Adsorption and superficial transport of oil on biological and bionic superhydrophobic surfaces: a novel technique for oil-water separation.

Superhydrophobicity is a physical feature of surfaces occurring in many organisms and has been applied (e.g. lotus effect) in bionic technical applications. Some aquatic species are able to maintain persistent air layers under water (Salvinia effect) and thus become increasingly interesting for drag reduction and other 'bioinspired' applications. However, another feature of superhydrophobic surfaces, i.e. the adsorption (not absorption) and subsequent superficial transportation and desorption capability for oil, has been neglected. Intense research is currently being carried out on oil-absorbing bulk materials like sponges, focusing on oleophilic surfaces and meshes to build membranes for oil-water separation. This requires an active pumping of oil-water mixtures onto or through the surface. Here, we present a novel passive, self-driven technology to remove oil from water surfaces. The oil is adsorbed onto a superhydrophobic material (e.g. textiles) and transported on its surface. Vertical and horizontal transportation is possible above or below the oil-contaminated water surface. The transfer in a bioinspired novel bionic oil adsorber is described. The oil is transported into a container and thus removed from the surface. Prototypes have proven to be an efficient and environmentally friendly technology to clean oil spills from water without chemicals or external energy supply. This article is part of the theme issue 'Bioinspired materials and surfaces for green science and technology (part 3)'.

Air retaining grids-a novel technology to maintain stable air layers under water for drag reduction.

Extreme water repellent 'superhydrophobic' surfaces evolved in plants and animals about 450 Ma: a combination of hydrophobic chemistry and hierarchical structuring causes contact angles of greater than 150°. Technical biomimetic applications and technologies for water repellency, self-cleaning (Lotus Effect) and drag reduction (Salvinia Effect) have become increasingly important in the last two decades. Drag reduction (e.g. for ship hulls) requires the presence of a rather thick and persistent air layer under water. All existing technical solutions are based on fragile elastic hairs, micro-pillars or other solitary structures, preferably with undercuts (Salvinia Effect). We propose and provide experimental data for a novel alternative technology to trap persistent air layers by superhydrophobic grids or meshes superimposed to the solid surface: AirGrids. AirGrids provide a simple and stable solution to generate air trapping surfaces for drag reduction under water as demonstrated by first prototypes. Different architectural solutions, including possible recovery techniques for the air layer under hydrodynamic conditions, are discussed. The most promising target backed by first results is the combination of Air Retaining Grids with the existing microbubble technology. This article is part of the theme issue 'Bioinspired materials and surfaces for green science and technology (part 2)'.

Bionics and green technology in maritime shipping: an assessment of the effect of Salvinia air-layer hull coatings for drag and fuel reduction.

To save energy and reduce environmental impacts, new technologies towards a development of a sustainable 'greener' economy are needed. The main opportunity to improve sustainability by reducing emissions is within the transport sector. More than 90% of all goods worldwide are transported by ships. Particularly maritime ships using heavy fuel oil and marine gas oil play a major role. The total fuel consumption of shipping in 2016 was about 250 m t (domestic ca. 50 m t, international shipping ca. 200 m t). The vast portion of the energy consumption of a ship is the need to overcome the drag between ship hull and water-depending on the shape of the vessel and its size up to 90% of total fuel consumption. This means reducing drag helps to save fuel and reduces carbon emissions as well as pollution considerably. Different techniques for drag reduction are known, e.g. the micro-bubble technique or the bulbous bow. We investigated a novel bioinspired technique since 2002: the application of biomimetic surfaces with long-term stable air layers on ship hulls, serving as a slip agent. This technology is based on the Salvinia Effect, allowing a permanent stabilization of air layers under water. In this case study, we analysed the possible savings, which also could be combined with modified micro-bubble technologies. We calculated, based on a selection of five ship types, representing 75% of the world fleet, that air-layer hull coatings could lead to estimated savings of 32.5 million tons of fuel (meaning 13.0% of the worldwide shipping fuel consumption), equal to 18.5 billion US$ and 130.0 million tons of CO2e per year. The positive impacts on global temperature and other greenhouse gases are calculated and could be a contributing factor in accomplishing the UN Sustainable Development Goals and the Paris Agreement to the UN Framework Convention on Climate Change. The study is a contribution to enhance our patchy knowledge concerning the potential economic and ecological benefit of bionics and biomimetic technologies. This article is part of the theme issue 'Bioinspired materials and surfaces for green science and technology'.

Superhydrophobic hierarchically structured surfaces in biology: evolution, structural principles and biomimetic applications.

A comprehensive survey of the construction principles and occurrences of superhydrophobic surfaces in plants, animals and other organisms is provided and is based on our own scanning electron microscopic examinations of almost 20 000 different species and the existing literature. Properties such as self-cleaning (lotus effect), fluid drag reduction (Salvinia effect) and the introduction of new functions (air layers as sensory systems) are described and biomimetic applications are discussed: self-cleaning is established, drag reduction becomes increasingly important, and novel air-retaining grid technology is introduced. Surprisingly, no evidence for lasting superhydrophobicity in non-biological surfaces exists (except technical materials). Phylogenetic trees indicate that superhydrophobicity evolved as a consequence of the conquest of land about 450 million years ago and may be a key innovation in the evolution of terrestrial life. The approximate 10 million extant species exhibit a stunning diversity of materials and structures, many of which are formed by self-assembly, and are solely based on a limited number of molecules. A short historical survey shows that bionics (today often called biomimetics) dates back more than 100 years. Statistical data illustrate that the interest in biomimetic surfaces is much younger still. Superhydrophobicity caught the attention of scientists only after the extreme superhydrophobicity of lotus leaves was published in 1997. Regrettably, parabionic products play an increasing role in marketing.This article is part of the themed issue 'Bioinspired hierarchically structured surfaces for green science'.

Hierarchical Surface Architecture of Plants as an Inspiration for Biomimetic Fog Collectors.

Fog collectors can enable us to alleviate the water crisis in certain arid regions of the world. A continuous fog-collection cycle consisting of a persistent capture of fog droplets and their fast transport to the target is a prerequisite for developing an efficient fog collector. In regard to this topic, a biological superior design has been found in the hierarchical surface architecture of barley (Hordeum vulgare) awns. We demonstrate here the highly wettable (advancing contact angle 16° ± 2.7 and receding contact angle 9° ± 2.6) barbed (barb = conical structure) awn as a model to develop optimized fog collectors with a high fog-capturing capability, an effective water transport, and above all an efficient fog collection. We compare the fog-collection efficiency of the model sample with other plant samples naturally grown in foggy habitats that are supposed to be very efficient fog collectors. The model sample, consisting of dry hydrophilized awns (DH awns), is found to be about twice as efficient (fog-collection rate 563.7 ± 23.2 µg/cm(2) over 10 min) as any other samples investigated under controlled experimental conditions. Finally, a design based on the hierarchical surface architecture of the model sample is proposed for the development of optimized biomimetic fog collectors.

Fog collecting biomimetic surfaces: Influence of microstructure and wettability.

We analyzed the fog collection efficiency of three different sets of samples: replica (with and without microstructures), copper wire (smooth and microgrooved) and polyolefin mesh (hydrophilic, superhydrophilic and hydrophobic). The collection efficiency of the samples was compared in each set separately to investigate the influence of microstructures and/or the wettability of the surfaces on fog collection. Based on the controlled experimental conditions chosen here large differences in the efficiency were found. We found that microstructured plant replica samples collected 2-3 times higher amounts of water than that of unstructured (smooth) samples. Copper wire samples showed similar results. Moreover, microgrooved wires had a faster dripping of water droplets than that of smooth wires. The superhydrophilic mesh tested here was proved more efficient than any other mesh samples with different wettability. The amount of collected fog by superhydrophilic mesh was about 5 times higher than that of hydrophilic (untreated) mesh and was about 2 times higher than that of hydrophobic mesh.

Mimicking natural superhydrophobic surfaces and grasping the wetting process: a review on recent progress in preparing superhydrophobic surfaces.

A typical superhydrophobic (ultrahydrophobic) surface can repel water droplets from wetting itself, and the contact angle of a water droplet resting on a superhydrophobic surface is greater than 150°, which means extremely low wettability is achievable on superhydrophobic surfaces. Many superhydrophobic surfaces (both manmade and natural) normally exhibit micro- or nanosized roughness as well as hierarchical structure, which somehow can influence the surface's water repellence. As the research into superhydrophobic surfaces goes deeper and wider, it is becoming more important to both academic fields and industrial applications. In this work, the most recent progress in preparing manmade superhydrophobic surfaces through a variety of methodologies, particularly within the past several years, and the fundamental theories of wetting phenomena related to superhydrophobic surfaces are reviewed. We also discuss the perspective of natural superhydrophobic surfaces utilized as mimicking models. The discussion focuses on how the superhydrophobic property is promoted on solid surfaces and emphasizes the effect of surface roughness and structure in particular. This review aims to enable researchers to perceive the inner principles of wetting phenomena and employ suitable methods for creation and modification of superhydrophobic surfaces.

A torch in the rain forest: thermogenesis of the Titan arum (Amorphophallus titanum).

An outstanding flagship species in the plant kingdom is the Titan arum (Amorphophallus titanum), which produces a fountain-like bloom up to 3 m high. The unique appearance of three simultaneous inflorescences in May 2006 was a chance to analyse the flowering behaviour and thermogenesis of this giant. For the first time, the heating of the central column (spadix) could be documented using a high-performance thermographic camera. Time series analyses of the infrared image sequences revealed that the 3-m high spadix surface heats up in pulses emanating from the base of the inflorescence. The surface temperature reaches over 36 degrees C, compared to the ambient temperature of 27 degrees C. Waves of the carrion-like odour are synchronised with these heat pulses. The combination of heat pulses, the fountain-like shape plus the enormous size lead to a unique type of 'convection flower'. On the basis of our observations, we assume that Amorphophallus titanum is able to overcome thermodynamic decoupling by a self-produced convective process.

Crystallinity of plant epicuticular waxes: electron and X-ray diffraction studies.

The crystal structure of the epicuticular waxes of 35 plant species has been examined by electron diffraction and X-ray powder diffraction. The waxes include the most common morphological wax types such as platelets, tubules, films and rodlets. Most of them were prepared with a special mechanical isolation method, which preserves the original crystal structure. Solvent-extracted recrystallized plant waxes were compared with mechanically isolated samples. The waxes were found to occur in three different crystal structures. Most of the waxes exhibited an orthorhombic structure which is the most common for aliphatic compounds. Tubules containing mainly secondary alcohols showed diffraction reflections of a triclinic phase; broad reflection peaks indicated a significant disorder. Ketones, in particular beta-diketone tubules, displayed the reflections of a hexagonal structure. Mixtures of different phases could be identified. For most of the waxes, the 'long spacing' diffraction reflections indicated a layer structure with the characteristics of the major component. Others showed no 'long spacing' reflections indicating a strong disorder of the molecular layers.

A unique cactus with scented and possibly bat-dispersed fruits: Rhipsalis juengeri.

Rhipsalis juengeri was described in 1995 as an unusual representative of epiphytic cacti, forming more than 3 m long curtains, hanging from the canopy of the Atlantic Rainforest in eastern Brazil. At the apex of thin, pendant shoots, green-brownish berries are formed. We report here as a novelty for the Cactaceae that these berries are strongly scented, and present an odour analysis along with an olfactoric survey of fruits of about 50 species and varieties of the cactus tribe Rhipsalideae. The volatile blend of berries of R. juengeri is dominated by ketones, some of which are responsible for the characteristic blackcurrant-like scent, as is shown by GC-olfactometry. The odour and inconspicuous colour stand out among fruits of other epiphytic cacti that are thought to be consumed by birds. Fruit characters of R. juengeri and the flagellicarpic presentation indicate adaptation to chiropterochory.

Recent progress in understanding the evolution of carnivorous lentibulariaceae (lamiales).

Carnivorous plants have emerged as model systems for addressing many ecological and evolutionary questions, and since Lentibulariaceae comprise more than half of all known carnivorous species (325 spp.), they are of particular interest. Studies using various molecular markers have established that Lentibulariaceae and their three genera are monophyletic with Pinguicula being sister to a Genlisea-Utricularia-clade, while the closest relatives of the family remain uncertain. Character states of the carnivorous syndrome in related proto-carnivorous lamialean families apparently emerged independently. In Utricularia, the terrestrial habit has been reconstructed as plesiomorphic, and an extension of subgenus Polypompholyx is warranted. In the protozoan-attracting Genlisea, subgenus Tayloria is revealed as basal lineage. In Pinguicula, the six major lineages found reflect radiations in clearly defined geographic regions, whereas most previously recognized subgeneric taxa are non-monophyletic. Genlisea and Utricularia exhibit substitutional rates that rank among the highest in angiosperms for the molecular markers analyzed. One possible explanation for this lies in selective constraints on a wide range of genomic regions that may have been lowered due to the use of an alternative mode of acquiring nutrients.

Smallest angiosperm genomes found in lentibulariaceae, with chromosomes of bacterial size.

Nuclear holoploid genome sizes (C-values) have been estimated to vary about 800-fold in angiosperms, with the smallest established 1C-value of 157 Mbp recorded in Arabidopsis thaliana. In the highly specialized carnivorous family Lentibulariaceae now three taxa have been found that exhibit significantly lower values: Genlisea margaretae with 63 Mbp, G. aurea with 64 Mbp, and Utricularia gibba with 88 Mbp. The smallest mitotic anaphase chromatids in G. aurea have 2.1 Mbp and are thus of bacterial size (NB: E. coli has ca. 4 Mbp). Several Utricularia species range somewhat lower than A. thaliana or are similar in genome size. The highest 1C-value known from species of Lentibulariaceae was found in Genlisea hispidula with 1510 Mbp, and results in about 24-fold variation for Genlisea and the Lentibulariaceae. Taking into account these new measurements, genome size variation in angiosperms is now almost 2000-fold. Genlisea and Utricularia are plants with terminal positions in the phylogeny of the eudicots, so that the findings are relevant for the understanding of genome miniaturization. Moreover, the Genlisea-Utricularia clade exhibits one of the highest mutational rates in several genomic regions in angiosperms, what may be linked to specialized patterns of genome evolution. Ultrasmall genomes have not been found in Pinguicula, which is the sister group of the Genlisea-Utricularia clade, and which does not show accelerated mutational rates. C-values in Pinguicula varied only 1.7-fold from 487 to 829 Mbp.

Structural analysis of wheat wax (Triticum aestivum, c.v. 'Naturastar' L.): from the molecular level to three dimensional crystals.

In order to elucidate the self assembly process of plant epicuticular waxes, and the molecular arrangement within the crystals, re-crystallisation of wax platelets was studied on biological and non-biological surfaces. Wax platelets were extracted from the leaf blades of wheat (Triticum aestivum L., c.v. 'Naturastar', Poaceae). Waxes were analysed by gas chromatography (GC) and mass spectrometry (MS). Octacosan-1-ol was found to be the most abundant chemical component of the wax mixture (66 m%) and also the determining compound for the shape of the wax platelets. The electron diffraction pattern showed that both the wax mixture and pure octacosan-1-ol are crystalline. The re-crystallisation of the natural wax mixture and the pure octacosan-1-ol were studied by scanning tunnelling microscopy (STM), atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Crystallisation of wheat waxes and pure octacosano-1-ol on the non polar highly ordered pyrolytic graphite (HOPG) led to the formation of platelet structures similar to those found on the plant surface. In contrast, irregular wax morphologies and flat lying plates were formed on glass, silicon, salt crystals (NaCl) and mica surfaces. Movement of wheat wax through isolated Convallaria majalis cuticles led to typical wax platelets of wheat, arranged in the complex patterns typical for C. majalis. STM of pure octacosan-1-ol monolayers on HOPG showed that the arrangement of the molecules strictly followed the hexagonal structure of the substrate crystal. Re-crystallisation of wheat waxes on non-polar crystalline HOPG substrate showed that technical surfaces could be used to generate microstructured, biomimetic surfaces. AFM and SEM studies proved that a template effect of the substrate determined the orientation of the re-grown crystals. These effects of the structure and polarity of the substrate on the morphology of the epicuticular waxes are relevant for understanding interactions between biological as well as technical surfaces and waxes.

Measuring the fate of plant diversity: towards a foundation for future monitoring and opportunities for urgent action.

Vascular plants are often considered to be among the better known large groups of organisms, but gaps in the available baseline data are extensive, and recent estimates of total known (described) seed plant species range from 200000 to 422000. Of these, global assessments of conservation status using International Union for the Conservation of Nature (IUCN) categories and criteria are available for only approximately 10000 species. In response to recommendations from the Conference of the Parties to the Convention on Biological Diversity to develop biodiversity indicators based on changes in the status of threatened species, and trends in the abundance and distribution of selected species, we examine how existing data, in combination with limited new data collection, can be used to maximum effect. We argue that future work should produce Red List Indices based on a representative subset of plant species so that the limited resources currently available are directed towards redressing taxonomic and geographical biases apparent in existing datasets. Sampling the data held in the world's major herbaria, in combination with Geographical Information Systems techniques, can produce preliminary conservation assessments and help to direct selective survey work using existing field networks to verify distributions and gather population data. Such data can also be used to backcast threats and potential distributions through time. We outline an approach that could result in: (i) preliminary assessments of the conservation status of tens of thousands of species not previously assessed, (ii) significant enhancements in the coverage and representation of plant species on the IUCN Red List, and (iii) repeat and/or retrospective assessments for a significant proportion of these. This would result in more robust Sampled Red List Indices that can be defended as more representative of plant diversity as a whole; and eventually, comprehensive assessments at species level for one or more major families of angiosperms. The combined results would allow scientifically defensible generalizations about the current status of plant diversity by 2010 as well as tentative comments on trends. Together with other efforts already underway, this approach would establish a firmer basis for ongoing monitoring of the status of plant diversity beyond 2010 and a basis for comparison with the trend data available for vertebrates.

Evolution of carnivory in Lentibulariaceae and the Lamiales.

As a basis for analysing the evolution of the carnivorous syndrome in Lentibulariaceae (Lamiales), phylogenetic reconstructions were conducted based on coding and non-coding chloroplast DNA (matK gene and flanking trnK intron sequences, totalling about 2.4 kb). A dense taxon sampling including all other major lineages of Lamiales was needed since the closest relatives of Lentibulariaceae and the position of "proto-carnivores" were unknown. Tree inference using maximum parsimony, maximum likelihood, and Bayesian approaches resulted in fully congruent topologies within Lentibulariaceae, whereas relationships among the different lineages of Lamiales were only congruent between likelihood and Bayesian optimizations. Lentibulariaceae and their three genera (Pinguicula, Genlisea, and Utricularia) are monophyletic, with Pinguicula being sister to a Genlisea-Utricularia clade. Likelihood and Bayesian trees converge on Bignoniaceae as sister to Lentibulariaceae, albeit lacking good support. The "proto-carnivores" (Byblidaceae, Martyniaceae) are found in different positions among other Lamiales but not as sister to the carnivorous Lentibulariaceae, which is also supported by Khishino-Hasegawa tests. This implies that carnivory and its preliminary stages ("proto-carnivores") independently evolved more than once among Lamiales. Ancestral states of structural characters connected to the carnivorous syndrome are reconstructed using the molecular tree, and a hypothesis on the evolutionary pathway of the carnivorous syndrome in Lentibulariaceae is presented. Extreme DNA mutational rates found in Utricularia and Genlisea are shown to correspond to their unusual nutritional specialization, thereby hinting at a marked degree of carnivory in these two genera.

Noncoding plastid trnT-trnF sequences reveal a well resolved phylogeny of basal angiosperms.

Recent contributions from DNA sequences have revolutionized our concept of systematic relationships in angiosperms. However, parts of the angiosperm tree remain unclear. Previous studies have been based on coding or rDNA regions of relatively conserved genes. A phylogeny for basal angiosperms based on noncoding, fast-evolving sequences of the chloroplast genome region trnT-trnF is presented. The recognition of simple direct repeats allowed a robust alignment. Mutational hot spots appear to be confined to certain sectors, as in two stem-loop regions of the trnL intron secondary structure. Our highly resolved and well-supported phylogeny depicts the New Caledonian Amborella as the sister to all other angiosperms, followed by Nymphaeaceae and an Austrobaileya-Illicium-Schisandra clade. Ceratophyllum is substantiated as a close relative of monocots, as is a monophyletic eumagnoliid clade consisting of Piperales plus Winterales sister to Laurales plus Magnoliales. Possible reasons for the striking congruence between the trnT-trnF based phylogeny and phylogenies generated from combined multi-gene, multi-genome data are discussed.

Quantitative assessment to the structural basis of water repellency in natural and technical surfaces.

Many plant surfaces are water-repellent because of a complex 3-dimensional microstructure of the epidermal cells (papillae) and a superimposed layer of hydrophobic wax crystals. Due to its surface tension, water does not spread on such surfaces but forms spherical droplets that lie only on the tips of the microstructures. Studying six species with heavily microstructured surfaces by a new type of confocal light microscopy, the number, height, and average distance of papillae per unit area were measured. These measurements were combined with those of an atomic force microscope which was used to measure the exposed area of the fine-structure on individual papillae. According to calculations based upon these measurements, roughening results in a reduction of the contact area of more than 95% compared with the projected area of a water droplet. By applying water/methanol solutions of decreasing surface tension to a selection of 33 water-repellent species showing different types of surface structures, the critical value at which wetting occurs was determined. The results impressively demonstrated the importance of roughening on different length scales for water-repellency, since extremely papillose surfaces, having an additional wax layer, are able to resist up to 70% methanol. Surfaces that lack papillae or similar structures on the same length scale are much more easily wetted.

Movement and regeneration of epicuticular waxes through plant cuticles.

Regeneration of plant epicuticular waxes was studied in 24 plant species by high-resolution scanning electron microscopy. According to their regeneration behaviour, four groups could be distinguished: (i) regeneration occurs at all stages of development; (ii) regeneration occurs only during leaf expansion; (iii) regeneration occurs only in fully developed leaves; (iv) plants were not able to regenerate wax. Wax was removed from the leaves with water-based glue and a liquid polymer, i.e. water-based polyurethane dispersion. In young leaves these coverings could not be removed without damaging the leaves. After a few days, waxes appeared on the surface of these polymer films, which still adhered to the leaves. It is concluded that waxes move through the cuticle in a process similar to steam distillation. This hypothesis could be further substantiated in refined in vitro experiments. Wax isolated from Eucalyptus globulus was applied to a filter paper, subsequently covered with a liquid polymer and fixed onto a diffusion chamber filled with water. The diffusion chamber was put into a desiccator. After 8-10 days at room temperature, crystals similar in dimensions and shape to in situ crystals appeared on the surface of the polyurethane film. This indicates that waxes in molecular dimensions move together with the water vapor that permeates through the polymer membrane. Based on these results, we propose a new and simple hypothesis for the mechanism of wax movement: the molecules that finally form the epicuticular wax crystals are moved in the cuticular water current.

Direct Access to Plant Epicuticular Wax Crystals by a New Mechanical Isolation Method.

A new method for the isolation of wax crystals from plant surfaces is presented. The wax-covered plant surface, e.g., a piece of a leaf or fruit, is brought into contact with a preparation liquid, e.g., glycerol or triethylene glycol, and cooled to ca. -100 degrees C. When the plant specimen is removed, the epicuticular wax remains embedded in the frozen liquid. After it warms up, the wax layer can be captured on appropriate carriers for further studies. This isolation method causes very little stress on the wax crystals; thus the shape and crystal structure are well preserved. In many cases it is possible, by choosing a preparation liquid with appropriate wettability, to isolate either the entire epicuticular wax layer or only discrete wax crystals without the underlying wax film. These crystals are well suited for electron diffraction studies by transmission electron microscopy and high resolution imaging by atomic force microscopy. The absence of intracuticular components and other impurities and the feasibility of the selective isolation of wax crystals enable improved chemical analysis and a more detailed study of their properties.