Regioselective Synthesis of 1,2‐ and 1,4‐Dihydroquinolines by Palladium‐Catalyzed Intramolecular N‐Arylation

A series of 1,2‐ and 1,4‐dihydroquinolines has been successfully prepared. The Pd‐catalyzed intramolecular N‐arylation of Z‐enamines, formally prepared by the Horner–Wadsworth–Emmons olefination, proceeded efficiently to furnish the cyclized products. Depending on the cyclization conditions, substituted 1,4‐dihydroquinolines and further isomerized 1,2‐dihydroquinolines were independently obtained in high yields with an excellent control of isomerization of the double bond.

     

Role of Nd3+ ions on the nucleation and growth of PbS quantum dots (QDs) in silicate glasses

The influence of Nd₂O₃ addition on the precipitation kinetics of lead chalcogenide (PbS) quantum dots (QDs) in silicate glasses was investigated. Energy dispersive X‐ray spectroscopy (EDS) indicated that the Nd³⁺ ions are preferentially located inside the PbS QDs rather than in the glass matrix. Changes in diameter (D) of PbS QDs exhibited smaller time dependencies (i.e., D≈t^{0.270‐0.286}) than that predicted by the classical Lifshitz–Slyozov–Wagner (LSW) theory. This is due to the limited concentrations of Pb²⁺ and S^2? ions and the large diffusion distance inside the glass matrix. In addition, extended X‐ray absorption fine structure (EXAFS) results indicated that the formation of PbS QDs was retarded due to the presence of Nd₂O₃ in the glasses, as the large NdO_x polyhedra interrupt the diffusion of Pb²⁺ and S^2? ions. We believe that these Nd³⁺ ions are primarily located in PbS QDs in the form of Nd–O clusters, and that the PbS QDs are built on top of these clusters.     

Effect of structural change of pitch on the thermal conductivity of epoxy‐based composites filled with heat‐treated pitch

Petroleum‐based pitches were used as filler materials to study the effects of heat‐treatment‐induced changes in pitch structure on the thermal conductivity of epoxy‐based composites. The heat treatment was performed in two steps: the first involved heating the pitch to 250 °C in order to remove the low‐molecular‐weight compounds from the pitch, and the second involved heating the pitch to either 430 or 450 °C. There was no significant difference in the curing behavior of the diglycidyl ether of bisphenol A (DGEBA)/pitch composites, regardless of the heat‐treatment temperature. However, the thermal conductivity of the DGEBA/pitch composites improved with increasing heat‐treatment temperature, and the epoxy composite prepared with pitch heat‐treated at 430 °C exhibited the maximum thermal conductivity. This can be attributed to structural changes in the pitch, such as the distance between adjacent planes (d‐spacing), crystallite height (L_c) and crystallite width (L_a). Although L_c of the pitch increased with increasing heat‐treatment temperature, the d‐spacings and L_a decreased. These results suggest that the heat treatment of the pitch led to a well‐stacked crystalline structure. However, compared with the pitch heat‐treated at 430 °C, that heat‐treated at 450 °C exhibited lower thermal conductivity in the DGEBA/pitch composite because of the low L_a, resulting in the loss of basal carbon as a consequence of in situ gasification, and pyrolysis of the low‐molecular‐weight compounds in the pitch. © 2013 Society of Chemical Industry     

Soluble polyimides with trifluoromethyl pendent groups

Unsymmetrical and symmetrical diamine monomers containing trifluoromethyl groups, 2-trifluoromethyl-4,4′-diaminodiphenyl sulfide and 2,2′-bis(trifluoromethyl)-4,4′-diamino-diphenyl sulfide, were synthesized from 2-chloro-5-nitrobenzotrifluoride as a starting material in two steps, respectively. Diamine monomers were polymerized with PMDA, BPDA, BTDA, and ODPA using a solution imidization method with N-methyl-2-pyrrolidone as a solvent at 190 °C to obtain the corresponding polyimides. They had inherent viscosities that ranged from 0.54 to 0.71 dL/g in N-methyl-2-pyrrolidone at 30 °C. All of the synthesized polyimides showed good solubility in polar aprotic solvents and phenolic solvents regardless of the number of trifluoromethyl groups. The 5% weight loss temperatures of the polyimides are in the range of 534–561 °C in nitrogen, and 505–542 °C in air. The T_g values and the thermal expansion coefficients of these polymers are in the range of 234–325 °C and in the range of 47.4–63.2 ppm/°C, respectively. Also, all of the synthesized polyimides have relatively low refractive indices (around 1.6) and birefringence (below 0.36).     

Enhancement of fibroblastic proliferation from photoreactive starch with immobilized epidermal growth factor

Carboxymethyl starch was modified by the incorporation of an azidophenyl group to prepare photoreactive starch, and characterized by Fourier transform infrared reflectance (FT‐IR), proton nuclear magnetic resonance (¹H‐NMR), and ultraviolet (UV) spectroscopy. Photo‐irradiation immobilized the Az‐starch on a polystyrene plate and it was stably retained on the surface. The protein containing immobilized Az‐starch was also immobilized on a stripe micropatterned plate. UV irradiation time and Az‐starch concentration were used to alter the physical properties of Az‐starch and consequently control the rate of epidermal growth factor (EGF) release. The Az‐starch that released growth factor was not cytotoxic to 3T3‐L1 fibroblast cells, and the immobilized EGF maintained its activity and induced cellular proliferation in vitro. These results suggest that Az‐starch could be useful as a clinical synthetic material for medical applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of sintering atmospheres on the densification behavior of CuO ceramics

In this study, the effect of oxygen partial pressure on the densification and the resultant microstructure change of CuO were examined. When CuO green bodies were heated up to 1100 °C for sintering in air, denser CuO samples were obtained than the samples sintered in oxygen. When the samples were kept at 1100 °C for a prolonged period of time, however, the densification of the sample in oxygen was accelerated whereas that of the sample in air was hindered. This is attributed to the phase transformation from CuO to Cu₂O which accompanies oxygen release during sintering in air. On the basis of the results, dense CuO samples could be obtained by switching the sintering atmosphere from air to oxygen at the suitable stage so that oxygen release by reduction could be suppressed.     

miR-22-3p and miR-30e-5p Are Associated with Prognosis in Cervical Squamous Cell Carcinoma

Alteration in expression of miRNAs can cause various malignant changes and the metastatic process. Our aim was to identify the miRNAs involved in cervical squamous cell carcinoma (SqCC) and metastasis, and to test their utility as indicators of metastasis and survival. Using microarray technology, we performed miRNA expression profiling on primary cervical SqCC tissue (n = 6) compared with normal control (NC) tissue and compared SqCC that had (SqC-M; n = 3) and had not (SqC-NM; n = 3) metastasized. Four miRNAs were selected for validation by qRT-PCR on 29 SqC-NM and 27 SqC-M samples, and nine metastatic lesions (ML-SqC), from a total of 56 patients. Correlation of miRNA expression and clinicopathological parameters was analyzed to evaluate the clinical impact of candidate miRNAs. We found 40 miRNAs differentially altered in cervical SqCC tissue: 21 miRNAs were upregulated and 19 were downregulated (≥2-fold, p < 0.05). Eight were differentially altered in SqC-M compared with SqC-NM samples: four were upregulated (miR-494, miR-92a-3p, miR-205-5p, and miR-221-3p), and four were downregulated (miR-574-3p, miR-4769-3p, miR-1281, and miR-1825) (≥1.5-fold, p < 0.05). MiR-22-3p might be a metastamiR, which was gradually further downregulated in SqC-NM > SqC-M > ML-SqC. Downregulation of miR-30e-5p significantly correlated with high stage, lymph node metastasis, and low survival rate, suggesting an independent poor prognostic factor.     

Primary water stress corrosion cracking in alloy 600 and intergranular crack growth rate

The effects of the stress intensity factor and dissolved hydrogen on the crack growth rate in primary water reactor environments was investigated with alloy 600 with continuous carbide films at grain boundaries. A primary water stress corrosion cracking of intergranular fracture mode was observed. The intergranular crack growth rate decreased with a decreasing stress intensity factor, and the dissolved hydrogen content influenced the crack growth rate. Such results are consistent with those reported previously.     

Deciphering the Binding Interactions between Acinetobacter baumannii ACP and β-ketoacyl ACP Synthase III to Improve Antibiotic Targeting Using NMR Spectroscopy

Fatty acid synthesis is essential for bacterial viability. Thus, fatty acid synthases (FASs) represent effective targets for antibiotics. Nevertheless, multidrug-resistant bacteria, including the human opportunistic bacteria, Acinetobacter baumannii, are emerging threats. Meanwhile, the FAS pathway of A. baumannii is relatively unexplored. Considering that acyl carrier protein (ACP) has an important role in the delivery of fatty acyl intermediates to other FAS enzymes, we elucidated the solution structure of A. baumannii ACP (AbACP) and, using NMR spectroscopy, investigated its interactions with β-ketoacyl ACP synthase III (AbKAS III), which initiates fatty acid elongation. The results show that AbACP comprises four helices, while Ca²⁺ reduces the electrostatic repulsion between acid residues, and the unconserved F47 plays a key role in thermal stability. Moreover, AbACP exhibits flexibility near the hydrophobic cavity entrance from D59 to T65, as well as in the α₁α₂ loop region. Further, F29 and A69 participate in slow exchanges, which may be related to shuttling of the growing acyl chain. Additionally, electrostatic interactions occur between the α₂ and α₃-helix of ACP and AbKAS III, while the hydrophobic interactions through the ACP α₂-helix are seemingly important. Our study provides insights for development of potent antibiotics capable of inhibiting A. baumannii FAS protein–protein interactions.     

Effects of Heat Treatment on the Microstructures and High Temperature Mechanical Properties of Hypereutectic Al–14Si–Cu–Mg Alloy Manufactured by Liquid Phase Sintering Process

Hypereutectic Al–Si alloy is an aluminum alloy containing at least 12.6 wt.% Si. It is necessary to evenly control the primary Si particle size and distribution in hypereutectic Al–Si alloy. In order to achieve this, there have been attempts to manufacture hypereutectic Al–Si alloy through a liquid phase sintering. This study investigated the microstructures and high temperature mechanical properties of hypereutectic Al–14Si–Cu–Mg alloy manufactured by liquid phase sintering process and changes in them after T6 heat treatment. Microstructural observation identified large amounts of small primary Si particles evenly distributed in the matrix, and small amounts of various precipitation phases were found in grain interiors and grain boundaries. After T6 heat treatment, the primary Si particle size and shape did not change significantly, but the size and distribution of CuAl₂ (θ) and AlCuMgSi (Q) changed. Hardness tests measured 97.36 HV after sintering and 142.5 HV after heat treatment. Compression tests were performed from room temperature to 300 °C. The results represented that yield strength was greater after heat treatment (RT?~?300 °C: 351?~?93 MPa) than after sintering (RT?~?300 °C: 210?~?89 MPa). Fracture surface analysis identified cracks developing mostly along the interface between the primary Si particles and the matrix with some differences among temperature conditions. In addition, brittle fracture mode was found after T6 heat treatment.