Conceptual model-based design and environmental evaluation of waste solvent technologies: Application to the separation of the mixture acetone-water

In this paper, two waste solvent technologies are presented as alternatives to the disposal of spent acetone-water mixtures.

In the first alternative, a batch rectifier is used to concentrate the waste in order to obtain a distillate with a higher calorific value, which is then sent to off-site incineration either in a cement kiln or in a conventional waste solvent incinerator. The second alternative is a hybrid process composed by a batch rectifier and a pervaporation unit that processes in batchwise mode the first cut from the distillation task to obtain a dehydrated solvent. Here, four scenarios are considered, comprising two kinds of membrane materials and two different vacuum systems.

For each alternative, the conceptual design was carried out with the aid of conceptual models of the unit operations involved. Quasi-optimal values for design and operation variables were used as input data to perform an economical and an environmental assessment of each alternative. The economic analysis suggests that the hybrid process is the best alternative given that the replacement cost of fresh solvent (about 850 U$S/ton) is considered as a credit value.

From the environmental analysis with life cycle assessment, two main conclusions can be drawn: i) the use of the distillate as an alternative fuel in a cement kiln leads to a reduction in emissions that is relevant for the categories related to human health and ecosystem quality; and ii) in terms of resource depletion, the hybrid process distillation/pervaporation with the ceramic membrane HybSi (Pervatech) shows the lowest impact due to the solvent recovery.     

pH-triggered conduction of amine-functionalized single ZnO wire integrated on a customized nanogap electronic platform

The electrical conductance response of single ZnO microwire functionalized with amine-groups was tested upon an acid pH variation of a solution environment after integration on a customized gold electrode array chip. ZnO microwires were easily synthesized by hydrothermal route and chemically functionalized with aminopropyl groups. Single wires were deposited from the solution and then oriented through dielectrophoresis across eight nanogap gold electrodes on a platform single chip. Therefore, eight functionalized ZnO microwire-gold junctions were formed at the same time, and being integrated on an ad hoc electronic platform, they were ready for testing without any further treatment. Experimental and simulation studies confirmed the high pH-responsive behavior of the amine-modified ZnO-gold junctions, obtaining in a simple and reproducible way a ready-to-use device for pH detection in the acidic range. We also compared this performance to bare ZnO wires on the same electronic platform, showing the superiority in pH response of the amine-functionalized material.     

The Mitochondrial Amidoxime Reducing Component (mARC): Involvement in Metabolic Reduction of N‐Oxides,Oximes and N‐Hydroxyamidinohydrazones

The mitochondrial amidoxime reducing component (mARC) is a molybdenum‐containing enzyme and capable of reducing N‐hydroxylated structures such as amidoxime prodrugs. In this study, we tested the involvement of mARC in the reduction of N‐oxides (amitriptyline‐N‐oxide, nicotinamide‐N‐oxide), oximes ((E)‐/(Z)‐2,4,6‐trimethylacetophenonoxime) and a N‐hydroxyamidinohydrazone (guanoxabenz). All groups are reduced by mARC proteins, and the enzymes are therefore involved in the interconversion of N‐oxygenated metabolites originating from cytochrome P450s and flavin‐containing monooxygenases. In addition, these structures open up further options for serving as prodrugs. Thus, with respect to these reactions, testing of candidates with N‐oxygenated structures should not solely be carried out in microsomal enzyme sources but as well in mitochondria. However, differences in the reduction of oximes and N‐oxides between the two isoforms, namely mARC1 and mARC2, were detectable; N‐oxides are exclusively reduced by mARC1. We therefore assume differences between the so far unknown 3D structures of the two proteins.     

Molecular Mechanism of Action of 2‐Ferrocenyl‐1,1‐diphenylbut‐1‐ene on HL‐60 Leukemia Cells

The aim of this work was to investigate the mechanism of action of 2‐ferrocenyl‐1,1‐diphenylbut‐1‐ene ( 1 ) on HL‐60 human leukemia cells. While inactive against noncancerous cells, 1 provoked a concentration‐dependent decrease in viable tumor cells, primarily via apoptosis, as evidenced by analysis of cell morphology, activation of caspases 3 and 7, increased DNA fragmentation, and externalization of phosphatidylserine. Necrosis was observed only at the highest tested concentration (4 μM ). Compound 1 interfered with the cell cycle, causing an accumulation of cells in the G₁/G₀ phase. Interaction of 1 with dsDNA and ssDNA was observed by differential pulse voltammetry and confirmed by hyperchromicity in the UV/Vis spectra of dsDNA, with an interaction constant of 2×10⁴ M ^?1. Both the organic analogue 1,1,2‐triphenylbut‐1‐ene ( 2 ) and ferrocene were inactive against cancer and noncancer cell lines and did not react with DNA. These results reinforce the idea that the hybrid strategy of conjugating ferrocene to the structure of tamoxifen derivatives is advantageous in finding new substances with antineoplastic activity.     

Self‐assembling amphiphilic PEGylated block copolymers obtained through RAFT polymerization for drug‐delivery applications

In this work, ring‐opening polymerization and reversible addition‐fragmentation chain transfer polymerization (RAFT) have been employed for the production of block copolymers where the backbone is brushed with poly(ethylene glycol) (PEG) and polyester chains. Because of their amphiphilic properties, they are able to self‐assemble in water, forming micelles. Molecular dynamics simulations have been accomplished to study the behavior of the copolymer single chain in water, and the self‐assembly properties have been characterized and correlated to the copolymer structure in terms of critical micellar concentration and particle size. As a proof of their flexibility, these materials have been employed for the production of polymer–lipid hybrid nanoparticles with tunable dimensions (from 120 to 260 nm) adopted for the controlled release of anticancer compounds (paclitaxel and curcumin). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43084.     

Dielectric Properties of the Fluorite-like Bi2O3–Nb2O5 Solid Solution and the Tetragonal Bi3NbO7

Our analysis of the microwave dielectric properties of the δ-Bi₂O₃–Nb₂O₅ solid solution (δ-BN_ss) showed a continuous increase in permittivity and dielectric losses with an increasing concentration of Nb₂O₅. The only discontinuity was found for the temperature coefficient of resonant frequency, which is negative throughout the entire homogeneity range but reaches a minimum value for the sample with 20 mol% Nb₂O₅. At the same composition there is a discontinuity in the grain size of the δ-BN_ss ceramics. For the sample containing 25 mol% Nb₂O₅ two structural modifications were observed. A single-phase tetragonal Bi₃NbO₇, in the literature referred to as a Type-III phase, is formed in a very narrow temperature range from 850° to 880°C. A synthesis performed below or above this temperature range resulted in the formation of the end member of the δ-BN_ss homogeneity range. Compared with the δ-BN_ss the Bi₃NbO₇ ceramics exhibit lower microwave dielectric losses, an increased conductivity, and a positive temperature coefficient of resonant frequency.     

Sub-Solidus Synthesis and Microwave Dielectric Characterization of Plagioclase Feldspars

Na _x Ca_{1− x} Al_{2− x} Si_{2+ x} O₈ plagioclase solid solutions (0≤ x ≤1) were synthesized under sub-solidus conditions using a solid-state reaction technique. The plagioclase formation and the sintering temperature decreased with an increase in x from the anorthite (CaAl₂Si₂O₈; x =0) to the albite (NaAlSi₃O₈; x =1).
Microwave (MW) dielectric measurements revealed that slow-cooled ( P 1 ) anorthite exhibited higher Q × f values than fast-cooled ( I 1 ) anorthite. Slow cooling also considerably improved the Q × f values of the sodium-rich Na _x Ca_{1− x} Al_{2− x} Si_{2+ x} O₈ solid solutions (0.8≤ x ≤1), where the highest Q × f value of 17 600 GHz was obtained for slow-cooled Na_0.8Ca_0.2Al_1.2Si_2.8O₈. The temperature coefficient of resonant frequency (τ_f) approached zero for 0.8≤ x ≤1.     

The Morphology Control of BaTiO3 Particles Synthesized in Water and a Water/Ethanol Solvent

The experimental conditions for the growth of shape‐controlled BaTiO₃ particles in NaOH and Ba(NO₃)₂ aqueous and water/ethanol solutions using various TiO₂‐containing precursors were studied at 80°C–100°C. The different chemistries and physical characteristics of the precursors resulted in different BaTiO₃ formation rates and morphologies_. Nanocrystalline anatase led to irregularly shaped BaTiO₃ particles, whereas star‐like, single‐crystalline BaTiO₃ particles grew from aerogel TiO₂ and sodium titanate (NT) belts in alkaline aqueous solutions. With the addition of ethanol, the star‐like BaTiO₃ particles changed to square‐like, the size of which decreased with an increase in the ethanol content. The electron microscopy observations supported a dissolution–precipitation mechanism as the primary reaction mechanism for the formation of BaTiO₃ nanocrystals, which further aggregated into single‐crystalline star‐ or square‐like particles by oriented attachment. The modification in the water solution with ethanol is believed to influence both the nucleation and aggregation process and consequently influence the particle shape and size.     

Glass-Free KxBa1−xGa2−xGe2+xO8 Ceramics for Low-Temperature Cofired Ceramics Technology: Synthesis, Phase Transitions, Sintering, and Microwave Dielectric Properties

K _x Ba_{1− x} Ga_{2− x} Ge_{2+ x} O₈ (0.6≤ x ≤1) polycrystalline ceramics are potential materials for glass-free low-temperature cofired ceramics (LTCC) substrates. We have made a comprehensive study of the kinetics of the monoclinic-to-monoclinic P 2₁/ a ⇔ C 2/ m phase transition. The low-temperature-stable P 2₁/ a phase with a high Q × f value was synthesized using a subsolidus method and was well sintered at the LTCC temperature with a H₃BO₃ additive. A good combination of low sintering temperature (910°–920°C), high Q × f values (96 700–104 500 GHz), low permittivities (5.6–6.0), and a small temperature coefficient of resonant frequency (∼−20 ppm/°C) was obtained for ceramics with x =0.67 and 0.9 and with 0.1 wt% of H₃BO₃.