CN109799230A - The device for fast detecting and detection method of a kind of metal complex and chiral isomer - Google Patents
The device for fast detecting and detection method of a kind of metal complex and chiral isomer Download PDFInfo
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- CN109799230A CN109799230A CN201910090439.0A CN201910090439A CN109799230A CN 109799230 A CN109799230 A CN 109799230A CN 201910090439 A CN201910090439 A CN 201910090439A CN 109799230 A CN109799230 A CN 109799230A
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- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 52
- 238000001514 detection method Methods 0.000 title claims abstract description 20
- HWYHZTIRURJOHG-UHFFFAOYSA-N luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000004088 simulation Methods 0.000 claims abstract description 10
- 238000002347 injection Methods 0.000 claims description 39
- 239000007924 injection Substances 0.000 claims description 39
- 238000004377 microelectronic Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 25
- 230000002572 peristaltic effect Effects 0.000 claims description 23
- 239000012488 sample solution Substances 0.000 claims description 21
- 239000012530 fluid Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000003957 anion exchange resin Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000523 sample Substances 0.000 claims description 10
- 238000004020 luminiscence type Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012086 standard solution Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000013016 damping Methods 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000004445 quantitative analysis Methods 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000013507 mapping Methods 0.000 claims description 2
- 230000005622 photoelectricity Effects 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract description 8
- 238000005259 measurement Methods 0.000 abstract description 6
- 238000004458 analytical method Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 230000003760 hair shine Effects 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 19
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 15
- 229960002163 hydrogen peroxide Drugs 0.000 description 13
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 12
- WAPNOHKVXSQRPX-SSDOTTSWSA-N (R)-1-phenylethanol Chemical compound C[C@@H](O)C1=CC=CC=C1 WAPNOHKVXSQRPX-SSDOTTSWSA-N 0.000 description 8
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- QMXOFBXZEKTJIK-UHFFFAOYSA-N Glycinol Natural products C1=C(O)C=C2OCC3(O)C4=CC=C(O)C=C4OC3C2=C1 QMXOFBXZEKTJIK-UHFFFAOYSA-N 0.000 description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 8
- BZPRATGFHKWAKR-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O BZPRATGFHKWAKR-UHFFFAOYSA-N 0.000 description 7
- MOMFXATYAINJML-UHFFFAOYSA-N 2-Acetylthiazole Chemical group CC(=O)C1=NC=CS1 MOMFXATYAINJML-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 5
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- -1 4- anisyl Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- CVZIHXRHSDYALS-UHFFFAOYSA-N 1-fluoropentane-2,4-dione Chemical class CC(=O)CC(=O)CF CVZIHXRHSDYALS-UHFFFAOYSA-N 0.000 description 3
- AQTFKGDWFRRIHR-UHFFFAOYSA-L 3-[18-(2-carboxylatoethyl)-8,13-bis(ethenyl)-3,7,12,17-tetramethylporphyrin-21,24-diid-2-yl]propanoate;cobalt(2+);hydron Chemical compound [Co+2].[N-]1C(C=C2C(=C(C)C(C=C3C(=C(C)C(=C4)[N-]3)C=C)=N2)C=C)=C(C)C(CCC(O)=O)=C1C=C1C(CCC(O)=O)=C(C)C4=N1 AQTFKGDWFRRIHR-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 235000013495 cobalt Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 2
- MREPUZZHXBXWLW-UHFFFAOYSA-N cobalt(2+);ethane-1,2-diamine Chemical compound [Co+2].NCCN MREPUZZHXBXWLW-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000007422 luminescence assay Methods 0.000 description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- WAPNOHKVXSQRPX-ZETCQYMHSA-N (S)-1-phenylethanol Chemical compound C[C@H](O)C1=CC=CC=C1 WAPNOHKVXSQRPX-ZETCQYMHSA-N 0.000 description 1
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SBNQJAHLGZCHCA-UHFFFAOYSA-N [Co].CC=1NC=CN1 Chemical compound [Co].CC=1NC=CN1 SBNQJAHLGZCHCA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000002038 chemiluminescence detection Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- ADLCQTOUBMFMFV-UHFFFAOYSA-L cobalt(2+);triphenylphosphane;dichloride Chemical compound Cl[Co]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ADLCQTOUBMFMFV-UHFFFAOYSA-L 0.000 description 1
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000000504 luminescence detection Methods 0.000 description 1
- FLESAADTDNKLFJ-UHFFFAOYSA-N nickel;pentane-2,4-dione Chemical compound [Ni].CC(=O)CC(C)=O FLESAADTDNKLFJ-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a kind of metal complex and the device for fast detecting and detection method of chiral isomer.It shines testing principle the present invention is based on cyclic chemical, using the fixed luminol reagent of resin, sample and luminol haptoreaction is utilized to generate chemiluminescence signal；By periodically switching current-carrying direction, enters sample cycle in microreactor and reaction is repeated, generate a series of signal of exponentially attenuation law variations；Digital simulation is carried out to gained signal and obtains the exponential equation of description signal intensity rule, it is excessive that metal complex, identification chiral isomer configuration and measurement isomers are quickly detected by attenuation coefficient in utilization index equation and primary quantity, it can qualitative and quantitative detection various structures be complicated and similar metal complex, described device structure is simple, cost and operating cost are low, easy to operate, identifies for complex, chiral analysis provides new technical support.
Description
Technical field
The present invention relates to the quick inspections of chemiluminescence detection field more particularly to a kind of metal complex and chiral isomer
Survey device and detection method.
Background technique
Metallic element can form various coordinate complex with different types of ligand binding.These metal complexs are not only
Structure is complicated, has certain similitude in structure；The phenomenon that there is also enantiomerisms simultaneously.Currently, metal complex
Quick detection be still a challenge, especially because the structure and chemical similarity of metal complex are difficult to it with conventional change
It learns and physical method is identified.
The identification of enantiomter configuration and the measurement of enantiomeric excess (ee) have in asymmetric syntheses and pharmaceutical chemistry
There is very important effect.Gas-chromatography, liquid chromatogram and nuclear magnetic resoance spectrum are common identification enantiomter and survey at present
Determine the method for ee.However there is time-consuming, instrument is costly and cumbersome and needs asking for professional's operation for these methods
Topic.
Summary of the invention
Aiming at the shortcomings in the prior art, the present invention provides the quick detections of a kind of metal complex and chiral isomer
Device identifies that existing time-consuming, expensive equipment and heaviness to solve metal combination analyte detection, enantiomter in the prior art
And problem complicated for operation, it can rapidly detect metal complex, identification chiral isomer configuration and measurement isomers mistake
Amount, device is simple, and cost and operating cost are low.
To achieve the above object, the present invention adopts the following technical solutions:
The device for fast detecting of a kind of metal complex and chiral isomer, it is characterised in that: including a high-pressure pump, one compacted
Dynamic pump, a certain amount of ring, a six-way injection valve, micro- electronic six cross valve and a Weak-luminescence detector, it is described micro- electronic
By piping connection, the Weak-luminescence detector includes a microreactor, immobilized for six cross valves and the six-way injection valve
There is the anion exchange resin of luminol to be filled in the microreactor, the output end of high-pressure pump and the output end point of peristaltic pump
It is not connected to the six-way injection valve, the both ends of quantitative loop are connected to the six-way injection valve；The six-way injection valve has ON
With two states of OFF, when the six-way injection valve is on state, the peristaltic pump is connected to the quantitative loop, the height
Press pump is isolated with the quantitative loop, is connected to micro- electronic six cross valve；When the six-way injection valve is in OFF state
When, the high-pressure pump is successively connected to the quantitative loop, micro- electronic six cross valve, the peristaltic pump and the quantitative loop
It is isolated；The both ends of microreactor are connected to micro- electronic six cross valve, micro- electronic six cross valve have ON and
Two states of OFF, the current-carrying direction phase when micro- electronic six cross valve is in two kinds of different conditions, in microreactor
Instead.
Specifically, set on the six-way injection valve there are six port, be along the circumferential direction followed successively by a1~f1, wherein a1 mouthful and
The high-pressure pump is connected, and b1 and e1 mouthfuls are connected with quantitative loop both ends respectively, and c1 mouthfuls are connected with the peristaltic pump, f1 mouthfuls with
Micro- electronic six cross valve is connected；When the six-way injection valve is on state, six ports form two-by-two three it is logical
Road, respectively a1-f1, e1-d1 and c1-b1；When in OFF state, six ports form three channels two-by-two, respectively
A1-b1, c1-d1 and e1-f1；Set on micro- electronic six cross valve there are six port, be along the circumferential direction followed successively by a2~
F2 is wherein connected for c2 mouthfuls with the six-way injection valve, and b2 is connected with microreactor inlet and outlet respectively with d2 mouthfuls, and f2 mouthfuls using stifled
Head closing；When micro- electronic six cross valve is on state, six ports form three channels two-by-two, respectively a2-f2,
E2-d2 and c2-b2；When in OFF state, six ports form three channels two-by-two, respectively c2-d2, e2-f2 and
b2-a2。
Further, the Weak-luminescence detector using photomultiplier tube as detector, with high sensitive
Degree and extremely short response time；The microreactor material is preferably high-purity quartz, and shape is straight-through cast.
Further, the six-way injection valve and micro- electronic six cross valves inner spool material are ceramics, and bore is preferred
It is 1/16 inch, ceramic cartridge has the features such as strong wearability, good airproof performance, long service life and high temperature resistant；The quantitative loop
Volume is preferably 50uL.
Further, the pump, valve and microreactor pass through peek pipe and connect, and outer diameter is preferably 1/16 inch,
Peek (polyethers ether copper) has high mechanical strength, high temperature resistant, impact resistance, fire-retardant, acid and alkali-resistance, hydrolysis, wear-resisting, endurance, resistance to
The advantages that irradiation and satisfactory electrical conductivity.
In addition, being examined the present invention also provides a kind of method of quickly detection metal complex using above-mentioned apparatus
It surveys, includes the following steps:
1) the immobilized anion exchange resin for having luminol is filled into the microreactor, opens high-pressure pump and wriggling
Pump；
2) carrier fluid is configured, for the oxidizing agent solution that can be generated active oxygen by metal complex catalyzed decomposition；The high pressure
Pump will carry
Liquid is delivered in microreactor, is balanced baseline；
3) sample solution is configured, sample solution is delivered to quantitative loop by the peristaltic pump, until it is full of；
4) converting the six-way injection valve mixes hydrogen peroxide with sample, and mixed solution enters microreactor and luminol
Haptoreaction generates apparent chemiluminescence signal；By periodically switching micro- electronic six cross valve to change current-carrying direction,
Enter sample cycle in microreactor and reaction is repeated, obtains a series of chemiluminescences by exponential damping law variation
Signal；
5) digital simulation is carried out as the chemiluminescence signal to obtained by and obtains an exponential equation for describing its changing rule,
Mathematical expression is In=A exp (- t/k)+I0, wherein InFor each signal strength, A is maximum chemical luminous signal intensity, and k is decaying
Coefficient, t are time, I0For background value；Metal complex is identified according to the k value of exponential equation.
Further, above-mentioned steps 5) in further include to metal complex carry out quantitative analysis, method are as follows: known to preparation
The metal complex standard solution to be measured of various concentration, respectively obtains a series of chemiluminescence signals using above-mentioned same procedure,
Digital simulation is carried out by gained chemiluminescence signal and obtains exponential equation, the metal complex standard solution of various concentration is being referred to
Each A value and its concentration in number equation form a linear equation, further according to the A value meter of resulting metal complex sample solution
Calculation obtains the concentration of metal complex sample solution.
In addition, the present invention also provides a kind of method of Rapid identification chirality enantiomter, using above-mentioned apparatus into
Row detection, includes the following steps:
1) the immobilized anion exchange resin for having luminol is filled into the microreactor, opens high-pressure pump and wriggling
Pump；
2) carrier fluid is configured, for the oxidizing agent solution that can be generated active oxygen by metal complex catalyzed decomposition；The high pressure
Carrier fluid is delivered in microreactor by pump, is balanced baseline；
3) it uses known chipal compounds for receptor, chipal compounds to be measured is added into its solution, be uniformly mixed and be made
Sample solution is delivered to quantitative loop by sample solution, the peristaltic pump, until it is full of；
4) converting the six-way injection valve mixes carrier fluid with sample solution, and mixed solution enters microreactor and luminol
Haptoreaction generates apparent chemiluminescence signal；By periodically switching micro- electronic six cross valve to change current-carrying direction,
Enter sample cycle in microreactor and reaction is repeated, obtains a series of chemiluminescences by exponential damping law variation
Signal；
5) digital simulation is carried out as the chemiluminescence signal to obtained by and obtains an exponential equation for describing its changing rule,
Mathematical expression is In=A exp (- t/k)+I0, wherein InFor each signal strength, A is maximum chemical luminous signal intensity, and k is decaying
Coefficient, t are time, I0For background value；It is identified according to configuration of the gained k value to chipal compounds to be measured.
Further, the method for the Rapid identification chirality enantiomter, further includes being measured to enantiomeric excess,
It the steps include: to measure two chiral enantiomter original attenuation coefficients and enantiomeric mixture respectively according to the method
Attenuation coefficient calculates enantiomeric excess according to following relationship:
Wherein ee is enantiomeric excess, k(R)And k(S)The original attenuation coefficient of respectively two chiral enantiomters,
k(R, S)For the original attenuation coefficient of enantiomeric mixture；
Further, step 1) the mesohigh pump and peristaltic pump setting flow velocity are preferably 10mL/min.
The device for fast detecting and detection method of metal complex and chiral isomer provided by the present invention have following
The utility model has the advantages that
Structure of the detecting device is simple, can pass through the load in the working condition realization device of the micro- electronic six logical conversion valve of change
Freely commutating for stream direction, it is easy to operate；The immobilized anion exchange resin for having luminol is used multiple times, cost and running cost
With low.Can the similar and complicated metal complex of qualitative and quantitative detection various structures and identification chiral isomer configuration, nothing
Standard curve, which need to be established, can quickly measure ee value, easy to operate, quick, provide for complex identification, chiral analysis new
Technical support.
In order to better understand and implement, the invention will now be described in detail with reference to the accompanying drawings.
Detailed description of the invention
Fig. 1 is the device for fast detecting structural schematic diagram of metal complex and chiral isomer of the present invention.
Wherein, 1: high-pressure pump；2: peristaltic pump；3: six-way injection valve；4: micro- electronic six cross valve；5: quantitative loop；6: Gu
It is loaded with the anion exchange resin of luminol；7: microreactor；8: Weak-luminescence detector；9: hydrogenperoxide steam generator；10: sample
Solution；11: plug；
Fig. 2 is luminol-hydrogen peroxide-acetylacetone cobalt (II) system cyclic chemical luminous signal changing rule.
Fig. 3 is acetylacetone cobalt (II) concentration and A, k value relationship.
Fig. 4 is concentration of hydrogen peroxide and A, k value relationship.
Fig. 5 is the k value dendrogram of different metal complex.
Wherein, 1:(triphenylphosphine) cobalt chloride (II)；- two salicylide ethylenediamine cobalt (II) of 2:N, N '；3:2- methylimidazole
Cobalt (II), 4: Cobalt Phthalocyanine (II)；5: acetylacetone,2,4-pentanedione platinum (II)；6: acetylacetone cobalt (II)；7: palladium acetylacetonate (II)；8: acetyl
Acetone nickel (II)；9: cobalt protoporphyrin；10:meso- CoTPP；11:[5,10,15,20- tetra- (4- anisyl) porphyrin]
It closes cobalt (II)；12: bis- (three fluoro- 2,4- pentanediones) cobalts (II)；13: hexafluoroacetylacetone cobalt (II).
Fig. 6 is that bis- two mesitylene of (2- acetyl -3- oxo -2- butenylidene) -1,2- of (1R, 2R)-N, N'- are respectively adopted
Base triethylenediamine cobalt (II) and the bis- two mesitylene bases of (2- acetyl -3- oxo -2- butenylidene) -1,2- of (1S, 2S)-N, N'-
Result of the triethylenediamine cobalt (II) as receptor identification chiral isomer
Wherein, 1:(R)-(+) -1- phenylethanol；2:(S)-(+) -1- phenylethanol；3:(R) -2- amylalcohol；4:(S) -2-
Amylalcohol；5:(R)-(+) -2- benzene glycinol；6:(S)-(+) -2- benzene glycinol.
Fig. 7 is using the bis- two mesitylene base second of (2- acetyl -3- oxo -2- butenylidene) -1,2- of (1R, 2R)-N, N'-
Diamines closes cobalt (II) and is used as receptor, measures (R)-(+) -1- phenylethanol and the mixing of (S)-(+) -1- phenylethanol of different proportion
The k value result of object.
Fig. 8 is using the bis- two mesitylene base second of (2- acetyl -3- oxo -2- butenylidene) -1,2- of (1S, 2S)-N, N'-
Diamines closes cobalt (II) and is used as receptor, measures (R)-(+) -1- phenylethanol and the mixing of (S)-(+) -1- phenylethanol of different proportion
The k value result of object.
Specific embodiment
Embodiment 1
The present invention will be further elaborated with reference to the accompanying drawings and examples, it should which explanation, following the description is only
It is not to be defined to its content to explain the present invention.
Referring to Fig. 1, it is the device for fast detecting structural representation of metal complex and chiral isomer of the present invention
Figure, the device for fast detecting of the metal complex and chiral isomer comprising a high-pressure pump 1, a peristaltic pump 2,1 are logical
Micro- electronic six cross valve 4 of sampling valve 3, one, a certain amount of ring 5 and a Weak-luminescence detector 8, described micro- electronic six logical conversions
Valve 4 and the six-way injection valve 3 pass through piping connection；The both ends of quantitative loop 5 are connected to the six-way injection valve 3；It is described faint
Luminometer 8 includes a microreactor 7, and the immobilized anion exchange resin 6 for having luminol is filled in the microreactor 7
In.
The output end of high-pressure pump 1 and the output end of peristaltic pump 2 are connected to the six-way injection valve 3.The high-pressure pump 1
For conveying carrier fluid, the carrier fluid is can be by the metal complex catalyzed oxidizing agent solution for decomposing generation active oxygen, in this implementation
It is hydrogenperoxide steam generator 9 in example；The peristaltic pump 2 is for conveying sample solution, and tube at one end is placed in sample solution 10, separately
One end is connected with six-way injection valve 3.
Set on the six-way injection valve 3 there are six port, be circumferentially followed successively by a1~f1 clockwise, wherein a1 mouthful and
The high-pressure pump 1 is connected, and b1 and e1 mouthfuls are connected with 5 both ends of quantitative loop respectively, and c1 mouthfuls are connected with the peristaltic pump 2, d1
For excessive liquid to be discharged, f1 mouthfuls are connected with micro- electronic six cross valve 4.The six-way injection valve 3 have ON and
Two states of OFF, when the six-way injection valve 3 is on state, as shown in figure 1 shown in I, the peristaltic pump 2 with it is described quantitative
Ring 5 is connected to the high-pressure pump and is isolated with the quantitative loop, is connected to micro- electronic six cross valve, specifically, at this time six
A port forms three channels, respectively a1-f1, e1-d1 and c1-b1 two-by-two；When the six-way injection valve is in OFF state
When, as shown in figure 1 shown in II, the high-pressure pump is successively connected to the quantitative loop, micro- electronic six cross valve, the wriggling
Pump is isolated with the quantitative loop, and specifically, three channels of six ports composition are a1-b1, c1-d1 and e1-f1 at this time.
Port there are six setting on micro- electronic six cross valve, is circumferentially followed successively by a2~f2 clockwise, wherein
C2 mouthfuls are connected with the six-way injection valve, and b2 is connected with microreactor inlet and outlet respectively with d2 mouthfuls, and a2 and c2 are used for discharge liquor
Body, f2 mouthfuls are closed using plug；Micro- electronic six cross valve has two states of ON and OFF, when described micro- electronic six logical
When switching valve is in two kinds of different conditions, the current-carrying in microreactor is contrary.When micro- electronic six cross valve is in
When ON state, as shown in figure 1 shown in II, six ports form three channels, respectively a2-f2, e2-d2 and c2-b2 two-by-two, micro-
Current-carrying direction in reactor is from left to right；When in OFF state, as shown in figure 1 shown in III, three of six ports composition are logical
Road is c2-d2, e2-f2 and b2-a2, and the current-carrying direction in microreactor is from right to left.
In the present embodiment, the six-way injection valve 3 and micro- 4 inner spool material of electronic six cross valve are high technology ceramics,
Bore is 1/16 inch.5 volume of quantitative loop is 50uL, but not limited to this, different volumes can be selected according to requirement of experiment
Quantitative loop.7 material of microreactor is high-purity quartz, and shape is straight-through cast, and outer diameter 4mm, internal diameter 2mm are long
Degree is 6cm, and specification and shape equally can be depending on requirement of experiment.The Weak-luminescence detector 8 uses photomultiplier tube
As detector, with high sensitivity and extremely short response time, but not limited to this detector of form also can be used
The detector of other detectable chemiluminescence signals.Said pump, valve, microreactor are connected through peek pipe, pipe outside diameter 1/16
Inch.
The method that following detailed description quickly detects metal complex and chiral isomer using above-mentioned apparatus, including it is following
Step:
1) the immobilized anion exchange resin for having luminol is filled to being filled in microreactor, opens high-pressure pump and compacted
Dynamic pump, sets flow velocity as 10mL/min；
2) configuration concentration is the hydrogenperoxide steam generator of 0.02mmol/L, adjusts pH value to 5.0, as shown in figure 1 shown in I, uses
It is delivered in microreactor 7 by high-pressure pump 1 through carrier fluid channel a1-f1, is balanced baseline；
3) sample solution is configured, adjusts pH value to 5.0；As shown in figure 1 shown in I, using peristaltic pump 2 by sample through sample intake passage
C1-b1 is delivered to quantitative loop 5 and is full of to it, and extra liquid is discharged through channel e1-d1.
4) conversion six-way injection valve 3 makes it complete the conversion of ON state and OFF state, mixes hydrogen peroxide with sample.
After conversion as shown in figure 1 shown in II, hydrogen peroxide carrier fluid is through sample solution in channel a1-b1 carrying quantitative loop 5 together by channel
E1-f1 is entered in the microreactor, with luminol haptoreaction, generates apparent chemiluminescence signal.It is micro- by converting
Electronic six cross valve 5 completes the switching of ON state and OFF state to change the current-carrying direction in microreactor: from six lead into
The testing liquid of sample valve, which is entered in microreactor 7 through channel c2-b2 by the direction in figure from left to right, to be reacted；After rotation,
Testing liquid enters in microreactor from right to left through the channel c2-d2.Micro- electronic six cross valve 5 of conversion in every 36 seconds, which changes, to be carried
Direction is flowed, enters sample cycle in microreactor 7 and reaction is repeated, generation is a series of to press what exponential damping law changed
Chemiluminescence signal；
5) its variation rule metal combination analyte detection: is described by obtaining one to chemiluminescence signal progress digital simulation
The exponential equation of rule, mathematical expression In=A exp (- t/k)+I0, wherein InFor each signal strength, A is the luminous letter of maximum chemical
Number intensity, k is attenuation coefficient, and t is time, I0For background value；Metal complex is identified according to the k of exponential equation；Separately
Outside, the metal complex standard solution to be measured for preparing known various concentration, respectively obtains a series ofization using above-mentioned same procedure
Luminous signal is learned, digital simulation is carried out by gained chemiluminescence signal and obtains exponential equation, by the metal complex of various concentration
Each A value of the standard solution in exponential equation and its concentration form a linear equation, are calculated further according to measured A value
The concentration of metal complex sample solution.
6) using known chipal compounds as receptor, hand to be measured chiral enantiomter detection: is added into its solution
Property compound, measured after mixing by above-mentioned the same terms and step, the structure of chipal compounds to be measured identified according to gained k value
Type；
7) enantiomeric excess detects: measuring two chiral enantiomter original attenuation coefficients and right respectively according to the above method
The attenuation coefficient for reflecting isomer mixture calculates enantiomeric excess according to following relationship:
Wherein ee is enantiomeric excess, k(R)And k(S)The original attenuation coefficient of respectively two chiral enantiomters,
k(R, S)For the original attenuation coefficient of enantiomeric mixture；
The present embodiment is using cyclic chemical luminescence detection apparatus for proving quickly detection metal complex and chiral photo-isomerisation
The basic principle of body is as follows:
1. cyclic chemical luminous signal changing rule
Configuration concentration is acetylacetone cobalt (II) solution of 0.2mol/L, adjusts pH to 5.0.It is surveyed by said determination step
It is fixed, obtain a series of chemiluminescence signals of cyclic chemical luminescence assays, obtain a chemiluminescence signal intensity as shown in Figure 2 with
The curve graph of time change.Digital simulation is the result shows that cyclic chemical luminous signal meets mono-exponential decay rule, mathematics
Expression formula are as follows:
In=A exp (- t/k)+I0
InFor each signal strength, A is maximum chemical luminous signal intensity, and k is attenuation coefficient, and t is time, I0For background value.
Description luminol-hydrogen peroxide-acetylacetone cobalt (II) system cyclic chemical luminous signal changing rule is obtained in this condition
Equation are as follows:
In=28292exp (- t/18)+94
2. reactant concentration influences A, k
Compound concentration range is acetylacetone cobalt (II) solution of 0.005-1.0mmol/L, adjusts pH to 5.0.Using dense
Degree is the prepared acetylacetone cobalt of hydrogen peroxide determination (II) of 0.05mmol/L.A, k value and levulinic that measurement is obtained
The mapping of ketone cobalt (II) concentration, acquired results are shown in Fig. 3.The result shows that A value and acetylacetone cobalt (II) concentration are in good linear pass
System, linear equation are as follows: A=295573c-924, correlation coefficient r 0.9971, wherein c is acetylacetone cobalt (II) concentration.And k
Value is kept approximately constant, unrelated with concentration, and k value average value corresponding to various concentration is 18.1 ± 0.7, RSD 3.9%.
Compound concentration range is the hydrogenperoxide steam generator of 0.008-2.0mmol/L, adjusts pH to 5.0.Using prepared
Hydrogen peroxide determination concentration is the acetylacetone cobalt (II) of 0.2mmol/L.A, k value and concentration of hydrogen peroxide that measurement is obtained are made
Figure, acquired results are shown in Fig. 4.The result shows that A value and concentration of hydrogen peroxide are in good linear relationship, linear equation are as follows: A=
307720c-360, correlation coefficient r 0.9958, wherein c is concentration of hydrogen peroxide.And k value is kept approximately constant, with concentration without
It closes, k value average value corresponding to various concentration is 17.5 ± 0.5, RSD 2.8%.
The above results show that k value is unrelated with reactant concentration, are its characteristic constants, can carry out qualitative analysis；And A value and anti-
It answers object concentration in a linear relationship, quantitative analysis can be carried out.
Embodiment 2
It is reactant characteristic constant by embodiment 1 it is found that k value is unrelated with reactant concentration.In the present embodiment, it uses
The series metal complex that concentration is 0.2mmol/L, including (triphenylphosphine) cobalt chloride (II) are determined with 1 method of embodiment,
- two salicylide ethylenediamine cobalt (II) of N, N ', 2-methylimidazole cobalt (II), Cobalt Phthalocyanine (II), acetylacetone,2,4-pentanedione platinum (II), acetylacetone,2,4-pentanedione
Cobalt (II), palladium acetylacetonate (II), nickel acetylacetonate (II), cobalt protoporphyrin, meso- CoTPP, [5,10,15,20-
Four (4- anisyl) porphyrins] cobalt (II) is closed, bis- (three fluoro- 2,4- pentanediones) cobalts (II), hexafluoroacetylacetone cobalt (II).
Referring to figure 5., Fig. 5 is the k value dendrogram of above each metal complex.As shown in figure 5, different metal complex
K value has differentiability, can the complicated complex of Rapid identification according to k value.Certain structures are extremely similar in these complexs,
Such as: cobalt protoporphyrin, meso- CoTPP and [5,10,15,20- tetra- (4- anisyl) porphyrin] close cobalt (II)；Levulinic
Ketone platinum (II), bis- (three fluoro- 2,4- pentanediones) cobalts (II) and hexafluoroacetylacetone cobalt (II), but their k value equally have it is aobvious
Write differentiability.Therefore, metal complex can be identified by its k value fast and easy.
Embodiment 3
The present embodiment is based on intermolecular chiral-chiral action principle, using the method Rapid identification chiral isomer and
Measure ee value.
1. identifying chiral isomer
The molecular formula of chiral enantiomer is identical, and only the orientation of atom or atomic group in space is different.In achirality
Their physics and chemical property are mostly identical in environment, it is therefore desirable to chiral photo-isomerisation could be effectively identified under chiral environment
Body.The bis- two mesitylene bases of (2- acetyl -3- oxo -2- butenylidene) -1,2- of (1R, 2R)-N, N'- are respectively adopted in the present embodiment
Triethylenediamine cobalt (II) (being abbreviated as R1) and bis- (2- acetyl -3- oxo -2- the butenylidene) -1,2- two of (1S, 2S)-N, N'- are equal
Trimethylphenyl triethylenediamine cobalt (II) (being abbreviated as S1) is receptor, is added respectively into R1 the and S1 solution that concentration is 0.2mol/L
(R)-(+) -1- phenylethanol of isoconcentration, (S)-(+) -1- phenylethanol, (R) -2- amylalcohol, (S) -2- amylalcohol, (R)-(+) -
2- benzene glycinol and (S)-(+) -2- benzene glycinol, the k value that cyclic chemical luminescence assays obtain are as shown in Figure 6.The result shows that hand
Property isomers between k value there is differentiability, such as: when using R1 as receptor, (R)-(+) -1- phenylethanol and (S)-(+) -
The k value of 1- phenylethanol is respectively 65 and 39；(R) -2- amylalcohol and (S) -2- amylalcohol k value are respectively 53 and 37；(R)-(+)-2-
The k value of benzene glycinol and (S)-(+) -2- benzene glycinol is respectively 59 and 47；When using S1 as receptor, (R)-(+) -1- phenyl
The k value of ethyl alcohol and (S)-(+) -1- phenylethanol is respectively 33 and 52；(R) -2- amylalcohol and (S) -2- amylalcohol k value are respectively 71 Hes
46；(R)-(+) the k value of -2- benzene glycinol and (S)-(+) -2- benzene glycinol is respectively 39 and 51.It therefore, can according to k value
Rapid identification chiral isomer.The outstanding advantages of the method first is that, can identify multipair chirality only with a kind of chiral receptor
Isomers.
2. measuring ee value
It is receptor that R1 and S1, which is respectively adopted, and (R)-(+) -1- phenylethanol and (S)-(+) -1- benzene of different weight percentage is added
Base alcohol mixed solution is measured, by chiral isomer mixture attenuation coefficient (k(R,S)) respectively with (R)-(+) -1- phenyl second
Percentage composition (the ω of pure and mild (S)-(+) -1- phenylethanol(R)And ω(S)) map, acquired results are as shown in Figure 7 and Figure 8.As a result
Show k(R,S)With ω(R)Or ω(S)With good linear relationship, and k(R,S)For (R)-(+) -1- phenylethanol and (S)-(+) -
1- phenylethanol attenuation coefficient (k(R)And k(S)) adduction average value, thus
According to the definition of ee value:
Ee=ω(R)-ω(S)(3)
Combining above-mentioned equation can obtain:
As long as equation 4 shows that measured in advance obtains the attenuation coefficient k of homochiral isomeric compound(R)And k(S), then measure
Chiral isomer is obtained to the attenuation coefficient k of mixture object(R,S), ee value can directly be calculated according to equation 4.Further
Ground, prepare a series of known proportions (R)-(+) -1- phenylethanol and (S)-(+) -1- phenylethanol mixed solution, then into
Row measurement obtains serial k(R,S)Value, then its ee value is calculated using equation 4, acquired results are as shown in table 1.Measure obtain ee value with
True ee value relative standard deviation shows that the method for the present invention can be without establishing standard curve and quickly measuring ee less than 12.8%
Value.
Table 1 is using R1 and S1 as receptor determination ee value result
Compared with the existing technology, the apparatus structure of quick detection metal complex and chiral isomer provided by the present invention
Simply, it is capable of freely commutating for current-carrying direction in the working condition realization device by changing micro- electronic six logical conversion valve, behaviour
Make easy；The immobilized anion exchange resin for having luminol is used multiple times simultaneously, and cost and operating cost are low.In addition, this hair
It is bright provided by quickly detection metal complex and chiral isomer method, can qualitative and quantitative detection various structures it is similar and
Complicated metal complex, while can identify chiral isomer configuration and can quickly measure ee without establishing standard curve
Value, it is easy to operate, quick, new technical support is provided for complex identification, chiral analysis.
The invention is not limited to above embodiment, if not departing from the present invention to various changes or deformation of the invention
Spirit and scope, if these changes and deformation belong within the scope of claim and equivalent technologies of the invention, then this hair
It is bright to be also intended to encompass these changes and deformation.
Claims (10)
1. the device for fast detecting of a kind of metal complex and chiral isomer, it is characterised in that: wriggle including a high-pressure pump, one
Pump, a certain amount of ring, a six-way injection valve, micro- electronic six cross valve and a Weak-luminescence detector, described micro- electronic six
Cross valve and the six-way injection valve pass through piping connection；The Weak-luminescence detector includes a microreactor, immobilized to have
The anion exchange resin of luminol is filled in the microreactor；
The output end of high-pressure pump and the output end of peristaltic pump are connected to the six-way injection valve, and the both ends of quantitative loop are connected to
The six-way injection valve, the six-way injection valve has two states of ON and OFF, when the six-way injection valve is on state
When, the peristaltic pump is connected to the quantitative loop, and the high-pressure pump and the quantitative loop be isolated, logical turns with described micro- electronic six
Change valve connection；When the six-way injection valve is in OFF state, the high-pressure pump successively with the quantitative loop, described micro- electronic
The connection of six cross valves, the peristaltic pump are isolated with the quantitative loop；
The both ends of microreactor are connected to micro- electronic six cross valve；Micro- electronic six cross valve has ON and OFF
Two states, when micro- electronic six cross valve is in two kinds of different conditions, the current-carrying in microreactor is contrary.
2. device for fast detecting according to claim 1, it is characterised in that: end there are six being set on the six-way injection valve
Mouthful, be along the circumferential direction followed successively by a1~f1, be wherein connected with the high-pressure pump for a1 mouthfuls, b1 and e1 mouthfuls respectively with quantitative loop both ends
It is connected, c1 mouthfuls are connected with the peristaltic pump, and f1 mouthfuls are connected with micro- electronic six cross valve；The six-way injection valve
When on state, six ports form three channels, respectively a1-f1, e1-d1 and c1-b1 two-by-two；In OFF state
When, six ports form three channels, respectively a1-b1, c1-d1 and e1-f1 two-by-two；On micro- electronic six cross valve
If there are six ports, it is along the circumferential direction followed successively by a2~f2, is wherein connected with the six-way injection valve for c2 mouthfuls, b2 and d2 mouthfuls of difference
It is connected with microreactor inlet and outlet, f2 mouthfuls are closed using plug；When micro- electronic six cross valve is on state, six
Port forms three channels, respectively a2-f2, e2-d2 and c2-b2 two-by-two；When in OFF state, six ports group two-by-two
At three channels, respectively c2-d2, e2-f2 and b2-a2.
3. device for fast detecting according to claim 1, it is characterised in that: the Weak-luminescence detector is using photoelectricity times
Increase pipe as detector, the microreactor material is high-purity quartz, and shape is straight-through cast.
4. device for fast detecting according to claim 1, it is characterised in that: the six-way injection valve and micro- electronic six logical turns
Valve inner spool material is changed as ceramics, bore is 1/16 inch；The quantitative loop volume is 50uL.
5. device for fast detecting according to claim 1, it is characterised in that: pump, valve and the microreactor passes through
The connection of peek pipe, the peek pipe outside diameter are 1/16 inch.
6. a kind of method for quickly detecting metal complex using any described device of claim 1-5, which is characterized in that including
Following steps:
1) the immobilized anion exchange resin for having luminol is filled into the microreactor, opens high-pressure pump and peristaltic pump；
2) carrier fluid is configured, for the oxidizing agent solution that can be generated active oxygen by metal complex catalyzed decomposition；The high-pressure pump will
Carrier fluid is delivered in microreactor, is balanced baseline；
3) sample solution is configured, sample solution is delivered to quantitative loop through six-way injection valve by the peristaltic pump, until it is full of；
4) converting the six-way injection valve mixes carrier fluid with sample solution, and mixed solution enters microreactor and contacts with luminol
Reaction, generates apparent chemiluminescence signal；By periodically switching micro- electronic six cross valve to change current-carrying direction, make sample
Product, which periodically enter in microreactor, is repeated reaction, obtains a series of chemiluminescence letters by exponential damping law variation
Number；
5) digital simulation is carried out as the chemiluminescence signal to obtained by and obtains an exponential equation for describing its changing rule, mathematics
Formula is In=A exp (- t/k)+I0, wherein InFor each signal strength, A is maximum chemical luminous signal intensity, and k is attenuation coefficient,
T is time, I0For background value；Metal complex is identified according to the k of exponential equation.
7. the method for quick detection metal complex according to claim 6, which is characterized in that also wrapped in the step 5)
It includes and quantitative analysis, method is carried out to metal complex are as follows: the metal complex standard solution to be measured of known various concentration is prepared,
A series of chemiluminescence signals are respectively obtained using above-mentioned same procedure, digital simulation is carried out by gained chemiluminescence signal and is obtained
Exponential equation, by each A value of the metal complex standard solution of various concentration in exponential equation and its concentration shape being aligned
Property equation, the concentration of metal complex sample solution is calculated further according to the A value of resulting metal complex sample solution.
8. a kind of method for quickly identifying chiral enantiomter using any described device of claim 1-5, which is characterized in that
Include the following steps:
1) the immobilized anion exchange resin for having luminol is filled into the microreactor, opens high-pressure pump and peristaltic pump；
2) carrier fluid is configured, for the oxidizing agent solution that can be generated active oxygen by metal complex catalyzed decomposition；The high-pressure pump will
Carrier fluid is delivered in microreactor, is balanced baseline；
3) it uses known chipal compounds for receptor, chipal compounds to be measured is added into its solution, be uniformly mixed obtained sample
Sample solution is delivered to quantitative loop by solution, the peristaltic pump, until it is full of；
4) converting the six-way injection valve mixes carrier fluid with sample solution, and mixed solution enters microreactor and contacts with luminol
Reaction, generates apparent chemiluminescence signal；By periodically switching micro- electronic six cross valve to change current-carrying direction, make sample
Product, which periodically enter in microreactor, is repeated reaction, obtains a series of chemiluminescence letters by exponential damping law variation
Number；
5) digital simulation is carried out as the chemiluminescence signal to obtained by and obtains an exponential equation for describing its changing rule, mathematics
Formula is In=A exp (- t/k)+I0, wherein InFor each signal strength, A is maximum chemical luminous signal intensity, and k is attenuation coefficient,
T is time, I0For background value；It is identified according to configuration of the gained k value to chipal compounds to be measured.
9. the method for quick identification chirality enantiomter according to claim 8, which is characterized in that further include to mapping
Body is excessively measured, and the steps include: to measure two chiral enantiomter original attenuation coefficients and right respectively according to the method
The attenuation coefficient for reflecting isomer mixture calculates enantiomeric excess according to following relationship:
Wherein ee is enantiomeric excess, k(R)And k(S)The original attenuation coefficient of respectively two chiral enantiomters, k(R, S)For
The original attenuation coefficient of enantiomeric mixture.
10. the method for quick detection metal complex according to claim 9 and chiral isomer, it is characterised in that: institute
It states step 1) mesohigh pump and peristaltic pump sets flow velocity as 10mL/min.
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