CN109187462A - A kind of solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion and its preparation and application - Google Patents
A kind of solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion and its preparation and application Download PDFInfo
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- CN109187462A CN109187462A CN201811012657.4A CN201811012657A CN109187462A CN 109187462 A CN109187462 A CN 109187462A CN 201811012657 A CN201811012657 A CN 201811012657A CN 109187462 A CN109187462 A CN 109187462A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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Abstract
The invention belongs to heavy metal analysis fields, disclose a kind of field portable Visual retrieval heavy metal Hg ion (Hg2+) solid phase nano composite membrane and its preparation and application.The present invention is by NFC suspension and GS-AuNPs solution, and mixing and naturally dry form a film up to the solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion in a mold.NFC suspension solvent is also water, and there are a large amount of hydrophilic hydroxyls in the surface NFC, has preferable dispersibility in water, two kinds of liquid are mutually mixed, there are the active forces of physical absorption between nanoparticle, finely dispersed mixture solution can be prepared, can finally prepare the clear bright composite films of excess of export.The transparency of film makes the fluorescence of gold nanoparticle not have loss, and film has good fluorescence property, has good sensitivity and selectivity to the detection of heavy metal Hg ion, is a kind of new material of very portable, stable on-site test heavy metal Hg ion.
Description
Technical field
The invention belongs to heavy metal analysis field, in particular to a kind of field portable Visual retrieval heavy metal Hg ion
Solid phase nano composite membrane and its preparation and application.
Background technique
Water is played a crucial role as the life of necessary substances on human in life.However, water quality but by
The pollution of toxic metals and it is increasingly severe.In numerous water pollution factors, water pollution caused by heavy metal use is to people
Threat caused by class is the most serious.Such as heavy metal Hg, as influence human health main factor, every million/
One concentration will generate serious damage to nerve system of human body.By a large amount of research, phase has been issued in European Union
The regulations of pass, it is desirable that the mercury ion (Hg in drinking water2+) for content no more than 1ppb, U.S.EPA (US EPA) establishes state
Family's regulation, it is desirable that the maximum mercury content of drinking water must not exceed 2ppb, otherwise will have an adverse effect to health.Therefore, aquatic
Extremely important to the conventional detection of metal mercury ions in Eco-Environment System, there is an urgent need to a kind of pair of metal mercury ions are fast
Fast, economic, sensitive and highly selective detection method.
The analysis method of existing heavy metal analysis includes: atomic absorption spectrum, cold vapor atoms fluorescence spectrum, inductance coupling
Close plasma mass, electrochemical method, gas chromatography and high performance liquid chromatography.These methods for heavy metal from
The detection of son can provide lower detection limit, however, the detection method of wherein most has some disadvantages, for example need
Expensive instrument and complicated preparation of samples process, it is quite time-consuming, it is not appropriate for on-site test.
With the development of science and technology, by nano material be designed to optical sensor be used for mercury ion detection mode by
Many concerns and research, being primarily due to this method, cost is relatively low, preparation and detection method are simple, rapidly and efficiently.According to
The source that optical signalling generates, these optical sensors can be divided into colorimetric method, fluorescence method, Surface enhanced Raman scattering (SERS)
Method sensor, by spectral transmittance, fluorescence intensity and surface enhanced Raman spectroscopic signals can be to the traces of heavy metal ion
Concentration carries out quantitative detection.
What is be concerned in recent years is nanogold in detection heavy metal Hg ion, its preparation method is simple, cost-effectiveness, easily
In visualization and high sensitivity.However most of related application is all based on liquid phase substrate (or substrate) at present, be
It is carried out in solution, visualization is poor, and which has limited the on-site tests that it is applied to mercury ion.In order to improve the visualization of detection
Using also the method report of useful solid substrate, mainly there is DNA base, polymeric substrates, electrostatic spinning substrate, log substrate
And substrate of glass etc., however all there are some the shortcomings that can not be ignored based on these base materials, for example need surface modification
The preparation process of the complexity such as process, sensitivity are lower, expensive and some has toxicant etc..If higher ratio can be possessed
Surface area, softness, transparent solid substrate, can overcome these disadvantages.
Nanofibrils cellulose (Nanofibrillated Cellulose, NFC) derives from native cellulose, is a kind of
Environmentally friendly high molecular material, there is excellent optical property, mechanical performance, high-specific surface area, chemistry can modify, is biological for it
A variety of excellent properties such as compatible, biodegradable are to be expected to that disadvantage mentioned above can be overcome, become the potential quality material of ideal substrate.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that provide a kind of scene portable
The preparation method of the solid phase nano composite membrane of formula Visual retrieval heavy metal Hg ion.
Another object of the present invention is to provide the field portable Visual retrieval heavy metal Hg ion of above method preparation
Solid phase nano composite membrane.
Still a further object of the present invention is to provide the solid phase nanometer of above-mentioned field portable Visual retrieval heavy metal Hg ion
Application of the composite membrane in the on-site test of heavy metal Hg ion.
The purpose of the present invention is realized by following proposal:
A kind of preparation method of the solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion, it is main to wrap
Include following steps:
(1) it prepares nanofibrils cellulose NFC suspension: slurry being crushed, is added to and is dispersed with stirring to obtain in buffer
Slurries add TEMPO (2,2,6,6-tetramethylpiperidine nitroxide), NaBr and NaClO, start to react, while using alkali
The pH value for adjusting slurries is 10, after reaction, is 7 with water filtering and washing to pH value, is prepared into after high pressure nano homogeneous
The suspension of nano-cellulose, adjusting suspension pH value is 9.5 to get NFC suspension；
(2) HAuCl the preparation of luminous gold nanoparticle GS-AuNPs solution: is added into l-Glutathione aqueous solution4Water
Solution, after mixing heating reaction, after reaction purifies gained reaction solution up to GS-AuNPs solution；
(3) preparation in the NFC suspension prepared in step (1) and step (2) preparation of composite membrane: is added into mold
GS-AuNPs solution, then ultrasonic mixing, mold is placed in constant-temperature constant-humidity environment after the completion of mixing be evaporated naturally film forming to get
The solid phase nano composite membrane of target product field portable Visual retrieval heavy metal Hg ion.
Slurry described in step (1) is at least one of softwood pulp, hardwood pulp, cotton pulp；Described in step (1)
Slurry crushing is referred to and is crushed to loose flocculence with pulverizer；
Buffer described in step (1) refers to that volume ratio is the 0.1mol/L aqueous sodium carbonate and 0.1mol/L carbon of 3:2
The mixed solution of sour hydrogen sodium water solution；
The dosage of buffer described in step (1) meets the corresponding buffer that 60mL is added of every 1g slurry；In step (1)
The dosage of described TEMPO, NaBr and NaClO (effective chlorine > 9%) meet TEMPO, NaBr and the mass ratio of solute NaClO is
0.08:0.5:0.04；It is 1 that the dosage of TEMPO described in step (1) and slurry, which meets slurry and the mass ratio of TEMPO:
0.016；
Add the pH of alkali adjusting slurries to refer to described in step (1) to be adjusted with the sodium hydrate aqueous solution of 0.1mol/L
Section；
Reaction described in step (1) refers to 16~20h of reaction at room temperature, preferably reacts 18h at room temperature；
The processing of high pressure homogenizer described in step (1) refers to carries out 8 homogeneous under 90bar pressure；
The suspension of nano-cellulose described in step (1) refers to receiving containing 1.667g in the suspension of every 100mL
Rice cellulose；
The concentration of l-Glutathione aqueous solution described in step (2) is 2.4~4.8mmol/L, preferably 4.8mmol/
L；HAuCl described in step (2)4The concentration of aqueous solution is 1.0~5.0mol/L, preferably 1.0mol/L；Institute in step (2)
The l-Glutathione aqueous solution and HAuCl stated4The dosage of aqueous solution meets l-Glutathione and HAuCl4Molar ratio be (0.8~
1.6): 1, preferably 1.6:1；
The reaction of heating described in step (2) refers in 95 DEG C of reaction 12h；
Purifying described in step (2) refers to gained reaction solution is cooled to room temperature after, adjust its pH value to 3~4, be added
The ethyl alcohol of reaction solution volume 1/3 is precipitated, and then obtains sediment in 4000g centrifugation 10min removal supernatant；Gained is precipitated
Object washing, is then dispersed in water, and adjusting pH is 7~8, then 21000g centrifugation removal bulky grain, the 10k ultrafiltration of gained suspension
Centrifuge tube isolate and purify the removal complete raw material of unreacted and extra impurity to get GS-AuNPs solution after purification；
The concentration of GS-AuNPs solution described in step (2) is 5mg/mL；
Mold described in step (3) is preferably polypropylene material, and mould inside is flat and smooth, after mixed liquor film forming
It directly takes out.
The dosage of NFC suspension described in step (3) and GS-AuNPs solution meets NFC suspension and GS-AuNPs is molten
The volume ratio of liquid is 1mL:(0~50) μ L, wherein the volume of GS-AuNPs solution is not 0；Preferably NFC suspension and GS-
The volume ratio of AuNPs solution is 1mL:(10~50) μ L.
Ultrasonic mixing described in step (3) refer to output power be 100%, 300Hz under the conditions of ultrasonic disperse 20~
50min；
Constant-temperature constant-humidity environment described in step (3) refers to that relative humidity is 50~70%, the ring that temperature is 20 ± 5 DEG C
Border；
Used in step (2) to glassware be both needed to before the use with chloroazotic acid (HCl:HNO3=3:1) it impregnates
12h reuses dehydrated alcohol, ultrapure water and cleans repeatedly for use；
Do not indicate that temperature refers both to carry out at room temperature in step (1)~(3), the room temperature refers to 20~30 DEG C；
A kind of solid phase nanometer of field portable Visual retrieval heavy metal Hg ion prepared by the above method is multiple
Close film.
The solid phase nano composite membrane of above-mentioned field portable Visual retrieval heavy metal Hg ion is in heavy metal Hg ion
On-site test in application.
Mechanism of the invention are as follows:
Mechanism of the invention is as shown in Figure 1.
Nanofibrils cellulose NFC is the one kind with high length-diameter ratio, high-specific surface area extracted from plant cellulose
Nano material, its surface have a large amount of hydroxyl and carboxylic group, and the networking that can interweave is prepared into the transparent flexibility of ultra high-definition
Thin-film material, density is low, has extraordinary mechanical performance, soft, and material is biodegradable, and cost is relatively low.Therefore, NFC
It is the good substrates support materials of GS-AuNPs.
Meanwhile the GS-AuNPs hydrosol has water solubility well, nanogold partial size is very small, about 2~4nm, tool
There are stronger luminous efficiency and higher fluorescence quantum efficiency.As shown in Fig. 1 (a), there are certain proportions on gold nanoparticle surface
Au+, these Au+(4f145d10) track and Hg2+(4f145d10) track has very high affinity and selectivity, meeting after contact
Generate strong specific binding (Hg2+-Au+Thermophilic metal reaction), it directly can rapidly cause nanogold after the two combines
The fluorescent quenching of particle, as shown in Fig. 1 (c).NFC suspension solvent is also water, and the surface NFC has a large amount of hydrophilic hydroxyls
Base has preferable dispersibility in water, and two kinds of liquid are mutually mixed, there are the active force of physical absorption between nanoparticle,
Finely dispersed mixture solution can be prepared, can finally prepare the clear bright composite films of excess of export.The transparency of film
So that the fluorescence of gold nanoparticle will not have loss, by the detection to the UV absorption light of different parts on transparent composite membrane,
It can detecte out dispersed homogeneous degree of the GS-AuNPs in film.Under the ultraviolet lamp of 365nm, composite membrane can issue strong red
Fluorescence contains Hg when touching as shown in Fig. 1 (b)2+Solution when, mercury ion can slowly penetrate into film from the surface of film, with it
In GS-AuNPs react, according to the amount of the mercury ion of contact, fluorescence can weaken even completely quenching, see in the UV lamp
Any fluorescence phenomenon is not detected, as shown in Fig. 1 (d).Due to Hg2+-Au+The high selectivity of thermophilic metal reaction is most heavy
Metal will not cause the quenching of GS-AuNPs.The composite membrane that sum up NFC loads GS-AuNPs may be implemented to visualize mercury ion
The highly selective and sensitivity of detection.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
(1) raw material is sufficient on the raw material NFC earth of the present invention, degradable；
(2) NFC substrate large specific surface area of the present invention, can be more with supported nano-gold quantity；
(3) NFC substrate translucency of the present invention is good, can effectively prevent nanogold fluorescence and decays because stopping；
(4) nano-complex substrate of the present invention is solid phase, and stability is good.
(5) nano-complex substrate of the present invention is soft, flexible, has good following process；
(6) present invention has good sensitivity and highly selective to heavy metal Hg ion detection.
Detailed description of the invention
Fig. 1 is mechanism figure of the invention；
Fig. 2 is that the microscopic appearance of the material in embodiment 1 observes figure, and wherein Fig. 2 (a) is the atomic force microscopy of NFC fiber
Mirror figure；Fig. 2 (b) is the high-resolution field emission scanning electron microscope figure of NFC blank film；The transmission electricity that Fig. 2 (c) is GS-AuNPs
Sub- microscope figure；The composite material film that Fig. 2 (d), which is the additional amount of GS-AuNPs solution in embodiment 1, to be prepared when being 40 μ L
High-resolution field emission scanning electron microscope figure.
Fig. 3 is the additional amount of GS-AuNPs solution in embodiment 1 composite membrane prepared when being 40 μ L, NFC blank film
Optical property test map, wherein Fig. 3 (a) is the pictorial diagram of composite membrane and NFC blank film；Fig. 3 (b) is composite membrane in different waves
Light transmittance figure under long；Fig. 3 (c) is the absorbance curve figure of eight arbitrary points at different wavelengths on NFC blank film；Fig. 3 (d)
For ten arbitrary points absorbance curve figure at different wavelengths of NFC/GS-AuNPs composite membrane prepared by embodiment 1.
Fig. 4 is made when GS-AuNPs solution additional amount is respectively 10 μ L, 20 μ L, 30 μ L, 40 μ L, 50 μ L in embodiment 1
Naked eye fluorescence photo figure of the standby obtained composite membrane under 365nm ultraviolet lamp photograph；
Fig. 5 is that the composite membrane prepared when GS-AuNPs solution additional amount is 50 μ L in embodiment 1 examines Hg ion-sensitive
Result figure is surveyed, wherein Fig. 5 (a) and Fig. 5 (b) is respectively under the ultraviolet lamp of 365nm, and composite membrane is acted in different ion concentration of mercury
Under quenching effect picture and fluorescence intensity column diagram；
Fig. 6 is that the composite membrane prepared when GS-AuNPs solution additional amount is 40 μ L in embodiment 1 examines Hg ion selectivity
Result figure is surveyed, wherein Fig. 6 (a) and Fig. 6 (b) is respectively under the ultraviolet lamp of 365nm, and composite membrane is in same concentrations same volume
Response effect picture and fluorescence intensity column diagram under different heavy metal ion effects.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.
Embodiment 1
(1) preparation of NFC suspension
0.1mol/L Na is used first2CO3Solution and 0.1mol/L NaHCO3Solution prepares 400mL with the volume ratio of 3:2
The buffer solution that pH is about 10 takes 300mL in the beaker of 500mL；5g slurry (needlebush pulpboard) is crushed to pulverizer
After loose flocculence, it is added in flask, it is abundant with magnetic stirrer.0.08g TEMPO and 0.5g are weighed respectively
NaBr, it is to be dissolved sufficiently after, measure 35mL NaClO (efficient > 9%) and be added in mixed liquor and starts to react；During reaction, use
It is 10.0 or so that the standard solution of sodium hydroxide of 0.1mol/L, which adjusts reaction solution pH,；Total reaction time is 18 hours.Reaction knot
Shu Hou sufficiently washs reaction mixture with deionized water using bottle,suction, the sample after washing is transferred to clean
In beaker, deionized water, which is added, makes the concentration 0.01667g/mL of nano-cellulose；Finally suspended using high pressure homogenizer processing
Liquid sample, under 90bar pressure, 8 dispersions finally obtain nanofibrils cellulose suspension, after the completion of preparation, adjust pH of suspension
It is 9.5 or so.
(2) preparation of GS-AuNPs solution
By all glasswares chloroazotic acid (HCl:HNO3=3:1) 12h is impregnated, it is anti-to reuse dehydrated alcohol, ultrapure water
Multiple cleaning, drying for standby.L-Glutathione (reduced form) aqueous solution of 50mL 4.8mmol/L is added first in conical flask, to
The HAuCl that 150 μ L concentration are 1mol/L is added in solution4Aqueous solution, the oil bath after magnetic agitation is uniform, by mixed liquor at 95 DEG C
Heating 12h obtains GS-AuNPs in pot, after being cooled to room temperature, the pH of acquired solution is adjusted to 3~4,1/3 volume ethanol is added
Afterwards, then 4000g is centrifuged 10 minutes isolated deposits, and supernatant is removed, and then takes gained precipitating milli-Q water
For several times, add 1mL ultrapure water to adjust pH value to 7~8, be completely dissolved gold nanoparticle, then 21000g, which is centrifuged off, reacted
The bulky grain generated in journey, then gained gold nanoparticle is purified with 10k super filter tube, it is spare to be finally configured to 5mg/mL.
(3) preparation of composite membrane
The mold for preparing film is polypropylene material, and mould inside is flat and smooth, convenient for directly taking out after mixed liquor film forming.For
The influence of the GS-AuNPs of different amounts to the fluorescence intensity of film is probed into, we take 6 identical molds (2 × 2cm), first
1mL NFC suspension (0.01667g/mL) respectively is added in a mold, then the GS- of different volumes is successively added into each mold
AuNPs solution, additional amount are respectively 0 μ L, 10 μ L, 20 μ L, 30 μ L, 40 μ L, 50 μ L, in order to make GS-AuNPs solution adequately with
NFC suspension is uniformly mixed, and mold is put into ultrasound 20min in supersonic wave cleaning machine by us, output power 100%,
300Hz；After the completion of ultrasound, by mold be put into laboratory with constant temperature and constant humidity (relative humidity 50~70%, 20 ± 5 DEG C of temperature) to its from
So it is evaporated film forming.
Performance detection:
1, the microscopic appearance observation of material
The microscopic appearance observation figure of material in embodiment 1 is as shown in Fig. 2, wherein Fig. 2 (a) is the atomic force of NFC fiber
Microscope figure, more can intuitively observe the form of single NFC fiber from figure, and diameter is about 8~10nm, draw ratio
Greatly, even size distribution；With high-resolution field emission scanning electron microscope observation NFC blank film (i.e. GS-AuNPs solution plus
Enter the film that is prepared when amount is 0 μ L) shown in surface microscopic topographic such as Fig. 2 (b), under the amplification factor of 50K, it can be seen that film
Surface is comparatively dense, and very smooth.Fig. 2 (c) is transmission electron microscope figure (the sample preparation reference scan/transmission of GS-AuNPs
Electron microscopyc sample preparation process: conducting resinl is attached on objective table, by hanging drop on conducting resinl, be evaporated naturally or hair dryer drying or
The drying of person's low temperature baking oven, then metal spraying), the uniform particle sizes of Au NPs and well dispersed as can be seen from Figure, diameter is about 2
~3nm or so.Composite membrane is characterized in Fig. 2 (d), it can be seen that the surface of film is more smooth, GS-AuNPs dispersion compared with
It is uniform.
When the additional amount of GS-AuNPs solution is 10 μ L, 20 μ L, 30 μ L, 50 μ L, with high-resolution Flied emission scanning electron
The figure that its surface microscopic topographic of micro- sem observation obtains is similar to Fig. 2 (d), illustrates that when the additional amount of GS-AuNPs solution be 10 μ
L, when 20 μ L, 30 μ L, 50 μ L, it can equally obtain more smooth and GS-AuNPs and disperse more uniform composite membrane.
2, optical performance test
Prepared composite membrane when the additional amount of GS-AuNPs solution is 40 μ L in embodiment 1, NFC blank film it is optical
Energy test map is as shown in figure 3, wherein Fig. 3 (a) is the pictorial diagram of composite membrane and NFC blank film, it is seen that NFC blank film and preparation
Nano composite membrane visually the transparency it is all fine；Fig. 3 (b) is the light transmittance figure of composite membrane at different wavelengths, from Fig. 3 (b)
From the point of view of, the light transmittance of composite membrane is up to 90%；Fig. 3 (c) is the absorbance of eight arbitrary points at different wavelengths on NFC blank film
Curve graph appoints at random on NFC blank film and takes eight points, obtains eight groups of absorption spectrum curves, can be seen from the chart this 8 points
Absorbance fit like a glove；Fig. 3 (d) is ten arbitrary points of NFC/GS-AuNPs composite membrane prepared by embodiment 1 in different waves
Absorbance curve figure under long takes an absorbance for each point of measurement to essentially coincide, at random as can be seen from Fig. so as to say
It is highly uniform that dispersion of the GS-AuNPs in NFC film is illustrated.
When the additional amount of GS-AuNPs solution is 10 μ L, 20 μ L, 30 μ L, 50 μ L, the NFC/GS- of the preparation of embodiment 1
The absorbance curve of ten arbitrary points of AuNPs composite membrane at different wavelengths also essentially coincides, and illustrates when GS-AuNPs solution
Additional amount be 10 μ L, 20 μ L, 30 μ L, 50 μ L when, dispersion of the GS-AuNPs in NFC film is highly uniform.
3, the detection of fluorescence property
It is prepared when by GS-AuNPs solution additional amount in embodiment 1 being respectively 10 μ L, 20 μ L, 30 μ L, 40 μ L, 50 μ L
To composite membrane to number respectively be 1,2,3,4,5.Naked eye fluorescence photo of this five composite membranes under 365nm ultraviolet lamp photograph is as schemed
Shown in 4, figure 4, it is seen that with the increase of GS-AuNPs additional amount, fluorescence enhancement.
4, detection of the composite membrane to metal mercury ions
4.1 sensitivity technique
The composite membrane prepared has stronger fluorescent emission, in order to improve the sensitivity of detection process, present invention choosing
The composite membrane for having selected identical GS-AuNPs content carries out Hg2+The experiment of detection.At room temperature, by mercuric sulfate powder with 2mol/L's
HNO3Solution is configured to the Hg of 0.01mol/L2+Stock solution.Then, by Hg2+It is made into 1000 μm of ol/L of concentration, 100 μm of ol/
L, 10 μm of ol/L, 1 μm of ol/L, 0.1 μm of ol/L, 0.01 μm of ol/L, 0.001 μm of ol/L, 0.0001 μm of ol/L respectively take 1mL stand-by.
The composite membrane punch that GS-AuNPs solution additional amount in embodiment 1 is 50 μ L is beaten and cuts 9 size shapes
Identical film drips the mercury ion solution one that eight films therein respectively drip above eight various concentrations, will after taking-up is dried
Film is placed in phosphorimager, and using 365nm ultraviolet source, time for exposure 1.5s obtains fluorescence picture.Composite membrane to Hg from
Sub- sensitivity testing result figure is as shown in figure 5, wherein Fig. 5 (a) is under the ultraviolet lamp of 365nm, and composite membrane is in different mercury ions
Quenching effect picture under concentration effect；Fig. 5 (b) is under the ultraviolet lamp of 365nm, and composite membrane is under the effect of different ion concentration of mercury
Fluorescence intensity column diagram；As shown in Fig. 5 (a), by nine films that the shearing of same composite membrane is lower, first be blank film (not
Reacted with mercury ion solution), remaining eight successively instill 0.001 μm of ol/L, 0.01 μm of ol/L, 0.1 μm of ol/L, 1 μm of ol/
L, 10 μm of ol/L, 102μm ol/L, 103μm ol/L, 104The 10 μ L of mercury ion solution of μm ol/L, then it is placed in the ultraviolet of 365nm wavelength
Under lamp, it can intuitively see very much that Quenching of fluorescence acts on, with the increase of ion concentration of mercury, quenching effect successively enhances.
When ion concentration of mercury is higher than 0.1 μm of ol/L, quenching effect is clearly.Under the ultraviolet lamp of 365nm, composite membrane is in different mercury
Shown in fluorescence intensity column diagram such as Fig. 5 (b) under ion concentration effect, Fig. 5 (b) is to utilize the collected fluorescence of phosphorimager
The datagram that averag density data are depicted as can also be seen when the concentration of mercury ion reaches 0.001 μm of ol/L, i.e. 1nmol/L
Measure certain fluorescence quenching.The highest content of inorganic mercury ion cannot in the drinking water of U.S.EPA (EPA) publication
More than 2ppb, i.e. 10nmol/L.And experimental result of the invention is apparently, composite membrane spirit with higher for the detection of mercury ion
Quick property 1nmol/L < 2ppb, therefore requirement is fully met, and have and be applied to the practical of daily life detection metal mercury ions
Potentiality and value.
When the additional amount of GS-AuNPs solution is 10 μ L, 20 μ L, 30 μ L, 40 μ L, under being sheared by same composite membrane
Nine films, first is blank film (not reacted with mercury ion solution), remaining eight successively instill 0.001 μm of ol/L,
0.01 μm of ol/L, 0.1 μm of ol/L, 1 μm of ol/L, 10 μm of ol/L, 102μm ol/L, 103μm ol/L, 104The mercury ion of μm ol/L is molten
10 μ L of liquid, then be placed under the ultraviolet lamp of 365nm wavelength can intuitively see that Quenching of fluorescence acts on very much, with mercury from
The increase of sub- concentration, quenching effect successively enhance.When ion concentration of mercury is higher than 0.1 μm of ol/L, quenching effect is clearly.
Illustrate when the additional amount of GS-AuNPs solution be 10 μ L, 20 μ L, 30 μ L, 40 μ L when, also can satisfy sensitivity 1nmol/L <
2ppb。
4.2 selective enumeration method
In inspection composite membrane to Hg2+It is first the compound of 40 μ L GS-AuNPs solution additional amount in the experiment of selectivity
Film is cut into that small big shape is 12 identical, has then prepared the Ag that concentration is 100 μm of ol/L+,Ca2+,Cr3+,Cu2+,K+,Co3 +,Na+,Al3+,Pb2+,Zn2+,Ni2+Nitrate aqueous solution.This 12 films are respectively dropped into the Ag that concentration is 100 μm of ol/L+,
Ca2+,Cr3+,Cu2+,K+,Co3+,Na+,Al3+,Pb2+,Zn2+,Ni2+,Hg2+Each drop of nitrate aqueous solution, taking-up is evaporated and is put into
The acquisition of fluorescent image is carried out in living body fluorescent imager, using 365nm ultraviolet source, time for exposure 1.5s passes through system
Software chooses the acquisition that same area carries out pixel on every film, obtains mean pixel dot density data, corresponds to corresponding
Fluorescence power variation.Composite membrane is to Hg ion selectivity testing result figure as shown in fig. 6, wherein Fig. 6 (a) is 365nm's
Under ultraviolet lamp, response effect picture of the composite membrane under the different heavy metal ion effect of same concentrations same volume；Fig. 6 (b) is
Under the ultraviolet lamp of 365nm, the fluorescence intensity column of the composite membrane under the different heavy metal ion effect of same concentrations same volume
Shape figure；From fig. 6 it can be seen that under the action of the heavy metal ion of same concentrations same volume, most heavy metal from
Son does not have apparent quenching effect to the fluorescence of composite membrane, and mercury ion solution is most strong for the effect of composite membrane fluorescent quenching, leads to
It crosses experimental result and observes that silver ion and copper ion also produce certain fluorescence quenching to composite membrane, but compared to mercury
Ion, function and effect are weaker.
Similarly, the composite membrane by the additional amount of GS-AuNPs solution to obtain when 10 μ L, 20 μ L, 30 μ L, 50 μ L carries out phase
The operation answered can also be observed that most heavy metal ion does not have an apparent quenching effect to the fluorescence of composite membrane, mercury from
Sub- solution is most strong for the effect of composite membrane fluorescent quenching, and it is sudden that silver ion and copper ion also produce certain fluorescence to composite membrane
The effect of going out, but compared to mercury ion, function and effect are weaker.Pass through these experimental results, it was demonstrated that nanometer prepared by the present invention is multiple
Closing film has very high selectivity to mercury ion detecting.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion, feature exist
In mainly comprising the steps that
(1) it prepares nanofibrils cellulose NFC suspension: slurry being crushed, is added to and is dispersed with stirring to obtain slurries in buffer,
TEMPO, NaBr and NaClO are added, starts to react, while being 10 with the pH value that alkali adjusts slurries, after reaction, is taken out with water
Filter washing to pH value is 7, and the suspension of nano-cellulose is prepared into after high pressure nano homogeneous, adjusts suspension pH value and is
9.5 to get NFC suspension；
(2) HAuCl the preparation of luminous gold nanoparticle GS-AuNPs solution: is added into l-Glutathione aqueous solution4Aqueous solution,
Heating reaction after mixing after reaction purifies gained reaction solution up to GS-AuNPs solution；
(3) GS- prepared in the NFC suspension prepared in step (1) and step (2) the preparation of composite membrane: is added into mold
AuNPs solution, then mold, is placed in constant-temperature constant-humidity environment after the completion of mixing and is evaporated film forming naturally to get mesh by ultrasonic mixing
Mark the solid phase nano composite membrane of product field portable Visual retrieval heavy metal Hg ion.
2. the system of the solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion according to claim 1
Preparation Method, it is characterised in that:
Slurry described in step (1) is at least one of softwood pulp, hardwood pulp, cotton pulp；General described in step (1)
Slurry crushing, which refers to, is crushed to loose flocculence with pulverizer；
Buffer described in step (1) refers to that volume ratio is the 0.1mol/L aqueous sodium carbonate and 0.1mol/L bicarbonate of 3:2
The mixed solution of sodium water solution；
The dosage of buffer described in step (1) meets the corresponding buffer that 60mL is added of every 1g slurry；Described in step (1)
The dosage of TEMPO, NaBr and NaClO to meet the mass ratio of TEMPO, NaBr and solute NaClO be 0.08:0.5:0.04；Step
Suddenly it is 1:0.016 that the dosage of TEMPO described in (1) and slurry, which meets slurry and the mass ratio of TEMPO,.
3. the system of the solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion according to claim 1
Preparation Method, it is characterised in that:
Add the pH of alkali adjusting slurries to refer to described in step (1) to be adjusted with the sodium hydrate aqueous solution of 0.1mol/L；
Reaction described in step (1) refers to 16~20h of reaction at room temperature；
The processing of high pressure homogenizer described in step (1) refers to carries out 8 homogeneous under 90bar pressure；Described in step (1)
The suspension of nano-cellulose refers to the nano-cellulose in the suspension of every 100mL containing 1.667g.
4. the system of the solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion according to claim 1
Preparation Method, it is characterised in that:
The concentration of l-Glutathione aqueous solution described in step (2) is 2.4~4.8mmol/L；
HAuCl described in step (2)4The concentration of aqueous solution is 1.0~5.0mol/L；
L-Glutathione aqueous solution and HAuCl described in step (2)4The dosage of aqueous solution meets l-Glutathione and HAuCl4
Molar ratio be (0.8~1.6): 1.
5. the system of the solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion according to claim 1
Preparation Method, it is characterised in that:
Reaction described in step (2) refers in 95 DEG C of reaction 12h；
Purifying described in step (2) refers to gained reaction solution is cooled to room temperature after, adjust its pH value to 3~4, reaction be added
The ethyl alcohol of liquid product 1/3 is precipitated, and then obtains sediment in 4000g centrifugation 10min removal supernatant；Gained sediment is washed
It washs, is then dispersed in water, adjusting pH is 7~8, then 21000g centrifugation removal bulky grain, gained suspension are centrifuged with 10k ultrafiltration
Pipe is isolated and purified to remove the complete raw material of unreacted and extra impurity to get GS-AuNPs solution after purification.
6. the system of the solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion according to claim 1
Preparation Method, it is characterised in that:
The concentration of GS-AuNPs solution described in step (2) is 5mg/mL.
7. the system of the solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion according to claim 1
Preparation Method, it is characterised in that:
The dosage of NFC suspension described in step (3) and GS-AuNPs solution meets NFC suspension and GS-AuNPs solution
Volume ratio is 1mL:(0~50) μ L, wherein the volume of GS-AuNPs solution is not 0；
Ultrasonic mixing described in step (3) refer to output power be 100%, 300Hz under the conditions of ultrasonic cleaning 20~
50min；
Constant-temperature constant-humidity environment described in step (3) refers to relative humidity 50~70%, the environment that 20 ± 5 DEG C of temperature.
8. the system of the solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion according to claim 1
Preparation Method, it is characterised in that:
Used in step (2) to glassware be both needed to impregnate 12h with chloroazotic acid before the use, reuse dehydrated alcohol, super
Pure water cleaning, it is stand-by after dry；
Do not indicate that temperature refers both to carry out at room temperature in step (1)~(3), the room temperature refers to 20~30 DEG C.
9. a kind of field portable Visual retrieval huge sum of money that methods described in any item according to claim 1~8 are prepared
Belong to the solid phase nano composite membrane of Hg ion.
10. the solid phase nano composite membrane of field portable Visual retrieval heavy metal Hg ion according to claim 9 exists
Application in the on-site test of heavy metal Hg ion.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811012657.4A CN109187462B (en) | 2018-08-31 | 2018-08-31 | Solid-phase nano composite membrane for on-site portable visual detection of heavy metal Hg ions and preparation and application thereof |
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| CN201811012657.4A CN109187462B (en) | 2018-08-31 | 2018-08-31 | Solid-phase nano composite membrane for on-site portable visual detection of heavy metal Hg ions and preparation and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109946272A (en) * | 2019-03-08 | 2019-06-28 | 广西师范学院 | The preparation method and applications of cellulose fluorescent balls |
| CN113842474A (en) * | 2021-10-19 | 2021-12-28 | 天津大学 | Near-infrared two-region fluorescent probe, preparation and application thereof in bone imaging |
| TWI806017B (en) * | 2021-03-17 | 2023-06-21 | 明志科技大學 | Composite chromatographic paper and method of producing composite chromatographic paper |
-
2018
- 2018-08-31 CN CN201811012657.4A patent/CN109187462B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109946272A (en) * | 2019-03-08 | 2019-06-28 | 广西师范学院 | The preparation method and applications of cellulose fluorescent balls |
| CN109946272B (en) * | 2019-03-08 | 2021-03-23 | 广西师范学院 | Preparation method and application of cellulose fluorescent sphere |
| TWI806017B (en) * | 2021-03-17 | 2023-06-21 | 明志科技大學 | Composite chromatographic paper and method of producing composite chromatographic paper |
| CN113842474A (en) * | 2021-10-19 | 2021-12-28 | 天津大学 | Near-infrared two-region fluorescent probe, preparation and application thereof in bone imaging |
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| Publication number | Publication date |
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| CN109187462B (en) | 2020-01-10 |
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