Photosynthetic Antenna‐Reaction Center Mimicry with a Covalently Linked Monostyryl Boron‐Dipyrromethene–Aza‐Boron‐Dipyrromethene–C60 Triad

An efficient functional mimic of the photosynthetic antenna‐reaction center has been designed and synthesized. The model contains a near‐infrared‐absorbing aza‐boron‐dipyrromethene (ADP) that is connected to a monostyryl boron‐dipyrromethene (BDP) by a click reaction and to a fullerene (C₆₀) using the Prato reaction. The intramolecular photoinduced energy and electron‐transfer processes of this triad as well as the corresponding dyads BDP‐ADP and ADP‐C₆₀ have been studied with steady‐state and time‐resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge‐separated states. Such calculations show that electron transfer from the singlet excited ADP (¹ADP*) to C₆₀ yielding ADP^.+‐C₆₀^.? is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from ¹BDP* to ADP in the dyad BDP‐ADP and electron transfer from ¹ADP* to C₆₀ in the dyad ADP‐C₆₀. Sequential energy and electron transfer have also been clearly observed in the triad BDP‐ADP‐C₆₀. By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈10¹¹ s^?1). The dynamics of electron transfer through ¹ADP* has also been studied by monitoring the formation of C₆₀ radical anion at 1000 nm. A fast charge‐separation process from ¹ADP* to C₆₀ has been detected, which gives the relatively long‐lived BDP‐ADP^.+C₆₀^.? with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge‐separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP‐ADP and ADP‐C₆₀, and the triad BDP‐ADP‐C₆₀ are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems.     

Fast,Reversible Lithium Storage with a Sulfur/Long‐Chain‐Polysulfide Redox Couple

The cathodic reactions in Li–S batteries can be divided into two steps. Firstly, elemental sulfur is transformed into long‐chain polysulfides (S₈?Li₂S₄), which are highly soluble in the electrolyte. Next, long‐chain polysulfides undergo nucleation reaction and convert into solid‐state Li₂S₂ and Li₂S (Li₂S₄?Li₂S) by slow processes. As a result, the second‐step of the electrochemical reaction hinders the high‐rate application of Li–S batteries. In this report, the kinetics of the sulfur/long‐chain‐polysulfide redox couple (theoretical capacity=419 mA h g^?1) are experimentally demonstrated to be very fast in the Li–S system. A Li–S cell with a blended carbon interlayer retains excellent cycle stability and possesses a high percentage of active material utilization over 250 cycles at high C rates. The meso‐/micropores in the interlayer are responsible for accommodating the shuttling polysulfides and offering sufficient electrolyte accessibility. Therefore, utilizing the sulfur/long‐chain polysulfide redox couple with an efficient interlayer configuration in Li–S batteries may be a promising choice for high‐power applications.     

Enthalpy–Entropy Compensation Combined with Cohesive Free‐Energy Densities for Tuning the Melting Temperatures of Cyanobiphenyl Derivatives

This work illustrates how minor structural perturbations produced by methylation of 4′‐(dodecyloxy)‐4‐cyanobiphenyl leads to enthalpy–entropy compensation for their melting processes, a trend which can be analyzed within the frame of a simple intermolecular cohesive model. The transformation of the melting thermodynamic parameters collected at variable temperatures into cohesive free‐energy densities expressed at a common reference temperature results in a novel linear correlation, from which melting temperatures can be simply predicted from molecular volumes.     

Improvement of TiO2/Dye/Electrolyte Interface Conditions by Positional Change of Alkyl Chains in Modified Panchromatic Ru Complex Dyes

A series of panchromatic ruthenium sensitizers ( MJ sensitizers) with attached thiophene and phenyl units bearing alkyl chains was synthesized. A new synthetic route was used to examine all possible positions for the alkyl chains. The absorption spectra showed the sum of a ruthenium complex and peripheral organic chromophore units. The hypochromic effect and blueshift of the metal‐to‐ligand charge‐transfer band observed in the modified ruthenium sensitizers were suppressed by changing the positions of the alkyl chains on the attached thiophene ring. Changing only one alkyl chain also influenced the performance of dye‐sensitized solar cells. Ruthenium sensitizer MJ‐10 with bulky substituent harvests visible and near‐infrared light, and solar cells sensitized by MJ‐10 exhibit an efficiency of 9.1 % under 1 sun irradiation.     

Dendron to Central Core S1–S1 and S2–Sn (n>1) Energy Transfers in Artificial Special Pairs Containing Dendrimers with Limited Numbers of Conformations

Two dendrimers consisting of a cofacial free‐base bisporphyrin held by a biphenylene spacer and functionalized with 4‐benzeneoxomethane (5‐(4‐benzene)tri‐10,15,20‐(4‐n‐octylbenzene)zinc(II)porphyrin) using either five or six of the six available meso‐positions, have been synthesized and characterized as models for the antenna effect in Photosystems I and II. The presence of the short linkers, ‐CH₂O‐, and long C₈H₁₇ soluble side chains substantially reduces the number of conformers (foldamers) compared with classic dendrimers built with longer flexible chains. This simplification assists in their spectroscopic and photophysical analysis, notably with respect to fluorescence resonance energy transfer (FRET). Both steady‐state and time‐resolved spectroscopic measurements indicate that the cofacial free bases and the flanking zinc(II)–porphyrin antennas act as energy acceptor and donor, respectively, following excitation in either the Q or Soret bands of the dendrimers. The rate constants for singlet electronic energy transfer (k_EET) extracted from the S₁ and S₂ fluorescence lifetimes of the donor in the presence and absence of the acceptor are ≤ (0.1–0.3)×10⁹ and ～2×10⁹ s^?1 for S₁→S₁ (range from a bi‐exponential decay model) and about 1.5×10¹² s^?1 for S₂→S_n (n>1). Comparisons of these experimental data with those calculated from Förster theory using orientation factors and donor–acceptor distances extracted from computer modeling suggest that a highly restricted number of the many foldamers facilitate energy transfer. These foldamers have the lowest energy by molecular modeling and consist of one or at most two of the flanking zinc porphyrin antennas folded so they lie near the central artificial special pair core with the remaining antennas located almost parallel to and far from it.     

ClF-分子离子的结构与势能函数

采用单、双取代包括三重激发的二次组态相互作用[QCISD(T)]方法和单、双取代包括非迭代三重激发的耦合簇理论[CCSD(T)]方法, 结合相关一致基组aug-cc-pVXZ (X=D, T, Q, 5)对基态³⁵ClF^-和³⁷ClF^- (X²Σ⁺)分子离子进行了结构优化计算. 对CCSD(T)方法的计算结果用四种方法分别外推至基组极限, 得到了体系在基组极限的平衡结构常数. 在CCSD(T)/aug-cc-pVXZ (X=D, T, Q, 5)理论水平进行了单点能扫描. 对扫描计算结果进行基组外推并用Murrell-Sorbie 势能函数拟合得到了体系的解析势能函数表达式, 并进一步得到了³⁵ClF^-和³⁷ClF^-的光谱常数. 拟合所得势能曲线准确地再现了其离解能和平衡结构特征. 对ClF 中性自由基采用完全相同的理论方法进行了计算. 所得结果与有关文献中的实验结果符合得很好, 而且在一定程度上证明了将该理论方法应用于ClF^-分子离子的计算是合适而可靠的. ClF 自由基的优化计算结果还被用于计算其电子亲和能.ClF^-的垂直解离能也同时计算得出. 基于ClF^-的结构优化和单点能扫描计算结果, 通过求解核运动的径向薛定谔方程, 得到了无转动³⁵ClF^-和³⁷ClF^-(X²Σ⁺)的全部振动态及相应的分子常数.     

正癸烷与二甲苯在超临界压力下的热裂解

采用连续流动装置对正癸烷和二甲苯在超临界压力下的热裂解对比研究. 用气相色谱和色质联用仪对其气相产物和液相产物进行分析, 计算气相产物产率和裂解转化率, 并运用计算化学方法获得正癸烷和二甲苯不同化学键的键能, 从实验和理论上分析其裂解反应的难易程度和裂解规律. 实验结果表明, 在4 MPa和650、700、750 ℃条件下, 正癸烷比二甲苯更容易裂解, 正癸烷裂解产物以C₁-C₃小分子的烃类和氢气为主, 而二甲苯裂解产物主要为乙苯、甲苯和其它芳香类化合物; 键能计算结果表明, 正癸烷碳链骨架的C－C键能和C－H键能均较小, 裂解反应的诱发步骤应该是C－C键断裂, 而二甲苯苯环上C－C和C－H键能均较大, 裂解诱发步骤应该是侧链甲基脱氢反应. 因此正癸烷裂解反应以C－C键断裂和脱氢反应为主, 二甲苯裂解主要发生侧链甲基C－C键断裂和脱氢反应, 而芳环则比较稳定, 理论计算键能分析与裂解实验结果一致.     

基于无线传感器网络的飞行器测控通信系统测量方案设计

随着航天技术的发展,飞行器测控通信系统需要测量的参数种类和数量不断增加,但同时要求系统在进行方案搭建时满足更高的可靠性、更小的体积和更小的设备质量。为解决这类问题,提出了基于无线传感器网络的飞行器测量方案,方案重点从节点配置、时间同步、网络拓扑、能源供应等方面对方案进行阐述,最后给出了应解决的关键技术攻关方向。     

广东省能源需求预测模型构建及实证分析

为了对广东省的能源需求进行准确的预测,首先分析了影响广东省能源需求的各种因素,构建了预测指标体系.在此基础上,针对能源系统非线性等复杂系统特征,结合粒子群算法和BP神经网络的优点,构建了改进的PSO-BP神经网络的预测模型,并通过主成分分析法对指标体系进行数据降维,以降低神经网络的规模和复杂程度.以广东省1985-2013年的能源需求数据进行模拟与仿真,并对2014-2018年的能源需求量进行预测,理论分析和实证研究表明,该方法能够很好的反映广东省能源需求的特征,预测结果较为准确合理.