CN112479961B - Method for preparing vitamin A palmitate by supercritical method - Google Patents
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- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/12—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by esterified hydroxy groups
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Abstract
The invention discloses a method for preparing vitamin A palmitate by a supercritical method, which utilizes the strong solubility of a supercritical fluid to strengthen mass transfer, and liquid-phase methanol generated by continuously resolving supercritical methanol in the reaction process promotes the ester exchange reaction to be carried out in the positive direction, thereby improving the reaction conversion rate. The process also entrains trifluoromethylthio compounds in the supercritical methanol, effectively promotes the formation of methyl palmitate carbenium ions, and improves the reaction yield.
Description
Technical Field
The invention belongs to the technical field of preparation of VA palmitate, and particularly relates to a method for preparing vitamin A palmitate by a supercritical method.
Background
Vitamin A palmitate (VA palmitate) has the advantages of long carbon chain, low melting point, good oil solubility and good low-temperature stability, is an indispensable substance for normal metabolism of human bodies and animals, and is widely applied to the fields of cosmetics, medicines, feeds and the like.
The VA palmitate is mainly prepared by a chemical synthesis method and a biological enzyme method. The chemical synthesis method mainly comprises the step of carrying out acylation reaction on VA alcohol and palmitoyl chloride to generate VA palmitate and HCl gas. The synthesis reaction conditions are harsh, more acidic byproducts are generated, high requirements on the corrosion resistance of production equipment are provided, and the industrial production is not facilitated. The biological enzyme method is to perform ester exchange or ester exchange reaction in the presence of lipase to obtain VA palmitate.
Patent CN104673870a discloses a method for preparing VA alcohol from VA acetate and methanol under catalysis of immobilized esterase e. And in the reaction, the filtration and the reduced pressure distillation are carried out for many times, and the process operation steps are complicated.
The existing preparation method of the VA palmitate has the problems of long production period, low conversion rate and the like, so that the method for searching the efficient and environment-friendly preparation method of the VA palmitate has good commercial significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing vitamin A palmitate by a supercritical method, which is carried out in a supercritical fluid, utilizes the electrophilicity of a trifluoromethylthio compound catalyst, effectively promotes the formation of methyl palmitate carbenium ions, and is beneficial to the attack of hydroxyl oxygen on VA alcohol, thereby improving the conversion rate of ester exchange reaction.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a method for preparing vitamin A palmitate by a supercritical method, which comprises the following steps: raw materials VA alcohol and methyl palmitate react in a supercritical fluid to prepare the vitamin A palmitate, wherein the catalyst is carried in the supercritical fluid.
The supercritical fluid is preferably supercritical methanol.
Preferably, the catalyst is a trifluoromethylthio compound, which is trifluoromethylthio chloride (SCF) 3 -Cl), trifluoromethylthiobromo (SCF) 3 -Br), N-trifluoromethylthioaniline ([ PhN (R) SCF) 3 ]) Trifluoromethylthiocuprous chloride (CuSCF) 3 ) Trifluoromethane thiol (SCF) 3 H) Preferably trifluoromethylthiobromine (SCF) 3 -Br). In the preparation method of VA palmitate, the trifluoromethylthio compound catalyst can provide a certain proton environment, promote the formation of carbonyl carbonium ions in methyl palmitate, facilitate the electron-rich oxygen atoms on VA alcoholic hydroxyl to attack the carbonium ions, and improve the conversion rate of ester exchange reaction
In some embodiments of the invention, the preparation method comprises the following steps:
(1) Mixing VA alcohol and methyl palmitate serving as reaction raw materials for later use;
(2) Mixing a reaction medium and a catalyst to prepare a supercritical fluid;
(3) And (3) mixing the supercritical fluid with the catalyst in the step (2) and the reaction raw material mixture in the step (1), and adding the mixture into a reactor for reaction.
In the step (2), the reaction medium is a medium capable of being prepared into a supercritical fluid, preferably methanol, the reaction medium in the raw material storage tank is heated to a certain temperature, the pressure reducing valve is opened, the reaction medium is dried by the dryer and then pumped into the mixer to a certain pressure by the high-pressure plunger pump at a certain flow rate, so that the reaction medium is in a supercritical state. At the same time, the trifluoromethylthio compound with a certain flow rate is pumped into the mixer by a high-pressure constant flow pump.
In the step (3), the raw material mixed liquor (VA alcohol and methyl palmitate) in the step (1) and the supercritical fluid carrying the trifluoromethylthio compound are simultaneously fed into the reactor.
The reactor is a filler reactor, and the supercritical fluid carrying the trifluoromethylthio compound continuously renews a gas/liquid film on the filler and contacts, adsorbs, reacts, desorbs and the like with VA alcohol and methyl palmitate, so that the mass transfer is enhanced. The packing layer is filled with a certain amount of non-metallic glass springs in order to increase the liquid contact area, and the filling volume is 0.1 mL-10 mL, preferably 0.5 mL-5 mL.
And the reacted product and unreacted materials enter a desorption tower along with the airflow for cooling and pressure reduction separation, the gas components can be recycled, the product VA palmitate enters a product collection tank, and crude oil obtained after concentration is subjected to quantitative analysis by liquid chromatography.
In the preparation method of VA palmitate of the present invention, in step (1), the molar ratio of VA alcohol and methyl palmitate is 1.8-1:3, preferably 1.1-1.5.
In some embodiments of the present invention, in the step (2), the heating temperature of the supercritical fluid is 250-300 ℃, preferably 239-280 ℃, and the pressure of the mixer is 7.0-12 MPa, preferably 8.1-10 MPa; so that the reaction medium is brought into a supercritical state.
In the step (3), the volume flow ratio of the supercritical fluid (containing the trifluoromethylthio compound) to the raw material mixed gas is 1:1-1, preferably 1:5-1. The flow rate of the supercritical fluid is 10L/min to 20L/min, preferably 12L/min to 16L/min (measured at 25 ℃ under normal pressure).
The volume flow ratio of the reaction medium to the trifluoromethylthio compound is 10 to 1, preferably 20.
In the preparation method of VA palmitate, in the step (3), the reaction temperature is 200-400 ℃, preferably 239-280 ℃; the reaction pressure is 7.0MPa to 20.0MPa, preferably 8.1MPa to 16.0MPa; preferably, the reaction temperature and pressure are the same as the temperature and pressure at which the reaction medium forms a supercritical fluid.
In the preparation method of VA palmitate, the reacted product and unreacted materials enter the desorption tower along with the gas flow for cooling and pressure reduction separation, and the cooling temperature enables the supercritical fluid to be gasified on the one hand and the methyl palmitate to be crystallized and separated on the other hand. The separation is cooled to-5 ℃ to 10 ℃, preferably-2 ℃ to 4 ℃. The condensed reaction medium methanol can be recycled, can meet the requirement of industrial continuous production, and is a green and environment-friendly novel method for continuously synthesizing the VA palmitate.
The invention has the beneficial effects that:
firstly, the VA palmitate is synthesized by adopting a supercritical method through ester exchange, and the excellent solubility and diffusivity of the supercritical fluid are utilized, so that the mass transfer resistance in the reaction process is greatly reduced, and the ester exchange reaction rate is improved.
Secondly, the supercritical fluid is modified by the electrophilic trifluoromethylthio compound through an entrainer, a certain proton environment is provided, the formation of hydroxyl carbenium ions in VA alcohol is promoted, the attack of oxygen atoms rich in electrons on the methyl palmitate on the carbenium ions is accelerated, and the reaction rate and the conversion rate are improved.
Thirdly, the VA palmitate can quickly resolve the generated methanol in the supercritical methanol, which is beneficial to separating the product in time, promoting the forward reaction and improving the reaction conversion rate.
Fourthly, after the reaction, a high-purity product can be quickly obtained through simple pressure reduction and temperature reduction treatment, and the method is suitable for large-scale industrial operation.
In addition, the content of VA palmitate prepared by the invention is over 97.5 percent detected by high performance liquid chromatography, and the VA palmitate can be widely applied to human medicines, additives and food additives.
Drawings
FIG. 1 is a schematic diagram of a reaction system for preparing vitamin A palmitate in the example of the present invention.
FIG. 2 is a liquid chromatogram of vitamin A palmitate prepared in example 1.
Wherein, 1 is a methanol gas tank; 2 is a gas tank pressure reducing valve; 3 is a dryer; 4 is a cooler; 5 is a high-pressure plunger pump; 6 is a mixer I; 7 is a high-pressure constant flow pump; 8 is a storage tank; 9 is a packing reactor, wherein ABCD is a packing position, a certain amount of non-metallic glass springs are filled, and the purpose is to increase the contact area of liquid and strengthen mass transfer; e is a liquid mixing and buffering component; 10 is a needle valve; 11 is a flowmeter; 12 is a cooling desorption tower; 13 is a back pressure valve; 14 is a product collecting tank; 18 is a second mixer; 19 is a raw material tank; 20 is a diaphragm pump.
Detailed Description
The present invention will be further described with reference to specific embodiments.
The reactor adopted in the embodiment of the invention has the height of 80cm and the inner diameter of 5cm, and is provided with a heating temperature control device.
The raw material sources are as follows: the VA alcohol and the VA palmitate standard crystal are purchased from Zhejiang medical science Inc., and the molecular formula of the VA alcohol is as follows, and the molecular weight is 286.5g/mol.
Trifluoromethylthiobromide was purchased from Shanghai Tatankojiki, inc.
Example 1
As shown in fig. 1, according to the molar ratio of raw materials VA alcohol and methyl palmitate of 1:1.2 5730gVA alcohol (20 mol) and 6480g methyl palmitate (24 mol) were weighed into a stock tank. And opening a methanol pressure reducing valve and a methanol gas tank pressure reducing valve, and pumping a mixture of supercritical methanol and trifluoro methyl bromide (the volume flow ratio of the supercritical methanol to the trifluoro methyl bromide is 20: 1) with the volume flow of 12L/min into a mixer, wherein the temperature of the mixed gas is 239.1 ℃, and the pressure is 8.1MPa. And then, mixing the prepared raw material liquid with a supercritical mixture at a volume flow of 60mL/min, conveying the mixture into a reactor, carrying out contact reaction at the temperature of 239.1 ℃ and under the pressure of 8.1MPa, and filling a certain amount of non-metallic glass springs into the reactor in order to increase the contact area of the liquid and strengthen mass transfer, wherein the filling amount of the glass springs is 5g, and the filling volume is 0.5mL. The pressure of the reaction system is regulated to be stable through a back pressure valve in the reaction process. After the reaction is complete (interval)Sampling and analyzing for a certain time, namely obtaining reaction equilibrium conversion rate when the content is stable, carrying out gas-liquid separation on the reaction liquid along with the fluid in an analytical tower at the temperature of-2 ℃, releasing methanol gas for recycling, and cooling the separated reaction liquid to crystallize to obtain a light yellow oily substance. The conversion rate of VA palmitate 95.15% is analyzed by high performance liquid chromatography, and the gas quality result shows that the molecular formula is C 36 H 60 O 2 Molecular weight 524.86, calculated using USP-29, with a biological potency of 173 ten thousand IU/g (of which 1iu =0.55 μ g vitamin a palmitate).
Example 2
As shown in fig. 1, according to the molar ratio of raw materials VA alcohol and methyl palmitate of 1:1.1 5270gVA alcohol (20 mol) and 5940g methyl palmitate (22 mol) were weighed into a stock tank. And opening a methanol pressure reducing valve and a methanol tank pressure reducing valve, and pumping a mixture of supercritical methanol and trifluoro methyl sulfur bromine (the volume flow ratio of the supercritical methanol to the trifluoro methyl sulfur bromine is 25) with the volume flow of 13L/min into a mixer, wherein the temperature of the mixed gas is 245 ℃, and the pressure is 8.93MPa. The prepared raw material liquid is mixed with supercritical methanol at a volume flow of 78mL/min and then is conveyed into a reactor for contact reaction at the temperature of 245 ℃ and the pressure of 7.8MPa, the filling amount of a glass spring is 4.5g, and the filling volume is 3mL. The pressure of the reaction system is regulated to be stable through a back pressure valve in the reaction process. After the reaction is completed (sampling and analyzing at certain time intervals, namely the reaction equilibrium conversion rate is obtained when the content is stable), the reaction liquid is subjected to gas-liquid separation with fluid at 0 ℃ in an analytical tower, the methanol gas is recycled after being released, and the reaction liquid is cooled to be crystallized after separation to obtain a light yellow oily substance. The conversion rate of VA palmitate 89.10% is analyzed by high performance liquid chromatography, and the biological potency is calculated to be 162 ten thousand IU/g.
Example 3
As shown in fig. 1, according to the molar ratio of raw materials VA alcohol and methyl palmitate of 1:1.3 2860gVA alcohol (10 mol) and 3510g methyl palmitate (13 mol) were weighed into a stock tank. And opening a methanol pressure reducing valve and a methanol gas tank pressure reducing valve, and pumping a mixture of supercritical methanol and trifluoro methyl bromide (the volume flow ratio of the supercritical methanol to the trifluoro methyl bromide is 30 1) with the volume flow of 14L/min into a mixer, wherein the temperature of the mixed gas is 250 ℃, and the pressure is 9.67MPa. The prepared and mixed raw material liquid is mixed with a supercritical mixture at a volume flow of 98mL/min and then is conveyed into a reactor for contact reaction at the temperature of 250 ℃ and the pressure of 9.67MPa, the filling amount of a glass spring is 3.5g, and the filling volume is 2mL. The pressure of the reaction system is regulated to be stable through a back pressure valve in the reaction process. After the reaction is completed (sampling and analyzing at certain time intervals, namely the reaction equilibrium conversion rate is obtained when the content is stable), the reaction liquid is subjected to gas-liquid separation with fluid at 0 ℃ in an analytical tower, the methanol gas is recycled after being released, and the reaction liquid is cooled to be crystallized after separation to obtain a light yellow oily substance. The conversion rate of VA palmitate is 83.05 percent by high performance liquid chromatography analysis, and the biological potency is calculated to be 151 ten thousand IU/g.
Example 4
As shown in fig. 1, according to the molar ratio of raw materials VA alcohol and methyl palmitate of 1: 2860gVA alcohol (10 mol) and 3780g methyl palmitate (14 mol) were weighed into stock tank 1.4. And opening a methanol pressure reducing valve and a methanol gas tank pressure reducing valve, and pumping a mixture of supercritical methanol and trifluoro methyl bromide (the volume flow ratio of the supercritical methanol to the trifluoro methyl bromide is 35 1) with the volume flow of 15L/min into a mixer, wherein the temperature of the mixed gas is 265 ℃, and the pressure is 12.28MPa. The prepared and mixed raw material liquid is mixed with a supercritical mixture at a volume flow rate of 120mL/min and then is conveyed into a reactor for contact reaction at a temperature of 265 ℃ and a pressure of 12.28MPa, the filling amount of a glass spring is 6.0g, and the filling volume is 3.5mL. The pressure of the reaction system is regulated to be stable through a back pressure valve in the reaction process. After the reaction is completed (sampling and analyzing at certain time intervals, namely the reaction equilibrium conversion rate is obtained when the content is stable and unchanged), the reaction liquid is subjected to gas-liquid separation with fluid in an analytical tower at the temperature of-2 ℃, the methanol gas is recycled after being released, and the reaction liquid is cooled to be crystallized after separation to obtain a light yellow oily substance. High performance liquid analysis shows that the conversion rate of VA palmitate 89.65% and the biological potency is 163 ten thousand IU/g.
Example 5
As shown in fig. 1, according to the molar ratio of raw materials VA alcohol and methyl palmitate of 1: 2860gVA alcohol (10 mol) and 4050g methyl palmitate (15 mol) were weighed into stock tank 1.5. And opening a methanol pressure reducing valve and a methanol gas tank pressure reducing valve, and pumping a mixture of supercritical methanol and trifluoro methyl bromide (the volume flow ratio of the supercritical methanol to the trifluoro methyl bromide is 40: 1) with the volume flow of 16L/min into a mixer, wherein the temperature of the mixed gas is 280 ℃, and the pressure is 15.33MPa. The prepared and mixed raw material liquid is mixed with a supercritical mixture at a volume flow of 160mL/min and then is conveyed into a reactor for contact reaction at a temperature of 280 ℃ and a pressure of 15.33MPa, the filling amount of a glass spring is 6.0g, and the filling volume is 4.5mL. The pressure of the reaction system is regulated to be stable through a back pressure valve in the reaction process. After the reaction is completed (sampling and analyzing at certain time intervals, namely the reaction equilibrium conversion rate is obtained when the content is stable and unchanged), the reaction liquid is subjected to gas-liquid separation with fluid in an analytical tower at the temperature of 2.5 ℃, the methanol gas is recycled after being released, and the reaction liquid is cooled to be crystallized after separation to obtain a light yellow oily substance. The conversion rate of VA palmitate is 86.35% and the biological value is 157 ten thousand IU/g by high performance liquid chromatography analysis.
Comparative example 1
According to the molar ratio of raw materials VA alcohol and methyl palmitate of 1:1.2 5730gVA alcohol (20 mol) and 6480g methyl palmitate (24 mol) were weighed into a stock tank. Opening a methanol pressure reducing valve and a methanol storage tank valve, and pumping supercritical methanol with the volume flow of 12L/min into a mixer, wherein the temperature of mixed gas is 239.1 ℃, and the pressure is 8.1MPa. And then the prepared raw material liquid is mixed with supercritical methanol at the volume flow rate of 60mL/min and then is conveyed into a reactor for contact reaction at the temperature of 239.1 ℃ and the pressure of 8.1MPa, the filling amount of a glass spring in the reactor is 5g, and the filling volume is 0.5mL. The pressure of the reaction system is regulated to be stable through a back pressure valve in the reaction process. After the reaction is completed (sampling and analyzing for a certain time in the compartment, namely the reaction equilibrium conversion rate is obtained when the content is stable), the reaction liquid is subjected to gas-liquid separation along with the fluid in an analytical tower at the temperature of-2 ℃, the methanol gas is recycled after being released, and the reaction liquid is cooled to be crystallized after separation to obtain a light yellow oily substance. The conversion rate of VA palmitate is 65% by high performance liquid analysis.
Comparative example 2
According to the molar ratio of raw materials VA alcohol and methyl palmitate of 1:1.2 5730gVA alcohol (20 mol) and 6480g methyl palmitate (24 mol) were weighed into a stock tank. And then conveying the prepared raw material liquid into a reactor at a volume flow of 60mL/min, and carrying out contact reaction at a temperature of 239.1 ℃ and a pressure of 8.1MPa, wherein the filling amount of a glass spring in the reactor is 5g, and the filling volume is 0.5mL. The pressure of the reaction system is regulated to be stable through a back pressure valve in the reaction process. After the reaction is completed (sampling and analyzing for a certain time in the compartment, namely the reaction equilibrium conversion rate is obtained when the content is stable), the reaction liquid is subjected to gas-liquid separation along with the fluid in an analytical tower at the temperature of-2 ℃, the methanol gas is recycled after being released, and the reaction liquid is cooled to be crystallized after separation to obtain a light yellow oily substance. The conversion rate of VA palmitate is 10% by high performance liquid analysis.
As can be seen from comparative example 1, in the absence of the trifluoromethyl sulfide bromine, the conversion rate of only VA palmitate in a supercritical system is 65%, and in the absence of the supercritical system, the conversion rate of VA palmitate is 10%, which indicates that the trifluoromethyl sulfide bromine compound in the supercritical system has a good catalytic effect.
Claims (13)
1. A method for preparing vitamin A palmitate by a supercritical method is characterized by comprising the following steps: raw materials of VA alcohol and methyl palmitate react in a supercritical fluid to prepare vitamin A palmitate, wherein the supercritical fluid is entrained with a catalyst;
the supercritical fluid is supercritical methanol;
the catalyst is a trifluoromethylthio compound, and the trifluoromethylthio compound is one or more selected from trifluoromethylthio chloride, trifluoromethylthio bromide, N-trifluoromethylthio aniline, trifluoromethylthio cuprous and trifluoromethylthiol.
2. The method of claim 1, comprising the steps of:
(1) Mixing VA alcohol and methyl palmitate serving as reaction raw materials for later use;
(2) Mixing a reaction medium and a catalyst to prepare a supercritical fluid;
(3) And (3) mixing the supercritical fluid with the catalyst in the step (2) and the reaction raw material mixture in the step (1), and adding the mixture into a reactor for reaction.
3. The preparation method according to claim 1 or 2, wherein the reactor is a packed reactor, and the packing layer is filled with a non-metallic glass spring and has a filling volume of 0.1 mL-10 mL.
4. The method of claim 3, wherein the packing volume of the packing layer is 0.5 mL-5 mL.
5. The preparation method according to claim 2, wherein in the step (1), the molar ratio of the compound VA alcohol to the methyl palmitate is 1.
6. The preparation method according to claim 5, wherein in the step (1), the molar ratio of the compound VA alcohol to the methyl palmitate is 1.
7. The production method according to claim 2, wherein in the step (2), the heating temperature of the supercritical fluid is 250 ℃ to 300 ℃ and the pressure of the mixer is 7.0MPa to 12MPa.
8. The production method according to claim 7, wherein in the step (2), the heating temperature of the supercritical fluid is 239 ℃ to 280 ℃ and the pressure of the mixer is 8.1MPa to 10MPa.
9. The preparation method according to claim 2, wherein in the step (3), the volume flow ratio of the supercritical fluid to the raw material mixed gas is 1:1-1; the flow rate of the supercritical fluid is 10L/min-20L/min;
the volume flow ratio of the reaction medium to the trifluoromethylthio compound is 10.
10. The preparation method according to claim 9, wherein in the step (3), the volume flow ratio of the supercritical fluid to the raw material mixed gas is 1:5-1; the flow rate of the supercritical fluid is 12L/min-16L/min;
the volume flow ratio of the reaction medium to the trifluoromethylthio compound is 20.
11. The preparation method according to claim 2, wherein in the step (3), the reaction temperature is 200 ℃ to 400 ℃; the reaction pressure is 7.0 MPa-20.0 MPa.
12. The method according to claim 11, wherein, in the step (3), the reaction temperature is 239 ℃ to 280 ℃; the reaction pressure is 8.1 MPa-16.0 MPa.
13. The method according to claim 11 or 12, wherein the reaction temperature and pressure are the same as those at which the reaction medium forms the supercritical fluid.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105969833A (en) * | 2016-03-17 | 2016-09-28 | 厦门金达威维生素有限公司 | Synthesis method of vitamin A palmitate |
| CN108623507A (en) * | 2017-03-15 | 2018-10-09 | 四川海思科制药有限公司 | The preparation method of Retinol Palmitate |
| CN109232213A (en) * | 2018-10-19 | 2019-01-18 | 浙江新和成股份有限公司 | The method of hydroxy pivalin aldehyde is prepared under a kind of super critical condition |
| CN109651150A (en) * | 2018-12-20 | 2019-04-19 | 万华化学集团股份有限公司 | A method of preparing vitamine A acetate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105969833A (en) * | 2016-03-17 | 2016-09-28 | 厦门金达威维生素有限公司 | Synthesis method of vitamin A palmitate |
| CN108623507A (en) * | 2017-03-15 | 2018-10-09 | 四川海思科制药有限公司 | The preparation method of Retinol Palmitate |
| CN109232213A (en) * | 2018-10-19 | 2019-01-18 | 浙江新和成股份有限公司 | The method of hydroxy pivalin aldehyde is prepared under a kind of super critical condition |
| CN109651150A (en) * | 2018-12-20 | 2019-04-19 | 万华化学集团股份有限公司 | A method of preparing vitamine A acetate |
Non-Patent Citations (1)
| Title |
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| Efficient synthesis of vitamin A palmitate in nonaqueous medium using self assembled lipase TLL apatite hybrid nanoflowers by mimetic biomineralization;Xu, Liqing;《Green Chemistry Letters and Reviews》;20181024;第11卷(第4期);476-483页 * |
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