CN102890061B - Method for high-sensitivity detection of silver ions through circular dichroism - Google Patents
Method for high-sensitivity detection of silver ions through circular dichroism Download PDFInfo
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Abstract
The invention discloses a method for high-sensitivity detection of silver ions through circular dichroism, belonging to the technical field of analytic chemistry. The method comprises the following steps: respectively coupling gold nanoparticles with two different grain sizes and two specific nucleic acids rich in a cytosine (C) sequence to obtain AuNPs10nm-DNA1 and AuNPs25nm-DNA2, adding silver ions to cause AuNPs10nm-DNA1 and AuNPs25nm-DNA2 to generate C-Ag<+>-C mispairing identification, reducing through trisodium citrate, reacting AuNPs10nm-DNA1, AuNPs25nm-DNA2 and silver ions under the liquid environment to form a binary assembly so as to form plasma chirality, and causing the gold nanoparticles to generate a circular dichroism CD signal in a visible region. The CD signal intensity in the liquid environment is measured through the circular dichroism so as to measure the content of the silver ions. According to the invention, reaction is only performed in the liquid environment, a step of cleaning is unnecessary, one-step reaction is only required, the reaction condition is simplified, the sensitivity of detection is improved, and the leading level in the world is achieved.
Description
Technical field
A method of using the highly sensitive detection silver ion of circular dichroism spectrum, belongs to technical field of analytical chemistry.
Background technology
Current conventional heavy metal detection method, all the method based on physics or chemistry, as inductive coupling plasma emission spectrum, flow injection atomic absorption spectrophotometer (AAS), inductive coupling plasma mass, polarography and volt-ampere electrode, atomic fluorescence spectrometry, atomic pile absorption spectrum.The maximum advantage of above-mentioned main instrument detection method is exactly accurate, but these classic methods all need complicated pre-treatment, analysis time is long, labour intensity is large and cost is expensive, can only in laboratory, by professional, carry out concrete operations, need technical professional to carry out a large amount of defects such as sample pretreatment, be difficult to be applied to Site Detection.Due to these obvious shortcomings, so the sample number detecting does not generally reach the best sampling observation amount of requirement, this brings larger uncertainty also can to heavy metal pollution degree subsequently and risk assessment etc.
Nano particle (nanoparticles, Nas) generally refers to that size has the particle of one dimension between l-100nm at least.Nanoscale is the transitional region that is in cluster and macro object boundary, and the material in this region has some peculiar properties, as small-size effect, surface and interface effect and quantum size effect etc.Although nano particle concentration is very low in air, there is very high particle number.Macro object is subdivided into after nano particle, and its optics, calorifics, electricity, magnetics, mechanics and chemical property and large volume solid-phase ratio will be significantly different.The small size of nano material, chemical composition, surface structure, dissolubility, profile and gathering situation are determining the physicochemical property that they are special, and these character make nano material have purposes widely in the future.
Along with the development of nanosecond science and technology, the research of nanoparticle assembly becomes and becomes increasingly active.The two and three dimensions ordered fabrication structure of nano particle also attracts widespread attention in recent years because of its important physics and chemistry character, they in a lot of fields as: sensor, catalyzer, Magnetized Material, surface-enhanced Raman and optical material etc. have potential application.
Gold nano-material binary assembly, can mediate and the mechanism such as chiral molecules induction produces circular dichroism spectra (CD) signal by surface plasma resonance.But by this package system bind nucleic acid mismatch binding principle, be used for building heavy metal Silver detection sensor and still belong to blank.
Summary of the invention
The object of the invention is to provide a kind of method of using the highly sensitive detection silver ion of circular dichroism spectrum, by the CD signal intensity cloth in circular dichroism spectroscopic assay liquid environment, measures silver ion content.The present invention only reacts in liquid environment, does not need the step of cleaning, only needs single step reaction, has simplified the condition of reaction, has improved the sensitivity detecting, and reaches the international leading level.
Technical scheme of the present invention: a kind of method of using the highly sensitive detection silver ion of circular dichroism spectrum, obtains AuNPs with two kinds of specific nucleotide sequence couplings of being rich in cytimidine (C) respectively with the golden nanometer particle of synthetic different-grain diameter
10nm-DNA1 and AuNPs
25nm-DNA2, adding of silver ion, makes AuNPs
10nm-DNA1 and AuNPs
25nm-DNA2 produces C-Ag
+-C identification, utilizes trisodium citrate reduction AuNPs under the environment of liquid
10nm-DNA1 and AuNPs
25nm-DNA2 and silver ion reaction form binary assembly, and the formation of binary assembly can cause the generation of plasma chirality, and golden nanometer particle produces CD signal in visible region.By the CD signal intensity in circular dichroism spectroscopic assay liquid environment, measure silver ion content; Comprise the coupling of nucleotide sequence and nm of gold, the selection of length nucleic acid, the mensuration of typical curve.
Processing step is:
(1) 10nm golden nanometer particle is synthetic
10nm golden nanometer particle is synthetic with tannic acid and trisodium citrate reduction gold chloride;
(2) 25nm golden nanometer particle is synthetic
25nm golden nanometer particle is synthetic by citrate three sodium reducing process;
(3) 10nm golden nanometer particle and DNA1 coupling
The 10nm golden nanometer particle that step (1) is synthesized and the DNA1 of sulfydryl modification carry out coupling and form golden nanometer particle-DNA1 complex;
(4) 25nm golden nanometer particle and DNA2 coupling
The 25nm golden nanometer particle that step (2) is synthesized and the DNA2 of sulfydryl modification carry out coupling and form Jin Na grain of rice – DNA2 complex;
(5) Jenner's particle assembling
Golden nanometer particle-DNA2 complex that golden nanometer particle-DNA1 complex that employing step (3) prepares and step (4) prepare is hybridized formation golden nanometer particle binary assembly;
(6) the DNA2 concentration that DNA1 step (3) being used and step (4) are used is selected;
(7) formation of binary assembly structure and sign
The golden nanometer particle binary assembly that step (5) is prepared carries out structural characterization.
(8) circular dichroism spectral detection, draws CD signal intensity～concentration of silver ions typical curve.
Control group arranges: Al
2+, Zn
2+, Mn
2+, Hg
+, Fe
2+, Cu
2+, Cr
2+, Co
2+and Cd
2+replace Ag
+, other operation is the same.Be specially:
(1) 10nm golden nanometer particle is synthetic
The synthetic schemes of 10nm golden nanometer particle is: in clean there-necked flask, add 60mL ultrapure water, 1mL mass concentration 1% chlorauric acid solution is as A liquid; Get the ampoule of a cleaning, add 4mL mass concentration 1% citric acid three sodium solution, 0.1mL mass concentration 1% tannic acid solution, 0.1mL 50mM solution of potassium carbonate and 16mL ultrapure water are as B liquid; A, B liquid are all heated to 60 ℃, then under high-speed stirred, B liquid is added rapidly in A liquid, end reaction liquid continues to stir 30min and forms dark red solution at 60 ℃, then vlil 10min is formed to shiny red solution, last cool to room temperature forms the stable 10nm golden nanometer particle of citric acid.
(2) 25nm golden nanometer particle is synthetic
The synthetic schemes of 25nm golden nanometer particle is: in clean there-necked flask, add 47.5mL ultrapure water, add 0.8mL 0.4% chlorauric acid solution, stir and be heated to boiling, after 7-8min, add 1mL 1% citric acid three sodium solution, solution becomes redness from colourless, stop heating, continue to stir 30min;
(3) 10nm golden nanometer particle and DNA1 coupling
Get 10nm golden nanometer particle prepared by 5mL step (1) and add two (p-sulfonyl-phenyl) the Phenylphosphine di-potassium solution of 50 μ L 2mg/mL bis-hydrations, room temperature concussion 12h, after the centrifugal 10min of 13000r/min, remove supernatant, add ultrapure water and return to original volume, obtain the 10nm golden nanometer particle of protective agent parcel; Getting 10 μ L concentration is DNA1(5 '-CTC TCT TCT CTT CTC TCT TCT CT TCA-(CH of 1 μ M
2)
6-SH-3 ') join in the 10nm gold nano solution of the above-mentioned protective agent parcel of 100 μ L, in system, add 25 ℃ of standing reaction 10h of 10 μ L 5 * tris-borate buffer; The centrifugal 10min of 13000r/min, removes supernatant, and precipitation is diluted with water to 2 times of liquid of original volume, obtains AuNPs
10nm-DNA1 complex, the refrigerator of putting into 4 ℃ is standby.
(4) 25nm golden nanometer particle and DNA2 coupling
Get 25nm golden nanometer particle prepared by 5mL step (2) and add two (p-sulfonyl-phenyl) the Phenylphosphine di-potassium solution of 50 μ L 1mg/mL bis-hydrations, room temperature concussion 12h, after the centrifugal 10min of 7200r/min, remove supernatant, add ultrapure water and return to original volume, obtain the 25nm golden nanometer particle of protective agent parcel; Getting 1 μ L concentration is DNA2(5 '-TCA ACA CAA CAC ACA ACA CAA CAC AC-(CH of 1 μ M
2)
6-SH-3 ') join in the 25nm gold nano solution of the above-mentioned protective agent parcel of 100 μ L, in system, add 10 μ L 5 * tris-borate buffers, 25 ℃ of standing reaction 10h; The centrifugal 10min of 7200r/min, removes supernatant, and precipitation is diluted with water to 2 times of liquid of original volume, obtains AuNPs
25nm– DNA2 complex, the refrigerator of putting into 4 ℃ is standby.
(5) selection of coupling DNA concentration
In order to improve the sensitivity of this method, therefore need to need to select the DNA concentration of golden coupling.Optimum DNA concentration is after the two mixing adds standard solution reaction, and after circular dichroism spectroscopic assay, CD signal intensity is maximum.Concrete step is:
1. in centrifuge tube, add 100 μ L golden nanometer particles respectively, then add after the DNA1 of 0.1 μ M, 0.2 μ M, 0.5 μ M, 1 μ M, 2 μ M, 5 μ M, 10 μ M, in system, add 10 μ L 5 * tris-borate buffers, mix room temperature reaction 30min;
2. reaction finishes, and the CD signal intensity with this reactant liquor of circular dichroism spectroscopic assay, repeats twice.
The concentration of DNA2 is selected to be undertaken by same steps.
(6) formation of binary assembly structure and sign
The AuNPs of 10 μ L
10nmthe AuNPs of-DNA1 complex and 100 μ L
25nm– DNA2 complex, adds 100ng/mL Nano silver grain titer and the 10 μ L 5 * tris-borate buffers of 10 μ L, after reaction 30min, hybridize formation golden nanometer particle binary assembly.Binary golden nanometer particle assembly carries out structural characterization, and completed knocked down products is carried out to Electronic Speculum and dynamic light scattering sign.
(7) circular dichroism spectral detection, draws CD signal intensity～concentration of silver ions typical curve
AuNPs prepared by 10 μ L steps (3)
10nmauNPs prepared by-DNA1 complex and 100 μ L steps (4)
25nmthe silver ion standard items that add 0ng/mL, 0.005ng/mL, 0.01ng/mL, 0.05ng/mL, 0.1ng/mL, 0.5ng/mL, 1ng/mL, 5ng/mL, 10ng/mL in – DNA2 complex, in system, add 10 μ L 5 * tris-borate buffers, react after 30 min, join in micro-cuvette, survey CD signal, with the increment of CD signal, draw CD signal intensity and concentration of silver ions typical curve;
Control group arranges: Al
2+, Zn
2+, Mn2
+, Hg
+, Fe
2+, Cu
2+, Cr
2+, Co
2+and Cd
2+replace, other operation is the same.
DNA used in the present invention is all purchased from Chinese Shanghai Sheng Gong bioengineering company limited, and carries out purifying by polyacrylamide gel electrophoresis.
Beneficial effect of the present invention: compare with traditional instrumental method, the present invention utilizes trisodium citrate reduction AuNPs under the environment of liquid
10nm-DNA1 and AuNPs
25nm-DNA2 and silver ion reaction form binary assembly, and the formation of binary assembly can cause the generation of plasma chirality, and golden nanometer particle produces CD signal in visible region.By the CD signal intensity cloth in circular dichroism spectroscopic assay liquid environment, measure silver ion content.The present invention only reacts in liquid environment, does not need the step of cleaning, only needs single step reaction, has simplified the condition of reaction, has improved the sensitivity detecting.
Accompanying drawing explanation
The typical binary golden nanometer particle of Fig. 1 assembly Electronic Speculum figure.
Fig. 2 binary golden nanometer particle assembly dynamic light scattering phenogram.
Fig. 3 circular dichroism spectral detection canonical plotting.
Embodiment
Embodiment 1
(1) 10nm golden nanometer particle is synthetic
The synthetic schemes of 10nm golden nanometer particle is: in clean there-necked flask, add 60mL ultrapure water, 1mL 1% chlorauric acid solution is as A liquid; Get the ampoule of a cleaning, add 4mL 1% citric acid three sodium solution, 0.1mL 1% tannic acid solution, 0.1mL 50mM solution of potassium carbonate and 16mL ultrapure water are as B liquid; A, B liquid are all heated to 60 ℃, then under high-speed stirred, B liquid is added rapidly in A liquid, end reaction liquid continues to stir 30min and forms dark red solution at 60 ℃, then vlil 10min is formed to shiny red solution, last cool to room temperature forms the stable 10nm golden nanometer particle of citric acid.
(2) 25nm golden nanometer particle is synthetic
The synthetic schemes of 25nm golden nanometer particle is: in clean there-necked flask, add 47.5mL ultrapure water, add 0.8mL 0.4% chlorauric acid solution, stir and be heated to boiling, after 7-8min, add 1mL 1% citric acid three sodium solution, solution becomes redness from colourless, stop heating, continue to stir 30min;
(3) 10nm golden nanometer particle and DNA1 coupling
Get 10nm golden nanometer particle prepared by 5mL step (1) and add two (p-sulfonyl-phenyl) the Phenylphosphine di-potassium solution of 50 μ L 2mg/mL bis-hydrations, room temperature concussion 12h, after the centrifugal 10min of 13000r/min, remove supernatant, add ultrapure water and return to original volume, obtain the 10nm golden nanometer particle of protective agent parcel; Getting 10 μ L concentration is DNA1(5 '-CTC TCT TCT CTT CTC TCT TCT CT TCA-(CH of 1 μ M
2)
6-SH-3 ') join in the 10nm gold nano solution of the above-mentioned protective agent parcel of 100 μ L, in system, add 10 μ L 5 * tris-borate buffers, 25 ℃ of standing reaction 10h; The centrifugal 10min of 13000r/min, removes supernatant, and precipitation is diluted with water to 2 times of liquid of original volume, obtains AuNPs
10nm-DNA1 complex, the refrigerator of putting into 4 ℃ is standby.
(4) 25nm golden nanometer particle and DNA2 coupling
Get 25nm golden nanometer particle prepared by 5mL step (2) and add two (p-sulfonyl-phenyl) the Phenylphosphine di-potassium solution of 50 μ L 1mg/mL bis-hydrations, room temperature concussion 12h, after the centrifugal 10min of 7200r/min, remove supernatant, add ultrapure water and return to original volume, obtain the 25nm golden nanometer particle of protective agent parcel; Getting 1 μ L concentration is DNA2(5 '-TCA ACA CAA CAC ACA ACA CAA CAC AC-(CH of 1 μ M
2)
6-SH-3 ') join in the 25nm gold nano solution of the above-mentioned protective agent parcel of 100 μ L, in system, add 10 μ L 5 * tris-borate buffers, 25 ℃ of standing reaction 10h; The centrifugal 10min of 7200r/min, removes supernatant, and precipitation is diluted with water to 2 times of liquid of original volume, obtains AuNPs
25nm– DNA2 complex, the refrigerator of putting into 4 ℃ is standby.
(5) selection of coupling DNA concentration
In order to improve the sensitivity of this method, therefore need to need to select the DNA concentration of golden coupling.Optimum DNA concentration is after the two mixing adds standard solution reaction, and after circular dichroism spectroscopic assay, CD signal intensity is maximum.Concrete step is:
1. in centrifuge tube, add 100 μ L golden nanometer particles respectively, then add after the DNA1 of 0.1 μ M, 0.2 μ M, 0.5 μ M, 1 μ M, 2 μ M, 5 μ M, 10 μ M, in system, add 10 μ L 5 * tris-borate buffers, mix room temperature reaction 30min;
2. reaction finishes, and the CD signal intensity with this reactant liquor of circular dichroism spectroscopic assay, repeats twice.
The concentration of DNA2 is selected to be undertaken by same steps.
(6) formation of binary assembly structure and sign
The AuNPs of 10 μ L
10nmthe AuNPs of-DNA1 complex and 100 μ L
25nm– DNA2 complex, adds 10 μ L 100ng/mL Nano silver grain titers and 10 μ L 5 * tris-borate buffers, after reaction 30min, hybridizes formation golden nanometer particle binary assembly and carries out structural characterization.Obtain binary golden nanometer particle assembly, completed knocked down products is carried out to Electronic Speculum and dynamic light scattering sign.
(7) circular dichroism spectra detects, and draws CD signal intensity～concentration of silver ions typical curve
AuNPs prepared by 10 μ L steps (3)
10nmauNPs prepared by-DNA1 complex and 100 μ L steps (4)
25nmthe silver ion standard items that add 0ng/mL, 0.005ng/mL, 0.01ng/mL, 0.05ng/mL, 0.1ng/mL, 0.5ng/mL, 1ng/mL, 5ng/mL, 10ng/mL in – DNA2 complex, in system, add 10 μ L 5 * tris-borate buffers, react after 30 min, join in micro-cuvette, survey CD signal, with the increment of CD signal, draw CD signal intensity and concentration of silver ions typical curve;
Control group arranges: Al
2+, Zn
2+, Mn2
+, Hg
+, Fe
2+, Cu
2+, Cr
2+, Co
2+and Cd
2+replace, other operation is the same.
Claims (1)
1. use a method for the highly sensitive detection silver ion of circular dichroism spectrum, it is characterized in that obtaining AuNPs with two kinds of specific nucleotide sequence couplings of being rich in cytimidine (C) respectively with the golden nanometer particle of synthetic different-grain diameter
10nm-DNA1 and AuNPs
25nm-DNA2, adding of silver ion makes AuNPs
10nm-DNA1 and AuNPs
25nm-DNA2 produces C-Ag
+-C identification, utilizes trisodium citrate reduction AuNPs under the environment of liquid
10nm-DNA1 and AuNPs
25nm-DNA2 and silver ion reaction form binary assembly, and the formation of binary assembly causes the generation of plasma chirality, and golden nanometer particle produces circular dichroism spectrum CD signal in visible region; Processing step is:
(1) 10nm golden nanometer particle is synthetic
10nm golden nanometer particle is synthetic with tannic acid and trisodium citrate reduction gold chloride: in clean there-necked flask, add 60mL ultrapure water, 1mL mass concentration 1% chlorauric acid solution is as A liquid; Get the ampoule of a cleaning, add 4mL mass concentration 1% citric acid three sodium solution, 0.1mL mass concentration 1% tannic acid solution, 0.1mL 50mM solution of potassium carbonate and 16mL ultrapure water are as B liquid; A, B liquid are all heated to 60 ℃, then under high-speed stirred, B liquid is added rapidly in A liquid, reactant liquor continues to stir 30min and forms dark red solution at 60 ℃, then vlil 10min is formed to shiny red solution, and cool to room temperature forms the stable 10nm golden nanometer particle of citric acid;
(2) 25nm golden nanometer particle is synthetic
25nm golden nanometer particle is synthetic by citrate three sodium reducing process: in clean there-necked flask, add 47.5mL ultrapure water, add 0.8mL 0.4% chlorauric acid solution, stir and be heated to boiling, after 7-8min, add 1mL 1% citric acid three sodium solution, solution becomes redness from colourless, stop heating, continue to stir 30min;
(3) 10nm golden nanometer particle and DNA1 coupling
The 10nm golden nanometer particle that step (1) is synthesized and the DNA1 of sulfydryl modification carry out coupling and form golden nanometer particle-DNA1 complex: get 10nm golden nanometer particle prepared by 5mL step (1) and add two (p-sulfonyl-phenyl) the Phenylphosphine di-potassium solution of 50 μ L 2mg/mL bis-hydrations, room temperature concussion 12h, after the centrifugal 10min of 13000r/min, remove supernatant, add ultrapure water and return to original volume, obtain the 10nm golden nanometer particle of protective agent parcel; The DNA1 that gets 10 μ L concentration and be 1 μ M joins in the 10nm gold nano solution of the above-mentioned protective agent parcel of 100 μ L, adds 10 μ L 5 * tris-borate buffers, 25 ℃ of standing reaction 10h in system; The centrifugal 10min of 13000r/min, removes supernatant, and precipitation adds ultrapure water and is diluted to 2 times of liquid of original volume, obtains AuNPs
10nm-DNA1 complex, the refrigerator of putting into 4 ℃ is standby;
DNA1：5’-CTC?TCT?TCT?CTT?CTC?TCT?TCT?CT?TCA-(CH
2)
6-SH-3’；
The DNA1 concentration that this step is used allows to select;
(4) 25nm golden nanometer particle and DNA2 coupling
The 25nm golden nanometer particle that step (2) is synthesized and the DNA2 of sulfydryl modification carry out coupling and form Jin Na grain of rice – DNA2 complex: get 25nm golden nanometer particle prepared by 5mL step (2) and add two (p-sulfonyl-phenyl) the Phenylphosphine di-potassium solution of 50 μ L 1mg/mL bis-hydrations, room temperature concussion 12h, after the centrifugal 10min of 7200r/min, remove supernatant, add ultrapure water and return to original volume, obtain the 25nm golden nanometer particle of protective agent parcel; The DNA2 that gets 1 μ L concentration and be 1 μ M joins in the 25nm gold nano solution of the above-mentioned protective agent parcel of 100 μ L, adds 10 μ L 5 * tris-borate buffers, 25 ℃ of standing reaction 10h in system; The centrifugal 10min of 7200r/min, removes supernatant, and precipitation adds ultrapure water and is diluted to 2 times of liquid of original volume, obtains AuNPs
25nm– DNA2 complex, the refrigerator of putting into 4 ℃ is standby;
DNA2：5’-TCA?ACA?CAA?CAC?ACA?ACA?CAA?CAC?AC-(CH
2)
6-SH-3’；
The DNA2 concentration that this step is used allows to select;
(5) golden nanometer particle assembling
The AuNPs that adopts step (3) to prepare
10nmthe AuNPs that-DNA1 complex and step (4) prepare
25nm-DNA2 complex is hybridized formation golden nanometer particle binary assembly: 10 μ L AuNPs
10nm-DNA1 complex and 100 μ L AuNPs
25nm– DNA2 complex, adds 10 μ L 100ng/mL Nano silver grain titers and 10 μ L 5 * tris-borate buffers, after reaction 30min, hybridizes and forms golden nanometer particle binary assembly; Binary golden nanometer particle completed knocked down products is carried out to Electronic Speculum and dynamic light scattering sign;
(6) circular dichroism spectral detection, draws CD signal intensity～concentration of silver ions typical curve
AuNPs prepared by 10 μ L steps (3)
10nmauNPs prepared by-DNA1 complex and 100 μ L steps (4)
25nmthe silver ion standard items that add 0ng/mL, 0.005ng/mL, 0.01ng/mL, 0.05ng/mL, 0.1ng/mL, 0.5ng/mL, 1ng/mL, 5ng/mL, 10ng/mL in – DNA2 complex, in system, add 10 μ L 5 * tris-borate buffers, after reaction 30min, join in micro-cuvette, survey CD signal, with the increment of CD signal, draw CD signal intensity and concentration of silver ions typical curve;
Control group arranges: Al
2+, Zn
2+, Mn
2+, Hg
+, Fe
2+, Cu
2+, Cr
2+, Co
2+, Cd
2+replace, other operation is the same.
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| CN103293108B (en) * | 2013-06-25 | 2015-05-13 | 北京理工大学 | A one-dimensional arrangement hotspot structure of gold nanoballs and applications thereof |
| CN103411889B (en) * | 2013-08-21 | 2015-11-11 | 江南大学 | A kind of method detecting endonuclease DNase I activity based on golden tetrahedron chirality nanostructured |
| CN103760332B (en) * | 2014-01-16 | 2015-07-08 | 江南大学 | Method for detecting bisphenol A by utilizing aptamer-based chiral sensor |
| CN104384523B (en) * | 2014-09-23 | 2017-02-08 | 南京农业大学 | Preparing method of three-dimensional chiral silver nanometer material |
| CN104263837B (en) * | 2014-10-13 | 2016-03-23 | 江南大学 | The trimerical surface enhanced Raman scattering effect of golden nanometer particle modified based on triple beacon detects Hg in the aqueous solution 2+and/or Ag +method |
| CN104965074A (en) * | 2015-05-28 | 2015-10-07 | 广东省生态环境与土壤研究所 | Rapid silver ion detection using label-free colloidal gold colorimetry, and detection kit |
| CN105866039B (en) * | 2016-03-31 | 2018-08-17 | 陕西师范大学 | A kind of preparation of achirality structure that realizing circular dichroism and measurement method |
| CN106290166A (en) * | 2016-09-20 | 2017-01-04 | 江南大学 | A kind of circular dichroism real-time detection method of intracellular ATP |
| CN106872595B (en) * | 2017-02-20 | 2019-04-16 | 中国计量科学研究院 | The measuring method of chiral molecules content based on circular dichroism technology |
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