CN105154064A - Production method of inorganic-organic hybrid fluorescent sensor based on naphthalimide small molecules - Google Patents
Production method of inorganic-organic hybrid fluorescent sensor based on naphthalimide small molecules Download PDFInfo
- Publication number
- CN105154064A CN105154064A CN201510487651.2A CN201510487651A CN105154064A CN 105154064 A CN105154064 A CN 105154064A CN 201510487651 A CN201510487651 A CN 201510487651A CN 105154064 A CN105154064 A CN 105154064A
- Authority
- CN
- China
- Prior art keywords
- bhn
- sio
- naphthalimide
- nanoparticle
- inorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Luminescent Compositions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a production method of an inorganic-organic hybrid fluorescent sensor based on naphthalimide small molecules. The production method comprises the following steps: preparing Fe3O4 magnetic nanoparticles; coating the obtained magnetic nanoparticles with SiO2 to obtain Fe3O4@SiO2 nanoparticles; obtaining BHN (N-butyl-4-bis(2-hydroxyethyl)amino-1.8-naphthalimide) through chemical synthesis; reacting BHN with IPTES (3-isocyanatopropyltriethoxysilane) to obtain BHN-IPTES; connecting BHN-IPTES with the Fe3O4@SiO2 nanoparticles to obtain the BHN-Fe3O4@SiO2 inorganic-organic hybrid fluorescent sensor. The sensor prepared with the method has the characteristics of non-toxic performance, biocompatibility and recyclability when used for detecting iron ions and is energy-saving and environment-friendly.
Description
Technical field
The present invention relates to fluorescent optical sensor field, particularly relate to the manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide.
Background technology
As one of element most important in metabolic processes, iron plays an important role in many physiological processs.But excessive iron also can cause serious problem.Therefore, being badly in need of at present can the effective ways of In vivo detection iron ion.In addition, exploitation is also badly in need of for separating of with the technology removing metal ion.Traditional analytical procedure causes it to be difficult to the detection of iron ion in organism due to the preprocessing process of complexity and high instrument cost.Based on these problems, the fluorescent probe that researchist has invented based on organic molecule detects metal ion.These fluorescent probes are efficiently sensitive, but itself have certain toxicity and can not be isolated or remove.This not returnability hinders the practical application of organic molecule fluorescent optical sensor, and it is combined with inorganic matrix and can improve its recyclability thus improve the application of fluorescent optical sensor.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide, aim to provide a kind of fluorescent optical sensor of detection iron ion of nontoxic reusable edible.
Technical scheme of the present invention is as follows:
Based on a manufacture method for the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide, wherein, comprising:
A, preparation Fe
3o
4magnetic nano-particle;
B, the magnetic nano-particle coated silica obtained is obtained Fe
3o
4siO
2nanoparticle;
C, to be obtained amino-1, the 8-naphthalimide (BHN) of N-butyl-4-two (2-hydroxyethyl) by chemosynthesis;
D, by BHN and 3-isocyanate group propyl-triethoxysilicane (IPTES) react, obtain BHN-IPTES;
E, by BHN-IPTES and Fe
3o
4siO
2nanoparticle is connected, and obtains BHN-Fe
3o
4siO
2inorganic-organic hybridization fluorescent optical sensor.
The described manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide, wherein, described steps A comprises:
A1, by the FeCl of mol ratio 1:2
2with FeCl
3with N
2join in the aqueous solution containing 25% ammoniacal liquor under protection, this solution is stirred 1 hour at 20 DEG C of mechanical stirring, 1 hour post-heating to 70 DEG C;
A2, mixture be heated to 90 DEG C and drip citric acid (0.5g/mL), stirring 30 minutes;
A3, reaction system is cooled to room temperature, washes away unnecessary citric acid, ammoniacal liquor with deionized water and do not have magnetic nanoparticle, after vacuum-drying, obtaining Fe
3o
4nanoparticle.
The described manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide, wherein, described step B comprises:
B1, by the Fe of 120mg citric acid-modified
3o
4nanoparticle, ultrasonic disperse is in 4mL deionized water;
B2, to be dispersed in the water magnetic fluid obtained under ultrasonic containing 5mL ammoniacal liquor 400mL ethanol/water (v/v=4:1) mixed solution, under mechanical stirring mixed system is warming up to 40 DEG C, and drip 6mL tetraethoxy wherein, maintain temperature of reaction and mechanical stirring 12 hours;
B3, reaction system is cooled to room temperature, with absolute ethanol washing 3 times, after vacuum-drying, obtains Fe
3o
4siO
2nanoparticle.
The described manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide, wherein, described step C comprises:
Bromo-1, the 8-naphthalene acid anhydride of 4-of C1,5g and the n-Butyl Amine 99 of 1.7g are dissolved in 40mL Glacial acetic acid, at N
2backflow 6 hours in lower, reaction solution is poured in 200mL frozen water after reacting completely, separate out the rear suction filtration of a large amount of precipitation, drying, crude product crosses chromatographic column purification (silicagel column, ethyl acetate/petroleum ether=1:40), obtain bromo-1, the 8-naphthalimide (60.3%) of 3gN-butyl-4-, product is oyster white chip solid;
N-butyl-the 4-bromo-1 of C2,3g, 8-naphthalimide is dissolved in 15mL ethylene glycol monomethyl ether, add 4.12g diethanolamine, reflux after 48 hours, question response liquid is poured into after being cooled to room temperature in frozen water and is stirred after 12 hours with after dichloromethane extraction, anhydrous magnesium sulfate drying, solvent is boiled off on Rotary Evaporators, crude product crosses chromatographic column purification (silicagel column, methylene chloride/methanol=150:1), obtain amino-1, the 8-naphthalimide (BHN) of 1.72g yellow powdery solid N-butyl-4-two (2-hydroxyethyl).
The described manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide, wherein, described step D comprises:
D1, BHN (356mg, 1mmol) and 3-isocyanate group propyl-triethoxysilicane (IPTES, 494mg, 2mmol) are at room temperature mixed in the tetrahydrofuran solution of 15mL Non-aqueous processing, at N
2the lower backflow of protection 48 hours;
D2, boil off solvent, crude product is crossed chromatographic column and is purified (silicagel column, sherwood oil/methylene chloride/methanol=50:50:1), and obtain the BHN-IPTES (30%) of 255mg, product is yellow powdery solid.
The described manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide, wherein, described step e comprises:
E1, by the Fe of 100mg drying
3o
4siO
2nanoparticle and 300mg (0.35mmol) BHN-IPTES are mixed in the toluene solution of 15mL Non-aqueous processing, at N
2in 110 DEG C of backflows 12 hours under protection, centrifugally obtain BHN-Fe
3o
4siO
2nanoparticle;
E2, use toluene, methylene dichloride, ethanol repetitive scrubbing nanoparticle to supernatant liquor unstressed configuration respectively, the product obtained is placed in vacuum drying oven dried overnight, finally obtains BHN-Fe
3o
4siO
2inorganic-organic hybridization fluorescent optical sensor.
Beneficial effect: the present invention is made into based on the micromolecular inorganic-organic hybridization fluorescent sensing material BHN-Fe with nucleocapsid structure of naphthalimide by described method
3o
4siO
2, it can at CH
3cN/H
2as detecting and being separated Fe in O1:1 (HEPESbuffer, pH7.36) solution
3+type material, and this Inorganic-Organic Hybrid Material is to Fe
3+there are good selectivity and sensitivity, simultaneously BHN-Fe
3o
4siO
2there is superparamagnetism, make material have good reversible magnetic response and Magneto separate character, thus when probing into its biologic applications, there is vital role, and the wider pH scope of application shows that material may be used in more complicated living things system or environment, Fe
3+with BHN-Fe
3o
4siO
2in conjunction with reversibility and the property of can be recycled, production cost can be reduced to a certain extent in actual applications, this material is expected to as detecting in organism or in environment and being separated Fe
3+novel material.
Accompanying drawing explanation
Fig. 1 is the flow chart of steps of described method of the present invention.
Fig. 2 is the schema of the step S1 of described method of the present invention.
Fig. 3 is the schema of the step S2 of described method of the present invention.
Fig. 4 is the schema of the step S3 of described method of the present invention.
Fig. 5 is the schema of the step S4 of described method of the present invention.
Fig. 6 is the schema of the step S5 of described method of the present invention.
Fig. 7 is embodiments of the invention BHN-Fe
3o
4siO
2transmission electron microscope picture (TEM).
Fig. 8 is embodiments of the invention Fe
3o
4(a), Fe
3o
4siO
2(b) and BHN-Fe
3o
4siO
2the X-ray powder diffraction pattern (XRD) of (c).
Fig. 9 is embodiments of the invention Fe
3o
4siO
2(a) and BHN-Fe
3o
4siO
2the infrared spectrogram (FT-IR) of (b).
Figure 10 is embodiments of the invention BHN-Fe
3o
4siO
2magnetic hysteresis loop figure.
Figure 11 is embodiments of the invention Fe
3o4SiO
2(a) and BHN-Fe
3o
4siO
2the thermogravimetric curve figure (TGA) of (b).
Figure 12 is embodiments of the invention BHN-IPTES (a), Fe
3o
4siO
2(b) and BHN-Fe
3o
4siO
2the ultraviolet spectrogram (UV-Vis) of (c).
Figure 13 is embodiments of the invention BHN-Fe
3o
4siO
2(0.2g/L) different concns Fe is added
3+ultraviolet spectrogram.
Figure 14 is embodiments of the invention BHN-Fe
3o
4siO
2to the fluorescence selectivity schematic diagram of different metal ion.
Figure 15 is embodiments of the invention Fe
3+to BHN-Fe
3o
4siO
2(0.2g/L) fluorometric titration curve synoptic diagram.
Figure 16 is embodiments of the invention Fe
3+with BHN-Fe
3o
4siO
2job graphic representation.
Figure 17 is embodiments of the invention Fe
3+-BHN-Fe
3o
4siO
2ion competition figure.
Figure 18 is embodiments of the invention BHN-Fe
3o
4siO
2with Fe
3+in conjunction with reversibility research schematic diagram.
Figure 19 is embodiments of the invention BHN-Fe
3o
4siO
2in repeatedly add Fe
3+and fluorescence intensity cycle diagram during EDTA.
Figure 20 is embodiments of the invention BHN-Fe
3o
4siO
2to Fe under different pH
3+fluorescence response schematic diagram.
Embodiment
The invention provides a kind of manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide, for making object of the present invention, technical scheme and effect clearly, clearly, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Refer to Fig. 1, a kind of manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide, wherein, comprising:
S1, preparation Fe
3o
4magnetic nano-particle;
S2, the magnetic nano-particle coated silica obtained is obtained Fe
3o
4siO
2nanoparticle;
S3, to be obtained amino-1, the 8-naphthalimide (BHN) of N-butyl-4-two (2-hydroxyethyl) by chemosynthesis;
S4, by BHN and 3-isocyanate group propyl-triethoxysilicane (IPTES) react, obtain BHN-IPTES;
S5, by BHN-IPTES and Fe
3o
4siO
2nanoparticle is connected, and obtains BHN-Fe
3o
4siO
2inorganic-organic hybridization fluorescent optical sensor.
Described method of the present invention, first prepares Fe
3o
4magnetic nano-particle, then obtains Fe by magnetic nano-particle coated silica
3o
4siO
2nanoparticle, chemosynthesis BHN, finally obtains BHN-IPTES, finally by BHN-IPTES and Fe by BHN and IPTES synthesis
3o
4siO
2nanoparticle is connected, and obtains BHN-Fe
3o
4siO
2inorganic-organic hybridization fluorescent optical sensor, wherein both organic/inorganic substance also has organism, synthesizing inorganic organic hybrid fluorescent optical sensor.
Further, as shown in Figure 2, be the schema of the step S1 of the described manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide, wherein, described step S1 comprises:
S101, by the FeCl of mol ratio 1:2
2with FeCl
3with N
2join in the aqueous solution containing 25% ammoniacal liquor under protection, this solution is stirred 1 hour at 20 DEG C of mechanical stirring, 1 hour post-heating to 70 DEG C;
S102, mixture be heated to 90 DEG C and drip citric acid (0.5g/mL), stirring 30 minutes;
S103, reaction system is cooled to room temperature, washes away unnecessary citric acid, ammoniacal liquor with deionized water and do not have magnetic nanoparticle, after vacuum-drying, obtaining Fe
3o
4nanoparticle.
Further, as shown in Figure 3, be the schema of the step S2 of the described manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide, wherein, described step S2 comprises:
S201, by the Fe of 120mg citric acid-modified
3o
4nanoparticle, ultrasonic disperse is in 4mL deionized water;
S202, to be dispersed in the water magnetic fluid obtained under ultrasonic containing 5mL ammoniacal liquor 400mL ethanol/water (v/v=4:1) mixed solution, under mechanical stirring mixed system is warming up to 40 DEG C, and drip 6mL tetraethoxy wherein, maintain temperature of reaction and mechanical stirring 12 hours;
S203, reaction system is cooled to room temperature, with absolute ethanol washing 3 times, after vacuum-drying, obtains Fe
3o
4siO
2nanoparticle.
Further, as shown in Figure 4, be the schema of the step S3 of the manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide of the present invention, wherein, described step S3 comprises:
Bromo-1, the 8-naphthalene acid anhydride of 4-of S301,5g and the n-Butyl Amine 99 of 1.7g are dissolved in 40mL Glacial acetic acid, at N
2backflow 6 hours in lower, reaction solution is poured in 200mL frozen water after reacting completely, separate out the rear suction filtration of a large amount of precipitation, drying, crude product crosses chromatographic column purification (silicagel column, ethyl acetate/petroleum ether=1:40), obtain bromo-1, the 8-naphthalimide (60.3%) of 3gN-butyl-4-, product is oyster white chip solid;
N-butyl-the 4-bromo-1 of S302,3g, 8-naphthalimide is dissolved in 15mL ethylene glycol monomethyl ether, add 4.12g diethanolamine, reflux after 48 hours, question response liquid is poured into after being cooled to room temperature in frozen water and is stirred after 12 hours with after dichloromethane extraction, anhydrous magnesium sulfate drying, solvent is boiled off on Rotary Evaporators, crude product crosses chromatographic column purification (silicagel column, methylene chloride/methanol=150:1), obtain amino-1, the 8-naphthalimide (BHN) of 1.72g yellow powdery solid N-butyl-4-two (2-hydroxyethyl).
Further, as shown in Figure 5, be the schema of the step S4 of the manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide of the present invention, wherein, described step S4 comprises:
S401, BHN (356mg, 1mmol) and 3-isocyanate group propyl-triethoxysilicane (IPTES, 494mg, 2mmol) are at room temperature mixed in the tetrahydrofuran solution of 15mL Non-aqueous processing, at N
2the lower backflow of protection 48 hours;
S402, boil off solvent, crude product is crossed chromatographic column and is purified (silicagel column, sherwood oil/methylene chloride/methanol=50:50:1), and obtain the BHN-IPTES (30%) of 255mg, product is yellow powdery solid.
Further, as shown in Figure 6, be the schema of the step S5 of the manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide of the present invention, wherein, described step S5 comprises:
S501, by the Fe of 100mg drying
3o
4siO
2nanoparticle and 300mg (0.35mmol) BHN-IPTES are mixed in the toluene solution of 15mL Non-aqueous processing, at N
2in 110 DEG C of backflows 12 hours under protection, centrifugally obtain BHN-Fe
3o
4siO
2nanoparticle;
S502, use toluene, methylene dichloride, ethanol repetitive scrubbing nanoparticle to supernatant liquor unstressed configuration respectively, the product obtained is placed in vacuum drying oven dried overnight, finally obtains BHN-Fe
3o
4siO
2inorganic-organic hybridization fluorescent optical sensor.
Fluorescent optical sensor prepared by described method of the present invention characterizes nano material mainly through TEM, XRD, FTIR, magnetic hysteresis loop, TGA etc.
First, as shown in Figure 7, be BHN-Fe
3o
4siO
2transmission electron microscope picture (TEM), namely throw and obtain transmission electron microscope picture by radio sub-microscope, can find out that from transmission electron microscope picture particle diameter is about the Fe of 10nm clearly
3o
4nanoparticle surface is well coated silicon dioxide layer, obtains the nanoparticle with typical nucleocapsid structure of particle diameter in the scope of 50-60nm.The nanoparticle that this diameter is less than the magnetic core-shell structure of 100nm has good dispersiveness, and the inertia silicon-dioxide of magnetic particle surface parcel effectively can stop particle reunion in the solution, the dispersiveness making nanoparticle have and chemical stability.
As shown in Figure 8, Fe
3o
4(a), Fe
3o
4siO
2(b) and BHN-Fe
3o
4siO
2c the X-ray powder diffraction pattern (XRD) of (), i.e. X-ray diffraction, obtains diffracting spectrum, from Fe
3o
4(a), Fe
3o
4siO
2(b) and BHN-Fe
3o
4siO
2can find out in the X-ray powder diffraction curve of (c) three kinds of nanoparticle 2 θ between 10-80 °, Fe
3o
4siO
2(b) and BHN-Fe
3o
4siO
2fe in (c)
3o
4the XRD diffraction peak of core meets not coated Fe
3o
4the diffraction peak index of nanoparticle, i.e. (220), (311), (400), (422), (511) and (440), this is consistent with the normal data of magnetic particle in the JCPDS card 19-629. of JCPDS (JCPDS).But, owing to making actual Fe after coated soft silica
3o
4the content of core reduces, so its diffraction peak is more weak.Meanwhile, broad peak very strong between 20-30 °, is and is coated on Fe
3o
4the diffraction peak of the soft silica around nanoparticle.
As shown in Figure 9, be Fe
3o
4siO
2(a) and BHN-Fe
3o
4siO
2b the infrared spectrogram (FT-IR) of (), i.e. fourier conversion infrared spectrum analysis instrument, ir data can prove that BHN-IPTES is successfully connected to Fe
3o
4siO
2the surface of nanoparticle.3400-3500cm
-1and 1000-1200cm
-1infrared absorption peak be Fe
3o
4siO
2the typical stretching vibration peak of surface silanol group.This surperficial Fe
3o
4siO
2surface is not be all connected to BHN-IPTES.1630cm
-1place is the flexural vibration of hydroxyl.1109cm
-1and 800cm
-1the strong peak at place can be attributed to the vibration of-Si-O-Si-.Above data all demonstrate the existence of silica shell in material.And BHN-Fe
3o
4siO
2infrared spectrum data at 2965cm
-1and 2934cm
-1there is the vibration peak of-CH in aliphatics and aromatic series, and 1697cm
-1, 1590cm
-1and 1516cm
-1three places are then BHN-Fe
3o
4siO
2on the flexural vibration of-CH3.These data show that BHN-IPTES is successfully connected to Fe
3o
4siO
2the surface of nanoparticle.
As shown in Figure 10, BHN-Fe
3o
4siO
2magnetic hysteresis loop figure, be the BHN-Fe under the 300K that magnetic hysteresis loop is measured by vibrating sample magnetometer between-15000 to 15000Oe
3o
4siO
2magnetic hysteresis loop show, at room temperature BHN-Fe
3o
4siO
2magnetic saturation intensity is 4.02emu/g.From magnetic hysteresis loop, demonstrate the superparamagnetic character of this particle without the phenomenon of remanent magnetism, this is due to Fe in nucleocapsid structure
3o
4the particle diameter of core, at about 10nm, meets the Fe being at room temperature less than 30nm
3o
4magnetic nano-particle is the character of superparamagnetism.Superparamagnetism makes BHN-Fe
3o
4siO
2nanoparticle has reversible magnetic response, only needs several minutes most of nanoparticle can be separated from solution under externally-applied magnetic field, vibrates gently and nanoparticle can be made again to disperse after removing magnetic field.This character makes BHN-Fe
3o
4siO
2there is returnability, and its Magneto separate ability makes after combining with reversibility fluorescent optical sensor simply, efficiently can identify Fe
3+while can also be separated
As shown in figure 11, be Fe
3o
4siO
2(a) and BHN-Fe
3o
4siO
2b the thermogravimetric curve (TGA) of (), can draw the connection amount of organic molecule at nano-material surface from the data of thermogravimetric analysis.In thermogravimetric curve, before 273K, the loss of prevailing quality is the evaporation of moisture, and the Mass lost between 273K to 973K is then for organic molecule occurs to decompose and cause.Be 14.22% by calculating the connection amount that can obtain organic molecule, and average each Fe
3o
4siO
2nanoparticle surface about connects 15000 BHN-IPTES molecules, the BHN-Fe of 0.2g/L
3o
4siO
2nanoparticle is then equivalent to 3.34 × 10
-5the BHN-IPTES of M.
As shown in figure 12, be BHN-IPTES (a), Fe
3o
4siO
2(b) and BHN-Fe
3o
4siO
2the ultraviolet spectrogram (UV-Vis) of (c), ultraviolet-visible absorption spectroscopy BHN-IPTES (1.0 × 10
-5m), Fe
3o
4siO
2(0.2g/L), andBHN-Fe
3o
4siO
2(0.2g/L) ultraviolet spectrogram further demonstrates BHN-IPTES and has been covalently attached to Fe
3o
4siO
2nanoparticle surface.With Fe
3o
4siO
2uv-absorbing compare, BHN-Fe
3o
4siO
2near 250nm and 350nm, occurred new absorption peak, this can be attributed to typical transition of electron between aromatic nucleus and amide group.New absorption peak also exists in the spectrum of BHN-IPTES, illustrates that BHN-IPTES is successfully connected to Fe
3o
4siO
2nanoparticle surface.
The BHN-Fe gone out of described method of the present invention
3o
4siO
2the character of inorganic-organic hybridization fluorescent optical sensor, have studied the character of nano material mainly through ultraviolet and fluorescence spectrum.
(1) ultraviolet response: as shown in figure 13, be BHN-Fe
3o
4siO
2(0.2g/L) different concns Fe is added
3+ultraviolet spectrogram, when to BHN-Fe
3o
4siO
2(0.2g/L) different concns Fe is dripped gradually in
3+time (0 to 200 μM), BHN-Fe
3o
4siO
2absorption peak strength near 250nm and 350nm strengthens gradually, and this illustrates BHN-Fe
3o
4siO
2with Fe
3+between define new title complex gradually.
(2) fluorescence response:
1. selectivity: is as shown in figure 14 BHN-Fe
3o
4siO
2to the fluorescence selectivity schematic diagram of different metal ion, the selectivity of nano material is by research 0.2g/LBHN-Fe
3o
4siO
2(be about equivalent to 3.34 × 10
-5the BHN-IPTES of M) at CH
3cN/H
2to each metal ion species Ag in O1:1 (HEPESbuffer, pH7.36) solution
+, Al
3+, Ca
2+, Cd
2+, Co
2+, Cr
3+, Cu
2+, Hg
2+, K
+, Li
+, Mg
2+, Mn
2+, Na
+, Pb
2+, Zn
2+and Fe
3+(be perchlorate, 5.0 × 10
-5m) fluorescence response obtains.Result shows, Fe
3+to BHN-Fe
3o
4siO
2cash out ' on-off ' type fluorescence response comparatively significantly, other metal ions are then without this phenomenon.Then can not produce such selectivity compared to BHN, this is that space constraint makes organic molecule be easier to chelating Fe due to after being connected to material surface
3+.The reason producing obvious fluorescent quenching can be interpreted as: BHN-Fe
3o
4siO
2in BHN-IPTES part there is larger conjugated structure electron-donating group, make it have stronger fluorescence.When with Fe
3+chelating is formed after stable complex, metal ion and O, atom N coordination thus and there is electron and energy transfer between fluorophore and destroy conjugated structure, thus create fluorescent quenching.
2. sensitivity: is as shown in figure 15 Fe
3+to BHN-Fe
3o
4siO
2(0.2g/L) fluorometric titration curve, shown in Figure 16, is Fe
3+with BHN-Fe
3o
4siO
2job curve.The sensitivity of nano material can be obtained by fluorescence titration result.To BHN-Fe
3o
4siO
2(0.2g/L) different concns Fe is dripped gradually in
3+time (0 to 100 μM), fluorescence intensity reduces gradually, and this illustrates Fe
3+quantitative combines with BHN-IPTES part on nanoparticle gradually, namely forms title complex.Fe is can be calculated by fluorometric titration data
3+with BHN-Fe
3o
4siO
2binding constant (log β) be 8.23.Work as Fe
3+when concentration is within the scope of 0 to 20 μM, the fluorescence intensity of nano material and concentration are similar to linear, can obtain detection be limited to 1.16 × 10 by calculating
-8m.Fe
3+with BHN-Fe
3o
4siO
2job curve near 0.5, there is flex point, therefore can infer that the coordination ratio between them is 1:1.In actual sample is measured, often have other particle and exist.BHN-Fe is in case deposited at interference particle in order to detect
3o
4siO
2to Fe
3+selectivity, carried out ion competition experiment, as shown in figure 17, be Fe
3+-BHN-Fe
3o
4siO
2ion competition figure, result shows the fluorescent quenching effect that can't affect Fe3+ when there is interfering ion in system.
3. reversibility: shown in Figure 18 is BHN-Fe
3o
4siO
2with Fe
3+in conjunction with reversibility research, Fe
3+the BHN-Fe caused
3o
4siO
2fluorescent quenching phenomenon be a reversible process, when to BHN-Fe
3o
4siO
2(0.2g/L) 2.50 × 10 are added in
-5the Fe of M
3+time, fluorescence intensity reduces about 24 times, produces fluorescent quenching phenomenon.2.50 × 10 are added again in system
-5during the EDTA of M, fluorescence returns to previous level substantially, this illustrate EDTA by title complex Fe
3+chelating out, causes system to launch autofluorescence.This character combines with its magnetic response, shows BHN-Fe
3o
4siO
2probably in living things system as identifying and being separated Fe
3+inorganic-organic hybridization fluorescent optical sensor.
4. recyclability: shown in Figure 19 is BHN-Fe
3o
4siO
2in repeatedly add Fe
3+and fluorescence intensity cycle diagram during EDTA, by repeatedly adding Fe in system
3+and fluorescence intensity loop test during EDTA, can BHN-Fe be studied
3o
4siO
2recycle character.Result shows, when to BHN-Fe
3o
4siO
2(0.2g/L) 2.50 × 10 are added in
-5the Fe of M
3+time, this hybrid material fluorescent quenching, when adding equivalent EDTA in system, fluorescence intensity is enhanced to about starting material fluorescence intensity; When again adding the Fe little over amount in system
3+after can produce fluorescent quenching phenomenon again; So repeatedly carry out 5 circulations, BHN-Fe
3o
4siO
2all to show Fe
3+obvious response.Therefore, hybrid material BHN-Fe
3o
4siO
2can as circulating repeatedly for detecting, being separated Fe
3+multi-functional hybrid fluorescent sensor, thus reduce practical application time production cost.
5. the scope of application: shown in Figure 20 is BHN-Fe
3o
4siO
2to Fe under different pH
3+fluorescence response figure, system under different pH to Fe
3+fluorescence response can obtain the scope of application of fluorescent optical sensor.Result shows, BHN-Fe
3o
4siO
2add Fe in acid condition
3+only can have slight impact to the fluorescence of system, this is because the protonation of N of 4 in 1,8-naphthalimide makes part and Fe
3+between only have faint binding ability.And when under neutrality and weak basic condition, namely pH is in 5.84 to 10.52 scopes, and system is to Fe
3+have comparatively significantly fluorescence response, this illustrates that this hybrid material has for the potential using value compared with complex biological system or environment.
In sum, the present invention is made into based on the micromolecular inorganic-organic hybridization fluorescent sensing material BHN-Fe with nucleocapsid structure of naphthalimide by described method
3o
4siO
2, it can at CH
3cN/H
2as detecting and being separated Fe in O1:1 (HEPESbuffer, pH7.36) solution
3+type material, and this Inorganic-Organic Hybrid Material is to Fe
3+there are good selectivity and sensitivity, simultaneously BHN-Fe
3o
4siO
2there is superparamagnetism, make material have good reversible magnetic response and Magneto separate character, thus when probing into its biologic applications, there is vital role, and the wider pH scope of application shows that material may be used in more complicated living things system or environment, Fe
3+with BHN-Fe
3o
4siO
2in conjunction with reversibility and the property of can be recycled, production cost can be reduced to a certain extent in actual applications, this material is expected to as detecting in organism or in environment and being separated Fe
3+novel material.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (6)
1., based on a manufacture method for the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide, it is characterized in that, comprising:
A, preparation Fe
3o
4magnetic nano-particle;
B, the magnetic nano-particle coated silica obtained is obtained Fe
3o
4siO
2nanoparticle;
C, to be obtained amino-1, the 8-naphthalimide (BHN) of N-butyl-4-two (2-hydroxyethyl) by chemosynthesis;
D, by BHN and 3-isocyanate group propyl-triethoxysilicane (IPTES) react, obtain BHN-IPTES;
E, by BHN-IPTES and Fe
3o
4siO
2nanoparticle is connected, and obtains BHN-Fe
3o
4siO
2inorganic-organic hybridization fluorescent optical sensor.
2. the manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide according to claim 1, it is characterized in that, described steps A comprises:
A1, by the FeCl of mol ratio 1:2
2with FeCl
3with N
2join in the aqueous solution containing 25% ammoniacal liquor under protection, this solution is stirred 1 hour at 20 DEG C of mechanical stirring, 1 hour post-heating to 70 DEG C;
A2, mixture be heated to 90 DEG C and drip citric acid (0.5g/mL), stirring 30 minutes;
A3, reaction system is cooled to room temperature, washes away unnecessary citric acid, ammoniacal liquor with deionized water and do not have magnetic nanoparticle, after vacuum-drying, obtaining Fe
3o
4nanoparticle.
3. the manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide according to claim 2, it is characterized in that, described step B comprises:
B1, by the Fe of 120mg citric acid-modified
3o
4nanoparticle, ultrasonic disperse is in 4mL deionized water;
B2, to be dispersed in the water magnetic fluid obtained under ultrasonic containing 5mL ammoniacal liquor 400mL ethanol/water (v/v=4:1) mixed solution, under mechanical stirring mixed system is warming up to 40 DEG C, and drip 6mL tetraethoxy wherein, maintain temperature of reaction and mechanical stirring 12 hours;
B3, reaction system is cooled to room temperature, with absolute ethanol washing 3 times, after vacuum-drying, obtains Fe
3o
4siO
2nanoparticle.
4. the manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide according to claim 3, it is characterized in that, described step C comprises:
Bromo-1, the 8-naphthalene acid anhydride of 4-of C1,5g and the n-Butyl Amine 99 of 1.7g are dissolved in 40mL Glacial acetic acid, at N
2backflow 6 hours in lower, reaction solution is poured in 200mL frozen water after reacting completely, separate out the rear suction filtration of a large amount of precipitation, drying, crude product crosses chromatographic column purification (silicagel column, ethyl acetate/petroleum ether=1:40), obtain bromo-1, the 8-naphthalimide (60.3%) of 3gN-butyl-4-, product is oyster white chip solid;
N-butyl-the 4-bromo-1 of C2,3g, 8-naphthalimide is dissolved in 15mL ethylene glycol monomethyl ether, add 4.12g diethanolamine, reflux after 48 hours, question response liquid is poured into after being cooled to room temperature in frozen water and is stirred after 12 hours with after dichloromethane extraction, anhydrous magnesium sulfate drying, solvent is boiled off on Rotary Evaporators, crude product crosses chromatographic column purification (silicagel column, methylene chloride/methanol=150:1), obtain amino-1, the 8-naphthalimide (BHN) of 1.72g yellow powdery solid N-butyl-4-two (2-hydroxyethyl).
5. the manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide according to claim 4, it is characterized in that, described step D comprises:
D1, BHN (356mg, 1mmol) and 3-isocyanate group propyl-triethoxysilicane (IPTES, 494mg, 2mmol) are at room temperature mixed in the tetrahydrofuran solution of 15mL Non-aqueous processing, at N
2the lower backflow of protection 48 hours;
D2, boil off solvent, crude product is crossed chromatographic column and is purified (silicagel column, sherwood oil/methylene chloride/methanol=50:50:1), and obtain the BHN-IPTES (30%) of 255mg, product is yellow powdery solid.
6. the manufacture method based on the micromolecular inorganic-organic hybridization fluorescent optical sensor of naphthalimide according to claim 5, it is characterized in that, described step e comprises:
E1, by the Fe of 100mg drying
3o
4siO
2nanoparticle and 300mg (0.35mmol) BHN-IPTES are mixed in the toluene solution of 15mL Non-aqueous processing, at N
2in 110 DEG C of backflows 12 hours under protection, centrifugally obtain BHN-Fe
3o
4siO
2nanoparticle;
E2, use toluene, methylene dichloride, ethanol repetitive scrubbing nanoparticle to supernatant liquor unstressed configuration respectively, the product obtained is placed in vacuum drying oven dried overnight, finally obtains BHN-Fe
3o
4siO
2inorganic-organic hybridization fluorescent optical sensor.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510487651.2A CN105154064A (en) | 2015-08-11 | 2015-08-11 | Production method of inorganic-organic hybrid fluorescent sensor based on naphthalimide small molecules |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510487651.2A CN105154064A (en) | 2015-08-11 | 2015-08-11 | Production method of inorganic-organic hybrid fluorescent sensor based on naphthalimide small molecules |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105154064A true CN105154064A (en) | 2015-12-16 |
Family
ID=54795124
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510487651.2A Pending CN105154064A (en) | 2015-08-11 | 2015-08-11 | Production method of inorganic-organic hybrid fluorescent sensor based on naphthalimide small molecules |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105154064A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106861629A (en) * | 2017-02-14 | 2017-06-20 | 江西中医药大学 | The nickel foam adsorbent of octadecyl modification and its application |
CN107652234A (en) * | 2017-09-13 | 2018-02-02 | 陕西科技大学 | Detect Cu (II) two-photon fluorescence probe and preparation method and application |
CN110790706A (en) * | 2019-10-25 | 2020-02-14 | 西北师范大学 | Molecular sensor capable of singly and selectively identifying picric acid molecules and synthesis and application thereof |
CN115611347A (en) * | 2022-11-04 | 2023-01-17 | 江南大学 | Preparation method of magnetic polydopamine modified CuS nano particles with high solar energy absorption |
CN116041791A (en) * | 2023-03-02 | 2023-05-02 | 江西广源新材料有限公司 | Naphthalene anhydride microencapsulated magnesium hydroxide composite powder and preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101671554A (en) * | 2008-09-10 | 2010-03-17 | 首都医科大学 | Silica-coated fluorescent magnetic nanoparticle, preparation method and application |
KR20130089491A (en) * | 2012-02-02 | 2013-08-12 | 고려대학교 산학협력단 | Zn2+ ion selective fluorescent probe and method for preparing the same |
-
2015
- 2015-08-11 CN CN201510487651.2A patent/CN105154064A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101671554A (en) * | 2008-09-10 | 2010-03-17 | 首都医科大学 | Silica-coated fluorescent magnetic nanoparticle, preparation method and application |
KR20130089491A (en) * | 2012-02-02 | 2013-08-12 | 고려대학교 산학협력단 | Zn2+ ion selective fluorescent probe and method for preparing the same |
Non-Patent Citations (6)
Title |
---|
CUICUI WANG等: "Efficient FRET-based fuorescent ratiometric chemosensors for Fe3þ and its application in living cells", 《JOURNAL OF LUMINESCENCE》 * |
SUMIN LEE,等: "Fluorescent turn-on Zn2+ sensing in aqueous and cellular media", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
YA MA,等: "A sensitive and selective chemosensor for GSSG detection based on the recovered fluorescence of NDPA-Fe3O4@SiO2-Cu(II) nanomaterial", 《BIOSENSORS AND BIOELECTRONICS》 * |
ZHIYUAN ZHANG,等: "A new 1,8-naphthalimide-based colorimetric and "turn-on" fluorescent Hg2+ sensor", 《SPECTROCHIMICA ACTA PART A: MOLECULAR AND BIOMOLECULAR SPECTROSCOPY》 * |
侍金敏: "巯基有机荧光小分子和无机_有机杂化荧光传感器的合成及性质研究", 《兰州大学硕士学位论文》 * |
田昕: "功能化磁性Fe3O4@SiO2荧光纳米探针的合成及应用研究", 《兰州大学博士学位论文》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106861629A (en) * | 2017-02-14 | 2017-06-20 | 江西中医药大学 | The nickel foam adsorbent of octadecyl modification and its application |
CN107652234A (en) * | 2017-09-13 | 2018-02-02 | 陕西科技大学 | Detect Cu (II) two-photon fluorescence probe and preparation method and application |
CN110790706A (en) * | 2019-10-25 | 2020-02-14 | 西北师范大学 | Molecular sensor capable of singly and selectively identifying picric acid molecules and synthesis and application thereof |
CN115611347A (en) * | 2022-11-04 | 2023-01-17 | 江南大学 | Preparation method of magnetic polydopamine modified CuS nano particles with high solar energy absorption |
CN116041791A (en) * | 2023-03-02 | 2023-05-02 | 江西广源新材料有限公司 | Naphthalene anhydride microencapsulated magnesium hydroxide composite powder and preparation method and application thereof |
CN116041791B (en) * | 2023-03-02 | 2024-05-24 | 江西广源新材料有限公司 | Naphthalene anhydride microencapsulated magnesium hydroxide composite powder and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105154064A (en) | Production method of inorganic-organic hybrid fluorescent sensor based on naphthalimide small molecules | |
CN103709321B (en) | Hyperchromic detection Cu 2+rhodamine B base hydrophilic polymer probe and preparation method and application | |
WO2019091389A1 (en) | Fluorescent probes for silver ion detection | |
CN108863922B (en) | AIE-based polymer ratio fluorescence sensor capable of rapidly detecting hypochlorous acid and preparation method and application thereof | |
CN107603592B (en) | Preparation method of magnetic fluorescent nano material and fluorescence detection method thereof | |
CN112209871B (en) | Zinc ion fluorescent probe based on tetraphenylethylene and preparation method and application thereof | |
CN106008343A (en) | Naphthalimide based mercury-ion fluorescence probe as well as preparation method and application thereof | |
CN113788789B (en) | Preparation method and application of fluorescent probe for continuously detecting copper ions and glyphosate | |
CN109265398B (en) | Supermolecule organogel and application thereof in fluorescent recognition of mercury ions | |
CN108772027B (en) | Preparation and application of supramolecular organogel and metal gel thereof | |
CN108088828B (en) | Double-column aromatic mercury ion fluorescent sensor and preparation and application thereof | |
CN105542750A (en) | Preparation method of HAN-Fe3O4@MSN-based inorganic-organic hybrid fluorescent sensor | |
CN106188102B (en) | A kind of water-soluble dendroid list imide compound fluorescence probe and its preparation method and application | |
CN110818646A (en) | Aggregation-induced emission-based small-molecule fluorescent probe and preparation method and application thereof | |
Eçik et al. | Synthesis of BODIPY-cyclotetraphosphazene triad systems and their sensing behaviors toward Co (II) and Cu (II) | |
CN107629036A (en) | A kind of fluorescence probe of visual detection copper ion and its preparation method and application | |
WO2023005099A1 (en) | α-NAPHTHOLPHTHALEIN DERIVATIVE MULTIFUNCTIONAL FLUORESCENT PROBE, PREPARATION METHOD THEREFOR, AND APPLICATION THEREOF | |
Wu et al. | Design of hybrid inorganic-organic nanosensor based on Fe3O4 as the core and recovery features | |
CN106221693A (en) | A kind of preparation method of the nitrite anions sensing nano material of repeatable utilization | |
CN106749240B (en) | It is a kind of can high selectivity detect and remove fluorescent optical sensor molecule and its synthesis and the application of mercury ion | |
CN106047340B (en) | The preparation and application of the graphene quantum dot of terpyridine moieties modification | |
Zhang et al. | Xylan derived carbon dots composite ZIF-8 and its immobilized carbon fibers membrane for fluorescence selective detection Cu2+ in real samples | |
CN104311568A (en) | Fluorescein hydrazide derivatives, preparation method of fluorescein hydrazide derivatives, modified TiO2 functional material, preparation method of modified TiO2 functional material, and sensor | |
Pourfallah et al. | Novel 4-amino-2-methyl-8-(trifluoromethyl) quinoline-based magnetic nanostructures for highly sensitive detection of zinc ions in aqueous solutions | |
CN105418941B (en) | A kind of nano composite material, preparation method and application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB03 | Change of inventor or designer information | ||
CB03 | Change of inventor or designer information |
Inventor after: Liu Weisheng Inventor after: Zhou Xi Inventor before: Zhou Xi Inventor before: Liu Weisheng |
|
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20151216 |