CN109738400A - A method of Visual retrieval caffeine is sensed based on nanometer porphyrin fluorescence paper - Google Patents

A method of Visual retrieval caffeine is sensed based on nanometer porphyrin fluorescence paper Download PDF

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CN109738400A
CN109738400A CN201811515590.6A CN201811515590A CN109738400A CN 109738400 A CN109738400 A CN 109738400A CN 201811515590 A CN201811515590 A CN 201811515590A CN 109738400 A CN109738400 A CN 109738400A
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caffeine
cdte quantum
paper
pyridyl group
solution
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CN109738400B (en
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付海燕
郭晓明
佘远斌
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South Central Minzu University
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South Central University for Nationalities
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Abstract

A method of Visual retrieval caffeine is sensed based on nanometer porphyrin fluorescence paper, belongs to technical field of analysis and detection.The following steps are included: the synthesis of CdTe quantum;The synthesis of four-(4- pyridyl group) zinc protoporphyrin self-assemblies;CdTe quantum is added dropwise on filter paper dick paper device, the filter paper dick on paper device, which absorbs, to be fixed after CdTe quantum up to CdTe quantum paper sensing device substrate;Prepare the caffeine of various concentration and the mixed solution of four-(4- pyridyl group) zinc protoporphyrin self-assemblies, it is added dropwise in CdTe quantum paper sensing device substrate, it observes, takes pictures to each CdTe quantum paper sensing substrate, arrangement obtains caffeine standards colorimetric card in ultraviolet camera bellows;The caffeine concentration in sample to be tested is detected, mixed liquor is made in caffeine to be measured and self-assembly and is added dropwise in quantum dot paper sensing substrate, compares standard color comparison card up to the concentration of caffeine.The method of the present invention is simply accurate.

Description

A method of Visual retrieval caffeine is sensed based on nanometer porphyrin fluorescence paper
Technical field
The invention belongs to nano material preparation and paper sensing analysis detection technique fields, and in particular to a kind of nanometer of porphyrin can Control standby and a kind of method based on CdTe quantum paper sensing detection caffeine.
Background technique
Caffeine is a kind of alkaloid, is primarily present in tea, coffee, cocoa, in kola nut and other plant, and is used extensively Make food, the additive of beverage and field of medicaments.The attention and working efficiency of people can be improved in appropriate intake caffeine, but Excess intake will lead to many adverse effects.One of main active of tealeaves is found to be caffeine, it is in bronchus flesh Relaxation, central nervous system stimulate, and play an important role still in the various physiological actions such as gastric acid secretion and diet, it may draw Play vomiting.It is considered as the risk factor of cardiovascular disease this is why being surveyed there are many reliable caffeine is researched and developed The reason of determining method.In recent years, many modern technologies have been applied to the analysis of caffeine, such as UV-VIS spectrophotometry, Ultrasonic wave extraction, high performance liquid chromatography, near infrared spectrometer etc..However, these technologies are usually expensive, it is complicated and time-consuming. Here, quickly, sensitive and inexpensive analytical technology is very important for analyzing the simple of caffeine.Colorimetric analysis is aobvious The huge prospect for solving relevant issues is shown, with the simplicity on theory and technology.It would therefore be desirable to a kind of efficient, letter Just, reliably means detect caffeine.
Summary of the invention
An object of the present invention, which is to provide, a kind of prepares nanometer porphyrin preparation method simple, that reaction condition is mild;Mesh Two be to provide it is a kind of based on CdTe quantum fluorescence color visualization paper sensing substrate detection caffeine method, can not only Caffeine is detected fast, in high sensitivity, and be can be realized and exempted from the detection immediately of instrument scene.
To achieve the above object, a kind of method for visualizing paper sensing detection caffeine of the present invention, which is characterized in that specific Steps are as follows:
(1) synthesis of CdTe quantum
Dichloride cadmium and N-acetyl-L-cysteine are dissolved in pure water and are uniformly mixed, sodium tellurite is then sequentially added Solution, sodium borohydride solution, finally baking oven in react after the CdTe quantum that is fluoresced;
The synthesis of (2) four-(4- pyridyl group) zinc protoporphyrin self-assemblies
Four-(4- pyridyl group) zinc protoporphyrin, that is, porphyrins are dissolved in n,N-Dimethylformamide solution, four-(4- pyridines are obtained Base) zinc protoporphyrin n,N-Dimethylformamide solution, four-(4- pyridyl groups) are added into dodecyl trimethyl ammonium bromide aqueous solution Zinc protoporphyrin n,N-Dimethylformamide solution, ultrasound, water-bath ageing, obtains four-(4- pyridyl group) zinc protoporphyrin self-assemblies and receives Rice porphyrin;
(3) preparation of CdTe quantum paper sensing device substrate
CdTe quantum is added dropwise on filter paper dick paper device, the filter paper dick on paper device absorbs fixed CdTe quantum Up to CdTe quantum paper sensing device substrate after point;
(4) caffeine standards colorimetric card is made
The caffeine of various concentration and the mixed solution of four-(4- pyridyl group) zinc protoporphyrin self-assemblies are prepared respectively, will be mixed It closes solution to be successively added dropwise in CdTe quantum paper sensing device substrate, be observed in ultraviolet camera bellows, it is different dense in mixed solution Spend the different color of caffeine and CdTe quantum paper sensing substrate reaction generation, to each CdTe quantum paper sensing substrate into Row is taken pictures, and arrangement obtains caffeine standards colorimetric card;
(5) the caffeine concentration in sample to be tested is detected
Mixed solution is made in caffeine sample to be measured and four-(4- pyridyl group) zinc protoporphyrin self-assemblies to be added dropwise in CdTe amount In son point paper sensing substrate, CdTe quantum paper, which senses substrate, has color response, the caffeine that control step (4) obtains to sample Standard color comparison card obtains the concentration of caffeine in sample.
Preferably, by the mixed solution pH tune of dichloride cadmium and N-acetyl-L-cysteine in the step (1) It is 8.0~8.5, oven temperature control is 200~220 DEG C, obtains launch wavelength and is 640~660nm, sends out the CdTe of red fluorescence Quantum dot.
Preferably, in the step (1), N-acetyl-L-cysteine, dichloride cadmium, sodium tellurite substance Amount ratio are as follows: 1.2~1.5:1:0.2 preferably, in the step (2), four-(4- pyridyl group) zinc protoporphyrins and 12 Alkyl trimethyl ammonium bromide the mass ratio of the material is 1:290~305.
Preferably, in the step (3), CdTe quantum concentration is 3~4 μm of ol/L.
Preferably, in the step (3), in the step (2), CdTe quantum dripping quantity is 8~10uL, filter Paper disk paper device is the circular filter paper that diameter is 4~6mm, and the paper that CdTe quantum has been added dropwise sensing substrate is placed in 36~39 DEG C baking oven in, dry 5~7 minutes.
Preferably, nanometer porphyrin partial size is 70~100nm in described four-(4- pyridyl group) zinc protoporphyrin self-assembly Nanosphere.
Preferably, in the step (4) and step (5) four-(4- pyridyl group) zinc protoporphyrin self-assemblies concentration It is identical, and be 30~33 μM.
Preferably, the concentration of caffeine is respectively in 1nM-1000nM in mixed solution in the step (4) Gradient concentration.(4- pyridyl group) zinc protoporphyrin self-assembly, that is, nanometer porphyrin concentration is 31.2 μM four-in mixed solution, further Preferably coffee because concentration be followed successively by 1000nM self-assembly, 500nM self-assembly, 100nM self-assembly, 50nM respectively from group Fill body, 10nM self-assembly, 1nM self-assembly.
Preferably, in the step (4), various concentration caffeine is reacted with CdTe quantum paper sensing substrate The color data in the photo importing PaintShop extraction picture of different colours is generated, simulates coffee using color data Because of standard colorimetric result.
Method or CdTe quantum paper chip substrate of the invention can detecte caffeine in pure sample and in Xihu Longjing Tea Aqua Folium Camelliae sinensis, cell culture fluid, human plasma, the concentration in newborn bovine serum complex matrices.
The present invention has the advantages that the present invention is based on CdTe quantum paper sensings compared with existing caffeine detection method The method that substrate detects caffeine have preparation it is simple, can rapid field detection, at low cost, fast response time, sensitivity and choosing The high feature of selecting property, and CdTe quantum paper sensing substrate has specific reaction to caffeine, can be used for complex matrices water The detection of caffeine in sample.
Detailed description of the invention
Fig. 1 is that the present invention is based on CdTe quantum paper to sense the mechanism schematic diagram that substrate detects caffeine;
Fig. 2 senses four-(4- pyridyl group) zinc protoporphyrins in nanometer porphyrin fluorescence sensor from group for present invention visualization paper The ultraviolet-visible spectrum of body is filled, abscissa is wavelength, and ordinate is absorbance;
Fig. 3 senses four-(4- pyridyl group) zinc protoporphyrins in nanometer porphyrin fluorescence sensor from group for present invention visualization paper The transmission electron microscope picture for filling body, is nanosphere;
Fig. 4 is the feasibility test figure that CdTe quantum paper of the present invention senses that substrate detects caffeine;Fig. 4 A is to be fixed with The color that CdTe quantum paper senses substrate is aubergine;Fig. 4 B is to sense substrate to CdTe quantum paper four-(4- pyridines are added Base) color reaction figure is navy blue after zinc nanometer porphyrin;Fig. 4 C is to sense substrate to CdTe quantum paper caffeine and four-is added Color reaction figure is light violet magenta after (4- pyridyl group) zinc nanometer porphyrin mixed solution, and the extraction that 4a~4c is Fig. 4 A~4C is colored The Colorimetric results that numerical value obtains;
Fig. 5 is that the present invention prepares the standard colorimetric result figure of caffeine, Fig. 5 A~5F be corresponding in turn to 1nM, 10nM, 50nM, The color that 100nM, 500nM, 1000nM caffeine generate, Fig. 5 G are blank control (color of paper sensing substrate);Fig. 5 a~5g The standard colorimetric result of caffeine is obtained for the extraction color data of Fig. 5 A~5G;The color of Fig. 5 a is navy blue, the face of Fig. 5 b Color is blue, the color of Fig. 5 c is bluish violet, the color of Fig. 5 d is lilac, the color that the color of Fig. 5 e is darkviolet, Fig. 5 f Color for light violet magenta, Fig. 5 g is aubergine.
Fig. 6 is to sense substrate based on CdTe quantum paper to detect caffeine in Xihu Longjing Tea tealeaves complex matrices aqueous solution Colorimetric results figure;The color of Fig. 6 A is bluish violet, the color of Fig. 6 B be bluish purple, Fig. 6 C color be purple, Fig. 6 D Color be light violet magenta, Fig. 6 E color be aubergine.
Fig. 7 is to sense substrate based on CdTe quantum paper to detect caffeine in cell culture fluid complex matrices aqueous solution Colorimetric results figure;The color of Fig. 7 A be blue, Fig. 7 B color be bluish violet, the color of Fig. 7 C be purple, Fig. 7 D color be Light violet magenta, Fig. 7 E color be aubergine.
Fig. 8 is to sense the colorimetric that substrate detects caffeine in human plasma complex matrices aqueous solution based on CdTe quantum paper Result figure.The color of Fig. 8 A is navy blue, the color of Fig. 8 B be blue, Fig. 8 C color be purple, Fig. 8 D color be grey violet Red, Fig. 8 E color is aubergine.
Fig. 9 is to sense substrate based on CdTe quantum paper to detect caffeine in newborn bovine serum complex matrices aqueous solution Colorimetric results figure.The color of Fig. 9 A is navy blue, the color of Fig. 9 B be blue, Fig. 9 C color be purple, Fig. 9 D color be Light violet magenta, Fig. 9 E color be aubergine.
Figure 10 is the specificity figure for sensing substrate the present invention is based on CdTe quantum paper and detecting caffeine;Figure 10 A-10G according to It is secondary to be mixed for theophylline, theobromine, adenine, hypoxanthine, purine, caffeine, blank with four-(4- pyridyl group) zinc nanometer porphyrins The color reaction figure in paper sensing substrate is added dropwise afterwards.The color of Figure 10 A is bluish violet, the color of Figure 10 B is blue, Figure 10 C Color be blue, Figure 10 D color be navy blue, the color of Figure 10 E is navy blue, the color of Figure 10 F be light violet magenta, figure The color of 10G is navy blue.
Specific embodiment
For a better understanding of the invention, invention is described in detail below with reference to drawings and concrete examples.
Complicated for there are instrumentations in the existing detection caffeine technology of solution, the problem of analysis time length, the present invention mentions For a kind of method based on CdTe quantum paper sensing substrate detection caffeine, specifically, the present invention utilizes caffeine and four- The mixed solution of (4- pyridyl group) zinc protoporphyrin self-assembly can make the changed principle of CdTe quantum fluorescence color, and preparation is not Standard colorimetric with concentration caffeine is as a result, judge the dense of caffeine to be measured by carrying out control color with standard colorimetric result Degree.Below by by specific embodiment come to it is of the invention using self assembly porphyrin detect caffeine method preferred embodiment It is described in detail.
Embodiment 1
Based on CdTe quantum paper sensing substrate detection plain coffee because of the method for solution, comprising steps of
(1) synthesis of CdTe quantum;
(1) synthesis of CdTe quantum
Dichloride cadmium (0.1142g) and N-acetyl-L-cysteine (0.098g) are dissolved in 40mL ultrapure water, normal PH value of solution is adjusted to 8.2 with sodium hydroxide solution after stirring 15 minutes under temperature, normal pressure, then inflated with nitrogen ice bath stirring 20 minutes, It is added sodium tellurite (0.0216g), stirs 15 minutes;It adds sodium borohydride (0.0113g), stirs 15 minutes, finally by this Solution is put into reaction kettle, is reacted 55 minutes in 200 DEG C of baking oven, and launch wavelength is obtained after being cooled to room temperature and is 645nm, sends out Red light, concentration are 7.138 × 10-6mol·L-1CdTe quantum.
The synthesis of (2) four-(4- pyridyl group) zinc protoporphyrin self-assemblies
It weighs 0.0032g tetra--(4- pyridyl group) zinc protoporphyrin solid powder and is dissolved in 5mLN, in dinethylformamide solution, Obtaining concentration is 9.356 × 10-4mol·L-1Four-(4- pyridyl group) zinc protoporphyrin N,N-dimethylformamide solution.By dodecane Base trimethyl bromination (0.0003g, 0.02molL-1) be dissolved in 14mL aqueous solution, 1mL tetra--(4- pyridyl group) zinc protoporphyrin is added N,N-Dimethylformamide solution obtains after ultrasonic 5-10min, 70 DEG C of heating water baths ageing 10-15min a kind of highly stable Green transparent colloidal solution.Obtain 6.237 × 10-5mol·L-1Four-(4- pyridyl group) zinc protoporphyrin self-assemblies, as shown in Fig. 2, Its transmission electron microscope characterizes the nanosphere for being shown as 70~100nm of partial size.
(3) preparation of CdTe quantum paper sensing substrate
10 μ L CdTe quantums (3.569 μM) are drawn with liquid-transfering gun to be added dropwise respectively in the circular filter paper that 3 diameters are 6mm On 3 CdTe quantum paper sensing substrates are made, 3 paper sensing substrates are placed into 37 DEG C of baking ovens and dry 5 minutes or so to pico- dry, It is in rose that paper sensing substrate is observed in the ultraviolet camera bellows of 365nm, is taken pictures.
(4) production plain coffee is because of solution standard color comparison card
Prepare the mixed solution of solution 1:1nM caffeine and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly;
The mixed solution of solution 2:10nM caffeine and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly;
The mixed solution of solution 3:50nM caffeine and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly;
The mixed solution of solution 4:100nM caffeine and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly;
The mixed solution of solution 5:500nM caffeine and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly;
The mixed solution of solution 6:1000nM caffeine and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly;
It draws the above-mentioned solution 1 to 6 of 10 μ L with liquid-transfering gun to be added dropwise respectively in CdTe quantum paper sensing substrate, ultraviolet camera bellows Middle observation has different color changes, takes pictures in the ultraviolet camera bellows of 365nm and saves picture, it is soft that picture is imported PhotoShop Part extracts the color data rgb value on picture, and goes out colored dot with the numerical simulation and obtain caffeine standards colorimetric card.
Caffeine standards colorimetric card as shown in connection with fig. 5, Fig. 5 A~5F be corresponding in turn to 1nM, 10nM, 50nM, 100nM, The color that 500nM, 1000nM caffeine generate, Fig. 5 G are blank control (color of paper sensing substrate).
In conjunction with shown in Fig. 1 and Fig. 4, it is glimmering can to quench CdTe quantum for four-(4- pyridyl group) zinc protoporphyrins as can be seen from Figure 1 The mixed solution of light, caffeine and four-(4- pyridyl group) zinc nanometer porphyrins can make CdTe quantum fluorescence color changed Principle.If Fig. 4 A is the paper sensing base color for being fixed with CdTe quantum;Such as Fig. 4 B, four-(4- pyrroles are added to paper sensing substrate Piperidinyl) fluorescent quenching of CdTe quantum becomes blue from rose after zinc nanometer porphyrin, such as Fig. 4 C, it is added to paper sensing substrate Caffeine and four-(4- pyridyl group) zinc nanometer porphyrin mixed solutions, become light red from blue, and with coffee in mixed solution Coffee because concentration it is different, the color of paper sensing substrate also changes, as shown in figure 5, in mixed solution caffeine concentration by 1nM increases to 1000nM, and the color of paper sensing substrate becomes aubergine from blue, then becomes shallow rose, eventually becomes rhodo Color achievees the effect that Visual retrieval caffeine on paper.
Embodiment 2
Based on the method for caffeine in CdTe quantum paper sensing substrate detection Xihu Longjing Tea tealeaves water sample, including step It is rapid:
(1) synthesis of CdTe quantum;
CdTe quantum is synthesized using the method for step (1) in embodiment 1
The synthesis of (2) four-(4- pyridyl group) zinc self assembly porphyrins
Four-(4- pyridyl group) zinc nanometer porphyrin solution are synthesized using the method for step (2) in embodiment 1.
(3) preparation of CdTe quantum paper sensing substrate
CdTe paper sensor substrate is prepared using the method for step (3) in embodiment 1.
(4) preparation of caffeine Xihu Longjing Tea tealeaves water sample solution
By all even high-quality green tea in 80 DEG C of bubble 10min, filtrate is diluted 100 times as solvent and prepares various concentration caffeine
(5) caffeine standards colorimetric card in Aqua Folium Camelliae sinensis is made
Solution 1:1nM caffeine Xihu Longjing Tea tealeaves water sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin are prepared from group Fill the mixed solution of body;
Solution 2:10nM caffeine Xihu Longjing Tea tealeaves water sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Mixed solution;
Solution 3:50nM caffeine Xihu Longjing Tea tealeaves water sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Mixed solution;
Solution 4:100nM caffeine Xihu Longjing Tea tealeaves water sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly The mixed solution of body;
Solution 5:500nM caffeine Xihu Longjing Tea tealeaves water sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly The mixed solution of body;
Solution 6:1000nM caffeine Xihu Longjing Tea tealeaves water sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly The mixed solution of body;
It draws the above-mentioned solution 1 to 6 of 10 μ L with liquid-transfering gun to be added dropwise respectively in CdTe quantum paper sensing substrate, ultraviolet camera bellows Middle observation has different color changes, takes pictures in the ultraviolet camera bellows of 365nm and saves picture, it is soft that picture is imported PhotoShop Part extracts the color data rgb value on picture, and goes out colored dot with the numerical simulation and obtain caffeine standards colorimetric card.
Embodiment 3
Based on the method for caffeine in CdTe quantum paper sensing substrate detection cell culture fluid samples, comprising steps of
(1) synthesis of CdTe quantum;
CdTe quantum is synthesized using the method for step (1) in embodiment 1
The synthesis of (2) four-(4- pyridyl group) zinc self assembly porphyrins
Four-(4- pyridyl group) zinc nanometer porphyrin solution are synthesized using the method for step (2) in embodiment 1.
(3) preparation of CdTe quantum paper sensing substrate
CdTe paper sensor substrate is prepared using the method for step (3) in embodiment 1.
(4) preparation of cell culture fluid sample solution
Cell culture fluid centrifuging and taking supernatant is diluted 100 times as solvent and prepares various concentration caffeine
(5) caffeine standards colorimetric card in cell culture fluid samples is made
Prepare solution 1:1nM caffeine cell culture fluid samples and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Mixed solution;
Solution 2:10nM caffeine cell culture fluid samples and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly it is mixed Close solution;
Solution 3:50nM caffeine cell culture fluid samples and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly it is mixed Close solution;
Solution 4:100nM caffeine cell culture fluid samples and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Mixed solution;
Solution 5:500nM caffeine cell culture fluid samples and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Mixed solution;
Solution 6:1000nM caffeine cell culture fluid samples and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Mixed solution;
It draws the above-mentioned solution 1 to 6 of 10 μ L with liquid-transfering gun to be added dropwise respectively in CdTe quantum paper sensing substrate, ultraviolet camera bellows Middle observation has different color changes, takes pictures in the ultraviolet camera bellows of 365nm and saves picture, it is soft that picture is imported PhotoShop Part extracts the color data rgb value on picture, and goes out colored dot with the numerical simulation and obtain caffeine standards colorimetric card.
Embodiment 4
Based on the method for caffeine in CdTe quantum paper sensing substrate detection human plasma sample, comprising steps of
(1) synthesis of CdTe quantum;
CdTe quantum is synthesized using the method for step (1) in embodiment 1
The synthesis of (2) four-(4- pyridyl group) zinc self assembly porphyrins
Four-(4- pyridyl group) zinc nanometer porphyrin solution are synthesized using the method for step (2) in embodiment 1.
(3) preparation of CdTe quantum paper sensing substrate
CdTe paper sensor substrate is prepared using the method for step (3) in embodiment 1.
(4) preparation of human plasma sample solution
Human plasma centrifuging and taking supernatant is diluted 100 times as solvent and prepares various concentration caffeine
(5) caffeine standards colorimetric card in producer's plasma samples
Prepare the mixed of solution 1:1nM caffeine human plasma sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Close solution;
The mixing of solution 2:10nM caffeine human plasma sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly is molten Liquid;
The mixing of solution 3:50nM caffeine human plasma sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly is molten Liquid;
The mixing of solution 4:100nM caffeine human plasma sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Solution;
The mixing of solution 5:500nM caffeine human plasma sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Solution;
The mixing of solution 6:1000nM caffeine human plasma sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Solution;
It draws the above-mentioned solution 1 to 6 of 10 μ L with liquid-transfering gun to be added dropwise respectively in CdTe quantum paper sensing substrate, ultraviolet camera bellows Middle observation has different color changes, takes pictures in the ultraviolet camera bellows of 365nm and saves picture, it is soft that picture is imported PhotoShop Part extracts the color data rgb value on picture, and goes out colored dot with the numerical simulation and obtain caffeine standards colorimetric card.
Embodiment 5
Based on the method for caffeine in CdTe quantum paper sensing substrate detection newborn bovine serum sample, comprising steps of
(1) synthesis of CdTe quantum;
CdTe quantum is synthesized using the method for step (1) in embodiment 1
The synthesis of (2) four-(4- pyridyl group) zinc self assembly porphyrins
Four-(4- pyridyl group) zinc nanometer porphyrin solution are synthesized using the method for step (2) in embodiment 1.
(3) preparation of CdTe quantum paper sensing substrate
CdTe paper sensor substrate is prepared using the method for step (3) in embodiment 1.
(4) preparation of newborn bovine serum sample solution
Newborn bovine serum centrifuging and taking supernatant is diluted 100 times as solvent and prepares various concentration caffeine
(5) caffeine standards colorimetric card in newborn bovine serum matrix is made
Prepare solution 1:1nM caffeine newborn bovine serum sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Mixed solution;
Solution 2:10nM caffeine newborn bovine serum sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly it is mixed Close solution;
Solution 3:50nM caffeine newborn bovine serum sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly it is mixed Close solution;
Solution 4:100nM caffeine newborn bovine serum sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Mixed solution;
Solution 5:500nM caffeine newborn bovine serum sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Mixed solution;
Solution 6:1000nM caffeine newborn bovine serum sample and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self-assembly Mixed solution;
It draws the above-mentioned solution 1 to 6 of 10 μ L with liquid-transfering gun to be added dropwise respectively in CdTe quantum paper sensing substrate, ultraviolet camera bellows Middle observation has different color changes, takes pictures in the ultraviolet camera bellows of 365nm and saves picture, it is soft that picture is imported PhotoShop Part extracts the color data rgb value on picture, and goes out colored dot with the numerical simulation and obtain caffeine standards Colorimetric results.
Method of the present invention has many advantages, including system compared to tradition in the method for chromatography hair method measurement caffeine It is good to the high sensitivity of caffeine detection, strong antijamming capability, response for simple, reaction condition is mild, visualization paper biography Sense nanometer porphyrin fluorescence sensor has practical application value in biochemistry, food, medicine and other fields.
Examples 1 to 5 is listed based on CdTe quantum paper sensing substrate detection caffeine pure sample and in Xihu Longjing Tea Aqua Folium Camelliae sinensis, cell culture fluid, human plasma, in newborn bovine serum complex matrices caffeine method.
5 kinds of embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but not Limitations on the scope of the patent of the present invention therefore can be interpreted as.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (10)

1. a kind of method based on nanometer porphyrin fluorescence paper sensing Visual retrieval caffeine, which is characterized in that comprising steps of
(1) synthesis of CdTe quantum
Dichloride cadmium and N-acetyl-L-cysteine are dissolved in pure water and are uniformly mixed, sodium tellurite, boron hydrogen are then sequentially added Change sodium, finally baking oven in react after the CdTe quantum that is fluoresced;
The synthesis of (2) four-(4- pyridyl group) zinc protoporphyrin self-assemblies
Four-(4- pyridyl group) zinc protoporphyrin, that is, porphyrins are dissolved in n,N-Dimethylformamide solution, four-(4- pyridyl group) zinc are obtained Four-(4- pyridyl group) zinc porphins are added into dodecyl trimethyl ammonium bromide aqueous solution for porphyrin n,N-Dimethylformamide solution Quinoline n,N-Dimethylformamide solution, ultrasound, 70 DEG C of water-bath ageings, obtains four-(4- pyridyl group) zinc protoporphyrin self-assemblies and receives Rice porphyrin;
(3) preparation of CdTe quantum paper sensing device substrate
CdTe quantum is added dropwise on paper device filter paper dick, after the filter paper dick on paper device absorbs fixed CdTe quantum Up to CdTe quantum paper sensing device substrate;
(4) caffeine standards colorimetric card is made
The caffeine of various concentration and the mixed solution of four-(4- pyridyl group) zinc protoporphyrin self assembly solution are prepared, by mixed solution It is successively added dropwise in CdTe quantum paper sensing substrate, is observed in ultraviolet camera bellows, various concentration caffeine and CdTe quantum Paper senses substrate reaction and generates different colors, takes pictures to each CdTe quantum paper sensing substrate, arrangement obtains coffee Because of standard color comparison card;
(5) the caffeine concentration in sample to be tested is detected
Mixed solution is made in sample and four-(4- pyridyl group) zinc protoporphyrin self assembly solution to be added dropwise in paper sensing substrate, paper passes Sense substrate has a color response to sample, and the caffeine standards colorimetric card that control step (4) obtains obtains the dense of caffeine in sample Degree.
2. the method according to claim 1 based on CdTe quantum paper sensing substrate detection caffeine, which is characterized in that The mixed solution pH of dichloride cadmium and N-acetyl-L-cysteine is adjusted to 8.0~8.5 in the step (1), oven temperature control 200~220 DEG C are made as, launch wavelength is obtained and is 640~660nm, sends out the CdTe quantum of red fluorescence.
3. the method according to claim 1 based on CdTe quantum paper sensing substrate detection caffeine, which is characterized in that The step (4) is identical with the concentration of four-(4- pyridyl group) zinc protoporphyrin self-assembly solution in step (5), is 30~33 μM; The concentration of caffeine is respectively the gradient concentration in 1nM-1000nM in mixed solution in the step (4).
4. the method based on CdTe quantum paper sensing substrate detection caffeine according to right 1, which is characterized in that described Mixed solution is respectively 1nM caffeine and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution, 10nM coffee in step (4) Coffee because and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution, 50nM caffeine and 31.2 μM of four-(4- pyridyl group) zinc porphin Quinoline self assembly solution, 100nM caffeine and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution, 500nM caffeine and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution, 1000nM caffeine and 31.2 μM of four-(4- pyridyl group) zinc protoporphyrin are certainly Assemble solution.
5. the method according to claim 1 based on CdTe quantum paper sensing substrate detection caffeine, which is characterized in that In the step (4), various concentration caffeine is reacted to the photo importing graphics process for generating different colours with paper sensing substrate Software extracts the color data in picture, simulates caffeine standards colorimetric card using color data.
6. the method according to claim 2 based on CdTe quantum paper sensing substrate detection caffeine, which is characterized in that In the step (1), N-acetyl-L-cysteine, dichloride cadmium, sodium tellurite substance amount ratio be 1.2~1.5: 1.0:0.2。
7. the method according to claim 1 based on CdTe quantum paper sensing substrate detection caffeine, which is characterized in that In the step (2), four-(4- pyridyl group) zinc protoporphyrins and dodecyl trimethyl ammonium bromide the mass ratio of the material be 1:290~ 305。
8. the method according to claim 1 based on CdTe quantum paper sensing substrate detection caffeine, which is characterized in that In the step (3), CdTe quantum concentration is 3~4 μm of ol/L.
9. the method according to claim 1 based on CdTe quantum paper sensing substrate detection caffeine, which is characterized in that In the step (3), in the step (2), CdTe quantum dripping quantity is 8~10uL, and it is 4 that filter paper dick paper device, which is diameter, The paper that CdTe quantum has been added dropwise sensing substrate is placed in 36~39 DEG C of baking oven, dries 5~7 points by the circular filter paper of~6mm Clock.
10. the method according to claim 1 based on CdTe quantum paper sensing substrate detection caffeine, feature exist In nanometer porphyrin partial size is the nanosphere of 70~100nm in described four-(4- pyridyl group) zinc protoporphyrin self assembly solution.
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