Chromatographic characterization of thermally upgraded products from alternative fuels

An overview is presented of the analytical approaches developed by our research group over the last ten years for analysis of alternative fuel, both biomass and fossil. The alternative fuels are analyzed successively by PLC-8 (preparative liquid chromatography–group-type) fractionation and high resolution gas chromatography. Some of the possibilities for fractionation and characterization of alternative fuels are herein exemplified with sugar cane bagasse pyrolysis products.     

Accommodation of the Lattice Mismatch at the VCx-WC Interface

A VC doped WC-Co alloy is investigated using high resolution transmission electron microscopy. The VC grain growth inhibitor induces the presence of a thin layer on the surfaces of the WC grains in contact with Co and precipitates in the corners of Co pockets. These (VW)C_x compounds adopt an epitaxial orientation relationship with regards to the (0001) base facets of the WC crystals. Due to the small difference in lattice parameters, misfit dislocations are expected in the interfaces. Unlike the thin layers where no defects are observed, two kinds of dislocations are pointed out for larger precipitates. 1/6〈112〉_VC interfacial dislocations are sometimes present while more often 1/2〈1¯10〉_VC dislocations lying above the interface in the (VW)C_x phase are visible.     

Phase separation of p53 precedes aggregation and is affected by oncogenic mutations and ligands

Mutant p53 tends to form aggregates with amyloid properties, especially amyloid oligomers inside the nucleus, which are believed to cause oncogenic gain-of-function (GoF). The mechanism of the formation of the aggregates in the nucleus remains uncertain. The present study demonstrated that the DNA-binding domain of p53 (p53C) underwent phase separation (PS) on the pathway to aggregation under various conditions. p53C phase separated in the presence of the crowding agent polyethylene glycol (PEG). Similarly, mutant p53C (M237I and R249S) underwent PS; however, the process evolved to a solid-like phase transition faster than that in the case of wild-type p53C. The data obtained by microscopy of live cells indicated that transfection of mutant full-length p53 into the cells tended to result in PS and phase transition (PT) in the nuclear compartments, which are likely the cause of the GoF effects. Fluorescence recovery after photobleaching (FRAP) experiments revealed liquid characteristics of the condensates in the nucleus. Mutant p53 tended to undergo gel- and solid-like phase transitions in the nucleus and in nuclear bodies demonstrated by slow and incomplete recovery of fluorescence after photobleaching. Polyanions, such as heparin and RNA, were able to modulate PS and PT in vitro. Heparin apparently stabilized the condensates in a gel-like state, and RNA apparently induced a solid-like state of the protein even in the absence of PEG. Conditions that destabilize p53C into a molten globule conformation also produced liquid droplets in the absence of crowding. The disordered transactivation domain (TAD) modulated both phase separation and amyloid aggregation. In summary, our data provide mechanistic insight into the formation of p53 condensates and conditions that may result in the formation of aggregated structures, such as mutant amyloid oligomers, in cancer. The pathway of mutant p53 from liquid droplets to gel-like and solid-like (amyloid) species may be a suitable target for anticancer therapy.

Mutant p53 tends to form aggregates with amyloid properties, especially amyloid oligomers inside the nucleus, which are believed to cause oncogenic gain-of-function (GoF).     

Protection against photoaging in the hairless mouse by the isoflavone equol

Topical application of the isoflavone equol immediately following solar-simulated UV (SSUV) radiation exposure has previously been demonstrated to have significant photoprotective effects. Equol reduced both the inflammatory edema and the systemic suppression of the contact hypersensitivity reaction in hairless mice. Furthermore, daily topical equol application immediately following irradiation during a 10-week chronic SSUV exposure regime also reduced photocarcinogenesis severity in the mouse. This study examines the potential for topical equol to prevent photoaging in response to chronic SSUV irradiation for up to 30 weeks. We did not find consistent expression of the characteristic markers of photoaging until 30 weeks, although moderate epidermal hyperplasia and a transient increase in dermal mast cell numbers were evident after 1 week. Daily application of 10 muM equol lotion significantly reduced these early changes. However after 30 weeks of SSUV exposure, photoaging was well developed, as shown histologically by markedly increased epidermal hyperplasia, increased dermal mast cell number, pronounced focal elastotic deposits, degraded dermal collagen and deposition of glycosaminoglycans in the lower dermis. Topical equol treatment protected significantly from each of these impairments, as demonstrated histologically and quantitatively. Additionally, equol was found to have strong antioxidant action against acute UVA (320-400 nm)-induced lipid peroxidation of mouse skin, this property accounting for its antiphotoaging mechanism. The evidence for equol's antiphotoaging activity, taken together with its anti-inflammatory, immunoprotective and anticarcinogenic efficacy against SSUV irradiation in the mouse, suggests that equol could be developed as a helpful topical photoprotective agent for daily use by humans.     

How can enzymes be so efficient?

Dudley Williams and his colleagues discuss how ligands can gain binding energy to their receptors, and substrate transition states to their enzymes, by tightening the protein structures, with a decrease in their dynamic behaviour.     

Self-assembled morphologies of monotethered polyhedral oligomeric silsesquioxane nanocubes from computer simulation

Self-assembly of functionalized nanoscale building blocks is a promising strategy for "bottom-up" materials design. Recent experiments have demonstrated that the self-assembly of polyhedral oligomeric silsesquioxane (POSS) "nanocubes" functionalized with organic tethers can be utilized to synthesize novel materials with highly ordered, complex nanostructures. We have performed molecular simulations for a simplified model of monotethered POSS nanocubes to investigate systematically how the parameters that control the assembly process and the resulting equilibrium structures, including concentration, temperature, tether lengths, and solvent conditions, can be manipulated to achieve useful structures via self-assembly. We report conventional lamellar and cylindrical structures that are typically found in block copolymer and surfactant systems, including a thermotropic order-order transition, but with interesting stabilization of the lamellar phase caused by the bulkiness and cubic geometry of the POSS nanocubes.     

Chromium(V) peptide complexes: synthesis and spectroscopic characterization

A series of stable Cr(V) model complexes that mimic the binding of Cr(V) to peptide backbones at the C-terminus of proteins have been prepared for N,N-dimethylurea derivatives of the tripeptides Aib3-DMF, AibLAlaAib-DMF, and AibDAlaAib-DMF (Aib = 2-amino-2-methylpropanoic acid, DMF = N,N-dimethylformamide). The Cr(ll) precursor complexes were synthesized by the initial deprotonation of the amide and acid groups of the peptide ligands in DMF with potassium tert-butoxide in the presence of CrCl2. The Cr(II) intermediates thus formed were then immediately oxidized to Cr(V) using tert-butyl hydroperoxide. Spectroscopic and mass-spectrometric analyses of the Cr(V) complexes showed that a new metal-directed organic transformation of the ligand had occurred. This involved a DMF solvent molecule becoming covalently bound to the amine group of the peptide ligand, yielding a urea group, and a third coordinated deprotonated urea nitrogen donor. A metal-directed oxidative coupling has been proposed as a possible mechanism for the organic transformation. The Cr(V/IV) reduction potential was determined for the three Cr(V) complexes using cyclic voltammetry, and in all cases it was quasi-reversible. These are the first isolated and fully characterized Cr(V) complexes with non-sulfur-containing peptide ligands.     

Morphological and chemical characteristics of airborne tungsten particles of Fallon, Nevada.

Morphological and chemical characteristics were determined for airborne tungsten particles in Fallon, Nevada, a town that is distinguishable environmentally by elevated airborne tungsten and cobalt. From samples of airborne dust collected previously at six different places in Fallon, tungsten-rich dust particles were isolated and analyzed with automated electron microprobe and wavelength-dispersive spectrometry. Representative W particles were further analyzed using transmission electron microscopy. Morphologically, Fallon W particles are angular and small, with minimum and maximum sizes of < or = 1 microm and 5.9 microm in diameter, respectively. The number and size of tungsten-rich particles decrease in Fallon with distance from a hard-metal facility located near the center of town. Chemically, Fallon airborne W particles include mixtures of tungsten with cobalt plus other metals such as chromium, iron, and copper. No W-rich particles were identifiable as CaWO4 (scheelite) or MnWO4 (huebnerite). From d-spacings, Fallon particles are most consistent with identification as tungsten carbide. Based on these multiple lines of evidence, airborne W particles in Fallon are anthropogenic in origin, not natural. The hard-metal facility in Fallon processes finely powdered W and W-Co, and further investigation using tracer particles is recommended to definitively identify the source of Fallon's airborne tungsten.