Unravelling the Role of Water in Ultrafast Excited-State Relaxation Dynamics within Nano-Architectures of Chlorophyll a

Water plays a pivotal role in structural stability of supramolecular pigment assemblies designed for natural light harvesting (for example, chlorosome antenna complex) as well as their artificial analogs. However, the dynamic role of water in the context of excite-state relaxation has not been explored till date, which we report here. Using femtosecond transient absorption spectroscopy, we investigate the excited-state dynamics of two types of nano-scale assemblies of chlorophyll a with different structural motifs, rod-shaped and micellar assemblies, that depend on the water content. We show how water participates in excess energy dissipation by vibrational cooling of the non-thermally populated Q_y band at different rates in different types of clusters but exhibits no polar solvation dynamics. For the micelles, we observe a bifurcation of stimulated emission line shape, whereas a positive-to-negative switching of differential absorption is observed for the rods; both these observations are correlated with their specific structural aspects. Density functional theory calculations reveal two possible stable ground state geometries of dimers, accounting for the bifurcation of line shape in micelles. Thus, our study elucidates water-mediated structure–function relationship within these pigment assemblies.     

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。     

无绝缘高温超导双饼线圈的瞬态电热特性分析

无绝缘高温超导线圈具有良好的电热稳定性和机械紧凑性,但其充电过程中却有明显的磁场延迟现象。为详细了解无绝缘高温超导线圈励磁过程的瞬态特性,建立了无绝缘高温超导线圈的同轴圆环等效电路模型。通过绕制一个670匝的无绝缘高温超导双饼线圈,在液氮温度下进行不同充电速率的励磁实验,初步验证了等效电路模型的正确性。基于该模型,针对线圈励磁过程的充电和恒流阶段,仿真得到了线圈各匝的径向电流分布规律和电热损耗特性。     

澄清对相对论性原理和协变性的误解

近来有些文章断言,在一个惯性参考系里能量守恒的物理系统,在别的参考系看来能量也一定守恒.实际上这些作者混淆了物理方程式的协变性和相对性原理.本文将澄清这一误解.     

Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).     

New soft porous frameworks based on lambda-zirconium phosphate and aliphatic dicarboxylates: Synthesis and structural characterization

New dicarboxylate-functionalized pillared materials with a general formula of λ-ZrPO₄(OH)_1-x(OOC(CH₂)_nCOO)_x/2(dmso) (n=6, 8 and 10) have been prepared by post-synthesis modification of the inorganic layers of λ-zirconium phosphate (λ-ZrP), where the superficial Chloride monovalent anionic ligands of λ-layer are partially exchanged with the divalent anionic ligands of a series of long-chain aliphatic dicarboxylic acids, namely octanedioic acid, decanedioic acid and dodecanedioic acid. The synthesized materials are characterized by X-ray diffractometry, FT-IR spectrophotometry, elemental and thermogravimetric analyses. The X-ray diffraction patterns show that the obtained solid phases are pure. Furthermore, the interlayer distance of λ-ZrP systematically increases from 1.02 to 1.59 nm as a result of the incorporation of the mentioned acids inside the interlayer gallery.     

Thermodynamic parameters for the complexation of water‐insoluble betulin derivatives with (2‐hydroxypropyl)‐γ‐cyclodextrin determined by phase‐solubility technique combined with capillary zone electrophoresis

The complexation of betulinic and betulonic acids (BIA and BOA) (pentacyclic lupane triterpenoids) with (2‐hydroxypropyl)‐γ‐cyclodextrin (HP‐γ‐CD) was studied at different temperatures using the method combining phase‐solubility technique and CZE. In contrast to mobility shift ACE utilizing the electrophoretic mobility, in this approach, the peak areas are used. The apparent binding (stability, formation) constants are obtained by the Higuchi and Connors method from the linear segment of compound solubility diagrams in CD solutions. It was found that the apparent binding constants of the HP‐γ‐CD complexes of BIA and BOA decrease with increasing temperature. The binding constants of BOA complexes are slightly higher than those of BIA complexes; this can be explained by difference in the hydration degrees of carbonyl and hydroxyl groups. On the basis of the binding constants obtained and their temperature dependences (van't Hoff plot), the enthalpy as well as entropy changes and Gibbs free energies were calculated. It was found that the complexation was characterized by negative changes of enthalpy and entropy, that is, it was controlled by enthalpy changes. The results obtained can be used for the optimization of microcapsulation processes of BOA and BIA with the HP‐γ‐CD application in order to increase solubility and bioavailability of these compounds.     

Concentrated steady vorticities of the Euler equation on 2-d domains and their linear stability

We consider concentrated vorticities for the Euler equation on a smooth domain $\mathrm{\Omega }?{\mathbf{R}}^2$ in the form of

$\omega =\sum _{j=1}^N{\omega }_j{\chi }_{{\mathrm{\Omega }}_j},|{\mathrm{\Omega }}_j|=\pi r_j^2,\underset{{\mathrm{\Omega }}_j}{\int }{\omega }_{j}d\mu ={\mu }_j\ne 0,$

supported on well-separated vortical domains ${\mathrm{\Omega }}_j$, $j=1,\dots ,N$, of small diameters $O(r_j)$. A conformal mapping framework is set up to study this free boundary problem with ${\mathrm{\Omega }}_j$ being part of unknowns. For any given vorticities ${\mu }_1,\dots ,{\mu }_N$ and small $r_1,\dots ,r_N\in {\mathbf{R}}^{+}$, through a perturbation approach, we obtain such piecewise constant steady vortex patches as well as piecewise smooth Lipschitz steady vorticities, both concentrated near non-degenerate critical configurations of the Kirchhoff–Routh Hamiltonian function. When vortex patch evolution is considered as the boundary dynamics of $?{\mathrm{\Omega }}_j$, through an invariant subspace decomposition, it is also proved that the spectral/linear stability of such steady vortex patches is largely determined by that of the 2N-dimensional linearized point vortex dynamics, while the motion is highly oscillatory in the 2N-codim directions corresponding to the vortical domain shapes.     

Triacetic acid lactone as a bioprivileged molecule in organic synthesis

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Stability of O3 + N2, O3 + O2 and O3 + CO2 double hydrates: DFT study

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