CN106290367A - A kind of complicated fraction holographic imaging method of chemically based combination disturbance - Google Patents
A kind of complicated fraction holographic imaging method of chemically based combination disturbance Download PDFInfo
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- CN106290367A CN106290367A CN201610700220.4A CN201610700220A CN106290367A CN 106290367 A CN106290367 A CN 106290367A CN 201610700220 A CN201610700220 A CN 201610700220A CN 106290367 A CN106290367 A CN 106290367A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
Abstract
The present invention establishes the i mage analysis methods of a kind of complicated fraction being common in environmental science, bioscience, medical science, Food Science.This technical method, based on high flux disturbance expression strategy, can be built a large-scale perturbation analysis system by limited species, provides the internal chemical information that complicated fraction to be measured is abundant.And made core devices preparation cost cheap by the disturbance egative film preparation that jet printing is core；Intensive detection execution greatly simplifies execution；And the artificial intelligence analysis for complex sample provides a big data acquisition approach.
Description
Technical field
The present invention relates to the detection technique field of analytical chemistry.In particular it relates to environmental science, biological section
The rendering method of complicated fraction Complex chemical information common in the practice such as, medical science, Food Science.
Background technology
Naturalness, many materials of artificial preparation or its ingredient exist with complicated fraction form；Citing
For, such as sewage, river, the soil liquid, blood, urine, saliva, plant tissue liquid, beverage, TCM liquid extract etc..Solid
The sample of form, uses some pre-treating methods to obtain the form being suitable for, and squeezes the juice such as by machinery or the method such as extraction, it is thus achieved that
Complicated fraction can also be analyzed.And this complicated fraction occurs the most as a mixture.The complexity of this mixing
Contain the interaction between various component inside solution, form the system of a relative equilibrium.In these complicated fraction
The relation in portion is the most extremely complex, and quantity is the hugest.The analysis of one Sewage Environment sample is shown by we, wherein
Inorganic, the main species of organic substance and form i.e. exceed hundreds of；By permutation and combination, the mutual relation between them surpasses
Cross 9 powers of 10.Scientific and technical personnel create certain methods, such as composition measuring, simple Calculation of chemical equilibrium etc., measure and characterize
These features.For the detection of solution composition, main employing chemical analysis and Instrumental Analysis.Wherein, divide with mass spectral analysis, chromatograph
The conventional meanses such as analysis method, x-ray spectrometry, electrochemical methods and nuclear magnetic resonance spectroscopy are main investigative technique.But for
Real complicated fraction but hardly results in a large amount of and comprehensive information, especially for each chemistry within complicated fraction
The relation information linearly or nonlinearly interacted between species.
In recent years, utilize electrochemical signals to be detected as main electronic tongues or electric nasus system gradually grows up, in complexity
Certain effect is served in the analysis of liquid, edema caused by disorder of QI.But due to its basis syntheti c route of sensing unit and measuring condition and code
Requirement, it can not develop the sensor array of extensive quantity at low cost.And use owing to it needs realization-cleaning-
The repeated detection re-used, so volatilizable or diffluent detector unit sensitive material can not be used.Separately there are some researchs logical
Cross visual response (the color change that causes such as chemical action, change in fluorescence etc.) and complete sensor array detection, have
With low cost, and the simple advantage of equipment needed thereby (list of references: one, Qian, S.and H.Lin (2015). " Colorimetric
Sensor Array for Detection and Identification of Organophosphorus and
Carbamate Pesticides. " Analytical Chemistry87 (10): 5395-5400. bis-, Schiller, A.,
B.Vilozny, R.A.Wessling and B.Singaram (2008). " Recognition of phospho sugars
and nucleotides with an array of boronic acid appended bipyridinium salts.″
Analytica Chimica Acta 627 (2): 203-211. tri-, Schiller, A., R.A.Wessling and
B.Singaram(2007).″A fluorescent sensor array for saccharides based on boronic
acid appended bipyridinium salts.″Angewandte Chemie International Edition 46
(34): 6457-6459. tetra-, yellow star are grand, South Korea triumphant (2014). the making side of a kind of all solid state visualization taste sensor array
Method. application publication number: CN104062292A. five, Wu Yu, Huo Danqun, Hou Changjun, etc. visualization sensor array is to oolong tea etc.
The quick Study of recognition of level. assay office, 2015,34 (1): 1-5.).Their manufacture thinking is: n to be formed each opposite sex
Cellular array, the most first prepares n kind sensitive material, then they is arranged in array.See list in the array of document case
Unit's quantity is the most several, ten several, twenty or thirties, utilizes this strategy process to be difficult to obtain easily big tens, hundreds of
The array of element number；Let alone thousand of, the array of several ten thousand grades.
For solving object, above mentioned prior art, it is mainly used in and specific components in testing sample is divided
Analysis or sample classification.For the internal chemical relation of complicated fraction sample presents, due to substance classes therein comprehensively
Various, mutual chemical relationship enormous amount.This big quantity is reflected merely with several, tens data measuring point
The system of parameter, it is clear that be unpractical.
In recent years, along with the development of artificial intelligence technology, for realizing the internal relations to complicated sample itself, Yi Jifu
The degree of depth of the interactively between miscellaneous sample and something outside is extensively analyzed and is provided possibility.But a precondition is intended to energy
It is simply the internal chemical information that artificial intelligence provides the sample to be analyzed of big quantity.So scientific and technological circle expect and find a class
The analysis that more can carry original determinand internal chemical relation information presents technology.The present invention i.e. pays close attention to this.
In order to be more fully understood that the method that the present invention proposes, referring initially to the analysis of a simple mechanism aspect.
Look first at this class phenomenon.A certain being in metastable complicated fraction L1, they are internal numerous various
Chemical relationship all can be in the state of relative equilibrium.Now, we are by a kind of common detection method, such as the hands such as fluorescence, colour developing
Section is analyzed operation, an available fluorescence intensity or the testing result of color to it, is labeled as F0.
With reference to the single operation 1 of Fig. 1, for original complicated fraction L1 to be analyzed, when there being a certain amount of composition solid
After other fixed chemical substances R1 are added into, the meeting disturbance original numerous equilibrium relations of complexity fraction system more or less；
And then allow the numerous chemical relationship in this system enter into another kind of poised state.Now use identical colour developing or fluoroscopic examination
Method, we can obtain a testing result likely differing from F0, be labeled as F1.
If similarly we repeat previous step, but the chemical substance being separately added into is different from the R2 ... of R1, Rn；
With reference to the batched operation 2 of Fig. 1, correspondingly we can be obtained by a series of testing result F2 ..., Fn.Disturbance compound
Ri (i=1 ..., the increase of kind n) can dramatically increase the expressed in abundance degree to determinand.When this quantity increases to
Thousand of, several ten thousand even more than million, quantity of information generation great change will be made.
It can be seen that Ri can be a kind of compound or mixture here.One forms the Ri of huge number cleverly
Method is: can mix numerous kinds by the bigger chemical substance of a limited number of kind of nature difference according to different proportional amount
The Ri of class.Such as can be allocated by the different proportional amount of 6 kinds of compounds；Simple computation, when with each compound
1% be changed to split unit time, number of combinations kind is about 6 powers of 100.It addition, these six kinds of basic allotments " raw material ", each
It itself can also be mixture.
In order to provide parallel, the big order of magnitude, the chemical disturbance junior unit of regularization characteristics of combination, we are based on height
Flux (HTE) principle, carries out the HTE combination (seeing the high flux combination 3 of Fig. 1) of system for numerous Rn.Mainly pass through
On flat carrier, regularization independent dispersion big quantification degree point realizes.In the face of when assembling of so big quantity, utilize ink
Water jet printing technology carries out operation can make whole operation become quick and low cost.It practice, ink jet print operation is
A kind of high efficiency method being assigned on two dimensional surface carrier that fraction materials quantitative is positioned, and this complicated fraction can be
Solution can also be the suspension of high degree of dispersion.Particularly there is the color inks jet printer of multiple cartridge, set rationally
In the case of putting print conditions, can be by allotment, print position and the setting of printing ink ejection amount to marking ink, it is achieved on
The combination of disturbance chemical substance R that face is mentioned and arrangement space.Described utilizes ink jet print technology, in planar substrates
Several setting regions, quantitatively add the chemical substance setting composition, be that printer is according to the printing electronic image masterplate set
Control what ink ejection amount and ink jetting position realized.It addition, screen printing technique can also be by coming real to the adjustment of preparation condition
More existing relatively simple preparation manipulations；The advantage of silk screen printing is that price is extremely low, and speed is faster.
Summary of the invention
In conjunction with above discussion, the particularly analysis to high throughput chemical combination disturbance, the present invention proposes new complicated liquid
The internal bulk properties holographic imaging method of shape thing.Holographic imaging said herein, actual result is the inside number to complicated fraction
Measuring numerous chemical relationship to carry out jumbo digitized and present and note down, its record is one to organize greatly chemical effect.Data are held
Amount is according to design, the most tens of, hundreds of, the most thousands of tens thousand of or more.The super large provided out for a complicated fraction
Effect data amount more can accurately portray comprehensive chemical property of this sample.
A kind of complicated fraction holographic imaging method of chemically based combination disturbance, at least includes step in detail below:
(1) ink jet print technology is utilized to prepare chemical combination disturbance holographic imaging egative film, the concrete operations of this step
For:
(1.1) selected chemistry disturbance agent number, definition chemistry disturbance agent number is R-D；And selected R-D is more than or equal to
Two；
(1.2) preparation R-D kind can be used for the chemical ink of ink jet print；In the composition of the arbitrary chemistry ink joined
Containing at least one chemistry disturbance agent, and at least chemical ink joined contains one and dissolves in complicated fraction to be measured
Chemical disturbance agent；During analyzing, this composition dissolved can be dispersed in complexity to be measured with the form of molecule or ion
In fraction, directly participate in the foundation of aqueous chemical balance；Described chemical disturbance agent refers to a kind of compound or mixture, will
It is added into complicated fraction to be measured, and the internal chemical balance of complicated fraction to be measured can be made to produce change；
(1.3) it is designed for guiding printer to carry out positioning and quantitative and sprays the electronic image masterplate of chemistry disturbance agent；
Described electronic image masterplate is made up of color dot, is uniform inside described color dot；The area of color dot I
To the size that the minimum resolution unit of the electronic image masterplate designed is corresponding；In all of color dot, include guiding at least two
Plant the color dot that chemistry disturbance agent ink sprays；Described electronic image masterplate can control the ink-jet operation of R-D independent cartridge；This
Requirement can be realized by arranging of the pattern (RGB, CMYK etc.) of electronic image masterplate, figure layer, passage etc.；Lift with CMYK pattern
For example, when controlling three independent cartridges, tri-passages of C, M, Y in an available figure layer, can be with two figures when controlling four
Any four in six passages of C1, M1, Y1, C2, M2, Y2 in Ceng, the rest may be inferred by analogy；The file of electronic image can be by conversion etc.
Operation obtains multiple appearance form, and the personnel with graphical design knowledge can complete；Described independent cartridge refers to ink
On jet printer, the ink of each color is noted the space deposited；Several independent cartridges can be distributed on a print cartridge, it is possible to
To be distributed on several print cartridge；
(1.4) the chemical ink prepared by R-D kind (1.2nd) step, utilizes ink-jet printer, according to (1.3rd) step
The guiding printing electronic image masterplate of design, rationed setting position on substrate；
The controllable independent ink of printing electronic image masterplate of the species number of the chemical ink selected and the design of (1.3rd) step
Storehouse quantity is identical；
(1.5) selection sprays, impregnates, prints one of three kinds of operational means or combination, positions and be applied with on planar substrates
Imaging agents；Here the imaging agents applied can be equally distributed, it is also possible to has Two dimensional Distribution variation characteristic；Institute
The imaging agents stated refers to can to produce some chemical property of complicated fraction to be measured or component color or fluorescence response
Single or mix reagent；Such as developer, fluorescent probe or its mixture；Here the Two dimensional Distribution variation characteristic that has also refers to several
Different imaging agents is distributed in the zones of different of approximately the same plane substrate；
Described substrate is ink jet printing paper, printing film, art paper, chromatography slide etc.；Although the substrate selected here is
Uniform and without imaging agents, if but use and comprised specified chemical reagent, particularly comprise the base of imaging agents
Sheet, dispenses execution certain step above, the most also meets the technology of the present invention route.
Closing before and after (1.4th) step, (1.5th) step perform and fasten, following sequence can reach similar effect, as
(1.5th) step is placed on after (1.4th) step and performs, or (1.5th) step is placed on before (1.4th) step and performs, or by each for this two step
It is divided into several operation, replaces or merge execution；Hereinafter described here replacing or merge execution is illustrated；For same
One substrate, ink jet print, spray, impregnating operation can be implemented by several times in batches, as several inks print by several times, a kind of
Ink prints by several times, imaging agents sprays by several times, several imaging agents sprays by several times, become imaging agents to use jet printing method
Operate with chemistry disturbance agent simultaneously, use jet printing method printing by several times etc. as reagent.
In terms of physical property, described imaging agents, chemistry disturbance agent can with solid content or absorption the form on substrate
It is present under room temperature and non-close environment；
(1.6) solvent is removed in volatilization, the chemical combination disturbance holographic imaging egative film described in dried acquisition；
Described chemical combination disturbance holographic imaging egative film is constituted by resolving to picture point；Described resolves to the internal one-tenth of picture point
As reagent is equally distributed, and each chemical disturbance agent resolving to comprise in picture point is only by the color dot of (1.3rd) step
Control to spray；And for the consideration of combinatorial chemistry quantity of information, in the case of lower limit set is for comprising Poor information demand,
On one described chemical combination disturbance holographic imaging egative film, the mutually different quantity of picture point that resolves to is more than or equal to 50；
For a chemical combination disturbance holographic imaging egative film, the quantity of the quantity and color dot that resolve to picture point is to have necessarily
Relation；When imaging agents is uniformly distributed, both are equal；(there is certain two dimension when imaging agents non-uniform Distribution
Changes in distribution), then the former is more than or equal to the latter；Here parsing also refers to: the numerous information datas in holographic imaging caned by
The lower limit that level is decomposed；
(2) complicated fraction quantitative and even to be measured is sprayed on the chemical combination disturbance holographic imaging egative film of preparation；
(3) the chemical combination disturbance holographic imaging egative film after (2nd) step effect utilize optical imaging device or fluorescence become
As device carries out shooting imaging.
In the hologram of design and preparation, can be by splicing, the method for embedding, the survey that directly develops the color of concrete component
Surely it is combined in hologram sheet；But the other parts in hologram sheet, if meeting the disturbance combination thinking of the present invention, then this part is also
Protected by this patent；
For concrete example, described imaging agents is: acid-base indicator, such as bromocresol green, C.I. 13020., Herba Cladoniae rangiferinae etc.；Oxygen
Change reduction indicator, such as methylene blue, diphenylamines etc.；Metal indicator, such as C.I. 14645., acid chromium blue k, calmagite etc.；And
Now exploitation and fast-developing novel agent, such as the compound of porphyrin, phthalocyanine and derivatives class thereof, specific dye, Schiff
Alkali etc., the most novel dye reagent for Measurement for Biotechnique.Described imaging agents can also be can be with complicated fraction
In material covalently or non-covalently combine the fluorometric reagent forming fluorescence, common such as 8-hydroxyquinoline, flavonol, Punica granatum L. alizarin
R, morin etc.；Or itself there is the fluorescent dye of fluorescence, such as fluorescein sodium, tetrabromofluorescein etc., and a large amount of novel use
Fluorescent probe etc. in Measurement for Biotechnique.Described imaging agents mixing, refers to the imaging agents mixing of several individual use
Together, use as a kind of imaging agents.
Chemistry disturbance agent is worked essentially by the chemical equilibrium participated within complicated fraction to be measured；So
From simple compound to complicated mixture, this effect much can be realized.But want selection differences big, dry in practice
Disturb the more efficiently species of effect.Because the distinct fluctuations of the image finally given is main still by chemistry perturbation action
Rich realize.It addition, when selecting chemistry disturbance agent, it is also noted that do not make chemistry rich to imaging agents of disturbance agent
Rich change has the negative effects such as too many coverage；The dark compound of such as colour stable is not the disturbance of good color development system
Agent.Can also there be some directions when chemistry disturbance agent selects, such as, select several simple classes of compounds, such as acid-alkali accommodation
Agent, chelating agent, ion competition agent, screening agent etc..
Chemistry disturbance agent can also be minute solid particles, and they can disperse in a liquid, their perturbation action
Methods is: disturbed composition and the chemical equilibrium of complicated fraction to be measured by effects such as absorption, catalysis.As gold colloidal,
The ultra-fine grain dispersion liquids etc. such as Ludox, ferrum collosol, nano zircite, nano yttrium oxide, nano-zinc sulfide.
The complicated fraction holographic imaging method of described a kind of chemically based combination disturbance, it is characterised in that: described
Utilize the step for that ink jet print technology prepares chemical combination disturbance holographic imaging egative film before, further comprise the steps of: and carry out
Imaging agents and the screening of chemistry disturbance agent for complicated fraction to be measured；Detailed process is:
By single or mixing imaging agents be quantitatively added into complicated fraction to be measured, determine its present be different from former multiple
The color of miscellaneous fraction or fluorescent characteristic；Chemistry disturbance agent is quantitatively added into the above-mentioned to be measured complicated liquid that with the addition of imaging agents
Shape thing, determines that it may result in being further change in of color or fluorescent characteristic.
Considering from increasing disturbance specific diversity, the complicated fraction holography of described a kind of chemically based combination disturbance becomes
Image space method, it is characterised in that: in (1.1st) described step, selected R-D is more than or equal to three.
Considering from increasing disturbance specific diversity, in the case of having the change of relatively horn of plenty, described one is chemically based
The complicated fraction holographic imaging method of combination disturbance, it is characterised in that: in (1.1st) described step, selected R-D is more than
Yu Si.
Considering from increasing disturbance specific diversity, in the case of having the change of more horn of plenty, described one is chemically based
The complicated fraction holographic imaging method of combination disturbance, it is characterised in that: in (1.1st) described step, selected R-D is more than
In five.
For verification and the purpose of reduction error, electronic image masterplate arranges repetition color dot, demarcation color dot etc. is set.
In the case of reaching equally to guide printing purpose, electronic image masterplate is one, or two and above subgraph
The a set of electronic image formed by modes such as plain splice, figure layer combinations.Can also be come by the mode of operation that color separation prints
Design electronic image masterplate.
For the consideration of combinatorial chemistry quantity of information, in the case of lower limit set is for comprising relatively Poor information demand, described
The complicated fraction holographic imaging method of a kind of chemically based combination disturbance, it is characterised in that: a described chemical group
Closing on disturbance holographic imaging egative film, the mutually different quantity of picture point that resolves to is more than or equal to 100.
In the case of lower limit set is for comprising medium quantity of information demand, answering of described a kind of chemically based combination disturbance
Miscellaneous fraction holographic imaging method, it is characterised in that: on a described chemical combination disturbance holographic imaging egative film, the most not phase
The same quantity resolving to picture point is more than or equal to 200.
Under same core thinking, the method preparing chemical combination disturbance holographic imaging egative film according to this, it is also possible to same
The imaging area that several chemical property is widely different is prepared on individual bare substrate；So can expand chemical combination disturbance holography
Quantity of information as egative film.Its external form is equivalent to several different chemical combination disturbance holographic imaging egative film and splices one
In individual plane, as the egative film that for subsequent detection is unified.This mode will be of density analysis accurate, big future
Important form.
The complicated fraction holographic imaging method of described a kind of chemically based combination disturbance, it is characterised in that: described
(3rd) step after, farther include: to shooting obtain image be further processed, obtain relatively sharp clear image
Form, such as gray-scale map, color separation figure, binary map, Fourier transform figure etc..
The complicated fraction holographic imaging method of described a kind of chemically based combination disturbance, it is characterised in that: described
It is to use jet spraying or ullrasonic spraying that complicated fraction quantitative and even to be measured sprays, and uses fixing spray amount and spray strip
Part realizes；Described spray condition refers to the spacing of fog-spray nozzle type, fog outlet and chemical combination disturbance holographic imaging egative film
With angle, hurricane globe size and position.
The complicated fraction holographic imaging method of described a kind of chemically based combination disturbance, it is characterised in that: described
Complicated fraction to be measured is one of following sample: after urine after stain disease, the soil liquid, original or processing, original or processing
Blood, beverage.
The present invention compared with prior art, has the advantage that and beneficial effect:
(1) a large-scale disturbance can be built by several compounds (the most several chemistry disturbance agent, imaging agents) to divide
Analysis system, provides the abundant internal chemical information of complicated fraction to be measured.These chemical informations may be used for complicated fraction
Qualitative or explore the exercising result of itself and other actor.
(2) due to the basic point of departure of this technology be use chemical constituent go the chemical equilibrium relation in disturbance determinand,
So the result of its detection more embodies the dynamic chemical relation of the inside complexity of determinand.
(3) this technical method at least can perform according to complexity the most suddenly: chemical combination disturbance holographic imaging
The preparation of egative film can be carried out standardization by specialty manufacturer and manufacture in a large number；Later stage, simple liquid application to be measured added and photographic actions,
Can be performed by general layman.So simple to operate, the testing cost manufactured in batch is the cheapest.
(4) high flux disturbance-expression strategy that this technical method is set up, can pass through standardization, divide for artificial intelligence
Analysis complicated chemical sample provides a big data acquisition approach.
Accompanying drawing explanation
Fig. 1 is the Analysis on Mechanism figure of the present invention.1-single operation, 2-batched operation, 3-high pass quantization operation.
Fig. 2 is the electronic image masterplate of design in embodiment 1.
Fig. 3 is the schematic diagram of complicated fraction quantitative ultrasound spraying weighing device to be measured in embodiment 1.1-ullrasonic spraying
Device, 2-plastics pallet, 3-analytical balance.
Fig. 4 is the detection imaging results figure of the complicated fraction of embodiment 1.
Fig. 5 is the electronic image masterplate of middle design in embodiment 3.
Fig. 6 is the testing result figure of embodiment 3.
Fig. 7 is the electronic image masterplate of embodiment 4 design.
Fig. 8 is the electronic image masterplate of embodiment 5 design.
Fig. 9 is the testing result figure of embodiment 8.
Figure 10 is the metered dose device schematic diagram in embodiment 9.
Figure 11 is the experimental result picture of embodiment 10 repeatability checking.
Detailed description of the invention
Being described principle and the feature of the present invention below in conjunction with specific embodiments and the drawings, example is served only for solving
Release the present invention, be not intended to limit the scope of the present invention.
The preparation of embodiment 1 complicated fraction sample to be measured
Have chosen from several samples such as plant, animal to beverage, medicine, environmental samples.
Plant: take watermelon flesh (western agriculture eight), tomato pulp (red No. 1 of capital), Fructus Cucumidis sativi sarcocarp (rich No. 6 of garden), Radix Dauci Sativae fruit
Meat (red No. one of spring) apple pulp (Luochuan, Shaanxi red fuji apple), oriental plane tree leaves, Folium Pini etc., squeeze the juice respectively, filters,
Respectively take 30mL supernatant, bottle stand-by.
Animal: buy live chickens, live crucian one, extract some blood, be stored in test tube stand-by.
Urine: take from the original urine in Hospital of Shaanxi Normal University laboratory.
Tea solution: weigh 10g black tea, oolong tea, green tea respectively, is separately added into 90g distilled water, 60 DEG C of water-bath 20min.
Obtain black solution, oolong tea solution, green tea solution naturally cool to room temperature.Filter, respectively take supernatant 30mL, bottle stand-by.
Red wine solution: take claret (Shandong Province of China Yantai Zhangyu claret) 30mL, bottle stand-by.
Middle drug solns: Radix Isatidis granules and LIUWEI DIHUANG WAN are ground to powder, weigh 2g, adds 50ml water vibration 6h,
Stand 2h, take supernatant bottling stand-by.
Bed mud Interstitial Water: take bed mud in river course, river, southern suburbs, Xi'an City, Shanxi Province, centrifugal, take supernatant 50mL, stand-by.
Percolate: take household garbage-compressing station, school district, Shaanxi Normal University Chang'an percolate, in shady and cool lucifuge
Place places one week, filters, takes supernatant, stand-by.
Sanitary sewage: take Shaanxi Normal University's students' dormitory sanitary sewage.Filter, take supernatant, stand-by.
Humic acid solution: select industry humic acid powder, the humic acid solution of preparation 1g/L, be placed in refrigerator, stand-by.
The preparation of embodiment 2 chemical combination disturbance holographic imaging egative film and application examples thereof
The to be measured complicated fraction obtained for embodiment 1, performs the present invention and proposes answering of chemically based combination disturbance
The internal character formation method of miscellaneous fraction, comprises the following steps that.(number of steps in specific embodiment likely differs from description
In " summary of the invention " part numbering)
(1) imaging agents and the screening of chemistry disturbance agent are carried out
In order to coordinate overall holographic imaging egative film scheme, convenient observation contrasts, and takes 0.5ml complicated fraction to be measured, dropping
On 20mm diameter filter paper, normal temperature drying, obtain complicated fraction-filter paper (being designated as sheet 1) to be measured.
Select 1,2,3-indantrione monohydrate as imaging agents to be determined, prepared 2% ninhydrin solution.Accurate weighing indenes three during preparation
Ketone 0.2g, adds anhydrous alcohol solution and is settled to 10mL (needing now with the current).Observe contrast for convenience, take this liquid of 0.5ml, drip
Being added on 20mm diameter filter paper, normal temperature drying removes solvent, obtains imaging agents-filter paper.Take 0.5ml complexity to be measured aqueous
Thing, adds the imaging agents of above-mentioned preparation-filter paper, volatile dry, obtains sheet 2.
Select DTPA, Glycine sodium, potassium dihydrogen phosphate, Na2CO3、CuCl2And AlCl3As chemistry disturbance agent.For side
Just observing contrast, will each be formulated as aqueous solution, concentration is respectively DTPA (0.01mol/L), Glycine sodium (0.1mol/L), phosphorus
Acid dihydride potassium (0.1mol/L), Na2CO3(0.25mol/L), CuCl2(0.1mol/L) and AlCl3(0.1mol/L).Respectively take
0.5ml liquid, drips respectively on sheet 2, volatilization, obtains sheet 3-1 to sheet 3-6, totally six.
Obtained sheet 1, sheet 2, sheet 3-1 to sheet 3-6 are heated 5 minutes under 110 degree, observes and determine that sheet 1,2 colors of sheet are deep
Shallow change difference；Observation determines that sheet 3-1 differs to shade between sheet 3-6 and sheet 2.
(2) utilize ink jet print technology to prepare chemical combination disturbance holographic imaging egative film, use four color inkjet printings
The flat-panel printer (association 3110) of machine transformation carries out experimental implementation.
The detailed process of this step is:
(2.1) devise as shown in Figure 2 for guiding printer to carry out the electronic image masterplate of positioning and quantitative ink-jet.Color
The CMYK printing model of color ink-jet printer is to be sprayed by the ink controlling in cyan C, fuchsin M, yellow Y, each cartridge of black K
Amount realizes what style printed, and the print throughput in plane can control with the electronic image masterplate designed.This enforcement
Cyan C, fuchsin M and tri-kinds of colors of yellow Y are only used.The depth of each color fluctuates along different directions, and (excursion is 0% in gradual change
～100%).It is designed as twice chromatography, i.e. when printing, on the identical location of same substrate, according to two kinds of CMY patterns
Each printing one time.Sheet is designed with repetition.Pattern stamp with the size can arrange regulation.The design accuracy of the circular portion of Fig. 2 is
1000x1000 pixel.It is made up of two figure layers.
(2.2) choosing ink jet printed photographic paper is substrate, by the 5ml 2% uniform spraying of ninhydrin solution spray gun in A4 size
On printing paper, air-dry 10 minutes.
(2.3) select six kinds of disturbance compound liquid of preparation in (1st) step, be added dropwise to surfactant ethylene glycol list respectively
Butyl ether, reconciliation statement surface tension is close to former print cartridge ink.
(2.4) the 6 kinds of chemical inks utilizing ink jet print technology (2.3rd) step to be prepared, are divided into two groups, fill respectively
Enter in the cartridge cleaned up corresponding to C, M, Y.Use two-shot chromatography, print electronic image masterplate according to (2.1st) step and guide,
Rationed setting position on substrate.
(2.5) solvent is removed in volatilization, the chemical combination disturbance holographic imaging egative film described in dried acquisition.Load black plastic
Bag, inserts deoxygenation, desiccant parcel simultaneously, seals cryopreservation.
(3) complicated fraction quantitative and even to be measured is sprayed on chemical combination disturbance holographic imaging egative film；In operation
Use the ullrasonic spraying weighing device shown in Fig. 3.During operation, the chemical combination disturbance holographic imaging egative film made is placed into
On plastics pallet 2.Secondly, the various to be measured complicated fraction prepared is loaded in ultrasonic nebulizer 1, work, make multiple
Miscellaneous fraction is atomized free settling to chemical combination disturbance holographic imaging egative film.Egative film sprays 2.0mg/cm2To be measured
Complicated fraction.
(4) optics digital camera is utilized to shoot on the chemical combination disturbance holographic imaging egative film after (3rd) step effect.Will
To picture be further processed as gray-scale map (as shown in Figure 4), the corresponding following source of sample number into spectrum 1～12: Fructus Cucumidis sativi, Citrullus vulgaris, west
Red Fructus Kaki, Radix Dauci Sativae, wine, urine, waste water, mushroom, black tea, oolong tea, green tea and Fructus Mali pumilae.
Embodiment 3 prints the another example of electronic image masterplate ()
The electronic image masterplate of design in (2.1st) step is changed into another kind such as Fig. 5 with reference to embodiment 2.Treat test sample
Product are tested, and can realize the purpose of the present invention equally.Fig. 5 is to resolve the electronic image masterplate (Fig. 2) in embodiment 2
Degree reduces；Obtain after adding telltale mark, calibration marks.The image obtaining shooting, is converted into gray-scale map；And in using
Between gray value as waypoint, gray-scale map is converted into binary map.Here intermediate grey values is equal to all coloration regions
Average gray on area.It is taken as zero (the most pure white) less than this value, is taken as gray scale 100% (black) more than this value.Institute
The result figure obtained is listed in Fig. 6, wherein the corresponding following source of sample number into spectrum 1～20: waste water, percolate, Radix Raphani, Radix Dauci Sativae, Buddhist
Hands melon, Fructus Cucumidis sativi, Fructus Lycopersici esculenti, Herba Spinaciae, Caulis et Folium Lactucae sativae, big green vegetable, Eugenia javanica Lam, garland chrysanthemum, Fructus Mali pumilae, Herba Herminii, pears, carambola, Fructus Vitis viniferae, Citrullus vulgaris, six
Taste Dihuang Wan, Fructus Lycii.
Embodiment 4 prints the another example of electronic image masterplate (two)
The electronic image masterplate of design in (2.1st) step is changed into two kinds of forms such as Fig. 7, to be measured with reference to embodiment 2
Sample is tested, and can realize the purpose of the present invention equally.In Fig. 71 is C, M two passage composition, each passage color from 0～
100% gradual change.In Fig. 72 are C, M, Y-site road composition, and the gradual manner of Y passage color is different from two other passage.
Embodiment 5 prints the another example of electronic image masterplate (three)
The electronic image masterplate of design in (2.1st) step is changed into form such as Fig. 8, to testing sample with reference to embodiment 2
Test, the purpose of the present invention can be realized equally.In Fig. 8, total figure includes four identical duplicate blocks, includes in each district
49 color dots.Cutting off each district can be as an independent utility；Four districts are used together, it is possible to have duplication check as one
Application examples.
The embodiment 6 chemistry another example of disturbance agent
With reference to embodiment 2, the screening of chemistry disturbance agent in (1st) step is launched for following material.Including FeCl3、
NiSO4、ZnSO4, NaF, tartaric acid, sodium benzoate, the single compound such as hexamethylenetetramine；The mixture of several simple salts, 1:
The mixture of 1: NiSO4+CuCl2、CuCl2+ZnSO4, DTPA+ tartaric acid etc.；The mixture of 1: 1: 1: NiSO4+CuCl2+
ZnSO4, DTPA+ tartaric acid+NaF etc..
The another example of embodiment 7 imaging agents
With reference to embodiment 2 by the screening operation of imaging agents in (1st) step, reelect following colour reagent or combination: bromine
Cresol is green, C.I. 13020., bromocresol green+C.I. 13020. (1: 1), C.I. 14645., zinc protoporphyrin, alizarin yellow, cupferron etc..
The application of embodiment 8 fluorescence imaging reagent
Following sample is related to the analysis process of fluorescence imaging, including bed mud Interstitial Water 1, percolate 2, life
Sewage 3, Carassius auratus blood 4, Radix Isatidis granules 5, Folium Camelliae sinensis 6, Folium firmianae 7 and flesh of Pulp Citrulli 8 etc..With reference to embodiment 2, imaging agents is elected as
Fluorescein sodium；To observe and shoot under natural light to color in former example, change in 365nm ultraviolet camera bellows the fluorescence produced
Carry out observing and shoot (time of exposure 1s).The picture obtained captured by Zhong is further processed as gray-scale map (as shown in Figure 9).
The quantitative example of embodiment 9 Simple atomizing
With reference to embodiment 2 into, spraying weighing device and operation in (3rd) step are changed a kind of simple solid mechanical spraying behaviour
Make.Concrete employing pressing type micro plastic fog-spray nozzle 1, feed tube 5 mouthfuls is inserted into the bottom of a micro test tube 4, and will spraying
Head is fixedly installed on cylindrical chamber 2 crown center (as shown in Figure 10).Chemical combination disturbance holographic imaging egative film 3 is placed on container
Fixed position, bottom.During operation, take 0.5ml complicated fraction sample to be measured and put into micro test tube, the most all ejections.The method
Simple special equipment with low cost can be prepared by integrated transformation.
Embodiment 10 repeatability checking
With reference to embodiment 3, we are to several different samples: percolate 1, Fructus Cucumidis sativi 2, Fructus Mali pumilae 3, LIUWEI DIHUANG WAN 4, respectively
Two replicate analysis groups are done.To verify the repeatability of this method.Result as shown in figure 11, through upper and lower two figure one_to_one corresponding
Comparison is it can be seen that two parallel analysis results of sample are essentially identical.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. a complicated fraction holographic imaging method for chemically based combination disturbance, at least includes step in detail below:
(1) utilizing ink jet print technology to prepare chemical combination disturbance holographic imaging egative film, the concrete operations of this step are:
(1.1) selected chemistry disturbance agent number, definition chemistry disturbance agent number is R-D；And selected R-D is more than or equal to two；
(1.2) preparation R-D kind can be used for the chemical ink of ink jet print；The composition of the arbitrary chemistry ink joined contains
At least one chemistry disturbance agent, and at least chemical ink joined contains and a kind of dissolves in complicated fraction to be measured
Chemistry disturbance agent；Described chemical disturbance agent refers to a kind of compound or mixture, is added into complicated fraction to be measured, can
The internal chemical balance making complicated fraction to be measured produces change；
(1.3) it is designed for guiding printer to carry out positioning and quantitative and sprays the electronic image masterplate of chemistry disturbance agent；
Described electronic image masterplate is made up of color dot, is uniform inside described color dot；The area of color dot I is to setting
The size that the minimum resolution unit of electronic image masterplate of meter is corresponding；In all of color dot, include at least two kinds of changes of guiding
Learn the color dot that disturbance agent ink sprays；Described electronic image masterplate can control the ink-jet operation of R-D independent cartridge；
(1.4) the chemical ink prepared by R-D kind (1.2nd) step, utilizes ink-jet printer, according to (1.3rd) step design
Print electronic image masterplate guiding, rationed setting position on substrate；
(1.5) selection sprays, impregnates, prints one of three kinds of operational means or combination, and on planar substrates, location is applied with imaging
Reagent；Here the imaging agents applied can be equally distributed, it is also possible to has Two dimensional Distribution variation characteristic；Described
Imaging agents refers to can to produce some chemical property of complicated fraction to be measured or component the single of color or fluorescence response
Or mix reagent；
(1.5th) step be placed on after (1.4th) step perform, or (1.5th) step be placed on before (1.4th) step perform, or by this two
Step is respectively divided into several operation, replaces or merges execution；
In terms of physical property, described imaging agents, chemistry disturbance agent can be presented in solid content or absorption be on substrate
Under room temperature and non-close environment；
(1.6) solvent is removed in volatilization, the chemical combination disturbance holographic imaging egative film described in dried acquisition；
Described chemical combination disturbance holographic imaging egative film is constituted by resolving to picture point；Described resolves to the examination of picture point internal imaging
Agent is equally distributed, and each chemical disturbance agent resolving to comprise in picture point is only controlled by the color dot of (1.3rd) step
System sprays；On a described chemical combination disturbance holographic imaging egative film, the mutually different quantity resolving to picture point is more than
Equal to 50；
(2) complicated fraction quantitative and even to be measured is sprayed on the chemical combination disturbance holographic imaging egative film of preparation；
(3) the chemical combination disturbance holographic imaging egative film after previous step effect is utilized optical imaging device or fluoroscopic imaging device
Carry out shooting imaging.
The complicated fraction holographic imaging method of a kind of chemically based combination disturbance the most according to claim 1, its feature
Be: described utilize the step for that ink jet print technology prepares chemical combination disturbance holographic imaging egative film before, also wrap
Include: carry out the imaging agents for complicated fraction to be measured and the screening of chemistry disturbance agent；Detailed process is:
Single or mixing imaging agents is quantitatively added into complicated fraction to be measured, determines that it presents and be different from former complicated liquid
The color of shape thing or fluorescent characteristic；Chemistry disturbance agent is quantitatively added into the above-mentioned complexity to be measured that with the addition of imaging agents aqueous
Thing, determines that it may result in being further change in of color or fluorescent characteristic.
The complicated fraction holographic imaging method of a kind of chemically based combination disturbance the most according to claim 1, its feature
Being: in (1.1st) described step, selected R-D is more than or equal to three.
The complicated fraction holographic imaging method of a kind of chemically based combination disturbance the most according to claim 1, its feature
Being: in (1.1st) described step, selected R-D is more than or equal to four.
The complicated fraction holographic imaging method of a kind of chemically based combination disturbance the most according to claim 1, its feature
Being: in (1.1st) described step, selected R-D is more than or equal to five.
6. the complicated fraction according to a kind of chemically based combination disturbance described in claim 1,2,3,4,5 any one is holographic
Formation method, it is characterised in that: on a described chemical combination disturbance holographic imaging egative film, mutually different resolve to picture
The quantity of point is more than or equal to 100.
7. the complicated fraction according to a kind of chemically based combination disturbance described in claim 1,2,3,4,5 any one is holographic
Formation method, it is characterised in that: on a described chemical combination disturbance holographic imaging egative film, mutually different resolve to picture
The quantity of point is more than or equal to 200.
8. the complicated fraction according to a kind of chemically based combination disturbance described in claim 1,2,3,4,5 any one is holographic
Formation method, it is characterised in that: after (3rd) described step, farther include: the image obtaining shooting is located further
Reason, obtains relatively sharp clear pictorial form, such as gray-scale map, color separation figure, binary map, Fourier transform figure etc..
9. the complicated fraction according to a kind of chemically based combination disturbance described in claim 1,2,3,4,5 any one is holographic
Formation method, it is characterised in that: it is to use jet spraying or ultrasonic spray that described complicated fraction quantitative and even to be measured sprays
Mist, and use fixing spray amount and spray condition to realize；Described spray condition refers to fog-spray nozzle type, fog outlet and chemistry
The spacing of combination disturbance holographic imaging egative film and angle, hurricane globe size and position.
10. the complicated fraction according to a kind of chemically based combination disturbance described in claim 1,2,3,4,5 any one is complete
Breath formation method, it is characterised in that: described complicated fraction to be measured is one of following sample: stain disease, the soil liquid, original
Or processing after urine, original or processing after blood, beverage.
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