Molecular Engineering of Conjugated Polybenzothiadiazoles for Enhanced Hydrogen Production by Photosynthesis

The search for metal‐free organic photocatalysts for H₂ production from water using visible light remains a key challenge. Reported herein is a molecular structural design of pure organic photocatalysts, derived from conjugated polybenzothiadiazoles, for photocatalytic H₂ evolution using visible light. By alternating the substitution position of the electron‐withdrawing benzothiadizole unit on the phenyl unit as a comonomer, various polymers with either one‐ or three‐dimensional structures were synthesized and the effect of the molecular structure on their catalytic activity was investigated. Photocatalytic H₂ evolution efficiencies up to 116 μmol h^?1 were observed by employing the linear polymer based on a phenyl‐benzothiadiazole alternating main chain, with an apparent quantum yield (AQY) of 4.01 % at 420 nm using triethanolamine as the sacrificial agent.     

How much carbon dioxide can be stored in the structure H clathrate hydrates?: a molecular dynamics study

The stability of structure H (sH) carbon dioxide clathrate hydrates at three temperature-pressure conditions are determined by molecular dynamics simulations on a 3x3x3 sH unit cell replica. Simulations are performed at 100 K at ambient pressure, 273 K at 100 bars and also 300 K and 5.0 kbars. The small and medium cages of the sH unit cell are occupied by a single carbon dioxide guest and large cage guest occupancies of 1-5 are considered. Radial distribution functions are given for guests in the large cages and unit cell volumes and configurational energies are studied as a function of large cage CO(2) occupancy. Free energy calculations are carried out to determine the stability of clathrates for large cage occupancies at three temperature/pressure conditions stated above. At the low temperature, large cage occupancy of 5 is the most stable while at the higher temperature, the occupancy of 3 is the most favored. Calculations are also performed to show that the CO(2) sH clathrate is more stable than the methane clathrate analog. Implications on CO(2) sequestration by clathrate formation are discussed.     

Numerical simulations of a Cu–water nanofluid-based parabolic-trough solar collector

Journal of Thermal Analysis and Calorimetry - In this study, the thermal and flow characteristics of a parabolic-trough solar collector have been numerically investigated. The turbulent flow inside...     

Cannabinoids,Phenolics, Terpenes and Alkaloids of Cannabis

Cannabis sativa is one of the oldest medicinal plants in the world. It was introduced into western medicine during the early 19th century. It contains a complex mixture of secondary metabolites, including cannabinoids and non-cannabinoid-type constituents. More than 500 compounds have been reported from C. sativa, of which 125 cannabinoids have been isolated and/or identified as cannabinoids. Cannabinoids are C₂₁ terpeno-phenolic compounds specific to Cannabis. The non-cannabinoid constituents include: non-cannabinoid phenols, flavonoids, terpenes, alkaloids and others. This review discusses the chemistry of the cannabinoids and major non-cannabinoid constituents (terpenes, non-cannabinoid phenolics, and alkaloids) with special emphasis on their chemical structures, methods of isolation, and identification.     

Endoscopic fuel film,chemiluminescence, and soot incandescence imaging in a direct-injection spark-ignition engine

In direct-injection spark-ignition engines, fuel films formed on the piston surface due to impinging sprays are a major source of soot. Previous studies investigating the fuel films and their correlation to soot production were mostly performed in model experiments or optical engines. These experiments have different operating conditions compared to commercial engines. In this work, fuel films and soot are visualized in an all-metal engine with endoscopic access via laser-induced fluorescence (LIF) and natural incandescence, respectively. Gasoline and a mixture of isooctane/toluene were used as fuel for the experiments. The fuel films were excited by 266 nm laser pulses and visualized by an intensified CCD camera through a modular UV endoscope. Gasoline yielded much higher signal-to-noise ratio, and this fuel typically took an order of magnitude longer to evaporate than isooctane/toluene. The effects of injection time, injection pressure, engine temperature, and combustion on the fuel-film evaporation time were investigated. This film survival time was reduced with higher engine temperature, higher injection pressure, and later injection time, with engine temperature being the most significant parameter, whereas skip-fired combustion had very little effect on the film survival time. In complementary experiments, LIF from fuel films and soot incandescence were simultaneously visualized by an intensified double-frame CCD camera. At lower engine temperatures the fuel films remained distinct, and soot formation was limited to regions above the films, whereas at higher temperatures, fuel films, and hence the soot, appeared to be spread over the whole piston surface. Finally, high-speed imaging showed the spray, chemiluminescence, and soot incandescence, with results broadly consistent with fuel-film LIF and soot incandescence imaging.     

An Optimal Extension of the Polak–Ribière–Polyak Conjugate Gradient Method

Based on a singular value analysis on an extension of the Polak–Ribière–Polyak method, a nonlinear conjugate gradient method with the following two optimal features is proposed: the condition number of its search direction matrix is minimum and also, the distance of its search direction from the search direction of a descent nonlinear conjugate gradient method proposed by Zhang et al. is minimum. Under proper conditions, global convergence of the method can be achieved. To enhance e?ciency of the proposed method, Powell’s truncation of the conjugate gradient parameters is used. The method is computationally compared with the nonlinear conjugate gradient method proposed by Zhang et al. and a modified Polak–Ribière–Polyak method proposed by Yuan. Results of numerical comparisons show e?ciency of the proposed method in the sense of the Dolan–Moré performance profile.     

Design,Synthesis, and Biological Evaluation of Quercetagetin Analogues as JNK1 Inhibitors

The recent discovery of c‐Jun NH₂‐terminal kinase JNK1 suppression by natural quercetagetin ( 1 ) is a promising lead for the development of novel anticancer agents. Using both X‐ray structure and docking analyses we predicted that 5′‐hydroxy‐ ( 2 ) and 5′‐hydroxymethyl‐quercetagetin ( 3 ) would inhibit JNK1 more actively than the parent compound 1 . Notably, our drug design was based on the active enzyme–ligand complex as opposed to the enzyme’s relatively open apo structure. In this paper we test our theoretical predictions, aided by docking‐model experiments, and report the first synthesis and biological evaluation of quercetagetin analogues 2 and 3 . As calculated, both compounds strongly suppress JNK1 activity. The IC₅₀ values were determined to be 3.4 μM and 12.2 μM , respectively, which shows that 2 surpasses the potency of the parent compound 1 (IC₅₀=4.6 μM ). Compound 2 was also shown to suppress matrix metalloproteinase‐1 expression with high specificity after UV irradiation.     

Effects of Sucrose and Trehalose on Stability,Kinetic Properties,and Thermal Aggregation of Firefly Luciferase

In this study, we used sugars as stabilizing additives to improve the thermostability and to inhibit aggregation of firefly luciferase. The combination of sucrose and trehalose has a strong stabilizing effect on firefly luciferase activity and prevents its thermoinactivation. These additives can also increase optimum temperature. It has been shown that the presence of both sucrose and trehalose can inhibit thermal aggregation of firefly luciferase and decrease bioluminescence decay rate. In order to understand the molecular mechanism of thermostabilization, we investigated the effects of sucrose and trehalose combination on the secondary structure of luciferase by Fourier transform infrared spectroscopy. Minor changes in content of secondary structure of firefly luciferase are observed upon treatment with additives.     

Design of a coupled bioluminescent assay for a recombinant pyruvate kinase from a thermophilic Geobacillus

A simple and rapid method using coupled bioluminescent assay was developed to determine level of ADP. ADP is involved in many biological reactions and ADP assay can be used for assaying some reactions universally by monitoring ADP formation or depletion. ADP analysis involves incubation of ADP or extracts containing ADP with pyruvate kinase (PK) and PEP. The ATP formed by this reaction is determined by measuring the intensity of the initial light flash produced when luciferin-luciferase preparation injected into the reaction mixture. In regard to the main role of the PK in this assay, the gene of PK from a Geobacillus species has been cloned in expression vector pET28a (+), sequenced and overexpressed in Escherichia coli. Recombinant protein was purified using Ni-NTA column and then the purified PK was used in a coupled bioluminescent assay for ADP measurement. Kinetic properties of PK are determined according to a bioluminescent assay using firefly luciferase.