CN110283231A - A kind of preparation and application based on the amphipathic novel lysotropic liquid crystal of oligopeptides self assembly - Google Patents

A kind of preparation and application based on the amphipathic novel lysotropic liquid crystal of oligopeptides self assembly Download PDF

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CN110283231A
CN110283231A CN201910475542.7A CN201910475542A CN110283231A CN 110283231 A CN110283231 A CN 110283231A CN 201910475542 A CN201910475542 A CN 201910475542A CN 110283231 A CN110283231 A CN 110283231A
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oligopeptides
liquid crystal
novel
amphipathic
rdcs
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CN110283231B (en
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秦四勇
丁文强
雷新响
张爱清
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South Central Minzu University
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South Central University for Nationalities
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07KPEPTIDES
    • C07K7/00Peptides having 5 to 20 amino acids in a fully defined sequence; Derivatives thereof
    • C07K7/04Linear peptides containing only normal peptide links
    • C07K7/06Linear peptides containing only normal peptide links having 5 to 11 amino acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/061Linear compounds without any rings

Abstract

A kind of preparation and application based on the amphipathic novel lysotropic liquid crystal of oligopeptides self assembly of the invention, wherein the structure of the oligopeptides isOligopeptides is added in dimethyl sulfoxide (DMSO) solvent by the present invention, and oligopeptides molecule can produce orderly nanofiber by noncovalent interaction after ultrasonic disperse.Simultaneously, the assembly system shows distinctive ordered structure and good mobility, it can be used as the residual dipolar coupling value (RDCs) of novel lysotropic liquid crystal Medium Measurement biomolecule, realize the parsing of the molecular structure based on nuclear-magnetism (NMR) detection.Oligopeptides can be automatically synthesized by instrument in the present invention, and preparation is easy;Liquid crystal media can be prepared by directly dissolving oligopeptides, method is simple, strong operability.In addition, solvent is DMSO in system, detected substrate undissolvable problem in Conventional solvents can effectively solve, to effectively extend the type and quantity of detected substrate.

Description

A kind of preparation and application based on the amphipathic novel lysotropic liquid crystal of oligopeptides self assembly
Technical field
The present invention relates to technical field of biological materials, and in particular to one kind is based on the novel molten cause liquid of amphipathic oligopeptides self assembly Brilliant preparation and application.
Background technique
Liquid crystal (LC) material has in biological tissue field and artificial synthesized system due to itself order and mobility It is widely applied.For example, the ordered arrangement and mobile performance of LC plays the formation of biological in-vivo tissue structure in biological tissue Vital effect.In recent years, artificial synthesized liquid crystal system has also shown wide application prospect.LC internal order Nanostructure can provide good channel for ion and electron-transport, the defects of topological structure is able to guide molecule from group The orientation of dress and inorganic particulate.In addition, LC template can mediate the oriented growth of other materials, to prepare novel orderly nanometer With sub-nanometer material.Therefore, constructing function liquid crystal system has important application value.
Currently, scientist has found that multiple polymers such as DNA, cellulose, polypeptide etc. can form LC material.But it passes through It would generally be related to harsh or cumbersome preparation method by liquid crystal material prepared by polymer.Such as: in order to ensure polymerizeing thing liquid Brilliant to realize internal effective orientation at low concentrations, the molecular weight of polymer must be very big, can involve harsh synthesis item in this way Part.Therefore, the great interest of researchers is caused dependent on simple molecules preparation LC.Recently, it is based on low molecular weight compound LC material rapid emergence.Wherein, oligopeptides is due to its simple mature synthetic method, the diversity of sequential structure and stronger Self-assembly ability is concerned in combinations of low molecular weight liquid crystals field.Studies have shown that oligopeptides can be in first by the sequential structure for adjusting peptide Various lysotropic liquid crystals are self-assembly of in alcohol, carbon disulfide and water equal solvent.However, being molten with absolute dimethyl sulfoxide (DMSO) The building of the lyotropic oligopeptides LC of agent is not still resolved, this is because oligopeptides is difficult to be self-assembly of orderly knot in DMSO Structure.In addition, structure must be residual containing aromatic ring containing such as phenylalanine and tyrosine in the oligopeptides LC system that these have built up The rigid segment of base.If it is possible to a kind of compatible submissive type oligopeptides liquid crystal of DMSO is constructed, it not only can be novel to design Liquid crystal without rigid radical provides foundation, while can study the performance new based on the lysotropic liquid crystal that DMSO solvent is system.
Summary of the invention
In order to solve the above technical problems, the present invention provides one kind and is self-assembled into novel molten cause liquid based on amphipathic oligopeptides Crystalline substance and preparation method thereof, it is intended that provide a kind of amphipathic oligopeptides of novel flexible, can in pure DMSO generation group Dress realizes the building of the compatible submissive type oligopeptides liquid crystal system of DMSO.This molten cause LC has preferable mobility and orientation, can Precise measurement to be applied to biomolecule RDCs as ordered media.Because DMSO used in the liquid crystal is perhaps polymolecular good molten Agent, DMSO-d6 are common deuterated reagent again, so liquid crystal system effectively expands the model of the tested substrate based on nuclear-magnetism detection It encloses.
The present invention provides one kind and is self-assembled into novel lysotropic liquid crystal based on amphipathic oligopeptides, which is characterized in that the oligopeptides As shown in structure formula (I):
As further improvement of the invention, novel lysotropic liquid crystal is self-assembled into based on amphipathic oligopeptides according to above-mentioned, it will The oligopeptides is added ultrasound in DMSO solvent and obtains after completely dissolution.
As further improvement of the invention, the liquid crystal is assembled in pure DMSO solvent by oligopeptides.
As further improvement of the invention, the liquid crystal is molten in DMSO-d6 when oligopeptide concentration is 2wt%-10wt% Deuterium resonance in liquid shows the remaining quadrupole coupling of 5-76Hz.
The present invention, which further also protects one kind above-mentioned and is self-assembled into novel lysotropic liquid crystal based on amphipathic oligopeptides and is used as, to be had The application of the RDCs of sequence medium precise measurement biomolecule.
As further improvement of the invention, the liquid crystal can measure the RDCs for being dissolved in the biomolecule of DMSO, and whereby Analyze its structure.
As further improvement of the invention, the liquid crystal can measure the RDCs of oestrone, and analyze the structure of oestrone.
As further improvement of the invention, the liquid crystal can measure the RDCs of 10-hydroxycamptothecine, and analyze 10- hydroxyl The structure of base camptothecine.
As further improvement of the invention, the medium can measure the RDCs of qinghaosu, and analyze the structure of qinghaosu.
The invention has the following beneficial effects:
1. the molten cause LC of the present invention is that self assembly constructs in DMSO by oligopeptides amphiphile (OPA).The oligopeptides all by Flexible chain is constituted, without rigid aromatic group.Deuterium resonance of the oligopeptides of 2wt% in DMSO shows the RQC of 5Hz, When concentration is 10wt%, RQC 76Hz.Low concentration, high RQC illustrate that self assembly OPA fiber has height-oriented property, It is the ordered media of ideal measurable biomolecule RDCs a kind of.
2. oligopeptides chain prepared by the present invention is free of rigid aromatic group, avoiding may between ordered media and analysis substrate Existing π-π interaction, therefore, the molten cause LC can be to aromatic molecule such as anti-tumor drug 10-hydroxycamptothecines and female Ketone carries out RDCs measurement.
3. the solvent of self-assembly oligo-peptide LC of the present invention is pure DMSO, realize using pure DMSO as the system of the oligopeptides LC of solvent It is standby, the type of analyte is greatly expanded, because many molecules are only dissolve in DMSO-d6 for common deuterated reagent Carry out RDCs measurement.
Detailed description of the invention
Fig. 1 is that OPA prepared by the present invention is self-assembled into nanofiber schematic diagram in DMSO;
Fig. 2 is the MALDI TOF MS instrument (MALDI- of OPA prepared by the embodiment of the present invention 1 TOFMS) figure;
Fig. 3 is high performance liquid chromatography (HPLC) figure of OPA prepared by the embodiment of the present invention 1, purity 95.67%;
Fig. 4 is dynamic light scattering (DLS) spectrogram of OPA prepared by the embodiment of the present invention 1;
Scanning electron microscope (SEM) figure prepared by the embodiment of the present invention 1 that Fig. 5 is 0.5wt%OPA;
SEM figure prepared by the embodiment of the present invention 1 that Fig. 6 is 4.0wt%OPA;
Fig. 7 is small angle x-ray scattering (SAXS) (SAXS) curve graph of OPA prepared by the embodiment of the present invention 1;
Fig. 8 is the OPA of the preparation of the embodiment of the present invention 1 in DMSO-d6 (1wt%)1HNMR (600MHz) spectrogram (A), Infrared (FT-IR) spectrogram (B) of OPA fiber prepared by the embodiment of the present invention 1, the OPA of self assembly prepared by the embodiment of the present invention 1 Extensive angle X-ray diffraction (WXRD) curve (C) of fiber;
Fig. 9 is cross polarization optical filter picture of the self assembly OPALC of the preparation of the embodiment of the present invention 1 in nuclear magnetic tube;
Nematic crystal under the petrographic microscope (POM) that Figure 10 is OPALC prepared by the embodiment of the present invention 1 of various concentration Texture maps;
Two dimension (2D) the SAXS figure that Figure 11 is OPALC prepared by the embodiment of the present invention 1;
Figure 12 be various concentration the embodiment of the present invention 1 prepare OPALC deuterium (2H) NMR schemes;
Figure 13 is the OPALC that 10mg oestrone is dissolved in the preparation of the embodiment of the present invention 1 (LC concentration is 40.0mg/mL)2HNMR figure;
Figure 14 be the self assembly liquid crystal that uses the embodiment of the present invention 1 to prepare as ordered media record oestrone [1H,13C]- JSB-HSQC spectrum;
Figure 15 is that the self assembly liquid crystal for using the embodiment of the present invention 1 to prepare measures the RDCs and meter of oestrone as ordered media Linear relationship chart after the RDCs fitting of calculation;
Figure 16 be 10mg10- hydroxycamptothecin be dissolved in the embodiment of the present invention 1 preparation OPALC (LC concentration is 40.0mg/ ML)2HNMR figure;
The self assembly LC that Figure 17 uses the embodiment of the present invention 1 to prepare records 10-hydroxycamptothecine as ordered media [1H,13C]-JSB-HSQC spectrum;
Figure 18 is the OPALC that 10mg qinghaosu is dissolved in the preparation of the embodiment of the present invention 3 (LC concentration is 40.0mg/mL)2HNMR figure;
Figure 19 be the self assembly LC that uses the embodiment of the present invention 1 to prepare as ordered media record qinghaosu [1H,13C]- JSB-HSQC spectrum;
Figure 20 is that the self assembly liquid crystal for using the embodiment of the present invention 1 to prepare measures 10-hydroxycamptothecine as ordered media RDCs and calculating RDCs fitting after linear relationship chart;
Figure 21 be the self assembly liquid crystal that uses the embodiment of the present invention 1 to prepare as the RDCs of ordered media measurement qinghaosu and Linear relationship chart after the RDCs fitting of calculating.
Specific embodiment
Below in conjunction with the embodiment of the present invention and attached drawing, technical solution in the embodiment of the present invention carries out clear, complete Description, it is clear that the embodiment described is the embodiment of part of representative of the invention, rather than whole embodiments, Other all embodiments obtained by those of ordinary skill in the art without making creative efforts belong to this hair Bright protection scope.
Embodiment 1
Amphipathic oligopeptides of the invention is palmitic acid-alanine-Alanine-Alanine-Alanine-alanine-lysine- Glu-Glu (C15H31-CONH-AAAAAKEE-CONH2), it is synthesized by standard FMOC chemical solid phase polypeptide synthesis.
The present invention also provides it is a kind of based on amphipathic oligopeptides be self-assembled into novel lysotropic liquid crystal the preparation method is as follows: will Above-mentioned oligopeptides chain is added ultrasound in DMSO solution and obtains after completely dissolution.
Wherein, the structure chart of the oligopeptides (OPA) of acquisition is as follows:
The present invention detects the accurate molecular masses of OPA by MALDI-TOFMS.Its test result is as shown in Fig. 2, in Fig. 2, Abscissa indicates mass-to-charge ratio, and ordinate indicates the relative intensity of ion stream, (m/z (%)): OPA:997.76 (100) [M]+, (m/ Z (%)): OPA:1019.75 (100) [M+Na]+, (m/z (%)): OPA:1035.72 (100) [M+K]+.Pass through experiment value and reason Want to compare by molecular weight, to discern the accuracy of its structure.Further, synthesized OPA is analyzed by high performance liquid chromatograph Purity, analysis test result is shown as its unimodal purity 95.67%, and analysis result is referring to attached drawing 3, in Fig. 3, abscissa Indicate retention time, ordinate is electric signal.
It is as shown in Fig. 1 that OPA is self-assembled into nanofiber in DMSO.It is worth noting that, self-assembled nanometer fiber exists Good ordered arrangement and molten cause LC behavior are shown in the organic system.By the study found that this orderly medium can be with Orientation biomolecule and the molecular motion for limiting them, are conducive to the RDCs of capture molecule.
In order to Primary Study OPA whether can the spontaneous assembling in DMSO, the present invention first by DLS assess OPA in DMSO Middle self assembly situation, it shows two peaks at 120nm and 550nm as the result is shown, as shown in figure 4, the abscissa in the figure Indicate particle size, ordinate indicates relative intensity, the presence of aggregation can be shown by Fig. 4.
Further, the present invention also passes through the form of SEM imaging self-assembled nanometer fiber, observes form such as Fig. 5 Shown, the OPA of 0.5wt% is self-assembled into the fibrous nano line that average diameter is about 70nm in DMSO.It can be with by observation It was found that nano wire shows orderly ordered state.OPA content is improved to 4.0wt%, the diameter of nano wire becomes smaller, such as Fig. 6.The size of self-assembled nanometer linear dimension in DMSO solution is measured using SAXS.When the content of OPA is lower than 4wt%, from It is only observed in scattering curve figure closePeak, such as Fig. 7 shows that similar nano wire is straight with about 6.2nm Diameter, the abscissa in Fig. 7 indicate q value, and ordinate indicates relative intensity.Therefore, the nano wire observed from SEM image is all It is made of several single nanofibers.Meanwhile when OPA content is more than 4%, it finds that closePlace has New signal peak, the size that high q value may be attributed to OPA molecule is 3.8nm.
In order to probe into the intermolecular interaction of OPA self assembly in DMSO, the present invention monitors amide matter by NMR The chemical potential in-migration of son at different temperatures determines whether the participation of hydrogen bond.As shown in figure 8, temperature increases to from 293K 323K causes the amide proton of peptide backbone mobile from low field to High-Field.However, the chemical shift of other protons and unaffected.It should The result shows that hydrogen bond participates in self-assembling peptide.In addition, the FT-IR spectrum of the OPA of freeze-drying is in 3295cm-1The characteristic absorption that place is shown Peak (amide A) is designated as NH vibration relevant to Hydrogenbond as shown in Figure 8 B.In Fig. 8 B, wavenumber indicates wave Long, intensity indicates relative intensity.
In addition, FT-IR spectrum also provides the information of molecules align in OPA nanofiber.FT-IR spectrum is shown in 1628cm-1And 1540cm-1Two neighbouring stretching vibration peaks correspond to the characteristic absorption of the amide I and II in beta sheet Peak.At the same time, the secondary conformation of beta sheet that 21 ° of diffraction maximums also show nanofiber in WXRD curve, as shown in Figure 8 C.
Self-assembled nanometer fiber solution is poured into NMR pipe, and observes its flowing by two cross polarization optical filters Property and birefringent main feature.As can be seen from Figure 9 significant birefringence.The OPALC drop of various concentration is being carried glass On piece observes typical nematic crystal texture by POM, as shown in Figure 10.Nematic crystal texture depends on The concentration (> 4.0wt%) of OPA.In addition, the two-dimentional SAXS pattern of 10wt%OPA generates the oval diffusing pattern with high axis ratio, Such as Figure 11, show that OPA nanofiber has orderly characteristic.With the increase of peptide concentration, corresponding 2D pattern displaying goes out typical case Diffusing reflection arc, this is attributed to Bragg reflection.
In order to further confirm the liquid crystal property of nanofiber solution, by deuterium (2H) NMR verifies its ordered arrangement.? 600MHz(1H) in spectrometer, deuterium resonance of the 2wt%OPA in DMSO-d6 solution shows the remaining quadrupole coupling value of 5Hz, Show that the nanofiber in solution has certain orientation.Observe that OPA is positively correlated in the RQC value of DMSO-d6 and its concentration.When When OPA concentration is 10wt%, RQC 76Hz, as shown in figure 12, wherein abscissa indicates frequency in Figure 12, and ordinate indicates Relative intensity.In nuclear-magnetism2The signal of H quadrupole splitting is high degree of symmetry, half-peak breadth 2.5Hz, relatively narrow half-peak breadth from Side shows that its viscosity is smaller.OPA self assembly LC shows excellent order and mobility, this shows OPALC as ideal Ordered media in the great potential that shows of measurement biomolecule RDCs.
Embodiment 2
The applicability for accurately obtaining RDCs in DMSO-d6 in order to study self assembly LC as medium, will be used below containing There is the oestrone of aromatic ring to be studied as Model Molecule.
Wherein, oestrone structural formula such as following formula (II), C-13 spectrum are given in Table 1.
The C-13 spectral catalogue of 1 oestrone of table
As shown in Fig. 13,10.0mg oestrone is dissolved in OPALC (LC concentration is 40.0mg/mL),2HNMR spectrum Display RQC is 20.42Hz.In Figure 13, abscissa indicates frequency, and ordinate indicates relative intensity.Use self assembly LC as Ordered media records [1H, the 13C]-JSB-HSQC spectrum of oestrone, and pure DMSO-d6 is used as control under isothermal condition, such as schemes Shown in 14, abscissa indicates hydrogen spectrum in figure, and ordinate indicates carbon spectrum, and the backgroundsignals in figure indicates background signal. According to analysis of experimental results, it can be deduced that all C-H coupling can detect in orderly OPALC medium on oestrone skeleton It arrives, shows that OPALC medium and oestrone have good compatibility.The RDCs magnitude range of oestrone is -10.8-30.9Hz (table 1). In order to examine the accuracy of these RDCs, the present invention carries out theoretical meter using singular value decomposition (SVD) method and MSpin program It calculates.The density functional theory (DFT) of B3LYP/6-31G* (d) level of introducing is used for the RDCs of computational theory.The RDCs of measurement and Linear relationship between the RDCs of calculating is as shown in Fig. 15, and wherein in Figure 15, ExperimentalRDCs meaning is experiment RDCs, CalculatedRDCs meaning are to calculate RDCs, and Estrone indicates oestrone.The Q factor of oestrone be 0.079 (Q value is lower, It is better to illustrate that modeling and forecasting configuration and its actual configuration coincide), show that self assembly LC is the excellent medium of precise measurement RDCs.
Embodiment 3
Anti-tumor drug 10-hydroxycamptothecine is proved to the compatibility of aromatic molecules Yu self assembly OPALC below, with into One step research self assembly LC accurately obtains RDCs applicability as medium in DMSO-d6.
The compatibility of aromatic molecules Yu self assembly OPALC is proved using anti-tumor drug 10-hydroxycamptothecine.Such as attached drawing Shown in 16,10.0mg10- hydroxycamptothecin is dissolved in OPALC (LC concentration is 40.0mg/mL),2HNMR spectrum is shown RQC is 25.39Hz.Wherein, Tu16Zhong, abscissa indicate frequency, and ordinate indicates relative intensity.Use self assembly LC as having Sequence medium recording 10-hydroxycamptothecine [1H,13C]-JSB-HSQC spectrum, and under isothermal condition by pure DMSO-d6 be used as pair According to, experimental result such as Figure 17, C-13 spectrum is given in Table 2, Tu17Zhong, and abscissa indicates hydrogen spectrum, and ordinate indicates carbon spectrum, Backgroundsignals meaning is background signal.The results show that C-H coupling all on 10-hydroxycamptothecine skeleton To detect in orderly OPALC medium, showing that OPALC medium is same as 10-hydroxycamptothecine has good compatibility. The RDCs of the 10-hydroxycamptothecine detected is -31.7-3.42Hz (table 2).Obtaining Q factor value by fitting is 0.076, low Q factor value show can with the medium effectively accurately measure 10-hydroxycamptothecine RDCs value, please join shown in Figure 20, horizontal seat Mark indicates hydrogen spectrum, and ordinate indicates carbon spectrum, and backgroundsignals is background signal.
Table 2
13C positioning δCppm 1H positioning δHppm 1JCH 1TCH 1DCH 1DCHCalculated value
C5 50.70 H5a,b 5.21 148.44 - - -
C7 129.65 H7 8.42 163.95 140.62 -23.33 -20.98
C9 109.22 H9 7.26 159.12 134.47 -24.65 -25.20
C11 123.36 H11 7.41 160.90 129.16 -31.74 -31.17
C12 131.03 H12 8.00 161.86 137.80 -24.06 -25.26
C14 96.29 H14 7.24 172.44 153.15 -19.29 -20.08
C17 65.70 H17a,b 5.41 152.35 - - -
C18 7.90 H18(Me) 0.88 128.08 131.50 3.42 6.52
C19 30.00 H19a,b 1.86 130.72 129.55 -1.17 -1.52
Embodiment 4
In order to further study OPALC to analyze other organic molecular structures feasibility, below will using qinghaosu as Substrate is inquired into.
Qinghaosu was a kind of effective anti-malarial drug, and in acquisition Nobel prize's soul in 2015.Such as attached drawing Shown in 18,10.0mg qinghaosu is dissolved in OPALC (LC concentration is 40.0mg/mL),2HNMR spectrum shows that RQC is 21.31Hz.In Figure 18, abscissa indicates frequency, and ordinate indicates relative intensity.Self assembly LC is used to remember as ordered media Record qinghaosu [1H,13C]-JSB-HSQC spectrum, and pure DMSO-d6 is used as control, such as Figure 19, C-13 under isothermal condition Spectrum is given in Table 3.Detect that the RDCs of qinghaosu is -1.71-6.95Hz (table 3).Qinghaosu is also obtained fabulous Fitting, low Q factor value be 0.088, as shown in figure 21, in Figure 20 and Figure 21,10-Hydroxycamptothecine indicate 10-hydroxycamptothecine, Artemisinin indicate qinghaosu.
Table 3
13C positioning δCppm 1H positioning δHppm 1JCH 1TCH 1DCH 1DCHCalculated value
C1 49.94 H1 1.32 131.76 138.37 6.61 6.81
C2 24.86 H2a,b 1.92,1.32 129.48 131.47 1.99 2.34
C3 35.92 H3a,b 2.26,2.05 128.55 132.64 4.09 3.66
C5 93.75 H5 6.13 179.25 177.54 -1.71 -1.65
C7 44.37 H7 1.78 133.10 140.05 6.95 6.58
C8 22.96 H8a,b 1.71,1.14 127.42 130.52 3.10 3.71
C9 33.53 H9a,b 1.62,1.01 126.90 128.37 1.47 1.74
C10 36.51 H10 1.53 127.00 133.84 6.84 6.82
C11 32.93 H11 3.16 127.25 126.86 -0.39 -0.50
C13 12.93 H13(Me) 1.06 129.09 128.65 -0.44 -0.14
C14 20.10 H14(Me) 0.91 126.29 127.07 0.78 1.35
C15 25.56 H15(Me) 1.35 129.86 130.71 0.85 0.91
Compared with existing peptide LC crystallographic system system, there are two advantages for present invention tool:
1) it can be constructed by flexible oligopeptide amphiphile, because being free of rigid structure required for traditional liquid crystal, for design It develops other novel liquid crystals and provides thinking.
2) solvent of self-assembling peptides LC is pure DMSO.
In view of above advantages, oligopeptides LC shows very big prospect in RDCs measurement.OPA can be by instrument in the present invention It is automatically synthesized, preparation is easy;Liquid crystal can be prepared by directly dissolving oligopeptides, method is simple, strong operability.It is not present in OPA Rigid aromatic group, avoiding problems the risks that strong π-π interaction occurs between ordered media and analyte.Body simultaneously The solvent used in system is DMSO, can effectively solve detected substrate undissolvable problem in Conventional solvents, thus effectively Extend the type and quantity of detected substrate.
Those skilled in the art is not under conditions of departing from the spirit and scope of the present invention that claims determine, also Various modifications can be carried out to the above content.Therefore the scope of the present invention is not limited in above explanation, but by The range of claims determines.

Claims (10)

1. one kind is self-assembled into novel lysotropic liquid crystal based on amphipathic oligopeptides, which is characterized in that the oligopeptides such as structural formula are as follows:
2. being self-assembled into novel lysotropic liquid crystal based on amphipathic oligopeptides according to claim 1, which is characterized in that the oligopeptides For flexible structure.
3. being self-assembled into novel lysotropic liquid crystal based on amphipathic oligopeptides according to claim 1, which is characterized in that by the widow Peptide is added direct ultrasound in DMSO solvent and obtains after completely dissolution.
4. being self-assembled into novel lysotropic liquid crystal based on amphipathic oligopeptides according to claim 3, which is characterized in that described novel Lysotropic liquid crystal is assembled in pure DMSO solvent by oligopeptides.
5. being self-assembled into novel lysotropic liquid crystal based on amphipathic oligopeptides according to claim 3, which is characterized in that described novel Lysotropic liquid crystal is when the concentration of oligopeptides is 2wt%-10wt%, deuterium resonance of the novel lysotropic liquid crystal in DMSO-d6 solution The remaining quadrupole coupling of 5-76 Hz is shown, order degree can be regulated and controled by oligopeptide concentration.
6. being self-assembled into novel molten cause liquid based on amphipathic oligopeptides as described in a kind of claim as described in claim any one of 1-4 Crystalline substance can be used as the RDCs of ordered media measurement biomolecule.
7. application according to claim 6, which is characterized in that the liquid crystal, which can measure, is based on deuterated dimethyl sulfoxide (DMSO- D6) the RDCs of the biomolecule of dicyandiamide solution, analysis obtain the structure of its biomolecule.
8. application according to claim 7, which is characterized in that the liquid crystal can measure the RDCs of oestrone, and analysis obtains female The structure of ketone.
9. application according to claim 7, which is characterized in that the liquid crystal can measure the RDCs of 10-hydroxycamptothecine, Analysis obtains the structure of 10-hydroxycamptothecine.
10. application according to claim 7, which is characterized in that the medium can measure the RDCs of qinghaosu, analyze To the structure of qinghaosu.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114409736A (en) * 2022-01-28 2022-04-29 中国科学院精密测量科学与技术创新研究院 Phased array medium based on amphiphilic oligopeptide and preparation method and application thereof
CN114604871A (en) * 2022-03-18 2022-06-10 中南民族大学 Two-dimensional layered material MXene oriented medium and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1905892A (en) * 2003-12-05 2007-01-31 西北大学 Self-assembling peptide amphiphiles and related methods for growth factor delivery
CN107286221A (en) * 2017-05-19 2017-10-24 中南民族大学 A kind of orientation medium for determining nuclear magnetic resonance residual dipolar coupling and its preparation and application
CN108070021A (en) * 2017-12-27 2018-05-25 中南民族大学 It can be assembled into the method for the small-molecular peptides and assembling structure high-sequential nanofiber of high-sequential nanofiber

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1905892A (en) * 2003-12-05 2007-01-31 西北大学 Self-assembling peptide amphiphiles and related methods for growth factor delivery
CN102225964A (en) * 2003-12-05 2011-10-26 西北大学 Self-assembling peptide amphiphiles and related methods for growth factor delivery
CN107286221A (en) * 2017-05-19 2017-10-24 中南民族大学 A kind of orientation medium for determining nuclear magnetic resonance residual dipolar coupling and its preparation and application
CN108070021A (en) * 2017-12-27 2018-05-25 中南民族大学 It can be assembled into the method for the small-molecular peptides and assembling structure high-sequential nanofiber of high-sequential nanofiber

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SI-YONG QIN,等: "Directing an oligopeptide amphiphile into an aligned nanofiber matrix for elucidating molecular structures", 《CHEMICAL COMMUNICATIONS》 *
王建勋,等: "两亲性多肽自组装及其应用", 《高等学校化学学报》 *
秦四勇,等: "寡肽自组装纳米材料研究进展", 《中国科学:化学》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114409736A (en) * 2022-01-28 2022-04-29 中国科学院精密测量科学与技术创新研究院 Phased array medium based on amphiphilic oligopeptide and preparation method and application thereof
CN114409736B (en) * 2022-01-28 2023-09-15 中国科学院精密测量科学与技术创新研究院 Phasing arrangement medium based on amphiphilic oligopeptide and preparation method and application thereof
CN114604871A (en) * 2022-03-18 2022-06-10 中南民族大学 Two-dimensional layered material MXene oriented medium and application thereof
CN114604871B (en) * 2022-03-18 2023-02-28 中南民族大学 Two-dimensional layered material MXene oriented medium and application thereof

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