Temperature and Composition Dependent Optical Properties of CdSe/CdS Dot/Rod-Based Aerogel Networks

Employing nanocrystals (NCs) as building blocks of porous aerogel network structures allows the conversion of NC materials into macroscopic solid structures while conserving their unique nanoscopic properties. Understanding the interplay of the network formation and its influence on these properties like size-dependent emission is a key to apply techniques for the fabrication of novel nanocrystal aerogels. In this work, CdSe/CdS dot/rod NCs possessing two different CdSe core sizes were synthesized and converted into porous aerogel network structures. Temperature-dependent steady-state and time-resolved photoluminescence measurements were performed to expand the understanding of the optical and electronic properties of these network structures generated from these two different building blocks and correlate their optical with the structural properties. These investigations reveal the influence of network formation and aerogel production on the network-forming nanocrystals. Based on the two investigated NC building blocks and their aerogel networks, mixed network structures with various ratios of the two building blocks were produced and likewise optically characterized. Since the different building blocks show diverse optical response, this technique presents a straightforward way to color-tune the resulting networks simply by choosing the building block ratio in connection with their quantum yield.     

Driving Organic Nanocrystals Dissolution Through Electrochemistry

We have recently discussed how organic nanocrystal dissolution appears in different morphologies and the role of the solution pH in the crystal detriment process. We also highlighted the role of the local molecular chemistry in porphyrin nanocrystals having comparable structures: in water-based acid solutions, protonation of free-base porphyrin molecules is the driving force for crystal dissolution, whereas metal (Zn^II) porphyrin nanocrystals remain unperturbed. However, all porphyrin types, having an electron rich π-structure, can be electrochemically oxidized. In this scenario, a key question is: does electrochemistry represent a viable strategy to drive the dissolution of both free-base and metal porphyrin nanocrystals? In this work, by exploiting electrochemical atomic force microscopy (EC-AFM), we monitor in situ and in real time the dissolution of both free-base and metal porphyrin nanocrystals, as soon as molecules reach the oxidation potential, showing different regimes according to the applied EC potential.     

How to Predict Excited State Geometry by Using Empirical Parameters Obtained from Franck-Condon Analysis of Optical Spectrum

Excited state geometries of molecules can be calculated with highly reliable wavefunction schemes. Most of such schemes, however, are applicable to small molecules and can hardly be viewed as error-free for excited state geometries. In this study, a theoretical approach is presented in which the excited state geometries of molecules can be predicted by using vibrationally resolved experimental absorption spectrum in combination with the theoretical modelling of vibrational pattern based on Franck-Condon approximation. Huang-Rhys factors have been empirically determined and used as input for revealing the structural changes occurring between the ground and the excited state geometries upon photoexcitation. Naphthalene molecule has been chosen as a test case to show the robustness of the proposed theoretical approach. Predicted 1B_2u excited state geometry of the naphthalene has similar but slightly different bond length alternation pattern when compared with the geometries calculated with CIS, B3LYP, and CC2 methods. Excited state geometries of perylene and pyrene molecules are also determined with the presented theoretical approach. This powerful method can be applied to other molecules and specifically to relatively large molecules rather easily as long as vibrationally resolved experimental spectra are available to use.     

Poly(Pyridinium Salt)s Containing 2,7-Diamino-9,9′-Dioctylfluorene Moieties with Various Organic Counterions Exhibiting Both Lyotropic Liquid-Crystalline and Light-Emitting Properties

A series of poly(pyridinium salt)s-fluorene main-chain ionic polymers with various organic counterions were synthesized by using ring-transmutation polymerization and metathesis reactions. Their chemical structures were characterized by Fourier Transform Infrared (FTIR), proton (¹H), and fluorine 19 (¹⁹F) nuclear magnetic resonance (NMR) spectrometers. These polymers showed a number-average molecular weight (M_ns) between 96.5 and 107.8 kg/mol and polydispersity index (PDI) in the range of 1.12–1.88. They exhibited fully-grown lyotropic phases in polar protic and aprotic solvents at different critical concentrations. Small-angle X-ray scattering for one polymer example indicates lyotropic structure formation for 60–80% solvent fraction. A lyotropic smectic phase contains 10 nm polymer platelets connected by tie molecules. The structure also incorporates a square packing motif within platelets. Thermal properties of polymers were affected by the size of counterions as determined by differential scanning calorimetry and thermogravimetric analysis measurements. Their ultraviolet-visible (UV-Vis) absorption spectra in different organic solvents were essentially identical, indicating that the closely spaced π-π* transitions occurred in their conjugated polymer structures. In contrast, the emission spectra of polymers exhibited a positive solvatochromism on changing the polarity of solvents. They emitted green lights in both polar and nonpolar organic solvents and showed blue light in the film-states, but their λ_em peaks were dependent on the size of the counterions. They formed aggregates in polar aprotic and protic solvents with the addition of water (v/v, 0–90%), and their λ_em peaks were blue shifted.     

Discrimination of Beers by Cyclic Voltammetry Using a Single Carbon Screen-printed Electrode

A fast, simple and costless methodology without sample pre-treatment is proposed for the discrimination of beers. It is based on cyclic voltammetry (CV) using commercial carbon screen-printed electrodes (SPCE) and includes a correction of the signals measured with different SPCE units. Data are submitted to partial least squares discriminant analysis (PLS−DA) and support vector machine discriminant analysis (SVM−DA), which allow a reasonable classification of the beers. Also, CV data from beers can be used to predict their alcoholic degree by partial least squares (PLS) and artificial neural networks (ANN). In general, non-linear methods provide better results than linear ones.     

用于红外激光防护的高开关率VO2薄膜

采用反应离子束溅射和后退火处理技术在石英玻璃基底上制备了具有纳米粒子的二氧化钒(VO₂)薄膜. 该薄膜具有半导体-金属相变特性,在3 μm处的开关率达到76.6%。 热致相变实验结果给出了准确的最佳退火温度为465 ℃. 仿真、热致相变和光致相变实验都显示VO₂薄膜在红外波段具有很高的光学开关特性. 光电池防护实验结果显示VO₂薄膜将硅光电池的抗干扰能力提升了2.6倍, 证明了VO₂在激光防护中的适用性. 采用连续可调节系统研究得到VO₂在室温条件下的相变阈值功率密度为4.35 W/cm², 损伤阈值功率密度为404 W/cm²。 低相变阈值和高损伤阈值都进一步证明VO₂薄膜适用于激光防护系统。本实验制备的VO₂薄膜在光开关、光电存储器、智能窗等方面也具有广泛的应用价值.     

基于拉锥结构的全光纤型内窥OCT探针研究

本文报道了一种基于拉锥结构的全光纤型内窥光学相干层析成像探针. 基于大纤芯多模光纤的低光束发散特性, 使用大纤芯多模光纤代替透镜作为成像元件, 并在单模光纤与大纤芯多模光纤之间引入过渡拉锥段以减少插入损耗. 首先利用光学仿真软件(Rsoft)确定探针的最佳结构, 然后通过拉锥、切割以及熔接工艺实现探针制作, 并对探针的出射光束特性与插入损耗进行测量, 最后将该探针与扫频光学相干层析成像主系统联机, 对人体指尖皮肤及鸡气管壁组织进行成像. 该探针直径为250 μm, 不锈钢保护管外径为325 μm, 硬端长度1 cm, 插入损耗约为0.3 dB, 空气中有效成像范围达800 μm. 该探针为内窥光学相干层析成像技术在心血管疾病的应用提供了高紧凑度、高传输效率与高灵活性的选择.     

基于联合分步APIT定位算法的改进

本文研究了无线传感网络( Wireless Sensor Network,WSNs)的节点定位问题,并针对APIT由于锚节点在低密度环境下的节点误判和节点失效等问题给出了改进,在APICT定位算法的基础提出了联合分步定位算法UNION-APICT(Union Approximate Point-In-Circumcircle Test),该算法是结合连通性的测距技术,RSSI测距技术以及质心定位和APICT等技术,来联合解决对未知节点定位问题。通过仿真实验结果表明,改进后的UNION-APICT在APICT算法的基础之上平均定位误差减少了10%-25%,定位性能有了明显的提升;随着通信半径R和最大探测距离rmax的增加,定位误差也在逐渐减小,该算法较APIT和APICT定位算法在锚节点密度、节点覆盖率和定位精度上都有所提高。     

光学观测中太阳夹角的分析与计算

对影响光学观测效果的太阳夹角计算方法进行了研究。首先给出了太阳夹角的定义及计算公式。然后重点研究了太阳视位置的计算方法,比较了几种赤纬角计算方法,给出了一种改进的时角计算方法,实现了高精度的太阳视位置计算,并对其计算精度进行了分析。最后提出了在实际光学观测应用中的太阳夹角计算算法。实验表明,太阳视位置计算精度比传统数值近似方法高一个数量级,能够满足光学观测中太阳光照分析的需要。