Solvent and electric field dependence of the photocurrent generation in donor：acceptor blend system

This paper reports that the blend films of poly (2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV) and N,N'-bis(1-ethylpropyl)-3,4: 9,10-perylene bis (tetracarboxyl diimide) (EP-PDI) with the weight ratio of 1:2.5 have been prepared by spin-coating from chloroform (CF) and chlorobenzene (CB) solutions respectively. The absorption spectra and the morphology of the blend films show that large crystal-like EP-PDI aggregates are formed in film prepared from CB solution, which corresponds to a new absorption shoulder near 590nm, while there is no shoulder around 590\,nm in the UV--Vis absorption spectra of the blend film from CF solution. The electric-field dependence spectra of the photocurrent generation quantum yield of the film from CB solution shows that at weak electric field the EP-PDI aggregates act as more efficient sensitizers, but at strong electric field the quantum yields become almost invariable over the entire spectral range no matter what the state of EP-PDI, monomer or aggregate. At strong electric field, the photocurrent generation yields of both films from CF and CB solution saturate and their yield spectra become spectrally similar, mentioning that at strong electric field the photoexcitons dissociate efficiently and the free charges are collected by the electrodes almost completely.     

Reconstruction of the acoustic impedance profile in a plate using an inverse spectral procedure

An inverse spectral procedure was applied to reconstruct the acoustic impedance profile along the thickness direction of a plate using its thickness resonance frequencies, density and thickness. For a successful reconstruction, the material-property profile must be symmetric about the mid-plane of the plate. Several cases of numerical simulations, including plates with a few layers and with a high number of layers are described. The calculated resonance frequencies were used to reconstruct the acoustic impedance profile, a process that was successful for all cases. We assume that a plate with a high number of layers, each with a different but constant acoustic impedance, simulates a plate with a smoothly varying acoustic impedance profile. It can be concluded that such a plate, which generates small, virtually undetectable, internally reflected waves, can also be reconstructed. In the special case of a plate of unknown thickness and unknown but constant density, the method is still useful, because a relative variation of the material property can be reconstructed using only the resonance frequencies. An experiment using a resonance-mode electromagnetic acoustic transducer (resonance-mode EMAT) is also described. EMAT is a non-contact ultrasonic method that can measure thickness resonance frequencies, making it appropriate for this method. Some examples of applications are measurement of the temperature profile inside a rolled metal sheet, measurement of a clad metal plate, and monitoring of a metal casting.     

Hydrolysis and retro‐aldol cleavage of ethyl threo‐2‐(1‐adamantyl)‐3‐hydroxybutyrate: competing reactions

The hydrolysis of ethyl threo‐2‐(1‐adamantyl)‐3‐hydroxybutyrate ( 1 ) and the parent ester ethyl 3‐hydroxybutyrate ( 4 ) has been studied experimentally and computationally. In the hydrolysis of threo‐ester 1 with 2 M NaOH, predominantly retro‐aldol product was observed, whereas the hydrolyzed product was present in a minor amount. When the reaction is carried out under the same conditions with the parent ester ethyl 3‐hydroxybutyrate ( 4 ), hydrolyzed product is exclusively observed. The competitive pathways, namely hydrolysis and the retro‐aldol reaction for 1 and 4 were investigated using DFT calculations in the both gas and solvent phase. The calculated results in the solvent phase at B3LYP/6–31 + G* level revealed that the formation of retro‐aldol products is kinetically preferred over the hydrolysis of threo‐ester 1 in the presence of a base. However, the parent ester 4 showed that the retro‐aldol process is less favored than the hydrolysis process under similar conditions. The steric effect imposed by the bulky adamantyl group to enhance the activation barriers for the hydrolysis of the ethyl threo‐2‐(1‐adamantyl)‐3‐hydroxybutyrate ( 1 ) was further supported by the calculations performed with tert‐butyl group at the α‐carbon atom of ethyl 3‐hydroxybutyrate ( 7 ). Copyright © 2010 John Wiley & Sons, Ltd.     

Mechanisms of Resonant Infrared Matrix-Assisted Pulsed Laser Evaporation

For the last decade, a variant of pulsed laser ablation, Resonant-Infrared Matrix-Assisted Pulsed Laser Evaporation (RIR-MAPLE), has been studied as a deposition technique for organic and polymeric materials. RIR-MAPLE minimizes photochemical damage from direct interaction with the intense laser beam by encapsulating the polymer in a high infrared-absorption solvent matrix. This review critically examines the thermally-induced ablation mechanisms resulting from irradiation of cryogenic solvent matrices by a tunable free electron laser (FEL). A semi-empirical model is used to calculate temperatures as a function of time in the focal volume and determine heating rates for different resonant modes in two model solvents, based on the thermodynamics and kinetics of the phase transitions induced in the solvent matrices. Three principal ablation mechanisms are discussed, namely normal vaporization at the surface, normal boiling, and phase explosion. Normal vaporization is a highly inefficient polymer deposition mechanism as it relies on collective collisions with evaporating solvent molecules. Diffusion length calculations for heterogeneously nucleated vapor bubbles show that normal boiling is kinetically limited. During high-power pulsed-FEL irradiation, phase explosion is shown to be the most significant contribution to polymer deposition in RIR-MAPLE. Phase explosion occurs when the target is rapidly heated (10⁸ to 10¹⁰ K/s) and the solvent matrix approaches its critical temperature. Spontaneous density stratification (spinodal decay) within the condensed metastable phase leads to rapid homogeneous nucleation of vapor bubbles. As these vapor bubbles interconnect, large pressures build up within the condensed phase, leading to target explosions and recoil-induced ejections of polymer to a near substrate. Phase explosion is a temperature (fluence) threshold-limited process, while surface evaporation can occur even at very low fluences.     

Solvent effects on the S0→S2 absorption spectra of β-carotene

Absorption spectra of β -carotene in 31 solvents are measured in ambient conditions. Solvent effects on the 0--0 band energy, the bandwidth, and the transition moment of the S₀ → S₂ transition are analysed. The discrepancies between published results of the solvent effects on the 0--0 band energy are explained by taking into account microscopic solute-solvent interactions. The contributions of polarity and polarizability of solvents to 0--0 band energy and bandwidth are quantitatively distinguished. The 0--0 transition energy of the S₂ state at the gas phase is predicted to locate between 23000 and 23600~cm^-1.     

Dimethyl sulfoxide/deep eutectic solvents mixtures as media in the reaction of 1‐fluoro‐2,4‐dinitrobenzene with piperidine: A solvent effect study

Aromatic nucleophilic substitution reaction of 1‐fluoro‐2,4‐dinitrobenzene with piperidine was kinetically investigated in ethylene glycol‐choline chloride and glycerol‐choline chloride as 2 deep eutectic solvents (DESs) mixed with dimethyl sulfoxide, in whole mole fractions, at room temperature. The investigation of the reaction in different concentrations of the piperidine shows that the reaction follows the base‐catalyzed mechanism. The measured rate coefficients of the reaction demonstrated a sharp decreasing in all mixtures with the increasing mole fraction of DESs. Linear free energy relationship investigations confirm that hydrogen bond donor ability in addition to polarity‐polarizability of the media has a major effect on the reaction rate. The decrease in the rate coefficient is attributed to not only hydrogen‐bonding donor interactions of the media with piperidine as both reactant and catalyst but also the preferential solvation of reactants by DES compared with the intermediate of the reaction.     

溶剂对石墨烯量子点荧光性质的影响

采用柠檬酸热解法制备了石墨烯量子点(GQDs),研究了非极性溶剂戊烷,极性溶剂乙醇、丙酮、乙二醇对GQDs荧光性质的影响。透射电子显微镜(TEM)和原子力显微镜(AFM)图像表明,制备的GQDs尺寸分布在2~12 nm(平均尺寸为4.9 nm),分散均匀,高度分布在0.5~2 nm。吸收光谱表明,GQDs具有明显的紫外吸收特性,吸收峰位于259 nm和274 nm。光致发光谱表明,GQDs的发光具有明显的溶剂依赖性。GQDs在极性溶剂乙醇、丙酮、乙二醇中,发光峰的位置依赖于激发波长,发射波长在可见光区。而在非极性溶剂戊烷中,GQDs表现出对激发波长不依赖的荧光性能,且发射波长在近紫外。     

Excited‐state hydrogen bond strengthening of coumarin 153 in ethanol solvent: a TDDFT study

So far, coumarin dyes have been extensively studied with various means to understand their photophysical behaviors and photochemical properties. Here, our performing time‐dependent density functional theory calculation is aimed at exploring the excited‐state hydrogen bonding dynamics of coumarin 153 (C153) in protic ethanol (EtOH) solvent. The calculated results suggest that the excited‐state hydrogen bond C?O?H?O between C?O group and O?H group in the C153‐EtOH complex is strengthened, and the S₀ → S₁ transition of the complex corresponds to the highest occupied molecular orbital (HOMO) hopping to the lowest unoccupied molecular orbital (LUMO). The excited‐state hydrogen bond strengthening has been further confirmed by its larger binding energy in the S₁ state than in the S₀ state. In addition, because of the formation of the hydrogen bond C?O?H?O, a red shift of about 7 nm occurs in the electronic spectra of the C153‐EtOH complex, which is in good accordance with the experiment result. Copyright © 2016 John Wiley & Sons, Ltd.     

薄层稠油藏溶剂辅助蒸汽驱产量预测模型

通过分析生产数据和数值模拟结果,将薄层稠油油藏溶剂辅助蒸汽驱生产过程分为蒸汽前缘垂向扩展阶段、蒸汽前缘水平扩展阶段及冷凝水产出阶段.针对每个生产阶段,通过联合质量守恒方程、运动方程、能量守恒方程及溶剂扩散方程得到描述蒸汽前缘扩展和产油量解析模型.能量守恒方程属于典型的第二类Volterra 积分函数,首先对其进行Laplace变换;之后运用半解析方法对该模型进行求解.为验证模型的正确性,将模型的溶剂辅助蒸汽驱计算结果与数值模拟结果对比,整体误差仅为4%.新模型可以方便简单地分析不同溶剂性能和注采参数对溶剂蒸汽驱开发效果的影响.     

Beiträge zur Mikrobestimmung von Kohlenstoff-14 und Tritium

Die Verwendung Con¹⁴C und Tritium zur Lösung kinetischer und analylischer Probleme erfordert zuverlässige Analysenmethoden. Es wird iiber die Herstellimg von Meβgasen durch Naβcerbrennung mil Chromsäure-Jodsäure-Gemischen, Trockenverbrennung in Gegenwart Con Katalysatoren wie Kupferoxid, Kobaltoxid und Zersetzungsprodukte des Silberpermanganats und durch Umsetziingentm geschlossenen Rohr berichtet. Die Aktivitätsniessungen erfolgten auf cerschiedene IVeise. Hier werden besonders die Ergebnisse diskutiert, die durch Ionisationskammermessungen erzielt wurden. Schlieβlich werden einfache Apparaturen zur routinemäβigen Durchfiihrung von Mikroanalysen beschrieben.