Crystal and molecular structures of three 2-sulphur-substituted cyclohexanones studied by X-ray crystallography and by ab initio molecular orbital calculations

The conformational features of three 2-sulphur-substituted cyclohexanone derivatives, which differ in the number of sulphur-bound oxygen atoms, i.e. zero (I), one (II) and two (III), were investigated by single crystal X-ray crystallography and geometry optimized structures determined using Hartree-Fock method. In each of (I)-(III) an intramolecular S center dot center dot center dot O(carbonyl) interaction is found with the magnitude correlated with the oxidation state of the sulphur atom, i.e. 2.838(3) angstrom in (I) to 2.924(2) angstrom in (II) to 3.0973(18) angstrom in (III). There is an inverse relationship between the strength of this interaction and the magnitude of the carbonyl bond. The supramolecular aggregation patterns are primarily determined by C-H center dot center dot center dot O contacts and are similarly influenced by the number of oxygen atoms in the molecular structures. Thus, a supramolecular chain is found in the crystal structure of (I). With an additional oxygen atom available to participate in C-H center dot center dot center dot O interactions, as in (II), a two-dimensional array is found. Finally, a three-dimensional network is found for (III). Despite there being differences in conformations between the experimental structures and those calculated in the gas-phase, the S center dot center dot center dot O interactions persist. The presence of intermolecular C-H center dot center dot center dot O interactions involving the cyclohexanone-carbonyl group in the solid-state, disrupts the stabilising intramolecular C-H center dot center dot center dot O interaction in the energetically-favoured conformation. (I): C(12)H(13)NO(3)S, triclinic space group P (1) over bar with a = 5.392(3) angstrom b = 10.731(6) angstrom, c = 11.075(6) angstrom, alpha = 113.424(4)degrees, beta = 94.167(9)degrees, gamma = 98.444(6)degrees, V = 575.5(6) angstrom(3), Z = 2, R(1) = 0.052; (II): C(12)H(13)NO(4)S, monoclinic P2(1)/n, a = 7.3506(15) angstrom, b = 6.7814(14) angstrom, c = 23.479(5) angstrom, beta = 92.94(3)degrees, V = 1168.8(4) angstrom(3), Z = 4, R(1) = 0.046; (III): C(12)H(13)NO(5)S, monoclinic P2(1)/c, a = 5.5491(11) angstrom, b = 24.146(3) angstrom, c = 11.124(3) angstrom, beta = 114.590(10)degrees, V = 1355.3(5) angstrom(3), Z = 4, R(1) = 0.051.

Testing of combined heating systems for small houses: Improved procedures for whole system test methods : Deliverable 2.3

Dynamic system test methods for heating systems were developed and applied by the institutes SERC and SP from Sweden, INES from France and SPF from Switzerland already before the MacSheep project started. These test methods followed the same principle: a complete heating system – including heat generators, storage, control etc., is installed on the test rig; the test rig software and hardware simulates and emulates the heat load for space heating and domestic hot water of a single family house, while the unit under test has to act autonomously to cover the heat demand during a representative test cycle. Within the work package 2 of the MacSheep project these similar – but different – test methods were harmonized and improved. The work undertaken includes:  • Harmonization of the physical boundaries of the unit under test. • Harmonization of the boundary conditions of climate and load. • Definition of an approach to reach identical space heat load in combination with an autonomous control of the space heat distribution by the unit under test. • Derivation and validation of new six day and a twelve day test profiles for direct extrapolation of test results.   The new harmonized test method combines the advantages of the different methods that existed before the MacSheep project. The new method is a benchmark test, which means that the load for space heating and domestic hot water preparation will be identical for all tested systems, and that the result is representative for the performance of the system over a whole year. Thus, no modelling and simulation of the tested system is needed in order to obtain the benchmark results for a yearly cycle. The method is thus also applicable to products for which simulation models are not available yet. Some of the advantages of the new whole system test method and performance rating compared to the testing and energy rating of single components are:  • Interaction between the different components of a heating system, e.g. storage, solar collector circuit, heat pump, control, etc. are included and evaluated in this test. • Dynamic effects are included and influence the result just as they influence the annual performance in the field. • Heat losses are influencing the results in a more realistic way, since they are evaluated under "real installed" and representative part-load conditions rather than under single component steady state conditions.   The described method is also suited for the development process of new systems, where it replaces time-consuming and costly field testing with the advantage of a higher accuracy of the measured data (compared to the typically used measurement equipment in field tests) and identical, thus comparable boundary conditions. Thus, the method can be used for system optimization in the test bench under realistic operative conditions, i.e. under relevant operating environment in the lab.   This report describes the physical boundaries of the tested systems, as well as the test procedures and the requirements for both the unit under test and the test facility. The new six day and twelve day test profiles are also described as are the validation results.

In-depth search focused on furans, lactones, volatile phenols, and acetals as potential age markers of Madeira wines by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction

The establishment of potential age markers of Madeira wine is of paramount significance as it may contribute to detect frauds and to ensure the authenticity of wine. Considering the chemical groups of furans, lactones, volatile phenols, and acetals, 103 volatile compounds were tentatively identified; among these, 71 have been reported for the first time in Madeira wines. The chemical groups that could be used as potential age markers were predominantly acetals, namely, diethoxymethane, 1,1-diethoxyethane, 1,1-diethoxy-2-methyl-propane, 1-(1-ethoxyethoxy)-pentane, trans-dioxane and 2-propyl-1,3-dioxolane, and from the other chemical groups, 5-methylfurfural and cis-oak-lactone, independently of the variety and the type of wine. GC × GC-ToFMS system offers a more useful approach to identify these compounds compared to previous studies using GC−qMS, due to the orthogonal systems, that reduce coelution, increase peak capacity and mass selectivity, contributing to the establishment of new potential Madeira wine age markers. Remarkable results were also obtained in terms of compound identification based on the organized structure of the peaks of structurally related compounds in the GC × GC peak apex plots. This information represents a valuable approach for future studies, as the ordered-structure principle can considerably help the establishment of the composition of samples. This new approach provides data that can be extended to determine age markers of other types of wines.

Stabilizing controller design for uncertain nonlinear systems using fuzzy models

A Lyapunov-based stabilizing control design method for uncertain nonlinear dynamical systems using fuzzy models is proposed. The controller is constructed using a design model of the dynamical process to be controlled. The design model is obtained from the truth model using a fuzzy modeling approach. The truth model represents a detailed description of the process dynamics. The truth model is used in a simulation experiment to evaluate the performance of the controller design. A method for generating local models that constitute the design model is proposed. Sufficient conditions for stability and stabilizability of fuzzy models using fuzzy state-feedback controllers are given. The results obtained are illustrated with a numerical example involving a four-dimensional nonlinear model of a stick balancer.

Critical temperature for first-order phase transitions in confined systems

We consider the Euclidean D-dimensional -lambda vertical bar phi vertical bar(4)+eta vertical bar rho vertical bar(6) (lambda,eta > 0) model with d (d <= D) compactified dimensions. Introducing temperature by means of the Ginzburg-Landau prescription in the mass term of the Hamiltonian, this model can be interpreted as describing a first-order phase transition for a system in a region of the D-dimensional space, limited by d pairs of parallel planes, orthogonal to the coordinates axis x(1), x(2),..., x(d). The planes in each pair are separated by distances L-1, L-2, ... , L-d. We obtain an expression for the transition temperature as a function of the size of the system, T-c({L-i}), i = 1, 2, ..., d. For D = 3 we particularize this formula, taking L-1 = L-2 = ... = L-d = L for the physically interesting cases d = 1 (a film), d = 2 (an infinitely long wire having a square cross-section), and for d = 3 (a cube). For completeness, the corresponding formulas for second-order transitions are also presented. Comparison with experimental data for superconducting films and wires shows qualitative agreement with our theoretical expressions.

Higher-derivative theory of (2+1)-dimensional gravity

Higher-derivative gravity in 2 + 1 dimensions is considered. The general solution of the linearized field equations in a three-dimensional version of the Teyssandier gauge is obtained, and from that the solution for a static pointlike source is found. The deflection of light rays is also analysed. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Stability analysis of the D-dimensional nonlinear Schrodinger equation with trap and two- and three-body interactions

Considering the static solutions of the D-dimensional nonlinear Schrodinger equation with trap and attractive two-body interactions, the existence of stable solutions is limited to a maximum critical number of particles, when D greater than or equal to 2. In case D = 2, we compare the variational approach with the exact numerical calculations. We show that, the addition of a positive three-body interaction allows stable solutions beyond the critical number. In this case, we also introduce a dynamical analysis of the conditions for the collapse. (C) 2000 Published by Elsevier B.V. B.V. All rights reserved.

QUASIDISTRIBUTIONS and COHERENT STATES FOR FINITE-DIMENSIONAL QUANTUM SYSTEMS

In recent years, an approach to discrete quantum phase spaces which comprehends all the main quasiprobability distributions known has been developed. It is the research that started with the pioneering work of Galetti and Piza, where the idea of operator bases constructed of discrete Fourier transforms of unitary displacement operators was first introduced. Subsequently, the discrete coherent states were introduced, and finally, the s-parametrized distributions, that include the Wigner, Husimi, and Glauber-Sudarshan distribution functions as particular cases. In the present work, we adapt its formulation to encompass some additional discrete symmetries, achieving an elegant yet physically sound formalism.

Phase Transition in Dynamical Systems: Defining Classes of Universality for Two-Dimensional Hamiltonian Mappings via Critical Exponents

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Mechanical properties and dimensional effects of ZnO- and SnO(2)-based varistors

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

An introduction to numerical methods in low-dimensional quantum systems

This is an introductory course to the Lanczos Method and Density Matrix Renormalization Group Algorithms (DMRG), two among the leading numerical techniques applied in studies of low-dimensional quantum models. The idea of studying the models on clusters of a finite size in order to extract their physical properties is briefly discussed. The important role played by the model symmetries is also examined. Special emphasis is given to the DMRG.