Method for measuring growth hormone level using electrochemiluminescence
By analyzing the light intensity change data of solution samples at different concentrations at different potentials, determining the optimal high potential and constructing a concentration-luminescence intensity curve, the problem of improper potential setting in the traditional electrochemiluminescence method in the determination of growth hormone is solved, and higher measurement accuracy and stability are achieved.
Patent Information
- Application Number
- CN202510127845.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-05
- Publication Date
- 2025-04-25
- Estimated Expiration
- 2045-02-05
AI Technical Summary
In the measurement of growth hormone level, traditional electrochemiluminescence method has caused measurement errors due to improper potential setting, and it is impossible to effectively detect growth hormones of different concentrations.
By collecting the light intensity change data of solution samples at different concentrations at different potentials, analyzing the differences in luminescence conditions, eliminating side reactions, determining the optimal high potential, constructing a concentration-luminescence intensity curve, and adjusting the working potential of the solution samples to be measured in real time to achieve accurate measurement.
It significantly improves the accuracy and stability of the determination of growth hormone concentration, avoids measurement errors caused by improper potential range settings in traditional methods, and has high practical value and promotional significance.
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Figure CN119555767B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of electrochemical detection, and in particular to a method for measuring growth hormone levels using an electrochemiluminescence method. Background Art
[0002] Growth hormone (GH) is a key hormone that regulates human growth, metabolism and immune system. It is widely used in many fields such as medicine, sports and drug development. Accurate determination of growth hormone levels is of vital importance for clinical diagnosis and formulation of treatment plans. Traditional growth hormone detection techniques, such as immunoassay and enzyme-linked immunosorbent assay (ELISA), have been verified to a certain extent in terms of accuracy and sensitivity, but these methods often have shortcomings such as long detection time, complex operation and limited sensitivity.
[0003] In recent years, electrochemiluminescence (ECL) has become a widely adopted technology in the field of growth hormone determination due to its advantages such as high sensitivity, low detection limit, rapid response and simple operation. This method triggers the reaction by controlling the potential in the electrochemical process to generate a light signal, and then uses a photodetector to measure the light intensity to calculate the concentration of the target substance; however, in the traditional electrochemiluminescence method, the determination of growth hormone levels depends on applying a specific working potential to induce the marker to undergo an electron transfer reaction on the electrode surface and release photons to achieve concentration determination; and the setting of the potential is usually based on the experimenter's experience or references. Due to the difference in growth hormone concentration in different solutions and possible impurities and other factors, the potential response of different samples is different, which may lead to insufficient or saturated luminescence signal intensity at a fixed potential, thereby affecting the sensitivity and accuracy of the measurement.
[0004] Specifically, if the potential is set too low, the reaction may not be fully activated, resulting in a weak measurement signal that cannot meet the detection requirements for low-concentration growth hormone; conversely, if the potential is set too high, it may cause excessive oxidation or reduction of the electrode surface, triggering side reactions, or saturation due to excessively strong luminescent signals, making it impossible to obtain accurate concentration data. Summary of the invention
[0005] In order to solve the technical problem of growth hormone level measurement error caused by improper potential setting of the existing electrochemiluminescence method, the purpose of the present invention is to provide a growth hormone level measurement method using electrochemiluminescence method, and the technical scheme adopted is as follows:
[0006] Collect light intensity change data of solution samples with different concentrations at different potentials, and perform preprocessing to generate historical light intensity change data;
[0007] Based on the historical light intensity change data, the differences in luminescence in solution samples of different concentrations are analyzed, the historical light intensity change data with side reactions are excluded, and the optimal high potential of solution samples of different concentrations is determined to obtain the concentration-luminescence intensity curve;
[0008] Obtain a sample of the solution to be tested, measure the light intensity change data of the sample of the solution to be tested, perform similarity analysis with the historical light intensity change data, calculate the predicted optimal high potential of the sample of the solution to be tested in real time and compare it with the current working potential, and adaptively adjust the working potential of the sample of the solution to be tested;
[0009] The concentration of growth hormone in the solution sample to be tested is obtained by adjusting the working potential and combining the concentration-luminescence intensity curve to complete the growth hormone level determination.
[0010] Preferably, light intensity change data of solution samples with different concentrations at different potentials are collected, and preprocessing is performed to generate historical light intensity change data, including: using PBS buffer solution, collecting light intensity change data of solution samples with different concentrations at different potentials based on a potential range of 0V to 1.5V, and generating historical light intensity change data through Gaussian filtering and denoising.
[0011] Preferably, the differences in luminescence conditions in solution samples of different concentrations are analyzed based on historical light intensity change data, historical light intensity change data of side reactions are excluded, and the optimal high potential of solution samples of different concentrations is determined to obtain a concentration-luminescence intensity curve, including:
[0012] Based on the historical light intensity change data, the luminescence intensity of any concentration solution sample at the highest potential changes with time, and record it as the target data. According to the target data, several maximum points that change with time are obtained, and the influence coefficient between any two maximum points is calculated;
[0013] The minimum value point is obtained by taking the maximum value point of one of the influencing coefficients, and the end point of the illumination range time is adjusted to obtain the improved illumination time period, and the sum of the luminous intensity is calculated based on the illumination time period;
[0014] Calculate the reference weight of any concentration solution sample, combine it with the sum of the luminescence intensity to get the improved correlation coefficient, calculate the optimal high potential of the current concentration solution sample through the correlation coefficient, obtain the corresponding light intensity based on the optimal high potential, analyze the change of luminescence intensity with respect to concentration, and generate a concentration-luminescence intensity curve.
[0015] Preferably, the influence coefficient between any two maximum points is calculated, and the corresponding calculation formula is:
[0016]
[0017] in, represents the influence coefficient; Indicates A maximum point; Indicates A maximum point; Indicates time and The time interval between Indicates that the concentration of growth hormone in the solution sample is , at the highest potential Luminous intensity data measured under At the moment The light intensity under Indicates The moment corresponding to the maximum point; Indicates that the concentration of growth hormone in the solution sample is , at the highest potential Luminous intensity data measured under In the The light intensity at the moment corresponding to the maximum point; Indicates The moment corresponding to the maximum point; Indicates that the concentration of growth hormone in the solution sample is , at the highest potential Luminous intensity data measured under In the The light intensity at the moment corresponding to the maximum point; express No. The moment corresponding to the maximum point; express No. The moment corresponding to the maximum point.
[0018] Preferably, the minimum point is obtained by taking the maximum point of one of the influencing coefficients, adjusting the time endpoint of the illumination range to obtain an improved illumination time period, and calculating the sum of the luminous intensities based on the illumination time period, including:
[0019] by Expand to the left and right sides at the central moment, record the first minimum point that appears and get the corresponding time as and ;
[0020] Adjust the illumination range time endpoint, the corresponding calculation formula is:
[0021]
[0022] in, Indicates the time endpoint of the illumination range after adjustment of the left minimum point; Indicates the time endpoint of the original illumination range corresponding to the minimum point on the left; represents the directional coefficient; Indicates that the current analysis time is less than The number of maximum points of ; represents the influence coefficient; It represents the time correction under unit influence coefficient;
[0023] And calculate according to the same formula , It indicates the time endpoint of the illumination range after the minimum point on the right is adjusted;
[0024] Get the improved light period , calculate the sum of luminous intensity based on the illumination time period .
[0025] Preferably, the reference weight of a solution sample of any concentration is calculated using the following calculation formula:
[0026]
[0027] in, Indicates that the concentration of growth hormone in the solution sample is The highest potential is related to the growth hormone concentration in the solution sample. The reference weight between Represents the normalization function.
[0028] Preferably, the improved correlation coefficient is obtained by combining the sum of the luminous intensity, and the corresponding calculation formula is:
[0029]
[0030] in, represents the improved correlation coefficient; Indicates the concentration range; Indicates that the concentration of growth hormone in the solution sample is The highest potential is related to the growth hormone concentration in the solution sample. The reference weight between represents the mean concentration; Indicates that the concentration of growth hormone in the solution sample is , at the highest potential The sum of the luminous intensities under express About concentration The mean of Represents the standard deviation function.
[0031] Preferably, the optimal high potential of the current concentration solution sample is calculated by the correlation coefficient, and the corresponding calculation formula is:
[0032]
[0033] in, Represents the function of finding the minimum point; express About concentration The size of the second-order difference.
[0034] Preferably, the light intensity change data of the solution sample to be tested is measured, and similarity analysis is performed with the historical light intensity change data. The corresponding calculation formula is:
[0035]
[0036] in, express and luminous similarity; It means that the solution sample to be tested reaches the potential The sequence of luminous intensity changes when Indicates that the historical light intensity change data is less than The sequence of luminous intensity changes when Indicates the working potential during the analysis; Indicates that the concentration of growth hormone in the solution sample is The highest potential; Indicates the light intensity change data of the solution sample to be tested when the potential is less than The sequence of luminous intensity changes when Indicates that the historical light intensity change data is less than The sequence of luminous intensity changes when Express request and and / or and Cosine similarity between two luminous intensity change sequences.
[0037] Preferably, the predicted optimal high potential of the solution sample to be tested is calculated in real time and compared with the current working potential, and the working potential of the solution sample to be tested is adaptively adjusted, including:
[0038] The predicted optimal high potential of the solution sample to be tested is calculated in real time, and the corresponding calculation formula is:
[0039]
[0040] in, represents the predicted optimal high potential of the solution sample to be tested; Indicates the concentration range; express and luminous similarity; It means that the solution sample to be tested reaches the potential The sequence of luminous intensity changes when Indicates that the historical light intensity change data is less than The sequence of luminous intensity changes when represents the maximum point function;
[0041] when When , the working potential of the solution sample to be tested is increased; when When the working potential of the solution sample to be tested remains unchanged.
[0042] The present invention has the following beneficial effects:
[0043] The present application solves the problem of improper and uncertain potential setting in traditional methods by introducing an adaptive potential design. Traditional methods fail to optimize the characteristics of solutions of different concentrations, which may lead to the occurrence of side reactions, electrode surface damage or luminescence intensity saturation, affecting the measurement accuracy. The present application obtains light intensity change data of solution samples of different concentrations at different potentials, analyzes the difference in luminescence intensity at different high potentials, accurately determines the adaptive high potential range suitable for solution samples of each concentration, constructs a concentration-luminescence intensity curve, and further determines the optimal high potential of the solution sample to be tested, thereby achieving luminescence measurement within a larger potential range. The method significantly improves the accuracy and stability of growth hormone concentration measurement, avoids the measurement error caused by improper potential range setting in traditional methods, and has high practical value and promotion significance. BRIEF DESCRIPTION OF THE DRAWINGS
[0044] In order to more clearly illustrate the technical solutions and advantages in the embodiments of the present invention or the prior art, the drawings required for use in the embodiments or the prior art descriptions are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0045] Figure 1 A flow chart of the steps of a method for measuring growth hormone levels using electrochemiluminescence provided by one embodiment of the present invention;
[0046] Figure 2 A schematic diagram of potential changes over time in a method for measuring growth hormone levels using electrochemiluminescence provided by an embodiment of the present invention. DETAILED DESCRIPTION
[0047] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description of the specific implementation method, structure, characteristics and effects of a growth hormone level determination method using electrochemiluminescence method proposed by the present invention in combination with the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "another embodiment" does not necessarily refer to the same embodiment. In addition, specific features, structures or characteristics in one or more embodiments may be combined in any suitable form.
[0048] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
[0049] The specific scheme of the method for measuring growth hormone level using electrochemiluminescence provided by the present invention is described in detail below in conjunction with the accompanying drawings.
[0050] See also Figure 1 , which shows a flow chart of the steps of a method for measuring growth hormone levels using electrochemiluminescence provided by one embodiment of the present invention, the method comprising:
[0051] Step S1: collecting light intensity change data of solution samples with different concentrations at different potentials, and performing preprocessing to generate historical light intensity change data;
[0052] Step S2: Analyze the differences in luminescence conditions in solution samples of different concentrations based on the historical light intensity change data, exclude the historical light intensity change data of side reactions, and determine the optimal high potential of solution samples of different concentrations to obtain a concentration-luminescence intensity curve;
[0053] Step S3: obtaining a sample of the solution to be tested, measuring the light intensity change data of the sample of the solution to be tested, performing similarity analysis with the historical light intensity change data, calculating in real time the predicted optimal high potential of the sample of the solution to be tested and comparing it with the current working potential, and adaptively adjusting the working potential of the sample of the solution to be tested;
[0054] Step S4: The concentration of growth hormone in the solution sample to be tested is obtained by combining the adjusted working potential with the concentration-luminescence intensity curve to complete the growth hormone level determination.
[0055] To better explain, electrochemiluminescence is a technology that combines electrochemical reactions with chemiluminescence. The electrochemical reaction on the electrode surface excites the luminescent substance to produce a light signal, and then the intensity of the light signal is detected to quantitatively analyze the specific substance in the sample; growth hormone is a protein hormone that plays a vital role in regulating human growth, metabolic processes and immune system functions. It is widely used in medicine, clinical, sports and drug development.
[0056] In the traditional electrochemiluminescence method, a certain working potential is usually applied so that the marker undergoes an electron transfer reaction on the electrode surface, thereby releasing photons to achieve the determination of the growth hormone level; however, the magnitude of the potential usually needs to be set by the experimenter based on personal experience or reference to relevant literature, and the concentration of growth hormone in different solutions is different, and the solution may contain various impurities. These factors will lead to differences in the potential response of different samples, which may cause the problem of insufficient luminescence signal intensity or signal saturation at a fixed potential, affecting the sensitivity and accuracy of the growth hormone level determination; in other words, if the potential is set too low, the electrochemical reaction may not be fully activated, resulting in a measurement signal that is too weak and unable to meet the requirements for effective detection of low-concentration growth hormone; conversely, if the potential is set too high, it may cause excessive oxidation or reduction reactions on the electrode surface, resulting in unnecessary side reactions, or the signal may be saturated due to the excessively strong luminescence signal, and accurate growth hormone concentration data cannot be obtained, affecting the reliability of the growth hormone level determination results; therefore, a growth hormone level determination method using electrochemiluminescence is proposed in the present application.
[0057] Further, step S1 includes:
[0058] Using PBS buffer solution, the light intensity change data of solution samples with different concentrations at different potentials were collected based on the potential range of 0V to 1.5V, and the historical light intensity change data were generated by Gaussian filtering and denoising.
[0059] Specifically, the Autolab PGSTAT302N electrochemical comprehensive tester provides accurate potential scanning and is equipped with a multi-channel data acquisition function. Combined with the Hamamatsu C9920-02 photodiode detector, the light intensity change data of solution samples of different concentrations at different potentials in the potential range of 0V to 1.5V can be accurately measured in the ultraviolet visible light range. It can be explained that the potential range is set to 0V to 1.5V to ensure that the full potential range of the redox reaction is covered; Gaussian filtering is based on the principle of Gaussian distribution. By weighted averaging each data point in the collected data with the data points in its surrounding neighborhood, the data sequence is smoothed to effectively remove random noise; Among them, the Autolab PGSTAT302N electrochemical comprehensive tester can provide accurate electrochemical measurement and analysis, combined with the multi-channel data acquisition function, so that multiple parameters can be monitored and recorded simultaneously during electrochemical experiments, which greatly improves the efficiency and accuracy of the experiment; the Hamamatsu C9920-02 photodiode detector, that is, the Hamamatsu The C9920-02 spectrometer uses the characteristics of photodiodes to detect optical signals and converts them into electrical signals for analysis and processing. It has a fast response time and can capture weak changes in optical signals. It is particularly suitable for application scenarios that require precise measurement of light intensity.
[0060] The historical light intensity change data refers to the change in the light source intensity in the electrochemiluminescence experiment. The growth hormone concentration in the subsequent solution sample to be tested is determined by analyzing the historical light intensity change data to complete the growth hormone level determination.
[0061] As an optional implementation, in this embodiment, the concentration of the solution sample is selected as 1 ng / mL, 5 ng / mL, 10 ng / mL, 50 ng / mL, 100 ng / mL, 500 ng / mL, and 1000 ng / mL to measure the subsequent light intensity change data.
[0062] To clarify, PBS (Phosphate-Buffered Saline) buffer solution refers to a PBS buffer solution with a pH of 7.4, which is used as a reaction solution to maintain a stable electrolyte concentration, prevent fluctuations in pH, and provide a constant environment for chemical reactions. PBS buffer solution helps ensure the accuracy and repeatability of experimental results.
[0063] See also Figure 2 , which shows a schematic diagram of the potential change over time in a method for measuring growth hormone levels using an electrochemiluminescence method; it is explained that the horizontal axis represents time and the vertical axis represents potential.
[0064] For better explanation, the initial potential refers to the potential at the beginning of the scan of the Autolab PGSTAT302N electrochemical comprehensive tester, which is recorded as 0V; the high potential refers to the highest potential during the scan. Specifically, in this embodiment, in the interval of 0.5 V to +1.5 V, an equidistant sampling method is adopted, that is, a sampling is performed each time an increase of 40 mV, and so on, to obtain multiple different potential values in the high potential interval and the corresponding light intensity change data; the low potential refers to the potential at the end of the scan, which is recorded as 0V.
[0065] It can be understood that during the electrochemiluminescence (ECL) measurement process, there is a close connection between the intensity of the luminescence signal and the redox reaction occurring on the electrode surface during the reaction. Specifically, the concentration of growth hormone or the presence of other substances in different solution samples will affect the rate of the electrochemical reaction, and this effect will be directly reflected in the intensity of the luminescence signal generated by the reaction. When the concentration of growth hormone in the solution sample is higher, the electrochemical reaction will be more intense, resulting in a higher intensity of the luminescence signal; conversely, when the concentration of growth hormone in the solution sample is lower, the reaction intensity weakens and the luminescence signal also weakens accordingly.
[0066] When analyzing the electrochemiluminescence process, the area within the peak neighborhood is a very important parameter, which comprehensively reflects the characteristics of the luminescence process. This area not only takes into account the height of the peak, but also includes the duration of the reaction. It actually reflects the degree of the total reaction within a certain period of time. Since there is a certain correlation between the total luminescence and the concentration of the substance, when analyzing the historical light intensity change data, the luminescence interval must be divided according to different light intensity change data, so that the luminescence data area of different samples at different potentials can be accurately obtained; it can be explained that in the traditional electrochemiluminescence curve acquisition process, in addition to the reaction of the target substance, some side reactions may also occur, and the existence of side reactions will introduce some small luminescence signal peaks in the luminescence intensity change curve. During the experiment, the side reaction may be due to the presence of impurities on the electrode surface, or because other substances in the reaction system, such as impurities in the solution or the solvent itself, have an incomplete reaction with the electrode. Therefore, in the process of obtaining the luminescence intensity, measures are taken to eliminate the mutual influence between the light intensity peaks produced by these side reactions to ensure that the luminescence signal of the target substance can be accurately measured and analyzed.
[0067] Further, step S2 includes:
[0068] Step S21: Based on the historical light intensity change data, the luminescence intensity of any concentration solution sample at the highest potential changes with time, and record it as target data. According to the target data, obtain several maximum points that change with time, and calculate the influence coefficient between any two maximum points.
[0069] To illustrate, in this embodiment, the target data refers to the concentration of growth hormone in the solution sample. , at the highest potential Luminous intensity data measured under .
[0070] Furthermore, in step S21, the influence coefficient between any two maximum points is calculated, and the corresponding calculation formula is:
[0071]
[0072] in, represents the influence coefficient; Indicates A maximum point; Indicates A maximum point; Indicates time and The time interval between Indicates that the concentration of growth hormone in the solution sample is , at the highest potential Luminous intensity data measured under At the moment The light intensity under Indicates The moment corresponding to the maximum point; Indicates that the concentration of growth hormone in the solution sample is , at the highest potential Luminous intensity data measured under In the The light intensity at the moment corresponding to the maximum point; Indicates The moment corresponding to the maximum point; Indicates that the concentration of growth hormone in the solution sample is , at the highest potential Luminous intensity data measured under In the The light intensity at the moment corresponding to the maximum point; express No. The moment corresponding to the maximum point; express No. The moment corresponding to the maximum point.
[0073] To explain, when selecting another maximum point, the maximum point with the largest luminous intensity among several maximum points is selected, that is, the first The maximum point is used to reflect the side reaction and calculate the The maximum point and the The influence coefficient of the maximum point is used to explain the difference between the potential range corresponding to the luminescence of the target substance and the potential range corresponding to the luminescence of the side reaction; when the time difference is large, the effect of the side reaction on the luminescence of the target substance is small, that is, the influence coefficient is small, which means that the side reaction has little effect on the luminescence signal of the target substance and can be ignored; conversely, when the time difference is small, it means that the side reaction has a greater effect on the luminescence signal of the target substance, that is, the influence coefficient is large, which means that the side reaction has a significant effect on the luminescence signal of the target substance, and measures need to be taken to reduce the influence of the side reaction to improve the accuracy of the experimental data.
[0074] Specifically, in the process of gradual increase in potential, that is, the oxidation reaction process, multiple maximum points of the target data changing with time are obtained respectively, and the moments corresponding to the maximum points are obtained; when there is no maximum point, the data point corresponding to the last moment point in the process of gradual increase in potential is taken as the maximum value in the oxidation process; it can be explained that each historical light intensity change data contains at least one maximum value.
[0075] Step S22: obtaining the minimum point with the maximum point of one of the influencing coefficients, adjusting the time endpoint of the illumination range, obtaining an improved illumination time period, and calculating the sum of the luminous intensities based on the illumination time period.
[0076] To explain, obtaining the minimum point by using the maximum point of one of the influence coefficients means obtaining the minimum point by using one of the maximum points used to calculate the influence coefficient in step S21. Specifically, in this embodiment, The minimum point is obtained by analyzing the time corresponding to the maximum point of the side reaction, that is, the minimum point is obtained by analyzing the maximum point corresponding to the side reaction.
[0077] Further, step S22 includes:
[0078] Step S221: Expand to the left and right sides at the central moment, record the first minimum point that appears and get the corresponding time as and .
[0079] To explain The center moment is expanded to the left and right sides to more comprehensively analyze the characteristics of the data or signal. During the expansion process, the first minimum point that appears is recorded, which is used to indicate the beginning or end of a trend.
[0080] Step S222: Adjust the illumination range time endpoint, the corresponding calculation formula is:
[0081]
[0082] in, Indicates the time endpoint of the illumination range after adjustment of the left minimum point; Indicates the time endpoint of the original illumination range corresponding to the minimum point on the left; represents the directional coefficient; Indicates that the current analysis time is less than The number of maximum points of ; represents the influence coefficient; It represents the time correction under unit influence coefficient;
[0083] And calculate according to the same formula , It indicates the time endpoint of the illumination range after the minimum point on the right is adjusted;
[0084] To illustrate, use the directional coefficient right When correcting, ;right When making corrections, ; represents the time correction amount under the unit influence coefficient. In this embodiment, .
[0085] Step S223: Obtaining the improved illumination time period , calculate the sum of luminous intensity based on the illumination time period .
[0086] It can be shown that the sum of the luminous intensity It refers to integrating the luminous intensity during the illumination period to obtain the sum of the luminous intensity during the entire period, which reflects the overall intensity of the electrochemiluminescence reaction of growth hormone during the illumination period.
[0087] Understandably, when the concentration of growth hormone in the solution sample is low, the reaction potential of electrochemiluminescence is relatively small, which is usually not enough to trigger an efficient electrochemiluminescence reaction. Therefore, under such conditions, the luminescence intensity will be relatively low; when the concentration of growth hormone in the solution sample is high, a very high maximum potential is not required, because at a larger working potential, the luminescence intensity of the solution sample can reach a saturated state; if the working potential is too high, the probability of side reactions will increase, which may have an adverse effect on the experimental results; therefore, as the concentration of growth hormone in the solution sample increases, in order to trigger efficient electrochemiluminescence, the corresponding high potential also needs to increase accordingly, so when analyzing the optimal high potentials of these different solution samples, it is necessary to first sort these solution samples according to the concentration of growth hormone from small to large, so as to accurately determine the luminescence characteristics of each solution sample at different potentials, and then find the optimal potential conditions.
[0088] Step S23: Calculate the reference weight of any concentration solution sample, combine it with the sum of the luminous intensity to obtain the improved correlation coefficient, calculate the optimal high potential of the current concentration solution sample through the correlation coefficient, obtain the corresponding light intensity based on the optimal high potential, analyze the change of luminous intensity with respect to concentration, and generate a concentration-luminous intensity curve.
[0089] Explain that the concentration of growth hormone in the calculated solution sample is When the optimal potential is reached, the solution samples with similar concentrations have a higher reference value.
[0090] Furthermore, in step S23, the reference weight of any concentration solution sample is calculated, and the corresponding calculation formula is:
[0091]
[0092] in, Indicates that the concentration of growth hormone in the solution sample is The highest potential is related to the growth hormone concentration in the solution sample. The reference weight between Represents the normalization function.
[0093] It can be understood that the reference weight of each solution sample is obtained based on the above logical formula, considering the correlation between the corresponding concentration and the luminescence intensity at different maximum potentials. However, in the calculation process of the traditional correlation coefficient, the reference weight for each solution sample is the same, and the different concentrations of growth hormone in each solution sample and the different contributions to the solution sample are not considered; therefore, in the actual process, as the concentration changes, the optimal high potential will also fluctuate to a certain extent, so the improved correlation coefficient is calculated based on the traditional correlation coefficient.
[0094] Furthermore, in step S23, the improved correlation coefficient is obtained by combining the sum of the luminous intensities, and the corresponding calculation formula is:
[0095]
[0096] in, represents the improved correlation coefficient; Indicates the concentration range; Indicates that the concentration of growth hormone in the solution sample is The highest potential is related to the growth hormone concentration in the solution sample. The reference weight between represents the mean concentration; Indicates that the concentration of growth hormone in the solution sample is , at the highest potential The sum of the luminous intensities under express About concentration The mean of Represents the standard deviation function.
[0097] To explain, With the highest potential As the concentration of growth hormone in different solution samples increases, the difference between them will be further amplified. However, as the luminescence intensity of growth hormone at low concentration in solution samples reaches saturation, The rate of increase will gradually decrease.
[0098] Furthermore, in step S23, the optimal high potential of the current concentration solution sample is calculated by the correlation coefficient, and the corresponding calculation formula is:
[0099]
[0100] in, Represents the function of finding the minimum point; express About concentration The size of the second-order difference.
[0101] To explain, express About concentration The second-order difference of This improved correlation coefficient increases with the concentration The rate of change.
[0102] Based on the above logical thinking, the optimal high potential is calculated after the solution samples are sorted according to the concentration of growth hormone from small to large. As the concentration of growth hormone increases, the high potential corresponding to the solution sample gradually increases. Therefore, the subsequent solution samples increase the potential range on the basis of the previous solution sample. That is, when hour, Understandably, There is a range of values. Assuming that the growth hormone concentration in the first solution sample is the smallest, the potential range is [0.5V, 1.5V], and the measured optimal high potential is 0.8V. Then the potential range of the next solution sample is [0.8V, 1.5V], and the measured optimal high potential is also within this potential range. Then, the optimal high potentials of multiple different solution samples are obtained, and the luminescence intensity is calculated according to the optimal high potentials. Specifically, in this embodiment, the growth hormone concentration in the solution sample is , its optimal high potential is , the corresponding luminous intensity is , and then according to the obtained luminous intensity About Growth Hormone Concentration The luminous intensity is obtained by using the traditional cubic spline interpolation method. About concentration The change curve, that is, the concentration-luminous intensity curve; wherein, cubic spline interpolation is used to construct a smooth curve between a given set of data points. Through cubic spline interpolation, it can be ensured that the curve not only passes through all given data points, but also forms continuous first-order and second-order derivatives between these points to achieve a smooth transition.
[0103] It can be understood that the above is the optimal high potential for obtaining a solution sample with a known growth hormone concentration based on the historical light intensity change data, while for a solution with an unknown growth hormone concentration, the optimal high potential cannot be determined directly based on the growth hormone concentration. In traditional analysis methods, the setting of the high potential often requires manual operation, which may lead to unreasonable high potential settings, affecting the accuracy of the growth hormone concentration measurement, and may result in large deviations in the measurement results. Therefore, when performing electrochemical analysis on a solution with an unknown growth hormone concentration, the high potential is not set in advance, and the luminescence intensity of the solution on the working electrode side gradually changes with the passage of time by gradually increasing the potential. By comparing and analyzing the similarity between the luminescence intensity of the unknown solution and the historical light intensity change data, the optimal high potential of the unknown solution can be inferred, which can improve the accuracy of the growth hormone concentration measurement and effectively avoid measurement errors caused by improper manual setting of the high potential.
[0104] Furthermore, in step S3, the light intensity change data of the solution sample to be tested is measured, and similarity analysis is performed with the historical light intensity change data. The corresponding calculation formula is:
[0105]
[0106] in, express and luminous similarity; It means that the solution sample to be tested reaches the potential The sequence of luminous intensity changes when Indicates that the historical light intensity change data is less than The sequence of luminous intensity changes when Indicates the working potential during the analysis; Indicates that the concentration of growth hormone in the solution sample is The highest potential; Indicates the light intensity change data of the solution sample to be tested when the potential is less than The sequence of luminous intensity changes when Indicates that the historical light intensity change data is less than The sequence of luminous intensity changes when Express request and and / or and Cosine similarity between two luminous intensity change sequences.
[0107] It can be explained that as the potential gradually increases, the light intensity change data of the solution sample to be tested is recorded; the luminous intensity change sequence refers to a data sequence composed of multiple light intensity change data, which records the luminous intensity change of the light source at different time points.
[0108] To explain, in the actual process, It means that the solution sample to be tested reaches the potential The sequence of luminous intensity changes when Indicates that the historical light intensity change data is less than The luminous intensity change sequence at the time of the two luminous intensity change sequences may have inconsistent lengths, so in the specific operation process, the luminous intensity change sequence is first preprocessed, such as interpolation, truncation or filling methods to adjust the sequence length so that the two sequences have the same dimension and ensure the same length. Among them, interpolation is used to estimate the missing data points in the luminous intensity change sequence to fill the blank area in the luminous intensity change sequence; truncation is to shorten the longer luminous intensity change sequence to match the length of the shorter sequence; filling is to extend the shorter sequence in some way to reach the same length as the longer sequence; the specific operation method is selected based on the matching method between the luminous intensity change sequences actually obtained; and then the cosine similarity is calculated; and The cosine similarity calculation between is similar.
[0109] It can be understood that according to the light intensity change data of the solution sample to be tested, when the working potential of the solution sample to be tested is increased to When the luminescence similarity between the light intensity change data of the solution sample to be tested and the historical light intensity change data obtained from the solution sample with a known growth hormone concentration is calculated, when the luminescence similarity between the two is high, it means that the current working potential has reached the required potential. On the contrary, when the luminescence similarity between the two is low, it is necessary to further increase the corresponding working potential.
[0110] Furthermore, in step S3, the predicted optimal high potential of the solution sample to be tested is calculated in real time and compared with the current working potential, and the working potential of the solution sample to be tested is adaptively adjusted, including:
[0111] The predicted optimal high potential of the solution sample to be tested is calculated in real time, and the corresponding calculation formula is:
[0112]
[0113] in, represents the predicted optimal high potential of the solution sample to be tested; Indicates the concentration range; express and luminous similarity; It means that the solution sample to be tested reaches the potential The sequence of luminous intensity changes when Indicates that the historical light intensity change data is less than The sequence of luminous intensity changes when represents the maximum point function;
[0114] when When , the working potential of the solution sample to be tested is increased; when When the working potential of the solution sample to be tested remains unchanged.
[0115] To explain, It indicates the predicted optimal high potential of the solution sample to be tested. When , it means that the current working potential does not meet the demand and needs to be further increased; when When the current working potential meets the requirements, it means that there is no need to further increase the potential; real-time calculation predicts the optimal high potential By comparing with the current working potential, adaptive adjustment of the working potential of the solution sample to be tested can be achieved.
[0116] It can be explained that step S4:
[0117] The concentration of growth hormone in the solution sample to be tested is obtained by adjusting the working potential and combining the concentration-luminescence intensity curve to complete the growth hormone level determination.
[0118] Specifically, according to the working potential after adaptive adjustment, the light intensity change data corresponding to the solution sample to be tested is obtained, and the aforementioned steps S1-S3 are repeated to obtain the sum of the luminescence intensities of the solution samples to be tested. Combined with the known concentration-luminescence intensity curve, the final luminescence intensity of the solution sample to be tested is substituted into the concentration-luminescence intensity curve to obtain the concentration of growth hormone in the solution sample to be tested, thereby achieving accurate determination of the growth hormone level.
[0119] It can be understood that the present application solves the problem of improper and uncertain potential setting in traditional methods by introducing the design of adaptive potential. Traditional methods fail to optimize the characteristics of solutions of different concentrations, which may lead to the occurrence of side reactions, electrode surface damage or luminescence intensity saturation, affecting the measurement accuracy. The present application obtains the light intensity change data of solution samples of different concentrations at different potentials, analyzes the difference in luminescence intensity at different high potentials, accurately determines the adaptive high potential range suitable for solution samples of each concentration, constructs a concentration-luminescence intensity curve, and further determines the optimal high potential of the solution sample to be tested, thereby realizing luminescence measurement within a larger potential range. This method significantly improves the accuracy and stability of growth hormone concentration measurement, avoids the measurement error caused by improper potential range setting in traditional methods, and has high practical value and promotion significance.
[0120] It should be noted that the sequence of the above embodiments of the present invention is for description only and does not represent the advantages and disadvantages of the embodiments. The processes depicted in the accompanying drawings do not necessarily require the specific order or continuous order shown to achieve the desired results. In some embodiments, multitasking and parallel processing are also possible or may be advantageous.
[0121] The various embodiments in this specification are described in a progressive manner, and the same or similar parts between the various embodiments can be referenced to each other, and each embodiment focuses on the differences from other embodiments.
Claims
1. A method for measuring growth hormone levels using electrochemiluminescence, characterized in that: The method comprises: Collect light intensity change data of solution samples with different concentrations at different potentials, and perform preprocessing to generate historical light intensity change data; Based on the historical light intensity change data, the differences in luminescence in solution samples of different concentrations are analyzed, the historical light intensity change data with side reactions are excluded, and the optimal high potential of solution samples of different concentrations is determined to obtain the concentration-luminescence intensity curve; Obtain a sample of the solution to be tested, measure the light intensity change data of the sample of the solution to be tested, perform similarity analysis with the historical light intensity change data, calculate the predicted optimal high potential of the sample of the solution to be tested in real time and compare it with the current working potential, and adaptively adjust the working potential of the sample of the solution to be tested; The concentration of growth hormone in the solution sample to be tested is obtained by combining the adjusted working potential with the concentration-luminescence intensity curve to complete the growth hormone level determination; Based on the historical light intensity change data, the differences in luminescence in solution samples of different concentrations are analyzed, the historical light intensity change data with side reactions are excluded, and the optimal high potential of solution samples of different concentrations is determined to obtain the concentration-luminescence intensity curve, including: Based on the historical light intensity change data, the luminescence intensity of any concentration solution sample at the highest potential changes with time, and record it as the target data. According to the target data, several maximum points that change with time are obtained, and the influence coefficient between any two maximum points is calculated; The minimum value point is obtained by taking the maximum value point of one of the influencing coefficients, and the end point of the illumination range time is adjusted to obtain the improved illumination time period, and the sum of the luminous intensity is calculated based on the illumination time period; Calculate the reference weight of any concentration solution sample, combine it with the sum of the luminescence intensity to get the improved correlation coefficient, calculate the optimal high potential of the current concentration solution sample through the correlation coefficient, obtain the corresponding light intensity based on the optimal high potential, analyze the change of luminescence intensity with respect to concentration, and generate a concentration-luminescence intensity curve; The predicted optimal high potential of the solution sample to be tested is calculated in real time and compared with the current working potential, and the working potential of the solution sample to be tested is adaptively adjusted, including: The predicted optimal high potential of the solution sample to be tested is calculated in real time, and the corresponding calculation formula is: in, represents the predicted optimal high potential of the solution sample to be tested; Indicates the concentration range; express and luminous similarity; It means that the solution sample to be tested reaches the potential The sequence of luminous intensity changes when Indicates that the historical light intensity change data is less than The sequence of luminous intensity changes when represents the maximum point function; when When , the working potential of the solution sample to be tested is increased; when When the working potential of the solution sample to be tested remains unchanged.
2. The method for measuring growth hormone level by electrochemiluminescence as claimed in claim 1, characterized in that: The light intensity change data of solution samples with different concentrations at different potentials are collected, and preprocessed to generate historical light intensity change data, including: using PBS buffer solution, collecting light intensity change data of solution samples with different concentrations at different potentials based on a potential range of 0V to 1.5V, and generating historical light intensity change data through Gaussian filtering and denoising.
3. The method for measuring growth hormone level by electrochemiluminescence as claimed in claim 1, characterized in that: Calculate the influence coefficient between any two maximum points. The corresponding calculation formula is: in, represents the influence coefficient; Indicates A maximum point; Indicates A maximum point; Indicates time and The time interval between Indicates that the concentration of growth hormone in the solution sample is , at the highest potential Luminous intensity data measured under At the moment The light intensity under Indicates The moment corresponding to the maximum point; Indicates that the concentration of growth hormone in the solution sample is , at the highest potential Luminous intensity data measured under In the The light intensity at the moment corresponding to the maximum point; Indicates The moment corresponding to the maximum point; Indicates that the concentration of growth hormone in the solution sample is , at the highest potential Luminous intensity data measured under In the The light intensity at the moment corresponding to the maximum point; express No. The moment corresponding to the maximum point; express No. The moment corresponding to the maximum point.
4. The method for measuring growth hormone level by electrochemiluminescence as claimed in claim 3, characterized in that: The minimum point is obtained by taking the maximum point of one of the influence coefficients, adjusting the end point of the illumination range time, obtaining the improved illumination time period, and calculating the sum of the luminous intensity based on the illumination time period, including: by Expand to the left and right sides at the central moment, record the first minimum point that appears and get the corresponding time as and ; Adjust the illumination range time endpoint, the corresponding calculation formula is: in, Indicates the time endpoint of the illumination range after adjustment of the left minimum point; Indicates the time endpoint of the original illumination range corresponding to the minimum point on the left; represents the directional coefficient; Indicates that the current analysis time is less than The number of maximum points of ; represents the influence coefficient; It represents the time correction under unit influence coefficient; And calculate according to the same formula , It indicates the time endpoint of the illumination range after the minimum point on the right is adjusted; Get improved light time period , calculate the sum of luminous intensity based on the illumination time period .
5. The method for measuring growth hormone level by electrochemiluminescence as claimed in claim 4, characterized in that: Calculate the reference weight of any concentration solution sample, the corresponding calculation formula is: in, Indicates that the concentration of growth hormone in the solution sample is The highest potential is related to the growth hormone concentration in the solution sample. The reference weight between Represents the normalization function.
6. The method for measuring growth hormone level using electrochemiluminescence as claimed in claim 5, characterized in that: The improved correlation coefficient is obtained by combining the sum of the luminous intensity, and the corresponding calculation formula is: in, represents the improved correlation coefficient; Indicates the concentration range; Indicates that the concentration of growth hormone in the solution sample is The highest potential is related to the growth hormone concentration in the solution sample. The reference weight between represents the mean concentration; Indicates that the concentration of growth hormone in the solution sample is , at the highest potential The sum of the luminous intensities under express About concentration The mean of Represents the standard deviation function.
7. The method for measuring growth hormone level by electrochemiluminescence according to claim 6, characterized in that: The optimal high potential of the current concentration solution sample is calculated by the correlation coefficient, and the corresponding calculation formula is: in, Represents the function of finding the minimum point; express About concentration The size of the second-order difference.
8. The method for measuring growth hormone level using electrochemiluminescence as claimed in claim 3, characterized in that: The light intensity change data of the solution sample to be tested is measured and similarity analysis is performed with the historical light intensity change data. The corresponding calculation formula is: in, express and luminous similarity; It means that the solution sample to be tested reaches the potential The sequence of luminous intensity changes when Indicates that the historical light intensity change data is less than The sequence of luminous intensity changes when Indicates the working potential during the analysis; Indicates that the concentration of growth hormone in the solution sample is The highest potential; Indicates the light intensity change data of the solution sample to be tested when the potential is less than The sequence of luminous intensity changes when Indicates that the historical light intensity change data is less than The sequence of luminous intensity changes when Express request and and / or and Cosine similarity between two luminous intensity change sequences.
Citation Information
Patent Citations
Electrochemiluminescence growth hormone sensing platform based on subject-object strategy
CN116124854A