On Fractional PI λ Controllers: Some Tuning Rules for Robustness to Plant Uncertainties

The objective of this work is to find out optimum settings for a fractional PI ^λ controller in order to fulfill three different robustness specifications of design for the compensated system, taking advantage of the fractional order, λ. Since this fractional controller has one parameter more than the conventional PI controller, one more specification can be fulfilled, improving the performance of the system and making it more robust to plant uncertainties, such as gain and time constant changes. For the tuning of the controller an iterative optimization method has been used, based on a nonlinear function minimization. Two real examples of application are presented and simulation results are shown to illustrate the effectiveness of this kind of unconventional controllers.     

Lanthanide dota-like complexes containing a picolinate pendant: structural entry for the design of Ln(III)-based luminescent probes

In this contribution we present two ligands based on a do3a platform containing a picolinate group attached to the fourth nitrogen atom of the cyclen unit, which are designed for stable lanthanide complexation in aqueous solutions. Potentiometric measurements reveal that the thermodynamic stability of the complexes is very high (log K = 21.2-23.5), being comparable to that of the dota analogues. Luminescence lifetime measurements performed on solutions of the Eu(III) and Tb(III) complexes indicate that the complexes are nine coordinate with no inner-sphere water molecules. A combination of density functional theory (DFT) calculations and NMR measurements shows that for the complexes of the heaviest lanthanides there is a major isomer in solution consisting of the enantiomeric pair Λ(δδδδ) and Δ(λλλλ), which provides square antiprismatic coordination (SAP) around the metal ion. Analysis of the Yb(III)-induced paramagnetic shifts unambiguously confirms that these complexes have SAP coordination in aqueous solution. For the light lanthanide ions however both the SAP and twisted-square antiprismatic (TSAP) isomers are present in solution. Inversion of the cyclen ring appears to be the rate-determining step for the Λ(δδδδ) ? Δ(λλλλ) enantiomerization process observed in the Lu(III) complexes. The energy barriers obtained from NMR measurements for this dynamic process are in excellent agreement with those predicted by DFT calculations. The energy barriers calculated for the arm-rotation process are considerably lower than those obtained for the ring-inversion path. Kinetic studies show that replacement of an acetate arm of dota by a picolinate pendant results in a 3-fold increase in the formation rate of the corresponding Eu(III) complexes and a significant increase of the rates of acid-catalyzed dissociation of the complexes. However, these rates are 1-2 orders of magnitude lower than those of do3a analogues, which shows that the complexes reported herein are remarkably inert with respect to metal ion dissociation.     

Generator Coalgebras are not Necessarily Quasi-coFrobenius

We study the problem of whether a coalgebra that generates its category of left (right) comodules is left (right) quasi-coFrobenius or not. We prove it does not hold in general, by giving a method of constructing counterexamples. This gives a negative answer to a question stated in Nastasescu et al. (Algebr Represent Theory 11(2):179–190, 2008). We also prove it is true for monomial pointed coalgebras and we characterize the quivers Q such that \mathbbkQ\mathbb{k}Q admits a monomial subcoalgebra that is left (right) quasi-coFrobenius.     

Single facility location on a network under mill and delivered pricing

^** E-mail: pelegrin{at}um.es Firms normally use either a mill price or a delivered pricepolicy, depending on market conditions (type of good, transportationway, customers location, costs, etc). In this paper, the problemof selecting the best location for an entering firm in competitionwith some pre-existing firms, under each price policy, is studiedon a network for the first time. With mill pricing, an equilibriumin price rarely exists and it is assumed that all competingfirms set a common mill price for all customers. With deliveredpricing, there exists a Nash equilibrium in price and it isassumed that the equilibrium price in each area is offered tothe customers in that area. In both cases, we consider thatcustomers buy from the cheapest facility and the same rulesare used for tie breaking in the lowest cost. While the profitmaximization problem for the entering firm always has optimalsolutions under mill pricing, this problem might not have anoptimal solution under delivered pricing. We show some discretizationresults and give procedures to find the full set of optimal,or -optimal, solutions to the problem under the two price policies.A comparison of results with the two price policies is givenby using an illustrative example.     

流动中边界面的识别

将流场的边界面定义为流动表面,在该表面上剪切率为0,并利用所建议的程序求解.该方法是基于速度向量场的计算,与坐标系的选择无关.     

Twisted Smash Products and L-R Smash Products for Biquasimodule Hopf Quasigroups

We consider two new algebras from an H-biquasimodule algebra A and a Hopf quasigroup H: twisted smash product A ? H and L-R smash product A?H, and find necessary and sufficient conditions for making them Hopf quasigroups. We generalize the main results in Brzeziński and Jiao [5] and Klim and Majid [9]. Moreover, if H is a cocommutative Hopf quasigroup, we prove that A ? H is isomorphic to A?H as Hopf quasigroups.     

Structured Hybrid Nanoparticles via Surface‐Initiated ATRP of Methyl Methacrylate from Ordered Mesoporous Silica

Structured hybrid nanoparticles were synthesized via surface‐initiated atom transfer radical polymerization of MMA from ordered mesoporous silica (OMS) nanoparticles with various morphologies. The design of the OMS particles was adjusted to target either spherical core‐shell or cylindrical morphologies with a mean diameter below 400 nm. The polymer growth via ATRP from the silica surface was well‐controlled as demonstrated by the macromolecular characteristics of the grafted chains. Original hybrid multilayered nanoparticles composed of either a dense silica core or hollow core; an inner OMS shell showing radial orientation of the mesopores and an outer PMMA shell with controlled thickness were successfully prepared.

     

Electrokinetic-based injection modes for separative microsystems

Miniaturization of analytical instruments has attracted a wide interest in Analytical Chemistry over the past decade because of the advantages such as reduced reagent consumption and shorter analysis time. For chips involving separation, injection is a key step to achieve efficient and sensitive analysis. Electrokinetic injection mode is mostly used in chips because it is easier to generate flow motion in microsystems via electric potential control at channel extremities than pressure-driven flow. The injection step usually involves several intersecting channels. For each injection design, different injection modes can be done, depending on electric field sequences and distributions. This paper is an up-to-date review of these different modes on a chip.     

Elaboration of monodisperse spherical hollow particles with ordered mesoporous silica shells via dual latex/surfactant templating: radial orientation of mesopore channels

Monodisperse spherical hollow nanoparticles of mesoporous silica featuring mesopores with a radial orientation in the silica shell were synthesized via a dual-templating method. Specifically designed polystyrene latexes with anionic or cationic surface charges acted as the core templates, while cetyltrimethylammonium bromide served as a co-template to structure the mesopore formation during tetraethoxysilane hydrolysis/condensation. The particles were well-separated and presented homogeneous mesoporous silica shells. Average particle diameters were less than 200 nm, and the particles displayed high values of specific surface area and pore volume. The shell thickness and the hollow core diameter could be tuned independently while the radial pore structure was preserved. A detailed analysis of the nitrogen adsorption-desorption isotherms proved that the central cavity was completely isolated from the external medium, that is, only accessible through the radial mesopores of the shell. Consequently, our particles gather the advantages of a well-defined structure, straight penetrating channels across the silica shell, and a high accessible porous volume of the central core. These properties make them far better candidates than simple mesoporous particles for any storage and/or controlled release applications.     

Lanthanide complexes based on a 1,7-diaza-12-crown-4 platform containing picolinate pendants: a new structural entry for the design of magnetic resonance imaging contrast agents

We have synthesized a new macrocyclic ligand, N,N'-Bis[(6-carboxy-2-pyridyl)methyl]-1,7-diaza-12-crown-4 (H 2bp12c4), designed for complexation of lanthanide ions in aqueous solution. The X-ray crystal structure of the Gd (III) complex shows that the metal ion is directly bound to the eight donor atoms of the bp12c4 ligand, the ninth coordination site being occupied by an oxygen atom of a carboxylate group of a neighboring [Gd(bp12c4)] (+) unit, while the structure of the Lu (III) analogue shows the metal ion being only eight-coordinate. The hydration numbers obtained from luminescence lifetime measurements in aqueous solution of the Eu (III) and Tb (III) complexes suggest an equilibrium in aqueous solution between a dihydrated ( q = 2), ten-coordinate and a monohydrated ( q = 1), nine-coordinate species. This has been confirmed by a variable temperature UV-vis spectrophotometric study on the Eu (III) complex. The structure of the complexes in solution has been investigated by (1)H and (13)C NMR spectroscopy, as well as by theoretical calculations performed at the DFT (B3LYP) level. The results indicate that the change in hydration number occurring around the middle of the lanthanide series is accompanied by a change in the conformation adopted by the complexes in solution [Delta(lambdalambdalambdalambda) for q = 2 and Lambda(deltalambdadeltalambda) for q = 1]. The structure calculated for the Yb (III) complex (Lambda(deltalambdadeltalambda)) is in good agreement with the experimental structure in solution, as demonstrated by the analysis of the Yb (III)-induced paramagnetic (1)H shifts.