手性光学活性金铜纳米颗粒的制备及分析应用研究

发布时间：2018-04-02 20:20

本文选题：手性荧光CuNCs　切入点：手性AuCu　出处：《西南大学》2017年硕士论文

【摘要】：自19世纪早期首次发现并提出天然手性光学活性(natural optical activity)以来,科学家们便致力于手性的相关研究工作。如今手性研究也促进了纳米科学技术的快速发展。2000年Schaaff和Whetten在用L-谷胱甘肽(glutathione,GSH)合成的金纳米团簇(gold nanoclusters,AuNCs)中首次观察到强的手性光学活性后,制备具有手性性质的金属纳米团簇(mental nanoclusters,MNCs)便成了研究热点。手性MNCs不仅具有大比表面积、荧光发射等特质,同时也有手性药物分子诱导的手性光学活性。更重要的是,手性MNCs为生命科学领域如生物大分子的识别传感、药物的不对称催化以及活体组织的靶向治疗等方面提供了一定的借鉴意义。关于MNCs的相关研究大部分局限于金(gold,Au)和银(silver,Ag),但含量丰富且广泛用于工业的非贵金属铜(copper,Cu)因其难以可控合成目标尺寸及在空气中易被氧化,使得关于手性铜纳米团簇(copper nanoclusters,CuNCs)研究依旧处于初期探索阶段。因此,本论文拟借纳米材料功能化修饰的技术和手性合成的研究成果,以手性配体青霉胺(penicillamine,Pen)作为稳定剂和还原剂,简单快速制备了稳定的手性荧光CuNCs。为进一步提高其稳定性,在合成过程中掺入Au而制备出更加稳定且具有优良手性光学活性响应的金铜纳米团簇(gold-copper nanoclusters,AuCu NCs)。因此,本文针对手性CuNCs与手性AuCu NCs在制备及分析应用方面开展了以下研究:1手性荧光CuNCs的制备及在p H传感与成像分析中的应用尽管关于AuNCs和银纳米团簇(silver nanoclusters,AgNCs)的手性光学活性研究已较为成熟,但现今对手性CuNCs及其潜在应用前景的了解非常局限。因此,我们通过Cu和手性药物Pen间的络合及还原作用成功制备了稳定的手性荧光CuNCs。除有优良的手性光学活性外(最大各向异性因子(anisotropy factor,g factor)为8.3×10-4),CuNCs还有对pH敏感的聚集诱导发光特性(aggregation-induced emission,AIE)。有趣的是,不同的Pen对映体对AIE有着重要的影响:rac-Pen的构型不支持电子间的相互作用,抑制了CuNCs的聚集。说明我们成功制备了兼药物手性、荧光且稳定的CuNCs。而高量子产率(quantum yield,QY)和较好生物相容性促使我们将其作为靶向定位染料,对细胞的生命活动进行了探索研究。虽然效果不明显,但将药物手性和MNCs荧光相结合作为信号探针用于生命活动的探索研究具有一定的借鉴价值。2手性AuCu NCs的制备及其手性光学活性分析尽管已有向AuNCs中掺入铂(platinum,Pt)、钯(palladium,Pd)、Cu等杂原子以获得独特的化学、催化和光学等性质报道,但用手性配体制备合金NCs并研究其手性光学活性的报道较少。因此我们通过直接合成法制备AuCu NCs:Pen对映体存在时加入不同摩尔比的氯金酸(chloroauric acid tetrahydrate,HAuCl4)和氯化铜(cupric chloride,CuCl_2),再经过硼氢化钠(sodium borohydride,Na BH4)进一步还原制得。AuCu NCs具有独特的科顿效应(cotton effects),且当二者摩尔比为1:1时有最大g factors(~0.57×10-4)。说明Cu的掺入会改变合金的手性光学活性。虽然单金属CuNCs不稳定,但制备的合金AuCu NCs却具备了类似于AuNCs稳定的特点。上述实验结果加深了对手性合金MNCs光学活性的认识,进一步拓展了其在不对称催化等领域的认识,具有重要的借鉴意义。
[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.

【学位授予单位】：西南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;O657.3

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