be slowly added to 1.5
1- bromooctanes, 2- bromobutane, 4- trifluoromethyl benzyls bromine, benzyl bromine or the 4- methoxybenzyl bromines of equivalent, at room temperature after reaction overnight,
Product is obtained by column chromatography.
In above-mentioned steps (1b), the reaction carries out in a solvent.The solvent is that can dissolve chemical combination shown in formula (III)
The organic solvent of thing, is, for example, epoxide, can be specifically Isosorbide-5-Nitrae-dioxane.
In above-mentioned steps (1b), formula (III) compound and R ' B (OH)2Equivalent proportion be 1:1.
In above-mentioned steps (1b), the reaction carries out in catalyst system, and the catalyst system includes four (triphenyls
Phosphine) palladium and cesium carbonate.Relative to formula (III) compound of 1 equivalent, the additive amount of tetrakis triphenylphosphine palladium is 5-15% equivalents,
The additive amount of cesium carbonate is 2.5~3.5 equivalents.
In above-mentioned steps (1b), the reaction carries out under inert gas shielding, and reaction temperature is 70~90 DEG C, during reaction
Between for 6~8 it is small when.
In one preferred embodiment, the step (1b) is specially：The step of (1b) takes 1 equivalent (1a) obtains
Product, be dissolved in Isosorbide-5-Nitrae-dioxane be configured to concentration be 1g/20ml solution, add 1 equivalent to carbomethoxybenzene boronic acid,
The tetrakis triphenylphosphine palladium of 10% equivalent, the cesium carbonate of 3 equivalents in the case where 80 DEG C of argon gas are protected, when reaction 6 is small after, pass through column chromatography
Obtain product.
In above-mentioned steps (1c) or (1c '), the reaction carries out in a solvent.The solvent is that can dissolve formula (III)
Or the organic solvent of compound shown in formula (III '), it is, for example, epoxide, can is specifically Isosorbide-5-Nitrae-dioxane.
In above-mentioned steps (1c) or (1c '), formula (III) or the equivalent proportion of formula (III ') compound and bis (pinacolato) diboron are 1:
4~6.
In above-mentioned steps (1c) or (1c '), the reaction carries out in catalyst system, and the catalyst system includes vinegar
Sour potassium and [double (diphenylphosphino) ferrocene of 1,1'-] palladium chloride.Relative to formula (III) formula (III ') compound of 1 equivalent,
The additive amount of potassium acetate is 10~20 equivalents, the additive amount of [1,1'- double (diphenylphosphino) ferrocene] palladium chloride for 5~
15% equivalent.
In above-mentioned steps (1c) or (1c '), the reaction carries out under inert gas shielding, and reaction temperature is 70~80
DEG C, when the reaction time is 4~8 small.
In one preferred embodiment, the carbazole derivates of n=3 in formula (I) are prepared, the step (1c) is specific
For：The product that the step of taking 1 equivalent (1a) obtains, adds in Isosorbide-5-Nitrae-dioxane the solution for being configured to that concentration is 1g/20ml, adds
Enter the bis (pinacolato) diboron of 5 equivalents, the potassium acetate of 14 equivalents, [double (diphenylphosphino) ferrocene of 1,1'-] dichloro of 10% equivalent
Change palladium in the case where 80 DEG C of argon gas are protected, when reaction 6 is small after, product is obtained by column chromatography.
In above-mentioned steps (1d) or (1d '), the reaction carries out in a solvent.The solvent for can dissolve formula (VI),
The organic solvent of compound shown in formula (V) and formula (V '), is, for example, aromatic hydrocarbon, can be specifically benzene or toluene.
In above-mentioned steps (1d) or (1d '), formula (VI) compound is 1 with the equivalent proportion of formula (V) or formula (V ') compound:
2.2。
In above-mentioned steps (1d) or (1d '), the reaction carries out in catalyst system, and the catalyst system includes four
(triphenylphosphine) palladium and potassium carbonate.Relative to formula (III) compound of 1 equivalent, the additive amount of potassium carbonate is 3~5 equivalents, four
The additive amount of (triphenylphosphine) palladium is 5~15% equivalents.
In above-mentioned steps (1d) or (1d '), the reaction carries out under inert gas shielding, and reaction temperature is 70~90
DEG C, when the reaction time is 12~48 small.
In one preferred embodiment, the carbazole derivates of n=3 in formula (I) are prepared, the step (1d) is specific
For：The product 1mmol and 2.2mmol for taking step (1c) and step (1b) to obtain respectively, are added in 20ml toluene solutions, add
10% tetrakis triphenylphosphine palladium, the potassium carbonate of 3 equivalents after reaction overnight, are obtained in the case where 80 DEG C of argon gas are protected by column chromatography
Product.
To further illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment, and with reference to attached
Figure, is described in detail the present invention.It will be appreciated by those skilled in the art that the invention is not limited in attached drawing and following implementation
Example.
Embodiment 1
It is straight chain octyl group to prepare the R with following molecule 1, and R ' is 4- methoxycarbonyl group phenyl, and n is 3 carbazole derivates, its
Preparation method is as follows：
(1) 1 gram of 2,7- dibromo carbazoles are dissolved in 30 milliliters of N, will be above-mentioned in N- dimethyl-formamidines (DMF) solution
Solution is placed in 0 DEG C of ice bath, is slowly added to the sodium hydride solid of the 74mg of 1.2 equivalents, after persistently stirring half an hour, is slowly added to
The 1- bromooctanes of 1.5 equivalents, at room temperature after reaction overnight, product are obtained by column chromatography.
(2) the product 500mg for taking step (1) to obtain, adds in 20ml Isosorbide-5-Nitraes-dioxane solution, adds the double of 5 equivalents
Two boron of valeryl, the potassium acetate of 14 equivalents, [double (diphenylphosphino) ferrocene of 1,1'-] palladium chloride of 10% equivalent are in 80 DEG C of argons
Under gas shielded, reaction 6 it is small when after, product (TM-1) is obtained by column chromatography.
(3) the product 500mg for taking step (1) to obtain, adds in 20ml Isosorbide-5-Nitraes-dioxane solution, adds pair of 1 equivalent
In the case where 80 DEG C of argon gas are protected, reaction 6 is small for methyl carbonyl phenyl boric acid, the tetrakis triphenylphosphine palladium of 10% equivalent, the cesium carbonate of 3 equivalents
Shi Hou, product is obtained by column chromatography.
(4) the product 1mmol and 2.2mmol for taking step (2) and step (3) to obtain respectively, are added to 20ml toluene solutions
In, 10% tetrakis triphenylphosphine palladium, the potassium carbonate of 3 equivalents are added in the case where 80 DEG C of argon gas are protected, and after reaction overnight, pass through column layer
Analysis obtains product (molecule 1)；Its nuclear magnetic resonance data figure is as shown in Figure 2；Mass spectrometric data figure is as shown in Figure 3.
(5) n for obtaining step (4) be 3 carry the carbazole derivates (molecule 2) of methylcarbonylphenyl are dissolved in it is good
Poor solvent is added after in solvent, the good solvent is one in ethyl acetate, dichloromethane, chloroform or 1,2- dichloroethanes
Kind, the poor solvent is one kind in methanol, ethanol or hexamethylene, and the volume ratio of good solvent and poor solvent is 1:3~1:
10；Stand, described carry obtains having not a few class explosives to the carbazole derivates of methyl carbonyl benzene by self assembly mode
With the organic semiconductor nanowires of fluorescence response or the suspension of nanobelt.
Embodiment 2
It is benzyl to prepare the R with following molecule 2, and R ' is 4- methoxycarbonyl group phenyl, and n is 3 carbazole derivates, it is prepared
Method is as follows：
(1) 1 gram of 2,7- dibromo carbazoles are dissolved in 30 milliliters of N, will be above-mentioned in N- dimethyl-formamidines (DMF) solution
Solution is placed in 0 DEG C of ice bath, is slowly added to the sodium hydride solid of the 74mg of 1.2 equivalents, after persistently stirring half an hour, is slowly added to
The benzyl bromine of 1.5 equivalents, at room temperature after reaction overnight, product is obtained by column chromatography.
(2) the product 500mg for taking step (1) to obtain, adds in 20ml Isosorbide-5-Nitraes-dioxane solution, adds the double of 5 equivalents
Two boron of valeryl, the potassium acetate of 14 equivalents, [double (diphenylphosphino) ferrocene of 1,1'-] palladium chloride of 10% equivalent are in 80 DEG C of argons
Under gas shielded, reaction 6 it is small when after, product (TM-1) is obtained by column chromatography.
(3) the product 500mg for taking step (1) to obtain, adds in 20ml Isosorbide-5-Nitraes-dioxane solution, adds pair of 1 equivalent
Carbomethoxybenzene boronic acid, the tetrakis triphenylphosphine palladium of 10% equivalent, the cesium carbonate of 3 equivalents are in the case where 80 DEG C of argon gas are protected, reaction 6
After hour, product is obtained by column chromatography.
(4) the product 1mmol and 2.2mmol for taking step (2) and step (3) to obtain respectively, are added to 20ml toluene solutions
In, 10% tetrakis triphenylphosphine palladium, the potassium carbonate of 3 equivalents are added in the case where 80 DEG C of argon gas are protected, and after reaction overnight, pass through column layer
Analysis obtains product (molecule 2)；Mass spectrometric data MALDI-TOF (m/z)=1035.4；Its nuclear magnetic resonance data figure is as shown in Figure 4.
(5) carbazole derivates that the n for obtaining step (4) is 3 add poor solvent after being dissolved in good solvent, described good
Solvent is one kind in dichloromethane, chloroform or 1,2- dichloroethanes, and the poor solvent is in methanol, ethanol or hexamethylene
The volume ratio of one kind, good solvent and poor solvent is 1:2~1:15；Stand, the carbazole derivates are obtained by self assembly mode
To the suspension of the organic semiconductor nanowires to a few class explosives with fluorescence response.
Embodiment 3
The suspension that the carbazole derivates that 4- cyano-phenyls are carried in 1 step of embodiment (5) prepare is used into liquid relief respectively
The sample that rifle takes out container bottom is placed in clean silicon chip surface, and being placed on ion after poor solvent volatilization is clean splashes
(Leica) is penetrated in machine, is evacuated down to vacuum as 10-4Start surface splash-proofing sputtering metal platinum grain 120s after pa.Taking-up silicon chip simultaneously will
It is placed in scanning electron microscope (Hitachi S8010) and observes its pattern.Such as a, b and the c in Fig. 5 it is observed that one-dimensional organic half
Unique netted loose structure that conductor nanobelt self assembly is knitted to form, this distinguishes for detection and provides special fluorescence response
Signal.
Embodiment 4
After when the suspension standing 24 that 1 step of embodiment (5) and 2 step of embodiment (5) are obtained is small, container bottom is taken out
Film, the diverse location being successively applied to respectively in same quartz glass tube, is prepared into the fluorescence sense array containing two kinds of materials.
Use 380 nanometers of excitation source excitations perforated membrane being applied in quartz glass tube.Using solid explosive detector, use
Liquid-transfering gun pipettes 0.3ng, 0.5ng respectively, and 0.8ng TNT are dropped in heating gun, and it is 170 DEG C to set heating-up temperature, to described
The TNT steam of various concentrations is blown on the surface of perforated membrane, and testing result occurs the change in fluorescence such as Fig. 6 in three concentration.
Embodiment 5
Using the same method of embodiment 4, detectable substance is simply replaced with into 0.3ng, 0.5ng, 0.8ng DNT, detection knot
Fruit occurs the change in fluorescence such as Fig. 7 in three concentration.
Embodiment 6
Using the same method of embodiment 4, detectable substance is simply replaced with into 0.2ng, 0.5ng, 1ng S, testing result exists
Occurs the change in fluorescence such as Fig. 8 during three concentration.
Embodiment 7
Using the same method of embodiment 4, detected material is changed to 0.1ng, 0.2ng, 0.5ng RDX, testing result exists
Occurs the change in fluorescence such as Fig. 9 during three concentration.
Embodiment 8
Using the same method of embodiment 4, detected material is changed to 0.5ng, 1ng, 2ng PETN, testing result is described
Occurs the change in fluorescence such as Figure 10 during three concentration.
Embodiment 9
Using the same method of embodiment 4, detected material is changed to 30ng, 50ng, 80ng DMNB, testing result is in institute
Occurs the change in fluorescence such as Figure 11 when stating three concentration.
Embodiment 10
Using the same method of embodiment 4, detected material is changed to 10ng, 20ng, 30ng AN, testing result is described
Occurs the change in fluorescence such as Figure 12 during three concentration.
Two that the carbazole derivates self assembly that different functional groups side chain is respectively come with embodiment 1 and embodiment 2 is obtained
The sensor array that kind organic fluorescence derivative (material 1 and material 2) is formed changes the fluorescence response of above-mentioned eight kinds of explosives
Carry out Interferogram Analysis.The fluorescence response of material 1 is named as Q1, the fluorescence response of material 2 is Q2, according to Q1/Q2's and Q2/Q1
Ratio Analysis, fluorescence response change of the sensor array to every a kind of explosive are exclusive such as Figure 13.Found by analysis, two kinds
The fluorescence response of DMNB and NM occurs for material to have the recovery (such as Figure 14) close to 100% after fluorescent quenching, and two kinds of materials
Other explosives are not recovered then, it is achieved that the differentiation to five class explosives.Therefore, can be formed according to two kinds of materials
The response of sensor array judge which kind of explosive detected explosive is.
Embodiment 11
(1) 1 gram of 2,7- dibromo carbazoles are dissolved in 30 milliliters of N, will be above-mentioned in N- dimethyl-formamidines (DMF) solution
Solution is placed in 0 DEG C of ice bath, is slowly added to the sodium hydride solid of the 74mg of 1.2 equivalents, after persistently stirring half an hour, is slowly added to
1.5 the 1- bromooctanes of equivalent, at room temperature after reaction overnight, product are obtained by column chromatography.
(2) the product 500mg for taking step (1) to obtain, adds in 20ml Isosorbide-5-Nitraes-dioxane solution, adds the double of 5 equivalents
Two boron of valeryl, the potassium acetate of 14 equivalents, [double (diphenylphosphino) ferrocene of 1,1'-] palladium chloride of 10% equivalent are in 80 DEG C of argons
Under gas shielded, reaction 6 it is small when after, product (TM-1) is obtained by column chromatography.
(3) the product 500mg for taking step (1) to obtain, adds in 20ml Isosorbide-5-Nitraes-dioxane solution, adds pair of 1 equivalent
Cyanophenylboronic acid, the tetrakis triphenylphosphine palladium of 10% equivalent, the cesium carbonate of 3 equivalents are in the case where 80 DEG C of argon gas are protected, when reaction 6 is small
Afterwards, product (TM-2) is obtained by column chromatography.
(4) the product 1mmol and 2.2mmol for taking step (2) and step (3) to obtain respectively, are added to 20ml toluene solutions
In, 10% tetrakis triphenylphosphine palladium, the potassium carbonate of 3 equivalents are added in the case where 80 DEG C of argon gas are protected, and after reaction overnight, pass through column layer
It is straight chain octyl group that analysis, which obtains R in formula (I), and R ' is 4- cyano-phenyls, and n is 4 carbazole derivates.
(5) carbazole derivates with 4- cyano-phenyls that the n for obtaining step (4) is 4 add after being dissolved in good solvent
Enter poor solvent, the good solvent is one kind in ethyl acetate, dichloromethane, chloroform or 1,2- dichloroethanes, described bad
Solvent is one kind in methanol, ethanol or hexamethylene, and the volume ratio of good solvent and poor solvent is 1:3~1:10；Stand, it is described
Carbazole derivates with 4- cyano-phenyls obtain there are different fluorescence responses to have a few class explosives by self assembly mode
The suspension of machine semiconductor nanowires or nanobelt.
Embodiment 12
(1) 1 gram of 2,7- dibromo carbazoles are dissolved in 30 milliliters of N, will be above-mentioned in N- dimethyl-formamidines (DMF) solution
Solution is placed in 0 DEG C of ice bath, is slowly added to the sodium hydride solid of the 74mg of 1.2 equivalents, after persistently stirring half an hour, is slowly added to
The 1- bromooctanes of 1.5 equivalents, at room temperature after reaction overnight, product are obtained by column chromatography.
(2) the product 500mg for taking step (1) to obtain, adds in 20ml Isosorbide-5-Nitraes-dioxane solution, adds the double of 5 equivalents
Two boron of valeryl, the potassium acetate of 14 equivalents, [double (diphenylphosphino) ferrocene of 1,1'-] palladium chloride of 10% equivalent are in 80 DEG C of argons
Under gas shielded, reaction 6 it is small when after, product (TM-1) is obtained by column chromatography.
(3) the product 500mg for taking step (1) to obtain, adds in 20ml Isosorbide-5-Nitraes-dioxane solution, adds pair of 1 equivalent
In the case where 80 DEG C of argon gas are protected, reaction 6 is small for methyl carbonyl phenyl boric acid, the tetrakis triphenylphosphine palladium of 10% equivalent, the cesium carbonate of 3 equivalents
Shi Hou, product (TM-2) is obtained by column chromatography.
(4) the product 1mmol and 2.2mmol for taking step (2) and step (3) to obtain respectively, are added to 20ml toluene solutions
In, 10% tetrakis triphenylphosphine palladium, the potassium carbonate of 3 equivalents are added in the case where 80 DEG C of argon gas are protected, and after reaction overnight, pass through column layer
It is straight chain octyl group that analysis, which obtains R in formula (I), and R ' is to methylcarbonylphenyl, and n is 4 carbazole derivates.
(5) n for obtaining step (4) is dissolved in good solvent for 4 with the carbazole derivates to methylcarbonylphenyl
After add poor solvent, the good solvent is one kind in ethyl acetate, dichloromethane, chloroform or 1,2- dichloroethanes, described
Poor solvent is one kind in methanol, ethanol or hexamethylene, and the volume ratio of good solvent and poor solvent is 1:3~1:10；Stand,
The carbazole derivates with 4- methylcarbonylphenyls obtain having different fluorescence to a few class explosives by self assembly mode
The organic semiconductor nanowires of response or the suspension of nanobelt.
After measured, above two n be 4 two kinds of sensing materials form sensor array have with embodiment 1 and implementation 2 in
Sensing material composition sensor array it is similar to a few class explosives response change, a few class explosives can equally be played glimmering
The effect that light detection is distinguished.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to the above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done, should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
- A kind of 1. fluorescence sense array, it is characterised in that：The fluorescence sense array can be to a few class explosives by two or more The organic fluorescence sensing material for carrying out fluorescence monitoring differentiation is arranged in order composition, each described organic fluorescence materials is by one Carbazole derivates of the kind as described in the formula (I) are obtained by π-π interaction self assemblies：In the formula (I), R' is identical or different, is independently from each other-(CH2)x’-R5-R6, wherein, x ' is 0,1 or 2, R5For Arlydene or halo arlydene, R6For H ,-COOR7、-COR7、C2-6Alkynyl, C ≡ N or C3-6Alkyl, R7For H, C1-4Alkyl；n For the integer of 3-40；R is selected from C1-10Straight or branched alkyl ,-(CH2)x-R1-O-R2、-(CH2)y-R1-R3Or-(CH2)z-R4, Wherein, x 0,1 or 2, y 0,1 or the integer that 2, z are 1-9, R1For arlydene or halo arlydene, R2For C1-10Straight chain or Branched alkyl, R3For-H ,-CHF2、-CF3、C1-10Straight or branched alkyl, by CHF2Or CF3Substituted C1-10Straight chain or branch Alkyl group, C3-10Cycloalkyl, by CHF2Or CF3Substituted C3-10Cycloalkyl, R4For-CHF2、-CF3。
- 2. fluorescence sense array according to claim 1, it is characterised in that：The fluorescence sense array is as described in 2~6 kinds Organic fluorescence sensing material be arranged in order composition.Preferably, in the fluorescence sense array, the length of every kind of organic fluorescence sensing material is 3mm-20mm, adjustable, preferably For 8-10mm；The spacing of two neighboring material is 5mm-50mm, adjustable, is preferably 15-20mm.
- 3. fluorescence sense array according to claim 1 or 2, it is characterised in that：The R' is identical or different, independently of one another Ground is selected from-(CH2)x’-R5-R6, wherein, x ' is 0 or 1, R5For arlydene, such as phenylene, naphthylene, or halo arylene (wherein halogen is selected from fluorine, chlorine, bromine), such as halophenylene, R6For-COOR7、C≡CH、C≡N；It is further preferred that R ' is identical or different ,-(CH is independently from each other2)x’-R5-R6, x ' is 0 or 1；R6For-COOR7、- COR7；R7For methyl or ethyl；It is further preferred that R' is identical or different, the one kind being independently from each other in following eight kinds of groups：Wherein, upside is connection site.
- 4. according to claim 1-3 any one of them fluorescence sense arrays, it is characterised in thatPreferably, R is selected from C3-10Straight or branched alkyl, (CH2)x-R1-O-R2、-(CH2)y-R1-R3Or-(CH2)z-R4, its In, x 0,1 or 2, y 0,1 or the integer that 2, z are 2-6, R1For phenylene or naphthylene or halophenylene, R2For C1-10's Straight or branched alkyl, R3For-H ,-CF3、C1-10Straight or branched alkyl or CF3Substituted C1-10Straight or branched alkyl, R4For-CF3；It is further preferred that R is selected from C3-10Straight or branched alkyl when, the branched alkyl is asymmetric alkyl；It is further preferred that the one kind of R in following radicals：In above-mentioned group, the upside of structural formula is connection site.
- 5. according to claim 1-4 any one of them fluorescence sense arrays, it is characterised in that the organic fluorescence sensing material Each material in material is to be obtained as a kind of carbazole derivates as described in the formula (I) by π-π interaction self assemblies Organic semiconductor nanowires or nanobelt.Preferably, each material in the organic fluorescence sensing material is by the organic semiconductor nanowires or receives The perforated membrane with net structure that rice is knitted to form with self assembly.
- 6. the preparation method of claim 1-5 any one of them fluorescence sense arrays, described method includes following steps：(1) several carbazole derivates with specific functional groups are synthesized first,(2) and then in the mixed liquor of good solvent and poor solvent, obtained by way of self assembly described several organic glimmering Light sensing material,(3) diverse location that will be assembled obtained several fluorescent materials and be applied to respectively on the inside of same glass tube, obtains the biography Feel array.
- 7. preparation method according to claim 6, it is characterised in that when preparing the carbazole derivates of n=3 in formula (I), The step (1) specifically includes：Compound shown in (1a) formula (II) and RX ' react, and compound shown in formula (III) is made；X in formula (II) and formula (III) is identical or different, is independently from each other halogen (such as Br, I)；X ' in RX ' is selected from Halogen (such as Br, I)；The same formula of definition (I) of formula (III) and the R in RX '；Compound shown in (1b) formula (III) and R ' B (OH)2Compound shown in formula (IV) is made in reaction；Formula (IV) and R ' B (OH)2In, the same formula of definition (I) of R '；In formula (IV), the same formula of definition (III) of R and X；Compound shown in formula (V) is made with bis (pinacolato) diboron reaction in compound shown in (1c) formula (III)；In formula (V), the same formula of definition (I) of R；Compound shown in (1d) formula (IV) reacts to obtain carbazole derivates, wherein n=shown in formula (I) with compound shown in formula (V) 3；Wherein, the molar ratio of compound shown in formula (IV) and compound shown in formula (V) is 2.1:1~2.5:1 (is, for example, 2.2:1)；When preparing 3 in formula (I)<During the carbazole derivates of n≤40, the step (1) specifically includes：Compound shown in (1a) formula (II) and RX ' react, and compound shown in formula (III) is made；X in formula (II) and formula (III) is identical or different, is independently from each other halogen (such as Br, I)；X ' in RX ' is selected from Halogen (such as Br, I)；The same formula of definition (I) of formula (III) and the R in RX '；Compound shown in (1a ') formula (II ') and RX ' react, and compound shown in formula (III ') is made；X in formula (II ') and formula (III ') is identical or different, is independently from each other halogen (such as Br, I)；X ' choosings in RX ' From halogen (such as Br, I)；The same formula of definition (I) of formula (III ') and the R in RX '；M is the integer of 2-38；Compound shown in (1b) formula (III) and R ' B (OH)2Compound shown in formula (IV) is made in reaction；Formula (IV) and R ' B (OH)2In, the same formula of definition (I) of R '；In formula (IV), the same formula of definition (III) of R and X；Compound shown in formula (V ') is made with bis (pinacolato) diboron reaction in compound shown in (1c ') formula (III ')；In formula (V '), the same formula of definition (I) of R, m is the integer of 2-38；Compound shown in (1d ') formula (IV) reacts to obtain carbazole derivates shown in formula (I) with compound shown in formula (V '), wherein 3< n≤40；Wherein, the molar ratio of compound shown in formula (IV) and compound shown in formula (V ') is 2.1:1~2.5:1 (is, for example, 2.2:1)。
- 8. the preparation method according to claim 6 or 7, it is characterised in that the step (2) includes：Step (1) is obtained The carbazole derivates with different specific functional groups be dissolved in good solvent, then add poor solvent, stand, the formula (I) suspension that the carbazole derivates shown in pass through organic fluorescence sensing material described in self assembly mode；Preferably, the step (2) further comprises：After the suspension of several organic fluorescence sensing materials is stood, take Go out positioned at the organic fluorescence sensing material for preparing container bottom, be again placed in shaking up scattered in poor solvent and wash repeatedly, obtain To the organic fluorescence sensing material；Preferably, the step (3) includes：The suspension of the organic fluorescence sensing material obtained in step (2) is implanted sequentially Same glass tube, after waiting solvent volatilization dry, remembers the organic fluorescence sensor array；Preferably, the volume ratio (ml of the good solvent and poor solvent:Ml it is) 1:3~1:10；Preferably, the good solvent is chloralkane and C2-5Esters, be, for example, dichloromethane, chloroform, 1,2- dichloroethanes, Ethyl acetate or methyl acetate；Preferably, the poor solvent is alcohol organic solvent or cycloalkane, is, for example, methanol, ethanol or hexamethylene.
- 9. claim 1-5 any one of them organic fluorescences sensing material, particularly described carry different functional groups side chain The perforated membrane for the special net structure that the organic semiconductor nanowires or nanobelt that carbazole derivates assemble are formed (has height Specific surface area) purposes, it is characterised in that these types of sensing material is combined into sensor array.
- 10. the purposes of claim 1-5 any one of them fluorescence sense arrays, it is characterised in that for solid explosive Detection is distinguished；Preferably, the fluorescence that the organic fluorescence sensing material of a few class explosives progress fluoroscopic examination differentiation can be combined into Sensor array can be used for distinguishing the trace detection of a few class explosives, and the trace is ng ranks；Several sensing materials When being contacted with trace explosive (explosive is preferably solid) steam, each material in sensor array has difference Physicochemical properties, various forms of fluorescence can occur to same explosive and change, analyze different materials in several arrays To the change in fluorescence of same explosive, these changes are unique to each explosive, thus be can be used for actual quick-fried to several classes The detection of fried thing is distinguished.Specifically, obtained different sensing materials are coated in quartz glass tube, by the way that explosive is placed in heating gun, passed through Different temperature is set to improve the vapour concentration of explosive, when different explosive steam in sensor array with difference with taking For functional group pendant organic fluorescence sensing material contact when, it is described difference fluorescent sensing materials fluorescence multi-form can occur Change, analyzing different materials in several arrays, to the change in fluorescence of same explosive, these changes are only to each explosive One, so as to achieve the purpose that to distinguish a few class explosive detections.Preferably, a few class explosives are selected from hexogen (RDX), trinitrotoluene (TNT), dinitrotoluene (DNT) (DNT), pentaerythrite Tetranitrate (PETN), black powder (S), ammonium nitrate (AN) and 2,3- dinitro -2,3- dimethylbutanes (DMNB).
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