CN107674003A - The double carbamide compounds and its gel of tetrahydroxy modification and the method based on gel detection mercury ion - Google Patents
The double carbamide compounds and its gel of tetrahydroxy modification and the method based on gel detection mercury ion Download PDFInfo
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Abstract
The invention discloses the double carbamide compounds and its gel of a kind of tetrahydroxy modification and the method based on gel detection mercury ion, the structural formula of the compound areR is represented in formulaThe compound and borate can form reversible covalent bonds gel in the in the mixed solvent of dimethyl sulfoxide and water by the hydrogen bond between boron oxygen key and urea groups, using the gel of formation as matrix, gold nano grain is prepared by in-situ reducing gold chloride, the gel and nano-Au composite of gained can be with high sensitivity, high selectivity detection mercury ions, and short, cost is low, simple operation and other advantages with taking.
Description
Technical field
The invention belongs to mercury ion detecting technical field, and in particular to a kind of double carbamide compounds of tetrahydroxy modification, with
And using the reversible covalent bonds molecular gel of compound preparation and the method based on the gel detection mercury ion.
Background technology
Poisonous metal ion has very serious influence to the health and environment of the mankind, therefore, detects Aquatic Ecosystem 2
These pollutants turn into focus of concern in system.Mercury is one of toxic metal ions most harmful in environment, is typically passed through
The approach such as burning of coal, power plant, ocean, volcanic eruption, the burning of gold mine and solid refuse produce.Mercury ion (Hg2+) most stable
Form be to form inorganic mercury, it has the high cell toxicities such as corrosivity and carcinogenicity, and it can make brain, nervous system, kidney
Dirty and internal system is severely damaged, and Long Term Contact inorganic mercury can cause the disease of self immune system.Therefore, to ring
The detection that border and Mercury in Biological Sample ion carry out high sensitivity and high selectivity has extremely important meaning.At present, it is conventional
Detect Hg2+Method mainly have atomic absorption spectrography (AAS) (Atomic absorption spectrometry, AAS), atom is glimmering
Light spectroscopic methodology (Atomic fluorescence spectrometry, AFS), inductively coupled plasma mass spectrometry
(Inductively oupled plasma mass spectrometry, ICPMS) and high performance liquid chromatography (High-
Performance liquid chromatography, HPLC) etc..Although these methods have many good qualities, they are logical
The often expensive instrument and equipment of needs, the preparation process of sample are cumbersome, it is necessary to be separated and be enriched with to sample, so as to need largely
Time.Therefore, a kind of high sensitivity, high selectivity, time-consuming measure Hg short, cost is low are established2+Method turn into grind now
The focus studied carefully.Optical sensor does not need special instrument, can also be to Hg2+Visual retrieval is carried out, causes that people's is extensive
Concern.Nowadays, it is proposed that based on organic chromophores and fluorophor, conjugated polymer, nucleic acid, DNA enzymatic, albumen, film and
The Hg of nano-particle2+Sensor.Although these optical sensors are simpler than conventional method a lot, most sensitivity and
Selectivity is low, and the synthesis step of probe material is numerous and diverse, or the inspection of unsuitable actual sample, its application is received very big limit
System.Therefore, a kind of not only sensitivity of design and selectivity are high, and detection Hg simply, economic, practical2+Method be still
The forward position focus studied at present.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of double carbamide compounds of tetrahydroxy modification, and are based on
The reversible covalent bonds molecular gel of the compound and the method that mercury ion is detected using the gel as matrix.
The structural formula for double carbamide compounds that tetrahydroxy is modified is as follows used by solution above-mentioned technical problem：
R is represented in formula
The preparation method of double carbamide compounds of above-mentioned tetrahydroxy modification is：2- amino -1,3- propane diols is dissolved in methanol
In, the dichloromethane solution of the diisocyanate shown in Formulas I is added dropwise in above-mentioned solution, wherein 2- amino -1,3- the third two
The mol ratio of alcohol and diisocyanate is 2:1；The volume ratio of methanol and dichloromethane is 1:75, stirring at normal temperature is reacted 16 hours,
Filtering, is washed with ethyl acetate, is dried, and obtains double carbamide compounds of tetrahydroxy modification, and specific synthetic route is as follows：
The reversible covalent bonds molecular gel of the present invention is by the double carbamide compounds and borate of above-mentioned tetrahydroxy modification
Formed in the in the mixed solvent of dimethyl sulfoxide and water by the hydrogen bond between reversible boron oxygen key and urea groups, wherein borate is boric acid
Any one in lithium, Boratex, tetrabutyl ammonium borate, described borate be by boric acid and hydroxide reaction generation, its
Described in hydroxide be lithium hydroxide, sodium hydroxide or TBAH.
The preparation method of above-mentioned reversible covalent bonds molecular gel is：The double carbamide compounds and boric acid that tetrahydroxy is modified are complete
Then fully dissolved adds the aqueous solution of hydroxide in dimethyl sulfoxide, be well mixed, and gained mixed liquor normal temperature stands 10~20
Minute, obtain reversible covalent bonds molecular gel.
In the preparation method of above-mentioned reversible covalent bonds molecular gel, double carbamide compounds, the boron of the modification of described tetrahydroxy
Acid, the mol ratio of hydroxide are 1:1:1, and in mixed liquor tetrahydroxy modify double carbamide compounds concentration be 0.018~
0.050g/mL；Described dimethyl sulfoxide and the volume ratio of water are 7:3~9:1.
Method based on reversible covalent bonds molecular gel of the present invention detection mercury ion is made up of following step：
1st, double carbamide compounds and boric acid that tetrahydroxy is modified are dissolved completely in dimethyl sulfoxide, then add and contain hydrogen-oxygen
The aqueous solution of compound and gold chloride, it is well mixed, normal temperature lucifuge stands 10~20 minutes, obtains colourless solidifying containing gold chloride
Glue.
2nd, the ethanol solution of hydrazine hydrate is added on the colorless gel containing gold chloride, lucifuge is put under air-proof condition
Put 12~48 hours, obtain the gel containing nanogold particle.
3rd, gel breaks down, then addition dimethyl sulfoxide are made solution by addition ultra-pure water on the gel containing nanogold particle
Clear, gel and the composite solution of nanogold are obtained, the table of the composite solution is determined using ultraviolet-visible spectrophotometer
Face plasma resonance absorption peak λ0, the mercury ion standard sample solution of various concentrations is added, using spectrophotometry
Meter measure various concentrations mercury ion corresponds to the surface plasma resonance absorbtion peak λ of system, and draws Δ λ and change with ion concentration of mercury
Standard curve, wherein Δ λ=λ0-λ。
4th, the surface of system is corresponded to ultraviolet-visible spectrophotometer measurement testing sample according to the method for above-mentioned steps 3
Plasma resonance absorption peak λ, according to formula Δ λ=λ0- λ, calculate testing sample corresponding to Δ λ, combined standard curve it is linear
Equation high selectivity identification mercury ion and can determine the concentration of mercury ion in testing sample.
In above-mentioned steps 1, the concentration of gold chloride is 0.5~2.0mmol/L in the colorless gel containing gold chloride.
Compared with prior art, the invention has the advantages that：
1st, the allophanamide class compound synthesis step of tetrahydroxy modification of the present invention is simple, and yield is high, and the compound and boric acid
Salt can form reversible covalent bonds gel in the in the mixed solvent of dimethyl sulfoxide and water by the hydrogen bond between boron oxygen key and urea groups, with
The gel of formation is matrix, and gold nano grain is prepared by in-situ reducing gold chloride, and the three-dimensional net structure of the gel can prevent
Nanogold particle is reunited, and obtained nanogold particle stability is good, size uniform, good dispersion, average grain diameter be 20~
30nm, and the compatibility of gel and nanogold particle is preferable, nanogold will not cause very big to plastic speed and plastic situation
Influence.
2nd, the composite solution that reversible covalent bonds gel of the invention and nanogold are formed can realize the highly sensitive of mercury ion
Degree, high selectivity detection, detection it is time-consuming it is short, cost is low, and nanogold particle is not susceptible to reunite in composite solution, stability
Good, the detection to mercury ion is brought great convenience, and high sensitivity and Gao Xuan are carried out to mercury ion in environmental and biological samples
The detection of selecting property has extremely important meaning.Present invention obtains National Natural Science Foundation of China (NSFC) (fund number is 21473110)
Support.
Brief description of the drawings
Fig. 1 is the photo of the reversible covalent bonds molecular gel formed in embodiment 4~12.
Fig. 2 is the stress scans curve of the reversible covalent bonds molecular gel formed in embodiment 7~9.
Fig. 3 is the thixotropic behavior curve of the reversible covalent bonds molecular gel formed in embodiment 7.
Fig. 4 is the thixotropic behavior curve of the reversible covalent bonds molecular gel formed in embodiment 8.
Fig. 5 is the thixotropic behavior curve of the reversible covalent bonds molecular gel formed in embodiment 9.
Fig. 6 is the stress scans curve of the reversible covalent bonds molecular gel formed in embodiment 9,13,14.
Fig. 7 is the stress scans curve of the reversible covalent bonds molecular gel formed in embodiment 9,15,16.
Fig. 8 is the transmission electron microscope picture for the gold grain separated in embodiment 17 in the gel containing nanogold particle.
Fig. 9 is the ultraviolet suction that the reversible covalent bonds molecular gel based on embodiment 8 detects various concentrations mercury ion for matrix
Receive spectrogram.
Figure 10 is the changing value Δ λ of the surface plasma resonance absorbtion peak of composite solution in embodiment 17 with ion concentration of mercury
The standard curve of change.
Figure 11 is double carbamide compounds b of tetrahydroxy modification, the influence of boric acid, sodium hydroxide to mercury ion detecting result.
Figure 12 is the photo of the different metal ions in the method detection environment using embodiment 17.
Embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
The allophanamide class compound a of the following tetrahydroxy modification of preparation structure formula
Take 1.476g (16.20mmol) 2- amino-1,3-propanediols to be dissolved in 2mL methanol, 150mL is contained into 1.524g
The dichloromethane solution of isocyanate group -3, the 3'- dimethyl diphenyls of (8.10mmol) 4,4'- bis- is added dropwise in above-mentioned solution, often
Warm stirring reaction 16 hours, filter and washed with ethyl acetate, normal-temperature vacuum is dried, and obtains the allophanamide class chemical combination of tetrahydroxy modification
Thing a.
Gained compound a passes through1H NMR, FTIR, which are characterized, to be confirmed, specific data are as follows：1H NMR(600MHz,DMSO-d6,
), TMS δ=2.17-2.28 (6H, s, 2-CH3), δ=3.40-3.46；3.49-3.55(8H,m,4-CH2-), δ=3.59-3.66
(2H, m, 2-CH-), δ=4.72-4.76 (4H, t, 4-OH), δ=6.59-6.66 (2H, d, 2-NH-), δ=7.32-7.36
(2H, d, 2-Ph), δ=7.37-7.41 (2H, s, 2-Ph), δ=7.83-7.88 (2H, s, 2-NH-), δ=7.91-7.95 (2H,
d,2-Ph).FTIR(KBr):υ=3312cm-1(O-H), υ=3041cm-1(C-H), υ=2970cm-1(N-H), υ=2883cm-1
(C-H), υ=1639cm-1(C=O), υ=1593cm-1(C=C).
Embodiment 2
Double carbamide compounds b of the following tetrahydroxy modification of preparation structure formula
In the present embodiment, with equimolar 4, the isocyanic acids of 4,4'- bis- in 4'- diphenylmethane diisocyanates alternative embodiment 1
Base -3,3'- dimethyl diphenyl, other steps are same as Example 1, obtain double carbamide compounds b of tetrahydroxy modification.
Gained compound b is passed through1H NMR, FTIR, which are characterized, to be confirmed, specific data are as follows：1H NMR(600MHz,DMSO-d6,
), TMS δ=3.37-3.42；3.45-3.50(8H,m,4-CH2-), δ=3.55-3.61 (2H, m, 2-CH-), δ=3.72-
3.75 (2H, s ,-CH-), δ=4.69-4.73 (4H, t, 4-OH), δ=5.79-6.01 (2H, d, 2-NH-), δ=7.00-7.06
(4H, d, 2-Ph), δ=7.23-7.29 (4H, s, 2-Ph), δ=8.50-8.54 (4H, d, 2-NH-) .FTIR (KBr):υ=
3380cm-1(O-H), υ=3290cm-1(N-H), υ=3100,3031cm-1(C-H), υ=2876cm-1(C-H), υ=1630cm-1(C=O), υ=1572cm-1(C=C).
Embodiment 3
Double carbamide compounds c of the following tetrahydroxy modification of preparation structure formula
In the present embodiment, with isocyanate group -3 of 4,4'- bis- in equimolar Isosorbide-5-Nitrae-phenylene diisocyanate alternative embodiment 1,
3'- dimethyl diphenyls, other steps are same as Example 1, obtain double carbamide compounds c of tetrahydroxy modification.
Gained compound b is passed through1H NMR, FTIR, which are characterized, to be confirmed, specific data are as follows：1H NMR(600MHz,DMSO-d6,
), TMS δ=3.37-3.42；3.46-3.51(8H,m,4-CH2-), δ=3.55-3.61 (2H, m, 2-CH-), δ=4.68-
4.73 (4H, t, 4-OH), δ=5.92-5.96 (2H, d, 2-NH-), δ=7.18-7.22 (4H, s, 2-Ph), δ=8.37-8.43
(2H,s,2-NH-).FTIR(KBr):υ=3312cm-1(O-H), υ=3041cm-1(C-H), υ=2974cm-1(N-H), υ=
2880cm-1(C-H), υ=1639cm-1(C=O), υ=1579cm-1(C=C).
Embodiment 4
The allophanamide class compound a that 0.04g (0.090mmol) tetrahydroxy is modified is dissolved in 344 μ L dimethyl sulfoxides, ultrasound is extremely
Solution is clarified, and then adds the dimethyl sulfoxide solution and 100 μ L 0.022g/mL of 556 μ L 0.01g/mL (0.090mmol) boric acid
(0.090mmol) lithium hydroxide aqueous solution, normal temperature concussion is uniform, stands 15 minutes, you can form opaque reversible covalent bonds
Molecular gel.
Embodiment 5
The allophanamide class compound a that 0.04g (0.090mmol) tetrahydroxy is modified is dissolved in 344 μ L dimethyl sulfoxides, ultrasound is extremely
Solution is clarified, and then adds the dimethyl sulfoxide solution and 100 μ L 0.036g/mL of 556 μ L 0.01g/mL (0.090mmol) boric acid
(0.090mmol) sodium hydrate aqueous solution, normal temperature concussion is uniform, stands 15 minutes, you can form the reversible covalent of water white transparency
Key molecular gel.
Embodiment 6
The allophanamide class compound a that 0.04g (0.090mmol) tetrahydroxy is modified is dissolved in 344 μ L dimethyl sulfoxides, ultrasound is extremely
Solution is clarified, and then adds the dimethyl sulfoxide solution and 100 μ L 0.232g/mL of 556 μ L 0.01g/mL (0.090mmol) boric acid
(0.090mmol) TBAH aqueous solution, normal temperature concussion is uniform, stands 15 minutes, you can is formed opaque reversible
Covalent bond molecular gel.
Embodiment 7
Double carbamide compounds b that 0.04g (0.092mmol) tetrahydroxy is modified are dissolved in 330 μ L dimethyl sulfoxides, ultrasound is extremely
Solution is clarified, and then adds the dimethyl sulfoxide solution and 100 μ L 0.022g/mL of 570 μ L 0.01g/mL (0.092mmol) boric acid
(0.092mmol) lithium hydroxide aqueous solution, normal temperature concussion is uniform, stands 15 minutes, you can form the reversible covalent of water white transparency
Key molecular gel.
Embodiment 8
Double carbamide compounds b that 0.04g (0.092mmol) tetrahydroxy is modified are dissolved in 330 μ L dimethyl sulfoxides, ultrasound is extremely
Solution is clarified, and then adds the dimethyl sulfoxide solution and 100 μ L 0.037g/mL of 570 μ L 0.01g/mL (0.092mmol) boric acid
(0.092mmol) sodium hydrate aqueous solution, normal temperature concussion is uniform, stands 15 minutes, you can form the reversible covalent of water white transparency
Key molecular gel.
Embodiment 9
Double carbamide compounds b that 0.04g (0.092mmol) tetrahydroxy is modified are dissolved in 330 μ L dimethyl sulfoxides, ultrasound is extremely
Solution is clarified, and then adds the dimethyl sulfoxide solution and 100 μ L 0.240g/mL of 570 μ L 0.01g/mL (0.092mmol) boric acid
(0.092mmol) TBAH aqueous solution, normal temperature concussion is uniform, stands 15 minutes, you can is formed translucent reversible
Covalent bond molecular gel.
Embodiment 10
Double carbamide compounds c that 0.04g (0.120mmol) tetrahydroxy is modified are dissolved in 178 μ L dimethyl sulfoxides, ultrasound is extremely
Solution is clarified, and then adds the dimethyl sulfoxide solution and 100 μ L 0.028g/mL of 722 μ L 0.01g/mL (0.120mmol) boric acid
(0.120mmol) lithium hydroxide aqueous solution, normal temperature concussion is uniform, stands 15 minutes, you can form translucent reversible covalent bonds
Molecular gel.
Embodiment 11
Double carbamide compounds c that 0.04g (0.120mmol) tetrahydroxy is modified are dissolved in 178 μ L dimethyl sulfoxides, ultrasound is extremely
Solution is clarified, and then adds the dimethyl sulfoxide solution and 100 μ L 0.048g/mL of 722 μ L 0.01g/mL (0.120mmol) boric acid
(0.120mmol) sodium hydrate aqueous solution, normal temperature concussion is uniform, stands 15 minutes, you can form the reversible covalent of water white transparency
Key molecular gel.
Embodiment 12
Double carbamide compounds c that 0.04g (0.120mmol) tetrahydroxy is modified are dissolved in 178 μ L dimethyl sulfoxides, ultrasound is extremely
Solution is clarified, and then adds the dimethyl sulfoxide solution and 100 μ L 0.303g/mL of 722 μ L 0.01g/mL (0.120mmol) boric acid
(0.120mmol) TBAH aqueous solution, normal temperature concussion is uniform, stands 15 minutes, you can is formed translucent reversible
Covalent bond molecular gel.
Embodiment 13
Double carbamide compounds b that 0.04g (0.092mmol) tetrahydroxy is modified are dissolved in 230 μ L dimethyl sulfoxides, ultrasound is extremely
Solution is clarified, and then adds the dimethyl sulfoxide solution and 200 μ L 0.120g/mL of 570 μ L 0.01g/mL (0.092mmol) boric acid
(0.092mmol) TBAH aqueous solution, normal temperature concussion is uniform, stands 15 minutes, you can is formed transparent reversible common
Valence link molecular gel.
Embodiment 14
Double carbamide compounds b that 0.04g (0.092mmol) tetrahydroxy is modified are dissolved in 130 μ L dimethyl sulfoxides, ultrasound is extremely
Solution is clarified, and then adds the dimethyl sulfoxide solution and 300 μ L 0.080g/mL of 570 μ L 0.01g/mL (0.092mmol) boric acid
(0.092mmol) TBAH aqueous solution, normal temperature concussion is uniform, stands 30 minutes, you can is formed transparent reversible common
Valence link molecular gel.
Embodiment 15
Double carbamide compounds b that 0.036g (0.083mmol) tetrahydroxy is modified are dissolved in 387 μ L dimethyl sulfoxides, ultrasound
Clarified to solution, then add the dimethyl sulfoxide solution and 100 μ L 0.217g/ of 513 μ L 0.01g/mL (0.083mmol) boric acid
ML (0.083mmol) TBAH aqueous solution, normal temperature concussion is uniform, stands 15 minutes, you can is formed transparent reversible
Covalent bond molecular gel.
Embodiment 16
Double carbamide compounds b that 0.045g (0.104mmol) tetrahydroxy is modified are dissolved in 256 μ L dimethyl sulfoxides, ultrasound
Clarified to solution, then add the dimethyl sulfoxide solution and 100 μ L 0.271g/ of 644 μ L 0.01g/mL (0.104mmol) boric acid
ML (0.104mmol) TBAH aqueous solution, normal temperature concussion is uniform, stands 15 minutes, you can formation is translucent can
Inverse covalent bond molecular gel.
The photo for the reversible covalent bonds molecular gel that above-described embodiment 4~12 is formed is as shown in figure 1, inventor have studied salt
The mechanical strength for the reversible covalent bonds molecular gel that effect is formed on embodiment 7~9 and thixotropic influence, as a result see Fig. 2~
5.From Figure 2 it can be seen that in the range of low-shearing force, the storage modulus G ' for the reversible covalent bonds molecular gel that embodiment 7~9 is formed is equal
Higher than loss mould G ", typical soft solid characteristic is shown, the modulus of elasticity and yield stress of three kinds of gels press embodiment 8>It is real
Apply example 7>Embodiment 9 reduces, in addition, from Fig. 2 it can also be seen that when shear stress is higher than yield value, the G ' of three kinds of gels
" numerical value drastically declines, G " illustrates that gel network structure is destroyed and showed under high shear forces obviously higher than G ' with G
Obvious liquid behavior.From the point of view of the test result of Fig. 3~5, the gel formed in embodiment 9 shows the shearing thixotroping of uniqueness
Property, system destroying and recovering " gel-sol " phase transformation almost completely reversibility in 10 effect cyclic processes, maintains molecule
The original viscoplasticity of gel.And the gel formed in embodiment 7 and 8 their " gel-sol " invertibity shows decline
Trend, this may be attributed under high shear force, and two gels, which can become, to fragmentate.
Inventor further study solvent effect in embodiment 9,13,14 to the reversible covalent bonds molecular gel of formation
The influence of rheologic behavio(u)r, is as a result shown in Fig. 6.As can be drawn from Figure 6, the volume ratio of dimethyl sulfoxide and water is respectively 9:1 (implements
Example 9), 8:2 (embodiments 13), 7:When 3 (embodiment 14), the yield value of gel be followed successively by 1778.0Pa, 891.2Pa,
630.9Pa, and " significant change does not occur for the G ' of gel and G.The result shows：The minor alteration of solvent will cause gel mechanics
The significant changes of intensity.
The mechanical strength and viscoplasticity of gel and the concentration of gelling agent are closely related, therefore inventor is investigated embodiment
9th, influence of the concentration effect to the rheologic behavio(u)r of the reversible covalent bonds molecular gel of formation in 15,16, is as a result shown in Fig. 7.By Fig. 7
(implement it can be seen that double carbamide compounds b of tetrahydroxy modification concentration is respectively 0.036g/mL (embodiment 15), 0.040g/mL
Example 9) and during 0.045g/mL (embodiment 16), the yield value of gained gel is followed successively by 223.8Pa, 777.0Pa, 6010.2Pa, table
The mechanical strength of bright gel strengthens with the rise of gelling agent concentration.
Embodiment 17
Reversible covalent bonds molecular gel based on embodiment 8 is that matrix detects mercury ion
1st, double carbamide compounds b that 0.04g (0.092mmol) tetrahydroxy is modified are dissolved in 330 μ L dimethyl sulfoxides, ultrasound
Clarified to solution, dimethyl sulfoxide solution, the 100 μ L for then adding 570 μ L 0.1g/mL (0.092mmol) boric acid contain 3.7mg
(0.092mmol) sodium hydroxide and 1.26mg (1.5 × 10-3Mmol) the aqueous solution of gold chloride, it is well mixed, normal temperature lucifuge is stood
15 minutes, obtain the colorless gel containing gold chloride.
2nd, the absolute ethyl alcohol that the hydrazine hydrate that 250 μ L volumetric concentrations are 88% is added on the colorless gel containing gold chloride is molten
Liquid, bottleneck is sealed, room temperature avoid light place 24 hours, obtain the purple gel containing nanogold particle.As seen from Figure 8, gained
The average grain diameter of gold grain is 20~30nm in gel.
3rd, the ethanol solution of the remaining hydrazine hydrate in gel top containing nanogold particle is outwelled, then added
For 150 μ L ultra-pure waters by gel breaks down, adding 350 μ L dimethyl sulfoxides makes solution clear, obtains answering for gel and nanogold
Solution is closed, the surface plasma resonance absorbtion peak λ of the composite solution is determined using ultraviolet-visible spectrophotometer0, then add respectively
Enter mercuric chloride solution of the concentration for 1,2,3 ... 18,19,20 μm of ol/L, determined using ultraviolet-visible spectrophotometer different dense
Degree mercury ion corresponds to the surface plasma resonance absorbtion peak λ of system, as a result sees Fig. 9, and draw what Δ λ changed with ion concentration of mercury
Standard curve, wherein Δ λ=λ0- λ, as a result see Figure 10.
As seen from Figure 9, as blue shift, absorption intensity is presented in the increase of ion concentration of mercury, surface plasma resonance absorbtion peak
It is increased slightly, isobestic point is observed at 556nm.As seen from Figure 10, when mercury ion in the range of low concentration (0~6 μ
When mol/L), Δ λ and ion concentration of mercury are linear, and linear equation is：Y=0.07143+2X, wherein Y represent Δ λ, X
Ion concentration of mercury, its coefficient R=0.9977.The detection that this method is calculated according to S/N=3 is limited to 0.2 μm of ol/L.
4th, the surface of system is corresponded to ultraviolet-visible spectrophotometer measurement testing sample according to the method for above-mentioned steps 3
Plasma resonance absorption peak λ, according to formula Δ λ=λ0- λ, calculate testing sample corresponding to Δ λ, combined standard curve it is linear
Equation high selectivity identification mercury ion and can determine the concentration of mercury ion in testing sample.
Inventor is according to double carbamide compounds b, boric acid, the hydrogen-oxygen for shown in table 1, having investigated tetrahydroxy modification in embodiment 17
Change influence of the sodium to mercury ion (6 μm of ol/L) testing result, experimental result is shown in Figure 11.
The control experiment of table 1
Note："-" represents to be free of the material in the cell of place in table, and " √ " represents to contain the material in the cell of place.
Experimental result shows, in the method for present invention detection mercury ion, double carbamide compounds b of tetrahydroxy modification, boric acid,
These three materials of sodium hydroxide are indispensable, show that reversible covalent bonds molecular gel of the present invention is played the part of in the detection process of mercury ion
Important role is drilled.
In order to prove beneficial effects of the present invention, inventor is using the method for embodiment 17 respectively to other gold in environment
Belong to ion for example iron ion, chromium ion, magnesium ion, cobalt ions, barium ions, nickel ion, calcium ion, cadmium ion, lead ion, zinc from
Son, the aqueous solution of copper ion are detected.Test result indicates that even if by iron ion, chromium ion, magnesium ion, cobalt ions, barium from
Son, nickel ion, calcium ion, cadmium ion, lead ion, zinc ion, the concentration of copper ion increase to 100 μm of ol/L, the color of system
Any change does not occur yet, and when ion concentration of mercury is 6 μm of ol/L, the color of system is changed into red from original purple at once
(see Figure 12), illustrate that this method can realize the selective enumeration method of mercury ion.
Claims (8)
1. a kind of double carbamide compounds of tetrahydroxy modification, it is characterised in that the structural formula of the compound is as follows：
R is represented in formula
A kind of 2. reversible covalent bonds molecular gel, it is characterised in that：The gel is modified double as the tetrahydroxy described in claim 1
Carbamide compounds and borate pass through the hydrogen bond shape between reversible boron oxygen key and urea groups in the in the mixed solvent of dimethyl sulfoxide and water
Into wherein described borate is any one in lithium borate, Boratex, tetrabutyl ammonium borate.
3. reversible covalent bonds molecular gel according to claim 2, it is characterised in that：Described borate be by boric acid and
Hydroxide reaction generation, wherein described hydroxide is lithium hydroxide, sodium hydroxide or TBAH.
4. reversible covalent bonds molecular gel according to claim 3, it is characterised in that：The allophanamide class that tetrahydroxy is modified
Compound and boric acid are dissolved completely in dimethyl sulfoxide, then add the aqueous solution of hydroxide, are well mixed, gained mixed liquor is normal
Temperature stands 10~20 minutes, obtains reversible covalent bonds molecular gel.
5. reversible covalent bonds molecular gel according to claim 4, it is characterised in that：The allophanamide of described tetrahydroxy modification
Class compound, boric acid, the mol ratio of hydroxide are 1:1:1, and double carbamide compounds that tetrahydroxy is modified in mixed liquor is dense
Spend for 0.018~0.050g/mL.
6. reversible covalent bonds molecular gel according to claim 4, it is characterised in that：Described dimethyl sulfoxide and the body of water
Product is than being 7:3~9:1.
A kind of 7. method of the reversible covalent bonds molecular gel detection mercury ion based on described in claim 2, it is characterised in that：
(1) double carbamide compounds and boric acid that tetrahydroxy is modified are dissolved completely in dimethyl sulfoxide, then add and contain hydroxide
The aqueous solution of thing and gold chloride, it is well mixed, normal temperature lucifuge stands 10~20 minutes, obtains the colorless gel containing gold chloride；
(2) ethanol solution of hydrazine hydrate, the avoid light place under air-proof condition are added on the colorless gel containing gold chloride
12~48 hours, obtain the gel containing nanogold particle；
(3) gel breaks down, then addition dimethyl sulfoxide are made solution clear by addition ultra-pure water on the gel containing nanogold particle
It is clear bright, gel and the composite solution of nanogold are obtained, the surface of the composite solution is determined using ultraviolet-visible spectrophotometer
Plasma resonance absorption peak λ0, the mercury ion standard sample solution of various concentrations is added, using ultraviolet-visible spectrophotometer
Measure various concentrations mercury ion corresponds to the surface plasma resonance absorbtion peak λ of system, and draws what Δ λ changed with ion concentration of mercury
Standard curve, wherein Δ λ=λ0-λ；
(4) surface of system etc. is corresponded to ultraviolet-visible spectrophotometer measurement testing sample according to the method for above-mentioned steps (3)
Ion resonance absworption peak λ, according to formula Δ λ=λ0- λ, calculate Δ λ corresponding to testing sample, the linear side of combined standard curve
Journey high selectivity identification mercury ion and can determine the concentration of mercury ion in testing sample.
8. the method for detection mercury ion according to claim 7, it is characterised in that：It is described to contain chlorine gold in step (1)
The concentration of gold chloride is 0.5~2.0mmol/L in the colorless gel of acid.
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| CN110483734A (en) * | 2019-08-27 | 2019-11-22 | 黄河三角洲京博化工研究院有限公司 | A kind of high softening temperature, high impact toughness and polyurethane optical resin material of yellowing-resistant and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110483734A (en) * | 2019-08-27 | 2019-11-22 | 黄河三角洲京博化工研究院有限公司 | A kind of high softening temperature, high impact toughness and polyurethane optical resin material of yellowing-resistant and preparation method thereof |
| CN110483734B (en) * | 2019-08-27 | 2021-05-28 | 山东益丰生化环保股份有限公司 | Polyurethane optical resin material with high softening temperature, high impact toughness and yellowing resistance and preparation method thereof |
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