超强频率梳激光场驱动下多光子共振谐波辐射的相位突变研究

本文从理论上研究了在双色频率梳激光场驱动下多光子谐波辐射光谱中的相位突变现象。我们利用Floquet理论非微扰地模拟了频率梳激光场与原子分子等量子系统的相互作用过程。谐波辐射信号是多光子偶极跃迁相干叠加的结果,通过调节频率梳激光场间的相对相位,可以相干地控制谐波辐射信号的强度。通过对谐波信号进行傅里叶变换,可以提取不同跃迁路径的相对相位信息。我们通过改变频率梳组激光场的强度和频率组分实现多光子跃迁频率,让其跨越共振跃迁频率时,谐波相位会发生突变。从而可以观测超强激光场驱动下量子系统共振跃迁频率的斯塔克能移。     

Oxidative Epigallocatechin Gallate Coating on Polymeric Substrates for Bone Tissue Regeneration

Plant derived flavonoids have not been well explored in tissue engineering applications due to difficulties in efficient formulations with biomaterials for controlled presentation. Here, the authors report that surface coating of epigallocatechin gallate (EGCG) on polymeric substrates including poly (L‐lactic acid) (PLLA) nanofibers can be performed via oxidative polymerization of EGCG in the presence of cations, enabling regulation of biological functions of multiple cell types implicated in bone regeneration. EGCG coating on the PLLA nanofiber promotes osteogenic differentiation of adipose‐derived stem cells (ADSCs) and is potent to suppress adipogenesis of ADSCs while significantly reduces osteoclastic maturation of murine macrophages. Moreover, EGCG coating serves as a protective layer for ADSCs against oxidative stress caused by hydrogen peroxide. Finally, the in vivo implantation of EGCG‐coated nanofibers into a mouse calvarial defect model significantly promotes the bone regeneration (61.52 ± 28.10%) as compared to defect (17.48 ± 11.07%). Collectively, the results suggest that EGCG coating is a simple bioinspired surface modification of polymeric biomaterials and importantly can thus serve as a promising interface for tuning activities of multiple cell types associated with bone fracture healing.     

Pentapnictogen heterocyclic monoanions: Structure,stability, and aromaticity

Inorganic planar ring-shape molecules with 4n + 2 π electrons are always the focus of experimental synthesis and theoretical research due to their potential aromaticity and stability. In this work, the whole series of five-membered heterocycle monoanions X _nY_5-n⁻ (X, Y = group 15 elements; n = 1-4) were thoroughly investigated by means of density functional theory calculations. They all have large formation energies and HOMO-LUMO gap energies, suggesting the potential thermodynamic and kinetic stability. Their aromaticities are comparable to that of typical aromatic hydrocarbons. Their thermal stabilities were firmly established by the ab initio molecular dynamics simulations. As most of them are predicted for the first time, their various spectra were simulated for experimental characterization. Furthermore, we demonstrate that these five-membered cyclic anions can be employed as η⁵-ligand to construct novel all-inorganic metallocenes, which may serve as the building blocks of low-dimensional nanomaterials.     

Global dynamics of a flexible asymmetrical rotor

Nonlinear Dynamics - Global dynamics of a flexible asymmetrical rotor resting on vibrating supports is investigated. Hamilton’s principle is used to derive the partial differential governing...     

Rational Development of Remote C−H Functionalization of Biphenyl: Experimental and Computational Studies

A simple and efficient nitrile-directed meta-C−H olefination, acetoxylation, and iodination of biaryl compounds is reported. Compared to the previous approach of installing a complex U-shaped template to achieve a molecular U-turn and assemble the large-sized cyclophane transition state for the remote C−H activation, a synthetically useful phenyl nitrile functional group could also direct remote meta-C−H activation. This reaction provides a useful method for the modification of biaryl compounds because the nitrile group can be readily converted to amines, acids, amides, or other heterocycles. Notably, the remote meta-selectivity of biphenylnitriles could not be expected from previous results with a macrocyclophane nitrile template. DFT computational studies show that a ligand-containing Pd–Ag heterodimeric transition state (TS) favors the desired remote meta-selectivity. Control experiments demonstrate the directing effect of the nitrile group and exclude the possibility of non-directed meta-C−H activation. Substituted 2-pyridone ligands were found to be key in assisting the cleavage of the meta-C−H bond in the concerted metalation–deprotonation (CMD) process.     

排名聚合算法在少量长列表聚合中的性能比较分析

排名聚合将多个排名列表聚合成一个综合排名列表,可应用于推荐系统、链路预测、元搜索、提案评选等.当前已有工作从不同角度对不同排名聚合算法进行了综述、比较,但存在算法种类较少、数据统计特性不清晰、评价指标不够合理等局限性.不同排名聚合算法在提出时均声称优于已有算法,但是用于比较的方法不同,测试的数据不同,应用的场景不同,因此何种算法最能适应某一任务在很多情况下仍不甚清楚.本文基于Mallows模型,提出一套生成统计特性可控的不同类型的排名列表的算法,使用一个可应用于不同类型排名列表的通用评价指标,介绍9种排名聚合算法以及它们在聚合少量长列表时的表现.结果发现启发式方法虽然简单,但是在排名列表相似度较高、列表相对简单的情况下,能够接近甚至超过一些优化类方法的结果;列表中平局数量的增长会降低聚合排名的一致性并增加波动;列表数量的增加对聚合效果的影响呈现非单调性.整体而言,基于距离优化的分支定界方法 (FAST)优于其他各类算法,在不同类型的排名列表中表现非常稳定,能够很好地完成少量长列表的排名聚合.     

Efficient Quantum Dot Light-Emitting Diodes Based on Well-Type Thick-Shell CdxZn1−xS/CdSe/CdyZn1−yS Quantum Dots

Device grade quantum dots (QDs) require QDs ensembles to retain their original superior optical properties as in solution. QDs with thick shells are proven effective in suppressing the inter-dot interaction and preserving the emission properties for QDs solids. However, lattice strain–induced defects may form as the shell grows thicker, resulting in a notable photoluminescence quenching. Herein, a well-type Cd_xZn_1−xS/CdSe/Cd_yZn_1−yS QDs is proposed, where ternary alloys CdZnS are adopted to match the lattice parameter of intermediate CdSe by separately adjusting the x and y parameters. The resultant thick-shell Cd_0.5Zn_0.5S/CdSe/Cd_0.73Zn_0.27S QDs reveal nonblinking properties with a high PL QY of 99% in solution and 87% in film. The optimized quantum dot light-emitting diodes (QLEDs) exhibit a luminance of 31547.5 cd m⁻² at the external quantum efficiency maximum of 21.2% under a bias of 4.0 V. The shell thickness shows great impact on the degradation of the devices. The T₅₀ lifetime of the QLEDs with 11.2 nm QDs reaches 251 493 h, which is much higher than that of 6.5 and 8.4 nm QDs counterparts. The performances of the well-type thick-shell QLEDs are comparable to state-of-the-art devices, suggesting that this type of QDs is a promising candidate for efficient optoelectronic devices.     

Two homosecoiridoids from the fl ower buds of Lonicera japonica

Two new homosecoiridoids, named loniaceticiridoside (1) and lonimalondialiridoside (2), were isolated from an aqueous extract of the flower buds of Lonicera japonica. Their structures including the absolute configuration were determined by extensive spectroscopic studies, especially by 2D NMR and CD data analysis. A proposed biosynthetic pathway and preliminary investigations of the biological activity of compounds 1 and 2 are also discussed.