CN104267028B - A kind of Cu2+ probes based on rhodamine B and preparation method thereof - Google Patents
A kind of Cu2+ probes based on rhodamine B and preparation method thereof Download PDFInfo
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- CN104267028B CN104267028B CN201410552491.0A CN201410552491A CN104267028B CN 104267028 B CN104267028 B CN 104267028B CN 201410552491 A CN201410552491 A CN 201410552491A CN 104267028 B CN104267028 B CN 104267028B
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Abstract
The invention discloses a kind of Cu based on rhodamine B2+Probe and preparation method thereof, belongs to metal ion analysis detection technique field.Structural formula is：The probe molecule is colourless in pH=7.2 HEPES buffer solution, adds Cu2+Afterwards, redness is rapidly gone to, and by 6 μM of copper ion is not less than in naked eyes directly observation color change semiquantitative determination water sample, using ultraviolet-uisible spectrophotometer, can detect the copper ion for being not less than 5.32 μM in water sample.After adding sulfur anion, sulphion is combined with copper ion, and the copper ion of coordination is discharged, and probe molecule is recycled.The probe molecule is coexisted in system in copper ion and other many kinds of metal ions, and the characteristics of show strong antijamming capability, selectivity is good, and sensitivity is high, can be very good to be applied to copper ion detection in environmental pollution.
Description
Technical field
The invention belongs to metal ion analysis detection technique field, and in particular to a kind of Cu based on rhodamine B2+Probe and
Its preparation method and the detection application to copper ion.
Background technology
Copper ion is a kind of common heavy metal ion being widely present in environment, and its existing in right amount in human body is beneficial
In the normal work for maintaining body, such as participate in internal hemoposieises, keep activity of various metals enzyme etc..If but internal
Copper ion metabolic balance is destroyed, and such as copper ion concentration is too high or too low, it is likely that cause a series of diseases, such as remote gram
This disease (Menkes), Wilson disease (Wilson disease), the very early property dementia of alzheimer's
(Alzheimer ' S disease) and prion disease (Prion disease) etc..Therefore, detect related to human lives
In various water quality, the content of copper ion is extremely important.The highest of EPA (EPA) regulation copper in drinking water ion is limited to 20 μ
M.Therefore, there is very great meaning to the analysis detection of copper ion to environmental conservation and health.
In detection water, the method for copper ion mainly has at present：Flameless atomic absorption spectrometry, formaldoxime light splitting light
Degree method and co-precipitation-atomic absorption spectrophotometry.But the apparatus structure of these analysis means is complicated, skilled skill is needed
Art personnel can just obtain reliable analysis result, and analysis test is time-consuming longer, and testing cost is high.Therefore, a kind of letter is researched and developed
Single, quickly, the copper ion sensor of real-time on-site detection is imperative.
Content of the invention
It is an object of the invention to provide a kind of specific recognition is strong, sensitivity is high, based on the colorimetry that rhodamine B is modified
Probe；Another object is to provide its preparation method and application.
For realizing that the purpose of the present invention, the present invention occur effectively to coordinate using the probe based on rhodamine B and copper ion
Effect causes the absorption spectrophotometric spectra absorbing wavelength of probe to change, and realizes the highly sensitive selection to copper ion in water quality
Property identification with detection.Based on rhodamine B, described detects that the probe of copper ion is rhodamine B hydroxamic acid derivs, its chemistry
Formula is：C43H51N5O7, structural formula is：
The present invention is referred to as probe L, and its syntheti c route is as follows：
The preparation method of probe L is achieved by the steps of：
Raw material 1 is dissolved in acetonitrile, potassium carbonate and potassium iodide is added, iminodiacetic acid diethyl under reflux state, is added
Ester, continues back flow reaction；After reaction terminates, solution is cooled to room temperature, precipitation is filtered, by filtrate reduced in volume；Use dichloromethane
Alkane/methanol is that developing solvent obtains grease after post silica gel, is vacuum dried to obtain probe L.
Raw material 1 and diethyl iminodiacetate mol ratio preferably 1:1.
Raw material 1 is according to document Chem.Asian J.2011,6,1987 1991 methods synthesis.
Using colorimetry and spectrophotography, it is applied to the analysis detection of copper ion in environment.PH=7.2's
In HEPES buffer solution, the probe L mother solutions that addition acetonitrile/water is configured to, dilution, after mix homogeneously, add testing sample
In, estimate or using the light absorption value in the range of spectrophotometry 200nm-650nm, copper ion in qualitative detection water phase.Visit
Pin molecule L is to Cu2+There is efficient recognition performance, add copper ion cause obvious color change：The color of solution is from colourless
Become red；Probe molecule L has very strong capacity of resisting disturbance and relatively low test limit simultaneously.Concrete application is as follows：By probe point
Sub- L is configured to the solution of 0.4mM, is then diluted to 10 μM.In pH=7.2HEPES buffer solution, add 10 equivalents copper from
After son, a new absworption peak is occurred in that in 500-600nm, after adding sulfur anion, sulphion is combined with copper ion, is matched somebody with somebody
The copper ion of position is discharged, and system is disappeared substantially in the absworption peak of 500-600nm, the color of solution also by add copper ion it
Significantly redness is changed into meat powder color afterwards, is recycled the probe molecule.And probe only has colour developing anti-to bivalent cupric ion
Should, after addition copper ion, the color of solution is changed into red from colourless, and the bivalent cupric ion (in test limit) with variable concentrations
Colour developing situation can reach that bore hole is qualitative, the purpose of half-quantitative detection copper ion in obvious color range graded.
Innovative point of the present invention and advantage：(1) probe molecule is colourless in pH=7.2HEPES buffer solution, adds
Cu2+Afterwards, redness is rapidly gone to, as human eye is to red most sensitive, by being changed into red colour developing pattern (500- from colourless
600nm absorbances strengthen) copper ion in qualitative, semiquantitative determination water sample.Naked eyes directly observe color change semiquantitative determination
6 μM of copper ion is not less than in water sample；Using ultraviolet-uisible spectrophotometer, can detect and in water sample, be not less than 5.32 μM
Copper ion.(2), when the solution is used for the measure of Determined Copper in Aqueous Solution, neutral HEPES buffer solution is used as solvent, behaviour
Make simple, without toxic solvent, to copper ion beyond various ion strong antijamming capabilities, and invertible operation, sensitivity can be realized
Height, selectivity are good, and probe can be recycled.(3) pass through naked eye or test its spectrum, you can recognition detection result, letter
Single, quickly, energy real-time on-site realizes the detection of copper ion.(4) preparation method is simple, and raw material is easy to get, it is easy to industrial applications, tool
There is good application prospect.
Description of the drawings
Fig. 1 adds different metal cation (100 μ in pH=7.2HEPES buffer solution for probe L of the present invention (10 μM)
M the ultraviolet spectra after), wherein 1 is L, Na+,K+,Ca2+,Mg2+,Mn2+,Ni2+,Zn2+,Co2+,Cd2+,Fe2+,Fe3+,Hg2+,Pb2 +,Ag+,Al3+,Cr3+Curve, 2 is Cu2+Curve.
Fig. 2 adds different metal cation (100 μ in pH=7.2HEPES buffer solution for probe L of the present invention (10 μM)
M) the photo of solution colour change afterwards.Probe L only just shows redness after copper ion is added, and is not added with or adds other metals
Ion does not have red appearance.
Fig. 3 adds molten after variable concentrations copper ion in pH=7.2HEPES buffer solution for probe L of the present invention (10 μM)
The photo of liquid color change.Probe L is colourless when copper ion is not added with, and just has redness, with copper after adding micro copper ion
The increase color of ion concentration can be increasingly deeper, and the test limit of naked eyes is up to 6 μM.
Fig. 4 is ultraviolet spectrograms of the probe L of the present invention (10 μM) to the copper ion of variable concentrations.Illustration is to add under visible ray
The fluorescence photo (concentration and probe concentration is 10 μM, 10 times for probe of copper ion concentration) of copper ion fore-and-aft architecture, when being not added with copper ion
For colourless, after the copper ion for adding 10 equivalents, it is changed into red.
Fig. 5 is ultraviolet lights of the probe L of the present invention (10 μM) in pH=7.2HEPES buffer solution to different metal ions
Spectrum response bar diagram；Lycoperdon polymorphum Vitt post：The change of absorbance after each metal ion species of 10 equivalents is added in probe L；Black post：Probe
Add in L 10 equivalents each metal ion species and 10 equivalents copper ion after absorbance change.
Fig. 6 be difference pH on probe L of the present invention and its copper complex formazan impact.
Fig. 7 be add sulphion after probe molecule L of the present invention to copper ion can reverse response, illustration for addition sulphion
Afterwards, it is seen that under light, the color of system has changed back to meat powder color from redness.
Specific embodiment
Below by example, the present invention is described further：
Embodiment 1：Synthesising probing needle L
Step one：Raw material 1 is according to document Chem.Asian J.2011,6,1987 1991 methods synthesis.
Step 2：180mg raw materials 1 (0.28mmol) are dissolved in 12ml acetonitriles, 77.6mg potassium carbonate and 46.7mg is added
Potassium iodide, adds 50 μ L diethyl iminodiacetates (0.28mmol) under 80 DEG C of reflux states, continue back flow reaction；Reaction knot
Solution is cooled to room temperature by Shu Hou, filters precipitation, by filtrate reduced in volume；With methylene chloride/methanol 20:1 passes through for developing solvent
Grease is obtained after post silica gel, 126.5mg probe L are vacuum dried to obtain.Yield：60%
1H NMR(400MHz,CDCl3, ppm) and δ=7.91 (d, 1H, J=7.6Hz), 7.54 (t, 1H, J=15.2Hz),
7.38 (m, 4H, J=76.8Hz), 7.05 (d, 1H, J=6.4Hz), 6.53 (d, 2H, J=8.8Hz), 6.36 (s, 2H), 6.25
(d, 2H, J=8.8Hz), 4.88 (s, 2H), 4.11 (m, 4H, J=21.2Hz), 3.93 (s, 2H), 3.53 (s, 4H), 3.31 (m,
8H, J=20.4Hz), 1.21 (t, 6H, J=14.4Hz), 1.14 (t, 12H, J=13.6Hz).
13C NMR(400MHz,CDCl3, ppm) and δ=171.08,164.57,157.59,155.49,153.61,150.54,
148.81,136.96,133.07,128.80,128.65,128.30,123.86,122.94,121.87,121.20,107.97,
104.95,97.81,79.98,65.46,60.43,59.72,54.76,44.33,14.20,12.61.
FT-IR(KBr,cm-1):3442,2970,2927,1717,1635,1616,1547,1516,1465,1399,
1384,1328,1305,1266,1219,1193,1150,1118,1077,1025,818,784,756,698,685,577,
536,457.
HR-MS:[M+Na]+772.3680.
Embodiment 2：Concrete applications of the probe L of the present invention to copper ion
Probe L acetonitrile/waters (1 by synthesis:1, V/V) 0.4mM mother solutions are configured to, and deionized water prepares each of 5mM
Plant metal salt solution.The HEPES buffer solution of the pH=7.2 of 3ml is added in cuvette, is then added thereto to 75 μ
The solution of the good probe molecule L of the present invention of the above-mentioned configuration of L0.4mM, is diluted to 10 μM.Add metal salt solution, mixing
After uniform, the light absorption value in the range of 200nm-650nm is determined.
The selectivity of probe molecule L of the present invention：The only faint extinctions at 567nm of 10 μM of probe molecule L of the present invention
Value, adds each metal ion species of 10 equivalents in system, and as shown in Figure 1, the addition of only copper ion can cause significantly
Absorbance strengthens.This result shows that probe molecule L of the present invention has the specificity of height to copper ion.Purple in copper ion
In outer spectra for titration Fig. 4, with being continuously increased for copper ion concentration, system is also increased in the uv absorption intensity of 567nm.
With the addition of copper ion, the color of solution is changed into red from colourless, it is achieved that the bore hole of copper ion is recognized.Detect that mechanism is
Based on the unique ring open mechanism of rhodamine, probe L is calculated to Cu from UV titration chart2+Lowest detection be limited to 5.32 × 10- 6Mol/L, Job ' the bright probe L and Cu of s plot charts2+It is with 1:1 coordination mode chelating.
The impact that coexisting ion is detected to copper ion：For further investigating what probe molecule L of the present invention was sensed to copper ion
Selectivity, has attempted the impact to system absorbance when the close each metal ion species of property are coexisted with copper ion.In Figure 5
The absorbance of system when grey histogram represents 100 μM of each metal ion species individualism, black histogram represent dense on an equal basis
The absorbance of system when degree copper ion is coexisted with other each metal ion species.As seen from the figure, the presence of other metal ions is not
There is change probe molecule L of the present invention for the testing result of copper ion.Embody the very strong anti-interferences of probe molecule L of the present invention
Energy.
PH is on molecular probe L and its copper complex formazan impact.From fig. 6 it can be seen that in the range of pH=4-11, molecule
Probe L and its copper complex are hardly affected by pH, and this explanation probe L and its copper complex are stable in the range of this pH
's.Thus can obtain, probe L can recognize copper ion in pH=4-11 this very wide scope in specific manner.
The invertible operation of probe molecule L of the present invention：S is added in the system after addition copper ion2-, system exists
Light absorption value at 567nm reduces rapidly, almost back to the level not plus before copper ion, the color of solution also from add copper from
It is to meat powder color that redness after son becomes again.
The probe molecule can be very good to be applied to its single-minded selectivity, strong capacity of resisting disturbance and high sensitivity
The detection of copper ion in environmental pollution.
Claims (3)
1. a kind of direct bore hole colorimetry or indirect ultraviolet visible spectrometry based on rhodamine B detects Cu2+Probe, its feature
It is, its structural formula is as follows：
.
2. direct bore hole colorimetry as claimed in claim 1 based on rhodamine B or the inspection of indirect ultraviolet visible spectrometry are prepared
Survey Cu2+Detecting probe method, it is characterised in that realized by following steps：
Raw material 1 is dissolved in acetonitrile, potassium carbonate and potassium iodide is added, diethyl iminodiacetate under reflux state, is added, after
Continuous back flow reaction；After reaction terminates, solution is cooled to room temperature, precipitation is filtered, by filtrate reduced in volume；With dichloromethane/first
Alcohol obtains grease for developing solvent after post silica gel, is vacuum dried to obtain probe L.
3. the direct bore hole colorimetry or indirect ultraviolet visible spectrometry based on rhodamine B as claimed in claim 1 detects Cu2+
The application of probe, it is characterised in that in the HEPES buffer solution of pH=7.2, the probe L that addition acetonitrile/water is configured to
Mother solution, dilution, after mix homogeneously, are added in testing sample, and range estimation utilizes spectrophotometry 200nm-650nm scopes
Interior light absorption value, copper ion in qualitative detection water phase.
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