基于金纳米棒的生物检测、细胞成像和癌症的光热治疗

由于金纳米棒颗粒独特的可调的表面等离子共振特性,使得金纳米棒颗粒在纳米复合材料和功能化纳米器件的构建、纳米生物技术、生物医学等领域具有广泛而重要的应用前景。本文综述了金纳米棒颗粒的生物检测、细胞成像和癌症的光热治疗方面的最新研究进展,并介绍了金纳米棒颗粒的光学性质和金纳米棒颗粒和几种主要的表面修饰方法,对金纳米棒颗粒在生物应用过程中存在的主要问题进行了讨论。     

金纳米棒——从可控制备与修饰到纳米生物学与生物医学应用

金纳米棒因其独特的光学活性(纵向和横向两个等离子体共振吸收峰,可调范围从可见光区到近红外区)、长径比可调,表面易于修饰,生物相容性良好而使得其在纳米生物学和生物医学等领域具有广泛的应用前景。金纳米棒的合成及表面修饰直接决定着其物理化学性质,进而影响其生物相容性及其在生物医学中的应用。本文综述了金纳米棒的可控制备方法(包括模板法、电化学法、光化学法和晶种法)、表面可控修饰方法及其在纳米生物学和生物医学中的应用新进展,重点总结了金纳米棒的表面可控修饰及其在分子探针、生物传感、生物成像、药物载体、基因载体和光热疗法的最新研究进展。最后针对金纳米棒在生物应用过程中的一些瓶颈问题(如:特异性识别能力需要增强和荧光量子产率尚待提高等)提出了将手性分子或智能聚合物引入到金纳米棒表面进行可控修饰,以期增强其特异性识别能力并提高荧光量子产率,为金纳米棒的发展提供了新的思路。     

金纳米棒的偏光特性及其作为方向探针在单分子水平成像上的应用

随着生物医学的发展,对生物成像技术和成像分辨率的要求越来越高,纳米材料和技术被越来越多地应用到生物医学领域.各向异性的金纳米棒由于具有较高的电子密度、较大的吸收截面、特殊的表面等离子共振光学特性、优良的生物相容性和化学稳定性而被广泛应用于生物成像领域.复杂的活细胞组织内纳米级目标的位置和动态的空间构型对于我们理解很多生物物理学过程的细节问题至关重要.本文结合本课题组在该领域的研究经验,并从金纳米棒局部等离子共振特性和偏光特性出发,综述了金纳米棒作为方向探针的3D跟踪定位成像技术与手段.包括暗场成像技术、微分干涉成像、光热成像、共聚焦显微镜成像等生物成像技术和脱焦成像、全内反成像和双通道等生物成像手段.同时阐述了金纳米棒作为方向探针在生物成像领域中的应用进展.     

金纳米棒的光学性质研究进展

金纳米棒在紫外-可见-近红外(UV-Vis-NIR)波段具有独特的可调节表面等离子体共振(SPR)光学特性,其良好的稳定性、低生物毒性、亮丽的色彩和在催化、信息存储、生物医学等领域广阔的应用前景受到相关研究领域的广泛关注.结合已有的研究基础,本文主要综述了金纳米棒光学性质的研究进展,包括表面等离子体共振、局域场增强效应、共振耦合效应及荧光特性,并对金纳米棒的应用做了展望.     

大长径比金纳米棒的合成及其单细胞毒性研究

利用三步晶种生长法合成长径比约为14的大长径比金纳米棒(GNR),利用巯基十一酸(MUDA)对金纳米棒表面进行了生物适应性修饰,并在宏观水平上研究了修饰前后的金纳米棒在对细胞活性的影响。利用单细胞方法分别考察了修饰后的纳米金棒对细胞贴壁过程、增殖速率、细胞内ROS以及骨架排布的影响。虽然MTT细胞活性结果显示内吞后的金纳米棒对细胞无毒,但单细胞毒性分析方法发现,不同浓度纳米金棒对早期贴壁过程有较小的影响,且内吞的纳米金棒在一定程度上促进了细胞的增殖,而高浓度下纳米金棒引起了细胞内ROS含量的升高,并破坏了细胞内骨架纤维排布。本研究建立了用单细胞行为分析纳米颗粒对细胞毒性的方法,证明了以往仅仅利用MTT等宏观手段分析纳米材料生物适应性是不足的。纳米材料在生物医学领域的进一步应用还应考虑单细胞及分子水平上的毒性效应。     

金纳米棒的合成及应用研究

金纳米棒具有独特的物理化学性质和良好的生物相容性,在众多的各向异性金纳米结构中引起了研究者的关注.本文综述了金纳米棒的各种制备方法,详尽评价了种子法制备金纳米棒过程的影响因素,介绍了金纳米棒用作药物载体和癌症的光热治疗方面的应用进展,并对金纳米棒的研究前景进行了展望.     

金纳米棒:合成、修饰、自组装、SERS及生物医学应用

纳米颗粒作为信号感应单元在化学与生物传感应用中已引起广泛关注,这些功能和金属纳米结构与光相互作用时产生的表面等离子体共振密切相关.表面增强拉曼散射(SERS),是指吸附在粗糙的金属纳米结构表面的被分析物,在光照射下其拉曼光谱获得显著增强的异常表面光学现象,近年来.SERS技术已广泛用于物质检测和生物传感等研究,在生物医学领域表现出巨大的应用潜力并取得了令人瞩目的研究成果.本文阐述了金纳米棒的制备方法、表面修饰和共轭生物分子的方法.并从金纳米棒表面增强拉曼散射的角度系统阐述基于金纳米棒表面增强拉曼散射的1D,2D,3D自组装,并介绍了近期金纳米棒表面增强拉曼散射在生物医学检测与成像中最具有代表性的应用研究.     

硫化金包覆金纳米棒局域等离子体共振的纳米生物传感器研究

纳米生物传感技术是近年来迅速发展起来的一种超微生物传感技术,具有高选择性、高灵敏度、快速、方便检测等优点.尤其基于金纳米颗粒的生物探针的研究备受关注.近年来,对基于棒状金纳米结构的生物探针合成及在生物传感及医学成像中的应用的研究是金纳米棒研究的重要方向.纳米金由于其制备简单、易于修饰、稳定性和生物相容性好等优点,被广泛应用于生物分子的识别和检测领域.     

金纳米棒的制备、生长机理及纯化

金纳米棒由于其独特物理性质而在众多的各向异性金纳米颗粒中赢得了关注。目前,金纳米棒在纳米电子学、光学、生物医药等研究领域均具有良好的应用前景。对金纳米棒合成的有效调控直接决定着其形状、尺寸和长径比,而这些又进一步影响着金纳米棒的物理性质。本文梳理了金纳米棒制备方法的发展脉络,以模板法、电化学方法、种子生长法以及近年来出现的无种子生长法为主线,系统综述了金纳米棒制备过程实验参数调控对产物结构、物理性质的影响,详细阐述了关于单晶以及孪晶金纳米棒的生长机理,并介绍了提高产物纯度的分离纯化手段。     

局域表面等离子体共振辅助的金纳米棒/聚合物纳米复合材料的双光子聚合

本文研究了金纳米棒的局域表面等离子体共振效应在双光子聚合过程中的作用,即当激发光与金纳米棒表面等离子体共振波长相匹配时,会在金纳米棒表面产生很强的局域电磁场,从而引发双光子聚合。通过采用与金纳米棒表面等离子体共振波长相同的飞秒激光,在低于光刻胶聚合阈值的功率下照射含有金纳米棒的光刻胶,制备聚合物包覆金纳米棒的纳米复合材料。透射电子显微镜结果表明,当飞秒激光功率为0.6 W、光斑直径为1.6 cm、照射时间为0.3 s时,金纳米棒表面成功聚合上厚度为5 nm左右的聚合物。本研究在制备聚合物/金属纳米粒子方面提供了一种简单可行的方法,有望在纳米光子学、纳米传感器等新兴领域得到应用。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.