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CN114324568A - Acoustic field-assisted preparation of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals - Google Patents

Acoustic field-assisted preparation of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals Download PDF

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CN114324568A
CN114324568A CN202111668768.2A CN202111668768A CN114324568A CN 114324568 A CN114324568 A CN 114324568A CN 202111668768 A CN202111668768 A CN 202111668768A CN 114324568 A CN114324568 A CN 114324568A
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guanine
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陶凯
章家豪
汪延成
梅德庆
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Zhejiang University ZJU
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Abstract

The invention discloses a sound field auxiliary preparation method of guanine peptide nucleic acid self-assembly nanosphere-based photonic crystals. Taking guanine peptide nucleic acid self-assembly nanospheres as a light reflection functional medium material, forming photonic crystals by adopting a compact hexagonal packing structure, and rapidly forming the photonic crystals by combining sound field control and micro-fluidic control; the morphology and the particle size of the self-assembled nanospheres are regulated and controlled by regulating the influence factors of self-assembly and the nucleic acid molecular structure of the guanine peptide, the arrangement is regulated and controlled by regulating and controlling sound field parameters, and finally the wavelength of the reflected light of the photonic crystal is regulated and controlled. The invention realizes the preparation of guanine peptide nucleic acid self-assembly nanosphere-based photonic crystals by utilizing a sound field, has good biocompatibility and excellent optical performance and dynamic response characteristic, and the photonic crystals can change lattice parameters under external excitation so as to realize the translation of reflected light wavelength and the change of visual color.

Description

鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备方法Acoustic field-assisted preparation of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals

技术领域technical field

本发明涉及一种生物有机光子晶体的制备方法,尤其涉及一种鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备。The invention relates to a preparation method of a biological organic photonic crystal, in particular to a sound field-assisted preparation of a guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal.

背景技术Background technique

光子晶体通过介电常数不同的介质进行有序规则的周期性堆叠,可以实现对入射光的选择性反射。与传统染料、荧光物质相比,光子晶体具有反射光可调控、反射光不易淬灭等特点,能够实现光学防伪、光学信息储存、信号传递等功能,在生物医学传感、智能纹身、人机交互、微应变检测、色度传感、光子芯片等领域存在广阔的应用前景。Photonic crystals are periodically stacked in order and regularity through media with different dielectric constants, which can achieve selective reflection of incident light. Compared with traditional dyes and fluorescent substances, photonic crystals have the characteristics of adjustable reflected light and difficult quenching of reflected light, which can realize optical anti-counterfeiting, optical information storage, signal transmission and other functions. There are broad application prospects in the fields of interaction, micro-strain detection, colorimetric sensing, and photonic chips.

现阶段的光子晶体大多采用无机氧化物(如二氧化硅、二氧化钛等)、高分子聚合物(如聚苯乙烯、聚氨酯等)为功能介质材料;制备工艺通常采用激光直写刻蚀、三维打印、模板印刷和胶体自组装等。然而,尽管聚合物光子晶体与无机氧化物制备的光子晶体具备较高的物理化学稳定性与较窄的反射带宽,能够应用于光学信息表达与光学防伪等领域;但随着光子探针与生物医学传感的发展,具有良好生物相容性的光子晶体将成为这一领域发展的必然趋势。而较弱的生物相容性导致传统光子晶体存在生物排异反应,且阵列形状不易操控、制备周期冗长、制备工艺复杂,难以适应新一代生物相容性光子晶体的发展要求。At present, most photonic crystals use inorganic oxides (such as silicon dioxide, titanium dioxide, etc.) and high molecular polymers (such as polystyrene, polyurethane, etc.) as functional medium materials; the preparation process usually adopts laser direct writing etching, three-dimensional printing, etc. , stencil printing and colloidal self-assembly. However, although photonic crystals prepared from polymer photonic crystals and inorganic oxides have high physicochemical stability and narrow reflection bandwidth, they can be applied in the fields of optical information expression and optical anti-counterfeiting. With the development of medical sensing, photonic crystals with good biocompatibility will become an inevitable trend in the development of this field. The weak biocompatibility leads to biological rejection of traditional photonic crystals, and the array shape is not easy to control, the preparation cycle is long, and the preparation process is complicated, which is difficult to meet the development requirements of a new generation of biocompatible photonic crystals.

发明内容SUMMARY OF THE INVENTION

基于上述技术背景,结合碱基与肽分子固有的生物相容性、自组装体形貌易于调控以及声场辅助可调控阵列形貌的特点,本发明提出了一种鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备方法。Based on the above technical background, combined with the inherent biocompatibility of base and peptide molecules, the easy regulation of self-assembly morphology, and the sound field-assisted regulation of the array morphology, the present invention proposes a guanine peptide nucleic acid self-assembled nanosphere A sound field-assisted preparation method of a base photonic crystal.

本发明实现利用声场对鸟嘌呤肽核酸自组装纳米球基光子晶体的制备,在兼具良好生物相容性的同时具有优良光学性能和动态响应特性。The invention realizes the preparation of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal by using the sound field, and has both good biocompatibility and excellent optical performance and dynamic response characteristics.

本发明解决其技术问题所采用的技术方案如下:The technical scheme adopted by the present invention to solve its technical problems is as follows:

方法是由鸟嘌呤肽核酸自组装纳米球采用体声波声场辅助方式进行制备,所述的鸟嘌呤肽核酸自组装纳米球是由鸟嘌呤肽核酸自组装而成。The method is to prepare guanine peptide nucleic acid self-assembled nanospheres by means of bulk acoustic wave sound field assistance. The guanine peptide nucleic acid self-assembled nanospheres are self-assembled from guanine peptide nucleic acid.

所述方法采用体声波换能器进行体声波声场辅助方式的形成。The method adopts the bulk acoustic wave transducer to form the auxiliary mode of the bulk acoustic wave sound field.

所述的鸟嘌呤肽核酸自组装纳米球基光子晶体使用平均分子量为200的聚乙二醇二丙烯酸酯(PEGDA200)进行封装。The guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal is encapsulated by polyethylene glycol diacrylate (PEGDA200) with an average molecular weight of 200.

具体采用以下方法过程制备:Specifically prepared by the following method:

1)选择鸟嘌呤肽核酸粉末溶解于超纯水,然后在25℃恒温、80%恒湿度静置36小时,制备形成鸟嘌呤肽核酸自组装纳米球悬浊液;1) Select the guanine peptide nucleic acid powder to dissolve in ultrapure water, and then stand at a constant temperature of 25°C and a constant humidity of 80% for 36 hours to prepare a suspension of guanine peptide nucleic acid self-assembled nanospheres;

2)基底预先布置在体声波换能器内的底部,将悬浊液泵入体声波换能器的腔室,打开体声波换能器的信号发生器调节激励频率至腔室内形成稳定一致的驻波场;2) The substrate is pre-arranged at the bottom of the bulk acoustic wave transducer, the suspension is pumped into the chamber of the bulk acoustic wave transducer, and the signal generator of the bulk acoustic wave transducer is turned on to adjust the excitation frequency to form a stable and consistent chamber. standing wave field;

3)静置待鸟嘌呤肽核酸自组装纳米球在体声波驻波场中形成稳定排布后抽去腔室内多余的悬浊液,使鸟嘌呤肽核酸自组装纳米球缓慢沉积在基底表面,制成附有鸟嘌呤肽核酸自组装纳米球基光子晶体的基底,获得鸟嘌呤肽核酸自组装纳米球基光子晶体。3) After standing until the guanine peptide nucleic acid self-assembled nanospheres form a stable arrangement in the standing wave field of bulk acoustic waves, the excess suspension in the chamber is removed, so that the guanine peptide nucleic acid self-assembled nanospheres are slowly deposited on the surface of the substrate, A substrate with guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals is prepared, and a guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal is obtained.

本发明以鸟嘌呤肽核酸自组装纳米球作为功能介质材料,使得光子晶体产物在兼具优良光学特性基础上具有固有的生物相容性及其他指定的生物活性功能。The present invention uses guanine peptide nucleic acid self-assembled nanospheres as functional medium materials, so that the photonic crystal product has inherent biocompatibility and other designated bioactive functions on the basis of excellent optical properties.

所述的鸟嘌呤肽核酸自组装纳米球基光子晶体采用玻璃片、石英片、硅片或柔性基底作为基底,所述的柔性基底为聚二甲基硅氧烷薄膜等。The guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal adopts a glass sheet, a quartz sheet, a silicon wafer or a flexible substrate as a substrate, and the flexible substrate is a polydimethylsiloxane film or the like.

通过对鸟嘌呤肽核酸分子结构的调整实现鸟嘌呤肽核酸自组装纳米球的形貌调控(粒径、空心/实心、表面光滑或粗糙等)。The morphology control (particle size, hollow/solid, smooth or rough surface, etc.) of guanine peptide nucleic acid self-assembled nanospheres is realized by adjusting the molecular structure of guanine peptide nucleic acid.

具体地,specifically,

通过调整鸟嘌呤肽核酸分子结构中亲疏水基团的长度和种类,调整鸟嘌呤肽核酸自组装纳米球中的空心/实心程度;Adjust the degree of hollow/solid in the self-assembled nanospheres of guanine peptide nucleic acid by adjusting the length and type of hydrophilic and hydrophobic groups in the molecular structure of guanine peptide nucleic acid;

通过调整鸟嘌呤肽核酸分子结构中亲疏水基团的个数和种类,调整鸟嘌呤肽核酸自组装纳米球中的表面光滑/粗糙程度。By adjusting the number and types of hydrophilic and hydrophobic groups in the molecular structure of guanine peptide nucleic acid, the degree of surface smoothness/roughness in the self-assembled nanospheres of guanine peptide nucleic acid can be adjusted.

通过对温度的调整实现对鸟嘌呤肽核酸自组装纳米球的粒径调控,The particle size of guanine peptide nucleic acid self-assembled nanospheres can be controlled by adjusting the temperature.

通过调控声场参数实现对鸟嘌呤肽核酸自组装纳米球基光子晶体的排布调控;The arrangement of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals can be controlled by adjusting the sound field parameters;

结合粒径调控和排布调控实现对鸟嘌呤肽核酸自组装纳米球基光子晶体反射光波长的调控。Combined with particle size regulation and arrangement regulation, the regulation of the reflected light wavelength of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal is realized.

所述的鸟嘌呤肽核酸是用鸟嘌呤作为侧链基团、酰胺键作为分子骨架的类氨基酸结构,用于人工合成鸟嘌呤肽核酸的基团为二苯甲氧羰基(Bhoc)、9-芴甲氧羰基(Fmoc)、甘氨酸、氨乙基、乙酰基与鸟嘌呤基团。The guanine peptide nucleic acid is an amino acid-like structure with guanine as a side chain group and an amide bond as a molecular skeleton, and the groups used for artificial synthesis of guanine peptide nucleic acid are diphenylmethoxycarbonyl (Bhoc), 9- Fluorene methoxycarbonyl (Fmoc), glycine, aminoethyl, acetyl and guanine groups.

所述的鸟嘌呤肽核酸具体分子式为Bhoc-G-(Bhoc)-aeg-OH、Bhoc-G、Fmoc-G、Fmoc-G-(Fmoc)-aeg-OH、G-(Bhoc)-aeg-OH、Fmoc-G-aeg-OH、Fmoc-G-(Bhoc)-aeg-OH。The specific molecular formula of the guanine peptide nucleic acid is Bhoc-G-(Bhoc)-aeg-OH, Bhoc-G, Fmoc-G, Fmoc-G-(Fmoc)-aeg-OH, G-(Bhoc)-aeg- OH, Fmoc-G-aeg-OH, Fmoc-G-(Bhoc)-aeg-OH.

所述的鸟嘌呤肽核酸自组装纳米球在体声波换能器内采用体声波驻波场辅助排列,排布形成的形状为一维条纹、二维点阵形状或二维曲线形状,二维曲线形状具体如波浪型形状。The guanine peptide nucleic acid self-assembled nanospheres are arranged in the bulk acoustic wave transducer with the aid of the standing wave field of bulk acoustic waves, and the shape of the arrangement is a one-dimensional stripe, a two-dimensional lattice shape or a two-dimensional curve shape, and a two-dimensional shape. The curvilinear shape is, in particular, a wavy shape.

形成二维点阵形状排布的体声波换能器主要由三维打印腔室、两对垂直分布的压电陶瓷和由注射泵控制的微流道构成。The bulk acoustic wave transducer formed in a two-dimensional lattice shape is mainly composed of a three-dimensional printing chamber, two pairs of vertically distributed piezoelectric ceramics and a micro-channel controlled by a syringe pump.

形成一维条纹形状排布的体声波换能器主要由三维打印腔室、一对垂直分布的压电陶瓷和由注射泵控制的微流道构成。The BAW transducers arranged in the shape of one-dimensional stripes are mainly composed of a three-dimensional printing chamber, a pair of vertically distributed piezoelectric ceramics and a microfluidic channel controlled by a syringe pump.

所述的体声波换能器在鸟嘌呤肽核酸自组装纳米球悬浊液中形成可调频体声波驻波场。The bulk acoustic wave transducer forms a frequency-tunable bulk acoustic wave standing wave field in the guanine peptide nucleic acid self-assembled nanosphere suspension.

所述的鸟嘌呤肽核酸自组装纳米球基光子晶体使用体声波声场辅助排布后点阵间距大于等于20微米,条纹阵列间距大于等于20微米。The guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal is arranged with the aid of a bulk acoustic wave sound field, and the lattice spacing is greater than or equal to 20 microns, and the fringe array spacing is greater than or equal to 20 microns.

所述的鸟嘌呤肽核酸自组装纳米球基光子晶体进一步采用以下过程进行处理,完成完整的封装制备:The guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal is further processed by the following process to complete the complete encapsulation preparation:

1)称取5毫升平均分子量为200的聚乙二醇二丙烯酸酯,加入占据聚乙二醇二丙烯酸酯质量分数0.8%比例的混合光引发剂TPO-L,形成混合物;1) Weighing 5 milliliters of polyethylene glycol diacrylate with an average molecular weight of 200, adding a mixed photoinitiator TPO-L that accounts for 0.8% of the polyethylene glycol diacrylate mass fraction to form a mixture;

2)将混合物使用行星搅拌仪进行充分混合并脱泡,制备形成光敏预聚物;2) fully mixing and defoaming the mixture using a planetary stirrer to prepare a photosensitive prepolymer;

3)将附有鸟嘌呤肽核酸自组装纳米球基光子晶体的基底置于旋涂仪上,将光敏预聚物均匀滴在不具有基底的鸟嘌呤肽核酸自组装纳米球基光子晶体表面,并使用旋涂法在鸟嘌呤肽核酸自组装纳米球基光子晶体表面形成均匀薄膜,使用紫外光固化,完成鸟嘌呤肽核酸自组装纳米球基光子晶体的封装。3) placing the substrate with the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal on a spin coater, and evenly dropping the photosensitive prepolymer on the surface of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal without the substrate, A uniform thin film is formed on the surface of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal by a spin coating method, and UV light curing is used to complete the encapsulation of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal.

所述步骤3)中,使用波长405纳米紫外光固化20秒。In the step 3), use ultraviolet light with a wavelength of 405 nm to cure for 20 seconds.

所述的鸟嘌呤肽核酸自组装纳米球基光子晶体封装后高度小于5毫米,直径大于20毫米。The self-assembled nanosphere-based photonic crystal of guanine peptide nucleic acid has a height of less than 5 mm and a diameter of more than 20 mm after being packaged.

所述的鸟嘌呤肽核酸自组装纳米球基光子晶体是由鸟嘌呤肽核酸自组装纳米球采用体声波声场辅助方式进行处理制备而成。The guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal is prepared by processing the guanine peptide nucleic acid self-assembled nanospheres with the aid of bulk acoustic wave sound field.

本发明鸟嘌呤肽核酸自组装纳米球作为光反射功能介质材料,可采用紧密六方堆积结构形成光子晶体,采用二氧化硅片、聚二甲基硅氧烷薄膜、石英片等作为基底,使用聚乙二醇二丙烯酸酯进行封装,采用声场操控与微流控结合的方法进行光子晶体的快速成型。通过对自组装环境条件和分子结构等影响因素的调整实现对鸟嘌呤肽核酸自组装纳米球的形貌与粒径调控,通过调控声场参数实现对鸟嘌呤肽核酸自组装纳米球基光子晶体的排布调控;从而实现对鸟嘌呤肽核酸自组装纳米球基光子晶体反射光波长的调控。The guanine peptide nucleic acid self-assembled nanospheres of the present invention can be used as light-reflecting functional medium materials, and photonic crystals can be formed by adopting a close hexagonal stacking structure, and silicon dioxide sheets, polydimethylsiloxane films, quartz sheets, etc. Ethylene glycol diacrylate is used for encapsulation, and the rapid prototyping of photonic crystals is carried out by the combination of sound field manipulation and microfluidics. The morphology and particle size of guanine peptide nucleic acid self-assembled nanospheres can be regulated by adjusting the environmental conditions and molecular structure of self-assembly. Arrangement regulation; thereby realizing the regulation of the reflected light wavelength of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal.

本发明的光子晶体可以在外界激励下(如温度、弯曲、拉伸、磁场、电场、pH、湿度)改变晶格参数进而实现反射光波长的平移和视觉色彩的改变。The photonic crystal of the present invention can change lattice parameters under external excitation (such as temperature, bending, stretching, magnetic field, electric field, pH, humidity), thereby realizing the translation of reflected light wavelength and the change of visual color.

本发明光子晶体采用鸟嘌呤肽核酸自组装纳米球作为功能介质材料,利用光的衍射原理,通过将鸟嘌呤肽核酸自组装纳米球进行一维或二维地规则有序堆叠,形成能够对不同角度入射光进行选择性反射的鸟嘌呤肽核酸自组装纳米球基光子晶体,同时使用声场辅助的手段进行鸟嘌呤肽核酸自组装纳米球基光子晶体的制备。The photonic crystal of the present invention adopts guanine peptide nucleic acid self-assembled nanospheres as functional medium materials, and utilizes the diffraction principle of light to form a one-dimensional or two-dimensional regular and orderly stacking of guanine peptide nucleic acid self-assembled nanospheres to form different Guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals with selective reflection of angle incident light, and the preparation of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals by means of sound field assistance.

本发明采用声场辅助的手段进行鸟嘌呤肽核酸自组装纳米球基光子晶体制备,通过对光子晶体基底亲疏水性、声场频率和电压幅值与微流控抽水速度的调整,可以实现对鸟嘌呤肽核酸自组装纳米球阵列形貌的调控。The invention adopts the means assisted by the sound field to prepare the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal. Modulation of the morphology of nucleic acid self-assembled nanosphere arrays.

本发明的鸟嘌呤肽核酸自组装纳米球基光子晶体可以使用分子修饰与自组装条件控制的方法进行纳米球粒径与形貌调控,进而实现对鸟嘌呤肽核酸纳米球基光子晶体的光学特性调控。The guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal of the present invention can use the methods of molecular modification and self-assembly condition control to control the size and shape of the nanospheres, thereby realizing the optical properties of the guanine peptide nucleic acid nanosphere-based photonic crystal. regulation.

本发明具有的有益效果是:The beneficial effects that the present invention has are:

(1)通过对鸟嘌呤肽核酸的分子结构进行设计修饰,实现对鸟嘌呤肽核酸自组装纳米球形貌(空心/实心、表面光滑或粗糙等)的调控;(1) By designing and modifying the molecular structure of guanine peptide nucleic acid, the morphology (hollow/solid, smooth or rough surface, etc.) of guanine peptide nucleic acid self-assembled nanospheres can be controlled;

(2)通过对自组装条件(如温度等)控制,实现鸟嘌呤肽核酸自组装纳米球基光子晶体内鸟嘌呤肽核酸自组装纳米球的粒径调控,从而实现光子晶体光学性能的调控;(2) By controlling the self-assembly conditions (such as temperature, etc.), the particle size regulation of the guanine peptide nucleic acid self-assembled nanospheres in the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal is realized, so as to realize the regulation of the optical properties of the photonic crystal;

(3)通过将鸟嘌呤肽核酸自组装纳米球进行有序堆叠与排布,实现对入射光的选择性反射,同时保持良好的生物相容性;(3) By orderly stacking and arranging guanine peptide nucleic acid self-assembled nanospheres, selective reflection of incident light is achieved while maintaining good biocompatibility;

(4)通过对鸟嘌呤肽核酸自组装纳米球基光子晶体基底亲疏水性、声场频率和电压幅值与微流控抽水速度的调整,可以实现对鸟嘌呤肽核酸自组装纳米球基光子晶体的形貌结构调控。(4) By adjusting the hydrophilicity and hydrophobicity of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal substrate, the frequency and voltage amplitude of the sound field, and the microfluidic pumping speed, the self-assembled nanosphere-based photonic crystal of guanine peptide nucleic acid can be realized. Morphology and structure control.

附图说明Description of drawings

图1是鸟嘌呤肽核酸自组装纳米球悬浊液制备流程示意图;Fig. 1 is a schematic diagram of the preparation process of guanine peptide nucleic acid self-assembled nanosphere suspension;

图2是表面粗糙实心鸟嘌呤肽核酸自组装纳米球扫描电子显微镜图像;Fig. 2 is the scanning electron microscope image of surface rough solid guanine peptide nucleic acid self-assembled nanospheres;

图3是表面光滑实心鸟嘌呤肽核酸自组装纳米球扫描电子显微镜图像;Figure 3 is a scanning electron microscope image of a solid guanine peptide nucleic acid self-assembled nanosphere with smooth surface;

图4是表面光滑空心鸟嘌呤肽核酸自组装纳米球扫描电子显微镜图像;Figure 4 is a scanning electron microscope image of a hollow guanine peptide nucleic acid self-assembled nanosphere with smooth surface;

图5是鸟嘌呤肽核酸自组装纳米球结构示意图;Figure 5 is a schematic diagram of the structure of guanine peptide nucleic acid self-assembled nanospheres;

图6是4摄氏度下制备得鸟嘌呤肽核酸自组装纳米球粒径统计图;Fig. 6 is the particle size statistics diagram of guanine peptide nucleic acid self-assembled nanospheres prepared at 4 degrees Celsius;

图7是25摄氏度下制备得鸟嘌呤肽核酸自组装纳米球粒径统计图;Fig. 7 is the particle size statistics diagram of guanine peptide nucleic acid self-assembled nanospheres prepared at 25 degrees Celsius;

图8是75摄氏度下制备得鸟嘌呤肽核酸自组装纳米球粒径统计图;Fig. 8 is the particle size statistics diagram of guanine peptide nucleic acid self-assembled nanospheres prepared at 75 degrees Celsius;

图9是不同抽水速度下鸟嘌呤肽核酸自组装纳米球基光子晶体条纹排布形貌的共聚焦显微镜图;Figure 9 is a confocal microscope image of the fringe arrangement of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals at different pumping speeds;

图10是不同自组装温度下制备的鸟嘌呤肽核酸纳米球基光子晶体实物图;Fig. 10 is the actual picture of guanine peptide nucleic acid nanosphere-based photonic crystals prepared under different self-assembly temperatures;

图11是鸟嘌呤肽核酸自组装纳米球基光子晶体透射光光谱图;Fig. 11 is the transmitted light spectrum of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal;

图12是鸟嘌呤肽核酸自组装纳米球基光子晶体透射峰值-光子晶体弯曲角度变化关系图。Figure 12 is a graph showing the relationship between the transmission peak value of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal and the bending angle of the photonic crystal.

具体实施方式Detailed ways

下面结合附图和实施例对本发明作进一步说明,但本发明的实施方式不限于此。The present invention will be further described below with reference to the accompanying drawings and examples, but the embodiments of the present invention are not limited thereto.

本发明的实施例及其实施过程如下:The embodiment of the present invention and its implementation process are as follows:

具体实施例1Specific Example 1

分别取4毫克鸟嘌呤肽核酸于烧杯中,按2毫克/毫升比例加入超纯水并使用水浴加热至90摄氏度以上,配合磁力搅拌配置鸟嘌呤肽核酸溶液。将配置的溶液于25摄氏度、80%恒湿度下静置36小时,使鸟嘌呤肽核酸自组装完全。由鸟嘌呤肽核酸自组装得到表面粗糙实心鸟嘌呤肽核酸自组装纳米球结构如图2所示,自组装得到表面光滑实心鸟嘌呤肽核酸自组装纳米球结构如图3所示,自组装得到表面光滑空心鸟嘌呤肽核酸自组装纳米球如图4所示。Take 4 mg of guanine peptide nucleic acid in a beaker, add ultrapure water at a ratio of 2 mg/ml, heat it to above 90 degrees Celsius in a water bath, and prepare a guanine peptide nucleic acid solution with magnetic stirring. The prepared solution was allowed to stand at 25 degrees Celsius and 80% constant humidity for 36 hours to complete the self-assembly of the guanine peptide nucleic acid. The self-assembled structure of solid guanine peptide nucleic acid self-assembled nanospheres obtained by self-assembly of guanine peptide nucleic acid is shown in Figure 2, and the self-assembled structure of self-assembled solid guanine peptide nucleic acid nanospheres is shown in Figure 3. The hollow guanine peptide nucleic acid self-assembled nanospheres with smooth surface are shown in Figure 4.

由本实施例可见,鸟嘌呤肽核酸自组装纳米球粒径与表面形貌(如空心/实心、表面光滑或粗糙等)可以通过调整鸟嘌呤肽核酸分子结构中的亲疏水基团个数与种类等进行调控。It can be seen from this example that the particle size and surface morphology (such as hollow/solid, smooth or rough surface, etc.) of guanine peptide nucleic acid self-assembled nanospheres can be adjusted by adjusting the number and type of hydrophilic and hydrophobic groups in the molecular structure of guanine peptide nucleic acid. etc. to control.

具体实施例2Specific embodiment 2

如图1所示,取12毫克鸟嘌呤肽核酸(具体分子式为Fmoc-G-(Bhoc)-aeg-OH)于烧杯中,按2毫克/毫升比例加入超纯水并使用水浴加热至90摄氏度以上,配合磁力搅拌配置鸟嘌呤肽核酸溶液。将配制的溶液三等分,分别在80%恒湿度下于4摄氏度、25摄氏度和75摄氏度下静置36小时,使鸟嘌呤肽核酸自组装完全,得到不同粒径空心鸟嘌呤肽核酸自组装纳米球。鸟嘌呤肽核酸自组装纳米球形貌如图4所示,鸟嘌呤肽核酸自组装纳米球结构示意图如图5所示,鸟嘌呤肽核酸自组装纳米球粒径统计结果如图6-8所示。As shown in Figure 1, take 12 mg of guanine peptide nucleic acid (specific molecular formula is Fmoc-G-(Bhoc)-aeg-OH) in a beaker, add ultrapure water at a ratio of 2 mg/ml and heat it to 90 degrees Celsius using a water bath In the above, the guanine peptide nucleic acid solution was prepared with magnetic stirring. Divide the prepared solution into three equal parts and let stand for 36 hours at 4 degrees Celsius, 25 degrees Celsius and 75 degrees Celsius under 80% constant humidity, so that the self-assembly of guanine peptide nucleic acid is complete, and the self-assembly of hollow guanine peptide nucleic acid with different particle sizes is obtained. Nanospheres. The appearance of guanine peptide nucleic acid self-assembled nanospheres is shown in Figure 4, the structure of guanine peptide nucleic acid self-assembled nanospheres is shown in Figure 5, and the particle size statistics of guanine peptide nucleic acid self-assembled nanospheres are shown in Figure 6-8 Show.

由本实施例可见,鸟嘌呤肽核酸自组装纳米球粒径可通过调整鸟嘌呤肽核酸的自组装环境(如温度等)进行调整。It can be seen from this example that the particle size of the guanine peptide nucleic acid self-assembled nanospheres can be adjusted by adjusting the self-assembly environment (such as temperature, etc.) of the guanine peptide nucleic acid.

具体实施例3Specific embodiment 3

(1)如图1所示,取12毫克鸟嘌呤肽核酸(具体分子式为Fmoc-G-(Bhoc)-aeg-OH)于烧杯中,按2毫克/毫升的比例加入超纯水并使用水浴加热至90摄氏度以上,配合磁力搅拌配置鸟嘌呤肽核酸溶液。将配制的溶液于25摄氏度、80%恒湿度下静置36小时,使鸟嘌呤肽核酸自组装完全,得到鸟嘌呤肽核酸自组装纳米球悬浊液。(1) As shown in Figure 1, take 12 mg of guanine peptide nucleic acid (specific molecular formula is Fmoc-G-(Bhoc)-aeg-OH) in a beaker, add ultrapure water at a rate of 2 mg/ml and use a water bath Heat to above 90 degrees Celsius, and prepare a guanine peptide nucleic acid solution with magnetic stirring. The prepared solution was allowed to stand at 25 degrees Celsius and a constant humidity of 80% for 36 hours, so that the self-assembly of guanine peptide nucleic acid was completed, and a suspension of guanine peptide nucleic acid self-assembled nanospheres was obtained.

(2)具体实施的一维和二维体声波换能器包括三维打印腔室、压电陶瓷与微流道部分。以25摄氏度下自组装制备的鸟嘌呤肽核酸纳米球进行一维排布的光子晶体为例,在基底上布置贴有压电陶瓷的三维打印腔室,并使用注射泵将配制的鸟嘌呤肽核酸自组装纳米球悬浊液通过微流道管道从悬浊液流入口泵入开放腔室。(2) The concretely implemented one-dimensional and two-dimensional bulk acoustic wave transducers include three-dimensional printing chambers, piezoelectric ceramics and micro-channel parts. Taking the photonic crystal with one-dimensional arrangement of guanine peptide nucleic acid nanospheres prepared by self-assembly at 25 degrees Celsius as an example, a three-dimensional printing chamber with piezoelectric ceramics is arranged on the substrate, and the prepared guanine peptide is injected by a syringe pump. The nucleic acid self-assembled nanosphere suspension is pumped into the open chamber through the microfluidic pipeline from the suspension inflow inlet.

(3)将自组装纳米球悬浊液完全泵入腔室后,启动信号发生器并输出频率为f1的电信号,压电陶瓷在腔室内产生体声波驻波场。鸟嘌呤肽核酸自组装纳米球悬浊液在流经体声波驻波场时,受到强度可控的声辐射力,在腔室宽度方向上运动不同的距离并在体声波驻波场波节位置完成排布。待鸟嘌呤肽核酸自组装纳米球完全排布后使用注射泵沿着悬浊液流出口以10-100微升/分钟速度抽去腔室内多余液体,使鸟嘌呤肽核酸自组装纳米球可以均匀沉积在基底表层,随后移除体声波换能器,形成一维排布条纹状鸟嘌呤肽核酸自组装纳米基光子晶体。不同抽水速度下鸟嘌呤肽核酸自组装纳米球基光子晶体形貌如图9所示。(3) After the self-assembled nanosphere suspension is completely pumped into the chamber, the signal generator is activated and an electrical signal with a frequency of f1 is output, and the piezoelectric ceramic generates a standing wave field of bulk acoustic waves in the chamber. When the suspension of guanine peptide nucleic acid self-assembled nanospheres flows through the standing wave field of bulk acoustic wave, it is subjected to the acoustic radiation force of controllable intensity, moves different distances in the width direction of the chamber, and reaches the node position of the standing wave field of bulk acoustic wave. Complete the arrangement. After the guanine peptide nucleic acid self-assembled nanospheres are completely arranged, use a syringe pump to remove the excess liquid in the chamber at a speed of 10-100 μl/min along the outflow port of the suspension, so that the guanine peptide nucleic acid self-assembled nanospheres can be uniform. It is deposited on the surface of the substrate, and then the bulk acoustic wave transducer is removed to form a one-dimensionally arranged striped guanine peptide nucleic acid self-assembled nano-based photonic crystal. Figure 9 shows the morphologies of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals at different pumping speeds.

(4)取5毫升平均分子质量为200的聚乙二醇二丙烯酸酯(PEGDA200),加入占据聚乙二醇二丙烯酸酯质量分数0.8%的光引发剂(TPO-L),配制用于鸟嘌呤肽核酸自组装纳米球基光子晶体封装的光敏预聚物。(4) Take 5 milliliters of polyethylene glycol diacrylate (PEGDA200) with an average molecular mass of 200, add a photoinitiator (TPO-L) occupying 0.8% of the mass fraction of polyethylene glycol diacrylate, and prepare for the Photosensitive prepolymers encapsulated by purine peptide nucleic acid self-assembled nanosphere-based photonic crystals.

(5)使用旋涂法将光敏预聚物均匀涂覆在鸟嘌呤肽核酸自组装纳米球基光子晶体表层,之后使用405纳米紫外光对光敏预聚物进行固化,完成鸟嘌呤肽核酸纳米球基光子晶体的封装。(5) The photosensitive prepolymer is uniformly coated on the surface layer of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal by the spin coating method, and then the photosensitive prepolymer is cured with 405 nm ultraviolet light to complete the guanine peptide nucleic acid nanosphere Encapsulation of base photonic crystals.

不同粒径鸟嘌呤肽核酸纳米球制备而成鸟嘌呤肽核酸自组装纳米球基光子晶体实物图如图10所示。Figure 10 shows the actual picture of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals prepared from guanine peptide nucleic acid nanospheres with different particle sizes.

(6)对制备的鸟嘌呤肽核酸自组装纳米球基光子晶体进行光学性能表征。(6) The optical properties of the prepared guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals were characterized.

不同入射角度下可见光区透射光谱如图11所示,透射峰值与鸟嘌呤肽核酸自组装纳米球基光子晶体弯曲角度变化关系与理论值曲线如图12所示。Figure 11 shows the transmission spectrum in the visible light region at different incident angles, and the relationship between the transmission peak and the bending angle of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal and the theoretical value curve are shown in Figure 12.

由本实施例可见,本发明实现了鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备,操作简便、工艺条件温和、工艺装置简单,且制备的鸟嘌呤肽核酸自组装纳米球基光子晶体具有优良的生物相容性与光学特性。It can be seen from this embodiment that the present invention realizes the sound field-assisted preparation of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals, the operation is simple, the process conditions are mild, the process equipment is simple, and the prepared guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals Has excellent biocompatibility and optical properties.

Claims (9)

1.一种鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备方法,其特征在于:方法是由鸟嘌呤肽核酸自组装纳米球采用体声波声场辅助方式进行制备,所述的鸟嘌呤肽核酸自组装纳米球是由鸟嘌呤肽核酸自组装而成。1. a sound field auxiliary preparation method of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal, is characterized in that: the method is to prepare by adopting bulk acoustic wave sound field auxiliary mode by guanine peptide nucleic acid self-assembled nanosphere, and described guanine Peptide nucleic acid self-assembled nanospheres are self-assembled from guanine peptide nucleic acid. 2.根据权利要求1所述的一种鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备方法,其特征在于:所述方法采用体声波换能器进行体声波声场辅助方式的形成。2 . The sound field-assisted preparation method of a guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal according to claim 1 , wherein the method adopts a bulk acoustic wave transducer to form the bulk acoustic wave sound field-assisted mode. 3 . 3.根据权利要求1所述的一种鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备方法,其特征在于:所述的鸟嘌呤肽核酸自组装纳米球基光子晶体使用平均分子量为200的聚乙二醇二丙烯酸酯进行封装。3. the sound field auxiliary preparation method of a kind of guanine peptide nucleic acid self-assembled nano-sphere-based photonic crystal according to claim 1, is characterized in that: described guanine peptide nucleic acid self-assembled nano-sphere-based photonic crystal uses an average molecular weight of 200 polyethylene glycol diacrylate for encapsulation. 4.根据权利要求1所述的一种鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备方法,其特征在于:具体采用以下方法过程制备:4. the sound field auxiliary preparation method of a kind of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal according to claim 1, is characterized in that: specifically adopt following method process preparation: 1)选择鸟嘌呤肽核酸粉末溶解于超纯水,然后在25℃恒温、80%恒湿度静置36小时,制备形成鸟嘌呤肽核酸自组装纳米球悬浊液;1) Select the guanine peptide nucleic acid powder to dissolve in ultrapure water, and then stand at a constant temperature of 25°C and a constant humidity of 80% for 36 hours to prepare a suspension of guanine peptide nucleic acid self-assembled nanospheres; 2)基底预先布置在体声波换能器内的底部,将悬浊液泵入体声波换能器的腔室,打开体声波换能器的信号发生器调节激励频率至腔室内形成驻波场;2) The substrate is pre-arranged at the bottom of the BAW transducer, the suspension is pumped into the chamber of the BAW transducer, and the signal generator of the BAW transducer is turned on to adjust the excitation frequency to form a standing wave field in the chamber ; 3)静置待鸟嘌呤肽核酸自组装纳米球在体声波驻波场中形成稳定排布后抽去腔室内多余的悬浊液,使鸟嘌呤肽核酸自组装纳米球沉积在基底表面,获得鸟嘌呤肽核酸自组装纳米球基光子晶体。3) After standing until the guanine peptide nucleic acid self-assembled nanospheres form a stable arrangement in the standing wave field of bulk acoustic waves, the excess suspension in the chamber is removed, so that the guanine peptide nucleic acid self-assembled nanospheres are deposited on the surface of the substrate to obtain Guanine peptide nucleic acid self-assembled nanosphere-based photonic crystals. 5.根据权利要求1或者4所述的一种鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备方法,其特征在于:所述的鸟嘌呤肽核酸自组装纳米球基光子晶体采用玻璃片、石英片、硅片或柔性基底作为基底。5. the sound field auxiliary preparation method of a kind of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal according to claim 1 or 4, it is characterized in that: described guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal adopts glass wafers, quartz wafers, silicon wafers or flexible substrates as substrates. 6.根据权利要求4所述的一种鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备方法,其特征在于:通过对鸟嘌呤肽核酸分子结构的调整实现鸟嘌呤肽核酸自组装纳米球的形貌调控。6. The sound field-assisted preparation method of a kind of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal according to claim 4, it is characterized in that: realize guanine peptide nucleic acid self-assembly nanometer by adjusting the molecular structure of guanine peptide nucleic acid Ball shape control. 7.根据权利要求1所述的一种鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备方法,其特征在于:所述的鸟嘌呤肽核酸是用鸟嘌呤作为侧链基团、酰胺键作为分子骨架的类氨基酸结构,用于人工合成鸟嘌呤肽核酸的基团为二苯甲氧羰基(Bhoc)、9-芴甲氧羰基(Fmoc)、甘氨酸、氨乙基、乙酰基与鸟嘌呤基团。7. the sound field assistant preparation method of a kind of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal according to claim 1, is characterized in that: described guanine peptide nucleic acid uses guanine as side chain group, amide The amino acid-like structure with the bond as the molecular backbone, the groups used for the artificial synthesis of guanine peptide nucleic acid are diphenylmethoxycarbonyl (Bhoc), 9-fluorenylmethoxycarbonyl (Fmoc), glycine, aminoethyl, acetyl and guanine purine group. 8.根据权利要求1或2所述的一种鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备方法,其特征在于:所述的鸟嘌呤肽核酸自组装纳米球在体声波换能器内采用体声波驻波场辅助排列,排布形成的形状为一维条纹、二维点阵形状或二维曲线形状。8. the acoustic field assistant preparation method of a kind of guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal according to claim 1 and 2, it is characterized in that: described guanine peptide nucleic acid self-assembled nanosphere is in the body acoustic wave transduction The device adopts the auxiliary arrangement of bulk acoustic wave standing wave field, and the shape of the arrangement is one-dimensional stripe, two-dimensional lattice shape or two-dimensional curve shape. 9.根据权利要求1或3所述的一种鸟嘌呤肽核酸自组装纳米球基光子晶体的声场辅助制备方法,其特征在于:所述的鸟嘌呤肽核酸自组装纳米球基光子晶体进一步采用以下过程进行处理:9. the sound field auxiliary preparation method of a kind of guanine peptide nucleic acid self-assembled nano-sphere-based photonic crystal according to claim 1 or 3, it is characterized in that: described guanine peptide nucleic acid self-assembled nano-sphere-based photonic crystal further adopts The following process is processed: 1)称取平均分子量为200的聚乙二醇二丙烯酸酯,加入占据聚乙二醇二丙烯酸酯质量分数0.8%比例的混合光引发剂TPO-L,形成混合物;1) Weighing polyethylene glycol diacrylate with an average molecular weight of 200, adding a mixed photoinitiator TPO-L that accounts for 0.8% of the mass fraction of polyethylene glycol diacrylate to form a mixture; 2)将混合物使用行星搅拌仪进行充分混合并脱泡,制备形成光敏预聚物;2) fully mixing and defoaming the mixture using a planetary stirrer to prepare a photosensitive prepolymer; 3)将附有鸟嘌呤肽核酸自组装纳米球基光子晶体的基底置于旋涂仪上,将光敏预聚物均匀滴在鸟嘌呤肽核酸自组装纳米球基光子晶体表面,并使用旋涂法在鸟嘌呤肽核酸自组装纳米球基光子晶体表面形成均匀薄膜,使用紫外光固化,完成鸟嘌呤肽核酸自组装纳米球基光子晶体的封装。3) Place the substrate with the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal on the spin coater, drop the photosensitive prepolymer evenly on the surface of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal, and use spin coating The method forms a uniform film on the surface of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal, and uses ultraviolet light curing to complete the encapsulation of the guanine peptide nucleic acid self-assembled nanosphere-based photonic crystal.
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