A dual-unit fluorescent sensor array for detecting oral anti-diabetic drugs and use thereof

Abstract

The application discloses a dual-unit fluorescent sensor array for detecting oral anti-diabetic drugs and application thereof, and relates to a supramolecular fluorescent sensor array which comprises a PAL@Q[8] sensing unit and a bpep-Am@Q[8] sensing unit, wherein the PAL@Q[8] sensing unit is composed of palmatine and Q[8], and the bpep-Am@Q[8] sensing unit is composed of a derivative of 1,4-bis[2-(4-pyridyl)vinyl]benzene and Q[8]. The dual-unit fluorescent sensor array can be used for qualitative detection and quantitative detection of metformin, phenformin, buformin hydrochloride, rosiglitazone and sitagliptin in serum or urine, and the method provides a simple and reliable analysis tool for rapid screening of oral hypoglycemic drugs, clinical blood drug concentration monitoring and identification of hypoglycemia causes, so as to realize on-site rapid visual analysis of oral hypoglycemic drugs.

Description

Technical Field

[0001] This invention belongs to the field of analytical chemistry technology, specifically relating to a dual-unit fluorescence sensor array for detecting oral antidiabetic drugs and its application. Background Technology

[0002] Hypoglycemia is the most common and dangerous complication of diabetes treatment, but it can also occur in non-diabetic individuals, making its etiology crucial. According to a joint statement by the American Diabetes Association and the European Association for the Study of Diabetes, a blood glucose level of 3.9–3.0 mmol / L (70–54 mg / dL) is considered the warning range for hypoglycemia, while levels below 3.0 mmol / L (<54 mg / dL) are defined as clinically significant severe hypoglycemia. Clearly defining this blood glucose threshold is important for assessing the safety of hypoglycemic drugs and identifying adverse reactions caused by drug overdose or accumulation. In cases of combined use of multiple drugs or under specific physiological conditions, drug concentration monitoring combined with blood glucose threshold assessment can provide important objective evidence for the clinical differential diagnosis of drug-induced hypoglycemia.

[0003] Detection of oral antidiabetic drugs (OADs) helps differentiate drug-induced hypoglycemia from hypoglycemia caused by other reasons. Metformin (MET) and sitagliptin (STG) are commonly used first-line and long-term oral hypoglycemic agents. Although newer OADs are considered to be of lower risk, the incidence of severe hypoglycemia has not decreased significantly. Most OADs are excreted by the kidneys and rapidly metabolized; therefore, establishing analytical methods for the simultaneous and accurate detection of multiple OADs is crucial for clinical drug monitoring, screening for illicit additives, and differential diagnosis of hypoglycemia.

[0004] Existing detection methods, such as high performance liquid chromatography and liquid chromatography-tandem mass spectrometry, have drawbacks such as complex sample preparation and high cost. This invention uses an optical sensor array based on an octagonal cucurbita ring (Q[8]). The sensing unit is formed by the interaction between the supramolecular host compound octagonal cucurbita ring (Q[8]) and compounds with optical properties. This enables highly sensitive detection and differentiation of five different oral diabetes drugs: metformin, phenformin, buformin hydrochloride, rosiglitazone, and sitagliptin, laying a good foundation for clinical application. Summary of the Invention

[0005] The purpose of this invention is to provide a dual-unit fluorescence sensor array for detecting oral antidiabetic drugs and its application. This sensor array can simultaneously and with high sensitivity detect and distinguish five different oral diabetes drugs: metformin, phenformin, buformin hydrochloride, rosiglitazone, and sitagliptin.

[0006] The present invention adopts the following technical solution to achieve the purpose of the invention: a dual-unit fluorescence sensor array for detecting oral antidiabetic drugs, wherein the supramolecular fluorescence sensor array is constructed from two sensing units, PAL@Q[8] and bpep-Am@Q[8]. The PAL@Q[8] sensing unit is composed of patrin and Q[8], and the bpep-Am@Q[8] sensing unit is composed of a derivative of 1,4-bis[2-(4-pyridyl)vinyl]benzene and Q[8].

[0007] The preparation method of the aforementioned PAL@Q[8] sensing unit is as follows: first, prepare a solution of barmatin with ultrapure water to a concentration of [missing information]. The barmatine stock solution was then prepared by adding Q[8] to ultrapure water to a concentration of [missing value]. The Q[8] stock solution was prepared by mixing the barmatine stock solution and the Q[8] stock solution, and adding ultrapure water to prepare a final concentration of [missing information]. The solution of the sensing unit is used to obtain the PAL@Q[8] sensing unit.

[0008] Specifically, the preparation method of the aforementioned PAL@Q[8] sensing unit is as follows: first, prepare balamarin with ultrapure water to a concentration of [missing information]. The Bama stock solution was then prepared by adding Q[8] to ultrapure water to a concentration of [missing information]. The Q[8] solution was prepared by mixing the barmatine stock solution and the Q[8] stock solution at a molar ratio of 2:1 and adding ultrapure water to achieve a final concentration of [missing value]. The solution of the sensing unit is used to obtain the PAL@Q[8] sensing unit.

[0009] The aforementioned bpep-Am@Q[8] sensing unit is prepared according to the following steps: (1) Dissolve 0.2 mmol of 1,4-bis[2-(4-pyridyl)vinyl]benzene and 0.6 mmol of 1-bromopentane in 6 mL of DMF. After mixing, reflux at 90-110°C for 70-74 hours. After cooling to room temperature, crude product is obtained. The crude product is washed with DMF 4-6 times, with each wash using 3-6 mL of DMF. Then, it is washed with petroleum ether 4-6 times, with each wash using 3-6 mL of petroleum ether. Finally, it is filtered and separated. The separated solid is dried under vacuum at 70°C to obtain bpep-Am for later use. (2) Prepare bpep-Am with ultrapure water to a concentration of [missing value]. bpep-Am stock solution, for later use; (3) Prepare Q[8] with ultrapure water to a concentration of Q[8] stock solution, for later use; (4) Mix the bpep-Am stock solution and Q[8] stock solution, and add ultrapure water to prepare a final concentration of The solution of the sensing unit is obtained by bpep-Am@Q[8] sensing unit.

[0010] Specifically, the fabrication method of the aforementioned bpep-Am@Q[8] sensing unit is carried out according to the following steps: (1) Dissolve 0.2 mmol of 1,4-bis[2-(4-pyridyl)vinyl]benzene and 0.6 mmol of 1-bromopentane in 6 mL of DMF. After mixing, reflux at 100°C for 72 hours. After cooling to room temperature, crude product is obtained. The crude product is washed 5 times with DMF, each time using 5 mL of DMF. Then it is washed 5 times with petroleum ether, each time using 5 mL of petroleum ether. Finally, it is filtered and separated. The separated solid is vacuum dried at 70°C to obtain bpep-Am for later use. (2) Prepare bpep-Am with ultrapure water to a concentration of [missing value]. bpep-Am stock solution, for later use; (3) Prepare Q[8] with ultrapure water to a concentration of Q[8] stock solution, for later use; (4) Mix the bpep-Am stock solution and Q[8] stock solution at a molar ratio of 2:3, and add ultrapure water to prepare a final concentration of The solution of the sensing unit is obtained by bpep-Am@Q[8] sensing unit.

[0011] The aforementioned dual-unit fluorescence sensor array can be used for qualitative and quantitative detection of oral antidiabetic drugs in serum or urine, including metformin, phenformin, buformin hydrochloride, rosiglitazone, and sitagliptin.

[0012] The aforementioned qualitative testing is performed according to the following steps: (1) Prepare with ultrapure water separately metformin solution, Phenformin solution, diguanidine hydrochloride solution, Rosiglitazone solution and The sitagliptin solution was used to prepare metformin stock solution, phenformin stock solution, butylguanidine hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution for later use; (2) Take 5-7 μL of each of metformin stock solution, phenformin stock solution, butylformin hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, and add them to five equal portions of 2.5-3.5 mL PAL@Q[8] sensor unit solution. Vortex mix to obtain metformin sample A1, phenformin sample A2, butylformin hydrochloride sample A3, rosiglitazone sample A4 and sitagliptin sample A5; (3) Take 5-7 μL of each of metformin stock solution, phenformin stock solution, butylformin hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, and add them to five equal portions of 2.5-3.5 mL bpep-Am@Q[8] sensor unit solution, and vortex mix to obtain metformin sample B1, phenformin sample B2, butylformin hydrochloride sample B3, rosiglitazone sample B4 and sitagliptin sample B5; (4) Fluorescence scanning conditions: The fluorescence scanning conditions for the test sample containing the PAL@Q[8] sensing unit are excitation wavelength 344nm, emission wavelength 536nm, voltage 500V, and slit width 10nm; the fluorescence scanning conditions for the test sample containing the bpep-Am@Q[8] sensing unit are excitation wavelength 381nm, emission wavelength 468nm, voltage 500V, and slit width 10nm. (6) Construction of dual-unit fluorescence sensor: Metformin sample A1, phenformin sample A2, butylguanidine hydrochloride sample A3, rosiglitazone sample A4, and sitagliptin sample A5 were taken respectively. The samples were transferred to a 96-well plate for testing. Separately, samples prepared in step (3) were taken: metformin sample B1, phenformin sample B2, butylguanidine hydrochloride sample B3, rosiglitazone sample B4, and sitagliptin sample B5. The sample was transferred to a 96-well plate and fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The measurement was repeated 5 times to construct a multidimensional data matrix consisting of 2 sensing units × 5 oral antidiabetic drugs × 5 parallel samples. LDA analysis was performed to obtain a unique differential fluorescence response fingerprint spectrum. (7) Serum qualitative test: The barmatine stock solution and Q[8] stock solution were mixed and the serum obtained after sterile blood collection, centrifugation and filtration was added to prepare a final concentration of The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification. (8) Qualitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to 96-well plates respectively, and fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification.

[0013] Specifically, the aforementioned qualitative testing is carried out according to the following steps: (1) Prepare with ultrapure water separately metformin solution, Phenformin solution, diguanidine hydrochloride solution, Rosiglitazone solution and The sitagliptin solution was used to obtain metformin stock solution, phenformin stock solution, butylguanidine hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, respectively; (2) Take 6 μL each of metformin stock solution, phenformin stock solution, butylformin hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, add them to 3 mL of PAL@Q[8] sensor unit solution, and vortex mix to obtain metformin test sample A1, phenformin sample A2, butylformin hydrochloride sample A3, rosiglitazone sample A4 and sitagliptin sample A5; (3) Take 6 μL each of metformin stock solution, phenformin stock solution, butylformin hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, add them to 3 mL of bpep-Am@Q[8] sensor unit solution, and vortex mix to obtain metformin test sample B, phenformin sample B, butylformin hydrochloride sample B, rosiglitazone sample B and sitagliptin sample B; (4) Fluorescence scanning conditions: The fluorescence scanning conditions for the test sample containing the PAL@Q[8] sensing unit are excitation wavelength 344nm, emission wavelength 536nm, voltage 500V, and slit width 10nm; the fluorescence scanning conditions for the test sample containing the bpep-Am@Q[8] sensing unit are excitation wavelength 381nm, emission wavelength 468nm, voltage 500V, and slit width 10nm. (6) Construction of dual-unit fluorescence sensor: Metformin sample A1, phenformin sample A2, butylguanidine hydrochloride sample A3, rosiglitazone sample A4, and sitagliptin sample A5 were taken respectively. The samples were transferred to a 96-well plate for testing. Separately, samples prepared in step (3) were taken: metformin sample B1, phenformin sample B2, butylguanidine hydrochloride sample B3, rosiglitazone sample B4, and sitagliptin sample B5. The samples were transferred to a 96-well plate for testing. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The measurements were repeated 5 times. A multidimensional data matrix consisting of 2 sensing units, 5 oral antidiabetic drugs and 5 parallel samples was constructed. LDA analysis was performed to establish different fluorescence response fingerprint spectra. (7) Serum qualitative test: The barmatine stock solution and Q[8] stock solution were mixed and the serum obtained after sterile blood collection, centrifugation and filtration was added to prepare a final concentration of The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification. (8) Qualitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to 96-well plates respectively, and fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification.

[0014] The aforementioned quantitative determination was performed according to the following steps: (1) Metformin, phenformin, butylguanidine hydrochloride, rosiglitazone and sitagliptin were added to ultrapure water and diluted to volume to prepare the following preparations. The stock solutions were used to obtain metformin stock solution, phenformin stock solution, butylguanidine hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, respectively, for later use; (2) Take 0 uL, 8 uL, 16 uL, 24 uL, 32 uL, 40 uL and 48 uL of each drug stock solution and add them to the 3mLPAL@Q[8] sensing unit respectively. Vortex mix to obtain 7 different concentrations of metformin test samples, 7 different concentrations of phenformin test samples, 7 different concentrations of butylguanidine hydrochloride test samples, 7 different concentrations of rosiglitazone test samples and 7 different concentrations of sitagliptin test samples; (3) Take 0 uL, 8 uL, 16 uL, 24 uL, 32 uL, 40 uL and 48 uL of each drug stock solution and add them to 3 mL bpep-Am@Q[8] sensing unit respectively. Vortex mix to obtain 7 different concentrations of metformin test samples, 7 different concentrations of phenformin test samples, 7 different concentrations of butylguanidine hydrochloride test samples, 7 different concentrations of rosiglitazone test samples and 7 different concentrations of sitagliptin test samples. (4) Fluorescence scanning conditions: The fluorescence scanning conditions for the test sample containing the PAL@Q[8] sensing unit are excitation wavelength 344nm, emission wavelength 536nm, voltage 500V, and slit width 10nm; the fluorescence scanning conditions for the test sample containing the bpep-Am@Q[8] sensing unit are excitation wavelength 381nm, emission wavelength 468nm, voltage 500V, and slit width 10nm. (5) Construction of dual-unit fluorescence sensor array and quantitative calibration curve: Take 7 different concentrations of metformin, 7 different concentrations of phenformin, 7 different concentrations of butylformin hydrochloride, 7 different concentrations of rosiglitazone and 7 different concentrations of sitagliptin prepared in step (2) and transfer them to 96-well plates for testing. Take 7 different concentrations of metformin, 7 different concentrations of phenformin, 7 different concentrations of butylformin hydrochloride, 7 different concentrations of rosiglitazone and 7 different concentrations of sitagliptin prepared in step (3) and transfer them to 96-well plates for testing. Perform fluorescence scanning measurement according to the fluorescence scanning conditions in step (4). Obtain the data matrix of 5 oral antidiabetic drugs with 2 sensing units and 7 different concentrations from the sensor array. Perform LDA processing and establish a quantitative calibration curve between LDA factor 1 and the concentration of 7 oral antidiabetic drugs. (6) Serum quantitative detection: The barmatine stock solution and Q[8] stock solution were mixed, and serum that had been sterilely collected, centrifuged and filtered was added to prepare a final concentration of The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] sensor unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The content of the urine test sample was determined by the linear relationship between LDA factor 1 and concentration in the quantitative calibration curve. (7) Quantitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] sensor unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to a 96-well plate respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). Data matrix of 2 sensor units and 7 different concentrations of 5 oral antidiabetic drugs was obtained from the sensor array. LDA processing was performed, and a quantitative calibration curve was established between LDA factor 1 and the concentration of 7 oral antidiabetic drugs. Specifically, the aforementioned quantitative determination is performed according to the following steps: (1) Metformin, phenformin, butylguanidine hydrochloride, rosiglitazone and sitagliptin were added to ultrapure water and diluted to volume to prepare the following preparations. The stock solutions were used to obtain metformin stock solution, phenformin stock solution, butylguanidine hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, respectively, for later use; (2) Take 0 uL, 8 uL, 16 uL, 24 uL, 32 uL, 40 uL and 48 uL of each drug stock solution and add them to the 3mLPAL@Q[8] sensing unit respectively. Vortex mix to obtain 7 different concentrations of metformin test samples, 7 different concentrations of phenformin test samples, 7 different concentrations of butylguanidine hydrochloride test samples, 7 different concentrations of rosiglitazone test samples and 7 different concentrations of sitagliptin test samples; (3) Take 0 uL, 8 uL, 16 uL, 24 uL, 32 uL, 40 uL and 48 uL of each drug stock solution and add them to 3 mL bpep-Am@Q[8] sensing unit respectively. Vortex mix to obtain 7 different concentrations of metformin test samples, 7 different concentrations of phenformin test samples, 7 different concentrations of butylguanidine hydrochloride test samples, 7 different concentrations of rosiglitazone test samples and 7 different concentrations of sitagliptin test samples. (4) Fluorescence scanning conditions: The fluorescence scanning conditions for the test sample containing the PAL@Q[8] sensing unit are excitation wavelength 344nm, emission wavelength 536nm, voltage 500V, and slit width 10nm; the fluorescence scanning conditions for the test sample containing the bpep-Am@Q[8] sensing unit are excitation wavelength 381nm, emission wavelength 468nm, voltage 500V, and slit width 10nm. (5) Construction of dual-unit fluorescence sensor array and quantitative calibration curve: Take the seven metformin test samples with different concentrations prepared in step (2) respectively. Seven samples of phenformin at different concentrations each Seven samples of guanidine hydrochloride at different concentrations each Seven samples of rosiglitazone at different concentrations each and 7 samples of sitagliptin at different concentrations The sample was transferred to a 96-well plate for testing. Seven different concentrations of metformin prepared in step (3) were also taken separately. Seven samples of phenformin at different concentrations were tested. Seven different concentrations of guanidine hydrochloride were tested. Seven different concentrations of rosiglitazone were tested. and 7 different concentrations of sitagliptin were tested. The sample was transferred to a 96-well plate for testing. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). Data matrix of 2 sensing units and 7 different concentrations of oral antidiabetic drugs was obtained from the sensor array. LDA processing was performed, and a quantitative calibration curve was established between LDA factor 1 and the concentrations of the 7 oral antidiabetic drugs. (6) Serum quantitative detection: The barmatine stock solution and Q[8] stock solution were mixed, and serum that had been sterilely collected, centrifuged and filtered was added to prepare a final concentration of The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] sensor unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The content of the urine test sample was determined by the linear relationship between LDA factor 1 and concentration in the quantitative calibration curve. (7) Quantitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] sensing unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The content of the urine sample to be tested was determined by the linear relationship between LDA factor 1 and concentration in the quantitative calibration curve.

[0015] Compared with the prior art, the present invention has the following beneficial effects: 1. This invention utilizes the interaction between palmatine and derivatives of 1,4-bis[2-(4-pyridyl)vinyl]benzene and an eight-membered cucurbit ring (Q[8]) to prepare two fluorescent sensing units, bpep-Am@Q[8] and PAL@Q[8]. This optical sensor array consists of multiple sensing units interacting with different drug molecules, and these interactions are converted into unique "fingerprint" signals. Since these signals can be analyzed using pattern recognition software, this method has a real advantage when it is necessary to identify several different components simultaneously. Cucurbit rings are supramolecular host compounds. Their structure is very special - they have a hydrophobic cavity inside and two negatively charged carbonyl groups at the ports. This structure enables them to selectively capture a variety of guest molecules. With this host-guest recognition capability, this invention uses cucurbit rings to construct sensors. In addition, natural compounds of palmatine (PAL) have excellent optical properties, and derivatives of 1,4-bis[2-(4-pyridyl)vinyl]benzene also have these excellent optical properties and are easy to modify. This invention utilizes the interaction between these compounds and the octagonal cucurbit ring (Q[8]) to prepare two fluorescent sensing units, PAL@Q[8] and bpep-Am@Q[8]. This array can detect and distinguish five different oral diabetes drugs (metformin, phenformin, buformin hydrochloride, rosiglitazone and sitagliptin) with high sensitivity, achieving efficient identification and quantitative analysis of five OADs.

[0016] 2. The dual-unit fluorescence sensor array prepared in this invention exhibits excellent discrimination ability and high sensitivity in both ultrapure water and complex biological matrices (artificial urine and guinea pig serum), with a detection limit as low as [missing value]. Furthermore, this array maintains stable detection performance even in the presence of multi-component drug mixtures or common biological interfering agents. Real-sample analysis shows that this method achieves good recoveries in detecting STG and DBI in artificial urine, thus demonstrating significant clinical application potential. This method provides a simple and reliable analytical tool for rapid screening of oral hypoglycemic drugs, clinical blood drug concentration monitoring, and identification of the causes of hypoglycemia. Attached Figure Description

[0017] Figure 1 This is the synthetic route for bpep-Am; Figure 2It is bpep-Am Spectrum (400 MHz, DMSO-d6); Figure 3 The fluorescence spectrum changes and the corresponding fluorescence scatter plot (a: Fluorescence spectrum changes with increasing concentration of the main component Q[8]; b: PAL fluorescence scatter plot; c: Fluorescence spectrum changes with increasing concentration of the main body Q[8]; d: bpep-Am fluorescence scatter plot; Figure 4 Oral antidiabetic drugs The fluorescence emission spectra of S1 and S2 are present; Figure 5 These are fluorescence response spectra of a sensor array used to distinguish oral antidiabetic drugs (a: fingerprint feature map; b: heat map; c: radar map; d: LDA score map). Figure 6 This is a graph showing the LDA scores of different concentrations of OADs; Figure 7 It is a linear calibration model between different concentrations of OADs and F1; Figure 8 This is an LDA score graph of binary and ternary oral antidiabetic drug mixtures with different concentration ratios; Figure 9 It is an oral antidiabetic drug and interfering substances LDA score plot; Figure 10 It is an oral antidiabetic drug and interfering substances The characteristic fingerprint histogram of the fluorescence response pattern; Figure 11 This is an LDA score chart that distinguishes five oral antidiabetic drugs in artificial urine and guinea pig serum; Figure 12 The concentrations of DBI and STG in artificial urine showed a linear relationship with the Factor 1 score. Detailed Implementation

[0018] The present invention will be further described below with reference to embodiments, but these embodiments are not intended to limit the scope of the invention.

[0019] Example 1: Method for fabricating the PAL@Q[8] sensing unit: First, prepare a solution of Parmatin with ultrapure water to a concentration of [concentration value missing]. The Bama stock solution was then prepared by adding Q[8] to ultrapure water to a concentration of [missing information]. The Q[8] solution was prepared by mixing the barmatine stock solution and the Q[8] stock solution at a molar ratio of 2:1 and adding ultrapure water to achieve a final concentration of [missing value]. The solution of the sensing unit is used to obtain the PAL@Q[8] sensing unit.

[0020] Example 2: Preparation method of bpep-Am@Q[8] sensing unit: (1) Dissolve 0.2 mmol of 1,4-bis[2-(4-pyridyl)vinyl]benzene and 0.6 mmol of 1-bromopentane in 6 mL of DMF. After mixing, reflux at 100°C for 72 hours. After cooling to room temperature, crude product is obtained. The crude product is washed 5 times with DMF, each time using 5 mL of DMF. Then it is washed 5 times with petroleum ether, each time using 5 mL of petroleum ether. Finally, it is filtered and separated. The separated solid is dried under vacuum at 70°C to obtain bpep-Am for later use. (2) Prepare bpep-Am with ultrapure water to a concentration of [missing value]. bpep-Am stock solution, for later use; (3) Prepare Q[8] with ultrapure water to a concentration of Q[8] stock solution, for later use; (4) Mix the bpep-Am stock solution and Q[8] stock solution at a molar ratio of 2:3, and add ultrapure water to prepare a final concentration of The solution of the sensing unit is obtained by bpep-Am@Q[8] sensing unit.

[0021] Example 3 Qualitative Detection: (1) Prepare with ultrapure water separately metformin solution, Phenformin solution, diguanidine hydrochloride solution, Rosiglitazone solution and The sitagliptin solution was used to obtain metformin stock solution, phenformin stock solution, butylguanidine hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, respectively; (2) Take 6 μL each of metformin stock solution, phenformin stock solution, butylformin hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, add them to 3 mL of PAL@Q[8] sensor unit solution, and vortex mix to obtain metformin test sample A1, phenformin sample A2, butylformin hydrochloride sample A3, rosiglitazone sample A4 and sitagliptin sample A5; (3) Take 6 μL each of metformin stock solution, phenformin stock solution, butylformin hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, add them to 3 mL of bpep-Am@Q[8] sensor unit solution, and vortex mix to obtain metformin test sample B1, phenformin sample B2, butylformin hydrochloride sample B3, rosiglitazone sample B4 and sitagliptin sample B5; (4) Fluorescence scanning conditions: The fluorescence scanning conditions for the test sample containing the PAL@Q[8] sensing unit are excitation wavelength 344nm, emission wavelength 536nm, voltage 500V, and slit width 10nm; the fluorescence scanning conditions for the test sample containing the bpep-Am@Q[8] sensing unit are excitation wavelength 381nm, emission wavelength 468nm, voltage 500V, and slit width 10nm. (6) Construction of dual-unit fluorescence sensor: Metformin sample A1, phenformin sample A2, butylguanidine hydrochloride sample A3, rosiglitazone sample A4, and sitagliptin sample A5 were taken respectively. The samples were transferred to a 96-well plate for testing. Separately, samples prepared in step (3) were taken: metformin sample B1, phenformin sample B2, butylguanidine hydrochloride sample B3, rosiglitazone sample B4, and sitagliptin sample B5. The samples were transferred to a 96-well plate for testing. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The measurements were repeated 5 times. A multidimensional data matrix consisting of 2 sensing units, 5 oral antidiabetic drugs and 5 parallel samples was constructed. LDA analysis was performed to establish different fluorescence response fingerprint spectra. (7) Serum qualitative test: The barmatine stock solution and Q[8] stock solution were mixed and the serum obtained after sterile blood collection, centrifugation and filtration was added to prepare a final concentration of The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification. (8) Qualitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to 96-well plates respectively, and fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification.

[0022] Example 4 Quantitative determination was performed according to the following steps: (1) Metformin, phenformin, butylguanidine hydrochloride, rosiglitazone and sitagliptin were added to ultrapure water and diluted to volume to prepare the following preparations. The stock solutions were used to obtain metformin stock solution, phenformin stock solution, butylguanidine hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, respectively, for later use; (2) Take 0 uL, 8 uL, 16 uL, 24 uL, 32 uL, 40 uL and 48 uL of each drug stock solution and add them to the 3mLPAL@Q[8] sensing unit respectively. Vortex mix to obtain 7 metformin test samples, 7 phenformin test samples, 7 butylguanidine hydrochloride test samples, 7 rosiglitazone test samples and 7 sitagliptin test samples with different concentrations. The specific concentrations are as follows: (3) Take 0 uL, 8 uL, 16 uL, 24 uL, 32 uL, 40 uL and 48 uL of each drug stock solution and add them to 3 mL bpep-Am@Q[8] sensing unit respectively. Vortex mix to obtain 7 different concentrations of metformin test samples, 7 different concentrations of phenformin test samples, 7 different concentrations of butylguanidine hydrochloride test samples, 7 different concentrations of rosiglitazone test samples and 7 different concentrations of sitagliptin test samples. (4) Fluorescence scanning conditions: The fluorescence scanning conditions for the test sample containing the PAL@Q[8] sensing unit are excitation wavelength 344nm, emission wavelength 536nm, voltage 500V, and slit width 10nm; the fluorescence scanning conditions for the test sample containing the bpep-Am@Q[8] sensing unit are excitation wavelength 381nm, emission wavelength 468nm, voltage 500V, and slit width 10nm. (5) Construction of dual-unit fluorescence sensor array and quantitative calibration curve: Take the seven metformin test samples with different concentrations prepared in step (2) respectively. Seven samples of phenformin at different concentrations each Seven samples of guanidine hydrochloride at different concentrations each Seven samples of rosiglitazone at different concentrations each and 7 samples of sitagliptin at different concentrations The sample was transferred to a 96-well plate for testing. Seven different concentrations of metformin prepared in step (3) were also taken separately. Seven samples of phenformin at different concentrations were tested. Seven different concentrations of guanidine hydrochloride were tested. Seven different concentrations of rosiglitazone were tested. and 7 different concentrations of sitagliptin were tested. The sample was transferred to a 96-well plate for testing. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). Data matrix of two sensing units and seven different concentrations of oral antidiabetic drugs was obtained from the sensor array. LDA processing was performed, and a quantitative calibration curve was established between LDA factor 1 and the concentrations of the seven oral antidiabetic drugs. (6) Serum quantitative detection: The barmatine stock solution and Q[8] stock solution were mixed, and serum that had been sterilely collected, centrifuged and filtered was added to prepare a final concentration of The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] sensor unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The content of the urine test sample was determined by the linear relationship between LDA factor 1 and concentration in the quantitative calibration curve. (7) Quantitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] sensing unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The content of the urine sample to be tested was determined by the linear relationship between LDA factor 1 and concentration in the quantitative calibration curve.

[0023] Example 5: Preparation method of PAL@Q[8] sensing unit First, prepare a solution of Parmatin with ultrapure water to a concentration of [concentration value missing]. The barmatine stock solution was then prepared by adding Q[8] to ultrapure water to a concentration of [missing value]. The Q[8] stock solution was prepared by mixing the barmatine stock solution and the Q[8] stock solution, and adding ultrapure water to prepare a final concentration of [missing information]. The solution of the sensing unit is used to obtain the PAL@Q[8] sensing unit.

[0024] Example 6: Method for fabricating the PAL@Q[8] sensing unit: First, prepare a solution of Parmatin with ultrapure water to a concentration of [concentration value missing]. The barmatine stock solution was then prepared by adding Q[8] to ultrapure water to a concentration of [missing value]. The Q[8] stock solution was prepared by mixing the barmatine stock solution and the Q[8] stock solution, and adding ultrapure water to prepare a final concentration of [missing information]. The solution of the sensing unit is used to obtain the PAL@Q[8] sensing unit.

[0025] Example 7: Fabrication method of bpep-Am@Q[8] sensing unit: (1) Dissolve 0.2 mmol of 1,4-bis[2-(4-pyridyl)vinyl]benzene and 0.6 mmol of 1-bromopentane in 6 mL of DMF. After mixing, reflux at 90°C for 70 hours. After cooling to room temperature, crude product is obtained. The crude product is washed 4 times with DMF, each time using 6 mL of DMF. Then it is washed 4 times with petroleum ether, each time using 6 mL of petroleum ether. Finally, it is filtered and separated. The separated solid is vacuum dried at 70°C to obtain bpep-Am for later use. (2) Prepare bpep-Am with ultrapure water to a concentration of [missing value]. bpep-Am stock solution, for later use; (3) Prepare Q[8] with ultrapure water to a concentration of Q[8] stock solution, for later use; (4) Mix the bpep-Am stock solution and Q[8] stock solution, and add ultrapure water to prepare a final concentration of The sensing unit solution is obtained by bpep-Am@Q[8] sensing unit.

[0026] Example 8: Fabrication method of bpep-Am@Q[8] sensing unit: (1) Dissolve 0.2 mmol of 1,4-bis[2-(4-pyridyl)vinyl]benzene and 0.6 mmol of 1-bromopentane in 6 mL of DMF. After mixing, reflux at 110°C for 74 hours. After cooling to room temperature, crude product is obtained. The crude product is washed 6 times with DMF, with 3 mL of DMF each time. Then it is washed 6 times with petroleum ether, with 3 mL of petroleum ether each time. Finally, it is filtered and separated. The separated solid is vacuum dried at 70°C to obtain bpep-Am for later use. (2) Prepare bpep-Am with ultrapure water to a concentration of [missing value]. bpep-Am stock solution, for later use; (3) Prepare Q[8] with ultrapure water to a concentration of Q[8] stock solution, for later use; (4) Mix the bpep-Am stock solution and Q[8] stock solution, and add ultrapure water to prepare a final concentration of The sensing unit solution is obtained by bpep-Am@Q[8] sensing unit. Example 9 Qualitative Detection

[0027] In the qualitative detection steps (1) to (6), except that the PAL@Q[8] sensing unit used was prepared in Example 5 and the bpep-Am@Q[8] sensing unit was prepared in Example 7, the other steps are the same as in Example 3, while steps (7) and (8) are as follows: (7) Serum qualitative test: The barmatine stock solution and Q[8] stock solution were mixed and the serum obtained after sterile blood collection, centrifugation and filtration was added to prepare a final concentration of The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification. (8) Qualitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to 96-well plates respectively, and fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification. Example 10 Qualitative Detection

[0028] In the qualitative detection steps (1) to (6), except that the PAL@Q[8] sensing unit used was prepared in Example 6 and the bpep-Am@Q[8] sensing unit was prepared in Example 8, the other steps are the same as in Example 3, while steps (7) and (8) are as follows: (7) Serum qualitative test: The barmatine stock solution and Q[8] stock solution were mixed and the serum obtained after sterile blood collection, centrifugation and filtration was added to prepare a final concentration of The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification. (8) Qualitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to 96-well plates respectively, and fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification. Example 11 Quantitative Detection

[0029] In the quantitative detection steps (1) to (5), except that the PAL@Q[8] sensing unit used was prepared in Example 5 and the bpep-Am@Q[8] sensing unit was prepared in Example 7, the other steps are the same as in Example 3, while steps (6) and (7) are as follows: Serum quantitative detection: Parbutin stock solution and Q[8] stock solution were mixed, and serum that had been sterilely collected, centrifuged and filtered was added to prepare a final concentration of [missing information]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] sensor unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The content of the urine test sample was determined by the linear relationship between LDA factor 1 and concentration in the quantitative calibration curve. (7) Quantitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] sensor unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). Data matrix of 2 sensor units and 7 different concentrations of 5 oral antidiabetic drugs was obtained from the sensor array. LDA processing was performed, and a quantitative calibration curve was established between LDA factor 1 and the concentrations of 7 oral antidiabetic drugs. Example 12 Quantitative Detection

[0030] In the quantitative detection steps (1) to (5), except that the PAL@Q[8] sensing unit used was prepared in Example 6 and the bpep-Am@Q[8] sensing unit was prepared in Example 8, the other steps are the same as in Example 3, while steps (6) and (7) are as follows: (7) Serum quantitative detection: The barmatine stock solution and Q[8] stock solution were mixed, and serum that had been sterilely collected, centrifuged and filtered was added to prepare a final concentration of . The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] sensor unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The content of the urine test sample was determined by the linear relationship between LDA factor 1 and concentration in the quantitative calibration curve. (7) Quantitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] sensor unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to a 96-well plate respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). Data matrix of 2 sensor units and 7 different concentrations of 5 oral antidiabetic drugs was obtained from the sensor array. LDA processing was performed, and a quantitative calibration curve was established between LDA factor 1 and the concentrations of 7 oral antidiabetic drugs.

[0031] To obtain the solution of this invention and verify its technical effects, the inventors conducted extensive experimental research, some of which are recorded below: 1. Reagents and Instruments Q[8] is an abbreviation for an octagonal cucurbit ring, and its molecular formula is: Palmatine (PAL), 1-bromopentane, 1,4-bis[2-(4-pyridyl)vinyl]benzene, ultra-dry N,N-dimethylformamide, petroleum ether, and the target analytes (metformin (MET), phenformin (DBI), buformin hydrochloride (BUF), rosiglitazone (RSG), and sitagliptin (STG)) were all purchased from Guizhou Hexi Biotechnology Co., Ltd. Artificial urine was purchased from Beijing Solarbio Science & Technology Co., Ltd., and guinea pig serum was purchased from Guangzhou Hongquan Biotechnology Co., Ltd. Analytical grade reagents were provided and used as is, without further purification. Ultrapure water was used exclusively in all experiments. The reagent DMF was N,N-dimethylformamide. Furthermore, all experiments were performed at room temperature.

[0032] Fluorescence emission spectra were recorded using a Varian Cary Eclipse fluorescence spectrophotometer. The fluorescence scanning conditions for PAL@Q[8] were set as follows: excitation wavelength 344 nm, emission wavelength 536 nm, voltage 500 V, and slit width 10 nm. Similarly, the scanning conditions for bpep-Am@Q[8] were set as follows: excitation wavelength 381 nm, emission wavelength 468 nm, voltage 500 V, and slit width 10 nm. At 25°C, the fluorescence emission spectra were recorded using a Bruker Avance NEO 400 MHz nuclear magnetic resonance spectrometer. Spectroscopy, with tetramethylsilane as an internal standard. DMSO-d6 was used for field frequency locking. Signals from the multivariate fluorescence channels were collected using a microplate reader. The instrument recorded the fluorescence responses of PAL@Q[8] and bpep-Am@Q[8] at excitation / emission wavelengths of 381 / 468 nm and 344 / 536 nm, respectively.

[0033] 2. Fabrication of bpep-Am@Q[8] sensing unit and PAL@Q[8] sensing unit 2.1 Preparation of Q[8] stock solution Q[8] was prepared with ultrapure water to a concentration of [missing value]. The Q[8] solution is obtained to prepare the Q[8] stock solution for later use; 2.2 Synthesis of bpep-Am 0.2 mmol of 1,4-bis[2-(4-pyridyl)vinyl]benzene and 0.6 mmol of 1-bromopentane were dissolved in 6 mL of DMF. After mixing, the mixture was refluxed at 100°C for 72 hours. After cooling to room temperature, a crude product was obtained. The crude product was washed five times with 5 mL of DMF each time, and then washed five times with 5 mL of petroleum ether each time. Finally, the product was filtered and separated. The separated solid was dried under vacuum at 70°C to obtain a yellow solid product bpep-Am (48.4 mg, yield 55.2%).

[0034] 2.2 Configuration of bpep-Am@Q[8] sensing unit bpep-Am was prepared with ultrapure water to a concentration of [missing value]. The bpep-Am stock solution was prepared by mixing the bpep-Am stock solution and the Q[8] stock solution; ultrapure water was added to prepare a final concentration of . The sensing unit is the bpep-Am@Q[8] sensing unit.

[0035] 2.3 Configuration of PAL@Q[8] sensing unit First, prepare a solution of Parbutin (PAL) with ultrapure water to a concentration of [concentration value missing]. The barmatine stock solution was prepared by mixing the barmatine stock solution and Q[8] stock solution, and adding ultrapure water to prepare a final concentration of [missing value]. The sensing unit is PAL@Q[8] sensing unit.

[0036] Array construction experiment Accurately weigh five oral antidiabetic drugs: metformin, phenformin, buformin hydrochloride, rosiglitazone, and sitagliptin, and dissolve and dilute with ultrapure water to prepare the solution. The stock solutions were prepared to obtain analyte stock solutions. Then, the stock solutions of each oral antidiabetic drug analyte were added to 3 mL of the sensor unit stock solution and vortexed thoroughly to obtain the final oral antidiabetic drug concentration. The mixed solution. Then, take the mixed solution... The samples were transferred to sterile black 96-well plates, and their fluorescence responses were measured under identical conditions, with each sample analyzed five times. Based on these measurements, a multidimensional data matrix was constructed consisting of 2 sensing units × 5 oral antidiabetic drugs × 5 parallel samples. The equations were then used to... Calculate the fluorescence response values ​​to obtain the fluorescence response pattern, where I and The fluorescence intensity of the sensing solution is represented by the presence and absence of oral antidiabetic drugs, respectively. This represents the average fluorescence intensity of bpep-Am or PAL under the same conditions. The obtained data were imported into IBM SPSS Statistics software for linear discriminant analysis. Combined with the LDA results, the linear relationship between Factor 1 and the concentration of the oral antidiabetic drug was selected for sensitivity analysis. The limits of detection and quantitation for each oral antidiabetic drug were determined using... and From calibration slope k and blank standard deviation It is concluded that, among them Based on five blank fluorescence readings, k was used to regress the concentration of oral antidiabetic drugs on factor 1.

[0037] 4. Preparation of real samples For actual sample analysis, guinea pig serum requires no additional treatment and can be used directly. Artificial urine is used first. Filter the solution through a membrane filter, then dilute the filtrate by two times before use. The specific method is as follows: Preparation of guinea pig serum samples: Parmatin stock solution and Q[8] stock solution were mixed, and guinea pig serum that had been sterilely collected, centrifuged, and filtered was added to prepare a PAL@Q[8] mixed sensor unit solution with a final concentration of 2×10⁻⁵ mol / L. The mixture was vortexed. Separately, bpep-Am stock solution and Q[8] stock solution were mixed, and guinea pig serum that had been sterilely collected, centrifuged, and filtered was added to prepare a solution with a final concentration of... The bpep-Am@Q[8] mixed sensing unit solution was vortex-mixed; Preparation of urine samples: Collect artificial urine for use. The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed, and the bpep-Am stock solution and Q[8] stock solution were mixed and added to urine solution to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortex-mixed.

[0038] The analysis process for guinea pig serum and urine samples is the same as the analysis procedure described above.

[0039] 5. Results and Discussion 5.1 Construction of the Sensing Unit First, bpep-Am was synthesized as a guest molecule according to the previously described route. Figure 1 ), and through Its structure was characterized ( Figure 2 To regulate the molecular properties and spectral characteristics of the guest molecules, Q[8] was introduced into their aqueous solutions to construct host-guest complexes bpep-Am@Q[8] and PAL@Q[8], respectively. The binding properties of these complexes in ultrapure water were then investigated. For the dye molecule PAL, fluorescence was excited at 268 nm, producing an emission peak at 530 nm. After the addition of Q[8], the fluorescence intensity gradually increased, reaching its maximum value at a Q[8] concentration of 2.0 equivalents. Further addition of Q[8] resulted in fluorescence quenching accompanied by a slight blue shift (…). Figure 3 a). The molar ratio fitting results show that ( Figure 3 b) PAL and Q[8] mainly form a complex with a molar ratio of 2:1, which is consistent with previously reported results. For bpep-Am, fluorescence excitation at 413 nm produces an emission peak at 475 nm. When the concentration of Q[8] is gradually increased to 0.5 equivalents, the fluorescence intensity of the system decreases and is accompanied by a slight red shift. When the concentration of Q[8] is further increased to 1.0 equivalents, the emission intensity at 518 nm increases significantly. When the concentration of Q[8] reaches 3.5 equivalents, the fluorescence intensity of the emission peak decreases significantly and is accompanied by a red shift ( Figure 3 c). This phenomenon can be attributed to a dynamic process, including the partial encapsulation of guest molecules, the formation of ordered assemblies, and the eventual aggregation. The molar ratio fitting curve shows ( Figure 3d), bpep-Am can form three types of host-guest complexes with Q[8]: 2:1, 1:1 and 2:3, which is consistent with the literature. Among them, the 2:3 complex was selected as the sensing unit because of its excellent response to oral antidiabetic drugs.

[0040] 5.2 Design and Construction of Sensor Array Based on the above results, we selected 2PAL@Q[8] (denoted as S1) and 2bpep-Am@3Q[8] (denoted as S2) as sensing units to construct a fluorescence sensing array. Next, we introduced five different oral diabetes drugs into each sensing unit, with the final concentration set at 20 μM. It can be clearly observed that the addition of different drugs triggered significantly different fluorescence reactions ( Figure 4 For S1, the introduction of all oral antidiabetic drugs except MET caused varying degrees of fluorescence quenching. RSG showed the most significant fluorescence quenching effect. We also observed that DBI, RSG, and STG all caused a certain degree of blue shift in the fluorescence spectrum. The difference lies in S2: the addition of BUF, RSG, and STG led to varying degrees of fluorescence quenching, while MET and DBI led to varying degrees of fluorescence enhancement. DBI exhibited the most significant fluorescence enhancement effect, accompanied by a slight red shift. This significant difference in response pattern confirms that the sensor array constructed in this study has the ability to simultaneously identify and distinguish multiple oral antidiabetic drugs.

[0041] 5.3 Sensor array differentiation of OADs 5.3.1 Qualitative Analysis Based on the aforementioned differential responses, the sensor array detected five oral antidiabetic drugs (20 μM each), generating different fluorescence response fingerprints, as well as corresponding heatmaps and radar maps. Figure 5 This visually demonstrates that the sensor array produced differential fluorescence response patterns to different oral antidiabetic drugs, indicating that each oral antidiabetic drug has a unique effect on the fluorescence sensing system. Further LDA processing was performed on the data matrix obtained from the sensor array (2 sensing units × 5 OADs × 5 replicates). The results show ( Figure 5 (d) These oral antidiabetic drugs formed separate and non-overlapping clusters in the discriminant space. Furthermore, their cross-validation classification accuracy reached 100%. These results collectively demonstrate that the constructed fluorescent sensor array exhibits excellent recognition and classification performance for oral antidiabetic drugs.

[0042] 5.3.2 Quantitative Detection To evaluate the sensitivity of the sensor array in detecting different concentrations of oral antidiabetic drugs, five repeated measurements were performed at each concentration. The obtained fluorescence data matrix was then analyzed by LDA (…). Figure 6 Data shows that we tested each of the five drugs within a concentration range of 0 to 24 μM. When we plotted the results in the discriminant space, each drug formed its own independent cluster. There was no overlap between different drugs, and no misclassification was found. Furthermore, cross-validation results showed that the classification accuracy for all oral antidiabetic drug concentration levels was 100%, indicating that the sensor array can effectively distinguish different oral antidiabetic drug concentrations. In addition, a quantitative calibration curve was established between the LDA factor 1 and the concentration of each oral antidiabetic drug. Figure 7 Taking RSG as an example, the LDA factor 1 is linearly related to the concentration in two ranges. The effective concentration (LOD) was 0.218 μM, and the LOQ was 0.727 μM. Other oral antidiabetic drugs also showed a good linear relationship between LDA factor 1 and concentration in the range of 4-24 μM. Their corresponding LODs were 2.60, 2.27, 0.66, and 0.34 μM, and their LOQs were 8.68, 7.55, 2.21, and 0.727 μM, respectively. (Table 1). These results indicate that the constructed sensor array has strong quantitative analysis capabilities.

[0043] Table 1. Linearity of sensor arrays with respect to five OADs, limit of detection (LOD), and limit of quantitation (LOQ).

[0044] To further evaluate the precision of the sensor array, ten repeated measurements were performed for each oral antidiabetic drug. The results showed that the relative standard deviations were all < 6% (Table 2), indicating good analytical precision. This result further confirms the excellent reproducibility of the supramolecular assembly-based fluorescence sensor array in detecting oral antidiabetic drugs.

[0045] Table 2. Precision of sensor array in identifying five types of OADs 5.4 Mixture Identification and Anti-interference Experiment To evaluate the ability of the constructed sensor array to identify mixtures of multi-component oral antidiabetic drugs, clinically common analytes MET, RSG, and STG were selected as representative analytes. In the experiments, various binary and ternary mixtures with different molar ratios were prepared. Clearly, the LDA score plot visually demonstrates ( Figure 8Different proportions of binary and ternary mixtures formed significantly separated data clusters with no overlap or intersection. Cross-validation results further demonstrated that the sensor array achieved 100% classification accuracy for all mixed samples. These results confirm the promising application potential of this sensor array in identifying complex oral antidiabetic drug mixtures.

[0046] To evaluate the anti-interference performance of the fluorescence sensor array, common inorganic ions and organic molecules found in biological fluids were introduced into the sensing system, with a final concentration of 100 μM. LDA results showed ( Figure 9 The data clusters for each oral antidiabetic drug and the interfering substances are separate. Furthermore, the clusters corresponding to different interfering substances cluster in the same region of the discrimination space, indicating that the sensor array has high selectivity for different oral antidiabetic drugs. The feature fingerprint further demonstrates the differentiated fluorescence response patterns of the sensor array to different oral antidiabetic drugs. Figure 10 These results indicate that the sensor array has good anti-interference capabilities when detecting oral antidiabetic drugs.

[0047] 5.5 Analysis of OADs in Real Biological Samples To ensure the analytical reliability of the sensor array constructed in real samples, we performed detection and differentiation of orally administered antidiabetic drugs in complex biological matrices. LDA results showed ( Figure 11 In artificial urine and guinea pig serum, orally administered antidiabetic drugs formed well-separated, non-overlapping data clusters in the discriminant space. Furthermore, cross-validation classification accuracy reached 100% in both matrices. These results demonstrate that the sensor array can still accurately identify and completely distinguish orally administered antidiabetic drugs in complex biological matrices such as artificial urine and guinea pig serum, exhibiting excellent matrix tolerance and reliable sample analysis capabilities.

[0048] STG is a widely used oral antidiabetic drug, while DBI has been withdrawn from the market due to safety concerns, but it may still be encountered in cases of illegal addition. Since oral antidiabetic drugs are primarily excreted through the kidneys, urine becomes a key biological matrix for detecting STG and other drugs. This study used the standard addition method to detect STG and DBI in artificial urine and established a calibration curve between factor 1 and the concentration of oral antidiabetic drugs. Figure 12 The results (Table 3) show that the recoveries of STG and DBI exceeded 93% at low, medium, and high concentrations. This further confirms that the sensor array method developed in this study can effectively detect STG and DBI in artificial urine, providing a practical solution for the detection and analysis of oral antidiabetic drugs in biological fluids and the determination of the causes of hypoglycemia.

[0049] Table 3. Spiked recoveries of STG and DBI in artificial urine using a sensor array.

[0050]

Claims

1. A dual-unit fluorescence sensor array for detecting oral antidiabetic drugs, characterized in that: The supramolecular fluorescence sensing array is constructed from two sensing units, PAL@Q[8] and bpep-Am@Q[8]. The PAL@Q[8] sensing unit is composed of barmatine and Q[8], and the bpep-Am@Q[8] sensing unit is composed of a derivative of 1,4-bis[2-(4-pyridyl)vinyl]benzene and Q[8].

2. The dual-unit fluorescence sensor array for detecting oral antidiabetic drugs according to claim 1, characterized in that: The preparation method of the PAL@Q[8] sensing unit is as follows: first, prepare a solution of barmatin with ultrapure water to a concentration of [missing information]. The barmatine stock solution was then prepared by adding Q[8] to ultrapure water to a concentration of [missing value]. The Q[8] stock solution was prepared by mixing the barmatine stock solution and the Q[8] stock solution, and adding ultrapure water to prepare a final concentration of [missing information]. The solution of the sensing unit is used to obtain the PAL@Q[8] sensing unit.

3. The dual-unit fluorescence sensor array for detecting oral antidiabetic drugs according to claim 2, characterized in that: The preparation method of the PAL@Q[8] sensing unit is as follows: first, prepare a solution of barmatin with ultrapure water to a concentration of [missing information]. The Bama stock solution was then prepared by adding Q[8] to ultrapure water to a concentration of [missing information]. The Q[8] solution was prepared by mixing the barmatine stock solution and the Q[8] stock solution at a molar ratio of 2:1 and adding ultrapure water to achieve a final concentration of [missing value]. The solution of the sensing unit is used to obtain the PAL@Q[8] sensing unit.

4. The dual-unit fluorescence sensor array for detecting oral antidiabetic drugs according to claim 1, characterized in that: The fabrication method of the bpep-Am@Q[8] sensing unit is carried out according to the following steps: (1) Dissolve 0.2 mmol of 1,4-bis[2-(4-pyridyl)vinyl]benzene and 0.6 mmol of 1-bromopentane in 6 mL of DMF. After mixing, reflux at 90-110°C for 70-74 hours. After cooling to room temperature, crude product is obtained. The crude product is washed with DMF 4-6 times, with each wash using 3-6 mL of DMF. Then, it is washed with petroleum ether 4-6 times, with each wash using 3-6 mL of petroleum ether. Finally, it is filtered and separated. The separated solid is dried under vacuum at 70°C to obtain bpep-Am for later use. (2) Prepare bpep-Am with ultrapure water to a concentration of [missing value]. bpep-Am stock solution, for later use; (3) Prepare Q[8] with ultrapure water to a concentration of Q[8] stock solution, for later use; (4) Mix the bpep-Am stock solution and Q[8] stock solution, and add ultrapure water to prepare a final concentration of The solution of the sensing unit is obtained by bpep-Am@Q[8] sensing unit.

5. The dual-unit fluorescence sensor array for detecting oral antidiabetic drugs according to claim 4, characterized in that: The fabrication method of the bpep-Am@Q[8] sensing unit is carried out according to the following steps: (1) Dissolve 0.2 mmol of 1,4-bis[2-(4-pyridyl)vinyl]benzene and 0.6 mmol of 1-bromopentane in 6 mL of DMF. After mixing, reflux at 100°C for 72 hours. After cooling to room temperature, crude product is obtained. The crude product is washed 5 times with DMF, each time using 5 mL of DMF. Then it is washed 5 times with petroleum ether, each time using 5 mL of petroleum ether. Finally, it is filtered and separated. The separated solid is vacuum dried at 70°C to obtain bpep-Am for later use. (2) Prepare bpep-Am with ultrapure water to a concentration of [missing value]. bpep-Am stock solution, for later use; (3) Prepare Q[8] with ultrapure water to a concentration of Q[8] stock solution, for later use; (4) Mix the bpep-Am stock solution and Q[8] stock solution at a molar ratio of 2:3, and add ultrapure water to prepare a final concentration of The solution of the sensing unit is obtained by bpep-Am@Q[8] sensing unit.

6. The application of the dual-unit fluorescence sensor array according to any one of claims 1-5 for detecting oral antidiabetic drugs, characterized in that: The dual-unit fluorescence sensor array can be used for qualitative and quantitative detection of oral antidiabetic drugs in serum or urine, including metformin, phenformin, buformin hydrochloride, rosiglitazone, and sitagliptin.

7. The application of the dual-unit fluorescence sensor array according to claim 6 for detecting oral antidiabetic drugs, characterized in that: The qualitative testing is performed according to the following steps: (1) Prepare with ultrapure water separately metformin solution, Phenformin solution, diguanidine hydrochloride solution, Rosiglitazone solution and The sitagliptin solution was used to prepare metformin stock solution, phenformin stock solution, butylguanidine hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution for later use; (2) Take 5-7 μL of each of metformin stock solution, phenformin stock solution, butylformin hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, and add them to five equal portions of 2.5-3.5 mL PAL@Q[8] sensor unit solution. Vortex mix to obtain metformin sample A1, phenformin sample A2, butylformin hydrochloride sample A3, rosiglitazone sample A4 and sitagliptin sample A5; (3) Take 5-7 μL of each of metformin stock solution, phenformin stock solution, butylformin hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, and add them to five equal portions of 2.5-3.5 mL bpep-Am@Q[8] sensor unit solution, and vortex mix to obtain metformin sample B1, phenformin sample B2, butylformin hydrochloride sample B3, rosiglitazone sample B4 and sitagliptin sample B5; (4) Fluorescence scanning conditions: The fluorescence scanning conditions for the test sample containing the PAL@Q[8] sensing unit are excitation wavelength 344nm, emission wavelength 536nm, voltage 500V, and slit width 10nm; the fluorescence scanning conditions for the test sample containing the bpep-Am@Q[8] sensing unit are excitation wavelength 381nm, emission wavelength 468nm, voltage 500V, and slit width 10nm. (6) Construction of dual-unit fluorescence sensor: Metformin sample A1, phenformin sample A2, butylguanidine hydrochloride sample A3, rosiglitazone sample A4, and sitagliptin sample A5 were taken respectively. The samples were transferred to a 96-well plate for testing. Separately, samples prepared in step (3) were taken: metformin sample B1, phenformin sample B2, butylguanidine hydrochloride sample B3, rosiglitazone sample B4, and sitagliptin sample B5. The sample was transferred to a 96-well plate and fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The measurement was repeated 5 times to construct a multidimensional data matrix consisting of 2 sensing units × 5 oral antidiabetic drugs × 5 parallel samples. LDA analysis was performed to obtain a unique differential fluorescence response fingerprint spectrum. (7) Serum qualitative test: The barmatine stock solution and Q[8] stock solution were mixed and the serum obtained after sterile blood collection, centrifugation and filtration was added to prepare a final concentration of The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification. (8) Qualitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to 96-well plates respectively, and fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification.

8. The application of the dual-unit fluorescence sensor array according to claim 6 for detecting oral antidiabetic drugs, characterized in that: The qualitative testing is performed according to the following steps: (1) Prepare with ultrapure water separately metformin solution, Phenformin solution, diguanidine hydrochloride solution, Rosiglitazone solution and The sitagliptin solution was used to obtain metformin stock solution, phenformin stock solution, butylguanidine hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, respectively; (2) Take 6 μL each of metformin stock solution, phenformin stock solution, butylformin hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, add them to 3 mL of PAL@Q[8] sensor unit solution, and vortex mix to obtain metformin test sample A1, phenformin sample A2, butylformin hydrochloride sample A3, rosiglitazone sample A4 and sitagliptin sample A5; (3) Take 6 μL each of metformin stock solution, phenformin stock solution, butylformin hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, add them to 3 mL of bpep-Am@Q[8] sensor unit solution, and vortex mix to obtain metformin test sample B, phenformin sample B, butylformin hydrochloride sample B, rosiglitazone sample B and sitagliptin sample B; (4) Fluorescence scanning conditions: The fluorescence scanning conditions for the test sample containing the PAL@Q[8] sensing unit are excitation wavelength 344nm, emission wavelength 536nm, voltage 500V, and slit width 10nm; the fluorescence scanning conditions for the test sample containing the bpep-Am@Q[8] sensing unit are excitation wavelength 381nm, emission wavelength 468nm, voltage 500V, and slit width 10nm. (6) Construction of dual-unit fluorescence sensor: Metformin sample A1, phenformin sample A2, butylguanidine hydrochloride sample A3, rosiglitazone sample A4, and sitagliptin sample A5 were taken respectively. The samples were transferred to a 96-well plate for testing. Separately, samples prepared in step (3) were taken: metformin sample B1, phenformin sample B2, butylguanidine hydrochloride sample B3, rosiglitazone sample B4, and sitagliptin sample B5. The samples were transferred to a 96-well plate for testing. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The measurements were repeated 5 times. A multidimensional data matrix consisting of 2 sensing units, 5 oral antidiabetic drugs and 5 parallel samples was constructed. LDA analysis was performed to establish different fluorescence response fingerprint spectra. (7) Serum qualitative test: The barmatine stock solution and Q[8] stock solution were mixed and the serum obtained after sterile blood collection, centrifugation and filtration was added to prepare a final concentration of The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification. (8) Qualitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] mixed sensing unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to 96-well plates respectively, and fluorescence scanning was performed according to the fluorescence scanning conditions in step (4) for identification and classification.

9. The application of the dual-unit fluorescence sensor array according to claim 6 for detecting oral antidiabetic drugs, characterized in that: The quantitative determination is performed according to the following steps: (1) Metformin, phenformin, butylguanidine hydrochloride, rosiglitazone and sitagliptin were added to ultrapure water and diluted to volume to prepare the following preparations. The stock solutions were used to obtain metformin stock solution, phenformin stock solution, butylguanidine hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, respectively, for later use; (2) Take 0 uL, 8 uL, 16 uL, 24 uL, 32 uL, 40 uL and 48 uL of each drug stock solution and add them to the 3mLPAL@Q[8] sensing unit respectively. Vortex mix to obtain 7 different concentrations of metformin test samples, 7 different concentrations of phenformin test samples, 7 different concentrations of butylguanidine hydrochloride test samples, 7 different concentrations of rosiglitazone test samples and 7 different concentrations of sitagliptin test samples; (3) Take 0 uL, 8 uL, 16 uL, 24 uL, 32 uL, 40 uL and 48 uL of each drug stock solution and add them to 3 mL bpep-Am@Q[8] sensing unit respectively. Vortex mix to obtain 7 different concentrations of metformin test samples, 7 different concentrations of phenformin test samples, 7 different concentrations of butylguanidine hydrochloride test samples, 7 different concentrations of rosiglitazone test samples and 7 different concentrations of sitagliptin test samples. (4) Fluorescence scanning conditions: The fluorescence scanning conditions for the test sample containing the PAL@Q[8] sensing unit are excitation wavelength 344nm, emission wavelength 536nm, voltage 500V, and slit width 10nm; the fluorescence scanning conditions for the test sample containing the bpep-Am@Q[8] sensing unit are excitation wavelength 381nm, emission wavelength 468nm, voltage 500V, and slit width 10nm. (5) Construction of dual-unit fluorescence sensor array and quantitative calibration curve: Take 7 different concentrations of metformin, 7 different concentrations of phenformin, 7 different concentrations of butylformin hydrochloride, 7 different concentrations of rosiglitazone and 7 different concentrations of sitagliptin prepared in step (2) and transfer them to 96-well plates for testing. Take 7 different concentrations of metformin, 7 different concentrations of phenformin, 7 different concentrations of butylformin hydrochloride, 7 different concentrations of rosiglitazone and 7 different concentrations of sitagliptin prepared in step (3) and transfer them to 96-well plates for testing. Perform fluorescence scanning measurement according to the fluorescence scanning conditions in step (4). Obtain the data matrix of 5 oral antidiabetic drugs with 2 sensing units and 7 different concentrations from the sensor array. Perform LDA processing and establish a quantitative calibration curve between LDA factor 1 and the concentration of 7 oral antidiabetic drugs. (6) Serum quantitative detection: The barmatine stock solution and Q[8] stock solution were mixed, and serum that had been sterilely collected, centrifuged and filtered was added to prepare a final concentration of The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] sensor unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The content of the urine test sample was determined by the linear relationship between LDA factor 1 and concentration in the quantitative calibration curve. (7) Quantitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] sensor unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to a 96-well plate respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). Data matrix of 2 sensor units and 7 different concentrations of 5 oral antidiabetic drugs was obtained from the sensor array. LDA processing was performed, and a quantitative calibration curve was established between LDA factor 1 and the concentrations of 7 oral antidiabetic drugs.

10. The application of the dual-unit fluorescence sensor array according to claim 9 for detecting oral antidiabetic drugs, characterized in that: The quantitative determination is performed according to the following steps: (1) Metformin, phenformin, butylguanidine hydrochloride, rosiglitazone and sitagliptin were added to ultrapure water and diluted to volume to prepare the following preparations. The stock solutions were used to obtain metformin stock solution, phenformin stock solution, butylguanidine hydrochloride stock solution, rosiglitazone stock solution and sitagliptin stock solution, respectively, for later use; (2) Take 0 uL, 8 uL, 16 uL, 24 uL, 32 uL, 40 uL and 48 uL of each drug stock solution and add them to the 3mLPAL@Q[8] sensing unit respectively. Vortex mix to obtain 7 different concentrations of metformin test samples, 7 different concentrations of phenformin test samples, 7 different concentrations of butylguanidine hydrochloride test samples, 7 different concentrations of rosiglitazone test samples and 7 different concentrations of sitagliptin test samples; (3) Take 0 uL, 8 uL, 16 uL, 24 uL, 32 uL, 40 uL and 48 uL of each drug stock solution and add them to 3 mL bpep-Am@Q[8] sensing unit respectively. Vortex mix to obtain 7 different concentrations of metformin test samples, 7 different concentrations of phenformin test samples, 7 different concentrations of butylguanidine hydrochloride test samples, 7 different concentrations of rosiglitazone test samples and 7 different concentrations of sitagliptin test samples. (4) Fluorescence scanning conditions: The fluorescence scanning conditions for the test sample containing the PAL@Q[8] sensing unit are excitation wavelength 344nm, emission wavelength 536nm, voltage 500V, and slit width 10nm; the fluorescence scanning conditions for the test sample containing the bpep-Am@Q[8] sensing unit are excitation wavelength 381nm, emission wavelength 468nm, voltage 500V, and slit width 10nm. (5) Construction of dual-unit fluorescence sensor array and quantitative calibration curve: Take the seven metformin test samples with different concentrations prepared in step (2) respectively. Seven samples of phenformin at different concentrations each Seven samples of guanidine hydrochloride at different concentrations each Seven samples of rosiglitazone at different concentrations each and 7 samples of sitagliptin at different concentrations The sample was transferred to a 96-well plate for testing. Seven different concentrations of metformin prepared in step (3) were also taken separately. Seven samples of phenformin at different concentrations were tested. Seven different concentrations of guanidine hydrochloride were tested. Seven different concentrations of rosiglitazone were tested. and 7 different concentrations of sitagliptin were tested. The sample was transferred to a 96-well plate for testing. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). Data matrix of 2 sensing units and 7 different concentrations of oral antidiabetic drugs was obtained from the sensor array. LDA processing was performed, and a quantitative calibration curve was established between LDA factor 1 and the concentrations of the 7 oral antidiabetic drugs. (6) Serum quantitative detection: The barmatine stock solution and Q[8] stock solution were mixed, and serum that had been sterilely collected, centrifuged and filtered was added to prepare a final concentration of The PAL@Q[8] mixed sensing unit solution was vortexed to obtain serum test sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the serum after sterile blood collection and centrifugation filtration to prepare a final concentration of The bpep-Am@Q[8] sensor unit solution was vortexed to obtain serum test sample B. Serum test sample A and serum test sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The content of the urine test sample was determined by the linear relationship between LDA factor 1 and concentration in the quantitative calibration curve. (7) Quantitative urine test: Collect artificial urine for use The solution was filtered through a membrane and diluted with an equal volume of ultrapure water to prepare a urine solution. The barmatine stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of [missing value]. The PAL@Q[8] mixed sensing unit solution was vortexed to obtain urine sample A. The bpep-Am stock solution and Q[8] stock solution were mixed and added to the urine solution to prepare a final concentration of The bpep-Am@Q[8] sensing unit solution was vortexed to obtain urine sample B. Urine sample A and urine sample B were transferred to 96-well plates respectively. Fluorescence scanning was performed according to the fluorescence scanning conditions in step (4). The content of the urine sample to be tested was determined by the linear relationship between LDA factor 1 and concentration in the quantitative calibration curve.

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