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Structural Stability (structural + stability)
Selected AbstractsProbing the ,-Helical Structural Stability of Stapled p53 Peptides: Molecular Dynamics Simulations and AnalysisCHEMICAL BIOLOGY & DRUG DESIGN, Issue 4 2010Zuojun Guo Reactivation of the p53 cell apoptosis pathway through inhibition of the p53-hDM2 interaction is a viable approach to suppress tumor growth in many human cancers and stabilization of the helical structure of synthetic p53 analogs via a hydrocarbon cross-link (staple) has been found to lead to increased potency and inhibition of protein,protein binding (J. Am. Chem. Soc. 129: 5298). However, details of the structure and dynamic stability of the stapled peptides are not well understood. Here, we use extensive all-atom molecular dynamics simulations to study a series of stapled ,-helical peptides over a range of temperatures in solution. The peptides are found to exhibit substantial variations in predicted ,-helical propensities that are in good agreement with the experimental observations. In addition, we find significant variation in local structural flexibility of the peptides with the position of the linker, which appears to be more closely related to the observed differences in activity than the absolute ,-helical stability. These simulations provide new insights into the design of ,-helical stapled peptides and the development of potent inhibitors of ,-helical protein,protein interfaces. [source] ChemInform Abstract: Structural Stability and Elastic and Electronic Properties of Rhenium Borides: First Principle Investigations.CHEMINFORM, Issue 12 2009Huiyang Gou Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Studies on the Configuration and Structural Stability for Subnitrosyl Fe(NO)n (n = 1,4)CHEMINFORM, Issue 30 2007W. J. Wang Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Structural Stability of Alkali Boron Tetrahydrides ABH4 (A: Li, Na, K, Rb, Cs) from First Principle Calculation.CHEMINFORM, Issue 15 2005P. Vajeeston No abstract is available for this article. [source] Study of Structural Stability of Cyclophilin A by NMR and Circular Dichroism SpectraCHINESE JOURNAL OF CHEMISTRY, Issue 7 2006Yan-Hong Shi Abstract The structural stability of cyclophilin A (CypA) was investigated using H/D exchange and temperature coefficients of chemical shifts of amide protons, monitored by 2D heteronuclear NMR spectroscopy. Amide proton exchange rates were measured by H/D exchange experiments for slow-exchange protons and measured by SEA (Solvent Exposed Amides)-HSQC experiments for fast-exchange protons. Temperature coefficients of chemical shifts and hydrogen exchange rates of amide protons show reasonably good correlation with the protein structure. Totally, 44 out of 153 non-proline assigned residues still exist in 86 d of hydrogen-deuterium exchange at 4 °C, suggesting that CypA structure should be highly stable. Residues in secondary structures of ,2, ,1, ,2, ,5, ,6 and ,7 might constitute the hydrophobic core of the protein. The change in free energy of unfolding (,Gu) of CypA was estimated to be (21.99±1.53) kJ·mol,1 by circular dichroism (CD). The large free energy change is also an indicator of the high structural stability. [source] Structural stability of Sclerotium rolfsii ATCC 201126 ,-glucan with fermentation time: a chemical, infrared spectroscopic and enzymatic approachJOURNAL OF APPLIED MICROBIOLOGY, Issue 1 2009J.I. Fariña Abstract Aims:,Sclerotium rolfsii ATCC 201126 exopolysaccharides (EPSs) recovered at 48 h (EPS I) and 72 h (EPS II) of fermentation, with differences in rheological parameters, hydrogel topography, salt tolerance, antisyneresis, emulsifying and suspending properties, were subjected to a polyphasic characterization in order to detect structural divergences. Methods and Results:, Fermenter-scale production led to productivity (Pr) and yield (YP/C) values higher at 48 h (Pr = 0·542 g l,1 h,1; YP/C = 0·74) than at 72 h (Pr = 0·336 g l,1 h,1; YP/C = 0·50). Both EPSs were neutral glucose-homopolysaccharides with a ,-(1,3)-glycosidic backbone and single ,-(1,6)-glucopyranosyl sidechains regularly attached every three residues in the main chain, as revealed by chemical analyses. The infra-red diagnostic peak at 890 cm,1 confirmed ,-glycosidic linkages, while gentiobiose released by ,-(1,3)-glucanases confirmed single ,-1,6-glycosidic branching for both EPSs. Conclusions:, The true modular repeating unit of S. rolfsii ATCC 201126 scleroglucan could be resolved. Structural stability was corroborated and no structural differences could be detected as to account for the variations in EPSs behaviour. Significance and Impact of the Study:, Recovery of S. rolfsii ATCC 201126 scleroglucan at 48 h might be considered based on better fermentation kinetic parameters and no detrimental effects on EPS structural features. [source] Structural stability of clean GaAs nanowires grown along the [111] directionPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 2 2010Rita Magri Abstract Using a first-principles approach we have calculated the formation energies of small diameter GaAs nanowires (NWs) with both zinc-blende and wurtzite structure grown along the [111] direction. The section of the wires is hexagonal and the side facets are oriented either {11-20} and {10-10} in the case of the wurtzite structure, and {110} and {112} for the zinc-blende structure. The formation energy of the nanowires as a function of their radius is then interpreted in terms of a model in which the energy contributions from the bulks, the flat surfaces and the ridges are taken explicitly into account. We find that the nanowire stability is mainly explained by the competition between the bulk energy, favoring the zincblende structure and the surface energies favoring the wurtzite structure. We find also that the directly calculated formation energies of some small diameter wurtzite NWs can be reproduced by our model taking into account only the bulk and flat surface contributions. That is, the ridges do not contribute substantially to the nanowire formation energy. Inspection of the ridge structure and band structure reveals that this good agreement occurs when the NWs are semiconducting and the ridges do not add more dangling bonds to the surface with respect to those provided by the sidewalls. Within our model we find the critical diameter for the wurtzite-zinc-blende transition at 6.3 nm. (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Structural stability and heat-induced conformational change of two complement inhibitors: C4b-binding protein and factor HPROTEIN SCIENCE, Issue 5 2004Lena Kask C4BP, C4b-binding protein; FH, factor H; CCP, complement control protein; CD, circular dichroism; FTIR, Fourier transform-infrared spectroscopy; PT, prothrombin; VCP, vaccinia virus complement control protein Abstract The complement inhibitors C4b-binding protein (C4BP) and factor H (FH) both consist of complement control protein (CCP) domains. Here we examined the secondary structure of both proteins by circular dichroism and Fourier-transform infrared technique at temperatures ranging from 30°C,90°C. We found that predominantly ,-sheet structure of both proteins was stable up to 70°C, and that a reversible conformational change toward ,-helix was apparent at temperatures ranging from 70°C to 90°C. The ability of both proteins to inhibit complement was not impaired after incubation at 95°C, exposure to extreme pH conditions, and storage at room temperature for several months. Similar remarkable stability was previously observed for vaccinia virus control protein (VCP), which is also composed of CCP domains; it therefore seems to be a general property of CCP-containing proteins. A typical CCP domain has a hydrophobic core, which is wrapped in ,-sheets and stabilized by two disulphide bridges. How the CCP domains tolerate harsh conditions is unclear, but it could be due to a combination of high content of prolines, hydrophobic residues, and the presence of two disulphide bridges within each domain. These findings are of interest because CCP-containing complement inhibitors have been proposed as clinical agents to be used to control unwanted complement activation that contributes to many diseases. [source] Structural stability and formability of ABO3 -type perovskite compoundsACTA CRYSTALLOGRAPHICA SECTION B, Issue 6 2007Huan Zhang On the basis of the bond-valence model (BVM) and structure-map technology, the structural stability and formability of ABO3 -type perovskite compounds were investigated in 376 ABO3 -type compounds. A new criterion of structural stability for ABO3 -type perovskite compounds has been established by the bond-valence calculated tolerance factors, which are in the range 0.822,1.139. All global instability indices for ABO3 -type perovskite compounds are found to be less than 1.2,v.u. (valence units) and increase with a decrease in oxidation state of the B cations (i.e. structural stability in the formation of an ideal cubic perovskite follows the order A+B5+O3 -type > A2+B4+O3 -type > A3+B3+O3 -type). Three new two-dimensional structure maps were constructed based on the ideal A,O and B,O bond distances derived from the BVM. These maps indicate the likelihood of particular perovskite compounds being formed. The present work enables novel perovskite and perovskite-related compounds to be explored by screening all the possible elemental combinations in future crystal engineering. [source] Structures and energies of D -galactose and galabiose conformers as calculated by ab initio and semiempirical methodsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 7 2003Majda Rahal-Sekkal Abstract Optimized geometries and total energies of some conformers of ,- and ,- D -galactose have been calculated using the RHF/6-31G* ab initio method. Vibrational frequencies were computed at the 6-31G* level for the conformers that favor internal hydrogen bonding, in order to evaluate their enthalpies, entropies, Gibbs free energies, and then their structural stabilities. The semiempirical AM1, PM3, MNDO methods have also been performed on the conformers GG, GT, and TG of ,- and ,- D -galactose. In order to test the reliability of each semiempirical method, the obtained structures and energies from the AM1, PM3, and MNDO methods have been compared to those achieved using the RHF/6-31G* ab initio method. The MNDO method has not been investigated further, because of the large deviation in the structural parameters compared with those obtained by the ab initio method for the galactose. The semiempirical method that has yielded the best results is AM1, and it has been chosen to perform structural and energy calculations on the galabiose molecule (the disaccharides constituted by two galactose units , 1,4 linked). The goal of such calculations is to draw the energy surface maps for this disaccharide. To realize each map, 144 different possible conformations resulting from the rotations of the two torsional angles , and , of the glycosidic linkage are considered. In each calculation, at each increment of , and ,, using a step of 30° from 0 to 330°, the energy optimization is employed. In this article, we report also calculations concerning the galabiose molecule using different ab initio levels such as RHF/6-31G*, RHF/6-31G**, and B3Lyp/6-31G*. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 806,818, 2003 [source] Stability of recombinant plasmids on the continuous culture of Bifidobacterium animalis ATCC 27536BIOTECHNOLOGY & BIOENGINEERING, Issue 2 2003Antonio González Vara Abstract Bifidobacterium animalis ATCC 27536 represents among bifidobacteria a host-model for cloning experiments. The segregational and structural stabilities of a family of cloning vectors with different molecular weights but sharing a common core were studied in continuous fermentation of the hosting B. animalis without selective pressure. The rate of plasmid loss (R) and the specific growth rate difference (,,) between plasmid-free and plasmid-carrying cells were calculated for each plasmid and their relationship with plasmid size was studied. It was observed that both R and the numerical value of ,, increased exponentially with plasmid size. The exponential functions correlating the specific growth rate difference and the rate of plasmid loss with the plasmid molecular weight were determined. Furthermore, the smallest of the plasmids studied, pLAV (4.3-kb) was thoroughly characterized by means of its complete nucleotide sequence. It was found that it contained an extra DNA fragment, the first bifidobacterial insertion sequence characterised, named IS 1999. © 2003 Wiley Periodicals, Inc. Biotechnol Bioeng 84: 145,150, 2003. [source] Particle clusters in gravel-bed rivers: an experimental morphological approach to bed material transport and stability conceptsEARTH SURFACE PROCESSES AND LANDFORMS, Issue 11 2005Lea Wittenberg Abstract Structured gravel river beds clearly exert a major influence on bed stability. Indexing structural stability by field measurements of bed strength neglects the processes operating to entrain and transport bed material in different parts of each structure. This study takes a morphological approach to interpreting the critical processes, using particle tracing to determine the movement of individual cluster particles over a range of flood event magnitudes and durations. The experiment was carried out on the River South Tyne, UK; it uses flow hydrographs measured nearby and also benefits from previous studies of historical development, channel morphology and sediment transport at the same site. More than 30 clusters were monitored over a seven-month period during which clusters occupied 7,16 per cent of the bed. Threshold flows delimiting three apparently contrasting bed sediment process regimes for cluster particles are tentatively set at 100 m3 s,1 and 183 m3 s,1; durations of flow at these levels are critical for cluster development, rather than flow peak values. Wake particles are transported most easily. Flow straightening in the wandering channel planform reduces the stability of clusters, since mechanical strength is markedly reduced by this change of direction. The overall area covered by clusters between significant transport events varies little, implying a dynamic equilibrium condition. Copyright © 2005 John Wiley & Sons, Ltd. [source] Mineral soil surface crusts and wind and water erosionEARTH SURFACE PROCESSES AND LANDFORMS, Issue 9 2004Michael J. Singer Abstract The ,rst few millimetres of soil largely control the soil's response to the eroding forces of wind and water. The tendency of soils to form surface seals and crusts in,uences the processes of wind and water erosion differently. For wind, dry particle size distribution and particle organization determine the shear strength and threshold wind velocity necessary to initiate particle movement. In loams and clay loams, seals and crusts decrease roughness but increase surface soil strength, generally decreasing wind erosion. Conversely, in sand and sandy loams, loose erodible sandy material may either deposit on the crust and is subject to erosion or it may disrupt the crust, accelerating the erosion process. For water erosion, particle size distribution and structure determine in,ltration rate, time to ponding, and energy required for soil particle detachment. Seals and crusts tend to decrease in,ltration rate and time to ponding thus increasing overland ,ow and soil erosion. This paper brie,y reviews how permanent and time-dependent soil properties in,uence surface seals and crusts and how these affect soil erosion by wind and water. The tendency of a soil to form a seal and crust depends to some degree on the time-dependent property of soil structural stability, which tends to increase with increasing clay content and smectitic mineralogy which are permanent properties. These permanent properties and their effect on structure are variable depending on dynamic properties of exchangeable sodium percentage and soil solution electrical conductivity. Antecedent water content prior to irrigation or rainfall, rate of wetting before an erosive event and aging, the time between wetting and an erosive event, greatly in,uence the response of soil structure to raindrop impact. The effect of these dynamic processes is further in,uenced by the static and dynamic properties of the soil. Weak structure will be less in,uenced by wetting rate than will a soil with strong structure. Process-based models of wind and water erosion need to consider the details of the interactions between soil static and dynamic properties and the dynamic processes that occur prior to erosive events. Copyright © 2004 John Wiley & Sons, Ltd. [source] Design of passive systems for control of inelastic structuresEARTHQUAKE ENGINEERING AND STRUCTURAL DYNAMICS, Issue 6 2009Gian Paolo Cimellaro Abstract A design strategy for control of buildings experiencing inelastic deformations during seismic response is formulated. The strategy is using weakened, and/or softened, elements in a structural system while adding passive energy dissipation devices (e.g. viscous fluid devices, etc.) in order to control simultaneously accelerations and deformations response during seismic events. A design methodology is developed to determine the locations and the magnitude of weakening and/or softening of structural elements and the added damping while insuring structural stability. A two-stage design procedure is suggested: (i) first using a nonlinear active control algorithm, to determine the new structural parameters while insuring stability, then (ii) determine the properties of equivalent structural parameters of passive system, which can be implemented by removing or weakening some structural elements, or connections, and by addition of energy dissipation systems. Passive dampers and weakened elements are designed using an optimization algorithm to obtain a response as close as possible to an actively controlled system. A case study of a five-story building subjected to El Centro ground motion, as well as to an ensemble of simulated ground motions, is presented to illustrate the procedure. The results show that following the design strategy, a control of both peak inter-story drifts and total accelerations can be obtained. Copyright © 2008 John Wiley & Sons, Ltd. [source] Photopolymerizable Hydrogels Made from Polymer-Conjugated Albumin for Affinity-Based Drug Delivery,ADVANCED ENGINEERING MATERIALS, Issue 1-2 2010Liat Oss-Ronen As a drug delivery vehicle, biodegradable albumin hydrogels can combine the high binding capacity of albumin with the structural stability of a polymeric hydrogel network to enable controlled release of small molecules based on both binding affinity and physical interactions. In the present study, we report on the development of a hybrid hydrogel composed of albumin conjugated to poly(ethylene glycol) (PEG) for drug delivery applications where controlled release is accomplished using the natural affinity of the drugs to the serum albumin. Bovine serum albumin was conjugated to PEG-diacrylate having a molecular weight of 1.5, 4, or 10,kDa to form a PEGylated albumin macromolecule (mono-PEGylated or multi-PEGylated). Biodegradable hydrogels were formed from the PEGylated albumin using photopolymerization. Two model drugs, Warfarin and Naproxen, were used for equilibrium dialysis and release experiments from the hydrogels, both having relatively low molecular weights and a known high affinity for albumin. Equilibrium dialysis experiments showed that multi-PEGylation of albumin significantly decreased the drug affinity to the protein compared to non-PEGylated controls, irrespective of the PEG molecular weight. However, the results from drug release experiments showed that mono-PEGylation of albumin did not change its natural affinity to the drug. Comparing the release profiles with a Fickian diffusion model provided strong evidence that hydrogels containing mono-PEGylated albumin exhibited sub-diffusive drug release properties based on the affinity of the drug to the tethered protein. [source] X-ray crystallography and structural stability of digestive lysozyme from cow stomachFEBS JOURNAL, Issue 8 2009Yasuhiro Nonaka In ruminants, some leaf-eating animals, and some insects, defensive lysozymes have been adapted to become digestive enzymes, in order to digest bacteria in the stomach. Digestive lysozyme has been reported to be resistant to protease and to have optimal activity at acidic pH. The structural basis of the adaptation providing persistence of lytic activity under severe gastric conditions remains unclear. In this investigation, we obtained the crystallographic structure of recombinant bovine stomach lysozyme 2 (BSL2). Our denaturant and thermal unfolding experiments revealed that BSL2 has high conformational stability at acidic pH. The high stability in acidic solution could be related to pepsin resistance, which has been previously reported for BSL2. The crystal structure of BSL2 suggested that negatively charged surfaces, a shortened loop and salt bridges could provide structural stability, and thus resistance to pepsin. It is likely that BSL2 loses lytic activity at neutral pH because of adaptations to resist pepsin. [source] Role of the surface charges D72 and K8 in the function and structural stability of the cytochrome c6 from Nostoc sp.FEBS JOURNAL, Issue 13 2005PCC 711 We investigated the role of electrostatic charges at positions D72 and K8 in the function and structural stability of cytochrome c6 from Nostoc sp. PCC 7119 (cyt c6). A series of mutant forms was generated to span the possible combinations of charge neutralization (by mutation to alanine) and charge inversion (by mutation to lysine and aspartate, respectively) in these positions. All forms of cyt c6 were functionally characterized by laser flash absorption spectroscopy, and their stability was probed by urea-induced folding equilibrium relaxation experiments and differential scanning calorimetry. Neutralization or inversion of the positive charge at position K8 reduced the efficiency of electron transfer to photosystem I. This effect could not be reversed by compensating for the change in global charge that had been introduced by the mutation, indicating a specific role for K8 in the formation of the electron transfer complex between cyt c6 and photosystem I. Replacement of D72 by asparagine or lysine increased the efficiency of electron transfer to photosystem I, but destabilized the protein. D72 apparently participates in electrostatic interactions that stabilize the structure of cyt c6. The destabilizing effect was reduced when aspartate was replaced by the small amino acid alanine. Complementing the mutation D72A with a charge neutralization or inversion at position K8 led to mutant forms of cyt c6 that were more stable than the wild-type under all tested conditions. [source] The Remarkable Thermal Stability of Amorphous In-Zn-O Transparent Conductors,ADVANCED FUNCTIONAL MATERIALS, Issue 20 2008Matthew P. Taylor Abstract Transparent conducting oxides (TCOs) are increasingly critical components in photovoltaic cells, low-e windows, flat panel displays, electrochromic devices, and flexible electronics. The conventional TCOs, such as Sn-doped In2O3, are crystalline single phase materials. Here, we report on In-Zn-O (IZO), a compositionally tunable amorphous TCO with some significantly improved properties. Compositionally graded thin film samples were deposited by co-sputtering from separate In2O3 and ZnO targets onto glass substrates at 100,°C. For the metals composition range of 55,84 cation% indium, the as-deposited IZO thin films are amorphous, smooth (RRMS,<,0.4,nm), conductive (,,,,3000,,,1,·,cm,1), and transparent in the visible (TVis,>,90%). Furthermore, the amorphous IZO thin films demonstrate remarkable functional and structural stability with respect to heating up to 600,°C in either air or argon. Hence, though not completely understood at present, these amorphous materials constitute a new class of fundamentally interesting and technologically important high performance transparent conductors. [source] Eutectic Gallium-Indium (EGaIn): A Liquid Metal Alloy for the Formation of Stable Structures in Microchannels at Room Temperature,ADVANCED FUNCTIONAL MATERIALS, Issue 7 2008Michael D. Dickey Abstract This paper describes the rheological behavior of the liquid metal eutectic gallium-indium (EGaIn) as it is injected into microfluidic channels to form stable microstructures of liquid metal. EGaIn is well- ;suited for this application because of its rheological properties at room temperature: it behaves like an elastic material until it experiences a critical surface stress, at which point it yields and flows readily. These properties allow EGaIn to fill microchannels rapidly when sufficient pressure is applied to the inlet of the channels, yet maintain structural stability within the channels once ambient pressure is restored. Experiments conducted in microfluidic channels, and in a parallel-plate rheometer, suggest that EGaIn's behavior is dictated by the properties of its surface (predominantly gallium oxide, as determined by Auger measurement s); these two experiments both yield approximately the same number for the critical surface stress required to induce EGaIn to flow (,0 .5,N/m). This analysis,which shows that the pressure that must be exceeded for EGaIn to flow through a microchannel is inversely proportional to the critical (i.e., smallest) dimension of the channel,is useful to guide future fabrication of microfluidic channels to mold EGaIn into functional microstructures. [source] Natural-Synthetic Polyblend Nanofibers for Biomedical ApplicationsADVANCED MATERIALS, Issue 27 2009Narayan Bhattarai The ability to produce well-blended nanofibers from natural and synthetic polymers represents a significant advancement in development of composite materials with desired structures and material properties. The nanofiber presented here exhibits excellent structural stability and mechanical and biological properties favorable for biomedical applications, and offers a new nanofibrous platform for development of matrices for various biomedical applications. [source] Strain Rate Effects in the Mechanical Response of Polymer-Anchored Carbon Nanotube Foams,ADVANCED MATERIALS, Issue 3 2009Abha Misra Strain rate effects on the mechanical properties of carbon nanotube forests are studied, and several related interesting new phenomena are reported. Dense vertically aligned foam-like forests of carbon nanotubes are anchored on a thin, flexible polymer layer to provide structural stability, particularly at the higher strain rates. Permanent deformation and for the first time the delamination and crumbling of carbon nanotube walls is observed. [source] DFT study of polymorphism of the DNA double helix at the level of dinucleoside monophosphatesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2010Valeri I. Poltev Abstract We apply DFT calculations to deoxydinucleoside monophosphates (dDMPs) which represent minimal fragments of the DNA chain to study the molecular basis of stability of the DNA duplex, the origin of its polymorphism and conformational heterogeneity. In this work, we continue our previous studies of dDMPs where we detected internal energy minima corresponding to the "classical" B conformation (BI-form), which is the dominant form in the crystals of oligonucleotide duplexes. We obtained BI local energy minima for all existing base sequences of dDMPs. In the present study, we extend our analysis to other families of DNA conformations, successfully identifying A, BI, and BII energy minima for all dDMP sequences. These conformations demonstrate distinct differences in sugar ring puckering, but similar sequence-dependent base arrangements. Internal energies of BI and BII conformers are close to each other for nearly all the base sequences. The dGpdG, dTpdG, and dCpdA dDMPs slightly favor the BII conformation, which agrees with these sequences being more frequently experimentally encountered in the BII form. We have found BII-like structures of dDMPs for the base sequences both existing in crystals in BII conformation and those not yet encountered in crystals till now. On the other hand, we failed to obtain dDMP energy minima corresponding to the Z family of DNA conformations, thus giving us the ground to conclude that these conformations are stabilized in both crystals and solutions by external factors, presumably by interactions with various components of the media. Overall the accumulated computational data demonstrate that the A, BI, and BII families of DNA conformations originate from the corresponding local energy minimum conformations of dDMPs, thus determining structural stability of a single DNA strand during the processes of unwinding and rewinding of DNA. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2548,2559, 2010 [source] Energetic stability of boron nitride nanostructures doped with one carbon atomINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 9 2010Rebeca D. Gonçalves Abstract We have investigated, using first-principles calculations, the role of a substitutional carbon atom on the geometric stability of boron nitride monolayers, nanotubes, and nanocones. It is shown that the formation of energy depends on the number of atoms for the monolayers and on the diameter for the tubes. It is also found, for the carbon-doped boron nitride nanotubes, that the value for the strain energy approaches the one obtained for nondoped tubes with increasing diameter. For the structural stability, we have verified that the doping, which introduces an excess of nitrogen or boron, makes each structure more favorable in its reverse atmosphere, i.e., excess of nitrogen is more stable in a boron-rich growth environment, whereas excess of boron is preferred in a nitrogen-rich condition. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Theoretical study of acetonitrile-exchange reactions on hexasolvated divalent cations in the first transition series elementsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 10 2009Hiroaki Wasada Abstract Penta-, hexa-, and heptaacetonitrile complexes of divalent cations of the first transition series are studied by ab initio molecular orbital calculations. The factors that determine the structural stability and the reaction mechanism of solvent-exchange reactions are discussed. All the penta- and hexaacetonitrile species are at local minima, whereas the geometrical stability of the heptacoordinated species depends on the 3d electron configurations. The structural stability of heptaacetonitrile species is intermediate between those of hydrogen cyanide complexes and hydrates. Acetonitrile exchange reactions have more dissociative character than hydrogen cyanide exchange reactions because the inductive effect of the methyl group in CH3CN destabilizes the heptacoordinated structures. The successive binding energies show that associative mechanisms are favorable for acetonitrile exchange with earlier members of the first transition series, whereas dissociative mechanisms become favorable for later members. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Formation and applications of stable 10 nm to 500 nm supramolecular porphyrinic materialsISRAEL JOURNAL OF CHEMISTRY, Issue 3 2005Charles Michael Drain Nanoscaled materials of organic dyes are of interest for a variety of potential applications because of the rich photonic properties that this class of molecules can impart. One mode to form such nanoscaled materials is via self-organization and self-assembly, using reasonably well understood methods in supramolecular chemistry. But there are inherent complexities that arise from the use of organic-based supramolecular materials, including stability toward dioxygen, structural stability, and nanoarchitectures that may change with environmental conditions. Porphyrinoids have rich photonic properties yet are remarkably stable, have a rigid core, are readily functionalized, and metalation of the macrocycle can impart a plethora of optical, electronic, and magnetic properties. While there are many <10 nm porphyrinic assemblies, which may or may not self-organize into crystals, there is a paucity of 10,500 nm porphyrinic materials that can be isolated and stored. A variety of strategies towards the latter nanoscopic porphyrinic materials are discussed in terms of design, construction, and nanoarchitecture. The hierarchical structures include colloids, nanorods, nanotubes, nanorings, and nano-crystalline materials. This prolegomenon emphasizes the supramolecular chemistry, structure-stability, and structure-function relationships. The goal herein is to examine general trends and delineate general principles. [source] Shape of ,-crystallin analyzed by small-angle neutron scatteringJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 2007Masaaki Sugiyama The size and shape of aggregates of human recombinant ,A-crystallin and ,B-crystallin are investigated with small-angle neutron scattering and dynamic light scattering. At a bioactive temperature (310,K), both polypeptides form aggregates with almost the same size and shape. The ,B-crystallin maintains an almost identical size and shape at 310 and 288,K, whereas the aggregate of ,A-crystallin shows deformation at 288,K. This result suggests that at the lower temperature there is a difference in structural stability between the two aggregates of the polypeptides. [source] Exploring the international linkages of the euro area: a global VAR analysisJOURNAL OF APPLIED ECONOMETRICS, Issue 1 2007Stephane Dees This paper presents a quarterly global model combining individual country vector error-correcting models in which the domestic variables are related to the country-specific foreign variables. The global VAR (GVAR) model is estimated for 26 countries, the euro area being treated as a single economy, over the period 1979,2003. It advances research in this area in a number of directions. In particular, it provides a theoretical framework where the GVAR is derived as an approximation to a global unobserved common factor model. Using average pair-wise cross-section error correlations, the GVAR approach is shown to be quite effective in dealing with the common factor interdependencies and international co-movements of business cycles. It develops a sieve bootstrap procedure for simulation of the GVAR as a whole, which is then used in testing the structural stability of the parameters, and for establishing bootstrap confidence bounds for the impulse responses. Finally, in addition to generalized impulse responses, the current paper considers the use of the GVAR for ,structural' impulse response analysis with focus on external shocks for the euro area economy, particularly in response to shocks to the US. Copyright © 2007 John Wiley & Sons, Ltd. [source] Timing structural change: a conditional probabilistic approachJOURNAL OF APPLIED ECONOMETRICS, Issue 2 2006David N. DeJong We propose a strategy for assessing structural stability in time-series frameworks when potential change dates are unknown. Existing stability tests are effective in detecting structural change, but procedures for identifying timing are imprecise, especially in assessing the stability of variance parameters. We present a likelihood-based procedure for assigning conditional probabilities to the occurrence of structural breaks at alternative dates. The procedure is effective in improving the precision with which inferences regarding timing can be made. We illustrate parametric and non-parametric implementations of the procedure through Monte Carlo experiments, and an assessment of the volatility reduction in the growth rate of US GDP. Copyright © 2006 John Wiley & Sons, Ltd. [source] Structural Modeling of Car Use on the Way to the University in Different Settings: Interplay of Norms, Habits, Situational Restraints, and Perceived Behavioral Control,JOURNAL OF APPLIED SOCIAL PSYCHOLOGY, Issue 8 2009Christian A. Klöckner This manuscript presents the results of the application of an extended norm activation model to the explanation of car use on the way to the university with a sample of 430 students of 3 German universities. The proposed two-stage structural model is supported by the data. First, a norm activation process starting with awareness of consequences activates subjective and personal norms. Second, behavior is determined by car-use habits, perceived behavioral control (PBC), car access, and effort to use public transportation. The influence of personal norms on behavior is mediated by habits. Subgroup analyses of the second stage of the model show a high structural stability, but differences in the regression weights. [source] Age Trends in Femur Stresses From a Simulated Fall on the Hip Among Men and Women: Evidence of Homeostatic Adaptation Underlying the Decline in Hip BMDJOURNAL OF BONE AND MINERAL RESEARCH, Issue 9 2006Thomas J Beck ScD Abstract Age trends in proximal femur stresses were evaluated by simulating a fall on the greater trochanter using femur geometry from hip DXA scans of 5334 white men and women in the NHANES III survey. Expansion of femur outer diameter seems to counter net bone loss so that stresses remain similar across age groups, but stresses are higher in older women than in older men. Introduction: The age decline in hip BMD is caused by both bone loss and expansion of outer diameter that increases the region size over which mass is measured in a DXA scan. Because expansion has an opposing effect on structural strength, it may be a homeostatic adaptation to net bone loss to ensure that load stresses are kept within a narrow range. Materials and Methods: Age trends in femur stresses were evaluated with an engineering beam simulation of a fall on the greater trochanter. Hip geometry was extracted from hip DXA scans using the Hip Structure Analysis (HSA) software on 2613 non-Hispanic white men and 2721 women from the third National Health and Nutrition Examination Survey (NHANES III). Using body weight as load, stresses were computed on the inferior-medial and superior-lateral femur neck at its narrowest point and the medial and lateral shaft 2 cm distal to the midpoint of the lesser trochanter. Stresses and the underlying geometries in men and women >50 years oaf age were compared with those 20,49 years of age. Results: Compared with men <50 years of age, stresses in older men were 6% lower on both surfaces of the shaft, 4% lower on the inferior-medial neck, and not different on the superior-lateral neck. In women >50 years of age, stresses on the proximal shaft and inferior-medial neck remained within 3% of young values but were 13% greater on the superior-lateral neck. Neck stresses in young women were lower on the superior-lateral than the inferior-medial neck, but lateral stress increased to the level on the medial surface in older women. Stresses were higher in women than in men, with a greater gender difference in those >50 years of age. Conclusions: We conclude that femur expansion has a homeostatic effect in men and women that opposes bone loss so that stresses change little with age. Because expansion preserves stresses with progressively less bone mass, the process may reduce structural stability in the femoral neck under fall conditions, especially in the elderly female. [source] | |||||||||||||||||||||||||||||||||||||||||||||||||