Plasticity of Acquired Secondary Metabolites in Clathria prolifera (Demospongia: Poecilosclerida): Putative Photoprotective Role of Carotenoids in a Temperate Intertidal Sponge

Several marine sponges sequester high concentrations of carotenoids in their tissues. The diversity of carotenoid compounds has been described in detail for a handful of species, but to date, little attention has been paid to natural variability in the concentration and constituency of carotenoid pools. Also lacking are experimental tests of some of the proposed adaptive benefits of carotenoids to the sponge. To address some of these deficits in our understanding of sponge ecology, we used a combination of analytic chemistry, field surveys, and manipulative experiments to determine what function these compounds might play. Attention was focused on the common, carotenoid-rich intertidal sponge Clathria (Microciona) prolifera from Chesapeake Bay, Virginia, USA. Surveys of pier pilings indicated that C. prolifera was most common towards the surface of the water, with an average depth of 1 m, and also occurred most frequently on pilings exposed to sunlight. Total carotenoid concentrations (as estimated from spectroscopy) were maximal when solar radiation was nearing its northern maximum. However, HPLC analysis of crude acetone extracts highlighted several instances where concentrations of individual putative carotenoids were maximal during thermal (not solar) maxima in Chesapeake Bay. Naturally occurring sponges growing in environments protected from direct sunlight were found to have significantly lower total carotenoid concentration. In a manipulative field experiment, sponges transplanted from exposed habitats to shaded habitats showed significant decreases in carotenoid concentrations. HPLC analysis demonstrated that concentrations for several of the pigmented compounds decreased under reduced light levels. Given that sponges do not produce carotenoids de novo, the ecological role that these compounds play in sponge physiology deserves greater attention. Our findings indicate that solar radiation is an important factor in shaping carotenoid profiles of C. prolifera. While the physiological role and ultimate source of these compounds remains unclear, our data point to an adaptive function and indicate that C. prolifera is a useful species to address these questions

Multi-technique Quantitative Analysis and Socioeconomic Considerations of Lead, Cadmium, and Arsenic in Children\u27s Toys and Toy Jewelry

A wide spectrum and large number of children’s toys and toy jewelry items were purchased from both bargain and retail vendors and analyzed for arsenic, cadmium, and lead metal content using multiple analytical techniques, including flame and furnace atomic absorption spectroscopy as well as X-ray fluorescence spectroscopy. Particularly dangerous for young children, metal concentrations in toys/toy jewelry were assessed for compliance with current Consumer Safety Product Commission (CPSC) regulations (F963-11). A conservative metric involving multiple analytical techniques was used to categorize compliance: one technique confirmation of metal in excess of CPSC limits indicated a “suspect” item while confirmation on two different techniques warranted a non-compliant designation. Sample matrix-based standard addition provided additional confirmation of non-compliant and suspect products. Results suggest that origin of purchase, rather than cost, is a significant factor in the risk assessment of these materials with 57% of toys/toy jewelry items from bargain stores non-compliant or suspect compared to only 15% from retail outlets and 13% if only low cost items from the retail stores are compared. While jewelry was found to be the most problematic product (73% of non-compliant/suspect samples), lead (45%) and arsenic (76%) were the most dominant toxins found in non-compliant/suspect samples. Using the greater Richmond area as a model, the discrepancy between bargain and retail children’s products, along with growing numbers of bargain stores in low-income and urban areas, exemplifies an emerging socioeconomic public health issue

Use of PDV to measure the overdriven products equation of state in PBX 9502 and PBX 9501 and the EOS in shocked foams

Author Institution: Los Alamos National LaboratorySlides presented at the 2014 Photonic Doppler Velocimetry (PDV) Workshop Hosted by National Security Technologies, LLC, and the University of Nevada Las Vegas, June 24-26, 2014, Las Vegas, Nevada

Structurally diverse hamigerans from the New Zealand marine sponge Hamigera tarangaensis: NMR-directed isolation, structure elucidation and antifungal activity

The NMR-directed investigation of the New Zealand marine sponge Hamigera tarangaensis has afforded ten new compounds of the hamigeran family, and a new 13-epi-verrucosane congener. Notably, hamigeran F (6) possesses an unusual carbon–carbon bond between C-12 and C-13, creating an unprecedented skeleton within this class. In particular, the structural features of 6, hamigeran H (10) and hamigeran J (12) imply a diterpenoid origin, which has allowed the putative biogenesis of three hamigeran carbon skeletons to be proposed based on geranyl geranyl pyrophosphate. All new hamigerans exhibited micromolar activity towards the HL-60 promyelocytic leukaemic cell line, and hamigeran G also selectively displayed antifungal activity in the budding yeast Saccharomyces cerevisiae. Homozygous deletion profiling (HOP) analysis suggests Golgi apparatus function as a potential target of this unusual class of sponge-derived terpenoids

An infrared probe of the insulator-to-metal transition in GaMnAs and GaBeAs

We report infrared studies of the insulator-to-metal transition (IMT) in GaAs doped with either magnetic (Mn) or non-magnetic acceptors (Be). We observe a resonance with a natural assignment to impurity states in the insulating regime of Ga$_{1-x}$Mn$_x$As, which persists across the IMT to the highest doping (16%). Beyond the IMT boundary, behavior combining insulating and metallic trends also persists to the highest Mn doping. Be doped samples however, display conventional metallicity just above the critical IMT concentration, with features indicative of transport within the host valence band

Distance Dependence of Electron Transfer Kinetics for Azurin Protein Adsorbed to Monolayer Protected Nanoparticle Film Assemblies

The distance dependence and kinetics of the heterogeneous electron transfer (ET) reaction for the redox protein azurin adsorbed to an electrode modified with a gold nanoparticle film are investigated using cyclic voltammetry. The nanoparticle films are comprised of nonaqueous nanoparticles, known as monolayer-protected clusters (MPCs), which are covalently networked with dithiol linkers. The MPC film assembly serves as an alternative adsorption platform to the traditional alkanethiolate self-assembled monolayer (SAM) modified electrodes that are commonly employed to study the ET kinetics of immobilized redox proteins, a strategy known as protein monolayer electrochemistry. Voltammetric analysis of the ET kinetics for azurin adsorbed to SAMs of increasing chain length results in quasi-reversible voltammetry with significant peak splitting. We observed rate constants (k°ET) of 12−20 s−1 for the protein at SAMs of shorter alkanethiolates that decays exponentially (β = 0.9/CH2 or 0.8/Å) at SAMs of longer alkanethiolates (9−11 methylene units) or an estimated distance of 1.23 nm and is representative of classical electronic tunneling behavior over increasing distance. Azurin adsorbed to the MPC film platforms of increasing thickness results in reversible voltammetry with very little voltammetric peaks splitting and nearly negligible decay of the ET rate over significant distances up to 20 nm. The apparent lack of distance dependence for heterogeneous ET reactions at MPC film assemblies is attributed to a two-step mechanism involving extremely fast electronic hopping through the MPC film architecture. These results suggest that MPC platforms may be used in protein monolayer electrochemistry to create adsorption platforms of higher architecture that can accommodate greater than monolayer protein coverage and increase the Faradaic signal, a finding with significant implications for amperometric biosensor design and development

A New Route to Fluorescent SWNT/Silica Nanocomposites: Balancing Fluorescence Intensity and Environmental Sensitivity

We investigate the relationship between photoluminescence (PL) intensity and environmental sensitivity of surfactant-wrapped single walled carbon nanotubes (SWNTs). SWNTs were studied under a variety of conditions in suspension as well as encapsulated in silica nanocomposites, which were prepared by an efficient chemical vapor into liquids (CViL) sol-gel process. The dramatically improved silica encapsulation process described here has several advantages, including fast preparation and high SWNT loading concentration, over other encapsulation methods used to prepare fluorescent SWNT/silica nanocomposites. Further, addition of glycerol to SWNT suspensions prior to performing the CViL sol-gel process allows for the preparation of freestanding fluorescent silica xerogels, which to the best of our knowledge is the first report of such nanocomposites. Our spectroscopic data on SWNTs suspended in aqueous surfactants or encapsulated in silica show that achieving maximum PL intensity results in decreased sensitivity of SWNT emission response to changes imparted by the local environment. In addition, silica encapsulation can be used to "lock-in" a surfactant micelle structure surrounding SWNTs to minimize interactions between SWNTs and ions/small molecules. Ultimately, our work demonstrates that one should consider a balance between maximum PL intensity and the ability to sense environmental changes when designing new SWNT systems for future sensing applications

Novel experimental setup for megahertz X-ray diffraction in a diamond anvil cell at the High Energy Density (HED) instrument of the European X-ray Free-Electron Laser (EuXFEL)

The high-precision X-ray diffraction setup for work with diamond anvil cells (DACs) in interaction chamber 2 (IC2) of the High Energy Density instrument of the European X-ray Free-Electron Laser is described. This includes beamline optics, sample positioning and detector systems located in the multipurpose vacuum chamber. Concepts for pump-probe X-ray diffraction experiments in the DAC are described and their implementation demonstrated during the First User Community Assisted Commissioning experiment. X-ray heating and diffraction of Bi under pressure, obtained using 20 fs X-ray pulses at 17.8 keV and 2.2 MHz repetition, is illustrated through splitting of diffraction peaks, and interpreted employing finite element modeling of the sample chamber in the DAC