Ternary Polymer Solutions with Hydrogen Bonds, 2

Experimental ternary phase diagrams for ternary systems CHL/PS‐MAA/PVPy with diverse MAA contents have been determined by GPC. The presence of MAA in the copolymers gives rise to specific interactions, by hydrogen bond formation between both polymeric components, so strong that the isotherm for the system with the highest MAA content so far studied, CHL/PS‐MAA(8%)/PVPy, is representative of a complex coacervation situation. By applying the theoretical background deduced by coupling the Flory‐Huggins lattice model to the AET developed for ternary polymeric systems SPP with specific intermolecular interactions (via hydrogen bonds), free energy surfaces for the CHL/PS‐MAA/PVPy systems are constructed. From these plots theoretical ternary phase diagrams are deduced and a fair agreement with those obtained experimentally is observed.

     

Control of microstructural properties in emulsion polymerization systems

Control strategies for the simultaneous control of microstructural properties of copolymer latexes (copolymer composition and molecular weight distribution) are presented. For linear polymers, on-line control strategies based on calorimetric measurements allowed to produce styrene/n-butyl acrylate emulsion polymers of predefined copolymer compositions and MWDs. The strategy failed for nonlinear polymers because the polymer produced at a certain process time might later in the process become active varying its molecular weight. Alternative open-loop control policies were developed for nonlinear polymers. These strategies required a mathematical model of the process that is used in an off-line optimization to determine the trajectories of the manipulated variables (feed flow rates of monomer and CTA) that allow producing the desired copolymers. The implementation of the open-loop control allowed the production of nonlinear MMA/n-BA emulsion copolymers of well-defined copolymer composition and MWD.     

Magnetic and Luminescence Properties of 8-Coordinate Holmium(III) Complexes Containing 4,4,4-Trifluoro-1-Phenyl- and 1-(Naphthalen-2-yl)-1,3-Butanedionates

A new series of mononuclear Ho³⁺ complexes derived from the β-diketonate anions: 4,4,4-trifluoro-1-phenyl-1,3-butanedioneate (btfa⁻) and 4,4,4-trifuoro-1-(naphthalen-2-yl)-1,3-butanedionate (ntfa⁻) have been synthesized, [Ho(btfa)₃(H₂O)₂] (1a), [Ho(ntfa)₃(MeOH)₂] (1b), (1), [Ho(btfa)₃(phen)] (2), [Ho(btfa)₃(bipy)] (3), [Ho(btfa)₃(di-^tbubipy)] (4), [Ho(ntfa)₃(Me₂bipy)] (5), and [Ho(ntfa)₃(bipy)] (6), where phen is 1,10-phenantroline, bipy is 2,2′-bipyridyl, di-^tbubipy is 4,4′-di-tert-butyl-2,2′-bipyridyl, and Me₂bipy is 4,4′-dimethyl-2,2′-bipyridyl. These compounds have been characterized by elemental microanalysis and infrared spectroscopy as well as single-crystal X-ray difraction for 2–6. The central Ho³⁺ ions in these compounds display coordination number 8. The luminescence-emission properties of the pyridyl adducts 2–6 display a strong characteristic band in the visible region at 661 nm and a series of bands in the NIR region (excitation wavelengths (λ_ex) of 367 nm for 2–4 and 380 nm for 5 and 6). The magnetic properties of the complexes revealed magnetically uncoupled Ho³⁺ compounds with no field-induced, single-molecule magnet (SMMs).     

Transformation of COUPY Fluorophores into a Novel Class of Visible-Light-Cleavable Photolabile Protecting Groups

Although photolabile protecting groups (PPGs) have found widespread applications in several fields of chemistry, biology and materials science, there is a growing interest in expanding the photochemical toolbox to overcome some of the limitations of classical caging groups. In this work, the synthesis of a new class of visible-light-sensitive PPGs based on low-molecular weight COUPY fluorophores with several attractive properties, including long-wavelength absorption, is reported. Besides being stable to spontaneous hydrolysis in the dark, COUPY-based PPGs can be efficiently photoactivated with yellow (560 nm) and red light (620 nm) under physiological-like conditions, thereby offering the possibility of unmasking functional groups from COUPY photocages under irradiation conditions in which other PPGs remain stable. Additionally, COUPY photocages exhibit excellent cellular uptake and accumulate selectively in mitochondria, opening the door to the delivery of caged analogues of biologically active compounds into these organelles.     

Interstage Pressures of a Multistage Compressor with Intercooling

This paper considers the criterion of minimum compression work to derive an expression for the interstage pressure of a multistage compressor with intercooling that includes the gas properties, pressure drops in the intercoolers, different suction gas temperatures, and isentropic efficiencies in each compression stage. The analytical expression for the interstage pressures is applied to estimate the number of compression stages and to evaluate its applicability in order to estimate interstage pressures in the operation of multistage compressors, which can be especially useful when their measurements are not available.     

Mechatronic design,experimental setup,and control architecture design of a novel 4 DoF parallel manipulator

Although parallel manipulators started with the introduction of architectures with six degrees of freedom, a vast number of applications require less than six degrees of freedom. Consequently, scholars have proposed architectures with three and four degrees of freedom, but relatively few four degrees of freedom parallel manipulators have become prototypes, especially of the two rotation and two translation motion types. In this article, we explain the mechatronics design, prototype, and control architecture design of a four degrees of freedom parallel manipulators with two rotation and two translation motions. We chose to design a four degrees of freedom manipulator based on the motion needed to complete the tasks of lower limb rehabilitation. To the author’s best knowledge, parallel manipulators between three and six degrees of freedom for rehabilitation of lower limb have not been proposed to date. The developed architecture enhances the three minimum degrees of freedom required by adding a four degrees of freedom, which allows combinations of normal or tangential efforts in the joints, or torque acting on the knee. We put forward the inverse and forward displacement equations, describe the prototype, perform the experimental setup, and develop the hardware and control architecture. The tracking accuracy experiments from the proposed controller show that the manipulator can accomplish the required application.     

Passivity-based control of a single-link flexible manipulator using fractional controllers

Nonlinear Dynamics - This work presents a new methodology for the design of passivity-based controllers of fractional order for single-link flexible robots. In this work, some previously developed...     

Use of MEA technology in the synthesis of pharmaceutical compounds: The electrosynthesis of N-acetyl-l-cysteine

The electrosynthesis of N-acetyl-l-cysteine (NAC) from the electroreduction of N,N-diacetyl-l-cystine (NNDAC) using a Polymer Electrolyte Membrane Electrochemical Reactor (PEMER) has been carried out. The Membrane Electrode Assembly (MEA) was formed by a cathode with a catalyst layer made of Pb/C 20 wt% supported on Toray Paper and a catalyst loading of 0.5 mg Pb cm^?2. The anode was a 2 mg Pt cm^?2 gas diffusion anode fed with H₂. The main advantages of this process are: (1) the electrochemical reactor allows to carry out the electrosynthesis without supporting electrolyte, improving in this way the NAC purification and (2) a pronounced decrease of the electrosynthesis energy consumption due to both, the small internal resistance of the PEMER (electrode gap very small and electrolyte very conductive) and the choice of the H₂ oxidation as anodic reaction in stead of the oxygen evolution reaction from water oxidation. The large number of pharmaceutical applications of NAC, as well as the high versatility of the PEMER for electrosynthesis processes, makes interesting the use of MEAs for electroorganic synthesis.     

Synthesis,characterization, and 2,4-dichlorophenoxyacetic acid degradation on In-Na<Subscript>2</Subscript>Ti<Subscript>6</Subscript>O<Subscript>13</Subscript> sol–gel prepared photocatalysts

Indium-Na₂Ti₆O₁₃ doped semiconductors were prepared by the sol–gel method using titanium and sodium alkoxides as precursors. The gelled samples were annealed at 700 °C for 4, 6, and 8 h, and then characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and UV–Vis diffused reflectance spectroscopy (DRS). XRD patterns of the samples show the formation of the Na₂Ti₆O₁₃ phase, whose crystallinity depends on the annealing time. The band gap calculated from the UV–Vis Kubelka–Munk function report similar values (3.2–3.4 eV) for all of the samples annealed at different times. SEM observations of the semiconductors showed microfiber bundle morphologies of about 5 μm. Meanwhile, by EDS analysis, indium oxide highly homogeneously dispersed on the hexatitanate surface was identified. The evaluation of the In-Na₂Ti₆O₁₃ semiconductors in the 2,4-dichlorophenoxyacetic acid (2,4-D) photodecomposition using ultraviolet light (λ = 254 nm) irradiation show that the photoactivity of the solids depends on the annealing time applied to the samples. The role of indium oxide is related to the indium oxide dispersed on the surface of the titanate diminishing the electron-hole recombination rate.