Functional Characterization of PyrG,an Unusual Nonribosomal Peptide Synthetase Module from the Pyridomycin Biosynthetic Pathway

Pyridomycin is an antimycobacterial cyclodepsipeptide assembled by a nonribosomal peptide synthetase/polyketide synthase hybrid system. Analysis of its cluster revealed a nonribosomal peptide synthetase (NRPS) module, PyrG, that contains two tandem adenylation domains and a PKS‐type ketoreductase domain. In this study, we biochemically validated that the second A domain recognizes and activates α‐keto‐β‐methylvaleric acid (2‐KVC) as the native substrate; the first A domain was not functional but might play a structural role. The KR domain catalyzed the reduction of the 2‐KVC tethered to the peptidyl carrier protein of PyrG in the presence of the MbtH family protein, PyrH. PyrG was demonstrated to recognize many amino acids. This substrate promiscuity provides the potential to generate pyridomycin analogues with various enolic acids moiety; this is important for binding InhA, a critical enzyme for cell‐wall biosynthesis in Mycobacterium tuberculosis.     

Morphologically dependent alternating‐current and direct‐current breakdown strength in silica–polypropylene nanocomposites

In this article, we report the synthesis of a new bimodal surface ligand morphology on silica nanoparticles. Combining grafting‐to and grafting‐from approaches, in this study, we demonstrated the efficacy of anthracene surface modification for improving the dielectric breakdown strength (DBS) under alternating‐current and direct‐current conditions and that of a matrix‐compatible polymer brush for controlling the nanofiller (NF) dispersion. Ligand‐modified spherical colloidal SiO₂ nanoparticles (～14 nm in diameter) were mixed into polypropylene, and the resulting dispersion was improved over the unmodified particles, as shown with transmission electron microscopy. The results suggest that the electronic structure of the anthracene‐modified particle surface was critical to the improvement in DBS. In addition, the DBS of the composite was shown to depend on the dispersion state of the filler and the mode of stress; this indicated that the individually dispersed nanoparticles were not necessarily the optimal morphology for all stress conditions. Additionally, the precise nature of the matrix‐compatible brush was less important than the NF dispersion it produced. The bimodal grafted architectural design has provided a promising solution for the control of the dispersion and surface properties, especially for high‐molecular‐weight polymer matrices. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44347.     

Strategy for robot motion and path planning in robot taping

Covering objects with masking tapes is a common process for surface protection in processes like spray painting, plasma spraying, shot peening, etc. Manual taping is tedious and takes a lot of effort of the workers. The taping process is a special process which requires correct surface covering strategy and proper attachment of the masking tape for an efficient surface protection. We have introduced an automatic robot taping system consisting of a robot manipulator, a rotating platform, a 3D scanner and specially designed taping end-effectors. This paper mainly talks about the surface covering strategies for different classes of geometries. The methods and corresponding taping tools are introduced for taping of following classes of surfaces: Cylindrical/extended surfaces, freeform surfaces with no grooves, surfaces with grooves, and rotational symmetrical surfaces. A collision avoidance algorithm is introduced for the robot taping manipulation. With further improvements on segmenting surfaces of taping parts and tape cutting mechanisms, such taping solution with the taping tool and the taping methodology can be combined as a very useful and practical taping package to assist humans in this tedious and time costly work.     

Three-dimensional microstructural changes in the Ni–YSZ solid oxide fuel cell anode during operation

Microstructural evolution in solid oxide fuel cell (SOFC) cermet anodes has been investigated using X-ray nanotomography along with differential absorption imaging. SOFC anode supports composed of Ni and yttria-stabilized zirconia (YSZ) were subjected to extended operation and selected regions were imaged using a transmission X-ray microscope. X-ray nanotomography provides unique insight into microstructure changes of all three phases (Ni, YSZ, pore) in three spatial dimensions, and its relation to performance degradation. Statistically significant 3D microstructural changes were observed in the anode Ni phase over a range of operational times, including phase size growth and changes in connectivity, interfacial contact area and contiguous triple-phase boundary length. These observations support microstructural evolution correlated to SOFC performance. We find that Ni coarsening is driven by particle curvature as indicated by the dihedral angles between the Ni, YSZ and pore phases, and hypothesize that growth occurs primarily by means of diffusion and particle agglomeration constrained by a pinning mechanism related to the YSZ phase. The decrease in Ni phase size after extended periods of time may be the result of a second process connected to a mobility-induced decrease in the YSZ phase size or non-uniform curvature resulting in a net decrease in Ni phase size.     

Flow patterns and oil—water dispersion in a 0.38 m diameter oscillatory baffled column

We report our experimental flow visualization observations of flow patterns and experimental oil‐water dispersion measurements in an oscillatory baffled column (OBC) of an internal diameter 380 mm. Both types of experiments were carried out covering an identical range of oscillation frequencies, amplitudes, orifice diameters and baffle spacings. The flow visualization observations show that eddy mixing has been achieved in the pilot OBC and the intensity of which is largely dependent on the operational and geometrical parameters tested, which is similar to that in a smaller scale OBC. The scale‐up correlation was found to be linear. The oil‐water dispersion measurements show that the degree of the dispersion depends significantly on the oscillation frequency and amplitude with an increase in either leading to an increase in dispersion. The effect of the orifice diameter on the oil—water dispersion is also evident, but the effect of the baffle spacing is much weaker. Based on the experimental data we have established a correlation relating the degree of oil—water dispersion to the power input to the system. We have also compared the power requirement to achieve a complete dispersion in the pilot OBC with that in a bench scale OBC of 50 mm diameter and found that the energy dissipation is more economical in the large scale application.     

Ultrafine particles from diesel vehicle emissions at different driving cycles induce differential vascular pro-inflammatory responses: Implication of chemical components and NF-κB signaling

Background

Nanometer silicon dioxide (nano-SiO₂) has a wide variety of applications in material sciences, engineering and medicine; however, the potential cell biological and proteomic effects of nano-SiO₂ exposure and the toxic mechanisms remain far from clear.

Results

Here, we evaluated the effects of amorphous nano-SiO₂ (15-nm, 30-nm SiO₂). on cellular viability, cell cycle, apoptosis and protein expression in HaCaT cells by using biochemical and morphological analysis, two-dimensional differential gel electrophoresis (2D-DIGE) as well as mass spectrometry (MS). We found that the cellular viability of HaCaT cells was significantly decreased in a dose-dependent manner after the treatment of nano-SiO₂ and micro-sized SiO₂ particles. The IC₅₀ value (50% concentration of inhibition) was associated with the size of SiO₂ particles. Exposure to nano-SiO₂ and micro-sized SiO₂ particles also induced apoptosis in HaCaT cells in a dose-dependent manner. Furthermore, the smaller SiO₂ particle size was, the higher apoptotic rate the cells underwent. The proteomic analysis revealed that 16 differentially expressed proteins were induced by SiO₂ exposure, and that the expression levels of the differentially expressed proteins were associated with the particle size. The 16 proteins were identified by MALDI-TOF-TOF-MS analysis and could be classified into 5 categories according to their functions. They include oxidative stress-associated proteins; cytoskeleton-associated proteins; molecular chaperones; energy metabolism-associated proteins; apoptosis and tumor-associated proteins.

Conclusions

These results showed that nano-SiO₂ exposure exerted toxic effects and altered protein expression in HaCaT cells. The data indicated the alterations of the proteins, such as the proteins associated with oxidative stress and apoptosis, could be involved in the toxic mechanisms of nano-SiO₂ exposure.     

Effects of magnetic field on calcium carbonate precipitation: Ionic and particle mechanisms

There are two most widely reported mechanisms to study the effect of magnetic fields on calcium carbonate (CaCO₃) precipitate, namely ionic and particle mechanisms. The effects are most debatable because they are contrary to each other. This study explored the effects of both mechanisms in CaCO₃ deposit and total CaCO₃ precipitation using ionic and particle methods. The ionic method showed reductions in CaCO₃ deposit and total precipitation rate of CaCO₃, whereas the particle method showed the opposite results. The particle number decreased and the average particle diameter of CaCO₃ deposit increased in the ionic method. Meanwhile in the particle method, the particle number increased, average particle diameter decreased and particle aggregation of CaCO₃ was observed. XRD measurement on all deposits showed that the crystal deposit was mostly of calcite and the traces of vaterite. However, the amount of the crystal in the particle method was observed to be less than that in the ionic method, indicating that CaCO₃ deposit was more amorphous. Particle mechanism decreased the Ca²⁺ ion concentration in solution during magnetization, and ionic mechanism reduced scale (CaCO₃) formation after magnetization and separation processes. This method could be applied for decreasing water hardness and prevent the formation of scaling.     

Catalytic oxidation of methane over hexaaluminates and hexaaluminate-supported Pd catalysts

An aqueous (NH₄)₂CO₃ coprecipitation method, based on that of Groppi et al. [Appl. Catal. A 104 (1993) 101–108] was used to synthesize Sr_1−xLa_xMnAl₁₁O₁₉₋ hexaaluminates. These materials were first synthesized by alkoxide hydrolysis. This synthesis route requires special handling of the starting materials and is not likely to be commercially practical. The materials prepared by (NH₄)₂CO₃ coprecipitation have similar surface areas as those prepared by the alkoxide hydrolysis method. Their CH₄ oxidation activity, measured as the temperature needed for 10% conversion of methane, is higher than those prepared by alkoxide hydrolysis. The La-substantiated material, LaMnAl₁₁O₁₉₋, shows high surface area with 19.3 m²/g after calcination at 1400°C for 2 h. It is active for CH₄ oxidation with T_10% at 450°C using 1% CH₄ in air and 70 000 cm³/h g space velocity. The stability and activity of LaMnAl₁₁O₁₉₋ prepared by (NH₄)₂CO₃ coprecipitation method is a simple and important step forward for the application of CH₄ catalytic combustion for gas turbines.     

Influence of the process parameters of an intermeshing co‐rotating twin screw extruder on the morphology and notched Izod impact strength of PBT/ABS/MGE blends

In this research, it was studied the effects of the processing parameters applied to a twin screw extruder on the morphology and impact strength of poly(butylene terephthalate)/acrylonitrile‐butadiene‐styrene blends with and without a reactive compatibilizer. It was found that the increase of the feed rate highly decreased the ductile brittle transition temperature (DBTT) and slightly increased the room temperature impact strength (RTIS) of the compatibilized blends. Besides the influence of the feed rate, it was also found that the compatibilized blends could reach high RTIS and low DBTT values by an appropriate combination of the compatibilizer feeding position in the extruder, the screw rotation speed and the width of the kneading discs of the screw. The DBTT was found to be at least partially controlled by the spatial distribution of the rubbery particles, which was quantified by finite body tessellation, a method applied for the first time in polymer blends. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Catalytic activity evaluation for hydrogen production via autothermal reforming of methane

A nickel catalyst (5.75 wt.%) supported on gamma-alumina was evaluated through autothermal reforming of methane (ATR). The reforming process was pointed to hydrogen production, following thermodynamic and stoichiometric predictions. The catalyst was characterised by several methods including atomic absorption spectroscopy (AAS), B.E.T.-N₂, X-ray diffraction (XRD), scanning electron microscope (SEM) and thermal analyses (thermogravimetry, TG; derivate thermogravimetry, DTG; and differential thermal analysis, DTA). Experimental evaluations in a fixed-bed reactor (1023–1123 K, 1.00 bar, 150–400 cm³/min feed) presented methane conversions in the range of 40–65%. The effluent mixtures provided hydrogen yields in the range of 78–84%, carbon monoxide 3–14%, and carbon dioxide 5–18%. High molar H₂/CO ratios, ranging from 8 to 90, were obtained. Operating autothermal conditions (excess of steam, 1023–1123 K, 1.00 bar) provided low coke formation and high hydrogen selectivity (81%) for methane reforming.