CN101581655A - Counter for metal nano particles in solution - Google Patents
Counter for metal nano particles in solution Download PDFInfo
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- CN101581655A CN101581655A CNA2009100537580A CN200910053758A CN101581655A CN 101581655 A CN101581655 A CN 101581655A CN A2009100537580 A CNA2009100537580 A CN A2009100537580A CN 200910053758 A CN200910053758 A CN 200910053758A CN 101581655 A CN101581655 A CN 101581655A
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- cover glass
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- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 25
- 239000006059 cover glass Substances 0.000 claims abstract description 21
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- 239000004065 semiconductor Substances 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 2
- 239000000523 sample Substances 0.000 abstract description 36
- 238000001514 detection method Methods 0.000 abstract description 5
- 239000012488 sample solution Substances 0.000 abstract description 3
- 230000005653 Brownian motion process Effects 0.000 abstract 1
- 238000005537 brownian motion Methods 0.000 abstract 1
- 239000002923 metal particle Substances 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 16
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 15
- 239000010931 gold Substances 0.000 description 15
- 229910052737 gold Inorganic materials 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000007747 plating Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 3
- -1 Argon ion Chemical class 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000003018 immunoassay Methods 0.000 description 2
- 238000007899 nucleic acid hybridization Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000010223 real-time analysis Methods 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000013399 early diagnosis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001209 resonance light scattering Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
本发明涉及一种溶液中金属纳米粒子计数器，用于溶液中金属纳米粒子相对浓度的测定。计数器由激光器、中性衰减片、扩束镜、盖玻片或样品池、显微镜物镜、双色镜、透镜、针孔、单光子检测器、数据采集卡及计算机组成。样品溶液置于盖玻片或样品池上，激光照射溶液中的金属纳米粒子，产生的散射光经物镜收集后通过透镜聚焦到针孔，针孔与单光子检测器耦合在一起。单光子检测器产生的信号经数据采集卡，由计算机输出。本发明的工作原理是基于一个很小的激光共焦照射微区内(～10－15升)，溶液中的金属粒子由于布朗运动进入或离开该微区时将产生光子的爆发，光子爆发数目与其浓度成正比。本发明可用于生物医学、化学和物理学等领域的研究和临床检测。
The invention relates to a metal nanoparticle counter in a solution, which is used for measuring the relative concentration of the metal nanoparticle in the solution. The counter consists of a laser, a neutral attenuator, a beam expander, a cover glass or a sample cell, a microscope objective, a dichromatic mirror, a lens, a pinhole, a single photon detector, a data acquisition card and a computer. The sample solution is placed on the cover glass or the sample cell, and the metal nanoparticles in the solution are irradiated with laser light. The scattered light generated is collected by the objective lens and then focused to the pinhole through the lens. The pinhole is coupled with a single-photon detector. The signal generated by the single photon detector is output by the computer through the data acquisition card. The working principle of the present invention is based on a very small laser confocal irradiation micro-area (~ 10-15 liters), metal particles in the solution will produce photon bursts when they enter or leave the micro-area due to Brownian motion, the number of photon bursts proportional to its concentration. The invention can be used for research and clinical detection in the fields of biomedicine, chemistry and physics.
Description
Technical field
The present invention relates to a kind of GOLD FROM PLATING SOLUTION and belong to the nano particle counter, be used for the mensuration of metal nanoparticle relative concentration, can be widely used in nano science, technical fields such as life science, chemistry, physics.
Background technology
Some metal (as Jin Heyin) nano particle is because its surface plasma bulk effect and quantum size effect show special optical property, as strong scattering properties and absorption characteristic.Simultaneously, gold (silver) nano particle has good biocompatibility, is easy to the characteristic that is connected with biomolecule, is a kind of bioprobe with wide application prospect.Gold nano-probe successfully is applied to nucleic acid hybridization and detects fields such as immunoassay and cell imaging at present.The method that detects metal (as gold) nano particle at present mainly contains: colourimetry, ultraviolet spectroscopy, scattering method and dynamic light scattering method.The used instrument of these methods is simple, but their main shortcoming is that the sensitivity that detects is not high, and the volume of required sample is bigger, and its application is very limited.In addition, these methods all belong to the set assay method.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of GOLD FROM PLATING SOLUTION to belong to the nano particle counter, can detect the photon outburst of single metal nano particle sensitive, exactly, and then the rule that is directly proportional with its concentration according to the photon of nano particle in solution outburst number, the concentration of mensuration metal nanoparticle.
For achieving the above object, the present invention is based on confocal laser configuration and metal nanoparticle and have strong resonance scattering characteristic, design a kind of brand-new metal nano detection system-metal nano counter.Described metal nano counter is made up of laser instrument, neutral attenuator, beam expanding lens, cover glass or sample cell, micro objective, dichroic mirror, lens, pin hole, single photon detector, data collecting card and computing machine.Sample solution places on cover glass or the sample cell, and laser radiation solution metal nano particle, the scattered light of generation scioptics after object lens are collected focus on pin hole, and pin hole and single photon detector are coupled.The signal that single photon detector produces is exported by computing machine through data collecting card.
Principle of work of the present invention is: in a very little confocal laser irradiation microcell (～10
-15Rise), the metal nanoparticle that has the strong scattering characteristic in the solution is because the outburst that Brownian movement will produce the fluctuation phenomenon-photon of scattered light signal when entering or leaving this irradiation microcell.The number of the outburst of nano particle photon is directly proportional with its concentration.Therefore, this method can be used for the mensuration of metal nanoparticle relative concentration.
It is excitation source with laser that GOLD FROM PLATING SOLUTION of the present invention belongs to the nano particle counter, adopt confocal configuration, object lens by beam expanding lens and high-NA obtain the high laser beam that focuses on, adopt single photon counter (or photomultiplier) that the scattered light signal of nano particle is converted to electric signal, data collecting card is used for data acquisition and real-time analysis.Its concrete structure is: be made up of laser instrument, neutral attenuator, beam expanding lens, cover glass or sample cell, micro objective, dichroic mirror, lens, pin hole, single photon detector, data collecting card and computing machine.Cover glass (or sample cell) is put on the sample stage, and sample drop places on the cover glass (or sample cell).The laser that laser instrument sends is regulated intensity and after beam expanding lens expands bundle, after the dichroic mirror reflection enters micro objective focusing, is shone the sample drop of cover glass (or sample cell) top again through neutral attenuator; Metal nanoparticle scattered light in the sample drop through micro objective collect pass dichroic mirror and through lens focus to pin hole, the light sensitive area coupling of pin hole and single photon detector, the signal that single photon detector produces is exported by computing machine through data collecting card.
When the present invention works, open laser instrument, treat that laser instrument is stable after, regulate neutral attenuator and make laser intensity reach requirement; Regulate beam expanding lens, make lasing beam diameter reach requirement.Laser beam shines dichroic mirror through behind the beam expanding lens, enters micro objective (high-NA objective) after the dichroic mirror reflection, focuses on the sample drop on the cover glass.Sample produces resonance light scattering through laser radiation, and its wavelength is identical with incident light.Collect scattered light at the focus place, this scattered light is directional light through dispersing behind the identical object lens, passes same dichroic mirror, and scioptics focus on pin hole then.Pin hole and single photon detector are coupled and place the focal area of lens, this focal area just in time is the picture plane of object lens.Pin hole can be limited to very little scope (less than 10 with the irradiated volume of laser on sample with object focal point is coaxial
-15Rise).The signal that single photon detector produces is exported from computing machine through data collecting card.
Laser instrument among the present invention can be selected according to different metal nanoparticles with dichroic mirror.
Laser instrument of the present invention comprises gas laser, solid state laser, semiconductor laser and dye laser.
The micro objective that the present invention adopts is the water logging or the oil immersion objective of high enlargement ratio (greater than 40) and high-NA (greater than 0.9).
The thickness of the cover glass (or sample cell) that the present invention adopts is 0.1～0.3 millimeter.
The pinhole diameter that the present invention adopts is variable, conveniently replaced to 300 microns from 10 microns.
The single photon detector that the present invention adopts has comprised the single photon counter (or photomultiplier) and the high-sensitive image intensifer of avalanche diode type.
The present invention adopts data collecting card to sample real-time, and sampling time interval is from 1 microsecond to 50 millisecond.
Counter for metal nano particles of the present invention can detect the photon outburst of single metal nano particle accurately, delicately.The present invention adopts simple optical configuration-confocal laser configuration, does not need exciter filter and emission optical filter, dwindles irradiated volume, reduces the influence of backscatter, thereby improves the ratio (that is: letter/back of the body ratio) of detection signal and background.In photon collection system, the light sensitive area of pin hole and single photon detector tightly is coupled, avoided light energy losses, and made easy to adjust.When system was regulated, pin hole and single photon detector moved simultaneously, realize that easily detecting device photosensitive area, pin hole and object focal point are coaxial, had improved significantly and had detected sensitivity.
Optical configuration of the present invention is simple, and good stability is easy to operate.Detection method sensitivity is very high, is fit to the fundamental research in fields such as life science, chemistry and physics, special having broad application prospects at aspects such as homogeneous immunoassay, high-flux medicaments sifting, early diagnosis of tumor, nucleic acid hybridization analysis.
Description of drawings
Fig. 1 is a structure principle chart of the present invention.
Among Fig. 1,1 is laser instrument, and 2 is neutral attenuator, and 3 is beam expanding lens, and 4 is cover glass (or sample cell), and 5 is micro objective, and 6 is dichroic mirror, and 7 is lens, and 8 is pin hole, and 9 is single photon counter (or photomultiplier), and 10 is data collecting card, and 11 is computing machine.
Fig. 2 is nm of gold photon outburst figure.Wherein, laser (632.8 nanometer) energy is 0.1 milliwatt, and gold nanometer particle grain size is 36 nanometers.
Fig. 3 is the linear relationship of photon outburst number and golden nanometer particle concentration.Wherein, laser (632.8 nanometer) energy is 0.1 milliwatt, and gold nanometer particle grain size is 36 nanometers.Detect and be limited to 1.288 * 10
-14Mol.
Fig. 4 is Nano silver grain photon outburst figure.Wherein, laser (488 nanometer) energy is 0.05 milliwatt, and the Nano silver grain particle diameter is 30 nanometers.
Fig. 5 is the linear relationship of photon outburst number and Nano silver grain concentration.Wherein, laser (488 nanometer) energy is 0.05 milliwatt, and the Nano silver grain particle diameter is 30 nanometers.
Fig. 6 is the photon outburst figure of Yin Nami under 532 nanometer lasers.Wherein, laser (532 nanometer) energy is 0.1 milliwatt, and the Nano silver grain particle diameter is 30 nanometers.
Fig. 7 is the photon outburst figure of gold nano under 532 nanometer lasers.Wherein, laser (532 nanometer) energy is 0.1 milliwatt, and gold nanometer particle grain size is 36 nanometers.
Embodiment
Below in conjunction with accompanying drawing and several specific embodiment technical scheme of the present invention is further described.Following examples do not constitute limitation of the invention.
The structural principle that GOLD FROM PLATING SOLUTION of the present invention belongs to the nano particle counter is made up of laser instrument 1, neutral attenuator 2, beam expanding lens 3, cover glass or sample cell 4, micro objective 5, dichroic mirror 6, lens 7, pin hole 8, single photon detector 9, data collecting card 10 and computing machine 11 as shown in Figure 1. Cover glass or sample cell 4 are put on the sample stage, and sample drop places on cover glass or the sample cell 4; The laser that laser instrument 1 sends is regulated intensity and after beam expanding lens 3 expands bundle, after dichroic mirror 6 reflections enter micro objective 5 focusing, is shone the sample drop of cover glass or sample cell 4 tops again through neutral attenuator 2.Metal nanoparticle scattered light process micro objective 5 collections in the sample drop are passed dichroic mirror 6 and are focused on the pin hole 8 through lens 7, pin hole 8 is coupled with the light sensitive area of single photon detector 9, and the signal that single photon detector 9 produces is exported by computing machine 11 through data collecting card 10.
During work, at first open laser instrument 1, stablized 20 minutes, regulate neutral attenuator 2 and make the intensity of illumination beam reach requirement.Regulating beam expanding lens 3 makes the diameter of illumination beam reach requirement.Suitable dichroic mirror 6 is selected in experimental requirement.Cover glass (or sample cell) 4 is placed on the sample stage, sample solution 1-10 microlitre to be analyzed is dripped on cover glass (or sample cell) 4, cover the sample lid then.Start single photon detector 9, data collecting card 10 and computing machine 11, draw back optical gate, the light beam that expands bundle reflects the metapore that enters micro objective 5 through dichroic mirror 6, focuses on the sample drop through micro objective.After passing dichroic mirror 6 after the nano particle scattered light is collected by micro objective 5, by lens 7 it is focused on pin hole 8 and enters single photon detector 9, the signal that single photon detector 9 produces is exported by computing machine 11 through data collecting card 10 collections and real-time analysis.
Be the detection embodiment and the photon outburst figure thereof of several different nano particles below.The employing assembly is:
Laser instrument: Argon ion laser (488 nanometer), semiconductor laser (543 nanometer) and he-Ne laser (632.8 nanometer).
Laser instrument: he-Ne laser (632.8 nanometer), dichroscope is 650 nanometers,
Adopt 35 microns pin hole, the sample determination process as described above.Fig. 2 has provided the photon outburst figure of golden nanometer particle.The horizontal ordinate of Fig. 2 is writing time (or being called Measuring Time), and ordinate is the outburst intensity of photon, each once outburst of peak representative.Fig. 3 is the linear relationship of photon outburst number and golden nanometer particle concentration.Horizontal ordinate is the concentration of golden nanometer particle, and ordinate is the number (i.e. peak number among the figure) of the outburst of photon.Can calculate the concentration of GOLD FROM PLATING SOLUTION nano particle to be measured according to the linear relationship of photon outburst number and golden nanometer particle concentration by measuring the luminous number of unknown GOLD FROM PLATING SOLUTION nano particle.
Laser instrument: Argon ion laser (488 nanometer), dichroscope is 505 nanometers.
Adopt 35 microns pin hole, the sample determination process as described above.Fig. 4 has provided the photon outburst figure of golden nanometer particle.The linear relationship of Fig. 5 photon outburst number and Nano silver grain concentration.
Laser instrument: semiconductor laser (543 nanometer), dichroscope is 550 nanometers.
Adopt 35 microns pin hole, the sample determination process as described above.Fig. 6 and Fig. 7 have provided the photon outburst figure of Nano silver grain and golden nanometer particle respectively.
By the foregoing description as can be known, counter for metal nano particles of the present invention can detect the photon outburst of single metal nano particle accurately, delicately.Simultaneously, because of the photon of nano particle in solution outburst number is directly proportional with the concentration of nanometer particle, can break out the concentration of number mensuration metal nanoparticle according to photon.
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100537580A CN101581655A (en) | 2009-06-25 | 2009-06-25 | Counter for metal nano particles in solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100537580A CN101581655A (en) | 2009-06-25 | 2009-06-25 | Counter for metal nano particles in solution |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102798584A (en) * | 2012-08-17 | 2012-11-28 | 珠海欧美克仪器有限公司 | Novel integrated laser tube pinhole adjustment mechanism |
| CN102902056A (en) * | 2012-09-25 | 2013-01-30 | 中国科学技术大学 | High-accuracy optical imaging device and method based on quantum statistics |
| CN102998293A (en) * | 2012-12-20 | 2013-03-27 | 武汉大学 | Multichannel quantitative detection device and detection method of two-photon fluorescence optical tweezers |
| CN103529208A (en) * | 2012-07-04 | 2014-01-22 | 上海交通大学 | Homogeneous-phase immunoassay method |
| CN104007087A (en) * | 2014-05-13 | 2014-08-27 | 北京大学 | Counting method for gold nanomaterial on transparent levelled sheet-shaped substrate surface |
-
2009
- 2009-06-25 CN CNA2009100537580A patent/CN101581655A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103529208A (en) * | 2012-07-04 | 2014-01-22 | 上海交通大学 | Homogeneous-phase immunoassay method |
| CN102798584A (en) * | 2012-08-17 | 2012-11-28 | 珠海欧美克仪器有限公司 | Novel integrated laser tube pinhole adjustment mechanism |
| CN102798584B (en) * | 2012-08-17 | 2014-04-30 | 珠海欧美克仪器有限公司 | Novel integrated laser tube pinhole adjustment mechanism |
| CN102902056A (en) * | 2012-09-25 | 2013-01-30 | 中国科学技术大学 | High-accuracy optical imaging device and method based on quantum statistics |
| CN102902056B (en) * | 2012-09-25 | 2015-05-27 | 中国科学技术大学 | High-accuracy optical imaging device and method based on quantum statistics |
| CN102998293A (en) * | 2012-12-20 | 2013-03-27 | 武汉大学 | Multichannel quantitative detection device and detection method of two-photon fluorescence optical tweezers |
| CN102998293B (en) * | 2012-12-20 | 2014-08-13 | 武汉大学 | Multichannel quantitative detection device and detection method of two-photon fluorescence optical tweezers |
| CN104007087A (en) * | 2014-05-13 | 2014-08-27 | 北京大学 | Counting method for gold nanomaterial on transparent levelled sheet-shaped substrate surface |
| CN104007087B (en) * | 2014-05-13 | 2016-07-13 | 北京大学 | A method for counting gold nanomaterials on the surface of a transparent flat sheet substrate |
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Open date: 20091118 |