Organic protomolecule assembly in igneous minerals

C—H stretching bands, νCH, in the infrared spectrum of single crystals of nominally high purity, of laboratory-grown MgO, and of natural upper mantle olivine, provide an “organic” signature that closely resembles the symmetrical and asymmetrical C—H stretching modes of aliphatic —CH2 units. The νCH bands indicate that H2O and CO2, dissolved in the matrix of these minerals, converted to form H2 and chemically reduced C, which in turn formed C—H entities, probably through segregation into defects such as dislocations. Heating causes the C—H bonds to pyrolyze and the νCH bands to disappear, but annealing at 70°C causes them to reappear within a few days or weeks. Modeling dislocations in MgO suggests that the segregation of C can lead to Cx chains, x = 4, with the terminal C atoms anchored to the MgO matrix by bonding to two O−. Allowing H2 to react with such Cx chains leads to [O2C(CH2)2CO2] or similar precipitates. It is suggested that such Cx—Hy—Oz entities represent protomolecules from which derive the short-chain carboxylic and dicarboxylic and the medium-chain fatty acids that have been solvent-extracted from crushed MgO and olivine single crystals, respectively. Thus, it appears that the hard, dense matrix of igneous minerals represents a medium in which protomolecular units can be assembled. During weathering of rocks, the protomolecular units turn into complex organic molecules. These processes may have provided stereochemically constrained organics to the early Earth that were crucial to the emergence of life.

Nondestructive, in situ, cellular-scale mapping of elemental abundances including organic carbon in permineralized fossils

The electron microprobe allows elemental abundances to be mapped at the μm scale, but until now high resolution mapping of light elements has been challenging. Modifications of electron microprobe procedure permit fine-scale mapping of carbon. When applied to permineralized fossils, this technique allows simultaneous mapping of organic material, major matrix-forming elements, and trace elements with μm-scale resolution. The resulting data make it possible to test taphonomic hypotheses for the formation of anatomically preserved silicified fossils, including the role of trace elements in the initiation of silica precipitation and in the prevention of organic degradation. The technique allows one to understand the localization of preserved organic matter before undertaking destructive chemical analyses and, because it is nondestructive, offers a potentially important tool for astrobiological investigations of samples returned from Mars or other solar system bodies.

Extracellular Matrix Assembly in Diatoms (Bacillariophyceae)1 : III. Organization of Fucoglucuronogalactans within the Adhesive Stalks of Achnanthes longipes

Achnanthes longipes is a marine, biofouling diatom that adheres to surfaces via adhesive polymers extruded during motility or organized into structures called stalks that contain three distinct regions: the pad, shaft, and collar. Four monoclonal antibodies (AL.C1–AL.C4) and antibodies from two uncloned hybridomas (AL.E1 and AL.E2) were raised against the extracellular adhesives of A. longipes. Antibodies were screened against a hot-water-insoluble/hot-bicarbonate-soluble-fraction. The hot-water-insoluble/hot-bicarbonate-soluble fraction was fractionated to yield polymers in three size ranges: F1, ≥ 20,000,000 Mr; F2, ≅100,000 Mr; and F3, <10,000 Mr relative to dextran standards. The ≅100,000-Mr fraction consisted of highly sulfated (approximately 11%) fucoglucuronogalactans (FGGs) and low-sulfate (approximately 2%) FGGs, whereas F1 was composed of O-linked FGG (F2)-polypeptide (F3) complexes. AL.C1, AL.C2, AL.C4, AL.E1, and AL.E2 recognized carbohydrate complementary regions on FGGs, with antigenicity dependent on fucosyl-containing side chains. AL.C3 was unique in that it had a lower affinity for FGGs and did not label any portion of the shaft. Enzyme-linked immunosorbent assay and immunocytochemistry indicated that low-sulfate FGGs are expelled from pores surrounding the raphe terminus, creating the cylindrical outer layers of the shaft, and that highly sulfated FGGs are extruded from the raphe, forming the central core. Antibody-labeling patterns and other evidence indicated that the shaft central-core region is related to material exuded from the raphe during cell motility.

Oxide Semiconductors For Organic Opto-electronic Devices

Development of transparent oxide semiconductors (TOS) from Earth-abundant materials is of great interest for cost-effective thin film device applications, such as solar cells, light emitting diodes (LEDs), touch-sensitive displays, electronic paper, and transparent thin film transistors. The need of inexpensive or high performance electrode might be even greater for organic photovoltaic (OPV), with the goal to harvest renewable energy with inexpensive, lightweight, and cost competitive materials. The natural abundance of zinc and the wide bandgap ($sim$3.3 eV) of its oxide make it an ideal candidate. In this dissertation, I have introduced various concepts on the modulations of various surface, interface and bulk opto-electronic properties of ZnO based semiconductor for charge transport, charge selectivity and optimal device performance. I have categorized transparent semiconductors into two sub groups depending upon their role in a device. Electrodes, usually 200 to 500 nm thick, optimized for good transparency and transporting the charges to the external circuit. Here, the electrical conductivity in parallel direction to thin film, i.e bulk conductivity is important. And contacts, usually 5 to 50 nm thick, are optimized in case of solar cells for providing charge selectivity and asymmetry to manipulate the built in field inside the device for charge separation and collection. Whereas in Organic LEDs (OLEDs), contacts provide optimum energy level alignment at organic oxide interface for improved charge injections. For an optimal solar cell performance, transparent electrodes are designed with maximum transparency in the region of interest to maximize the light to pass through to the absorber layer for photo-generation, plus they are designed for minimum sheet resistance for efficient charge collection and transport. As such there is need for material with high conductivity and transparency. Doping ZnO with some common elements such as B, Al, Ga, In, Ge, Si, and F result in n-type doping with increase in carriers resulting in high conductivity electrode, with better or comparable opto-electronic properties compared to current industry-standard indium tin oxide (ITO). Furthermore, improvement in mobility due to improvement on crystallographic structure also provide alternative path for high conductivity ZnO TCOs. Implementing these two aspects, various studies were done on gallium doped zinc oxide (GZO) transparent electrode, a very promising indium free electrode. The dynamics of the superimposed RF and DC power sputtering was utilized to improve the microstructure during the thin films growth, resulting in GZO electrode with conductivity greater than 4000 S/cm and transparency greater than 90 %. Similarly, various studies on research and development of Indium Zinc Tin Oxide and Indium Zinc Oxide thin films which can be applied to flexible substrates for next generation solar cells application is presented. In these new TCO systems, understanding the role of crystallographic structure ranging from poly-crystalline to amorphous phase and the influence on the charge transport and optical transparency as well as important surface passivation and surface charge transport properties. Implementation of these electrode based on ZnO on opto-electronics devices such as OLED and OPV is complicated due to chemical interaction over time with the organic layer or with ambient. The problem of inefficient charge collection/injection due to poor understanding of interface and/or bulk property of oxide electrode exists at several oxide-organic interfaces. The surface conductivity, the work function, the formation of dipoles and the band-bending at the interfacial sites can positively or negatively impact the device performance. Detailed characterization of the surface composition both before and after various chemicals treatment of various oxide electrode can therefore provide insight into optimization of device performance. Some of the work related to controlling the interfacial chemistry associated with charge transport of transparent electrodes are discussed. Thus, the role of various pre-treatment on poly-crystalline GZO electrode and amorphous indium zinc oxide (IZO) electrode is compared and contrasted. From the study, we have found that removal of defects and self passivating defects caused by accumulation of hydroxides in the surface of both poly-crystalline GZO and amorphous IZO, are critical for improving the surface conductivity and charge transport. Further insight on how these insulating and self-passivating defects cause charge accumulation and recombination in an device is discussed. With recent rapid development of bulk-heterojunction organic photovoltaics active materials, devices employing ZnO and ZnO based electrode provide air stable and cost-competitive alternatives to traditional inorganic photovoltaics. The organic light emitting diodes (OLEDs) have already been commercialized, thus to follow in the footsteps of this technology, OPV devices need further improvement in power conversion efficiency and stable materials resulting in long device lifetimes. Use of low work function metals such as Ca/Al in standard geometry do provide good electrode for electron collection, but serious problems using low work-function metal electrodes originates from the formation of non-conductive metal oxide due to oxidation resulting in rapid device failure. Hence, using low work-function, air stable, conductive metal oxides such as ZnO as electrons collecting electrode and high work-function, air stable metals such as silver for harvesting holes, has been on the rise. Devices with degenerately doped ZnO functioning as transparent conductive electrode, or as charge selective layer in a polymer/fullerene based heterojunction, present useful device structures for investigating the functional mechanisms within OPV devices and a possible pathway towards improved air-stable high efficiency devices. Furthermore, analysis of the physical properties of the ZnO layers with varying thickness, crystallographic structure, surface chemistry and grain size deposited via various techniques such as atomic layer deposition, sputtering and solution-processed ZnO with their respective OPV device performance is discussed. We find similarity and differences in electrode property for good charge injection in OLEDs and good charge collection in OPV devices very insightful in understanding physics behind device failures and successes. In general, self-passivating surface of amorphous TCOs IZO, ZTO and IZTO forms insulating layer that hinders the charge collection. Similarly, we find modulation of the carrier concentration and the mobility in electron transport layer, namely zinc oxide thin films, very important for optimizing device performance.

Enhancement of the Electrochemical Performance of SWCNT dispersed in a Silica Sol-gel Matrix by Reactive Insertion of a Conducting Polymer

The electroassisted encapsulation of Single-Walled Carbon Nanotubes was performed into silica matrices (SWCNT@SiO2). This material was used as the host for the potentiostatic growth of polyaniline (PANI) to yield a hybrid nanocomposite electrode, which was then characterized by both electrochemical and imaging techniques. The electrochemical properties of the SWCNT@SiO2-PANI composite material were tested against inorganic (Fe3+/Fe2+) and organic (dopamine) redox probes. It was observed that the electron transfer constants for the electrochemical reactions increased significantly when a dispersion of either SWCNT or PANI was carried out inside of the SiO2 matrix. However, the best results were obtained when polyaniline was grown through the pores of the SWCNT@SiO2 material. The enhanced reversibility of the redox reactions was ascribed to the synergy between the two electrocatalytic components (SWCNTs and PANI) of the composite material.

Characterisation of montmorillonites simultaneously modified with an organic dye and an ammonium salt at different dye/salt ratios. Properties of these modified montmorillonites EVA nanocomposites

In this work, a sodium montmorillonite (Na+-Mt) was modified with two molecules simultaneously, an organic dye, methylene blue (MB), and ethyl hexadecyl dimethyl ammonium (EHDDMA). The synthesised organo-montmorillonites (OMt) combining different proportions of the two molecules were thoroughly characterised and mixed with ethylene vinyl acetate copolymer (EVA) in order to check the ability of these OMt as pigments and reinforcing additives. The synthesised OMt combining both surfactants, MB and EHDDMA, present higher interlayer distances than those with only MB, which were employed in previous works as nanopigments. When these OMt were incorporated in the EVA matrix, the obtained clay polymer nanocomposites (CPN) showed a high exfoliation degree of the OMt in the polymer, in such a way that at 80% of the cationic exchange capacity (CEC) of the Mt exchanged with EHDDMA, most of the OMt was exfoliated. Moreover, all the obtained CPN showed an increase in the Young's Moduli compared to the EVA reference, and especially those containing higher amounts of MB. The thermal stability of the CPN also increases with the MB content, compared to other CPN including conventional surfactants. The hiding power and colouring power achieved in the CPN are higher even with a much lower load of MB when EHDDMA is exchanged in the Mt.

Ash layers, hyaloclastite, and alteration of basaltic glass at DSDP Leg 65 Holes

Three types of tephra deposits were recovered on Leg 65 of the Deep Sea Drilling Project (DSDP) from three drill sites at the mouth of the Gulf of California: (1) a series of white ash layers at Sites 483, 484, and 485; (2) a layer of plagioclase- phyric sideromelane shards at Site 483; and (3) an indurated, cross-bedded hyaloclastite in Hole 483B. The ash layers in (1) are composed of colorless, fresh rhyolitic glass shards with minor dacitic and rare basaltic shards. These are thought to be derived from explosive volcanoes on the Mexican mainland. Most of the shards in (2) are fresh, but some show marginal to complete alteration to palagonite. The composition of the glass is that of a MORB-type tholeiite, low in Fe and moderately high in Ti, and possibly erupted from off-axis seamounts. Basaltic glass shards occurring in silt about 45 meters above the basement at Site 484 A in the Tamayo Fracture Zone show a distinctly alkalic composition similar to that of the single basement basalt specimen drilled at this site. The hyaloclastite in (3) is made up chiefly of angular sideromelane shards altered to smectite and zeolites (mainly phillipsite) and minor admixtures of terrigenous silt. A very high K and Ba content indicates significant uptake of at least these elements from seawater. Nevertheless, the unusual chemical composition of the underlying massive basalt flow is believed to be reflected in that of the hyaloclastite. This is a powerful argument for interpreting the massive basalt as a surface flow rather than an intrusion. Glass alteration is different in the glassy margins of flows than in thicker glassy pillow rinds. Also, it appears to proceed faster in coarse- than fine-grained sediments.

Organic geochemistry of ODP Hole 162-985A sediments

Dark, organic-rich sediments were recovered from the lower Miocene section (~16.6 Ma) in Hole 985A in the Norway Basin during Ocean Drilling Program Leg 162. Organic carbon and total sulfur contents of the dark sediments showed a maximum concentration of 5.6 and 26.1 wt%, respectively. Sulfur enrichment in the sediments indicates that these dark layers were formed under anoxic conditions in bottom water. Four dark and eight greenish gray sediment samples, ranging in age from early Miocene to Pleistocene, were analyzed for lipid-class compounds (aliphatic hydrocarbons, fatty alcohols, and sterols) using gas chromatography (GC) and GC/mass spectrometry to better understand the formation processes of the organic-rich dark layers and to reconstruct the paleoenvironmental changes. The molecular distributions of n-alkanes and fatty alcohols indicate that terrigenous organic matter largely contributed to both types of sediments. Significant amounts of hopanoid hydrocarbons, such as diploptene and hop-17(21)-ene, however, were detected characteristically in the dark sediments, which suggests that prokaryotes such as methane-oxidizing bacteria or cyanobacteria may have significantly contributed to the formation of these organic-rich, dark sediments. These results indicate that the bottom waters of the Norway Basin had been subjected to anoxic conditions during the early Miocene.