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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- -1 silver ions Chemical class 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 14
- 239000004332 silver Substances 0.000 title claims abstract description 14
- 238000001514 detection method Methods 0.000 title claims abstract description 10
- 238000002983 circular dichroism Methods 0.000 title abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 48
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010931 gold Substances 0.000 claims abstract description 31
- 229910052737 gold Inorganic materials 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 238000001142 circular dichroism spectrum Methods 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 28
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 239000001509 sodium citrate Substances 0.000 claims abstract description 7
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 7
- 150000007523 nucleic acids Chemical class 0.000 claims abstract description 4
- OPTASPLRGRRNAP-UHFFFAOYSA-N cytosine Chemical compound NC=1C=CNC(=O)N=1 OPTASPLRGRRNAP-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000000978 circular dichroism spectroscopy Methods 0.000 claims abstract 2
- 229940104302 cytosine Drugs 0.000 claims abstract 2
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- GZNIDISKGRVFNR-UHFFFAOYSA-N [K].[K].C1(=CC=CC=C1)P Chemical compound [K].[K].C1(=CC=CC=C1)P GZNIDISKGRVFNR-UHFFFAOYSA-N 0.000 claims description 5
- 238000011896 sensitive detection Methods 0.000 claims description 5
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 5
- 229940033123 tannic acid Drugs 0.000 claims description 5
- 235000015523 tannic acid Nutrition 0.000 claims description 5
- 229920002258 tannic acid Polymers 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
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- 238000003786 synthesis reaction Methods 0.000 claims 2
- OQUFOZNPBIIJTN-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium Chemical compound [Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OQUFOZNPBIIJTN-UHFFFAOYSA-N 0.000 claims 1
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- 238000001493 electron microscopy Methods 0.000 claims 1
- 238000009775 high-speed stirring Methods 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 claims 1
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- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 4
- 230000009514 concussion Effects 0.000 description 4
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
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- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
一种运用圆二色光谱高灵敏检测银离子的方法，属于分析化学技术领域。本发明合成的两种不同粒径的金纳米粒子分别与两种特定富含胞嘧啶（C）序列的核酸偶联得AuNPs10nm-DNA1和AuNPs25nm-DNA2，银离子的加入，使AuNPs10nm-DNA1和AuNPs25nm-DNA2产生C-Ag+-C错配识别，利用柠檬酸三钠还原在液体的环境下AuNPs10nm-DNA1和AuNPs25nm-DNA2及银离子反应形成二元组装体，二元组装体的形成可以导致等离子手性的产生，金纳米粒子在可见光区产生圆二色光谱CD信号。通过圆二色光谱测定液体环境中的CD信号强度来测定银离子含量。本发明只在液体环境中反应，不需要清洗的步骤，只需要一步反应，简化了反应的条件，提高了检测的灵敏度，达到国际领先水平。
The invention discloses a highly sensitive method for detecting silver ions by using circular dichroism spectrum, which belongs to the technical field of analytical chemistry. Two kinds of gold nanoparticles with different particle sizes synthesized by the present invention are respectively coupled with two specific cytosine (C)-rich sequence nucleic acids to obtain AuNPs 10nm -DNA1 and AuNPs 25nm -DNA2, and the addition of silver ions makes AuNPs 10nm -DNA2. DNA1 and AuNPs 25nm -DNA2 produce C-Ag + -C mismatch recognition, use trisodium citrate to reduce AuNPs 10nm -DNA1 and AuNPs 25nm -DNA2 and silver ions in a liquid environment to form a binary assembly, binary assembly The formation of the body can lead to the generation of plasmonic chirality, and the gold nanoparticles produce circular dichroism CD signal in the visible region. Silver ion content was determined by measuring the CD signal intensity in a liquid environment by circular dichroism spectroscopy. The invention only reacts in a liquid environment, does not need a cleaning step, only needs one-step reaction, simplifies the reaction conditions, improves the detection sensitivity, and reaches the international advanced level.
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.
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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 |
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| 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 | A method for the detection of Hg2+ and/or Ag+ in aqueous solutions based on the surface-enhanced Raman scattering effect of triple beacon-modified gold nanoparticle trimers |
| 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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