“Self-repairing” nanoshell for cell protection

Self-repair is nature''s way of protecting living organisms. However, most single cells are inherently less capable of self-repairing, which greatly limits their wide applications. Here, we present a self-assembly approach to create a nanoshell around the cell surface using nanoporous biohybrid aggregates. The biohybrid shells present self-repairing behaviour, resulting in high activity and extended viability of the encapsulated cells (eukaryotic and prokaryotic cells) in harsh micro-environments, such as under UV radiation, natural toxin invasion, high-light radiation and abrupt pH-value changes. Furthermore, an interaction mechanism is proposed and studied, which is successful to guide design and synthesis of self-repairing biohybrid shells using different bioactive molecules.     

Mechanically strong and stiff supramolecular polymers enabled by fiber reinforced long-chain alkane matrix

Fiber-reinforced-concrete (FRC) mechanism refers short discrete fibers that are uniformly distributed and randomly oriented, which offers an effective way to improve the mechanical performance of concrete. In the design of supramolecular polymers, an analogous concept of FRC appears to have been considered very rarely-although fibrous structure has been frequently observed/generated during the supramolecular polymerization. In this work, we apply the alkane thermosets, octadecane (C₁₈H₃₈) and tetracosane (C₂₄H₅₀), taking the role of “concrete”, and the low-molecular-weight monomer with long alkyl chains as the essential “fiber” component, to fabricate the “fiber reinforced supramolecular polymer”. Very much like FRC mechanism in material science, the resulting fiber reinforced supramolecular polymer thus exhibit unusually high mechanical strength and stiffness, which is unprecedented in the conventional supramolecular strategy.     

Half‐sandwich Ruthenium (II) complexes with triphenylamine modified dipyridine skeleton and application in biology/luminescence imaging

Four half‐sandwich ruthenium^II (Ru^II) complexes with triphenylamine‐modifed dipyridine frameworks were synthesized and characterized. The cytotoxicity of target complexes toward A549 (lung cancer cells), HeLa (cervical cancer cells) and HepG2 (hepatoma cells) were obtained by the MTT assay, which were superior to cisplatin with the IC₅₀ values changed from 2.4 ± 0.1 μM to 9.2 ± 2.7 μM. Meanwhile, complexes possess the ability of antimetastasis to cancer cells. Ru^II complexes could be transported by serum albumin, catalyze the conversion of NADH (the reduced state of nicotinamide‐adenine dinucleotide) to NAD⁺ and induce the accumulation of reactive oxygen species, which confirmed the antineoplastic mechanism of oxidation. Ru^II complexes could enter A549 cells followed by a non‐energy dependent cellular uptake mechanism, target lysosomes with the Pearson's colocalization coefficient of 0.75, lead to lysosomal damage, disturb the cell cycle (S phase), and eventually induce apoptosis. The results demonstrate that these Ru^II complexes are potential anticancer agents with dual functions, including metastasis inhibition and lysosomal damage.     

Reaction for the preparation of unique cyclic polysiloxanes with large size and narrow distribution

Utilizing collective forces between reactant and multiple catalyst molecules has been unprecedented due to the difficulty in realizing high order catalysis. Inspired by the power of collective forces in enzymes and organic catalysts, herein we report a rare example of high order catalysis for ring opening reaction (ROR) of strained rings by methanol. ROR is an important way to produce various polysiloxanes, but usually suffers from serious side reactions especially at high conversion, and currently there is a need to design new reaction pathway to achieve low molecular dispersity. In our study, the judiciously designed strained spiral cyclosiloxanes enable a high order catalysis by methanol, and this new methodology leads to a cyclic polysiloxane with high molecular weight and low dispersity even at full conversion of reactants. Kinetic study indicates an extremely unusual high-order reaction involving multiple methanol molecules per reaction, also confirmed by quantum calculation which reveals the presence of zwitterionic ions stabilized by collecting force of hydrogen bonds by methanol molecules. The inherent driving force for this unusual phenomenon is dominated by enthalpy stabilization of the reactive intermediates through hydrogen bonding. The selective formation of Si O Si bonds, instead of silanol products, reflects the power of scientific design.     

改性二氧化硅纳米颗粒提高二氧化碳泡沫稳定性的研究

通过纳米二氧化硅的硅烷化改性, 使其在高矿化度盐水中可以稳定存在的前提下, 研究了改性纳米颗粒与阳离子表面活性剂十二烷基三甲基氯化铵混合体系的溶液稳定性及协同稳定CO₂泡沫的效果. 研究结果表明, 无机盐离子对改性纳米颗粒与阳离子表面活性剂间的静电吸引力具有屏蔽作用, 且矿化度越高, 屏蔽效果越明显, 从而混合溶液更易于在高盐水中稳定; 纳米颗粒表面的活性剂吸附层受二者浓度的影响, 进而影响了颗粒的亲/疏水性; 当混合体系中的表面活性剂浓度低于临界胶束浓度(CMC)时, 混合溶液与CO₂的界面张力高于单独活性剂溶液, 而当活性剂浓度高于CMC时, 对CO₂-溶液界面张力几乎无影响, 最低界面张力可降至6 mN/m左右; 改性纳米颗粒的加入可以进一步提高CO₂体相泡沫半衰期一倍以上, 但受二者浓度比例的影响; 纳米颗粒的加入有效提高了多孔介质中泡沫的表观黏度, 最大增幅由20 mPa·s增至55 mPa·s左右, 泡沫黏度增加接近3倍, 增强了CO₂泡沫驱的封堵作用.