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Stabilization
Kinds of Stabilization Terms modified by Stabilization Selected AbstractsTHE RATE OF GENOME STABILIZATION IN HOMOPLOID HYBRID SPECIESEVOLUTION, Issue 2 2008C. Alex Buerkle Homoploid hybrid speciation has been recognized for its potential rapid completion, an idea that has received support from experimental and modeling studies. Following initial hybridization, the genomes of parental species recombine and junctions between chromosomal blocks of different parental origin leave a record of recombination and the time period before homogenization of the derived genome. We use detailed genetic maps of three hybrid species of sunflowers and models to estimate the time required for the stabilization of the new hybrid genome. In contrast to previous estimates of 60 or fewer generations, we find that the genomes of three hybrid sunflower species were not stabilized for hundreds of generations. These results are reconciled with previous research by recognizing that the stabilization of a hybrid species' genome is not synonymous with hybrid speciation. Segregating factors that contribute to initial ecological or intrinsic genetic isolation may become stabilized quickly. The remainder of the genome likely becomes stabilized over a longer time interval, with recombination and drift dictating the contributions of the parental genomes. Our modeling of genome stabilization provides an upper bound for the time interval for reproductive isolation to be established and confirms the rapid nature of homoploid hybrid speciation. [source] ARE LONG-RUN PRICE STABILITY AND SHORT-RUN OUTPUT STABILIZATION ALL THAT MONETARY POLICY CAN AIM FOR?METROECONOMICA, Issue 2 2007Giuseppe Fontana ABSTRACT A central tenet of the so-called new consensus view in macroeconomics is that there is no long-run trade-off between inflation and unemployment. The main policy implication of this principle is that all monetary policy can aim for is (modest) short-run output stabilization and long-run price stability, i.e. monetary policy is neutral with respect to output and employment in the long run. However, research on the different sources of path dependency in the economy suggests that persistent but nevertheless transitory changes in aggregate demand may have a permanent effect on output and employment. If this is the case, then, the way monetary policy is run does have long-run effects on real variables. This paper provides an overview of this research and explores conceptually how monetary policy should be implemented once these long-run effects are acknowledged. [source] DELAYS IN STABILIZATION OR IN REFORMS?THE DEVELOPING ECONOMIES, Issue 3 2008THE DEBT CRISIS F13; F34; 010 Empirical analyses attributing the 1980s' debt crisis to inconsistent stabilization policies rest on an inappropriate long-run approach. Revising this long-run approach yields opposite results: terms of trade shocks and foreign indebtedness explain this crisis, regardless of domestic stabilization policies. This prompts us to consider a new hypothesis, of delays in trade-policy reforms, with a model in which terms-of-trade variation (under shocks) is endogenous to export structure and efficiency of resource allocation. Evidence from the structural equations model shows that allocation distortions negatively affect changes in terms of trade, which then explain this crisis. A political economy extension demonstrates that income inequality and regional trade policy determine the distortions, which in turn leads to this crisis. [source] ROBUST H, CONTROL AND QUADRATIC STABILIZATION OF DISCRETE-TIME SWITCHED SYSTEMS WITH NORM-BOUNDED TIME-VARYING UNCERTAINTIESASIAN JOURNAL OF CONTROL, Issue 3 2007Zhijian Ji ABSTRACT We focus on robust H, control analysis and synthesis for discretetime switched systems with norm-bounded time-varying uncertainties. Sufficient conditions are derived to guarantee quadratic stability along with a prescribed H, -norm bound. Each of them can be dealt with as a linear matrix inequality (LMI) which can be tested with efficient algorithms. All the switching rules are constructively designed, and do not rely on any uncertainties. [source] ROBUST STABILITY AND STABILIZATION OF A CLASS OF SINGULAR SYSTEMS WITH MULTIPLE TIME-VARYING DELAYSASIAN JOURNAL OF CONTROL, Issue 1 2006S. M. Saadni ABSTRACT This paper deals with the problem of robust stability and robust stabilization for uncertain continuous singular systems with multiple time-varying delays. The parametric uncertainty is assumed to be norm bounded. The purpose of the robust stability problem is to give conditions such that the uncertain singular system is regular, impulse free, and stable for all admissible uncertainties. The purpose of the robust stabilization problem is to design a feedback control law such that the resulting closed-loop system is robustly stable. This problem is solved via generalized quadratic stability approach. A strict linear matrix inequality (LMI) design approach is developed. Finally, a numerical example is provided to demonstrate the application of the proposed method. [source] GENERALIZED QUADRATIC STABILIZATION FOR DISCRETE-TIME SINGULAR SYSTEMS WITH TIME-DELAY AND NONLINEAR PERTURBATIONASIAN JOURNAL OF CONTROL, Issue 3 2005Guoping Lu ABSTRACT This paper discusses a generalized quadratic stabilization problem for a class of discrete-time singular systems with time-delay and nonlinear perturbation (DSSDP), which the satisfies Lipschitz condition. By means of the S-procedure approach, necessary and sufficient conditions are presented via a matrix inequality such that the control system is generalized quadratically stabilizable. An explicit expression of the static state feedback controllers is obtained via some free choices of parameters. It is shown in this paper that generalized quadratic stability also implies exponential stability for linear discrete-time singular systems or more generally, DSSDP. In addition, this new approach for discrete singular systems (DSS) is developed in order to cast the problem as a convex optimization involving linear matrix inequalities (LMIs), such that the controller can stabilize the overall system. This approach provides generalized quadratic stabilization for uncertain DSS and also extends the existing robust stabilization results for non-singular discrete systems with perturbation. The approach is illustrated here by means of numerical examples. [source] STOCHASTIC STABILIZATION AND H, CONTROL FOR DISCRETE JUMPING SYSTEMS WITH TIME DELAYSASIAN JOURNAL OF CONTROL, Issue 3 2005Jing Wu ABSTRACT In this paper, robust stochastic stabilization and H, control for a class of uncertain discrete-time linear systems with Markovian jumping parameters are considered. Based on a new bounded real lemma derived upon an inequality recently proposed, a new iterative state-feedback controller design procedure for discrete time-delay systems is presented. Sufficient conditions for stochastic stabilization are derived in the form of linear matrix inequalities (LMIs) based on an equivalent model transformation, and the corresponding H, control law is given. Finally, numerical examples are given to illustrate the solvability of the problems and effectiveness of the results. [source] IMPROVED CONDITIONS FOR DELAY-DEPENDENT ROBUST STABILITY AND STABILIZATION OF UNCERTAIN DISCRETE TIME-DELAY SYSTEMSASIAN JOURNAL OF CONTROL, Issue 3 2005Shengyuan Xu ABSTRACT This paper provides improved delay-dependent conditions for the robust stability and robust stabilization of discrete time-delay systems with norm-bounded parameter uncertainties. It is theoretically established that the proposed conditions are less conservative than those discussed in the literature. The new approach proposed in this paper in a derivation of delay-dependent conditions and involves the use of neither model transformation nor bounding techniques for some cross terms. A numerical example is provided to demonstrate the reduced conservatism of the proposed conditions. [source] Stabilization of Radiation-Condensation Instability by Light Impurity InjectionCONTRIBUTIONS TO PLASMA PHYSICS, Issue 3-5 2010A. A. Pshenov Abstract As it has been shown in [1,2], Radiation-Condensation Instability (RCI) may initiate Microfaceted Asymmetric Radiation from the Edge (MARFE) in tokamaks (see also review papers [3-5]). Nevertheless, experiments demonstrate the stable regimes with strongly radiated edge plasmas after Ne injection [6-8] or in siliconized discharges. Two effects destabilize radiative plasmas, the decrease of radiation losses Q with the electron temperature Te increase, and the increase of Q with electron and impurity densities rise. The finite relaxation time of impurity distribution over ionization states [6] as well as the thermal force acting on the growth rate doesn't shift the instability margin. Hence, one can examine the stability margin using the approximation of the coronal equilibrium. Radiation losses of intrinsic impurities like beryllium, carbon and nitrogen usually decrease with the temperature increase at the temperature range typical for the edge (see Fig. 1, curve 1). The situation may be significantly different for impurity mixtures. Radiation losses L , Q /(nenI)normalized by electron and impurity densities ne and nI for the mixture of carbon and neon are shown in Fig. 1, curves 2-5. One can see that ,Q/,T > 0 for practically any temperature at the edge if the concentration ratio nNe/nC , 5. Hence, one can expect the stabilization of RCI by injection of additional impurity and achievement of stable regime with the strongly radiated edge plasmas. The stability of plasmas with few impurity mixtures is examined in the present paper numerically (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Volatility, Stabilization and Union Wage-setting: The Effects of Monetary Policy on the ,Natural' Unemployment RateECONOMIC NOTES, Issue 1 2002Luigi Bonatti In a unionized economy with nominal-wage contracts, the ,natural' (rational-expectations equilibrium) employment level is not invariant with respect to the stabilization rule followed by the monetary authority. This is because alternative monetary policies change the variance of the inflation rate (price level) relatively to the variance of some measure of economic activity (employment level), thereby influencing the trade-off desired by union members between the real wage and the probability of employment. Indeed, a more volatile employment level induces the (risk-neutral) union members to prefer a higher expected real wage. (J.E.L: E5, J5). [source] Comparison of two glutaraldehyde immobilization techniques for solid-phase tryptic peptide mapping of human hemoglobin by capillary zone electrophoresis and mass spectrometryELECTROPHORESIS, Issue 9 2004Isabelle Migneault Abstract Stabilization of proteolytic enzymes, especially by immobilization, is of considerable interest because of their potential applications in medicine and the chemical and pharmaceutical industries. We report here a detailed comparison of two procedures for trypsin immobilization using the same homobifunctional agent, glutaraldehyde, for the purpose of peptide mapping. These methods include covalent coupling either to controlled pore glass (solid support) or via a cross-linking reaction (without any solid support). The immobilized trypsin preparations were characterized by the determination of immobilization efficiency, which ranged from 68 to > 95%, and measurement of apparent kinetic parameters toward a synthetic peptide-like substrate. Batch digestions of whole denaturated human normal adult hemoglobin (HbA) were performed to obtain peptide maps by capillary zone electrophoresis (CZE). Migration time reproducibility of the CZE maps was excellent, with a mean relative standard deviation of 1.5%. Moreover, the two immobilized enzyme preparations showed excellent reproducibility for repeated digestions. Matrix-assisted laser desorption/ionization (MALDI)-mass spectrometry was also used for peptide mass mapping of denaturated HbA digested using the two immobilized trypsin preparations. Even though the two immobilized trypsin preparations do not behave identically, similar sequence coverages of 57% and 61% (for the two HbA chains merged) were achieved for the support-based and cross-linked trypsin preparations, respectively. [source] Molecular Iodine Stabilization in an Extended N···I,I···N AssemblyEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2009Francesco Isaia Abstract The adduct [bis(quinoxaline)-2,2,,3,3,-disulfide·I2], (Q2S2·I2), (1) can be easily synthesised from the reaction of Q2S2 and I2 in CH2Cl2 or, in the absence of any solvent, through diffusion of I2 vapours at 60 °C. X-ray diffraction analysis shows the presence of an extended N···I,I···N assembly in which each I2 molecule links a Q2S2 molecule at both ends through a nitrogen atom to form a polymeric species; the d(I,I) and d(N,I) bond lengths confirm a very weak nitrogen,iodine interaction at the base of the N···I,I···N assembly. DFT calculations provide optimised distances for the N···I and I,I bonds and explanation for the zigzag chain formation: the mPW1PW functional and the B3LYP hybrid functional with a variety of basis sets for the I atomic species [CRENBL, LANL2DZ, LANL2DZ(d,p), LANL08(d), SBKJC, SBKJC polarised-LFK and Stuttgart RLC] have been tested. Compound 1 proved stable up to nearly 100 °C, and the stability is to be mainly attributed to the lattice energy of its polymeric structure then to donor,acceptor stabilisation. The facile insertion of molecular iodine into the Q2S2 network makes this compound an interesting iodine sponge, suitable for I2 storage; moreover, Q2S2 can easily collect and release I2(g) by a temperature-controlled process (60 and 97 °C, respectively). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Stabilization of Long Cationic EMACs by Reduction or Loss of One Metal IonEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 27 2008Rayyat H. Ismayilov Abstract The new pyrimidyl- and naphthyridyl-modulated pentapyridyltetramine ligand (H3N9 -2pm) and its linear nona- and octanickel chain complexes were successfully synthesized. The nonanickel complex [Ni9(,9 -N9 -2pm)4Cl2](PF6)2 (1) contains two fully delocalized, mixed-valence [Ni2(napy)4]3+ units. Magnetic measurements performed on the defective octanuclear complex [Ni8(,8 -N9 -2pm)4Cl2](PF6)2 (2) demonstrate that the metal chain provides a pathway of magnetic superexchange coupling over the extended metal atom chain (EMAC). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Dual Supermesityl Stabilization: A Room-Temperature-Stable 1,2,4-Triphosphole Radical, Sigmatropic Hydrogen Rearrangements, and Tetraphospholide Anion,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2008Alex S. Ionkin Abstract Cesium 3,5-bis(2,4,6-tri- tert -butylphenyl)-1,2,4-triphospholide (12) and cesium 5-(2,4,6-tri- tert -butylphenyl)tetraphospholide (13) were synthesized and isolated with flat five-membered rings, which are an indication of the aromaticity in these anions. Compound 13 is the first example of a stable tetraphospholide anion, which is structurally characterized. Kinetic stabilization of the 1,2,4-triphospholide system by two supermesityl groups resulted in the detection of the room-temperature-stable radical 17 and the observation of a series of successive sigmatropic hydrogen shifts in the first stable 1H -1,2,4-triphosphole 14 with a P,H bond.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Theoretical Study on a Class of Organometallic Complexes Based on All-Metal Aromatic Ga3, Through Sandwiching StabilizationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2008Li-ming Yang Abstract We report the theoretical study on a class of organometallic complexes containing the all-metal aromatic unit Ga3, on the basis of density functional theory calculations on a series of model sandwich-like compounds [DM(Ga3)]q, as well as those of the saturated compounds [DMn(Ga3)] [D = Ga3,, Cp,(C5H5,); M = Li, Na, K, Be, Mg, Ca] and extended compounds (Cp,)m(Li+)n(Ga3,)o (m, n, and o are integers). For the six metals, the all-metal aromatic Ga3, can only be assembled and stabilized in the "heterodecked sandwich" scheme (e.g. [CpM(Ga3)]q,) so as to avoid cluster fusion. Moreover, we designed a novel class of all-metal aromatic "metalloid" compounds. The ground state heterodecked sandwich species (Cp),(M)q+(Ga3), (M = Li, Na, K, q = 1; M = Be, Mg, Ca, q = 2) and the extended sandwich species (Cp,)m(Li+)n(Ga3,)o are mainly ionic bonded, cluster-assembled "polyatomic molecule", grown from the combination of Cp,, M atoms, and Ga3,. As a prototype for ionic bonding involving intact Ga3, subunits, [CpM(Ga3)]q, may be a stepping stone toward forming ionic, cluster-assembled all-metal aromatic Ga3 -based bulk solids or materials. Additionally, our results for the first time showed that the electronic, structural, and aromatic properties of the all-metal aromatic Ga3, could be well retained during cluster assembly, which is indicative of "building block" character. Bearing the significant difference in bonding patterns between our designed metalloid compounds and the known metalloid species, synthesis of these novel species might present an attractive challenge to experimental chemists. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Use of Molecular Scaffolding for the Stabilization of an Intramolecular Dative PIII -PV SystemEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2003Petr Kilian Abstract The reaction of NapP2S4 (1; Nap = naphthalene-1,8-diyl) with chlorine gas gave [Nap(PCl2)(PCl4)] (2), displaying a rare ,4P-,6P bonding interaction. An X-ray structure analysis confirmed the PCl5 -like, P,P bond containing phosphonium-phosphoride structure of 2 in the crystal, which was also found in solution at low temperature. At ambient and higher temperatures, dynamic behaviour on the NMR time-scale was observed, which was assigned to interchange of the ionic phosphonium-phosphoride form 2 and the molecular bis(phosphorane) Nap(PCl3)2 form 3, rather than to the ionic phosphonium salt-phosphorane form [Nap(PCl3)(PCl2)][Cl] 4. Electronic structure calculations were performed at the B3LYP/6,31G(d,p) level of theory on structures 2 and 3; structure 3 was located as a local minimum on the potential energy surface, 15 kcal·mol,1 higher in energy than structure 2. The crystal structure and calculated P,P distances are 2.34 and 2.31 Å for 2 and 3, respectively. An activation energy of 19.7 kcal·mol,1 was found for the transition state structure by coordinate driving calculations; the line-shape analysis of variable temperature 31P{1H} NMR spectra gave an activation energy of 14.4 kcal·mol,1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Stabilization of phytosterols in rapeseed oil by natural antioxidants during heatingEUROPEAN JOURNAL OF LIPID SCIENCE AND TECHNOLOGY, Issue 11 2009Dominik Kmiecik Abstract Antioxidants are substances that can reduce negative changes in fat. Many antioxidants are very effective during storage, but during heating they lose their properties. It is very important to find antioxidants that will be stable at high temperatures and protect fat throughout the entire frying process. The aim of this study was to estimate the effect of natural and synthetic antioxidants on changes in phytosterols of rapeseed oil during heating. Oil with antioxidants was heated at 180,°C for 4,h in a Rancimat® and in an Oxidograph®. Ethanol extract of rosemary, ethanol extract of green tea, and BHT were used in the study. The contents of phytosterols (sitosterol, campesterol, avenasterol, brassicasterol, stigmasterol) and oxyphytosterols (7,- and 7,-hydroxysterol, 5,,6,- and 5,,6,-epoxysterol, 7-ketosterol and triols) were estimated by gas chromatography. In all samples with antioxidants, a lower decrease of phytosterols and a lower increase of total oxyphytosterols were observed in comparison with the control sample (without antioxidant). The antioxidant effect depends on the type of the antioxidant and the heating conditions. The best results were observed in samples with natural antioxidants. BHT was a substance that protected phytosterols as well, but not as effectively as the other antioxidants. [source] Stabilization of mutant Cu/Zn superoxide dismutase (SOD1) protein by coexpressed wild SOD1 protein accelerates the disease progression in familial amyotrophic lateral sclerosis miceEUROPEAN JOURNAL OF NEUROSCIENCE, Issue 12 2001Kei Fukada Abstract Transgenic mice carrying familial amyotrophic lateral sclerosis (FALS)-linked mutant Cu/Zn superoxide dismutase (SOD1) genes such as G93A (G93A-mice) and G85R (G85R-mice) genes develop limb paresis. Introduction of human wild type SOD1 (hWT-SOD1) gene, which does not cause motor impairment by itself, into different FALS mice resulted in different effects on their clinical courses, from no effect in G85R-mice to acceleration of disease progression in G93A-mice. However, the molecular mechanism which causes the observed difference, has not been clarified. We hypothesized that the difference might be caused by the stability of mutant SOD1 proteins. Using a combination of mass spectrometry and enzyme-linked immunosorbent assay, we found that the concentration of G93A-SOD1 protein was markedly elevated in tissues of transgenic mice carrying both G93A - and hWT-SOD1 genes (G93A/hWT-mice) compared to that in G93A-mice, and also found that the concentration of G93A-SOD1 protein had a close relation to the disease duration. The concentration of metallothionein-I/II in the spinal cord, reflecting the degree of copper-mediated oxidative stress, was highest in G93A/hWT-mice, second in G93A-mice, and normal in the mice carrying hWT-SOD1 gene. These results indicated that the increase of G93A-SOD1 protein was responsible for the increase of oxidative stress and disease acceleration in G93A/hWT-mice. We speculate that coexpression of hWT-SOD1 protein is deleterious to transgenic mice carrying a stable mutant such as G93A-SOD1, because this mutant protein is stabilized by hWT-SOD1 protein, but not to transgenic mice carrying an unstable mutant such as G85R-SOD1, because this mutant protein is not stabilized by hWT-SOD1. [source] Enol Forms of 1,3-Indanedione, Their Stabilization by Strong Hydrogen Bonding, and Zwitterion-Assisted InterconversionEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 14 2010Mark Sigalov Abstract By analyzing NMR spectroscopic data, and supported by IR, UV/Vis, Raman, dielectrometry, and DFT techniques, a comprehensive study of the 1:2 adducts of picolinaldehyde and 1,3-indanediones is presented. The parent indanedione derivative 5 exists in an equilibrium between all-keto and enol forms, the latter being stabilized by an intramolecularO,H···N hydrogen bond. Only the all-keto form was observed in the 5,6-dimethoxy compound 6, whereas solely the enol tautomer was observed with its 5,6-dichloro analogue 7. Polar solvents and low temperatures shift the equilibrium towards the enol tautomer in 5. The structure of adduct 8, formed with isonicotinaldehyde, prevents the formation of intramolecular O,H···N hydrogen bonds and thus it exists in the all-keto form in low polar solvents. However, in DMSO solutions it adopts a zwitterionic form with a strong anionic O,···H···O hydrogen bond. Thus, the enol form in indanedione adducts was unequivocally characterized in solution and the factors that determine the keto,enol tautomerism, namely electronic effects, solvent, temperature, and intramolecular hydrogen bonds, have been methodically studied by spectroscopic and quantum mechanical methods. [source] Twisted Intercalating Nucleic Acids , Intercalator Influence on Parallel Triplex StabilitiesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 17 2006Vyacheslav V. Filichev Abstract Phosphoramidites of several new twisted intercalating nucleic acid (TINA) monomers and the previously discovered (R)-1- O -[4-(1-pyrenylethynyl)phenylmethyl]glycerol (1) were synthesized and used in DNA synthesis. Stabilization of Hoogsteen-type triplexes was observed in cases of insertion of the novel (R)-1- O -[3-(naphthalen-1-ylethynyl)phenylmethyl]glycerol (2) as a bulge into homopyrimidine oligodeoxynucleotides (ONs), whereas phenylethynyl and 4-(biphenylylethynyl) derivatives of TINAs resulted in destabilization of parallel triplexes relative to the wild-type triplex. It was concluded that TINA monomers should possess at least two fused phenyl rings attached through the triple bond at the 4-position of bulged (R)-1- O -(phenylmethyl)glycerol in homopyrimidine ONs in order to stabilize parallel triplexes. Slight destabilization of DNA/DNA Watson,Crick type duplexes (,Tm = 1.0,4.5 °C) was detected for 2 inserted as a bulge, while RNA/DNA duplexes and duplexes with other TINA analogues were considerably destabilized (,Tm > 6.0 °C). In cases of double insertion of 1 opposite to base inversions in dsDNA, the thermal stabilities of the triplexes were higher than that of the wild-type triplex, which is a new solution to overcome the problem of targeting homopurine stretches with single base pair inversions. A DNA three-way junction was considerably stabilized (,Tm in a range of 10.0,15.5 °C) upon insertion of TINA monomers in the junction point as a bulge. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Encapsulation and Stabilization of Reactive Aromatic Diazonium Ions and the Tropylium Ion Within a Supramolecular HostEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 24 2004Julia L. Brumaghim Abstract Supramolecular assemblies with internal cavities are being developed as nanoscale reaction vessels to protect or modify the reactivity of guest species through encapsulation. Diazonium cations and the tropylium cation were examined for their ability to encapsulate in the tetrahedral [Ga4L6]12, supramolecular assembly. The 4-(diethylamino)benzenediazonium cation 1 readily formed a 1:1 host,guest complex with this assembly, and this encapsulation prevented 1 from reacting with 2,4-pentanedione in D2O. The tropylium cation also formed a 1:1 host,guest complex with the [Ga4L6]12, assembly, greatly slowing its decomposition in D2O. Encapsulation in the protected environment of this host cavity alters the reactivity of these guest molecules, giving them greater stability. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Hydrophobic Chemistry in Aqueous Solution: Stabilization and Stereoselective Encapsulation of Phosphonium Guests in a Supramolecular HostEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 22 2004Julia L. Brumaghim Abstract Encapsulation of guest molecules inside supramolecular host assemblies provides a way to stabilize reactive species in aqueous solution. The stabilization of reactive phosphonium/ketone adducts of the general formula [R1MeC(OH)PR3]+ by encapsulation as guest molecules within a [Ga4L6]12, tetrahedral metal,ligand assembly is reported; although these cations decompose in aqueous solution, encapsulation inside the hydrophobic cavity of the assembly lengthens their lifetimes considerably, in some cases up to weeks. By varying the phosphane (PMe3, PEt3, PPhMe2, and PPh2Me) and ketone (acetone, methyl ethyl ketone, 1,1,1-trifluoroacetone, and fluoroacetone) which form these adducts, as well as the pD of the solutions, it was determined that the pH of the solution as well as the size and shape of the guest cations play an important role in the stability of these host,guest complexes. Encapsulation of chiral guests in the chiral [Ga4L6]12, assembly results in the formation of diastereomers, as characterized by 1H, 19F, and 31P NMR spectroscopy. Although the [Ga4L6]12, assembly is formed from non-chiral ligands, the assembly itself has ,,,, or ,,,, chirality around the metal centers. Due to the chirality of this assembly, diastereomeric selectivity is observed upon initial guest encapsulation (typical diastereomeric excesses are 30,50%). This initial diastereomeric selectivity decreases over time to reach an equilibrium but does not become 1:1, indicating both kinetic and thermodynamic processes promote selective guest encapsulation. These experiments demonstrate further the applications of nanoscale reaction vessels, self-assembled by design from non-chiral ligands, in providing a chiral and hydrophobic environment for guest molecules in aqueous solution. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Stabilization of organic matter in temperate soils: mechanisms and their relevance under different soil conditions , a reviewEUROPEAN JOURNAL OF SOIL SCIENCE, Issue 4 2006M. v. Lützow Summary Mechanisms for C stabilization in soils have received much interest recently due to their relevance in the global C cycle. Here we review the mechanisms that are currently, but often contradictorily or inconsistently, considered to contribute to organic matter (OM) protection against decomposition in temperate soils: (i) selective preservation due to recalcitrance of OM, including plant litter, rhizodeposits, microbial products, humic polymers, and charred OM; (ii) spatial inaccessibility of OM against decomposer organisms due to occlusion, intercalation, hydrophobicity and encapsulation; and (iii) stabilization by interaction with mineral surfaces (Fe-, Al-, Mn-oxides, phyllosilicates) and metal ions. Our goal is to assess the relevance of these mechanisms to the formation of soil OM during different stages of decomposition and under different soil conditions. The view that OM stabilization is dominated by the selective preservation of recalcitrant organic components that accumulate in proportion to their chemical properties can no longer be accepted. In contrast, our analysis of mechanisms shows that: (i) the soil biotic community is able to disintegrate any OM of natural origin; (ii) molecular recalcitrance of OM is relative, rather than absolute; (iii) recalcitrance is only important during early decomposition and in active surface soils; while (iv) during late decomposition and in the subsoil, the relevance of spatial inaccessibility and organo-mineral interactions for SOM stabilization increases. We conclude that major difficulties in the understanding and prediction of SOM dynamics originate from the simultaneous operation of several mechanisms. We discuss knowledge gaps and promising directions of future research. [source] Dynamic COI-tracking concept for the control of generators in multi-machine power systemsEUROPEAN TRANSACTIONS ON ELECTRICAL POWER, Issue 1 2008Zhou Lan Abstract In the conventional excitation control concept, the power angle and frequency of a generator are driven to a pre-designed operation point after the fault occurs. It is named as Constant Point Stabilization (CPS) concept in this paper. A novel concept, called dynamic Center of Inertia (COI)-tracking concept is proposed in this paper. In the concept, the power angle and frequency of each generator track the dynamic COI of the power system. Compared to CPS concept, a salient feature the suggested dynamic COI-tracking concept has is that the generators are not restricted to constant angle point or frequency any longer but track the dynamic COI trajectory of the system to keep synchronous in rotor angle and frequency. Wide area measurement system (WAMS) will be used to transform COI signals to each generator. The time delay within a certain limit of WAMS signals is permitted. To make comparison between the two concepts, the control system models based on the two concepts are first established. Then, using the back-stepping method, two robust controllers are designed to achieve the control objectives of the two concepts. At last, dynamic simulations are carried out based on a 2-area-4-machine test power system, and the control effects of the two controllers, together with that of the conventional AVR,+,PSS excitation system, are compared. Copyright © 2007 John Wiley & Sons, Ltd. [source] Surface-Protected Etching of Mesoporous Oxide Shells for the Stabilization of Metal NanocatalystsADVANCED FUNCTIONAL MATERIALS, Issue 14 2010Qiao Zhang Abstract Nanoparticles of transition metals, particularly noble metals, are widely used in catalysis. However, enhancing their stability during catalytic reactions has been a challenge that has limited the full use of the benefits associated with their small size. In this Feature Article, a general "encapsulation and etching" strategy for the fabrication of nanocatalyst systems is introduced in which catalyst nanoparticles are protected within porous shells. The novelty of this approach lies in the use of chemical etching to assist the creation of mesopores in a protective oxide shell to promote efficient mass transfer to encapsulated metal nanoparticles. The etching process allows for the direct transformation of dense silica coatings into porous shells so that chemical species can reach the catalyst surface to participate in reactions while the shells act as physical barriers against aggregation of the catalyst particles. By using the surface-protected etching process, both yolk,shell and core,satellite type nanoreactors are synthesized and their utilization in liquid- and gas-phase catalysis is demonstrated. The thermal and chemical stability of the metallic cores during catalytic reactions is also investigated, and further work is carried out to enhance recyclability via the introduction of superparamagnetic components into the nanoreactor framework. [source] Stabilization of PbS Nanocrystals by Bovine Serum Albumin in its Native and Denatured StatesADVANCED FUNCTIONAL MATERIALS, Issue 9 2009Mandeep Singh Bakshi Abstract PbS nanocrystals (NCs) are synthesized in aqueous phase within a temperature range of 40,80,°C in the presence of native and denatured states of bovine serum albumen (BSA) as the capping/stabilizing agent. The NCs are characterized with the help of field-emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, and energy-dispersive X-ray analysis. At 40,°C, large ball-shaped NCs (145,±,37,nm) with small surface protrusions are formed when 1,×,10,4,g mL,1 BSA is used. As the reaction temperature is increased towards 80,°C, the size of NCs decreases and they acquire somewhat cubic geometries (49.1,±,7.0,nm) due to a change in the capping behavior of BSA between its native and denatured states. The native and denatured states of BSA are simultaneously studied by fluorescence spectroscopy using tryptophan emission, and pH measurements with respect to time and temperature. Gel electrophoresis is used to determine the polarity of the BSA capped NCs. Only the small sized NCs conjugated with relatively larger amounts of BSA show a displacement towards the positively charged electrode in comparison to larger NCs with lower amounts of BSA capping. It was concluded that the denatured state of BSA is more effective in controlling the crystal growth of PbS than its native state especially in the low concentration range. [source] Luminescent Core/Shell Nanoparticles with a Rhabdophane LnPO4 - xH2O Structure: Stabilization of Ce3+ -Doped Compositions,ADVANCED FUNCTIONAL MATERIALS, Issue 3 2006V. Buissette Abstract The core/shell strategy has been successfully developed for rhabdophane lanthanide phosphate aqueous colloids. The growth of a LaPO4 - xH2O shell around Ce,Tb-doped core nanoparticles increases their stability against oxidation. A bright green luminescence is thus preserved in sol,gel films whose fabrication requires silica coating and thermal treatment of the core/shell nanoparticles. [source] Temperature as a Single On-Off Parameter Controlling Nanoparticles Growing, Stabilization and Fast DisentanglementADVANCED MATERIALS, Issue 38 2010Paula M. López-Pérez Thermoresponsive nanoparticles are synthesized from ionic random terpolymer precursors. A distinct temperature-dependent aggregation-redissolution behavior is observed within a subtle balance between polymer ionic charge and hydrophobic content, which is used for colloidal synthesis of nanoparticles in aqueous medium and without surfactants. The solution thermal history provides a robust mean to customize the size of nanoparticles that can be disentangled on command. [source] Inhibition of CK2 Activity by TGF-,1 Promotes I,B-, Protein Stabilization and Apoptosis of Immortalized HepatocytesHEPATOLOGY, Issue 6 2003Lakita G. Cavin Nuclear factor ,B (NF-,B) is an antiapoptotic factor involved in development, regeneration, and neoplastic progression of the liver. Previously, we have shown that stabilization of inhibitor ,B (I,B)-, protein following treatment of hepatocytes with transforming growth factor (TGF)-,1 promoted NF-,B repression, which then permitted induction of AP-1/SMAD-mediated liver cell death. Because basal I,B-, protein turnover is regulated by protein kinase CK2, here we have elucidated the regulation of CK2 kinase activity and its role in control of NF-,B levels following treatment with TGF-,1. We show that both messenger RNA (mRNA) and protein levels of the CK2, catalytic subunit are down-regulated following TGF-,1 stimulation in murine hepatocyte cells. The ensuing inhibition of CK2 kinase activity promotes stabilization of I,B protein, which is followed by the shutoff of constitutive NF-,B activity and induction of apoptosis. Ectopic expression of CK2, inhibits TGF-,1-induced apoptosis through sustained activation of NF-,B. Conversely, expression of a kinase-dead mutant of CK2, potentiates TGF-,1 cell killing. Importantly, we show that hepatocellular carcinomas (HCCs) derived from TGF-,1 transgenic mice and human HCC cell lines display enhanced CK2 I,B kinase activity that contributes in part to an elevated NF-,B activity in vivo. In conclusion, inhibition of CK2 expression levels by TGF-,1 is crucial for the induction of apoptosis of hepatocytes. Circumvention of this process by up-regulation of CK2 activity in transformed cells may contribute to the promotion of TGF-,1-induced liver carcinogenesis. [source] Aqueous Stabilization and Self-Assembly of Graphene Sheets into Layered Bio-Nanocomposites using DNAADVANCED MATERIALS, Issue 31 2009Avinash J. Patil Stabilization of aqueous suspensions of graphene single sheets by single-stranded DNA is demonstrated using a range of physical methods. The negatively charged bio-functionalized graphene sheets are spontaneously assembled into layered hybrid nanocomposites containing intercalated DNA molecules, or co-intercalated mixtures of DNA and the redox protein, cytochrome c. Small-molecule reducing agents readily access the intercalated proteins. [source] |