200840643 九、發明說明: 【發明所屬之技術領域】 本發明涉及一種三維水相分散膠體球的製備方法,尤 其涉及將奈米晶組裝成三維水相分散膠體球的方法。 【先前技術】200840643 IX. Description of the Invention: [Technical Field] The present invention relates to a method for preparing a three-dimensional aqueous phase dispersed colloidal sphere, and more particularly to a method for assembling nanocrystals into a three-dimensional aqueous phase dispersed colloidal sphere. [Prior Art]
奈来粒子具有的優異的光學、電學、催化及傳感等性 ,,這些性能的調節可藉由尺寸及幾何形態的變化來獲 仔/。功能性奈練子的可控分級有序自組裝係目前乃至未 來很長-段0销裏奈米科技發展的重要方向。將奈米粒子 自、、且衣為維、—維或二維有序結構,可獲得新穎的整體 ί同特性,並且可以藉由控制奈綠子_相互作用來調 即其性能。準補設収獅合_方絲奈米粒子組裝 成具有新型結構及新型性能的材料尤為重要。 狀目月J已、、'工報導了夜多方法,如:溶劑揮發、界面自組 降組裝等方法’可以將奈米晶級裝形成二維或三維 的有序結構。然,這些方法都係在特定的基體材料上進行, 了這些方法的適用制。如,Zh卿等人藉由四 來導向金奈米晶自組裝成為球形聚集體, 惟,该方賴翻于金、轉特定材料的奈米晶。 另,目刖為止,還沒有-種通 組裝形成三維膠體球。 月b刃肘不水日曰 有鑒於此 ,提供一種通用性強、工蓺簡 維朦體球的方法實 原料多樣且低毒性的將奈米晶組裝成 ;呆、 爲必要。 8 200840643 【發明内容】 一種將奈米晶組裝成三維水相分散膠體球的方法,其 包括如下步驟: (1) 將預先合成的表面含有穩定配體的奈米晶溶解在 有機溶劑中’配成濃度為1毫克/毫升至30毫克/毫升的溶 液A ; (2) 將表面活性劑溶于水,配成濃度為〇· 〇〇2毫摩爾 /毫升至0· 05毫摩爾/亳升的溶液B ; (3) 將溶液A與溶液B按體積比為1: (5〜3〇)混合, 將所得混合液經乳化後得到均勻穩定的乳液C ; (4) 將乳液C中的有機溶劑去除後,得到沈殿物;及 (5) 將所得到的沈澱物經分離後,以去離子水洗滌,. 即可得到由奈米晶組裝而成的三維水相分散膠體球。 所述步驟(3)中乳化採用高速攪拌方法、超聲方法、 膠體磨方法及玻璃膜乳化(SPG)方法中的至少一種。 • 所述步”驟⑷中去除有機溶劑採用直接加熱法,加敎 溫度為4此至肌,加熱時間為1小時至20小時。…、 所述步驟⑷中去除有機溶劑採用減壓蒸德法,基餘 時間為1小時至20小時。 與先前技術相比,Nailai particles have excellent optical, electrical, catalytic, and sensing properties, and these properties can be adjusted by changes in size and geometry. The controllable grading and orderly self-assembly of functional na[beta] is very important in the future and the long-term development of the segment. The nanoparticles are self-contained, and the coatings are dimensional, dimensional or two-dimensional ordered structures, and the novel overall characteristics can be obtained, and the properties can be adjusted by controlling the nematode-interaction. It is especially important to assemble a lion-filled _ square nano-particle into a material with a new structure and new properties. The shape of the month has been, the 'work reported that many methods, such as: solvent volatilization, interface self-assembly assembly and other methods can be installed into a two-dimensional or three-dimensional ordered structure. However, these methods are carried out on specific substrate materials, and the application of these methods. For example, Zh Qing et al. guided the gold nanocrystals to self-assemble into spherical aggregates by four, but the square crystals turned to gold and turned to specific materials. In addition, as far as witnessing, there is no one-piece assembly to form a three-dimensional colloidal sphere. In view of this, it is necessary to provide a method for versatility and workmanship of the corpus callosum. The raw materials of various materials and low toxicity are assembled into nanocrystals; 8 200840643 SUMMARY OF THE INVENTION A method for assembling nanocrystals into a three-dimensional aqueous phase dispersed colloidal sphere includes the following steps: (1) dissolving a previously synthesized nanocrystal containing a stable ligand in an organic solvent. Solution A with a concentration of 1 mg/ml to 30 mg/ml; (2) Dissolving the surfactant in water to a concentration of 〇·〇〇2 mmol/ml to 0.05 μmol/μl Solution B; (3) Mixing solution A and solution B in a volume ratio of 1: (5 to 3 Torr), and emulsification to obtain a uniformly stable emulsion C; (4) Organic solvent in emulsion C After the removal, the sediment is obtained; and (5) the obtained precipitate is separated and washed with deionized water to obtain a three-dimensional aqueous phase dispersed colloidal sphere assembled from nanocrystals. The emulsification in the step (3) employs at least one of a high-speed stirring method, an ultrasonic method, a colloid mill method, and a glass film emulsification (SPG) method. • In the step (4), the organic solvent is removed by direct heating, the temperature is 4 to the muscle, and the heating time is 1 hour to 20 hours...., the organic solvent is removed in the step (4) by vacuum distillation. The base time is from 1 hour to 20 hours. Compared with the prior art,
基於水包油(0/W)乳液, 氣有親水性的官能團,而使得該 I廣泛的應用乾圍;(2)本方法 有I好的通用性;(3)以於油相 9 200840643 •的條件下能夠均勻分散的奈米晶為原料,故,無論奈米晶 •的材料、形態、粒徑及表面配體的任何變化,選擇合適的 組裝條件都能夠形成水相分散三维膠體球,·⑷該方法中 =步及的材料的毒性較低。故,該方法具有通用性強、工 藝間單、易於操作、原料多樣且低毒性的特點。該方法所 形成的膠體微球具有原始奈米晶的物理及化學特性,且膠 體微球的表面包覆有不同的電荷或官能團,這些特徵為膠 _ 體,球應用於搭建檢測器件、構建新型光子晶體及介孔材 料提供了可能,同時其在生物標記、感測器、催化劑、資 訊存儲等領域都具有廣泛的應用前景。 、 【實施方式】 本發明提供一種將奈米晶組裝成三維水相分散 膠體球的方法,其包括如下步驟: 太“ ^ (1)將預先合成的表面包覆有穩定配體的 不米曰曰’合解在有機溶劑中,配成濃度為卜毫克/毫升 • 至30毫克/毫升的溶液A。 不米晶包括金屬、無機半導體化合物、金屬氧化 物及金屬氟化物的奈米晶,奈米晶的形態為球狀、棒 太片狀或立方體狀,奈米晶的粒徑為0· 5奈米至1〇〇 、人匕设在奈米晶表面的穩定配體為油酸、油胺、 十 /乂 、+ - T-h 3:-»- 丁一、醇、三辛基氧膦及三辛基膦中至少一 種。 有機/奋劑為環己烷、正己烷、三氯曱烷及曱笨中 至少一種。 200840643 • 步驟(2 )將表面活性劑溶于水,配成濃度為〇 . Q Q 2 . 毫摩爾/毫升至0. 05毫摩爾/毫升的溶液B。 表面活性劑包括陰離子表面活性劑、陽離子表面 活性劑、兩性離子表面活性劑及非離子表面活性劑。 陰離子表面活性劑為硬脂酸鈉、硬脂酸鉀、硬脂 酸鎂、油酸鉀、油酸鈉的脂肪酸鹽型,十二烧基苯石黃 酸、十二烧基笨續酸鈉、十二烧基苯磺酸録、十二烧 _ 基笨磺酸鈣、辛基磺酸鈉、C13〜17仲烷基磺酸鈉、 C14〜18 α-烯基磺酸鈉的磺酸鹽型,辛基硫酸鈉、月 桂基硫酸鈉、月桂基疏酸鉀、十二烷基硫酸鈉的硫酸 鹽型及癸基聚氧乙烯醚磷酸酯、月桂基聚氧乙烯醚磷 酸酯鈉、C12〜18烷基聚氧乙烯醚磷酸酯鈉的磷酸酯 鹽型中至少一種。 陽離子表面活性劑為椰油醯胺基丙基二曱基胺 乳酸鹽、硬脂醯胺基丙基二曱基胺乳酸鹽的胺鹽型, • 十六烧基三曱基溴化銨、月桂基三曱基氯化銨、二硬 月曰基一甲基氯化銨、C12〜18烷基乙氧基二甲基节基氣 化銨的季銨鹽型及月桂基二曱基氧化胺、牛油基二羥 乙基氧化胺、椰油基二羥乙基氧化胺的氧化胺型中至 少一種。 一兩性離子表面活性劑為月桂基甜菜域、椰油基甜 采域、硬脂基甜菜域、油菜基甜菜域、C12〜18烷基 二甲基甜菜域銨鹽的甜菜域型’卜羥乙基—2—椰油 基咪唑啉乙酸鹽、新醯胺基乙基一N—羥乙基氨基乙 11 200840643 氧基丙酸二納的咪㈣型,&甲基甘氨酸納、牛油基 亞氨基二丙酸二鈉的氨基酸型及磷脂中至少一種。 非離子表面活性劑為脂肪醇醚、烷基酚醚、烷基 胺醚、聚_、脂肪酸聚烷氧化合物脂的烷氧基化物 型’甘油醋、山梨醇醋、季戊四醇醋、嚴糖醋的多元 醇酉旨型,脂肪酸絲型L胺型,烧基糖苦型及 院基σ比17各烧酮中至少一種。 步驟(3)將洛液Α與溶液Β按體積比為工:(5〜3〇) 混合嘴所得混合液經乳化後得到均勻穩定的乳液卜 乳化可採用高速擾拌方法、超聲方法、膠體磨方 法及SPG方法中至少一種。 步驟(4)將乳液c中的有機溶劑去除後,得到 沈殿物。 。去除有機溶劑可採用直接加熱法,加熱溫度為4〇 C至95 C ’加熱時間為丄小時至2〇小時,或採用減 壓蒸餾法,蒸餾時間為i小時至2〇小時。 步驟(5)將所得到的沈澱物經分離後,以去離 子水洗;條,即可㈣由奈米晶組裝而成的三維水相分 散膠體球。 下面將結合附圖對本發明實施例作進一步的詳 細說明。 、第貝%例·以單分散鉻酸鋇(BaCr〇4)奈米晶 為結構單域由自组裝以形成水相分散的具有有序 結構的三維膠體球。 200840643 將預先合成的粒徑約為7奈米(nm)、分散係數 為4. 3%的表面包覆有油酸的單分散BaCrCU奈米晶溶 解在環己烷中,配製濃度為5毫克/毫升(mg/ml)的 環己炫溶液。將28毫克(mg)的十二院基硫酸納(SDS ) 溶於10毫升(ml)去離子水中,得到濃度為0. 01 (mmol/ml)的水溶液。取1ml的上述環己燒溶液加 入到上述水溶液中,採用超聲方法乳化所得的混合 物,將乳化所得的乳液於70°C的溫度下水浴中加熱5 小時,以去除乳液中的有機溶劑,得到沈澱物。將所 得的沈澱物經離心分離、去離子水洗滌後,即得到鉻 酸鋇的三維膠體球。將鉻酸鋇的三維膠體球分散於水 中,可防止膠體球再次團聚。 請參閱圖1為第一實施例中由鉻酸鋇奈米晶自組 裝形成的三維膠體球的透射電鏡照片(TEM),插圖為 其高分辨透射電鏡照片(HRTEM),由圖1可知該三維 膠體球係由多個奈米晶組裝形成的有序結構。 請參閱圖2為第一實施例中由鉻酸鋇奈米晶自組 裝形成的二維膠體球的粒徑分佈圖’由圖2可知二維 膠體球的粒徑分佈在100奈米(nm)至140nm的範圍 内,粒徑較均勻。 請參閱圖3為第一實施例中由鉻酸鋇奈米晶自組裝形 成的三維膠體球的表面電核(Zeta)電位圖,由圖3 可知該三維膠體球表面帶有負電荷,易於分散於水 中,於通電條件下具有可操縱性。 13 200840643 . 第二實施例:以單分散硒化銀(Ag2Se)奈米晶為 結構單元藉由自組裝以形成水相分散的具有有序結 會 構的三維膠體球。 將預先合成的粒徑約為10nm、分散係數為4.8% 的表面包覆有十八胺的單分散Ag2Se奈米晶溶解在環 己烧中,配製濃度為5mg/ml的環己烧溶液。將35mg 的十六说基二曱基 >臭化敍(CTAB)溶於1 Om 1去離子 水中,得到濃度為〇. 01 mmol/ml的水溶液。取2ml ® 的上述環己烷溶液加入到上述水溶液中,採用超聲方 法乳化所得的混合物,將乳化所得的乳液於80°C的溫 度下水浴中加熱2小時,以去除乳液中的有機溶劑, 得到沈殿物。將所得的沈殿物經離心分離、去離子水 洗滌後,即得到Ag2Se的三維膠體球。將Ag2Se的三 維膠體球分散於水中,可防止膠體球再次團聚。 請參閱圖4為第二實施例中由Ag2Se奈米晶自組 赢 裝形成的三維膠體球的透射電鏡照片(ΤΈΜ),由圖4 可知該三維膠體球係由多個奈米晶組裝形成的有序 結構,該三維膠體球的粒徑為140nm至180nm。 請參閱圖5為第二實施例中由Ag2Se奈米晶自組 裝形成的三維膠體球的Zeta電點陣圖,由圖5可知 該三維膠體球表面帶有正電荷,易於分散於水中,於 通電條件下具有可操縱性。 第三實施例··以單分散硫化鎘(CdS)奈米晶為 結構單元藉由自組裝以形成水相分散的具有有序結 14 200840643 構的三維膠體球。 將預先合成的粒徑約為4_、分散係數為 7· 5%的Based on the oil-in-water (0/W) emulsion, the gas has a hydrophilic functional group, which makes the I widely used for drying; (2) the method has good versatility; (3) for the oil phase 9 200840643 • Under the condition of uniformly dispersed nanocrystals as raw materials, regardless of any changes in the material, morphology, particle size and surface ligand of nanocrystals, the selection of suitable assembly conditions can form a water-phase dispersed three-dimensional colloidal sphere. (4) The material of the step = step is less toxic. Therefore, the method has the characteristics of strong versatility, single process, easy operation, diverse raw materials and low toxicity. The colloidal microspheres formed by the method have the physical and chemical characteristics of the original nanocrystals, and the surface of the colloidal microspheres is coated with different charges or functional groups. These features are gelatinous bodies, and the balls are used to construct detection devices and construct new types. Photonic crystals and mesoporous materials offer possibilities, and they have broad application prospects in biomarkers, sensors, catalysts, and information storage. [Embodiment] The present invention provides a method for assembling nanocrystals into a three-dimensional aqueous phase dispersed colloidal sphere, which comprises the following steps: too "^ (1) pre-synthesized surface coated with a stable ligand of non-rice曰 'Recombination in an organic solvent, a concentration of Bu mg / ml • to 30 mg / ml of solution A. Non-crystalline crystals including metals, inorganic semiconductor compounds, metal oxides and metal fluoride nanocrystals, Nai The shape of the rice crystal is spherical, rod-like or cubic, the crystal size of the nanocrystal is 0.5 to 1 nanometer, and the stable ligand of the human crystal on the surface of the nanocrystal is oleic acid and oil. At least one of an amine, a ruthenium, an anthracene, an alcohol, a trioctylphosphine oxide, and a trioctylphosphine. The organic/exciting agent is cyclohexane, n-hexane, trichloromethane and At least one of the stupid. 200840643 • Step (2) Dissolve the surfactant in water to a concentration of 〇. QQ 2. mM/ml to 0.05 mmol/ml of solution B. Surfactant includes anion Surfactants, cationic surfactants, zwitterionic surfactants and nonionics Surfactant. Anionic surfactant is a fatty acid salt type of sodium stearate, potassium stearate, magnesium stearate, potassium oleate, sodium oleate, dodecapine benzoic acid, twelve burning base Sustained sodium, dodecylbenzenesulfonic acid, twelve calcined sulfonate, calcium octylsulfonate, sodium C13~17 secondary alkyl sulfonate, sodium C14~18 alpha-alkenyl sulfonate Sulfonate type, sodium octyl sulfate, sodium lauryl sulfate, potassium lauryl sulfate, sulfate type of sodium lauryl sulfate and mercapto polyoxyethylene ether phosphate, sodium lauryl polyoxyethylene ether phosphate And at least one of the phosphoric acid ester forms of sodium C12-18 alkyl polyoxyethylene ether phosphate. The cationic surfactant is cocoamidopropyl decylamine lactate, stearyl propyl hydrazine Amine salt type of arylamine lactate, • Hexadecyl tridecyl ammonium bromide, lauryl tridecyl ammonium chloride, di-hardyrene-methyl ammonium chloride, C12-18 alkyl ethoxy Quaternary ammonium salt type of dimethyl-salt ammonium sulphate and amine oxide of lauryl dinonyl amine oxide, tallow dihydroxyethyl amine oxide, cocoyl dihydroxy ethyl amine oxide At least one of the bis-ionic surfactants is a sugar beet domain of a lauryl beet domain, a coconut oil-based sweet-soil field, a stearyl beet field, a canola-based sugar beet field, and a C12-18 alkyl dimethyl beet domain ammonium salt. 'Buhydroxyethyl-2-cocoalkyl imidazoline acetate, neodecylamino-N-hydroxyethylaminoethyl 11 200840643 Iso(tetra) type of dipropionate, & methyl glycinate, At least one of amino acid type and phospholipid of disodium tallow iminodipropionate. Nonionic surfactant is a fatty alcohol ether, alkylphenol ether, alkylamine ether, poly-, fatty acid polyalkoxylate The oxylate type 'glycerin vinegar, sorbitol vinegar, pentaerythritol vinegar, sucrose sucrose polyol type, fatty acid silk type L amine type, burnt sugar type and hospital base σ ratio of at least one of 17 ketones. Step (3) The ratio of the liquid sputum to the solution enthalpy is: (5~3 〇) The mixture obtained by mixing the mouth is emulsified to obtain a uniform and stable emulsion. The emulsification can be carried out by high-speed scrambling method, ultrasonic method, colloid mill. At least one of the method and the SPG method. Step (4) After removing the organic solvent in the emulsion c, a sediment is obtained. . The organic solvent may be removed by direct heating at a heating temperature of 4 ° C to 95 ° C for a heating time of from 丄 to 2 Torr, or by a reduced pressure distillation method for a period of from 1 hour to 2 hours. Step (5) After separating the obtained precipitate, it is washed with deionized water; and then, (4) a three-dimensional aqueous phase dispersed colloidal sphere assembled from nanocrystals. The embodiments of the present invention will be further described in detail below with reference to the accompanying drawings. % of the first case · Three-dimensional colloidal spheres having an ordered structure formed by self-assembly by monodisperse bismuth chromite (BaCr〇4) nanocrystals to form an aqueous phase. 200840643 The pre-synthesized monodisperse BaCrCU nanocrystals with a particle size of about 7 nm (nm) and a dispersion coefficient of 4.3% coated with oleic acid were dissolved in cyclohexane at a concentration of 5 mg/ Milliliter (mg/ml) of cyclohexyl choline solution. The solution of 28 mg (mg) of sodium dodecyl sulfate (SDS) was dissolved in 10 ml (ml) of deionized water to give an aqueous solution having a concentration of 0.01 (mmol/ml). 1 ml of the above cyclohexane solution was added to the above aqueous solution, the obtained mixture was emulsified by ultrasonication, and the emulsion obtained by the emulsification was heated in a water bath at 70 ° C for 5 hours to remove the organic solvent in the emulsion to obtain a precipitate. Things. After the obtained precipitate was centrifuged and washed with deionized water, a three-dimensional colloidal sphere of strontium chromate was obtained. Dispersing the three-dimensional colloidal spheres of strontium chromate in water prevents the colloidal spheres from agglomerating again. 1 is a transmission electron micrograph (TEM) of a three-dimensional colloidal sphere formed by self-assembly of strontium chromate nanocrystals in the first embodiment, and its inset is a high-resolution transmission electron micrograph (HRTEM), which is known from FIG. Colloidal spheres are ordered structures formed by the assembly of multiple nanocrystals. 2 is a particle size distribution diagram of a two-dimensional colloidal sphere formed by self-assembly of strontium chromate nanocrystals in the first embodiment. FIG. 2 shows that the particle size distribution of the two-dimensional colloidal sphere is at 100 nm (nm). The particle size is relatively uniform in the range of 140 nm. 3 is a surface electronuclear (Zeta) potential diagram of a three-dimensional colloidal sphere formed by self-assembly of strontium chromate nanocrystals in the first embodiment. It can be seen from FIG. 3 that the surface of the three-dimensional colloidal sphere has a negative charge and is easily dispersed. It is manoetable in water under energized conditions. 13 200840643 . Second embodiment: self-assembly by monodisperse silver selenide (Ag2Se) nanocrystals to form an aqueous phase-dispersed three-dimensional colloidal sphere having an ordered structure. A pre-synthesized monodisperse Ag2Se nanocrystal coated with octadecylamine having a particle diameter of about 10 nm and a dispersion coefficient of 4.8% was dissolved in cyclohexane to prepare a cyclohexane solution having a concentration of 5 mg/ml. A solution of 35 mg of hexamethylenediamine > ruthenium (CTAB) was dissolved in 1 mM deionized water to give an aqueous solution having a concentration of 0.1 mmol/ml. 2 ml of the above cyclohexane solution was added to the above aqueous solution, the obtained mixture was emulsified by ultrasonication, and the emulsion obtained by emulsification was heated in a water bath at 80 ° C for 2 hours to remove the organic solvent in the emulsion. Shen Temple. After the obtained sediments were separated by centrifugation and deionized water, a three-dimensional colloidal sphere of Ag2Se was obtained. Dispersing the three-dimensional colloidal sphere of Ag2Se in water prevents the colloidal sphere from agglomerating again. 4 is a transmission electron micrograph (ΤΈΜ) of a three-dimensional colloidal sphere formed by Ag2Se nanocrystal self-assembly in the second embodiment. FIG. 4 shows that the three-dimensional colloidal sphere is formed by assembling a plurality of nanocrystals. In an ordered structure, the three-dimensional colloidal sphere has a particle diameter of from 140 nm to 180 nm. Please refer to FIG. 5 , which is a Zeta electric lattice diagram of a three-dimensional colloidal sphere formed by self-assembly of Ag 2 Se nanocrystals in the second embodiment. It can be seen from FIG. 5 that the surface of the three-dimensional colloidal sphere has a positive charge and is easily dispersed in water. It is maneuverable under conditions. THIRD EMBODIMENT · Three-dimensional colloidal spheres with ordered structure 14 200840643 are formed by self-assembly by monodisperse cadmium sulfide (CdS) nanocrystals as structural units. The pre-synthesized particle size is about 4 mm and the dispersion coefficient is 7.5%.
表面包覆有油酸的單分散Cds冑米晶溶解在正己烧 中,配製濃度I lQmg/ml的正己燒溶液。將28mg的 SDS溶於去離子水中,#到濃度為請麵㈣ 的水溶液。取lml的上紅己院溶液加人到上述水溶 液中’採“速方法乳化所得的混合物,將乳化 所得的乳液於阶的溫度下水浴巾加熱丨小時,以去 除f液中的有機溶劑,得到沈殿物。將所得的沈殿物 經離心分離、去離子水洗務後,即得到⑽的三維膠 體球。將CdS的三維膠體球分散於水中,可防止膠體 球再次團聚。 請參閱圖6為第三實施例中由Cds奈米晶自組裝 形成的三維膠體球的TEM照片,由圖6可知該三維膠 體球係由多個奈米晶組裝形成的有序結構,該三維膠 體球的粒徑為50nm至1微米(//m)。 第四實施例:以單分散四氧化三鐵(Fe3〇4)奈米 晶為結構單元藉由自組裝以形成水相分散的具有有 序結構的三維膠體球。 將預先合成的粒徑約^7nm、分散係數為4,_ 表面包覆有油酸的單分散Fe3〇4奈米晶溶解在環己烧 中’配製濃度為15mg/ml的環己燒溶液。將28呢的 娜溶於舰去離子水中,得到濃度為〇. 〇l_al/ml 的水溶液。取lml的上述環己院溶》夜加人到上述水溶 15 200840643 液中’採料聲枝乳化所得的混 的乳液於_的溫度下水浴中加熱丨〇小時:: 雜、、八絲; i b&物。將所得的沈澱物經 厂刀離、去離子水洗蘇後,即得到Fe 球。將Fe3〇4的三維膠體 :、则 再次團^水巾,可防止膠體球 明食阅園The monodisperse Cds(R) rice crystal coated with oleic acid was dissolved in n-hexane, and a positive hexane solution having a concentration of I lQmg/ml was prepared. Dissolve 28 mg of SDS in deionized water, # to an aqueous solution of the concentration (4). Take 1 ml of the Shanghongjiyuan solution and add the mixture to the above aqueous solution to extract the mixture obtained by the method of "speeding". The emulsion obtained by emulsification is heated at a temperature of the bath for a few hours to remove the organic solvent in the liquid f to obtain the After the obtained sediments are separated by centrifugation and deionized water, the three-dimensional colloidal spheres of (10) are obtained. Dispersing the three-dimensional colloidal spheres of CdS in water prevents the colloidal spheres from re-agglomerating. See Figure 6 for the third embodiment. In the example, a TEM photograph of a three-dimensional colloidal sphere formed by self-assembly of Cds nanocrystals, and FIG. 6 shows an ordered structure of the three-dimensional colloidal sphere assembled by a plurality of nanocrystals having a particle diameter of 50 nm. 1 micrometer (//m). Fourth embodiment: self-assembly by monodisperse triiron tetroxide (Fe3〇4) nanocrystals to form an aqueous phase-dispersed three-dimensional colloidal sphere having an ordered structure. A previously prepared cyclohexane solution having a particle size of about 7 nm and a dispersion coefficient of 4,_ surface coated with oleic acid and monodisperse Fe3〇4 nanocrystals was dissolved in cyclohexane to prepare a concentration of 15 mg/ml. Dissolve 28 of the Na in the ship deionization In the middle, an aqueous solution having a concentration of 〇. 〇l_al/ml is obtained. Take 1 ml of the above-mentioned cyclohexine dissolved in the above-mentioned water-soluble 15 200840643 liquid, and the mixed emulsion obtained by emulsification of the sounding branch is watered at a temperature of _ Heating in the hour:: miscellaneous, eight wire; i b& the obtained precipitate is removed by the knife and deionized water, then the Fe ball is obtained. The three-dimensional colloid of Fe3〇4: Tuan ^ water towel, can prevent colloidal ball clear food reading garden
4弟四實施例中由Fe3〇4奈米晶 衣形成的二維膠體球的TEM照片,由圖 谬體球係由多個奈米晶組裝形成的有序結構, 膠體球的粒徑為1⑽nm至12〇nm。 為二例以早分散二氟化鑭(LaF3)奈米差 為、、口構早兀猎由自組裝以形成水相分散的具有有月 結構的三維膠體球。 將預先合成的粒徑約為8nm、分散係數為3. 8%的 單分散LaF3奈米晶溶解在環己燒中,配製濃度為 5mg/ml的環己烧溶液。將㈣的哪溶於遍去離 子水中;^到浪度為〇. 〇1_〇1/ι^的水溶液。取W 的上述環己燒溶液加人到上述水溶液巾,採用超聲方 法乳化所得的混合物,將乳⑽得的該於腕的溫 度下夂/口中力π熱5小時’以去除乳液中的有機溶劑, 得到沈殿物。將所得的沈殿物經離心分離、去離子水 洗蘇後,即得到LaF3的三維膠體球。將三維膝 體球分散於水中,可防止膠體球再次團聚。 請參閱圖8為第五實施例中由UF3奈米晶自組裝 16 200840643 =的三維膠體球的™照片,由圖δ可知該三維勝 •=係由多個奈米晶組裝形成的有序結構,該三維膠 體球的粒徑為15〇nm至2〇〇nm。 / 第六實施例··以單分散二氧化鈦(Tl〇2)奈米晶 :::早兀藉由自組裝以形成水相分散的具有有序 、、、°構的二維膠體球。 將預先合成的長度約為40nm至7〇nm的Τι〇2棒狀 鲁 示未晶溶解在環己烧中’配製濃度為5mg/mi的環己 ^溶液。將28mg的SDS溶於1〇ml去離子水中,得到 $度為〇.oimm〇i/ml的水溶液。取2ml的上述環己烧 =液加人到上述水溶液中’採用超聲方法乳化所得二 混合物,將乳化所得的乳液於8 〇。〇的溫度下水浴中加 熱2小& ’以去除乳液中的有機溶劑,得到沈殿物。 將所得的沈殿物經離心分離、去離子水洗蘇後,即得 到Τι〇2的二維膠體球。將抓的三維膠體球分散於水 •中,可防止膠體球再次團聚。 、 /口月茶閱圖9為第六實施例中由Ti〇2奈米晶自組裝 形成的三維膠體球的葡照片,由圖9可知該三維膠 體球係由多個奈米晶組裝形成的有序結構,該三維膠 體球的粒徑為80nm至l〇〇nm。 、,曰第七實施例:以單分散Lai?3奈米晶與金(Au)奈 米曰曰為結構單元藉由自組裝以形成水相分散的具有 特殊核殼結構的三維膠體球。 將質量比為2〇:1的LaFs奈米晶與Au奈米晶溶解 17 200840643 在環己烷中,配製濃度為5nig/ml的環己烷溶液。將 28mg的SDS溶於10ml去離子水中,得到濃度為 0. 01匪〇Ι/ml的水溶液。取1ml的上述環己炫溶液加 入到上述水溶液中,採用超聲方法乳化所得的混合 物,將乳化所得的乳液於70°C的溫度下水浴中加熱5 小時,以去除乳液中的有機溶劑,得到沈澱物。將所 得的沈殿物經離心分離、去離子水洗滌後,即得到LaF3 與Au的三維膠體球。將該三維膠體球分散於水中, 可防止膠體球再次團聚。 請參閱圖10為第七實施例中由LaF3奈米晶與Au 奈米晶自組裝形成的三維膠體球的TEM照片,由圖10 可知該三維膠體球係由以Au為核、LaF3為殼的有序核 殼結構,該三維膠體球的粒徑為150nm至200nm。 本發明提供了一種通用的由油相分散奈米晶藉 由自組裝以形成水相分散三維膠體球的方法,該方法 中以預先合成的表面包覆有穩定配體的奈米晶為結 構單元,以乳液液滴為模版,藉由直接加熱或者減壓 蒸餾的方法去除低沸點的有機溶液,即獲得水相分散 三維膠體球。該方法具體的作用機理為:隨著有機溶 劑的揮發,由於穩定配體中的烧基鏈間相互的凡德瓦 爾力的作用,使得奈米晶在乳液液滴内藉由自組裝形 成水相分散三維膠體球。 與先前技術相比,本發明提供的方法具有如下優 點:(1 )三維膠體微球繼承了原始奈米晶的物理及化 18 200840643 =特性,^由於膠體微球表面包覆有μ性的官能 而使得泫方法製備的膠體球具有 圍;(2)本方法基於水包油(〇/w)产泛的應用範 通用性;⑺以在油相㈣很好的 晶為原料,@此無論奈米晶的材料 ^散的奈米 面配體的任何變化,選擇合適的 〜、粒控及表TEM photograph of a two-dimensional colloidal sphere formed by Fe3〇4 nanocrystals in the fourth embodiment, an ordered structure formed by assembly of a plurality of nanocrystals in the corpus callosum sphere, and the particle diameter of the colloidal sphere is 1 (10) nm. To 12〇nm. In the case of two cases, the three-dimensional colloidal sphere having a monthly structure was dispersed by self-assembly to form an aqueous phase dispersed by early dispersion of lanthanum difluoride (LaF3) nanometer. A pre-synthesized monodisperse LaF3 nanocrystal having a particle diameter of about 8 nm and a dispersion coefficient of 3.8% was dissolved in cyclohexane to prepare a cyclohexane solution having a concentration of 5 mg/ml. Dissolve (4) in the ionic water; ^ to an aqueous solution with a wave width of 〇. 〇1_〇1/ι^. The above-mentioned cyclohexane burning solution of W is added to the above aqueous solution towel, and the obtained mixture is emulsified by ultrasonication, and the emulsion (10) is subjected to 夂/mouth force π heat for 5 hours at the temperature of the wrist to remove the organic solvent in the emulsion. , get the sink temple. The obtained sediments were centrifuged and deionized water was washed to obtain a three-dimensional colloidal sphere of LaF3. Dispersing the three-dimensional knee ball in water prevents the colloidal ball from re-agglomerating. Please refer to FIG. 8 which is a TM photograph of a three-dimensional colloidal sphere self-assembled by UF3 nanocrystals 16 200840643 in the fifth embodiment. It can be seen from the graph δ that the three-dimensional structure is composed of a plurality of nanocrystals. The three-dimensional colloidal sphere has a particle diameter of 15 〇 nm to 2 〇〇 nm. / Sixth embodiment······················································ A previously synthesized Τι〇2 rod of about 40 nm to 7 Å in length was dissolved in cyclohexane to prepare a cyclohexane solution having a concentration of 5 mg/mi. 28 mg of SDS was dissolved in 1 ml of deionized water to give an aqueous solution of 度.oimm〇i/ml. 2 ml of the above cyclohexanone = liquid was added to the above aqueous solution. The obtained two mixtures were emulsified by ultrasonication, and the emulsion obtained by emulsifying was applied at 8 Torr. Heat 2 small & amps in a water bath at the temperature of the crucible to remove the organic solvent in the emulsion to obtain a sediment. After the obtained sediments were separated by centrifugation and deionized water, a two-dimensional colloidal sphere of Τι〇2 was obtained. Disperse the captured three-dimensional colloidal spheres in water to prevent the colloidal balls from re-agglomerating. Fig. 9 is a photograph of a three-dimensional colloidal sphere formed by self-assembly of Ti〇2 nanocrystals in the sixth embodiment. It can be seen from Fig. 9 that the three-dimensional colloidal sphere is formed by assembling a plurality of nanocrystals. In an ordered structure, the three-dimensional colloidal sphere has a particle diameter of 80 nm to 10 nm. The seventh embodiment is characterized in that a monodisperse Lai? 3 nanocrystal and a gold (Au) nanocrystal are used as a structural unit to form a water-phase dispersed three-dimensional colloidal sphere having a special core-shell structure by self-assembly. LaFs nanocrystals and Au nanocrystals having a mass ratio of 2〇:1 were dissolved 17 200840643 A cyclohexane solution having a concentration of 5 nig/ml was prepared in cyclohexane. The aqueous solution was dissolved in 10 ml of deionized water to give an aqueous solution having a concentration of 0.01 匪〇Ι/ml. 1 ml of the above cyclohexyl solution was added to the above aqueous solution, the obtained mixture was emulsified by ultrasonication, and the emulsion obtained by the emulsification was heated in a water bath at 70 ° C for 5 hours to remove the organic solvent in the emulsion to obtain a precipitate. Things. After the obtained sediments were separated by centrifugation and deionized water, a three-dimensional colloidal sphere of LaF3 and Au was obtained. Dispersing the three-dimensional colloidal sphere in water prevents the colloidal sphere from re-agglomerating. 10 is a TEM photograph of a three-dimensional colloidal sphere formed by self-assembly of LaF3 nanocrystals and Au nanocrystals in the seventh embodiment. It can be seen from FIG. 10 that the three-dimensional colloidal spheres are made of Au as a core and LaF3 as a shell. The ordered core-shell structure has a particle size of 150 nm to 200 nm. The present invention provides a general method for self-assembly of oil-phase dispersed nanocrystals to form an aqueous phase-dispersed three-dimensional colloidal sphere, in which a pre-synthesized nanocrystal coated with a stable ligand is used as a structural unit. The emulsion solution is used as a template to remove the low-boiling organic solution by direct heating or vacuum distillation, thereby obtaining an aqueous phase-dispersed three-dimensional colloidal sphere. The specific mechanism of action of the method is as follows: with the volatilization of the organic solvent, the nanocrystals form a water phase by self-assembly in the emulsion droplets due to the interaction of the van der Waals forces between the alkyl groups in the stabilized ligand. Disperse the three-dimensional colloidal sphere. Compared with the prior art, the method provided by the invention has the following advantages: (1) the three-dimensional colloidal microsphere inherits the physical and chemical properties of the original nanocrystal 18 200840643 = characteristic, ^ due to the surface of the colloidal microsphere coated with μ functional The colloidal sphere prepared by the hydrazine method has a circumference; (2) the method is based on the general application of the oil-in-water (〇/w) ubiquitous application; (7) the crystal in the oil phase (four) is used as a raw material, @this no matter Any change in the material of the rice crystals, choose the appropriate ~, grain control and table
水相分散三維膠體球;⑷該方法中::都能夠形成 毒性較低。故,該方法具有通用性強、1 =料的 於知作、原料多樣且低毒性的特點。:間早易 膠體微球具有原始奈米晶的物理及化士 /所形成的 ,面包覆有不同的電荷或官能圈: =球應用於搭建檢測器件、構建新型光;晶體及 =料提供了可能,同時其在生物標記、感測器、 催化劑、f訊存料領域都具有歧的應用前景。 本發財已符合發明糊之要件,遂依法 π ΙΉχ上魏者僅為本發明之較佳實施例, 能以此限制杨之申請專利。舉凡熟悉本案技藝 之人士援依本發明之精神所作之等效修飾或變化,皆應涵 蓋於以下申請專利範圍内。 【圖式簡單說明】 圖1係本發明第—實施例中由絡酸鎖奈米晶自組裝开》 成的二維膠體球的透射電鏡(ΤΕΜ)照片,插圖為其高分辯 透射電鏡(hrtem )只召片。 圖2係本發明第一實施例中由鉻酸鋇奈米晶自組裝形 19 200840643 成的二維膠體球的粒徑分佈 圖 圖3係本發明第一實施例中由鉻駿鎖奈米晶自岭开; 成的二維膠體球的表面電荷(Zeta)電伋圖。 、’ =係本發㈣二實_中由慨銀;;米晶自组裝形 成的二維膠體球的TEM照片。 圖5係本發明第二實施例中由碼化银奈米晶自址裝形 成的一維膠體球的Zeta電位圖。The aqueous phase disperses the three-dimensional colloidal sphere; (4) in the method:: all can form less toxicity. Therefore, the method has the characteristics of strong versatility, 1 = material knowledge, diverse raw materials and low toxicity. : The early easy colloidal microspheres have the physical and chemical properties of the original nanocrystals, and the surface is covered with different charges or functional circles: = ball is used to build detection devices, build new light; crystal and = material supply It is possible, and at the same time it has different application prospects in the fields of biomarkers, sensors, catalysts, and materials. This wealth has been in accordance with the requirements of the invention, and it is only a preferred embodiment of the invention according to the law, which can limit Yang's patent application. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the present invention are intended to be included in the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a TEM image of a two-dimensional colloidal sphere formed by self-assembly of complex acid-locked nanocrystals in the first embodiment of the present invention, and its illustration is a high-resolution transmission electron microscope (hrtem). ) Only call the film. 2 is a particle size distribution diagram of a two-dimensional colloidal sphere formed by a strontium chromate nanocrystal self-assembly form 19 200840643 in the first embodiment of the present invention. FIG. 3 is a chrome-locked nanocrystal in the first embodiment of the present invention. Self-ridged; surface charge (Zeta) electrogram of a two-dimensional colloidal sphere. , ' = TEM photo of the two-dimensional colloidal sphere formed by the self-assembly of rice crystals. Fig. 5 is a zeta potential diagram of a one-dimensional colloidal sphere formed by coded silver nanocrystals in a second embodiment of the present invention.
、圖6係本發明第三實施例中由琉化錢奈米晶自組裝形 成的三維膠體球的TEM照片。 /圖7係本發明第四實施例中由四氧化三鐵奈米晶自组 裝形成的三維膠體球的TEM照片。 ,、圖—8係本發明第五實施例中由三氟化鑭奈米晶自組裝 形成的二維膠體球的TEM照片。 、圖一9係本發明第六實施例中由二氧化鈦奈米晶自組裝 形成的三維膠體球的TEM照片。 、=係本發明第七實施例中由三i化齡米晶與金 奈米晶自組裝形成的三維膠體球的TEM照片。 【主要元件符號說明】 益 20Fig. 6 is a TEM photograph of a three-dimensional colloidal sphere formed by self-assembly of deuterated crystals of the third embodiment of the present invention. Fig. 7 is a TEM photograph of a three-dimensional colloidal sphere formed by self-assembling of ferroferric oxide nanocrystals in the fourth embodiment of the present invention. Fig. 8 is a TEM photograph of a two-dimensional colloidal sphere formed by self-assembly of yttrium trifluoride crystallites in the fifth embodiment of the present invention. Figure 9 is a TEM photograph of a three-dimensional colloidal sphere formed by self-assembly of titanium dioxide nanocrystals in a sixth embodiment of the present invention. And = a TEM photograph of a three-dimensional colloidal sphere formed by self-assembly of three i-age rice crystals and gold nanocrystals in the seventh embodiment of the present invention. [Main component symbol description] Benefit 20