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50 records · Page 3

Self-assembly of mesoscopically ordered chromatic polydiacetylene/silica nanocomposites

Nature abounds with intricate composite architectures composed of hard and soft materials synergistically intertwined to provide both useful functionality and mechanical integrity. Recent synthetic efforts to mimic such natural designs have focused on nanocomposites, prepared mainly by slow procedures like monomer or polymer infiltration of inorganic nanostructures or sequential deposition. Here we report the self-assembly of conjugated polymer/silica nanocomposite films with hexagonal, cubic or lamellar mesoscopic order using polymerizable amphiphilic diacetylene molecules as both structure-directing agents and monomers. The self-assembly procedure is rapid and incorporates the organic monomers uniformly within a highly ordered, inorganic environment. Polymerization results in polydiacetylene/silica nanocomposites that are optically transparent and mechanically robust. Compared to ordered diacetylene-containing films prepared as Langmuir monolayers or by Langmuir-Blodgett deposition, the nanostructured inorganic host alters the diacetylene polymerization behaviour, and the resulting nanocomposite exhibits unusual chromatic changes in response to thermal, mechanical and chemical stimuli. The inorganic framework serves to protect, stabilize, and orient the polymer, and to mediate its function. The nanocomposite architecture also provides sufficient mechanical integrity to enable integration into devices and microsystems.

NASA Discipline Life Support Systems↗

Molecular and biochemical evidence for the involvement of calcium/calmodulin in auxin action

The use of (35)S-labeled calmodulin (CaM) to screen a corn root cDNA expression library has led to the isolation of a CaM-binding protein, encoded by a cDNA with sequence similarity to small auxin up RNAs (SAURs), a class of early auxin-responsive genes. The cDNA designated as ZmSAUR1 (Zea mays SAURs) was expressed in Escherichia coli, and the recombinant protein was purified by CaM affinity chromatography. The CaM binding assay revealed that the recombinant protein binds to CaM in a calcium-dependent manner. Deletion analysis revealed that the CaM binding site was located at the NH(2)-terminal domain. A synthetic peptide of amino acids 20-45, corresponding to the potential CaM binding region, was used for calcium-dependent mobility shift assays. The synthetic peptide formed a stable complex with CaM only in the presence of calcium. The CaM affinity assay indicated that ZmSAUR1 binds to CaM with high affinity (K(d) approximately 15 nM) in a calcium-dependent manner. Comparison of the NH(2)-terminal portions of all of the characterized SAURs revealed that they all contain a stretch of the basic alpha-amphiphilic helix similar to the CaM binding region of ZmSAUR1. CaM binds to the two synthetic peptides from the NH(2)-terminal regions of Arabidopsis SAUR-AC1 and soybean 10A5, suggesting that this is a general phenomenon for all SAURs. Northern analysis was carried out using the total RNA isolated from auxin-treated corn coleoptile segments. ZmSAUR1 gene expression began within 10 min, increased rapidly between 10 and 60 min, and peaked around 60 min after 10 microM alpha-naphthaleneacetic acid treatment. These results indicate that ZmSAUR1 is an early auxin-responsive gene. The CaM antagonist N-(6-aminohexyl)5-chloro-1-naphthalenesulfonamide hydrochloride inhibited the auxin-induced cell elongation but not the auxin-induced expression of ZmSAUR1. This suggests that calcium/CaM do not regulate ZmSAUR1 at the transcriptional level. CaM binding to ZmSAUR1 in a calcium-dependent manner suggests that calcium/CaM regulate ZmSAUR1 at the post-translational level. Our data provide the first direct evidence for the involvement of calcium/CaM-mediated signaling in auxin-mediated signal transduction.

NASA Program Fundamental Space Biology↗

Pre-biotic stage of life origin under non-photosynthetic conditions

Spontaneous assembling of a simplest bacterial cell even if all necessary molecules are present in a solution seems to be extremely rare event and from the scientific standpoint has to be considered as impossible. Therefore, a predecessor of a living cell has to be very simple for providing its self-assembling and at the same time it should be able of progressive increase in complexity. Now phase-separated particles, first of all micelles, are put forward as possible predecessors of living cell. According to the offered working concept only phase-separated particles possessing autocatalytic properties can be considered as predecessors of living cells. The first stage of evolution of these phase-separated autocatalytic systems is the appearance of pre-biotic metabolism providing synthesis of amphiphiles for formation of capsules of these systems. This synthesis is maintained by the energy of a base reaction being a component of a planet-chemical cycle. Catalytic system providing functioning of pre-biotic metabolism is based on multivariate oligomeric autocatalyst, which reproduces itself from monomers, penetrating the particles from the outside. Since the autocatalyst realizes random polymerization then a collection of other oligomers possessing different catalytic functions is produced. In the paper the functioning of multivariate oligomeric autocatalyst in flow reactor is analyzed. c2005 Published by Elsevier Ltd on behalf of COSPAR.

Biogenesis↗

Hydrophobic effect at aqueous interfaces

Conceptual basis for hydrophobic effects in bulk water and at aqueous interfaces have similar conceptual basis but often manifests itself differently. Using a wide range of computer simulations as the basis, I will review different forms of hydrophobic effects at a variety of interfaces starting from simple liquid-vapor and water-oil interfaces and progressing to water-membrane interfaces. I will start with discussing how water is organized at different interfaces, stressing both similarities and differences. The main thread is that, as in the bulk liquid, hydrophobic effects have profound influence on conformational equilibria and organization of both small molecules and macromolecules, but the result of this influence is quite different. Specifically, it will be shown that many small, but not necessarily amphiphilic molecules tend to accumulate at the interface and, and this tendency will be explained. Furthermore, I will show that many short peptides that are disordered in water spontaneously fold into well-defined structures in the interfacial environment. Biological implications of this self-organizing effect will be discussed.

Pohorille, Andrew↗

Ice photochemistry as a source of amino acids and other organic molecules in meteorites, and implications for the origin of life and the search for life in the Solar System

The tons of extraterrestrial organic material that come to the Earth every day probably helped to made the Earth habitable, and possibly played a role in the origin of life. At the astrochemistry lab (http://www.astrochem.orq) we investigate the formation and distribution of organic molecules in space and consider the impact such molecules may have on the habitability of planets and the search for life in the Solar System. The organic compounds in meteorites include amino acids, aromatics of various sorts including purine and pyrimidine bases, and fatty acids that form bi-layer vesicles. The origin of many of these species remains mysterious, but in recent years we and others have performed experiments that suggest low temperature radiation chemistry could account for the presence and deuterium enrichment of many of these molecules. . I will present our laboratory experiments that show the viability of low temperature radiation chemistry as a source of organic molecules such as;amino acids (Nature, 2002, 416, 401-403), amphiphiles (Astrobiology, 2003, 2, 371, Proc. Nat. Acad. Sci. 2001, 98, 815), quinones (Science, 1999, 283, 1135) and other functionalized aromatic compounds (Meteoritics, 2001, 36, 351 ; Astrophysical Journal., 2003, 582, L25), some of which were invoked as potential biomarkers in the Alan Hills 84001 Martian meteorite. Understanding how components of proteins and DNA could form in sterile space environments is also of relevance to our search for life elsewhere in the Solar System, the great task now ahead of NASA. If we find evidence of Life elsewhere in the Solar System it will probably be in form of chemical biomarkers, quintessentially biological molecules that indicate the presence of micro-organisms. While most people think of molecules such as amino acids, and nucleo-bases as good candidate biomarkers, these molecules are produced non-biotically in space and are expected to be present on the surface of other planets even in the absence of Life. Understanding the range of non-biological organic molecules which could act as false biomarkers in space is a prerequisite for any reasonable search for Life on other worlds.

Bernstein, Max↗

Comparison of the Organic Composition of Cometary Samples with Residues Formed from the UV Irradiation of Astrophysical Ice Analogs

The NASA Stardust mission successfully collected material from Comet 81P/Wild 2 [1], including authentic cometary grains [2]. X-ray absorption near-edge structure (XANES) spectroscopy analysis of these samples indicates the presence of oxygen-rich and nitrogen-rich organic materials, which contain a broad variety of functional groups (carbonyls, C=C bonds, aliphatic chains, amines, arnides, etc.) [3]. One component of these organics appears to contain very little aromatic carbon and bears some similarity to the organic residues produced by the irradiation of ices of interstellar/cometary composition, Stardust samples were also recently shown to contain glycine, the smallest biological amino acid [4]. Organic residues produced froth the UV irradiation of astrophysical ice analogs are already known to contain a large suite of organic molecules including amino acids [5-7], amphiphilic compounds (fatty acids) [8], and other complex species. This work presents a comparison between XANES spectra measured from organic residues formed in the laboratory with similar data of cometary samples collected by the Stardust mission

Milam, S. N.↗

Amplifying Electrochemical Indicators

Dendrimeric reporter compounds have been invented for use in sensing and amplifying electrochemical signals from molecular recognition events that involve many chemical and biological entities. These reporter compounds can be formulated to target specific molecules or molecular recognition events. They can also be formulated to be, variously, hydrophilic or amphiphilic so that they are suitable for use at interfaces between (1) aqueous solutions and (2) electrodes connected to external signal-processing electronic circuits. The invention of these reporter compounds is expected to enable the development of highly miniaturized, low-power-consumption, relatively inexpensive, mass-producible sensor units for diverse applications.

Fan, Wenhong↗

XANES Analysis of Organic Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

Organic residues formed in the laboratory from the ultraviolet (UV) photo-irradiation or ion bombardment of astrophysical ice analogs have been extensively studied for the last 15 years with a broad suite of techniques, including infrared (IR) and UV spectroscopies, as well as mass spectrometry. Analyses of these materials show that they consist of complex mixtures of organic compounds stable at room temperature, mostly soluble, that have not been fully characterized. However, the hydrolysis products of these residues have been partly identified using chromatography techniques, which indicate that they contain molecular precursors of prebiotic interest such as amino acids, nitrile-bearing compounds, and amphiphilic compounds. In this study, we present the first X-ray absorption near-edge structure (XANES) spectroscopy measurements of three organic residues made from the UV irradiation of ices having different starting compositions. XANES spectra confirm the presence of different chemical functions in these residues, and indicate that they are rich in nitrogenand oxygen-bearing species. These data can be compared with XANES measurements of extraterrestrial materials. Finally, this study also shows how soft X rays can alter the chemical composition of samples.

XANES(X-RAY ABSORPTION NEAR-EDGE STRUCTURE)↗

The Formation of Organic Compounds of Astrobiological Interest by the Irradiation Processing of Astrophysical Ices

Many environments in space contain very low temperature mixed molecular ices that are exposed to ionizing radiation in the form of cosmic rays and high-energy photons. While traditional chemistry would not be expected to occur at the temperatures typical of these ices (T < 50 K), ionizing radiation can break bonds in the original molecules in the ices to form highly reactive ions and radicals. These ions and radicals are subsequently free to react despite the low temperatures of the original ices. Laboratory experiments, many of them carried out at the Astrochemistry Laboratory at NASA-Ames, show that the irradiation of ices made of even simple molecules like H2O, CO, CO2, CH4, NH3, etc. can result in the robust formation of large numbers of far more complex organic compounds. Many of these new products are of direct interest to astrobiology. For example, the irradiation of mixed molecular ices has been shown to produce amino acids, amphiphiles, quinones, sugars, heterocyclic compounds, and nucleobases, all molecular building blocks used by terrestrial life. Insofar as the presence of these materials plays a role in the origin of life on planets, this has profound implications for the potential abundance of life in the universe since these experiments simulate universal conditions that are expected to be found wherever new stars and planets form.

Astrobiology↗

Ice Chemistry in Interstellar Dense Molecular Clouds, Protostellar Disks, and Comets

Despite the low temperatures (T less than 20K), low pressures, and low molecular densities found in much of the cosmos, considerable chemistry is expected to occur in many astronomical environments. Much of this chemistry happens in icy grain mantles on dust grains and is driven by ionizing radiation. This ionizing radiation breaks chemical bonds of molecules in the ices and creates a host of ions and radicals that can react at the ambient temperature or when the parent ice is subsequently warmed. Experiments that similar these conditions have demonstrated a rich chemistry associated with these environments that leads to a wide variety of organic products. Many of these products are of considerable interest to astrobiology. For example, the irradiation of simple ices has been shown to abiotically produce amino acids, nucleobases, quinones, and amphiphiles, all compounds that play key roles in modern biochemistry. This suggests extraterrestrial chemistry could have played a role in the origin of life on Earth and, by extension, do so on planets in other stellar systems.

Ice Irradiation↗

The Role of Extraterrestrial Materials in the Origin of Life

It has been well established for some time now that C-rich organic materials are relatively common in a number of environments in space. This is known through the telescopic detection of these materials using spectroscopy techniques in the infrared and sub-millimeter wavelength ranges and through the identification of organics in extraterrestrial materials. Extraterrestrial materials in which organics have been found include collected meteorites and interplanetary dust particles, and samples returned by NASA spacecraft from comets. These organics are produced by a variety of astrochemical processes. Despite their abiotic origins, these organic materials of are considerable interest to astrobiology for several reasons. First, organic materials of any composition are important as a means of delivering the elements C, H, O, and N to the surfaces of newly formed planets, and these elements are likely critical to the origin and subsequent evolution of life (certainly for life as we know it). In addition, it is clear that at least a portion of the organics found in space are in the form of molecules that play important roles in modern biology - for example, molecules like amino acids, amphiphiles, quinones, etc. Thus, the delivery of extraterrestrial organics to planetary surfaces brings not only bulk C, H, O, and N, but also molecular complexity in forms that are potentially useful for the origin and early evolution of life. This suggests that the production and delivery of cosmic organic compounds may have played key roles in the origin of life on Earth and, by extension, on other planets in the universe.

Astrochemistry↗

Search for Sugars and Related Compounds in Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

A large variety of organics of biological and prebiotic interests have been detected in meteorites, including one sugar and several sugar acids and sugar alcohols [1]. The presence of these compounds in meteorites, along with amino acids, amphiphiles, and nucleobases [2-4], indicates that molecules essential to life can be formed abiotically under astrophysical conditions. This hypothesis is supported by extensive laboratory studies involving the formation of complex organic molecules from the ultraviolet (UV) irradiation of astrophysical ice analogs (H2O, CO, CO2, CH3OH, CH4, NH3, etc.). These studies show that the organic residues recovered at room temperature contain many of the same compounds as those found in meteorites[3,58]. However, to the best of our knowledge, no systematic search for the presence of sugars and sugar derivatives in such laboratory residues have been reported to date. Only a limited number of small (greater than 4 C atoms) sugar-related compounds such as glycerol and glyceric acid [9], and more recently small (2-4 C atoms) aldehydes [10] have been detected in residues.

Astrophysics↗

Detailed Study of the Formation of Sugar Derivatives Produced from the UV Irradiation of Astrophysical Ice Analogs

Carbonaceous meteorites such as Murchison contain a large variety of organic compounds of astrobiological interest such as amino acids, other amphiphilic compounds, functionalized nitrogen heterocycles (including nucleobases), functionalized polycylic aromatic hydro-carbons (including quinones), and sugar derivatives. The presence of such a broad variety of organics in meteorites strongly suggests that molecules essential to life can form abiotically under astrophysical conditions. This hypothesis is strongly supported by laboratory studies in which astrophysical ice analogs (i.e., mixtures of H2O, CO, CO2, CH3OH, CH4, NH3, etc.) are subjected to ultraviolet (UV) irradiation at low temperature (less than 15 K) to simulate cold interstellar environments. These studies have shown that the organic residues recovered at room temperature after irradiation contain organic compounds that are very similar to those found in meteorites. No systematic search for the presence of sugar derivatives in laboratory residues had been carried out until the recent detection of ribose, the sugar of RNA, as well as other sugars, sugar alcohols, and sugar acids in one residue produced from the UV irradiation of an ice mixture containing H2O, CH3OH, and NH3 at 80 K. In this work, we present a detailed study of the formation of sugar derivatives contained in organic residues that are produced from the UV irradiation of ice mixtures of different starting compositions (H2O, CH3OH, CO, CO2, and/or NH3) at less than 15 K. While the presence of sugar alcohols, sugars, and sugar acids-in some cases with up to 6 carbon atoms-could be confirmed in all these residues, their distribution was shown to vary with the composition of the starting ices. In particular, only a few ices result in the formation of sugar derivatives displaying a distribution that resembles that of meteorites, in which sugar alcohols and sugar acids are very abundant while sugars are mostly absent.

Photochemistry↗

Emergence of Simple Ion Channels by Self-Assembly of Short Peptides

As protocells transitioned from structures bound by membranes made of simple amphiphiles, such as fatty acids, to structures containing phospholipid membranes, they became nearly impermeable to charged species. Yet, the ability to transport ions across membranes was vital to regulating cellular volume, pH homeostasis, generating energy and sensing the environment. For this reason, life evolved ion channels, protein structures surrounding water-filled pores in the membrane that facilitated ion transport. In contemporary cells, ion channels are complex protein assemblies. Could the same function be carried out, even if less efficiently and selectively, by much simpler peptides at the origins of life? To answer this question, we turned to trichogen (GAIV), an 11-residue peptide that was found to permeabilize membrane, causing leakage of the vesicle content including ions. Since GAIV is synthesized non-gnomically, it represents as excellent model for the earliest, poorly optimized channels. Understanding the mechanism by which short peptides, such as GAIV, mediate ion transport across membranes provides crucial information on the emergence, structure and the mechanism of action of the earliest ion channels. In this study, we used extensive molecular dynamics (MD) simulations to investigate directly spontaneous assembly of GAIV peptide and its structural dynamics, the formation of an induced water pore across the membrane and consequently ion conduction through the membrane.

Wei, Chenyu↗