Semiconductor Quantum Dots as Components of Photoactive Supramolecular Architectures

Luminescent quantum dots (QDs) are colloidal semiconductor nanocrystals consisting of an inorganic core covered by a molecular layer of organic surfactants. Although QDs have been known for more than thirty years, they are still attracting the interest of researchers because of their unique size-tunable optical and electrical properties arising from quantum confinement. Moreover, the controlled decoration of the QD surface with suitable molecular species enables the rational design of inorganic-organic multicomponent architectures that can show a vast array of functionalities. This minireview highlights the recent progress in the use of surface-modified QDs – in particular, those based on cadmium chalcogenides – as supramolecular platforms for light-related applications such as optical sensing, triplet photosensitization, photocatalysis and phototherapy.     

Engineering Sensitized Photon Upconversion Efficiency via Nanocrystal Wavefunction and Molecular Geometry

Triplet energy transfer from inorganic nanocrystals to molecular acceptors has attracted strong attention for high‐efficiency photon upconversion. Here we study this problem using CsPbBr₃ and CdSe nanocrystals as triplet donors and carboxylated anthracene isomers as acceptors. We find that the position of the carboxyl anchoring group on the molecule dictates the donor‐acceptor coupling to be either through‐bond or through‐space, while the relative strength of the two coupling pathways is controlled by the wavefunction leakage of nanocrystals that can be quantitatively tuned by nanocrystal sizes or shell thicknesses. By simultaneously engineering molecular geometry and nanocrystal wavefunction, energy transfer and photon upconversion efficiencies of a nanocrystal/molecule system can be improved by orders of magnitude.     

阵列波导光栅梳状带通滤波器的传输效率

在光波导模场分布高斯近似条件下,根据星形光波导耦合器的耦合特性,推导出了基于累加运算和卷积运算近似表达的阵列波导光栅梳状带通滤波器光谱响应效率的函数表达式。给出了阵列波导光栅梳状带通滤波器光谱响应效率曲线的半最大值全宽度和阵列波导光栅梳状带通滤波器的通道中心波长的光谱响应度与器件参数的关系。在输入信号光谱分布高斯近似条件下,给出了阵列波导光栅梳状带通滤波器信号通道传输效率的计算表达式和输入信号光谱宽度对阵列波导光栅梳状带通滤波器信号通道输出特性的影响。给出了物理意义明确的函数表达式,它们可为快速分析阵列波导光栅梳状带通滤波器的特性提供理论基础。     

天文导航中星体高精度细分定位方法研究

介绍了一种从星体图像中高精度提取恒星位置的方法.这种方法把星光成像看成是高斯点扩散函数模型,利用线性内插和最小二乘法拟合得到高斯曲面参数,从高斯曲面模型中得到亚像素级的恒星位置.由于直接进行高斯曲面拟合计算非常复杂,将二维曲面拟合转化为两个方向上的一维曲线拟合,分别得到不同的曲面系数.仿真结果表明当信噪比小于0.05时,定位精度能达到1/20像素,与质心法比较,高斯曲面拟合法精度高,抗噪声能力强.     

对地观测平台恒星敏感器离焦成像折中设计分析

从对地观测平台角秒量级姿态确定需求出发,在构建星敏感器惯性系成像模型的基础上指出,恒星在成像面上的定位误差是星敏感器姿态确定误差的主要来源。同时,结合理想光学系统离焦模型,分析了星敏感器主要性能指标间的量化关系,并给出了成像面定位误差最低限。仿真结果表明,从优化系统性能考虑,成像模糊区直径为2~3个像元的配置是利用星敏感器焦平面的“轻微离焦”来实现亚像元定位的最佳方案,定位误差可达0.2个像元,能够满足星敏感器惯性姿态确定精度4″~5″的要求。理论分析和数值仿真结果可为后续星敏感器指标的提出及仪器设计提供技术参考。     

Triallylstannyllithium-allyllithium as an initiator for the anionic reversible chain transfer polymerization of 1,3-butadiene

The anionic polymerization of 1,3-butadiene using a novel metalloidal anion initiator, triallylstannyllithium (TALi)-allyllithium (ALi), was studied. The TALi-ALi initiated anionic polymerization of 1,3-butadiene gave the star polymer along with the linear polybutadiene (PBD). The star polymer consisted of three PBD branches and a central tin atom. What is striking is a fact that the number-average molecular weights (M_n) and molecular weight distribution of three PBD branches and linear PBD were almost identical. A reversible chain transfer polymerization mechanism, which includes the equilibrium between tri(macroallyl)-stannyllithium and macroallylic anion, is proposed. © 1996 John Wiley & Sons, Inc.     

Long‐Lived Charge‐Transfer State Induced by Spin‐Orbit Charge Transfer Intersystem Crossing (SOCT‐ISC) in a Compact Spiro Electron Donor/Acceptor Dyad

We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long‐lived triplet charge‐transfer (³CT) state, based on the electron spin control using spin‐orbit charge transfer intersystem crossing (SOCT‐ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT‐ISC takes 8 ns to produce the ³NI* state. Then the slow secondary CS (125 ns) gives the long‐lived ³CT state (0.94 μs in deaerated n‐hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as ¹NI*→¹CT→³NI*→³CT. With time‐resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron‐spin polarization pattern was observed for the naphthalimide‐localized triplet state. Our spiro compact dyad structure and the electron spin‐control approach is different to previous methods for which invoking transition‐metal coordination or chromophores with intrinsic ISC ability is mandatory.     

Application of Linear and Branched Poly(Ethylene Glycol)‐Poly(Lactide) Block Copolymers for the Preparation of Films and Solution Electrospun Meshes

Poly(ethylene glycol)‐poly(lactide) (PEG‐PLA) block copolymers are processed to solvent cast films and solution electrospun meshes. The effect of polymer composition, architecture, and number of anchoring points for the plasticizer on swelling, degradation, and mechanical properties of these films and meshes is investigated as potential barrier device for the prevention of peritoneal adhesions. As a result, adequate properties are achieved for the massive films with a longer retention of the plasticizer PEG for star‐shaped block copolymers than for the linear triblock copolymers and consequently more endurable mechanical properties during degradation. For electrospun meshes fabricated using the same polymers, similar trends are observed, but with an earlier start of fragmentation and lower tensile strengths. To overcome the poor mechanical strengths and an occurring shrinkage during incubation, which may impair the coverage of the wound, further adaptions of the meshes and the fabrication process are necessary.

     

PHOTOPHYSICAL STUDIES ON ORGANIC COMPOUNDS——TIME-RESOLVED TRANSIENT ABSORPTION SPECTRA STUDIES ON TRIPHENYLAMINE IN VARIOUS SOLVENTS

The transient absorption spectra of triphenylamine (TPA) in various solvents have beeninvestigated by the methods of nanosecond laser photolysis. The lifetimes of TPA were meas-ured. In hexane and ethanol, the transient absorptions of triplet state and triplet excimer ofTPA were observed. However, the transient absorptions of the TPA cation radical was alsoobserved in acetonitrile besides that of the triplet TPA monomer and excimer. According tothe experimental facts, the transient photophysical mechanism of TPA in various solvents hasbeen proposed.