CN105907389B - Noble-metal nanoclusters show the preparation of reagent and show the method for Sweat latent fingerprint - Google Patents

Noble-metal nanoclusters show the preparation of reagent and show the method for Sweat latent fingerprint Download PDF

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CN105907389B
CN105907389B CN201610283026.0A CN201610283026A CN105907389B CN 105907389 B CN105907389 B CN 105907389B CN 201610283026 A CN201610283026 A CN 201610283026A CN 105907389 B CN105907389 B CN 105907389B
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CN105907389A (en
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黄锐
陈虹宇
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Southwest University Of Political Science And Law
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Abstract

The present invention proposes that a kind of noble-metal nanoclusters show the preparation of reagent and show the method for Sweat latent fingerprint.Noble-metal nanoclusters are any one in gold nanoclusters, silver nanoclusters, electrum nano-cluster and platinum noble metals nano-cluster in the present invention;And the noble-metal nanoclusters show reagent and cooperate with preparation method to prepare by ultrasonic-microwave.Show the method for outmoded Sweat latent fingerprint, including prepared by reagent, restrain finger mark, drips aobvious finger mark, washes away loose colour, 6 steps are fixed in finger mark drying and finger mark observation.The present invention covers four kinds of metal nanometre clusters and shows the preparation of reagent and its show the method for outmoded finger mark, and gold, silver, electrum, the platinum fluorescence noble-metal nanoclusters fluorescence quantum yield of preparation are high, and fluorescence duration time is grown, and has hypotoxicity;Finger mark shows operation rapidly and efficiently, can clearly show the outmoded finger mark of 30 days, and effect shows the process for show of reagent better than tradition.

Description

Noble-metal nanoclusters show the preparation of reagent and show the method for Sweat latent fingerprint
Technical field
The invention belongs to public security criminal technique finger mark to identify field, and in particular to a kind of noble-metal nanoclusters show reagent The method for preparing and showing Sweat latent fingerprint.
Background technology
Noble-metal nanoclusters refer to be made up of several to dozens of precious metal atoms as a kind of new luminescent material Particle diameter in 2nm or so cluster, there is relatively stable fluorescence property, high-biocompatibility, hypotoxicity, last decade Come, the photoluminescent property of noble-metal nanoclusters is mainly used in fluorescence probe detection metal ion, live cell fluorescent imaging, fluorescence biography Sensor etc..But the research in science and technology concerning criminal matters field rarely has document report with application, is still at the initial stage.
Fingerprint have people it is variant, it is constant throughout one's life, touch thing trace characteristic, the U.S. for having " human body identity card " and " king of evidence " Claim, to disclosing, confirming that crime and identification criminal have considerable effect.It is distributed with the mastoid process decorative pattern of people's both hands finger finger Pore, the sweat of pore secretion often contain grease and other small materials.Therefore the Sweat latent fingerprint composition being retained on object Include the organic matters such as a small amount of water, a small amount of inorganic matter, protein, grease.
Upper century-old history, traditional process for show have 502 smoked aobvious methods, ninhydrin method, DFO methods to finger mark appearing technique Deng.With the rapid development of nanometer technology, novel nano-material shows the concern for causing researcher applied to latent, There is the methods of showing finger mark using metal, up-conversion luminescence, magnetic Nano material.
Traditional fluorescent material, such as organic dyestuff, fluorescin, there is cost of manufacture height, high toxicity, fluorescence duration time It is short and the shortcomings of outmoded finger mark can not be shown.At present, noble-metal nanoclusters synthesis uses traditional heating method and is incubated method, such as Ying seminars are that protective agent and stabilizer are prepared for the Jenner that fluorescence quantum efficiency is 6% using BSA under the conditions of 12h is incubated Rice cluster, but the method time loss is long, power consumption is larger, reaction speed is slow, particle diameter is larger, it is low to prepare product property, in real work In be difficult to be promoted.
The application for showing aspect in latent of gold nanoclusters:Bovine serum albumin(BSA) guarantor is made in patent 201310364617.7 The red fluorescence gold nanoclusters of shield, it is applied to the mark of latent fingerprint on PVDF membrane and adhesive tape substrate and shows It is existing, but the research is shown only for latent on semi-permeable object, and application is small.Patent 201210443554.X is made The fluorescence gold nanoclusters of glutathione functionalization, and be applied to silicon chip, Sweat latent fingerprint, blood finger mark show on glass, widen The application that finger mark shows.Above-mentioned two research incubates heating means in preparation process using tradition, takes longer (12h- 72h), it is cumbersome, do not possess the advantages of green high-efficient, combined coefficient is relatively low, and does not explore and show outmoded effect.
From the foregoing, it will be observed that in existing finger mark appearing technique, there is cost of manufacture height, high toxicity, fluorescence for conventional fluorescent material Duration is short and the shortcomings of can not showing outmoded finger mark;Gold nanoclusters there is time-consuming longer (12h-72h), cumbersome, The problems such as combined coefficient is relatively low.
The content of the invention
To solve above mentioned problem present in existing finger mark appearing technique, the present invention proposes that a kind of noble-metal nanoclusters show The preparation of reagent and the method for showing Sweat latent fingerprint.
A kind of noble-metal nanoclusters of the present invention show the preparation method of reagent, it is characterised in that the noble-metal nanoclusters For any one in gold nanoclusters, silver nanoclusters, electrum nano-cluster and platinum noble metals nano-cluster;And the noble metal is received Rice cluster shows reagent and prepared by ultrasound-microwave cooperating preparation method.
Further, the noble-metal nanoclusters show reagent and prepared by ultrasound-microwave cooperating preparation method, including,
The method that gold nanoclusters show reagent is prepared, is comprised the following steps:
(1) solution is prepared, and gold chloride is dissolved in into the solution that pure water is configured to 0.01 mol/L;Bovine serum albumin(BSA) is at 37 DEG C Under the conditions of be dissolved in pure water and be configured to 50 mg/mL solution;Potassium hydroxide is dissolved in pure water and is configured to 1 mol/L solution;
(2) hybrid reaction, it is by volume 1:1, chlorauric acid solution is added into bovine serum albumin solution, will be mixed molten Liquid reacts 3min in the presence of magnetic stirring apparatus;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise into the chlorauric acid solution and bovine serum albumin obtained by step (2) In the mixed liquor of white solution, regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40 ~ 60s of microwave radiation, made Obtain gold nanoclusters and show reagent;
The method that silver nanoclusters show reagent is prepared, is comprised the following steps:
(1) solution is prepared, and silver nitrate is dissolved in into the solution that pure water is configured to 0.01 mol/L;Bovine serum albumin(BSA) is at 37 DEG C Under the conditions of be dissolved in pure water and be configured to 50 mg/mL solution;Potassium hydroxide is dissolved in pure water and is configured to 1 mol/L solution;
(2) hybrid reaction, it is by volume 1:1, silver nitrate solution is added into bovine serum albumin solution, will be mixed molten Liquid reacts 3min in the presence of magnetic stirring apparatus;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise into silver nitrate solution obtained by step (2) and ox blood is pure In the mixed liquor of protein solution, regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40 ~ 60s of microwave radiation, made Obtain silver nanoclusters and show reagent;
The method that gold and silver nano-cluster shows reagent is prepared, is comprised the following steps:
(1) solution is prepared, and gold chloride is dissolved in into the solution that pure water is configured to 0.01 mol/L;Silver nitrate is dissolved in pure water and matched somebody with somebody It is set to 0.01 mol/L solution;Bovine serum albumin(BSA) is dissolved in pure water under the conditions of 37 DEG C and is configured to 50 mg/mL solution;By hydrogen Potassium oxide is dissolved in pure water and is configured to 1 mol/L solution;
(2) hybrid reaction, it is by volume 1:1:2, chlorauric acid solution, silver nitrate solution are added into bovine serum albumin(BSA) Solution, mixed solution is reacted into 3min in the presence of magnetic stirring apparatus;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise in the mixed liquor obtained by step (2), and regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40 ~ 60s of microwave radiation, made Obtain silver nanoclusters and show reagent;
The method that platinum cluster shows reagent is prepared, is comprised the following steps:
(1) solution is prepared, and chloroplatinic acid is dissolved in into the solution that pure water is configured to 0.01 mol/L;Bovine serum albumin(BSA) is 37 Pure water is dissolved under the conditions of DEG C and is configured to 50 mg/mL solution;Potassium hydroxide is dissolved in pure water and is configured to 1 mol/L solution;
(2) hybrid reaction, it is by volume 1:1, platinum acid chloride solution is added into bovine serum albumin solution, will be mixed molten Liquid reacts 3min in the presence of magnetic stirring apparatus;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise into platinum acid chloride solution obtained by step (2) and ox blood is pure In the mixed liquor of protein solution, regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40 ~ 60s of microwave radiation, made Obtain silver nanoclusters and show reagent.
Present invention additionally comprises showing the method that reagent shows outmoded Sweat latent fingerprint using above-mentioned noble-metal nanoclusters, including with Lower step:
Prepared by S1, reagent, prepare noble-metal nanoclusters and show reagent;
S2, finger mark is restrained, after volunteer will hand-wash net dry, the stamp sweat on glass, plastics, preservative film, metal object Latent, obtain finger mark sample.
The aobvious finger mark of S3, drop, Sweat latent fingerprint made from the aobvious step S2 of reagent drop, reaction 1- will be shown made from step S1 3h;
S4, loose colour is washed away, the Sweat latent fingerprint loose colour after step S3 drops show is washed away using ultra-pure water;
S5, finger mark drying, step S4 are washed away the drying of the Sweat latent fingerprint after loose colour;
S6, finger mark observation are fixed, in the case where showing observing system, the Sweat latent fingerprint image after the S5 drying of observation fixing step;
Characterized in that, the noble-metal nanoclusters are gold nanoclusters, silver nanoclusters, electrum nano-cluster and the expensive gold of platinum Belong to any one in nano-cluster.
Further, in the step S1 prepared by reagent, including,
The method that gold nanoclusters show reagent is prepared, is comprised the following steps:
(1) solution is prepared, and gold chloride is dissolved in into the solution that pure water is configured to 0.01 mol/L;Bovine serum albumin(BSA) is 37 Pure water is dissolved under the conditions of DEG C and is configured to 50 mg/mL solution;Potassium hydroxide is dissolved in pure water and is configured to 1 mol/L solution;
(2) hybrid reaction, it is by volume 1:1, chlorauric acid solution is added into bovine serum albumin solution, will be mixed molten Liquid reacts 3min in the presence of magnetic stirring apparatus;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise into chlorauric acid solution obtained by step (2) and ox blood is pure In the mixed liquor of protein solution, regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40 ~ 60s of microwave radiation, made Obtain gold nanoclusters and show reagent;
The method that silver nanoclusters show reagent is prepared, is comprised the following steps:
(1) solution is prepared, and silver nitrate is dissolved in into the solution that pure water is configured to 0.01 mol/L;Bovine serum albumin(BSA) is 37 Pure water is dissolved under the conditions of DEG C and is configured to 50 mg/mL solution;Potassium hydroxide is dissolved in pure water and is configured to 1 mol/L solution;
(2) hybrid reaction, it is by volume 1:1, silver nitrate solution is added into bovine serum albumin solution, will be mixed molten Liquid reacts 3min in the presence of magnetic stirring apparatus;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise into silver nitrate solution obtained by step (2) and ox blood is pure In the mixed liquor of protein solution, regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40 ~ 60s of microwave radiation, made Obtain silver nanoclusters and show reagent;
The method that gold and silver nano-cluster shows reagent is prepared, is comprised the following steps:
(1) solution is prepared, and gold chloride is dissolved in into the solution that pure water is configured to 0.01 mol/L;Silver nitrate is dissolved in pure water and matched somebody with somebody It is set to 0.01 mol/L solution;Bovine serum albumin(BSA) is dissolved in pure water under the conditions of 37 DEG C and is configured to 50 mg/mL solution;By hydrogen Potassium oxide is dissolved in pure water and is configured to 1 mol/L solution;
(2) hybrid reaction, it is by volume 1:1:2, chlorauric acid solution, silver nitrate solution are added into bovine serum albumin(BSA) Solution, mixed solution is reacted into 3min in the presence of magnetic stirring apparatus;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise in the mixed liquor obtained by step (2), and regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40 ~ 60s of microwave radiation, made Obtain silver nanoclusters and show reagent;
The method that platinum cluster shows reagent is prepared, is comprised the following steps:
(1) solution is prepared, and chloroplatinic acid is dissolved in into the solution that pure water is configured to 0.01 mol/L;Bovine serum albumin(BSA) is 37 Pure water is dissolved under the conditions of DEG C and is configured to 50 mg/mL solution;Potassium hydroxide is dissolved in pure water and is configured to 1 mol/L solution;
(2) hybrid reaction, it is by volume 1:1, platinum acid chloride solution is added into bovine serum albumin solution, will be mixed molten Liquid reacts 3min in the presence of magnetic stirring apparatus;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise into platinum acid chloride solution obtained by step (2) and ox blood is pure In the mixed liquor of protein solution, regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40 ~ 60s of microwave radiation, made Obtain silver nanoclusters and show reagent.
Further, the step S2 restrains finger mark, including, the resting period of the finger mark sample of acquisition is 7-30 days.
Further, the step S3 drops show finger mark, including, received with the noble metal obtained by rubber head dropper aspiration step S1 Rice cluster shows reagent, and making it, drop is aobvious clockwise along finger mark mastoid process streakline, and fully reacts 2h with finger mark material.
Further, step S5 finger marks drying, including, in baking oven machine vacuum, dry under the conditions of 37 DEG C.
Further, the step S6 finger marks observation, including, show observing system to utilize alternative light source, coloured filter What light microscopic, digital single-lens reflex camera were built shows observing system.
Fermi wavelength of the present invention using noble-metal nanoclusters size closer to metal electron, itself and protein, amino acid In sulfydryl combine, there is the characteristics of good fluorescent characteristic, and by ultrasound and microwave cooperating effect, prepare gold, silver, gold and silver Alloy, platinum fluorescence metal nano-cluster show reagent, can fast and efficiently show outmoded finger mark.
The present invention has following advantageous effects:
1. the present invention covers four kinds of metal nanometre clusters and shows the preparation of reagent and its show the method for outmoded finger mark, this shows Tube- nursery is compared to quick (about 1h or so) prepared by the method for other patent reports;
2. the gold, silver prepared, electrum, platinum fluorescence noble-metal nanoclusters fluorescence quantum yield are high, and during phosphor persistence Between it is long, there is hypotoxicity;
3. finger mark shows operation rapidly and efficiently, it can clearly show the outmoded finger mark of 30 days;
4. the effect that four kinds of noble-metal nanoclusters prepared by the present invention show outmoded finger mark, which is superior to tradition, shows reagent Show effect;
5. finger mark, which shows observing system, can preferably fix finger mark information, be advantageous to test sensitivity.
Brief description of the drawings
Fig. 1 is gold nanoclusters, silver nanoclusters, electrum nano-cluster and platinum cluster composition principle figure.
Fig. 2 is hydro-thermal method, ultrasonic method, microwave method and ultrasound-microwave cooperating method to gold nanoclusters fluorescence intensity and average grain The influence schematic diagram in footpath.
Fig. 3 is gold nanoclusters, silver nanoclusters, electrum nano-cluster, platinum cluster fluorescence color figure.
Fig. 4 is gold nanoclusters, silver nanoclusters, electrum nano-cluster, platinum cluster ultraviolet spectrogram.
Fig. 5 is gold nanoclusters, silver nanoclusters, electrum nano-cluster, platinum cluster transmission electron microscope picture.
Fig. 6 is gold nanoclusters, silver nanoclusters, electrum nano-cluster, the infrared spectrogram of platinum cluster.
Fig. 7 is that finger mark shows observing system and shows principle schematic.
Fig. 8 is gold nanoclusters, silver nanoclusters, electrum nano-cluster, platinum cluster show outmoded finger mark in glass object Figure.
Fig. 9 is that the present invention shows preparation method of reagent thereof flow chart.
Figure 10 is that the present invention shows outmoded Sweat latent fingerprint method flow diagram.
Embodiment
Accompanying drawing 1 is gold nanoclusters, silver nanoclusters, electrum nano-cluster, platinum cluster composition principle figure, bovine serum albumin It is complicated containing the amino acid such as tyrosine, cysteine, molecular structure in vain.Stable structure can be formed with gold, silver, pt atom.Adopt It is nano-cluster Stability Analysis of Structures prepared by stabilizer reducing agent with bovine serum albumin(BSA).
Fig. 2 is hydro-thermal method, ultrasonic method, microwave method and ultrasound-microwave cooperating method to gold nanoclusters fluorescence intensity and average grain The influence schematic diagram in footpath.Obviously, the nanocluster fluorescence intensity that prepared by ultrasound-microwave cooperating heating is substantially better than with particle size Other preparation methods;Nanocluster size prepared by microwave method is smaller, and this makes solution thermally equivalent relevant with microwave heating;Ultrasonic method The particle diameter of preparation is more bigger than microwave method, but fluorescence property is excellent;Nano-cluster performance prepared by traditional heating method is worst.It is super By ultrasonic method, each advantage is combined sound-microwave cooperating heating with microwave method, the characteristics of having fully demonstrated efficient green.Its is efficient Property be embodied in and can not only reduce particle diameter, dispersion effect and fluorescence property enhancing, moreover it is possible to substantially reduce the reaction time, instead Efficiency is answered to improve;Its green is embodied in BSA bioactivity in building-up process and not changed, whole course of reaction safety, Reaction time, which reduces, causes power consumption to reduce, while reduces the amount of reagent of preparation same amount nano-cluster needs.
Fig. 3 is gold nanoclusters, silver nanoclusters, electrum nano-cluster, platinum cluster fluorescence color figure(Abcd is followed successively by gold Nano-cluster, silver nanoclusters, electrum nano-cluster, platinum cluster).It can be seen that gold nanoclusters irradiate in alternative light source Under send fluorescent red-orange;Silver nanoclusters send fluorescent orange under alternative light source irradiation;Electrum nano-cluster is in more ripples Yellow fluorescence is sent under Duan Guangyuan irradiations;Platinum cluster sends blue-green fluorescent under alternative light source irradiation.Noble metal nano The fluorescence intensity of cluster is strong.
Fig. 4 is gold nanoclusters, silver nanoclusters, electrum nano-cluster, platinum cluster ultraviolet spectrogram(Abcd is followed successively by gold Nano-cluster, silver nanoclusters, electrum nano-cluster, platinum cluster).It is expensive as we know from the figure under 280 nm or so ultraviolet radioactive Metal nanometre cluster has a stronger ultraviolet absorption peak, and tryptophan and tyrosine residue UV absorption in bovine serum albumin(BSA) Peak also is located at 280 nm or so.Bovine serum albumin(BSA), which is wrapped in outside precious metal atom, plays protection stabilization, therefore nano-cluster Ultraviolet spectra property it is close with bovine serum albumin(BSA), this explanation ultrasound-microwave heating coordination technique prepares nano-cluster and not destroyed The bioactivity of bovine serum albumin(BSA).
Fig. 5 is gold nanoclusters, silver nanoclusters, electrum nano-cluster, platinum cluster transmission electron microscope picture.(Abcd is followed successively by Gold nanoclusters, silver nanoclusters, electrum nano-cluster, platinum cluster).Find that nano-cluster dispersing uniformity is good as we know from the figure, Its average particle size it is small about 3-5nm. this compared with particle diameter that Du Juan in 2013 is reported is 13.3 nm Conventional nano particle, chi It is very little to be much smaller than nano-particle.Therefore nano-cluster is bigger compared to nano-particle energy level discontinuity, and the ability of transition occurs for electronics Stronger, caused fluorescence is stronger.
Fig. 6 is gold nanoclusters, silver nanoclusters, electrum nano-cluster, the infrared spectrogram of platinum cluster(Abcd is followed successively by Gold nanoclusters, silver nanoclusters, electrum nano-cluster, platinum cluster).It can be seen that the characteristic absorption peak of these three solution Significant change does not occur, but sulfydryl characteristic absorption peak of the nano-cluster at 2300 cm-1 or so place disappears, and illustrates to pass through Ultrasonic Heating Reaction bovine serum albumin(BSA) molecule has successfully been modified to the surface of nano-cluster.And the characteristic absorption peak of bovine serum albumin(BSA) itself Do not changed significantly after before the reaction, illustrate that the conformation of protein changes without obvious.
Fig. 7 is that finger mark shows observing system and shows principle schematic.Utilize alternative light source, colour light filter mirror, number Slr camera, which is independently built, to be shown observing system and carries out observation fixation to Sweat latent fingerprint., will as we know from the figure under dark condition The Sweat latent fingerprint that alternative light source irradiation stamp is shown by gold nanoclusters powder, fluorescent red-orange caused by finger mark pass through coloured filter Light microscopic is recorded by digital single-lens reflex camera, and finger mark mastoid process streakline and its minutia are fixed up.Its of finger mark feature is not reflected He can not pass through colour light filter mirror so that can not be by cameras record by veiling glare.Finger mark shows that effect is good, can examine the one-level for seeing finger mark, two Level even three-level feature.
Fig. 8 is gold nanoclusters, silver nanoclusters, electrum nano-cluster, platinum cluster show outmoded finger mark in glass object Figure.From in figure, the effect that noble-metal nanoclusters show outmoded finger mark is good, show reagent better than traditional powder.Wherein platinum nanometer Cluster shows best results, and finger mark mastoid process streakline is smooth, and the minutia such as spillikin, dot protrudes.Electrum nano-cluster, Yin Na The effect that shows of rice cluster is taken second place, and it is slightly worse that gold nanoclusters show effect.
Embodiment 1
A kind of noble-metal nanoclusters of the present invention show the preparation method of reagent, comprise the following steps:1% gold chloride is molten 0.01 mol/L solution is configured in pure water;Bovine serum albumin(BSA) is dissolved in pure water under the conditions of 37 DEG C and is configured to 50 mg/mL Solution;Potassium hydroxide is dissolved in pure water and is configured to 1 mol/L solution;By the good chlorauric acid solution of above-mentioned configuration, bovine serum albumin White solution by volume 1:1 mixing, is placed under magnetic stirring apparatus and reacts 3min;Slowly potassium hydroxide solution is added dropwise with transfusion needle Into the mixed liquor of chlorauric acid solution and bovine serum albumin solution described in this step, regulation pH is 12, now used 0.01 Mol/L chlorauric acid solution, 50 mg/mL bovine serum albumin solution, 1 mol/L potassium hydroxide solution volume ratio are 10: 10:1;The mixed solution that pH is 12 is first placed in ultrasonic 1h in ultrasonic washing instrument;It is placed in again in household microwave oven, setting is high (800W) microwave radiation 50s under the conditions of fire, obtained gold nanoclusters show reagent.
Embodiment 2
A kind of noble-metal nanoclusters of the present invention show the preparation method of reagent, comprise the following steps:1% silver nitrate is molten 0.01 mol/L solution is configured in pure water;Bovine serum albumin(BSA) is dissolved in pure water under the conditions of 37 DEG C and is configured to solution;Will Potassium hydroxide is dissolved in pure water and is configured to 1 mol/L solution;The good silver nitrate solution of above-mentioned configuration, bovine serum albumin solution are pressed Volume ratio 1:1 mixing, is placed under magnetic stirring apparatus and reacts 3min;Potassium hydroxide solution is slowly added drop-wise to this step with transfusion needle In the mixed liquor of the silver nitrate solution and bovine serum albumin solution, regulation pH is 12,0.01 mol/L's now used Silver nitrate solution, 50 mg/mL bovine serum albumin solution, 1 mol/L potassium hydroxide solution volume ratio are 10:10:1;Will The mixed solution that pH is 12 is first placed in ultrasonic 1h in ultrasonic washing instrument;It is placed in again in household microwave oven, under the conditions of the high fire of setting (800W) microwave radiation 60s, obtained silver nanoclusters show reagent.
Embodiment 3
A kind of noble-metal nanoclusters of the present invention show the preparation method of reagent, comprise the following steps:1% gold chloride is molten 0.01 mol/L solution is configured in pure water;1% silver nitrate is dissolved in the solution that pure water is configured to 0.01 mol/L;By ox Seralbumin is dissolved in pure water under the conditions of 37 DEG C and is configured to solution;Potassium hydroxide is dissolved in pure water and is configured to 1 mol/L solution; By the good chlorauric acid solution of above-mentioned configuration, silver nitrate solution, bovine serum albumin solution by volume 1:1:2 mixing, are placed in magnetic 3min is reacted under power agitator;Slowly potassium hydroxide solution is added drop-wise in above-mentioned mixed liquor with transfusion needle, regulation pH is 12, this Shi Suoyong 0.01 mol/L chlorauric acid solution, 0.01 mol/L silver nitrate solution, 50 mg/mL bovine serum albumin(BSA) Solution, 1 mol/L potassium hydroxide solution volume ratio are 5:5:10:1;The mixed solution that pH is 12 is first placed in ultrasonic washing Ultrasonic 1h in instrument;It is placed in again in household microwave oven, sets (800W) microwave radiation 40s under the conditions of high fire, gold and silver nano-cluster is made Show reagent.
Embodiment 4
A kind of noble-metal nanoclusters of the present invention show the preparation method of reagent, comprise the following steps:Chloroplatinic acid is dissolved in pure Water is configured to 0.01 mol/L solution;Bovine serum albumin(BSA) is dissolved in pure water under the conditions of 37 DEG C and is configured to solution;By hydrogen-oxygen Change potassium is dissolved in pure water and is configured to 1 mol/L solution;The good platinum acid chloride solution of above-mentioned configuration, bovine serum albumin solution are pressed into volume Than 1:1 mixing, is placed under magnetic stirring apparatus and reacts 3min;Slowly potassium hydroxide solution is added drop-wise to described in this step with transfusion needle In the mixed liquor of platinum acid chloride solution and bovine serum albumin solution, regulation pH is 12,0.01 mol/L now used chlorine platinum Acid solution, 50 mg/mL bovine serum albumin solution, 1 mol/L potassium hydroxide solution volume ratio are 10:10:1;It is by pH 12 mixed solution is first placed in ultrasonic 1h in ultrasonic washing instrument;It is placed in again in household microwave oven, under the conditions of the high fire of setting (800W) microwave radiation 45s, obtained platinum cluster show reagent.
Embodiment 5
A kind of method for being shown outmoded Sweat latent fingerprint using noble-metal nanoclusters, is comprised the following steps:
S1,1% gold chloride is dissolved in the solution that pure water is configured to 0.01 mol/L;By bovine serum albumin(BSA) in 37 DEG C of bars Pure water is dissolved under part and is configured to 50 mg/mL solution;Potassium hydroxide is dissolved in pure water and is configured to 1 mol/L solution;By above-mentioned configuration Good chlorauric acid solution, bovine serum albumin solution by volume 1:1 mixing, is placed under magnetic stirring apparatus and reacts 3min;With defeated Potassium hydroxide solution is slowly added drop-wise in the mixed liquor of chlorauric acid solution and bovine serum albumin solution described in this step by liquid pin, It is 12 to adjust pH, 0.01 mol/L now used chlorauric acid solution, 50 mg/mL bovine serum albumin solution, 1 mol/ L potassium hydroxide solution volume ratio is 10:10:1;The mixed solution that pH is 12 is first placed in ultrasonic 1h in ultrasonic washing instrument; It is placed in again in household microwave oven, sets (800W) microwave radiation 50s under the conditions of high fire, obtained gold nanoclusters shows reagent;
After S2, volunteer will hand-wash net dry, the stamp Sweat latent fingerprint on glass, finger mark sample, finger mark sample pendulum are obtained Put that spacing is moderate, to imitate the outmoded Sweat latent fingerprint left on criminal-scene, this experiment finger mark sample is deposited under field conditions (factors) In clean pallet, resting period 30d;
S3, with the gold nanoclusters obtained by rubber head dropper aspiration step S1 show reagent, make it suitable along finger mark mastoid process streakline Hour hands drop is aobvious, and fully reacts 1h with finger mark material;
S4, the Sweat latent fingerprint loose colour after step S3 drops show is washed away with ultra-pure water;
S5, step S4 washed away the Sweat latent fingerprint after loose colour in baking oven machine vacuum, dry 0.5h under the conditions of 37 DEG C;
S6, independently built using alternative light source, colour light filter mirror, digital single-lens reflex camera and show observing system to fluorescence sweat Latent carries out observation fixation, and under dark condition, alternative light source is irradiated to the Sweat latent fingerprint shown by gold nanoclusters, finger mark Caused fluorescence is recorded through colour light filter mirror by digital single-lens reflex camera, under finger mark mastoid process streakline and its minutia are fixed Come.
Embodiment 6
A kind of method for being shown outmoded Sweat latent fingerprint using noble-metal nanoclusters, is comprised the following steps:
S1,1% silver nitrate is dissolved in the solution that pure water is configured to 0.01 mol/L;By bovine serum albumin(BSA) in 37 DEG C of bars Pure water, which is dissolved in, under part is configured to solution;Potassium hydroxide solution pure water is configured to 1 mol/L solution;By the good nitric acid of above-mentioned configuration Silver-colored solution, bovine serum albumin solution by volume 1:1 mixing, is placed under magnetic stirring apparatus and reacts 3min;It is slow with transfusion needle Potassium hydroxide is dissolved in and is added drop-wise in the mixed liquor of silver nitrate solution and bovine serum albumin solution described in this step, regulation pH is 12,0.01 mol/L now used silver nitrate solution, 50 mg/mL bovine serum albumin solution, 1 mol/L hydrogen-oxygen It is 10 to change potassium solution volume ratio:10:1;The mixed solution that pH is 12 is first placed in ultrasonic 1h in ultrasonic washing instrument;It is placed in again In household microwave oven, (800W) microwave radiation 60s under the conditions of high fire is set, obtained silver nanoclusters show reagent;
After S2, volunteer will hand-wash net dry, the stamp Sweat latent fingerprint on plastics, finger mark sample, finger mark sample pendulum are obtained Put that spacing is moderate, to imitate the outmoded Sweat latent fingerprint left on criminal-scene, this experiment finger mark sample is deposited under field conditions (factors) In clean pallet, resting period 30d;
S3, with the silver nanoclusters obtained by rubber head dropper aspiration step S1 show reagent, make it suitable along finger mark mastoid process streakline Hour hands drop is aobvious, and fully reacts 2h with finger mark material;
S4, the Sweat latent fingerprint loose colour after step S3 drops show is washed away with ultra-pure water;
S5, step S4 washed away the Sweat latent fingerprint after loose colour in baking oven machine vacuum, dry 10min under the conditions of 37 DEG C;
S6, independently built using alternative light source, colour light filter mirror, digital single-lens reflex camera and show observing system to fluorescence sweat Latent carries out observation fixation, and under dark condition, alternative light source is irradiated to the Sweat latent fingerprint shown by silver nanoclusters, finger mark Caused fluorescence is recorded through colour light filter mirror by digital single-lens reflex camera, under finger mark mastoid process streakline and its minutia are fixed Come.
Embodiment 7
A kind of method for being shown outmoded Sweat latent fingerprint using noble-metal nanoclusters, is comprised the following steps:
S1,1% gold chloride is dissolved in the solution that pure water is configured to 0.01 mol/L;1% silver nitrate is dissolved in into pure water to match somebody with somebody It is set to 0.01 mol/L solution;Bovine serum albumin(BSA) is dissolved in pure water under the conditions of 37 DEG C and is configured to solution;By potassium hydroxide It is dissolved in pure water and is configured to 1 mol/L solution;The good chlorauric acid solution of above-mentioned configuration, silver nitrate solution, bovine serum albumin(BSA) is molten Liquid by volume 1:1:2 mixing, are placed under magnetic stirring apparatus and react 3min;Slowly potassium hydroxide solution is added drop-wise to transfusion needle In above-mentioned mixed liquor, regulation pH is 12, and 0.01 mol/L now used chlorauric acid solution, 0.01 mol/L silver nitrate is molten Liquid, 50 mg/mL bovine serum albumin solution, 1 mol/L potassium hydroxide solution volume ratio are 5:5:10:1;It is 12 by pH Mixed solution be first placed in ultrasonic 1h in ultrasonic washing instrument;It is placed in household microwave oven, is set under the conditions of high fire (800W) again Microwave radiation 40s, gold and silver nano-cluster is made and shows reagent;
After S2, volunteer will hand-wash net dry, the stamp Sweat latent fingerprint on preservative film, finger mark sample, finger mark sample are obtained Put that spacing is moderate, to imitate the outmoded Sweat latent fingerprint left on criminal-scene, this experiment finger mark sample is deposited under field conditions (factors) It is placed in clean pallet, resting period 30d;
S3, with the gold and silver nano-cluster obtained by rubber head dropper aspiration step S1 show reagent, make it along finger mark mastoid process streakline Drop is aobvious clockwise, and fully reacts 3h with finger mark material;
S4, the Sweat latent fingerprint loose colour after step S3 drops show is washed away with ultra-pure water;
S5, step S4 washed away the Sweat latent fingerprint after loose colour in baking oven machine vacuum, dry 10min under the conditions of 37 DEG C;
S6, independently built using alternative light source, colour light filter mirror, digital single-lens reflex camera and show observing system to fluorescence sweat Latent carries out observation fixation, under dark condition, alternative light source is irradiated to the Sweat latent fingerprint shown by gold and silver nano-cluster, referred to Fluorescence caused by print is recorded through colour light filter mirror by digital single-lens reflex camera, under finger mark mastoid process streakline and its minutia are fixed Come.
A kind of method for being shown outmoded Sweat latent fingerprint using noble-metal nanoclusters of embodiment 8, is comprised the following steps:
S1, chloroplatinic acid is dissolved in the solution that pure water is configured to 0.01 mol/L;By bovine serum albumin(BSA) under the conditions of 37 DEG C It is dissolved in pure water and is configured to solution;Potassium hydroxide is dissolved in pure water and is configured to 1 mol/L solution;The good chloroplatinic acid of above-mentioned configuration is molten Liquid, bovine serum albumin solution by volume 1:1 mixing, is placed under magnetic stirring apparatus and reacts 3min;With transfusion needle slowly by hydrogen Potassium oxide solution is added drop-wise in the mixed liquor of platinum acid chloride solution and bovine serum albumin solution described in this step, and regulation pH is 12, 0.01 mol/L now used platinum acid chloride solution, 50 mg/mL bovine serum albumin solution, 1 mol/L potassium hydroxide Liquor capacity ratio is 10:10:1;The mixed solution that pH is 12 is first placed in ultrasonic 1h in ultrasonic washing instrument;Family expenses are placed in again In micro-wave oven, (800W) microwave radiation 45s under the conditions of high fire is set, obtained platinum cluster shows reagent;
After S2, volunteer will hand-wash net dry, the stamp Sweat latent fingerprint on metal, finger mark sample, finger mark sample pendulum are obtained Put that spacing is moderate, to imitate the outmoded Sweat latent fingerprint left on criminal-scene, this experiment finger mark sample is deposited under field conditions (factors) In clean pallet, resting period 30d;
S3, with the platinum cluster obtained by rubber head dropper aspiration step S1 show reagent, make it suitable along finger mark mastoid process streakline Hour hands drop is aobvious, and fully reacts 2.5h with finger mark material;
S4, the Sweat latent fingerprint loose colour after step S3 drops show is washed away with ultra-pure water;
S5, step S4 washed away the Sweat latent fingerprint after loose colour in baking oven machine vacuum, dry 20min under the conditions of 37 DEG C;
S6, independently built using alternative light source, colour light filter mirror, digital single-lens reflex camera and show observing system to fluorescence sweat Latent carries out observation fixation, and under dark condition, alternative light source is irradiated to the Sweat latent fingerprint shown by platinum cluster, finger mark Caused fluorescence is recorded through colour light filter mirror by digital single-lens reflex camera, under finger mark mastoid process streakline and its minutia are fixed Come.
The present invention is acted on by ultrasound and microwave cooperating, is prepared gold, silver, electrum, platinum fluorescence metal nano-cluster and is shown Reagent, it can fast and efficiently show outmoded finger mark.This method is simple for process;Gold, silver, electrum, the platinum of preparation are glimmering Light noble-metal nanoclusters fluorescence quantum yield is high, and fluorescence duration time is grown, and has hypotoxicity;30 days outmoded can clearly be shown Finger mark;Autonomous build shows observing system and can preferably fix finger mark information, is advantageous to test sensitivity.
The above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to preferred embodiment to this hair It is bright to be described in detail, it will be understood by those within the art that, technical scheme can be modified Or equivalent substitution, without departing from the objective and scope of technical solution of the present invention, it all should cover the claim in the present invention Among scope.

Claims (7)

1. a kind of noble-metal nanoclusters show the preparation method of reagent, it is characterised in that the noble-metal nanoclusters are silver nanoparticle Any one in cluster, electrum nano-cluster and platinum noble metals nano-cluster;And the noble-metal nanoclusters show reagent and passed through It is prepared by ultrasound-microwave cooperating preparation method;The noble-metal nanoclusters show the preparation method of reagent, including,
The method that silver nanoclusters show reagent is prepared, is comprised the following steps:
(1) solution is prepared, and silver nitrate is dissolved in into the solution that pure water is configured to 0.01mol/L;Bovine serum albumin(BSA) is in 37 DEG C of conditions Under be dissolved in pure water and be configured to 50mg/mL solution;Potassium hydroxide is dissolved in pure water and is configured to 1mol/L solution;
(2) hybrid reaction, it is by volume 1:1, silver nitrate solution is added into bovine serum albumin solution, by mixed solution in magnetic 3min is reacted in the presence of power agitator;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise into silver nitrate solution obtained by step (2) and bovine serum albumin(BSA) is molten In the mixed liquor of liquid, regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40~60s of microwave radiation, silver is made Nano-cluster shows reagent;
The method that gold and silver nano-cluster shows reagent is prepared, is comprised the following steps:
(1) solution is prepared, and gold chloride is dissolved in into the solution that pure water is configured to 0.01mol/L;Silver nitrate is dissolved in pure water and is configured to 0.01mol/L solution;Bovine serum albumin(BSA) is dissolved in pure water under the conditions of 37 DEG C and is configured to 50mg/mL solution;By potassium hydroxide It is dissolved in pure water and is configured to 1mol/L solution;
(2) hybrid reaction, it is by volume 1:1:2, chlorauric acid solution, silver nitrate solution are added into bovine serum albumin solution, Mixed solution is reacted into 3min in the presence of magnetic stirring apparatus;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise in the mixed liquor obtained by step (2), and regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40~60s of microwave radiation, silver is made Nano-cluster shows reagent;
The method that platinum cluster shows reagent is prepared, is comprised the following steps:
(1) solution is prepared, and chloroplatinic acid is dissolved in into the solution that pure water is configured to 0.01mol/L;Bovine serum albumin(BSA) is in 37 DEG C of conditions Under be dissolved in pure water and be configured to 50mg/mL solution;Potassium hydroxide is dissolved in pure water and is configured to 1mol/L solution;
(2) hybrid reaction, it is by volume 1:1, platinum acid chloride solution is added into bovine serum albumin solution, by mixed solution in magnetic 3min is reacted in the presence of power agitator;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise into platinum acid chloride solution obtained by step (2) and bovine serum albumin(BSA) is molten In the mixed liquor of liquid, regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40~60s of microwave radiation, silver is made Nano-cluster shows reagent.
2. a kind of noble-metal nanoclusters show the method that reagent shows outmoded Sweat latent fingerprint, comprise the following steps:Will using right The noble-metal nanoclusters for asking 1 preparation method to prepare show reagent and show outmoded Sweat latent fingerprint, comprise the following steps,
Prepared by S1, reagent, prepare noble-metal nanoclusters and show reagent;
S2, finger mark is restrained, after volunteer will hand-wash net dry, stamp sweat is latent on glass, plastics, preservative film, metal object refers to Print, obtain finger mark sample;
The aobvious finger mark of S3, drop, Sweat latent fingerprint made from the aobvious step S2 of reagent drop, reaction 1-3h will be shown made from step S1;
S4, loose colour is washed away, the Sweat latent fingerprint loose colour after step S3 drops show is washed away using ultra-pure water;
S5, finger mark drying, step S4 are washed away the drying of the Sweat latent fingerprint after loose colour;
S6, finger mark observation are fixed, in the case where showing observing system, the Sweat latent fingerprint image after the S5 drying of observation fixing step;
Characterized in that, the noble-metal nanoclusters are in silver nanoclusters, electrum nano-cluster and platinum noble metals nano-cluster Any one.
3. the method according to claim 2 for showing outmoded Sweat latent fingerprint, it is characterised in that your gold the step S1 prepares Category nano-cluster shows reagent, including,
The method that silver nanoclusters show reagent is prepared, is comprised the following steps:
(1) solution is prepared, and silver nitrate is dissolved in into the solution that pure water is configured to 0.01mol/L;Bovine serum albumin(BSA) is in 37 DEG C of conditions Under be dissolved in pure water and be configured to 50mg/mL solution;Potassium hydroxide is dissolved in pure water and is configured to 1mol/L solution;
(2) hybrid reaction, it is by volume 1:1, silver nitrate solution is added into bovine serum albumin solution, by mixed solution in magnetic 3min is reacted in the presence of power agitator;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise into silver nitrate solution obtained by step (2) and bovine serum albumin(BSA) is molten In the mixed liquor of liquid, regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40~60s of microwave radiation, silver is made Nano-cluster shows reagent;
The method that gold and silver nano-cluster shows reagent is prepared, is comprised the following steps:
(1) solution is prepared, and gold chloride is dissolved in into the solution that pure water is configured to 0.01mol/L;Silver nitrate is dissolved in pure water and is configured to 0.01mol/L solution;Bovine serum albumin(BSA) is dissolved in pure water under the conditions of 37 DEG C and is configured to 50mg/mL solution;By potassium hydroxide It is dissolved in pure water and is configured to 1mol/L solution;
(2) hybrid reaction, it is by volume 1:1:2, chlorauric acid solution, silver nitrate solution are added into bovine serum albumin solution, Mixed solution is reacted into 3min in the presence of magnetic stirring apparatus;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise in the mixed liquor obtained by step (2), and regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40~60s of microwave radiation, silver is made Nano-cluster shows reagent;
The method that platinum cluster shows reagent is prepared, is comprised the following steps:
(1) solution is prepared, and chloroplatinic acid is dissolved in into the solution that pure water is configured to 0.01mol/L;Bovine serum albumin(BSA) is in 37 DEG C of conditions Under be dissolved in pure water and be configured to 50mg/mL solution;Potassium hydroxide is dissolved in pure water and is configured to 1mol/L solution;
(2) hybrid reaction, it is by volume 1:1, platinum acid chloride solution is added into bovine serum albumin solution, by mixed solution in magnetic 3min is reacted in the presence of power agitator;
(3) pH value is adjusted, and potassium hydroxide solution is added drop-wise into platinum acid chloride solution obtained by step (2) and bovine serum albumin(BSA) is molten In the mixed liquor of liquid, regulation pH is 12;
(4) ultrasonic disperse, the mixed solution obtained by step (3) is placed in ultrasonic disperse 1h in ultrasonic washing instrument;
(5) microwave radiation, then the solution obtained by step (4) is placed in micro-wave oven, 40~60s of microwave radiation, silver is made Nano-cluster shows reagent.
4. the method for showing outmoded Sweat latent fingerprint according to Claims 2 or 3, it is characterised in that the step S2 is restrained Finger mark, including, the resting period of the finger mark sample of acquisition is 7-30 days.
5. the method for showing outmoded Sweat latent fingerprint according to Claims 2 or 3, it is characterised in that the step S3 drops are aobvious Finger mark, including, show reagent with the noble-metal nanoclusters obtained by rubber head dropper aspiration step S1, make it along finger mark mastoid process streakline Drop is aobvious clockwise, and fully reacts 2h with finger mark material.
6. the method for showing outmoded Sweat latent fingerprint according to Claims 2 or 3, it is characterised in that the step S5 finger marks Drying, including, in baking oven machine vacuum, dry under the conditions of 37 DEG C.
7. the method for showing outmoded Sweat latent fingerprint according to Claims 2 or 3, it is characterised in that the step S6 finger marks Observation, including, it is to show observation using what alternative light source, colour light filter mirror, digital single-lens reflex camera were built to show observing system System.
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