Spontaneous generation, the origin of life, and self assembly.
Self assembly relation to origin of life and spontaneous generation applied to precellular polymers, biopolymers and cellular structures
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Self assembly relation to origin of life and spontaneous generation applied to precellular polymers, biopolymers and cellular structures
Designs of single-end-operative reconfigurable genderless connectors that include a base, a plurality of movable jaws that are formed on the base and can engage to the jaws of another connector, and an actuator that is mounted on the base and can engage and move the jaws of the reconfigurable connector to connect the reconfigurable connector with another connector.
A self-assembling structure using non-equilibrium driving forces leading to 'living crystals' and other maniputable particles with a complex dynamics. The dynamic self-assembly assembly results from a competition between self-propulsion of particles and an attractive interaction between the particles. As a result of non-equilibrium driving forces, the crystals form, grow, collide, anneal, repair themselves and spontaneously self-destruct, thereby enabling reconfiguration and assembly to achieve a desired property.
Self assembled monolayers are commonly used to modify surfaces. Within the last 15 years, self assembled monolayers have been investigated as a way to protect from corrosion[1,2] or biofouling.[3] In this study, self assembled monolayers of decitriethoxysilane (C10H21Si(OC2H5)3) and octadecyltriethoxysilane (C18H37Si(OC2H5)3) were formed on aluminum 2024-T3. The modified surfaces and bare Al 2024 were characterized by dynamic water contact angle measurements, x-ray photoelectron spectroscopy (XIPS) and infrared spectroscopy. Electrochemical impedance spectroscopy (EIS) in 0.5 M NaCl was used to characterize the monolayers and evaluate their corrosion protection properties. The advancing water contact angle and infrared measurements show that the mono layers form a surface where the hydrocarbon chains are packed and oriented away from the surface, consistent with what is found in similar systems. The contact angle hysteresis measured in these systems is relatively large, perhaps indicating that the hydrocarbon chains are not as well packed as monolayers formed on other substrates. The results of the EIS measurements were modeled using a Randle's circuit modified by changing the capacitor to a constant phase element. The constant phase element values were found to characterize the monolayer. The capacitance of the monolayer modified surface starts lower than the bare Al 2024, but approaches values similar to the bare Al 2024 within 24 hours as the monolayer is degraded. The n values found for bare Al 2024 quickly approach the value of a true capacitor and are greater than 0.9 within hours after the start of exposure. For the monolayer modified structure, n can stay lower than 0.9 for a longer period of time. In fact, n for the monolayer modified surfaces is different from the bare surface even after the capacitance values have converged. This indicates that the deviation from ideal capacitance is the most sensitive indicator of the presence of the monolayer.
Conjugated polymer/silica nanocomposites with hexagonal, cubic, or lamellar mesoscopic order were synthesized by self-assembly 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. By tailoring the size of the oligo(ethylene glycol) headgroup of the diacetylene-containing surfactant, we varied the resulting self-assembled mesophases of the composite material. The nanostructured inorganic host altered the diacetylene polymerization behavior, and the resulting nanocomposites show unique thermo-, mechano-, and solvatochromic properties. Polymerization of the incorporated surfactants resulted in polydiacetylene (PDA)/silica nanocomposites that were optically transparent and mechanically robust. Molecular modeling and quantum calculations and (13)C spin-lattice relaxation times (T(1)) of the PDA/silica nanocomposites indicated that the surfactant monomers can be uniformly organized into precise spatial arrangements prior to polymerization. Nanoindentation and gas transport experiments showed that these nanocomposite films have increased hardness and reduced permeability as compared to pure PDA. Our work demonstrates polymerizable surfactant/silica self-assembly to be an efficient, general approach to the formation of nanostructured conjugated polymers. The nanostructured inorganic framework serves to protect, stabilize, and orient the polymer, mediate its performance, and provide sufficient mechanical and chemical stability to enable integration of conjugated polymers into devices and microsystems.
Self-assembled InAsSb quantum dots (QD) on (001) InP substrates have been grown using metalorganic vapor phase epitaxy. The dot density and size are found to be strongly dependent on the presence of arsine. Direct deposition of InSb on InP and GaSb substrates formed large islands of InSb with low density of less than 53109/cm², however, InAsSb QDs of density as high as 4 X10¹º/cm² could be self-assembled by alternating group III and group V precursors, and high density almost pure InSb QDs were achieved on In0.53Ga0.47As/InP. The formation of high density InAsSb QDs is a result of a local nonequilibrium process and a reduction in mobility of In adatoms on the growth surface due to the presence of arsenic atoms, and in the case of high density almost pure InSb QDs on InGaAs/InP, the InAs interface layer is believed to be responsible. Photoluminescence shows that InSb QDs emit light at room temperature in the range of 1.7–2.2µm.
We present the charge transport and tunneling conductance of self assembled organic thiol molecules and discuss the influence of order and dynamics in the monolayer on the transport behavior and the effect of temperature. Conjugated thiol molecular wires and organometals such as terpyridine metal complexes provide a new platform for molecular electronic devices and we study their self assembly on Au(111) substrates by the scanning tunneling microscope. Determining the organization of the molecule and the ability to control the nature of its interface with the substrate is important for reliable performance of the molecular electronic devices. By concurrent scanning tunneling microscopy and spectroscopy studies on SAMs formed from oligo (phenelyne ethynelyne) monolayers with and without molecular order, we show that packing and order determine the response of a self assembled monolayer (SAM) to competing interactions. Molecular resolution STM imaging in vacuum shows that the OPES adopt an imcommensurate SAM structure on Au(111) with a rectangular unit cell. Tunneling spectroscopic measurements were performed on the SAM as a function of junction resistance. STS results show that the I-Vs are non linear and asymmetric due to the inherent asymmetry in the molecular structure, with larger currents at negative sample biases. The asymmetry increases with increasing junction resistance due to the asymmetry in the coupling to the leads. This is brought out clearly in the differential conductance, which also shows a gap at the Fermi level. We also studied the effect of order and dynamics in the monolayer on the charge transport and found that competing forces between the electric field, intermolecular interactions, tip-molecule physisorption and substrate-molecule chemisorption impact the transport measurements and its reliability and that the presence of molecular order is very important for reproducible transport measurements. Thus while developing new electronic platforms based on molecules, it is important to have a good control of the molecule-substrate interface, for the devices to perform reliably. While such a control would minimize fluctuations and dynamics in the ensemble, the real challenge is to develop device architectures that are tolerant to fluctuations, since they cannot be totally eliminated in these low dimensional soft systems. Results of temperature dependent STS measurements will also be discussed.
Self-assembling biomolecules that form highly ordered structures have attracted interest as potential alternatives to conventional lithographic processes for patterning materials. Here we introduce a general technique for patterning materials on the nanoscale using genetically modified protein cage structures called chaperonins that self-assemble into crystalline templates. Constrained chemical synthesis of transition metal nanoparticles is specific to templates genetically functionalized with poly-Histidine sequences. These arrays of materials are ordered by the nanoscale structure of the crystallized protein. This system may be easily adapted to pattern a variety of materials given the rapidly growing list of peptide sequences selected by screening for specificity for inorganic materials.
Electron spin dephasing and decoherence by its interaction with nuclear spins in self-assembled quantum dots are investigated in the framework of the empirical tight-binding model. Electron spin dephasing in an ensemble of dots is induced by the inhomogeneous precession frequencies of the electron among dots, while electron spin decoherence in a single dot arises from the inhomogeneous precession frequencies of nuclear spins in the dot. For In(x)Ga(1-x) As self-assembled dots containing ~30000 nuclei, the dephasing and decoherence times are predicted to be on the order of 100 ps and 1 (micro)s.
A central event in the origin of life was the self-assembly of amphiphilic, lipid-like compounds into closed microenvironments. If a primitive macromolecular replicating system could be encapsulated within a vesicular membrane, the components of the system would share the same microenvironment, and the result would be a step toward true cellular function. The goal of our research has been to determine what amphiphilic molecules might plausibly have been available on the early Earth to participate in the formation of such boundary structures. To this end, we have investigated primitive organic mixtures present in carbonaceous meteorites such as the Murchison meteorite, which contains 1-2 percent of its mass in the form of organic carbon compounds. It is likely that such compounds contributed to the inventory of organic carbon on the prebiotic earth, and were available to participate in chemical evolution leading to the emergence of the first cellular life forms. We found that Murchison components extracted into non-polar solvent systems are surface active, a clear indication of amphiphilic character. One acidic fraction self-assembles into vesicular membranes that provide permeability barriers to polar solutes. Other evidence indicates that the membranes are bimolecular layers similar to those formed by contemporary membrane lipids. We conclude that bilayer membrane formation by primitive amphiphiles on the early Earth is feasible. However, only a minor fraction of acidic amphiphiles assembles into bilayers, and the resulting membranes require narrowly defined conditions of pH and ionic composition to be stable. It seems unlikely, therefore, that meteoritic infall was a direct source of membrane amphiphiles. Instead, the hydrocarbon components and their derivatives more probably would provide an organic stock available for chemical evolution. Our current research is directed at possible reactions which would generate substantial quantities of membranogenic amphiphiles. One possibility is photochemical oxidation of hydrocarbons.
Organic films self-assembled from a liquid phase, as in Langmuir-Blodgett or adsorption from solution, have received much attention in the past decade as techniques to achieve highly oriented-ordered polymeric thin films. Many organic compounds including some of the same fatty acids have been vapor deposited as well. However, organic pigments and dyes comprise a major class of important materials which have very low solubilities yet excellent thermal stabilities, making them ideally suited for film deposition from the vapor phase. Surprisingly, such molecular systems exhibit a significant propensity to self order, a high sensitivity to deposition parameters, and a range of microstructural forms that cannot be duplicated by the less energetic mechanisms associated with solution adsorption processes. Molecular solids such as heterocyclic polynuclear aromatics are excellent candidates for film formation by vacuum deposition means. Over the past decade, our work and that of others investigating a wide variety of perylene and phthalocyanine derivatives identified five deposition parameters that can significantly affect film morphology, physical microstructure, and type and extent of ordering developed in vacuum and vapor transport grown films. These parameters are substrate temperature, deposition rate, substrate chemistry and epitaxy, ambient gas convective flows, and post deposition annealing. Examples of how each of these conditions manifest themselves in the film structure and ordering, most frequently revealed by scanning electron microscopy, reflection absorption infrared spectroscopy (RAIR), and grazing incidence x-ray diffraction (GIX), are presented.
Origin of life in terms of polymers synthesis under thermodynamic and geological conditions
Interest in ordered porous structures has grown because of there unique properties such as photonic bandgaps, high backing packing density and high surface to volume ratio. Inspired by nature, biometric strategies using self assembled organic molecules dominate the development of hierarchical inorganic structures. Directional solidification of eutectics (DSE) also exhibit self assembly characteristics to form hierarchical metallic and inorganic structures. Crystallization of diphasic materials by DSE can produce two dimensional ordered structures consisting of rods or lamella. By selective removal of phases, DSE is capable to fabricate ordered pore arrays or ordered pin arrays. Criteria and limitations to fabricate hierarchical structures will be presented. Porous structures in silicon base alloys and ceramic systems will be reported.
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.
Formation of ordered polypeptide sequences in thermal protenoid microspheres
In this work, we demonstrate a realistic modeling of the electronic structure for InAs self-assembled quantum dots and investigate the magneto-optical response, i.e., Zeeman splitting and transition rates between electron and hole levels.
The Phase I study included a detailed exploration of a specific mission concept based on this architecture - a 31-meter diameter version of the LUVOIR (Large Ultraviolet Optical Infrared Surveyor) mission concept with the same wavelength coverage and wave-front quality requirements. The study focused on establishing the feasibility of the proposed concept with respect to what were identified as the most challenging aspects of the mission: the ability to find orbital solutions using solar sail propulsion for both the initial transfers and subsequent rendezvous trajectories; and the ability to generate the required final primary mirror surface out of uniformly polished individual module mirrors using deformation via mechanical degrees of freedom. As a result of the Phase I work it was shown that both orbital and optical solutions are feasible, but will require technology advancement in multiple key areas. In particular, improvements to solar sail areal densities and loading factors will allow us to more easily find fully general solutions for the transfer trajectories, while lower mass, ultra-precise cryogenic linear actuators will likely be needed to form the final mirror shape. However, it was found that current state of the art in solar sails was sufficient for rendezvous trajectories once on-orbit, that the requisite wave-front quality could be achieved with actuation requirements not more stringent than those being carried by LUVOIR, and that there exists a well-defined design space in which the module spacecraft designs can be optimized. The technology development required to progress this work overlaps significantly with numerous NASA technology roadmaps, as well as the Exoplanet Exploration Program's technologies gap list, meaning that continued development of this concept would directly benefit a variety of NASA programs, as well as enabling the completely unique capabilities provided by a 31-meter optical space telescope...Our architecture requires only a single module type allowing us to directly leverage the cost and efficiency benefits of true mass production, in direct contrast to previously explored self-assembling swarm concepts, which typically include multiple module types.
In this innovation, light weight, high temperature, compact aerospace structures with increased design options are made possible by using self-assembling, flexible, pre-ceramic composite materials. These materials are comprised of either ceramic or carbon fiber performs, which are infiltrated with polymer precursors that convert to ceramics upon thermal exposure. The preform architecture can vary from chopped fibers formed into blankets or felt, to continuous fibers formed into a variety of 2D or 3D weaves or braids. The matrix material can also vary considerably. For demonstration purposes, a 2D carbon weave was infiltrated with a SiC polymer precursor. The green or unfired material is fabricated into its final shape while it is still pliable. It is then folded or rolled into a much more compact shape, which will occupy a smaller space. With this approach, the part remains as one continuous piece, rather than being fabricated as multiple sections, which would require numerous seals for eventual component use. The infiltrated preform can then be deployed in-situ. The component can be assembled into its final shape by taking advantage of the elasticity of the material, which permits the structure to unfold and spring into its final form under its own stored energy. The pre-ceramic composites are converted to ceramics and rigidized immediately after deployment. The final ceramic composite yields a high-temperature, high-strength material suitable for a variety of aerospace structures. The flexibility of the material, combined with its high-temperature structural capacity after rigidization, leads to a less complex component design with an increased temperature range. The collapsibility of these structures allows for larger components to be designed and used, and also offers the potential for increased vehicle performance. For the case of collapsible nozzle extensions, a larger nozzle, and thus a larger nozzle exit plane, is possible because interference with surrounding structures can be avoided in the collapsed state. The larger exit plane leads to an increase in expansion area ratio, which has the potential to increase thrust and overall rocket performance. In general, the use of advanced ceramic materials can lead to improved engine and vehicle performance. The ceramics can run hotter, so less cooling is required. Fuel to coolant ratios can be balanced more readily to reduce weight. Engine efficiency can also be increased with hotter combustion and exhaust temperatures. In addition, the ceramic composites themselves can reduce the component weight by as much as 50 percent, which can translate into greater payload for the vehicle