CN103389300A - Method for detecting quaternary ammonium salt cationic surfactant - Google Patents
Method for detecting quaternary ammonium salt cationic surfactant Download PDFInfo
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- CN103389300A CN103389300A CN2013103514089A CN201310351408A CN103389300A CN 103389300 A CN103389300 A CN 103389300A CN 2013103514089 A CN2013103514089 A CN 2013103514089A CN 201310351408 A CN201310351408 A CN 201310351408A CN 103389300 A CN103389300 A CN 103389300A
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- quaternary ammonium
- ammonium salt
- salt cationic
- citrate
- nano silver
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- 239000003093 cationic surfactant Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 30
- 239000004094 surface-active agent Substances 0.000 claims description 26
- 238000001514 detection method Methods 0.000 claims description 16
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 10
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000012086 standard solution Substances 0.000 claims description 4
- 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 description 4
- 229940038773 trisodium citrate Drugs 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 2
- 238000004445 quantitative analysis Methods 0.000 abstract 2
- 238000007865 diluting Methods 0.000 abstract 1
- 229960002233 benzalkonium bromide Drugs 0.000 description 8
- 238000005345 coagulation Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 238000004737 colorimetric analysis Methods 0.000 description 4
- 239000000645 desinfectant Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 3
- 238000005251 capillar electrophoresis Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010850 salt effect Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000004007 reversed phase HPLC Methods 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a qualitative method and a quantitative method for detecting a quaternary ammonium salt cationic surfactant. The qualitative method comprises the following steps: taking nano-silver sol modified by citric acid radicals; adding liquor to be detected to the nano-silver sol modified by the citric acid radicals; performing a reaction for over 2 minutes at room temperature; and observing whether the color of the liquor is changed or not after reaction of the system so as to determine whether the liquor to be detected contains the quaternary ammonium salt cationic surfactant. The quantitative method comprises the following steps: taking nano-silver sol modified by the citric acid radicals; respectively adding standard liquors containing quaternary ammonium salt cationic surfactants in different concentrations to the nano-silver sol modified by the citric acid radicals; performing a reaction for over 2 minutes at room temperature to form standard color liquor; then, diluting the liquor to be detected of the quaternary ammonium salt cationic surfactant to different multiples and then adding into the nano-silver sol modified by the citric acid radicals; and performing a reaction in same conditions, and comparing the liquor with the standard color liquor to determine concentration of the cationic surfactant in the liquor to be detected.
Description
Technical field
The present invention relates to a kind of method that detects quaternary ammonium salt cationic type surfactant, especially Tetradecyl Trimethyl Ammonium Bromide (TTAB) etc. is contained the detection of the cationic surfactant of high hydrophobicity group, belong to the detection fields of measurement of surfactant.
Background technology
Surfactant has been widely used in the fields such as commodity, cosmetics and medicine, and is well-known,, when surfactant is thrown in underground water or soil, just becomes a kind of environmental contaminants.At present, the detection method of cationic surfactant mainly contained Capillary Electrophoresis (CE), reverse high performance liquid chromatography (RP-HPLC), the methods such as vapor-phase chromatography (GC) and gas chromatography and mass spectrometry (GC-MS).But these methods all need expensive experimental apparatus, and trivial operations is consuming time and be unfavorable for Site Detection.Therefore develop a kind of low cost, fast, sensitive detection method is significant.
Summary of the invention
Technical matters to be solved by this invention is to provide a kind of method that detects cationic surfactant, to overcome the at present deficiency of the detection method of main cationic surfactant such as gas chromatography and mass spectrometry (GC-MS), such as expensive, the shortcoming such as consuming time, by utilizing the Nano Silver colourimetry, detection method of the present invention can realize the quick of quaternary ammonium salt cationic type surfactant, sensitive and detection cheaply.
The technical solution used in the present invention is as follows:
Surfactants based hydrophobic effect, utilize ultimate principle that nano silver colloidal sol that citrate is modified detects quaternary ammonium salt cationic type surfactant (take Tetradecyl Trimethyl Ammonium Bromide as example) as shown in Figure 1, the nano silver colloidal sol that the citrate that disperses is modified presents yellow, when adding quaternary ammonium salt cationic type surfactant, because occurring to assemble, Nano Silver presents redness, can, by the visual inspection change color, carry out the detection of quaternary ammonium salt cationic type surfactant this moment.
A kind of method (qualitative checking method) that detects quaternary ammonium salt cationic type surfactant: get the nano silver colloidal sol after citrate is modified, solution to be measured is added in nano silver colloidal sol after above-mentioned citrate is modified, more than at room temperature reacting 2min, whether the reacted color of observe system changes to determine whether contain cationic surfactant in solution to be measured.
Wherein, the nano silver colloidal sol after described citrate is modified, its particle size range is 10~20nm, resonance absorbing peak is 390~400nm.
Wherein, the nano silver colloidal sol of described citrate modification is prepared by following scheme:
Under stirring condition with 100mL, 0.05mmol/L~0.5mmol/L citric acid three sodium solution adds 100mL, 0.05mmol/L in~0.5mmol/L liquor argenti nitratis ophthalmicus, and the mol ratio of trisodium citrate and silver nitrate is 0.5~5:1, mix, under strong agitation, add fast 5mg~20mg sodium borohydride solids, abundant stirring reaction 1~4h, just can make the nano silver colloidal sol that yellow citrate is modified under 20 ℃~50 ℃.
Wherein, described quaternary ammonium salt cationic type surfactant is any one or a few the mixing in DTAB, dodecyl dimethyl benzyl ammonium bromide (benzalkonium bromide), Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethyl ammonium bromide, Cetyltrimethylammonium bromide and tetrabutylammonium chloride.
a kind of method (quantitative detecting method) that detects cationic surfactant: get the nano silver colloidal sol after citrate is modified, the standard solution that will contain the cationic surfactant of variable concentrations adds respectively in nano silver colloidal sol after above-mentioned citrate is modified, at room temperature react 2min above (suggestion supplements a numerical value to guarantee that any cationic surfactant is through the fully reaction of this time), form the standard color solution of different colours, the solution to be measured that will contain again quaternary ammonium salt cationic surfactant of the same race adds in nano silver colloidal sol after above-mentioned citrate is modified, reaction under the same conditions, by with standard color solution, contrasting the concentration of determining quaternary ammonium salt cationic surfactant in solution to be measured.
Wherein, the nano silver colloidal sol after described citrate is modified, its particle size range is 10~20nm, resonance absorbing peak is 390~400nm.
Wherein, the nano silver colloidal sol of described citrate modification is prepared by following scheme:
Under stirring condition with 100mL, 0.05mmol/L~0.5mmol/L citric acid three sodium solution adds 100mL, 0.05mmol/L in~0.5mmol/L liquor argenti nitratis ophthalmicus, and the mol ratio of trisodium citrate and silver nitrate is 0.5~5:1, mix, under strong agitation, add fast 5mg~20mg sodium borohydride solids, abundant stirring reaction 1~4h, just can make the nano silver colloidal sol that yellow citrate is modified under 20 ℃~50 ℃.
Wherein, described quaternary ammonium salt cationic type surfactant is any one in DTAB, dodecyl dimethyl benzyl ammonium bromide (benzalkonium bromide), Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethyl ammonium bromide, Cetyltrimethylammonium bromide and tetrabutylammonium chloride.
Beneficial effect of the present invention is:
Need not expensive experimental apparatus because colourimetry has, low cost, fast and the intrinsic advantage such as high sensitivity, the Nano Silver colourimetry of therefore utilizing citrate to modify can realize cationic surfactant fast, sensitive and detection cheaply.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is ultimate principle figure of the present invention; Wherein (1) is that Nano silver grain, (2) are citrate group, (3)
The nano silver colloidal sol of modifying for citrate for cationic surfactant, (4);
Fig. 2 is the experimental result picture of embodiment 1;
Fig. 3 is the experimental result picture of embodiment 2;
Fig. 4 is the experimental result picture of embodiment 3;
Fig. 5 and Fig. 6 are the experimental result picture of embodiment 4.
Embodiment
Following embodiment will describe more comprehensively to detection method of the present invention.
Pipette Nano silver solution that citrate modifies in the clean sample bottle of 2mL, and then add solution to be measured, react at ambient temperature 2min, it the results are shown in accompanying drawing Fig. 2.Can find that yellow Nano silver solution becomes is bordering on colourless solution, and hence one can see that, and this solution to be measured contains quaternary ammonium salt cationic surfactant.And this solution to be measured is exactly 10 of preparation
-5M Tetradecyl Trimethyl Ammonium Bromide (TTAB) solution, contain quaternary ammonium salt cationic surfactant.
Pipette Nano silver solution that citrate modifies in the clean sample bottle of 2mL, then DTAB (DTAB) solution, Tetradecyl Trimethyl Ammonium Bromide (TTAB), cetyl trimethyl ammonium bromide (CTAB), Cetyltrimethylammonium bromide (STAB) and the tetrabutylammonium chloride (TBAB) that add respectively variable concentrations, react at ambient temperature 2min, it the results are shown in accompanying drawing 3.List shows as shown in table 1.
By the observation experiment result as can be known, the cationic surfactant that the alkyl hydrophobicity is stronger makes the silver nanoparticle colloidal sol generation gathering that citrate is modified produce lower by the transformation concentration of the red transformation of xanthochromia.And the concentration difference that the quaternary ammonium salt cationic surfactant that contains different hydrophobicity hydrophobic groupings changes the nano silver colloidal sol reaction system change color of citric acid modification is very large.Hence one can see that, at cationic surfactant, makes in the process of the nano silver colloidal sol reaction system change color that citrate modifies, and the hydrophobicity of cationic surfactant hydrophobic grouping has play a part main.And in the middle of salt effect made the process that Nano Silver is polymerized to, common kation can't make the Nano Silver coagulation when low concentration, only in concentration higher than 10
-2Mol/L is above just can be because salt effect makes the Nano Silver coagulation.Hence one can see that, and it is diverse that quaternary ammonium salt cationic type surfactant makes the mechanism of nano silver colloidal sol coagulation and common cation make the mechanism of nano silver colloidal sol coagulation.Comparatively speaking, quaternary ammonium salt cationic type surfactant makes the concentration of nano silver colloidal sol coagulation lower.
Table 1
Pipette Nano silver solution that citrate modifies in the clean sample bottle of 2mL, then add respectively the benzalkonium bromide solution of variable concentrations, react at ambient temperature 2min, with the standard solution that forms its benzalkonium bromide solution,, than chromatic graph, the results are shown in accompanying drawing Fig. 4., along with the continuous increase of benzalkonium bromide concentration, can find yellow Nano silver solution (10
-6Mol/L) first become redness (3 * 10
-6Mol/L), become subsequently and be bordering on colourless solution (5 * 10
-6Mol/L), become again finally redness (5 * 10
-4Mol/L) and yellow (5 * 10
-3Mol/L) solution.
Pipette in the Nano silver solution that the citrate that adds respectively of the disinfectant that contains benzalkonium bromide of dilution different multiples modifies, extension rate is respectively 2 times, and 4 times, 20 times, 40 times, 66 times, 200 times (from left to right), along with improving constantly of disinfectant concentration, Nano silver solution first becomes redness (200 times of dilutions), become and be bordering on colourless solution (66 times of dilutions), become finally the solution that is bordering on redness (20 times of dilutions) and yellow (2 times of dilutions), it the results are shown in accompanying drawing Fig. 5.According to change color in figure as can be known, dilution 200 times the time with the standard solution of benzalkonium bromide than in chromatic graph (Fig. 4) 3 * 10
-6The mol/L color is corresponding, and can calculate benzalkonium bromide concentration in disinfectant is 3 * 10
-6* 200=6 * 10
-4Mol/L.This disinfectant of getting same concentrations adopts the HPLC method to analyze, result as shown in Figure 6, its chromatographic condition: mobile phase 0.02mol/LNaClO
4(pH=2.7): acetonitrile (30:70), C18 reverse-phase chromatographic column (100A, 5um), flow velocity: 1ml/min, sample size: 20ul, detect wavelength 258nm.Analyze data as can be known, good linear relationship is arranged between 0.05mg/ml---1.00mg/ml, linear relation: S=396.2x+26.68, R=0.999.Be 7.07 * 10 according to peak area (138.33) result of calculation
-4Mol/L, compare comparatively approaching with the colourimetry result.
Claims (8)
1. method that detects quaternary ammonium salt cationic type surfactant, it is characterized in that: get the nano silver colloidal sol after citrate is modified, solution to be measured is added in nano silver colloidal sol after above-mentioned citrate is modified, more than at room temperature reacting 2min, the reacted change color of observe system is to determine whether contain quaternary ammonium salt cationic type surfactant in solution to be measured.
2. the method for detection quaternary ammonium salt cationic type surfactant as claimed in claim 1 is characterized in that: the nano silver colloidal sol after described citrate is modified, and its particle size range is 10~20nm, resonance absorbing peak is 390~400nm.
3. the method for detection quaternary ammonium salt cationic type surfactant as claimed in claim 1 or 2 is characterized in that: the nano silver colloidal sol that described citrate is modified is prepared by following scheme:
Under stirring condition with 100mL, 0.05mmol/L~0.5mmol/L citric acid three sodium solution adds 100mL, 0.05mmol/L in~0.5mmol/L liquor argenti nitratis ophthalmicus, and the mol ratio of trisodium citrate and silver nitrate is 0.5~5:1, mix, under strong agitation, add fast 5mg~20mg sodium borohydride solids, abundant stirring reaction 1~4h under 20 ℃~50 ℃.
4. the method for detection quaternary ammonium salt cationic type surfactant as claimed in claim 1 is characterized in that: described quaternary ammonium salt cationic type surfactant is any one or a few the mixing in DTAB, dodecyl dimethyl benzyl ammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethyl ammonium bromide, Cetyltrimethylammonium bromide and tetrabutylammonium chloride.
5. method that detects quaternary ammonium salt cationic type surfactant, it is characterized in that: get the nano silver colloidal sol after citrate is modified, the standard solution that will contain the quaternary ammonium salt cationic surfactant of variable concentrations adds respectively in nano silver colloidal sol after above-mentioned citrate is modified, more than at room temperature reacting 2min, form the standard color solution of different colours, to contain again after the solution dilution different multiples to be measured of quaternary ammonium salt cationic surfactant in the nano silver colloidal sol that adds after above-mentioned citrate is modified, reaction under the same conditions, by with standard color solution, contrasting the concentration of determining cationic surfactant in solution to be measured.
6. the method for detection quaternary ammonium salt cationic type surfactant as claimed in claim 5 is characterized in that: the nano silver colloidal sol after described citrate is modified, and its particle size range is 10~20nm, resonance absorbing peak is 390~400nm.
7. the method for detection quaternary ammonium salt cationic type surfactant as described in claim 5 or 6 is characterized in that: the nano silver colloidal sol that described citrate is modified is prepared by following scheme:
Under stirring condition with 100mL, 0.05mmol/L~0.5mmol/L citric acid three sodium solution adds 100mL, 0.05mmol/L in~0.5mmol/L liquor argenti nitratis ophthalmicus, and the mol ratio of trisodium citrate and silver nitrate is 0.5~5:1, mix, under strong agitation, add fast 5mg~20mg sodium borohydride solids, abundant stirring reaction 1~4h under 20 ℃~50 ℃.
8. the method for detection quaternary ammonium salt cationic type surfactant as claimed in claim 5, it is characterized in that: described quaternary ammonium salt cationic type surfactant is any one in DTAB, dodecyl dimethyl benzyl ammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethyl ammonium bromide, Cetyltrimethylammonium bromide and tetrabutylammonium chloride.
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Cited By (4)
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CN104198480A (en) * | 2014-08-20 | 2014-12-10 | 浙江大学 | Aqueous quaternary ammonium salt detection test paper and preparation method thereof |
CN104237219A (en) * | 2014-08-20 | 2014-12-24 | 浙江大学 | Semi-quantitative detection method of quaternary ammonium salt of water quality |
CN105115957A (en) * | 2015-07-24 | 2015-12-02 | 齐齐哈尔大学 | Quantitative detection method for hexadecyl trimethyl ammonium bromide |
CN115046984A (en) * | 2022-06-16 | 2022-09-13 | 海澳华(黑龙江)生物医药技术有限公司 | Method for detecting medicine in blood based on surface enhanced Raman spectroscopy technology |
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CN101256174A (en) * | 2008-02-02 | 2008-09-03 | 深圳市华测检测技术股份有限公司 | Method for testing alkyl quaternaries cationic surfactant |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104198480A (en) * | 2014-08-20 | 2014-12-10 | 浙江大学 | Aqueous quaternary ammonium salt detection test paper and preparation method thereof |
CN104237219A (en) * | 2014-08-20 | 2014-12-24 | 浙江大学 | Semi-quantitative detection method of quaternary ammonium salt of water quality |
CN104237219B (en) * | 2014-08-20 | 2016-08-24 | 浙江大学 | A kind of water quality quaternary ammonium salt semi-quantitative detection method |
CN105115957A (en) * | 2015-07-24 | 2015-12-02 | 齐齐哈尔大学 | Quantitative detection method for hexadecyl trimethyl ammonium bromide |
CN115046984A (en) * | 2022-06-16 | 2022-09-13 | 海澳华(黑龙江)生物医药技术有限公司 | Method for detecting medicine in blood based on surface enhanced Raman spectroscopy technology |
CN115046984B (en) * | 2022-06-16 | 2023-01-03 | 海澳华(黑龙江)生物医药技术有限公司 | Method for detecting medicine in blood based on surface enhanced Raman spectroscopy technology |
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