CN116813923A - Be applicable to fertilizer Cu II Process for preparing coordination polymer urease inhibitor - Google Patents
Be applicable to fertilizer Cu II Process for preparing coordination polymer urease inhibitor Download PDFInfo
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- CN116813923A CN116813923A CN202310648277.4A CN202310648277A CN116813923A CN 116813923 A CN116813923 A CN 116813923A CN 202310648277 A CN202310648277 A CN 202310648277A CN 116813923 A CN116813923 A CN 116813923A
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- fertilizer
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 62
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 62
- 239000003337 fertilizer Substances 0.000 title claims abstract description 33
- 239000002601 urease inhibitor Substances 0.000 title claims abstract description 33
- 229940090496 Urease inhibitor Drugs 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000010949 copper Substances 0.000 claims abstract description 29
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- GATPGSPJEIEAGL-UHFFFAOYSA-N 3-N,3-N-dipyridin-3-ylbenzene-1,3-dicarboxamide Chemical compound C(C1=CC(C(=O)N)=CC=C1)(=O)N(C=1C=NC=CC=1)C=1C=NC=CC=1 GATPGSPJEIEAGL-UHFFFAOYSA-N 0.000 claims abstract description 18
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000618 nitrogen fertilizer Substances 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 7
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 108010046334 Urease Proteins 0.000 abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002689 soil Substances 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 5
- 230000001934 delay Effects 0.000 abstract description 4
- 239000003112 inhibitor Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 230000004720 fertilization Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- -1 ammonium ions Chemical class 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002681 soil colloid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 102000006410 Apoproteins Human genes 0.000 description 2
- 108010083590 Apoproteins Proteins 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HDNXZVCYAQPBHP-UHFFFAOYSA-N 3-n-pyridin-3-ylbenzene-1,3-dicarboxamide Chemical compound NC(=O)C1=CC=CC(C(=O)NC=2C=NC=CC=2)=C1 HDNXZVCYAQPBHP-UHFFFAOYSA-N 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940058303 antinematodal benzimidazole derivative Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229960003531 phenolsulfonphthalein Drugs 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Soil Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
The invention relates to a Cu fertilizer II A preparation method of coordination polymer urease inhibitor relates to a preparation method of urease inhibitor suitable for fertilizer, which synthesizes 5-hydroxy-N by taking 5-hydroxy isophthalic acid and 3-aminopyridine as raw materials 1 ，N 3 Bis (pyridin-3-yl) isophthalamide, and 1.3.5-trimellitic acid are used as ligands, and a copper-based urease inhibitor is synthesized by a hydrothermal method, and the coordination polymer is used as a urease inhibitor to inhibit the urease activity by analyzing the crystal structure and a urease inhibition experiment and is added into a fertilizer as an inhibitor, so that the conversion rate of urea in soil to ammonium nitrogen is reduced in the agricultural fertilization process, the fertilizer utilization rate is improved, and the loss of nitrogen element in a nitrogen fertilizer is reduced. Cu (Cu) Ⅱ Is a urease inhibitor, delays the hydrolysis of urea into ammonia gas, and ensures that ammonium nitrogen is kept in soil for a long timeThereby improving the utilization rate of the fertilizer.
Description
Technical Field
The invention relates to a preparation method of a fertilizer inhibitor, in particular to a method suitable for fertilizer Cu II A method for preparing a coordination polymer urease inhibitor.
Background
Coordination polymers are inorganic or metal-organic polymers containing metal cation centers and are connected by organic ligands, and are crystalline materials with certain rules. Metal organic coordination polymers, also known as metal-organic framework structures. The recent focus of attention of scientists in various countries has been on the fact that it has various special properties. MOFs contain organic ligands and metal ions, so materials of this type of structure may contain both metal and organic compound characteristics, and may also contain properties that are not available with both metal and organic compounds.
Compared with metal salts, organic matters and plant extracts, the compound urease inhibitor has the characteristics of low toxicity, strong inhibition, stability and the like, wherein the transition metal-containing coordination polymer is widely focused as the urease inhibitor, and the copper coordination polymer has the best effect, can inhibit the activation process of urease apoprotein, can well fill in an active pocket of urease, and establishes interaction with the active site of the urease to occupy a binding site which is supposed to belong to nickel, thereby irreversibly inhibiting the activity of the urease, further blocking the path of urea entering the active site, and achieving the effect of inhibiting the activity of the urease. By adding Cu to the fertilizer Ⅱ The coordination polymer can relieve the hydrolysis of nitrogenous fertilizer, reduce ammonia volatilization and improve the utilization rate of nitrogenous fertilizer.
Urease is a nickel-dependent metalloenzyme widely existing in the biological world and can catalyze urea to hydrolyze into ammonia and carbon dioxide, and provide a nitrogen source for organisms. Urease has important uses in agriculture and medicine because it can catalyze the production of ammonia. The research content comprises urease inhibition, structure-activity relationship, molecular docking and the like. Importantly, most of the copper metal complexes exhibit greater urease inhibition, IC, among the potent urease inhibitors 50 The values range from 0.46. Mu.M to 41.11. Mu.M.
Further development and research on the properties of the copper coordination polymer can lead the copper coordination polymer to play an important role in the fertilizer field.
Disclosure of Invention
The invention aims to provide a Cu fertilizer II Coordination polymerizationThe invention selects 5-hydroxy isophthalic acid, 3-aminopyridine, triphenyl phosphite and pyridine as raw materials, and prepares the nitrogen-containing tetradentate ligand 5-hydroxy-N by an organic synthesis method 1 ，N 3 Bis (pyridin-3-yl) isophthalamide, which has more coordination sites and is more easily coordinated to transition metal ions. Construction of a Cu by hydrothermal method II The coordination polymer has better activity of inhibiting urease bacteria in soil, delays the decomposition of nitrogen fertilizer, blocks ammonia volatilization by soil layers, and leads soil colloid to generate ammonium ions (NH) on urea decomposition 4 + ) The adsorption of the nitrogen fertilizer is enhanced, so that the loss of the nitrogen fertilizer can be reduced, and nitrogen remains in the soil for a long time in the form of ammonium nitrogen which is easier to adsorb in the soil, thereby improving the utilization rate of the fertilizer.
The invention aims at realizing the following technical scheme:
be applicable to fertilizer Cu II A method of preparing a coordination polymer urease inhibitor, the method comprising the steps of:
the Cu is II Coordination polymer, the crystal form belongs to monoclinic system, the space group is P21/n, cu II The ion adopts a four-coordination mode and is respectively connected with two independent 5-hydroxy-N 1 ，N 3 -two nitrogen atoms in the bis (pyridin-3-yl) isophthalamide ligand and two carboxyl oxygen atoms in two separate 1,3, 5-trimellitic acid anions coordinated, exhibiting a tetragonal cone geometry; cu (Cu) II The coordination environment of the coordination polymer is shown as (I):cu of it II The preparation of the coordination polymer comprises the following steps: taking ligand 5-hydroxy-N 1 ，N 3 -bis (pyridin-3-yl) isophthalamide, 1,3, 5-benzenetricarboxylic acid and CuCl 2 ·2H 2 O, placing the mixture into a tetrafluoroethylene liner, adding deionized water and sodium hydroxide, sealing a reaction kettle, performing hydrothermal reaction, washing, filtering and drying the product after the reaction is finished to obtain a target product Cu II Coordination polymers.
Said one is suitable for fertilizer Cu II Process for preparing coordination polymer urease inhibitor, ligand 5-hydroxy-N 1 ，N 3 -bis (pyridin-3-yl) isophthalamide preparation comprising the steps of:
dissolving 5-hydroxy isophthalic acid in pyridine solution, dissolving 3-aminopyridine in pyridine solution, slowly transferring to 5-hydroxy isophthalic acid solution, stirring at room temperature for 30min, dropwise adding triphenyl phosphite in 15min, and heating and refluxing for 10h; standing at room temperature overnight, adding water to separate out solid, filtering, washing with water, and drying in air to obtain white powdery solid.
Said one is suitable for fertilizer Cu II Process for preparing coordination polymer urease inhibitor, ligand 5-hydroxy-N 1 ，N 3 -synthesis of bis (pyridin-3-yl) isophthalamide starting from 5-hydroxyisophthalic acid: the molar ratio of the 3-aminopyridine is 1:1-2.
Said one is suitable for fertilizer Cu II A method for preparing a coordination polymer urease inhibitor, wherein the hydrothermal reaction is that at 120 ℃ for 4d.
Said one is suitable for fertilizer Cu II Process for preparing coordination polymer urease inhibitor, ligand 5-hydroxy-N 1 ，N 3 -bis (pyridin-3-yl) isophthalamide: copper chloride dihydrate: the molar ratio of the benzene tricarboxylic acid is 1:1-2:1-2.
Said one is suitable for fertilizer Cu II Preparation method of coordination polymer urease inhibitor, and Cu II Coordination polymers are used as urease inhibitors in fertilizers, which are nitrogen fertilizers.
Said one is suitable for fertilizer Cu II A process for the preparation of a coordination polymer urease inhibitor, the nitrogen fertilizer being urea.
The beneficial effects of the invention are as follows:
1. the invention selects 5-hydroxy isophthalic acid and 3-aminopyridine as raw materials, and obtains the ligand 5-hydroxy-N containing nitrogen through a one-pot method 1 ，N 3 -bis (pyridin-3-yl) isophthalamideAmides, which make it easier to coordinate with metal chlorides, increase the coordination sites.
2. The invention constructs Cu by a hydrothermal method II Coordination polymer, cu II The activation process of ion inhibition urease apoprotein simultaneously occupies the binding site near the active center nickel atom, delays the decomposition of nitrogen fertilizer, the ammonia volatilization is blocked by soil layer, and the soil colloid decomposes ammonium ion (NH) generated by urea 4 + ) And the adsorption of the nitrogen fertilizer is enhanced, so that the loss of the nitrogen fertilizer can be reduced, and the nitrogen remains in the soil for a long time in the form of ammonium nitrogen which is easier to adsorb in the soil.
3. Cu provided by the invention II The coordination polymer has better activity of inhibiting urease bacteria in soil, delays the decomposition of nitrogen fertilizer, blocks ammonia volatilization by soil layers, and soil colloid generates ammonium ions (NH) on urea decomposition 4 + ) The adsorption of the nitrogen fertilizer is enhanced, so that the loss of the nitrogen fertilizer can be reduced, and nitrogen remains in the soil for a long time in the form of ammonium nitrogen which is easier to adsorb in the soil, thereby improving the utilization rate of the fertilizer.
4. Cu provided by the invention II The coordination polymer has the advantages of low dosage, high inhibition rate, long half-life, low toxicity and small influence on environment.
Drawings
FIG. 1 is Cu II A coordination environment diagram of the coordination polymer;
FIG. 2 is Cu II Coordination polymer X-ray diffraction patterns and simulated data patterns;
FIG. 3 is Cu II Coordination polymer semi-inhibitory concentration.
Description of the embodiments
1. Ligand 5-hydroxy-N 1 ，N 3 The preparation method of the-bis (pyridin-3-yl) isophthalamide is as follows:
5-Hydroxyisophthalic acid (0.05 mol) was dissolved in 20mL of a pyridine solution, 3-aminopyridine (0.1 mol) was dissolved in 35mL of a pyridine solution, then slowly transferred to the 5-hydroxyisophthalic acid solution, stirred at room temperature for 30min, and then triphenyl phosphite (15.5 g,0.05 mol) was added dropwise over 15min, followed by heating and refluxing at 120℃for 10h. Standing at room temperature overnight, adding water to separate out solid, filtering, washing with water, and drying in air to obtain white powdery solid.
2.Cu Ⅱ Coordination polymer preparation method
Weighing ligand 5-hydroxy-N 1 ，N 3 Bis (pyridin-3-yl) isophthalamide 0.033g (0.1 mmol), 1.3.5-trimellitic acid 0.032g (0.15 mmol), cuCl 2 ·2H 2 O0.034g (0.2 mmol) was placed in a tetrafluoroethylene liner, 8ml deionized water was added, and then 0.016g NaOH solution was added, the reaction vessel was sealed and placed at 120 o And C, calcining in a drying box for 4d, and washing, filtering and drying the blocky crystals to obtain blue crystals.
(II) characterization
Diffraction intensity data for single crystals were collected on a Bruker D8-ray diffractometer using graphite monochromating Mo kα (λ= 0.71073 a) radiation as the diffraction light source. Bonding Cu II SC-XRD data of coordination polymer, cu was further obtained II The structure of the coordination polymer is shown in FIG. 1. FIG. 1 shows metallic Cu II Coordination environment of ions. Cu (Cu) II The ion adopts a four-coordination mode and is respectively matched with two groups derived from independent 5-hydroxy-N 1 ，N 3 Two nitrogen atoms in the bis (pyridin-3-yl) isophthalamide ligand, two carboxyl oxygen atom coordinates from two separate 1,3, 5-benzene tricarboxylic acid anions, (Cu-n= 2.055 (4) -2.068 (4) a, cu-o= 1.938 (3) -1.953 (3) a) (principal bond lengths and bond angles see table 1)
TABLE 1 coordination Polymer Crystal data sheet
| Empirical formula | C 30 H 30 CuN 4 O 7 |
| Formula weight | 622.13 |
| Temperature/K | 296.0 |
| Crystal system | Monoclinic |
| Space group | C2/c |
| a/Å | 21.2585(17) |
| b/Å | 5.5487(4) |
| c/Å | 25.050(2) |
| α/° | 90 |
| β/° | 101.173(3) |
| γ/° | 90 |
| Volume/Å 3 | 2898.8(19) |
| Z | 4 |
| ρcalcg/cm 3 | 1.426 |
| μ/mm1 | 0.807 |
| F(000) | 1292.0 |
| R int | 0.0492(2520) |
| s | 1.024 |
| Rf/wRf | 0.0492/0.1086 |
| All data Rf/wRf | 0.0928/0.1245 |
Powder diffraction experiments were performed on the crystals using a Bruker D8 advanced X-ray powder diffractometer. The graphite monochromized CuK alpha radiation is used, the wavelength lambda= 1.54056A is used for a solid detector, the step length is 0.01 DEG, the step time is 0.3 sec, and the scanning range is more than or equal to 5 DEG and less than or equal to 45 DEG. Prepared Cu II The X-ray diffraction pattern and the simulated data pattern of the coordination polymer are shown in figure 2, and sharp diffraction peaks in the two crystals indicate that the coordination polymer has better crystal quality. In addition, the powder X-ray diffraction pattern was identical in characteristic peak position and intensity to the corresponding single crystal structure simulation pattern, confirming that the powder sample and the crystal were in the same crystalline phase.
EXAMPLE 1 Cu Ⅱ Coordination polymers and their preparation
By reacting 5-hydroxy-N 1 ，N 3 0.033g (0.1 mmol) of bis (pyridin-3-yl) isophthalamide, 0.032g of 1.3.5-trimellitic acid0.15mmol），CuCl 2 ·2H 2 0.034g (0.2 mmol) of O is put into a tetrafluoroethylene liner, the reaction kettle is sealed, the reaction kettle is calcined at constant temperature in a 120 ℃ oven for 4 days to obtain blue blocky crystals, and then the blocky crystals are washed, filtered and dried to obtain the copper coordination polymer with the yield of about 45 percent.
EXAMPLE 2 Cu Ⅱ Coordination polymers and their preparation
By reacting 5-hydroxy-N 1 ，N 3 Bis (pyridin-3-yl) isophthalamide 0.033g (0.1 mmol), 1.3.5-trimellitic acid 0.064g (0.3 mmol), cuCl 2 ·2H 2 0.068g (0.4 mmol) of O is put into a tetrafluoroethylene liner, the reaction kettle is sealed, the reaction kettle is calcined at constant temperature in a 120 ℃ oven for 4 days, blue blocky crystals are obtained, and then the blocky crystals are washed, filtered and dried to obtain the copper coordination polymer with the yield of about 40 percent.
Example 3 Cu Ⅱ Coordination polymers and their preparation
By reacting 5-hydroxy-N 1 ，N 3 Bis (pyridin-3-yl) isophthalamide 0.033g (0.1 mmol), 1.3.5-trimellitic acid 0.064g (0.3 mmol), cuCl 2 ·2H 2 Placing 0.034g (0.2 mmol) of O into a tetrafluoroethylene inner container, sealing a reaction kettle, calcining at constant temperature in a 120 ℃ oven for 4 days to obtain blue blocky crystals, and then washing, filtering and drying the blocky crystals to obtain Cu Ⅱ The coordination polymer was produced in about 38%.
EXAMPLE 4 Cu Ⅱ Coordination polymers and their preparation
By reacting 5-hydroxy-N 1 ，N 3 Bis (pyridin-3-yl) isophthalamide 0.033g (0.1 mmol), 1.3.5-trimellitic acid 0.032g (0.15 mmol), cuCl 2 ·2H 2 Placing 0.068g (0.4 mmol) of O into a tetrafluoroethylene inner container, sealing a reaction kettle, calcining at constant temperature in a 120 ℃ oven for 4 days to obtain blue blocky crystals, and then washing, filtering and drying the blocky crystals to obtain Cu Ⅱ The coordination polymer was produced in about 32% yield.
Determination of urease inhibiting Activity: urease was purchased from Shanghai microphone Biochemical technologies Co. 1mL (10 KU/L) of urease and 1mL were takenCu with the same content II Coordination polymer samples (DMSO for samples dissolved in DMSO: H) 2 O=1: 1) After mixing homogeneously, after preculture in a shaking incubator at 37 ℃ for 1h, 8mL of phosphate buffer solution (containing 500mM urea and 0.002% phenol red indicator) at ph=6.8 was added thereto, and absorbance was measured at 570nm with an ultraviolet spectrometer at intervals of 1 h. The end point of the test was determined by a phenol red indicator and the test was stopped when the solution changed from pale yellow to red.
IC 50 Is calculated by (1): the absorbance was measured by phenol red method and IC was calculated 50 Obtaining Cu II Coordination polymers as a measure of urease inhibition, a modified kosmo method was used:
lgIC 50 =Xm-I(P-(3-Pm-Pn)/4)，
wherein Xm is the maximum dose of lg;
lg (maximum dose/adjacent dose);
p is the sum of positive reaction rates;
pm is the maximum positive reaction rate;
pn is the minimum positive reaction rate;
the result is shown in FIG. 3, calculated to obtain IC 50 IC of organic compound with =1.60+ -0.01 μM 50 At 0.62. Mu.M< IC 50 <42.74 IC of part of organic compounds between μm 50 The values are shown in Table II.
TABLE 2 half inhibition concentration comparison Table for different classes of inhibitors
| Inhibitor type | Semi-inhibitory concentration IC 50 Value (mu M) |
| Benzimidazole derivatives | 22±6.2-99±0.4 |
| Thiourea derivatives | 11.73±0.28-212.24±0.42 |
| Thiadiazole derivatives | 3.4±0.01-33.20±1.20 |
| Biphosphamide derivatives | 1.91±0.03-3.4±0.03 |
| Cu of the invention II Coordination polymers | 1.6±0.01 |
As can be seen from Table 2, when Cu II The coordination polymer has lower half inhibition concentration as a urease inhibitor and small dosage of the additive. It can thus be concluded that: cu of the invention II The coordination polymer may be used as a urease inhibitor in the fertilizer urea.
Claims (7)
1. Be applicable to fertilizer Cu II A process for preparing a coordination polymer urease inhibitor, the process comprising the steps of:
the Cu is II Coordination polymer, the crystal form belongs to monoclinic system, the space group is P21/n, cu II The ion adopts a four-coordination mode and is respectively connected with two independent 5-hydroxy-N 1 ，N 3 -two nitrogen atoms in the bis (pyridin-3-yl) isophthalamide ligand and two carboxyl oxygen atoms in two separate 1,3, 5-trimellitic acid anions coordinated, exhibiting a tetragonal cone geometry; cu (Cu) II The coordination environment of the coordination polymer is shown as (I):
（I）
cu of it II The preparation of the coordination polymer comprises the following steps: taking ligand 5-hydroxy-N 1 ，N 3 -bis (pyridin-3-yl) isophthalamide, 1,3, 5-benzenetricarboxylic acid and CuCl 2 ·2H 2 O, placing the mixture into a tetrafluoroethylene liner, adding deionized water and sodium hydroxide, sealing a reaction kettle, performing hydrothermal reaction, washing, filtering and drying the product after the reaction is finished to obtain a target product Cu II Coordination polymers.
2. A fertilizer suitable for use in Cu according to claim 1 II A process for preparing a coordination polymer urease inhibitor, characterized in that the ligand 5-hydroxy-N 1 ，N 3 -bis (pyridin-3-yl) isophthalamide preparation comprising the steps of:
dissolving 5-hydroxy isophthalic acid in pyridine solution, dissolving 3-aminopyridine in pyridine solution, slowly transferring to 5-hydroxy isophthalic acid solution, stirring at room temperature for 30min, dropwise adding triphenyl phosphite in 15min, and heating and refluxing for 10h; standing at room temperature overnight, adding water to separate out solid, filtering, washing with water, and drying in air to obtain white powdery solid.
3. A fertilizer suitable for use in Cu according to claim 1 II A process for preparing a coordination polymer urease inhibitor, characterized in that the ligand 5-hydroxy-N 1 ，N 3 -synthesis of bis (pyridin-3-yl) isophthalamide starting from 5-hydroxyisophthalic acid: the molar ratio of the 3-aminopyridine is 1:1-2.
4. A fertilizer suitable for use in Cu according to claim 1 II A method for preparing a coordination polymer urease inhibitor, which is characterized in that the hydrothermal reaction is carried out for 4 days at 120 ℃.
5. A fertilizer suitable for use in Cu according to claim 1 II A process for preparing a coordination polymer urease inhibitor, characterized in that the ligand 5-hydroxy-N 1 ，N 3 -bis (pyridin-3-yl) isophthalamide: copper chloride dihydrate:the molar ratio of the benzene tricarboxylic acid is 1:1-2:1-2.
6. A fertilizer suitable for use in Cu according to claim 1 II A process for producing a coordination polymer urease inhibitor, characterized in that the Cu II Coordination polymers are used as urease inhibitors in fertilizers, which are nitrogen fertilizers.
7. A fertilizer Cu according to claim 6 II A process for the preparation of a coordination polymer urease inhibitor, characterized in that the nitrogen fertilizer is urea.
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