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At least 523 records · Page 29

Electronic structures and magnetic/optical properties of metal phthalocyanine complexes

Electronic structures and magnetic / optical properties of metal phthalocyanine complexes were studied by quantum calculations using density functional theory. Effects of central metal and expansion of π orbital on aromatic ring as conjugation system on the electronic structures, magnetic, optical properties and vibration modes of infrared and Raman spectra of metal phthalocyanines were investigated. Electron and charge density distribution and energy levels near frontier orbital and excited states were influenced by the deformed structures varied with central metal and charge. The magnetic parameters of chemical shifts in {sup 13}C-nuclear magnetic resonance ({sup 13}C-NMR), principle g-tensor, A-tensor, V-tensor of electric field gradient and asymmetry parameters derived from the deformed structures with magnetic interaction of nuclear quadruple interaction based on electron and charge density distribution with a bias of charge near ligand under crystal field.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Structural and chemical complexity of minerals: An update

The complexities of chemical composition and crystal structure are fundamental characteristics of minerals that have high relevance to the understanding of their stability, occurrence and evolution. This review summarises recent developments in the field of mineral complexity and outlines possible directions for its future elaboration. The database of structural and chemical complexity parameters of minerals is updated by H-correction of structures with unknown H positions and the inclusion of new data. The revised average complexity values (arithmetic means) for all minerals are 3.54(2) bits/atom and 345(10) bits/cell (based upon 4443 structure reports). The distributions of atomic information amounts, chemIG and strIG, versus the number of mineral species fit the normal modes, whereas the distributions of total complexities, chemIG,total and strIG,total, along with numbers of atoms per formula and per unit cell are log normal. The three most complex mineral species known today are ewingite, morrisonite and ilmajokite, all either discovered or structurally characterised within the last five years. The most important complexity-generating mechanisms in minerals are: (1) the presence of isolated large clusters; (2) the presence of large clusters linked together to form three-dimensional frameworks; (3) formation of complex three-dimensional modular frameworks; (4) formation of complex modular layers; (5) high hydration state in salts with complex heteropolyhedral units; and (6) formation of ordered superstructures of relatively simple structure types. The relations between symmetry and complexity are considered. The analysis of temporal dynamics of mineralogical discoveries since 1875 with the step of 25 years show the increasing chemical and structural complexities of human knowledge of the mineral kingdom in the history of mineralogy. In the Earth’s history, both diversity and complexity of minerals experience dramatic increases associated with the formation of Earth’s continental crust, initiation of plate tectonics and the Great Oxidation event.

complexity↗

Structural insights into the unique recognition module between α-synuclein peptide and nanobody

Nanobodies are single-domain fragments of antibodies with comparable specificity and affinity to antibodies. They are emerging as versatile tools in biology due to their relatively small size. Here, we report the crystal structure of a specific nanobody Nbα-syn01, bound to a 14 amino acid long peptide of α-synuclein (αSyn), a 140-residue protein whose aggregation is associated with Parkinson's disease. The complex structure exhibits a unique binding pattern where the αSyn peptide replaces the N-terminal region of nanobody. Recognition is mediated principally by extended main chain interaction of the αSyn peptide and specificity of the interaction lies in the central 48–52 region of αSyn peptide. Structure-guided truncation of Nbα-syn01 shows tighter binding to αSyn peptide and improved inhibition of α-synuclein aggregation. The structure of the truncated complex was subsequently determined and was indistinguishable to full length complex as the full-length form had no visible electron density for the N-terminal end. These findings reveal the molecular basis for a previously unobserved binding mode for nanobody recognition of α-synuclein, providing an explanation for the enhanced binding, and potential for an alternate framework for structure-based protein engineering of nanobodies to develop better diagnostic and therapeutic tools.

59 BASIC BIOLOGICAL SCIENCES↗

Paddlewheelite, a New Uranyl Carbonate from the Jáchymov District, Bohemia, Czech Republic

Paddlewheelite, MgCa 5 Cu 2 [(UO 2 )(CO 3 ) 3 ] 4 ·33H 2 O, is a new uranyl carbonate mineral found underground in the Svornost mine, Jáchymov District, Bohemia, Czech Republic, where it occurs as a secondary oxidation product of uraninite. The conditions leading to its crystallization are complex, likely requiring concomitant dissolution of uraninite, calcite, dolomite, chalcopyrite, and andersonite. Paddlewheelite is named after its distinctive structure, which consists of paddle-wheel clusters of uranyl tricarbonate units bound by square pyramidal copper “axles” and a cubic calcium cation “gearbox.” Paddle wheels share edges with calcium polyhedra to form open sheets that are held together solely by hydrogen bonding interactions. The new mineral is monoclinic, Pc, a = 22.052(4), b = 17.118(3), c = 19.354(3) Å, β = 90.474(2)°, V = 7306(2) Å 3 and Z = 4. Paddlewheelite is the second-most structurally complex uranyl carbonate mineral known after ewingite and its structure may provide insights into the insufficiently described mineral voglite, as well as Cu–U–CO 3 equilibrium in general.

58 GEOSCIENCES↗

Computer program for determining mass properties of a rigid structure

A computer program was developed for the rapid computation of the mass properties of complex structural systems. The program uses rigid body analyses and permits differences in structural material throughout the total system. It is based on the premise that complex systems can be adequately described by a combination of basic elemental shapes. Simple geometric data describing size and location of each element and the respective material density or weight of each element were the only required input data. From this minimum input, the program yields system weight, center of gravity, moments of inertia and products of inertia with respect to mutually perpendicular axes through the system center of gravity. The program also yields mass properties of the individual shapes relative to component axes.

Hull, R. A.↗

Revealing excitonic structure and charge transfer in photosynthetic proteins by time-resolved circular dichroism spectroscopy

The author has designed and built a time-resolved circular dichroism (CD) spectrometer with previously unmatched sensitivity making for the first time this technique suitable to studies of energy transfer and structure of photosynthetic light-harvesting and charge transfer complexes. The nanosecond version of the new CD spectrometer was successfully applied to studies of the Fenna Matthews Olson pigment-protein complex showing a number of features incompatible with currently proposed Hamiltonians and providing a wealth in information for refining our current understanding of this complex structure and dynamics. The work on femtosecond variant of ultra sensitive CD spectrometer was initiated and demonstrated its capability to resolve CD differences in the order of 10 -8 , which is 2-3 orders of magnitude better than previously proposed spectrometers.

59 BASIC BIOLOGICAL SCIENCES↗

Unraveling the Origin of Structural Disorder in High Temperature Transition Al2O3: Structure of θ-Al2O3

The crystallography of transition Al2O3 has been extensively studied in the past due to the advantageous properties of the oxide in catalytic and a range of other technological applications. However, existing crystallographic models are insufficient to describe the structure of many important Al2O3 polymorphs due to their highly disordered nature. In this work, we investigate structure and disorder in high-temperature treated transition Al2O3, and provide a structural description for θ-Al2O3 by using a suite of complementary imaging, spectroscopy and quantum calculation techniques. Contrary to current understanding, our high-resolution imaging shows that θ-Al2O3 is a disordered composite phase of at least two different end members. By correlating imaging and spectroscopy results with DFT calculations, we propose a model that describes θ-Al2O3 as a disordered intergrowth of two crystallographic variants at the unit cell level. One variant is based on β-Ga2O3, and the other on a monoclinic phase that is closely-related to δ-Al2O3. The overall findings and interpretations afford new insight into the origin of poor crystallinity in transition Al2O3, and also provide new perspectives on structural complexity that can emerge from intergrowth of closely related structural polymorphs.

Environmental Molecular Sciences Laboratory↗

Ultrasonic guided waves in eccentric annular pipes

This paper studies the feasibility of using ultrasonic guided waves to rapidly inspect tubes and pipes for possible eccentricity. While guided waves are well established in the long range inspection of structures such as pipes and plates, studies for more complex cross sections are limited and analytical solutions are often difficult to obtain. Recent developments have made the Semi Analytical Finite Element (SAFE) method widely accessible for researchers to study guided wave properties in complex structures. Here the SAFE method is used to study the effect of eccentricity on the modal structures and velocities of lower order guided wave modes in thin pipes of diameters typically of interest to the industry. Results are validated using experiments. The paper demonstrates that even a small eccentricity in the pipe can strongly affect guided wave mode structures and velocities and hence shows potential for pipe eccentricity inspection.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

ALMA OBSERVATIONS OF A HIGH-DENSITY CORE IN TAURUS: DYNAMICAL GAS INTERACTION AT THE POSSIBLE SITE OF A MULTIPLE STAR FORMATION

Starless dense cores eventually collapse dynamically, forming protostars inside them, and the physical properties of the cores determine the nature of the forming protostars. We report ALMA observations of dust continuum emission and molecular rotational lines toward MC27 or L1521F, which is considered to be very close to the first protostellar core phase. We found a few starless high-density cores, one of which has a very high density of ∼10{sup 7} cm{sup –3}, within a region of several hundred AU around a very low-luminosity protostar detected by Spitzer. A very compact bipolar outflow with a dynamical timescale of a few hundred years was found toward the protostar. The molecular line observation shows several cores with an arc-like structure, possibly due to the dynamical gas interaction. These complex structures revealed in the present observations suggest that the initial condition of star formation is highly dynamical in nature, which is considered to be a key factor in understanding fundamental issues of star formation such as the formation of multiple stars and the origin of the initial mass function of stars.

79 ASTRONOMY AND ASTROPHYSICS↗

PACOSS program overview and status

Many future civilian and military large space structures (LSS) will have as performance objectives stringent pointing accuracies, short settling times, relatively fast response requirements, or combinations thereof. Many of these structures will be large, light weight, and will exhibit high structural modal density at low frequency and within the control bandwidth. Although it is possible in principle to achieve structural vibration control through purely active means, experience with complex structures has shown that the realities of plant model inaccuracies and sensor/actuator dynamics frequently combine to produce substandard performance. A more desirable approach is to apply passive damping technology to reduce the active control burden. Development of the technology to apply this strategy is the objective of the PACOSS (Passive and Active Control OF Space Structures) program. A key element in the PACOSS program is the Representative System Article (RSA). The RSA is a generic paper system that serves as a testbed for damping and controls studies. It also serves as a basis for design of the smaller Dynamic Test Article (DTA), a hardware testbed for the laboratory validation of analysis and design practices developed under PACOSS.

Rogers, L. C.↗

PACOSS program status and results

Future large space systems (LSS), both civilian and military, will have performance objectives which require stringent pointing accuracies, relatively fast retargeting times, short settling times, accurate dynamic shape requirements, or combinations thereof. Many of these structures will be large but lightweight and will exhibit a dense, low-frequency modal spectrum with significant content within the control bandwidth. Although it is possible in principle to achieve structural vibration control with purely active means, experience with complex structures has shown that the realities of plant model inaccuracies and real sensor and actuator dynamics frequently combine to produce disappointing results. It was shown that a combination of passive and active control will result in a simpler system which can be expected to be more reliable and less expensive than a corresponding system utilizing active control exclusively. The goals of the Passive and Active Control of Space Structures (PACOSS) program consist of a thorough investigation of the relative roles of passive active vibration control, and the development of validated means of vibration control. The program approach, representative system article, dynamic test article, and test status and results are outlined.

Richards, K. E., Jr.↗

Preliminary Work for Examining the Scalability of Reinforcement Learning

Researchers began studying automated agents that learn to perform multiple-step tasks early in the history of artificial intelligence (Samuel, 1963; Samuel, 1967; Waterman, 1970; Fikes, Hart & Nilsonn, 1972). Multiple-step tasks are tasks that can only be solved via a sequence of decisions, such as control problems, robotics problems, classic problem-solving, and game-playing. The objective of agents attempting to learn such tasks is to use the resources they have available in order to become more proficient at the tasks. In particular, each agent attempts to develop a good policy, a mapping from states to actions, that allows it to select actions that optimize a measure of its performance on the task; for example, reducing the number of steps necessary to complete the task successfully. Our study focuses on reinforcement learning, a set of learning techniques where the learner performs trial-and-error experiments in the task and adapts its policy based on the outcome of those experiments. Much of the work in reinforcement learning has focused on a particular, simple representation, where every problem state is represented explicitly in a table, and associated with each state are the actions that can be chosen in that state. A major advantage of this table lookup representation is that one can prove that certain reinforcement learning techniques will develop an optimal policy for the current task. The drawback is that the representation limits the application of reinforcement learning to multiple-step tasks with relatively small state-spaces. There has been a little theoretical work that proves that convergence to optimal solutions can be obtained when using generalization structures, but the structures are quite simple. The theory says little about complex structures, such as multi-layer, feedforward artificial neural networks (Rumelhart & McClelland, 1986), but empirical results indicate that the use of reinforcement learning with such structures is promising. These empirical results make no theoretical claims, nor compare the policies produced to optimal policies. A goal of our work is to be able to make the comparison between an optimal policy and one stored in an artificial neural network. A difficulty of performing such a study is finding a multiple-step task that is small enough that one can find an optimal policy using table lookup, yet large enough that, for practical purposes, an artificial neural network is really required. We have identified a limited form of the game OTHELLO as satisfying these requirements. The work we report here is in the very preliminary stages of research, but this paper provides background for the problem being studied and a description of our initial approach to examining the problem. In the remainder of this paper, we first describe reinforcement learning in more detail. Next, we present the game OTHELLO. Finally we argue that a restricted form of the game meets the requirements of our study, and describe our preliminary approach to finding an optimal solution to the problem.

Clouse, Jeff↗

Structures technology applications for the National AeroSpace Plane

The National AeroSpace Plane (NASP) presents a unique set of very complex structural problems that challenge our computational capabilities. Complex analyses are required in the conceptual design phase to achieve sufficient accuracy to address the extreme load conditions and to adequately evaluate vehicle weight. The computational capability must be available to perform these analyses in a rapid manner to accommodate the design process.

Little, T. E.↗

Three-dimensional geologic mapping to assess geothermal potential: examples from Nevada and Oregon

Geologic structure plays an important role in controlling fluid flow in geothermal systems. In particular, very complex structural settings, consisting of many closely spaced and intersecting faults, host many geothermal systems. To elucidate the key geologic factors that affect fault-controlled geothermal circulation, it is critical to precisely characterize the structural and stratigraphic geometries in these complex settings. Here, we present a methodology and the results of 3D geologic analyses of two geothermal systems in the Basin and Range, USA. This methodology is a quantitative and geologically focused technique that can be used to precisely characterize geothermal areas, in a time when future geothermal growth demands increased exploration precision and efficiency. Surficial and subsurface geologic and geophysical data are synthesized in the construction of detailed 3D geologic maps of geothermal areas. Based on these 3D geologic maps, we examine several geologic attributes that control permeability development and geothermal fluid flow along faults. We use the stress state of faults and the distribution of structural discontinuities (i.e., fault intersections and fault terminations) to identify locations of upflow along faults in these geothermal systems. These results and the methodology presented herein are directly applicable to structurally controlled geothermal fields in the Basin and Range and worldwide. As development focus shifts toward blind geothermal resources, integration of precisely characterized subsurface structural information into exploration methods will be increasingly critical to continued growth in geothermal exploration and development.

15 GEOTHERMAL ENERGY↗

Composite Development and Applications for RLV Tankage

The development of polymer composite cryogenic tanks is a critical step in creating the next generation of launch vehicles. Future launch vehicles need to minimize the gross liftoff weight (GLOW), which is possible due to the 28%-41% reduction in weight that composite materials can provide over current aluminum technology. The development of composite cryogenic tanks, feedlines, and unpressurized structures are key enabling technologies for performance and cost enhancements for Reusable Launch Vehicles (RLVs). The technology development of composite tanks has provided direct and applicable data for feedlines, unpressurized structures, material compatibility, and cryogenic fluid containment for highly loaded complex structures and interfaces. All three types of structure have similar material systems, processing parameters, scaling issues, analysis methodologies, NDE development, damage tolerance, and repair scenarios. Composite cryogenic tankage is the most complex of the 3 areas and provides the largest breakthrough in technology. A building block approach has been employed to bring this family of difficult technologies to maturity. This approach has built up composite materials, processes, design, analysis and test methods technology through a series of composite test programs beginning with the NASP program to meet aggressive performance goals for reusable launch vehicles. In this paper, the development and application of advanced composites for RLV use is described.

Wright, Richard J.↗

Novel complex MAD phasing and RNase H structural insights using selenium oligonucleotides

Selenium-derivatized oligonucleotides may facilitate phase determination and high-resolution structure determination for protein–nucleic acid crystallography. The Se atom-specific mutagenesis (SAM) strategy may also enhance the study of nuclease catalysis. The crystal structures of protein–nucleic acid complexes are commonly determined using selenium-derivatized proteins via MAD or SAD phasing. Here, the first protein–nucleic acid complex structure determined using selenium-derivatized nucleic acids is reported. The RNase H–RNA/DNA complex is used as an example to demonstrate the proof of principle. The high-resolution crystal structure indicates that this selenium replacement results in a local subtle unwinding of the RNA/DNA substrate duplex, thereby shifting the RNA scissile phosphate closer to the transition state of the enzyme-catalyzed reaction. It was also observed that the scissile phosphate forms a hydrogen bond to the water nucleophile and helps to position the water molecule in the structure. Consistently, it was discovered that the substitution of a single O atom by a Se atom in a guide DNA sequence can largely accelerate RNase H catalysis. These structural and catalytic studies shed new light on the guide-dependent RNA cleavage.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effects of the advanced organosolv pretreatment strategies on structural properties of woody biomass

Plants have evolved their lignocellulosic cell walls through complex structural and chemical mechanisms to protect itself against microbial attacks, which makes native lignocellulosic biomass recalcitrant to enzymatic deconstruction. Pretreatment is a crucial step in the biological conversion of biomass as it can render structural changes in the plant cell wall to reduce the biomass recalcitrance, thus enhancing its sugar release performance. There have been many efforts to develop effective pretreatment technologies to overcome the biomass recalcitrance with a primary focus on the efficient conversion of biomass carbohydrates to liquid fuels, while lignin is significantly underutilized despite its bulk amount and high-value opportunities. In this study, the effects of two recent organosolv pretreatment strategies, co-solvent enhanced lignocellulosic fractionation (CELF) and γ-Valerolactone (GVL) pretreatments, on physicochemical properties of poplar were investigated and compared with the effects of conventional ethanol organosolv pretreatment. Diverse physicochemical properties of biomass including chemical compositions, molecular weights of cellulose and lignin, aromatics and inter-unit linkages of lignin, lignin hydroxyl group contents, cellulose crystallinity, and accessible surface area of cellulose were analyzed before and after pretreatments. The results revealed how each organic solvent pretreatment system affected biomass structural characteristics and recalcitrance.

Meng, Xianzhi↗