本文關(guān)鍵詞：聚合物修飾的納米通道膜中物質(zhì)的傳輸及其分析應(yīng)用　出處：《湖南大學(xué)》2015年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 納米通道 聚合物 自組裝 誘導(dǎo)電滲 誘導(dǎo)電泳

【摘要】：納流控(Nanofluidics)研究的是流體在納米通道中的傳輸行為,它要求通道至少有一個(gè)維度低于100 nm。當(dāng)通道的尺度從微米下降到納米時(shí),由于尺寸的縮小,比表面積的增大,各種表面力如位阻作用、范德華力和靜電力對物質(zhì)的傳輸將起著重要的影響,許多在納米尺度下特有的傳輸現(xiàn)象都根源于此。例如,在納米通道中雙電層的厚度與通道的尺度相當(dāng),這會導(dǎo)致雙電層的重疊,產(chǎn)生離子傳輸選擇性、離子的富集與耗散和離子整流等納流控現(xiàn)象。研究和利用納流控傳輸現(xiàn)象對于理解發(fā)生在納米限域空間中的各種作用力,操控分子和離子在其中的傳輸,發(fā)展能夠用于檢測和分離的納流控器件等都具有重要意義。近年來由于納米通道的制備和加工技術(shù)的進(jìn)步,為納流控研究提供了良好的實(shí)驗(yàn)平臺。本論文就是在這樣的背景下,以核徑跡刻蝕的聚碳酸酯(PCTE)膜為模板,采用層層自組裝(LBL)的方法,構(gòu)建了不同聚合物修飾的納米通道陣列膜,通過對納米通道所在溶液環(huán)境的調(diào)控,開展了基于納米通道的傳輸現(xiàn)象的研究,并探索了其在分離和檢測等方面的應(yīng)用。具體研究工作包括以下四個(gè)方面:1.將聚電解質(zhì)通過層層自組裝的方法修飾到PCTE膜中,構(gòu)建了表面帶正電荷或負(fù)電荷的納米通道膜,研究了在電解質(zhì)濃度梯度下,水通過這些荷電納米通道的傳輸現(xiàn)象。結(jié)果表明,在一定電解質(zhì)濃度范圍內(nèi),水通過荷電納米通道膜的傳輸方向可以從裝有電解質(zhì)溶液的一側(cè)流向純水的一側(cè),這是一種異常的滲透現(xiàn)象。為此建立了一個(gè)簡潔的模型來說明產(chǎn)生這些異常效應(yīng)的條件,即在電解質(zhì)濃度梯度下,由于陰、陽離子擴(kuò)散速度不同,會在荷電納米通道膜的兩側(cè)形成膜擴(kuò)散電勢,同時(shí)由于荷電通道壁對反離子的吸引會形成雙電層,膜擴(kuò)散電勢作用于雙電層,會產(chǎn)生誘導(dǎo)電滲,因此水的傳輸是誘導(dǎo)電滲和濃差擴(kuò)散共同作用的結(jié)果。通過調(diào)節(jié)通道的表面電荷、電解質(zhì)的濃度和電解質(zhì)的類型,當(dāng)誘導(dǎo)電滲大于水的濃差擴(kuò)散且方向相反時(shí),就能產(chǎn)生異常滲透現(xiàn)象。根據(jù)這一水傳輸?shù)哪Ｐ?中性分子和離子通過荷電納米通道的傳輸行為,也可通過建立電解質(zhì)濃度梯度來進(jìn)行調(diào)節(jié)。該工作有助于理解水在荷電納米通道膜中的傳輸行為,同時(shí)也為納流控器件中流體流向的調(diào)控提供了一種新思路。2.在上一個(gè)研究工作的基礎(chǔ)上,利用電解質(zhì)濃度梯度在荷電納米通道膜的兩側(cè)形成膜擴(kuò)散電勢,實(shí)現(xiàn)了荷正電納米通道膜離子選擇性的調(diào)節(jié)。由于膜電勢在通道膜兩端的建立會產(chǎn)生誘導(dǎo)電滲和誘導(dǎo)電泳,陰、陽離子在通道中的傳輸是由擴(kuò)散、誘導(dǎo)電滲和誘導(dǎo)電泳三者共同作用決定的。調(diào)節(jié)磷酸濃度梯度、傳輸時(shí)間和進(jìn)樣液體積,可以改變離子傳輸?shù)耐可踔吝x擇性。以甲基紫精(MV2+)和1,5-萘二磺酸鈉(NDS2-)為例,納米通道膜對MV2+的分離選擇性可達(dá)到19.5。這種調(diào)節(jié)納米通道離子選擇性的方法無需在通道壁上修飾刺激響應(yīng)性材料,也不用對通道壁或者通道兩側(cè)施加外加電場,具有節(jié)能、經(jīng)濟(jì)和易于操作等特點(diǎn),有望在納流控器件中實(shí)現(xiàn)離子的傳輸和分離。3.采用層層自組裝的方法,將聚丙烯胺(PAH)修飾到PCTE膜中,構(gòu)建了具有p H響應(yīng)的納米通道,并結(jié)合甘露醇使硼酸酸性增強(qiáng)的原理,實(shí)現(xiàn)了硼酸的檢測。該納米通道表面富含-NH2,對NDS2-的傳輸表現(xiàn)出明顯的p H響應(yīng)特性。如果固定甘露醇的濃度,NDS2-的傳輸通量隨硼酸濃度增大而增大,從而實(shí)現(xiàn)了硼酸的檢測,檢測限為0.07 m M。相對于滴定法而言,這種基于納米通道的硼酸檢測方法試劑消耗少,便于操作。該工作為納米通道中物質(zhì)傳輸調(diào)控的應(yīng)用提供了一種新的思路,即通過物質(zhì)間的相互作用產(chǎn)生能夠影響通道傳輸?shù)沫h(huán)境,從而實(shí)現(xiàn)對相關(guān)物質(zhì)的檢測。4.利用自組裝技術(shù)將聚乙烯醇(PVA-124)修飾到PCTE膜中,構(gòu)建了一種對硼酸根和順式羥基化合物具有級聯(lián)識別響應(yīng)的納米通道,具有IMP(蘊(yùn)涵)邏輯門性質(zhì)。首先,PVA與硼酸根結(jié)合形成帶負(fù)電荷的PVA-硼酸根復(fù)合物,增加了通道表面的負(fù)電荷,阻礙NDS2-在通道中的傳輸,顯示通道對硼酸根有響應(yīng),且響應(yīng)是可逆的;此后再加入順式羥基化合物,又能將結(jié)合到PVA上的硼酸根競爭下來,減少了通道表面的負(fù)電荷,促進(jìn)NDS2-在通道中的傳輸,顯示通道對順式羥基化合物有響應(yīng),且響應(yīng)也是可逆的,不同的順式羥基化合物對通道的響應(yīng)程度不同。這種識別模式有望用于構(gòu)建納米傳感器件,以及進(jìn)行硼的生理功能的模擬。
[Abstract]:Nanofluidic (Nanofluidics) is the study of transfer behavior of fluid in nano channel in the channel, it requires at least one dimension less than 100 nm. when the channel scales from microns down to nanometer, the size is reduced, the increase of surface area of various surface forces such as steric effect, static force and van Edward the power of mass transport will play an important influence, many unique on the nanoscale transport phenomena are rooted in this. For example, the thickness of electric double layer and channel in nano channel in size, which will lead to the overlapping of electric double layer, ion transport selectivity, ion concentration and ion and dissipation rectifier nanofluidic phenomenon. The research and utilization of nanofluidic transport phenomena occurred in the limit for understanding the nano forces in the domain space, manipulation of molecules and ions in the transmission, development can be used for the detection and isolation of nanofluidic devices It is of great significance. In recent years due to the nano channel fabrication and processing technology, provides a good experimental platform for the research of microfluidic. This paper is in this context, the nuclear track etched polycarbonate (PCTE) membrane as template, using layer by layer self-assembly (LBL) method, construct nanotube membranes of different polymer modified, through the regulation of the nano channel where the solution environment, carried out the research of transport phenomena based on the nano channel, and explore its application in separation and detection. The specific research work includes the following four aspects: 1. the method of polyelectrolyte by self-assembly modification the PCTE membrane, constructed the nano channel membrane surface with positive or negative charge, in the study of the electrolyte concentration gradient, water transport phenomena through these charged nano channel. The results show that in a certain electrolysis Mass concentration range, the water through the transmission direction of charged nanochannel membrane from the electrolyte solution is arranged on one side of one side of the flow of water, which is an abnormal phenomenon of osmosis. So as to establish a simple model to illustrate the effect of abnormal conditions in the electrolyte concentration gradient, due to Yin that cation diffusion speed is different, will be on both sides of the charged nano channel film formed by film diffusion potential, at the same time as the charged channel wall on the attraction of counter ions to form double layer film, diffusion potential effect on electric double layer, produced by electro osmosis, so water transport is induced by electroosmosis and concentration diffusion interaction the results of surface charge. By regulating channel type, concentration of electrolyte and electrolyte, when induced by electroosmosis than water concentration diffusion and in the opposite direction, can produce abnormal infiltration phenomenon. According to the water transmission mode Type, neutral molecules and ions through the transmission behavior of charged nano channel, but also through the establishment of electrolyte concentration gradient to adjust. This work helps to understand the water in charged nano channel in the film transmission behavior, but also for the regulation of nano fluid flow in microfluidic devices provides a new way of basic research work.2. in a on both sides using electrolyte concentration gradient in charged nano channel film formed by film diffusion potential, the regulation of positively charged nano channel membrane ion selective. Because the membrane potential induced electroosmosis and electrophoresis induced, established from both ends of the transmission channel film Yin, in the channel is composed of cations diffusion induced by electroosmosis and electrophoresis determined effect induced by three. Regulation of phosphate concentration gradient, transmission time and sample solution volume, can change the ion transport flux even with methyl viologen selectivity. (MV 2+) and two 1,5- naphthalene sulfonate (NDS2-) as an example, methods of separation selectivity to MV2+ nanotube membranes can reach 19.5. the regulation of ion selective nano channel without modification in the channel wall of stimuli responsive materials, nor to wall on both sides of the channel or channel applied electric field, has the advantages of energy saving, economical and easy to operation, is expected to achieve the transmission and separation of.3. ions through layer by layer self-assembly method in microfluidic devices, the polyacrylamide (PAH) modified PCTE film, with the construction of nano channel P H response, and combined with the principle of mannitol boric acid enhanced, realized the detection of the nano boric acid. The surface of the channel is rich in -NH2, P H transmission showed obvious response to NDS2-. If the concentration of mannitol fixed, flux of NDS2- increases with the increase of the concentration of boric acid, boric acid in order to achieve the detection, the detection limit is 0.07 M M. relative to the titration, the reagent boric acid nano channel detection method based on consumption, easy to operate. Provides a new way for application of the work material nano channel transmission control, namely through interaction between substances produced can affect the channel transmission environment, so as to realize the detection of related substances by.4. the use of self assembly technology of polyvinyl alcohol (PVA-124) modified PCTE film, build a nano channel response cascade identification for borate and CIS hydroxyl compounds, with IMP (Yun Han) logic gate properties. First, the combination of PVA and borate formed PVA- borate complexes with negative charge and increase the negative charge surface of the channel, the transmission block in the channel of an NDS2- display channel in response to the borate, and the response is reversible; then adding CIS compounds of formula hydroxyl, and can be combined to PVA on the boron Radical competition down, reduce the negative charge of the surface of the channel, to promote NDS2- transmission in the channel, display the channel in response to CIS hydroxyl compounds, and the response is reversible, different smoothness of the channel response type hydroxyl compounds. This pattern is expected to use different recognition to construct nano sensors, and the simulation of physiological function boron.

【學(xué)位授予單位】：湖南大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TB383.1;O631

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