CN102443620B - Application of 8, 9-tetradeuterium hexadecane as tracer - Google Patents
Application of 8, 9-tetradeuterium hexadecane as tracer Download PDFInfo
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- CN102443620B CN102443620B CN 201110278636 CN201110278636A CN102443620B CN 102443620 B CN102443620 B CN 102443620B CN 201110278636 CN201110278636 CN 201110278636 CN 201110278636 A CN201110278636 A CN 201110278636A CN 102443620 B CN102443620 B CN 102443620B
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Abstract
The invention relates to application of 8, 9-tetradeuterium hexadecane as a tracer, which is used for detecting a metabolic pathway in the methane production process via alkane anaerobic degradation by taking the 8, 9-tetradeuterium hexadecane as the tracer. In comparison with the prior art, the invention has the characteristics of not affecting initial activation of alkane and meanwhile acquiring information of intermediate metabolites for offering help to the research of the petroleum hydrocarbon anaerobic degradation mechanism.
Description
Technical field
The present invention relates to deuterium for the hydrocarbon tracer agent, especially relate to 8,9-, four deuterium n-Hexadecanes as the application of tracer agent.
Background technology
Deuterium is that hydrogen atom in the hydrocarbon molecule is replaced the formed mark substance in back by its stable isotope D atom (D) for hydrocarbon.With the hydrocarbon phase ratio of labelled with radioisotope, the stable isotope deuterium is higher for hydrocarbon security in transportation and use, stability better, radioactivity and toxicity is lower.Because lower production cost and the high isotopic purity of deuterated reagent make deuterium for the synthetic of hydrocarbon and use more convenient extensive.Deuterium can be used for exploring reaction mechanism and the biochemical metabolism approach that may exist for hydrocarbon.Simultaneously, deuterium also can be used as uses such as inside and outside mark and reference substance for hydrocarbon.
At present, the relevant report of also not using as tracer agent about 8,9-, four deuterium n-Hexadecanes.
8,9-, four deuterium n-Hexadecanes can be used for exploring the pathways metabolism that may exist in the alkane anaerobic degradation process.At present the initial activation mode of known alkane anaerobic degradation mainly comprises and adds fumaric acid and carboxylation, these two kinds of activation methods all act on the alkane end of the chain, wherein, add on the inferior end carbon that fumaric acid usually occurs in alkane chain, carboxylation is to introduce a carboxyl at C-3, takes off two carbon atoms of chain end again.In the research of anaerobism alkane degradation, adopt the alkane in full deuterium generation as substrate mostly.Because the C-D bond energy can be stronger than c h bond, so the activation of C-D key is more difficult than c h bond.Therefore, than the full deuterium n-Hexadecane in generation, the interposition deuterium is cultivated as substrate for n-Hexadecane, microorganism can more be partial to utilize and contain the c h bond n-Hexadecane in more part deuterium generation, carries out Metabolic activity quickly.Simultaneously, the deuterium of 8,9-, four deuterium n-Hexadecanes is subrogated and is positioned at the alkane chain middle, neither can influence the initial activation of alkane, also can obtain the information of mesostate simultaneously, for petroleum hydrocarbon anaerobic degradation Study on Mechanism is offered help.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of initial activation that neither can influence alkane in order to overcome the defective that above-mentioned prior art exists, also can obtain simultaneously mesostate information 8,9-four deuterium n-Hexadecanes are as the application of tracer agent.
Purpose of the present invention can be achieved through the following technical solutions:
8,9-, four deuterium n-Hexadecanes is characterized in that as the application of tracer agent 8,9-, four deuterium n-Hexadecanes are used for surveying the pathways metabolism that the alkane anaerobic degradation is produced the methane process as tracer agent.
Described application specifically may further comprise the steps: add 8 in 50mL product methane-rich substratum, 9-four deuterium n-Hexadecanes 30 μ L cultivate methanogen floras as sole carbon source, cultivated 365 days down at 38 ℃, the culture middle acid substance is being determined whether contain 8 in the acidic substance through extraction, esterification, analysis, 9-four deuterium palmitic acids, thus judge n-Hexadecane bio anaerobic degradation pathway.
Described 8,9-four deuterium n-Hexadecanes have following structure:
Described 8,9-four deuterium n-Hexadecanes make by the following method, specifically may further comprise the steps:
(1) be that 1: 3～1: 100 n-nonanoic acid and deuterium chloride-heavy aqueous solution adds reactor with volume ratio, under the condition of sealing, under 150～200 ℃ temperature, reaction 12～72h makes 2-two deuterium n-nonanoic acids;
(2) the 2-two deuterium n-nonanoic acids that step (1) obtained and methanol-water solution (1: 2～1: 20) by volume join in the electrolysis reactor, and the pH value of regulating solution in the electrolysis reactor is 8～10, and temperature is 40～60 ℃, and current density is 0.2～0.8A/cm
2, electrolytic reaction 1～7h makes 8,9-, four deuterium n-Hexadecane products;
Its synthetic route is:
The concentration of the deuterium chloride-heavy aqueous solution described in the step (1) is 0.5～3.5mol/L, and described n-nonanoic acid and deuterium chloride-heavy aqueous solution reaction finishes the back and adopts extracted with diethyl ether to obtain 2-two deuterium n-nonanoic acids.
The volume ratio 1: 4～4: 1 of methyl alcohol and water in the methanol-water solution described in the step (2) adopts n-hexane extraction to obtain 8,9-, four deuterium n-Hexadecane products after the described electrolytic reaction technology.
The pH value of solution adopts salt of wormwood to regulate in the adjusting electrolysis reactor described in the step (2).
Compared with prior art, the present invention cultivates for n-Hexadecane the interposition deuterium as tracer agent, and microorganism can more be partial to utilize and contain the c h bond n-Hexadecane in more part deuterium generation, carries out Metabolic activity quickly.Simultaneously, the deuterium of 8,9-, four deuterium n-Hexadecanes is subrogated and is positioned at the alkane chain middle, neither can influence the initial activation of alkane, also can obtain the information of mesostate simultaneously, for petroleum hydrocarbon anaerobic degradation Study on Mechanism is offered help.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1:
Be deuterium chloride-heavy aqueous solution (n-nonanoic acid and deuterium chloride-heavy aqueous solution volume ratio is 1: 3) of 1.5mol/L with n-nonanoic acid and concentration, join in the reactor, reactor is sealed, temperature of reaction is 150 ℃, reaction times is 48h, after reaction kettle for reaction, use extracted with diethyl ether, obtain 2-two deuterium n-nonanoic acids; With 2-two deuterium n-nonanoic acid 1mL and 10.0mL methanol-water solution (volume ratio 1: 4), join in the electrolysis reactor, add salt of wormwood and transfer pH=10, add the 4mL normal hexane again; Conductance electrode is inserted, add the sealing of backflow device, current density is 0.2A/cm
2, water bath heating temperature is 40 ℃, the induction stirring reaction times is 1h; Obtain 8,9-, four deuterium n-Hexadecanes.
In 50mL product methane-rich substratum, add 8,9-four deuterium n-Hexadecanes 30 μ L cultivate methanogen floras as sole carbon source, cultivated 365 days down at 38 ℃, system output methane 20 μ M, the culture middle acid substance is through extraction, esterification, adopt GC-MS to analyze, retention time determines to contain in the acidic substance 8,9-, four deuterium palmitic acids in conjunction with mass spectrum.Show, experienced the terminal oxidising process of n-Hexadecane in the n-Hexadecane bio anaerobic degradation pathway, produce corresponding acid.
Embodiment 2
Be deuterium chloride-heavy aqueous solution (n-nonanoic acid and deuterium chloride-heavy aqueous solution volume ratio is 1: 3) of 0.5mol/L with n-nonanoic acid and concentration, join in the reactor, reactor is sealed, temperature of reaction is 150 ℃, reaction times is 12h, after reaction kettle for reaction, use extracted with diethyl ether, obtain 2-two deuterium n-nonanoic acids; Be 1: 2 2-two deuterium n-nonanoic acids and methanol-water solution (volume ratio of methyl alcohol and water is 1: 4) with volume ratio, join in the electrolysis reactor, add salt of wormwood and transfer pH=10, add the 4mL normal hexane again; Conductance electrode is inserted, add the sealing of backflow device, current density is 0.2A/cm
2, water bath heating temperature is 40 ℃, the induction stirring reaction times is 1h, 8 of acquisition, 9-four deuterium n-Hexadecanes.
With adopt that aforesaid method makes 8,9-four deuterium n-Hexadecanes are used for surveying the pathways metabolism that the alkane anaerobic degradation is produced the methane process as tracer agent, described application specifically may further comprise the steps: add 8 in 50mL product methane-rich substratum, 9-four deuterium n-Hexadecanes 30 μ L cultivate methanogen floras as sole carbon source, cultivated 365 days down at 38 ℃, the culture middle acid substance is being determined whether contain 8 in the acidic substance through extraction, esterification, analysis, 9-four deuterium palmitic acids, thus judge n-Hexadecane bio anaerobic degradation pathway.
Embodiment 3:
Be deuterium chloride-heavy aqueous solution (n-nonanoic acid and deuterium chloride-heavy aqueous solution volume ratio is 1: 100) of 3.5mol/L with n-nonanoic acid and concentration, join in the reactor, reactor is sealed, temperature of reaction is 200 ℃, reaction times is 72h, after reaction kettle for reaction, use extracted with diethyl ether, obtain 2-two deuterium n-nonanoic acids; Be 1: 20 2-two deuterium n-nonanoic acids and methanol-water solution (volume ratio of methyl alcohol and water is 4: 1) with volume ratio, join in the electrolysis reactor, add salt of wormwood and transfer pH=8, add the 4mL normal hexane again; Conductance electrode is inserted, add the sealing of backflow device, current density is 0.8A/cm
2, water bath heating temperature is 60 ℃, the induction stirring reaction times is 7h, 8 of acquisition, 9-four deuterium n-Hexadecanes.
With adopt that aforesaid method makes 8,9-four deuterium n-Hexadecanes are used for surveying the pathways metabolism that the alkane anaerobic degradation is produced the methane process as tracer agent.
Claims (5)
1.8 9-four deuterium n-Hexadecanes is characterized in that as the application of tracer agent 8,9-, four deuterium n-Hexadecanes are used for surveying the pathways metabolism that the alkane anaerobic degradation is produced the methane process as tracer agent;
Described application specifically may further comprise the steps: add 8 in 50mL product methane-rich substratum, 9-four deuterium n-Hexadecanes 30 μ L cultivate methanogen floras as sole carbon source, cultivated 365 days down at 38 ℃, the culture middle acid substance is being determined whether contain 8 in the acidic substance through extraction, esterification, analysis, 9-four deuterium palmitic acids, thus judge n-Hexadecane bio anaerobic degradation pathway;
Described 8,9-four deuterium n-Hexadecanes have following structure:
2. according to claim 18,9-four deuterium n-Hexadecanes is characterized in that as the application of tracer agent, and are described 8, and 9-four deuterium n-Hexadecanes make by the following method, specifically may further comprise the steps:
(1) be that 1: 3～1: 100 n-nonanoic acid and deuterium chloride-heavy aqueous solution adds reactor with volume ratio, under the condition of sealing, under 150～200 ℃ temperature, reaction 12～72h makes 2-two deuterium n-nonanoic acids;
(2) the 2-two deuterium n-nonanoic acids and the methanol-water solution that step (1) are obtained joined in the electrolysis reactor in 1: 2 by volume～1: 20, and the pH value of regulating solution in the electrolysis reactor is 8～10, and temperature is 40～60 ℃, and current density is 0.2～0.8A/cm
2, electrolytic reaction 1～7h makes 8,9-, four deuterium n-Hexadecane products;
Its synthetic route is:
3. according to claim 28,9-four deuterium n-Hexadecanes are as the application of tracer agent, it is characterized in that, the concentration of the deuterium chloride-heavy aqueous solution described in the step (1) is 0.5～3.5mol/L, and described n-nonanoic acid and deuterium chloride-heavy aqueous solution reaction finishes the back and adopts extracted with diethyl ether to obtain 2-two deuterium n-nonanoic acids.
4. according to claim 28,9-four deuterium n-Hexadecanes is characterized in that as the application of tracer agent, the volume ratio 1: 4～4: 1 of methyl alcohol and water in the methanol-water solution described in the step (2), adopt n-hexane extraction to obtain 8,9-, four deuterium n-Hexadecane products after the described electrolytic reaction technology.
5. according to claim 38,9-four deuterium n-Hexadecanes is characterized in that as the application of tracer agent the pH value of solution adopts salt of wormwood to regulate in the adjusting electrolysis reactor described in the step (2).
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088956A (en) * | 1988-07-27 | 1994-07-06 | 韦恩州立大学校董会 | Contain stable state 1, the composition and the application thereof of 2-dioxane and the fluorescent chemicals that interrelates with narrow spacing with it |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088956A (en) * | 1988-07-27 | 1994-07-06 | 韦恩州立大学校董会 | Contain stable state 1, the composition and the application thereof of 2-dioxane and the fluorescent chemicals that interrelates with narrow spacing with it |
Non-Patent Citations (4)
| Title |
|---|
| Direct stereochemical resolution of aspartame stereoisomers and their degradation products by high-performance liquid chromatography on a chiral crown ether based stationary phase;sylvie motellier ect.al;《journal of chromatography A》;19901231;365-373 * |
| jose-luis abad ect.al.Synthesis and use of stereospecifically deuterated alalogues of palmitic acid to investigate the stereochemical course of the △11 desaturase of the processionary moth..《J.ORG.CHEM》.2004,7108-7113. |
| sylvie motellier ect.al.Direct stereochemical resolution of aspartame stereoisomers and their degradation products by high-performance liquid chromatography on a chiral crown ether based stationary phase.《journal of chromatography A》.1990,365-373. |
| Synthesis and use of stereospecifically deuterated alalogues of palmitic acid to investigate the stereochemical course of the △11 desaturase of the processionary moth.;jose-luis abad ect.al;《J.ORG.CHEM》;20040914;7108-7113 * |
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