The first dimeric trioganotin fluoride : stabilization by unsymmetrically oriented menthyl substituents

In the solid state, (-)-tris([1R,2S,5R]-menthyl)tin fluoride, Men₃SnF (6), exhibits a dimeric structure in which one tin atom is four-coordinate and the other five-coordinate. This novel dimeric association mode is attributed to the orientation of the unsymmetrical menthyl groups, which are arranged to allow a minimum Sn···Sn separation of 4.84 Å within the dimer. The exocyclic isopropyl groups of the menthyl groups point in opposite directions on each tin atom of the dimer, thus preventing further association (Sn···Sn separation outside the dimer 10.49 Å). ¹¹⁹Sn and ¹⁹F MAS NMR spectroscopy were utilized to probe the diverse coordination numbers found by X-ray crystallography for the geometries of the two tin and fluorine sites. In solution, 6 is a monomer at both room temperature and -100 °C. However, upon addition of Bu₄NF, 6 is in equilibrium with [(Men₃SnF)₂F]- (6a), [Men₃SnF₂]^- (6b), and noncoordinating fluoride anions.

Dispersion statistics and a sampling plan for Helicoverpa (Lepidoptera : Noctuidae) on fresh-market tomatoes (Lycopersicon esculentum)

Helicoverpa spp. is the primary pest in the Australian fresh-market tomato industry. We describe the spatial distribution of Helicoverpa spp. eggs on fresh-market tomato crops in the Goulburn Valley region of Victoria, and present a sequential sampling plan for monitoring population densities. The distribution of Helicoverpa spp. eggs was highly contagious, as indicated by a Taylor's b-value of 1.59. This high level of contagion meant that relatively large sample sizes would need to be collected to obtain an estimate of population density. High-precision sampling plans generally necessitated impractical sample sizes, and thus the plan we present is a relatively low-precision level plan (SE/mean = 0.3). Nonetheless, this level of precision is considered adequate for most agronomic scenarios. The plan was validated using a statistical re-sampling approach. The level of precision achieved was generally close to the nominal level. Likewise, the number of samples collected generally showed little departure from the theoretically calculated minimum sample size.

Global and regional dispersion of publishing in the field of international marketing

This paper empirically examines the research productivity of academic institutions in the leading international marketing journals, leading generalist marketing journals, and leading international business journals between the years 1999 and 2003 from a regional and country-specific perspective. The research found that across the three groups of journals, the majority of works were authored by academics at institutions located in North America, although North Americans contribute significantly less in the international marketing and international business journals than leading generalist marketing journals. The findings suggest that there is a broadening of non-U.S. influence within the international marketing and international business journals, which should lead to a broadening of international marketing theory.

Immunostimulatory polysaccharides from Chlorella pyrenoidosa. A new galactofuranan. Measurement of molecular weight and molecular weight dispersion by DOSY NMR.

Fractionation of the hot water extract of Chlorella pyrenoidosa was performed using a combination of ethanol precipitation, size exclusion chromatography, and anion exchange chromatography. One fraction contained a new polysaccharide, and this compound was shown to be a 1→2-linked β-d-galactofuranan from its 1D and 2D 1H and 13C NMR spectra, with a molecular weight of 15 kDa from DOSY NMR measurements. A number of other fractions were shown to have the same repeating unit as the previously identified arabinogalactan. However, arabinogalactans from different fractions were shown by DOSY NMR to have different molecular weights, which ranged from 27 to 1020 kDa. Agreement with molecular weights measured for some of these fractions by SEC-MALS was very good, further confirming the relationship established by Viel et al. between molecular weights of neutral polysaccharides and self-diffusion coefficients. The smaller molecular weight polysaccharides, the galactofuranan and the 27 and 50 kDa arabinogalactans, were shown to be close to monodisperse by analysis of the distributions of the self-diffusion coefficients for the polymers. The larger arabinogalactans had considerable variation in their molecular weights (188 ± 109 kDa and 1020 ± 370 kDa). Only the two larger arabinogalactans showed immunostimulatory activity.

Dispersion of information or market behaviour : general public trading in S & P 500 index futures

This paper considers 15 minute records of trading volume and traded prices coinciding with the reporting intervals required by the Commodity Futures Trading Commission. Records are extracted from trade records for two way trade between market makers (CTI1) and the general public (CTI4) from January 1994 to June 2004. Futures price records are matched with S&P500 cash index price records. Simultaneous volatility models are specified and estimated to test trading volume to futures volatility lead/lag effects and also futures volatility to cash index volatility lead/lag effects. There is evidence that existing theoretical models of the general public trading behaviour do not explain such behaviour in these very actively traded markets. These effects can depend more on market conditions than what is suggested in theoretical models.

Dispersion characterization of Mechanochemically Synthesized nanoparticles using UV/Vis Spectroscopy

Dispersion characterization of nanoparticles was carried out using UV/Vis spectroscopy. ZnO and CeO2 nanoparticles of sizes ranging 10 - 250 nm were investigated for slurries having various concentrations. The particles were synthesized by mechanochemical processing, which allows the formation of agglomeration-free nanoparticles. It was found that the UV/Vis spectra were highly sensitive to mean particle sizes and agglomeration states. The results showed that UV/Vis spectroscopy is a highly promising technique for studying nanoparticle dispersions having a wide range of concentrations in various media.

Dispersion of boron nitride nanotubes in aqueous solution with the help of ionic surfactants

We report that ammonium oleate surfactants can help the dispersion of multiwalled boron nitride nanotubes (BNNTs) in water to form a BNNT solution stable for several months, which was due to the non-covalent functionalization of nanotube surfaces. Fourier Transform Infrared Spectroscopy (FTIR) and Photoluminescence (PL) analysis with synchrotron radiation source revealed that this BNNT aqueous solution preserves the intrinsic optical properties of BNNTs. © 2009 Elsevier Ltd. All rights reserved.

Exponential stabilization of neural networks with various activation functions and mixed time-varying delays

This paper presents some results on the global exponential stabilization for neural networks with various activation functions and time-varying continuously distributed delays. Based on augmented time-varying Lyapunov-Krasovskii functionals, new delay-dependent conditions for the global exponential stabilization are obtained in terms of linear matrix inequalities. A numerical example is given to illustrate the feasibility of our results.

Stabilization of highly unsaturated fatty acids and delivery into foods

Highly unsaturated fatty acids derived from fish or algal oils, particularly EPA and DHA, are in high demand as healthy food ingredients in fortified foods. Due to their oxidative instability most food products incorporate stabilized microencapsulated EPA and DHA oils to avoid negative sensory impact associated with oxidation of these fatty acids. Complex coacervation has been particularly successful in stabilizing fish oil and providing an ingredient with a sensory shelf-life consistent with that of the food product. Overcoming the technical challenges associated with the instability of these oils will help drive growth of the omega-3 fortified healthy food ingredient market.

Angiotensin I-converting enzyme transition state stabilization by HIS1089 : evidence for a catalytic mechanism distinct from other gluzincin metalloproteinases

Angiotensin (Ang) I-converting enzyme (ACE) is a member of the gluzincin family of zinc metalloproteinases that contains two homologous catalytic domains. Both the N- and C-terminal domains are peptidyl-dipeptidases that catalyze Ang II formation and bradykinin degradation. Multiple sequence alignment was used to predict His¹⁰⁸⁹ as the catalytic residue in human ACE C-domain that, by analogy with the prototypical gluzincin, thermolysin, stabilizes the scissile carbonyl bond through a hydrogen bond during transition state binding. Site-directed mutagenesis was used to change His¹⁰⁸⁹ to Ala or Leu. At pH 7.5, with Ang I as substrate, k_cat/K_m values for these Ala and Leu mutants were 430 and 4,000-fold lower, respectively, compared with wild-type enzyme and were mainly due to a decrease in catalytic rate (k_cat) with minor effects on ground state substrate binding (K_m). A 120,000-fold decrease in the binding of lisinopril, a proposed transition state mimic, was also observed with the His¹⁰⁸⁹ --> Ala mutation. ACE C-domain-dependent cleavage of AcAFAA showed a pH optimum of 8.2. H1089A has a pH optimum of 5.5 with no pH dependence of its catalytic activity in the range 6.5-10.5, indicating that the His¹⁰⁸⁹ side chain allows ACE to function as an alkaline peptidyl-dipeptidase. Since transition state mutants of other gluzincins show pH optima shifts toward the alkaline, this effect of His¹⁰⁸⁹ on the ACE pH optimum and its ability to influence transition state binding of the sulfhydryl inhibitor captopril indicate that the catalytic mechanism of ACE is distinct from that of other gluzincins.

Evolutionary specialization of a tryptophan indole group for transition-state stabilization by eukaryotic transglutaminases

Covalent posttranslational protein modifications by eukaryotic transglutaminases proceed by a kinetic pathway of acylation and deacylation. Ammonia is released as the acylenzyme is formed, whereas the cross-linked product is released later in the deacylation step. Superposition of the active sites of transglutaminase type 2 (TG2) and the structurally related cysteine protease, papain, indicates that in the formation of tetrahedral intermediates, the backbone nitrogen of the catalytic Cys-277 and the N_Ɛ1 nitrogen of Trp-241 of TG2 could contribute to transition-state stabilization. The importance of this Trp-241 side chain was demonstrated by examining the kinetics of dansylcadaverine incorporation into a model peptide. Although substitution of the Trp-241 side chain with Ala or Gly had only a small effect on the Michaelis constant K_m (1.5-fold increase), it caused a >300-fold lowering of the catalytic rate constant k_cat. The wild-type and mutant TG2-catalyzed release of ammonia showed kinetics similar to the kinetics for the formation of cross-linked product, indicating that transitionstate stabilization in the acylation step was rate-limiting. In papain, a Gln residue is at the position of TG2-Trp-241. The conservation of Trp-241 in all eukaryotic transglutaminases and the finding that W241Q-TG2 had a much lower k_cat than wild-type enzyme suggest evolutionary specialization in the use of the indole group. This notion is further supported by the observation that transitionstate- stabilizing side chains of Tyr and His that operate in some serine and metalloproteases only partially substituted for Trp.

The "refoldability" of selected proteins in ionic liquids as a stabilization criterion, leading to a conjecture on biogenesis

The folding of proteins is usually studied in dilute aqueous solutions of controlled pH, but it has recently been demonstrated that reversible unfolding can occur in other media. Particular stability is conferred on the protein (folded or unfolded) when the process occurs in ‘protic ionic liquids’ (pILs) of controlled proton activity. This activity (‘effective pH’) is determined by the acid and base components of the pIL and is characterized in the present study by the proton chemical shift of the N–H proton. Here we propose a ‘refoldability’ or ‘refolding index’ (RFI) metric for assessing the stability of folded biomolecules in different solvent media, and demarcate high RFI zones in hydrated pIL media using ribonuclease A and hen egg white lysozyme as examples. Then we show that, unexpectedly, the same high RFIs can be obtained in pIL media that are 90% inorganic in character (simple ammonium salts). This leads us to a conjecture related to the objections that have been raised to ‘primordial soup’ theories for biogenesis, objections that are based on the observation that all the bonds involved in biomacromolecule formation are hydrolyzed in ordinary aqueous solutions unless specifically protected. The ingredients for primitive ionic liquids (NH3, CO, HCN, CO2, and water) were abundant in the early earth atmosphere, and many experiments have shown how amino acids could form from them also. Cyclical concentration in evaporating inland seas could easily produce the type of ambient-temperature, non-hydrolyzing, media that we have demonstrated here may be hospitable to biomolecules, and that may be actually encouraging of biopolymer assembly. Thus a plausible variant of the conventional ‘primordial soup’ model of biogenesis is suggested.

A finite-time stability theorem of stochastic nonlinear systems and stabilization designs

This paper focuses on the finite-time stability and stabilization designs of stochastic nonlinear systems. We first present and discuss a definition on the finite-time stability in probability of stochastic nonlinear systems, then we introduce a stochastic Lyapunov theorem on the finite-time stability, which has been established by Yin et al. We also employ this theorem to design a continuous state feedback controller that makes a class of stochastic nonlinear systems to be stable in finite time. An example and a simulation are given to illustrate the theoretical analysis.