Template-assisted patterning of functional polymers

In this thesis, anodic aluminum oxide (AAO) membranes, which provide well-aligned uniform mesoscopic pores with adjustable pore parameters, were fabricated and successfully utilized as templates for the fabrication of functional organic nanowires, nanorods and the respective well-ordered arrays. The template-assisted patterning technique was successfully applied for the realization of different objectives:rnHigh-density and well-ordered arrays of hole-conducting nanorods composed of cross-linked triphenylamine (TPA) and tetraphenylbenzidine (TPD) derivatives on conductive substrates like ITO/glass have been successfully fabricated. By applying a freeze-drying technique to remove the aqueous medium after the wet-chemical etching of the template, aggregation and collapsing of the rods was prevented and macroscopic areas of perfectly freestanding nanorods were feasible. Based on the hole-conducting nanorod arrays and their subsequent embedding into an electron-conducting polymer matrix via spin-coating, a novel routine concept for the fabrication of well-ordered all-organic bulk heterojunction for organic photovoltaic applications was successfully demonstrated. The increased donor/acceptor interface of the fabricated devices resulted in a remarkable increase of the photoluminescence quenching compared to a planar bilayer morphology. Further, the fundamental working principle of the templating approach for the solution-based all-organic photovoltaic device was demonstrated for the first time.rnFurthermore, in order to broaden the applicability of patterned surfaces, which are feasible via the template-based patterning of functional materials, AAO with hierarchically branched pores were fabricated and utilized as templates. By pursuing the common templating process hierarchically polymeric replicas, which show remarkable similarities with interesting biostructures, like the surface of the lotus leaf and the feet of a gecko, were successfully prepared.rnIn contrast to the direct infiltration of organic functional materials, a novel route for the fabrication of functional nanowires via post-modification of reactive nanowires was established. Therefore, reactive nanowires based on cross-linked pentafluorophenylesters were fabricated by utilizing AAO templates. The post-modification with fluorescent dyes was demonstrated. Furthermore, reactive wires were converted into well-dispersed poly(N-isopropylacrylamide) (PNIPAM) hydrogels, which exhibit a thermal-responsive reversible phase transition. The reversible thermal-responsible swelling of the PNIPAM nanowires exhibited a more than 50 % extended length than in the collapsed PNIPAM state. rnLast but not least, the shape-anisotropic pores of AAO were utilized to uniformly align the mesogens of a nematic liquid crystalline elastomer. Liquid crystalline nanowires with a narrow size distribution and uniform orientation of the liquid crystalline material were fabricated. It was shown that during the transition from the nematic to the isotropic phase the rod’s length shortened by roughly 40 percent. As such these liquid crystalline elastomeric nanowires may find application, as wire-shaped nanoactuators in various fields of research, like lab-on-chip systems, micro fluidics and biomimetics.rn

Numerical simulation of the edge stress singularity and the adhesion strength for compliant mushroom fibrils adhered to rigid substrates

Open Access funded by European Research Council Acknowledgements RB thanks GRADUS, Faculty 8.4. Natural Sciences, of Saarland University for partially funding his research visit to the University of California, Santa Barbara. RB would also thank to Dr. S. Khaderi for his help in setting up the model. He also thanks Dr. R. Hensel and Dr. N. Guimard for fruitful discussions and for their continuous support. EA acknowledges funding from the European Research Council under the European Union's Seventh Framework Program (FP/2007-2013)/ERC Advanced Grant no. 340929.

Identification, retinoid binding, and x-ray analysis of a human retinol-binding protein

Two cellular retinol-binding proteins (CRBP I and II) with distinct tissue distributions and retinoid-binding properties have been recognized thus far in mammals. Here, we report the identification of a human retinol-binding protein resembling type I (55.6% identity) and type II (49.6% identity) CRBPs, but with a unique H residue in the retinoid-binding site and a distinctively different tissue distribution. Additionally, this binding protein (CRBP III) exhibits a remarkable sequence identity (62.2%) with the recently identified ι-crystallin/CRBP of the diurnal gecko Lygodactylus picturatus [Werten, P. J. L., Röll, B., van Alten, D. M. F. & de Jong, W. W. (2000) Proc. Natl. Acad. Sci. USA 97, 3282–3287 (First Published March 21, 2000; 10.1073/pnas.050500597)]. CRBP III and all-trans-retinol form a complex (Kd ≈ 60 nM), the absorption spectrum of which is characterized by the peculiar fine structure typical of the spectra of holo-CRBP I and II. As revealed by a 2.3-Å x-ray molecular model of apo-CRBP III, the amino acid residues that line the retinol-binding site in CRBP I and II are positioned nearly identically in the structure of CRBP III. At variance with the human CRBP I and II mRNAs, which are most abundant in ovary and intestine, respectively, the CRBP III mRNA is expressed at the highest levels in kidney and liver thus suggesting a prominent role for human CRBP III as an intracellular mediator of retinol metabolism in these tissues.

Evidence that ultraviolet markings are associated with patterns of molecular gene flow

Recent studies have shown UV vision and markings to be important in vertebrates, particularly birds, where behavioral experiments have demonstrated its potential importance in sexual selection. However, there has been no genetic evidence that UV markings determine patterns of evolution among natural populations. Here we report molecular evidence that UV markings are associated with the pattern of gene flow in the Tenerife lizard (Gallotia galloti). This species has vicariance-induced, approximate east–west lineages in Tenerife closely congruent with the primary lineages of the sympatric gecko species. Against expectations, these molecular phylogeographic lineages (representing geological history) and isolation-by-distance do not appear to influence gene flow. Sexually mature males from populations either side of a latitudinal ecotone have different UV markings and gene flow appears to be linked to this difference in UV markings. It may be that these groups with different UV sexual markings mate assortatively, restricting the gene flow between them. This has implications for debate on the relative importance of vicariance and biotopes in influencing biodiversity, with this evidence supporting the latter.

Geographic parthenogenesis in the Australian arid zone: I. A climatic analysis of the Heteronotia binoei complex (Gekkonidae)

Patterns of geographic parthenogenesis can provide insight into the ecological implications of the transition from sexual to parthenogenetic reproduction. We analysed quantitatively the environmental niches occupied by sexual and parthenogenetic geckos of the Heteronotia binoei complex in the Australian and zone. This complex consists of two independently derived maternal lineages of hybrid parthenogens, which, in turn, include two different triploid races that resulted from reciprocal backcrossing with the parental sexual taxa. The sexual progenitors are still extant and occupy very distinct environmental niches. The triploid parthenogenetic races are biased in their environmental niche towards those of the sexual races for which their genomes are biased and this dosage effect is apparent in both maternal lineages. Thus triploidy may have benefited the parthenogens through partial recovery of the parental niches. Although the parthenogens have a broader geographic distribution than their sexual progenitors, their environmental niche is narrower and biased towards one of the sexual races. In keeping with general patterns of geographic parthenogenesis. parthenogenetic H. binoei occupy a harsher environment than the sexual forms. occurring in regions of persistently low rainfall. Bioclimatic modelling suggests patterns of rainfall are important in limiting the distribution of sexual and parthenogenetic taxa. and extrapolation from the current bioclimatic profiles indicates potential for further eastward range expansion by the parthenogens.

Fibrillar Elastomeric Micropatterns Create Tunable Adhesion Even to Rough Surfaces

Acknowledgements V.B., N.K.G., and E.A. contributed with conception and experimental design. V.B. performed the experiments. V.B., R.H., A.G., and R.M.M. carried out analysis and interpretation of data. V.B., R.H., A.G., and E.A. wrote the manuscript. V.B. and R.H. contributed equally to this work. V.B. acknowledges funding by SPP 1420 of the German Science Foundation DFG. E.A., N.K.G., and R.H. acknowledge funding from the European Research Council under the European Union/ERC Advanced Grant “Switch2Stick,” Agreement No. 340929.

Modeling the Effect of Vapor Wall Deposition on the Formation of Secondary Organic Aerosol in Chamber Studies

Laboratory chamber experiments are used to investigate formation of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors under a variety of environmental conditions. Simulations of these experiments test our understanding of the prevailing chemistry of SOA formation as well as the dynamic processes occurring in the chamber itself. One dynamic process occurring in the chamber that was only recently recognized is the deposition of vapor species to the Teflon walls of the chamber. Low-volatility products formed from the oxidation of volatile organic compounds (VOCs) deposit on the walls rather than forming SOA, decreasing the amount of SOA formed (quantified as the SOA yield: mass of SOA formed per mass of VOC reacted). In this work, several modeling studies are presented that address the effect of vapor wall deposition on SOA formation in chambers.

A coupled vapor-particle dynamics model is used to examine the competition among the rates of gas-phase oxidation to low volatility products, wall deposition of these products, and mass transfer to the particle phase. The relative time scales of these rates control the amount of SOA formed by affecting the influence of vapor wall deposition. Simulations show that an effect on SOA yield of changing the vapor-particle mass transfer rate is only observed when SOA formation is kinetically limited. For systems with kinetically limited SOA formation, increasing the rate of vapor-particle mass transfer by increasing the concentration of seed particles is an effective way to minimize the effect of vapor wall deposition.

This coupled vapor-particle dynamics model is then applied to α-pinene ozonolysis SOA experiments. Experiments show that the SOA yield is affected when changing the oxidation rate but not when changing the rate of gas-particle mass transfer by changing the concentration of seed particles. Model simulations show that the absence of an effect of changing the seed particle concentration is consistent with SOA formation being governed by quasi-equilibrium growth, in which gas-particle equilibrium is established much faster than the rate of change of the gas-phase concentration. The observed effect of oxidation rate on SOA yield arises due to the presence of vapor wall deposition: gas-phase oxidation products are produced more quickly and condense preferentially onto seed particles before being lost to the walls. Therefore, for α-pinene ozonolysis, increasing the oxidation rate is the most effective way to mitigate the influence of vapor wall deposition.

Finally, the detailed model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to simulate α-pinene photooxidation SOA experiments. Unexpectedly, α-pinene OH oxidation experiments show no effect when changing either the oxidation rate or the vapor-particle mass transfer rate, whereas GECKO-A predicts that changing the oxidation rate should drastically affect the SOA yield. Sensitivity studies show that the assumed magnitude of the vapor wall deposition rate can greatly affect conclusions drawn from comparisons between simulations and experiments. If vapor wall loss in the Caltech chamber is of order 10^-5 s^-1, GECKO-A greatly overpredicts SOA during high UV experiments, likely due to an overprediction of second-generation products. However, if instead vapor wall loss in the Caltech chamber is of order 10^-3 s^-1, GECKO-A greatly underpredicts SOA during low UV experiments, possibly due to missing autoxidation pathways in the α-pinene mechanism.

The taxonomy, zoogeography and ecology of amphibians and reptiles of Hin Nam No National Protected Area (Laos) in comparison with data from Phong Nha – Ke Bang National Park (Vietnam).

In this thesis the mostly unknown herpetofauna in Hin Nam No National Protected Area Laos in the northern Truong Son Range was for the first time intensively investigated, and its diversity was compared to the bordering, and well-investigated Phong Nha - Ke Bang National Park in Vietnam. Twelve new vertebrate species were described comprising 11 geckonids (Cyrtodactylus bansocensis, C. calamei, C. hinnamnoensis, C. jaegeri, C. rufford, C. sommerladi, C. soudthichaki, Gekko boehmei, G. bonkowskii, G. sengchanthavongi, G. thakhekensis, Lycodon banksi and one colubrid snake (Lycodon banksi). Seven species were discovered for the first time in Laos including three frogs (Gracixalus quyeti, G. supercornutus, Rhacophorus maximus), two geckos (Cyrtodactylus cryptus, C. pseudoquadrivirgatus) and two snakes (Lycodon futsingensis, L. ruhstrati abditus). The main hypothesis that the Truong Son Range acted as a biogeographic barrier for the distribution of amphibians and reptiles could be confirmed at least for karst adapted gekkonids. Compared to other herpetofaunal groups the number of gekkonids in karst formations was particularly high (seven bent-toed geckos, four true geckos). By comparing the relative amounts of shared species in Hin Nam No and Phong Nha - Ke Bang, it is interesting to note that fewer reptile species (38%) than amphibian species (66%) were shared between both regions. This might indicate that the Truong Son Range acts as a stronger biogeographical barrier for reptiles than for amphibians. Two pairs of karst-adapted cryptic gecko species (i.e. species with distinct genetic differences, but a similar phenotype) occurred on both sides of the Truong Son Range. Only in one case these were sibling species (Crytodactylus sommerladi in Laos versus C. roesleri in Vietnam), but not in the other (C. hinnamnoensis in Laos versus C. phongnhakebangensis in Vietnam). On the Laotian side, nine gecko species (Cyrtodactylus bansocensis, C. calamei, C. darevskii, C. hinnamnoensis, C. khammouanensis, C. multiporus, C. sommerladi, G. boehmei, G. sengchanthavongi) currently have to be regarded as endemic to the Hin Nam No region. On the Vietnamese side, seven species including two bent-toed geckos (Cyrtodactylus phongnhakebangensis and C. roesleri), three skinks (Lygosoma boehmei, Sphenomorphus tetradactylus and Tropidophorus noggei), and two snakes (Hebius andreae and Boiga bourreti) are currently only known from Phong Nha - Ke Bang and adjacent regions. These high numbers of potential endemic species together with the cryptic species complex in Cyrtodactylus provide strong evidence that the karst formations in the northern Truong Son Range represent a hot spot of reptile diversity and of speciation in Crytodactylus in particular. Correct species identification is a fundamental requirement for conservation measures. The discovery of cryptic species complexes poses a challenge for alpha taxonomy and species conservation, because the true distribution ranges of the species are in fact much smaller than previously assumed. Species conservation in this area of Laos is facing a number of further problems. New and potentially endemic species were discovered in highly populated and disturbed areas. Conversion of the Ho Chi Minh Trail into a highway provided easy access for farmers and still continues to accelerate the destruction of remote forest areas. Southern Hin Nam No with its high diversity of endemic species was identified as the first priority area for conservation. Also Ban Soc, an area isolated from Hin Nam No, should be among the conservation priorities because this region houses a so far overlooked population of the critically endangered Siamese crocodile. Efforts to establish a legal conservation status for this habitat are in progress.

Pasture height and crop direction influence reptile movement in an agricultural matrix

Tackling the global threat of habitat fragmentation on biodiversity requires knowledge of how species move within agricultural landscapes. However, the specific mechanisms influencing dispersal within such landscapes remain poorly understood. The objective of our study was to assess how matrix type (improved pasture, native pasture or crop) and structure (grass height) influence fine-scale reptile movement, as well as influences of crop sowing direction and setting-sun position. In an agricultural region of south-eastern Australia, we first released 20 individuals of an arboreal gecko (Christinus marmoratus) at set distances from trees to determine the distance at which they could perceive their tree habitat (perceptual range). We then translocated 36 individuals into six matrix environments within their perceptual range of isolated trees to examine how gecko movement was modified by the type and structure of the matrix. We also recorded crop sowing direction and setting-sun position and examined all recorded tracks using angular statistics. We found that geckos exhibited a perceptual range of 40–80m. Short matrix environments promoted direct movements towards trees, irrespective of matrix type. Furthermore, movements were significantly affected by crop sowing direction with individuals following the planted lines. Our study has three significant implications: (i) restoring mature tree spacing to 80 m apart will assist gecko movements, (ii) targeted management for low pasture height, such as by maintaining directional narrow strips of low vegetation among taller pastures, might assist movement and facilitate increased connectivity, (iii) directional sowing of crops between habitat patches presents a simple but potentially effective tool for reconnecting fragmented landscapes.

Somewhat saved : a captive breeding programme for two endemic Christmas Island lizard species, now extinct in the wild

As with many islands, Christmas Island in the Indian Ocean has suffered severe biodiversity loss. Its terrestrial lizard fauna comprised five native species, of which four were endemic. These were abundant until at least the late 1970s, but four species declined rapidly thereafter and were last reported in the wild between 2009 and 2013. In response to the decline, a captive breeding programme was established in August 2009. This attempt came too late for the Christmas Island forest skink Emoia nativitatis, whose last known individual died in captivity in 2014, and for the non-endemic coastal skink Emoia atrocostata. However, two captive populations are now established for Lister's gecko Lepidodactylus listeri and the blue-tailed skink Cryptoblepharus egeriae. The conservation future for these two species is challenging: reintroduction will not be possible until the main threats are identified and controlled.