Aminocyclodextrins to facilitate the deprotonation of 4-tert-butyl-alpha-nitrotoluene

6A-Amino-6A-deoxy-beta-cyclodextrin enhances the rate of the deprotonation of 4-tert-butyl-alpha-nitrotoluene. The rate constants for reaction of the cyclodextrin-bound species, kinc = 4 x 10(-3), 9 x 10(-3) and 19 x 10(-3) s(-1), at pH 6.0, 6.5 and 7.0, respectively, in 0.1 mol dm(-3) aqueous phosphate buffer containing 1% methanol at 298 K. These rate constants correspond to a rate acceleration (kinc/kun) of ca. 10 times at each pH. Under the same conditions, 6A-dimethylamino-6A-deoxy-beta-cyclodextrin and 6A-(2-aminoethylamino)-6A-deoxy-beta-cyclodextrin are more effective; at pH 6.0, 6.5 and 7.0, for the former, kinc = 3 x 10(-2), 7 x 10(-2) and 12 x 10(-2) s(-1), whilst for the latter, kinc = 4 x 10(-2), 5 x 10(-2) and 9 x 10(-2) s(-1), respectively. Each cyclodextrin also decreases the pKa of the nitrotoluene, from 6.8 in free solution, to 6.2 when bound. The accelerated deprotonation by 6A-amino-6A-deoxy-beta-cyclodextrin is reflected in the enhanced rates of hydrogen-deuterium exchange of the nitrotoluene in deuterium oxide, and in the conjugate addition of the nitrotoluene to methyl vinyl ketone in aqueous solution.     

Application of partial observability for analysis and design of synchronized systems

Synchronization in identical drive-response systems is a problem that can be cast in an observer design framework. In this paper we extend this approach by studying the analysis/design of partial synchronization by means of observer theory. In doing so, we introduce the concept of partial observer--an observer to reconstruct a part of the system state vector. It is also shown how the observability condition can be utilized to analyze the dynamics in an array of coupled identical systems.     

Nonlinear resonances in an axially excited beam carrying a top mass: simulations and experiments

In this paper, nonlinear resonances in a coupled shaker-beam-top mass system are investigated both numerically and experimentally. The imperfect, vertical beam carries the top mass and is axially excited by the shaker at its base. The weight of the top mass is below the beam’s static buckling load. A semi-analytical model is derived for the coupled system. In this model, Taylor-series approximations are used for the inextensibility constraint and the curvature of the beam. The steady-state behavior of the model is studied using numerical tools. In the model with a single beam mode, parametric and direct resonances are found, which affect the dynamic stability of the structure. The model with two beam modes not only shows an additional second harmonic resonance, but also reveals some extra small resonances in the low-frequency range, some of which can be identified as combination resonances. The experimental steady-state response is obtained by performing a (stepped) frequency sweep-up and sweep-down with respect to the harmonic input voltage of the amplifier-shaker combination. A good correspondence between the numerical and experimental steady-state responses is obtained.     

Die Erscheinung der Fraktionierung von Kristallgemischen bei der Kataphorese

Zusammenfassung Wir haben eine bei der kataphoretischen Herstellung von Oxydkathoden aufgetretene Erscheinung untersucht und mit Hilfe von Modellversuchen festgestellt, da? bei der Kataphorese von Suspensionen mit K?rnchen von inhomogener Zusammensetzung eine Fraktionierung der einzelnen Kristallsorten eintritt. Bei den Karbonaten des Bariums, Strontiums und Kalziums besteht diese Fraktionierung darin, da? die kataphoretische Abscheidung der K?rnchen mit Ca-Gehalt langsamer ist als die Abscheidung der K?rnchen mit Ba- und Sr- Gehalt.     

Nonsmooth bifurcations of equilibria in planar continuous systems

In this paper we present a procedure to find all limit sets near bifurcating equilibria in a class of hybrid systems described by continuous, piecewise smooth differential equations. For this purpose, the dynamics near the bifurcating equilibrium is locally approximated as a piecewise affine systems defined on a conic partition of the plane. To guarantee that all limit sets are identified, conditions for the existence or absence of limit cycles are presented. Combining these results with the study of return maps, a procedure is presented for a local bifurcation analysis of bifurcating equilibria in continuous, piecewise smooth systems. With this procedure, all limit sets that are created or destroyed by the bifurcation are identified in a computationally feasible manner.     

Stable isotope analysis of white-tailed deer teeth as a paleoenvironmental proxy at the Maya site of La Joyanca,northwestern Petén,Guatemala*

ABSTRACT

Carbon and oxygen isotopes ratios from herbivore teeth have previously been used as paleo-environmental proxies in temperate zones. However, their utility in tropical zones remains uncertain. In this study, sequential sub-samples from white-tailed deer (Odocoileus virginianus) teeth (second and third molars) from the Maya archaeological site of La Joyanca, located in northwestern Petén, Guatemala, show that δ¹⁸O of enamel carbonate corresponds broadly to modern observed precipitation δ¹⁸O over the 10-month period of tooth formation, capturing rainfall seasonality. The analyses also detect significant diachronic differences in the δ¹⁸O between the periods 1100–1000 BP (850–950 A.D.) and 1000–900 BP (950–1050 A.D.) at La Joyanca. The δ¹³C in both periods are indicative of a C₃-plant based diet, which suggests cultivation of maize did not differentially affect deer diet during this period.     

Transitions in structure in oil-in-water emulsions as studied by diffusing wave spectroscopy

Transitions in structure of sodium caseinate stabilized emulsions were studied using conventional rheometry as well as diffusing wave spectroscopy (DWS). Structural differences were induced by different amounts of stabilizer, and transitions in structure were induced by acidification. Special attention was given to the sol-gel transition. In this study the criterion of the sol-gel transition being frequency independent was verified for emulsions using DWS. It was shown that this sol-gel transition did not correspond to the so-called ergodic-nonergodic transition. Differences, as a function of the pH, were found for emulsions containing different amounts of stabilizer. The emulsion droplets in an emulsion without extra stabilizer formed a continuous network upon acidification, while the droplets in emulsions with an excess of stabilizer formed a network of oil droplets at neutral pH. Upon acidification of the latter one, the initial network of oil droplets fell apart, and eventually a network of sodium caseinate, in which the oil droplets were embedded, was formed. This caused the appearance of two sol-gel transitions. The breaking of the initial network as well as the network formation of sodium caseinate in time was observed by DWS.     

Nonlinear dynamic analysis of a structure with a friction-based seismic base isolation system

Many dynamical systems are subject to some form of non-smooth or discontinuous nonlinearity. One eminent example of such a nonlinearity is friction. This is caused by the fact that friction always opposes the direction of movement, thus changing sign when the sliding velocity changes sign. In this paper, a structure with friction-based seismic base isolation is regarded. Seismic base isolation can be employed to decouple a superstructure from the potentially hazardous surrounding ground motion. As a result, the seismic resistance of the superstructure can be improved. In this case study, the base isolation system is composed of linear laminated rubber bearings and viscous dampers and nonlinear friction elements. The nonlinear dynamic modelling of the base-isolated structure with the aid of constraint equations, is elaborated. Furthermore, the influence of the dynamic characteristics of the superstructure and the nonlinear modelling of the isolation system, on the total system’s dynamic response, is examined. Hereto, the effects of various modelling approaches are considered. Furthermore, the dynamic performance of the system is studied in both nonlinear transient and steady-state analyses. It is shown that, next to (and in correlation with) transient analyses, steady-state analyses can provide valuable insight in the discontinuous dynamic behaviour of the system. This case study illustrates the importance and development of nonlinear modelling and nonlinear analysis tools for non-smooth dynamical systems.     

Fabrication of nanoporous templates from diblock copolymer thin films on alkylchlorosilane-neutralized surfaces

The fabrication of nanoporous templates from poly(styrene)-b-poly(methyl methacrylate) diblock copolymer thin films (PS-b-PMMA, volume ratio 70:30) on silicon requires precise control of interfacial energies to achieve a perpendicular orientation of the PMMA cylindrical microdomains relative to the substrate. To provide a simple, rapid, yet tunable approach for surface neutralization, we investigated the self-assembled ordering of PS-b-PMMA diblock copolymer thin films on silicon substrates modified with a partial monolayer of octadecyldimethyl chlorosilane (ODMS), i.e., a layer of ODMS with a grafting density less than the maximum possible monolayer surface coverage. We demonstrate herein the fabrication of nanoporous PS templates from annealed PS-b-PMMA diblock copolymer thin films on these partial ODMS SAMs.     

Steady-state dynamics of a 3D tensegrity structure: Simulations and experiments

This paper considers a modeling and analysis approach for the investigation of the linear and nonlinear steady-state dynamics of a base excited 3D tensegrity module carrying a top mass. The tensegrity module contains three compressive members, which may buckle and six cables (tendons). First, a dynamic model of the system is derived using Lagrange’s equation with constraints. The buckling modeling of the compressive members is based on the assumed-mode method with a single mode discretization. The tendons are modeled as piecewise linear springs, which can only take tensile forces. This research focusses on the dynamic stability of the tensegrity structure by defining the geometrical and material properties in such a way that the system is just below the static stability boundary. Static and linear dynamic analysis is performed. In the nonlinear steady-state analysis, frequency-amplitude plots, power spectral density plots, bifurcation point continuation diagrams, and Poincaré maps are presented. A tensegrity structure is designed and manufactured and an experimental set-up is realized in order to validate the model by comparing experimentally and numerically obtained responses. In the validation stage, the numerical results are based on an amplifier-shaker-tensegrity structure model. It can be concluded that the numerical results match partly quantitatively and partly qualitatively with the experimentally obtained responses.