CN109557066A - Copper nano-cluster Sweat latent fingerprint shows preparation method of reagent thereof and Sweat latent fingerprint process for show - Google Patents
Copper nano-cluster Sweat latent fingerprint shows preparation method of reagent thereof and Sweat latent fingerprint process for show Download PDFInfo
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- 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
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Abstract
The present invention provides copper nano-cluster Sweat latent fingerprint visualization reagent preparation method and Sweat latent fingerprint process for show, using the polyethyleneimine of branching as template, using ascorbic acid as reducing agent, using copper sulphate as raw material, heating condition when control reaction, the smaller copper nano-cluster with variable fluorescence of reduction partial size.Show Sweat latent fingerprint using the aobvious method of solution drop and show observing system by the latent independently built and finger mark is observed, taken pictures and is fixed.The advantages that nano particle of preparation has size small, and stability is good, and fluorescence is strong.The aobvious finger mark of drop equal streakline under natural light and multiband light source excitation is clear, and minutia is obvious.The aobvious finger mark of drop capable of emitting difference fluorescence under alternative light source, can exclude the interference of background color.Opposite conventional method the method solves conventional reagents and shows that fingerprint sensitivity is low, binding ability is weak, it is difficult to which the shortcomings that removing background colour interference, finger mark process for show high sensitivity, fluorescence are strong, nontoxic and economical.
Description
Technical field
The present invention relates to public security criminal technique finger marks to identify field, and in particular to copper nano-cluster Sweat latent fingerprint shows reagent system
Preparation Method and Sweat latent fingerprint process for show.
Background technique
Fingerprint is cooperatively formed by nature-nurture, has each one different, unchangeable characteristic.Due to heredity
The mastoid process streakline of the influence of many factors such as substance, skin texture, pathology and wound, fingerprint has specificity, diversity
And stability, these characteristics is identify to the person and identification is provided by analysis to fingerprint ridge, identification, identification
Scientific basis.Simultaneously as having the characteristic of touching object trace, the finger mark being retained on object can really reflect the finger for leaving people
Line feature is disclosing crime fact, locking suspect, is providing investigation direction, trial for investigator in criminal case
It plays an important role in terms of scientific basis is provided.
In finger mark appearing technique, traditional method has luminescence method, solwution method, powder method, smoked aobvious method etc., by selecting phase
Using sweat, grease, blood, the dirt etc. in the substance and finger mark that show finger mark association reaction or utilization occur for the method answered
Light irradiation, so that potential finger mark be made to display in coloured finger mark.With the continuous development of science and technology, in recent years, nanometer
Material is of interest by the scientific research personnel in each field with its special light, magnetic, electricity, sound and mechanical characteristic.It is answered in showing for latent
In, it was discovered by researchers that nano material is easier to and inorganic, the organic species knot in latent compared with common material
It closes.In addition, some fluorescent nano materials of tool can produce fluorescence by the irradiation excitation of the light sources such as ultraviolet light, pass through detection
The fluorescence imaging that the nano material being incorporated on finger mark is issued is to clearly reflect fingerprint characteristic.Meanwhile nano material is also
It can be combined with other materials, and form nanocomposite, not only can effectively shown crime point and be retained in various visitors
Difficulty on body, complicated finger mark, additionally it is possible to overcome and existing show that reagent is poisonous and harmful, there are the difficulties such as security risk for process for show
Topic.
It is applied to cadmium sulfide, the cadmium selenide, three oxidations that the fluorescent nano material that latent shows has molecule to coat at present
Two aluminium and Zinc oxide nanoparticle etc..But due to the poor fingerprint line for causing to show of the selective binding of finger mark residue
Line is unintelligible, contrast is unobvious, it is difficult to get a desired effect；And there are heavy metal ion for this kind of reagent, are synthesizing and are making
During, it is most likely that generate harm to the health of operator.Therefore, applications to nanostructures progresses into people
Sight.
In nano material, metal nanometre cluster is to be in single metal by several to dozens of former molecular condensates
The size of transition state between atom and biggish metal nanoparticle, metal nanometre cluster is less than 2nm, and size is between single
Between atom and nanocrystal.Compared with biggish nano particle, metal nanometre cluster has more unique physicochemical properties,
With good fluorescence, water solubility.Meanwhile quantum size effect, photostability be strong, good biocompatibility because it also has
The features such as, bio-imaging, biomedicine, biological tracing, environment measuring, in terms of be widely used, but in punishment
The research of thing science and technology field and application are fresh it has been reported that being still at the initial stage.
In nano material, metal nanometre cluster is in addition to small-size effect, skin effect, quantum size effect and macroscopic view
Other than the shared property of the nano materials such as quantum tunneling effect, also there is unique optical property and good bio-compatible
Property, it is easy to carry out surface-functionalized and modification, non-covalent bond absorption such as occurs with amino, Ji Yiyu sulfydryl generates covalent bond
Deng.In the prior art, the gold nanoclusters Sweat latent fingerprint as described in number of patent application 201610384933.4 shows reagent preparation side
Method and Sweat latent fingerprint process for show, using nanogold particle as seed, one layer of bovine serum albumin(BSA) BSA is wrapped up on surface, in water phase
In using BSA be template in nanogold particle surface reduction gold nanoclusters, gold nanoclusters powder is obtained after separation, drying and grinding
Show reagent；It is heavy metal that it, which uses gold particle, and costly, and pole has price during synthesis and use
Harm may be generated to the health of operator.
In addition, there is also following deficiencies for existing finger mark appearing technique: 1, being difficult to exclude the interference of background colour: in practical case
In the shootings of some finger marks will receive the interference of left object background patterns, such as cigarette case, bank card, beverage bottle, quilt at present
The material shown applied to latent generally has bronze, silver powder, magnetic powder, ninhydrin etc., but the color shown is single, is easy quilt
Complicated background colour influences；2, the latent of the coarse object of finger mark appearing technique shows difficulty: for coarse object, working as visitor
The depth of body surface face depressed area relatively larger than finger dermal papilla streakline height, when people contact the phase separation of object position when,
Even if pressure is big again, it will not be left at object surface indentation position and be worth too high fingerprint form, there is no the conditions shown；
In addition, the scraggly feature on coarse object surface determines the incoherence of its sweat fingerprint streakline, cause the showing of impression of the hand,
It extracts, the difficulty of analysis.For the diving hand print with perspiration on coarse object plane, glazed thread irradiation in surface can only be diffusing reflection, impression of the hand substance
Object contrast is faint with leaving, legacy conditional itself is not enough to provide direct extraction, and laser method is examined for impression of the hand primary fluorescence
Excitation have certain limitation, it is necessary to it could be played to greatest extent in conjunction with other physics and chemical method and show effect.
In summary, the heavy metal that the prior art has the disadvantage that 1, uses, price costly, and are being closed
Harm very likely is generated to the health of operator at during with use；2, it is difficult to exclude background in use process
The interference of color；3, the latent of the coarse object of finger mark appearing technique shows difficulty.
Summary of the invention
The object of the present invention is to provide copper nano-cluster Sweat latent fingerprints to show preparation method of reagent thereof, it not only high sensitivity, at
This cheap, safety and environmental protection, good developing effect, fluorescence is variable, stablizes, and can also exclude the interference of background colour, and in coarse table
Show effect with excellent on the object on face and uneven surface.
Another object in the present invention is to provide a kind of Sweat latent fingerprint process for show, easy to operate, safety and environmental protection.
It is realized the purpose of the present invention is technical solution in this way, with the polyethyleneimine (BPEI) of branching for mould
Plate, with ascorbic acid (AA) for reducing agent, using copper sulphate as raw material, heating condition preparation when control is reacted shows reagent.
Copper nano-cluster Sweat latent fingerprint shows preparation method of reagent thereof, comprising the following steps:
BPEI is dissolved in ultrapure water by S101, is configured to the solution of 0.01g/ml, 5~10min of ultrasound；AA is dissolved in ultrapure water, is matched
The solution of 0.1M/ml is made；By CuSO4It is dissolved in ultrapure water, is configured to the solution of 0.1g/ml；
S102 takes BPEI solution 0.1ml, is added dropwise in 10ml ultrapure water, CuSO is slowly added dropwise under stiring4Solution 1ml
After 3~5min, 1mlAA(0.1M is added dropwise in (0.625mM))；
S103 reacts 6~8 hours respectively at 30 DEG C, 60 DEG C, 90 DEG C, 120 DEG C, 150 DEG C, and the copper obtained at each temperature is received
Rice cluster solution；
Solution is mixed S104,10~15min of ultrasound.
It is in the present invention another object is that technical solution in this way was realized, a method of showing Sweat latent fingerprint,
Copper nano-cluster Sweat latent fingerprint prepared by preparation method of reagent thereof is shown using above-mentioned finger mark and shows reagent to Sweat latent fingerprint progress
Show, comprising the following steps:
S201, reagent preparation show preparation method of reagent thereof using finger mark described in claim or 2 and prepare the latent finger of copper nano-cluster sweat
Print shows reagent；
S202 restrains finger mark, and volunteer restrains finger mark on object surface, makes finger mark sample；
S203 drips aobvious finger mark, and by the reagent that shows in step S201, to carry out drop to the Sweat latent fingerprint on different objects respectively aobvious；
S204 dries drop aobvious latent in baking oven machine under the conditions of vacuum, 30~50 DEG C；
S205, independently builds that show observing system latent to fluorescence sweat using alternative light source, colour light filter mirror, digital single-lens reflex camera
Finger mark is observed and fixation of taking pictures；
S206 drips the Sweat latent fingerprint showed by the reagent that shows prepared by the method with alternative light source irradiation, refers in darkroom
The fluorescence that print generates penetrates colour light filter mirror, is recorded by digital single-lens reflex camera, finger mark mastoid process streakline and its minutia are fixed
Get off.
The present invention provides copper nano-cluster Sweat latent fingerprints to show preparation method of reagent thereof, is reduction with AA using BPEI as template
Agent changes reaction condition, restores the copper nano-cluster that partial size is smaller, can be changed with fluorescence, and this novel by what is prepared
Nano material shows for latent.The diameter of copper nano-cluster is usually less than 2 nm, close to Fermi's wavelength of electronics, therefore copper
Stronger photoluminescent property can be presented in nano-cluster.It is nano combined compared to luminescence generated by lights such as other small molecule fluorescent dyestuffs and quantum dots
Material, such as gold, silver, platinum material, copper nano-cluster have many advantages, such as safe and non-toxic, surface be easy to modify, fluorescent stability it is strong, and
Price is relatively low.Controllability and good biocompatibility based on nano-cluster particle size are using polyethyleneimine
Template restores to form copper nano-cluster, achieves the regulation of size to obtain fluorescence changeability, is prepared with this novel
Fluorescence show reagent to Sweat latent fingerprint carry out fluorescent marker, and using alternative light source detection present fluorescence finger mark.It holds
By finger mark object (such as various metals, plastics, leather and fur products, paint and true qualities woodenware surface) in ultraviolet light, blue green light etc.
It does not shine under irradiation, is in deep dark tone.Copper nano-cluster issues fluorescence under multiband irradiation, to improve background and finger mark
Contrast, when background has week fluorescent, using the fluorescence changeability of copper nano-cluster, the iridescent for selecting effect best, thus
Exclude the interference of background colour.
In Sweat latent fingerprint process for show, under acid condition, organic species and the meeting of substance containing amino in latent
In positive electricity, and metal nanoparticle surface is in negative electricity due to absorption hydroxyl, and the nano particle of negative electrical charge can be by quiet
Electro Sorb effect is combined with latent streakline.According to coordination principle, copper atom can with the molecule containing lone pair electrons, ion or
Group forms stable complex, thus copper nano-cluster etc. can with containing lone pair electrons group such as sulfydryl (- SH), amino (-
NH2), the groups such as carboxyl (- COOH) combined by coordinate bond, potential line is made by electrostatic adsorption, coordinate bond combination
Line is shown by the fluorescence that CuNCs is issued.Copper nano-cluster can be in conjunction with the large biological molecule in latent, even if thick
It rough object surface can be with sulfydryl (- SH), the amino (- NH in finger mark with the presence of fingerprint2 ), the groups such as carboxyl (- COOH) it is logical
Coordinate bond combination is crossed, can effectively increase contrast using its fluorescence, to show latent.
In addition, copper nano-cluster Sweat latent fingerprint shows preparation method of reagent thereof in the present invention, entire manufacturing process is relative to existing
The manufacturing process such as gold, silver, platinum on it is relatively simple, relative to gold nanoclusters, silver nanoclusters, platinum cluster, copper nano-cluster etc., copper
The element generally existing as nature, for the nano-clusters such as gold, silver, platinum, raw material very abundant, and also it is economical real
Favour, production and use process in, have the advantages that raw material easily obtain, low manufacture cost.Copper nano-cluster also has nontoxic spy
Point has stronger safety in use.
The method for showing Sweat latent fingerprint is shown using only to need to drip, and the brushing relative to powder is easier
It is easy, and the heavy metal for avoiding the phenomenon that dust is drawn into operator during painting, and using also can be direct or indirect
Influence Environmental security；Use relative to nano materials such as Au-Ag-Pts is sensitiveer, and effect more meets fingerprint requirement, and
Entire production and use process are more reliable and more stable.In ultrapure water other than hydrone, almost without what impurity, more without thin
The organic matters such as bacterium, virus, dioxin containing chlorine, the also not no mineral trace element of needed by human body certainly, that is, almost remove
The water of all atoms other than oxygen and hydrogen, the influence of impurity etc. during being greatly reduced relative to light water, so that result is more
Accurately.
By adopting the above-described technical solution, the present invention has the advantage that: copper nano-cluster Sweat latent fingerprint shows reagent
Preparation method, not only high sensitivity, low in cost, safety and environmental protection, good developing effect, fluorescence are variable for it, stablize, and can also arrange
Show effect with excellent except the interference of background colour, and on the object on rough surface and uneven surface；Sweat latent fingerprint
Process for show, easy to operate, safety and environmental protection.
Detailed description of the invention
Fig. 1 is copper nano-cluster reaction principle figure in the present invention；
Fig. 2 is independently to build to show observing system and show schematic illustration in the present invention；
Fig. 3 is copper nano-cluster natural lighting schematic diagram in the present invention；
Fig. 4 is copper nano-cluster ultraviolet spectrogram in the present invention；
Fig. 5 is the CuNCs fluorescence illumination schematic diagram synthesized under different heating temperature environment in the present invention；
Fig. 6 is the CuNCs fluorescence spectra synthesized under different heating temperature environment in the present invention；
It is that latent shows effect picture on glass surface that Fig. 7, which is in the present invention,.
Specific embodiment
The present invention is further illustrated with reference to the accompanying drawings and examples.
Embodiment 1
Copper nano-cluster Sweat latent fingerprint shows preparation method of reagent thereof, comprising the following steps:
S1, polyethyleneimine, ascorbic acid, the copper sulphate of branching are that raw material preparation shows reagent；Specifically includes the following steps:
BPEI is dissolved in ultrapure water by S101, is configured to the solution of 0.01g/ml, 5~10min of ultrasound；AA is dissolved in ultrapure water, is matched
The solution of 0.1M/ml is made；By CuSO4It is dissolved in ultrapure water, is configured to the solution of 0.1g/ml；
S102 takes BPEI solution 0.1ml, is added dropwise in 10ml ultrapure water, CuSO is slowly added dropwise under stiring4Solution 1ml
After 3~5min, 1mlAA(0.1M is added dropwise in (0.625mM))；
S103 reacts 6~8 hours respectively at 30 DEG C, 60 DEG C, 90 DEG C, 120 DEG C, 150 DEG C, and the copper obtained at each temperature is received
Rice cluster solution；
Solution is mixed S104,10~15min of ultrasound.
Embodiment 2
Copper nano-cluster Sweat latent fingerprint shows preparation method of reagent thereof, comprising the following steps:
BPEI is dissolved in ultrapure water by S101, is configured to the solution of 0.01g/ml, 6~8min of ultrasound；AA is dissolved in ultrapure water, is matched
The solution of 0.1M/ml is made；By CuSO4It is dissolved in ultrapure water, is configured to the solution of 0.1g/ml；
S102 takes BPEI solution 0.1ml, is added dropwise in 10ml ultrapure water, CuSO is slowly added dropwise under stiring4Solution 1ml
After 3~5min, 1mlAA(0.1M is added dropwise in (0.625mM))；
S103 reacts 6~8 hours respectively at 30 DEG C, 60 DEG C, 90 DEG C, 120 DEG C, 150 DEG C, and the copper obtained at each temperature is received
Rice cluster solution；
Solution is mixed S104,12~14min of ultrasound.
Embodiment 3
A method of showing Sweat latent fingerprint, comprising the following steps:
S201, reagent preparation, prepares copper nano-cluster Sweat latent fingerprint and shows reagent；
S202 restrains finger mark, and volunteer restrains finger mark on object surface, makes finger mark sample；
S203 drips aobvious finger mark, and by the reagent that shows in step S201, to carry out drop to the Sweat latent fingerprint on different objects respectively aobvious；
S204 dries drop aobvious latent in baking oven machine under the conditions of vacuum, 30~50 DEG C；
S205, independently builds that show observing system latent to fluorescence sweat using alternative light source, colour light filter mirror, digital single-lens reflex camera
Finger mark is observed and fixation of taking pictures；
S206 drips the Sweat latent fingerprint showed by the reagent that shows prepared by the method with alternative light source irradiation, refers in darkroom
The fluorescence that print generates penetrates colour light filter mirror, is recorded by digital single-lens reflex camera, finger mark mastoid process streakline and its minutia are fixed
Get off.
Embodiment 4
S201, reagent preparation, prepares copper nano-cluster Sweat latent fingerprint and shows reagent；
S202, restrains finger mark, same volunteer soaps both hands dry only after, with thumb contact forehead and wing of nose two sides,
Then the stamp Sweat latent fingerprint on object obtains clearly finger mark sample and stores finger mark sample in its natural state；
S203 drips aobvious finger mark, will show reagent respectively to the Sweat latent fingerprint on glass along finger mark mastoid process streakline in step S201
It is aobvious that uniformly drop is carried out clockwise；
S204 dries drop aobvious latent in baking oven machine under the conditions of vacuum, 30~50 DEG C；
S205, independently builds that show observing system latent to fluorescence sweat using alternative light source, colour light filter mirror, digital single-lens reflex camera
Finger mark is observed and fixation of taking pictures；
S206 drips the sweat showed by the reagent that shows prepared by the method with the irradiation of ST55-12F alternative light source in darkroom
Latent, the fluorescence that finger mark generates penetrate colour light filter mirror, are recorded by digital single-lens reflex camera, by finger mark mastoid process streakline and its details
Feature is fixed up.
In the present invention, in order to imitate the latent on practical criminal-scene as far as possible, this experiment finger mark sample is in natural shape
It is stored under state；It is more in substances such as sweat, the greases at these positions with thumb contact forehead and wing of nose two sides, the fingerprint of stamp
It can be relatively good.It is aobvious that rubber head dropper takes amount of copper nano-cluster to drip clockwise along finger mark mastoid process streakline respectively, and finger mark can be greatly lowered
The failure probability of mastoid process streakline guarantees its integrality as far as possible.Baking oven machine vacuum condition avoids in air other substances (such as water
Point) influence, guarantee drying rapidly and efficiently.
The present invention provides copper nano-cluster Sweat latent fingerprints to show reagent, using BPEI as template, using AA as reducing agent, changes anti-
Condition is answered, reduction partial size is smaller, uses with the variable copper nano-cluster of fluorescence, and by this novel nano-material prepared
In showing for latent.The diameter of copper nano-cluster is usually less than 2 nm, and close to Fermi's wavelength of electronics, therefore copper nano-cluster can be in
Existing stronger photoluminescent property.Compared to the nanocomposite of the luminescence generated by lights such as other small molecule fluorescent dyestuffs and quantum dot, such as golden,
The materials such as silver, platinum, copper nano-cluster have many advantages, such as safe and non-toxic, surface be easy to modify, fluorescent stability it is strong, and price is relatively
It is low.Controllability and good biocompatibility based on nano-cluster particle size are template also original shape using polyethyleneimine
At copper nano-cluster, the regulation of size is achieved to obtain fluorescence changeability, novel fluorescence is prepared with this and is shown
Reagent carries out fluorescent marker to Sweat latent fingerprint, and the finger mark of fluorescence is presented using alternative light source detection.Bear the visitor of finger mark
Body (such as various metals, plastics, leather and fur products, paint and true qualities woodenware surface) is not sent out under the irradiation such as ultraviolet light, blue green light
Light is in deep dark tone.Copper nano-cluster issues fluorescence under multiband irradiation, so that the contrast of background and finger mark is improved, when
When background has week fluorescent, the fluorescence changeability of copper nano-cluster, the iridescent for selecting effect best, to exclude background colour are utilized
Interference.
Show reagent in copper nano-cluster Sweat latent fingerprint in use, under acid condition, in latent organic species and
Substance containing amino can be in positive electricity, and metal nanoparticle surface is in negative electricity due to absorption hydroxyl, the nanometer of negative electrical charge
Particle can be combined by electrostatic adsorption with latent streakline.According to coordination principle, copper atom can with containing orphan to electricity
Molecule, ion or the group of son form stable complex, thus copper nano-cluster etc. can with contain lone pair electrons group such as mercapto
Base (- SH), amino (- NH2), the groups such as carboxyl (- COOH) combined by coordinate bond, pass through electrostatic adsorption, coordination bond
Cooperation is with enabling potential streakline to show by the fluorescence that CuNCs is issued.Copper nano-cluster can be with big point of biology in latent
Son combines, even if on coarse object surface, it, can be with sulfydryl (- SH), the amino (- NH in finger mark with the presence of fingerprint2 ), carboxyl
Groups such as (- COOH) are combined by coordinate bond, can effectively increase contrast using its fluorescence, to show latent.
In addition, copper nano-cluster Sweat latent fingerprint shows reagent in the present invention, entire manufacturing process relative to existing gold, silver,
Relatively simple in the manufacturing process such as platinum, relative to gold nanoclusters, silver nanoclusters, platinum cluster, copper nano-cluster etc., copper is as nature
The generally existing element in boundary, for the nano-clusters such as gold, silver, platinum, raw material very abundant, and also it is economical and practical, it is making
In use process, have the advantages that raw material easily obtain, low manufacture cost.Copper nano-cluster also has the characteristics that nontoxic, is using
In have stronger safety.And Sweat latent fingerprint process for show is provided, it uses and only needs drop aobvious, relative to powder
The brushing huge sum of money that is more simple and easy to do, and avoiding the phenomenon that dust is drawn into operator during painting, and use at end
Belong to influence Environmental security that also can be direct or indirect；Use relative to nano materials such as Au-Ag-Pts is sensitiveer, and effect is more
Toe line requirement is filled it up with, and entire production and use process are more reliable and more stable.In ultrapure water other than hydrone, almost without
What impurity, more without organic matters such as bacterium, virus, dioxin containing chlorine, the also not no micro member of the minerals of needed by human body certainly
Element, that is, the water of all atoms other than deoxygenation and hydrogen is almost removed, impurity etc. during being greatly reduced relative to light water
It influences, so that result is more accurate.
Fig. 1 is copper nano-cluster reaction principle figure, takes the polyethyleneimine (BPEI) of branching to be dissolved in ultrapure water, is stirring
Under CuSO is slowly added dropwise4Solution is uniformly mixed the two, is added dropwise ascorbic acid (AA).BPEI is template, and AA is reducing agent, gold
Belong to copper ion and template interacts, by reducing agent copper ion is restored as atom, is gathered in be formed in template and receive
Rice cluster, while the BPEI as template protection agent then make restored atom will not because of interaction each other to
Aggregation is excessive, the formation of bulky grain metallic particles is avoided, to ensure that copper nano-cluster is with good stability.
Fig. 2 is independently to build to show observing system and show schematic illustration in the present invention；It is taken with rubber head dropper suitable
Copper nano-cluster uniformly drips aobvious latent, is sufficiently combined to solution with finger mark substance, and drying is fixed.Using alternative light source, have
Color optical filtering, digital single-lens reflex camera, which are independently built, to be shown observing system and is observed fluorescence Sweat latent fingerprint and fixation of taking pictures；?
In darkroom, the Sweat latent fingerprint showed is dripped by the reagent that shows prepared by the method with alternative light source irradiation, finger mark generates glimmering
Light penetrates colour light filter mirror, is recorded by digital single-lens reflex camera, finger mark mastoid process streakline and its minutia are fixed up.Currently,
Show latent in practice and often carries out that brush is aobvious with powder, since the powder for brushing aobvious is tiny, drift easy to form in use
Floating object generates greatly damage to human body.This patent is to show latent in the aobvious method of solution drop, efficiently solves dust and asks
Topic, while the copper nano-cluster itself for preparing formation has nontoxicity, will not cause substantially to human body and environment in use
Pollution, the characteristic with safety and environmental protection.
Fig. 3 is copper nano-cluster natural lighting schematic diagram in the present invention, and Fig. 4 is copper nano-cluster ultraviolet spectrogram in the present invention；
Fig. 4 (a)~(e) is the ultraviolet spectrogram of the CuNCs generated under the conditions of 30 DEG C, 60 DEG C, 90 DEG C, 120 DEG C, 150 DEG C respectively.By
Figure it is found that with temperature change, the ultraviolet spectrogram of CuNCs has apparent change at 365nm, with the liter of temperature
Height, CuNCs are become having peak at 365nm from no peak, and the intensity at peak constantly enhances also with the raising of temperature.It is presumed that
This may be because CuNCs has size adjustable characteristic, and different heating conditions changes the particle size of CuNCs particle
Become, temperature increases, and the partial size of CuNCs particle increases, so that corresponding change occurs for the property of CuNCs.It can be seen that CuNCs
It experienced the process to turn yellow from indigo plant, CuNCs is blue at 30 DEG C, and CuNCs becomes blue-green at 60 DEG C, and CuNCs becomes at 90 DEG C
Yellow green, CuNCs becomes bottle green at 120 DEG C, and CuNCs becomes light yellow when to 150 DEG C.Temperature has also been confirmed in the change of color
The particle size of CuNCs can be changed, different heating conditions obtains various sizes of CuNCs.
Fig. 5 is the CuNCs fluorescence illumination schematic diagram synthesized under different heating temperature environment in the present invention, and Fig. 6 is this
The CuNCs fluorescence spectra synthesized under different heating temperature environment in invention；By Fig. 5 and Fig. 6 it is found that as temperature is from 30
DEG C increase to 150 DEG C, the fluorescence intensity of CuNCs from 420nm (blue emission) to 565nm (yellow emission) show it is apparent red
It moves (145nm).In the environment of 30 DEG C, when excitation wavelength is 345nm, the launch wavelength of CuNCs is located at 420nm, obtains
To the fluorescence of blue；In the environment of 60 DEG C, when excitation wavelength is 365nm, the launch wavelength of CuNCs is located at 460nm,
Obtain glaucous fluorescence；In the environment of 90 DEG C, when excitation wavelength is 400nm, the launch wavelength of CuNCs is located at
At 490nm, the fluorescence of yellow green is obtained；In the environment of 120 DEG C, when excitation wavelength is 450nm, the transmitted wave of CuNCs
It is long to be located at 530nm, obtain lurid fluorescence；In the environment of 150 DEG C, when excitation wavelength is 470nm, CuNCs's
Launch wavelength is located at 550nm, obtains the fluorescence of yellow.In figure it is clear that see CuNCs changing from blue to yellow
Become, this demonstrate that CuNCs has tunability.It is presumed that leading to the fluorescence of CuNCs this is because the size of CuNCs increases
The absorption peak red shift of spectrum, this also further demonstrates emission mechanism of the nano-cluster under Particle size.
Fig. 7 is that latent shows effect picture on glass surface in embodiment 4 in the present invention；A~c is respectively Jenner in figure
The latent that rice cluster, platinum cluster and copper nano-cluster solution show on glass.As shown in Figure 7, copper nano-cluster solution is to latent finger
Print to show effect best, finger mark streakline is clear, mastoid process streakline and ditch dug with a plow line level are obvious, minutia is clearly distinguishable.Jenner
To compare copper nano-cluster solution poor for show effect of rice cluster solution and the platinum cluster solution to latent.Gold nanoclusters solution drop is aobvious
Latent elementary contour as it can be seen that most of streakline is clear, but minutia show it is weaker.The finger mark that platinum cluster solution shows
Although contour feature as it can be seen that but streakline clarity and minutia show it is all poor.This is because the progress of copper nano-cluster is excellent
After change, the combination of BPEI and copper ion is more complete, and copper particle is easier to and sulfydryl (- SH), amino (- NH2), carboxyl in latent
Groups such as (- COOH) are combined by coordinate bond.To enable potential streakline to show by the fluorescence that CuNCs is issued.Gold nano
Cluster solution is to prepare by template of BSA, but since BSA is large biological molecule, when finger mark shows, shell membrane shape easy to form, makes
Nano particle, which combines the specific ability of mastoid process streakline, to be weakened, and is reduced with the contrast of ditch dug with a plow line.Platinum cluster and copper nano-cluster
It is all prepared by template of BPEI, the combination of platinum ion and BPEI do not have copper thorough when due to reaction, and the platinum formed on BPEI is former
Son aggregation is sparse, and weaker, the contrast reduction of mastoid process streakline and ditch dug with a plow line is shown to the identification of biomolecule contained in latent.
By above-mentioned experiment and relevant drawings it is found that copper nano-cluster Sweat latent fingerprint shows preparation method of reagent thereof in the present invention,
Not only high sensitivity, low in cost, safety and environmental protection, good developing effect, fluorescence are variable for it, stablize, and can also exclude background colour
Interference, and show effect with excellent on the object on rough surface and uneven surface；Sweat latent fingerprint process for show,
Its easy to operate, safety and environmental protection.
Claims (8)
1. the preparation method that bronze medal nano-cluster Sweat latent fingerprint shows reagent, which is characterized in that with the polyethyleneimine (BPEI) of branching
For template, with ascorbic acid (AA) for reducing agent, using copper sulphate as raw material, heating condition preparation when control is reacted shows examination
Agent.
2. the preparation method that copper nano-cluster Sweat latent fingerprint according to claim 1 shows reagent, which is characterized in that including with
Lower step:
BPEI is dissolved in ultrapure water by S101, is configured to the solution of 0.01g/ml, 5~10min of ultrasound；AA is dissolved in ultrapure water, is matched
The solution of 0.1M/ml is made；By CuSO4It is dissolved in ultrapure water, is configured to the solution of 0.1g/ml；
S102 takes BPEI solution 0.1ml, is added dropwise in 10ml ultrapure water, CuSO is slowly added dropwise under stiring4Solution 1ml
After 3~5min, 1mlAA(0.1M is added dropwise in (0.625mM))；
S103 reacts 6~8 hours respectively at 30 DEG C, 60 DEG C, 90 DEG C, 120 DEG C, 150 DEG C, and the copper obtained at each temperature is received
Rice cluster solution；
Solution is mixed S104,10~15min of ultrasound.
3. a kind of method for showing Sweat latent fingerprint, which is characterized in that prepared using finger mark visualization reagent of any of claims 1 or 2
Copper nano-cluster Sweat latent fingerprint prepared by method shows reagent and shows to Sweat latent fingerprint, comprising the following steps:
S201, reagent preparation, prepares copper nano-cluster Sweat latent fingerprint using finger mark visualization reagent preparation method described in claim or 2
Show reagent；
S202 restrains finger mark, and volunteer restrains finger mark on object surface, makes finger mark sample；
S203 drips aobvious finger mark, and by the reagent that shows in step S201, to carry out drop to the Sweat latent fingerprint on different objects respectively aobvious；
S204 dries drop aobvious latent in baking oven machine under the conditions of vacuum, 30~50 DEG C；
S205, independently builds that show observing system latent to fluorescence sweat using alternative light source, colour light filter mirror, digital single-lens reflex camera
Finger mark is observed and fixation of taking pictures；
S206 drips the Sweat latent fingerprint showed by the reagent that shows prepared by the method with alternative light source irradiation, refers in darkroom
The fluorescence that print generates penetrates colour light filter mirror, is recorded by digital single-lens reflex camera, finger mark mastoid process streakline and its minutia are fixed
Get off.
4. the method according to claim 3 for showing Sweat latent fingerprint, which is characterized in that S202 is the following steps are included: aspiration
After both hands are soaped net dry by person, with thumb contact forehead and wing of nose two sides, then the stamp Sweat latent fingerprint on object, is obtained
It obtains clearly finger mark sample and stores finger mark sample in its natural state.
5. the method according to claim 4 for showing Sweat latent fingerprint, which is characterized in that finger mark sample standard deviation is by same volunteer
It provides.
6. the method according to claim 3 for showing Sweat latent fingerprint, which is characterized in that S203 is the following steps are included: use glue
Head dropper takes amount of copper nano-cluster aobvious along finger mark mastoid process streakline drop respectively, is sufficiently combined to solution with finger mark substance.
7. the method according to claim 6 for showing Sweat latent fingerprint, which is characterized in that take amount of copper nano-cluster along finger mark cream
Uniformly drop is aobvious clockwise for lug line.
8. the method according to claim 3 for showing Sweat latent fingerprint, it is characterised in that: it is glass that finger mark, which leaves object, in S203
Glass, plastics, preservative film or metal object.
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