Computer-controlled Raman microspectroscopy (CC-Raman): A method for the rapid characterization of individual atmospheric aerosol particles

The ability of an atmospheric aerosol particle to impact climate by acting as a cloud condensation nucleus (CCN) or an ice nucleus (IN), as well as scatter and absorb solar radiation is determined by its physicochemical properties at the single particle level, specifically size, morphology, and chemical composition. The identification of the secondary species present in individual aerosol particles is important as aging, which leads to the formation of these species, can modify the climate relevant behavior of particles. Raman microspectroscopy has a great deal of promise for identifying secondary species and their mixing with primary components, as it can provide detailed information on functional groups present, morphology, and internal structure. However, as with many other detailed spectroscopic techniques, manual analysis by Raman microspectroscopy can be slow, limiting single particle statistics and the number of samples that can be analyzed. Herein, the application of computer-controlled Raman (CC-Raman) for detailed physicochemical analysis that increases throughput and minimizes user bias is described. CC-Raman applies automated mapping to increase analysis speed allowing for up to 100 particles to be analyzed in an hour. CC-Raman is applied to both laboratory and ambient samples to demonstrate its utility for the analysis of both primary and, most importantly, secondary components (sulfate, nitrate, ammonium, and organic material). Reproducibility and precision are compared to computer controlled-scanning electron microscopy (CCSEM). The greater sample throughput shows the potential for CC-Raman to improve particle statistics and advance our understanding of aerosol particle composition and mixing state, and, thus, climate-relevant properties.

© 2017 American Association for Aerosol Research     

Adhesion of a chemically deposited monetite coating to a Ti substrate

Monetite is a promising biomaterial for restoring the function of the compromised skeletal structures due to its superior osteoconductive and resorption properties. However, its potential as a coating for orthopaedic implants in load bearing applications has not yet been investigated. The aim of this study was to prepare monetite coating on Ti substrate in mild conditions, which may allow incorporation of protein-based drugs during the coating deposition. Coatings were prepared using chemical deposition of monetite on Ti substrate in acidic conditions at 75 °C for 24 h. Coatings were characterised by scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Adhesion of the coatings to Ti substrate was measured using tensile tests. EDS confirmed the calcium phosphate nature of the coating and XRD and FTIR confirmed the monetite phase of the coatings. SEM revealed that the coatings were formed of densely packed plate-like monetite crystals, with the crystal size approximately 20 × 10 × 5 μm. Adhesion tests showed cohesive failure of the monetite coatings and the tensile strength of the coating was in the range of 15.43 ± 0.20 MPa. Mechanical tests showed that monetite coatings were stable and could be considered for use with Ti orthopaedic implants.     

Plasma LCAT Activity and Lipid Subfraction Composition in Obese Beagles Undergoing Weight Loss

The relationship between lecithin:cholesterol acyltransferase (LCAT) activity and weight loss in dogs was investigated. Four experimental weight-loss diets were fed to 12 obese female beagles for 56 days in a partial crossover design (n = 6). High- (HGI) or low- (LGI) glycemic index starch and diacylglycerol or triacylglycerol oils were combined to compose experimental diets with similar fatty acid profiles. Food intake and body weights were measured daily and weekly, respectively. Fasted blood samples were drawn at day 0, day 28, and day 56 to measure plasma LCAT activity and total (TC), unesterified (UC), and esterified (EC) cholesterol concentrations, and for fatty acid analysis of the phospholipid (PL) and EC fractions. The LGI groups lost more weight than the HGI groups due to starch digestibility differences. An HGI starch effect on TC and UC concentrations was observed but was unrelated to weight loss. LCAT activities increased over time but were not different after controlling for percentage weight loss. However, a positive linear correlation was found between LCAT and UC concentrations in all groups. Plasma PL fatty acid profiles reflected the diets fed, but increases in 16 and 18 carbon saturated and monounsaturated fatty acids in all groups appeared to be an effect of fatty acid mobilization from storage sites. Both plasma PL and EC fatty acid profiles were similar with both acylglycerol types and EC fatty acids reflected linoleic acid specificity with minimal diet or time effects.     

New Pacidamycin Antibiotics Through Precursor‐Directed Biosynthesis

Pacidamycins, mureidomycins and napsamycins are structurally related uridyl peptide antibiotics that inhibit translocase I, an as yet clinically unexploited target. This potentially important bioactivity coupled to the biosynthetically intriguing structure of pacidamycin make this natural product a fascinating subject for study. A precursor‐directed biosynthesis approach was employed in order to access new pacidamycin derivatives. Strikingly, the biosynthetic machinery exhibited highly relaxed substrate specificity with the majority of the tryptophan analogues that were administered; this resulted in the production of new pacidamycin derivatives. Remarkably, 2‐methyl‐, 7‐methyl‐, 7‐chloro‐ and 7‐bromotryptophans produced their corresponding pacidamycin analogues in larger amounts than the natural pacidamycin. Low levels or no incorporation was observed for tryptophans substituted at positions 4, 5 and 6. The ability to generate bromo‐ and chloropacidamycins opens up the possibility of further functionalising these compounds through chemical cross‐coupling in order to access a much larger family of derivatives.     

Effects of carbon fillers on the thermal conductivity of highly filled liquid‐crystal polymer based resins

The thermal conductivity of insulating polymers can be increased by the addition of conductive fillers. One potential market for these thermally conductive resins is for fuel cell bipolar plates. In this study, various amounts of three different carbon fillers (carbon black, synthetic graphite particles, and carbon fiber) were added to Vectra A950RX liquid crystal polymer. Because the resulting composites were anisotropic, they were tested for both through‐plane and in‐plane thermal conductivities. The effects of single fillers and combinations of the different fillers were studied via a factorial design. Each single filler caused a statistically significant increase in composite through‐plane and in‐plane thermal conductivities at the 95% confidence level, with synthetic graphite causing the largest increase. All of the composites containing combinations of the different fillers caused statistically significant increases in the composite through‐plane and in‐plane thermal conductivities. It is possible that thermally conductive pathways were formed that linked these carbon fillers, which resulted in increased composite thermal conductivity. Composites containing 70, 75, and 80 wt % synthetic graphite and the composite containing all three fillers (2.5 wt % carbon black, 65 wt % synthetic graphite, and 5 wt % carbon fiber) had in‐plane thermal conductivities of 20 W m^?1 K^?1 or higher, which is desirable for bipolar plates. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Chemical Defenses Against Fish Predation in Three Brazilian Octocorals: 11β,12β-Epoxypukalide as a Feeding Deterrent in Phyllogorgia dilatata

The feeding-deterrence properties of crude extracts of three Brazilian octocoral species, Neospongodes atlantica Kükenthal (Alcyonacea, Nephtheidae), Plexaurella regia Castro (Gorgonacea, Plexauridae), and Phyllogorgia dilatata Esper (Gorgonacea, Gorgoniidae), were investigated. All the extracts were incorporated into food strips at the concentrations occurring in the living organisms. Crude extract and its ethyl acetate fraction obtained from P. dilatata collected in Armação dos Búzios (Rio de Janeiro State), when incorporated into artificial diets and tested in the habitat of origin, reduced consumption of food strips by fishes, relative to controls. Crude extracts from two octocoral species collected at the National Marine Park of Abrolhos (Bahia State), N. atlantica and P. regia, had no apparent feeding-deterrence properties; in fact, they seemed to stimulate feeding. Bioassay-guided fractionation of the bioactive P. dilatata crude extract revealed that the deterrent property was restricted to a medium polarity fraction. Field palatability experiments with two pure compounds isolated from this fraction revealed that the furanocembranolide 11,12-epoxypukalide is a potent feeding deterrent produced by P. dilatata against fish. Apparently, furanocembranolides are a particular class of compounds with feeding deterrent properties, protecting some octocorals from potential fish predator species in both tropical and temperate environments.     

The Innate Immune Glycoprotein Lactoferrin Represses the Helicobacter pylori cag Type IV Secretion System

Chronic infection with Helicobacter pylori increases risk of gastric diseases including gastric cancer. Despite development of a robust immune response, H. pylori persists in the gastric niche. Progression of gastric inflammation to serious disease outcomes is associated with infection with H. pylori strains which encode the cag Type IV Secretion System (cag T4SS). The cag T4SS is responsible for translocating the oncogenic protein CagA into host cells and inducing pro-inflammatory and carcinogenic signaling cascades. Our previous work demonstrated that nutrient iron modulates the activity of the T4SS and biogenesis of T4SS pili. In response to H. pylori infection, the host produces a variety of antimicrobial molecules, including the iron-binding glycoprotein, lactoferrin. Our work shows that apo-lactoferrin exerts antimicrobial activity against H. pylori under iron-limited conditions, while holo-lactoferrin enhances bacterial growth. Culturing H. pylori in the presence of holo-lactoferrin prior to co-culture with gastric epithelial cells, results in repression of the cag T4SS activity. Concomitantly, a decrease in biogenesis of cag T4SS pili at the host-pathogen interface was observed under these culture conditions by high-resolution electron microscopy analyses. Taken together, these results indicate that acquisition of alternate sources of nutrient iron plays a role in regulating the pro-inflammatory activity of a bacterial secretion system and present novel therapeutic targets for the treatment of H. pylori-related disease.     

Theory of mind associations with other cognitive functions and brain imaging in normal aging.

The study investigated age-related differences in theory of mind and explored the relationship between this ability, other cognitive abilities, and structural brain measures. A cohort of 106 adults (ages 50–90 years) was recruited. Participants completed tests of theory of mind, verbal and performance intelligence, executive function, and information processing speed and underwent structural magnetic resonance imaging (measurement of whole brain volume, volume of white matter hyperintensities, and diffusion tensor imaging of white matter integrity). Theory of mind ability declined with increasing age, and the relationship between theory of mind and age was fully mediated by performance intelligence, executive function, and information processing speed and was partially mediated by verbal intelligence. Theory of mind performance correlated significantly with diffusion tensor imaging measures of white matter integrity but not with volume of white matter hyperintensities or whole-brain volume. Theory of mind age-related decline may not be independent of other cognitive functions; it may also be particularly susceptible to changes in white matter integrity. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

A study of diffusion in poly(ethyleneglycol)-gelatin based semi-interpenetrating networks for use in wound healing

Semi-interpenetrating networks (sIPNs) designed to mimic extracellular matrix via covalent crosslinking of poly(ethylene glycol) diacrylate in the presence of gelatin have been shown to aid in wound healing, particularly when loaded with soluble factors. Ideal systems for tissue repair permit an effective release of therapeutic agents and flow of nutrients to proliferating cells. Appropriate network characterization can, consequently, be used to convey an understanding of the mass transfer kinetics necessary for materials to aid in the wound healing process. Solute transport from and through sIPNs has not yet been thoroughly evaluated. In the current study, the diffusivity of growth factors and nutrients through the polymeric system was determined. Transport of keratinocyte growth factor was modeled by treating the sIPN as a plane sheet into which the protein was loaded. The diffusion coefficient was determined to be 4.86 × 10⁻⁹ ± 1.86 × 10⁻¹² cm²/s. Glucose transport was modeled as flow through a semi-permeable membrane. Using lag-time analysis, the diffusion coefficient was calculated to be 2.25 × 10⁻⁶ ± 1.98 × 10⁻⁷ cm²/s. The results were evaluated in conjunction with previous studies on controlled drug release from sIPNs. As expected from Einstein-Stokes equation, diffusivity decreased as molecular size increased. The results offer insight into the structure-function design paradigm and show that release from the polymeric system is diffusion controlled, rather than dissolution controlled.