Pseudoperiodic "Living" and/or controlled cationic ring-opening copolymerization of oxetane with tetrahydropyran:microstructure of polymers vs kinetics of chain growth

The "living" and/or controlled cationic ring-opening bulk copolymerization of oxetane (Ox) with tetrahydropyran (THP) (cyclic ether with no homopolymerizability) at 35°C was examined using ethoxymethyl-1 -oxoniacyclohexane hexafluoroantimonate (EMOA) and (BF3 · CH3OH)THP as fast and slow initiator, respectively, yielding living and nonliving polymers with pseudoperiodic sequences (i.e., each pentamethylene oxide fragment inserted into the polymer is flanked by two trimethylene oxide fragments). Good control over number-average molecular weight (Mn up to 150000 g mol-1) with molecular weight distribution (MWD ∼ 1.4-1, 5) broader than predicted by the Poison distribution (MWDs > 1 +1/DPn) was attained using EMOA as initiating system, i.e., C 2H5OCH2Cl with 1.1 equiv of AgSbF6 as a stable catalyst and 1.1 equiv of 2,6-di-tert-butylpyridine used as a non-nucleophilic proton trap. With (BF3 · CH 3OH)THP, a drift of the linear dependence M n(GPC) vs Mn(theory) to lower molecular weight was observed together with the production of cyclic oligomers, ∼3-5% of the Ox consumed in THP against ∼30% in dichloromethane. Structural and kinetics studies highlighted a mechanism of chains growth where the rate of mutual conversion between "strain ACE species" (chain terminated by a tertiary 1-oxoniacyclobutane ion, Al) and "strain-free ACE species" (chain terminated by a tertiary 1-oxoniacyclohexane ion, Tl) depends on the rate at which Ox converts the stable species T1 (kind of "dormant" species) into a living "propagating" center A1 (i.e., k aapp[Ox]). The role of the THP solvent associated with the suspension of irreversible and reversible transfer reactions to polymer, when the polymerization is initiated with EMOA, was predicted by our kinetic considerations. The activation -deactivation pseudoequilibrium coefficient (Qt) was then calculated in a pure theoretical basis. From the measured apparent rate constant of Ox (kOxapp) and THP (kTHPapp = ka(endo)app) consumption, Qt and reactivity ratio (kp/kd, k a(endo)/ka(exo), and ks/ka(endo) were calculated, which then allow the determination of the transition rate constant of elementary step reactions that governs the increase of Mu with conversion. © 2009 American Chemical Society.

Solving Ratio-Dependent Predator-Prey System with Constant Effort Harvesting using Variational Iteration Method

Due to wide range of interest in use of bio-economic models to gain insight into the scientific management of renewable resources like fisheries and forestry,variational iteration method (VIM) is employed to approximate the solution of the ratio-dependent predator-prey system with constant effort prey harvesting.The results are compared with the results obtained by Adomian decomposition method and reveal that VIM is very effective and convenient for solving nonlinear differential equations.

New Bounds for the Maximum Size of Ternary Constant Weight Codes

This work was partially supported by the Bulgarian National Science Fund under Grant I–618/96.

A comparison of in situ constant and falling head permeameter tests to assess the distribution of clogging within horizontal subsurface flow constructed wetlands

Clogging is the main operational problem associated with horizontal subsurface flow constructed wetlands (HSSF CWs). The measurement of saturated hydraulic conductivity has proven to be a suitable technique to assess clogging within HSSF CWs. The vertical and horizontal distribution of hydraulic conductivity was assessed in two full-scale HSSF CWs by using two different in situ permeameter methods (falling head (FH) and constant head (CH) methods). Horizontal hydraulic conductivity profiles showed that both methods are correlated by a power function (FH= CH 0.7821, r 2=0.76) within the recorded range of hydraulic conductivities (0-70 m/day). However, the FH method provided lower values of hydraulic conductivity than the CH method (one to three times lower). Despite discrepancies between the magnitudes of reported readings, the relative distribution of clogging obtained via both methods was similar. Therefore, both methods are useful when exploring the general distribution of clogging and, specially, the assessment of clogged areas originated from preferential flow paths within full-scale HSSF CWs. Discrepancy between methods (either in magnitude and pattern) aroused from the vertical hydraulic conductivity profiles under highly clogged conditions. It is believed this can be attributed to procedural differences between the methods, such as the method of permeameter insertion (twisting versus hammering). Results from both methods suggest that clogging develops along the shortest distance between water input and output. Results also evidence that the design and maintenance of inlet distributors and outlet collectors appear to have a great influence on the pattern of clogging, and hence the asset lifetime of HSSF CWs. © Springer Science+Business Media B.V. 2011.

Build-up of auditory stream segregation induced by tone sequences of constant or alternating frequency and the resetting effects of single deviants

Three experiments investigated the dynamics of auditory stream segregation. Experiment 1 used a 2.0-s constant-frequency inducer (10 repetitions of a low-frequency pure tone) to promote segregation in a subsequent, 1.2-s test sequence of alternating low- and high-frequency tones. Replacing the final inducer tone with silence reduced reported test-sequence segregation substantially. This reduction did not occur when either the 4th or 7th inducer was replaced with silence. This suggests that a change at the induction/test-sequence boundary actively resets buildup, rather than less segregation occurring simply because fewer inducer tones were presented. Furthermore, Experiment 2 found that a constant-frequency inducer produced its maximum segregation-promoting effect after only 3 tone cycles - this contrasts with the more gradual build-up typically observed for alternating sequences. Experiment 3 required listeners to judge continuously the grouping of 20-s test sequences. Constant-frequency inducers were considerably more effective at promoting segregation than alternating ones; this difference persisted for ∼10 s. In addition, resetting arising from a single deviant (longer tone) was associated only with constant-frequency inducers. Overall, the results suggest that constant-frequency inducers promote segregation by capturing one subset of test-sequence tones into an on-going, pre-established stream and that a deviant tone may reduce segregation by disrupting this capture. © 2013 Acoustical Society of America.

Codon-precise, synthetic, antibody fragment libraries built using automated hexamer codon additions and validated through next generation sequencing

We have previously described ProxiMAX, a technology that enables the fabrication of precise, combinatorial gene libraries via codon-by-codon saturation mutagenesis. ProxiMAX was originally performed using manual, enzymatic transfer of codons via blunt-end ligation. Here we present Colibra™: an automated, proprietary version of ProxiMAX used specifically for antibody library generation, in which double-codon hexamers are transferred during the saturation cycling process. The reduction in process complexity, resulting library quality and an unprecedented saturation of up to 24 contiguous codons are described. Utility of the method is demonstrated via fabrication of complementarity determining regions (CDR) in antibody fragment libraries and next generation sequencing (NGS) analysis of their quality and diversity.

Best Constant in the Weighted Hardy Inequality: The Spatial and Spherical Version

Mathematics Subject Classification: 26D10.

On the 3-Wave Equations with Constant Boundary Conditions

2010 Mathematics Subject Classification: 37K40, 35Q15, 35Q51, 37K15.

On Optimal Quadratic Lagrange Interpolation: Extremal Node Systems with Minimal Lebesgue Constant via Symbolic Computation

ACM Computing Classification System (1998): G.1.1, G.1.2.

Hermitian Manifolds of Pointwise Constant Antiholomorphic Sectional Curvatures

2000 Mathematics Subject Classification: Primary 53B35, Secondary 53C50.

Assembly of a high-dielectric constant thin TiOX layer directly on H-terminated semiconductor diamond

A high-dielectric constant (high-k) TiOx thin layer was fabricated on hydrogen-terminated diamond (H-diamond) surface by low temperature oxidation of a thin titanium layer in ambient air. The metallic titanium layer was deposited by sputter deposition. The dielectric constant of the resultant TiOx was calculated to be around 12. The capacitance density of the metal-oxide-semiconductor (MOS) based on the TiOx/H-diamond was as high as 0.75 µF/cm2 contributed from the high-k value and the very thin thickness of the TiOx layer. The leakage current was lower than 10-13 A at reverse biases and 10-7A at the forward bias of -2 V. The MOS field-effect transistor based on the high-k TiOx/H-diamond was demonstrated. The utilization of the high-k TiOx with a very thin thickness brought forward the features of an ideally low subthreshold swing slope of 65 mV per decade and improved drain current at low gate voltages. The advantages of the utilization high-k dielectric for diamond MOSFETs are anticipated.

Sequence-related structural DNA anomalies affect restriction enzyme activity and DNA polymerase I binding

DNA serves as a target molecule for several types of enzymes and may assume a wide variety of structural motifs depending upon the local sequence. The BssHII restriction site (GC)3 resides in a 9bp region of alternating pyrimidine and purine residues within the &phis;X174 genome. Such sequences are known to demonstrate non-canonical helical behavior under the appropriate conditions. The kinetics of BssHII cleavage was investigated in supercoiled and linear plasmid DNA, and in a 323bp DNA fragment obtained via amplification of &phis;X174. The rate of enzyme cleavage was enhanced in the supercoiled form and in the presence of 50μM cobalt hexamine. Similarly, cobalt hexamine was also found to enhance TaqI activity directly adjacent to the (GC)3 region. ^ Initial DNA polymerase I binding studies (including a gel mobility shift assay and a protection assay) indicated a notable interaction between DNA polymerase I and the BssHII site. An in-depth study revealed that equilibrium binding of DNA polymerase I to the T7 RNA polymerase promoter was comparable to that of the (GC)3 site, however the strongest interaction was observed with a cruciform containing region. Increasing the ionic strength of the solution environment, including the addition of DNA polymerase I reaction buffer significantly decreased the equilibrium dissociation constant values. ^ It is suggested that the region within or around the BssHII site experiences a conformational change generating a novel structure under the influence of supercoiled tension or 50μM cobalt hexamine. It is proposed that this transition may enhance enzyme activity and binding by providing an initial enzyme-docking site—the rate-limiting step in restriction enzyme kinetics. The high binding potential of DNA polymerase I for each of the motifs described, is hypothesized to be due to recognition of the structural DNA anomalies by the 3′–5′ exonuclease domain. ^

Development of a binary positive and negative protein fragment complementation assay using yeast cytosine deaminase

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Constant Beauty Within and PCOS as Cacti

Travail créatif / Creative Work