Different apolipoproteins impact nanolipoprotein particle formation

Spontaneous interaction of purified apolipoproteins and phospholipids results in formation of lipoprotein particles with nanometer-sized dimensions; we refer to these assemblies as nanolipoprotein particles or NLPs. These bilayer constructs can serve as suitable mimetics of biological membranes and are fully soluble in aqueous environments. We made NLPs from dimyristoylphospatidylcholine (DMPC) in combination with each of four different apolipoproteins: apoA-I, Delta-apoA-I fragment, apoE4 fragment, and apolipophorin III (apoLp-III) from the silk moth B. mori. Predominately discoidal in shape, these particles have diameters between 10 and 20 nm, share uniform heights between 4.5 and 5 nm, and can be produced in yields ranging between 40 and 60%. The particular lipoprotein, the lipid to lipoprotein ratio, and the assembly parameters determine the size and homogeneity of nanolipoprotein particles and indicate that apoA-I NLP preparations are smaller than the larger apoE422K and apoLp-III NLP preparations.     

Dissociative wave packets and dynamic resonances

The authors examine the role of dynamic resonances in laser driven molecular fragmentation. The yields of molecular fragments can undergo dramatic changes as an impulsively excited dissociative wave packet passes through a dynamic resonance. The authors compare three different kinds of dynamic resonances in a series of molecular families and highlight the possibility of characterizing the dissociative wave function as it crosses the resonance location.     

Automated post-collection concentration for purified preparative fractions via solid phase extraction

Recent advancements in preparative HPLC have improved and streamlined compound purification. However, fraction evaporation remains a bottleneck within the process. An alternative to fraction evaporation is to remove the water and reduce the overall volume of the collection by trapping the fraction onto a solid phase extraction (SPE) cartridge. This method (as opposed to analytical applications involving SPE) works by collecting and then diluting the fraction(s), passing the fraction(s) through a SPE, drying the SPE with nitrogen and ultimately eluting the concentrated fraction(s) in a small amount of 100% organic solvent. An appreciable breakthrough is not observed using this method. In addition, recovery from the SPE for the tested compounds rosmarinic acid and carvacrol, two naturally occurring antioxidants in oregano, was found to be 95-98% for a 100mg injection via preparative HPLC purification at 50mg/compound.     

Synthesis of 2,2′‐bipyridyl‐type compounds via the suzuki‐miyaura cross‐coupling reaction

2,2′‐Bipyridyl‐type compounds may be prepared by Suzuki‐Miyaura coupling of a 2‐pyridylboronic ester with 2‐haloazines and ‐azoles. Ten examples are presented with yields of 47 to 84%. Both arylbromides and arylchlorides undergo the coupling, but the reaction is sensitive to ring substitution adjacent to the halogen.     

High-throughput five minute microwave accelerated glycosylation approach to the synthesis of nucleoside libraries

The Vorbrüggen glycosylation reaction was adapted into a one-step 5 min/130 degrees C microwave assisted reaction. Triethanolamine in acetontrile containing 2% water was determined to be optimal for the neutralization of trimethylsilyl triflate allowing for direct MPLC purification of the reaction mixture. When coupled with a NH3/methanol deprotection reaction, a high-throughput method of nucleoside library synthesis was enabled. The method was demonstrated by examining the ribosylation of 48 nitrogen containing heteroaromatic bases that included 25 purines, four pyrazolopyrimidines, two 8-azapurines, one 2-azapurine, two imidazopyridines, two benzimidazoles, three imidazoles, three 1,2,4-triazoles, two pyrimidines, two 3-deazapyrimidines, one quinazolinedione, and one alloxazine. Of these, 32 yielded single regioisomer products, and six resulted in separable mixtures. Seven examples provided inseparable regioisomer mixtures of -two to three compounds (16 nucleosides), and three examples failed to yield isolable products. For the 45 single isomers isolated, the average two-step overall yield +/- SD was 26 +/- 16%, and the average purity +/- SD was 95 +/- 6%. A total of 58 different nucleosides were prepared of which 15 had not previously been accessed directly from glycosylation/deprotection of a readily available base.     

Pharmaceuticals and personal care products in biosolids/sewage sludge: the interface between analytical chemistry and regulation

Modern sanitary practices result in large volumes of human waste, as well as domestic and industrial sewage, being collected and treated at common collection points, wastewater treatment plants (WWTPs). In recognition of the growing use of sewage sludge as fertilizers and soil amendments, and the scarcity of current data regarding the chemical constituents in sewage sludge, the US National Research Council (NRC) in 2002 produced a report on sewage sludge. Among the NRC’s recommendations was the need for investigating the occurrence of pharmaceuticals and personal care products (PPCPs) in sewage sludge. PPCPs are a diverse array of non-regulated contaminants that had not been studied in previous sewage sludge surveys but which are likely to be present. The focus of this paper will be to review the current analytical methodologies available for investigating whether pharmaceuticals are present in WWTP-produced sewage sludge, to summarize current regulatory practices regarding sewage sludge, and to report on the presence of pharmaceuticals in sewage sludge.     

Structure and dynamics of water near the interface with oligo(ethylene oxide) self-assembled monolayers

We performed molecular dynamics simulations of the oligo(ethylene oxide) (OEO) self-assembled monolayers in water to determine the nature of the systems' interfacial structure and dynamics. The density profiles, hydrogen bonding, and water dynamics are calculated as a function of the area per molecule A of OEO. At the highest coverages, the interface is hydrophobic, and a density drop is found at the interface. The interfacial region becomes more like bulk water as A increases. The OEO and water become progressively more mixed, and hydrogen bonding increases within the interfacial region. Water mobility is slower within the interfacial region, but not substantially. The implications of our results on the resistance of OEO SAMs to protein adsorption are discussed. Our principal result is that as A increases the increasingly waterlike interfacial region provides a more protein-resistant surface. This finding supports recent experimental measurements that protein resistance is maximal for less than full coverage on Au.     

Anomalous pH dependent stability behavior of surfactant-free nonpolar oil drops in aqueous electrolyte solutions

Recent advances in atomic force microscopy (AFM) force measurement techniques have allowed the direct measurement and theoretical interpretation of the interaction between a liquid droplet and a solid surface or between two liquid droplets. In this study, we investigated the interaction across an aqueous thin film between fluorocarbon (perfluoropentane) droplets, hydrocarbon (tetradecane) droplets, and a droplet and a flat mica surface in the absence of stabilizers. It was found that even at a relatively elevated electrolyte concentration of 0.1 M NaNO3, depending on the solution pH, interactions between two identical droplets or a droplet and a mica surface could be repulsive. A simple theoretical analysis of the magnitude and range of these interactive forces suggests that the DLVO theory cannot explain the observed behavior. The measured force behavior is discussed in the context of ion adsorption, and the arising charging effects, at the bare oil-water interface.     

Multiscale structure of the underwater adhesive of Phragmatopoma californica: a nanostructured latex with a steep microporosity gradient

Phragmatopoma Californica builds a tubular dwelling by gluing bits of sand and seashell together underwater with a proteinaceous adhesive. In the lab, the animals will build with 0.5 mm glass beads. Two spots of glue with a consistent volume of about 100 pL each are deposited on the glass beads before placement on the end of the tube. The animals wriggled the particles for 20-30 s before letting go, which suggested that the adhesive was sufficiently set within 30 s to support the glass beads. The structure of the adhesive joints was examined at the micro- and nanoscopic length scales using laser scanning confocal and atomic force microscopies. At the microscale, the adhesive was a cellular solid with cell diameters ranging from 0.5 to 6.0 mum, distributed to create a steep porosity gradient that ranged from near zero at the outside edges to about 50% at the center of the adhesive joint. At the nanoscale, the adhesive appeared to be an accretion of trillions of deformable nanospheres, reminiscent of a high-solids-content latex adhesive. The implications of the structure for the functionality of the adhesive is discussed.