CN107056667B - A kind of mercury ion probe and its preparation method and application - Google Patents
A kind of mercury ion probe and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/04—Derivatives of thiourea
- C07C335/16—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The invention discloses a kind of mercury ion probe GC/HD/AuNS/PT+MB and preparation method thereof, the organic functional molecular phenylthiourea PT with mercury ion specific recognition and combination is synthesized first, and it is modified on electrode, using the method for deposited Au and nano gold spherical amplified signal, mercury ion probe GC/HD/AuNS/PT+MB is prepared.The present invention also provides application of the mercury ion probe GC/HD/AuNS/PT+MB in detection mercury ion, mercury ion probe of the invention has high sensitivity, high accuracy, it is highly selective, the advantages of low detection limits, and can be realized while detecting mercury ion, achieve the purpose that efficiently to remove mercury ion, be with a wide range of applications.
Description
Technical field
The invention belongs to organic molecule analysis and detection technology, be related to it is a kind of for mercury in specific recognition and detection water sample from
The small organic molecule mercury ion probe of son.
Background technique
The mercury ion heavy metal ion toxic as a kind of pair of environment and organism, not only to the digestive system of the mankind, mind
There is serious damage through system, liver and other organs, it is especially even more serious to pregnant woman and fetus damage, it is even very low
Concentration will also result in serious damage.Environmental Protection Agency (EPA) and world health organization (WHO) regulation, the energy in drinking water
The ion concentration of mercury detected is necessarily less than 2ppb.However, the real time measure low concentration in complex environment and biosystem
Mercury ion still has huge challenge, and in addition to this mercury pollution is also very serious, and in order to handle mercury pollution, people are not only needed
Develop the mercury ion of new material detection lower concentration, it is often more important that it can quickly be removed from solution.So development one
Kind method, the detection for environment and Mercury In Food ion that energy is highly sensitive, highly selective, and reach removal mercury ion simultaneously
Purpose, will have very important significance.
Detecting the method for mercury ion in the prior art includes fluorescence, atomic emissions method, ICP-MS etc., but these methods
All have detection limit higher, detection range is narrow, cannot reach the requirement of EPA and WHO；Sample pre-treatments step is more numerous
Trivial, testing cost is higher；Sensitivity is low, and mercury ion is the limitations such as cannot be removed to from solution.It can remove in the prior art
The method of mercury ion, but it is long there are the response time, to be unable to reach the purpose for truly removing mercury ion.In addition, also
There is no any document report while detecting low concentration mercury ion, it can be removed from solution.
Summary of the invention
The purpose of the present invention is for the defects in the prior art, design and synthesize a kind of high sensitivity, highly selective inspection
The organic functional molecular phenylthiourea (Pheny thiourea, PT) of mercury ion is surveyed, and is applied to electrochemical field for the first time, preparation
Mercury ion probe GC/HD/AuNS/PT+MB, the mercury ion probe GC/HD/AuNS/PT+MB can examine mercury ion
It surveys, has the characteristics that high sensitivity, high specific, high accuracy etc.；And the mercury ion probe GC/HD/AuNS/PT+MB tool
There is the features such as high stability, favorable reproducibility.
The invention proposes a kind of organic functional molecular phenylthioureas, shown in structure such as formula (A):
The invention proposes the preparation methods of mercury ion probe GC/HD/AuNS/PT+MB a kind of
(1) synthesis of organic functional molecular phenylthiourea (Pheny thiourea, PT)
In organic solvent, ethylenediamine, phenyl isothiocyanate carry out addition reaction, obtain organic functional molecular phenylthiourea
(Phenythiourea,PT)；Shown in reaction process such as reaction equation (1):
In step (1), the organic solvent is selected from ethyl alcohol, methanol, toluene；It preferably, is ethyl alcohol.
In step (1), the ethylenediamine, phenyl isothiocyanate molar ratio be 10:1~2；It preferably, is 10:1.
In step (1), the temperature of the addition reaction is 0~30 DEG C；It preferably, is 25 DEG C of room temperature.
In step (1), the time of the addition reaction is 3h~8h；It preferably, is room temperature 5h.
In step (1), it is preferable that first ethylenediamine is dissolved in organic solution, forms mixed solution 1；Then by different sulphur
Phenyl-cyanate is dissolved in ethanol solution, forms mixed solution 2；Finally, the mixing that mixed solution 2 is added dropwise to ice bath is molten
In liquid 1.
In step (1), the organic functional molecular PT of preparation can be specifically bound with mercury ion, can further modify electricity
On extremely, it is used to prepare the stable mercury ion probe of performance.
(2) synthesis of nano gold spherical
In a solvent, HAuCl4Reduction reaction is carried out with sodium citrate, obtains nano gold spherical.
In step (2), the solvent is selected from aqueous solution.
In step (2), the HAuCl4, sodium citrate molar ratio be 1:2~4；It preferably, is 1:3.88.
In step (2), the temperature of the reduction reaction is 10 DEG C~30 DEG C；It preferably, is 25 DEG C of room temperature.
In step (2), the time of the reduction reaction is 10min~25min；It preferably, is room temperature 15min.
In step (2), it is preferable that first by HAuCl4With oil bath heating, to boiling, then, reducing agent is added in solution thereto
Sodium citrate solution quickly stirs, and waits solution colours to become to stop heating after claret from bright orange, oil bath is removed, in room temperature
It persistently stirs 15 minutes down, obtains the nano gold spherical, be then saved in refrigerator；Low temperature can be such that nano gold spherical solution saves more
For a long time.
(3) preparation of mercury ion probe GC/HD/AuNS/PT+MB
The mercury ion of preparation is made by optimizing modification condition using the method for deposited Au and nano gold spherical amplified signal
For probe GC/HD/AuNS/PT+MB to mercury ion detecting high sensitivity, the range of linearity is wide.
(3.1) glass-carbon electrode is immersed into HAuCl4In solution, current-time curvel method is selected, is deposited under -0.2V current potential,
Obtain GC/Au electrode；
(3.2) GC/Au electrode is immersed into 1,6- ethanthiol 12h, obtains GC/HD electrode；
(3.3) GC/HD electrode is immersed in 12h in the nano gold spherical solution of step (2) synthesis, obtains GC/HD/AuNS electricity
Pole；
(3.4) GC/HD/AuNS electrode is immersed in PT solution, and EDC and NHS is added thereto as catalyst, obtained
GC/HD/AuNS/PT electrode；
(3.5) GC/HD/AuNS/PT electrode is immersed in HS-DNA-MB (MB=Methylene Blue methylenum careuleum) solution
12h obtains mercury ion probe GC/HD/AuNS/PT+MB.
In step (3.1), the time of the deposition is 120s-200s；It preferably, is 180s.
In step (3.1), the HAuCl4The concentration of solution is 5mmol/L-20mmol/L；It preferably, is 5mmol/L.
In step (3.1), sodium citrate is by HAuCl4It is reduced to nano gold spherical.
In step (3.2), first 1,6- ethanthiol is diluted with ethyl alcohol, the volume ratio of 1, the 6- ethanthiol, ethyl alcohol
For 1:100 to 1:200；It preferably, is 1:100.
In step (3.2), since there are two sulfydryls for 1,6- ethanthiol, the sulfydryl and gold in 1,6- ethanthiol are utilized
Between strong chemical bond (Au-S) interaction, realize one end for being connected with nano gold spherical of 1,6- ethanthiol one end and be deposited on electricity
Nanogold particle in pole surface is connected.
In step (3.2), the time of the immersion is 2-5 hours；Preferably, it is 3 hours.
In step (3.3), the concentration of the nano gold spherical is 1mmol/L-9mmol/L；It preferably, is 9mmol/L.
In step (3.3), the effect of the nano gold spherical is to improve detection sensitivity.
In step (3.3), the time of the immersion is 8h-16h；It preferably, is 12h.
In step (3.4), the concentration of the PT solution is 10mmol/L-30mmol/；It preferably, is 20mmol/L.
In step (3.4), the dosage of the EDC and NHS are 0.5mg and 0.25mg.
In step (3.4), the effect of the PT solution is that the S atom of PT intramolecular can be specific in conjunction with mercury ion,
It is the basis that the present invention realizes mercury ion detecting；Secondly, containing-NH in PT molecule2, can be with the nanometer of reduction of sodium citrate
- the COOH on gold goal surface occurs condensation reaction and generates amido bond, and therefore, PT molecule can be connected further to electrode surface.
In step (3.4), the time of the immersion is 12h-18h；It preferably, is 16h.
In step (3.5), the concentration of the HS-DNA-MB solution is 10mmol/L-50mmol；It preferably, is 30mmol/
L。
In step (3.5), the effect of the HS-DNA-MB solution is to be connected to electrode surface, as interior reference, Ke Yiti
The mercury ion probe GC/HD/AuNS/PT+MB accuracy that the high present invention is finally prepared.
In step (3.5), the time of the immersion is 8h-16h；It preferably, is 12h.
In a specific embodiment, the preparation method of mercury ion probe GC/HD/AuNS/PT+MB of the present invention is specifically wrapped
Include following steps:
(1) synthesis of organic functional molecular Pheny thiourea (PT)
0.5mol ethylenediamine is dissolved in 30mL ethanol solution, the 0.05mol being then dissolved in 30mL ethyl alcohol is different
Thiocyanic acid phenyl ester solution is added dropwise in the ethylenediamine solution of ice bath, and 5 hours are then stirred at room temperature, and filtering obtains
White solid product.
(2) synthesis of nano gold spherical
Synthesis nano gold spherical before all glasswares used will be impregnated using chloroazotic acid, with secondary water clean drying to
With.1mM HAuCl is added into the round-bottomed flask of a 250mL4Solution 100mL, with oil bath heating to boiling, then, Xiang Qi
The middle sodium citrate solution that 10mL 38.8mM is added, is quickly stirred, and solution colours is waited to become to stop adding after claret from bright orange
Heat removes oil bath, is continuously stirred at room temperature 15 minutes, is saved in refrigerator.
(3) electrode modification process
First with 0.1 and 0.05 μm of Al2O3Polishing glassy carbon electrode surface, then the ultrasonic irrigation in acetone and water, uses nitrogen
Drying.Then glass-carbon electrode is electrochemically immersed into 5mM HAuCl4- 0.2V in solution (Ag/AgCl makees reference electrode)
180s is deposited, GC/Au is obtained, Au/GC electrode is immersed in 50mM 1,6- ethanthiol (1,6-hexanedithiol) 12h,
Extra 1,6- ethanthiol is washed off with ethyl alcohol later, then is dried up electrode surface with nitrogen, obtains GC/HD electrode.Then
GC/HD electrode is immersed in 12h in the nano gold spherical solution of above-mentioned synthesis, obtains GC/HD/AuNS electrode, then by GC/HD/
AuNS electrode is put into 1mM PT solution and EDC and NHS is added thereto as catalyst, obtains GC/HD/AuNS/PT electrode
12h in 25 μM of HS-DNA-MB solution is immersed, mercury ion probe GC/HD/AuNS/PT+MB is obtained.
The invention also provides the organic functional molecular phenylthiourea (Pheny that method as described above is prepared
thiourea,PT)。
The invention also provides organic functional molecular phenylthioureas as described above (Pheny thiourea, PT) to prepare mercury
Application in ion probe GC/HD/AuNS/PT+MB.
The invention also provides the mercury ion probe GC/HD/AuNS/PT+MB that method as described above is prepared, and are one
Kind Ratio-type electrochemical sensor, can be using the detection and efficient removal of mercury ion in water (for mercury/Trace Hg height
99%) efficiency removal, removal efficiency are up to, the Ratio-type performance of electrochemical sensors is stablized, can be highly selective, highly sensitive
Degree detection Trace Hg, while can be avoided other metal ions, such as Cu2+、Ag+、Fe2+Deng interference, have well selectivity.
The mercury ion probe GC/HD/AuNS/PT being prepared the invention also provides method as described above detection mercury from
Application in son；Wherein, the mercury ion probe GC/HD/AuNS/PT can be used in including but not limited to water sample, biological sample etc.
Mercury ion detection.
(preferably, being 25 DEG C of room temperature), mercury ion probe GC/HD/AuNS/ of the present invention in 15 DEG C~28 DEG C temperature ranges
PT+MB and Hg2+It reacts 3~10 minutes (being preferably, 7 minutes), the PT and Hg when applying current potential2+It aoxidizes
Reduction reaction generates C9H11N13, it is [M+H] that the present invention, which carries out mass spectral characteristi to product,+162.1027. illustrating to have obtained really pre-
The product C thought9H11N13(as shown in Figure 4).
Electrode is measured in the Hg of various concentration by square wave voltammetry2+Generated current value, current signal exist in solution
Hg2+Current value be denoted as Jp, interior reference generate current value be denoted as JpR, pass through (Jp/JpR) value and Hg2+Concentration relationship can
To obtain its range of linearity, and then Hg can be detected according to this linear relationship2+Concentration；Corresponding E=1.266C+
0.064, wherein E Jp/JpR, C are the concentration of mercury ion, and unit is μM.
The invention also provides the mercury ion probe GC/HD/AuNS/PT+MB that method as described above is prepared is being removed
Application in mercury ion；Wherein, the GC/HD/AuNS/PT electrode can be used in including but not limited to water sample, biological sample etc.
The removal of mercury ion.
The invention also provides a kind of methods that electrochemical method detected and went simultaneously mercury ion in water removal, investigate mercury ion
Probe GC/HD/AuNS/PT+MB draws working curve to the electrochemical response signals of different ion concentration of mercury, is examined with this
Survey mercury ion.Specific step is as follows:
Using platinum filament as to electrode, Ag/AgCl electrode is as reference electrode, the mercury ion being prepared with the present invention
Probe GC/HD/AuNS/PT+MB records the letter of the electric current under different ion concentration of mercury as working electrode, using square wave voltammetry
Number, obtain the linear pass between the ratio and ion concentration of mercury of current value caused by current value and MB caused by mercury ion
System.Corresponding linear relationship equation are as follows: E=1.266C+0.064, wherein E Jp/Jp R, C is the concentration of mercury ion, unit
It is μM.
While measuring ion concentration of mercury, different time current signal is recorded, the removal efficiency of mercury ion is calculated.Such as this hair
In a bright specific embodiment, the current signal that the different time that measurement mercury ion initial concentration is 1 μM measures, such as Figure 10 institute
Show；Wherein, a is 0 minute, and b is 1 minute, and c is 2 minutes, and d is 3 minutes, and e is 7 minutes.
In the specific embodiment of the present invention, it is applied to three using 832 electrochemical workstation of Shanghai Chen Hua CHI
Electrode system, wherein platinum filament is used as to electrode, and Ag/AgCl electrode is as reference electrode, mercury ion probe GC/ that (3) are modified
HD/AuNS/PT+MB is as working electrode, using square wave voltammetry in 0.05M-0.1M (preferably, being 0.1M) PBS (pH=
7.4) electrochemical window from 0.8V sweeps to -0.4V in solution, the current signal being recorded under different ion concentration of mercury.Obtain mercury ion institute
Linear relationship between the ratio and ion concentration of mercury of current value caused by the current value and MB of generation.Take 300 μ L 0.1M
PBS (pH=7.4), mercury ion initial concentration are 1 μM, the removal efficiency of record different time mercury ion, 1 minute, 2 minutes, 3 points
Clock, 7 minutes removal efficiency are respectively 18%, 67%, 89%, 99%.
In a specific embodiment, Huangpu River is detected using mercury ion probe GC/HD/AuNS/PT+MB of the invention
The ion concentration of mercury of water and tap water takes 5mL water sample first by Water of Huangpu River spline filter, adjusts pH=7.4, then uses square wave
Voltammetry measured size of current after 7 minutes, and obtaining ion concentration of mercury is 2.63 ± 0.01ppb.Same method takes 5mL originally
Water sample adjusts pH=7.4, then uses square wave voltammetry, measures size of current after 7 minutes, and obtaining ion concentration of mercury is 0.09
±0.01ppb。
The beneficial effects of the present invention are (1) present invention design synthesis and characterization can be with mercury ion specific recognitions simultaneously
Organic functional molecular phenylthiourea PT, the PT in conjunction with mercury ion have high sensitivity, high precision for detecting mercury ion
Property, highly selective feature, and for the first time be applied to electrochemical field, modify on glass-carbon electrode, using deposited Au with
The method of nano gold spherical amplified signal, by optimizing modification condition, ingenious building mercury ion probe GC/HD/AuNS/PT+MB (ratio
Rate type electrochemical sensor).The preparation method of mercury ion probe GC/HD/AuNS/PT+MB of the invention is simple, at low cost, sample
Product are without complicated pre-treatment.(2) the mercury ion probe GC/HD/AuNS/PT+MB linear detection range being prepared is wide,
For 1nM~1.3 μM, high sensitivity, down to 0.12nM (0.024ppb), (this numerical value is far below Environmental Protection Agency to detection limit
(EPA) and 2ppb as defined in world health organization (WHO))；Interior reference HS-DNA-MB's is advantageously selected for reduction evaluated error,
So that mercury ion probe GC/HD/AuNS/PT+MB accuracy with higher, measures modified electrode not by square wave voltammetry
With the Hg of concentration2+Generated current value in solution, current signal is in Hg2+Current value be denoted as Jp, in the generation of interior reference
Current value is denoted as Jp R, pass through (Jp/Jp R) value and Hg2+Its available range of linearity of concentration relationship, and then can be according to this line
Sexual intercourse detects Hg2+Concentration；Ratio-type electrochemical sensor of the present invention can be avoided other metal ions such as Cu2+、Ag+、
Fe2+Deng interference, have well selectivity.(3) with traditional detection method such as inductively coupled plasma mass spectrometry (ICP-
MS it) is compared discovery, mercury ion probe GC/HD/AuNS/PT+MB sensitivity of the present invention is higher, detects speed faster, equipment
Simply, at low cost, and it is easy to implement real-time online detection.(4) mercury ion probe GC/HD/AuNS/PT+MB of the present invention can be used
In detection trace amount mercury ion, and it can be realized the efficient removal reached while accurately detection mercury ion to mercury, in 7 minutes
The efficiency of removal mercury ion is up to 99%, it is therefore not necessary to further be separated to mercury ion.Therefore, using mercury of the present invention
Ion probe GC/HD/AuNS/PT+MB can highly selective, highly sensitive, high accuracy inspection using electrochemical probe method
Mercury ion in water is surveyed, the inspection particularly suitable for the detection and removal of mercury ion in water sample (such as lake water), biological sample, to environment heavy metal
It surveys and removal is of great significance.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance phenogram of PT prepared by embodiment 1.
Fig. 2 is nano gold spherical transmission electron microscope picture prepared by embodiment 1.
Fig. 3 is the electron scanning electron microscope of deposition gold prepared by embodiment 1.
Fig. 4 PT and Hg2+The mass spectrogram of reaction product.
Fig. 5 is SWV response signal graph in the presence of no mercury ion, wherein a GC/Au, bGC/HD, c GC/HD/
AuNS, d GC/HD/AuNS/PT；And SWV of mercury ion probe GC/HD/AuNS/PT+MB in the presence of mercury ion responds letter
Number curve (e).
Fig. 6 is that different ion concentration of mercury are added in mercury ion probe GC/HD/AuNS/PT+MB in 0.1M PBS solution
SWV responds variation diagram, and (a 0, b 1nM, c 10nM, d are 0.1 μM, and e is 0.5 μM, and f is 1 μM, and g is 1.3 μM, and h is 1.7 μ
M)。
Fig. 7 is the line between the ratio and ion concentration of mercury of current value caused by current value caused by mercury ion and MB
Sexual intercourse (1nM~1.9 μM).
Fig. 8 is that SWV signal becomes after the SWV signal response diagram (a) and 7min in 0.1M PBS solution containing 1.0 μM of mercury ions
Change figure (b).
Fig. 9 is the SWV signal response diagram (a) of Huangpu River water sample and SWV signal response diagram (b) after 7min in embodiment 1.
Figure 10 is that mercury ion probe GC/HD/AuNS/PT+MB measurement initial concentration prepared by the embodiment of the present invention 1 is 1 μM
Mercury ion when, the corresponding SWV current responsing signal figure of different time, wherein a be 0 minute, b be 1 minute, c be 2 minutes, d
It is 3 minutes, e is 7 minutes.
Figure 11 is current signal of two kinds of different mercury ion probes in 1 μM of mercury ion solution；Wherein, a is unmodified receives
The mercury ion probe (GC/HD/PT+MB) of meter Jin Qiu, b are mercury ion probe (GC/HD/AuNS/ prepared by the embodiment of the present invention 1
PT+MB)。
Figure 12 is the selectivity experiment of mercury ion probe (GC/HD/AuNS/PT+MB) prepared by embodiment 1.
Specific embodiment
In conjunction with following specific embodiments and attached drawing, the present invention is described in further detail.Implement process of the invention,
Condition, experimental method etc. are among the general principles and common general knowledge in the art, this hair in addition to what is specifically mentioned below
It is bright that there are no special restrictions to content.
The preparation of 1 mercury ion probe GC/HD/AuNS/PT+MB of embodiment
First with 0.1 and 0.05 μm of Al2O3Powder polishing glassy carbon electrode surface, then the ultrasonic irrigation in acetone and water, uses nitrogen
Air-blowing is dry.Then glass-carbon electrode is electrochemically immersed into 5mM HAuCl4In -0.2V, (Ag/AgCl makees reference electricity in solution
Pole) deposition 180s, GC/Au is obtained, Au/GC electrode is immersed in 50mM 1,6- ethanthiol (1,6-hexanedithiol)
Extra 1,6- ethanthiol is washed off with ethyl alcohol later, then is dried up electrode surface with nitrogen by 12h, obtains GC/HD electrode.
Then GC/HD electrode is immersed in 12h in the nano gold spherical solution of above-mentioned synthesis, obtains GC/HD/AuNS electrode, then by GC/
HD/AuNS electrode is put into 1mM PT solution and EDC and NHS is added thereto as catalyst, obtains GC/HD/AuNS/PT electricity
12h in 25 μM of HS-DNA-MB solution is immersed in pole, obtains mercury ion probe GC/HD/AuNS/PT+MB.
Wherein, the transmission electron microscope picture of the nano gold spherical of preparation is as shown in Figure 2.As seen from Figure 2, the partial size of nano gold spherical
It is uniform, 12 ran of average out to, the mercury ion probe GC/HD/ that the homogeneity of nanogold particle finally prepares the present invention
The performance of AuNS/PT+MB has great influence, and nanogold particle is too big or too small be unable to reach improves mercury ion probe GC/HD/
The sensitivity of AuNS/PT+MB and stability and the effect for reducing detection limit, as inventor attempts with golden 38 face bodies and gold nano
Stick, and the not up to present invention ideal high sensitivity, low detection limits, the effect of high stability.
Fig. 3 is the electron scanning electron microscope for the deposition gold that sedimentation time selects obtain for 180 seconds, and the partial size of nano particle is resonable
Between 30~150 nanometers thought.Sedimentation time is too short or too long, not within the scope of 120s-200s when, be all unable to get suitable grain
The nanogold of diameter, therefore the mercury ion probe GC/HD/AuNS/PT+MB that will lead to preparation is unable to reach highly sensitive, high precision
Property, the effect of low detection limits.
Measurement and removal of the 2 probe GC/HD/AuNS/PT+MB of embodiment to mercury ion
The mercury ion probe GC/HD/AuNS/PT+MB that the present invention is prepared is lied prostrate as working electrode using square wave
Peace method records the current signal under different ion concentration of mercury, obtains current value caused by current value caused by mercury ion and MB
Ratio and ion concentration of mercury between linear relationship.
Corresponding linear relationship equation are as follows: E=1.266C+0.064.
Different time current signal is recorded simultaneously, calculates the removal efficiency of mercury ion.Figure 10 is the preparation of the embodiment of the present invention 1
Mercury ion probe GC/HD/AuNS/PT+MB measurement initial concentration when being 1 μM of mercury ion, the corresponding SWV electric current of different time
Response signal figure, wherein a is 0 minute, and b is 1 minute, and c is 2 minutes, and d is 3 minutes, and e is 7 minutes.
PT and Hg2+It reacts, the PT and Hg when applying current potential2+Redox reaction occurs and generates C9H11N13, this
It is [M+H] that invention, which carries out mass spectral characteristi to product,+162.1027. the product C that explanation is envisioned really9H11N13(Fig. 4).
The detection and its removal of the ion concentration of mercury of 3 Huangpu River water sample of embodiment
(1) electrochemical method detects mercury ion
Using mercury ion probe GC/HD/AuNS/PT+MB as working electrode, using square wave voltammetry in 0.1M PBS (pH
=7.4) current potential from 0.8V sweeps to -0.4V in solution, the current signal being recorded under different ion concentration of mercury.Obtain mercury ion institute
Linear relationship between the ratio and ion concentration of mercury of current value caused by the current value and MB of generation；E=1.266C+
0.064, wherein E Jp/Jp R, C is ion concentration of mercury, and unit is μM.
(2) it detects the ion concentration of mercury of Huangpu River water sample and removes it
First by Water of Huangpu River spline filter, 5mL water sample is taken, adjusts pH=7.4, square wave voltammetry is then used, is surveyed after 7 minutes
Constant current size obtains ion concentration of mercury 2.67ppb (Fig. 9 a).This root electrode is then taken out, is surveyed with another new working electrode
Out in water sample remaining mercury ion concentration 0.41ppb (Fig. 9 b).According to a, the current value of b curve obtains mercury by linear equation
Ion concentration.
The detection and its removal of ion concentration of mercury in 4 tap water of embodiment
(1) electrochemical method detects mercury ion
Using mercury ion probe GC/HD/AuNS/PT+MB as working electrode, using square wave voltammetry in 0.1M PBS (pH
=7.4) -0.4V is swept to from 0.8V in solution, the current signal being recorded under different ion concentration of mercury.It obtains produced by mercury ion
Current value and MB caused by current value ratio and ion concentration of mercury between linear relationship.E=1.266C+0.064,
In, E Jp/Jp R, C is ion concentration of mercury, and unit is μM.
(2) ion concentration of mercury of tap water is detected
It takes tap water 5mL to filter, adjusts pH=7.4, then use square wave voltammetry, size of current, band are measured after 7 minutes
Enter linear equation and obtains ion concentration of mercury.
5 sensitivity determination of embodiment
Mercury ion probe (mercury ion probe GC/HD/AuNS/PT+MB) and unmodified nanometer prepared by the embodiment of the present invention 1
The comparison of the mercury ion probe (GC/HD/PT+MB) of gold goal.
As shown in figure 11, a is the mercury ion probe (GC/HD/PT+MB) of unmodified nano gold spherical in 1 μM of mercury ion solution
In current signal, b is electricity of the mercury ion probe prepared by the present invention (GC/HD/AuNS/PT+MB) in 1 μM of mercury ion solution
Flow signal.By calculating, compared with the mercury ion probe (GC/HD/PT+MB) of unmodified nano gold spherical, the present invention modifies nanometer
The mercury ion probe GC/HD/AuNS/PT+MB detection sensitivity of gold goal improves nearly 5.7 times, and (sensitivity of a is 0.22A cm-2M-1, the sensitivity of b is 1.25A cm-2M-1).Therefore, mercury ion probe (GC/HD/AuNS/PT+MB) of the present invention can be applied to
Detect the mercury ion of lower concentration.
6 interference--free experiments of embodiment
Anti-interference measurement is carried out to mercury ion probe GC/HD/AuNS/PT+MB of the present invention using CHI electrochemical workstation,
As shown in figure 12, to Hg2+Other interfering ions (being 1 μM) is added in (10nM) solution, comprising: Co2+, Zn2+, K+, Na+, Mg2 +, Ca2+, Ag+, Ni2+, Mn2+, Cd2+, Cu2+, Fe3+And Fe2+, caused current variation value indicates by black histogram；To packet
Hg is added in solution (being 1 μM) containing these interfering ions2+Current variation value caused by (10nM) solution is by twill column
Figure indicates；As shown in Figure 12, other metal ions are for Hg2+Measurement interference be lower than 2.0%, can be ignored.As a result table
It is bright, Hg of the present invention2+Probe GC/HD/AuNS/PT+MB is for Hg2+With very high selectivity.
Embodiment 7 is compared with ICP-MS measurement result
Detected value is compared with ICP-MS, according to t (a=0.1) method of inspection, the measurement of measured value of the invention and ICP-MS
Value is consistent.
The Comparative result that the probe of the present invention of table 1 detects the detection of water sample and ICP-MS
Protection content of the invention is not limited to above embodiments.Without departing from the spirit and scope of the invention, originally
Field technical staff it is conceivable that variation and advantage be all included in the present invention, and with appended claims be protect
Protect range.
Claims (9)
1. a kind of preparation method of mercury ion probe GC/HD/AuNS/PT+MB
(1) synthesis of organic functional molecular phenylthiourea Pheny thiourea, PT
In organic solvent, ethylenediamine, phenyl isothiocyanate carry out addition reaction, obtain organic functional molecular phenylthiourea
Pheny thiourea,PT；Shown in reaction process such as reaction equation (1):
(2) synthesis of nano gold spherical
In a solvent, HAuCl4Reduction reaction is carried out with sodium citrate, obtains nano gold spherical；
(3) preparation of mercury ion probe GC/HD/AuNS/PT+MB
(3.1) glass-carbon electrode is immersed into HAuCl4In solution, current-time curvel method is selected, deposits, obtains under -0.2V current potential
GC/Au electrode；
(3.2) GC/Au electrode is immersed into 1,6- ethanthiol 12h, obtains GC/HD electrode；
(3.3) GC/HD electrode is immersed in 12h in the nano gold spherical solution of step (2) synthesis, obtains GC/HD/AuNS electrode；
(3.4) GC/HD/AuNS electrode is immersed in PT solution, and EDC and NHS is added thereto as catalyst, obtain GC/
HD/AuNS/PT electrode；
(3.5) GC/HD/AuNS/PT electrode is immersed into 12h in HS-DNA-MB solution, obtains mercury ion probe GC/HD/AuNS/
PT+MB, wherein the MB=Methylene Blue methylenum careuleum.
2. the method as described in claim 1, which is characterized in that in step (1), the ethylenediamine, phenyl isothiocyanate rub
You are than being 10:1~2；In step (1), the temperature of the addition reaction is 0~30 DEG C；In step (2), the HAuCl4, lemon
The molar ratio of sour sodium is 1:2~4.
3. the method as described in claim 1, which is characterized in that in step (3.1), the time of the deposition is 120s-200s；
In step (3.1), the HAuCl4The concentration of solution is 5mmol/L-20mmol/L；In step (3.2), the time of the immersion
It is 2-5 hours；In step (3.3), the concentration of the nano gold spherical is 1mmol/L-9mmol/L；In step (3.3), the leaching
The time entered is 8h-16h；In step (3.4), the concentration of the PT solution is 10mmol/L-30mmol/；In step (3.5),
The concentration of the HS-DNA-MB solution is 10mmol/L-50mmol.
4. the method as described in claim 1, which is characterized in that in step (1), the ethylenediamine, phenyl isothiocyanate rub
, than being 10:1, the temperature of the addition reaction is 25 DEG C of room temperature for you；In step (2), the HAuCl4, sodium citrate molar ratio
For 1:3.88, the temperature of the reduction reaction is 25 DEG C of room temperature.
5. the method as described in claim 1, which is characterized in that in step (3.1), the time of the deposition is 180s, institute
State HAuCl4The concentration of solution is 5mmol/L；In step (3.2), the time of the immersion is 3 hours；In step (3.3), institute
The concentration for stating nano gold spherical is 9mmol/L, and the time of the immersion is 12h；In step (3.4), the concentration of the PT solution is
20mmol/L；In step (3.5), the concentration of the HS-DNA-MB solution is 30mmol/L.
6. a kind of mercury ion probe GC/HD/AuNS/PT+MB that any one the method such as Claims 1 to 5 is prepared.
7. application of the mercury ion probe GC/HD/AuNS/PT+MB as claimed in claim 6 in measurement mercury ion.
8. application of the mercury ion probe GC/HD/AuNS/PT+MB as claimed in claim 6 in removal mercury ion.
9. a kind of method for measuring simultaneously and removing mercury ion, which is characterized in that by mercury ion probe as claimed in claim 6
Hg in GC/HD/AuNS/PT+MB and sample2+It reacts, shown in reaction process such as reaction equation (2), when application current potential
When PT and Hg2+Redox reaction occurs and generates C9H11N13:
Electrode is measured in the Hg of various concentration by square wave voltammetry2+Generated current value in solution, current signal is in Hg2+'s
Current value is denoted as Jp, J is denoted as in the current value that interior reference generatesp R, pass through Jp/Jp RValue and Hg2+Its available line of concentration relationship
Property range, and then Hg can be detected according to this linear relationship2+Concentration；Corresponding E=1.266C+0.064, wherein E is
Jp/Jp R, C is the concentration of mercury ion, and unit is μM；While measuring ion concentration of mercury, mercury ion can be removed substantially simultaneously.
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| US2088523A (en) * | 1934-02-14 | 1937-07-27 | Belz Gaspar | Multicolor photographic material |
| US2160242A (en) * | 1934-07-05 | 1939-05-30 | Robert Laing Bruce Gall | Photomechanical printing surface |
| CN103254118A (en) * | 2012-02-17 | 2013-08-21 | 温州大学 | A kind of preparation method of Hg2+ probe |
| CN103864655A (en) * | 2013-10-09 | 2014-06-18 | 广西大学 | Synthetic method of dehydroabietic acid group thiourea derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2088523A (en) * | 1934-02-14 | 1937-07-27 | Belz Gaspar | Multicolor photographic material |
| US2160242A (en) * | 1934-07-05 | 1939-05-30 | Robert Laing Bruce Gall | Photomechanical printing surface |
| CN103254118A (en) * | 2012-02-17 | 2013-08-21 | 温州大学 | A kind of preparation method of Hg2+ probe |
| CN103864655A (en) * | 2013-10-09 | 2014-06-18 | 广西大学 | Synthetic method of dehydroabietic acid group thiourea derivative |
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