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.      

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.     

Selenium Alleviates the Adverse Effect of Drought in Oilseed Crops Camelina (Camelina sativa L.) and Canola (Brassica napus L.)

Drought poses a serious threat to oilseed crops by lowering yield and crop failures under prolonged spells. A multi-year field investigation was conducted to enhance the drought tolerance in four genotypes of Camelina and canola by selenium (Se) application. The principal aim of the research was to optimize the crop yield by eliciting the physio-biochemical attributes by alleviating the adverse effects of drought stress. Both crops were cultivated under control (normal irrigation) and drought stress (skipping irrigation at stages i.e., vegetative and reproductive) conditions. Four different treatments of Se viz., seed priming with Se (75 μM), foliar application of Se (7.06 μM), foliar application of Se + Seed priming with Se (7.06 μM and 75 μM, respectively) and control (without Se), were implemented at the vegetative and reproductive stages of both crops. Sodium selenite (Na₂SeO₃), an inorganic compound was used as Se sources for both seed priming and foliar application. Data regarding physiochemical, antioxidants, and yield components were recorded as response variables at crop maturity. Results indicated that WP, OP, TP, proline, TSS, TFAA, TPr, TS, total chlorophyll contents, osmoprotectant (GB, anthocyanin, TPC, and flavonoids), antioxidants (APX, SOD, POD, and CAT), and yield components (number of branches per plant, thousand seed weight, seed, and biological yields were significantly improved by foliar Se + priming Se in both crops under drought stress. Moreover, this treatment was also helpful in boosting yield attributes under irrigated (non-stress) conditions. Camelina genotypes responded better to Se application as seed priming and foliar spray than canola for both years. It has concluded that Se application (either foliar or priming) can potentially alleviate adverse effects of drought stress in camelina and canola by eliciting various physio-biochemicals attributes under drought stress. Furthermore, Se application was also helpful for crop health under irrigated condition.     

Effect of Botanical Extracts on the Growth and Nutritional Quality of Field-Grown White Head Cabbage (Brassica oleracea var. capitata)

Nutraceuticals and functional foods are gaining more attention amongst consumers interested in nutritious food. The consumption of foodstuffs with a high content of phytochemicals has been proven to provide various health benefits. The application of biostimulants is a potential strategy to fortify cultivated plants with beneficial bioactive compounds. Nevertheless, it has not yet been established whether the proposed higher plants (St. John’s wort, giant goldenrod, common dandelion, red clover, nettle, and valerian) are appropriate for the production of potential bio-products enhancing the nutritional value of white cabbage. Therefore, this research examines the impact of botanical extracts on the growth and nutritional quality of cabbage grown under field conditions. Two extraction methods were used for the production of water-based bio-products, namely: ultrasound-assisted extraction and mechanical homogenisation. Bio-products were applied as foliar sprays to evaluate their impact on total yield, dry weight, photosynthetic pigments, polyphenols, antioxidant activity, vitamin C, nitrates, micro- and macroelements, volatile compounds, fatty acids, sterols, and sugars. Botanical extracts showed different effects on the examined parameters. The best results in terms of physiological and biochemical properties of cabbage were obtained for extracts from common dandelion, valerian, nettle, and giant goldenrod. When enriched with nutrients, vegetables can constitute a valuable component of functional food.     

Drying Effects on Chemical Composition and Antioxidant Activity of Lippia thymoides Essential Oil,a Natural Source of Thymol

Leaves of Lippia thymoides (Verbenaceae) were dried in an oven at 40, 50 and 60 °C and the kinetic of drying and the influence of the drying process on the chemical composition, yield, and DPPH radical scavenging activity of the obtained essential oils were evaluated. The composition of the essential oils was determined with gas chromatography-mass spectrometry and gas chromatography-flame ionization detection analyses. The influence of drying on the chemical composition of the essential oils of L. thymoides was evaluated by multivariate analysis, and their antioxidant activity was investigated via the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. The Midilli model was the most appropriate to describe the behavior of drying kinetic data of L. thymoides leaves. Thymol was the major compound for all analyzed conditions; the maximum content was obtained from fresh leaves (62.78 ± 0.63%). The essential oils showed DPPH radical scavenging activity with an average of 73.10 ± 12.08%, and the fresh leaves showed higher inhibition (89.97 ± 0.31%). This is the first study to evaluate the influence of drying on the chemical composition and antioxidant activity of L. thymoides essential oils rich in thymol.     

Nature of Alkali- and Coinage-Metal Bonds versus Hydrogen Bonds

We have quantum chemically studied the structure and nature of alkali- and coinage-metal bonds (M-bonds) versus that of hydrogen bonds between A−M and B⁻ in archetypal [A−M⋅⋅⋅B]⁻ model systems (A, B=F, Cl and M=H, Li, Na, Cu, Ag, Au), using relativistic density functional theory at ZORA-BP86-D3/TZ2P. We find that coinage-metal bonds are stronger than alkali-metal bonds which are stronger than the corresponding hydrogen bonds. Our main purpose is to understand how and why the structure, stability and nature of such bonds are affected if the monovalent central atom H of hydrogen bonds is replaced by an isoelectronic alkali- or coinage-metal atom. To this end, we have analyzed the bonds between A−M and B⁻ using the activation strain model, quantitative Kohn-Sham molecular orbital (MO) theory, energy decomposition analysis (EDA), and Voronoi deformation density (VDD) analysis of the charge distribution.     

The Chemical Bond: When Atom Size Instead of Electronegativity Difference Determines Trend in Bond Strength

We have quantum chemically analyzed element−element bonds of archetypal H_nX−YH_n molecules (X, Y=C, N, O, F, Si, P, S, Cl, Br, I), using density functional theory. One purpose is to obtain a set of consistent homolytic bond dissociation energies (BDE) for establishing accurate trends across the periodic table. The main objective is to elucidate the underlying physical factors behind these chemical bonding trends. On one hand, we confirm that, along a period (e. g., from C−C to C−F), bonds strengthen because the electronegativity difference across the bond increases. But, down a period, our findings constitute a paradigm shift. From C−F to C−I, for example, bonds do become weaker, however, not because of the decreasing electronegativity difference. Instead, we show that the effective atom size (via steric Pauli repulsion) is the causal factor behind bond weakening in this series, and behind the weakening in orbital interactions at the equilibrium distance. We discuss the actual bonding mechanism and the importance of analyzing this mechanism as a function of the bond distance.     

Simultaneous studies of pressure effect on charge transport and photophysical properties in organic semiconductors: A theoretical investigation

High-mobility and strong luminescent materials are essential as an important component of organic photodiodes, having received extensive attention in the field of organic optoelectronics. Beyond the conventional chemical synthesis of new molecules, pressure technology, as a flexible and efficient method, can tune the electronic and optical properties reversibly. However, the mechanism in organic materials has not been systematically revealed. Here, we theoretically predicted the pressure-depended luminescence and charge transport properties of high-performance organic optoelectronic semiconductors, 2,6-diphenylanthracene (DPA), by first-principle and multi-scale theoretical calculation methods. The dispersion-corrected density functional theory (DFT-D) and hybrid quantum mechanics/molecular mechanics (QM/MM) method were used to get the electronic structures and vibration properties under pressure. Furthermore, the charge transport and luminescence properties were calculated with the quantum tunneling method and thermal vibration correlation function. We found that the pressure could significantly improve the charge transport performance of the DPA single crystal. When the applied pressure increased to 1.86 GPa, the hole mobility could be doubled. At the same time, due to the weak exciton coupling effect and the rigid flat structure, there is neither fluorescence quenching nor obvious emission enhancement phenomenon. The DPA single crystal possesses a slightly higher fluorescence quantum yield ～ 0.47 under pressure. Our work systematically explored the pressure-dependence photoelectric properties and explained the inside mechanism. Also, we proposed that the external pressure would be an effective way to improve the photoelectric performance of organic semiconductors.     

Xe~(26+)入射Au靶离子L壳层空穴的产生与退激辐射

基于两体碰撞过程的能量与角动量守恒,推导出Xe26+离子与Au原子碰撞过程,单离子的L壳层空穴产额与离子动能的理论关系.实验测定了动能2.4-3.6Me V的Xe26+离子入射Au靶,产生的Xe的L-X射线谱,获得了射线产额与离子入射动能的实验关系.结果表明,碰撞过程产生Xe L壳层空穴的同时,产生了一定数目的 M壳层空穴,导致L壳层空穴平均荧光产额显著变大,在实验能量范围,空穴产额的理论值与射线产额的实验值存在较好的一致性.