Ferroelectric Properties of Polymer-Semiconductor Hybrid Material or Composite under Optical Excitation.

Polymer-semiconductor hybrid materials or composites have been investigated with respect to their microstructure, optical, photoconductive, and ferroelectric properties. For this purpose, either CdSe quantum dots or (Cd:Zn)S microparticles were dispersed in poly(vinylidenefluoride-trifluoroethylene) solution and hot pressed to films. In both material systems, the electrical conductivity and the polarization behavior could be controlled by the intensity of the optical excitation. The simultaneous high optical transparency of the CdSe quantum-dot-based hybrid materials makes them particularly interesting for applications in the field of flexible, high-resolution sensors.

Dual Laser Beam Processing of Semiconducting Thin Films by Excited State Absorption.

We present a unique dual laser beam processing approach based on excited state absorption by structuring 200 nm thin zinc oxide films sputtered on fused silica substrates. The combination of two pulsed nanosecond-laser beams with different photon energies-one below and one above the zinc oxide band gap energy-allows for a precise, efficient, and homogeneous ablation of the films without substrate damage. Based on structuring experiments in dependence on laser wavelength, pulse fluence, and pulse delay of both laser beams, a detailed concept of energy transfer and excitation processes during irradiation was developed. It provides a comprehensive understanding of the thermal and electronic processes during ablation. To quantify the efficiency improvements of the dual-beam process compared to single-beam ablation, a simple efficiency model was developed.

Large-Area Fabrication of Laser-Induced Periodic Surface Structures on Fused Silica Using Thin Gold Layers.

Despite intensive research activities in the field of laser-induced periodic surface structures (LIPSS), the large-area nanostructuring of glasses is still a challenging problem, which is mainly caused by the strongly non-linear absorption of the laser radiation by the dielectric material. Therefore, most investigations are limited to single-spot experiments on different types of glasses. Here, we report the homogeneous generation of LIPSS on large-area surfaces of fused silica using thin gold layers and a fs-laser with a wavelength λ = 1025 nm, a pulse duration τ = 300 fs, and a repetition frequency frep = 100 kHz as radiation source. For this purpose, single-spot experiments are performed to study the LIPSS formation process as a function of laser parameters and gold layer thickness. Based on these results, the generation of large-area homogenous LIPSS pattern was investigated by unidirectional scanning of the fs-laser beam across the sample surface using different line spacing. The nanostructures are characterized by a spatial period of about 360 nm and a modulation depth of around 160 nm. Chemical surface analysis by Raman spectroscopy confirms a complete ablation of the gold film by the fs-laser irradiation. The characterization of the functional properties shows an increased transmission of the nanostructured samples accompanied by a noticeable change in the wetting properties, which can be additionally modified within a wide range by silanization. The presented approach enables the reproducible LIPSS-based laser direct-writing of sub-wavelength nanostructures on glasses and thus provides a versatile and flexible tool for novel applications in the fields of optics, microfluidics, and biomaterials.

Femtosecond Laser-Induced Periodic Surface Structures on Fused Silica: The Impact of the Initial Substrate Temperature.

The formation and properties of laser-induced periodic surface structures (LIPSS) were investigated upon fs-laser irradiation of fused silica at different initial substrate temperatures, TS. For substrate heating between room temperature, TRT, and TS = 1200 °C, a continuous wave CO2 laser was used as the radiation source. The surface structures generated in the air environment at normal incidence with five successive fs-laser pulses (pulse duration, τ = 300 fs, laser wavelength, λ = 1025 nm, repetition frequency, frep = 1 kHz) were characterized by using optical microscopy, scanning electron microscopy, and 2D-Fourier transform analysis. The threshold fluence of fused silica was systematically investigated as a function of TS. It was shown that the threshold fluence for the formation of low-spatial frequency LIPSS (LSFL) decreases with increasing TS. The results reveal that the initial spatial period observed at TRT is notably increased by increasing TS, finally leading to the formation of supra-wavelength LIPSS. The findings are discussed in the framework of the electromagnetic interference theory, supplemented with an analysis based on thermo-convective instability occurring in the laser-induced molten layer. Our findings provide qualitative insights into the formation mechanisms of LIPSS, which allow improvements of the control of nanostructure formation to be made for corresponding applications of dielectric materials in the future.

Polarization Properties and Polarization Depth Profiles of (Cd:Zn)S/P(VDF-TrFE) Composite Films in Dependence of Optical Excitation.

The influence of optical excitation intensity on the electrical, ferroelectric and pyroelectric properties of ferroelectric-semiconductor-composites was investigated. For this purpose, composite thin films consisting of poly(vinylidene fluoride-co-trifluoroethylene) and 10 vol % (Cd:Zn)S particles with a thickness of 34 µm were fabricated. The samples were used to measure the absolute pyrocoefficient and to determine the relative pyroelectric depth profile using Laser Intensity Modulated Method. It was shown that a polarization of the samples without an optical excitation at the utilized relatively small peak-to-peak voltages could not be verified by the Sawyer⁻Tower circuit and the measurement setup of the pyroelectric coefficient, respectively. Both remanent polarization and pyroelectric coefficients increased with increasing optical excitation intensity during poling as well as increasing peak-to-peak voltage. The pyrocoefficient shows a temporal decay in the first hours after poling. The specific heat and thermal conductivity or the thermal diffusivity are required for the calibration of the pyroelectric depth profile. Rule of mixture and photo-acoustic investigations proved that the thermal properties of the utilized composites do not differ significantly from those of the pristine polymer. Based on the pyroelectric depth profile which is proportional to the polarization profile, the existing "three phase model" has been extended to generate a replacement circuit diagram, explaining the local polarization due to the optical excitation dependency for both local resistivity and local field strength.

A Review of Hemolysis Prediction Models for Computational Fluid Dynamics.

Flow-induced hemolysis is a crucial issue for many biomedical applications; in particular, it is an essential issue for the development of blood-transporting devices such as left ventricular assist devices, and other types of blood pumps. In order to estimate red blood cell (RBC) damage in blood flows, many models have been proposed in the past. Most models have been validated by their respective authors. However, the accuracy and the validity range of these models remains unclear. In this work, the most established hemolysis models compatible with computational fluid dynamics of full-scale devices are described and assessed by comparing two selected reference experiments: a simple rheometric flow and a more complex hemodialytic flow through a needle. The quantitative comparisons show very large deviations concerning hemolysis predictions, depending on the model and model parameter. In light of the current results, two simple power-law models deliver the best compromise between computational efficiency and obtained accuracy. Finally, hemolysis has been computed in an axial blood pump. The reconstructed geometry of a HeartMate II shows that hemolysis occurs mainly at the tip and leading edge of the rotor blades, as well as at the leading edge of the diffusor vanes.

Effect of (Cd:Zn)S Particle Concentration and Photoexcitation on the Electrical and Ferroelectric Properties of (Cd:Zn)S/P(VDF-TrFE) Composite Films.

The influence of semiconductor particle concentration and photoexcitation on the electrical and ferroelectric properties of ferroelectric-semiconductor-composites was investigated. For this purpose, 32 µm thin films of poly(vinylidene fluoride-co-trifluoroethylene) with (Cd:Zn)S particle concentrations of between 0 and 20 vol % were fabricated and characterized by scanning electron microscopy, Fourier transformed infrared spectroscopy, X-ray diffraction, and optical spectroscopy. It was shown that the particle concentration has only a negligible influence on the molecular structure of the polymer but strongly determines the optical properties of the composite. For (Cd:Zn)S particle concentrations below 20 vol %, the I-V characteristics of the composites is only marginally affected by the particle concentration and the optical excitation of the composite material. On the contrary, a strong influence of both parameters on the ferro- and pyroelectric properties of the composite films was observed. For particle fractions that exhibit ferroelectric hysteresis, an increased remanent polarization and pyroelectric coefficient due to optical excitation was obtained. A theoretical approach that is based on a "three phase model" of the internal structure was developed to explain the observed results.

Femtosecond laser-induced surface structures on carbon fibers.

The influence of different polarization states during the generation of periodic nanostructures on the surface of carbon fibers was investigated using a femtosecond laser with a pulse duration τ=300 fs, a wavelength λ=1025 nm, and a peak fluence F=4 J/cm². It was shown that linear polarization results in a well-aligned periodic pattern with different orders of magnitude concerning their period and an alignment parallel and perpendicular to fiber direction, respectively. For circular polarization, both types of uniform laser-induced periodic surface structures (LIPSS) patterns appear simultaneously with different dominance in dependence on the position at the fiber surface. Their orientation was explained by the polarization-dependent absorptivity and the geometrical anisotropy of the carbon fibers.

Marine and terrestrial herbivores display convergent chemical ecology despite 400 million years of independent evolution.

Chemical cues regulate key ecological interactions in marine and terrestrial ecosystems. They are particularly important in terrestrial plant-herbivore interactions, where they mediate both herbivore foraging and plant defense. Although well described for terrestrial interactions, the identity and ecological importance of herbivore foraging cues in marine ecosystems remain unknown. Here we show that the specialist gastropod Elysia tuca hunts its seaweed prey, Halimeda incrassata, by tracking 4-hydroxybenzoic acid to find vegetative prey and the defensive metabolite halimedatetraacetate to find reproductive prey. Foraging cues were predicted to be polar compounds but instead were nonpolar secondary metabolites similar to those used by specialist terrestrial insects. Tracking halimedatetraacetate enables Elysia to increase in abundance by 12- to 18-fold on reproductive Halimeda, despite reproduction in Halimeda being rare and lasting for only ∼36 h. Elysia swarm to reproductive Halimeda where they consume the alga's gametes, which are resource rich but are chemically defended from most consumers. Elysia sequester functional chloroplasts and halimedatetraacetate from Halimeda to become photosynthetic and chemically defended. Feeding by Elysia suppresses the growth of vegetative Halimeda by ∼50%. Halimeda responds by dropping branches occupied by Elysia, apparently to prevent fungal infection associated with Elysia feeding. Elysia is remarkably similar to some terrestrial insects, not only in its hunting strategy, but also its feeding method, defense tactics, and effects on prey behavior and performance. Such striking parallels indicate that specialist herbivores in marine and terrestrial systems can evolve convergent ecological strategies despite 400 million years of independent evolution in vastly different habitats.

Bromophycoic acids: bioactive natural products from a Fijian red alga Callophycus sp.

Bioassay-guided fractionation of extracts from a Fijian red alga in the genus Callophycus resulted in the isolation of five new compounds of the diterpene-benzoate class. Bromophycoic acids A-E (1-5) were characterized by NMR and mass spectroscopic analyses and represent two novel carbon skeletons, one with an unusual proposed biosynthesis. These compounds display a range of activities against human tumor cell lines, malarial parasites, and bacterial pathogens including low micromolar suppression of MRSA and VREF.

High content live cell imaging for the discovery of new antimalarial marine natural products.

BACKGROUND: The human malaria parasite remains a burden in developing nations. It is responsible for up to one million deaths a year, a number that could rise due to increasing multi-drug resistance to all antimalarial drugs currently available. Therefore, there is an urgent need for the discovery of new drug therapies. Recently, our laboratory developed a simple one-step fluorescence-based live cell-imaging assay to integrate the complex biology of the human malaria parasite into drug discovery. Here we used our newly developed live cell-imaging platform to discover novel marine natural products and their cellular phenotypic effects against the most lethal malaria parasite, Plasmodium falciparum. METHODS: A high content live cell imaging platform was used to screen marine extracts effects on malaria. Parasites were grown in vitro in the presence of extracts, stained with RNA sensitive dye, and imaged at timed intervals with the BD Pathway HT automated confocal microscope. RESULTS: Image analysis validated our new methodology at a larger scale level and revealed potential antimalarial activity of selected extracts with a minimal cytotoxic effect on host red blood cells. To further validate our assay, we investigated parasite's phenotypes when incubated with the purified bioactive natural product bromophycolide A. We show that bromophycolide A has a strong and specific morphological effect on parasites, similar to the ones observed from the initial extracts. CONCLUSION: Collectively, our results show that high-content live cell-imaging (HCLCI) can be used to screen chemical libraries and identify parasite specific inhibitors with limited host cytotoxic effects. All together we provide new leads for the discovery of novel antimalarials.

Effects of herbivory, nutrients, and reef protection on algal proliferation and coral growth on a tropical reef.

Maintaining coral reef resilience against increasing anthropogenic disturbance is critical for effective reef management. Resilience is partially determined by how processes, such as herbivory and nutrient supply, affect coral recovery versus macroalgal proliferation following disturbances. However, the relative effects of herbivory versus nutrient enrichment on algal proliferation remain debated. Here, we manipulated herbivory and nutrients on a coral-dominated reef protected from fishing, and on an adjacent macroalgal-dominated reef subject to fishing and riverine discharge, over 152 days. On both reefs, herbivore exclusion increased total and upright macroalgal cover by 9-46 times, upright macroalgal biomass by 23-84 times, and cyanobacteria cover by 0-27 times, but decreased cover of encrusting coralline algae by 46-100% and short turf algae by 14-39%. In contrast, nutrient enrichment had no effect on algal proliferation, but suppressed cover of total macroalgae (by 33-42%) and cyanobacteria (by 71% on the protected reef) when herbivores were excluded. Herbivore exclusion, but not nutrient enrichment, also increased sediment accumulation, suggesting a strong link between herbivory, macroalgal growth, and sediment retention. Growth rates of the corals Porites cylindrica and Acropora millepora were 30-35% greater on the protected versus fished reef, but nutrient and herbivore manipulations within a site did not affect coral growth. Cumulatively, these data suggest that herbivory rather than eutrophication plays the dominant role in mediating macroalgal proliferation, that macroalgae trap sediments that may further suppress herbivory and enhance macroalgal dominance, and that corals are relatively resistant to damage from some macroalgae but are significantly impacted by ambient reef condition.

Macroalgal terpenes function as allelopathic agents against reef corals.

During recent decades, many tropical reefs have transitioned from coral to macroalgal dominance. These community shifts increase the frequency of algal-coral interactions and may suppress coral recovery following both anthropogenic and natural disturbance. However, the extent to which macroalgae damage corals directly, the mechanisms involved, and the species specificity of algal-coral interactions remain uncertain. Here, we conducted field experiments demonstrating that numerous macroalgae directly damage corals by transfer of hydrophobic allelochemicals present on algal surfaces. These hydrophobic compounds caused bleaching, decreased photosynthesis, and occasionally death of corals in 79% of the 24 interactions assayed (three corals and eight algae). Coral damage generally was limited to sites of algal contact, but algae were unaffected by contact with corals. Artificial mimics for shading and abrasion produced no impact on corals, and effects of hydrophobic surface extracts from macroalgae paralleled effects of whole algae; both findings suggest that local effects are generated by allelochemical rather than physical mechanisms. Rankings of macroalgae from most to least allelopathic were similar across the three coral genera tested. However, corals varied markedly in susceptibility to allelopathic algae, with globally declining corals such as Acropora more strongly affected. Bioassay-guided fractionation of extracts from two allelopathic algae led to identification of two loliolide derivatives from the red alga Galaxaura filamentosa and two acetylated diterpenes from the green alga Chlorodesmis fastigiata as potent allelochemicals. Our results highlight a newly demonstrated but potentially widespread competitive mechanism to help explain the lack of coral recovery on many present-day reefs.

Structure and biological evaluation of novel cytotoxic sterol glycosides from the marine red alga Peyssonnelia sp.

Bioactivity-guided fractionation of the extract from a Fijian red alga Peyssonnelia sp. led to the isolation of two novel sterol glycosides 19-O-ß-d-glucopyranosyl-19-hydroxy-cholest-4-en-3-one (1) and 19-O-ß-d-N-acetyl-2-aminoglucopyranosyl-19-hydroxy-cholest-4-en-3-one (2), and two known alkaloids indole-3-carboxaldehyde (3) and 3-(hydroxyacetyl)indole (4). Their structures were characterized by 1D and 2D NMR and mass spectral analysis. The sterol glycosides inhibited cancer cell growth with mean IC50 values (for 11 human cancer cell lines) of 1.63 and 1.41µM for 1 and 2, respectively. The most sensitive cancer cell lines were MDA-MB-468 (breast) and A549 (lung), with IC50's in of 0.71-0.97µM for 1 and 2. Modification of the sterol glycoside structures revealed that the α,ß-unsaturated ketone at C-3 and oxygenation at C-19 of 1 and 2 are crucial for anticancer activity, whereas the glucosidic group was not essential but contributed to enhanced activity against the most sensitive cell lines.

Ecological leads for natural product discovery: Novel sesquiterpene hydroquinones from the red macroalga Peyssonnelia sp.

Pharmacologically-motivated marine natural product investigations have yielded a large variety of structurally unique compounds with interesting biomedical properties, but the natural roles of these molecules often remain unknown. While secondary metabolites may function as antimicrobial chemical defenses, few studies have examined this hypothesis. In the present investigation, chromatographic fractions from 69 collections of Fijian red macroalgae representing at least 43 species were evaluated for growth inhibition of three microbial pathogens and saprophytes of marine macrophytes. At least one microbe was suppressed by fraction(s) of all evaluated algae, suggesting that antimicrobial defenses are common among tropical seaweeds. From these leads, peyssonoic acids A-B (1-2), novel sesquiterpene hydroquinones, were isolated from the crustose red alga Peyssonnelia sp. At ecologically realistic concentrations, both compounds inhibited growth of Pseudoalteromonas bacteriolytica, a bacterial pathogen of marine algae, and Lindra thalassiae, a fungal pathogen of marine algae, and exhibited modest antineoplastic activity against ovarian cancer cells. The peyssonoic acids included one novel carbon skeleton and illustrated the utility of ecological studies in natural product discovery.

Antibacterial neurymenolides from the Fijian red alga Neurymenia fraxinifolia.

Two novel alpha-pyrone macrolides, neurymenolides A (1) and B (2), were isolated from the Fijian red alga Neurymenia fraxinifolia and characterized using a combination of NMR and mass spectral analyses. These molecules represent only the second example of alpha-pyrone macrolides, with 1 existing as interchanging atropisomers due to restricted rotation about the alpha-pyrone ring system. Neurymenolide A (1) displayed moderately potent activities against methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin-resistant Enterococcus faecium (VREF).

Chemical ecology of marine microbial defense.

Because marine animals and plants are continuously exposed to a large diversity of potentially harmful microorganisms, it seems reasonable to hypothesize that potential hosts might produce bioactive compounds to deter microbial attack. However, little is known about how host metabolites may defend against harmful microbes or facilitate the growth or colonization of helpful symbionts. While there is a large body of literature describing the antimicrobial activities of marine secondary metabolites, we are only now beginning to understand how these compounds function in an ecological context. For example, there is mounting evidence that nontoxic concentrations of secondary metabolites can have significant effects on microbial behavior, suggesting that certain host-microbe interactions are chemically mediated. Herein, we discuss the importance of employing ecologically relevant assays to elucidate microbiological effects and the need to develop a better understanding of host-microbe associations within an ecologically realistic context. Continued research in this field along with improved techniques will certainly provide further insight into how microbes have influenced the evolution of secondary metabolite production in marine organisms.

Multiple defensive roles for triterpene glycosides from two Caribbean sponges.

Despite their high nutritional value and a lack of physical defenses, most marine sponges appear to be minimally affected by predators, competitors, and fouling organisms, possibly due to sponge chemical defenses. In the last 15 years, several triterpene glycosides have been isolated from sponges, but their ecological or physiological roles are largely unknown. We tested triterpene glycosides from Erylus formosus and Ectyoplasia ferox, Caribbean sponges belonging to two different orders, in field and laboratory assays for effects on fish feeding, attachment by potential biofilm-forming bacteria, fouling by invertebrates and algae, and overgrowth by neighboring sponges. Formoside and other triterpene glycosides from Erylus formosus deterred predation, microbial attachment, and fouling by invertebrates and algae. Triterpene glycosides from Ectyoplasia ferox were found to be antipredatory and allelopathic. Thus, triterpene glycosides in these sponges appear to have multiple ecological functions. Tests with different triterpene glycosides at several concentrations indicated that small differences in molecular structure affect ecological activity. In order to establish whether triterpene glycosides could be involved in water-borne versus surface-mediated interactions, the presence of triterpene glycosides in the seawater surrounding live sponges was measured using two in situ sampling methods followed by HPLC and NMR spectral analysis. Water-borne triterpene glycosides were below detection limits for both species. However, top sponge layers and swabs of the surfaces of both sponges contained sufficiently high concentrations of triterpene glycosides to deter bacterial settlement and fouling of Erylus formosus surfaces and overgrowth of Ectyoplasia ferox by neighboring sponges. Enemies of these sponges appear to be deterred by surface contact of triterpene glycosides rather than by water-borne interactions. The dual strategy of employing one group of compounds for multiple purposes and minimizing the loss of compounds into seawater suggests that these organisms utilize chemical defenses with efficiency.