CN103776781A - Nano material for detecting dimethoate and preparation method thereof - Google Patents
Nano material for detecting dimethoate and preparation method thereof Download PDFInfo
- Publication number
- CN103776781A CN103776781A CN201410051064.4A CN201410051064A CN103776781A CN 103776781 A CN103776781 A CN 103776781A CN 201410051064 A CN201410051064 A CN 201410051064A CN 103776781 A CN103776781 A CN 103776781A
- Authority
- CN
- China
- Prior art keywords
- preparation
- nano material
- gel
- tpps
- plant esterase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention aims at providing a nano material for detecting dimethoate. The nano material comprises the following components by weight percent: 97.43 to 99.31 percent of sodium silicate, 0.06 to 0.23 percent of TPPS4 and 0.63 to 2.34 percent of plant-esterase. The plant-esterase is fixed by adopting a sol-gel technology, the fixation process is a physical embedding process, a gel network is gradually formed surrounding the enzyme, the structure completeness and isotropy and biological activity of surface microstructure of the enzyme can be maintained by virtue of the moderate reaction condition, amorphous structure of the gel and biological compatibility. Then the TPPS4 enters the gel network by virtue of the micropores on the surface of the gel to be reacted with the plant-esterase so as to form aggregation on the surface of the enzyme. In the gel network, the enzyme and the aggregation have less possibility of being subjected to the unfavorable influence of unfavorable environmental factors, but also the structure is more stable, the precipitate is unlikely to form, the enzyme and the aggregation are easy to store, the reaction activity can be well protected, and the detection reaction is favored.
Description
Technical field
The invention belongs to the material and the preparing technical field thereof that detect organophosphorus pesticide, particularly a kind of nano material that detects Rogor and preparation method thereof.
Background technology
Rogor (Dimethoate) is a kind of organophosphorus systemic insecticide of tagging with stomach poison function that has, its chemistry O by name, O-dimethyl-S-(N-methylamino formyl methyl) phosphorodithioate.Rogor is the pesticide that a kind of purposes is wide, output is larger, to sucking pest, as aphid, aleyrodid etc., has good prevention effect.But Rogor is volatile, a large amount of lost agricultural chemicals evaporate into air, water body or sedimentation and are gathered in and in soil, pollute farming animals fishing secondary product, and transfer to human body by the inrichment of food chain, and human body is produced to harm.Studies show that, Rogor has potential teratogenesis, mutagenesis and carcinogenesis.Therefore, research Determination of Dimethoate Residues detects very necessary.
At present, aspect Rogor test material, both at home and abroad researcher is many is placed on biology enzyme by research emphasis, especially acetylcholinesterase, development and utilization on.But, acetylcholinesterase generally extracts from electric eel organ or cow's serum, the inconvenience of not only drawing materials, commercialization finished product price is very expensive (being 5077.80 yuan/50UN with reference to the quotation of Sigma-Aldrich official) also, greatly limited its application of context of detection at the scene.Therefore, some scholars of China use plant esterase to replace acetylcholinesterase, are successfully applied in Rogor detection.As the ZL patent No. " plant-esterase tablet of the Fast Measurement organophosphorus pesticide " patent that is 99114268.3, disclosed plant-esterase tablet, its component and proportioning (% by weight) are: flour 54.90～98.27, potassium dihydrogen phosphate (KH
2pO
4) 0.15～15.12, sodium hydrogen phosphate (Na
2hPO
4) 1.58～59.98.Survey a sample and only need 0.1 yuan of left and right.For another example " quick test box of residual agricultural organophosphorus chemical and manufacture method " patent that publication number is CN1293363, disclosed testing cassete is made up of zymophore, indophenols ester carrier and glass test tube.Zymophore is wherein that physisorption carrier is put into by flour and the formulated enzyme liquid of water, soak, dry forming.In these two patents, owing to using abundant, the cheap and easy to get plant esterase in source to replace animal esterase, greatly reduce testing cost.But because they have all done immobilization processing to enzyme, the activity of enzyme incurs loss, and has reduced detection effect.So, also have scholar directly to use plant esterase enzyme liquid to carry out Rogor detection, as magazine " ACTA Scientiae Circumstantiae " 2002,22 (5): " plant esterase concentration is on detecting the impact research of Rogor sensitivity " literary composition of 653-657, in the highest best enzyme concentration of disclosed detection Rogor resolution and sensitivity, its test material used is the phytoenzyme enzyme liquid extracting from wheat.In this literary composition, although used enzyme liquid, the activity of enzyme is protected, while detection, except testing sample, also need to add in addition substrate and developer.So not only increase detecting step, extended detection time, used inconvenient.In addition, no matter be acetylcholinesterase or plant esterase, it realizes the principle detecting is the inhibiting effect to enzymatic activity based on Rogor, but, except Rogor, other organophosphorus insecticides, or even carbamate chemicals for agriculture all can produce inhibiting effect to acetylcholinesterase and plant esterase.Therefore, this class test material lacks selectivity, easily causes the inaccurate of testing result.
Summary of the invention
The object of the invention is the weak point for existing biology enzyme test material, a kind of nano material that detects Rogor and preparation method thereof is provided, there is production cost low, can realize Rogor fast, selectivity detects, and in testing process, do not need the features such as other reagent outside sample.
The nano material of detection Rogor of the present invention, includes sodium silicate, 5,10,15,20-tetra-(4-sulfonic group phenyl) porphyrin (TPPS
4) and plant esterase, the percent by weight of its component is:
Sodium silicate: 97.43%～99.31%,
TPPS
4：0.06%～0.23%、
Plant esterase: 0.63%～2.34%.
The preparation method of the nano material of above-mentioned detection Rogor, is take sol-gel as carrier, fixes plant esterase molecule in the mesopore orbit of carrier, then at immobilization plant esterase surface preparation TPPS
4j-aggregation, finally by separating, the dry finished product that to obtain.
Its concrete method step is as follows:
1) preparation of plant esterase enzyme liquid
Take commercially available flour as raw material, in flour: the ratio that the weight ratio of distilled water is 1:4～6, in flour, add distilled water, stir after 10～60min, with the centrifugal speed of 3000～6000r/min, centrifuging 10～15min, collects supernatant liquor again, leave standstill 8～24h, just prepare plant esterase enzyme liquid;
2) preparation of sol solutions
In sodium silicate: the ratio that the weight ratio of distilled water is 1:3.17～4, in sodium silicate, add distilled water, and with hydrochloric acid regulation system pH be 4～5, after ultrasonic mixing 20～40s, just prepare sol solutions;
3) immobilization of plant esterase
By the 1st) the plant esterase enzyme liquid prepared of step, the 2nd) sol solutions of step preparation, the ratio of 1:0.33～1 by volume, after mixing, leave standstill 0.5～1h, sol solutions becomes gel, then with distilled water washing 3～5 times, just obtain being fixed with the gel of plant esterase, complete the immobilization of plant esterase;
4) TPPS
4the preparation of solution
In water, add TPPS
4pressed powder, stirs after fully dissolving, just prepares the TPPS that concentration is 0.1～0.3mmol/L
4solution;
5) nano material preparation
By the 3rd) prepared by the step gel that is fixed with plant esterase, put into the 4th) TPPS of step preparation
4solution, and with hydrochloric acid regulation system pH be 1.15～4, after lucifuge reaction 3～12h, gel is taken out, and the hydrochloric acid solution that is 1.15～4 with pH washing 3～5 times, dry 23～25h at 25～27 ℃, just prepares the nano material of detection Rogor.
The present invention also provides a kind of kit for detection of Rogor, and this kit includes the nano material of above-mentioned preparation, aqueous hydrochloric acid solution and the anhydrous propanone that pH is 1.15～4.
Inspection nano material of the present invention can be widely used in the dimethoate pesticide residue detection in the agricultural product such as vegetables, fruit and environment, also can be used for food and environmental safety assessment, monitors the pollution condition of its dimethoate pesticide etc.
The present invention adopts after technique scheme, mainly contains following effect:
(1) testing cost is low.The biology enzyme of selecting in the present invention directly extracts from commercially available flour, compared with acetylcholinesterase, greatly reduces testing cost.
(2) good stability.The fixing plant esterase of sol-gel technique adopting in the present invention, it is a kind of physically trapping process, gel network forms gradually around enzyme, and gentle reaction conditions, amorphous structure and the biocompatibility of gel are all conducive to keep the structural intergrity of enzyme, isotropy and the biologically active of surface microstructure.And then by TPPS
4enter in gel network by gel surface micropore, react with plant esterase and form nanometer J-aggregation on enzyme surface.In this gel network; enzyme and J-aggregation are not only vulnerable to the harmful effect of extraneous adverse environmental factors (as organic solvent, heavy metal ion etc.); structure is more stable; be difficult for forming precipitation; be easy to preserve; and its reactivity obtained good protection, be conducive to the carrying out of detection reaction.
(3) surface effect increases.In gel network, not only the local concentration of enzyme and nanometer J-aggregation is improved, and the nanostructured forming has high specific surface area, and surface can increase, and makes it have high activity.In Rogor detects, surface effect is greatly enhanced.
(4) photosensitivity is good.Gel has outstanding light transmission, and in gel network, nanometer J-aggregation still has photosensitivity and spectral response, can be applicable in spectral detection.
(5) detection selectivity is good.Take absorption spectrum as detection signal, new material prepared by application the present invention detects, and can realize Rogor selectivity and detect, and gets rid of other organophosphorus insecticide impacts, makes testing result more accurate, and this does not reach with fermentoid sheet or enzyme liquid.
(6) easy to use.When the kit that employing comprises nano material of the present invention detects Rogor, do not need to prepare other reagent except sample, directly detect, easy to operate.
Accompanying drawing explanation
Fig. 1: be TPPS
4chemical equilibrium in aqueous solution;
Fig. 2: be the detection of Application Example 3 gained nano materials to reference solution and eight kinds of organophosphorus pesticides including Rogor;
Fig. 3: be the signal response of Application Example 3 gained nano materials to different organophosphorus pesticides;
Fig. 4: be the stability of Application Example 3 gained nano materials.
Embodiment
Below in conjunction with embodiment, the nano material of detection Rogor of the present invention is described in detail.
Component and the percent by weight of the nano material of the detection Rogor that the present embodiment provides are:
Sodium silicate: 97.43%
TPPS
4：0.23%
Plant esterase: 2.34%
The concrete method step of its preparation method is as follows:
1) preparation of plant esterase enzyme liquid
Take commercially available flour as raw material, in flour: the ratio that the weight ratio of distilled water is 1:6 adds distilled water in flour, stir after 10min, then with the centrifugal speed of 3000r/min, centrifuging 10min, collect supernatant liquor, leave standstill 8h, just prepare plant esterase enzyme liquid;
2) preparation of sol solutions
In sodium silicate: the ratio that the weight ratio of distilled water is 1:4, in sodium silicate, add distilled water, and with hydrochloric acid regulation system pH be 5, after ultrasonic mixing 20s, just prepare sol solutions;
3) immobilization of plant esterase
By the 1st) the plant esterase enzyme liquid prepared of step, the 2nd) sol solutions of step preparation, the ratio of 1:0.33 by volume, after mixing, leave standstill 0.5h, sol solutions becomes gel, with distilled water washing 3 times, just obtain being fixed with the gel of plant esterase again, complete the immobilization of plant esterase;
4) TPPS
4the preparation of solution
In water, add TPPS
4pressed powder, stirs after fully dissolving, just prepares the TPPS that concentration is 0.3mmol/L
4solution;
5) nano material preparation
By the 3rd) prepared by the step gel that is fixed with plant esterase, put into the 4th) TPPS of step preparation
4solution, and with hydrochloric acid regulation system pH be 4, after lucifuge reaction 3h, gel is taken out, and the hydrochloric acid solution that is 4 with pH washing 3 times, dry 23h at 27 ℃, just prepares the nano material of detection Rogor.
Component and the percent by weight of the nano material of the detection Rogor that the present embodiment provides are:
Sodium silicate: 99.31%
TPPS
4：0.06%
Plant esterase: 0.63%
The concrete method step of its preparation method is as follows:
1) preparation of plant esterase enzyme liquid
Take commercially available flour as raw material, in flour: the ratio that the weight ratio of distilled water is 1:4 adds distilled water in flour, stir after 60min, then with the centrifugal speed of 6000r/min, centrifuging 15min, collect supernatant liquor, leave standstill 24h, just prepare plant esterase enzyme liquid;
2) preparation of sol solutions
In sodium silicate: the ratio that the weight ratio of distilled water is 1:3.17, in sodium silicate, add distilled water, and with hydrochloric acid regulation system pH be 4, after ultrasonic mixing 40s, just prepare sol solutions;
3) immobilization of plant esterase
By the 1st) the plant esterase enzyme liquid prepared of step, the 2nd) sol solutions of step preparation, the ratio of 1:1 by volume, after mixing, leave standstill 1h, sol solutions becomes gel, with distilled water washing 5 times, just obtain being fixed with the gel of plant esterase again, complete the immobilization of plant esterase;
4) TPPS
4the preparation of solution
In water, add TPPS
4pressed powder, stirs after fully dissolving, just prepares the TPPS that concentration is 0.1mmol/L
4solution;
5) nano material preparation
By the 3rd) prepared by the step gel that is fixed with plant esterase, put into the 4th) TPPS of step preparation
4solution, and with hydrochloric acid regulation system pH be 1.15, after lucifuge reaction 12h, gel is taken out, and the hydrochloric acid solution that is 1.15 with pH washing 5 times, dry 25h at 25 ℃, just prepares the nano material of detection Rogor.
Embodiment 3
Component and the percent by weight of the nano material of the detection Rogor that the present embodiment provides are:
Sodium silicate: 98.51%
TPPS
4：0.13%
Plant esterase: 1.36%
The concrete method step of its preparation method is as follows:
1) preparation of plant esterase enzyme liquid
Take commercially available flour as raw material, in flour: the ratio that the weight ratio of distilled water is 1:5 adds distilled water in flour, stir after 30min, then with the centrifugal speed of 4000r/min, centrifuging 12min, collect supernatant liquor, leave standstill 12h, just prepare plant esterase enzyme liquid;
2) preparation of sol solutions
In sodium silicate: the ratio that the weight ratio of distilled water is 1:3.45, in sodium silicate, add distilled water, and with hydrochloric acid regulation system pH be 4, after ultrasonic mixing 30s, just prepare sol solutions;
3) immobilization of plant esterase
By the 1st) the plant esterase enzyme liquid prepared of step, the 2nd) sol solutions of step preparation, the ratio of 1:0.5 by volume, after mixing, leave standstill 0.7h, sol solutions becomes gel, with distilled water washing 4 times, just obtain being fixed with the gel of plant esterase again, complete the immobilization of plant esterase;
4) TPPS
4the preparation of solution
In water, add TPPS
4pressed powder, stirs after fully dissolving, just prepares the TPPS that concentration is 0.2mmol/L
4solution;
5) nano material preparation
By the 3rd) prepared by the step gel that is fixed with plant esterase, put into the 4th) TPPS of step preparation
4solution, and with hydrochloric acid regulation system pH be 1.3, after lucifuge reaction 10h, gel is taken out, and the hydrochloric acid solution that is 1.3 with pH washing 4 times, dry 24h at 26 ℃, just prepares the nano material of detection Rogor.
Experimental result
(1) nano material detects the selectivity of Rogor
Carry out Rogor with the kit that includes the nano material that embodiment 3 prepares and detect test: first nano material is distributed in 5mL pH1.3 aqueous hydrochloric acid solution, and to add 10 μ L reference solutions (being acetone) or sample solution (be the acetone soln of eight kinds of organophosphorus pesticides such as Rogor, flolimat, chlopyrifos, fenifrothion, parathion, phosmet, isocarbophos, thimet, concentration is 100 μ g/mL), then use Shimadzu (SHIMADZU) UV-2450 ultraviolet-visible pectrophotometer to gather successively its absorption spectrum information; The UV Probe software finally carrying by system, analyzes reference solution and the affect difference of sample solution on nano material absorption spectrum, realizes the selectivity of Rogor is detected.Experimental result as shown in Figures 2 and 3.
(2) stability test of nano material
The nano material that embodiment 3 is prepared is stored under 4 ℃ of temperature conditions, and the detection effect of routine test nano material to Rogor.
Interpretation
(1) nano material detects the selectivity of Rogor
As can be seen from Figure 2, no matter whether the nano material of the embodiment of the present invention 3 contain agricultural chemicals in detection system, and absorption spectrum all exists obvious absorption peaks at 490nm and 707nm place, is consistent with the characteristic absorption peak of J-aggregation.This explanation, plant esterase and TPPS in test material
4under effect, form nanometer J-aggregation.And adding of dimethoate pesticide has obvious facilitation to J-aggregation, 490nm place absorbance is obviously strengthened.And other seven kinds of organophosphorus pesticides except Rogor all can not promote J-aggregation to form.This phenomenon can obviously be observed in Fig. 3.With (A
490 (samples)-A
490 (references))/A
490 (references)for detection signal (wherein A
490represent that wavelength is the absorbance at 490nm place), the signal response of Rogor is far away higher than other agricultural chemicals.Therefore, by plant esterase and TPPS
4the nano material that common reaction forms under acid condition has higher selectivity to dimethoate pesticide.Result shows that nano material prepared by the present invention can effectively detect the residual of Rogor.
(2) stability test of nano material
As seen from Figure 4, the storage of the nano material of the embodiment of the present invention 3 is after 28 days, and the response signal of Rogor is reduced to 0.72 from initial 0.74, only declined 3%; Preserve after 56 days, the response signal of Rogor is reduced to 0.70, drop to 94.7%; Preserve after 91 days, the response signal of Rogor is dropped to 91.6%.The stability of the nano material that as can be seen here, prepared by the inventive method obviously improves.
Claims (5)
1. a nano material that detects Rogor, is characterized in that, described nano material includes sodium silicate, 5,10,15,20-tetra-(4-sulfonic group phenyl) porphyrin TPPS
4and plant esterase, the percent by weight of its component is:
Sodium silicate: 97.43%～99.31%,
TPPS
4：0.06%～0.23%、
Plant esterase: 0.63%～2.34%.
2. the preparation method of nano material claimed in claim 1, is characterized in that, is take sol-gel as carrier, fixes plant esterase molecule in the mesopore orbit of carrier, then at immobilization plant esterase surface preparation TPPS
4j-aggregation prepare.
3. preparation method as claimed in claim 1, is characterized in that, includes following steps:
1) preparation of plant esterase enzyme liquid
In flour: the ratio that the weight ratio of distilled water is 1:4～6, in flour, add distilled water, stir after 10～60min, again with centrifugal speed centrifuging 10～15min of 3000～6000r/min, collect supernatant liquor, leave standstill 8～24h, just prepare plant esterase enzyme liquid;
2) preparation of sol solutions
In sodium silicate: the ratio that the weight ratio of distilled water is 1:3.17～4, in sodium silicate, add distilled water, and with hydrochloric acid regulation system pH be 4～5, after ultrasonic mixing 20～40s, just prepare sol solutions;
3) immobilization of plant esterase
Plant esterase enzyme liquid prepared by step 1), step 2) preparation sol solutions, the ratio of 1:0.33～1 by volume, after mixing, leave standstill 0.5～1h, after sol solutions becomes gel, then with distilled water washing 3～5 times, just obtain being fixed with the gel of plant esterase, complete the immobilization of plant esterase;
4) TPPS
4the preparation of solution
In water, add TPPS
4pressed powder, stirs after fully dissolving, prepares the TPPS that concentration is 0.1～0.3mmol/L
4solution;
5) nano material preparation
The gel that is fixed with plant esterase prepared by step 3), puts into the TPPS of step 4) preparation
4solution, and with hydrochloric acid regulation system pH be 1.15～4, after lucifuge reaction 3～12h, gel is taken out, and the hydrochloric acid solution that is 1.15～4 with pH washing 3～5 times, dry 23～25h at 25～27 ℃, just prepares the nano material of detection Rogor.
4. the application of nano material claimed in claim 1 in Determination of Dimethoate Residues detects.
5. for detection of a kit for Rogor, it is characterized in that, described kit includes aqueous hydrochloric acid solution and the anhydrous propanone that nano material claimed in claim 1, pH are 1.15～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410051064.4A CN103776781B (en) | 2014-02-14 | 2014-02-14 | A kind of nano material detecting Rogor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410051064.4A CN103776781B (en) | 2014-02-14 | 2014-02-14 | A kind of nano material detecting Rogor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103776781A true CN103776781A (en) | 2014-05-07 |
| CN103776781B CN103776781B (en) | 2015-11-18 |
Family
ID=50569285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410051064.4A Active CN103776781B (en) | 2014-02-14 | 2014-02-14 | A kind of nano material detecting Rogor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103776781B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105749975A (en) * | 2016-03-04 | 2016-07-13 | 江苏大学 | Immobilized metal porphyrin enzyme catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113955A (en) * | 2007-08-28 | 2008-01-30 | 重庆大学 | Material for detecting micro-trace dimethyl methyl phosphomate and method for making same |
| CN101613537A (en) * | 2009-07-31 | 2009-12-30 | 孝感学院 | A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide |
| CN102841067A (en) * | 2012-09-18 | 2012-12-26 | 泸州品创科技有限公司 | Method for testing trace carbofuran |
-
2014
- 2014-02-14 CN CN201410051064.4A patent/CN103776781B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113955A (en) * | 2007-08-28 | 2008-01-30 | 重庆大学 | Material for detecting micro-trace dimethyl methyl phosphomate and method for making same |
| CN101613537A (en) * | 2009-07-31 | 2009-12-30 | 孝感学院 | A kind of preparation method of nano silicon dioxide coated by nano titanium dioxide |
| CN102841067A (en) * | 2012-09-18 | 2012-12-26 | 泸州品创科技有限公司 | Method for testing trace carbofuran |
Non-Patent Citations (6)
| Title |
|---|
| DIANA YU ET.AL: "Aqueous sol–gel encapsulation of genetically engineered Moraxella spp. cells for the detection of organophosphates", 《BIOSENSORS AND BIOELECTRONICS》 * |
| JURGA VALANCIUNAITE ET. AL: "Spectroscopic study of TPPS4 nanostructure in the presence of bovine serum albumin", 《PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES》 * |
| 姜彬等: "用于有机磷农药检测的植物酯酶生物传感器的研究", 《食品工业科技》 * |
| 张叔平等: "氨基甲酸酯类农药的快速检测", 《粮油食品科技》 * |
| 杨丽敏: "酶—卟啉复合体系构建及其传感作用机制", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 高慧丽等: "溶胶-凝胶法固定乙酰胆碱酯酶生物传感器测定有机磷农药", 《环境化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105749975A (en) * | 2016-03-04 | 2016-07-13 | 江苏大学 | Immobilized metal porphyrin enzyme catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103776781B (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Adesipo et al. | Smart and climate-smart agricultural trends as core aspects of smart village functions | |
| Rendón-von Osten et al. | Glyphosate residues in groundwater, drinking water and urine of subsistence farmers from intensive agriculture localities: a survey in Hopelchén, Campeche, Mexico | |
| Zamora-Sequeira et al. | What are the main sensor methods for quantifying pesticides in agricultural activities? A review | |
| Luo et al. | Facile colorimetric nanozyme sheet for the rapid detection of glyphosate in agricultural products based on inhibiting peroxidase-like catalytic activity of porous Co3O4 nanoplates | |
| Knight et al. | Differentiating microbial and stabilized β-glucosidase activity relative to soil quality | |
| Powlson et al. | Soil organic matter | |
| Xue et al. | Effect of clay mineralogy and soil organic carbon in aggregates under straw incorporation | |
| CN105628758A (en) | Preparation method and application for photoelectrochemical parathion sensor based on two-dimensional nanometer light-sensitive material | |
| Elbl et al. | Response of microbial activities in soil to various organic and mineral amendments as an indicator of soil quality | |
| Cerasa et al. | Searching nanoplastics: From sampling to sample processing | |
| Islam et al. | Mineralization of farm manures and slurries for successive release of carbon and nitrogen in incubated soils varying in moisture status under controlled laboratory conditions | |
| Govindaraju et al. | Waste to wealth: value recovery from bakery wastes | |
| Zhang et al. | Ultrasensitive and on-site detection of carbaryl pesticides via dual-mode nanosensors utilizing portable devices | |
| CN103776781B (en) | A kind of nano material detecting Rogor and preparation method thereof | |
| Liyanage et al. | Carbon mineralization dynamics of organic materials and their usage in the restoration of degraded tropical tea-growing soil | |
| Piccardo et al. | Use of Sediqualsoft® to determine the toxicity of cigarette butts to marine species: a weather simulation test | |
| Vannini et al. | Biochar amendment reduces the availability of Pb in the soil and its uptake in lettuce | |
| Ullah et al. | Partial substitution of urea with biochar induced improvements in soil enzymes activity, ammonia-nitrite oxidizers, and nitrogen uptake in the double-cropping rice system | |
| Lull et al. | Seasonal variation and soil texture-related thinning effects on soil microbial and enzymatic properties in a semi-arid pine forest | |
| Tripathi et al. | The effects of understorey dwarf bamboo (Sasa kurilensis) removal on soil fertility in a Betula ermanii forest of northern Japan | |
| Kama et al. | Treated livestock wastewater irrigation is safe for maize (zea mays) and soybean (glycine max) intercropping system considering heavy metals migration in soil–plant system | |
| Zeng et al. | Characterization of sodium cellulose sulphate/poly‐dimethyl‐diallyl‐ammonium chloride biological capsules for immobilized cultivation of microalgae | |
| Frene et al. | Early effect of pine biochar on peach-tree planting on microbial community composition and enzymatic activity | |
| CN101892215A (en) | Luminous bacteria biosensor and preparation method and preservation method thereof | |
| CN104099397A (en) | Method for detecting cytotoxicity of nano materials through yeast mutant strains |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |