CN109799230B - Rapid detection device and detection method for metal complex and chiral isomer - Google Patents
Rapid detection device and detection method for metal complex and chiral isomer Download PDFInfo
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Abstract
The invention discloses a rapid detection device and a rapid detection method for a metal complex and a chiral isomer. The method is based on a circulating chemiluminescence detection principle, a luminol reagent is fixed by resin, and a chemiluminescence signal is generated by utilizing a contact reaction of a sample and luminol; periodically converting the current-carrying direction to enable the sample to periodically enter the microreactor for repeated reaction to generate a series of signals changing in an exponential decay rule; the device has the advantages of simple structure, low manufacturing cost and operating cost, simplicity and convenience in operation, and provides new technical support for complex identification and chiral analysis.
Description
Technical Field
The invention relates to the field of chemiluminescence detection, and in particular relates to a device and a method for quickly detecting a metal complex and a chiral isomer.
Background
The metal element can be combined with different types of ligands to form various coordination complexes. The metal complexes not only have complex structures, but also have certain similarity in structures; enantiomeric phenomena also occur. At present, rapid detection of metal complexes remains a challenge, especially because of their structural and chemical similarities, which make them difficult to identify using conventional chemical and physical methods.
The identification of the enantiomeric configuration and the determination of the enantiomeric excess (ee) play a very important role in asymmetric syntheses and in pharmaceutical chemistry. Gas chromatography, liquid chromatography and nuclear magnetic resonance spectroscopy are common methods for identifying enantiomers and determining ee at present. However, these methods have problems of long time consumption, expensive and heavy equipment, and professional operation.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a rapid detection device for a metal complex and a chiral isomer, which solves the problems of long time consumption, expensive and heavy instrument and complex operation existing in the detection and enantiomer identification of the metal complex in the prior art, can rapidly detect the metal complex, identify the configuration of the chiral isomer and determine the excessive isomer, and has the advantages of simple device, low manufacturing cost and low operating cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
a metal complex and chiral isomer's quick detection device which characterized in that: the device comprises a high-pressure pump, a peristaltic pump, a quantitative ring, a six-way sample injection valve, a micro-electric six-way conversion valve and a weak luminescence detector, wherein the micro-electric six-way conversion valve is connected with the six-way sample injection valve through a pipeline; the six-way sampling valve has an ON state and an OFF state, when the six-way sampling valve is in the ON state, the peristaltic pump is communicated with the quantitative ring, and the high-pressure pump is isolated from the quantitative ring and is communicated with the micro-electric six-way switching valve; when the six-way sampling valve is in an OFF state, the high-pressure pump is sequentially communicated with the quantitative ring and the micro-electric six-way conversion valve, and the peristaltic pump is isolated from the quantitative ring; two ends of the micro-reactor are connected with the micro-electric six-way switching valve, the micro-electric six-way switching valve has two states of ON and OFF, and when the micro-electric six-way switching valve is in two different states, the current carrying directions in the micro-reactor are opposite.
Specifically, six ports are arranged on the six-way sample injection valve, and are a1-f1 in sequence along the circumferential direction, wherein a1 port is connected with the high-pressure pump, b1 and e1 ports are respectively connected with two ends of a quantitative ring, a c1 port is connected with the peristaltic pump, and an f1 port is communicated with the micro-electric six-way conversion valve; when the six-way sampling valve is in an ON state, the six ports form three channels in pairs, namely a1-f1, e1-d1 and c1-b 1; when the switch is in an OFF state, two ports of the six ports form three channels which are a1-b1, c1-d1 and e1-f 1; six ports are arranged on the micro-electric six-way switching valve and are a2-f2 in sequence along the circumferential direction, wherein a c2 port is connected with the six-way sample injection valve, b2 and d2 ports are respectively connected with an inlet and an outlet of the microreactor, and an f2 port is sealed by a plug; when the micro-electric six-way switching valve is in an ON state, the six ports form three channels in pairs, namely a2-f2, e2-d2 and c2-b 2; when the switch is in an OFF state, two ports of the six ports form three channels which are respectively c2-d2, e2-f2 and b2-a 2.
Furthermore, the weak luminescence detector adopts a photomultiplier as a detector, and has extremely high sensitivity and extremely short response time; the material of the microreactor is preferably high-purity quartz and the microreactor is in a straight-through tube shape.
Furthermore, the valve cores in the six-way sample injection valve and the micro-electric six-way conversion valve are made of ceramics, the preferred caliber is 1/16 inches, and the ceramic valve cores have the characteristics of strong wear resistance, good sealing property, long service life, high temperature resistance and the like; the quantification loop volume is preferably 50 uL.
Furthermore, the pump, the valve and the microreactor are all connected through a peek tube, the outer diameter of the pump, the valve and the microreactor is preferably 1/16 inches, and the peek (polyether ether copper) has the advantages of high mechanical strength, high temperature resistance, impact resistance, flame retardance, acid and alkali resistance, hydrolysis resistance, wear resistance, fatigue resistance, irradiation resistance, good conductivity and the like.
In addition, the invention also provides a method for rapidly detecting the metal complex, which uses the device for detection and comprises the following steps:
1) filling anion exchange resin immobilized with luminol into the microreactor, and starting a high-pressure pump and a peristaltic pump;
2) preparing carrier liquid which is oxidant solution capable of generating active oxygen by catalytic decomposition of metal complex; the high-pressure pump conveys carrier liquid into the microreactor to obtain a balance baseline;
3) preparing a sample solution, and conveying the sample solution to the quantitative ring by the peristaltic pump until the quantitative ring is full;
4) converting the six-way sampling valve to mix the hydrogen peroxide with the sample, and allowing the mixed solution to enter a microreactor to contact and react with luminol to generate an obvious chemiluminescent signal; the direction of current carrying is changed by periodically converting a micro-electric six-way conversion valve, so that a sample periodically enters a microreactor to repeatedly react to obtain a series of chemiluminescence signals changing according to an exponential decay rule;
5) obtaining an exponential equation describing the change rule of the chemiluminescence signal by performing data simulation on the chemiluminescence signal, wherein the mathematical formula is In＝A exp(-t/k)+I0In which InFor each signal intensity, A is the maximum chemiluminescent signal intensity, k is the decay coefficient, t is the time, I0Is a background value; and identifying the metal complex according to the k value of the exponential equation.
Further, the step 5) above further comprises a quantitative analysis of the metal complex, and the method comprises: preparing known metal complex standard solutions to be detected with different concentrations, respectively obtaining a series of chemiluminescence signals by adopting the same method, performing data simulation on the obtained chemiluminescence signals to obtain an exponential equation, forming a linear equation by each A value and the concentration of the metal complex standard solutions with different concentrations in the exponential equation, and calculating according to the A value of the obtained metal complex sample solution to obtain the concentration of the metal complex sample solution.
In addition, the invention also provides a method for rapidly identifying chiral enantiomers, which uses the device for detection and comprises the following steps:
1) filling anion exchange resin immobilized with luminol into the microreactor, and starting a high-pressure pump and a peristaltic pump;
2) preparing carrier liquid which is oxidant solution capable of generating active oxygen by catalytic decomposition of metal complex; the high-pressure pump conveys carrier liquid into the microreactor to obtain a balance baseline;
3) adding a chiral compound to be detected into a solution of a known chiral compound serving as a receptor, uniformly mixing to obtain a sample solution, and conveying the sample solution to a quantitative ring by using a peristaltic pump until the quantitative ring is filled with the sample solution;
4) converting the six-way sample injection valve to mix the carrier liquid with the sample solution, and allowing the mixed solution to enter a microreactor to contact and react with luminol to generate an obvious chemiluminescent signal; the direction of current carrying is changed by periodically converting a micro-electric six-way conversion valve, so that a sample periodically enters a microreactor to repeatedly react to obtain a series of chemiluminescence signals changing according to an exponential decay rule;
5) obtaining an exponential equation describing the change rule of the chemiluminescence signal by performing data simulation on the chemiluminescence signal, wherein the mathematical formula is In＝A exp(-t/k)+I0In which InFor each signal intensity, A is the maximum chemiluminescent signal intensity, k is the decay coefficient, t is the time, I0Is a background value; and identifying the configuration of the chiral compound to be detected according to the obtained k value.
Further, the method for rapidly identifying chiral enantiomers further comprises the step of determining the enantiomeric excess, wherein the method comprises the following steps: the original attenuation coefficients of the two chiral enantiomers and the attenuation coefficient of the enantiomeric mixture are determined separately according to the method, and the enantiomeric excess is calculated according to the following relation:
wherein ee is enantiomeric excess, k(R)And k(S)The original attenuation coefficients, k, of the two chiral enantiomers respectively(R，S)Is the original attenuation coefficient of the enantiomeric mixture;
further, the set flow rates of the high-pressure pump and the peristaltic pump in the step 1) are preferably 10 mL/min.
The rapid detection device and the detection method for the metal complex and the chiral isomer provided by the invention have the following beneficial effects:
the detection device has a simple structure, can realize free reversing of the current carrying direction in the device by changing the working state of the micro-electric six-way conversion valve, and is simple and convenient to operate; the anion exchange resin loaded with luminol can be used for a plurality of times, and the manufacturing cost and the operating cost are low. The method can qualitatively and quantitatively detect various complex metal complexes with similar structures and identify chiral isomer configurations, can quickly determine the ee value without establishing a standard curve, is simple and quick to operate, and provides a new technical support for complex identification and chiral analysis.
For a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic structural diagram of a rapid detection device for metal complexes and chiral isomers according to the present invention.
Wherein, 1: a high pressure pump; 2: a peristaltic pump; 3: a six-way sampling valve; 4: a micro-electric six-way change-over valve; 5: a dosing ring; 6: anion exchange resin loaded with luminol; 7: a microreactor; 8: a weak luminescence detector; 9: a hydrogen peroxide solution; 10: a sample solution; 11: a plug;
FIG. 2 shows the change law of the circulating chemiluminescence signal of the luminol-hydrogen peroxide-cobalt (II) acetylacetonate system.
FIG. 3 is a graph of cobalt (II) acetylacetonate concentration versus A, k values.
Figure 4 is a graph of hydrogen peroxide concentration versus A, k values.
FIG. 5 is a k value dendrogram for different metal complexes.
Wherein, 1: (triphenylphosphine) cobalt (II) chloride; 2: n, N' -bis (salicylaldehyde) ethylenediamine cobalt (II); 3: 2-methylimidazolium cobalt (II), 4: cobalt (II) phthalocyanine; 5: platinum (II) acetylacetonate; 6: cobalt (II) acetylacetonate; 7: palladium (II) acetylacetonate; 8: nickel (II) acetylacetonate; 9: protoporphyrin cobalt; 10: meso-cobalt tetraphenylporphyrin; 11: [5,10,15, 20-tetrakis (4-methoxyphenyl) porphyrin ] cobalt (II); 12: bis (trifluoro-2, 4-pentanedionate) cobalt (II); 13: cobalt (II) hexafluoroacetylacetonate.
FIG. 6 shows the results of identifying chiral isomers using (1R,2R) -N, N '-bis (2-acetyl-3-oxo-2-butenylidene) -1, 2-ditrimethylphenylethylenediaminecobalt (II) and (1S,2S) -N, N' -bis (2-acetyl-3-oxo-2-butenylidene) -1, 2-ditrimethylphenylethylenediaminecobalt (II) as acceptors, respectively
Wherein, 1: (R) - (+) -1-phenylethanol; 2: (S) - (+) -1-phenylethanol; 3: (R) -2-pentanol; 4: (S) -2-pentanol; 5: (R) - (+) -2-phenylglycinol; 6: (S) - (+) -2-phenylglycinol.
FIG. 7 shows the results of determining the k-values of mixtures of (R) - (+) -1-phenylethanol and (S) - (+) -1-phenylethanol in various proportions using (1R,2R) -N, N' -bis (2-acetyl-3-oxo-2-butenylidene) -1, 2-ditrimethylphenylethanediaminato cobalt (II) as acceptor.
FIG. 8 shows the results of determining the k-value of mixtures of (R) - (+) -1-phenylethanol and (S) - (+) -1-phenylethanol in various proportions using (1S,2S) -N, N' -bis (2-acetyl-3-oxo-2-butenylidene) -1, 2-ditrimethylphenylethanediaminato cobalt (II) as acceptor.
Detailed Description
Example 1
The present invention will be further described with reference to the accompanying drawings and examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the invention.
Please refer to fig. 1, which is a schematic structural diagram of a device for rapidly detecting a metal complex and a chiral isomer according to the present invention, the device for rapidly detecting a metal complex and a chiral isomer includes a high pressure pump 1, a peristaltic pump 2, a six-way sample injection valve 3, a micro-electric six-way switching valve 4, a quantitative ring 5 and a weak luminescence detector 8, wherein the micro-electric six-way switching valve 4 is connected to the six-way sample injection valve 3 through a pipeline; two ends of the quantitative ring 5 are connected with the six-way sampling valve 3; the weak luminescence detector 8 comprises a microreactor 7, and anion exchange resin 6 immobilized with luminol is filled in the microreactor 7.
The output end of the high-pressure pump 1 and the output end of the peristaltic pump 2 are respectively connected with the six-way sample injection valve 3. The high-pressure pump 1 is used to deliver a carrier liquid which is an oxidant solution capable of being catalytically decomposed by a metal complex to generate active oxygen, in this example a hydrogen peroxide solution 9; the peristaltic pump 2 is used for conveying sample solution, one end of a conduit of the peristaltic pump is arranged in the sample solution 10, and the other end of the conduit is connected with the six-way sampling valve 3.
Six ports are arranged on the six-way sample injection valve 3 and are a1-f1 in sequence along the clockwise direction of the circumference, wherein a1 port is connected with the high-pressure pump 1, b1 and e1 ports are respectively connected with two ends of the quantitative ring 5, a c1 port is connected with the peristaltic pump 2, d1 is used for discharging excessive liquid, and a f1 port is communicated with the micro-electric six-way conversion valve 4. The six-way injection valve 3 has two states of ON and OFF, when the six-way injection valve 3 is in the ON state, as shown in I in FIG. 1, the peristaltic pump 2 is communicated with the quantitative ring 5, the high-pressure pump is isolated from the quantitative ring and is communicated with the micro-electric six-way switching valve, and specifically, at the moment, six ports are formed into three channels in pairs, namely a1-f1, e1-d1 and c1-b 1; when the six-way sample injection valve is in an OFF state, as shown in II in FIG. 1, the high-pressure pump is sequentially communicated with the quantitative ring and the micro-electric six-way switching valve, the peristaltic pump is isolated from the quantitative ring, and specifically, three channels composed of six ports are a1-b1, c1-d1 and e1-f 1.
Six ports are arranged on the micro-electric six-way switching valve and are a2-f2 in sequence along the clockwise direction of the circumference, wherein a c2 port is connected with the six-way sample injection valve, b2 and d2 ports are respectively connected with an inlet and an outlet of the microreactor, a2 and c2 are used for discharging liquid, and a f2 port is sealed by a plug; the micro-electric six-way switching valve has two states of ON and OFF, and when the micro-electric six-way switching valve is in two different states, the current carrying directions in the microreactor are opposite. When the micro-electric six-way switching valve is in an ON state, as shown in II in fig. 1, two of the six ports form three channels, namely a2-f2, e2-d2 and c2-b2, and the current carrying direction in the micro-reactor is from left to right; in the OFF state, as shown in III in FIG. 1, three channels consisting of six ports are c2-d2, e2-f2 and b2-a2, and the current carrying direction in the microreactor is from right to left.
In this embodiment, the valve cores of the six-way sample injection valve 3 and the micro-electric six-way conversion valve 4 are made of precision ceramics, and the caliber of the valves is 1/16 inches. The volume of the quantitative ring 5 is 50uL, but the quantitative ring is not limited to the volume, and quantitative rings with different volumes can be selected according to experimental requirements. The micro reactor 7 is made of high-purity quartz, is in a straight-through pipe shape, has the outer diameter of 4mm, the inner diameter of 2mm and the length of 6cm, and can be specified according to the experimental requirements in specification and shape. The weak luminescence detector 8 uses a photomultiplier as a detector, which has a very high sensitivity and a very short response time, but is not limited to this type of detector, and other detectors capable of detecting chemiluminescence signals may be used. The pumps, valves, microreactors were connected via peek tubes, with an outside diameter of 1/16 inches.
The method for rapidly detecting the metal complex and the chiral isomer by using the device is described in detail below, and comprises the following steps:
1) filling anion exchange resin immobilized with luminol into a micro-reactor, starting a high-pressure pump and a peristaltic pump, and setting the flow rate to be 10 mL/min;
2) preparing a hydrogen peroxide solution with the concentration of 0.02mmol/L, adjusting the pH value to 5.0, and conveying the hydrogen peroxide solution into a microreactor 7 through a liquid-carrying channel a1-f1 by using a high-pressure pump 1 to obtain an equilibrium base line as shown in I in figure 1;
3) preparing a sample solution, and adjusting the pH value to 5.0; as shown in FIG. 1, I, a peristaltic pump 2 is used to pump the sample through sample channels c1-b1 to the dosing loop 5 until it is full, and excess fluid is drained through channels e1-d 1.
4) The six-way injection valve 3 is switched to complete the switching between the ON state and the OFF state, so that the hydrogen peroxide is mixed with the sample. After conversion, as shown in fig. 1 ii, the hydrogen peroxide carrier liquid carries the sample solution in the quantitative ring 5 through the channels a1-b1, enters the microreactor through the channels e1-f1, and reacts with luminol in a contact manner to generate a remarkable chemiluminescent signal. The switching of the ON state and the OFF state is completed by switching the micro-electric six-way switching valve 4 to change the current carrying direction in the microreactor: the liquid to be detected from the six-way sample injection valve enters the microreactor 7 through a channel c2-b2 from left to right in the figure for reaction; after rotating, the liquid to be detected enters the microreactor from right to left through a c2-d2 channel. The micro-electric six-way conversion valve 4 is converted every 36 seconds to change the current carrying direction, so that the sample periodically enters the microreactor 7 to repeatedly react, and a series of chemiluminescent signals changing according to the exponential decay rule are generated;
5) and (3) detecting a metal complex: obtaining an exponential equation describing the change law of the chemiluminescence signal by performing data simulation on the chemiluminescence signal, and mathematics of the exponential equationFormula In＝A exp(-t/k)+I0In which InFor each signal intensity, A is the maximum chemiluminescent signal intensity, k is the decay coefficient, t is the time, I0Is a background value; identifying the metal complex according to k of an exponential equation; in addition, preparing known metal complex standard solutions to be detected with different concentrations, respectively obtaining a series of chemiluminescence signals by adopting the same method, performing data simulation on the obtained chemiluminescence signals to obtain an index equation, forming a linear equation by each A value and the concentration of the metal complex standard solutions with different concentrations in the index equation, and calculating according to the measured A value to obtain the concentration of the metal complex sample solution.
6) Chiral enantiomer detection: adopting a known chiral compound as a receptor, adding a chiral compound to be detected into the solution of the receptor, uniformly mixing, then determining according to the same conditions and steps, and identifying the configuration of the chiral compound to be detected according to the obtained k value;
7) enantiomeric excess detection: the original attenuation coefficients of the two chiral enantiomers and the attenuation coefficient of the enantiomeric mixture were determined separately as described above, and the enantiomeric excess was calculated according to the following relationship:
wherein ee is enantiomeric excess, k(R)And k(S)The original attenuation coefficients, k, of the two chiral enantiomers respectively(R，S)Is the original attenuation coefficient of the enantiomeric mixture;
the basic principle that the cyclic chemiluminescence detection device is used for demonstrating rapid detection of the metal complex and the chiral isomer is as follows:
1. cyclic chemiluminescence signal change law
Preparing 0.2mol/L cobalt (II) acetylacetonate solution, and adjusting the pH value to 5.0. A series of chemiluminescence signals of the cyclic chemiluminescence assay were obtained by measurement according to the above assay procedure, and a graph of the intensity of the chemiluminescence signal as a function of time was obtained as shown in FIG. 2. The data simulation result shows that the cyclic chemiluminescence signal meets the first-order exponential decay rule, and the mathematical expression is as follows:
In＝A exp(-t/k)+I0
Infor each signal intensity, A is the maximum chemiluminescent signal intensity, k is the decay coefficient, t is the time, I0Is a background value. The equation for describing the change rule of the circulating chemiluminescence signal of the luminol-hydrogen peroxide-cobalt acetylacetonate (II) system is obtained under the condition as follows:
In＝28292exp(-t/18)+94
2. effect of reactant concentration on A, k
Preparing cobalt (II) acetylacetonate solution with concentration range of 0.005-1.0mmol/L, and regulating pH to 5.0. The formulated cobalt (II) acetylacetonate was measured with hydrogen peroxide at a concentration of 0.05 mmol/L. The A, k values obtained were plotted against the cobalt (II) acetylacetonate concentration and the results are shown in FIG. 3. The result shows that the A value and the concentration of cobalt (II) acetylacetonate have a good linear relation, and the linear equation is as follows: a-295573 c-924 with a correlation coefficient r of 0.9971, where c is the cobalt (II) acetylacetonate concentration. The k value is almost unchanged, and the average value of the k values corresponding to different concentrations is 18.1 +/-0.7, and the RSD is 3.9 percent, regardless of the concentration.
Preparing hydrogen peroxide solution with concentration range of 0.008-2.0mmol/L, and adjusting pH to 5.0. Cobalt (II) acetylacetonate at a concentration of 0.2mmol/L was determined using the prepared hydrogen peroxide. The A, k values obtained were plotted against the hydrogen peroxide concentration and the results are shown in FIG. 4. The result shows that the A value and the hydrogen peroxide concentration have good linear relation, and the linear equation is as follows: a-307720 c-360, and a correlation coefficient r of 0.9958, where c is the hydrogen peroxide concentration. The k value is almost unchanged, and the average value of the k values corresponding to different concentrations is 17.5 +/-0.5, and the RSD is 2.8 percent, regardless of the concentration.
The above results show that the k value is independent of the reactant concentration, is a characteristic constant thereof, and can be qualitatively analyzed; and the A value and the reactant concentration are in a linear relation, so that quantitative analysis can be carried out.
Example 2
As is clear from example 1, the k value is a characteristic constant of the reactant regardless of the concentration of the reactant. In this example, a series of metal complexes having a concentration of 0.2mmol/L were determined by the same method as in example 1, including (triphenylphosphine) cobalt (II) chloride, N, N' -bis (salicylaldehyde) ethylenediamine cobalt (II), 2-methylimidazolium cobalt (II), cobalt (II) phthalocyanine, platinum (II) acetylacetonate, cobalt (II) acetylacetonate, palladium (II) acetylacetonate, nickel (II) acetylacetonate, protoporphyrin cobalt, meso-tetraphenylporphyrin cobalt, [5,10,15, 20-tetrakis (4-methoxyphenyl) porphyrin ] cobalt (II), bis (trifluoro-2, 4-pentanedione) cobalt (II), and cobalt (II) hexafluoroacetylacetonate.
Referring to FIG. 5, FIG. 5 is a k value dendrogram of each of the above metal complexes. As shown in FIG. 5, the k values of different metal complexes have discriminability, and the complex with complex structure can be rapidly identified according to the k values. Some of these complexes are very similar in structure, such as: protoporphyrin cobalt, meso-tetraphenylporphyrin cobalt and [5,10,15, 20-tetrakis (4-methoxyphenyl) porphyrin ] cobalt (II); platinum (II) acetylacetonate, cobalt (II) bis (trifluoro-2, 4-pentanedionate) and cobalt (II) hexafluoroacetylacetonate, but their k values are likewise distinguished. Therefore, the metal complex can be conveniently and rapidly identified through the k value thereof.
Example 3
The method is used for rapidly identifying the chiral isomer and determining the ee value based on the principle of intermolecular chirality-chirality action.
1. Identification of chiral isomers
The molecular formulae of the chiral enantiomers are identical except that the orientation of the atoms or groups of atoms in space is different. Their physical and chemical properties are largely the same in achiral environments, and thus chiral isomers need to be efficiently identified in chiral environments. In this example, (1R,2R) -N, N '-bis (2-acetyl-3-oxo-2-butenylidene) -1, 2-ditrimethylphenylethanediaminecobalt (II) (abbreviated as R1) and (1S,2S) -N, N' -bis (2-acetyl-3-oxo-2-butenylidene) -1, 2-ditrimethylphenylethanediaminecobalt (II) (abbreviated as S1) were used as acceptors, and (R) - (+) -1-phenylethanol, (S) - (+) -1-phenylethanol, (R) -2-pentanol, (S) -2-pentanol, (R) - (+) -2-phenylglycinol and (S) - (+) -one were added to solutions of R1 and S1 at a concentration of 0.2mol/L, respectively The k values obtained from 2-phenylglycinol, cyclic chemiluminescence assay are shown in FIG. 6. The results show that the k values between the chiral isomers are distinguishable, for example: the k values of (R) - (+) -1-phenylethanol and (S) - (+) -1-phenylethanol are 65 and 39, respectively, when R1 is used as acceptor; the k values of (R) -2-pentanol and (S) -2-pentanol are 53 and 37, respectively; the k values of (R) - (+) -2-phenylglycinol and (S) - (+) -2-phenylglycinol are 59 and 47, respectively; the k values of (R) - (+) -1-phenylethanol and (S) - (+) -1-phenylethanol are 33 and 52, respectively, using S1 as acceptor; (R) -2-pentanol and (S) -2-pentanol have k values of 71 and 46, respectively; the k values of (R) - (+) -2-phenylglycinol and (S) - (+) -2-phenylglycinol were 39 and 51, respectively. Therefore, chiral isomers can be rapidly identified according to k values. One of the outstanding advantages of this method is that multiple chiral isomers can be identified using only one chiral acceptor.
2. Determination of the ee value
Respectively adopting R1 and S1 as receptors, adding different percentages of (R) - (+) -1-phenyl ethanol and (S) - (+) -1-phenyl ethanol mixed solution for determination, and measuring the attenuation coefficient (k) of the chiral isomer mixture(R,S)) With the percentage contents (. omega.) of (R) - (+) -1-phenylethanol and (S) - (+) -1-phenylethanol, respectively(R)And ω(S)) The results are plotted in FIGS. 7 and 8. The results show that k(R,S)And omega(R)Or ω(S)Has a good linear relationship, and k(R,S)Is the attenuation coefficient (k) of (R) - (+) -1-phenylethanol and (S) - (+) -1-phenylethanol(R)And k(S)) Is added and averaged, thereby obtaining
According to the definition of ee value:
ee＝ω(R)-ω(S)(3)
combining the above equations yields:
Table 1 results of ee value measurement using R1 and S1 as acceptors
Compared with the prior art, the device for rapidly detecting the metal complex and the chiral isomer has a simple structure, can realize free reversing of the current carrying direction in the device by changing the working state of the micro-electric six-way conversion valve, and is simple and convenient to operate; meanwhile, the anion exchange resin immobilized with luminol can be used for many times, and the manufacturing cost and the operating cost are low. In addition, the method for rapidly detecting the metal complex and the chiral isomer provided by the invention can qualitatively and quantitatively detect various metal complexes with similar and complex structures, can identify the chiral isomer configuration, can rapidly determine the ee value without establishing a standard curve, is simple and rapid to operate, and provides a new technical support for complex identification and chiral analysis.
The present invention is not limited to the above-described embodiments, and various modifications and variations of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention.
Claims (9)
1. A metal complex and chiral isomer's quick detection device which characterized in that: the device comprises a high-pressure pump, a peristaltic pump, a quantitative ring, a six-way sample injection valve, a micro-electric six-way conversion valve and a weak light-emitting detector, wherein the micro-electric six-way conversion valve is connected with the six-way sample injection valve through a pipeline; the weak luminescence detector comprises a microreactor, and luminol-immobilized anion exchange resin is filled in the microreactor;
the output end of the high-pressure pump and the output end of the peristaltic pump are respectively connected with the six-way sample injection valve, the two ends of the quantitative ring are connected with the six-way sample injection valve, six ports are arranged on the six-way sample injection valve and are a1-f1 in sequence along the circumferential direction, wherein a1 port is connected with the high-pressure pump, b1 and e1 ports are respectively connected with the two ends of the quantitative ring, c1 port is connected with the peristaltic pump, and f1 port is connected with the micro-electric six-way conversion valve; the six-way sample injection valve has an ON state and an OFF state, when the six-way sample injection valve is in the ON state, the peristaltic pump is communicated with the quantitative ring, the high-pressure pump is isolated from the quantitative ring and is communicated with the micro-electric six-way switching valve, and six ports are formed into three channels in pairs, namely a1-f1, e1-d1 and c1-b 1; when the six-way sampling valve is in an OFF state, the high-pressure pump is sequentially communicated with the quantitative ring and the micro-electric six-way switching valve, the peristaltic pump is isolated from the quantitative ring, and six ports are formed into three channels in pairs, namely a1-b1, c1-d1 and e1-f 1;
two ends of the micro-reactor are connected with the micro-electric six-way switching valve; six ports are arranged on the micro-electric six-way switching valve and are a2-f2 in sequence along the circumferential direction, wherein a c2 port is connected with the six-way sample injection valve, b2 and d2 ports are respectively connected with an inlet and an outlet of the microreactor, and an f2 port is sealed by a plug; the micro-electric six-way switching valve has two states of ON and OFF, when the micro-electric six-way switching valve is in the ON state, six ports form three channels in pairs, namely a2-f2, e2-d2 and c2-b 2; when the micro-electric six-way switching valve is in an OFF state, two ports of the six ports form three channels, namely c2-d2, e2-f2 and b2-a2, and when the micro-electric six-way switching valve is in two different states, the current carrying directions in the micro-reactor are opposite.
2. The rapid detection device according to claim 1, wherein: the weak light emitting detector adopts a photomultiplier as a detector, and the microreactor is made of high-purity quartz and is in a straight-through tube shape.
3. The rapid detection device according to claim 1, wherein: the valve cores in the six-way sample injection valve and the micro-electric six-way conversion valve are made of ceramics, and the caliber of the valves is 1/16 inches; the quantification loop volume was 50 uL.
4. The rapid detection device according to claim 1, wherein: the pump, valves and microreactor were all connected via peek tubes with an outside diameter of 1/16 inches.
5. A method for rapid detection of metal complexes using the device of any of claims 1 to 4, comprising the steps of:
1) filling anion exchange resin immobilized with luminol into the microreactor, and starting a high-pressure pump and a peristaltic pump;
2) preparing carrier liquid which is oxidant solution capable of generating active oxygen by catalytic decomposition of metal complex; the high-pressure pump conveys carrier liquid into the microreactor to obtain a balance baseline;
3) preparing a sample solution, and conveying the sample solution to a quantitative ring through a six-way sampling valve by a peristaltic pump until the quantitative ring is full of the sample solution;
4) converting the six-way sample injection valve to mix the carrier liquid with the sample solution, and allowing the mixed solution to enter a microreactor to contact and react with luminol to generate an obvious chemiluminescent signal; the direction of current carrying is changed by periodically converting a micro-electric six-way conversion valve, so that a sample periodically enters a microreactor to repeatedly react to obtain a series of chemiluminescence signals changing according to an exponential decay rule;
5) by passingPerforming data simulation on the obtained chemiluminescence signal to obtain an exponential equation describing the change rule of the chemiluminescence signal, wherein the mathematical formula is In＝A exp(-t/k)+I0In which InFor each signal intensity, A is the maximum chemiluminescent signal intensity, k is the decay coefficient, t is the time, I0Is a background value; and identifying the metal complex according to k of an exponential equation.
6. The method for rapidly detecting a metal complex according to claim 5, wherein the step 5) further comprises performing quantitative analysis on the metal complex by: preparing known metal complex standard solutions to be detected with different concentrations, respectively obtaining a series of chemiluminescence signals by adopting the same method, performing data simulation on the obtained chemiluminescence signals to obtain an exponential equation, forming a linear equation by each A value and the concentration of the metal complex standard solutions with different concentrations in the exponential equation, and calculating according to the A value of the obtained metal complex sample solution to obtain the concentration of the metal complex sample solution.
7. A method for rapid identification of chiral enantiomers using the device of any one of claims 1-4, comprising the steps of:
1) filling anion exchange resin immobilized with luminol into the microreactor, and starting a high-pressure pump and a peristaltic pump;
2) preparing carrier liquid which is oxidant solution capable of generating active oxygen by catalytic decomposition of metal complex; the high-pressure pump conveys carrier liquid into the microreactor to obtain a balance baseline;
3) adding a chiral compound to be detected into a solution of a known chiral compound serving as a receptor, uniformly mixing to obtain a sample solution, and conveying the sample solution to a quantitative ring by using a peristaltic pump until the quantitative ring is filled with the sample solution;
4) converting the six-way sample injection valve to mix the carrier liquid with the sample solution, and allowing the mixed solution to enter a microreactor to contact and react with luminol to generate an obvious chemiluminescent signal; the direction of current carrying is changed by periodically converting a micro-electric six-way conversion valve, so that a sample periodically enters a microreactor to repeatedly react to obtain a series of chemiluminescence signals changing according to an exponential decay rule;
5) obtaining an exponential equation describing the change rule of the chemiluminescence signal by performing data simulation on the chemiluminescence signal, wherein the mathematical formula is In＝A exp(-t/k)+I0In which InFor each signal intensity, A is the maximum chemiluminescent signal intensity, k is the decay coefficient, t is the time, I0Is a background value; and identifying the configuration of the chiral compound to be detected according to the obtained k value.
8. The method for the rapid identification of chiral enantiomers as claimed in claim 7, further comprising the step of measuring the enantiomeric excess by: the original attenuation coefficients of the two chiral enantiomers and the attenuation coefficient of the enantiomeric mixture are determined separately according to the method, and the enantiomeric excess is calculated according to the following relation:
wherein ee is enantiomeric excess, k(R)And k(S)The original attenuation coefficients, k, of the two chiral enantiomers respectively(R，S)Is the original attenuation coefficient of the enantiomeric mixture.
9. The method for the rapid identification of chiral enantiomers as claimed in claim 8, characterized in that: the flow rate of the high-pressure pump and the peristaltic pump in the step 1) is set to be 10 mL/min.
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