CN101963564B - Chiral sensor and preparation method thereof - Google Patents
Chiral sensor and preparation method thereof Download PDFInfo
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- CN101963564B CN101963564B CN2010102579256A CN201010257925A CN101963564B CN 101963564 B CN101963564 B CN 101963564B CN 2010102579256 A CN2010102579256 A CN 2010102579256A CN 201010257925 A CN201010257925 A CN 201010257925A CN 101963564 B CN101963564 B CN 101963564B
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Abstract
The invention discloses a chiral sensor and a preparation method thereof. The chiral sensor comprises a micro-cantilever structure and a chiral compound which is unilaterally modified on a deformation beam of a micro-cantilever by a covalent method or a non-covalent method and is used for identifying D-type and L-type chiral molecules. The sensor is placed in air which contains the chiral molecules to be detected, and the micro-cantilever generates static bending or frequency variation with the mass change of the micro-cantilever due to the adsorbed chiral molecules, so that the D-type and L-type chiral molecules in the air are detected. By using the chiral sensor, the chiral molecules are easily and conveniently detected, and simultaneously the sensor has low preparation cost and is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of sensor that is used for chiral Recognition research, relate in particular to chiral sensor of a kind of micro cantilever structure that is used to discern D type and L type chiral molecules and preparation method thereof.
Background technology
Micro cantilever structure is the simplest a kind of MEMS (MEMS), and it is easy to carry out little processing and a large amount of production.In recent years, the sensor based on different micro cantilever structures is widely used in chemistry and biological real-time detection.It is found that a spot of molecular adsorption will cause the variation of micro-cantilever curved deflector amount and oscillation frequency on the surface of micro-cantilever.The variation of the micro-cantilever curved deflector amount that causes owing to the absorption of molecule mainly is because molecular adsorption behind the micro-cantilever surface, has produced different stress at upper and lower surfaces.Molecular adsorption is before the semi-girder surface; The stress of semi-girder upper surface and lower surface is in balance, produces the radial force along the micro-cantilever mid-plane, after molecular adsorption arrives the micro-cantilever upper and lower surfaces; They are different to the upper and lower surfaces stress influence; For example can be limited to a surface to the absorption of molecule on the micro-cantilever surface, the different stress changes of upper and lower surfaces has produced an additional bending force, makes the tip of micro-cantilever move to new position.In general, the absorption of molecule has reduced surface energy.For the bending among a small circle of micro-cantilever, the variation of surface stress equals the variation of surface free energy.Degree that semi-girder is crooked and because the ratio that is varied to of the surface free energy that molecular adsorption causes.Therefore, the cantilever deflection of beam depends on that each absorbing molecules is to the change amount of semi-girder surface free energy and the quantity that is adsorbed on all molecules on semi-girder surface.The degree that semi-girder is crooked depends on the elasticity coefficient of semi-girder.In order to obtain bigger semi-girder curved deflector, can use the little semi-girder of elasticity coefficient.
The oscillation frequency of the molecule absorption on semi-girder surface change semi-girder mainly is because the absorption of molecule has changed the gross mass of semi-girder.The semi-girder oscillation frequency depends on the size of semi-girder, elastic modulus and density.The oscillation frequency of semi-girder is very sensitive to the mass loading of semi-girder, and the ultimate sensitivity of detection individual molecule might be able to be provided based on the method for oscillation frequency skew.Yet; The damping effect of liquid medium has had a strong impact on the oscillatory response of semi-girder device; And can not receive the influence of dielectric viscosity based on the measuring method of semi-girder curved deflector, therefore, the measuring method crooked based on semi-girder has more attractive force in biological and chemical is surveyed.
At present, chipal compounds has caused people's extensive concern in Application for Field such as medicine, agricultural chemicals, spices, food additives, new materials, and synthetic, the fractionation of chipal compounds and the mensuration of enantiomeric purity become one of field, forward position of current chemistry.For adapting with it, the chiral sensor that is used to detect chipal compounds composition, quality characteristic also becomes the research emphasis that those skilled in the art pay much attention to.
Summary of the invention
Present condition for application in view of above-mentioned micro cantilever structure the purpose of this invention is to provide a kind of chiral sensor, a kind of method for making of this chiral sensor is provided simultaneously, to realize a kind of sensor that is used for chiral Recognition research with low cost, convenient-to-running.
Above-mentioned first purpose of the present invention is to be achieved through following technical scheme:
A kind of chiral sensor is characterized in that: the sensing probe of said sensor is the micro cantilever structure on the silicon base, and is modified with the chipal compounds that is used for specific adsorption D type and L type chiral molecules on the variable shaped beam of said micro-cantilever.
Further, this chipal compounds that is used for specific adsorption D type and L type chiral molecules comprises amino acid, macrocyclic compounds, porphyrins.Wherein macrocyclic compounds comprises cyclodextrin, calixarenes, crown ether etc. at least.
Further, this micro-cantilever comprises the micro cantilever structure of silicon, the micro cantilever structure of silicon dioxide and the micro cantilever structure of silicon nitride, and any micro cantilever structure includes variable shaped beam and supports bottom girder.
The technical solution that above-mentioned another purpose of the present invention realizes can be:
A kind of method for making of chiral sensor is characterized in that: on silicon base, utilize earlier lithographic method to make micro-cantilever; The chipal compounds that will be used for specific adsorption D type and L type chiral molecules is again modified the variable shaped beam of micro-cantilever through method covalently or non-covalently; Process sensing probe, and said sensing probe and oscillation frequency detector are overlapped integrated integrated chiral sensor.
Further, the method for making of aforementioned a kind of chiral sensor before lithographic method is made micro-cantilever, also is included in deposition preparation silicon dioxide layer or silicon nitride layer on the silicon base, and the object of etching is the silicon dioxide layer or the silicon nitride layer of back preparation.
The technical solution that above-mentioned another purpose of the present invention realizes can also be:
A kind of method for making of chiral sensor is characterized in that: on silicon base, utilize earlier lithographic method to make micro-cantilever; On the support bottom girder of micro-cantilever, prepare piezoelectric membrane again; The chipal compounds that will be used for specific adsorption D type and L type chiral molecules is at last modified the variable shaped beam of micro-cantilever through method covalently or non-covalently, processes the chiral sensor of band micro cantilever structure sensing probe.
Further, the method for making of aforementioned a kind of chiral sensor before lithographic method is made micro-cantilever, also is included in deposition preparation silicon dioxide layer or silicon nitride layer on the silicon base, and the object of etching is the silicon dioxide layer or the silicon nitride layer of back preparation.
The appearance of this kind chiral sensor of the present invention and method for making thereof and practice after; Combine the micro-cantilever sensing technology to chipal compounds to D type and the attraction of L type chiral molecules specificity; Improved the simplicity that detects chiral molecules greatly; The low preparation cost of sensor itself is suitable for large-scale production simultaneously.
Description of drawings
Fig. 1 is the structural representation of chiral sensor one embodiment of the present invention;
Fig. 2 is the structural representation of another embodiment of chiral sensor of the present invention.
Embodiment
The present invention further excavates the application of MEMS (MEMS), and a kind of chiral sensor and method for making thereof based on micro-cantilever is provided to innovation.This chiral sensor, simple structure, easy to process.The selection of micro-cantilever is cheap; Can utilize traditional micro-processing method; Make cantilever beam structure; Again chiral molecules is modified on the micro-cantilever, in the adsorption process on micro-cantilever surface, made semi-girder generation static buckling, perhaps in micro-cantilever surface adsorption process, make frequency shift realize sensing through chiral molecules through chiral molecules; Thereby be implemented in the air the detection of chiral molecules, can discern chiral molecules quickly and easily.
A kind of chiral sensor of the present invention's design, its sensing probe is the micro cantilever structure on the silicon base, and is modified with the chipal compounds that is used for specific adsorption D type and L type chiral molecules on the variable shaped beam of said micro-cantilever.Wherein this chipal compounds that is used for specific adsorption D type and L type chiral molecules comprises amino acid, macrocyclic compounds, porphyrins.Further, wherein macrocyclic compounds comprises cyclodextrin, calixarenes, crown ether etc. at least.
In addition, this micro-cantilever comprises the micro cantilever structure of silicon, the micro cantilever structure of silicon dioxide and the micro cantilever structure of silicon nitride, and any micro-cantilever includes variable shaped beam and supports the basic structure of bottom girder.
The chiral sensor by covalent or non-covalent modification method, the amino acids, aromatic macrocyclic compounds, morpholine compounds Pu modification to the micro-cantilever beam deformation, the air present in the D-and L-type chiral it easy to bind to molecules on micro-cantilever, making deformation The beams bent or frequency changes.Thus, nationality can realize detecting the D type and the L type chiral molecules that exist in the air by this kind chiral sensor with low cost, convenient-to-running.
Below in conjunction with accompanying drawing, respectively the preparation method of this chiral sensor is described from two embodiment.Need to prove, below only provide as an example for the detailed description of embodiment, is not to limit the diversified embodiment of the present invention with this.
Embodiment one
This chiral sensor has the micro cantilever structure of silicon, and this micro cantilever structure is that etching forms the vertical support bottom girder and the variable shaped beam of level, and chemical modification has amino acid on the variable shaped beam.
Its method for making is: on silicon base 1, utilize earlier lithographic method to make micro-cantilever 2a; The chipal compounds 3 (being amino acid) that will be used for specific adsorption D type and L type chiral molecules is again modified the variable shaped beam of micro-cantilever through method covalently or non-covalently; Process sensing probe, and with said sensing probe and the integrated integrated chiral sensor of oscillation frequency detector 4 overlap joints.In micro-cantilever surface adsorption process, make frequency shift realize sensing detection through chiral molecules gradually.
Embodiment two
This chiral sensor has the micro cantilever structure of silicon dioxide, and its this micro cantilever structure is that etching forms the vertical support bottom girder and the variable shaped beam of level, and chemical modification has calixarenes on the variable shaped beam.
Its method for making is: deposition prepares silicon dioxide layer on silicon base 1 earlier, utilizes lithographic method to make the micro-cantilever 2b that is merely silicon dioxide; On the support bottom girder of micro-cantilever, prepare piezoelectric membrane 5 again; The chipal compounds 3 (being calixarenes) that will be used for specific adsorption D type and L type chiral molecules is at last modified the variable shaped beam of micro-cantilever through method covalently or non-covalently, processes the chiral sensor of band micro cantilever structure sensing probe.In the adsorption process on micro-cantilever surface, make semi-girder generation static buckling through chiral molecules, the voltage fluctuation that embodies with piezoelectric membrane realizes sensing detection.
Claims (4)
1. the method for making of a chiral sensor is characterized in that: on silicon base, utilize earlier lithographic method to make micro-cantilever; The chipal compounds that will be used for specific adsorption D type and L type chiral molecules is again modified the variable shaped beam of micro-cantilever through method covalently or non-covalently; Process sensing probe, and said sensing probe and oscillation frequency detector are overlapped integrated integrated chiral sensor.
2. the method for making of a kind of chiral sensor according to claim 1; It is characterized in that: said lithographic method is made before the micro-cantilever; Also be included in deposition preparation silicon dioxide layer or silicon nitride layer on the silicon base, the object of etching is the silicon dioxide layer or the silicon nitride layer of back preparation.
3. the method for making of a chiral sensor is characterized in that: on silicon base, utilize earlier lithographic method to make micro-cantilever; On the support bottom girder of micro-cantilever, prepare piezoelectric membrane again; The chipal compounds that will be used for specific adsorption D type and L type chiral molecules is at last modified the variable shaped beam of micro-cantilever through method covalently or non-covalently, processes the chiral sensor of band micro cantilever structure sensing probe.
4. the method for making of a kind of chiral sensor according to claim 3; It is characterized in that: said lithographic method is made before the micro-cantilever; Also be included in deposition preparation silicon dioxide layer or silicon nitride layer on the silicon base, the object of etching is the silicon dioxide layer or the silicon nitride layer of back preparation.
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| CN102269615B (en) * | 2011-05-07 | 2012-11-14 | 大连理工大学 | Micro mass sensor based on groove-shaped cantilever beam structure |
| CN105300953B (en) * | 2015-12-10 | 2018-03-06 | 新乡医学院 | Chiral fluorescent optical sensor and chiral molecules detection method |
| CN105910945A (en) * | 2016-06-13 | 2016-08-31 | 常州大学 | Micro-cantilever device for weighing DNA molecule mass |
| CN106124008A (en) * | 2016-06-13 | 2016-11-16 | 常州大学 | A kind of micro-simply supported beam device weighing DNA molecular quality |
| CN106706591B (en) * | 2017-02-27 | 2019-05-10 | 中南民族大学 | A kind of reversible nanometer porphyrin fluorescence sensor recognition quantitative chiral amino acid method |
| CN110443994B (en) * | 2018-05-03 | 2020-05-22 | 浙江农林大学 | Wireless remote switch controller |
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| US5719324A (en) * | 1995-06-16 | 1998-02-17 | Lockheed Martin Energy Systems, Inc. | Microcantilever sensor |
| CN1793884A (en) * | 2005-12-08 | 2006-06-28 | 复旦大学 | Chiral identification senser and its preparation method |
| CN1828297A (en) * | 2005-12-28 | 2006-09-06 | 天津大学 | Biological molecular mass amplification method for applying in biological sensor |
| CN100427941C (en) * | 2006-04-06 | 2008-10-22 | 复旦大学 | Chiral sensor based on ox seralbumin and preparing process thereof |
| CN1866007B (en) * | 2006-05-12 | 2010-06-09 | 中国科学院上海微系统与信息技术研究所 | Ultra trace detection sensor with integrated piezoresistance SiO2 cantilever, making method and application thereof |
| CN101788525A (en) * | 2010-03-05 | 2010-07-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Chiral sensor and preparation method thereof |
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