CN108562621A - 2- acetyl -1- pyrrolins sensitive material film and preparation method and 2- acetyl -1- pyrrolins sensing device and application - Google Patents
2- acetyl -1- pyrrolins sensitive material film and preparation method and 2- acetyl -1- pyrrolins sensing device and application Download PDFInfo
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Abstract
The present invention provides the applications of a kind of 2 acetyl, 1 pyrrolin sensitive material film and preparation method thereof and a kind of 2 acetyl, 1 pyrrolin sensing device and sensing device, after sensitive material film provided by the invention is contacted with 2 acetyl, 1 pyrrolin, the resistance of sensitive material film changes, and the resistance variations situation by detecting sensitive material film can quickly, easily detect the concentration of 2 acetyl, 1 pyrrolin.
Description
Technical field
The present invention relates to technical field of agricultural information more particularly to a kind of sensitive material film and preparation method thereof and one kind
The application of 2- acetyl -1- pyrrolins sensing device and sensing device.
Background technology
Rice is one of most important cereal crops in China, accounts for about the 45% of total output of grain, Chinese society life and
It is play an important role in economic development.In recent years, with the raising of China's Living consumption, the improvement of diet structure and people
Health care consciousness enhancing, rice quality gradually causes the concern of people.Rice quality refers to from paddy production to be processed into can
In the product process directly consumed, as grain or the various qualitative characters of commodity, generally include exterior quality, processing quality,
Cooking and eating quality and nutritional quality, wherein fragrance are the important characters of rice eating-quality.The existing volatilization of rice outer layer
Property ingredient 2- acetyl -1- pyrrolins play an important role to the formation of grain of rice fragrance.
2- acetyl -1- pyrrolin gas fragrance is strong, volatile, oxidizable, unstable chemcial property, 2- acetyl-in rice
1- pyrrolin audible threshold values are 0.1ppb, detect in different rice 2- acetyl -1- pyrrolin concentration be only 0.006~
0.09ppm, since 2- acetyl -1- pyrrolin contents are relatively low in rice aroma, 2- acetyl -1- pyrrolin contents in rice aroma
There are certain difficulties for detection.Currently, mainly use first passes through solvent extraction to the detection method of 2- acetyl -1- pyrrolins in rice aroma
It follows the example of, the extracting methods such as Water distillation extractor, column extracting method, solid phase extraction, Solid-phase Microextraction and supercritical fluid extraction
2- acetyl -1- the pyrrolins in rice are extracted, 2- acetyl -1- pyrroles in rice is then measured by gas-chromatography or mass spectrometry method
The concentration of quinoline.But the above method has that the detection process time is long, detection process complexity.
Invention content
The present invention provides a kind of 2- acetyl -1- pyrrolin sensitive material films and preparation method thereof and a kind of 2- acetyl -
The application of 1- pyrrolins sensing device and sensing device, sensitive material film provided by the invention and 2- acetyl -1- pyrrolins
After contact, the resistance of sensitive material film changes, and the resistance by detecting sensitive material film quickly, can be examined easily
Measure the concentration of 2- acetyl -1- pyrrolins.
In order to achieve the goal above, the present invention provides following technical schemes：
The present invention provides a kind of 2- acetyl -1- pyrrolin sensitive material films, including substrate and sensitive material；It is described
Sensitive material includes the graphene oxide of the polymethyl hydrogen siloxane and hexafluoroisopropanol modification of hexafluoroisopropanol modification；It is described
The mass ratio of the polymethyl hydrogen siloxane of hexafluoroisopropanol modification and the graphene oxide of hexafluoroisopropanol modification is 1:0.5~1.
Preferably, the thickness of the 2- acetyl -1- pyrrolin sensitive material films is 80~200nm；The sensitive material
The thickness of layer is 100~250nm.
The present invention provides the preparation methods of the 2- acetyl -1- pyrrolin sensitive material films, include the following steps：
(1) by alkenyl replace hexafluoroisopropanol, polymethyl hydrogen siloxane and the first catalyst in polar organic solvent into
The reaction solution of the addition reaction is filtered by row addition reaction successively, filtrate distills and is dried to obtain hexafluoroisopropanol and repaiies
The polymethyl hydrogen siloxane of decorations；First catalyst is platinum；The temperature of the addition reaction is 152~157 DEG C；
(2) amination hexafluoroisopropanol, graphene oxide and the second catalyst are subjected to condensation reaction in water, it will be described
The reaction solution of condensation reaction is filtered successively, the graphene oxide of hexafluoroisopropanol modification is distilled and be dried to obtain to filtrate；Institute
It is dicyclohexyl carbodiimide to state the second catalyst；The temperature of the condensation reaction is 95~100 DEG C；
(3) obtain the polymethyl hydrogen siloxane of hexafluoroisopropanol that the step (1) obtains modification and step (2) six
The graphene oxide of fluorine isopropanol modification is dispersed in low boiling point organic solvent, obtains mixed liquor；The mixed liquor is sprayed
It is coated in substrate surface, obtains sensitive material film；
The graphite oxide for polymethyl hydrogen siloxane and the hexafluoroisopropanol modification that hexafluoroisopropanol is modified in the step (3)
The mass ratio of alkene is 1:0.5~1；
The step (1) and step (2) are limited without chronological order.
Preferably, in the step (1) alkenyl substitution hexafluoroisopropanol, polymethyl hydrogen siloxane and the first catalyst matter
Amount is than being 1：0.2~0.3：0.002~0.005.
Preferably, the mass ratio of amination hexafluoroisopropanol, graphene oxide and the second catalyst is in the step (2)
1：10~13：0.002~0.005.
Preferably, the mass concentration for the polymethyl hydrogen siloxane that hexafluoroisopropanol is modified in step (3) mixed liquor
It is 0.03%~0.05%.
The present invention provides a kind of 2- acetyl -1- pyrrolin sensing devices, including power module and respectively with the electricity
The sensor assembly and display module of source module electrical connection, the sensor assembly include the sensor unit and signal of electrical connection
Processing unit, the display module are electrically connected with sensor die signal processing unit in the block；
The sensor unit includes sensor substrate and sensitive material film, and the sensitive material film is above-mentioned technology
The 2- second that preparation method is prepared described in 2- acetyl -1- pyrrolins sensitive material film or above-mentioned technical proposal described in scheme
Acyl -1- pyrrolin sensitive material films.
Preferably, the sensor substrate includes the flexible substrate of silicon chip, printed circuit board or carried metal.
Preferably, the signal processing unit is handled signal using short circuit zero self calibration and analog-to-digital conversion；Institute
It includes the high-precision A/D conversions carried out successively and microprocessor to state analog-to-digital conversion.
The present invention provides application of the sensing device described in above-mentioned technical proposal in detecting rice flavouring essence quality.
The present invention provides a kind of 2- acetyl -1- pyrrolin sensitive material films, the film includes substrate and sensitive material
The bed of material；The sensitive material includes the oxidation stone of the polymethyl hydrogen siloxane and hexafluoroisopropanol modification of hexafluoroisopropanol modification
Black alkene；The mass ratio of the polymethyl hydrogen siloxane of hexafluoroisopropanol modification and the graphene oxide of hexafluoroisopropanol modification is
1:0.5~1.Sensitive material film provided by the invention has stronger suction-operated to escaping gas 2- acetyl -1- pyrrolins,
After sensitive material film and 2- acetyl -1- pyrrolins contact, since 2- acetyl -1- pyrrolins have oxidisability, 2- acetyl -1-
Pyrrolin changes the hole concentration of sensitive material in sensitive material film by way of contributing electronics so that sensitive material is thin
The resistance of film changes.By the resistance for detecting sensitive material film, you can quickly, easily detect 2- acetyl -1- pyrroles
Cough up the concentration of quinoline.Embodiment the result shows that, can be real-time using 2- acetyl -1- pyrrolins sensitive material film provided by the invention
The concentration of 2- acetyl -1- pyrrolins in rice is detected.
Description of the drawings
Fig. 1 is the internal structure schematic diagram of 2- acetyl -1- pyrrolin sensing devices of the present invention, wherein 101- air admission holes,
102- is switched, 103- crusts of the device, 104- power supply modules, 105- circuit modules, 106- signal processing modules, 107-2- acetyl-
1- pyrrolin sensor assemblies；
Fig. 2 is the left view of 2- acetyl -1- pyrrolin sensing devices of the present invention；
Fig. 3 is the vertical view of 2- acetyl -1- pyrrolin sensing devices of the present invention；
Fig. 4 is test result of 1 sensing device of the embodiment of the present invention to 2- acetyl -1- pyrrolins；
Fig. 5 is test result of 2 sensing device of the embodiment of the present invention to 2- acetyl -1- pyrrolins；
Fig. 6 is test result of 3 sensing device of the embodiment of the present invention to 2- acetyl -1- pyrrolins；
Fig. 7 is test result of 4 sensing device of the embodiment of the present invention to 2- acetyl -1- pyrrolins.
Specific implementation mode
The present invention provides a kind of 2- acetyl -1- pyrrolin sensitive material films, including substrate and sensitive material；It is described
Sensitive material includes the graphene oxide of the polymethyl hydrogen siloxane and hexafluoroisopropanol modification of hexafluoroisopropanol modification；It is described
The mass ratio of the polymethyl hydrogen siloxane of hexafluoroisopropanol modification and the graphene oxide of hexafluoroisopropanol modification is 1:0.5~1.
The present invention provides a kind of 2- acetyl -1- pyrrolin sensitive material films, including substrate and sensitive material.At this
In invention, the thickness of the sensitive material film is preferably 80~200nm, further preferably 100~180nm, more preferably
120~160nm, most preferably 140~150nm.
In the present invention, the thickness of the sensitive material is preferably 100~250nm, further preferably 150~
200nm。
In the present invention, the substrate is preferably silicon substrate, ceramic base or the flexible interdigital electrode substrate of carried metal.At this
In invention, when the substrate is preferably the silicon substrate of carried metal, the carried metal is preferably gold；When the substrate is preferably
When flexible interdigital electrode substrate, the flexibility interdigital electrode substrate is preferably poly terephthalic acid class plastics, polyimides, poly- two
Methylsiloxane or polyethylene naphthalate.
In the present invention, the sensitive material includes the polymethyl hydrogen siloxane and hexafluoro isopropyl of hexafluoroisopropanol modification
The graphene oxide of alcohol modification.In the present invention, hexafluoroisopropanol in the polymethyl hydrogen siloxane of the hexafluoroisopropanol modification
Alkyl on group is connected with the silicon in polymethyl hydrogen siloxane；Amino six in the graphene oxide of the hexafluoroisopropanol modification
Dehydrating condensation connection occurs for the carboxyl in the amino and graphene oxide in fluorine isopropyl alcohol groups.In the present invention, the sensitivity
The mass ratio of the polymethyl hydrogen siloxane of hexafluoroisopropanol modification and the graphene oxide of hexafluoroisopropanol modification is in material layer
1:0.5~1, preferably 1:0.6~0.9, further preferably 1:0.7~0.8.
In the present invention, the preparation method of the polymethyl hydrogen siloxane of the hexafluoroisopropanol modification preferably includes following step
Suddenly：
Hexafluoroisopropanol, polymethyl hydrogen siloxane and the first catalyst is replaced to be added in polar organic solvent alkenyl
At reaction, the reaction solution of the addition reaction is filtered successively, hexafluoroisopropanol modification is distilled and be dried to obtain to filtrate
Polymethyl hydrogen siloxane.
Alkenyl is replaced hexafluoroisopropanol, polymethyl hydrogen siloxane and the first catalyst in polar organic solvent by the present invention
Mixing, obtains mixed material.
In the present invention, first catalyst is zeroth order platinum, preferably 1,3- divinyl -1,1,3,3- tetramethyls two
Siloxanes platinum (0) catalyst, i.e. Karstedt catalyst.
In the present invention, the polar organic solvent is preferably tetrahydrofuran or chloroform.
In the present invention, the alkenyl substitution hexafluoroisopropanol is preferably 2- vinyl hexafluoroisopropanol and/or 2- allyls
Base hexafluoroisopropanol.
In the present invention, the mass ratio of alkenyl substitution hexafluoroisopropanol, polymethyl hydrogen siloxane and the first catalyst is preferred
It is 1：0.2~0.3：0.002~0.005, further preferably 1：0.22~0.28：0.003~0.004.
In the present invention, first catalyst is preferably dispersion liquid of the zeroth order platinum in benzene series organic solvent, the benzene
Be organic solvent it is preferably toluene, dimethylbenzene or isopropanol, the dilution mass ratio of the zeroth order platinum and benzene series organic solvent is preferred
It is 1：40~60, further preferably 1:45~55.
Alkenyl is preferably first replaced hexafluoroisopropanol, polymethyl hydrogen siloxane and organic solvent to mix by the present invention, then again
It is mixed with the first catalyst, obtains mixed material.Mixed method is not particularly limited in the present invention, using people in the art
Material mixed method known to member.
The present invention carries out addition reaction to the mixed material, obtains reaction solution.
In the present invention, the temperature of the addition reaction is preferably 152~157 DEG C, further preferably 155~156 DEG C,
The time of the addition reaction is preferably 24~28h, further preferably 25~26h.
The present invention is preferably stirred mixed material while addition reaction, and the present invention is to the rotating speed of stirring without spy
It does not limit, using mixing speed commonly used in this field.The present invention preferably by stir process, makes addition reaction carry out
More fully.
The present invention during addition reaction, with polymethyl hydrogen siloxane urging by the alkenyl substitution hexafluoroisopropanol
It reacts under agent, generates the polymethyl hydrogen siloxane of hexafluoroisopropanol modification.In the present invention, different with 2- vinyl hexafluoros
For propyl alcohol and 2- allyl hexafluoroisopropanols, addition reaction process is illustrated, the addition reaction process such as Formulas I institute
Show：
In the present invention, the alkenyl substitution hexafluoroisopropanol reacts with polymethyl hydrogen siloxane under catalyst,
Alkenyl replaces the double bond of hexafluoroisopropanol to open, and addition reaction occurs with polymethyl hydrogen siloxane.
Preferably activated carbon is added into the reaction solution of addition reaction in the present invention, obtains the reaction solution of activated carbon adsorption.At this
In invention, the dosage of the activated carbon and zeroth order platinum is preferably 1~1.5:1.Activated carbon is preferably added in the present invention into reaction solution,
Be conducive to absorption, removal zeroth order platinum catalyst.
The present invention is preferably filtered the product of addition reaction successively, filtrate distills and is dried to obtain hexafluoroisopropanol and repaiies
The polymethyl hydrogen siloxane of decorations.
The method of filtering is not particularly limited in the present invention, is using filter method well-known to those skilled in the art
It can.The present invention preferably collects the filtrate being obtained by filtration.
The present invention preferably carries out distillation processing to filtrate.In the present invention, the temperature of the distillation is preferably room temperature.This hair
It is bright that distillation is preferably stopped when no longer generation distillate according to the time of the amount of distillate control distillation.The present invention preferably collects
Distill obtained solid.The present invention preferably by being distilled to filtrate, keeps volatile substances complete.
Processing is dried in the solid that the present invention preferably obtains distillation, obtains the poly- methyl hydrogen silicon of hexafluoroisopropanol modification
Oxygen alkane.In the present invention, the temperature of the drying is preferably 80~100 DEG C, and the time of the drying is preferably 2~4h.
In the present invention, the polymethyl hydrogen siloxane of hexafluoroisopropanol modification to 2- acetyl -1- pyrrolins have compared with
Strong Hydrogen Binding Adsorption effect, the present invention add the polymethyl hydrogen siloxane of hexafluoroisopropanol modification in sensitive material, favorably
Escaping gas 2- acetyl -1- pyrrolins are fully adsorbed in sensitive material film, quickly obtain testing result.
In the present invention, the sensitive material includes the graphene oxide of hexafluoroisopropanol modification.
In the present invention, the preparation method of the graphene oxide of the hexafluoroisopropanol modification preferably includes following steps：
Amination hexafluoroisopropanol, graphene oxide and the second catalyst are subjected to condensation reaction in water, by the contracting
The reaction solution of conjunction reaction is filtered successively, the graphene oxide that hexafluoroisopropanol is modified is distilled and be dried to obtain to filtrate.
The present invention preferably mixes amination hexafluoroisopropanol, graphene oxide and the second catalyst in water, is mixed
Close feed liquid.
In the present invention, second catalyst is dicyclohexyl carbodiimide.
In the present invention, the graphene oxide is preferably prepared or is commercially available by Hummers methods.The present invention couple
The specific implementation mode of the Hummers methods does not have particular/special requirement, using well-known to those skilled in the art.
In the present invention, the mass ratio of the amination hexafluoroisopropanol, graphene oxide and the second catalyst is preferably
1：10~13：0.002~0.005, further preferably 1：11~12：0.003~0.004.
Mixed mode and mixed sequence is not particularly limited in the present invention, common using those skilled in the art institute
Hybrid mode and order by merging.
After obtaining mixed liquor, the present invention carries out condensation reaction to the mixed liquor, obtains the reaction solution of condensation reaction.
In the present invention, the temperature of the condensation reaction is preferably 95~100 DEG C, further preferably 96~98 DEG C；Institute
The time for stating condensation reaction is preferably 24~28h, further preferably 25~26h.
The present invention is in the condensation reaction, and the amination hexafluoroisopropanol is with graphene oxide under catalyst
It reacts, generates the graphene oxide of hexafluoroisopropanol modification.In the present invention, the condensation reaction such as Formula II institute
Show：
The present invention is preferably filtered the reaction solution of condensation reaction successively, hexafluoroisopropanol is distilled and be dried to obtain to filtrate
The graphene oxide of modification.
The method of filtering is not particularly limited in the present invention, is using filter method well-known to those skilled in the art
It can.The present invention preferably collects the filtrate being obtained by filtration.
The present invention preferably carries out distillation processing to the filtrate.In the present invention, the temperature of the distillation is preferably room temperature.
The present invention, when not having distillate, stops distillation preferably according to the time of the amount of distillate control distillation.The present invention preferably collects
Distill obtained solid.The present invention preferably by being distilled to filtrate, makes volatile compound fully volatilize.
Processing is dried in the solid that the present invention preferably obtains distillation, obtains the graphite oxide of hexafluoroisopropanol modification
Alkene.In the present invention, the temperature of the drying is preferably 80~100 DEG C, and the time of the drying is preferably 2~4h.
In the present invention, the graphene oxide of the hexafluoroisopropanol modification has 2- acetyl -1- pyrrolins stronger
Hydrogen Binding Adsorption acts on, and the present invention adds the graphene oxide of hexafluoroisopropanol modification in sensitive material, is conducive to sensitive material
Material film can fully adsorb escaping gas 2- acetyl -1- pyrrolins, quickly obtain testing result.
In addition, the present invention adds the polymethyl hydrogen siloxane and six of hexafluoroisopropanol modification simultaneously in sensitive material film
The advantages of graphene oxide of fluorine isopropanol modification, is, using the synergistic effect between two kinds of sensitive materials, on the one hand enhances
Strong hydrogen bonding functionality absorption to 2- acetyl -1- pyrrolins helps to increase senser element to the sensitive of 2- acetyl -1- pyrrolins
Degree response reduces the response time；The polymethyl hydrogen siloxane of another aspect hexafluoroisopropanol modification does not have electric conductivity, and hexafluoro
Isopropanol modification graphene oxide have good conductive property, it is compound after sensitive material can pass through its electrical properties
Variation judges adsorbed 2- acetyl -1- pyrrolin concentration.
In the present invention, after the sensitive material film is contacted with 2- acetyl -1- pyrrolins, due to 2- acetyl -1- pyrroles
There is quinoline oxidisability, 2- acetyl -1- pyrrolins to change sensitive material in sensitive material film by way of contributing electronics
Hole concentration so that the resistance of sensitive material film increases, and resistance becomes smaller.By the resistance for detecting sensitive material film, you can
Quickly, the concentration of 2- acetyl -1- pyrrolins is easily detected.
The present invention also provides the preparation methods of sensitive material film described in above-mentioned technical proposal, include the following steps：
(1) by alkenyl replace hexafluoroisopropanol, polymethyl hydrogen siloxane and the first catalyst in benzene series organic solvent into
The reaction solution of the addition reaction is filtered by row addition reaction successively, filtrate distills and is dried to obtain hexafluoroisopropanol and repaiies
The polymethyl hydrogen siloxane of decorations；First catalyst includes zeroth order platinum；The temperature of the addition reaction is 152~157 DEG C；
(2) amination hexafluoroisopropanol, graphene oxide and the second catalyst are subjected to condensation reaction in water, it will be described
The reaction solution of condensation reaction is filtered successively, the graphene oxide of hexafluoroisopropanol modification is distilled and be dried to obtain to filtrate；Institute
It is dicyclohexyl carbodiimide to state the second catalyst；The temperature of the condensation reaction is 95~100 DEG C；
(3) obtain the polymethyl hydrogen siloxane of hexafluoroisopropanol that the step (1) obtains modification and step (2) six
The graphene oxide of fluorine isopropanol modification is dispersed in low boiling point organic solvent, obtains mixed liquor；The mixed liquor is sprayed
It is coated in substrate surface, obtains sensitive material film；
The graphite oxide for polymethyl hydrogen siloxane and the hexafluoroisopropanol modification that hexafluoroisopropanol is modified in the step (3)
The mass ratio of alkene is 1:0.5~1；
The step (1) and step (2) are not limited in sequence.
The poly- first of hexafluoroisopropanol modification has already been described in detail in above-mentioned sensitive material film technical solution part in the present invention
The preparation method of base hydrogen siloxane and the graphene oxide of hexafluoroisopropanol modification, details are not described herein.
After obtaining the polymethyl hydrogen siloxane of hexafluoroisopropanol modification and the graphene oxide of hexafluoroisopropanol modification, this hair
The bright polymethyl hydrogen siloxane for modifying the hexafluoroisopropanol and the graphene oxide of hexafluoroisopropanol modification are dispersed in low boiling
In point organic solvent, mixed liquor is obtained；The mixed liquor is sprayed on substrate surface, obtains sensitive material film.
The graphite oxide for polymethyl hydrogen siloxane and the hexafluoroisopropanol modification that the present invention modifies the hexafluoroisopropanol
Alkene is dispersed in low boiling point organic solvent, obtains mixed liquor.
In the present invention, the polymethyl hydrogen siloxane and hexafluoroisopropanol that hexafluoroisopropanol is modified in the mixed liquor are repaiied
The mass ratio of the graphene oxide of decorations is 1:0.5~1, preferably 1:0.6~0.9, further preferably 1:0.7~0.8.
In the present invention, the low boiling point organic solvent is preferably ethyl alcohol, chloroform or acetone.In the present invention, institute
The concentration for stating the polymethyl hydrogen siloxane of the hexafluoroisopropanol modification in mixed liquor is preferably 0.5~2mg/mL, further excellent
It is selected as 1.0~1.5mg/mL, more preferably 1.2~1.3mg/mL.
After obtaining mixed liquor, the mixed liquor is sprayed on substrate surface by the present invention, obtains sensitive material film.
In the present invention, the substrate is preferably silicon substrate, ceramic base or flexible interdigital electrode substrate.The present invention is preferably by base
Bottom is fixed on hot plate, and the temperature of the hot plate is preferably 50~80 DEG C, further preferably 60~70 DEG C.
In the present invention, the flow of the spraying nitrogen buffer gas, the nitrogen is preferably 8~10uL/s, nitrogen gas
Pressure is preferably 18~20psi；The highly preferred airbrush of the spraying is 5~10cm.
In the present invention, after the spraying forms wet film, the present invention preferably makes annealing treatment wet film, obtains sensitive material
Expect film.
In the present invention, the temperature of the annealing is preferably 200~300 DEG C, further preferably 220~280 DEG C；It is described
The time of annealing is preferably 10~20min, further preferably 12~18min.The present invention preferably by annealing, promotes to have
The abundant volatilization of solvent, makes sensitive material and substrate better contact with.
The present invention also provides a kind of 2- acetyl -1- pyrrolin sensing devices, including sensor assembly, power module and aobvious
Show that module, the sensor assembly include the sensor unit and signal processing unit of connection, the sensor unit includes passing
Sensor substrate and sensitive material film, the sensitive material film are sensitive material film or above-mentioned described in above-mentioned technical proposal
The sensitive material film that preparation method described in technical solution is prepared.
In the present invention, the 2- acetyl -1- pyrrolin sensing devices include sensor assembly, the sensor assembly packet
Include the sensor unit and signal processing unit of connection.
In the present invention, the sensor unit includes sensitive material film.In the present invention, the sensitive material film
For the sensitive material that preparation method is prepared described in sensitive material film described in above-mentioned technical proposal or above-mentioned technical proposal
Film.
In the present invention, the signal processing unit using short circuit zero self calibration and analog-to-digital conversion to signal at
Reason, the analog-to-digital conversion include the high-precision A/D conversions carried out successively and microprocessor.
In the present invention, the 2- acetyl -1- pyrrolin sensing devices include power module.In the present invention, the electricity
Source module is connect with sensor assembly and display module simultaneously, for providing power supply for sensor assembly and display module；It is described
Power module preferably uses storage battery power supply form.
In the present invention, the 2- acetyl -1- pyrrolin sensing devices include display module.In the present invention, described aobvious
Show that module is preferably made of LED display and digital circuit；The LED display is connected with digital circuit, the digital circuit
It is connect with the signal processing unit of sensor assembly.In the present invention, the sensor assembly output signal passes to the number
Word circuit, display screen show detected 2- acetyl -1- pyrrolin concentration.
In the present invention, the sensing device preferably includes crust of the device.In the present invention, described device shell be not necessarily to
Other modules connection in the sensing device, described device shell are used for protective device, convenient for the 2- to volatilize in aggregation rice
Acetyl -1- pyrrolins.
In the present invention, it is preferably provided with air inlet on described device shell, makes escaping gas 2- acetyl -1- pyrrolins
It is contacted with sensor assembly.
In the present invention, as shown in Figure 1, wherein 101 be air admission hole, 102 are the 2- acetyl -1- pyrrolins sensing device
Switch, 103 be crust of the device, and 104 be power supply module, and 105 be circuit module, and 106 be signal processing module, and 107 be 2- acetyl-
1- pyrrolin sensor assemblies；Wherein power supply module respectively with switch and circuit module connect, circuit module respectively with power mould
Block is connected with signal processing module, and signal processing module connects with circuit module and 2- acetyl -1- pyrrolin sensor assemblies respectively
It connects.
The present invention also provides application of the sensing device in detecting rice flavouring essence quality.
The detection method when present invention detects rice flavouring essence quality to the sensing device is not particularly limited, using ability
The method of detection gas content known to field technique personnel.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.
Embodiment 1
The tetrahydrofuran that the polymethyl hydrogen siloxane of the 2- vinyl hexafluoroisopropanol and 0.2g that take 1g is mixed in 40mL is molten
In agent, the Karstedt catalyst of 0.002g is added, heating stirring for 24 hours, fully after reaction, is added 0.003g and lives at 152 DEG C
Property charcoal, it is lasting to stir, be cooled to room temperature after complete reaction, filter, distill, dry after obtain the poly- first of hexafluoroisopropanol modification
Base hydrogen siloxane.
0.1g aminations hexafluoroisopropanol, 1g graphene oxides and 100mL water are mixed, 0.002g dicyclohexyl carbon is added
Change diimine catalysts, by reacting for carboxyl and amino, hexafluoroisopropanol functional group is connected on graphene oxide, obtains six
The graphene oxide of fluorine isopropanol modification.
By the mass ratio of the polymethyl hydrogen siloxane of hexafluoroisopropanol modification and the graphene oxide of hexafluoroisopropanol modification
Control is 1：In ethanol after mixing, the polymethyl hydrogen siloxane of hexafluoroisopropanol modification is dense in ethyl alcohol for 0.5 ratio
Degree is 0.5mg/mL, and film is prepared on device using gas blowout thin film-forming method：Device substrate is fixed on 50 DEG C of hot plates, is used
Holder-180 type airbrush, nitrogen is as carrier gas, N2Pressure be 18psi, N2Flow be 8ul/s.Solution will be prepared and instill stream
Dynamic cup, solution on substrate from nozzle spraying, obtain sensitive material film under the drive of stream of nitrogen gas.
Embodiment 2
The tetrahydrofuran that the polymethyl hydrogen siloxane of the 2- vinyl hexafluoroisopropanol and 0.3g that take 1g is mixed in 60mL is molten
In agent, the Karstedt catalyst of 0.005g is added, the heating stirring 28h at 157 DEG C fully after reaction, is added 0.005g and lives
Property charcoal, it is lasting to stir, be cooled to room temperature after complete reaction, filter, distill, dry after obtain the poly- first of hexafluoroisopropanol modification
Base hydrogen siloxane.
0.1g aminations hexafluoroisopropanol, 1g graphene oxides and 100mL water are mixed, 0.002g dicyclohexyl carbon is added
Change diimine catalysts, by reacting for carboxyl and amino, hexafluoroisopropanol functional group is connected on graphene oxide, obtains six
The graphene oxide of fluorine isopropanol modification.
By the mass ratio of the polymethyl hydrogen siloxane of hexafluoroisopropanol modification and the graphene oxide of hexafluoroisopropanol modification
Control is 1:1 ratio in ethanol after mixing, the concentration for the polymethyl hydrogen siloxane that hexafluoroisopropanol is modified in ethyl alcohol
For 2mg/mL, film is prepared on device using gas blowout thin film-forming method：Device substrate is fixed on 80 DEG C of hot plates, is used
Holder-180 type airbrush, nitrogen is as carrier gas, N2Pressure be 20psi, N2Flow be 8ul/s.Solution will be prepared and instill stream
Dynamic cup, solution on substrate from nozzle spraying, obtain sensitive material film under the drive of stream of nitrogen gas.
Embodiment 3
The polymethyl hydrogen siloxane of the 2- vinyl hexafluoroisopropanol and 0.2g that take 1g is mixed in the toluene solvant of 40mL,
The Karstedt catalyst of 0.002g is added, fully after reaction, 0.003g activity is added in the heating stirring 24min at 152 DEG C
Charcoal, it is lasting to stir, be cooled to room temperature after complete reaction, filter, distill, dry after obtain the poly- methyl of hexafluoroisopropanol modification
Hydrogen siloxane.
0.1g aminations hexafluoroisopropanol, 1.3g graphene oxides and 100mL water are mixed, 0.005g dicyclohexyls are added
Hexafluoroisopropanol functional group is connected on graphene oxide, is obtained by reacting for carboxyl and amino by carbodiimides catalyst
The graphene oxide of hexafluoroisopropanol modification.
By the mass ratio of the polymethyl hydrogen siloxane of hexafluoroisopropanol modification and the graphene oxide of hexafluoroisopropanol modification
Control is 1：In ethanol after mixing, the polymethyl hydrogen siloxane of hexafluoroisopropanol modification is dense in ethyl alcohol for 0.8 ratio
Degree is 0.5mg/mL, and film is prepared on device using gas blowout thin film-forming method：Device substrate is fixed on 60 DEG C of hot plates, is used
Holder-180 type airbrush, nitrogen is as carrier gas, N2Pressure be 18psi, N2Flow be 10ul/s.Solution will be prepared to instill
Flow cup, solution on substrate from nozzle spraying, obtain sensitive material film under the drive of stream of nitrogen gas.
Embodiment 4
The polymethyl hydrogen siloxane of the 2- vinyl hexafluoroisopropanol and 0.3g that take 1g is mixed in the toluene solvant of 60mL,
The Karstedt catalyst of 0.005g is added, 0.005g activated carbons are added fully after reaction in the heating stirring 28h at 157 DEG C,
Lasting stirring, is cooled to room temperature after complete reaction, filter, distill, dry after obtain the poly- methyl hydrogen of hexafluoroisopropanol modification
Siloxanes.
0.1g aminations hexafluoroisopropanol, 1.3g graphene oxides and 100mL water are mixed, 0.005g dicyclohexyls are added
Hexafluoroisopropanol functional group is connected on graphene oxide, is obtained by reacting for carboxyl and amino by carbodiimides catalyst
The graphene oxide of hexafluoroisopropanol modification.
By the mass ratio of the polymethyl hydrogen siloxane of hexafluoroisopropanol modification and the graphene oxide of hexafluoroisopropanol modification
Control is 1：In ethanol after mixing, the polymethyl hydrogen siloxane of hexafluoroisopropanol modification is dense in ethyl alcohol for 0.6 ratio
Degree is 2mg/mL, and film is prepared on device using gas blowout thin film-forming method：Device substrate is fixed on 70 DEG C of hot plates, is used
Holder-180 type airbrush, nitrogen is as carrier gas, N2Pressure be 20psi, N2Flow be 10ul/s.Solution will be prepared to instill
Flow cup, solution on substrate from nozzle spraying, obtain sensitive material film under the drive of stream of nitrogen gas.
Embodiment 5
The sensitive material film that Examples 1 to 4 is prepared is assembled into 2- acetyl -1- pyrrolin sensing devices, it is described
The internal structure of sensing device as shown in Figure 1, left view as shown in Fig. 2, vertical view is as shown in Figure 3.
By the sensing device for the sensitive material film composition that Examples 1 to 4 obtains for detecting rice fragrance, rice is put
It sets at the air inlet of sensing device, device for opening switch, power supply module work, sensing module detects 2- second in rice fragrance
After acyl -1- pyrrolins, the resistance value of sensing unit changes in sensing module, at signaling module and circuit module through rear end
After reason, the resistance variations of sensor unit in sensor assembly are changed into the concentration of 2- acetyl -1- pyrrolins, while being shown
2- acetyl -1- pyrrolin concentration in detected rice fragrance is shown in module.The detection case of sensor unit such as Fig. 4
Shown in~7,2- acetyl -1- pyrrolin concentration results are as shown in table 1 in response time and rice fragrance.
The present invention by test sensor unit resistance variations situation, to obtain the concentration of -1 pyrrolin of 2- acetyl.
The method for obtaining 2- acetyl -1- pyrrolin concentration by resistance variations situation is not particularly limited in the present invention, using this field skill
Method known to art personnel.
Testing result of the sensing device that 1 Examples 1 to 4 of table obtains to rice fragrance
| Response time (s) | Responsiveness | 2- acetyl -1- pyrrolins concentration (ppm) | |
| Embodiment 1 | 650 | 0.013 | 0.05 |
| Embodiment 2 | 583 | 0.04 | 0.05 |
| Embodiment 3 | 624 | 0.017 | 0.05 |
| Embodiment 4 | 153 | 0.051 | 0.05 |
As seen from the above embodiment, the sensing device of sensitive material film composition provided by the invention detects rice fragrance
Time is short, the response time be 153~650s, show quickly to respond, detection process in real time, dynamic, compared to current chromatography
Detection technique has quick, the real-time and simple advantage of operating process.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of 2- acetyl -1- pyrrolin sensitive material films, including substrate and sensitive material；The material of the sensitive material
Material includes the graphene oxide of the polymethyl hydrogen siloxane and hexafluoroisopropanol modification of hexafluoroisopropanol modification；The hexafluoro isopropyl
The mass ratio of the polymethyl hydrogen siloxane of alcohol modification and the graphene oxide of hexafluoroisopropanol modification is 1:0.5~1.
2. 2- acetyl -1- pyrrolin sensitive material films according to claim 1, which is characterized in that the 2- acetyl -1-
The thickness of pyrrolin sensitive material film is 80~200nm；The thickness of the sensitive material is 100~250nm.
3. the preparation method of 2- acetyl -1- pyrrolin sensitive material films as claimed in claim 1 or 2, includes the following steps：
(1) hexafluoroisopropanol, polymethyl hydrogen siloxane and the first catalyst is replaced to be added in polar organic solvent alkenyl
At reaction, the reaction solution of the addition reaction is filtered successively, hexafluoroisopropanol modification is distilled and be dried to obtain to filtrate
Polymethyl hydrogen siloxane；First catalyst includes zeroth order platinum；The temperature of the addition reaction is 152~157 DEG C；
(2) amination hexafluoroisopropanol, graphene oxide and the second catalyst are subjected to condensation reaction in water, by the condensation
The reaction solution of reaction is filtered successively, the graphene oxide of hexafluoroisopropanol modification is distilled and be dried to obtain to filtrate；Described
Two catalyst are dicyclohexyl carbodiimide；The temperature of the condensation reaction is 95~100 DEG C；
(3) polymethyl hydrogen siloxane that the hexafluoroisopropanol that the step (1) obtains is modified and the hexafluoro that step (2) obtains is different
The graphene oxide of propyl alcohol modification is dispersed in low boiling point organic solvent, obtains mixed liquor；The mixed liquor is sprayed on
Substrate surface obtains sensitive material film；
The graphene oxide for polymethyl hydrogen siloxane and the hexafluoroisopropanol modification that hexafluoroisopropanol is modified in the step (3)
Mass ratio is 1:0.5~1；
The step (1) and step (2) are limited without chronological order.
4. preparation method according to claim 3, which is characterized in that in the step (1) alkenyl substitution hexafluoroisopropanol,
The mass ratio of polymethyl hydrogen siloxane and the first catalyst is 1：0.2~0.3：0.002~0.005.
5. preparation method according to claim 3, which is characterized in that amination hexafluoroisopropanol, oxygen in the step (2)
The mass ratio of graphite alkene and the second catalyst is 1：10~13：0.002~0.005.
6. preparation method according to claim 3, which is characterized in that hexafluoroisopropanol in step (3) mixed liquor
The mass concentration of the polymethyl hydrogen siloxane of modification is 0.03%~0.05%.
7. a kind of 2- acetyl -1- pyrrolin sensing devices, including power module and it is electrically connected respectively with the power module
Sensor assembly and display module, the sensor assembly includes the sensor unit and signal processing unit of electrical connection, described
Display module is electrically connected with sensor die signal processing unit in the block；
The sensor unit includes sensitive material film, and the sensitive material film is 2- acetyl-described in claims 1 or 2
2- acetyl -1- the pyrroles that any one of 1- pyrrolins sensitive material film or claim 3~6 preparation method are prepared
Quinoline sensitive material film.
8. sensing device according to claim 7, which is characterized in that the sensor substrate includes silicon chip, printed circuit
The flexible substrate of plate or carried metal.
9. sensing device according to claim 7 or 8, which is characterized in that the signal processing unit uses short circuit zero
Self calibration and analog-to-digital conversion handle signal；The analog-to-digital conversion includes the high-precision A/D conversions carried out successively and micro- place
Reason.
10. a kind of application of claim 7~9 any one of them sensing device in detecting rice flavouring essence quality.
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| US6274183B1 (en) * | 2000-06-12 | 2001-08-14 | Travis Richard | Rice composition for coating foods |
| CN101363810A (en) * | 2008-09-11 | 2009-02-11 | 电子科技大学 | Gas-sensitive sensor and method for making same |
| CN102634030A (en) * | 2012-04-25 | 2012-08-15 | 电子科技大学 | Low-toxicity synthesis method of siloxane gas-sensitive material |
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| CN106486209A (en) * | 2015-08-31 | 2017-03-08 | 中国科学院宁波材料技术与工程研究所 | A kind of patterning 3D graphene conductive film and its environment-friendly preparation method thereof and application |
| CN107652868A (en) * | 2017-10-17 | 2018-02-02 | 厦门大学 | A kind of fluorine-containing graphene oxide modified polyurethane paint and its preparation method and application |
| JP6309181B1 (en) * | 2016-11-21 | 2018-04-11 | アサヒビール株式会社 | Beer-like alcoholic beverage |
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| US6274183B1 (en) * | 2000-06-12 | 2001-08-14 | Travis Richard | Rice composition for coating foods |
| CN101363810A (en) * | 2008-09-11 | 2009-02-11 | 电子科技大学 | Gas-sensitive sensor and method for making same |
| CN102634030A (en) * | 2012-04-25 | 2012-08-15 | 电子科技大学 | Low-toxicity synthesis method of siloxane gas-sensitive material |
| CN106486209A (en) * | 2015-08-31 | 2017-03-08 | 中国科学院宁波材料技术与工程研究所 | A kind of patterning 3D graphene conductive film and its environment-friendly preparation method thereof and application |
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| JP6309181B1 (en) * | 2016-11-21 | 2018-04-11 | アサヒビール株式会社 | Beer-like alcoholic beverage |
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