CN105962947B - Fluorescence magnetic noble metal nano egg and its preparation and the method for showing finger mark - Google Patents
Fluorescence magnetic noble metal nano egg and its preparation and the method for showing finger mark Download PDFInfo
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- A61B5/117—Identification of persons
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Abstract
The object of the present invention is to provide a kind of fluorescence magnetic noble metal nano egg and its preparation and the methods for showing finger mark.The fluorescence magnetic noble metal nano egg is any one in fluorescence magnetic gold nano egg, fluorescence magnetic silver nanoparticle egg and fluorescence magnetic platinum nanometer egg；The fluorescence magnetic noble metal nano egg is the nanometer PEI-Fe that surface is coated with fluorescence phycoerythrin3O4The combination of particle and nano noble metal particles；The nanometer PEI-Fe3O4Particle refers to the Nanometer Magnetite particle amine-modified by polyethyleneimine.Fluorescence magnetic nanogold egg fluorescence quantum yield prepared by the present invention is high, and fluorescence duration time is long, has hypotoxicity；Finger mark process for show operation of the invention rapidly and efficiently, can clearly show 30 days outmoded finger marks and effect is better than the process for show of conventional reagents.
Description
Technical field
The invention belongs to public security criminal technique finger marks to identify field, and in particular to a kind of fluorescence magnetic noble metal nano egg and
It prepares and shows the method for finger mark.
Background technique
Fingerprint have people it is variant, throughout one's life it is constant, touching object trace characteristic, have the beauty of " human body identity card " and " king of evidence "
Claim, to exposure, confirms that crime and identification criminal have considerable effect.It is distributed on the mastoid process decorative pattern of people's both hands finger finger
The sweat of pore, pore secretion often contains grease and other small substances.Therefore the Sweat latent fingerprint ingredient being retained on object
Include the organic matters such as a small amount of water, a small amount of inorganic matter, protein, grease.
Finger mark appearing technique has the history of upper a century, and traditional process for show has 502 smoked aobvious methods, ninhydrin method, DFO method
Deng.With the rapid development of nanotechnology, novel nano-material is applied to latent and shows the concern for causing researcher,
Occur showing the methods of finger mark using metal, up-conversion luminescence, magnetic Nano material.
As the magnetic powder of traditional process for show, granular size is about 800 mesh, since particle has magnetism, is used for latent
Attracted by magnetic powder brush without being suspended in the air when brush is aobvious, therefore is first choice when punishment section personnel investigate on the spot at the scene.It is inspired by this,
Magnetic particle also starts to attract attention, and is included into the method reagent that latent shows.Report about functionalized nano magnetic bead
Very much, one of which is the nanometer Fe of the nanogold functionalization of similar dumbbell shaped3O4(size Control 4-20nm).Nanogold has
The features such as special stability, small-size effect, enables it to combine with organic matter such as protein etc. containing sulfydryl, amino, and contains
The fluorescein of phenyl ring forms covalent bond, enhances the fluorescent effect etc. of fluorescein.Therefore, Au-Fe after the functionalization3O4Nanoparticle
With alternative, compatibility and superparamagnetic characteristic, biomedical, MRI imaging, cancer cell diagnosis, control poison can be applied to
The fields such as product dispersion, also about it in the report of developing latent finger printss, but the compound magnetic nano-particle is because of particle
The features such as color, receives certain limitation in the developing latent finger printss little applied to background reflectance.
Phycoerythrin is as a kind of novel fluorescent labeling reagent, and under specific wavelength excitation, phycoerythrin can emit by force
Strong fluorescence, fluorescence intensity are 30-100 times of fluorescein.With good photo absorption performance and very high quantum yield, can
See that spectral regions have very wide excitation and transmitting range.The excessively conventional labeling method of its multi-pass and biotin, Avidin and various lists
Clonal antibody, which combines, is made fluorescence probe, is used for clinical diagnosis and biotechnology such as immune detection, fluorescence microscopy skill
Art and fluidic cell fluoremetry etc..But it is fresh it has been reported that still locating to start to walk in the research in science and technology concerning criminal matters field and application
Stage.
Summary of the invention
The object of the present invention is to provide a kind of fluorescence magnetic noble metal nano egg and its preparation and the methods for showing finger mark.
A kind of fluorescence magnetic noble metal nano egg of the present invention, which is characterized in that the fluorescence magnetic noble metal nano egg is
Any one in fluorescence magnetic gold nano egg, fluorescence magnetic silver nanoparticle egg and fluorescence magnetic platinum nanometer egg；The fluorescence magnetic
Noble metal nano egg is the nanometer PEI- Fe that surface is coated with fluorescence phycoerythrin3O4The combination of particle and nano noble metal particles
Body；The nanometer PEI- Fe3O4Particle refers to the Nanometer Magnetite particle amine-modified by polyethyleneimine.
A kind of production method of fluorescence magnetic noble metal nano egg of the present invention, which is characterized in that the expensive gold of fluorescence magnetic
Category nanometer egg is any one in fluorescence magnetic gold nano egg, fluorescence magnetic silver nanoparticle egg and fluorescence magnetic platinum nanometer egg；Institute
Stating production method is using electrostatic adsorption by nanometer PEI- Fe3O4Nano-noble metal in particle and nano-noble metal solution
Particle combines；Fluorescence phycoerythrin is coated on PEI- Fe again3O4The combination surface of particle and nano-noble metal forms fluorescence
Magnetic noble metal nano egg；The nanometer PEI- Fe3O4Particle refers to be aoxidized by the amine-modified nano-magnetic four of polyethyleneimine
Three iron particles.
Further, the nanometer PEI- Fe3O4Particle refers to be aoxidized by the amine-modified nano-magnetic four of polyethyleneimine
Three iron particles, comprising the following steps:
Prepare nanometer Fe3O4, by 3mol divalent iron salt FeSO4·7H2O and 6mol trivalent iron salt FeCl3·6H2O is dissolved in
It in 250mL distilled water and adds it in 500mL three-necked flask, ammonia spirit is added to reactant under nitrogen atmosphere protection
PH >=10 for making system in system, are vigorously stirred, constant temperature water bath；Reaction was completed after stirring 30min, is washed with distilled water in
Property, incline supernatant liquor, after being dried in vacuo at 60 DEG C, grinds up to nanometer Fe3O4；
Prepare nanometer PEI-Fe3O4Particle, by 0.37g nanometer Fe3O4The polyethyleneimine PEI solution of 20mL, 4g/L is added
In, it in frequency 2450MHz, power 800W heated under microwave conditions 120min, is separated after reaction with externally-applied magnetic field, then will
Sediment fraction is washed with deionized to neutrality, is freeze-dried to obtain nanometer PEI-Fe3O4Particle.
Further, the nano-noble metal solution is appointing in nanometer Au solution, nanometer Ag solution and Pt nano particle solution
It anticipates one kind；The preparation of the nano-noble metal solution, comprising:
Nanometer Au solution is prepared, by the lemon of the HAuCl4 solution of 100mL, 0.0206mol/L and 25mL, 0.0025mol/L
It is put into Ultrasound Instrument after lemon acid three sodium solutions mixing and vibrates 30min, then added at power 700W, 250 DEG C of microwave conditions of temperature
Solution, is cooled to room temperature by hot 1min after reaction, is settled to 100mL with ultrapure water, and obtaining concentration is about 0.0206mol/L
Nanometer Au solution and saved in 4 DEG C of refrigerator；
Nanometer Ag solution is prepared, by the lemon of the silver nitrate solution of 100mL, 0.0103mol/L and 25mL, 0.0025mol/L
It is put into Ultrasound Instrument after lemon acid three sodium solutions mixing and vibrates 30min, then added at power 700W, 245 DEG C of microwave conditions of temperature
Solution, is cooled to room temperature by hot 5min after reaction, is settled to 100ml with ultrapure water, and obtaining concentration is about 0.0103mol/L
Nanometer Ag solution and saved in 4 DEG C of refrigerator；
Pt nano particle solution is prepared, the addition 2.5mL ethylene glycol into beaker, the platinum acid chloride solution of 13mL, 10g/50mL,
It is put into supersonic oscillations instrument after the KOH solution of 0.4mL, 0.04mol/L and vibrates 30min, then microwave heating 30S, microwave function
Rate is 700W, 245 DEG C of temperature, is after reaction cooled to room temperature solution, is settled to 100mL with ultrapure water, obtains concentration about
For 0.4746mol/L Pt nano particle solution and saved in 4 DEG C of refrigerator.
Further, described to use electrostatic adsorption by nanometer PEI-Fe3O4Particle and receiving in nano-noble metal solution
Rice noble metal combines；Include:
Prepare nanometer Fe3O4@Au, by 2mL PEI- Fe3O410mL nanometers of Au seed solutions are added in aqueous solution, use Ultrasound Instrument
Frequency be 80KHz disperse 3min after carry out Magnetic Isolation, disperse sediment fraction in 20mL water, then be added 110mL,
The NaOH solution of 0.1mol/L, and 0.5mL, 1%HAuCl is gradually added dropwise4The NH of solution and 0.75mL, 0.2mol/L2OH-HCl is molten
Liquid, nanometer Fe finally separating obtained using externally-applied magnetic field3O4@Au；
Prepare nanometer Fe3O4@Ag takes 2mL PEI-Fe3O4 aqueous solution that 10mL nanometer Ag seed solution is added, uses Ultrasound Instrument
Frequency be 80KHz disperse 2min after carry out Magnetic Isolation, disperse sediment fraction in 20mL water, then be added 110mL,
The NaOH solution of 0.1mol/L, and the AgNO of 0.35mL, 0.1552mol/L is gradually added dropwise3Solution and 0.75mL, 0.2mol/L
NH2OH-HCl solution, nanometer Fe finally separating obtained using externally-applied magnetic field3O4@Ag；
Prepare nanometer Fe3O4@Pt takes 2mL PEI- Fe3O410mL Pt nano particle seed solution is added in solution, is washed with ultrasonic wave
Washing instrument frequency is to carry out Magnetic Isolation after 80KHz disperses 1min.Disperse sediment fraction in 20mL water, then be added 110mL,
The NaOH aqueous solution of 0.1mol/L, and 0.5mL, 1%H is gradually added dropwise2PtCl5The NH of aqueous solution and 0.75mL, 0.2mol/L2OH-
HCL aqueous solution, nanometer Fe finally separating obtained using externally-applied magnetic field3O4@Pt。
Further, described that fluorescence phycoerythrin is coated on PEI-Fe3O4The combination surface of particle and nano-noble metal
Form fluorescence magnetic noble metal nano egg system, comprising:
Fluorescence magnetic gold nano egg is prepared, 0.06g nanometer Fe is weighed3O4@Au is scattered in the deionized water of 2ml, and ultrasound is molten
Take upper solution after solution, separated under magnetic field, spent after separation it is secondary from water washing magnetic nano-particle, then, be added 50 μ L,
The phycoerythrin PE of the 1.0mg/mL and PBS of 950 μ L, 10mmol/L, and the pH of the PBS is 7.4, is reacted after shaking up in 37 DEG C
12h, after Magnetic Isolation, with the PBS solution of 10mmol/L, and the pH of the PBS solution is 7.4, and washing nanoparticle is secondary, obtains
Have both the magnetic fluorescence magnetic gold nano egg reagent with fluorescence property；
Fluorescence magnetic silver nanoparticle egg is prepared, 0.04g nanometer Fe is weighed3O4@Ag is scattered in the deionized water of 2m1, and ultrasound is molten
Take upper solution after solution, separated under magnetic field, spent after separation it is secondary from water washing magnetic nano-particle, then, be added 50 μ L,
The phycoerythrin PE of the 1.0mg/mL and PBS of 950 μ L, 10mmol/L, and the pH of the PBS is 7.4, is reacted after shaking up in 37 DEG C
12h, after Magnetic Isolation, with the PBS solution of 10mmol/L, and the pH of the PBS solution is 7.4, and washing nanoparticle is secondary, obtains
Have both the magnetic fluorescence magnetic silver nanoparticle egg reagent with fluorescence property；
Fluorescence magnetic platinum nanometer egg is prepared, 0.05g nanometer Fe is weighed3O4@Pt is scattered in the deionized water of 2m1, ultrasound
Take upper solution after dissolution, separated under magnetic field, spent after separation it is secondary from water washing magnetic nano-particle, then, be added 50 μ L
The PBS of 1.0mg/mL, phycoerythrin PE and 950 μ L, 10mmol/L, and the pH of the PBS is 7. 4, it is anti-in 37 DEG C after shaking up
Answer 12h, after Magnetic Isolation, with the PBS solution of 10mmol/L, and the pH of the PBS solution is 7. 4, and washing nanoparticle is secondary,
It obtains having both the magnetic fluorescence magnetic platinum nanometer egg reagent with fluorescence property.
The present invention also provides a kind of methods that fluorescence magnetic noble metal nano egg reagent shows outmoded Sweat latent fingerprint, including
Following steps:
S1, configuration Sweat latent fingerprint show reagent, and it is fluorescence magnetic noble metal nano egg, the fluorescence magnetic that this, which shows reagent,
Noble metal nano egg is any one in fluorescence magnetic gold nano egg, fluorescence magnetic silver nanoparticle egg and fluorescence magnetic platinum nanometer egg
Kind；The fluorescence magnetic noble metal nano egg is the nanometer PEI- Fe that surface is coated with fluorescence phycoerythrin3O4Particle and nanometer
The combination of noble metal；The nanometer PEI- Fe3O4Particle refers to nano-magnetic four oxygen amine-modified by polyethyleneimine
Change three iron particles；
After S2, volunteer will hand-wash net dry, the stamp Sweat latent fingerprint on glass, plastics, preservative film, metal object is obtained
Obtain finger mark sample.
S3, Sweat latent fingerprint made from the aobvious step S2 of reagent drop will be shown made from step S1, reacted 10 minutes；
S4, the Sweat latent fingerprint loose colour after step S3 drop is shown is washed away using ultrapure water；
S5, step S4 is washed away to the Sweat latent fingerprint drying after loose colour；
S6, the Sweat latent fingerprint image in the case where showing observing system, after observation fixing step S5 drying.
Further, the resting period of the finger mark sample of the step S2 is 7-30 days.
Further, the step S3 is that the noble-metal nanoclusters obtained by rubber head dropper aspiration step S1 show examination
Agent drips it clockwise along finger mark mastoid process streakline aobvious, and sufficiently reacts 2h with finger mark substance.
Further, it is to utilize alternative light source, colour light filter mirror, digital single-lens reflex camera that observing system is shown in the step S6
What camera was built shows observing system.
The present invention provides a kind of novel Sweat latent fingerprints to show reagent, and innovation has used phycoerythrin to modify nanometer
The magnetic ferroferric oxide nano-particles of gold, silver, platinum cladding.Small, stable system and magnetic and Gao Ying is had both using their partial sizes
The features such as quantum yield, shows observing system by independently building, the sweat shown to fluorescence magnetic noble metal nano egg system
Latent carries out observation fixation.
The present invention has the advantage that
1. the magnetic ferroferric oxide system that phycoerythrin is applied to nano-noble metal cladding is belonged to pioneering by the present invention；
2. the fluorescence magnetic nanogold egg fluorescence quantum yield of preparation is high, and fluorescence duration time is long, has hypotoxicity；
3. finger mark shows operation rapidly and efficiently, it can clearly show 30 days outmoded finger marks；
4. the performance that fluorescence magnetic noble metal nano egg prepared by the present invention shows outmoded finger mark shows reagent better than tradition；
5. showing the higher fixed finger mark information of observing system energy, be conducive to test sensitivity.
Detailed description of the invention
Fig. 1 is fluorescence magnetic noble metal gold nano egg system composition principle figure (silver, platinum class are seemingly).
Fig. 2 is fluorescence magnetic gold nano egg, fluorescence magnetic silver nanoparticle egg, fluorescence magnetic platinum nanometer egg show in glass object
Outmoded finger mark figure.
(A) show outmoded finger mark figure in glass object for fluorescence magnetic gold nano egg；
(B) show outmoded finger mark figure in glass object for fluorescence magnetic silver nanoparticle egg；
(C) show outmoded finger mark figure in glass object for fluorescence magnetic platinum nanometer egg.
Fig. 3 is to show observing system and show schematic illustration.
Fig. 4 is that noble-metal nanoclusters show the process flow chart that reagent shows Sweat latent fingerprint.
Specific embodiment
Embodiment 1
The preparation of fluorescence magnetic gold nano egg:
(1) nanometer Au solution is prepared, by the HAuCl4 solution of 100mL0.0206mol/L and 25mL0.0025mol/L
It is put into Ultrasound Instrument after citric acid three sodium solution mixing and vibrates 30min, then at power 700W, 250 °C of microwave conditions of temperature
1min is heated, solution is cooled to room temperature after reaction, is settled to 100mL with ultrapure water, obtaining concentration is about
The nanometer Au solution of 0.0206mol/L simultaneously saves in 4 °C of refrigerator；
(2) nanometer Fe is prepared3O4, by 3mol divalent iron salt (FeSO4・7H2) and 6mol trivalent iron salt (FeCl O3・6H2O)
It is dissolved in 250mL distilled water and adds it in 500mL three-necked flask, be added to ammonia spirit instead under nitrogen atmosphere protection
PH >=10 for making system in system are answered, are vigorously stirred, constant temperature water bath.Stir 30min after reaction was completed, be washed with distilled water until
Neutrality, incline supernatant liquor, after being dried in vacuo at 60 DEG C, grinds up to nanometer Fe3O4；
(3) nanometer PEI- Fe is prepared3O4Particle, by 0.37g nanometer Fe3O4It is added 20mL4g/L polyethyleneimine (PEI)
In solution, in frequency 2450MHz, power 800W heated under microwave conditions 120min, separated after reaction with additional magnet, so
Sediment fraction is washed with deionized to neutrality afterwards, is freeze-dried to obtain nanometer PEI- Fe3O4Particle；
(4) nanometer Fe is prepared3O4@Au, by 2mL PEI- Fe3O4Aqueous solution be added 10mL nanometer Au seed solutions, with surpass
Sound instrument disperses to carry out Magnetic Isolation after 3min (frequency 80KHz), disperse sediment fraction in 20mL water, be then added
110mL0.1mol/L NaOH solution, and 0.5mL1%HAuCl is gradually added dropwise4Solution and 0.75mL0.2mol/L NH2OH-HCl is molten
Liquid, nanometer Fe finally separating obtained using externally-applied magnetic field3O4@Au；
(5) fluorescence magnetic gold nano egg is prepared, 0.06g nanometer Fe is weighed3O4@Au is scattered in the deionized water of 2m1, is surpassed
Sound dissolution after take upper solution, separated under magnetic field, spent after separation it is secondary from water washing magnetic nano-particle, then, be added 50 μ
The 1.0mg.mL-1 phycoerythrin PE of L and 950 μ L10mmol/L PBS, and the pH of the PBS is 7. 4, it is anti-in 37 DEG C after shaking up
Answer 12h, after Magnetic Isolation, with 10mmol/LPBS solution, and the pH of the PBS solution is 7. 4, and washing nanoparticle is secondary, obtains
To the fluorescence magnetic gold nano egg for having both magnetic and fluorescence property.
Embodiment 2
The preparation of fluorescence magnetic silver nanoparticle egg:
(1) nanometer Ag solution is prepared, by the silver nitrate solution of 100mL 0.0103mol/L and 25mL0.0025mol/L
It is put into Ultrasound Instrument after citric acid three sodium solution mixing and vibrates 30min, then at power 700W, 245 °C of microwave conditions of temperature
5min is heated, solution is cooled to room temperature after reaction, is settled to 100ml with ultrapure water, obtaining concentration is about
The nanometer Ag solution of 0.0103mol/L simultaneously saves in 4 °C of refrigerator；
(2) nanometer Fe is prepared3O4, by 3mol divalent iron salt (FeSO4・7H2) and 6mol trivalent iron salt (FeCl O3・6H2O)
It is dissolved in 250mL distilled water and adds it in 500mL three-necked flask, be added to ammonia spirit instead under nitrogen atmosphere protection
PH >=10 for making system in system are answered, are vigorously stirred, constant temperature water bath.Stir 30min after reaction was completed, be washed with distilled water until
Neutrality, incline supernatant liquor, after being dried in vacuo at 60 DEG C, grinds up to nanometer Fe3O4；
(3) nanometer PEI- Fe is prepared3O4Particle, by 0.37g nanometer Fe3O4It is added 20mL4g/L polyethyleneimine (PEI)
In solution, in frequency 2450MHz, power 800W heated under microwave conditions 120min, separated after reaction with additional magnet, so
Sediment fraction is washed with deionized to neutrality afterwards, is freeze-dried to obtain nanometer PEI- Fe3O4Particle；
(4) nanometer Fe is prepared3O4@Ag takes 2mL PEI-Fe3O4 aqueous solution that 10mL nanometer Ag seed solution is added, with super
Sound instrument disperses to carry out Magnetic Isolation after 2min (frequency 80KHz), disperse sediment fraction in 20mL water, be then added
110mL0.1mol/L NaOH solution, and the AgNO of 0.35mL0.1552moL/L is gradually added dropwise3Solution and 0.75mL 0.2mol/
L NH2OH-HCl solution, nanometer Fe finally separating obtained using externally-applied magnetic field3O4@Ag；
(5) fluorescence magnetic silver nanoparticle egg is prepared, 0.04g nanometer Fe is weighed3O4@Ag is scattered in the deionized water of 2m1, is surpassed
Sound dissolution after take upper solution, separated under magnetic field, spent after separation it is secondary from water washing magnetic nano-particle, then, be added 50 μ
The 1.0mg.mL-1 phycoerythrin PE of L and 950 μ L10mmol/L PBS, and the pH of the PBS is 7. 4, it is anti-in 37 DEG C after shaking up
Answer 12h, after Magnetic Isolation, with 10mmol/LPBS solution, and the pH of the PBS solution is 7. 4, and washing nanoparticle is secondary, obtains
To the fluorescence magnetic silver nanoparticle egg for having both magnetic and fluorescence property.
Embodiment 3
The preparation of fluorescence magnetic platinum nanometer egg:
(1) prepare Pt nano particle solution, into beaker be added 2.5mL ethylene glycol, 13 mL 10g/50mL platinum acid chloride solutions,
It is put into supersonic oscillations instrument after 0.4mL 0.04mol/LKOH solution and vibrates 30min, then microwave heating 30S, microwave power
For 700W, 245 DEG C of temperature, solution is cooled to room temperature after reaction, is settled to 100mL with ultrapure water, obtaining concentration is about
The Pt nano particle solution of 0.4746mol/L simultaneously saves in 4 DEG C of refrigerator；
(2) nanometer Fe is prepared3O4, a certain amount of divalent iron salt (FeSO4 7H2O) and trivalent iron salt (FeCl3 6H2O) is mixed
It closes solution to be added in three-necked flask, certain density precipitating reagent NH3 H2O is added in dropping funel, in a nitrogen atmosphere by ammonia
Aqueous solution is added in reaction reagent, is made pH >=10 of reagent, is vigorously stirred, constant temperature water bath.Reaction was completed after stirring 30min, uses
Water washing is distilled until neutral, and incline supernatant liquor, after being dried in vacuo at 60 DEG C, grinds up to nanometer Fe_3O_4；
(3) nanometer PEI- Fe is prepared3O420mL4g/L polyethyleneimine (PEI) is added in 0.37g nanometer Fe_3O_4 by particle
In solution, in frequency 2450MHz, power 800W heated under microwave conditions 120min, separated after reaction with additional magnet, so
Sediment fraction is washed with deionized to neutrality afterwards, is freeze-dried to obtain nanometer PEI- Fe3O4 particle；
(4) nanometer Fe is prepared3O4@Pt takes 2mL PEI-Fe3O4 solution that 10mL Pt nano particle seed solution is added, with ultrasound
Wave washs after instrument dispersion 1min (frequency 80KHz), carries out Magnetic Isolation.Disperse sediment fraction in 20mL water, then plus
Enter 110mL 0.1mol/L NaOH aqueous solution, and 0.5mL1%H2PtCl5 aqueous solution and 0.75mL 0.2mol/L is gradually added dropwise
NH2OH-HCl aqueous solution, nanometer Fe_3O_4@Pt finally separating obtained using externally-applied magnetic field；
(5) fluorescence magnetic platinum nanometer egg is prepared, 0.05g nanometer Fe_3O_4@Pt is weighed and is scattered in the deionized water of 2m1,
Take upper solution after ultrasonic dissolution, separated under magnetic field, spent after separation it is secondary from water washing magnetic nano-particle, then, be added
The 1.0mg.mL-1 phycoerythrin PE of 50 μ L and 950 μ L10mmol/L PBS, and the pH of the PBS is 7. 4, in 37 DEG C after shaking up
12h is reacted, after Magnetic Isolation, with 10mmol/LPBS solution, and the pH of the PBS solution is 7. 4, and washing nanoparticle is secondary,
It obtains having both the magnetic fluorescence magnetic platinum nanometer egg with fluorescence property.
Embodiment 4
A method of showing outmoded Sweat latent fingerprint using fluorescence magnetic noble metal nano egg reagent, comprising the following steps:
S1, noble metal nano egg show the preparation of reagent；
After S2, volunteer will hand-wash net dry, the stamp Sweat latent fingerprint on glass obtains finger mark sample, finger mark sample pendulum
Put that spacing is moderate, to imitate the outmoded Sweat latent fingerprint left on criminal-scene, this experiment finger mark sample is stored under field conditions (factors)
In clean pallet, resting period 30d；
S3, the gold nanoclusters obtained by rubber head dropper aspiration step S1 show reagent, keep it suitable along finger mark mastoid process streakline
Hour hands drop is aobvious, and sufficiently reacts 1h with finger mark substance；
S4, the Sweat latent fingerprint loose colour after step S3 drop is shown is washed away with ultrapure water；
S5, it step S4 is washed away to the Sweat latent fingerprint after loose colour dries 0.5h under the conditions of vacuum, 37 DEG C in baking oven machine；
S6, it is built using alternative light source, colour light filter mirror, digital single-lens reflex camera and shows that observing system is latent to fluorescence sweat to be referred to
Print carries out observation fixation, under dark condition, alternative light source is irradiated to the Sweat latent fingerprint shown by gold nanoclusters, finger mark generates
Fluorescence recorded by digital single-lens reflex camera through colour light filter mirror, finger mark mastoid process streakline and its minutia are fixed up.
The above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferred embodiment to this hair
It is bright to be described in detail, those skilled in the art should understand that, it can modify to technical solution of the present invention
Or equivalent replacement should all cover without departing from the objective and range of technical solution of the present invention in claim of the invention
In range.
Claims (10)
1. a kind of fluorescence magnetic noble metal nano egg, which is characterized in that the fluorescence magnetic noble metal nano egg is fluorescence magnetic
Any one in gold nano egg, fluorescence magnetic silver nanoparticle egg and fluorescence magnetic platinum nanometer egg；The fluorescence magnetic noble metal is received
Rice egg is the nanometer PEI- Fe that surface is coated with fluorescence phycoerythrin3O4The combination of particle and nano noble metal particles；It is described
Nanometer PEI- Fe3O4Particle refers to the Nanometer Magnetite particle amine-modified by polyethyleneimine.
2. a kind of fluorescence magnetic noble metal nano egg preparation method, which is characterized in that the fluorescence magnetic noble metal nano egg is
Any one in fluorescence magnetic gold nano egg, fluorescence magnetic silver nanoparticle egg and fluorescence magnetic platinum nanometer egg；Using Electrostatic Absorption
It acts on nanometer PEI- Fe3O4Particle is in conjunction with the nano noble metal particles in nano-noble metal solution；Again by fluorescence algae red egg
It is white to be coated on PEI- Fe3O4The combination surface of particle and nano-noble metal forms fluorescence magnetic noble metal nano egg；It is described to receive
Rice PEI- Fe3O4Particle refers to the Nanometer Magnetite particle modified by polyethyleneimine PEI.
3. fluorescence magnetic noble metal nano egg preparation method according to claim 2, which is characterized in that the nanometer PEI-
Fe3O4Particle refers to the Nanometer Magnetite particle modified by polyethyleneimine PEI, comprising the following steps:
Prepare nanometer Fe3O4, by 3mol divalent iron salt FeSO4·7H2O and 6mol trivalent iron salt FeCl3·6H2O is dissolved in 250mL steaming
It in distilled water and adds it in 500mL three-necked flask, ammonia spirit, which is added in reaction system, under nitrogen atmosphere protection makes
PH >=10 of system, are vigorously stirred, constant temperature water bath；Reaction was completed after stirring 30min, is washed with distilled water until neutrality, inclines
Supernatant liquor after being dried in vacuo at 60 DEG C, grinds up to nanometer Fe3O4；
Prepare nanometer PEI- Fe3O4Particle, by 0.37g nanometer Fe3O4It is added in 20mL, 4g/L polyethyleneimine PEI solution,
Frequency 2450MHz, power 800W heated under microwave conditions 120min, are separated after reaction with externally-applied magnetic field, then will precipitating
Part is washed with deionized to neutrality, and freeze-drying obtains aoxidizing by the nano-magnetic four that polyethyleneimine PEI is modified
Three iron particles.
4. fluorescence magnetic noble metal nano egg preparation method according to claim 2, which is characterized in that the nano-noble metal
Solution is any one in nanometer Au solution, nanometer Ag solution and Pt nano particle solution；
The preparation of the nano-noble metal solution, comprising:
Nanometer Au solution is prepared, by the HAuCl of 100mL, 0.0206mol/L4The citric acid three of solution and 25mL, 0.0025mol/L
It is put into Ultrasound Instrument after sodium solution mixing and vibrates 30min, then in power 700W, 250 °C of heated under microwave conditions 1min of temperature,
Solution is cooled to room temperature after reaction, is settled to 100mL with ultrapure water, obtains the nanometer Au that concentration is 0.0206mol/L
Solution simultaneously saves in 4 °C of refrigerator；
Nanometer Ag solution is prepared, by the citric acid of the silver nitrate solution of 100mL, 0.0103mol/L and 25mL, 0.0025mol/L
It is put into Ultrasound Instrument after the mixing of three sodium solutions and vibrates 30min, then in power 700W, 245 °C of heated under microwave conditions of temperature
Solution is cooled to room temperature by 5min after reaction, is settled to 100ml with ultrapure water, and obtaining concentration is receiving for 0.0103mol/L
Rice Ag solution simultaneously saves in 4 °C of refrigerator；
Pt nano particle solution is prepared, the addition 2.5mL ethylene glycol into beaker, 13 mL, 10g/50mL platinum acid chloride solutions, 0.4mL,
It is put into supersonic oscillations instrument after 0.04mol/LKOH solution and vibrates 30min, then microwave heating 30S, microwave power 700W,
245 DEG C of temperature, solution is cooled to room temperature after reaction, is settled to 100mL with ultrapure water, obtaining concentration is
The Pt nano particle solution of 0.4746mol/L simultaneously saves in 4 DEG C of refrigerator.
5. fluorescence magnetic noble metal nano egg preparation method according to claim 2, which is characterized in that described to be inhaled using electrostatic
It is attached to act on nanometer PEI- Fe3O4Particle is in conjunction with the nano noble metal particles in nano-noble metal solution；Include:
Prepare nanometer Fe3O4@Au, by 2mL PEI- Fe3O410mL nanometers of Au seed solutions are added in aqueous solution, with Ultrasound Instrument frequency
Magnetic Isolation is carried out after dispersing 3min for 80KHz, disperses sediment fraction in 20mL water, 110mL, 0.1mol/L is then added
NaOH solution, and gradually be added dropwise 0.5mL, 1%HAuCl4The NH of solution and 0.75mL, 0.2mol/L2OH-HCl solution, last benefit
With the separating obtained nanometer Fe of externally-applied magnetic field3O4@Au；
Prepare nanometer Fe3O4@Ag takes 2mL PEI-Fe3O4 aqueous solution that 10mL nanometer Ag seed solution is added, with Ultrasound Instrument frequency
Magnetic Isolation is carried out after dispersing 2min for 80KHz, disperses sediment fraction in 20mL water, 110mL, 0.1mol/L is then added
NaOH solution, and gradually be added dropwise 0.35mL, 0.1552moL/L AgNO3The NH of solution and 0.75mL, 0.2mol/L2OH-HCl
Solution, nanometer Fe finally separating obtained using externally-applied magnetic field3O4@Ag；
Prepare nanometer Fe3O4@Pt takes 2mL PEI- Fe3O410mL Pt nano particle seed solution is added in solution, is with Ultrasound Instrument frequency
Magnetic Isolation is carried out after 80KHz dispersion 1min, disperses sediment fraction in 20mL water, 110mL, 0.1mol/L is then added
NaOH aqueous solution, and 0.5mL, 1%H is gradually added dropwise2PtCl5The NH of aqueous solution and 0.75mL, 0.2mol/L2OH-HCl aqueous solution,
Nanometer Fe finally separating obtained using externally-applied magnetic field3O4@Pt。
6. fluorescence magnetic noble metal nano egg preparation method according to claim 2, which is characterized in that described by fluorescence algae red
Albumen is coated on PEI- Fe3O4The combination surface of particle and nano-noble metal forms fluorescence magnetic noble metal nano egg system,
Include:
Fluorescence magnetic gold nano egg is prepared, 0.06g nanometer Fe is weighed3O4@Au is scattered in the deionized water of 2m1, after ultrasonic dissolution
Take upper solution, separated under magnetic field, spent after separation it is secondary from water washing magnetic nano-particle, then, be added 50 μ L, 1.0mg/
The phycoerythrin PE of the mL and PBS of 950 μ L, 10mmol/L, and the pH of the PBS is 7.4, in 37 DEG C of reaction 12h, magnetic after shaking up
Property separation after, with the PBS solution of 10mmol/L, and the pH of the PBS solution is 7.4, and washing nanoparticle is secondary, obtains having both magnetic
The fluorescence magnetic gold nano egg reagent of property and fluorescence property；
Fluorescence magnetic silver nanoparticle egg is prepared, 0.04g nanometer Fe is weighed3O4@Ag is scattered in the deionized water of 2m1, after ultrasonic dissolution
Take upper solution, separated under magnetic field, spent after separation it is secondary from water washing magnetic nano-particle, then, be added 50 μ L, 1.0mg/
The phycoerythrin PE of the mL and PBS of 950 μ L, 10mmol/L, and the pH of the PBS is 7. 4, in 37 DEG C of reaction 12h, magnetic after shaking up
Property separation after, with the PBS solution of 10mmol/L, and the pH of the PBS solution is 7. 4, and washing nanoparticle is secondary, is had both
The magnetic fluorescence magnetic silver nanoparticle egg reagent with fluorescence property；
Fluorescence magnetic platinum nanometer egg is prepared, 0.05g nanometer Fe is weighed3O4@Pt is scattered in the deionized water of 2m1, ultrasonic dissolution
After take upper solution, separated under magnetic field, spent after separation it is secondary from water washing magnetic nano-particle, then, be added 50 μ L,
The phycoerythrin PE of the 1.0mg/mL and PBS of 950 μ L, 10mmol/L, and the pH of the PBS is 7. 4, is reacted after shaking up in 37 DEG C
12h, after Magnetic Isolation, with the PBS solution of 10mmol/L, and the pH of the PBS solution is 7. 4, and washing nanoparticle is secondary, obtains
To the fluorescence magnetic platinum nanometer egg reagent for having both magnetic and fluorescence property.
7. a kind of fluorescence magnetic noble metal nano egg reagent shows the method for outmoded Sweat latent fingerprint, which is characterized in that use right
It is required that the 1 fluorescence magnetic noble metal nano egg shows outmoded Sweat latent fingerprint, or using any one of claim 2 to 6
The fluorescence magnetic noble metal nano egg of the preparation method preparation shows outmoded Sweat latent fingerprint, comprising the following steps:
S1, configuration Sweat latent fingerprint show reagent, and it is fluorescence magnetic noble metal nano egg, the expensive gold of fluorescence magnetic that this, which shows reagent,
Category nanometer egg is any one in fluorescence magnetic gold nano egg, fluorescence magnetic silver nanoparticle egg and fluorescence magnetic platinum nanometer egg；Institute
Stating fluorescence magnetic noble metal nano egg is the nanometer PEI- Fe that surface is coated with fluorescence phycoerythrin3O4Particle and nano-noble metal
The combination of particle；The nanometer PEI- Fe3O4Particle refers to the Nanometer Magnetite amine-modified by polyethyleneimine
Particle；
After S2, volunteer will hand-wash net dry, the stamp Sweat latent fingerprint on glass, plastics, preservative film, metal object is referred to
Pull sheet；
S3, Sweat latent fingerprint made from the aobvious step S2 of reagent drop will be shown made from step S1, reacted 10 minutes；
S4, the Sweat latent fingerprint loose colour after step S3 drop is shown is washed away using ultrapure water；
S5, step S4 is washed away to the Sweat latent fingerprint drying after loose colour；
S6, the Sweat latent fingerprint image in the case where showing observing system, after observation fixing step S5 drying.
8. the method according to claim 7 for showing outmoded Sweat latent fingerprint, which is characterized in that the finger mark sample of the step S2
This resting period is 7-30 days.
9. the method according to claim 7 for showing outmoded Sweat latent fingerprint, which is characterized in that the step S3 is to use rubber head
Noble-metal nanoclusters obtained by dropper aspiration step S1 show reagent, drip it clockwise along finger mark mastoid process streakline aobvious, and with
Finger mark substance sufficiently reacts 2h.
10. the method according to any one of claims 7 to 9 for showing outmoded Sweat latent fingerprint, which is characterized in that the step
Showing observing system in rapid S6 is to show observing system using what alternative light source, colour light filter mirror, digital single-lens reflex camera were built.
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