CN109400800A - A kind of N- rhodamine 6G lactams-N,Acryloxy hydrazine fluorescence probe polyalcohol hydrogel and preparation method thereof - Google Patents

A kind of N- rhodamine 6G lactams-N,Acryloxy hydrazine fluorescence probe polyalcohol hydrogel and preparation method thereof Download PDF

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CN109400800A
CN109400800A CN201810537175.4A CN201810537175A CN109400800A CN 109400800 A CN109400800 A CN 109400800A CN 201810537175 A CN201810537175 A CN 201810537175A CN 109400800 A CN109400800 A CN 109400800A
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CN109400800B (en
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段洪东
王珍媜
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Qilu University of Technology
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Abstract

The fluorescence probe polyalcohol hydrogel that fluorescence significantly increases in the presence of a kind of fluorescence probe polyalcohol hydrogel and its application in detection mercury ion are related to one kind in mercury ion.The present invention provides one kind can be used for selective enumeration method mercury ion N- rhodamine 6G lactams-N'- acryloxy hydrazine fluorescence probe polyalcohol hydrogel and preparation method thereof.First using rhodamine 6G and hydroxyethylhydrazine as raw material, prepare rhodamine 6G contracting hydrazine hydrate, it is recycled to react with acryloyl chloride, N- rhodamine 6G lactams-N'- acryloxy hydrazine is obtained, then N- rhodamine 6G lactams-N'- acryloxy hydrazine and acrylamide are copolymerized to obtain fluorescence probe hydrogel.The technique synthesis cost is lower, and yield is high, and purifying products are simple, easy control of reaction conditions.The features such as mercury ion fluorescence probe hydrogel has selectivity good, and anti-metal ion interference ability is strong, detects quick response is a kind of simple, quick, sensitive mercury ion specific detection material, can be applied to Material Field or sensor field.

Description

A kind of N- rhodamine 6G lactams-N,Acryloxy hydrazine fluorescence probe polymer water Gel and preparation method thereof
Technical field
The present invention relates to a kind of fluorescence probe polyalcohol hydrogels and preparation method thereof, and the fluorescence probe is with conjugation and just Property planar structure, shows preferable fluorescence property, contains C=O simultaneously, N-H functional group is capable of providing coordination side abundant Formula has very strong metal coordination ability and good ion selectivity, and the fluorescence probe and acrylamide are copolymerized to obtain water Gel, to solve the Recycling of regeneration fluorescence probe.
Background technique
Probe based on fluorescence signal has been widely studied, at low cost, synthetic method simple, high sensitivity, The good, fast response time of selectivity and detection limit are low and the advantages that can be used for temporal and spatial sampling and in-vivo imaging, thus a large amount of use In detection metal ion.In the course of the research, it has been found that small-molecule fluorescent probe has the shortcomings that much to be difficult to overcome.Small point Sub- fluorescence probe generally has biggish rigidity conjugation group, and dissolubility is usually poor, cannot be directly used to municipal sewage and work The detection of industry heavy metal ions in wastewater；It can change its water solubility by carrying out molecular modification, but fluorescence property is but easy It changes.The inspection that small-molecule fluorescent probe must have the structural unit very sensitive to tested measured ion to be just able to achieve ion It surveys, these structural units usually reactivity is stronger, and stability is poor, is easy to react with many chaff interferents.Small molecule fluorescent Probe does not allow easy processing, limits its application in terms of detecting device.
Hydrogel as a kind of intellectual material, is crosslinked by chemical (covalent bond) or physics (noncovalent interaction) It is formed, the three-dimensional structure with water-swellable.Due to having hydrophilic radical (- OH ,-COOH ,-NH in structure2,-CONH2,- SO3H), up to a hundred or even thousands of times can be increased with water swelling to volume.These characteristics enable them to apply in drug delivery system System, anti-biotic material, sensor, agricultural, matrix organization engineering material, catalyst carrier material, separation, immobilization and Environmental Technology Etc..This patent introduces unsaturated double-bond on small-molecule fluorescent probe, it is copolymerized with acrylamide, prepares and has height The macromolecule hydrogel fluorescence probe of transparency, high-hydrophilic and excellent mechanical performances, to solve following for regeneration fluorescence probe Ring uses problem, and the workload of fluorescence probe synthesis can be greatly reduced in this research achievement, to reduce the pollution to environment With the consumption of the energy, is conducive to the fluorescence probe based on high molecular material and moves towards practical application from laboratory research.
Summary of the invention:
In view of the deficiencies of the prior art, it is an object of the present invention to provide a new class of fluorescence probe polyalcohol hydrogels, should Fluorescence probe monomer has special conjugated structure and good chemical coordination performance, and the synthesis technology has operation letter The advantages that list, yield are high, at low cost, detection is quick.
It is a further object of the present invention to provide the preparation methods of the fluorescence probe monomer.
It is a further object of the present invention to provide the preparation methods of the fluorescence probe polyalcohol hydrogel.
It is a further object of the present invention to provide the applications of the fluorescence probe polyalcohol hydrogel.
In order to realize such purpose, technical scheme is as follows:
The compound is mainly used in Material Field or sensor field；
A kind of preparation method of fluorescence probe polyalcohol hydrogel, preparation method are as follows:
1) preparation of N- rhodamine 6G lactams-N'- hydrazine hydrate:
Rhodamine 6G is weighed in there-necked flask, dehydrated alcohol is added, after there-necked flask return stirring 30min, into solution Hydrazine hydrate is added dropwise, after being added dropwise, mixed solution continues 5~10h of back flow reaction, is cooled to room temperature, filters, with dehydrated alcohol weight Crystallization is dried in vacuo to get N- rhodamine 6G lactams-N'- hydrazine hydrate；
2) preparation of N- rhodamine 6G lactams-N'- acryloxy hydrazine:
It weighs triethylamine and N- rhodamine 6G lactams-N'- hydrazine hydrate that step 1) obtains is in there-necked flask, dichloro is added Methane weighs acryloyl chloride and is added drop-wise in there-necked flask, and dropwise addition process carries out under -5~0 DEG C of constant temperature, is added dropwise, and is warming up to room Simultaneously 6~12h is stirred at room temperature in temperature, extracts, and dry water removal, vacuum distillation removes solvent, and pillar layer separation obtains purple powder Shape solid is dried in vacuo up to N- rhodamine 6G lactams-N'- acryloxy hydrazine；
3) preparation of N- rhodamine 6G lactams-N'- acryloxy hydrazide polymer hydrogel:
Distilled water is boiled sealing to be cooled to room temperature to remove the oxygen in water, acrylamide is weighed and is dissolved in distilled water, It weighs the N- rhodamine 6G lactams-N'- acryloxy hydrazine that step 2) obtains to be dissolved in dimethyl sulfoxide, two kinds of solution mixing Stirring is vacuumized under room temperature afterwards, persistently stirs 30min, until mixing is completely, successively by crosslinking agent, catalyst, initiator addition Above-mentioned mixed solution, stirs evenly, and solution is transferred in glass mold, it is ensured that after not being mixed into bubble, covers glass lid Water-setting sealing rubber die is placed on 3~5h of holding in 50~55 DEG C of insulating box, Raolical polymerizable is carried out, after taking-up by sealing It is cooling to stablize for 24 hours, glass lid is opened, molding hydrogel is slowly taken out, impregnates for 24 hours, removes in dimethyl sulphoxide solution Unreacted N- rhodamine 6G lactams-N'- acryloxy hydrazine monomer is removed, then impregnates for 24 hours, is removed not in distilled water The acrylamide monomer of reaction.
Preferably, the molar ratio of rhodamine 6G described in step 1) and hydrazine hydrate is 2:13~2:16；It is furthermore preferred that sieve The molar ratio of red bright 6G and hydrazine hydrate is 2:15；
Preferably, the Molar of dehydrated alcohol described in step 1) and rhodamine 6G ratio is 20mL:1~4mmol； It is furthermore preferred that the Molar of dehydrated alcohol and rhodamine 6G ratio is 20mL:2mmol；
Preferably, the reaction time in step 1) is 7~10h；It is furthermore preferred that the reaction time is 8h；
Preferably, the molar ratio 1:1 of the lactams-N'- hydrazine hydrate of N- rhodamine 6G described in step 2) and triethylamine~ 1:2；The molar ratio 1:1.5 of preferred N- rhodamine 6G lactams-N'- hydrazine hydrate and triethylamine；
Preferably, the molar ratio of the lactams-N'- hydrazine hydrate of N- rhodamine 6G described in step 2) and acryloyl chloride is 1: 1~1:2；It is furthermore preferred that the molar ratio of N- rhodamine 6G lactams-N'- hydrazine hydrate and acryloyl chloride is 1:1；
Preferably, the Molar ratio of methylene chloride described in step 2) and N- rhodamine 6G lactams-N'- hydrazine hydrate For 20~30mL:1mmol；It is furthermore preferred that the Molar ratio of methylene chloride and N- rhodamine 6G lactams-N'- hydrazine hydrate is 24mL:1mmol；
Preferably, dropping temperature described in step 2) is at -5~0 DEG C；Preferred dropping temperature is -2 DEG C；
Preferably, the reaction time described in step 2) is 10~12h；The preferred reaction time is 12h；
Crosslinking agent described in step 3), initiator, catalyst are respectively N, N '-methylene-bisacrylamide, persulfuric acid Ammonium, tetramethylethylenediamine；
Acrylamide described in step 3), N- rhodamine 6G lactams-N'- acryloxy hydrazine, crosslinking agent, initiator The mass percent for accounting for total solid component is respectively 89~99%, 0.14~9%, 0.4~0.6%, 0.5~0.7%；
The mass volume ratio of acrylamide described in step 3) and distilled water is 1g:1~1.2mL；
The quality volume of-N'- acryloxy hydrazine of N- rhodamine 6G lactams described in step 3) and dimethyl sulfoxide Than for 0.001g:0.04~1.6mL；
The volume mass of catalyst described in step 3) and initiator ratio is 100 μ L:0.02~0.04g；
The isothermal reaction time described in step 3) is 3~5h, and isothermal reaction temperature is 50~55 DEG C；
The synthetic route of fluorescence probe polyalcohol hydrogel of the present invention is as follows:
Rhodamine 6G and hydration hydrazine reaction are prepared rhodamine 6G contracting hydrazine hydrate, recycle itself and propylene by the present invention Acyl chloride reaction obtains N- rhodamine 6G lactams-N'- acryloxy hydrazine, then N- rhodamine 6G lactams-N'- propylene Acyloxy hydrazine and acrylamide are copolymerized to obtain fluorescence probe hydrogel, after tested, N- rhodamine 6G lactams-N'- acryloyl-oxy Base hydrazine and its polymer fluorescent probe hydrogel have good selectivity metal mercury ion.
In hydrogel preparation process, the process entirely stirred carries out in 100mL eggplant-shape bottle, by eggplant-shape bottle frame in constant temperature magnetic On power blender, bottle plug perforated rubber stopper is connect in multi-purpose circulating water type vacuum pump, in this way by self-control glass tube and rubber tube It can vacuumize while stirring in order to which the gas in mixed solution is discharged, guarantee to be not easily formed bubble when plastic, reduce Hydrogel ratio of defects after molding.
Novel compound of present invention can be used as probe application in ion detection field.Acyl in the compound N-rhodamine 6G Amine-N'- acryloxy hydrazine and its fluorescence probe hydrogel being copolymerized with acrylamide all have good, the anti-metal of selectivity The features such as ion interference ability is strong, detects quick response is a kind of simple, quick, sensitive mercury ion specific detection material, It can be applied to Material Field or sensor field.
Detailed description of the invention:
(1) Fig. 1 is compound N-rhodamine 6G lactams-N'- acryloxy hydrazine hydrogen nuclear magnetic resonance spectrogram.
(2) Fig. 2 is compound N-rhodamine 6G lactams-N'- acryloxy hydrazine and metallic ion mixed liquor can Color change schematic diagram under light-exposed.
(3) Fig. 3 is ultra-violet absorption spectrum of the N- rhodamine 6G lactams-N'- acryloxy hydrazine to different metal ions Scheme (abscissa is absorbing wavelength, and ordinate is absorption intensity).
(4) Fig. 4 is fluorogram of the N- rhodamine 6G lactams-N'- acryloxy hydrazine to metalloform-selective (abscissa is launch wavelength, and ordinate is fluorescence intensity).
(5) Fig. 5 is that the color of N- rhodamine 6G lactams-N'- acryloxy hydrazide polymer fluorescence probe identification mercury ion becomes Change and regenerate schematic diagram.
Specific embodiment:
For a better understanding of the technical solution of the present invention, being described in further detail below by way of specific embodiment.
Embodiment 1
1) it weighs rhodamine 6G 0.9580g (2mmol) and is dissolved in 20mL hot ethanol, after being completely dissolved, hydrazine hydrate is added dropwise 0.7509g (15mmol), is added dropwise, mixed solution return stirring 8h, until solution fluorescence disappears, contact plate confirmation has been reacted Entirely, reaction solution is cooled to room temperature, and precipitating is precipitated, and precipitating is filtered and washed with hot ethanol, and obtained crude product recrystallized from acetonitrile obtains Product N- rhodamine 6G lactams-N'- hydrazine hydrate 0.7344g, yield 85%；
2) N- rhodamine 6G lactams-N'- hydrazine hydrate 0.4285g (1mmol) is weighed to be dissolved into 24mL methylene chloride, to Triethylamine 0.1518g (1.5mmol) is added dropwise in above-mentioned solution, mixed solution cooling, solution to be mixed is cooled to -3 DEG C, keeps temperature Degree is stablized, and starts that acryloyl chloride 0.0905g (1mmol) is added dropwise, is added dropwise, is warming up to room temperature and 12h is stirred at room temperature, point It after plate confirms fully reacting, extracts, concentration, pillar layer separation obtains product Compound N- rhodamine 6G lactams-N'- acryloyl Oxygroup hydrazine 0.3915g, yield 81%；
3) distilled water is boiled into deoxygenation, is cooled to room temperature after sealing for use, takes 0.0073gN- rhodamine 6G lactams-N'- Acryloxy hydrazine is dissolved in 11.7mL DMSO, and 5.1480g acrylamide is taken to be dissolved in 5.1mL water, and two kinds of solution are mixed, 30min is persistently stirred, until mixing is completely, by 0.0312g N, N '-methylene-bisacrylamide is dissolved in above-mentioned mixed solution, 100 μ L tetramethylethylenediamines are injected into mixed solution again, 0.0364g ammonium persulfate is eventually adding, stirs evenly, solution is turned It moves in glass mold, it is ensured that after not being mixed into bubble, cover glass lid sealing, mold is placed in 50 DEG C of insulating box 5h is kept, Raolical polymerizable is carried out, it is cooling after taking-up to stablize for 24 hours, glass lid is opened, molding hydrogel is slowly taken Out, it is impregnated in dimethyl sulphoxide solution for 24 hours, removes unreacted N- rhodamine 6G lactams-N'- acryloxy hydrazine list Then body impregnates for 24 hours in distilled water, remove unreacted acrylamide monomer.
Embodiment 2
1) it weighs rhodamine 6G 0.9580g (2mmol) and is dissolved in 40mL hot ethanol, after being completely dissolved, hydrazine hydrate is added dropwise 0.6508g (13mmol), is added dropwise, mixed solution return stirring 7h, until solution fluorescence disappears, contact plate confirmation has been reacted Entirely, reaction solution is cooled to room temperature, and precipitating is precipitated, and precipitating is filtered and washed with hot ethanol, and obtained crude product recrystallized from acetonitrile obtains Product N- rhodamine 6G lactams-N'- hydrazine hydrate 0.5530g, yield 64%；
2) it weighs N- rhodamine 6G lactams-N'- hydrazine hydrate 0.4285g (1.0mmol) and is dissolved into 20mL methylene chloride In, triethylamine 0.1012g (1.1mmol) is added dropwise in Xiang Shangshu solution, mixed solution cooling, solution to be mixed is cooled to 0 DEG C, protects It holds temperature to stablize, starts that acryloyl chloride 0.0905g (1.0mmol) is added dropwise, be added dropwise, be warming up to room temperature and be stirred at room temperature 9h after contact plate confirms fully reacting, is extracted, and concentration, pillar layer separation obtains product Compound N- rhodamine 6G lactams-N'- third Alkene acyloxy hydrazine 0.3625g, yield 75%；
3) distilled water is boiled into deoxygenation, is cooled to room temperature after sealing for use, takes 0.0073gN- rhodamine 6G lactams-N'- Acryloxy hydrazine is dissolved in 11.7mL DMSO, and 5.1480g acrylamide is taken to be dissolved in 5.1mL water, and two kinds of solution are mixed, 30min is persistently stirred, until mixing is completely, by 0.0312g N, N '-methylene-bisacrylamide is dissolved in above-mentioned mixed solution, 100 μ L tetramethylethylenediamines are injected into mixed solution again, 0.0364g ammonium persulfate is eventually adding, stirs evenly, solution is turned It moves in glass mold, it is ensured that after not being mixed into bubble, cover glass lid sealing, mold is placed in 50 DEG C of insulating box 5h is kept, Raolical polymerizable is carried out, it is cooling after taking-up to stablize for 24 hours, glass lid is opened, molding hydrogel is slowly taken Out, it is impregnated in dimethyl sulphoxide solution for 24 hours, removes unreacted N- rhodamine 6G lactams-N'- acryloxy hydrazine list Then body impregnates for 24 hours in distilled water, remove unreacted acrylamide monomer.
Embodiment 3
1) it weighs rhodamine 6G 0.9580g (2mmol) and is dissolved in 60mL hot ethanol, after being completely dissolved, hydrazine hydrate is added dropwise 0.7008g (14mmol), is added dropwise, mixed solution return stirring 9h, until solution fluorescence disappears, contact plate confirmation has been reacted Entirely, reaction solution is cooled to room temperature, and precipitating is precipitated, and precipitating is filtered and washed with hot ethanol, and obtained crude product recrystallized from acetonitrile obtains Product N- rhodamine 6G lactams-N'- hydrazine hydrate 0.6912g, yield 80%；
2) N- rhodamine 6G lactams-N'- hydrazine hydrate 0.4285g (1mmol) is weighed to be dissolved into 28mL methylene chloride, to Triethylamine 0.1012g (1.0mmol) is added dropwise in above-mentioned solution, mixed solution cooling, solution to be mixed is cooled to -2 DEG C, keeps temperature Degree is stablized, and starts that acryloyl chloride 0.1358g (1.5mmol) is added dropwise, is added dropwise, is warming up to room temperature and 10h is stirred at room temperature, It after contact plate confirms fully reacting, extracts, concentration, pillar layer separation obtains product Compound N- rhodamine 6G lactams-N'- propylene Acyloxy hydrazine 0.3770g, yield 78%；
3) distilled water is boiled into deoxygenation, is cooled to room temperature after sealing for use, takes 0.0073gN- rhodamine 6G lactams-N'- Acryloxy hydrazine is dissolved in 11.7mL DMSO, and 5.1480g acrylamide is taken to be dissolved in 5.1mL water, and two kinds of solution are mixed, 30min is persistently stirred, until mixing is completely, by 0.0312g N, N '-methylene-bisacrylamide is dissolved in above-mentioned mixed solution, 100 μ L tetramethylethylenediamines are injected into mixed solution again, 0.0364g ammonium persulfate is eventually adding, stirs evenly, solution is turned It moves in glass mold, it is ensured that after not being mixed into bubble, cover glass lid sealing, mold is placed in 50 DEG C of insulating box 5h is kept, Raolical polymerizable is carried out, it is cooling after taking-up to stablize for 24 hours, glass lid is opened, molding hydrogel is slowly taken Out, it is impregnated in dimethyl sulphoxide solution for 24 hours, removes unreacted N- rhodamine 6G lactams-N'- acryloxy hydrazine list Then body impregnates for 24 hours in distilled water, remove unreacted acrylamide monomer.
Embodiment 4
1) it weighs rhodamine 6G 0.9580g (2mmol) and is dissolved in 80mL hot ethanol, after being completely dissolved, hydrazine hydrate is added dropwise 0.8010g (16mmol), is added dropwise, mixed solution return stirring 10h, until solution fluorescence disappears, contact plate confirmation reaction Completely, reaction solution is cooled to room temperature, and precipitating is precipitated, and precipitating is filtered and washed with hot ethanol, obtained crude product recrystallized from acetonitrile, Obtain product N- rhodamine 6G lactams-N'- hydrazine hydrate 0.6566g, yield 76%；
2) N- rhodamine 6G lactams-N'- hydrazine hydrate 0.4285g (1mmol) is weighed to be dissolved into 30mL methylene chloride, to Triethylamine 0.1810g (2.0mmol) is added dropwise in above-mentioned solution, mixed solution cooling, solution to be mixed is cooled to -3 DEG C, keeps temperature Degree is stablized, and starts that acryloyl chloride 0.2024 (2.0mmol) is added dropwise, is added dropwise, is warming up to room temperature and 8h is stirred at room temperature, point It after plate confirms fully reacting, extracts, concentration, pillar layer separation obtains product Compound N- rhodamine 6G lactams-N'- acryloyl Oxygroup hydrazine 0.3721g, yield 77%；
3) distilled water is boiled into deoxygenation, is cooled to room temperature after sealing for use, takes 0.0073gN- rhodamine 6G lactams-N'- Acryloxy hydrazine is dissolved in 11.7mL DMSO, and 5.1480g acrylamide is taken to be dissolved in 5.1mL water, and two kinds of solution are mixed, 30min is persistently stirred, until mixing is completely, by 0.0312g N, N '-methylene-bisacrylamide is dissolved in above-mentioned mixed solution, 100 μ L tetramethylethylenediamines are injected into mixed solution again, 0.0364g ammonium persulfate is eventually adding, stirs evenly, solution is turned It moves in glass mold, it is ensured that after not being mixed into bubble, cover glass lid sealing, mold is placed in 50 DEG C of insulating box 5h is kept, Raolical polymerizable is carried out, it is cooling after taking-up to stablize for 24 hours, glass lid is opened, molding hydrogel is slowly taken Out, it is impregnated in dimethyl sulphoxide solution for 24 hours, removes unreacted N- rhodamine 6G lactams-N'- acryloxy hydrazine list Then body impregnates for 24 hours in distilled water, remove unreacted acrylamide monomer.
Embodiment 5
1) it weighs rhodamine 6G 0.9580g (2mmol) and is dissolved in 20mL hot ethanol, after being completely dissolved, hydrazine hydrate is added dropwise 0.7509g (15mmol), is added dropwise, mixed solution return stirring 8h, until solution fluorescence disappears, contact plate confirmation has been reacted Entirely, reaction solution is cooled to room temperature, and precipitating is precipitated, and precipitating is filtered and washed with hot ethanol, and obtained crude product recrystallized from acetonitrile obtains Product N- rhodamine 6G lactams-N'- hydrazine hydrate 0.5530g, yield 64%；
2) N- rhodamine 6G lactams-N'- hydrazine hydrate 0.4285g (1mmol) is weighed to be dissolved into 24mL methylene chloride, to Triethylamine 0.1518g (1.5mmol) is added dropwise in above-mentioned solution, mixed solution cooling, solution to be mixed is cooled to -3 DEG C, keeps temperature Degree is stablized, and starts that acryloyl chloride 0.0905g (1mmol) is added dropwise, is added dropwise, is warming up to room temperature and 12h is stirred at room temperature, point It after plate confirms fully reacting, extracts, concentration, pillar layer separation obtains product Compound N- rhodamine 6G lactams-N'- acryloyl Oxygroup hydrazine 0.3625g, yield 75%；
3) distilled water is boiled into deoxygenation, is cooled to room temperature after sealing for use, takes 0.0412gN- rhodamine 6G lactams-N'- Acryloxy hydrazine is dissolved in 53.7mL DMSO, and 5.0470g acrylamide is taken to be dissolved in 5.0mL water, and two kinds of solution are mixed, 30min is persistently stirred, until mixing is completely, by 0.0309gN, N '-methylene-bisacrylamide is dissolved in above-mentioned mixed solution, 200 μ L tetramethylethylenediamines are injected into mixed solution again, 0.0361g ammonium persulfate is eventually adding, stirs evenly, solution is turned It moves in glass mold, it is ensured that after not being mixed into bubble, cover glass lid sealing, mold is placed in 55 DEG C of insulating box 4.5h is kept, Raolical polymerizable is carried out, it is cooling after taking-up to stablize for 24 hours, glass lid is opened, slowly by molding hydrogel It takes out, is impregnated in dimethyl sulphoxide solution for 24 hours, remove unreacted N- rhodamine 6G lactams-N'- acryloxy hydrazine list Then body impregnates for 24 hours in distilled water, remove unreacted acrylamide monomer.
Embodiment 6
1) it weighs rhodamine 6G 0.9580g (2mmol) and is dissolved in 20mL hot ethanol, after being completely dissolved, hydrazine hydrate is added dropwise 0.7509g (15mmol), is added dropwise, mixed solution return stirring 8h, until solution fluorescence disappears, contact plate confirmation has been reacted Entirely, reaction solution is cooled to room temperature, and precipitating is precipitated, and precipitating is filtered and washed with hot ethanol, and obtained crude product recrystallized from acetonitrile obtains Product N- rhodamine 6G lactams-N'- hydrazine hydrate 0.5530g, yield 64%；
2) N- rhodamine 6G lactams-N'- hydrazine hydrate 0.4285g (1mmol) is weighed to be dissolved into 24mL methylene chloride, to Triethylamine 0.1518g (1.5mmol) is added dropwise in above-mentioned solution, mixed solution cooling, solution to be mixed is cooled to -3 DEG C, keeps temperature Degree is stablized, and starts that acryloyl chloride 0.0905g (1mmol) is added dropwise, is added dropwise, is warming up to room temperature and 12h is stirred at room temperature, point It after plate confirms fully reacting, extracts, concentration, pillar layer separation obtains product Compound N- rhodamine 6G lactams-N'- acryloyl Oxygroup hydrazine 0.3625g, yield 75%；
3) distilled water is boiled into deoxygenation, is cooled to room temperature after sealing for use, takes 0.0859gN- rhodamine 6G lactams-N'- Acryloxy hydrazine is dissolved in 85.9mL DMSO, and 4.8985g acrylamide is taken to be dissolved in 4.9mL water, and two kinds of solution are mixed, 30min is persistently stirred, until mixing is completely, by 0.0253gN, N '-methylene-bisacrylamide is dissolved in above-mentioned mixed solution, 150 μ L tetramethylethylenediamines are injected into mixed solution again, 0.0303g ammonium persulfate is eventually adding, stirs evenly, solution is turned It moves in glass mold, it is ensured that after not being mixed into bubble, cover glass lid sealing, mold is placed in 54 DEG C of insulating box 3.5h is kept, Raolical polymerizable is carried out, it is cooling after taking-up to stablize for 24 hours, glass lid is opened, slowly by molding hydrogel It takes out, is impregnated in dimethyl sulphoxide solution for 24 hours, remove unreacted N- rhodamine 6G lactams-N'- acryloxy hydrazine list Then body impregnates for 24 hours in distilled water, remove unreacted acrylamide monomer.
Embodiment 7
1) it weighs rhodamine 6G 0.9580g (2mmol) and is dissolved in 20mL hot ethanol, after being completely dissolved, hydrazine hydrate is added dropwise 0.7509g (15mmol), is added dropwise, mixed solution return stirring 8h, until solution fluorescence disappears, contact plate confirmation has been reacted Entirely, reaction solution is cooled to room temperature, and precipitating is precipitated, and precipitating is filtered and washed with hot ethanol, and obtained crude product recrystallized from acetonitrile obtains Product N- rhodamine 6G lactams-N'- hydrazine hydrate 0.5530g, yield 64%；
2) N- rhodamine 6G lactams-N'- hydrazine hydrate 0.4285g (1mmol) is weighed to be dissolved into 24mL methylene chloride, to Triethylamine 0.1518g (1.5mmol) is added dropwise in above-mentioned solution, mixed solution cooling, solution to be mixed is cooled to -3 DEG C, keeps temperature Degree is stablized, and starts that acryloyl chloride 0.0905g (1mmol) is added dropwise, is added dropwise, is warming up to room temperature and 12h is stirred at room temperature, point It after plate confirms fully reacting, extracts, concentration, pillar layer separation obtains product Compound N- rhodamine 6G lactams-N'- acryloyl Oxygroup hydrazine 0.3625g, yield 75%；
3) distilled water is boiled into deoxygenation, is cooled to room temperature after sealing for use, takes 0.1733gN- rhodamine 6G lactams-N'- Acryloxy hydrazine is dissolved in 121.28mLDMSO, and 4.7030g acrylamide is taken to be dissolved in 4.7mL water, and two kinds of solution are mixed It closes, persistently stirs 30min, until mixing is completely, by 0.0248gN, it is molten that N '-methylene-bisacrylamide is dissolved in above-mentioned mixing Liquid, then 150 μ L tetramethylethylenediamines are injected into mixed solution, it is eventually adding 0.0297g ammonium persulfate, is stirred evenly, it will be molten Liquid is transferred in glass mold, it is ensured that after not being mixed into bubble, covers glass lid sealing, mold is placed on to 53 DEG C of constant temperature 4h is kept in case, carries out Raolical polymerizable, it is cooling after taking-up to stablize for 24 hours, glass lid is opened, molding hydrogel is slow It is slow to take out, it is impregnated in dimethyl sulphoxide solution for 24 hours, removes unreacted N- rhodamine 6G lactams-N'- acryloxy hydrazine Then monomer impregnates for 24 hours in distilled water, remove unreacted acrylamide monomer.
Embodiment 8
1) it weighs rhodamine 6G 0.9580g (2mmol) and is dissolved in 20mL hot ethanol, after being completely dissolved, hydrazine hydrate is added dropwise 0.7509g (15mmol), is added dropwise, mixed solution return stirring 8h, until solution fluorescence disappears, contact plate confirmation has been reacted Entirely, reaction solution is cooled to room temperature, and precipitating is precipitated, and precipitating is filtered and washed with hot ethanol, and obtained crude product recrystallized from acetonitrile obtains Product N- rhodamine 6G lactams-N'- hydrazine hydrate 0.5530g, yield 64%；
2) N- rhodamine 6G lactams-N'- hydrazine hydrate 0.4285g (1mmol) is weighed to be dissolved into 24mL methylene chloride, to Triethylamine 0.1518g (1.5mmol) is added dropwise in above-mentioned solution, mixed solution cooling, solution to be mixed is cooled to -3 DEG C, keeps temperature Degree is stablized, and starts that acryloyl chloride 0.0905g (1mmol) is added dropwise, is added dropwise, is warming up to room temperature and 12h is stirred at room temperature, point It after plate confirms fully reacting, extracts, concentration, pillar layer separation obtains product Compound N- rhodamine 6G lactams-N'- acryloyl Oxygroup hydrazine 0.3625g, yield 75%；
3) distilled water is boiled into deoxygenation, is cooled to room temperature after sealing stand-by.Take 0.2571gN- rhodamine 6G lactams-N'- Acryloxy hydrazine is dissolved in 102.8mLDMSO, and 4.5105 acrylamides is taken to be dissolved in 4.5mL water, and two kinds of solution are mixed, are held Continuous stirring 30min, until mixing is completely, by 0.0243N, N '-methylene-bisacrylamide is dissolved in above-mentioned mixed solution, then will 150 μ L tetramethylethylenediamines are injected into mixed solution, are eventually adding 0.0291g ammonium persulfate, stir evenly, solution is transferred to In glass mold, it is ensured that after not being mixed into bubble, cover glass lid sealing, mold is placed in 52 DEG C of insulating box and is kept 3h carries out Raolical polymerizable, cooling after taking-up to stablize for 24 hours, opens glass lid, molding hydrogel is slowly taken out, It is impregnated in dimethyl sulphoxide solution for 24 hours, removes unreacted N- rhodamine 6G lactams-N'- acryloxy hydrazine monomer, so It is impregnated in distilled water afterwards for 24 hours, removes unreacted acrylamide monomer.
Embodiment 9
1) it weighs rhodamine 6G 0.9580g (2mmol) and is dissolved in 20mL hot ethanol, after being completely dissolved, hydrazine hydrate is added dropwise 0.7509g (15mmol), is added dropwise, mixed solution return stirring 8h, until solution fluorescence disappears, contact plate confirmation has been reacted Entirely, reaction solution is cooled to room temperature, and precipitating is precipitated, and precipitating is filtered and washed with hot ethanol, and obtained crude product recrystallized from acetonitrile obtains Product N- rhodamine 6G lactams-N'- hydrazine hydrate 0.5530g, yield 64%；
2) N- rhodamine 6G lactams-N'- hydrazine hydrate 0.4285g (1mmol) is weighed to be dissolved into 24mL methylene chloride, to Triethylamine 0.1518g (1.5mmol) is added dropwise in above-mentioned solution, mixed solution cooling, solution to be mixed is cooled to -3 DEG C, keeps temperature Degree is stablized, and starts that acryloyl chloride 0.0905g (1mmol) is added dropwise, is added dropwise, is warming up to room temperature and 12h is stirred at room temperature, point It after plate confirms fully reacting, extracts, concentration, pillar layer separation obtains product Compound N- rhodamine 6G lactams-N'- acryloyl Oxygroup hydrazine 0.3625g, yield 75%；
3) distilled water is boiled into deoxygenation, is cooled to room temperature after sealing stand-by.Take 0.3420gN- rhodamine 6G lactams-N'- Acryloxy hydrazine is dissolved in 34.2mL DMSO, and 4.3225g acrylamide is taken to be dissolved in 4.3mL water, and two kinds of solution are mixed, 30min is persistently stirred, until mixing is completely, by 0.0190gN, N '-methylene-bisacrylamide is dissolved in above-mentioned mixed solution, 200 μ L tetramethylethylenediamines are injected into mixed solution again, 0.0238g ammonium persulfate is eventually adding, stirs evenly, solution is turned It moves in glass mold, it is ensured that after not being mixed into bubble, cover glass lid sealing, mold is placed in 51 DEG C of insulating box 5h is kept, Raolical polymerizable is carried out, it is cooling after taking-up to stablize for 24 hours, glass lid is opened, molding hydrogel is slowly taken Out, it is impregnated in dimethyl sulphoxide solution for 24 hours, removes unreacted N- rhodamine 6G lactams-N'- acryloxy hydrazine list Then body impregnates for 24 hours in distilled water, remove unreacted acrylamide monomer.
Embodiment 10
1) it weighs rhodamine 6G 0.9580g (2mmol) and is dissolved in 20mL hot ethanol, after being completely dissolved, hydrazine hydrate is added dropwise 0.7509g (15mmol), is added dropwise, mixed solution return stirring 8h, until solution fluorescence disappears, contact plate confirmation has been reacted Entirely, reaction solution is cooled to room temperature, and precipitating is precipitated, and precipitating is filtered and washed with hot ethanol, and obtained crude product recrystallized from acetonitrile obtains Product N- rhodamine 6G lactams-N'- hydrazine hydrate 0.5530g, yield 64%；
2) N- rhodamine 6G lactams-N'- hydrazine hydrate 0.4285g (1mmol) is weighed to be dissolved into 24mL methylene chloride, to Triethylamine 0.1518g (1.5mmol) is added dropwise in above-mentioned solution, mixed solution cooling, solution to be mixed is cooled to -3 DEG C, keeps temperature Degree is stablized, and starts that acryloyl chloride 0.0905g (1mmol) is added dropwise, is added dropwise, is warming up to room temperature and 12h is stirred at room temperature, point It after plate confirms fully reacting, extracts, concentration, pillar layer separation obtains product Compound N- rhodamine 6G lactams-N'- acryloyl Oxygroup hydrazine 0.3625g, yield 75%；
3) distilled water is boiled into deoxygenation, is cooled to room temperature after sealing for use, takes 0.4185gN- rhodamine 6G lactams-N'- Acryloxy hydrazine is dissolved in 16.7mLDMSO, and 4.1385g acrylamide is taken to be dissolved in 4.1mL water, and two kinds of solution are mixed, 30min is persistently stirred, until mixing is completely, by 0.0186gN, N '-methylene-bisacrylamide is dissolved in above-mentioned mixed solution, 100 μ L tetramethylethylenediamines are injected into mixed solution again, 0.0233g ammonium persulfate is eventually adding, stirs evenly, solution is turned It moves in glass mold, it is ensured that after not being mixed into bubble, cover glass lid sealing, mold is placed in 50 DEG C of insulating box 5h is kept, Raolical polymerizable is carried out, it is cooling after taking-up to stablize for 24 hours, glass lid is opened, molding hydrogel is slowly taken Out, it is impregnated in dimethyl sulphoxide solution for 24 hours, removes unreacted N- rhodamine 6G lactams-N'- acryloxy hydrazine list Then body impregnates for 24 hours in distilled water, remove unreacted acrylamide monomer.
N- rhodamine 6G lactams-N'- acryloxy hydrazine elemental analysis: C31H34N4O4: %C:72.15 (72.18)；%H:6.25 (6.27)；%N:9.97 (9.95)；%O:11.63 (11.60) (being measured value in bracket).
Final products N- rhodamine 6G lactams-N'- acryloxy hydrazine nmr analysis (nuclear magnetic spectrogram is shown in attached drawing 1):1H NMR (400MHz, DMSO) δ 7.65 (d, J=6.6Hz, 1H), 7.42-7.35 (m, 2H), 6.86 (d, J=6.7Hz, 1H), 6.11 (s, 3H), 5.95 (s, 3H), 5.77 (s, 1H), 4.87 (dt, J=10.2,5.6Hz, 3H), 3.65 (t, J=5.7Hz, 2H), 3.0-2.97 (m, 4H), 2.62 (d, J=5.8Hz, 2H), 1.72 (s, 6H), 1.07 (t, J=7.1Hz, 6H).Compound One kind has 30 hydrogen, and the signal peak of the hydrogen in C=C double bond is occurred that at 4.22ppm and 3.15ppm, is occurred at 5.00ppm Triplet is the signal peak of secondary amine (- NH-), and the triplet occurred at 3.13ppm is the signal peak of methylene hydrogen, 1.87ppm and The signal peak of methyl hydrogen is occurred that at 1.21ppm, is gone out at 6.10ppm, 6.27ppm, 6.93ppm, 7.45ppm and 7.76ppm Existing is the signal peak of hydrogen on phenyl ring.Pass through above each hydrogen and their chemical shift and peak area comparative analysis, compound Structure it is consistent with the information on spectrogram, it can thus be appreciated that successfully synthesize compound N-rhodamine 6G lactams-N'- acryloxy Hydrazine.
The purposes of fluorescence probe and its polyalcohol hydrogel of the present invention
Experimental example 1
Fluorescence probe monomer N- rhodamine 6G lactams-N'- acryloxy hydrazine prepared by Example 1 is dissolved in dimethyl Sulfoxide: in distilled water=4:1 mixed solution, it is made 1 × 10-3Mol/L stock solution is taken out 1mL from stock solution and is added to In 100mL measuring bottle, 1mL aluminium ion standard solution (1 × 10 is added-3Mol/L dimethyl sulfoxide: distilled water=4:1 mixing) is used Solution constant volume is made 1.0 × 10-5The compound and metal ion 1:1 mixed solution of mol/L, 1.0 × 10-5Mol/L compound Under visible light with metallic ion mixed liquor, it can be observed that color change illustrates compound N-Luo Dan as shown in Fig. 2 Bright 6G lactams-N'- acryloxy hydrazine can be with visual detection Hg2+。
Experimental example 2
Fluorescence probe monomer N- rhodamine 6G lactams-N'- acryloxy hydrazine prepared by Example 1 is dissolved in dimethyl Sulfoxide: in distilled water=4:1 mixed solution, it is made 1 × 10-3Mol/L stock solution is taken out 1mL from stock solution and is added to In 100mL measuring bottle, 1mL aluminium ion standard solution (1 × 10 is added-3Mol/L dimethyl sulfoxide: distilled water=4:1 mixing) is used Solution constant volume is made 1.0 × 10-5The compound and metal ion 1:1 mixed solution of mol/L, tests compound and metal ion The ultra-violet absorption spectrum of solution (the results are shown in attached figure 3), it has been found that as the Mg that equivalent is added in solution2+, Cu2+, Co2+, Cr2 +, Al3+, Ni2+, Zn2+And Cd2+Afterwards, fluorescence spectrum does not change significantly, only addition Hg2+Afterwards, ultraviolet spectra just produces A degree of enhancing, so synthesized fluorescence probe has preferable selectivity for mercury ion (II).
Experimental example 3
The fluorescence probe monomer N- rhodamine 6G lactams-N'- acryloxy hydrazine by purification process is taken, diformazan is utilized Base sulfoxide: the dissolution of distilled water=4:1 mixed solution, dilution are configured to 1.0 × 10-5The sample solution of mol/L, utilization are ultraviolet Visible spectrophotometer measures the uv absorption spectra of sample, according to the uv-absorption maximum wavelength of the compound measured, benefit With the fluorescence exciting wavelength of F-4600 fluorescent spectrophotometer assay compound, and the fluorescence emission spectrum of compound is measured, so The different metal ions Al of equivalent is separately added into backward solution3+, Ag+, Co2+, Mg2+, Cu2+, Ni2+, Pb2+And Zn2+, measurement In the presence of each metal ion, the fluorescence emission spectrum of fluorescent probe molecule (the results are shown in attached figure 4)；
We have found that the compound is when no metal ion is added, the fluorescence intensity of itself is very weak, so that It is difficult to be observed in figure, but as the Mg that equivalent is added in solution2+, Cu2+, Co2+, Cr2+, Al3+, Ni2+, Zn2+And Cd2 +Afterwards, fluorescence spectrum has a degree of enhancing, and only as addition Hg2+Afterwards, fluorescence spectrum just produces very aobvious The enhancing of work, this feature quickly identify us metal aluminium ion is of great significance, synthesized fluorescence probe for Mercury ion (II) has preferable selectivity.
Experimental example 4
It cannot function as visual sensor by test discovery acrylamide gel and detect any metal ion, but work as N- When rhodamine 6G lactams-N'- acryloxy hydrazine is copolymerized to form hydrogel as monomer and acrylamide, which has Detect Hg2+Ability, as shown in Fig. 5, hydrogel pass through Hg2+Solution becomes pink colour after impregnating, and then uses the EDA of 1mol/L Hydrogel after the discoloration of aqueous solution soaking bind metal ion, can restore original color.

Claims (7)

1. a kind of N- rhodamine 6G lactams-N'- acryloxy hydrazine fluorescence probe polyalcohol hydrogel, it is characterised in that: should Hydrogel is to be copolymerized N- rhodamine 6G lactams-N'- acryloxy hydrazine fluorescence probe and acrylamide, and structural formula is such as Under:
2. fluorescence probe polyalcohol hydrogel as described in claim 1, it is characterised in that: in Material Field or sensor field Application.
3. the method for preparing fluorescence probe polyalcohol hydrogel as described in claim 1, it is characterised in that: specific steps are such as Under:
1) preparation of N- rhodamine 6G lactams-N'- hydrazine hydrate:
Rhodamine 6G is weighed in there-necked flask, dehydrated alcohol is added, after there-necked flask is stirred 30min under 60~80 DEG C of constant temperature, Hydrazine hydrate is added dropwise into solution, the reaction was continued 5~10h is cooled to room temperature, filters, is recrystallized with dehydrated alcohol, it is dried in vacuo, Up to N- rhodamine 6G lactams-N'- hydrazine hydrate；
2) preparation of N- rhodamine 6G lactams-N'- acryloxy hydrazine:
It weighs triethylamine and N- rhodamine 6G lactams-N'- hydrazine hydrate that step 1) obtains is in there-necked flask, dichloromethane is added Alkane weighs acryloyl chloride and is added drop-wise in there-necked flask, and dropwise addition process carries out under -5~0 DEG C of constant temperature, is added dropwise, and is to slowly warm up to Simultaneously 6~12h is stirred at room temperature in room temperature, extraction, and dry water removal, vacuum distillation removes solvent, and pillar layer separation obtains pink colour powder Last shape solid is dried in vacuo up to N- rhodamine 6G lactams-N'- acryloxy hydrazine；
3) preparation of N- rhodamine 6G lactams-N'- acryloxy hydrazide polymer hydrogel:
Distilled water is boiled sealing to be cooled to room temperature to remove the oxygen in water, acrylamide is weighed and is dissolved in distilled water, weigh The N- rhodamine 6G lactams-N'- acryloxy hydrazine that step 2) obtains is dissolved in dimethyl sulfoxide, after two kinds of solution mixing often Stirring is vacuumized under temperature, persistently stirs 30min, until mixing is completely, successively by crosslinking agent, catalyst, initiator is added above-mentioned Mixed solution stirs evenly, and solution is transferred in glass mold, it is ensured that after not being mixed into bubble, glass lid sealing is covered, Water-setting sealing rubber die is placed on to 3~5h of holding in 50~55 DEG C of insulating box, carries out Raolical polymerizable, it is cooling steady after taking-up It is fixed to open glass lid for 24 hours, molding hydrogel is slowly taken out, it impregnates for 24 hours, removes not anti-in dimethyl sulphoxide solution Then the N- rhodamine 6G lactams-N'- acryloxy hydrazine monomer answered impregnates for 24 hours in distilled water, removes unreacted third Acrylamide monomer.
4. the method according to claim 3 for preparing fluorescence probe polyalcohol hydrogel, it is characterised in that: institute in step 1) The molar ratio of the rhodamine 6G and hydrazine hydrate stated is 2:13~2:16；The body of dehydrated alcohol described in step 1) and rhodamine 6G Product molar ratio is 20mL:1~4mmol.
5. the method according to claim 3 for preparing fluorescence probe polyalcohol hydrogel, it is characterised in that: institute in step 2) Molar ratio 1:1~1:2 of the N- rhodamine 6G lactams-N'- hydrazine hydrate and triethylamine stated；Acyl in the N- rhodamine 6G The molar ratio of amine-N'- hydrazine hydrate and acryloyl chloride is 1:1~1:2；The methylene chloride and N- rhodamine 6G lactams-N'- The Molar ratio of hydrazine hydrate is 20~30mL:1mmol.
6. the method according to claim 3 for preparing fluorescence probe polyalcohol hydrogel, it is characterised in that: institute in step 3) Crosslinking agent, initiator, the catalyst stated are respectively N, N '-methylene-bisacrylamide, ammonium persulfate, tetramethylethylenediamine.
7. the method according to claim 3 for preparing fluorescence probe polyalcohol hydrogel, it is characterised in that: institute in step 3) Acrylamide, N- rhodamine 6G lactams-N'- acryloxy hydrazine, crosslinking agent, the initiator stated account for the quality of total solid component Percentage is respectively 89~99%, 0.14~9%, 0.4~0.6%, 0.5~0.7%；The acrylamide and distilled water Mass volume ratio is 1g:1~2mL；The matter of N- rhodamine 6G the lactams-N'- acryloxy hydrazine and dimethyl sulfoxide Amount volume ratio is 0.001g:0.04~1.6mL；The volume mass ratio of the catalyst and initiator be 100 μ L:0.02~ 0.04g。
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