An Aptamer-Nanotrain Assembled from Six-Letter DNA Delivers Doxorubicin Selectively to Liver Cancer Cells

Expanding the number of nucleotides in DNA increases the information density of functional DNA molecules, creating nanoassemblies that cannot be invaded by natural DNA/RNA in complex biological systems. Here, we show how six-letter GACTZP DNA contributes this property in two parts of a nanoassembly: 1) in an aptamer evolved from a six-letter DNA library to selectively bind liver cancer cells; and 2) in a six-letter self-assembling GACTZP nanotrain that carries the drug doxorubicin. The aptamer-nanotrain assembly, charged with doxorubicin, selectively kills liver cancer cells in culture, as the selectivity of the aptamer binding directs doxorubicin into the aptamer-targeted cells. The assembly does not kill untransformed cells that the aptamer does not bind. This architecture, built with an expanded genetic alphabet, is reminiscent of antibodies conjugated to drugs, which presumably act by this mechanism as well, but with the antibody replaced by an aptamer.     

“非保护型”金属胶体纳米簇形成机理研究

碱-乙二醇法制备的"非保护型"金属及合金纳米簇由表面吸附的溶剂分子和简单离子实现稳定化,它们被广泛用于制备高性能复相催化剂和研究复相催化剂中的尺寸、组成、载体表面基团以及修饰剂对催化性能的影响。关于此类非保护金属纳米簇的形成过程及机理的认识尚有待进一步深化。本文采用原位快速扫描X射线吸收精细结构谱(QXAFS)、原位紫外-可见(UV-Vis)吸收光谱、透射电子显微镜和动态光散射技术研究了碱-乙二醇法合成中非保护型金属胶体纳米簇的形成过程与机理。结果表明,在碱-乙二醇法合成非保护型Pt金属纳米簇的过程中,室温下即有部分Pt(IV)被还原至Pt(II)。随着反应温度的升高,OH-逐渐取代与Pt离子配位的Cl-,在Pt―Pt键形成之前,反应体系的UV-Vis吸收光谱中可观察到明显的纳米粒子的散射信号,原位QXAFS分析表明Pt纳米簇是由Pt氧化物纳米粒子还原所形成的;在Ru金属纳米簇的形成过程中,OH-首先取代了Ru Cl_3中的Cl~-,形成羟基配合物Ru(OH) _6~(3-),后者进一步缩合形成氧化钌纳米粒子,最终Ru金属纳米簇由乙二醇还原氧化钌纳米粒子形成。由于先形成了氧化物纳米粒子,后续的还原反应被限制在氧化物纳米粒子内,使最终得到的非保护型金属纳米簇具有尺寸小、分布窄的特点。本工作所获得的知识对发展高性能能源转化催化剂、精细化学合成催化剂、传感器等功能体系具有重要意义。     

Uptake and Reduction of Arsenate by Dunaliella sp.

Uptake and reduction of arsenate [AS(V)] by Dunaliella sp. cells were determined to investigate the metabolic processes of arsenic in the alga. Cellular uptake of arsenic by Dunaliella sp. cells was markedly affected by the form of arsenic in the medium. The content of arsenic taken up by Dunaliella sp. cells increased rapidly with time on addition of As(V) to the medium. However, in the case of addition of arsenite [As(III)], the gradient of arsenic uptake by Dunaliella sp. cells was low, and arsenic content was small. In the water-soluble fraction of arsenic taken up by Dunaliella sp. cells with exposure to As(V), arsenic was in the forms of organic arsenic, As(V) and As(III). The content of As(V) in the water-soluble fraction increased with exposure time. The content of As(III) also increased with time, but remained constant after 5 h of exposure. On the other hand, organic arsenic content was small and did not increase with time. It was found that Dunaliella sp. takes up As(V) and readily reduces it to As(III)     

Photoinduced Specific Acylation of Phenolic Hydroxy Groups with Aldehydes

A convenient method is reported to specifically acylate phenolic hydroxyl groups through a radical pathway. When a mixture of an aldehyde and a phenol in ethyl acetate is irradiated with blue light in the presence of iridium and nickel bromide catalysts at ambient temperature, phenoxyl and acyl radicals are transiently generated in situ and cross‐couple to furnish an ester. Aliphatic hydroxy groups remain untouched under the reaction conditions.     

One‐Pot Synthetic Procedure for2,2′‐Disubstituted Biaryls via the Suzuki Coupling Reaction of Aryl Triflates in a Biphasic Solvent System

A one‐pot synthetic procedure for 2,2′‐disubstituted biaryls was developed via a Suzuki cross‐coupling reaction of aryl triflates in a biphasic solvent system. The effects of various bases and solvents were investigated. Results showed that the Na₂CO₃–toluene/H₂O combination gave the highest yields.     

Fe K‐Edge X‐ray Absorption Fine Structure Determination of γ‐Al2O3‐Supported Iron‐Oxide Species

The structure of FeO_x species supported on γ‐Al₂O₃ was investigated by using Fe K‐edge X‐ray absorption fine structure (XAFS) and X‐ray diffraction (XRD) measurements. The samples were prepared through the impregnation of iron nitrate on Al₂O₃ and co‐gelation of aluminum and iron sulfates. The dependence of the XRD patterns on Fe loading revealed the formation of α‐Fe₂O₃ particles at an Fe loading of above 10 wt %, whereas the formation of iron‐oxide crystals was not observed at Fe loadings of less than 9.0 wt %. The Fe K‐edge XAFS was characterized by a clear pre‐edge peak, which indicated that the Fe?O coordination structure deviates from central symmetry and that the degree of Fe?O?Fe bond formation is significantly lower than that in bulk samples at low Fe loading (<9.0 wt %). Fe K‐edge extended XAFS oscillations of the samples with low Fe loadings were explained by assuming an isolated iron‐oxide monomer on the γ‐Al₂O₃ surface.     

Thermodynamically Induced Conformational Changes of the Cyanobacterial Circadian Clock Protein KaiB

Site-directed spin labeling electron spin resonance (ESR) was applied to investigate the local environment of the cyanobacterial circadian clock protein KaiB. We prepared five cysteine residue-substituted mutants of KaiB labeled with maleimide spin label (MSL). By comparing the ESR spectra of KaiBs carrying MSL at different positions (Thr64, Lys67, Tyr94, Gly98, and Ala101), local conformational changes were identified. The ESR spectra of MSL-T64C and MSL-K67C showed the relatively slow motion of MSL characterized by τ?=?79 and 59?ns at 4°C, respectively. The spectra of MSL-Y94C, MSL-G98C and MSL-A101C showed relatively fast motion characterized by τ?=?8.0, 4.1 and 3.1?ns at 4°C, respectively. These differences were explained by the local environments of the position in KaiB. On incubation at 40°C for 24?h, all ESR spectra of the labeled KaiBs changed, which can be explained by the structural relaxation of KaiB.