CN110006858A - A method of iron ion and glutathione are detected using difunctional fluorescent optical sensor - Google Patents

A method of iron ion and glutathione are detected using difunctional fluorescent optical sensor Download PDF

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CN110006858A
CN110006858A CN201810009186.5A CN201810009186A CN110006858A CN 110006858 A CN110006858 A CN 110006858A CN 201810009186 A CN201810009186 A CN 201810009186A CN 110006858 A CN110006858 A CN 110006858A
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ldh
ants
gsh
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glutathione
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李蕾
邹浩伟
刘鹏飞
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Beijing University of Chemical Technology
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    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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Abstract

The invention belongs to fields of nano material application, it is related to being used as difunctional fluorescent optical sensor detection iron ion and glutathione using organic/inorganic composite Nano fluorescent material.It selects based on hydrotalcite (LDH), organic fluorescence molecule 8- amino naphthalenes -1,3,6- trisulfonic acid disodium salt (ANTS) is object, guest molecule is supported on bulk material surface, difunctional fluorescent optical sensor ANTS-LDH is prepared, there is fluorescence sense performance to iron ion (Fe3+) and glutathione (GSH).Fe3+ and GSH selectivity with higher is detected using difunctional fluorescent optical sensor ANTS-LDH, detection limit is respectively 0.6436 μM, 2.42 nM, and detectable concentration range is respectively 1 ~ 200 μM, 5 nM ~ 10 μM.Testing conditions of the present invention are mild, simple to operate, are a kind of methods using difunctional fluorescent optical sensor detection iron ion and glutathione.

Description

A method of iron ion and glutathione are detected using difunctional fluorescent optical sensor
Technical field
The invention belongs to fields of nano material application, it is related to being used as using organic/inorganic composite Nano fluorescent material double Function fluorescent optical sensor detects iron ion and glutathione.
Background technique
Iron not only has hematopoiesis function in human body, may also participate in blood as transition metal element the most abundant in human body The synthesis of Lactoferrin, cytochromes and various enzymes.When human body iron content deficiency, it be easy to cause cellulous anemia, immune function The symptoms such as decline and metabolic disturbance；As internal Fe3+Too high levels can cause some diseases and certain organs such as heart, liver With the dysfunction of pancreas etc., can cause vomiting, the damage of diarrhea and intestines；In addition, iron can also cause serious pollution to environment, most Important iron pollution source is the iron content waste water of smelting iron and steel and plant emissions.Therefore, Fe is realized3+Rapid sensitive detection exist Environmental science and life science etc. have great importance in fields.
Glutathione is a kind of natural activity peptide with important physiological function, is widely present in all biological cells, It exists in the form of 2 kinds in vivo, i.e. reduced glutathione (reduced glutathione, abbreviation GSH) and oxidized form paddy The sweet peptide of Guang (oxidized glutathione, abbreviation GSSG), that largely exist and play a major role in body is the former.It is logical The glutathione of ordinary persons' meaning is reduced glutathione.Glutathione in human metabolism and every physiological activity all It plays an important role, important enzyme protein sulfhydryl is not oxidized in its energy protective, inactivates, and is conducive to the performance of enzymatic activity；In addition, It can maintain the stability of molecule and participate in transhipment amino acid and participate in the metabolism of cholic acid.The content of human body GSH-PX activity is high It is low to can be used as the important indicator for judging human health degree.Therefore its content is fast and accurately measured in clinical diagnosis side Mask is significant.
Hydrotalcite be a kind of layer of column double-metal hydroxide (Layered double hydroxide compounds, Abbreviation LDH), it is a kind of anionic clay quickly grown in recent years.The composition general formula of hydrotalcite are as follows: [M2+ 1-xM3+ x (OH)2]x+(Am-)x/m•nH2O, wherein M2+、M3+Respectively divalent (Mg2+, Zn2+, Ca2+, Ni2+, Fe2+) and trivalent (Ga3、V3+、 Fe3+、Cr3+、Al3+) metal cation；X is M3+/(M2++M3+) molar ratio, 0.2≤x≤0.33；Am-For interlayer anion, Such as NO3 -, CO3 2-, SO4 2-、Cl-Equal inorganic anions；N is the quantity of crystalline water molecules.LDH have laminate composition adjustability with And good biocompatibility, hypotoxicity, and preparation process is simple and safe, and organic fluorescent dye molecule can be supported on outside hydrotalcite On surface, the photostability and fluorescent emission performance of dyestuff are not only increased, also acts as the fluorescence sense of detection living matter Device.
Summary of the invention
It is difunctional it is an object of the invention to be used as using a kind of area load type organic/inorganic composite Nano fluorescent material Fluorescent optical sensor detects iron ion and glutathione.
In order to achieve the above objectives, the present invention adopts the following technical scheme that.
A method of iron ion and glutathione being detected using difunctional fluorescent optical sensor, which is characterized in that this method Using material based on hydrotalcite (LDH), organic fluorescent dye molecule 8- amino naphthalenes -1,3,6- trisulfonic acid disodium salt (ANTS) is ANTS is carried on hydrotalcite outer surface by interacting, prepares nano-luminescent material (ANTS-LDH), wherein neatly by object The mass ratio that feeds intake of stone and ANTS are as follows: (2 ~ 10): 1.
The average grain diameter of the nano-luminescent material (ANTS-LDH) prepared in this method is 150 ~ 200 nm.
The general structure of the hydrotalcite used in this method are as follows: [M2+ 1-xM3+ x(OH)2]x+(Am-)x/m•nH2O, wherein M2+For Mg2+、Zn2+、Ni2+、Co2+、Ca2+Deng；M3+For Al3+、Cr3+、Fe3+Deng；X is M3+/(M2++M3+) molar ratio, 0.2≤x≤ 0.33；Am-For interlayer anion such as CO3 2-、SO4 2-、NO3 -、Cl-Deng；N combines the number of water between every mole of hydrotalcite middle layer.
The hydrotalcite, especially M2+For Zn2+；M3+For Al3+；Am-For CO3 2-；m=2；x=0.2~0.33；n=0.4~ 6.0。
Above-mentioned nano-luminescent material (ANTS-LDH) is used as difunctional fluorescent optical sensor detection iron ion and glutathione, Specific step is as follows for it.
(1) by ZnSO4·7H2O and Al2(SO4)3·18H2O dissolution obtains salting liquid A in deionized water, and controls Zn2 +、Al3+And H2The molar ratio of O is (2 ~ 4): 1:(60 ~ 100).
(2) by NaOH and Na2CO3It is dissolved in deionized water and obtains aqueous slkali B, and control OH-And H2The molar ratio 1:(10 of O ~ 100).
(3) two kinds of solution of A and B are added drop-wise in deionized water simultaneously, control pH=9 ~ 11, is then refluxed for 6 ~ 24 h of crystallization, It is washed with deionized water 3 ~ 10 times, every time 2200 ~ 3000 r/min centrifuge washing, 10 ~ 40 min, 50 ~ 90 DEG C of vacuum drying 12 ~ Hydrotalcite material of main part can be obtained in 36 h.
(4) the hydrotalcite material of main part of above-mentioned preparation is dispersed in the polar solvent (such as ethylene glycol) dissolved with ANTS, is controlled M(LDH processed): m(ANTS)=(2 ~ 10): 1, lasting stirring is lower to control 70 ~ 90 DEG C of reaction temperature 6 ~ 24 h of reaction, use later from Scheming centrifugation, and be washed with deionized, 2200 ~ 3000 r/min are centrifuged 10 ~ 40 min every time, it is centrifuged repeatedly washing 2 ~ 5 times, 50 ~ 90 DEG C of 12 ~ 36 h of vacuum drying obtain the nano-luminescent material (ANTS- that a kind of ANTS is supported on hydrotalcite outer surface LDH).
(5) 0.5 ~ 2.5 mg/mL the measurement of iron ion: is prepared using phosphoric acid-borate buffer solution (PBS) of pH=7.4 ANTS-LDH is added uses FeCl wherein3·6H2The certain density Fe that O and deionized water are prepared3+Solution makes it in PBS Dispersion concentration is 1 ~ 200 μM in buffer, stands 5 ~ 10 min and measures 500 nm or so fluorescence under 355 nm exciting lights later The fluorescence intensity of emission peak is measured in parallel five times and is averaged.Fig. 1 is ANTS-LDH detection Fe3+Linear graph, linear relationship is full Sufficient Stern-Volmer equation I0/I=1+KSVC, wherein I0ANTS-LDH detection Fe is respectively represented with I3+The fluorescent emission of front and back is strong Degree, C represent Fe3+Concentration (be denoted as [Fe3+]), KSVRepresent the quenching constant of Stern-Volmer equation；Obtain equation I0/I= 1.00785+0.00241[Fe3+], linearly dependent coefficient R2=0.999, the range of linearity is 1 ~ 200 μM, and detection limit (LOD) is adopted Calculated with 3 σ/s, wherein s be equation of linear regression slope, σ represent detection blank sample when standard deviation, obtain LOD= 0.6436 μM。
Fig. 2 is shown as ANTS-LDH and detects 20 μM of Fe3+When, allowing relative error is ± 5%, common carbohydrates, such as grape Sugar, sucrose, fructose and common metal ion such as Na+、K+、Mg2+、Ca2+To noiseless, the common transition ion Cu of detection2 +、Co2+、Ni2+It is noiseless to detecting under 5 times of concentration；Fe2+、Mn2+It is noiseless to detecting at 1 times of concentration；And above-mentioned mixing Object is noiseless to detecting.
(6) measurement of glutathione: ANTS-LDH+Fe is prepared by step (5)3+PBS dispersion liquid, wherein ANTS-LDH Concentration is 0.5 ~ 2.5 mg/mL, Fe3+Concentration be 100 ~ 200 μM；5 ~ 10 min are stood to be added thereto using paddy again later The certain density GSH solution that the sweet peptide of Guang and deionized water are prepared, so that the dispersion concentration of GSH is 5 nM ~ 200 μM；Standing 5 ~ The fluorescence intensity of 500 nm or so fluorescence emission peak is measured after 10 min under 355 nm exciting lights, is measured in parallel five times and is averaged Value.Fig. 3 is ANTS-LDH+Fe3+PBS dispersion liquid detection GSH linear graph, linear equation be I=637.2795+ 25.8123lg [GSH] (concentration unit of GSH is nM), linearly dependent coefficient R2=0.998, the range of linearity is 5 nM ~ 10 μM, Detection limit (LOD) is calculated using 3 σ/s, obtains the nM of LOD=2.42.
Fig. 4 shows ANTS-LDH+Fe3+When dispersion liquid detects 100 nM GSH, allowing relative error is ± 5%, common sugar Class, such as glucose, sucrose, fructose and common metal ion Na+、K+、Mg2+、Ca2+、Ni2+、Cu2+For detecting noiseless, Co2 +、Mn2+It is noiseless to detecting under 20 times of GSH concentration；Meanwhile the tyrosine of same concentrations, cysteine, homocysteine It is noiseless to detecting, and the above mixture is noiseless to detecting.
Difunctional fluorescent optical sensor of the present invention, ANTS are carried on hydrotalcite outer surface, average grain diameter 150 ~ 200 nm.The fluorescent emission performance and photostability of ANTS are greatly increased after area load, and are passed as difunctional fluorescence Sensor detects iron ion and glutathione, is a kind of novel, highly sensitive and highly selective nano fluorescent biosensor. Testing conditions of the present invention are mild, easy to operate, are a kind of environmental-friendly novel biological detecting methods.
Detailed description of the invention
Fig. 1 is shown as with Fe3+Concentration is abscissa, detects Fe with ANTS-LDH3+The ratio I of the fluorescence intensity of front and back0/I The linear graph drawn for ordinate；n=5.
Fig. 2 is shown with ANTS-LDH detection Fe3+When add the fluorescence intensities (F) of other interfering substances again and do not add Fluorescence intensity (the F of other interfering substances0) ratio (F/ F0).Fe in figure3+Concentration be 20 μM, glucose (Glucose), Sucrose (Sucrose), fructose (Fructose), Na+、K+、Mg2+、Ca2+Concentration be 5 mM, Cu2+、Co2+、Ni2+Concentration be 100 μM；Fe2+、Mn2+Concentration be 20 μM, mix chaff interferent concentration be above-mentioned each chaff interferent concentration；n=5.
Fig. 3 is shown as with lg [GSH] being abscissa (concentration unit of GSH is nM), with ANTS-LDH+Fe3+Dispersion liquid inspection The fluorescence intensity for surveying 5 nM ~ 10 μM GSH is the linear graph of ordinate drafting；n=5.
Fig. 4 is shown with ANTS-LDH+Fe3+Dispersion liquid adds the fluorescence intensity of other interfering substances again when detecting GSH (F) fluorescence intensity (F of other interfering substances and is not added0) ratio (F/ F0).The concentration of GSH is 100 nM, grape in figure Sugar (Glucose), sucrose (Sucrose), fructose (Fructose), Na+、K+、Mg2+、Ca2+、Ni2+、Cu2+Concentration be 100 μ M, Co2+、Mn2+Concentration be 2 μM, tyrosine (Tyr), cysteine (Cys), homocysteine (Hcy) concentration be 100 NM, the concentration for mixing chaff interferent is the concentration of above-mentioned each chaff interferent；n=5.
Specific embodiment
Embodiment 1.
(1) n (Zn is pressed2+): n (Al3+): n (H2O)=2:1:60 molar feed ratio, by ZnSO4·7H2O and Al2 (SO4)3·18H2O, which is add to deionized water, prepares salting liquid A；By n (OH-): n (H2O)=1:10 molar feed ratio, will NaOH and Na2CO3It is add to deionized water and prepares aqueous slkali B.
(2) two kinds of solution of A and B are added drop-wise in deionized water simultaneously, control pH=9, flow back 6 h of crystallization, and centrifugation is washed later It washs, 3000 r/min are centrifuged 10 min every time, are centrifuged repeatedly washing 6 times, hydrotalcite master can be obtained in 70 DEG C of 24 h of vacuum drying Body material.
(3) by m(LDH): m(ANTS)=2:1 mass ratio feeds intake, by LDH obtained in step (2) be dispersed in dissolved with In the ethylene glycol of ANTS, 6 h are reacted at 70 DEG C, later centrifuge washing, 3000 r/min are centrifuged 10 min every time, are centrifuged repeatedly and wash It washs 3 times, 70 DEG C of 24 h of vacuum drying.Obtain a kind of difunctional fluorescent optical sensor ANTS-LDH.
(4) in the PBS buffer solution of pH=7.4 containing 140.0 mmol/L NaCl and 4.5mmol/L KCl, 20 are added μM Fe3+；5 mM glucose (Glucose), sucrose (Sucrose), fructose (Fructose), Mg2+、Ca2+；100 μM Cu2+、 Co2+、Ni2+；20 μM Fe2+、Mn2+, step (3) resulting 0.5 mg/mL ANTS-LDH detection wherein Fe is added3+Content. 5 fluorescence intensities are measured in parallel, average detectable value is 19.4 μM, and relative standard deviation 1.49% shows using difunctional Fluorescent optical sensor ANTS-LDH detects Fe3+With good repeatability and accuracy.
(5) it in the PBS buffer solution of pH=7.4 containing 140.0 mmol/L NaCl and 4.5mmol/L KCl, is added 100 μM Fe3+, 0.5 mg/mL ANTS-LDH, be sufficiently mixed uniformly stand 5 min, 100 nM paddy are added thereto again later The sweet peptide of Guang (GSH), tyrosine (Tyr), cysteine (Cys), homocysteine (Hcy)；100 μM of glucose, sucrose, fructose, Mg2+、Ca2+、Ni2+、Cu2+；2 μM Co2+、Mn2+, it is sufficiently mixed after uniformly standing 5 min, is measured in parallel 5 fluorescence intensities, Its average detectable value is 97.3 nM, and relative standard deviation 1.02% shows using ANTS-LDH+Fe3+Dispersion liquid detects GSH tool There are good repeatability and accuracy.
Embodiment 2.
(1) n (Zn is pressed2+): n (Al3+): n (H2O)=3:1:80 molar feed ratio, by ZnSO4·7H2O and Al2 (SO4)3·18H2O, which is add to deionized water, prepares salting liquid A；By n (OH-): n (H2O)=1:30 molar feed ratio, will NaOH and Na2CO3It is add to deionized water and prepares aqueous slkali B.
(2) two kinds of solution of A and B are added drop-wise in deionized water simultaneously, control pH=9.5, flow back 10 h of crystallization, Zhi Houli Heart washing, 3000 r/min are centrifuged 10 min every time, are centrifuged repeatedly washing 6 times, neatly can be obtained in 70 DEG C of 24 h of vacuum drying Stone material of main part.
(3) by m(LDH): m(ANTS)=4:1 mass ratio feeds intake, by LDH obtained in step (2) be dispersed in dissolved with In the ethylene glycol of ANTS, 10 h are reacted at 75 DEG C, later centrifuge washing, 3000 r/min are centrifuged 10 min every time, are centrifuged repeatedly Washing 3 times, 70 DEG C of 24 h of vacuum drying.Obtain a kind of difunctional fluorescent optical sensor ANTS-LDH.
(4) in the PBS buffer solution of pH=7.4 containing 140.0 mmol/L NaCl and 4.5mmol/L KCl, 20 are added μM Fe3+；5 mM glucose (Glucose), sucrose (Sucrose), fructose (Fructose), Mg2+、Ca2+；100 μM Cu2+、 Co2+、Ni2+；20 μM Fe2+、Mn2+, step (3) resulting 1.0 mg/mL ANTS-LDH detection wherein Fe is added3+Content. 5 fluorescence intensities are measured in parallel, average detectable value is 20.5 μM, and relative standard deviation 1.26% shows using difunctional Fluorescent optical sensor ANTS-LDH detects Fe3+With good repeatability and accuracy.
(5) it in the PBS buffer solution of pH=7.4 containing 140.0 mmol/L NaCl and 4.5mmol/L KCl, is added 120 μM Fe3+, 1.0 mg/mL ANTS-LDH, be sufficiently mixed uniformly stand 5 min, 100 nM paddy are added thereto again later The sweet peptide of Guang (GSH), tyrosine (Tyr), cysteine (Cys), homocysteine (Hcy)；100 μM of glucose, sucrose, fructose, Mg2+、Ca2+、Ni2+、Cu2+；2 μM Co2+、Mn2+, it is sufficiently mixed after uniformly standing 5 min, is measured in parallel 5 fluorescence intensities, Its average detectable value is 98.5 nM, and relative standard deviation 0.97% shows using ANTS-LDH+Fe3+Dispersion liquid detects GSH tool There are good repeatability and accuracy.
Embodiment 3.
(1) n (Zn is pressed2+): n (Al3+): n (H2O)=4:1:100 molar feed ratio, by ZnSO4·7H2O and Al2 (SO4)3·18H2O, which is add to deionized water, prepares salting liquid A；By n (OH-): n (H2O)=1:50 molar feed ratio, will NaOH and Na2CO3It is add to deionized water and prepares aqueous slkali B.
(2) two kinds of solution of A and B are added drop-wise in deionized water simultaneously, control pH=10, flow back 14 h of crystallization, is centrifuged later Washing, 3000 r/min are centrifuged 10 min every time, are centrifuged repeatedly washing 6 times, hydrotalcite can be obtained in 70 DEG C of 24 h of vacuum drying Material of main part.
(3) by m(LDH): m(ANTS)=6:1 mass ratio feeds intake, by LDH obtained in step (2) be dispersed in dissolved with In the ethylene glycol of ANTS, 14 h are reacted at 80 DEG C, later centrifuge washing, 3000 r/min are centrifuged 10 min every time, are centrifuged repeatedly Washing 3 times, 70 DEG C of 24 h of vacuum drying.Obtain a kind of difunctional fluorescent optical sensor ANTS-LDH.
(4) in the PBS buffer solution of pH=7.4 containing 140.0 mmol/L NaCl and 4.5mmol/L KCl, 20 are added μM Fe3+；5 mM glucose (Glucose), sucrose (Sucrose), fructose (Fructose), Mg2+、Ca2+；100 μM Cu2+、 Co2+、Ni2+；20 μM Fe2+、Mn2+, step (3) resulting 1.5 mg/mL ANTS-LDH detection wherein Fe is added3+Content. 5 fluorescence intensities are measured in parallel, average detectable value is 20.4 μM, and relative standard deviation 1.12% shows using difunctional Fluorescent optical sensor ANTS-LDH detects Fe3+With good repeatability and accuracy.
(5) it in the PBS buffer solution of pH=7.4 containing 140.0 mmol/L NaCl and 4.5mmol/L KCl, is added 150 μM Fe3+, 1.5 mg/mL ANTS-LDH, be sufficiently mixed uniformly stand 5 min, 100 nM paddy are added thereto again later The sweet peptide of Guang (GSH), tyrosine (Tyr), cysteine (Cys), homocysteine (Hcy)；100 μM of glucose, sucrose, fructose, Mg2+、Ca2+、Ni2+、Cu2+；2 μM Co2+、Mn2+, it is sufficiently mixed after uniformly standing 5 min, is measured in parallel 5 fluorescence intensities, Its average detectable value is 98.9 nM, and relative standard deviation 1.08% shows using ANTS-LDH+Fe3+Dispersion liquid detects GSH tool There are good repeatability and accuracy.
Embodiment 4.
(1) n (Zn is pressed2+): n (Al3+): n (H2O)=2:1:80 molar feed ratio, by ZnSO4·7H2O and Al2 (SO4)3·18H2O, which is add to deionized water, prepares salting liquid A；By n (OH-): n (H2O)=1:70 molar feed ratio, will NaOH and Na2CO3It is add to deionized water and prepares aqueous slkali B.
(2) two kinds of solution of A and B are added drop-wise in deionized water simultaneously, control pH=10.5, flow back 18 h of crystallization, Zhi Houli Heart washing, 3000 r/min are centrifuged 10 min every time, are centrifuged repeatedly washing 6 times, neatly can be obtained in 70 DEG C of 24 h of vacuum drying Stone material of main part.
(3) by m(LDH): m(ANTS)=8:1 mass ratio feeds intake, by LDH obtained in step (2) be dispersed in dissolved with In the ethylene glycol of ANTS, 18 h are reacted at 85 DEG C, later centrifuge washing, 3000 r/min are centrifuged 10 min every time, are centrifuged repeatedly Washing 3 times, 70 DEG C of 24 h of vacuum drying.Obtain a kind of difunctional fluorescent optical sensor ANTS-LDH.
(4) in the PBS buffer solution of pH=7.4 containing 140.0 mmol/L NaCl and 4.5mmol/L KCl, 20 are added μM Fe3+；5 mM glucose (Glucose), sucrose (Sucrose), fructose (Fructose), Mg2+、Ca2+；100 μM Cu2+、 Co2+、Ni2+；20 μM Fe2+、Mn2+, step (3) resulting 2.0 mg/mL ANTS-LDH detection wherein Fe is added3+Content. 5 fluorescence intensities are measured in parallel, average detectable value is 19.1 μM, and relative standard deviation 1.06% shows using difunctional Fluorescent optical sensor ANTS-LDH detects Fe3+With good repeatability and accuracy.
(5) it in the PBS buffer solution of pH=7.4 containing 140.0 mmol/L NaCl and 4.5mmol/L KCl, is added 170 μM Fe3+, 2.0 mg/mL ANTS-LDH, be sufficiently mixed uniformly stand 5 min, 100 nM paddy are added thereto again later The sweet peptide of Guang (GSH), tyrosine (Tyr), cysteine (Cys), homocysteine (Hcy)；100 μM of glucose, sucrose, fructose, Mg2+、Ca2+、Ni2+、Cu2+；2 μM Co2+、Mn2+, it is sufficiently mixed after uniformly standing 5 min, is measured in parallel 5 fluorescence intensities, Its average detectable value is 97.7 nM, and relative standard deviation 1.25% shows using ANTS-LDH+Fe3+Dispersion liquid detects GSH tool There are good repeatability and accuracy.
Embodiment 5.
(1) n (Zn is pressed2+): n (Al3+): n (H2O)=2:1:80 molar feed ratio, by ZnSO4·7H2O and Al2 (SO4)3·18H2O, which is add to deionized water, prepares salting liquid A；By n (OH-): n (H2O)=1:100 molar feed ratio, will NaOH and Na2CO3It is add to deionized water and prepares aqueous slkali B.
(2) two kinds of solution of A and B are added drop-wise in deionized water simultaneously, control pH=11, flow back 22 h of crystallization, is centrifuged later Washing, 3000 r/min are centrifuged 10 min every time, are centrifuged repeatedly washing 6 times, hydrotalcite can be obtained in 70 DEG C of 24 h of vacuum drying Material of main part.
(3) by m(LDH): m(ANTS)=10:1 mass ratio feeds intake, by LDH obtained in step (2) be dispersed in dissolved with In the ethylene glycol of ANTS, 22 h are reacted at 90 DEG C, later centrifuge washing, 3000 r/min are centrifuged 10 min every time, are centrifuged repeatedly Washing 3 times, 70 DEG C of 24 h of vacuum drying.Obtain a kind of difunctional fluorescent optical sensor ANTS-LDH.
(4) in the PBS buffer solution of pH=7.4 containing 140.0 mmol/L NaCl and 4.5mmol/L KCl, 20 are added μM Fe3+；5 mM glucose (Glucose), sucrose (Sucrose), fructose (Fructose), Mg2+、Ca2+；100 μM Cu2+、 Co2+、Ni2+；20 μM Fe2+、Mn2+, step (3) resulting 2.5 mg/mL ANTS-LDH detection wherein Fe is added3+Content. 5 fluorescence intensities are measured in parallel, average detectable value is 21.1 μM, and relative standard deviation 1.34% shows using difunctional Fluorescent optical sensor ANTS-LDH detects Fe3+With good repeatability and accuracy.
(5) it in the PBS buffer solution of pH=7.4 containing 140.0 mmol/L NaCl and 4.5mmol/L KCl, is added 200 μM Fe3+, 2.5 mg/mL ANTS-LDH, be sufficiently mixed uniformly stand 5 min, 100 nM paddy are added thereto again later The sweet peptide of Guang (GSH), tyrosine (Tyr), cysteine (Cys), homocysteine (Hcy)；100 μM of glucose, sucrose, fructose, Mg2+、Ca2+、Ni2+、Cu2+；2 μM Co2+、Mn2+, it is sufficiently mixed after uniformly standing 5 min, is measured in parallel 5 fluorescence intensities, Its average detectable value is 101.3 nM, and relative standard deviation 1.17% shows using ANTS-LDH+Fe3+Dispersion liquid detects GSH With good repeatability and accuracy.
The above is only preferred embodiments of the invention, is not made in any form to technical solution of the present invention Limitation.Any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the invention, In the range of still falling within technical solution of the present invention.

Claims (8)

1. it is a kind of using difunctional fluorescent optical sensor detection iron ion and glutathione method, which is characterized in that this method with Hydrotalcite (LDH) is carrier, and with organic fluorescent dye molecule 8- amino naphthalenes -1,3,6- trisulfonic acid disodium salt (ANTS) is object； ANTS is carried on the outer surface hydrotalcite (LDH) to prepare nano-luminescent material (ANTS-LDH), is substantially increased after area load The fluorescent emission performance and photostability of ANTS, ANTS-LDH can be used as difunctional fluorescent optical sensor detection iron ion (Fe3+) and Glutathione (GSH).
2. the method according to claim 1 using difunctional fluorescent optical sensor detection iron ion and glutathione, special Sign is that the average grain diameter of the ANTS-LDH of this method preparation is 150~200 nm, and the mass ratio that feeds intake of LDH and ANTS is m (LDH): m(ANTS)=(2 ~ 10): 1.
3. the method according to claim 1 using difunctional fluorescent optical sensor detection iron ion and glutathione, special Sign is, the general structure for the hydrotalcite (LDH) that this method uses are as follows: [M2+ 1-xM3+ x(OH)2]x+(Am-)x/m•nH2O, wherein M2+ For Mg2+、Zn2+、Ni2+、Co2+、Ca2+Deng；M3+For Al3+、Cr3+、Fe3+Deng；X is M3+/(M2++M3+) molar ratio, 0.2≤x ≤0.33；Am-For interlayer anion such as CO3 2-、SO4 2-、NO3 -、Cl-Deng；N combines the number of water between every mole of hydrotalcite middle layer； Especially M2+For Zn2+, M3+For Al3+, Am-For CO3 2-, m=2, x=0.2 ~ 0.33, n=0.4 ~ 6.0.
4. the method according to claim 1 using difunctional fluorescent optical sensor detection iron ion and glutathione, special Sign is, the preparation condition for the hydrotalcite (LDH) that this method uses are as follows: Zn in salting liquid2+、Al3+And H2The molar ratio of O be (2 ~ 4): 1:(60 ~ 100), OH in aqueous slkali-And H2Molar ratio 1:(10 ~ 100 of O), salting liquid is added dropwise admixed together with aqueous slkali PH=9 ~ 11 are controlled, flow back 6 ~ 24 h of crystallization.
5. the method according to claim 1 using difunctional fluorescent optical sensor detection iron ion and glutathione, special Sign is, the reaction condition of hydrotalcite (LDH) and organic fluorescent dye molecule ANTS in this method are as follows: dispersant nonpolar liquid (such as Ethylene glycol) in, LDH and ANTS is persistently uniformly mixed, and controls 70 ~ 90 DEG C of reaction temperature 6 ~ 24 h of reaction.
6. the method according to claim 1 using difunctional fluorescent optical sensor detection iron ion and glutathione, special Sign is that wherein ANTS-LDH detects Fe3+The ratio and iron concentration of the fluorescent emission intensity of front and back are in 1 ~ 200 μM of range Interior is in good linear relationship, equation I0/I=1.00785+0.00241[Fe3+], R2=0.999, detection limit LOD=0.6436 μM；ANTS-LDH detects 20 μM of Fe3+When, allowing relative error is ± 5%, common carbohydrates, such as glucose, sucrose, fructose, with And common metal ion such as Na+、K+、Mg2+、Ca2+To noiseless, the common transition ion Cu of detection2+、Co2+、Ni2+At 5 times It is noiseless to detecting under concentration；Fe2+、Mn2+It is noiseless to detecting at 1 times of concentration；And said mixture is noiseless to detecting.
7. the method according to claim 1 using difunctional fluorescent optical sensor detection iron ion and glutathione, special Sign is, is being further used for detecting the ANTS-LDH+Fe of GSH3+Phosphate-borax dispersion liquid (PBS dispersion liquid) in, Fe3+ Concentration be 100 ~ 200 μM.
8. the method according to claim 1 using difunctional fluorescent optical sensor detection iron ion and glutathione, special Sign is, wherein ANTS-LDH+Fe3+Dispersion liquid detects the fluorescence intensity of GSH and lg [GSH] (concentration unit of GSH is nM) exists It is in good linear relationship within the scope of 5 nM ~ 10 μM GSH of GSH concentration, linear equation is I=637.2795+25.8123lg [GSH] (concentration unit of GSH is nM), linearly dependent coefficient R2=0.998, the detection limit nM of LOD=2.42； ANTS-LDH+Fe3+ When dispersion liquid detects 100 nM GSH, allowing relative error is ± 5%, common carbohydrates, such as glucose, sucrose, fructose and common Metal ion Na+、K+、Mg2+、Ca2+、Ni2+、Cu2+For detecting noiseless, Co2+、Mn2+To detection under 20 times of GSH concentration It is noiseless；Meanwhile the tyrosine of same concentrations, cysteine, homocysteine are noiseless to detecting, and the above mixture is to inspection It surveys noiseless.
CN201810009186.5A 2018-01-04 2018-01-04 A method of iron ion and glutathione are detected using difunctional fluorescent optical sensor Pending CN110006858A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113791056A (en) * 2021-09-12 2021-12-14 广西师范大学 Method for detecting ferric ions and glutathione based on HOF-PyTTA fluorescent material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113791056A (en) * 2021-09-12 2021-12-14 广西师范大学 Method for detecting ferric ions and glutathione based on HOF-PyTTA fluorescent material
CN113791056B (en) * 2021-09-12 2024-05-14 河北健海医学检验实验室有限公司 Method for detecting ferric ions and glutathione based on HOF-PyTTA fluorescent material

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