CN114773222B - Synthesis method of azo micromolecules for zinc oxide nanoparticle stable ligand - Google Patents

Synthesis method of azo micromolecules for zinc oxide nanoparticle stable ligand Download PDF

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CN114773222B
CN114773222B CN202210537276.8A CN202210537276A CN114773222B CN 114773222 B CN114773222 B CN 114773222B CN 202210537276 A CN202210537276 A CN 202210537276A CN 114773222 B CN114773222 B CN 114773222B
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CN114773222A (en
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耿家厚
王金辉
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Ningbo University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
    • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
    • C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium

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Abstract

The invention discloses a synthesis method of azo micromolecules for a zinc oxide nanoparticle stable ligand. Two-step method for synthesizing target molecule AZO-NH 2 The first step synthesizes a white intermediate by using reagents such as 4-phenylazophenol, N- (6-bromohexyl) phthalimide and the like as raw materials, and the second step adds reagents such as hydrazine hydrate and the like into the intermediate obtained in the first step, and finally obtains AZO-NH through a series of steps such as extraction, drying, column chromatography and the like 2 . The reagents used in the experimental process are nontoxic reagents, so that the safety of the experimental process can be ensured.

Description

Synthesis method of azo micromolecules for zinc oxide nanoparticle stable ligand
Technical Field
The invention relates to the field of material chemistry, in particular to a synthesis method of azo micromolecules for a zinc oxide nanoparticle stable ligand.
Background
Azobenzene molecules are typical photoisomerization molecules, the structure of the azobenzene molecules can be changed by light irradiation with different wavelengths, and the azobenzene has been applied to various fields such as dyes, medicines, liquid crystal materials, intelligent packaging and the like. The synthesis method of azobenzene and derivatives thereof is numerous and mainly comprises a diazo coupling method, a nitro reduction method, an aryl hydrazine oxidation method, an aromatic amine oxidation method and the like. However, there are few reports on the synthesis of amino alcohols substituted azobenzene, the following steps are shown, and toxic or explosive compounds (such as ammonia gas, sodium azide and the like) or strong reducing agents (such as lithium aluminum hydride and the like) are commonly used in the synthesis method, so that great potential safety hazards exist.
The invention adopts a two-step method to synthesize the target molecule AZO-NH 2 The structural formula of the intermediate synthesized in the first step is shown in the following formula 1, and the target molecule AZO-NH synthesized in the second step 2 The structural formula of (2) is shown in the following formula. The synthetic method avoids the use of toxic or explosive chemical reagents and is safer.
There have been a number of previous works to demonstrate that alkylamines of different alkyl chains can be used as stabilizing ligands for the preparation of zinc oxide nanoparticles, and it is based on these works that AZO-NH, which is synthesized in the present invention, also has long alkyl chains 2 Zinc oxide nanoparticles can be prepared as stabilizing ligands.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a synthesis method of AZO micromolecules for stabilizing ligands of zinc oxide nanoparticles, which adopts a two-step method to synthesize a target molecule AZO-NH 2 The first step synthesizes a white intermediate by using reagents such as 4-phenylazophenol, N- (6-bromohexyl) phthalimide and the like as raw materials, and the second step adds reagents such as hydrazine hydrate and the like into the intermediate obtained in the first step, and finally obtains AZO-NH through a series of steps such as extraction, drying, column chromatography and the like 2 . The reagents used in the experimental process are nontoxic reagents, so that the safety of the experimental process can be ensured.
The invention is realized by the following technical scheme:
the invention discloses a synthesis method of azo micromolecules for nanoparticle stable ligands, which comprises the following steps:
1) Adding 4-phenylazophenol, potassium carbonate and N, N-dimethylformamide under the protection of inert gas, adding N- (6-bromohexyl) phthalimide, heating the system to above 100 ℃ under stirring, placing the obtained suspension in a separating funnel after the reaction is finished, adding an organic solvent and a water solution, extracting a water phase with the organic solvent, merging the organic phases, washing the organic phases with alkali liquor and water respectively, drying, filtering, and concentrating under reduced pressure to obtain an intermediate product white solid;
2) Dissolving the white solid of the intermediate product obtained in the step 1) in an alcohol solution, heating and refluxing the system, adding hydrazine hydrate, enabling the mixture to be colorless, forming white precipitate, continuously stirring and refluxing, spin-drying, adding an organic solvent, water and alkali liquor, separating an organic phase, extracting the water phase by the organic solvent, merging the organic phase, respectively washing the organic phase by the alkali liquor and the water, drying, filtering, concentrating under reduced pressure, and purifying by column chromatography to obtain a light yellow product AZO-NH 2 ；
3) Two equivalents of AZO-NH obtained in step 2) by taking diethyl zinc as a precursor 2 Zinc oxide nanoparticles are prepared for the ligand.
As a further improvement, in the step 1) of the present invention, the structural formula of the synthesized intermediate product is shown in formula 1:
as a further improvement, in the step 2) of the invention, the synthesized AZO-NH 2 The structural formula is shown in formula 2:
as a further improvement, in the step 1) of the invention, the molar usage ratio of the compound 4-phenylazophenol and N- (6-bromohexyl) phthalimide is 1:1 to 1.5: 1.
As a further improvement, in step 1) according to the present invention, the molar ratio of the compound N- (6-bromohexyl) phthalimide to potassium carbonate is 1:2.
as a further improvement, in step 1) according to the invention, in the synthesis step 1), the reaction is carried out with stirring at 120℃and the suspension obtained is partitioned with ethyl acetate, chloroform and water (to aid in the partition) and the organic phases are combined and washed with saturated sodium hydroxide solution.
As a further improvement, in the step 2) of the invention, alkali liquor is slowly added dropwise before the organic phase is separated, so that the pH of the solution is more than 10.
As a further improvement, in the step 2) of the invention, the eluent used for column chromatography purification is methylene dichloride and methanol or a mixed solvent of chloroform and methanol in the ratio of 83:155:1.55, and an ammonia water balance system is added.
As a further improvement, in step 2) according to the present invention, the reaction is carried out in an ethanol solution and heated to 90 ℃ for reflux; hydrazine hydrate is slowly added into the reaction system in a dropwise manner.
The beneficial effects of the invention are as follows:
the preparation method provided by the invention can synthesize amino alcohols substituted azobenzene compound through two steps of continuous reactions, and the reaction intermediate 1 does not need column chromatography separation, so that the yield can be improved. The raw materials used in the reaction do not contain toxic and harmful reagents such as ammonia gas, sodium azide and the like, so that the experimental risk is effectively reduced, and the environmental pollution is reduced.
In the method, during the synthesis of the intermediate 1, ethyl acetate, chloroform and water are added into the obtained suspension during liquid separation, so that layering is facilitated, the problems of difficult separation and the like caused by solution emulsification are solved, and the product yield is improved.
The method is used for preparing the compound AZO-NH 2 When the final pH of the system is more than 10 by using alkali liquor before separating the organic phase, the loss of the product can be reduced. When the column chromatography is used for purification, a small amount of ammonia water is added to prevent tailing and achieve better separation effect.
The long alkyl chain compound AZO-NH synthesized by the preparation method provided by the invention 2 Can be used as a stable ligand of zinc oxide nano particles to efficiently prepare stable nano particles, and the prepared zinc oxide nano particles have gradually enhanced absorption spectrum under blue light irradiation and good optical activity.
The preparation method provided by the invention has relatively mild conditions, does not need to add strong reducibility or acyl chloridizing reagents such as lithium aluminum hydride, thionyl chloride and the like, can generate target products by heating, and reduces the problems of low yield, great heat release of reaction, cost increase caused by three wastes treatment and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the intermediate obtained in example 1;
FIG. 2 is AZO-NH obtained in example 1 2 A polarized light microscopic photograph of (2);
FIG. 3 is a transmission electron micrograph of the zinc oxide nanoparticles obtained in example 1 at 50000 Xmagnification;
FIG. 4 is a transmission electron micrograph of the zinc oxide nanoparticles obtained in example 1 at 200000 magnification;
FIG. 5 is a two equivalent AZO-NH obtained in example 1 2 Polarized light microscopic photograph of zinc oxide nano particles under ligand stabilization;
FIG. 6 is AZO-NH obtained in example 1 2 An ultraviolet visible absorption spectrum diagram of the molecular chloroform solution under 365nm ultraviolet irradiation;
FIG. 7 is AZO-NH obtained in example 1 2 Ultraviolet visible absorption spectrum of molecular chloroform solution under 436nm blue light irradiation.
Detailed Description
The invention discloses a synthesis method of azo micromolecules for nanoparticle stable ligands, which comprises the following steps:
(1) 4-N-phenylbenzamide, potassium carbonate and N, N-dimethylformamide were added to a pre-dried round-bottomed flask under an argon atmosphere, and then N- (6-bromohexyl) phthalimide was added thereto, and the mixture was stirred at 120℃until the reaction was complete. The resulting suspension was placed in a separatory funnel and some ethyl acetate, chloroform and water were added. The residue in the aqueous solution was extracted using the organic phase as the starting material and ethyl acetate as the extractant. The organic phase was collected and washed with saturated sodium hydroxide solution. Drying the obtained solution with anhydrous magnesium sulfate, filtering, and concentrating under reduced pressure to obtain intermediate product as white solid shown in formula 1 below
(2) The ethanol suspension of the product obtained in step (1) was placed in a pre-dried two-necked round bottom flask. The mixture was heated to 90 ℃ and the hydrazine hydrate solution was added dropwise for 10 minutes. It was found that the mixture turned colorless and then a white precipitate formed. The mixture system was allowed to stir at reflux at the specified temperature until the reaction was complete. Volatile components were removed under vacuum and the residue was dissolved in a mixture of water, chloroform, and methanol, separated in a separatory funnel, some precipitate was observed to be insoluble in the organic phase, and then 2ml of sodium hydroxide solution was added dropwise to a pH of greater than 10. The organic phase was separated, the aqueous phase was extracted three times with chloroform, the organic extracts were combined and washed with saturated sodium bicarbonate solution, then the organic extracts were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Finally, performing column chromatography purification by using an eluent of chloroform, methanol and ammonia water (83:155:1.55) to obtain a pale yellow product AZO-NH 2 As shown in the following formula 2.
The technical scheme of the invention is further described by the following specific examples:
example 1:
(1) 4-N-phenylbenzamide (1.88 g,9.47 mmol), potassium carbonate (2.35 g,17.0 mmol) and N, N-dimethylformamide (50 ml) were added to a pre-dried round-bottomed flask under an argon atmosphere, and then N- (6-bromohexyl) phthalimide (2.63 g,8.5 mmol) was added and the mixture stirred at 120℃until the reaction was complete. The resulting suspension was placed in a separatory funnel and 100mL of ethyl acetate, chloroform and water (3:2:5 by volume) were added. The residue in the aqueous solution was extracted using the organic phase as the starting material and ethyl acetate as the extractant. The organic phase was collected and washed with saturated sodium hydroxide solution. The obtained product is then processedThe solution was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give a white solid (3.25 g, yield 90%) which was characterized by nuclear magnetic resonance spectroscopy (figure 1), 1 H NMR(500MHz,DMSO-d6)δ7.91-7.84(m,6H),7.71-7.62(m,2H),7.58-7.37(m,2H),6.88-7.05(m,2H),4.03(t,J＝6.5Hz,2H),3.71(t,J＝6.5Hz,2H),1.90-1.72(m,4H),1.38-1.65(m,4H)。
(2) The ethanol suspension of the product obtained in step (1) was placed in a pre-dried two-necked round bottom flask. The mixture was warmed to 90℃and hydrazine hydrate (740. Mu.l) was added dropwise for 10 minutes. It was found that the mixture turned colorless and then a white precipitate formed. The mixture system was allowed to stir at reflux at the specified temperature until the reaction was complete. Volatile components were removed under vacuum and the residue was dissolved in a mixture of water (200 ml), chloroform (200 ml), and methanol (5 ml) and separated in a separating funnel, some precipitate was observed to be insoluble in the organic phase, and thus 2ml of sodium hydroxide solution was added dropwise to a pH of greater than 10. The organic phase was separated, the aqueous phase was extracted three times with chloroform (3×100 ml), the organic extracts were combined and washed with saturated sodium bicarbonate solution, then the organic extracts were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Finally, performing column chromatography purification by using an eluent of chloroform, methanol and ammonia water (83:155:1.55) to obtain a pale yellow product AZO-NH 2 (1.89 g, 75% yield), and magnetic core characterization 1 H NMR(500MHz,CDCl 3 ) 8.42-8.37 (m, 2H), 8.21-8.28 (m, 2H), 7.94-7.78 (m, 4H), 4.05 (t, j=6.4 hz,2H, ch 2), 2.72 (t, j=7.2 hz,2H, ch 2), 2.21 (t, j=6.4 hz,2H, ch 2), 1.65-1.56 (m, 2H), 1.31-1.22 (m, 4H). Observation of AZO-NH compound by polarizing microscope 2 Is of the form (fig. 2). The compound was dissolved in chloroform solution and its UV-visible absorption spectra were measured as a function of time under 365nm UV light (FIG. 6) and 436nm blue light (FIG. 7), respectively.
(3) Diethyl zinc is used as a precursor, and two equivalents of AZO-NH 2 Zinc oxide nanoparticles can be prepared for ligands. The transmission electron microscope photograph is shown in FIG. 3 (magnification 50000) and FIG. 4 (magnification 200000), and the compound AZO-NH is observed by a polarizing microscope 2 Is shown in fig. 5.
Example 2:
(1) 4-N-phenylbenzamide (2.15 g,10.85 mmol), potassium carbonate (2.70 g,19.5 mmol) and N, N-dimethylformamide (50 ml) were added to a pre-dried round-bottomed flask under an argon atmosphere, and then N- (6-bromohexyl) phthalimide (2.70 g,9.8 mmol) was added and the mixture stirred at 120℃until the reaction was complete. The resulting suspension was placed in a separatory funnel and 100mL of ethyl acetate, chloroform and water were added. The residue in the aqueous solution was extracted using the organic phase as the starting material and ethyl acetate as the extractant. The organic phase was collected and washed with saturated sodium hydroxide solution. The resulting solution was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give a white solid (3.45 g, yield 83%).
(2) The ethanol suspension of the product obtained in step (1) was placed in a pre-dried two-necked round bottom flask. The mixture was heated to 90℃and hydrazine hydrate (850. Mu.l) was added dropwise for 10 minutes. It was found that the mixture turned colorless and then a white precipitate formed. The mixture was allowed to stir at reflux at the specified temperature until the reaction was complete. Volatile components were removed under vacuum and the residue was dissolved in a mixture of water (200 ml), chloroform (200 ml), and methanol (5 ml) and separated in a separating funnel, some precipitate was observed to be insoluble in the organic phase, thus 3ml of sodium hydroxide solution was added dropwise to a pH of greater than 10. The organic phase was separated, the aqueous phase was extracted three times with chloroform (3×100 ml), the organic extract was collected and washed with saturated sodium bicarbonate solution, then the organic extract was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Finally, performing column chromatography purification by using an eluent of chloroform, methanol and ammonia water (83:155:1.55) to obtain a pale yellow product AZO-NH 2 (1.87 g, yield 78%).
(3) Diethyl zinc is used as a precursor, and two equivalents of AZO-NH 2 Zinc oxide nanoparticles can be prepared for ligands.
Example 3:
(1) 4-N-phenylbenzamide (1.43 g,7.21 mmol), potassium carbonate (1.80 g,13.0 mmol) and N, N-dimethylformamide (50 ml) were added to a pre-dried round-bottomed flask under an argon atmosphere, and then N- (6-bromohexyl) phthalimide (2.02 g,6.5 mmol) was added and the mixture stirred at 120℃until the reaction was complete. The resulting suspension was placed in a separatory funnel and 100mL of ethyl acetate, chloroform and water were added. The residue in the aqueous solution was extracted using the organic phase as the starting material and ethyl acetate as the extractant. The organic phase was collected and washed with saturated sodium hydroxide solution. The resulting solution was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give a white solid (2.60 g, yield 94%).
(2) The ethanol suspension of the product obtained in step (1) was placed in a pre-dried two-necked round bottom flask. The mixture was heated to 90℃and hydrazine hydrate solution (570. Mu.l) was added dropwise for 10 minutes. It was found that the mixture turned colorless and then a white precipitate formed. The mixture was allowed to stir at reflux at the specified temperature until the reaction was complete. Volatile components were removed under vacuum and the residue was dissolved in a mixed solvent of water (200 ml), chloroform (200 ml), and methanol (5 ml) and separated in a separating funnel, some precipitate was observed to be insoluble in the organic phase, and thus 2ml of sodium hydroxide solution was added dropwise to a pH of greater than 10. The organic phase was separated, the aqueous phase was extracted three times with chloroform (100 ml), the organic extract was collected and washed with saturated sodium bicarbonate solution, then the organic extract was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Finally, performing column chromatography purification by using an eluent of chloroform, methanol and ammonia water (83:155:1.55) to obtain a pale yellow product AZO-NH 2 (1.81 g, yield 80%).
(3) Diethyl zinc is used as a precursor, and two equivalents of AZO-NH 2 Zinc oxide nanoparticles can be prepared for ligands.
Example 4:
(1) 4-N-phenylbenzamide (2.69 g,13.6 mmol), potassium carbonate (3.40 g,24.6 mmol) and N, N-dimethylformamide (50 ml) were added to a pre-dried round-bottomed flask under an argon atmosphere, and then N- (6-bromohexyl) phthalimide (3.82 g,12.3 mmol) was added and the mixture stirred at 120℃until the reaction was complete. The resulting suspension was placed in a separatory funnel and 150mL of ethyl acetate, chloroform and water were added. The residue in the aqueous solution was extracted using the organic phase as the starting material and ethyl acetate as the extractant. The organic phase was collected and washed with saturated sodium hydroxide solution. The resulting solution was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give a white solid (4.88 g, yield 93%).
(2) The ethanol suspension of the product obtained in step (1) was placed in a pre-dried two-necked round bottom flask. The mixture was warmed to 90℃and hydrazine hydrate solution (1070. Mu.l) was added dropwise for 10 minutes. It was found that the mixture turned colorless and then a white precipitate formed. The mixture was allowed to stir at reflux at the specified temperature until the reaction was complete. Volatile components were removed under vacuum and the residue was dissolved in a mixed solvent of water (200 ml), chloroform (200 ml), and methanol (5 ml) and separated in a separating funnel, some precipitate was observed to be insoluble in the organic phase, and thus 6ml of sodium hydroxide solution was added dropwise to a pH of greater than 10. The organic phase was separated, the aqueous phase was extracted three times with chloroform (3×100 ml), the organic extract was collected and washed with saturated sodium bicarbonate solution, then the organic extract was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Finally, performing column chromatography purification by using an eluent of chloroform, methanol and ammonia water (83:155:1.55) to obtain a pale yellow product AZO-NH 2 (2.58 g, 76% yield).
(3) Diethyl zinc is used as a precursor, and two equivalents of AZO-NH 2 Zinc oxide nanoparticles can be prepared for ligands.
The above-mentioned embodiments of the present invention are only some of the specific embodiments, and it is apparent that the present invention is not limited to the above embodiments, but many variations are possible, and all modifications that can be directly derived or suggested from the disclosure of the present invention by those skilled in the art should be considered as the scope of the present invention.

Claims (6)

1. The synthesis method of the zinc oxide nano particle is characterized by comprising the following steps:
1) Adding 4-phenylazophenol, potassium carbonate and N, N-dimethylformamide into N- (6-bromohexyl) phthalimide under the protection of inert gas, heating a system under stirring, placing the obtained suspension in a separating funnel after the reaction is finished, adding an organic solvent and a water solution, extracting a water phase with the organic solvent, merging the organic phases, washing the organic phases with alkali liquor and water respectively, drying, filtering and concentrating under reduced pressure to obtain an intermediate product white solid;
2) Dissolving the white solid of the intermediate product obtained in the step 1) in an alcohol solution, heating and refluxing the system, adding hydrazine hydrate, enabling the mixture to be colorless, forming white precipitate, continuously stirring and refluxing, spin-drying, adding an organic solvent, water and alkali liquor, separating an organic phase, extracting the water phase by the organic solvent, merging the organic phase, respectively washing the organic phase by the alkali liquor and the water, drying, filtering, concentrating under reduced pressure, and purifying by column chromatography to obtain a light yellow product AZO-NH 2 ；
3) Two equivalents of AZO-NH obtained in step 2) by taking diethyl zinc as a precursor 2 Preparing zinc oxide nano particles for the ligand;
in the step 1), the structural formula of the synthesized intermediate product is shown as formula 1:
in the step 2), the synthesized AZO-NH 2 The structural formula is shown in formula 2:
2. the method according to claim 1, wherein in the step 1), the molar ratio of the 4-phenylazophenol to the N- (6-bromohexyl) phthalimide is 1:1 to 1.5: 1.
3. The method according to claim 1, wherein in the step 1), the molar ratio of the N- (6-bromohexyl) phthalimide to the potassium carbonate is 1:2.
4. the method according to claim 1, wherein in step 1), the reaction is carried out with stirring at 120 ℃.
5. The method according to claim 1, 2, 3 or 4, wherein in step 2), the alkaline solution is slowly added dropwise before the separation of the organic phase, so that the pH of the solution is more than 10.
6. The method according to claim 5, wherein in the step 2), the eluent used for the column chromatography purification is methylene chloride and methanol or a mixed solvent of chloroform and methanol, and an ammonia water balance system is added.
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Photoresponsive crown ethers. 19. Photocontrol of reversible association-dissociation phenomena in tail(ammonium)-biting crown ethers;，Shinkai Seiji et al.;Bull. Chem. Soc. Jpn.;第60卷(第5期);1819-1824 *
Photoresponsive Crown Ethers. Part 14.t Photoregulated Crown-Metal Complexation by Competitive Intramolecular Tail(Ammonium)-biting;Shinkai Seiji et al.;J. CHEM. SOC. PERKIN TRANS. II(第4期);511-518 *

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