Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the flow cell which is small in size, convenient to assemble and disassemble, good in sealing performance, less in interference and high in stability.
The invention aims at realizing the following technical scheme:
a flow-through cell for use in the on-line detection of liquids, the flow-through cell comprising:
the pressing block is provided with a first through hole, a second through hole and a third through hole, the lower bottom surface of the pressing block is provided with a first array groove, and a first group of magnetic pieces are embedded in the first array groove;
the sealing piece is provided with a fourth through hole and a fifth through hole, the projections of the first through hole and the second through hole on the plane where the sealing piece is positioned fall into the fourth through hole, and the first through hole, the second through hole and the fourth through hole form a liquid channel of the flow cell; the sealing element is made of elastic materials and is positioned between the pressing block and the supporting element;
the upper surface of the support piece is provided with a second array groove, a second group of magnetic pieces are embedded in the second array groove, and the second group of magnetic pieces are arranged opposite to the first group of magnetic pieces and are attracted to each other so that the pressing block, the sealing piece and the optical waveguide chip form a sealed liquid channel; the upper surface of the supporting piece is also provided with a groove for placing an elastic piece, and the upper surface of the elastic piece is higher than the upper surface of the supporting piece;
the optical waveguide chip is provided with a signal sensing area and an optical fiber interface, the projection of the signal sensing area on the plane of the sealing element falls into the fourth through hole, and a modification film for adsorbing a substance to be detected is fixed on the signal sensing area; the third through hole and the fifth through hole are vertically communicated, and the beam-shaped optical fibers are connected with the optical fiber interface and extend out of the vertically communicated channels; the optical waveguide chip is positioned between the elastic piece and the sealing piece, and the distance from the edge of the projection area of the upper surface of the supporting piece to the second group of magnetic pieces is larger than zero.
According to the above flow cell, preferably, the side surface of the support member is provided with two mounting holes for inserting the heating element and the temperature measuring element.
According to the flow cell, optionally, a constant temperature tank is arranged on the lower bottom surface of the support piece, a liquid inlet pipeline is embedded in the constant temperature tank, and an outlet of the liquid inlet pipeline is communicated with the liquid channel.
According to the flow cell described above, optionally, the thermostatic bath is sealed by a cover plate.
According to the flow cell described above, preferably, the first set of magnetic elements comprises magnetic elements of two polarities, and the magnetic elements of the second set of magnetic elements are of opposite polarity to the magnetic elements of the first set of magnetic elements that are located opposite;
if the number of the magnetic parts in the first group of magnetic parts is 3-5, the polarities of at least two adjacent magnetic parts are the same;
if the number of the magnetic parts in the first group of magnetic parts is N, N is more than or equal to 6 and is an even number, the polarities of at least N/2 adjacent magnetic parts are the same;
if the number of the magnetic parts in the first group of magnetic parts is M, M is more than or equal to 7 and is an odd number, the polarities of at least (M-1)/2 adjacent magnetic parts are the same.
According to the flow cell, preferably, the distance from the edge of the projection area of the sealing element on the upper surface of the supporting element to the second set of magnetic elements is greater than zero, so that the first set of magnetic elements and the second set of magnetic elements are in direct contact attraction, and the tightness between the pressing block and the supporting element is improved.
According to the flow cell described above, optionally, at least two of the magnetic elements of the first and/or second set of magnetic elements are centrosymmetric with respect to a central axis of the flow cell.
According to the flow cell described above, optionally, the first set of magnetic elements and the second set of magnetic elements are uniformly distributed along the perimeter of the respective faces.
According to the above-described flow cell, preferably, the optical waveguide chip further includes: a reference zone, the reference zone not passing through the liquid channel;
the light source is injected into the flow cell through the beam-shaped optical fiber and is divided into two paths, and one path enters the reference area to form a reference light path; one path enters the signal sensing area to form a detection light path.
According to the flow cell described above, optionally, the elastic member is an O-ring.
According to the flow cell described above, preferably the briquette is made of plexiglass.
According to the flow cell described above, preferably the support is of aluminium material.
The invention also provides a working method of the flow cell applied to the online detection of the liquid, which comprises the following steps:
(A1) The sample enters a liquid channel, and the component to be detected is adsorbed by a modification film on the signal sensing area;
(A2) The buffer solution enters a liquid channel to replace a sample;
(A3) The light source is emitted into the flow cell, one path of the light source enters the reference light path, and the other path of the light source enters the detection light path;
(A4) The reference light path outputs a reference signal I 1 The simultaneous detection light path outputs a detection signal I 2 According to I 2 /I 1 And obtaining the content of the component to be measured in the sample according to the relation between the ratio and the concentration of the component to be measured.
According to the working method described above, preferably, the working method further includes:
(B1) Washing the liquid channel by eluent, and eluting the component to be detected adsorbed by the modified membrane;
(B2) The buffer solution flows through the liquid channel to displace the eluent.
According to the working method, optionally, the signal sensing area comprises at least two partitions, the at least two partitions are fixed with the modification films for adsorbing different components to be detected, the detection light path outputs detection signals of each partition, and the content of the different components to be detected in the sample is obtained.
The invention also provides a working method of the flow cell applied to the online detection of the liquid, which comprises the following steps:
(C1) The buffer solution enters a liquid channel, a light source is shot into the flow cell, one path of the buffer solution enters a reference light path, and the other path of the buffer solution enters a detection light path;
(C2) Taking the output signal of the reference light path as a temperature indication signal, and outputting a comparison signal I by the detection light path after the temperature indication signal is stable 0 ;
(C3) The sample enters the liquid channel, and the component to be detected is adsorbed by the modification film;
(C4) The buffer solution enters the liquid channel to replace the sample, and after the temperature indicating signal is stable, the detection light path outputs a detection signal I 2 ;
(C5) According to I 2 /I 0 And obtaining the content of the component to be detected in the sample according to the relation between the ratio and the concentration of the component to be detected.
Compared with the prior art, the invention has the following beneficial effects:
1. the flow cell adopts the arrangement of the opposite magnetic parts on the upper and lower sides of the sealing part, and the pressing block and the supporting part are sealed in a mode of mutual attraction of the magnetic parts, so that the flow cell is convenient to assemble and disassemble and good in sealing performance.
2. According to the invention, the heating element and the temperature measuring element are arranged on the supporting piece, so that the temperature is constant in the detection process, the influence of external temperature is eliminated, and the detection stability is improved.
3. The through holes formed in the pressing block and the through holes formed in the sealing piece form a micro-channel for liquid circulation, so that the sample consumption is low, the manufacturing is simple, and the device is small in size.
4. The invention adopts the optical waveguide chip to detect, detects in the environment of buffer solution, ensures the consistent refractive index of the matrix and eliminates the interference of the matrix; meanwhile, the accuracy of the detection result is improved by outputting the reference signal and the detection signal.
Detailed Description
Figures 1-4 and the following description depict alternative embodiments of the invention to teach those skilled in the art how to make and reproduce the invention. In order to teach the technical solution of the present invention, some conventional aspects have been simplified or omitted. Those skilled in the art will appreciate variations or alternatives derived from these embodiments that fall within the scope of the invention. Those skilled in the art will appreciate that the features described below can be combined in various ways to form multiple variations of the invention. Thus, the present invention is not limited to the following embodiments, but only by the claims and their equivalents.
Example 1
Fig. 1 schematically shows a schematic perspective structure separation diagram of a flow cell for on-line detection of a liquid according to embodiment 1 of the present invention, fig. 2 schematically shows structures of upper and lower bottom surfaces of a compact, fig. 3 schematically shows structures of upper and lower bottom surfaces of a sealing member (the structures of the lower and upper bottom surfaces of the sealing member are the same), fig. 4 schematically shows structures of upper and lower bottom surfaces of a supporting member, as shown in fig. 1 to 4, the flow cell comprising:
the pressing block 1 is provided with a first through hole 11, a second through hole 12 and a third through hole 13, wherein the first through hole is a liquid inlet channel, and the second through hole is a liquid outlet channel; the lower bottom surface of the pressing block is provided with a first array of grooves, and a first group of magnetic pieces 14 are embedded in the first array of grooves;
a sealing element 2, wherein the sealing element is provided with a fourth through hole 21 and a fifth through hole 22, the projection of the first through hole and the second through hole on the plane of the sealing element falls into the fourth through hole, and the first through hole, the second through hole and the fourth through hole form a liquid channel of the flow cell; the sealing element is made of elastic materials and is positioned between the pressing block and the supporting element;
the support piece 3, the upper surface of the support piece is provided with a second array groove, a second group of magnetic pieces 31 are embedded in the second array groove, and the second group of magnetic pieces are oppositely arranged with the first group of magnetic pieces and are attracted to each other so that the pressing block, the sealing piece and the optical waveguide chip form a sealed liquid channel; the upper surface of the supporting piece is also provided with a groove for placing an elastic piece 32, and the upper surface of the elastic piece is higher than the upper surface of the supporting piece;
the optical waveguide chip 4 is provided with a signal sensing area and an optical fiber interface, the projection of the signal sensing area on the plane of the sealing element falls into the fourth through hole, and a modification film for adsorbing a substance to be detected is fixed on the signal sensing area; the third through hole and the fifth through hole are vertically communicated and correspond to the positions of the optical fiber interfaces, and the bundle optical fibers extend out of the vertically communicated channels; the optical waveguide chip is positioned between the elastic piece and the sealing piece, covers the elastic piece, and has a distance from the edge of the projection area of the upper surface of the supporting piece to the second group of magnetic pieces larger than zero.
Further, the first through hole and the second through hole are equally divided into an upper part and a lower part, and the aperture of the through hole at the upper end is larger than that of the through hole at the lower end, so that the connection among the liquid inlet channel, the liquid outlet channel and the liquid pipeline is facilitated.
Further, projections of lower end through holes of the first through hole and the second through hole on a plane where the sealing piece is located fall into the fourth through hole.
In order to eliminate the interference of the external environment temperature and improve the stability and the accuracy of the detection result, the method comprises the following steps:
further, the side of the support member is provided with a mounting hole 33 and a mounting hole 34 for inserting the heating element and the temperature measuring element, and the support member is made of aluminum material so as to improve the heat conducting property. The heating element heats the support, and the temperature measuring element transmits a temperature signal to the optical waveguide chip.
In order to shorten the heating time of the liquid, the sample is preheated before entering the liquid channel, so:
further, a constant temperature groove is arranged on the lower bottom surface of the support piece, a liquid inlet pipeline is embedded in the constant temperature groove, and an outlet of the liquid inlet pipeline is communicated with the liquid channel; the constant temperature tank is sealed through a cover plate (such as a magnetic cover plate), so that the heat preservation performance of the constant temperature tank is improved.
The first magnetic pieces and the second magnetic pieces are oppositely arranged and attracted to each other, so that the pressing blocks and the supporting pieces are kept sealed, and in order to ensure that the magnetic pieces in the first magnetic pieces and the magnetic pieces in the second magnetic pieces have unique corresponding relations, namely the corresponding relations of the pressing blocks and the supporting pieces are fixed, the pressing blocks and the supporting pieces cannot rotate and shift when the magnetic pieces are attracted and fixed, so that the pressing blocks and the supporting pieces are prevented from rotating and shifting when the magnetic pieces are attracted and fixed:
further, the first set of magnetic elements includes two magnetic elements of opposite polarity, and the magnetic elements in the second set of magnetic elements are of opposite polarity to the magnetic elements in the first set of magnetic elements;
if the number of the magnetic parts in the first group of magnetic parts is 3-5, the polarities of at least two adjacent magnetic parts are the same;
if the number of the magnetic parts in the first group of magnetic parts is N, N is more than or equal to 6 and is an even number, the polarities of at least N/2 adjacent magnetic parts are the same;
if the number of the magnetic parts in the first group of magnetic parts is M, M is more than or equal to 7 and is an odd number, the polarities of at least (M-1)/2 adjacent magnetic parts are the same.
In order to improve the sealing performance between the press block and the support piece, the following is adopted:
further, the distance from the edge of the projection area of the sealing element on the upper surface of the supporting element to the second set of magnetic elements is greater than zero, so that the first set of magnetic elements and the second set of magnetic elements are in direct contact attraction.
Further, the first group of magnetic pieces and the second group of magnetic pieces are uniformly distributed along the perimeter direction of the surface where each magnetic piece is located; alternatively, at least two magnetic elements of the first set of magnetic elements and/or the second set of magnetic elements are centrosymmetric with respect to a central axis of the flow cell.
In order to exclude uncertain factors such as temperature, ambient humidity and the like, the optical waveguide chip of the embodiment is provided with a reference area, and the reference area does not pass through the liquid channel; the light source is injected into the flow cell through the beam-shaped optical fiber and is divided into two paths, and one path enters the reference area to form a reference light path; one path enters the signal sensing area to form a detection light path.
The embodiment also provides a working method of the flow cell in the liquid online detection process, which comprises the following steps:
(A1) The sample enters a liquid channel, and the component to be detected is adsorbed by a modification film on the signal sensing area;
(A2) The buffer solution enters a liquid channel to replace a sample;
(A3) The light source is emitted into the flow cell, one path of the light source enters the reference light path, and the other path of the light source enters the detection light path;
(A4) The reference light path outputs a reference signal I 1 The simultaneous detection light path outputs a detection signal I 2 According to I 2 /I 1 And obtaining the content of the component to be measured in the sample according to the relation between the ratio and the concentration of the component to be measured.
The components to be detected in the sample are detected in the buffer solution after being adsorbed by the modified film, so that the interference of the matrix is eliminated. After the detection of the primary sample is finished, the adsorbed component to be detected needs to be eluted, and the liquid channel and the signal sensing area are stored in the buffer solution environment to protect the optical waveguide chip, so that:
further, the working method further comprises the following steps:
(B1) Washing the liquid channel by eluent, and eluting the component to be detected adsorbed by the modified membrane;
(B2) The buffer solution flows through the liquid channel to displace the eluent.
Example 2
The difference between the working method of the flow cell of the embodiment 1 of the present invention and the working method of the embodiment 1 of the present invention for online detection of liquid is that the embodiment uses the signal output by the reference light path as the temperature indication signal, and after the temperature indication signal is stable, the detection light path sequentially measures the control signal and the detection signal, thereby obtaining the content of the component to be detected in the sample, and the specific steps are as follows:
(C1) The buffer solution enters a liquid channel, a light source is shot into the flow cell, one path of the buffer solution enters a reference light path, and the other path of the buffer solution enters a detection light path;
(C2) Taking the output signal of the reference light path as a temperature indication signal, and outputting a comparison signal I by the detection light path after the temperature indication signal is stable 0 ;
(C3) The sample enters the liquid channel, and the component to be detected is adsorbed by the modification film;
(C4) The buffer solution enters the liquid channel to replace the sample, and after the temperature indicating signal is stable, the detection light path outputs a detection signal I 2 ;
(C5) According to I 2 /I 0 And obtaining the content of the component to be detected in the sample according to the relation between the ratio and the concentration of the component to be detected.
Example 3
The present embodiment provides a flow cell for online detection of liquid and a working method thereof, which are different from embodiment 1 in that: the signal sensing area of the embodiment comprises at least two subareas, each subarea is fixedly provided with a modification film for adsorbing different components to be detected, and the detection light path outputs detection signals of each subarea to obtain the content of different components to be detected in the sample.
Example 4
The embodiment is an application example of the flow cell in the online detection field of water samples in embodiment 1 of the invention.
In the application example, the pressing block is a cylinder made of organic glass, 4 grooves are uniformly formed in the circumferential direction close to the edge of the lower bottom surface of the pressing block, and magnets with N, N, S, S polarity are sequentially embedded in the clockwise direction; the support piece is a cylinder made of aluminum material, and a heating rod and a temperature measuring element are inserted into a side mounting hole of the support piece; grooves which are in one-to-one correspondence with the grooves on the lower bottom surface of the pressing block are arranged on the circumference close to the edge of the upper bottom surface of the supporting piece, and magnets with S, S, N, N polarity are sequentially embedded in the grooves; the middle of the upper bottom surface of the support piece is provided with a circular groove, an O-shaped ring serving as an elastic piece is embedded in the circular groove, the upper surface of the O-shaped ring is higher than the upper bottom surface of the support piece, and the optical waveguide chip is supported and protected; covering an optical waveguide chip on the O-shaped ring, wherein the maximum value of the distance from the edge of the optical waveguide chip to the central axis of the flow cell is smaller than the minimum value of the distance from the edge of the magnet to the central axis of the flow cell; the sealing element is made of elastic sealing material, and the projection of the sealing element on the upper surface of the supporting element falls into the magnet enclosing area; the modification film on the optical waveguide chip signal sensing area is a molecular imprinting film, is not partitioned, and is only used for detecting the algae toxins in the water sample to be detected.
The online detection process of the water sample is as follows:
s1, connecting a liquid inlet channel of the flow cell with a liquid inlet pipeline, and connecting a liquid outlet channel with a waste liquid bottle; the light source is injected into the flow cell through the beam-shaped optical fiber connected with the optical waveguide chip and is divided into two paths, one path enters the reference area to form a reference light path, and the other path enters the signal sensing area to form a detection light path;
s2, the sample enters a liquid channel, and the algae toxin is adsorbed by a molecular imprinting film on a signal sensing area; the heating rod starts to heat;
s3, enabling the buffer solution to enter a liquid channel to replace a sample;
s4, outputting a reference signal I by a reference light path 1 The simultaneous detection light path outputs a detection signal I 2 According to I 2 /I 1 Obtaining the content of the algae toxin in the water sample according to the relation between the ratio and the concentration of the component to be detected;
s5, washing the liquid channel by eluent, and eluting adsorbed algae toxins;
s6, enabling the buffer solution to flow through the liquid channel, displacing the eluent, and preserving the flow cell under the buffer solution condition.
The bottom surfaces of the pressing block, the sealing element and the supporting element in the embodiment of the invention are not limited to round, rectangular, square, polygonal and the like, and are all within the protection scope of the invention.