Tuning the Solid‐State Optical Properties of Tetracene Derivatives by Modification of the Alkyl Side‐Chains: Crystallochromy and the Highest Fluorescence Quantum Yield in Acenes Larger than Anthracene

In the solution state, there were no notable differences between the optical properties of a range of alkyl‐substituted tetracenes. However, in the solid state, their photophysical properties changed with respect to the length, shape, number, and substitution pattern of the alkyl side chains, as well as the distribution of two regioisomers. Remarkably, in the solid state, 1,4,7,10‐tetraisopropyltetracene exhibited the highest reported fluorescence quantum yield of any tetracene derivative (0.90). The changes in the optical characteristics of these tetracenes according to the arrangement of the tetracene rings and the color‐change mechanism in the solid state are discussed. Moreover, the world record in solid‐state fluorescence efficiency in acenes larger than anthracene is described. DOI 10.1002/tcr.201200003     

Effect of nematic ordering on the elasticity and yielding in disordered polymeric solids

The relation between elasticity and yielding is investigated in a model polymer solid by Molecular‐Dynamics simulations. By changing the bending stiffness of the chain and the bond length, semicrystalline and disordered glassy polymers — both with bond disorder — as well as nematic glassy polymers with bond ordering are obtained. It is found that in systems with bond disorder the ratio τ_Y/G between the shear yield strength τ_Y and the shear modulus G is close to the universal value of the atomic metallic glasses. The increase of the local nematic order in glasses leads to the increase of the shear modulus and the decrease of the shear yield strength, as observed in experiments on nematic thermosets. A tentative explanation of the subsequent reduction of the ratio τ_Y/G in terms of the distributions of the per‐monomer stress is offered. © 2017 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2017 , 55, 1760–1769     

The synthesis and fluorescence properties of novel chromenone-crown ethers

o-Dihyroxy-3-phenylchromenone derivatives, namely, 6,7-dihydroxy-3-(3′,4′-dimethoxyphenyl)chromenone and 6,7-dimethoxy-3-(3′,4′-dihydroxyphenyl)chromenone, were obtained from 2,4,5-trihydroxybenzaldehyde/3,4-dimethoxyphenylacetic acid and 2-hydroxy-4,5-dimethoxybenzaldehyde/3,4-dihydroxyphenylacetic acid, respectively, in the presence of acetic anhydride and sodium acetate under an inert atmosphere, after treatment with MeOH/HCl(aq). The chromenone-crown ethers were prepared from cyclic condensation of o-dihydroxy-3-phenylchromenones with poly(ethylene glycol) ditosylates in the presence of CH₃CN/alkali metal carbonates. The chromatographically purified novel chromenone-crown ethers were identified by ¹H NMR, MALDI-TOF mass spectrometry and elemental analysis. The fluorescence and UV–vis spectroscopic properties of the obtained chromenone-crown ethers and their complexes with Li⁺, Na⁺ and K⁺ perchlorate salts were estimated in acetonitrile. The quantum yields of novel chromenone-crown ethers were determined by the comparative method.

     

氯化铜的少溶剂固态连串配位化学反应

在少量水的存在下,由于 NH₄[CuCl₃]对水不稳定,CuCl₂·2H₂O 与氯化铵的配位化学反应只能得到 1:2 产物(NH₄)₂[CuCl₄(H₂O)₂];但在无水乙醇中,无水 CuCl₂与氯化铵按 1:1或 1:2的物质的量之比混合时,能相应地得到 NH₄[CuCl₃]或(NH₄)₂[CuCl₄]。CuCl₂·2H₂O与 2,2''-联吡啶(bipy)的少溶剂固态化学反应仍能像固态化学反应一样,根据反应物的配比生成相应的唯一产物,但在物质的量之比为1:1的反应中发现1:2产物曾经形成。热力学分析说明,如果连串反应的后一步的Δ_rG^⊖大于前一步的,则上述反应现象是可能的。     

Rheological Properties of Model and Crude Oil Systems when Wax Precipitate under Quiescent and Flowing Conditions

Wax precipitation and deposition is a recurring challenge in transportation of crude oil, and increased knowledge about the behavior of such systems is necessary. Microscopy and differential scanning calorimetry were used to follow the crystallisation of wax for two model systems. The amount of solid was also determined by the latter method as well. The flow and viscoelastic behavior were investigated around the wax precipitation temperature, and the yield stress was determined both after dynamic and static cooling. Interpretation of the results was carried out in view of crystal growth and microstructure of the wax crystals. The variables that were studied were wax composition, amount of wax and thermal and shear history.     

Effect of Water Fraction on Rheological Properties of Waxy Crude Oil Emulsions

This article discusses the effect of water fraction on the rheological properties of waxy crude oil emulsions including gel point, yield stress, viscosity, and thixotropy. The experimental results reveal that the rheological behaviors of the w/o emulsion samples all intensify with the increase of water volume fraction within 60%. Of more significance is that a correlation for w/o emulsions between yield stress and water volume fraction is put forward with an average relative error of 6.75%. In addition, some mainstream viscosity prediction models of w/o emulsions are evaluated, and Elgibaly model is the best-fit for the emulsions in this study.     

Experimental Investigation on Yield Stress of Water-in-Heavy Crude Oil Emulsions in Order to Improve Pipeline Flow

An experimental study on yield stress of water-in-heavy crude oil emulsions has been carried out by using a HAAKE RS6000 Rheometer with a vane-type rotor. Several factors such as oil volume fraction, shear rate, temperature, and emulsifying agent on the yield stress of emulsions were investigated. Zero shear viscosity of heavy crude oil was 6000 mPas at 30°C, with a density 955 kg/m³. This study shows that the yield stress increases linearly with the increasing shear rate, and displays an exponential decay with increasing the temperature and oil volume fraction. Although the addition of emulsifying agent enhanced the stability of the emulsion, to some extent it also increased the yield stress, especially for the emulsions with high oil volume fractions. Therefore, to reduce the start-up force for the pipeline transport of water-in-heavy crude oil emulsions, the starting rate should be decreased, temperature increased, or oil volume fraction increased. These results are helpful to improve the transportation of water-in-heavy crude oil in pipeline.      

(Yb3+, Mn2+) Co-doped CdTe nanocrystals with enhanced quantum yields and red-shift emission

We prepared the nanocrystals (NCs) of CdTe, CdTe:Yb, and CdTe:Yb, Mn vis water phase synthesis and examined their structural, morphological, and optical properties. All NCs have a particle diameter of about 2–4 nm, and the monodispersed, uniform spherical, cubic structure of the CdTe NC remains largely unchanged after the doping with Yb and Mn. According to the X-ray diffraction results, the CdTe, CdTe:Yb, and CdTe:Yb, Mn NCs all have a cubic structure, and the diffraction peak of CdTe:Yb NC is at a lower 2θ angle compared with that of the CdTe NC. With the CdTe NC as the reference, the UV–Vis absorption of the CdTe:Yb and the CdTe:Yb, Mn NCs exhibits a blueshift and a redshift, and the emission of CdTe:Yb and CdTe:Yb, Mn has a blueshift of about 12 nm and a redshift of about 73 nm, respectively. The CdTe:Yb, Mn NCs have higher quantum yields than the CdTe:Yb NC, and the quantum yield is the highest when CdTe is doped with 1:1 Mn²⁺/Yb³⁺. In addition, both the CdTe:Yb and CdTe:Yb, Mn NCs have a shorter fluorescence lifetime than the CdTe NC.     

Beyond green with synthetic chlorophylls – Connecting structural features with spectral properties

The distinct features of chlorophylls in photosynthesis have led to the formation of numerous derivatives for applications encompassing solar energy conversion, molecular photonics, photodynamic therapy, and molecular imaging. Synthetic chlorins created de novo and bearing a geminal dimethyl group in the reduced ring have proved invaluable for fundamental studies. Four decades of research have led to accumulation of tabulated spectra for > 400 such synthetic chlorins with distinct structural frameworks (17-oxochlorins, 13¹-oxophorbines, chlorinimides) and substituents (alkyl, aryl, ethynyl, phenylethynyl, acetyl, formyl) located at specific (meso, β) positions. In this review, spectral traces (324 absorption, 247 fluorescence) are assembled along with photophysical data including the molar absorption coefficient (ε), fluorescence quantum yield (Φ_f) and singlet excited-state lifetime (τ_s). The review uses the accumulated spectral data derived from chlorins all containing a uniform molecular scaffold to (1) highlight the effects of molecular structure on spectral features, and (2) identify trends including how ε, Φ_f and τ_s vary with wavelength and other features. Use of a common geminal-dimethyl-substituted chlorin scaffold – beginning with no substituents, to one substituent at designated sites, and to 2 or more substituents – provides a systematic Aufbau approach for understanding the absorption spectra of chlorins on a path to and beyond the native chlorophylls. The review provides insights concerning the rational design of potent analogues of Nature’s preeminent red-region absorbers for potential utilization in diverse applications and is aimed at multiple audiences: those interested in spectral properties, tetrapyrrole photophysics, and the molecular design of new chromophores.     

Rational hydrothermal synthesis of graphene quantum dots with optimized luminescent properties for sensing applications

Hydrothermal synthesis using graphene oxide (GO) as a precursor has been used to produce luminescent graphene quantum dots (GQDs). However, such a method usually requires many reagents and multistep pretreatments, while can give rise to GQDs with low quantum yield (QY). Here, we investigated the concentration, the temperature of synthesis, and the pH of the GO solution used in the hydrothermal method through factorial design experiments aiming to optimize the QY of GQDs to reach a better control of their luminescent properties. The best synthesis condition (2 mg/mL, 175 °C, and pH = 8.0) yielded GQDs with a relatively high QY (8.9%) without the need of using laborious steps or dopants. GQDs synthesized under different conditions were characterized to understand the role of each synthesis parameter in the materials' structure and luminescence properties. It was found that the control of the synthesis parameters enables the tailoring of the amount of specific oxygen functionalities onto the surface of the GQDs. By changing the synthesis' conditions, it was possible to prioritize the production of GQDs with more hydroxyl or carboxyl groups, which influence their luminescent properties. The as-developed GQDs with tailored composition were used as luminescent probes to detect Fe³⁺. The lowest limit of detection (0.136 μM) was achieved using GQDs with higher amounts of carboxylic groups, while wider linear range was obtained by GQDs with superior QY. Thus, our findings contribute to rationally produce GQDs with tailored properties for varied applications by simply adjusting the synthesis conditions and suggest a pathway to understand the mechanism of detection of GQDs-based optical sensors.