Borepin Rings as "Sigma-Free" Reporters of Aromaticity within Polycyclic Aromatic Scaffolds.

The definition and measurement of local and global aromaticity in fused ring polycyclic aromatic compounds is a complex issue. Historically, these types of molecules have been explored in this capacity by way of experimental (NMR, thermochemistry) and computational (NICS, HOMA) analyses. We previously showed how borepin rings with [ b, f] arene fusions can be used as experimental magnetic aromaticity reporters via the remaining protons attached to the borepin rings. In this report, we describe a joint experimental and computational analysis of several borepin-containing polycyclic aromatic molecules in order to draw conclusions about the influence of ring fusion on aromaticity. We find that the borepin ring within these extended structures is a unique motif with limited σ-contribution to aromaticity while still displaying a wide range of structural and magnetic aromatic character.

Benzo[b]thiophene Fusion Enhances Local Borepin Aromaticity in Polycyclic Heteroaromatic Compounds.

This report documents the synthesis, characterization, and computational evaluation of two isomeric borepin-containing polycyclic aromatics. The syntheses of these two isomers involved symmetrical disubstituted alkynes that were reduced to Z-olefins followed by borepin formation either through an isolable stannocycle intermediate or directly from the alkene via the trapping of a transient dilithio intermediate. Comparisons of their magnetic, crystallographic, and computational characterization to literature compounds gave valuable insights about the aromaticity of these symmetrically fused [b,f]borepins. The fusion of benzo[b]thiophene units to the central borepin cores forced a high degree of local aromaticity within the borepin moieties relative to other known borepin-based polycyclic aromatics. Each isomer had unique electronic responses in the presence of fluoride anions. The experimental data demonstrate that the local borepin rings in these two compounds have a relatively high amount of aromatic character. Results from quantum chemical calculations provide a more comprehensive understanding of local and global aromatic characters of various rings in fused ring systems built upon boron heterocycles.

Aromaticity Competition in Differentially Fused Borepin-Containing Polycyclic Aromatics.

This report describes the synthesis and characterization of a series of borepin-based polycyclic aromatics bearing two different arene fusions. The borepin synthesis features streamlined Ti-mediated alkyne reduction, leading to Z-olefins, followed by direct lithiation and borepin formation. These molecules allow for an assessment of aromatic competition between the fused rings and the central borepin core. Crystallographic, magnetic, and computational studies yielded insights about the aromaticity of novel, differentially fused [b,f]borepins and allowed for comparison to literature compounds. Multiple borepin motifs were also incorporated into polycyclic aromatics with five or six rings in the main backbone, and their properties were also evaluated.

Iron Sequestration by Galloyl-Silane Nano Coatings Inhibits Biofilm Formation of Sulfitobacter sp.

Microbially-induced corrosion is the acceleration of corrosion induced by bacterial biofilms. The bacteria in the biofilms oxidize metals on the surface, especially evident with iron, to drive metabolic activity and reduce inorganic species such as nitrates and sulfates. Coatings that prevent the formation of these corrosion-inducing biofilms significantly increase the service life of submerged materials and significantly decrease maintenance costs. One species in particular, a member of the Roseobacter clade, Sulfitobacter sp., has demonstrated iron-dependent biofilm formation in marine environments. We have found that compounds that contain the galloyl moiety can prevent Sulfitobacter sp. biofilm formation by sequestering iron, thus making a surface unappealing for bacteria. Herein, we have fabricated surfaces with exposed galloyl groups to test the effectiveness of nutrient reduction in iron-rich media as a non-toxic method to reduce biofilm formation.

Membrane curvature recognition by C-reactive protein using lipoprotein mimics.

It has been reported that the oxidation of phosphatidylcholine (PC) is necessary for C-reactive protein (CRP) to bind to lipid membranes, but it remains elusive why CRP only binds oxidized membranes. Here we offer a new perspective on the role of membrane curvature and CRP binding using engineered lipoprotein particle (LPP) mimics. We show that CRP binds preferentially to LPP mimics with diameters of ≤ 28 nm, and binding of CRP to these mimics leads to the dissociation of native CRP into monomeric CRP, exposing CRP neo-epitopes that bind C1q. We also show that the smaller LPP mimics compete for CRP binding to oxidized low density lipoproteins (oxLDLs), suggesting that these mimics expose the same PC epitopes as those found on oxLDLs. Results from this study suggest that membrane curvature could be an additional factor influencing CRP binding of damaged membranes distinct from the oxidation of PC lipids.

Using the Localized Surface Plasmon Resonance of Gold Nanoparticles to Monitor Lipid Membrane Assembly and Protein Binding.

Gold nanoparticles provide a template for preparing supported lipid layers with well-defined curvature. Here, we utilize the localized surface plasmon resonance (LSPR) of gold nanoparticles as a sensor for monitoring the preparation of lipid layers on nanoparticles. The LSPR is very sensitive to the immediate surroundings of the nanoparticle surface and it is used to monitor the coating of lipids and subsequent conversion of a supported bilayer to a hybrid membrane with an outer lipid leaflet and an inner leaflet containing hydrophobic alkanethiol. We demonstrate that both decanethiol and propanethiol are able to form hybrid membranes and that the membrane created over the shorter thiol can be stripped from the gold along with the lipid leaflet using ß-mercaptoethanol. The sensitivity of the nanoparticle LSPR to the refractive index (RI) of its surroundings is greater when the shorter thiol is used (37.8 ± 1.5 nm per RI unit) than when the longer thiol is used (27.5 ± 0.5 nm per RI unit). Finally, C-reactive protein binding to the membrane is measured using this sensor allowing observation of both protein-membrane and nanoparticle-nanoparticle interactions without chemical labeling of protein or lipids.