Construction of Asymmetrical Hexameric Biomimetic Motors with Continuous Single‐Directional Motion by Sequential Coordination

The significance of bionanomotors in nanotechnology is analogous to mechanical motors in daily life. Here the principle and approach for designing and constructing biomimetic nanomotors with continuous single‐directional motion are reported. This bionanomotor is composed of a dodecameric protein channel, a six‐pRNA ring, and an ATPase hexamer. Based on recent elucidations of the one‐way revolving mechanisms of the phi29 double‐stranded DNA (dsDNA) motor, various RNA and protein elements are designed and tested by single‐molecule imaging and biochemical assays, with which the motor with active components has been constructed. The motor motion direction is controlled by three operation elements: (1) Asymmetrical ATPase with ATP‐interacting domains for alternative DNA binding/pushing regulated by an arginine finger in a sequential action manner. The arginine finger bridges two adjacent ATPase subunits into a non‐covalent dimer, resulting in an asymmetrical hexameric complex containing one dimer and four monomers. (2) The dsDNA translocation channel as a one‐way valve. (3) The hexameric pRNA ring geared with left‐/right‐handed loops. Assessments of these constructs reveal that one inactive subunit of pRNA/ATPase is sufficient to completely block motor function (defined as K = 1), implying that these components work sequentially based on the principle of binomial distribution and Yang Hui's triangle.     

White‐Emissive Self‐Assembled Organic Microcrystals

Organic semiconductor micro‐/nanocrystals with regular shapes have been demonstrated for many applications, such as organic field‐effect transistors, organic waveguide devices, organic solid‐state lasers, and therefore are inherently ideal building blocks for the key circuits in the next generation of miniaturized optoelectronics. In the study, blue‐emissive organic molecules of 1,4‐bis(2‐methylstyryl)benzene (o‐MSB) can assemble into rectangular microcrystals at a large scale via the room‐temperature solution‐exchange method. Because of the Förster resonance energy transfer, the energy of the absorbed photons by the host matrix organic molecules of o‐MSB can directly transfer to the dopant organic molecules of tetracene or 1,2:8,9‐dibenzopentacene (DBP), which then emit visible photons in different colors from blue to green, and to yellow. More impressively, by modulating the doping molar ratios of DBP to o‐MSB, bright white‐emissive organic microcrystals with well‐preserved rectangular morphology can be successfully achieved with a low doping ratio of 1.5%. These self‐assembled organic semiconductor microcrystals with multicolor emissions can be the white‐light sources for the integrated optical circuits at micro‐/nanoscale.     

水杨醛亚胺前过渡金属烯烃聚合催化剂研究进展

水杨醛亚胺前过渡金属催化剂是由水杨醛亚胺配体和前过渡金属配位生成的一种性能优越、用途广泛的烯烃聚合催化剂。水杨醛亚胺配体具有易于通过有机合成手段引入不同取代基的特点,因此通过改变催化活性中心附近的空间位阻效应、电子效应及金属活性中心数量,可以实现对聚合活性、聚合产物及产物分布的调控。文中综述了水杨醛亚胺前过渡金属催化剂的开发现状,重点阐述了水杨醛亚胺前过渡金属催化剂的配体结构对催化性能的影响,涉及到高选择性乙烯三聚、乙烯/α-烯烃、乙烯/极性单体共聚、乙烯聚合生产超高分子量聚乙烯等众多烯烃聚合领域,为这类催化剂的深入研究及工业化应用提供参考。     

Study of DNA Origami Dimerization and Dimer Dissociation Dynamics and of the Factors that Limit Dimerization

Organizing DNA origami building blocks into higher order structures is essential for fabrication of large structurally and functionally diverse devices and molecular machines. Unfortunately, the yields of origami building block attachment reactions are typically not sufficient to allow programed assembly of DNA devices made from more than a few origami building blocks. To investigate possible reasons for these low yields, a detailed single‐molecule fluorescence study of the dynamics of rectangular origami dimerization and origami dimer dissociation reactions is conducted. Reactions kinetics and yields are investigated at different origami and ion concentrations, for different ion types, for different lengths of bridging strands, and for the “sticky end” and “weaving welding” attachment techniques. Dimerization yields are never higher than 86%, which is typical for such systems. Analysis of the dynamic data shows that the low yield cannot be explained by thermodynamic instability or structural imperfections of the origami constructs. Atomic force microscopy and gel electrophoresis evidence reveal self‐dimerization of the origami monomers, likely via blunt‐end interactions made possible by the presence of bridging strands. It is suggested that this mechanism is the major factor that inhibits correct dimerization and means to overcome it are discussed.     

All‐Organic Dual Spin Valves with Well‐Resolved Four Resistive‐States

The formation of all‐organic dual spin valves (DSVs) with three organic spin‐selective layers, that is, spin‐injection, spin‐detection, and an additional spin‐filtering layer at the intermediate, is reported. As spin‐selective layers, manganese‐ and cobalt phthalocyanines, which are well‐known single‐molecule magnets, are used in their immobilized forms, so that all‐organic DSVs can be prefabricated for characterization. The three spin‐selective layers have provided four configurations with at most two spin‐flip interfaces enforcing spin‐flipping at the two nonmagnetic organic spacer layers, for which copper phthalocyanine is used. Since a couple of the four configurations have exhibited similar resistivities, the degeneracy in the resistive‐states is broken through asymmetric spin‐injection and spin‐detection layers and also through asymmetric thickness of the nonmagnetic spacer layers. When both the spin‐flip interfaces are made operative independently, a 2‐bit logic with four distinct resistive states can be achieved.     

高聚物中渗入C_(60)/C_(70)后计算内阻的压力函数法

应用宏观力学模型对高聚物渗入Ｃ６０／Ｃ７０后的微观内阻机理进行力学分析,提出分子滚珠轴承的设想,得出计算内阻的压力函数法和滚滑内阻权函数的概念。     

Application of the independent molecule model to elucidate the dynamics of structure I methane hydrate: a second report

Two model systems of methane hydrate are constructed. One has a small cage surrounded by 12 large cages. The other has a large cage surrounded by four small cages and ten large cages. Three different H-bonding network patterns between waters are formed, and three random configurations of methane in each cage are chosen. A new method called the surface water fixed model is presented in which the energy minimum conformations for both model systems are preserved close to the X-ray crystallized structure. With normal mode analysis, we calculated frequencies of 2916.6 cm⁻¹ for a small cage at a centre, 2915.9 cm⁻¹ not at a centre, and 2911.7 cm⁻¹ for a large cage at a centre, and 2911.3 cm⁻¹ not at a centre. These frequencies are in moderate agreement with the corresponding Raman spectra, though not adequate. With our new method, however, it should be possible to improve agreement with the Raman spectra, if a model system vastly larger than the present model systems were constructed.