A kind of method of cyanide in super sensitivity detection water body
Technical field
The present invention relates to the detection fields of cyanide, are based on nanometer gold substrate SERS technology hypersensitive more particularly to one kind
The method for detecting cyanide.
Background technique
In recent years, the timely early warning of environmental pollution and effectively improvement have become particularly important one in national development link
Ring.Due to the fast development of modern industry, many cyanides by the industries such as plating, paint, dyestuff, rubber discharge sewage into
Enter in natural water, seriously endangers the health of the mankind.So far from 2009, China has occurred and that a lot of cyanide poisoning things
Part has seriously affected health of the masses.China is in new " standards for drinking water quality " to cyanide in daily drinking water
Content has carried out stringent restriction, and has put into effect " water prevention and cure of pollution action plan " on April 2nd, 2015, in pollution processing, work
Industry waste water, comprehensively control pollutant emission etc. be many-sided to be carried out strong supervision and simultaneously starts stringent system of accountability, and iron hand pollution treatment will be into
Enter " new normality ".
The method of comparative maturity and common detection cyanide has spectroscopic methodology, titration, voltammetry, electrification both at home and abroad at present
Method etc., however, these methods are there are instrument price valuableness, detection time is longer, detection sensitivity is not up to standard, other ions are dry
Disturb it is serious, need the defects of professional operation technical staff.
Therefore, this field is badly in need of developing a kind of novel simple to operate, strong antijamming capability, at low cost and detection spirit
The method of the high detection cyanide of sensitivity.
Summary of the invention
It is an object of the invention to: a kind of novel simple to operate, strong antijamming capability, at low cost and detection are provided
The method of the detection cyanide of high sensitivity.
To achieve the goals above, the invention provides the following technical scheme:
The method of cyanide, includes the following steps: in a kind of super sensitivity detection water body
(1) various concentration cyanide solution and aqueous solution multiple groups are mixed to get with nanogold detection substrate respectively to mix
Liquid measures the SERS intensity value of every group of mixed liquor, then draws the canonical plotting of concentration of cyanide and SERS intensity value;
(2) prepare liquid and nanogold detection substrate are mixed to get mixed liquor to be measured, the SERS for measuring mixed liquor to be measured is strong
Then angle value obtains concentration of cyanide value from curve graph.
Preferably, the cyanide is hydrogen cyanide, Cymag, potassium cyanide, cyanogen chloride, acrylonitrile, one in n-Butyronitrile
Kind is a variety of.
Preferably, the concentration limit of cyanide to be checked is 0.01 μm of ol/L in the liquid to be checked.
Preferably, the nanogold detection substrate is nano gold spherical substrate, nanometer gold bar substrate, nanometer Venus substrate, receives
One of meter Jin Li cube substrate, gold nano-plates substrate are a variety of.
Preferably, the nanogold detection substrate includes cyanide indicator, nanogold detection substrate presoma and Raman
Signaling molecule;The concentration of the cyanide indicator is 0.001-100mmol/L;The nanogold detects the dense of substrate presoma
Degree is 0.01-100mmol/L;The concentration of the Raman signal molecule is 0.01-100mmol/L.
Preferably, the cyanide indicator is papain, Lysozyme, cytochrome oxidase, thiosulfuric acid
One of sodium, peroxidase, lactic dehydrogenase are a variety of;
The nanogold detection substrate presoma is gold oxide, gold hydroxide, chlorauride, gold chloride, gold potassium chloride, tetrachloro
Sodium aurate dichloro, (2- pyridine carboxylic acid) gold, tetra chlorauric acid ammonium, tetra chlorauric acid are one or more;
The Raman signal molecule be 4- mercaptopyridine, 4- mercaptobenzoic acid, rhodamine 6G, p-Mercaptoaniline, Nile blue,
Crystal violet mercaptonaphthalene, to one of fluorine thiophenol, graphene or a variety of.
Preferably, the mixed volume ratio of the liquid to be checked and nanogold detection substrate is 1-50:50-1.
Preferably, the nanogold detection substrate also includes functionalized reagent.
Preferably, the functionalized reagent be sodium citrate, ascorbic acid, sodium thiosulfate, disodium ethylene diamine tetraacetate,
One of tween, polyvinylpyrrolidone, cetyl trimethylammonium bromide, gelatin, polysaccharide, protein, nucleic acid are a variety of.
Preferably, the concentration of the functionalized reagent in the nanogold detection substrate is 0.01-1000 μm of ol/L.
The beneficial effects of the present invention are:
(1) it may be implemented in high specific under low-detection lower limit, with sensitivity to the quick detection of cyanide;
(2) in the case where the concentration decades of times at concentrations up to cyanide to be checked of chaff interferent, it still can efficiently realize and treat
Examine the detection of cyanide;
(3) using the nanogold detection substrate qualitative detection on the basis of, based on the nanogold detection substrate with
The rapid chemical of cyanide to be checked responds, in conjunction with SERS intensity value must change can quantitative detection go out the content of cyanide to be checked;
(4) detection method rapid sensitive detection cyanide easy to operate, at low cost, achievable;
(5) detection method is good to measuring samples adaptability, and any restrictions are substantially not present, easy to promote and utilize;
(6) detection method can realize detection while to a variety of cyanides.
Detailed description of the invention
Fig. 1 is the corresponding Raman spectrogram of cyanide of various concentration;
Fig. 2 is the canonical plotting of concentration of cyanide and SERS intensity value.
Specific embodiment
The method of cyanide, includes the following steps: in a kind of super sensitivity detection water body
(1) various concentration cyanide solution and aqueous solution multiple groups are mixed to get with nanogold detection substrate respectively to mix
Liquid measures the SERS intensity value of every group of mixed liquor, then draws the canonical plotting of concentration of cyanide and SERS intensity value, such as schemes
Shown in 1;
(2) prepare liquid and nanogold detection substrate are mixed to get mixed liquor to be measured, the SERS for measuring mixed liquor to be measured is strong
Then angle value obtains concentration of cyanide value from curve graph.
Preferably, the cyanide is hydrogen cyanide, Cymag, potassium cyanide, cyanogen chloride, acrylonitrile, one in n-Butyronitrile
Kind is a variety of.
Preferably, the concentration limit of cyanide to be checked is 0.01 μm of ol/L in the liquid to be checked.
Preferably, the nanogold detection substrate is nano gold spherical substrate, nanometer gold bar substrate, nanometer Venus substrate, receives
One of meter Jin Li cube substrate, gold nano-plates substrate are a variety of.
Preferably, the nanogold detection substrate includes cyanide indicator, nanogold detection substrate presoma and Raman
Signaling molecule;The concentration of the cyanide indicator is 0.001-100mmol/L, and preferred concentration is 0.05-50mmol/L;
The concentration of the nanogold detection substrate presoma is 0.01-100mmol/L, and preferred concentration is 0.2-80mmol/L;Institute
The concentration for stating Raman signal molecule is 0.01-100mmol/L, and preferred concentration is 0.2-100mmol/L.
Preferably, the cyanide indicator is papain, Lysozyme, cytochrome oxidase, thiosulfuric acid
One of sodium, peroxidase, lactic dehydrogenase are a variety of;
The nanogold detection substrate presoma is gold oxide, gold hydroxide, chlorauride, gold chloride, gold potassium chloride, tetrachloro
Sodium aurate dichloro, (2- pyridine carboxylic acid) gold, tetra chlorauric acid ammonium, tetra chlorauric acid are one or more;
The Raman signal molecule be 4- mercaptopyridine, 4- mercaptobenzoic acid, rhodamine 6G, p-Mercaptoaniline, Nile blue,
Crystal violet mercaptonaphthalene, to one of fluorine thiophenol, graphene or a variety of.
Preferably, the mixed volume ratio of the liquid to be checked and nanogold detection substrate is 1-50:50-1.
Preferably, the nanogold detection substrate also includes functionalized reagent.
Preferably, the functionalized reagent be sodium citrate, ascorbic acid, sodium thiosulfate, disodium ethylene diamine tetraacetate,
One of tween, polyvinylpyrrolidone, cetyl trimethylammonium bromide, gelatin, polysaccharide, protein, nucleic acid are a variety of.
Preferably, the concentration of the functionalized reagent in the nanogold detection substrate is 0.01-1000 μm of ol/L, more preferably
Concentration be 0.1-300 μm of ol/L.
1 accuracy of embodiment detection
The aqueous solution that known cyanide ion concentration is made in deionized water: C is added in the cryanide ion of various dose0-C6, wherein C0
For blank control.
Configuration nanometer Venus detects substrate: taking the aqueous solution of chloraurate 3mL of 5mmol/L to be added in 50mL deionized water, so
1mL0.1M CTAB is added afterwards, 50mM silver nitrate solution is added in stirring ten minutes later, and golden kind of solution is made after stirring half an hour.It takes
5mL gold kind of solution rapidly joins 5mL 20mg/mL ascorbic acid solution, and stirring is protected from light ageing 2 hours after 30 seconds.It takes and prepares
The papain solution of 100 μ L 0.1mM is added in nano-Au solution 10mL, rapidly joins 50 μ L40mM's after stirring half an hour
4- mercaptobenzoic acid solution continues stirring and obtains within ten minutes a nanometer Venus detection substrate.
The liquid to be checked of 200 μ L difference cyanide ion concentrations is separately added into 800 μ L to match in detection substrate, utilizes Raman spectrum
Instrument measures SERS intensity value.
As a result
Substituted into after eight times measured SERS values are averaged corresponding mark curve (X-SERS intensity value) obtain respectively to
Examine (being shown in Table 1) containing numerical quantity of cyanide in liquid.
Table 1
As it can be seen from table 1 it is very close using measured concentration obtained by the method for the present invention and the known concentration of liquid to be checked, it returns
(wherein, the rate of recovery refers to is added quantitative reference substance in the blank sample matrix of not measured matter to yield between 90~96
Matter is analyzed, the ratio of obtained result and theoretical value according to the processing step of sample), even if at very low concentrations, still may be used
Realize the highly sensitive detection to cryanide ion to be checked, this shows high to realize to be checked precisely, with sensitivity using the method for the present invention
The measurement of cryanide ion.
2 specific detection of embodiment
Other interfering ions (F is added in the present embodiment into the cryanide ion aqueous solution of the various concentration of configuration-, Cl-,Br-,
I-,NO3 -,NO2 -,CO3 2-,SCN-,S2-,SO4 2-) (being added in the form of salts, the total concentration of interfering substance be added is 10 μm of ol/L),
Method used in embodiment 1 is repeated to measure the aqueous solution of known concentration.
As a result
Substituted into after eight times measured SERS values are averaged corresponding mark curve (X-SERS intensity value) obtain respectively to
Examine (being shown in Table 2) containing numerical quantity of cyanide in liquid.
Table 2
From table 2 it can be seen that it is very close using measured concentration obtained by the method for the present invention and the known concentration of liquid to be checked, it returns
Yield is between 86~103, even if at very low concentrations, can still realize the highly sensitive detection to cryanide ion to be checked, this table
It is bright can the high measurement realized precisely, with sensitivity to cryanide ion to be checked using the method for the present invention.
In addition, further compared with the testing result of embodiment 1, it is known that even if there are a large amount of interfering substances the case where
Under, gained testing result is still very accurate, differs also little with 1 gained testing result of embodiment, shows the method for the present invention
Strong antijamming capability has very strong specificity.
The detection of cryanide ion in 3 river water of embodiment, lake water water sample
Acquire water sample S3.1~S3.4 to be detected: the same depth water sampling bottle acquisition in different location in river, lake
Water sample is placed to be checked.Method used in embodiment 1 is repeated to measure the aqueous solution of known concentration.
As a result
Substituted into after eight times measured SERS values are averaged corresponding mark curve (X-SERS intensity value) obtain respectively to
Examine (being shown in Table 3) containing numerical quantity of cyanide in liquid.
Table 3
The detection of cryanide ion in 4 plant chimney stalk of embodiment
It acquires water sample S4.1-S4.4 to be detected: being in different time acquisition same volume in the discharge of wastewater mouth of factory
Water sample, after be mixed uniformly, obtain water sample to be detected.Remaining method is the same as embodiment 3.Repeat method pair used in embodiment 1
The aqueous solution of known concentration measures.
As a result
Substituted into after eight times measured SERS values are averaged corresponding mark curve (X-SERS intensity value) obtain respectively to
Examine (being shown in Table 4) containing numerical quantity of cyanide in liquid.
Table 4
The detection of dicyanogen in 5 atmosphere of embodiment
It acquires sample to be tested S5.1-S5.2: by specific impinger, detection zone being needed to extract one with constant speed
The air for determining volume is trapped within suspended particulate substance of the air particle diameter less than 100 μm in specific filter membrane, the suspension that will be collected into
Particulate matter is acidified with the hydrochloric acid of 0.1mol/L, is made it dissolve.Remaining method is the same as embodiment 3.Repeat method pair used in embodiment 1
The aqueous solution of known concentration measures.
As a result
Substituted into after eight times measured SERS values are averaged corresponding mark curve (X-SERS intensity value) obtain respectively to
Examine (being shown in Table 5) containing numerical quantity of cyanide in liquid.
Table 5
The detection of cryanide ion in 6 food of embodiment
Acquisition testing liquid: obtaining sample (about 2 grams) from food, with mixed solution acidification, then with 2% hydrochloric acid
Then dissolution adjusts pH to neutrality, obtains liquid to be detected.Remaining method is the same as embodiment 3.Repeat method pair used in embodiment 1
The aqueous solution of known concentration measures.
As a result
Substituted into after eight times measured SERS values are averaged corresponding mark curve (X-SERS intensity value) obtain respectively to
That examines cyanide in liquid contains numerical quantity, as a result illustrates in food samples to be detected without containing cryanide ion or contains only micro cryanide ion.
All documents referred in the present invention are incorporated herein by reference, just as each document coverlet
It is solely incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art
The present invention can be made various changes or modifications, such equivalent forms equally fall within the application model as defined in the appended claims
It encloses.