Measurement of intraparticle diffusion in reversed phase liquid chromatography

The intraparticle diffusion coefficient was measured using a method based on the fitting of a set of experimental chromatographic profiles to the lumped pore diffusion model. For this purpose, both the analytical solution of the model in the Laplace domain and a numerical method were used. There was an excellent agreement between the results given by the two methods. These results are compared to those obtained by moment analysis of the same set of chromatographic profiles and by the determination of the intraparticle diffusion coefficient from the second central moment of these bands. Nearly identical results were obtained with these two independent methods. The values of the intraparticle diffusion coefficient, D_e, for rubrene in pure methanol was found to be by the modeling method and by the moment analysis method. These values increase with increasing water concentration, to 1.10×10⁻⁶ and , respectively, in a methanol/water solution and to 1.63×10⁻⁶ and , respectively, in a solution.These results confirm the validity and the consistency of the lumped pore model and the moment analysis theory. They show that both approaches describe correctly the mass transfer kinetics in the particles of packing material during the chromatographic process. Systematic determinations of the intraparticle diffusion coefficient can now be undertaken and the influence of various experimental parameters on this important property of packing materials can be investigated.     

“Smart” polymeric nanospheres as new materials for possible biomedical applications

Novel random terpolymers of N-isopropylacrylamide (NIPAM), sodium 2-acrylamido-2-methyl-1-propanesulfonate (AMPS), and cinnamoyloxyethylmethacrylate (CEMA) were synthesized by free radical copolymerization using AIBN as an initiator. Five terpolymers were obtained by copolymerization of the monomer mixtures containing a fixed amount of 10 mol % of AMPS while the content of CEMA ranged from 5 to 25 mol % and was changed in 5 mol % increments. The terpolymers obtained are water-soluble. Because of their amphiphilic nature they undergo self-organization in the aqueous solution with the formation of micelles capable of solubilizing sparingly water soluble organic compounds, such as drugs. The terpolymers are susceptible to three external stimuli, i.e. temperature, ionic strength and UV light. Due to the presence of NIPAM in the terpolymers they display the lower critical solution temperature (LCST), the presence of AMPS makes them sensitive to the ionic strength of the solution, while the light-responsiveness of the terpolymers is due to the presence of cinnamoyl chromophores, which undergo photodimerization when irradiated with UV light at about 280 nm. Application of any of these stimuli alone or in combination with other stimuli allows changing the copolymer properties in a controlled way.     

Positive real control of two-dimensional systems: Roesser models and linear repetitive processes

This paper considers the problem of positive real control for two-dimensional (2-D) discrete systems described by the Roesser model and also discrete linear repetitive processes, which are another distinct sub-class of 2-D linear systems of both systems theoretic and applications interest. The purpose of this paper is to design a dynamic output feedback controller such that the resulting closed-loop system is asymptotically stable and the closed-loop system transfer function from the disturbance to the controlled output is extended strictly positive real. We first establish a version of positive realness for 2-D discrete systems described by the Roesser state space model, then a sufficient condition for the existence of the desired output feedback controllers is obtained in terms of four LMIs. When these LMIs are feasible, an explicit parameterization of the desired output feedback controllers is given. We then apply a similar approach to discrete linear repetitive processes represented in their equivalent 1-D state-space form. Finally, we provide numerical examples to demonstrate the applicability of the approach.     

Iterative learning control and the singularity robust Jacobian inverse for mobile manipulators

The method of iterative learning control, to a large extent, has been inspired by robotics research, focused on the control of stationary manipulators. In this article we deal with the inverse kinematics problem for mobile manipulators, and show that a very basic singularity robust Jacobian inverse can be derived in a natural way within the framework of iterative learning control. To achieve this objective we have exploited the endogenous configuration space approach. The introduced Jacobian inverse defines the singularity robust Jacobian inverse kinematics algorithm for mobile manipulators. A Kantorovich-type estimate of the region of guaranteed convergence of the algorithm is derived. For two example kinematics, this estimate has been computed efficiently.     

Extended Jacobian inverse kinematics algorithm for nonholonomic mobile robots

By a generalization of the well-known extended Jacobian method for stationary manipulators, we derive the extended Jacobian inverse kinematics algorithm for nonholonomic mobile robots. Key points of the derivation consist in defining the kinematics of a mobile robot as the end-point map of a driftless control system, decomposing the space of control functions of this system into a finite and an infinite dimensional subspaces, and introducing an augmenting kinematics map subordinated to this decomposition. The original kinematics and the augmenting kinematics constitute the extended kinematics. The inverse Jacobian of the extended kinematics defines the extended Jacobian inverse kinematics algorithm. By design, the algorithm is repeatable. As an example, we derive a specific extended Jacobian inverse kinematics algorithm and illustrate its performance with the computer simulations.     

The microstructure of liquid immiscible Fe–Cu-based in situ formed amorphous/crystalline composite

In the microstructures of slowly and rapidly cooled liquid of the immiscible alloy Fe₃₀Cu₃₂Ni₁₀Si₁₃Sn₄B₉Y₂ two distinct regions were observed following arc melting and slow cooling, confirming that liquid/liquid phase separation had occurred. Rapid cooling from a temperature within the liquid immiscibility gap, melt spinning, resulted in an amorphous/crystalline composite, formed from the previously melted Fe- and Cu-rich regions, respectively. Transmission electron microscopic studies of this melt-spun ribbon revealed the glassy nature of the Fe-rich matrix, as well as of the Fe-rich spheres formed within the previously existing Cu-rich liquid.     

Modelling characteristics of the impulse transformer in a wide frequency range

In the paper, a new compact electrothermal model of the impulse transformer is proposed. This model has a form of a subcircuit dedicated for SPICE and could be used for low power impulse transformers applicable in switch-mode power supplies used in electronics. It takes into account simultaneously electric, thermal, and magnetic phenomena occurring in the considered device and describe nonidealities of the core and windings. The form of the elaborated model and analytical dependences describing all its components are presented. Correctness of this model is verified experimentally in a wide range of frequency and load resistance for selected constructions of transformers. Satisfactory agreement between the results of computations and measurements is obtained     

Clickable poly(ionic liquid)s for modification of glass and silicon surfaces

Covalent attachment of poly(ionic liquid)s (PILs) by click chemistry on glass or silicon (Si) surfaces was performed. Poly[1-(4-vinylbenzyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (polyVBBI⁺Tf₂N⁻), and copolymers of polyVBBI⁺Tf₂N⁻ with fluorescein O-methacrylate were synthesized by conducting an atom transfer radical polymerization (ATRP) from initiators containing azide or thioacetate groups. The azide- and thiol-terminated PILs were then successfully grafted onto alkyne and alkene modified glass/Si wafers by thermal azide–alkyne cycloaddition and photoinitiated thiol-ene click reactions, respectively. The modified surfaces were characterized by contact angle measurements and ellipsometry. The fluorescent PIL functionalized surfaces showed strong fluorescence under UV irradiation. This procedure of tethering PILs to substrates also provides an easy way to change the surface hydrophilicity by replacing the anions in the grafted PILs. The present approach could be readily applied for surface modifications with other types of PILs or their copolymers to achieve different functionalities on various surfaces.