Comparative study using different infrared zones of the solventless activation of organic reactions

In this work, the results of a study comparing the use of irradiation from different regions of the infrared spectrum for the promotion of several organic reactions, are presented and discussed. This use of eco-conditions provides a green approach to chemical synthesis. A set of ten different organic reactions were evaluated, including the Knoevenagel, Hantzsch, Biginelli and Meldrum reactions. It is important to highlight the use of a commercial device that produces infrared irradiation in the near infrared region and its distribution by convection providing heating uniformity, significantly reducing reaction times, achieving good yields and proceeding in the absence of solvent. It is also worth noting that a variety of different reactions may be performed at the same time. Finally, the products obtained were identified using TLC, together with corresponding MS-data, complementarily in comparison of NMR (1)H and (13)C data with literature information.     

In vitro release profiles of β-carotene encapsulated in PHBV by means of supercritical carbon dioxide micronization technique

The main objective of this work was to investigate the characteristics of the in vitro release of β-carotene encapsulated in poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) using the solution enhanced dispersion by supercritical fluids (SEDS) technique. The release tests were performed using encapsulated complex with solute loading from 2.24 to 27.5% and encapsulation efficiency from 7.75 to 55.54%. The release profile assays were performed in ethyl acetate, n-hexane and anhydrous ethanol, and monitored by UV-vis spectrophotometer concentration analysis. Results indicated higher initial release rates in ethyl acetate and in n-hexane, with cumulative release percentage varying from 31.50 to 69.58% and from 42.08 to 55.96%, respectively. For anhydrous ethanol the maximum concentration was reached at 180 min, 300 min and 10 days, depending on the initial amount of β-carotene, with cumulative release ranging from 45.27 to 88.22%. In general, the β-carotene release can be controlled by the organic solvent used and by the initial amount of solute encapsulated, aspects that help the selection of the conditions to achieve the desired release profiles for a specific application.     

Phase transition on the Si(001) clean surface prepared in UHV MBE chamber: a study by high-resolution STM and <Emphasis Type="Italic">in situ</Emphasis> RHEED

The Si(001) surface deoxidized by short annealing at T ~ 925°C in the ultrahigh vacuum molecuar beam epitaxy chamber has been in situ investigated using high-resolution scanning tunneling microscopy (STM)and redegreesected high-energy electron diffraction (RHEED. RHEED patterns corresponding to (2 × 1) and (4 × 4) structures were observed during sample treatment. The (4 × 4) reconstruction arose at T ≲ 600°C after annealing. The reconstruction was observed to be reversible: the (4 × 4) structure turned into the (2 × 1) one at T ≳ 600°C, the (4 × 4) structure appeared again at recurring cooling. The c (8 × 8) reconstruction was revealed by STM at room temperature on the same samples. A fraction of the surface area covered by the c (8 × 8) structure decreased, as the sample cooling rate was reduced. The (2 × 1) structure was observed on the surface free of the c (8 × 8) one. The c (8 × 8) structure has been evidenced to manifest itself as the (4 × 4) one in the RHEED patterns. A model of the c (8 × 8) structure formation has been built on the basis of the STM data. Origin of the high-order structure on the Si(001) surface and its connection with the epinucleation phenomenon are discussed.     

Synthesis and structural characterization of a liquid polyisoprene bearing amidoxime end groups

Azo-bis(isobutyroamidoxime) was synthesized and used as functionalized initiator to prepare a liquid isoprene bearing amidoxime end groups via radical polymerization. The polymer was characterized by FT-IR, Gel Permeation Chromatography and NMR. In particular, the structure of the polymer was investigated using 1D and 2D NMR techniques. The distribution of the different isoprene units (1,4-trans, 1,4-cis, 1,2 and 3,4), as well as the structure of the amidoxime end-groups was determined. It was found that the structure of the end groups was governed by the steric hindrance of the initiator. Only 1,4 and 4,1 functionalized end units were evidenced, with a majority of 4,1 end units.     

Phase Equilibrium Measurements of Sacha Inchi Oil (<Emphasis Type="Italic">Plukenetia volubilis</Emphasis>) and CO<Subscript>2</Subscript> at High Pressures

New data on phase equilibria for Sacha inchi seed oil in carbon dioxide have been measured using a variable volume cell phase equilibria system at temperatures of 303, 313 and 323 K and at pressures ranging from 4.3 to 27.7 MPa. The CO₂ mole fraction varied from 0.7488 to 0.9997. At the studied concentrations, phase transitions of vapor-liquid, liquid-liquid-vapor and liquid-liquid were observed. Sacha inchi oil contains 47% of omega-3 fatty acids, with a ratio of 0.76:1 for omega-6:omega-3, which is good for human health. The Peng-Robinson equation of state was used to describe the experimental data. A qualitative agreement was obtained between experimental and calculated data for the binary system CO₂ and Sacha inchi seed oil.     

Phase and Rheological Behavior of Cetyldimethylbenzylammonium Salicylate (CDBAS) and Water

The temperature–composition phase diagram in the diluted region of the cationic surfactant cetyldimethylbenzylammonium salicylate/water system was studied with a battery of techniques. The Krafft temperature (T _k = 33 ± 1 °C) was measured by differential scanning calorimetry, polarizing microscopy, conductimetry, viscosimetry, and rheometry. The critical vesicle concentration (cvc, ~0.002 wt%) and a vesicle–micellar transition (cvm, ~0.005 wt%) was detected at a temperature of 35 °C. Below T _k and concentrations ≤2 wt%, a transparent solution is formed (I). Above 2–8.5 wt%, a lamellar (L₁) phase forms. At higher concentrations and up to 12 wt%, a second lamellar phase (L₂) is detected. From 12.4 to 15.5 wt%, an emulsion phase (E) is formed. Rheological dynamic measurements for the I phase indicate that the system exhibits a predominantly viscous behavior (G′ < G″) for concentrations lower than the overlap or entanglement concentration (C _e, ~0.75 wt%). At higher concentrations, wormlike micelles form and the elastic behavior predominates (G′ > G″). The elastic (G′) modulus collapses in a concentration–time master curve in the whole reduced frequencies range ωτ _c examined, whereas the viscous modulus (G″) collapses only at reduced frequencies lower than 0.1. Reduced stress plotted as a function of the reduced shear rate yields a good superposition of the curves at the different concentrations up to the onset of the non-linear behavior.     

Hydrogen sensor based on a graphene – palladium nanocomposite

A composite material was prepared from graphene and palladium nanoparticles (PdNP) by layer-by-layer deposition on gold electrodes. The material was characterized by absorption spectroscopy, scanning electron microscopy, Raman spectroscopy and surface plasmon resonance. Cyclic voltammetry demonstrated the presence of electrocatalytic centers in the palladium decorated graphene. This material can serve as a sensor material for hydrogen at levels from 0.5 to 1% in synthetic air. Pure graphene is poorly sensitive to hydrogen, but incorporation of PdNPs increases its sensitivity by more than an order of magnitude. The effects of hydrogen, nitrogen dioxide and humidity were studied. Sensor regeneration is accelerated in humid air. The sensitivity of the nanocomposite depends on the number of bilayers of graphene–PdNPs.     

Effective harvesting,detection, and conversion of IR radiation due to quantum dots with built-in charge

We analyze the effect of doping on photoelectron kinetics in quantum dot [QD] structures and find two strong effects of the built-in-dot charge. First, the built-in-dot charge enhances the infrared [IR] transitions in QD structures. This effect significantly increases electron coupling to IR radiation and improves harvesting of the IR power in QD solar cells. Second, the built-in charge creates potential barriers around dots, and these barriers strongly suppress capture processes for photocarriers of the same sign as the built-in-dot charge. The second effect exponentially increases the photoelectron lifetime in unipolar devices, such as IR photodetectors. In bipolar devices, such as solar cells, the solar radiation creates the built-in-dot charge that equates the electron and hole capture rates. By providing additional charge to QDs, the appropriate doping can significantly suppress the capture and recombination processes via QDs. These improvements of IR absorption and photocarrier kinetics radically increase the responsivity of IR photodetectors and photovoltaic efficiency of QD solar cells.     

Method for Calculating Cartesian Coordinates of Operator’s Arm Joints for Anthropomorphic Manipulator Master-Slave Control Using Exoskeleton

The main goal of the work is to increase the accuracy of the anthropomorphic manipulator master-slave teleoperation by calculating the coordinates of the operator’s arm joints. The master device is an exoskeleton worn on the operator’s arm, and the slave device is an anthropomorphic manipulator. A method based on the solution of the forward kinematics and empirical simplifications is proposed in this paper. The position of the nodal points of the exoskeleton was calculated by solving the direct kinematics problem. The coordinates of the operator’s arm joints, which were rigidly connected to the exoskeleton nodal points, were calculated geometrically. For the operator’s arm elbow joint, which was flexibly connected to the exoskeleton, an empirical relation was proposed. It simplified the calculation of the elbow joint position. The experiment showed a decrease in the mismatch between the operator’s arm angles and the manipulator joint angles from 20.7° to 2.9°. The proposed method increases the convenience of the master-slave control.