CN105241878B - A kind of aldehydes rapidly measuring device part based on capillarity and Nano Silver recognition principle and its preparation method and application - Google Patents
A kind of aldehydes rapidly measuring device part based on capillarity and Nano Silver recognition principle and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of aldehydes rapidly measuring device part based on capillarity Yu argentum nano composite material recognition principle, is made up of capillary with the argentum nano composite material solidified in capillary inner surface, and argentum nano composite material is the silver ion and silver nano-grain of gelatin coatings.Additionally provide its preparation method and application simultaneously.By the argentum nano composite material that gelatin coatings are modified in treated capillary tube inner wall, and then occur visualization color reaction by argentum nano composite material on aldehyde compound in sample and tube wall, the quantitative analysis to aldehydes in aquatic products is realized, complicated photoelectric instrument is not related to and is used.The capillary platform of use has cheap, portable, presentation integrated design feature, has the advantages that simple to operate, detection time is short, sensitivity is high, sample dosage is few, device is portable, amount of samples is few, can be achieved to aldehydes in aquatic products（Such as formaldehyde）Scene speed survey.
Description
Technical field
The invention belongs to technical field of analytical chemistry, it is related to a kind of aldehydes based on capillarity Yu Nano Silver recognition principle
Rapidly measuring device part and its preparation method and application.
Background technology
Food security is great livelihood issues, the stable breath breath of the healthy and social harmony with numerous people
It is related.Particularly, since the objective of the struggle of " 18 the is big " proposition " conservation culture " of party, food and Environmental security have been ensured
Turn into a great and urgent task in China's socio-economic development.Particularly in recent years, nearly river and paralic environment pollution
（Containing illegal additive in production）Situation is increasingly severe, when environmental poisonous substance enters human body with aquatic products ecological chain and causes poisoning
There is generation.Therefore, researching and developing effective regulation technique of aquatic products and promoting marine industry to develop in a healthy way turns into the task of top priority.
The aldehydes such as formaldehyde are a kind of conventional adhesives of industrial circle, particularly in construction material, such as wood furniture, oil
Paint etc..Be used for a long time and contact these materials, indoor formaldehyde concentration can be made gradually to accumulate, to a certain extent will harmful to human it is strong
Health.For example, research discovery formaldehyde is relevant with room air syndrome, such as eye nose is stimulated, fatigue, headache and cough.At present, not only
It is that Formaldehyde Pollution of Indoor Air needs people to pay close attention to, in food in such as potential poisonous substance of fish and shellfish aquatic products, with the harm of aldehyde material
It is the most serious and common.Research shows, the aldehyde materials such as formaldehyde are added in aquatic products with anti-corrosion, such as formalin（It is commonly called as Fu Er
Malin）, Long Term Contact formalin may result in cancer.Trace formaldehyde accumulates in human body and may result in cell degeneration.
So formaldehyde is classified as a kind of " suspected carcinogens matter " by the World Health Organization.At present, the side of detection food and Formaldehyde in Environment
The main chromatographic method of method, electrophoresis, fluorescence analysis, the biology sensor based on enzyme and with metal oxide basis
Gas sensor.Though these technologies selectivity and sensitivity are high, there is that valuable instrument, complex operation, analyze speed are slow, be difficult to
The limitations such as field monitoring application.The method using colorimetric detection formaldehyde is occurred in that in recent years, but for food（Such as aquatic products）
The quick test technique of middle formaldehyde is just at the early-stage.For example, scientific research personnel, which uses, is soaked with tollens reagent and ATP perfluorinated sulfonic acid diaphragm ratio
Color have detected formaldehyde.But this method detection duration is up to 1 hour, significantly impacts its detection sensitivity.Suslick etc. passes through primary
A kind of method of Rapid Detection of Formaldehyde of the reaction designing of amine and formaldehyde.Although this method can realize reversible detection, necessary
Dependent on a series of pH indicator and substantial amounts of statistical information；In addition, a kind of agar caramel of the exploitation such as Jingbin Zeng
Based on colorimetric detection formaldehyde method, but this method mainly relies on tollens reagent, and its stability is not good enough.Therefore, open
Send out quick detection a kind of, sensitive practicality, it is easy to operate and can field application portable inspectiont formaldehyde method have it is important
Meaning.
Capillary glass tube is usually that internal diameter is equal to or less than 1.0 millimeters of glass tubule, because caliber have it is thin such as hair therefore
Claim capillary.Some special natures and low cost and other advantages of capillary and be applied in various research and analyse.For example, capillary
Electrophoresis tube is that a class analyzes skill using capillary as split tunnel, using the high DC electric field of high pressure as the common liquid phase separation of driving force
Art, includes electrophoresis, chromatogram and its intersection content.In addition, the sensor based on capillary is also applied to photochemistry detection and electricity
Chemical analysis, for example《Determination of pyruvic acid by using enzymic fluorescence
capillary analysis 》Propose a kind of pyruvic acid " fluorescence capillary analysis (FCA) " based on enzymic catalytic reaction.Should
Method, to substitute conventional fluorescent pond, is realized in micro-example third using a special stand and conventional medical capillary
The analysis of ketone acid, but extrinsic power is needed with pipette samples, and large-scale luminoscope need to be used to complete to determine operation.Recently,
《Development of a long-life capillary enzyme bioreactor for the determination
of blood glucose》Constructing a kind of enzymic catalytic reaction analytical equipment using capillary as reactor is used for the inspection of blood glucose
Survey, the device is by capillary wall surface fixing glucose oxidase, realizing the electrochemical gaging to glucose in blood.But
It is that in these current analysis methods, capillary is only sample split tunnel or active material（Such as enzyme）Immobilization surface, sample
Suction still need using the auxiliary such as flow injection or pump, be not directed to the capillarity of capillary, meanwhile, dependence of still needing is outer to write letters
Number detecting instrument（Such as luminoscope and electrochemical instrument）Quantitative analysis could be completed, it is impossible to quickly and intuitively obtain quantitative analysis knot
Really.
The content of the invention
The disadvantages mentioned above that the present invention exists for prior art, using normal capillary pipe as detection platform, there is provided a kind of letter
Just it is, sensitive, quick, cheap, can field application portable aldehydes rapidly measuring device part.
Present invention also offers above-mentioned aldehydes rapidly measuring device part preparation method, gelatin coatings are synthesized using a cooking-pot type reaction path
Argentum nano composite material（Mixture comprising silver ion and silver nano-grain）, and solidify in capillary inner surface.
Aldehydes rapidly measuring device part of the present invention is mainly used in the speed survey of aldehyde content in aquatic products.
Technical solution of the present invention is as follows：
A kind of aldehydes rapidly measuring device part based on capillarity Yu Nano Silver recognition principle, it is characterised in that：By capillary and
Solidify the argentum nano composite material composition in capillary inner surface, the argentum nano composite material load capacity of capillary inner surface is
2.0×10-4~3.2 × 10-4mg/mm2；Described argentum nano composite material is the mixture of silver ion and silver nano-grain, silver
Nano composite material outer surface is enclosed with gelatin.
Described capillary inner diameter is 0.9~1.1mm, and thickness is 0.10~0.15mm, and length is 10cm, and material is glass
Glass.
Priming color is colourless in described aldehydes rapidly measuring device part, capillary.
The above-mentioned preparation method based on capillarity Yu the aldehydes rapidly measuring device part of Nano Silver recognition principle, including following step
Suddenly：
1）Prepare the argentum nano composite material of gelatin coatings：
By 20 mM/L silver nitrate aqueous solution and the % of mass fraction 4 aqueous gelatin solution by volume 0.2 ~ 0.6：1, mix
Close uniform, simultaneously lucifuge reacts 2~3 h for 37 DEG C of incubation stirrings, then by reaction solution in -20~-10 DEG C of cryogenic freezings 20~30
Min terminating reactions, must solidify the argentum nano composite material of the gelatin coatings of state, standby；
2）Argentum nano composite material solidifies in capillary inner surface：
A) it is 2.5 ~ 4.0 in volume ratio by capillary：10~12 h are soaked in 1 Sulfuric-acid-hydrogen-peroxide mixed liquor, then are divided
Not Yong distilled water and washes of absolute alcohol three times, then capillary is placed in the 3- aminopropyl triethoxysilanes of volume fraction 6%
（APTES）10~12 h are soaked in-ethanol solution, capillary uses alcohol flushing three times after taking out, dry for standby；
B) by step 1）The argentum nano composite material of preparation is warming up to 35 DEG C and is changed into liquid solution, and uses 0.01 M/L
Sodium hydrate aqueous solution regulation pH value of solution be 10.0~11.0, then take 20~40 μ L solution be added to step a) processing after
Capillary in, make solution uniform fold in after capillary tube inner wall, incubate and remained in 30~40 min, blowout capillary in 37 DEG C
Remaining solution, obtains aldehydes rapidly measuring device part.
Step b) the solution is expelled in capillary with syringe.
Described aldehydes rapidly measuring device part is placed in 4 DEG C of preservations.
Application of the invention based on capillarity Yu the aldehydes rapidly measuring device part of argentum nano composite material recognition principle：For sample
The speed survey of aldehydes total content in product, the speed survey of content of formaldehyde preferably in aquatic products.Because aldehydes is generally not in actual sample
With single aldehyde（Such as formaldehyde, acetaldehyde）In the presence of, therefore it is not easily achieved in detection process the detection of single aldehydes.In addition, this hair
Bright rapidly measuring device part is the quick detection on aldehydes, and formaldehyde is as a kind of preservative and antistaling agent, using than wide, in water
Content is very high in product, can be as typical case's detection.
Described application, step is as follows：
1）Set up standard color control collection of illustrative plates：The standard liquid of compound concentration gradient aldehyde-containing type, aldehydes rapidly measuring device part is inserted
In the standard liquid for entering preparation, the argentum nano composite material solidified in capillary inner surface is carried out with the aldehydes in suction capillary
Chromogenic reaction, is stood after 7~8 min, colour stable, and reacted color and concentration of standard solution are corresponded, mark is set up
Quasi- color contrast collection of illustrative plates；
2）Sample detection：Testing sample is crushed through ultrasonic cell disruptor, then soaks 2~3h, sample is in water
Middle concentration is 150 mg/L, takes supernatant, is diluted with water 10~100 times, inserts aldehydes rapidly measuring device part, solidifies in table in capillary
The argentum nano composite material in face carries out chromogenic reaction, stands after 7~8 min, colour stable, by color after reaction and step 1）Build
Vertical standard color control collection of illustrative plates color is compared, and determines the concentration of aldehydes in sample.
Described application, aldehydes rapidly measuring device part is limited to 2.0nM to the lowest detection of aldehydes.
The argentum nano composite material of gelatin coatings of the present invention is to aldehydes Response Mechanism, by taking formaldehyde as an example：Gelatin bag
The argentum nano composite material wrapped up in is cured in capillary tube inner wall, and wherein silver ion is inhaled under silver nano-grain catalysis with capillary
Reduction reaction occurs for aldehydes in the sample taken, and the silver-colored simple substance formed is attached to silver nano-grain surface and grows up and form visualization
Discoloration, is compared with standard capillary color, and compareing collection of illustrative plates by standard color determines its concentration, realizes to the visual speed of aldehydes
Survey, the mechanism schematic diagram of chromogenic reaction is as shown in figure 1, involved chromogenic reaction formula is：
。
Aldehydes of the invention based on capillarity Yu argentum nano composite material recognition principle（Such as formaldehyde）Rapidly measuring device part, with hair
Tubule is carrier and carries out specially treated and functionalization using chemically and physically method, constitutes and portable or miniaturization optical telecommunications
The sensing fast measuring platform that number output device matches；Present invention also offers above-mentioned aldehydes rapidly measuring device part preparation method, using one
Cooking-pot type reaction path synthesizes the argentum nano composite material of gelatin coatings（Mixture comprising silver ion and silver nano-grain）, due to
The unique sol-gel transition behavior of gelatin（Less than 35 DEG C are solid, are liquid above）, therefore, by low temperature（-20 ℃）
The quick-frozen in good time reaction for terminating gelatine reduction silver ion, obtains the nano composite material for including gelatin, silver ion and silver nano-grain,
And solidified in capillary tube inner wall, aldehydes rapidly measuring device part is obtained, is calculated through weighing, the % of 60 %~80 argentum nano composite material will
It is fixed on capillary tube inner wall.The application of above-mentioned aldehydes rapidly measuring device part, is the capillarity automatic sucking sample by capillary, enters
And the specific reduction metachromasia of aldehyde radical in the silver ion and sample of its catalysis parcel is utilized, realize to aquatic products such as fish and shellfish
The scene speed of middle aldehydes is surveyed, have the advantages that it is easy, sensitive, quick, cheap, can field application, portable.
Compared with prior art, its advantage is the present invention：
（1）By the argentum nano composite material that gelatin coatings are modified in treated capillary tube inner wall（Comprising silver ion and
The mixture of silver nano-grain）, and then combined hair with argentum nano composite material on tube wall by aldehyde compound in sample
Raw visualization color change, realizes the quantitative analysis to aldehydes in aquatic products, complicated photoelectric instrument is not related to and is used.
（2）The capillary platform of use have it is cheap, portable, present integrated design feature, be both tested liquid container and
Reaction vessel, is the fixation support of identification of function molecule again；Meanwhile, by the capillarity of capillary, self-service pipette samples,
Its quantitative manner is directly perceived, quick, can carry out quantitative analysis by color change degree in capillary.
（3）With simple to operate, detection time is short, sensitivity is high, sample dosage is few, device is portable, amount of samples is few etc.
Advantage, can be achieved to aldehydes in aquatic products（Such as formaldehyde）Scene speed survey.
Brief description of the drawings
Fig. 1 is the mechanism schematic diagram of aldehydes rapidly measuring device part chromogenic reaction of the present invention；
Fig. 2 is absorbance-concentration standard curve that aldehydes rapidly measuring device part of the present invention detects formaldehyde；
Fig. 3 is the standard color control collection of illustrative plates that aldehydes rapidly measuring device part of the present invention detects formaldehyde.
Embodiment
Technical scheme is further illustrated below by specific embodiment.
Embodiment 1
Aldehydes rapidly measuring device part method is prepared, is comprised the following steps：
1）Prepare the argentum nano composite material of gelatin coatings：
By the aqueous gelatin solution of 20mM/L silver nitrate aqueous solution and mass fraction 4% by volume 0.4:1 is well mixed,
Stirring is incubated in 37 DEG C and lucifuge reacts 2 h, reaction solution is then moved into -15 DEG C of min of cryogenic freezing 25, gelatin is terminated also
The reaction of former silver ion, obtains the argentum nano composite material of gelatin coatings, standby；
2）Argentum nano composite material solidifies in capillary inner surface：
A) it is 3 in volume ratio by capillary：12 h are soaked in 1 Sulfuric-acid-hydrogen-peroxide mixed liquor, then respectively with distillation
Capillary, is then placed in the % of volume fraction 6 3- aminopropyl triethoxysilanes by water and washes of absolute alcohol three times
（APTES）12 h are soaked in-ethanol solution, capillary uses alcohol flushing three times after taking out, dry for standby；
B) by step 1）The 500 μ L argentum nano composite materials prepared are warming up to 35 DEG C and are changed into liquid solution, i.e. colloidal sol
State, is 10.0~11.0 with 0.01 M/L sodium hydrate aqueous solution regulation pH value of solution, and it is molten then to draw 20 μ L with syringe
Liquid is expelled in the capillary after step a) processing, is laid flat and is rotated capillary, solution uniform fold in after capillary tube inner wall,
Surplus solution in 30 min, blowout capillary is incubated in 37 DEG C, aldehydes rapidly measuring device part is obtained, is placed in 4 DEG C of preservations.
Aldehydes rapidly measuring device part of the embodiment 1 based on capillarity Yu Nano Silver recognition principle, by capillary and solidifying in hair
The argentum nano composite material of inner tubule surface is constituted, and argentum nano composite material is the mixture of silver ion and silver nano-grain, silver
Nano composite material outer surface is enclosed with gelatin；The argentum nano composite material load capacity of capillary inner surface is 2.0 × 10-4~
3.2×10-4mg/mm2；Capillary inner diameter is：1.0 mm, thickness is 0.15 mm, and length is 10 cm, and material is glass, capillary
Priming color is colourless in pipe.
Aldehydes rapidly measuring device part performance verification of the present invention, using embodiment 1 prepare aldehydes rapidly measuring device part be used for detect formaldehyde as
Example：
Set up standard curve and compare collection of illustrative plates with standard color：Standard liquid of the compound concentration gradient containing Formaldehyde-water, formaldehyde is dense
Degree is followed successively by 2 nM/L, 10 nM/L, 20 nM/L, 50 nM/L, 100 nM/L, 200 nM/L, 400 nM/L and 800 nM/L,
Aldehydes rapidly measuring device part is inserted in the standard liquid of preparation respectively, solidifies the argentum nano composite material in capillary inner surface and suction
The formaldehyde entered in capillary carries out chromogenic reaction, stands 7 ~ 8 min, after color no longer changes, liquid in discharge pipe.
1）The absorbance of liquid in colour developing capillary is determined, the standard curve of absorbance and concentration of formaldehyde is set up, such as Fig. 2 institutes
Show；
2）Record colour developing postcapillary color, reacted color and formaldehyde concentration of standard solution are corresponded, set up
The standard color control collection of illustrative plates of aldehydes rapidly measuring device part detection formaldehyde of the present invention, as shown in Figure 3.
From Fig. 2 and 3 as can be seen that the embodiment of the present invention 1 prepare aldehydes rapidly measuring device part detect formaldehyde when, 10 nM~
Good linear relationship is presented in 800 nM concentration ranges, coefficient correlation 0.9865, lowest detection is limited to 2.0 nM.Fig. 3 is set up
Aldehydes rapidly measuring device part detection formaldehyde standard color control collection of illustrative plates, can be as development criteria, the formaldehyde examination with other samples
Comparative result, quantitative detection formaldehyde.
The aldehydes rapidly measuring device part speed prepared using the embodiment of the present invention 1 surveys aldehydes in Common Aquatic Products（By taking formaldehyde as an example）Contain
Amount.
Embodiment 2：The speed survey of aldehyde content in live fish
So that fresh crucian surveys formaldehyde as an example.In market grab sample, choose crucian part fish body and crushed with supersonic cell
Machine is crushed, and is added water to sample concentration for 150 mg/L, is soaked 3 h, take immersion supernatant, and 10 times, insertion aldehydes speed are diluted with water
Device is surveyed, the argentum nano composite material solidified in capillary inner surface carries out chromogenic reaction, stands 7~8 min, colour stable
Afterwards, color after reaction is compareed into collection of illustrative plates color with Fig. 3 standard colors to compare, determines the concentration of formaldehyde in crucian sample.
Result verification：Determine the capillary absorbance after the colour developing of above-mentioned crucian sample, and according to the absorbance of Fig. 2 formaldehyde-
Concentration standard curve calculates concentration of formaldehyde, is consistent with the concentration that the formaldehyde that collection of illustrative plates color is compared is compareed according to standard color.
Aldehydes is measured in this way in other fish, as a result such as table 1 below：
Content of formaldehyde speed surveys result in the live fish of table 1
Embodiment 3：The speed survey of aldehyde content in frozen fish
Frozen fish is taken at random in supermarket, detection method be the same as Example 2 draws aldehyde content in frozen fish, the results are shown in Table
2。
Result verification：The capillary absorbance after above-mentioned fish sample colour developing is determined, and according to absorbance-concentration of aldehydes
Standard curve calculates concentration of aldehyde species, is consistent with the concentration that the aldehydes that collection of illustrative plates color is compared is compareed according to standard color.
Aldehyde content speed surveys result in the frozen fish of table 2
Embodiment 4：The speed survey of shellfish aldehyde content
So that scallop middling speed surveys formaldehyde as an example, scallop is taken at random in supermarket, detection method be the same as Example 2 is drawn in scallop
Aldehyde content, the results are shown in Table 3.
Result verification：The capillary absorbance after above-mentioned scallop sample colour developing is determined, and according to absorbance-concentration of formaldehyde
Standard curve calculates concentration of formaldehyde, is consistent with the concentration that the formaldehyde that collection of illustrative plates color is compared is compareed according to standard color.
Aldehyde content is measured in this way in other shellfishes, as a result such as table 3 below：
Aldehyde content speed surveys result in the shellfish of table 3
Claims (9)
1. a kind of formaldehyde rapidly measuring device part based on capillarity Yu Nano Silver recognition principle, it is characterised in that：By capillary and admittedly
Change the argentum nano composite material composition in capillary inner surface, the argentum nano composite material load capacity of capillary inner surface is 2.0
×10-4~3.2 × 10-4 mg/mm2；Described argentum nano composite material is the mixture of silver ion and silver nano-grain, Yin Na
Nano composite material outer surface is enclosed with gelatin.
2. formaldehyde rapidly measuring device part according to claim 1, it is characterised in that：Described capillary inner diameter is 0.9~1.1
Mm, thickness is 0.10~0.15 mm, and length is 10 cm, and material is glass.
3. formaldehyde rapidly measuring device part according to claim 1, it is characterised in that：In described formaldehyde rapidly measuring device part, capillary
Priming color is colourless.
4. the preparation method of any one of a kind of claim 1-3 formaldehyde rapidly measuring device parts, it is characterised in that including following step
Suddenly：
1）Prepare the argentum nano composite material of gelatin coatings：
By the aqueous gelatin solution of 20 mM/L silver nitrate aqueous solution and mass fraction 4% by volume 0.2~0.6：1, mixing is equal
Even, 37 DEG C incubate stirring and lucifuge 2~3 h of reaction, then by reaction solution in -20~-10 DEG C of min of cryogenic freezing 20~30
Terminating reaction, must solidify the argentum nano composite material of the gelatin coatings of state, standby；
2）Argentum nano composite material solidifies in capillary inner surface：
A) it is 2.5~4.0 in volume ratio by capillary：10~12 h are soaked in 1 Sulfuric-acid-hydrogen-peroxide mixed liquor, then are distinguished
With distilled water and washes of absolute alcohol three times, then by capillary be placed in the 3- aminopropyl triethoxysilanes of volume fraction 6%-
10~12 h are soaked in ethanol solution, capillary uses alcohol flushing three times after taking out, dry for standby；
B) by step 1）The argentum nano composite material of preparation is warming up to 35 DEG C and is changed into liquid solution, and with 0.01 M/L hydrogen
Aqueous solution of sodium oxide regulation pH value of solution is 10.0~11.0, the hair for then taking 20~40 μ L solution to be added to after step a) processing
In tubule, solution uniform fold incubates 30~40 min in after capillary tube inner wall in 37 DEG C, blows out surplus solution in capillary,
Obtain formaldehyde rapidly measuring device part.
5. preparation method according to claim 4, it is characterised in that：Described formaldehyde rapidly measuring device part is placed in 4 DEG C of preservations.
6. a kind of application of any one of claim 1-3 formaldehyde rapidly measuring device parts, it is characterised in that：It is total for formaldehyde in sample
The speed survey of content.
7. application according to claim 6, it is characterised in that：Speed for content of formaldehyde in aquatic products is surveyed.
8. application according to claim 6, it is characterised in that step is as follows：
1）Set up standard color control collection of illustrative plates：Standard liquid of the compound concentration gradient containing formaldehyde, the insertion of formaldehyde rapidly measuring device part is matched somebody with somebody
In the standard liquid of system, the argentum nano composite material solidified in capillary inner surface is developed the color with the formaldehyde in suction capillary
Reaction, is stood after 7~8 min, colour stable, and reacted color and concentration of standard solution are corresponded, reference colour is set up
Coloured silk control collection of illustrative plates；
2）Sample detection：Testing sample is crushed through ultrasonic cell disruptor, then soaks 2~3h, and sample is dense in water
Spend for 150 mg/L, take supernatant, be diluted with water 10~100 times, insert formaldehyde rapidly measuring device part, solidify in capillary inner surface
Argentum nano composite material carries out chromogenic reaction, stands after 7~8 min, colour stable, by color after reaction and step 1）Set up
Standard color control collection of illustrative plates color is compared, and determines the concentration of formaldehyde in sample.
9. application according to claim 6, it is characterised in that：The lowest detection of formaldehyde rapidly measuring device part PARA FORMALDEHYDE PRILLS(91,95) is limited to 2.0
nM。
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Non-Patent Citations (4)
| Title |
|---|
| One-pot synthesis of gelatin-based, slow-release polymermicroparticles containing silver nanoparticles and their application inanti-fouling paint;Tamás Szabóa et.al;《Progress in Organic Coatings》;elsevier;20140315;第77卷;1226-1232 * |
| Use of a Silver - Gelatin Complex for the Microdetermination of Hydrogen Sulphide in the Atmosphere;Tarasankar Pal et.al;《ANALYST》;19860630;第111卷;691-693 * |
| 明胶纳米银的一锅式合成及其高效催化性能的研究;孙宗招等;《化学传感器》;20140331;第34卷(第1期);17-22 * |
| 用明肢为助剎合成鈉米银;关越鹏等;《明胶科学与技术》;20150630;第35卷(第2期);85-91 * |
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