Ecotoxicological effects of combined UVB and organic contaminants in coastal waters: A review

Organisms living in coastal waters are exposed to anthropogenic contaminants from terrestrial drainage, ice melting and maritime traffic and to enhanced UVB radiation (UVBR; 280-320 nm) caused by decreased concentrations of ozone in the stratosphere. This article reviews available information about the combined effects of UVBR and selected hydrosoluble contaminants potentially present in surface waters on marine species and especially on plankton community structure in high-latitude coastal zones. Effects of UVBR on three selected pesticides (Atrazine, carbaryl and Acifluorfen) and possible induction of phototoxicity are reviewed. Most toxicological studies have been conducted under laboratory conditions with questionable relevance for coastal marine ecosystems. Similarly, photoactivation of polycyclic aromatic hydrocarbons (PAHs) has been closely examined and reported effects on aquatic species summarized. Experiments with field-sampled communities demonstrated the complexity and the difficulty in determining the impact of multiple stressors on an aquatic ecosystem, even for ecosystems simplified by eliminating large grazers and fish. Nutrient status, specific composition and light history have influenced the different responses of planktonic assemblages exposed to enhanced UVBR and water-soluble fraction (WSF) from crude oil or to tributyltin. Plankton assemblages subjected to changes in the ozone hole were physiologically stressed and more susceptible to WSF toxicity than communities from less enhanced UVBR-impacted sites. A close relationship between phytoplankton assemblages and bacteria was observed in all experiments in mesocosms. A contaminant-induced phytoplankton crash after a bloom event may release important carbon and nutrient sources for bacteria. The magnitude of phytoplanktonic mortality induced by a contaminant probably influenced how rapidly bacteria grew over time. The transition from a herbivorous food web to a microbial food web has significant ecological implications for carbon cycling and energy flow in pelagic systems. A high phytoplankton mortality implies a situation in which the potential for downward carbon export from surface waters is high. In contrast, high bacterial enrichment implies that the phytoplankton carbon is largely recycled in surface waters through a microbial loop and does not contribute significantly to sinking particle flux. The most ecologically relevant results were obtained with mesocosm studies using field-collected communities. The enhancement of hydrocarbon toxicity in the presence of a high level of UVBR cannot be described as being a synergistic or an additive effect, because the WSF alone is not toxic and may even be beneficial by increasing bacterial activity. This is a case in which one stressor has the ability to modify another stressor to cause it to be toxic to target organisms. These abiotically induced interactions may be important for biological communities exposed to extreme conditions when physical, chemical or photochemical reactions modify the nature of environmental stressors before they interact with biological functions. The need for models on the impacts of multiple stressors on biodiversity and ecosystem functioning is emphasized.     

Measurement of in vivo multi-component T2 relaxation times for brain tissue using multi-slice T2 prep at 1.5 and 3 T

The objective of this study was to implement a clinically relevant multi-slice multi-echo imaging sequence in order to quantify multi-component T2 relaxation times for normal volunteers at both 1.5 and 3 T. Multi-echo data were fitted using a nonnegative least square algorithm. Twelve echo data with nonlinear echo sampling were acquired using a receive-only eight-channel phased array coil and volume head coil for phantoms and normal volunteers, and compared to 32-echo data with linear echo sampling. It was observed that the performance of the 180 degrees refocusing trains was more spatially uniform for the receive-only eight-channel phased array coil than for the head coil, particularly at 3 T. The phantom study showed that the estimated T2 relaxation times were accurate and reproducible for both single- and multi-slice acquisition from a commercial phantom with known T2 relaxation times. Short T2 components (T2 <50 ms) were mainly observed within the white matter for normal volunteers, and the fraction of short T2 water components (i.e., myelin water) was 7-12% of total water. It was observed that the calculated myelin water fraction map from the nonlinearly sampled 12-echo data was comparable with that from the linearly sampled 32-echo data. Quantification of T2 relaxation times from multi-slice images was accomplished with a clinically acceptable scan times (16 min) for normal volunteers by using a nonselective T2 prep imaging sequence. The use of the eight-channel head coil involved more accurate quantification of T2 relaxation times particularly when the number of echoes was limited.     

Investigations on the geometrical isomers of astaxanthin: Raman spectroscopy of conjugated polyene chain with electronic and mechanical confinement

Recent research interests in geometrical isomers of astaxanthin (AST) are motivated by their metabolic activities in aquatic animals and human. It has been established that cis‐isomers of AST are selectively absorbed in human plasma during the metabolic process; however, exact absorption mechanism is still unclear. Hence, a detailed investigation of the structural and optical properties of geometrical isomers of AST is required. Among the techniques available for the study of AST and other carotenoids, Raman spectroscopy has been much acclaimed. Raman spectra have been shown to be influenced by the electronic and mechanical confinement effects arising from the conjugated polyene chain of carotenoids. In this work, we present Raman studies of geometrical isomers of AST, along with their optical absorption characteristics. Geometrical isomers of AST were prepared by heating all trans‐AST in solution form, and the isomers were separated using high performance liquid chromatography. Optical absorption spectra of cis‐isomers of AST showed hypsochromic shifts in the main absorption band and formation of new bands at lower wavelengths. A detailed Raman spectral analysis performed on the cis‐isomers of AST showed new modes which have not been observed and accounted for so far. In addition, we demonstrate that the electronic and mechanical confinement effects in the polyene chain of AST play an important role in the Raman spectra of geometrical isomers of AST. It is anticipated that this work will demonstrate that Raman spectroscopy is an important diagnostic tool in distinguishing and identifying the geometrical isomers of AST. Copyright © 2014 John Wiley & Sons, Ltd.     

3-D echo planar (1)HMRS imaging in MS: metabolite comparison from supratentorial vs. central brain

To determine if metabolite ratios as measured by 3-dimensional echo planar spectroscopy imaging (3D-EPSI) from central brain regions of interest (ROI) centered at the corpus callosum reflect imaging metrics of large volumes of supratentorial brain (STB) from patients with multiple sclerosis. METHODS: 48 MS patients with relapsing-remitting, secondary progressive, and primary progressive disease underwent a 3D-EPSI sequence covering large volumes of STB. Metabolite ratios were first estimated from all voxels within a STB mask using a linear regression of N-acetylaspartate (NAA) over Creatine (Cr), NAA over choline (Cho) and Cho over Cr. Secondly, spectroscopic voxels from a central brain (CB) ROI centered at the corpus callosum were selected within the STB. Ratios were compared using Bland-Altman regression analysis and Spearman's correlation coefficients between STB versus central brain. Ratios from studied ROIs were correlated with the EDSS and compared to normal controls. RESULTS: Very strong correlations ranging from 0.884 and 0.938 (p < 0.0001) were found for all metabolite ratios between STB versus central brain. NAA/Cr ratios were similarly and negatively correlated with the EDSS across all ROIs, trends ranging from -0.257 to -0.314 (p < 0.1). NAA/Cr from all MS patients was similarly decreased compared to controls across all ROIs (p < 0.01). CONCLUSION: Metabolite ratios from a central brain ROI were statistically equivalent and highly correlated with ratios from the STB. The study of NAA/Cr using (1)HMRS from a central brain ROI centered at the corpus callosum seems to be representative of brainwide axonal changes in patients with MS.     

Penetration of drugs through skin,a complex rate-controlling membrane

Penetration of molecules and particles inside and through skin has long been well documented but it now merits renewed attention as a result of new areas of concern such as transdermal therapies, safety of cosmetic products, penetration of environmental compounds and skin decontamination.The topic is complex as skin structure is heterogeneous and because there are a number of penetration routes through the stratum corneum barrier: the intercellular, intracellular and follicular pathways. Recent advances in the study of penetration mechanisms deal with the control of the intercellular penetration route by the crystalline state of lipids, and the penetration through skin appendages (the follicular pathway) that appears to contribute much more than was previously thought.Applications dependent on skin penetration that have received special attention include transdermal delivery of nano- and microparticles by hair follicles, targeting of the skin immune system in order to develop new vaccination strategies, and problems relating to the risk assessment of nanoparticles and skin decontamination.     

Verification and validation of impinging round jet simulations using an adaptive FEM

This paper illustrates the use of an adaptive finite element method as a means of achieving verification of codes and simulations of impinging round jets, that is obtaining numerical predictions with controlled accuracy. Validation of these grid‐independent solution is then performed by comparing predictions to measurements. We adopt the standard and accepted definitions of verification and validation (Technical Report AIAA‐G‐077‐1998, American Institute of Aeronautics and Astronautics, 1998; Verification and Validation in Computational Science and Engineering. Hermosa Publishers: Albuquerque, NM, 1998). Mesh adaptation is used to perform the systematic and rigorous grid refinement studies required for both verification and validation in CFD. This ensures that discrepancies observed between predictions and measurements are due to deficiencies in the mathematical model of the flow. Issues in verification and validation are discussed. The paper presents an example of code verification by the method of manufactured solution. Examples of successful and unsuccessful validation for laminar and turbulent impinging jets show that agreement with experiments is achieved only with a good mathematical model of the flow physics combined with accurate numerical solution of the differential equations. The paper emphasizes good CFD practice to systematically achieve verification so that validation studies are always performed on solid grounds. Copyright © 2004 John Wiley & Sons, Ltd.     

Copolymerization of 2-sulfoethyl methacrylate

Copolymers of 2-sulfoethyl methacrylate, (SEM) were prepared with ethyl methacrylate, ethyl acrylate, vinylidene chloride, and styrene in 1,2-dimethoxyethane solution with N,N′-azobisisobutyronitrile as initiator. The monomer reactivity ratios with SEM (M₁) were: vinylidene chloride, r₁ = 3.6 ± 0.5, r₂ = 0.22 ± 0.03; ethyl acrylate, r₁ = 3.2 ± 0.6, r₂ = 0.30 ± 0.05; ethyl methacrylate, r₁ = 2.0 ± 0.4, r₂ = 1.0 ± 0.1; styrene, r₁ = 0.6 ± 0.2, r₂ = 0.37 ± 0.03. The values of the copolymerization parameters calculated from the monomer reactivity ratios were e = +0.6 and Q = 1.4. Comparison of the monomer reactivities indicates that SEM is similar to ethyl methacrylate with regard to copolymerization reactivity in 1,2-dimethoxyethane solution. The sodium salt of 2-sulfoethyl methacrylate, SEM^?Na^⊕, was copolymerized with 2-hydroxyethyl methacrylate (M₂) in water solution. Reactivity ratios of r₁ = 0.7 ± 0.1 and r₂ = 1.6 ± 0.1 were obtained, indicating a lower reactivity of SEM^?Na^⊕ in water as compared to SEM in 1,2-dimethoxyethane. This decreased reactivity was attributed to greater ionic repulsion between reacting species in the aqueous medium.     

7-Azabicycloheptane carboxylic acid: a proline replacement in a boroarginine thrombin inhibitor

[formula: see text] The synthesis of thrombin inhibitor 3, which incorporates conformationally constrained 7-azabicycloheptane carboxylic acid (1) as a proline replacement, is described. The inhibition constant (Ki(thrombin) = 2.9 nM) indicates that 1 is a reasonable replacement of proline in the formation of a beta-turn tripeptide mimetic.