The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Flow-induced shear stress and deformation of a core–shell-structured microcapsule in a microchannel

A numerical model was developed and validated to investigate the fluid–structure interactions between fully developed pipe flow and core–shell-structured microcapsule in a microchannel. Different flow rates and microcapsule shell thicknesses were considered. A sixth-order rotational symmetric distribution of von Mises stress over the microcapsule shell can be observed on the microcapsule with a thinner shell configuration, especially at higher flow rate conditions. It is also observed that when being carried along in a fully developed pipe flow, the microcapsule with a thinner shell tends to accumulate stress at a higher rate compared to that with a thicker shell. In general, for the same microcapsule configuration, higher flow velocity would induce a higher stress level over the microcapsule shell. The deformation gradient was used to capture the microcapsule's deformation in the present study. The effect of Young's modulus on the microcapsule shell on the microcapsule deformation was investigated as well. Our findings will shed light on the understanding of the stability of core–shell-structured microcapsule when subjected to flow-induced shear stress in a microfluidic system, enabling a more exquisite control over the breakup dynamics of drug-loaded microcapsule for biomedical applications.     

Functional Binding Surface of a β‐Hairpin VEGF Receptor Targeting Peptide Determined by NMR Spectroscopy in Living Cells

In this study, the functional interaction of HPLW peptide with VEGFR2 (Vascular Endothelial Growth Factor Receptor 2) was determined by using fast ¹⁵N‐edited NMR spectroscopic experiments. To this aim, ¹⁵N uniformly labelled HPLW has been added to Porcine Aortic Endothelial Cells. The acquisition of isotope‐edited NMR spectroscopic experiments, including ¹⁵N relaxation measurements, allowed a precise characterization of the in‐cell HPLW epitope recognized by VEGFR2.     

The spin-isospin decomposition of the nuclear symmetry energy from low to high density

The energy per particle BA in nuclear matter is calculated up to high baryon density in the whole isospin asymmetry range from symmetric matter to pure neutron matter.The results,obtained in the framework of the Brueckner-Hartree-Fock approximation with two-and three-body forces,confirm the well-known parabolic dependence on the asymmetry parameterβ=(N?Z)/A(β^2 law)that is valid in a wide density range.To investigate the extent to which this behavior can be traced back to the properties of the underlying interaction,aside from the mean field approximation,the spin-isospin decomposition of BA is performed.Theoretical indications suggest that theβ^2 law could be violated at higher densities as a consequence of the three-body forces.This raises the problem that the symmetry energy,calculated according to theβ^2 law as a difference between BA in pure neutron matter and symmetric nuclear matter,cannot be applied to neutron stars.One should return to the proper definition of the nuclear symmetry energy as a response of the nuclear system to small isospin imbalance from the Z=N nuclei and pure neutron matter.     

驻波声场中单分散细颗粒的相互作用特性

利用外加声场促进悬浮在气相中的细颗粒发生相互作用,进而引起颗粒的碰撞和凝并,使得颗粒平均粒径增大、数目浓度降低,是控制细颗粒排放的重要技术途径.为探究驻波声场中单分散细颗粒的相互作用,建立包含曳力、重力、声尾流效应的颗粒相互作用模型,采用四阶经典龙格-库塔算法和二阶隐式亚当斯插值算法对模型进行求解.将数值模拟得到的颗粒声波夹带速度和相互作用过程与相应的解析解和实验结果进行对比,验证模型的准确性.进而研究颗粒初始条件和直径对相互作用特性的影响.结果表明,初始时刻颗粒中心连线越接近声波波动方向、颗粒位置越接近波腹点,颗粒间的声尾流效应就越强,颗粒发生碰撞所需要的时间就越短.研究还发现,颗粒直径对颗粒相互作用的影响取决于初始时刻颗粒中心连线偏离声波波动方向的程度.当偏离较小时,颗粒直径越大,颗粒发生碰撞所需要的时间越短;当偏离很大时,直径较小的颗粒能够发生碰撞,而直径较大的颗粒则无法发生碰撞.     

Effect of high intensity ultrasound on gelation properties of silver carp surimi with different salt contents

Surimi from silver carp with different salt contents (0–5%) was obtained treated by high intensity ultrasound (HIU, 100 kHz 91 W·cm⁻²). The gelation properties of samples were evaluated by puncture properties, microstructures, water-holding capacity, dynamic rheological properties and intermolecular interactions. As the salt content increased from 0 to 5%, gel properties of surimi without HIU significantly improved. For samples with low-salt (0–2% NaCl) content, HIU induced obvious enhancement in breaking force and deformation. HIU promoted the protein aggregation linked by SS bonds, hydrophobic interactions and non-disulfide covalent bonds in surimi gels with low-salt content. Moreover, microstructures of HIU surimi gels with low-salt content were more compact than those of the corresponding control samples. HIU also improved the gelation properties of surimi with 3% NaCl to an extent. However, for high-salt (4–5% NaCl) samples, HIU decreased the breaking force and deformation of surimi gels due to the degradation of proteins suggested by increased TCA-soluble peptides. In conclusion, HIU effectively improved the gelation properties of surimi with low-salt content (0–2% NaCl), but was harmful for high-salt (4–5% NaCl) surimi. This might provide the theoretical basis for the production of low-salt surimi gels.     

Flow physics of normal and abnormal bioprosthetic aortic valves

Flow physics of transvalvular flows in the aorta with bioprosthetic valves are investigated using computational modelling. For the efficient simulations of flow-structure-interaction in transvalvular flows, a simplified, reduced degree of freedom valve model is employed with a sharp interface immersed boundary based incompressible flow solver. Simulations are performed for normal as well as abnormal valves with reduced leaflet motion that models the effect of early leaflet thrombosis. The structure of the aortic jet and the hemodynamic stresses on the aortic wall are analysed to understand the hemodynamic impacts and possible long-term clinical implications of sub-clinical, reduced leaflet motion. The simulation results have shown that the reduced leaflet motion tilts the direction of aortic jet and generates stronger flow separation and re-attachment on the aortic wall downstream from the reduced motion leaflets. The modified flow pattern increases the wall pressure fluctuation and average wall shear stress on the downstream aortic wall, and results in the asymmetric oscillatory shear index distributions, which may have long-term clinical implications such as aortic wall damage and remodelling.     

The mechanism of ethylene polymerization by nickel salicylaldiminato catalysts - Agostic interactions and their kinetic isotope effects

The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (k_H/k_D = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active.