CN106748846B - Copper surface is effectively improved to the method for serine separating capacity by surface modification - Google Patents
Copper surface is effectively improved to the method for serine separating capacity by surface modification Download PDFInfo
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- CN106748846B CN106748846B CN201611239711.XA CN201611239711A CN106748846B CN 106748846 B CN106748846 B CN 106748846B CN 201611239711 A CN201611239711 A CN 201611239711A CN 106748846 B CN106748846 B CN 106748846B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/30—Preparation of optical isomers
- C07C227/34—Preparation of optical isomers by separation of optical isomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses one kind can effectively improve metal surface to the method for serine isomers separating capacity, and step includes: that pure Cu (531) surface is obtained from copper body phase；Its structure is optimized using DFT calculation method to obtain its lattice constant；Chiral molecules serine is constructed, and structure optimization is carried out to it；The serine isomers optimized is individually placed to again on a variety of different locations in Cu (531) face optimized, its structure is optimized respectively；Check optimized as a result, finding out the structure that can be stabilized；To left and right, chiral serine (L and D) makes the difference Δ E in the adsorption energy of Cu (531), to obtain difference of the chiral serine in left and right on adsorption energy, difference is bigger, and its separating capacity is better.The present invention makes bimetallic surface improve 36% to the pure copper surface of the separating capacity ratio of serine isomers using novel and accurate DFT calculation method, Binding experiment data by the surface modification for mix Ni to Cu (531).
Description
Technical field
The present invention relates to chiral amino acids to be adsorbed on Metal Substrate field, more particularly to enhancing serine in surface modification
The separating capacity design method on copper surface.
Background technique
Serine (serine) is a kind of to help to maintain a kind of important in the amino acid and pharmaceutical industry of immune system
Chiral organic molecule, so-called chiral molecules refers to structure mirror symmetry in chemistry but the molecule that is not exclusively overlapped, they point
For left hand and right hand enantiomer, left and right optical isomer has similar physics and chemical property and left and right rotation in the gas phase
Chiral molecules energy is almost the same to be difficult to distinguish.But a kind of enantiomer of serine is beneficial to treating, and another is harmful,
Therefore, it is particularly important for properly separating the enantiomter of serine.
During chiral molecules and metallic substrates interaction self-assembled growth, left and right rotation enantiomter has
The entirely different direction of growth, therefore can realize spontaneous separation.Self assembly refers under without external direct interference, by molecule in base
The spontaneous process of a large amount of, orderly shape or structure is formed on bottom using natural gravitation and repulsion.Self-assembly systems are logical
Often by amino acid chiral molecule (such as: alanine, proline, phenylglycine, cysteine and tartaric acid) in metallic substrates
(such as: copper, silver, gold and nickel Low index surfaces) on pass through vapor deposition method obtain.Organic molecule can be by self assembly
Many different structures are formed in substrate, due to the special design feature of serine, not all metal interface is suitable for
As substrate, in certain metal surfaces dehydrogenation reaction can occur for experimental observation to serine at room temperature, and this dehydrogenation reaction
It must be avoided in the separation process of serine enantiomter.The method simulated using first principle, research circle face silk
The research of the structure, stability and the effect of the directionality of growth of propylhomoserin monolayer.Suction only to serine in metal surface
After attached structure and adsorption machine have been formed with clearly understanding and have understood, is possible to finally realization and efficiently separates control.
Document J.Am.Chem.Soc.2012,134,9615-9621. teaches serine and is adsorbed on Cu (531) surface
Theory and experiment research method, as a result, it has been found that Cu (531) surface has the ability of preferable good differentiation serine；
Document Topics in Catalysis, 2011,54,1414-1428. teach serine on Cu (531) surface for being doped with Au
Design method, but the better separating capacity of fine copper for not being found ratio.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides separating capacity of the enhancing serine on the copper surface of surface modification and sets
Meter method is able to solve the problem of the broad range ability of amino acid deficiency in metallic substrates Disengagement zone.
In order to solve the above technical problems, one technical scheme adopted by the invention is that:
Enhance serine in the separating capacity design method on the copper surface of surface modification, at least include the following steps:
(1) pure Cu (531) surface is obtained from copper body phase, its structure is optimized, withWithFor
Basic vector is madeUnit cell；
(2) the chiral Serine molecule in left and right is constructed, its structure is optimized, its total energy is obtained；
(3) again by the chiral Serine molecule absorption in the left and right after optimization Cu (531) face (110) after optimization and
(311) on micro- face position, then its structure is optimized respectively；
(4) it checks as a result, and finding out the structure that the chiral serine in left and right can be stabilized respectively；
(5) the adsorption energy adsorption energy for calculating separately the chiral serine in left and right, determines the difference (Δ E) of its adsorption energy.
Compared with prior art, the method that serine of the present invention is adsorbed on the Cu (531) of surface doping Ni, effectively improves
The separating capacity of the chiral serine in copper surface has and preferably distinguishes compared with traditional Cu (531) and Cu (110) surface
Ability, while serine is adsorbed on the absorption system formed on Cu (531) surface of doping Ni and in pure Cu (531) and Cu
(110) surface, which is compared, has higher stability.The present invention is adsorbed on Cu (531) surface of doping Ni by serine, makes it
With better separating capacity and higher stability, requirement of the substrate to serine separating capacity and full can be met
Wanting for system stability of foot, makes it have both the two-fold advantage of performance and structure.
Detailed description of the invention
Fig. 1 is the method chirality silk ammonia of the invention for effectively improving copper surface to serine separating capacity by surface modification
The top view (b) of acid molecule figure (a) and Cu (531).
Fig. 2 is the L- and D- of the invention for effectively improving copper surface to the method for serine separating capacity by surface modification
The chemisorption figure of 2 kinds of adsorption potentials of serine/Cu (531).
Fig. 3 is of the invention to effectively improve copper surface to the not Tongfang of the method for serine separating capacity by surface modification
Adsorption energy curve graph under method calculating.
Fig. 4 is of the invention to effectively improve copper surface to the L- of the method for serine separating capacity by surface modification
Serine is adsorbed in Ni/Cu (531) to scheme.
Fig. 5 is of the invention to effectively improve copper surface to the D- of the method for serine separating capacity by surface modification
Serine is adsorbed in Ni/Cu (531) to scheme
Fig. 6 is of the invention to effectively improve copper surface to the L- of the method for serine separating capacity by surface modification
Analog scanning tunnel figure of the serine in Ni/Cu (531).
Fig. 7 is of the invention to effectively improve copper surface to the D- of the method for serine separating capacity by surface modification
Analog scanning tunnel figure of the serine in Ni/Cu (531).
Fig. 8 is the method L-serine of the invention for effectively improving copper surface to serine separating capacity by surface modification
In the molecular state density map of Ni/Cu (531).
Fig. 9 is of the invention to effectively improve copper surface to the D- of the method for serine separating capacity by surface modification
Molecular state density map of the serine in Ni/Cu (531).
Figure 10 is of the invention to effectively improve copper surface to the difference of the method for serine separating capacity by surface modification
Separating capacity comparison diagram of the substrate to Serine molecule.
Specific embodiment
The preferred embodiments of the present invention will be described in detail with reference to the accompanying drawing.
Case study on implementation one
The present invention provides through surface modifications to effectively improve copper surface to the method for serine separating capacity, such as Fig. 1 (a) institute
Show, including chiral Serine molecule L and D, as shown in Fig. 1 (b), clean Cu (531) surface.
Using Materials Studio software, copper single cell structure is imported, changes its lattice constant and makesIt will
Its indices of crystallographic plane is changed to (531), is addedVacuum layer, and establishUnit cell, by surface two layers of replacement topmost
For Ni atom and exported.
We used VASP softwares to carry out structure optimization to it, using first principle as theoretical basis, using PBE+
vdwsurfFunctional, energy convergence precision be 1*10-5, the convergence precision of power is 10-4, using the k dot grid of 7*5*1.
Check obtaining as a result, finding out total energy size in result exporting.
Chiral Serine molecule is by tetra- kinds of atomic buildings of C, H, O, N, molecular formula C3H7O3N.Right-hand man is constructed in MS
The structure of sex pilus propylhomoserin molecule L and D, and it is carried out the structure optimized is calculated.Calculation method and precision and upper step phase
Together.
Check after optimizing as a result, finding out molecule total energy size in result exporting.
Right-hand man's sex pilus propylhomoserin molecular is placed on to (311) and (110) micro- face on Cu (531) surface of doping Ni
On position.It is optimized respectively using method identical with upper step with precision.
It is after checking optimization as a result, to find out stable structure as shown in Figures 4 and 5, calculate separately its adsorption energy: calculating separately
Absorption system, substrate, the total energy of molecule；Substrate and molecule total energy can be individually subtracted with system；To obtain right-hand man's sex pilus
The adsorption energy of propylhomoserin, then the two is made the difference, obtain discrimination Δ E.
Case study on implementation two
Present case is the further improvement to aforementioned any embodiment, is only illustrated to improved part.
The invention is not limited thereto, and Serine molecule first can be adsorbed on pure Cu (531) surface, and left and right by the above method
Serine respectively has two different adsorptive behaviors, such as Fig. 2, more different adsorption potentials, it is determined that (311) micro- face is more steady
It is fixed, thus, the adsorption potential of chiral serine absorption Ni/Cu (531) is (311) micro- face.For determination separating capacity calculated
The scanning tunneling microscopic figure of correctness, simulation shows different configurations, as Fig. 6 and 7 make molecular state density map, such as in turn
Fig. 8 and 9 has apparent difference.
Due to the concentration of different doping Ni, might have it is different as a result, thus, select different doping concentrations.Point
Its adsorption energy is not calculated, obtains its discrimination size delta E, such as Figure 10.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (4)
1. effectively improving copper surface to the method for serine separating capacity by surface modification, which is characterized in that the design side
Method at least includes the following steps:
(1) pure Cu (531) surface is obtained from copper body phase, its structure is optimized, withWithFor basic vector,
It makesUnit cell；
(2) the chiral Serine molecule in left and right is constructed, its structure is optimized, its total energy is obtained；
(3) again that Cu (531) face (110) and (311) of the chiral Serine molecule absorption in the left and right after optimization after optimization is micro-
On the position of face, then its structure is optimized respectively；
(4) it checks as a result, and finding out the structure that the chiral serine in left and right can be stabilized respectively；
(5) adsorption energy for calculating separately the chiral serine in left and right, determines the difference DELTA E of its adsorption energy；
The chiral Serine molecule in the left and right is configured as L and D；Described Cu (531) surface has carried out surface and has mixed repairing for Ni
Decorations, wherein 0.67,1 or 2ML of Ni/Cu.
2. the method as described in claim 1, which is characterized in that obtain the method on pure Cu (531) surface from copper body phase
It is as follows:
Using Materials Studio software, copper single cell structure is imported, its indices of crystallographic plane is changed to (531), is addedIt is true
Sky, and establishUnit cell is finally exported.
3. the method as described in claim 1, which is characterized in that obtain the method on pure Cu (531) surface from copper body phase
It is as follows:
Using Materials Studio software, empty face-centered cubic type structure cell is first established, then copper atom is put into its corresponding seat
Mark, changes its lattice constant according to the experiment value of copper, establishesUnit cell is simultaneously exported.
4. the method as described in claim 1, which is characterized in that obtain the method on pure Cu (531) surface from copper body phase
It is as follows:
Using VESTA software, face-centered cubic crystal space group is imported, copper atom is added at its lattice, and its crystal face is referred to
Number is changed to (531), is establishedUnit cell is simultaneously exported.
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| CN109107534B (en) * | 2017-06-23 | 2021-01-08 | 南京理工大学 | Method for doping gold surface to enhance separation capability of cysteine molecule |
| CN109261126B (en) * | 2018-08-13 | 2021-09-03 | 南京理工大学 | Method for regulating cysteine molecule separation capacity by applying strain |
| CN114974443B (en) * | 2022-06-06 | 2024-06-11 | 河北工业大学 | Method for obtaining optimal doping material for improving fusion welding resistance of environment-friendly silver-nickel contact |
Citations (1)
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| CN102321695A (en) * | 2011-09-29 | 2012-01-18 | 重庆邮电大学 | Chemical-enzymatic method for preparing D-serine |
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| JPH0751546B2 (en) * | 1987-04-01 | 1995-06-05 | 味の素株式会社 | Method for separating leucine |
| JPH0780822B2 (en) * | 1987-07-15 | 1995-08-30 | 住友化学工業株式会社 | Method for separating and purifying amino acids |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102321695A (en) * | 2011-09-29 | 2012-01-18 | 重庆邮电大学 | Chemical-enzymatic method for preparing D-serine |
Non-Patent Citations (4)
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| TATP-铜(II)-L-丝氨酸(L-精氨酸)配合物与DNA的相互作用;古琴 等;《物理化学学报》;20080630;第24卷(第6期);第1068-1072页 |
| The Importance of Attractive Three-Point Interaction in Enantioselective Surface Chemistry: Stereospecific Adsorption of Serine on the Intrinsically Chiral Cu{531} Surface;Tugce Eralp等;《J.Am.Chem.Soc.》;20120514;第134卷;第9615-9621页 |
| The Study of Chiral Adsorption Systems using Synchrotron-based Structural and Spectroscopic Techniques: Stereospecific Adsorption of Serine on Au-Modified Chiral Cu{531} Surfaces;Tugce Eralp等;《Topics in Catalysis》;20111231;第54卷(第19-20期);第2页摘要，第13-17页，第27页图示1 |
| Tuning the Surface Chemistry of Chiral Cu(531)S for Enhanced Enantiospecific Adsorption of Amino Acids;Ho Seong Song，Jeong Woo Han;《J.Phys.Chem.C》;20150608;第119卷;第15195-15203页 |
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