Total Synthesis of Pyrolaside B: Phenol Trimerization through Sequenced Oxidative C−C and C−O Coupling

A facile method to oxidatively trimerize phenols using a catalytic aerobic copper system is described. The mechanism of this transformation was probed, yielding insight that enabled cross-coupling trimerizations. With this method, the natural product pyrolaside B was synthesized for the first time. The key strategy used for this novel synthesis is the facile one-step construction of a spiroketal trimer intermediate, which can be selectively reduced to give the natural product framework without recourse to stepwise Ullmann- and Suzuki-type couplings. As a result, pyrolaside B can be obtained expeditiously in five steps and 16 % overall yield. Three other analogues were synthesized, thus highlighting the utility of the method, which provides new accessibility to this area of chemical space. A novel xanthene was also synthesized through controlled Lewis acid promoted rearrangement of a spiroketal trimer.     

Effects of hydrostaticity on the structural stability of carbonates at lower mantle pressures: the case study of dolomite

We have conducted high pressure far-infrared absorbance and Raman spectroscopic investigations on a natural iron-free dolomite sample up to 40?GPa. Comparison between the present observations and literature results unraveled the effect of hydrostatic conditions on the high pressure dolomite polymorph adopted close to 40?GPa, i.e. the triclinic Dol-IIIc modification. In particular, non-hydrostatic conditions impose structural disorder at these pressures, whereas hydrostatic conditions allow the detection of an ordered Dol-IIIc vibrational response. Hence, hydrostatic conditions appear to be a key ingredient for modeling carbon subduction at lower mantle conditions. Our complementary first-principles calculations verified the far-infrared vibrational response of the ambient- and high pressure dolomite phases.     

Lignosulfonate/silica hybrid nanoparticles as a novel biobased filler in polybenzoxazine matrix

Lignin is an abundant and sustainable resource that exhibits numerous attractive functional properties as a reinforcing agent for benzoxazine-based composites, due to its stiffness, thermal stability, and high carbon content. However, the low quality of lignin particles dispersions associated with the weak particles-matrix interactions reduces the reinforcement capability. In this work, hybrid lignin/silica (NaLS/SiO₂) nanoparticles were obtained from sodium lignosulfonate (NaLS) and tetraethylorthosilicate (TEOS) under basic conditions. The particles were characterized by transmission electron microscopy (TEM) confirming their spherical morphology and narrow nanometric-size distributions. The hybrid particles were incorporated into conventional benzoxazine (BA-a) and a difuran biobased benzoxazine (SA-dfda) to prepare nanocomposites with different mass compositions (3, 5, and 10 wt%). Morphological, mechanical, dynamo-mechanical, and thermal properties of the obtained composites were assessed. All the materials exhibited a homogenous filler dispersion that contributed to improve the reinforcement properties. Hybrid nanoparticles proved to be an interesting alternative as a filler in the benzoxazine matrix to prepare high-performance thermosetting composites.     

Heavy element chemistry facilities at Texas A&M University

A new program to study the chemistry of the homologs of the transactinide elements is under development, and is centered at the Texas A&M University Cyclotron Institute. New facilities have been designed and/or implemented to enable this research. These include equipment for the production of lanthanide and other targets, a rotating target wheel, an improved recoil transfer chamber, and a customized on-line radiochemical laboratory. Additional target development is being performed at Argonne National Laboratory. The new facilities and equipment are discussed.     

Chemical-Genetic Interactions of Bacopa monnieri Constituents in Cells Deficient for the DNA Repair Endonuclease RAD1 Appear Linked to Vacuolar Disruption

Colorectal cancer is a common cancer worldwide and reduced expression of the DNA repair endonuclease XPF (xeroderma pigmentosum complementation group F) is associated with colorectal cancer. Bacopa monnieri extracts were previously found to exhibit chemical-genetic synthetic lethal effects in a Saccharomyces cerevisiae model of colorectal cancer lacking Rad1p, a structural and functional homologue of human XPF. However, the mechanisms for B. monnieri extracts to limit proliferation and promote an apoptosis-like event in RAD1 deleted yeast was not elucidated. Our current analysis has revealed that B. monnieri extracts have the capacity to promote mutations in rad1∆ cells. In addition, the effects of B. monnieri extracts on rad1∆ yeast is linked to disruption of the vacuole, similar to the mammalian lysosome. The absence of RAD1 in yeast sensitizes cells to the effects of vacuole disruption and the release of proteases. The combined effect of increased DNA mutations and release of vacuolar contents appears to induce an apoptosis-like event that is dependent on the meta-caspase Yca1p. The toxicity of B. monnieri extracts is linked to sterol content, suggesting saponins may be involved in limiting the proliferation of yeast cells. Analysis of major constituents from B. monnieri identified a chemical-genetic interaction between bacopasaponin C and rad1∆ yeast. Bacopasaponin C may have potential as a drug candidate or serve as a model for the development of analogs for the treatment of colorectal cancer.     

Structure-Acid Lability Relationship of N-alkylated α,α-dialkylglycine Obtained via a Ugi Multicomponent Reaction

Using the classical Ugi four-component reaction to fuse an amine, ketone, carboxylic acid, and isocyanide, here we prepared a short library of N-alkylated α,α-dialkylglycine derivatives. Due to the polyfunctionality of the dipeptidic scaffold, this highly steric hindered system shows an interesting acidolytic cleavage of the C-terminal amide. In this regard, we studied the structure-acid lability relationship of the C-terminal amide bond (cyclohexylamide) of N-alkylated α,α-dialkylglycine amides 1a–n in acidic media and, afterward, it was established that the most important structural features related to its cleavage. Then, it was demonstrated that electron-donating effects in the aromatic amines, flexible acyl chains (Gly) at the N-terminal and the introduction of cyclic compounds into dipeptide scaffolds, increased the rate of acidolysis. All these effects are related to the ease with which the oxazolonium ion intermediate forms and they promote the proximity of the central carbonyl group to the C-terminal amide, resulting in C-terminal amide cleavage. Consequently, these findings could be applied for the design of new protecting groups, handles for solid-phase synthesis, and linkers for conjugation, due to its easily modulable and the fact that it allows to fine tune its acid-lability.     

On the morphology of BaMoO4 crystals: A theoretical and experimental approach

BaMoO₄ crystals were obtained by a co‐precipitation method, and their structures were characterized by X‐ray diffraction and Rietveld refinement techniques. Field emission scanning electron microscopy was utilized to investigate the morphology of the as‐synthesized aggregates.‐ Through systematic first principle calculations within the density functional theory method at the B3LYP level, we investigated the structure; the surface stability of the (001), (101), (110), (100), (111), and (112) surfaces; and the morphological transformations of BaMoO₄. The relative surfaces energies were further varied to predict a complete map of the available morphologies through a Wulff construction approach. This revealed that the obtained experimental and theoretical morphologies coincided when the surface energy values of the (001) surface decreased while those of the (100) and (101) facets increased simultaneously. Analysis of the surface structures showed that the electronic properties were associated with the presence of undercoordinated [BaO_x] (x = 4, 5, and 6) and [MoO_y] (y = 3) clusters. The presented results provide a comprehensive catalog of the morphologies most likely to be present under realistic conditions, and will serve as a starting point for future studies on the surface chemistry of BaMoO₄ crystals.     

Rapid characterisation of agro-industrial effluents for environmental fate by UV–visible and infrared spectroscopy from fractions obtained by centrifugation

Agro-industrial systems (e.g. dairy farms, feed lot, pig breeding and food processing plants) provide large quantity of organic wastes that could be recycled within the productive systems. However, the basic chemical characterisation is not enough to predict the effect that they may generate on the environment. In this study, a centrifugation process was applied at various speeds between 3000 and 15,000 rpm and carried out separately on two different livestock effluents (dairy farm and pig anaerobic digestate), in order to obtain supernatants and precipitates, which were studied separately. The more water soluble fractions, with lighter components and/or simpler structures, remained as liquid supernatants, while the more complex fractions, with higher molecular weight and/or water insoluble fractions, constituted the solid precipitates. An increase in the centrifugation rate did not produce the differential precipitation of dissimilar functional groups. Hence, 5000 rpm was the most adequate velocity since it generated clear supernatants without denaturation of the organic matter. A basic cost-effective chemical analysis, complemented with ultraviolet–visible and Fourier transform infrared spectroscopy, enables a set of properties to be established qualitatively and quickly for the multiple components of the organic matter for its later use as fertilisers or amendments. This rapid and economical technique allows for a characterisation prior to the reuse of the effluents, which is necessary to optimise their application and avoid environmental problems.