CN109647311B - Magnetic liquid marble and optical control method thereof - Google Patents
Magnetic liquid marble and optical control method thereof Download PDFInfo
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- CN109647311B CN109647311B CN201811542772.2A CN201811542772A CN109647311B CN 109647311 B CN109647311 B CN 109647311B CN 201811542772 A CN201811542772 A CN 201811542772A CN 109647311 B CN109647311 B CN 109647311B
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- 239000007788 liquid Substances 0.000 title claims abstract description 110
- 239000004579 marble Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000003287 optical effect Effects 0.000 title description 4
- 230000033001 locomotion Effects 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008395 negative phototaxis Effects 0.000 claims abstract description 9
- 238000005286 illumination Methods 0.000 claims abstract description 8
- 230000029264 phototaxis Effects 0.000 claims abstract description 5
- 230000001276 controlling effect Effects 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- -1 oleic acid modified ferroferric oxide Chemical class 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 239000011553 magnetic fluid Substances 0.000 claims 3
- 230000027227 positive phototaxis Effects 0.000 abstract description 5
- 238000001704 evaporation Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 230000001678 irradiating effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000027870 phototropism Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultraviolet light
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
- B01L3/50273—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the means or forces applied to move the fluids
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- Dispersion Chemistry (AREA)
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Abstract
The invention discloses a magnetic liquid marble light control method. Wrapping hydrophobic ferroferric oxide nano particles on the surface of a water drop to obtain a magnetic liquid marble, and placing the magnetic liquid marble on the water surface; irradiating the surface of the liquid marble at a certain angle by using a light source, and causing the surface tension of water to change under the action of the photo-thermal effect of the ferroferric oxide nanoparticles to generate a surface tension gradient and push the phototaxis movement of the magnetic liquid marble on the water surface; phototaxis of the magnetic liquid marble can be switched through a light source irradiation area, and the movement speed can be controlled through illumination intensity and an incidence angle. The invention has simple operation, high flexibility and controllable direction and speed, realizes the switching of the positive phototaxis and the negative phototaxis of the magnetic liquid marble as required under the condition of not changing the composition and the light source type, also effectively solves the liquid evaporation and pollution of the magnetic liquid marble in the transportation process under the action of a magnetic field, and provides an effective solution for the magnetic liquid marble as a liquid transportation carrier.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a magnetic liquid marble and an optical control method thereof.
Background
The control of small-volume liquid in a micro system has important significance and has wide application prospect in the fields of biomedicine, microfluid and the like. At present, the micro-fluidic device is mainly used for realizing the movement of small-volume liquid, and has obvious defects, such as low freedom of movement caused by limited channels, inevitable liquid adsorption and the like. The liquid marble is a stable liquid-solid complex composed of tiny liquid drops and hydrophobic particles, and not only tends to form a non-sticky liquid-solid interface, effectively reduces the motion resistance generated by the hysteresis of the dynamic contact angle of the liquid drops, but also can control the motion of the liquid marble by combining the inherent characteristics of the externally coated hydrophobic particles, such as magnetism or photosensitivity and the like, so as to realize the control of the internal liquid.
Magnetic liquid marbles are widely concerned by researchers due to the application potential in the biotechnology. However, although the movement of the magnetic liquid marble reported at present can be driven by a magnetic field depending on its magnetic field responsiveness, the magnetic hydrophobic particles coated on the surface of the magnetic liquid marble often move under the action of the magnetic field while being driven, so that the surface of the magnetic liquid marble is opened. This feature is advantageous for using magnetic liquid marble as a micro-reactor, but there are some problems in using liquid marble as a carrier for liquid transportation, such as evaporation and pollution during the liquid transportation process.
Disclosure of Invention
The invention aims to provide a magnetic liquid marble and a light control method thereof, wherein the method has the characteristics of simple operation, high flexibility, adjustable motion start and stop, adjustable direction and speed and capability of realizing the switching of positive phototaxis and negative phototaxis as required under the condition of not changing the composition and the type of a light source.
In order to achieve the purpose, the technical scheme is as follows:
a light-operated magnetic liquid marble is characterized in that the marble is formed by wrapping hydrophobic ferroferric oxide nano particles on the surface of a water drop; the hydrophobic ferroferric oxide nano particles are oleic acid modified ferroferric oxide nano spherical or quasi-spherical particles, the size is 10-15nm, the hydrophobic ferroferric oxide nano particles have superparamagnetism, and the static water contact angle is 140-155 degrees; the volume of the water drop is not more than 45 μ L.
According to the scheme, the hydrophobic ferroferric oxide nano particles are prepared in the following mode: FeCl with the molar ratio of 2:1 is added under the protection of nitrogen3·6H2O and FeCl2·4H2Dissolving O in deionized water at 60 deg.C under stirring, sequentially adding ammonia water and oleic acid, stirring for 15min, cooling to room temperature, performing magnetic separation, washing with deionized water and ethanol, and drying at room temperature.
The light control method of the magnetic liquid marble realizes the control of the motion state of the liquid marble by regulating the incident direction of the light source; when the light source is obliquely incident from top to bottom, the magnetic liquid marble generates light-taxiing motion; the light source irradiates horizontally, and the magnetic liquid marble is static.
According to the scheme, the phototaxis is controlled by controlling the irradiation area of the light source; when light obliquely irradiates the upper half part of the magnetic liquid marble, positive light-convergence movement is realized; when light obliquely irradiates the lower half part of the magnetic liquid marble, negative phototaxis movement is realized.
According to the scheme, the movement rate of the magnetic liquid marble is controlled by adjusting and controlling the intensity of the light source and the illumination angle.
According to the scheme, the light source is a point light source with the wavelength of 365-808 nm.
According to the scheme, the magnetic liquid marble is applied to micro-transportation.
The invention utilizes a rolling dropping method to coat oleic acid modified ferroferric oxide nano particles on the surface of a water drop to form a magnetic liquid marble. The magnetic liquid marble is placed on a water surface, a light beam with a specific wavelength is used for irradiating the magnetic liquid marble at a certain angle, the ferroferric oxide nano particles are excited by light to generate electron-hole pairs, the temperature of the water surface is raised by heat energy released by non-radiative recombination of the electron-hole pairs, the surface tension is reduced, and a surface tension gradient is generated on the light-facing side and the backlight side of the magnetic liquid marble to push the magnetic liquid marble to perform phototaxis movement. When light irradiates the lower half part of the magnetic liquid marble from an oblique upper part at a certain angle, the surface tension of the water surface at the light-facing side of the magnetic liquid marble is reduced due to the temperature rise, and a local surface tension gradient is generated at the light-facing side and the backlight side of the liquid marble to push the liquid marble to perform negative phototropism; when light is incident from an oblique upper part at a certain angle and irradiates the upper half part of the magnetic liquid marble, the incident light penetrates through the liquid marble, so that the surface tension of the water surface at the backlight side is reduced due to the temperature rise, and the marble is pushed to perform positive light convergence movement; when light is incident horizontally, the surface tension of the water surface is not changed, and the liquid marble is still. The movement speed of the device is increased along with the increase of the illumination intensity and the incident angle of the light source, the movement starting and stopping of the device are controlled according to the incident direction of the light, and the movement direction of the device presents the movement characteristic of positive phototaxis or negative phototaxis according to different light source irradiation areas. The light-operated magnetic liquid marble motion strategy can be applied to controlling the magnetic liquid marble to serve as a micro conveying system.
The invention has the beneficial effects that:
the invention provides a method for controlling the marble light of magnetic liquid, which has the characteristics of simple operation and high flexibility.
The starting and stopping of the light-taxiing movement of the magnetic liquid marble can be controlled by controlling the switch or the incident direction of incident light.
The invention can realize the switching of the positive phototaxis and the negative phototaxis of the magnetic liquid marble under the condition of not changing the composition and the type of a light source by controlling the light irradiation area; the movement speed can be controlled by the illumination intensity and the incident angle.
The invention can be used as a micro transportation system due to the light control characteristic of the magnetic liquid marble.
The invention adopts the illumination mode to drive the magnetic liquid marble, effectively solves the problems of liquid evaporation and pollution in the transportation process of the magnetic liquid marble under the action of a magnetic field, and provides an effective solution for the magnetic liquid marble as a liquid transportation carrier.
Drawings
FIG. 1: the light irradiates the lower half part of the magnetic liquid marble from the oblique upper part at an angle of 30 degrees, and the schematic drawing and the timing chart of the light movement are shown;
FIG. 2: the movement rates of the magnetic liquid marbles with different volumes;
FIG. 3: the movement rate of the magnetic liquid marble under the excitation of different light intensity and wavelength of 808 nm;
FIG. 4: the movement locus of the magnetic liquid marble under the excitation of different light intensity and wavelength of 365 nm;
FIG. 5: the light irradiates the top half of the magnetic liquid marble from the oblique upper direction at an angle of 30 degrees, and the schematic diagram and the timing chart of the light movement.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
The hydrophobic ferroferric oxide nano particles used in the examples are prepared in the following way:
FeCl with the molar ratio of 2:1 is added under the protection of nitrogen3·6H2O and FeCl2·4H2Dissolving O in deionized water at 60 deg.C under stirring, sequentially adding 25 vt% ammonia water and oleic acid, stirring for 15min, cooling to room temperature, performing magnetic separation, washing with deionized water and ethanol, and drying at room temperature.
Example 1
A magnetic liquid pearly luster-bouncing control strategy comprises the following steps: the hydrophobic ferroferric oxide nano particles are flatly laid in a culture dish, 15 mu L of water is dripped on the particles, the culture dish is slightly shaken to enable the liquid drops to freely roll, and the hydrophobic particles are automatically adsorbed on the surface of the liquid drops to form liquid marbles.
Placing the magnetic liquid marble on the water surface in a culture dish, using a light source with wavelength of 808nm and light spot size of 2mm, and setting output power to be 490mWmm-2The lower half part of the liquid marble is irradiated from the oblique upper part in the direction of forming an included angle of 30 degrees with the horizontal direction by manually operating the light source, and then the negative phototaxis movement of the magnetic liquid marble can be obtained. Fig. 1a is a schematic view of the lower half of a magnetic liquid marble illuminated by light. FIG. 1b is a time-series photograph of a typical negative taxiing motion of a magnetic liquid marble.
Example 2
The volume of the water drop in example 1 was adjusted to 5 μ L, 25 μ L, 35 μ L and 45 μ L, and the above procedure in example 1 was repeated, and the magnetic liquid marble exhibited negative phototropism, and the movement speed was as shown in fig. 2, which shows that the phototropism movement speed of the magnetic liquid marble is related to the volume of the magnetic liquid marble.
Example 3
The output power of the light source in example 1 was adjusted to 160mWmm-2,330mWmm-2,680mWmm-2And 830mWmm-2Repeating the above steps of embodiment 1, the magnetic liquid marble exhibits negative light-taxiing motion, and the motion speed increases with the increase of the optical power, as shown in fig. 3, which illustrates that the control of the light intensity can realize the control of the motion speed of the magnetic liquid marble.
Example 4
The light source in example 1 was adjusted to a wavelength of 365nm and an output of 11.5mWmm-2Repeating the above steps of example 1, the magnetic liquid marble exhibits negative phototaxis movement with a movement speed of 2mms-1. Fig. 4 is a graph showing the movement trace of the magnetic liquid marble under different power of ultraviolet light, which illustrates that the magnetic liquid marble can be driven by ultraviolet light.
Example 5
The light source irradiation area in the embodiment 1 is adjusted to irradiate the upper half part of the liquid marble from the oblique upper direction in the direction of 30 degrees from the horizontal angle, and the steps of the embodiment 1 are repeated, so that the magnetic liquid marble presents positive light-driving motion, mainly because the magnetic liquid marble has better light transmittance, when the light irradiates on the upper half part of the magnetic liquid marble, the magnetic liquid marble can penetrate through, and ferroferric oxide nano particles on the backlight side close to the water surface are heated, so that a surface tension gradient opposite to the negative light-driving motion is generated, and the positive light-driving motion is realized. The embodiment explains that the irradiation area of the light source can be controlled to control the movement direction of the magnetic liquid marble, and then the flexible switching of the positive phototaxis and the negative phototaxis of the magnetic liquid marble can be realized. Wherein, FIG. 5a is a schematic view of the magnetic liquid marble being illuminated on the upper half. FIG. 5b is a time series photograph of a typical positive light-trending motion of a magnetic liquid marble.
Example 6
The irradiation direction of the light source in example 5 is adjusted to be horizontally incident on the surface of the magnetic liquid marble, and the steps in example 5 are repeated, so that the magnetic liquid marble presents a static state, which indicates that the start and stop of the magnetic liquid marble can be controlled by controlling the incident direction of the light source.
EXAMPLE 7
The incident angle of the light source in the embodiment 5 is increased to 45 degrees, and the steps in the above embodiment 5 are repeated, so that the positive convergent movement of the magnetic liquid marble is obviously accelerated, which shows that the control of the incident angle of the light source can realize the control of the movement speed of the magnetic liquid marble.
The magnetic liquid marble, the light source, the illumination intensity, the illumination area, the direction, the angle and other parameters and interval values related to the magnetic liquid marble can realize the magnetic liquid marble, and the embodiments are not listed.
Claims (4)
1. A light control method of a magnetic liquid marble is characterized in that: the control of the motion state of the liquid marble is realized by regulating the incident direction of the light source; when the light source is obliquely incident from top to bottom, the magnetic liquid marble generates light-taxiing motion; the light source irradiates horizontally, and the magnetic liquid marble is static;
the magnetic liquid marble is formed by wrapping hydrophobic ferroferric oxide nano particles on the surface of a water drop; the hydrophobic ferroferric oxide nano particles are oleic acid modified ferroferric oxide nano spherical or quasi-spherical particles, the size is 10-15nm, the hydrophobic ferroferric oxide nano particles have superparamagnetism, and the static water contact angle is 140-155 degrees; the volume of the water drop is not more than 45 μ L.
2. The method for optically manipulating a magnetic fluid marble as recited in claim 1, wherein: the phototaxis is controlled by controlling the irradiation area of the light source; when light obliquely irradiates the upper half part of the liquid marble, positive light-convergence movement is realized; when light obliquely irradiates the lower half part of the magnetic liquid marble, negative phototaxis movement is realized.
3. The method for optically manipulating a magnetic fluid marble as recited in claim 1, wherein: the movement rate of the magnetic liquid marble is controlled by adjusting and controlling the intensity of the light source and the illumination angle.
4. The method for optically manipulating a magnetic fluid marble as recited in claim 1, wherein: the light source is a point light source with the wavelength of 365-808 nm.
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| CN110426325A (en) * | 2019-07-31 | 2019-11-08 | 武汉理工大学 | The method for carrying inert particle using micro-nano motor cluster |
| CN111298731B (en) * | 2020-03-05 | 2021-06-15 | 清华大学 | Light-driven liquid marble and preparation method and movement method thereof |
| CN114700000B (en) * | 2022-03-09 | 2024-03-29 | 华南理工大学 | Magnetic liquid marble and preparation method and application thereof |
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