Ring-Closure Reactions. 13.1 A Convenient Synthesis of Many-Membered Thiacycloalkanes

Interaction of α,ω-dihaloalkanes with sulfide ion (eq. 1) is a common route for the synthesis in good yield of 5- and 6-membered polymethylene sulfides.     

Hierarchical Analysis of Self‐Assembled PEGylated Hexaphenylalanine Photoluminescent Nanostructures

Despite the growing literature about diphenylalanine‐based peptide materials, it still remains a challenge to delineate the theoretical insight into peptide nanostructure formation and the structural features that could permit materials with enhanced properties to be engineered. Herein, we report the synthesis of a novel peptide building block composed of six phenylalanine residues and eight PEG units, PEG₈‐F6. This aromatic peptide self‐assembles in water in stable and well‐ordered nanostructures with optoelectronic properties. A variety of techniques, such as fluorescence, FTIR, CD, DLS, SEM, SAXS, and WAXS allowed us to correlate the photoluminescence properties of the self‐assembled nanostructures with the structural organization of the peptide building block at the micro‐ and nanoscale. Finally, a model of hexaphenylalanine in aqueous solution by molecular dynamics simulations is presented to suggest structural and energetic factors controlling the formation of nanostructures.     

Actively compensated aerostatic thrust bearing: design,modelling and experimental validation

Active compensation is an effective method for increasing air bearing static and dynamic performance. This paper describes the design, modelling and experimental validation of an actively compensated externally pressurized gas bearing. The active compensation is obtained through the support compensation strategy. With this strategy, the system’s initial working position is restored by compensating for air gap variations through adjustments to the bearing vertical dimension. The described bearing consists in a conventional thrust bearing which is integrated with a multilayer piezoelectric actuator, a compliant mechanism and a digital controller. Nevertheless the non-linear nature of the air system, a simple linear model results to be an effective choice for neighbour of equilibrium conditions. Results demonstrate the good accuracy of the model and the system’s good capacity of rejecting external force disturbances.     

Carbon and nitrogen distribution in the sediments of lagoon of Ravenna (Italy)

The distribution and the origin of carbon and nitrogen in sediments of an Italian lagoon--located north-east of Ravenna town--were investigated. From 1957 to 1976, the lagoon had been affected by a strong industrial pollution due to an important petrochemical complex. At present, industrial and domestic waste waters undergo a treatment process before being discharged into the lagoon. Sediment samples from 10 locations throughout the lagoon were analysed, in order to document the spatial and vertical distribution of C and N. Data show a very strong variability (organic carbon content varies between 8.9% and 0.14%) and the highest values were found in the immediate vicinity of the industrial discharge. Sediment organic matter shows allochthonous origin in proximity of industrial discharge and autochthonous origin in the remaining areas.     

rH-metric controls and primary standardization in aqueous-organic media

The rationale for the extension of the rH-metric standardization and measurements to aqueous-organic solvent mixtures is here introduced, and examples of establishment of the ranges of conventional rH-metric scales as well as primary standards rHs in some typical aqueous-organic solvent mixtures are described.     

The solute-solvent system: solvent constraints on the conformational dynamics of acetylcholine

The objective of this study was to determine if and how a solvent influences internal motions in a solute molecule. Acetylcholine was chosen as the object of study given its interesting molecular structure and major biological significance. Molecular dynamics simulations were carried out in the vacuum (10 ns), water (5 ns), methanol (5 ns), and octanol (1.5 ns). Seven clusters of conformers were identified, namely, +g+g, -g-g, +gt, -gt, t+g, t-g, and tt, where the gauche and trans labels refer to the dihedral angles tau(2) and tau(3), respectively. As expected, the relative proportion of these conformational clusters was highly solvent-dependent and corresponded to a progressive loss of conformational freedom with increasing molecular weight of the solvent. More importantly, the conformational clusters were used to calculate instantaneous and median angular velocity (omega and omega(M), respectively) and instantaneous and median angular acceleration (alpha and alpha(M), respectively). Angular velocity and angular acceleration were both found to decrease markedly with increasing molecular weight of the solvent, i.e., vacuum (epsilon = 1) > water > methanol > octanol. The decrease from the vacuum to octanol was approximately 40% for tau(2) and approximately 60% for tau(3). Such solvent-dependent constraints on a solute's internal motions may be biologically and pharmacologically relevant.     

Chaos control by using Motor Maps

In this paper a new method for chaos control is proposed, consisting of an unsupervised neural network, namely a Motor Map. In particular a feedback entrainment scheme is adopted: a chaotic system with a given parameter set generates the reference trajectory for another chaotic system with different parameters to be controlled: the Motor Map is required to provide the appropriate time-varying gain value for the feedback signal. The state of the controlled system is considered as input to the Motor Map. Particular efforts have been paid to the feasibility of the implementation. Indeed, the simulations performed have been oriented to design a Motor Map suitable for an hardware realization, thus some restrictive hypotheses, such as for example a low number of neurons, have been assumed. A huge number of simulations has been carried out by considering as system to be controlled a Double Scroll Chua Attractor as well as other chaotic attractors. Several reference trajectories have also been considered: a limit cycle generated by a Chua's circuit with different parameters values, a double scroll Chua attractor, a chaotic attractor of the family of the Chua's circuit attractors. In all the simulations instead of controlling the whole state space, only two state variables have been fed back. Good results in terms of settling time (namely, the period in which the map learns the control task) and steady state errors have been obtained with a few neurons. The Motor Map based adaptive controller offers high performances, specially in the case when the reference trajectory is switched into another one. In this case, a specialization of the neurons constituting the Motor Map is observed: while a group of neurons learns the appropriate control law for a reference trajectory, another group specializes itself to control the system when the other trajectory is used as a reference. A discrete components electronic realization of the Motor Map is presented and experimental results confirming the simulation results are shown. (c) 2002 American Institute of Physics.