Hydrogen donor and acceptor abilities of pitch: 1H n.m.r. study of hydrogen transfer to anthracene

Petroleum pitches, coal-extract solutions and hydrogenated coal-extract solutions are co-carbonized with anthracene at 673 K. Chloroform-soluble fractions of the system are monitored by ¹H n.m.r. for formation of 9.10 dihydroanthracene (DHA). A hydrogenated coal-extract solution is also co-carbonized at 673 K with anthracene together with thianthrene and sulphur. Ashland A240 petroleum pitch and anthracene are co-carbonized with hydrogenated anthracene oil and resultant ¹H n.m.r. spectra are analysed for DHA. The pitches and coal-extract solutions are carbonized to 823 K and the optical textures of resultant cokes are assessed by optical microscopy. The purpose of the study is to assess if pitches which form cokes with larger optical textures or have greater abilities to modify the carbonization behaviour of coals also have the ability to act as ‘hydrogen shuttles’ in the carbonization system. Results would indicate that such pitches produce the largest amounts of DHA. It is proposed that the most efficient of the modifying pitches operate by extending the zone of temperature of maximum fluidity and by increasing the value of maximum fluidity by removal by proton transfer of radicals which if left in the carbonizing system would interact to form cokes of smaller optical texture.     

Porphyromonas gingivalis Lipopolysaccharides Promote Proliferation and Migration of Human Vascular Smooth Muscle Cells through the MAPK/TLR4 Pathway

Atherosclerosis is a major cause of mortality worldwide. The initial change in atherosclerosis is intimal thickening due to muscle cell proliferation and migration. A correlation has been observed between periodontal disease and atherosclerosis. Here, we investigated the proliferation and migration of human aortic smooth muscle cells (HASMCs) using Porphyromonas gingivalis-derived LPS (Pg-LPS). To elucidate intracellular signaling, toll-like receptor 4 (TLR4) and myeloid differentiation factor 88 (MyD88) of HASMCs were knocked down, and the role of these molecules in Pg-LPS-stimulated proliferation and migration was examined. The role of mitogen-activated protein kinase (MAPK) in HASMC proliferation and migration was further elucidated by MAPK inhibition. Pg-LPS stimulation increased the proliferation and migration of HASMCs and activated the TLR4/MyD88 pathway. TLR4 knockdown inhibited Pg-LPS stimulated HASMCs proliferation and migration. Pg-LPS stimulation led to the phosphorylation of P38 MAPK, JNK, and ERK, and MyD88 knockdown inhibited the phosphorylation of P38 MAPK and JNK but not ERK. P38 MAPK and SAPK/JNK inhibition did not suppress the proliferation of HASMCs upon Pg-LPS stimulation, but ERK inhibition significantly inhibited proliferation. SAPK/JNK and ERK inhibition suppressed Pg-LPS-stimulated migration of HASMCs. In conclusion, our findings suggest that Pg-LPS may promote atherosclerosis via the activation of MAPK through TLR4.     

Developing Superplastic Ductilities in Ultrafine-Grained Metals

Conventional superplasticity is generally achieved in metals having grain sizes in the range of ∼2 to 5 μm, but processing by equal-channel angular pressing (ECAP) provides the opportunity of introducing exceptional grain refinement and producing materials with ultrafine grain sizes in the submicrometer range. These materials have the potential for exhibiting excellent superplastic properties when tested in tension at elevated temperatures and examples are presented for representative aluminum and magnesium alloys. When these ultrafine-grained materials deform in superplasticity, internal cavities develop as in conventional superplastic alloys. An example is presented for an aluminum-based alloy, and it is shown that the cavity growth processes are also similar to those in conventional alloys. This article is based on a presentation made in the symposium entitled “Ultrafine-Grained Materials: From Basics to Application”, which occurred September 25–27, 2006, in Kloster Irsee, Germany.     

Microwave Dielectric Study on Water Structure and Physical Properties of Aqueous Systems Using Time Domain Reflectometry with Flat-End Cells

Microwave dielectric measurements were performed in the frequency range from 1 mHz up to 30 GHz using a time domain reflectometry (TDR) method for emulsions and gels. Flat-end sample cells have been used in the TDR measurement to contact a small spot of the surface of those viscoelastic and solid samples without any destruction. Relaxation processes due to various water structures were observed for these aqueous systems. Relaxation parameters thus obtained offer information about these water structures and amounts. The relaxation strength obtained from the high frequency process due to free water can be an adequate measure of water content in spite of some ambiguities for different water structures in some materials. Comparisons of actual water contents in emulsion with those estimated from the relaxation strength indicate that water structure is affected by the interaction between water and micelle. Unfreezable water observed in DNA gel under the freezing point consists of bound water and a fraction of free water. Bound water molecules are still unfreezable to keep the double helical structure of DNA, when the fraction of free water is frozen at lower temperatures. These water structures determine physical properties of moist materials. TDR measuring technique with the flat-end cell is effective to investigate water structures in viscoelastic moist materials and to evaluate physical properties and structures of complex molecular systems.     

Microstructural evolution and the mechanical properties of an aluminum alloy processed by high-pressure torsion

Processing by high-pressure torsion (HPT) was performed on disks of an Al-7075 alloy at room temperature. The alloy was initially annealed at 753 K and then processed by HPT under a pressure of 6.0 GPa up to a maximum of ten turns. Measurements of the Vickers microhardness showed lower values at the centers of the disks after small numbers of turns but higher numbers of turns led to a reasonable hardness homogeneity across each disk. After five turns, the grain size at the edge of the disk was ~250 nm. It is demonstrated that results from mechanical testing are consistent with the hardness and microstructural data.     

Spectroscopic study of lactonic rhodamine B immobilised on polytetrafluoroethylene porous film

Rhodamine B (RB) is frequently used in chemical sensors, where the sensing principle depends on its structural changes to lactone (L), zwitterion (Z), and cation (C) forms in response to the local environment. Compared to the Z- and C-forms, stabilising the L-form in matrices is difficult because of the required low environmental polarity. In this study, we report a simple and easy method to stabilise the L-form of RB on the surface of a polytetrafluoroethylene porous film (p-PTFE), in which the film is dipped in an ethanol solution containing RB and dried. This phenomenon was not observed on polyethylene film and cellulose filter paper in RB solutions. Furthermore, a chemical stability test for colourless RB/p-PTFE samples was conducted by exposing these samples to a humid environment. The test result indicated that, with an increase in the environmental humidity, the equilibrium shifted from the L-form to the Z-form of RB immobilised on the p-PTFE film.     

Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes

The exploration of the synthetic space of halide perovskites hinges on an enormous number of parameters requiring time‐consuming experimentation to decouple and optimize. Here, the formation of the prototype material CH₃NH₃PbI₃ (MAPbI₃) is investigated at different time and length scales using multimodal in situ measurements to monitor the evolution of crystalline phases, morphology, and photoluminescence as a function of the lead precursors. Kinetically fast formation of crystalline precursor phases already during the spin‐coat deposition is observed using lead iodide (PbI₂) or lead chloride (PbCl₂) routes. These precursor phases most likely template final MAPbI₃ film morphology. In particular, the emergence of the “needle‐like” structure is shown to appear before film annealing. In situ photoluminescence measurements suggest nanoscale nucleation followed by rapid nuclei densification and growth. Using this multimodal in situ approach, different formation pathways can be identified either via precursor phases in the PbI₂ and PbCl₂ routes or direct perovskite formation from molecular building blocks as observed in the lead acetate (PbAc₂) route. Correlation of in situ results with photovoltaic device performance demonstrates the power of in situ multimodal techniques, paves the way to a fast screening of synthetic parameters, and ultimately leads to controlled synthetic procedures that yield high‐efficiency devices.