本文選題：手性熒光CuNCs　切入點：手性AuCu　出處：《西南大學》2017年碩士論文

【摘要】：自19世紀早期首次發(fā)現(xiàn)并提出天然手性光學活性(natural optical activity)以來,科學家們便致力于手性的相關(guān)研究工作。如今手性研究也促進了納米科學技術(shù)的快速發(fā)展。2000年Schaaff和Whetten在用L-谷胱甘肽(glutathione,GSH)合成的金納米團簇(gold nanoclusters,AuNCs)中首次觀察到強的手性光學活性后,制備具有手性性質(zhì)的金屬納米團簇(mental nanoclusters,MNCs)便成了研究熱點。手性MNCs不僅具有大比表面積、熒光發(fā)射等特質(zhì),同時也有手性藥物分子誘導的手性光學活性。更重要的是,手性MNCs為生命科學領(lǐng)域如生物大分子的識別傳感、藥物的不對稱催化以及活體組織的靶向治療等方面提供了一定的借鑒意義。關(guān)于MNCs的相關(guān)研究大部分局限于金(gold,Au)和銀(silver,Ag),但含量豐富且廣泛用于工業(yè)的非貴金屬銅(copper,Cu)因其難以可控合成目標尺寸及在空氣中易被氧化,使得關(guān)于手性銅納米團簇(copper nanoclusters,CuNCs)研究依舊處于初期探索階段。因此,本論文擬借納米材料功能化修飾的技術(shù)和手性合成的研究成果,以手性配體青霉胺(penicillamine,Pen)作為穩(wěn)定劑和還原劑,簡單快速制備了穩(wěn)定的手性熒光CuNCs。為進一步提高其穩(wěn)定性,在合成過程中摻入Au而制備出更加穩(wěn)定且具有優(yōu)良手性光學活性響應(yīng)的金銅納米團簇(gold-copper nanoclusters,AuCu NCs)。因此,本文針對手性CuNCs與手性AuCu NCs在制備及分析應(yīng)用方面開展了以下研究:1手性熒光CuNCs的制備及在p H傳感與成像分析中的應(yīng)用盡管關(guān)于AuNCs和銀納米團簇(silver nanoclusters,AgNCs)的手性光學活性研究已較為成熟,但現(xiàn)今對手性CuNCs及其潛在應(yīng)用前景的了解非常局限。因此,我們通過Cu和手性藥物Pen間的絡(luò)合及還原作用成功制備了穩(wěn)定的手性熒光CuNCs。除有優(yōu)良的手性光學活性外(最大各向異性因子(anisotropy factor,g factor)為8.3×10-4),CuNCs還有對pH敏感的聚集誘導發(fā)光特性(aggregation-induced emission,AIE)。有趣的是,不同的Pen對映體對AIE有著重要的影響:rac-Pen的構(gòu)型不支持電子間的相互作用,抑制了CuNCs的聚集。說明我們成功制備了兼藥物手性、熒光且穩(wěn)定的CuNCs。而高量子產(chǎn)率(quantum yield,QY)和較好生物相容性促使我們將其作為靶向定位染料,對細胞的生命活動進行了探索研究。雖然效果不明顯,但將藥物手性和MNCs熒光相結(jié)合作為信號探針用于生命活動的探索研究具有一定的借鑒價值。2手性AuCu NCs的制備及其手性光學活性分析盡管已有向AuNCs中摻入鉑(platinum,Pt)、鈀(palladium,Pd)、Cu等雜原子以獲得獨特的化學、催化和光學等性質(zhì)報道,但用手性配體制備合金NCs并研究其手性光學活性的報道較少。因此我們通過直接合成法制備AuCu NCs:Pen對映體存在時加入不同摩爾比的氯金酸(chloroauric acid tetrahydrate,HAuCl4)和氯化銅(cupric chloride,CuCl_2),再經(jīng)過硼氫化鈉(sodium borohydride,Na BH4)進一步還原制得。AuCu NCs具有獨特的科頓效應(yīng)(cotton effects),且當二者摩爾比為1:1時有最大g factors(~0.57×10-4)。說明Cu的摻入會改變合金的手性光學活性。雖然單金屬CuNCs不穩(wěn)定,但制備的合金AuCu NCs卻具備了類似于AuNCs穩(wěn)定的特點。上述實驗結(jié)果加深了對手性合金MNCs光學活性的認識,進一步拓展了其在不對稱催化等領(lǐng)域的認識,具有重要的借鑒意義。
[Abstract]:For the first time since the discovery in early nineteenth Century and put forward the natural chiral optical activity (natural optical activity) since the related research work, scientists have devoted to the study of chiral chiral. It also promotes the rapid development of nano science and technology.2000 Schaaff and Whetten in L- with glutathione (glutathione, GSH) synthesis of gold nanoclusters (gold nanoclusters AuNCs) was firstly observed in chiral optical strong activity, the preparation of metal nanoclusters chiral properties (mental nanoclusters MNCs) has become a hotspot. The chiral MNCs not only has a large specific surface area, fluorescence emission and other characteristics, but also has a chiral optically active chiral drug molecules induced. More importantly, chiral MNCs recognition and sensing field of life science such as biological macromolecules, catalytic asymmetric drugs and living tissue targeted therapy provided a certain reference The significance of research on MNCs. Most limited to gold (gold, Au) and silver (silver, Ag), but the content is rich and widely used in non noble metal copper industry (copper, Cu) because of its difficult to controlled synthesis of the size of the target and is easily oxidized in air, making a chiral copper nanocluster (copper nanoclusters, CuNCs) research is still at the initial stage. Therefore, this thesis intends to borrow nano materials functionalized chiral synthesis technology and Research on chiral ligand penicillamine (penicillamine, Pen) as a stabilizer and reducing agent, simple and rapid preparation of chiral fluorescent CuNCs. to further improve its stability stability, in the synthesis process of mixing Au prepared more stable and has a gold copper nanoclusters response excellent chiral optical activity (gold-copper nanoclusters, AuCu NCs). Therefore, the needle of chiral CuNCs and chiral AuCu NCs in preparing Carry out the following aspects: 1 research and application of chiral fluorescent CuNCs preparation and analysis of P H sensing and imaging application while on AuNCs and silver nanoclusters (silver, nanoclusters, AgNCs) on the activity of chiral optical has been mature, but the opponents of CuNCs and its potential application prospect of understanding is very limited. Therefore, we use Cu and chiral drugs between Pen complexation and reduction were successfully prepared stable chiral fluorescent CuNCs. in chiral optical activity excellent outside (the maximum anisotropy factor (factor anisotropy factor, g) 8.3 * 10-4), CuNCs and pH on sensitive aggregation induced emission (aggregation-induced emission, AIE). Interestingly, different Pen enantiomers on AIE have important effect: rac-Pen configuration does not support electronic interaction, inhibit the aggregation of CuNCs. We successfully prepared and Chiral drugs, fluorescent and stable CuNCs. and high quantum yield (quantum yield, QY) and good biocompatibility which prompted us targeting of dyes, the life activity of cells was studied. Although the effect is not obvious, but the combination of chiral drugs and MNCs fluorescence study as a signal probe for life activity has certain reference value of.2 AuCu NCs chiral preparation and chiral optical activity analysis has been to platinum doped into AuNCs (platinum, Pt), palladium (palladium, Pd), Cu atoms to obtain unique chemical, catalytic and optical properties, but the preparation of chiral ligands NCs alloy and study the chiral optical activity reported less. Therefore we adopt the direct synthesis of AuCu NCs:Pen of chloroauric acid enantiomers exist with different molar ratio (chloroauric acid tetrahydrate HAuCl4 (Cu) and copper chloride Pric chloride, CuCl_2), followed by sodium borohydride (sodium borohydride, Na BH4) and further reduction of prepared.AuCu NCs has the unique effect of cotton (cotton effects), and when the two molar ratio is 1:1 maximum g factors (~0.57 * 10-4). Chiral optically active Cu doped can change the alloy. Although the single metal CuNCs is not stable, but the preparation of AuCu NCs alloy has the characteristics similar to the AuNCs stable. These results deepen the understanding of the opponent alloy MNCs optical activity, to further expand its understanding in asymmetric catalysis, has important significance.

【學位授予單位】：西南大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TB383.1;O657.3

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