CN114604871A - Two-dimensional layered material MXene oriented medium and application thereof - Google Patents

Two-dimensional layered material MXene oriented medium and application thereof Download PDF

Info

Publication number
CN114604871A
CN114604871A CN202210271967.8A CN202210271967A CN114604871A CN 114604871 A CN114604871 A CN 114604871A CN 202210271967 A CN202210271967 A CN 202210271967A CN 114604871 A CN114604871 A CN 114604871A
Authority
CN
China
Prior art keywords
mxene
layered material
medium
dimensional layered
orientation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210271967.8A
Other languages
Chinese (zh)
Other versions
CN114604871B (en
Inventor
秦四勇
赵优
张爱清
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South Central Minzu University
Original Assignee
South Central University for Nationalities
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South Central University for Nationalities filed Critical South Central University for Nationalities
Priority to CN202210271967.8A priority Critical patent/CN114604871B/en
Publication of CN114604871A publication Critical patent/CN114604871A/en
Application granted granted Critical
Publication of CN114604871B publication Critical patent/CN114604871B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/90Carbides
    • C01B32/914Carbides of single elements
    • C01B32/921Titanium carbide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/082Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/0828Carbonitrides or oxycarbonitrides of metals, boron or silicon
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N24/00Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
    • G01N24/08Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data

Abstract

The invention provides a two-dimensional layered material MXene oriented medium and application thereof, wherein the structural formula of the two-dimensional layered material MXene is TiaCbTXT is O, F, N with hydrophilicity, and when a is 3, b is 2, when a is 2, b is 1; placing MXene in H2And the construction of a novel directional medium can be realized by ultrasonic dispersion in O. The MXene oriented medium can effectively orient biomolecules, can realize accurate measurement of Residual Dipole Coupling (RDCs) of the biomolecules and is used for structure analysis. Because MXene material still has orientation ability after freeze-drying and redispersion, long-term storage and use of the material can be realized. As a directional medium, the method has the characteristic of no background residual signal, and avoids the interference of the background signal on the atlas analysis. In addition, MXene materials are various in types, and the surface of the MXene materials contains a large number of active sites, so that surface chemical modification is facilitated, a foundation is laid for constructing directional media of different solvent systems for determination of anisotropic nuclear magnetic parameters, and the MXene materials have good application prospects.

Description

Two-dimensional layered material MXene oriented medium and application thereof
Technical Field
The invention relates to the technical field of nano materials, in particular to a two-dimensional layered material MXene oriented medium and application thereof.
Background
Molecular Residual Quadrupole Coupling (RQC) and Residual Dipole Coupling (RDC) in anisotropic parameters of nuclear magnetic resonance have unique application advantages for the analysis of organic molecular configuration and dominant conformation. When nuclear magnetic resonance spectroscopy (NMR) is used to measure anisotropic nuclear magnetic parameters, an orientation medium is usually introduced to create an anisotropic environment for the molecules to be measured, so that the molecules to be measured have appropriate orientation properties. Therefore, the preparation of the oriented medium with excellent performance has important significance for obtaining the anisotropic parameters of the organic molecules. Alignment media for the determination of anisotropy parameters of organic compounds fall mainly into two categories, one being stretchable or compressible polymer gels and the other being lyotropic liquid crystals.
In recent years, with the development and utilization of new alignment media, the anisotropy parameter has become one of the tools for analyzing the structure of small organic molecules. The development of the directional medium has great significance for the development of medicaments and the research of natural products. Based on the problems of complicated preparation process, background interference and the like of the existing directional medium, the development of a directional medium with more excellent performance for organic molecular structure identification is urgently needed. MXenes, a metal carbide or nitride material with a two-dimensional layer structure, has attracted a great deal of attention since its unique characteristics and various application prospects since its discovery in 2011. In recent years, researchers have found that MXenes exhibit liquid crystal behavior when they reach a certain concentration. Based on the characteristics of simple MXenes preparation, spontaneous directional arrangement of molecules, less hydrogen atom containing structure, no background interference and the like, the MXenes material can be constructed as a directional medium for analyzing the organic molecular structure.
Disclosure of Invention
In order to solve the technical problems, the invention provides a Ti-based alloy3C2TxThe MXene oriented medium is constructed and applied to the field of nuclear magnetism, and the aim is to provide a two-dimensional layered material which can be applied to H2Dispersing in O to realize the construction of novel directional medium. The MXene dispersion liquid has good fluidity and orientation, and can be used as an orientation medium for application in biomolecule RDCAnd (4) accurate measurement of s. The oriented medium can be dispersed in water, and has the characteristics of no background and adjustable size, so that the oriented medium system effectively simplifies the analytic process based on nuclear magnetic detection, and the MXene has the advantages of adjustability, controllability, large amount of active sites on the surface, and good application prospect.
According to one aspect of the invention, a two-dimensional layered material MXene oriented medium is provided, wherein the structural formula of the two-dimensional layered material MXene is TiaCbTxT is O, F, N having hydrophilicity, and when a is 3, b is 2; when a is 2, b is 1; the oriented medium is formed by enabling the two-dimensional layered material MXene to be in H2Forming a dispersion with a concentration of 0.1 wt% to 5 wt% in O for measurement of anisotropic nuclear magnetic parameters.
Preferably, based on the above scheme, the orientation ability of the orientation medium is determined by the aspect ratio and the concentration of the dispersion liquid.
On the basis of the scheme, preferably, the two-dimensional layered material MXene is added into water after being freeze-dried, and can quickly generate orientation capacity after being ultrasonically redispersed.
On the basis of the scheme, preferably, when the concentration of the two-dimensional layered material MXene is 0.1-5 wt%, the oriented medium has 10% D2Deuterium resonance in O solution shows residual quadrupole coupling values (RQCs) of 0-71 Hz.
On the basis of the scheme, the two-dimensional layered material MXene is an inorganic layered material and has no C-H coupling signal in an NMR spectrum.
The invention also provides an application of the two-dimensional layered material MXene orientation medium, wherein the two-dimensional layered material MXene orientation medium can induce biomolecules to generate orientation and is used for measuring molecular RDCs and analyzing structures.
On the basis of the scheme, preferably, the two-dimensional layered material MXene oriented medium can be used for measuring RDCs of water-soluble biomolecules to obtain structural information of the RDCs.
On the basis of the scheme, the two-dimensional layered material MXene oriented medium can measure RDCs of L-proline to obtain the proline structure.
On the basis of the scheme, preferably, the two-dimensional layered material MXene oriented medium can measure the RDCs of the sucrose to obtain the structure of the sucrose.
Preferably, on the basis of the scheme, MXene is Ti3C2Tx、Ti2CTxOr Ti3CNTxOne of (1) and (b).
The invention has the following beneficial effects:
1. the oriented medium is constructed by ultrasonic dispersion of MXene in water, wherein the MXene is formed by Ti3AlC2The two-dimensional nano material obtained by etching the Al layer does not contain organic carbon hydrogen, and the material can be used for obtaining a solid sample which is easier to store through freeze-drying and simultaneously keeping the original performance. 0.5 wt% MXene in H2The resonance of deuterium in O showed RQC at 4Hz, and RQC at 5 wt% was 71 Hz. The low critical concentration, high RQC, indicates that MXene has highly oriented property as an oriented medium, and is an excellent ordered medium for measuring the biological molecules RDCs.
2. The MXene sheet material prepared by the method does not contain organic carbon-hydrogen bonds in the structure, so that the problem of difficult analysis caused by complex signals of an oriented medium in a spectrogram is solved.
3. The MXene prepared by the method can further realize the regulation and control of the orientation capability of the oriented medium by changing the ultrasonic time regulation and control size.
4. MXene prepared by the invention contains Ti3C2TxBut not limited to, Ti is obtained by further using the homologous family as an etching object2CTx、Ti3MXene such as CN as orientation medium.
Drawings
Fig. 1 is a flow diagram of the MXene preparation of the present invention;
FIG. 2 shows MXene colloid of the present invention in H2The tyndall phenomenon of O dispersion;
fig. 3 shows Dynamic Light Scattering (DLS) spectra of MXene prepared in example 3 of the present invention at different ultrasound times: a)0min, b)30min, c)120min, d)300 min;
FIG. 4 shows MXene as Ti prepared in inventive example 13C2TxMXene Zeta potential analysis table;
FIG. 5 is MXene Ti prepared in inventive example 13C2TxMXene X-ray diffraction (XRD) pattern;
FIG. 6a shows MXene as Ti prepared in inventive example 13C2TxMXene X-ray photoelectron spectrum;
FIG. 6b Ti prepared in example 1 of the present invention3C2TxMXene Atomic Force Microscope (AFM) images;
FIG. 6c Ti prepared according to example 1 of the present invention3C2TxMXene Transmission Electron Microscope (TEM) image;
FIG. 6d Ti prepared according to inventive example 13C2TxSelected Area Electron Diffraction (SAED) pattern of MXene,
FIG. 6e Ti prepared according to example 1 of the present invention3C2TxHigh power TEM images of MXene;
FIG. 7 shows Ti prepared in example 1 of the present invention3C2TxFESEM images of MXene under different ultrasonic times;
FIG. 8a is a graph showing Ti at 0min for the ultrasonic treatment time prepared in example 1 of the present invention3C2TxA polarization diagram of MXene in the dispersion;
FIG. 8b shows Ti at a sonication time of 30min for the preparation of example 1 according to the present invention3C2TxA polarization diagram of MXene in the dispersion;
FIG. 8c is a graph of Ti content at 120min for sonication prepared in example 1 of the present invention3C2TxA polarization diagram of MXene in the dispersion;
FIG. 8d shows Ti at 300min for the sonication time prepared in example 1 of the present invention3C2TxA polarization diagram of MXene in the dispersion;
FIG. 9a shows MXene Ti concentrations of 0.1%, 0.5%, and 2% prepared in example 1 of the present invention3C2TxViscosity of the dispersion as a function of shear rate (a);
FIG. 9b is a schematic representation of the preparation of Ti in example 1 of the present invention3C2TxPlots of elasticity (G') and viscous modulus (G ") versus frequency for MXene dispersions;
FIG. 9c shows Ti prepared in example 1 of the present invention3C2TxPlots of elasticity (G') and viscous modulus (G ") versus frequency for MXene dispersions;
FIG. 9d shows preparation of Ti in example 1 of the present invention3C2TxPlots of elasticity (G') and viscous modulus (G ") versus frequency for MXene dispersions;
FIG. 10 shows Ti prepared in accordance with the present invention in accordance with example 1 of the present invention with different sonication times3C2TxDeuterium of MXene: (2H) NMR chart;
FIG. 11a shows Ti concentrations of 30min in the ultrasonic treatment of example 1 of the present invention3C2TxDeuterium of MXene: (2H) NMR chart;
FIG. 11b shows a concentration of 5% Ti prepared in example 1 of the present invention3C2TxMXene hydrogen spectrogram;
FIG. 11c is a graph showing Ti concentration at 30min of sonication time for preparation prepared in example 1 of the present invention3C2TxDeuterium of MXene with time: (2H) NMR chart;
FIG. 12 shows 10mg proline dissolved in Ti prepared in example 1 of the present invention3C2TxMXene (concentration 20.0mg/mL)2A HNMR map;
FIG. 13 is a value of proline recorded using the MXene dispersion prepared in example 1 of the present invention as an ordered medium1H,13C]-CLIP-HSQC spectrum;
fig. 14 is a graph of the fitted linear relationship of the RDCs of proline measured using the MXene dispersion prepared in example 1 of the present invention as an ordered medium and the calculated RDCs;
FIG. 15 shows 10mg of sucrose dissolved in Ti prepared in example 1 of the present invention3C2TxMXene (concentration 20.0mg/mL)2A HNMR map;
FIG. 16 is a [ solution of ] sucrose recorded using MXene dispersion prepared in example 1 of the present invention as an ordered medium1H,13C]-JSB-HSQC spectra;
fig. 17 is a graph of the fitted linear relationship of the RDCs of sucrose measured using the MXene dispersion prepared in example 1 of the present invention as an ordered medium and the calculated RDCs.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
Example 1
The meaning of the two-dimensional material MXene is that M is metal titanium with different valence states, X is carbon-ene refers to alkene substances, wherein the structural formula of MXene is TiaCbTxAnd when a is 3, b is 2, when a is 2, b is 1, T is O, F, N with better hydrophilicity.
A common MXene is Ti3C2Tx、Ti2CTx、Ti3CNTxThe MXene dispersion liquid is prepared by adopting an in-situ lithium ion intercalation method, a hydrogen fluoride-free system of lithium fluoride and hydrochloric acid is adopted for etching, and the phase A is etched and ultrasonically stripped to obtain the MXene dispersion liquid.
Referring to fig. 1, the two-dimensional material MXene of the present invention is prepared by the following steps:
s1, placing LiF in a polytetrafluoroethylene substrate, adding concentrated hydrochloric acid, stirring for dissolving, and preparing HF;
s2, adding MAX into the polytetrafluoroethylene substrate, heating to 45 ℃, stirring, and starting an etching process;
s3, after the etching is finished, transferring the reaction liquid into a centrifuge tube, and centrifugally washing the reaction liquid to be neutral to obtain MXene dispersion liquid;
s4, transferring the MXene dispersion liquid into a glass bottle, and introducing inert gas for protection;
s5, placing the dispersion liquid obtained in the step S4 in an ultrasonic machine for ultrasonic stripping for 0-300 min;
and S6, transferring the liquid in the glass bottle to a centrifuge tube, centrifuging for 30min at 2500r/min, and then obtaining a solid by adopting a freeze-drying technology.
S7, wherein MAX comprises Ti3AlC2、Ti3AlCN、Ti2AlC。
The MXene size can be regulated and controlled by different ultrasonic etching times, and the ultrasonic time is respectively 0min, 30min, 120min and 300 min.
And in order to verify the structural information of MXene, the invention can also detect the structural information of MXene through X-ray diffraction (XRD). The results are shown in FIG. 5, the abscissa indicates the angle, the ordinate indicates the intensity of the diffraction peak of the crystal, the diffraction peak in the vicinity of 40 degrees disappears, and the 002 peak shifts to a low angle, indicating that Ti is present3AlC2Is successfully etched into Ti3C2TxMaterial, and Ti3C2TxThe interlayer spacing of (2) becomes large. By comparing the spectrum of the MAX phase and the MXene material, the change of the interlayer spacing of 5.04 angstroms can be calculated according to the Sheer formula, and the increase of the interlayer spacing further indicates the successful etching and the successful intercalation of water molecules.
Further, the element composition of MXene was analyzed by XPS, and the analysis results are shown in FIG. 6a, the abscissa represents bond energy and the ordinate represents strength.
In order to preliminarily study whether the MXene can obtain a relatively uniform nano size under the etching condition, the dimension of the MXene under different ultrasonic times is evaluated by DLS, and as can be known from the attached drawings, when the ultrasonic time is within the range of 0-300min, the dimension of the material related to the MXene can maximally reach the micron level, as shown in FIGS. 3a-d, the material with the dimension of about 200nm can be obtained along with the extension of the ultrasonic time, and the combination of scanning electron microscope images in FIGS. 7a-d can also show that the sheet dimension of the MXene is gradually reduced along with the extension of the ultrasonic time. Further, the size of the material obtained by the invention can be further regulated and controlled by changing the ultrasonic time.
Further, the method can be used for preparing a novel materialThe invention also discusses the charging property of the MXene dispersion liquid through Zeta potential, as shown in figure 4, the potential of MXene under different ultrasonic time is about-30 mV, which shows that the MXene surface contains a large amount of negative charges, and the surface contains-OH and-O combined with XPS spectrogram analysis-And so on, and thus can form hydrogen bonds with water to obtain a stable dispersion, while obtaining a more negative potential through negative electrical repulsion.
Wherein MXene is in H2Having liquid crystal behavior in O is shown in FIGS. 8 a-d.
The invention also provides a two-dimensional layered material MXene oriented medium, wherein the oriented medium is prepared by arranging the two-dimensional layered material MXene in H2Forming a dispersion with a concentration of 0.1 wt% to 5 wt% in O for measurement of anisotropic nuclear magnetic parameters.
Notably, the two-dimensional layered material is in H2O shows lyotropic liquid crystal behavior, 90mg/mL MXenes material of different sizes dispersed in water was dropped onto a glass slide, and then another glass slide was pressed over the sample and observed for birefringence by a polarizing microscope. As can be seen from fig. 8a-d, larger sized MXene has stronger birefringence while the dispersion concentration remains the same.
In addition, FIG. 9a shows 0.1 wt% Ti3C2TxThe viscosity of MXene is only 0.01Pa.s, and although the viscosity of MXene dispersion increases with the concentration of the MXene dispersion, the MXene dispersion has the characteristic of shear thinning, and the shear rate increases to 100s-1When the viscosity is reduced to 0.001Pa.s, the MXene dispersion liquid has better fluidity. Further study on its visco-elastic behavior to investigate Ti concentration at different concentrations3C2TxMXene interaction. According to Ti in FIGS. 9b-d3C2TxCompared with the scanning frequency, the elasticity (G ') modulus and the viscosity (G') modulus of MXene are increased in three groups along with the increase of the scanning frequency. Also, the advantage of G' over G "was observed throughout the scanning frequency range and all concentrations, indicating the formation of a gel. Further description of the inventionBy Ti3C2TxThe MXene sheets have interaction force but can still keep better fluidity.
It has been found through research that such ordered mediators can direct biomolecules and limit their molecular motion, which has the potential to act as directed mediator capture molecules for RDCs. To further demonstrate the potential of MXene solutions as directing media by deuterium: (2H) NMR confirmed the ordered arrangement.
As shown in fig. 10a-d, at 600MHz ((m))1H) In the spectrometer, 2 wt% MXene at D under different ultrasonic time is studied2Deuterium resonance in O solution shows residual quadrupole coupling values in the range of 0-18 Hz. Further investigating the concentration dependence, FIG. 11a shows that 0.5 wt% MXene is in D2Deuterium resonance in O solution showed a residual quadrupole coupling value of 4.2Hz, indicating that the two-dimensional layered material in solution has a certain orientation. And MXene was observed at D2The RQCs value of O is positively correlated with its concentration. When the MXene concentration was 5 wt%, it was RQC of 71.0Hz, as shown in FIG. 11a, where the abscissa of FIG. 11a and FIG. 11b represents frequency and the ordinate represents relative intensity. Meanwhile, the time stability of the compound is researched, and FIG. 11c shows that MXene deuterium resonance with the concentration of 2 wt% in a certain time shows the residual quadrupole coupling value of 4.2Hz, so that the compound has good time stability and is used in nuclear magnetism2The signal of the H quadrupole splitting is highly symmetric with a half-width of 0.05Hz, and a relatively narrow half-width indicates less viscous from the side. MXene exhibits excellent ordering and flowability after dispersion in water, which indicates the great potential that MXene has shown as an ideal ordered medium in the measurement of biomolecule RDCs.
Example 2
To study MXene as an oriented Medium in D2The applicability of RDCs was accurately obtained in O, and studies using proline as a model molecule are performed below.
Wherein the proline has the structural formula shown as the following formula (II), and the spectrum of C-13 is given in Table 1.
Figure BDA0003553830730000091
Figure BDA0003553830730000092
Figure BDA0003553830730000101
As shown in FIG. 11, 10.0mg of proline was dissolved in MXene dispersion (concentration 20.0mg/mL), which was2The H NMR spectrum showed RQC to be 22.50 Hz. In fig. 12, the abscissa represents frequency and the ordinate represents relative intensity. Proline [ 2 ] using MXene dispersion as ordered medium1H,13C]CLIP-HSQC spectra and in isothermal conditions pure D2O was used as a control, as shown in fig. 13, in which the abscissa represents the hydrogen spectrum and the ordinate represents the carbon spectrum. According to the analysis of the experimental result, all the C-H coupling on the proline skeleton can be detected in the ordered MXene oriented medium, which shows that the MXene oriented medium has good compatibility with proline. The RDCs for proline range in size from-1.4 to 37.0Hz (Table 1).
To test the accuracy of these RDCs, the present invention performed theoretical calculations using the Singular Value Decomposition (SVD) method and the program MSpin 45. Density Functional Theory (DFT) at the level of B3LYP/6-31G (d) was introduced for calculation of theoretical RDCs. The linear relationship between the measured RDCs and the Calculated RDCs is shown in FIG. 14, wherein in FIG. 14, Experimental RDCs means Experimental RDCs, scaled RDCs means Calculated RDCs, and proline means proline. Proline has a Q factor of 0.093, indicating that MXene can be an excellent medium for accurate measurement of RDCs.
Example 3
To study MXene as an oriented Medium in D2The applicability of RDCs was accurately obtained in O, and studies using sucrose as a model molecule were conducted below.
Sucrose was used to further demonstrate the compatibility of MXene as an orienting medium. As shown in FIG. 14, 10.0mg of sucrose was dissolved in MXene dispersion(concentration: 20.0mg/mL), which2The H NMR spectrum showed RQC at 25.39 Hz. In fig. 15, the abscissa represents frequency, and the ordinate represents relative intensity. Use of MXene as an ordered Medium for the recording of sucrose1H,13C]JSB-HSQC spectra, and pure D under isothermal conditions2O was used as a control, and the experimental results are shown in FIG. 15, in which the C-13 spectrum is shown in Table 2, and in FIG. 16, the abscissa represents the hydrogen spectrum and the ordinate represents the carbon spectrum. The results show that all C-H couplings on the sucrose backbone can be detected in the ordered MXene directing medium, indicating that the MXene directing medium has good compatibility with sucrose as well. The RDCs of the sucrose detected were-7.63-18.02 Hz (Table 2). The Q factor value obtained by fitting is 0.13, and a low Q factor value indicates that the medium can be used for effectively and accurately measuring the RDC value of the sucrose, please refer to FIG. 17, wherein the abscissa represents the experimental RDCs value, and the ordinate represents the theoretical RDCs value.
13C positioning δCppm 1H positioning δHppm 1JCH 1TCH 1DCH 1DCHCalculated value
C1 72.29 H1 3.72 144.31 162.33 18.02 17.56
C2 69.07 H2 3.34 144.36 160.34 15.98 15.71
C3 72.46 H3 3.63 145.11 162.5 17.39 16.99
C4 70.95 H4 3.43 137.3 161.61 17.29 17.47
C5 92.08 H5 5.28 169.77 182.46 12.69 12.42
C9 76.24 H9 4.09 144.17 140.91 -3.26 -3.82
C10 73.84 H10 3.92 144.39 143.73 -0.66 -1.14
C11 81.27 H11 3.76 149.09 141.46 -7.63 -7.90
C13 61.15 H13a,b 3.54 144.37 148.24 3.51 5.67
C18 62.24 H18a,b 3.69 144.06 151.66 7.60 3.23
Compared with the existing directional medium, the invention has two advantages:
1) the MXene dispersion liquid still keeps good fluidity at the concentration of 5 wt%, and meanwhile, the MXene dispersion liquid can show narrow half-peak width in nuclear magnetic spectrum, so that higher-quality spectrogram information can be obtained conveniently.
2) The MXene nano material subjected to freeze-drying treatment still keeps the orientation capability after being redispersed, and a sample can be stored in a solid form, so that great advantages are provided for storage and transportation.
3) MXene is an inorganic material, does not contain a background signal in a two-dimensional nuclear magnetic spectrum, and avoids the interference of the background signal on the map analysis.
4) The orientation medium constructed by MXene has the behavior characteristic of lyotropic liquid crystal, and further can achieve the aim of adjusting the orientation capability of the medium by regulating and controlling the concentration, the critical concentration of the orientation capability is 0.1 wt%, and the surface of the orientation medium has more reactive active sites, so that the method provides an idea for designing and developing other novel orientation media.
In view of the above advantages, MXene constructed oriented media showed great promise in RDCs measurements. In the invention, MXene is easy to prepare by adopting a lithium fluoride and hydrochloric acid system to etch MAX phase; MXene obtained by etching can be subjected to vacuum freeze drying to obtain a solid, and the MXene has the advantage of simple storage; meanwhile, due to the redispersion characteristic, the MXene can be directly and ultrasonically redispersed to prepare the dispersion liquid for measuring the molecular RDCs, and the method is simple, has strong operability and can be used for accurate quantification. The absence of rigid aromatic groups and organic hydrocarbons in MXene avoids the risk of strong pi-pi interactions between the ordered medium and the analyte, while avoiding the effects of background signals.
Finally, the method of the present application is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The two-dimensional layered material MXene directional medium is characterized in that the structural formula of the two-dimensional layered material MXene is TiaCbTxT is O, F, N with hydrophilicity, and when a is 3, b is 2; when a is 2, b is 1; the oriented medium is formed by enabling the two-dimensional layered material MXene to be in H2Forming a dispersion with a concentration of 0.1 wt% to 5 wt% in O for measurement of anisotropic nuclear magnetic parameters.
2. The MXene oriented media of two-dimensional layered material of claim 1, wherein the orientation ability of the oriented media is determined by its aspect ratio and dispersion concentration.
3. The two-dimensional layered material MXene orientation medium of claim 1, wherein the two-dimensional layered material MXene is lyophilized and then added into water, and can rapidly generate orientation ability after being ultrasonically redispersed.
4. The two-dimensional layered material MXene orientation medium of claim 1, wherein the orientation medium has a concentration of 10% D when the concentration of the two-dimensional layered material MXene is 0.1 wt% to 5 wt%2Deuterium resonance in O solution shows residual quadrupole coupling values (RQCs) of 0-71 Hz.
5. The two-dimensional layered material MXene oriented medium of claim 1, wherein the two-dimensional layered material MXene is an inorganic layered material having no C-H coupling signal in NMR spectrum.
6. Use of the two-dimensional layered material MXene orientation medium of claim 1, which induces biomolecule orientation for molecular RDCs measurement and structure analysis.
7. The use according to claim 6, wherein the two-dimensional layered material MXene orientation medium can be used to measure RDCs of water-soluble biomolecules to obtain structural information thereof.
8. The use according to claim 7, wherein the MXene oriented mediator in a two-dimensional layered material is capable of measuring the proline structure from the RDCs of L-proline.
9. The use according to claim 7, wherein the MXene oriented media is capable of measuring sucrose RDCs to obtain sucrose structure.
10. Use according to claim 7, wherein MXene is Ti3C2Tx、Ti2CTxOr Ti3CNTxOne of (1) and (b).
CN202210271967.8A 2022-03-18 2022-03-18 Two-dimensional layered material MXene oriented medium and application thereof Active CN114604871B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210271967.8A CN114604871B (en) 2022-03-18 2022-03-18 Two-dimensional layered material MXene oriented medium and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210271967.8A CN114604871B (en) 2022-03-18 2022-03-18 Two-dimensional layered material MXene oriented medium and application thereof

Publications (2)

Publication Number Publication Date
CN114604871A true CN114604871A (en) 2022-06-10
CN114604871B CN114604871B (en) 2023-02-28

Family

ID=81864373

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210271967.8A Active CN114604871B (en) 2022-03-18 2022-03-18 Two-dimensional layered material MXene oriented medium and application thereof

Country Status (1)

Country Link
CN (1) CN114604871B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170088429A1 (en) * 2015-09-24 2017-03-30 Samsung Electronics Co., Ltd. Mxene nanosheet and manufacturing method thereof
US20190092641A1 (en) * 2017-09-28 2019-03-28 Murata Manufacturing Co., Ltd. Aligned film and method for producing the same
CN110283231A (en) * 2019-06-03 2019-09-27 中南民族大学 A kind of preparation and application based on the amphipathic novel lysotropic liquid crystal of oligopeptides self assembly
CN111122534A (en) * 2019-10-28 2020-05-08 苏州大学 Raman test method of compound based on two-dimensional titanium carbide nanosheet
US20200240000A1 (en) * 2017-10-16 2020-07-30 Drexel University Mxene layers as substrates for growth of highly oriented perovskite thin films
US20210269664A1 (en) * 2020-02-13 2021-09-02 Korea Institute Of Science And Technology 2-dimensional mxene surface-modified with catechol derivative, method for preparing the same, and mxene organic ink including the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170088429A1 (en) * 2015-09-24 2017-03-30 Samsung Electronics Co., Ltd. Mxene nanosheet and manufacturing method thereof
US20190092641A1 (en) * 2017-09-28 2019-03-28 Murata Manufacturing Co., Ltd. Aligned film and method for producing the same
US20200240000A1 (en) * 2017-10-16 2020-07-30 Drexel University Mxene layers as substrates for growth of highly oriented perovskite thin films
CN110283231A (en) * 2019-06-03 2019-09-27 中南民族大学 A kind of preparation and application based on the amphipathic novel lysotropic liquid crystal of oligopeptides self assembly
CN111122534A (en) * 2019-10-28 2020-05-08 苏州大学 Raman test method of compound based on two-dimensional titanium carbide nanosheet
US20210269664A1 (en) * 2020-02-13 2021-09-02 Korea Institute Of Science And Technology 2-dimensional mxene surface-modified with catechol derivative, method for preparing the same, and mxene organic ink including the same

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HONGYE HUANG ET.AL: "Recent development and prospects of surface modification and biomedical applications of MXenes", 《NANOSCALE》 *
KAINING LI ET.AL: "MXenes as noble-metal-alternative co-catalysts in photocatalysis", 《CHINESE JOURNAL OF CATALYSIS》 *
毛琳: "细菌纤维素/Ti3C2-MXene电活性复合水凝胶的制备及其在皮肤伤口敷料方面的应用", 《中国化学会2017全国高分子学术论文报告会摘要集》 *

Also Published As

Publication number Publication date
CN114604871B (en) 2023-02-28

Similar Documents

Publication Publication Date Title
Dessombz et al. Design of liquid-crystalline aqueous suspensions of rutile nanorods: Evidence of anisotropic photocatalytic properties
US20100298600A1 (en) Nanodiamond compounds synthesized by surface functionalization
Hsieh et al. Adsorption of sodium dodecyl sulfate on functionalized graphene measured by conductometric titration
Jalili et al. Processable 2D materials beyond graphene: MoS 2 liquid crystals and fibres
US20050156144A1 (en) Composition in gel form comprising carbon nanotube and ionic liquid and method for production thereof
Barkauskas et al. Interaction between graphite oxide and Congo red in aqueous media
CN103639421A (en) Preparation method for high-conductivity graphene and silver nanoparticle composite materials
Wei et al. A general chiral selector immobilized on silica magnetic microspheres for direct separation of racemates
CN104452436A (en) Nano-cellulose dispersing agent as well as preparation method and application of nano-cellulose dispersing agent
Ghosh et al. Electric modulus approach to the analysis of electric relaxation and magnetodielectric effect in reduced graphene oxide–poly (vinyl alcohol) nanocomposite
Mitroova et al. The sensitivity of liquid crystal doped with functionalized carbon nanotubes to external magnetic fields
CN108439383A (en) A kind of method that ultrasound supercritical carbon dioxide-shearing coupling stripping expanded graphite prepares form the few-layer graphene nanometer sheet
Zhao et al. Ti3C2T x MXene Liquid Crystal: Access to Create Background-Free and Easy-Made Alignment Medium
Dichiarante et al. Superfluorinated and NIR-luminescent gold nanoclusters
Tezel et al. Interparticle interactions and rheological signatures of Ti3C2Tz MXene dispersions
Anastasescu et al. SiO2 nanospheres and tubes obtained by sol–gel method
EP3031846B1 (en) Multifunctional supramolecular hybrids encompassing hierarchical self-ordering of metal-organic framework nanoparticles and method of preparing same
CN103242217A (en) Fullerene derivative micron sheet and preparation method thereof
CN108192137B (en) Preparation method of high-dispersion carbon nano tube used as rubber filler
Nie et al. Nanoporous Supramolecular Liquid Crystal Polymeric Material for Specific and Selective Uptake of Melamine
CN114604871B (en) Two-dimensional layered material MXene oriented medium and application thereof
CN103754863B (en) Preparation method of gold-graphene composite nano material
Jayalakshmi et al. Probing the pore structure of a chiral periodic mesoporous organosilica using liquid crystals
CN110283231B (en) Preparation and application of novel lyotropic liquid crystal based on amphiphilic oligopeptide self-assembly
Hiroi et al. Transitions of aggregation states for concentrated carbon nanotube dispersion

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant