CN114163466A - Rapid detection Cr3+Preparation method and application of rhodamine B boron cluster derivative ultraviolet probe - Google Patents
Rapid detection Cr3+Preparation method and application of rhodamine B boron cluster derivative ultraviolet probe Download PDFInfo
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- CN114163466A CN114163466A CN202111475804.3A CN202111475804A CN114163466A CN 114163466 A CN114163466 A CN 114163466A CN 202111475804 A CN202111475804 A CN 202111475804A CN 114163466 A CN114163466 A CN 114163466A
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- rhodamine
- boron cluster
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 title claims abstract description 86
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 70
- 229940043267 rhodamine b Drugs 0.000 title claims abstract description 68
- 239000000523 sample Substances 0.000 title claims abstract description 66
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001514 detection method Methods 0.000 title claims description 41
- 238000010992 reflux Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 15
- ACMNJGTVINIZKR-UHFFFAOYSA-N boron;1,4-dioxane Chemical compound [B].C1COCCO1 ACMNJGTVINIZKR-UHFFFAOYSA-N 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 14
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 41
- 239000002904 solvent Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002835 absorbance Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000003068 molecular probe Substances 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 3
- 238000004847 absorption spectroscopy Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 16
- 229910021645 metal ion Inorganic materials 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000012488 sample solution Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- -1 amine derivative of rhodamine Chemical class 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000825 ultraviolet detection Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 206010003210 Arteriosclerosis Diseases 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 208000011775 arteriosclerosis disease Diseases 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a method for rapidly detecting Cr3+The preparation method and the application of the ultraviolet probe of the rhodamine B boron cluster derivative comprise the following steps: firstly, mixing 1, 4-dioxane, TBA boron cluster and sodium fluoborate, adding the mixture into a flask, adding 1, 4-dioxane solution of hydrogen chloride into the flask, and heating and refluxing to prepare 1, 4-dioxane-boron cluster; secondly, dissolving rhodamine B and diethylenetriamine in ethanol, and heating and refluxing to prepare a rhodamine derivative RB-I; and thirdly, dissolving the 1, 4-dioxane-boron cluster, RB-I and sodium carbonate in acetonitrile, heating and refluxing to prepare the yellow-green solid rhodamine ultraviolet probe. The preparation method is simple, the prepared rhodamine B boron cluster derivative ultraviolet probe has high sensitivity and good anti-interference performance,has good water solubility, and can be used for Cr3+And (4) rapidly detecting ions.
Description
Technical Field
The invention discloses a method for rapidly detecting Cr3+Preparation method of rhodamine B boron cluster derivative ultraviolet probe and rapid detection of Cr3+Belonging to the field of ultraviolet probe material synthesis and detection methods.
Background
Chromium (III) (Cr)3+) The chromium (III) deficiency can cause disorder of sugar and fat metabolism systems, and cause arteriosclerosis and other diseases; however, the excessive content of chromium (III) can cause serious physiological pathological changes of human bodies. At present, due to the wide application of chromium and compounds thereof, the chromium and compounds thereof finally enter the natural environment in an ion form through the discharge of waste gas, waste liquid and the like, and the finding of a simple, convenient and quick analysis and detection has important significance.
The main methods for detecting chromium ions at present are: high performance liquid chromatography, mass spectrometry, atomic absorption spectrometry, atomic emission spectrometry, etc., but such methods generally require pretreatment when used for analytical detection of complex samples, and in addition, such detection instruments are high in equipment cost and poor in selectivity. Fluorescence is also commonly used for the detection of metal ions, but the following disadvantages still exist: poor selectivity, large influence by interference of solvents or anions, and the like.
In the application of rapid detection of metal ions, besides the detection method, the method can also be used for detecting the metal ions by an ultraviolet spectroscopy, and the manufacturing cost of an ultraviolet spectroscopy analyzer is cheaper than that of other analyzers, but the ultraviolet spectroscopy analyzer is easily interfered by other metal ions in the practical application process, so the application of the ultraviolet spectroscopy analyzer is limited to a certain extent.
Disclosure of Invention
The invention aims to provide a method for rapidly detecting Cr3+The method for preparing the ultraviolet probe of the rhodamine B boron cluster derivative and the prepared ultraviolet probe of the rhodamine B boron cluster derivative solve the problem of Cr3+The detection conditions are harsh, and the ions are easily interfered in the detection processThe technical problem is that the synthesis route is simple, the production cost is low, and the ultraviolet spectrophotometer is used for realizing Cr3+The rapid detection of (2).
The invention also aims to provide the ultraviolet probe for rapidly detecting Cr from the rhodamine B boron cluster derivative3+The application in detection adopts ultraviolet detection, and compared with other detection instruments, the ultraviolet detection instrument has the following advantages: fluorescence, mass spectrum, atomic absorption and the like, so that the cost of an analysis instrument is lower; the anti-interference of other metal ions is strong, and the detection can be well carried out even in the presence of other metal ions.
In order to further achieve the purpose, the invention adopts the following technical scheme:
rapid detection Cr3+The ultraviolet probe of the rhodamine B boron cluster derivative has the following structural formula:
rapid detection Cr3+The preparation method of the rhodamine B boron cluster derivative ultraviolet probe comprises the following steps:
step (1): dispersing TBA boron cluster and sodium fluoborate in 1, 4-dioxane at room temperature, rapidly adding 1, 4-dioxane solution of hydrogen chloride under stirring, heating and refluxing, filtering, drying, recrystallizing and drying to obtain white acicular solid product 1, 4-dioxane-boron cluster;
step (2): completely dissolving rhodamine B in ethanol, stirring at room temperature, adding diethylenetriamine, heating for refluxing, filtering insoluble substances after reaction, concentrating the filtrate, recrystallizing and drying to obtain the rhodamine B derivative;
and (3): dissolving 1, 4-dioxane boron cluster, rhodamine B derivative and sodium carbonate in acetonitrile, heating and refluxing, concentrating the filtrate after the reaction is finished, recrystallizing and purifying, filtering and drying.
In the step (1): the molar ratio of TBA boron cluster, sodium fluoborate and hydrogen chloride is (0.2-0.4) to 1: 2;
in the step (1): 1,4 of hydrogen chlorideThe concentration of hydrogen chloride in the dioxane solution is 3-5 mol.L-1The heating reflux temperature is 100-110 ℃;
in the step (1): heating and refluxing for 2-4 hours;
in the step (1): the solvent used for recrystallization is a mixed solution of acetone, ethanol and water, wherein the solution comprises acetone, ethanol and water in a volume ratio of 2:3 (0.2-1).
In the step (2): the molar ratio of rhodamine B to diethylenetriamine is as follows: 1:(5-10).
In the step (2): heating and refluxing for 15-25h at 84 deg.C;
in the step (2): the solvent used for recrystallization is a mixed solution of dichloromethane and methanol, wherein the solvent composition is dichloromethane to methanol (10-20) to 1 in volume ratio.
In the step (3): 1, 4-dioxane boron cluster, rhodamine B derivative and sodium carbonate, wherein the molar ratio of the sodium carbonate is as follows: 1:(1-1.5):(1.5-3).
In the step (3): heating and refluxing at 80 deg.C for 7-10 h;
in the step (3): the solvent used for recrystallization is a mixed solution of dichloromethane and methanol, wherein the solvent composition is dichloromethane to methanol (10-20) to 1 in volume ratio.
The rhodamine B boron cluster derivative is a new synthesized compound in the synthesis process, has no report before, and is particularly used for detecting heavy metal ions;
1. under the condition of detecting the rhodamine B boron cluster derivative, the solution to be detected does not need to be prepared into an acid solution, so that the operation is simpler;
2. the rhodamine B boron cluster derivative is detected by ultraviolet, and compared with other detection instruments, the rhodamine B boron cluster derivative has the following advantages that: fluorescence, mass spectrum, atomic absorption and the like, so that the cost of an analysis instrument is lower;
3. the ultraviolet probe of the rhodamine B boron cluster derivative has strong anti-interference performance of other metal ions, and can well detect the rhodamine B boron cluster derivative even in the presence of other metal ions;
4. the invention relates to a screwThe danmin B boron cluster derivative has high detection limit of an ultraviolet probe, and can be used for detecting Cr with lower concentration3+。
The ultraviolet probe for rapidly detecting Cr from rhodamine B boron cluster derivative3+Use in detection, comprising: preparing a rhodamine B boron cluster derivative probe into a probe solution by using methanol, and then detecting Cr in the solution3+Adding probe solution into the solution, measuring the volume with solvent, detecting the absorbance at 560nm by ultraviolet-visible absorption spectrometry, and measuring the absorbance according to the relative ultraviolet intensity and Cr3+Determining the corresponding relation of the concentration to determine Cr in the solvent to be detected3+The content of (a).
The concentration of the ultraviolet molecular probe is 0.06 mmol.L-1-1.2mmol·L-1；
Cr to be detected3+Has a concentration of 0.06 mmol.L-1-1.18mmol·L-1；
Deionized water is adopted as the probe solution;
the solvent for constant volume adopts methanol/water with the volume ratio of 1: 1;
Cr3+the detection limit of concentration is 5.32 multiplied by 10-5mol·L-1。
Compared with the prior art, the invention has the advantages that: the rhodamine B boron cluster derivative ultraviolet probe has simple synthetic route and low production cost; when detecting pollutants, the method has low requirement on detection environment and Cr3+The identification operation is simple and practical, the sensitivity is high, the anti-interference capability is strong, and the accurate determination can be realized by using an ultraviolet spectrophotometer; in addition, the ultraviolet probe containing Cr to be detected for the rhodamine B boron cluster derivative3+Has obvious color change and can be used for Cr3+The boron cluster has no obvious toxicity in naked eye detection, and has good application prospect.
Drawings
FIG. 1 is an IR spectrum of RB-I;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum (solvent: DMSO) of RB-I;
FIG. 3 is an infrared spectrum of an ultraviolet probe of a rhodamine B boron cluster derivative;
FIG. 4 is an ESI-MS diagram of a rhodamine B boron cluster derivative, and an insertional diagram is a divalent anion structural formula of the rhodamine B boron cluster derivative after ultraviolet probe molecule ionization;
FIG. 5 is an ultraviolet-visible absorption spectrum of rhodamine B boron cluster derivative ultraviolet probe methanol solution and different metal ion aqueous solutions after isovolumic mixing; the inset shows the prepared sample solution, wherein the contained metal ions are as follows from left to right: blank, K+、Mg2+、Ba2+、Mn2+、Co2+、Zn2+、Ni2+、Cd2+、Pb2+、Cu2+、Hg2+、Fe2+、Cr3+、Fe3+；
FIG. 6 shows rhodamine B boron cluster derivative ultraviolet probes and Cr with different concentrations3+A normalization curve of ultraviolet-visible absorbance after equal-volume mixing of aqueous solutions;
FIG. 7 shows ultraviolet probe-Cr of B-B cluster derivative of rhodamine3+Ultraviolet-visible absorption titration spectrogram.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for rapidly detecting Cr3+The ultraviolet probe of the rhodamine B boron cluster derivative has a structural formula as follows:
rapid detection Cr3+The preparation method of the rhodamine B boron cluster derivative ultraviolet probe comprises the following steps:
step (1): dispersing TBA boron cluster and sodium fluoborate in 1, 4-dioxane at room temperature, rapidly adding 1, 4-dioxane solution of hydrogen chloride while stirring, and heating and refluxing. Filtering, drying, recrystallizing and drying the product to obtain a white acicular solid product which is a 1, 4-dioxane-boron cluster.
Step (2): and completely dissolving rhodamine B in ethanol, stirring at room temperature, adding diethylenetriamine, heating for refluxing, filtering insoluble substances after reaction, concentrating the filtrate, recrystallizing and drying to obtain the rhodamine B derivative.
And (3): dissolving 1, 4-dioxane boron cluster, rhodamine B derivative and sodium carbonate in acetonitrile, heating and refluxing, concentrating the filtrate after the reaction is finished, recrystallizing and purifying, filtering and drying.
In the step (1): the molar ratio of TBA boron cluster, sodium fluoborate and hydrogen chloride is (0.2-0.4) to 1: 2;
in the step (1): the concentration of hydrogen chloride in the 1, 4-dioxane solution of hydrogen chloride is 3-5 mol.L-1The heating reflux temperature is 100-110 ℃;
in the step (1): heating and refluxing for 2-4 hours;
in the step (1): the solvent used for recrystallization is a mixed solution of acetone, ethanol and water, wherein the solution comprises acetone, ethanol and water in a volume ratio of 2:3 (0.2-1).
In the step (2): the molar ratio of rhodamine B to diethylenetriamine is as follows: 1, (5-10);
in the step (2): heating and refluxing for 15-25h at 84 deg.C;
in the step (2): the solvent used for recrystallization is a mixed solution of dichloromethane and methanol, wherein the solvent composition is dichloromethane to methanol (10-20) to 1 in volume ratio.
In the step (3): 1, 4-dioxane boron cluster, RB-I (rhodamine B derivative), and the molar ratio of sodium carbonate is as follows: 1, (1-1.5) and (1.5-3);
in the step (3): heating and refluxing at 80 deg.C for 7-10 h;
in the step (3): the solvent used for recrystallization is a mixed solution of dichloromethane and methanol, wherein the solvent composition is dichloromethane to methanol (10-20) to 1 in volume ratio.
Detection shows that the infrared spectrum of the intermediate product rhodamine B derivative is shown in figure 1.
The detection shows that the nuclear magnetic spectrum of the intermediate rhodamine B derivative is shown in figure 2.
Detection shows that the infrared spectrogram of the ultraviolet probe related to the rhodamine B boron cluster derivative is shown in figure 3.
Detection shows that an ESI-MS diagram of the ultraviolet probe of the rhodamine B boron cluster derivative is shown in figure 4.
By comparing the infrared detailed diagrams of the rhodamine B derivative and the rhodamine B boron cluster derivative, the synthesized probe is 2470-2480 cm higher than that of the intermediate rhodamine B boron cluster derivative-1A new strong peak appears, the strong peak is the stretching vibration peak of the B-H bond, and in addition, the infrared spectrum is 3430cm-1、～2960cm-1、～1680cm-1、1510～1611cm-1、～1116cm-1The peaks are respectively an N-H stretching vibration absorption peak, a saturated C-H stretching vibration absorption peak, a lactam C ═ O stretching vibration absorption peak, an aromatic ring framework absorption peak and a C-O-C stretching vibration absorption peak combined nuclear magnetic resonance hydrogen spectrum (figure 2), the chemical shift and the integral area of H corresponding to the molecular structure can be in one-to-one correspondence, and the successful combination of the 1, 4-dioxane-boron cluster and the amine derivative of rhodamine is preliminarily demonstrated.
Further performing mass spectrometry on the rhodamine B boron cluster derivative (fig. 4), wherein the relative molecular mass of the rhodamine B boron cluster derivative is 1021, the anion part of the rhodamine B boron cluster derivative is charged with two charges, the relative molecular mass is 756, and the peak corresponding to the position where m/z is 756.9 in the figure completely accords with the combination of the divalent anion and one hydrogen ion, which indicates that the rhodamine B boron cluster derivative is successfully synthesized.
The foregoing for Cr3+The use method of the ultraviolet probe for detecting the rhodamine B boron cluster derivative is carried out according to the following steps:
will be used for Cr3+Dissolving the detected rhodamine B boron cluster derivative ultraviolet probe into methanol to obtain an ultraviolet molecular probe solution, wherein the concentration of the ultraviolet molecular probe in the ultraviolet molecular probe solution is 0.06 mmol.L-1-1.2mmol·L-1；
Secondly, taking the ultraviolet molecular probe solution, adding a sample to be detected into the ultraviolet molecular probe solution, and uniformly mixing to obtain a sample solution;
(III) testing the ultraviolet molecular probe solution with an ultraviolet spectrophotometer, the absorbance of the ultraviolet molecular probe solution at the wavelength of 560nm is obviously enhanced, and the sample solution is rapidly converted into bright rose-red from nearly colorless, as shown in figure 5.
In FIG. 5, ultraviolet-visible absorption spectra of rhodamine B boron cluster derivative ultraviolet probe methanol solution and different metal ion aqueous solutions after isovolumic mixing; the inset shows the prepared sample solution, wherein the contained metal ions are as follows from left to right: blank, K+、Mg2+、Ba2+、Mn2+、Co2+、Zn2+、Ni2+、Cd2+、Pb2+、Cu2+、Hg2+、Fe2+、Cr3+、Fe3+。
The foregoing for Cr3+Ultraviolet probe Cr for detecting rhodamine B boron cluster derivative3+Has an extremely high detection limit of 5.32X 10-5mol·L-1It is shown that the detectable metal ion concentration is low and should be in a wider range, and the test results are shown in fig. 6.
Example 1
Synthesis of 1, 4-dioxane-boron cluster
70mL of 1, 4-dioxane, 1.25g of TBA boron cluster and 1.1g of sodium fluoroborate are added into a 250mL three-neck flask, and 5mL of 4 mol. L is rapidly added while stirring-1Hydrogen chloride in 1, 4-dioxane and refluxing at 105 deg.c for 2 hr. After cooling, the mixture was filtered through a funnel, and the filtrate was distilled under reduced pressure and concentrated to dryness as much as possible. Dissolving the obtained light yellow viscous liquid in a mixed solution of 20mL of acetone, 30mL of ethanol and 10mL of deionized water, carrying out rotary evaporation on the solution until the volume of the residual liquid is about 25mL, placing the solution in an ice water bath for cooling to obtain a white crystalline precipitate, carrying out suction filtration, and placing the obtained solid in a vacuum drying oven for drying, wherein the yield is 59.9%. The synthetic route of the 1, 4-dioxane-boron cluster is shown as follows:
synthesis of rhodamine derivatives
A100 mL three-necked flask was charged with 4.8g (10mmol) of rhodamine B and 40mL of ethanol, stirred at room temperature for half an hour, then charged with 10mL of diethylenetriamine, and refluxed at 84 ℃ for 20 hours. After the reaction was stopped, insoluble matter was filtered off, the filtrate was concentrated under reduced pressure, 30mL of deionized water was added, extraction was performed twice with 50mL of dichloromethane, the organic phases were combined, washed twice with 20mL of saturated sodium chloride solution, and dried for 8 hours with an appropriate amount of anhydrous sodium sulfate. After concentrating the resulting solution under reduced pressure, the reaction mixture was concentrated with a volume ratio of dichloromethane: the product was recrystallized from methanol 20:1 and dried under vacuum at 60 ℃ for 6 h, 46.8% yield. The synthetic route of the rhodamine derivative is shown as follows:
synthesis of rhodamine B boron cluster derivative ultraviolet probe
In a 100mL three-necked flask, 0.4716g (1mmol) of 1, 4-dioxane-boron cluster, 0.6749g (1.2mmol) of rhodamine B derivative, 0.2120g (2mmol) of sodium carbonate solid and 50mL of acetonitrile were added, and the mixture was heated under reflux at 80 ℃ for 8 hours. After the reaction was stopped, the reaction mixture was filtered, and the filtrate was purified with dichloromethane: and (3) recrystallizing with methanol at the ratio of 20:1, and drying the product at 60 ℃ in vacuum for 6 hours to obtain the product, namely the rhodamine B boron cluster derivative ultraviolet probe, wherein the yield is 73.5%. The synthetic route of the rhodamine B boron cluster derivative ultraviolet probe is shown as follows:
example 2: solution preparation
Preparing a solution: reagents used in the experiment are analytically pure and are not further processed; the water used was secondary high purity water.
1mmol·L-1Preparation of Probe stock solution
Weighing 0.25mmol of rhodamine B boron cluster derivative ultraviolet probe, namely 255.3mg in a beaker, fully dissolving the ultraviolet probe by using a small amount of methanol, completely transferring the ultraviolet probe into a 250mL volumetric flask, and then adding methanol to the constant volume.
10mmol·L-1Preparation of metal ion stock solution
Weighing 0.1mmol of potassium chloride, magnesium sulfate, barium chloride, manganese sulfate, cobalt nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, cadmium chloride, lead acetate trihydrate, copper chloride dihydrate, mercury chloride, ferrous chloride tetrahydrate, chromium nitrate nonahydrate and ferric chloride solid (the system acidity is maintained in the dissolving process, the system acidity is adjusted by HCl), and respectively dissolving the solid in 10mL of deionized water to obtain the solution with the concentration of 10 mmol.L-1An aqueous solution of 14 different metal ions.
Example 3: cr (chromium) component3+Determination of detection Limit
2mL of the solution with the concentration of 1 mmol.L is taken-1The rhodamine B boron cluster derivative ultraviolet probe methanol solution has the concentration of 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500 mu mol.L with 2mL-1Cr concentration3+The metal ion solution is mixed evenly. The prepared sample was tested for absorbance at 560nm after scanning the baseline with 50% by volume aqueous methanol. The cuvette used for the test had a width of 1cm and the volume of sample added to the cuvette was about 3 mL. The results are shown in FIG. 7, which is dependent on Cr3+The ion concentration is increased, the absorbance of the solution at the 560nm absorption wavelength is regularly increased, and under the action of the rhodamine B boron cluster derivative ultraviolet probe, Cr can be well indicated3+The ion concentration changes.
Example 4: spectral analysis
Adding 10 mmol. L-1K+、Mg2+、Ba2+、Mn2+、Co2+、Zn2+、Ni2+、Cd2+、Pb2+、Cu2+、Hg2+、Fe2+、Cr3+、Fe3+The solution was diluted to 0.1 mmol. L-1Then, respectively taking 2mL of the sample, respectively and uniformly mixing the sample with 2mL of rhodamine B boron cluster derivative ultraviolet probe stock solution, and preparing another group of control samples, namely taking 2mL of the rhodamine B boron cluster derivative ultraviolet probeThe needle stock was mixed with 2mL of deionized water, respectively. The volume ratio of the components is 1:1, testing the prepared sample in a wavelength range of 450-650nm after scanning a base line by using a methanol aqueous solution, wherein the width of a cuvette used for testing is 1cm, and the volume of the sample added into the cuvette is about 3mL, and the result shows that the absorbance of the rhodamine B boron cluster derivative ultraviolet probe at 560nm is remarkably increased, so that the sample solution is rapidly converted into bright rose-red from nearly colorless, and the sample solution has good visual property.
The foregoing lists merely illustrate specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments but that many variations are possible. The insubstantial changes of the invention, such as insubstantial changes of the structure of the boron cluster derivative, insubstantial changes of the structure of the rhodamine derivative, etc., are considered to be within the protection scope of the invention.
Claims (10)
1. Rapid detection Cr3+The ultraviolet probe of the rhodamine B boron cluster derivative is characterized in that the structural formula is as follows:
2. rapid detection Cr3+The preparation method of the rhodamine B boron cluster derivative ultraviolet probe is characterized by comprising the following steps:
step (1): dispersing TBA boron cluster and sodium fluoborate in 1, 4-dioxane at room temperature, rapidly adding 1, 4-dioxane solution of hydrogen chloride under stirring, heating and refluxing, filtering, drying, recrystallizing and drying to obtain white acicular solid product 1, 4-dioxane-boron cluster;
step (2): completely dissolving rhodamine B in ethanol, stirring at room temperature, adding diethylenetriamine, heating for refluxing, filtering insoluble substances after reaction, concentrating the filtrate, recrystallizing and drying to obtain the rhodamine B derivative;
and (3): dissolving 1, 4-dioxane boron cluster, rhodamine B derivative and sodium carbonate in acetonitrile, heating and refluxing, concentrating the filtrate after the reaction is finished, recrystallizing, filtering and drying to obtain the rhodamine B derivative.
3. The rapid detection of Cr as claimed in claim 23+The preparation method of the rhodamine B boron cluster derivative ultraviolet probe is characterized in that in the step (1): the molar ratio of TBA boron cluster, sodium fluoborate and hydrogen chloride is (0.2-0.4) to 1: 2;
the concentration of hydrogen chloride in the 1, 4-dioxane solution of hydrogen chloride is 3-5 mol.L-1；
The heating reflux temperature is 100-110 ℃, and the heating reflux time is 2-4 hours.
4. The rapid detection of Cr as claimed in claim 23+The preparation method of the rhodamine B boron cluster derivative ultraviolet probe is characterized in that in the step (1): the solvent used for recrystallization is a mixed solution of acetone, ethanol and water, wherein the solution comprises acetone, ethanol and water in a volume ratio of 2:3 (0.2-1).
5. The rapid detection of Cr as claimed in claim 23+The preparation method of the rhodamine B boron cluster derivative ultraviolet probe is characterized in that in the step (2): the molar ratio of rhodamine B to diethylenetriamine is as follows: 1, (5-10);
the heating reflux time is 15-25h, and the temperature is 84 ℃.
6. The rapid detection of Cr as claimed in claim 23+The preparation method of the rhodamine B boron cluster derivative ultraviolet probe is characterized in that in the step (2): the solvent used for recrystallization is a mixed solution of dichloromethane and methanol, wherein the solvent composition is dichloromethane to methanol (10-20) to 1 in volume ratio.
7. The rapid detection of Cr as claimed in claim 23+The preparation method of the rhodamine B boron cluster derivative ultraviolet probe is characterized in that in the step (3): 1, 4-dioxane boron cluster, rhodamine B derivative and sodium carbonate, wherein the molar ratio of the sodium carbonate is as follows: 1:(1-1.5):(1.5-3)；
The heating reflux temperature is 80 ℃, and the time is 7-10 h.
8. The rapid detection of Cr as claimed in claim 23+The preparation method of the rhodamine B boron cluster derivative ultraviolet probe is characterized in that in the step (3): the solvent used for recrystallization is a mixed solution of dichloromethane and methanol, wherein the solvent composition is dichloromethane to methanol (10-20) to 1 in volume ratio.
9. The ultraviolet probe for rapidly detecting Cr from rhodamine B boron cluster derivative as claimed in claim 13+The application in detection is characterized in that a rhodamine B boron cluster derivative probe is prepared into a probe solution by using methanol, and then Cr to be detected3+Adding probe solution into the solution, measuring the volume with solvent, detecting the absorbance at 560nm by ultraviolet-visible absorption spectrometry, and measuring the absorbance according to the relative ultraviolet intensity and Cr3+Determining the corresponding relation of the concentration to determine Cr in the solvent to be detected3+The content of (a).
10. The use of rhodamine B boron cluster derivatives as in claim 9 in uv probes, wherein the concentration of said uv molecular probes is 0.06 mmol-L-1-1.2mmol·L-1；
Cr to be detected3+Has a concentration of 0.06 mmol.L-1-1.18mmol·L-1；
Deionized water is adopted as the probe solution;
the solvent for constant volume adopts methanol/water with the volume ratio of 1: 1;
Cr3+the detection limit of concentration is 5.32 multiplied by 10-5mol·L-1。
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