SOLUBILIZATION OF P-ALKYLPHENOLS IN PLURONICS F-68 AND F-127 MICELLES: PARTITION COEFFICIENTS AND EFFECT OF SOLUTE ON THE AGGREGATE STRUCTURE

Indexación: Web of Science; Scielo.The partition of a series of substituted phenols between water and polymer micelles formed by Pluronic F-68 and F-127 has been studied. The formation of micelles by these block copolymers has been evidenced by steady-state fluorescence and dynamic light scattering. The data show that micelles and larger aggregates are formed above the critical micelle concentration. In presence of p-alkylphenols a micelle rearrangement occurs that leads to the formation of just one and large aggregate. This effect depends both on polymer and phenols structures. The partition coefficients and the standard free energies of transfer from the aqueous to the micellar phases were determined. The incremental free energy for a methylene group are 2.88 kJ mol-1 and 1.65 kJ mol-1 for F-127 and F-68, respectively. This difference is explained in terms of the core sizes that are determined by the length of the PPO block.http://ref.scielo.org/xfqmx

Self-assembly of triblock copolymers in aqueous solution

Indexación: ScieloThe aggregation of PE4VP-b-PS-b-PE4VP block copolymers was studied in aqueous solution. Triblock copolymers P4VP-b-PS-b-P4VP were synthesized by sequential anionic polymerization of poly(styrene) and poly(4-vinylpirydine) using sodium naphthalene as a bifunctional initiator. Subsequently, the 4-vinylpyridine units were quaternized with ethyl bromide to obtain cationic PE4VP-b-PS-b-PE4VP block copolymers. Both star and crew-cut micelles were formed. The concentrations at which micelles are formed cmc were determined, by steady-state and time-resolved fluorescence probing methods, as a function of quatemization degree. The results indicate that cmc of crew-cut micelles increases with increasing charge density of the PE4VP blocks. For star micelles there is not a clear dependency of cmc with the percentage of quatemization. The lifetime of pyrene fluorescence and the ratio I1/I3 were determined at concentrations of copolymers well above the cmc, and the results show that the location of pyrene into the micelle changes with the charge density of the micelle corona. The micropolarity sensed by pyrene decreases with increasing quatemization degree. The presence of aggregates was confirmed by transmission electronic microscopy.http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072008000200013&lng=es&nrm=is

Hydrophobically modified polyelectrolytes as potential drugs reservoirs of n-alkyl-nitroimidazoles

Indexación: ScieloThe solubilization of three commercial drugs (ornindazole, metronidazole and tinidazole) and model compounds (N-alkyl-2-methyl-4-nitroimidazoles) on aggregates formed by anionic polyelectrolytes, carrying alkyl side chains of different length, have been investigated in aqueous solution at pH 3.0, 7.0 and 11.0. Potassium salts of poly(maleic acid-co-1-olefins), PA-nK2 with n ranging from 8 to 18, were used as micelle-forming polymers. The partition of these drugs between water and the hydrophobic microdomains provided by PA-nK2 was studied by the pseudo-phase model to determinate the distribution coefficient KS, and the standard free energy of transfer Δμºt. The results indicate that solubility of alkyl-nitroimidazoles on these polymer micelles depends moderately on the length of the alkyl chain, and therefore is mainly determined by the heterocyclic group. On the other hand, the solubilization of 1-hexyl-2-methyl-4-nitroimidazole increase with decreasing length of the side alkyl chain; i.e. KS follows the order PA-8K2 > PA-10K2 > PA-12K2 > PA-14K2 > PA-16K2 >PA-18K2.http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072007000100014&nrm=is

Inversion charge study in TMO hole-selective contact-based solar cells

© 2023 IEEE. Personal use of this material is permitted. Permission from IEEE must be obtained for all other uses, in any current or future media, including reprinting/republishing this material for advertising or promotional purposes,creating new collective works, for resale or redistribution to servers or lists, or reuse of any copyrighted component of this work in other works.In this article, we study the effect of the inversion charge ( Q inv ) in a solar cell based on the hole-selective characteristic of substoichiometric molybdenum oxide (MoO x ) and vanadium oxide (VO x ) deposited directly on n-type silicon. We measure the capacitance–voltage ( C – V ) curves of the solar cells at different frequencies and explain the results taking into account the variation of the space charge and the existence of Q inv in the c-Si inverted region. The high-frequency capacitance measurements follow the Schottky metal–semiconductor theory, pointing to a low inversion charge influence in these measurements. However, for frequencies lower than 20 kHz, an increase in the capacitance is observed, which we relate to the contribution of the inversion charge. In addition, applying the metal–semiconductor theory to the high-frequency measurements, we have obtained the built-in voltage potential and show new evidence about the nature of the conduction process in this structure. This article provides a better understanding of the transition metal oxide/n-type crystalline silicon heterocontact.The authors would like to acknowledge the CAI de Técnicas Físicas of the Universidad Complutense de Madrid. The authors would also like to thank the Mexican grants program CONACyT for its financial collaboration.Peer ReviewedPostprint (author's final draft

High-quality single-crystalline epitaxial regrowth on pulsed laser melting of Ti implanted GaAs

8 pags., 8 figs.We present a detailed investigation on the formation of supersaturated GaAs using Ti+ implantation followed by nanosecond Pulsed Laser Melting (PLM). We have synthesized high-crystal quality supersaturated GaAs layers with concentrations of Ti above the insulator to metal transition (Mott limit). The Ti-implanted concentration depth profiles after PLM obtained by Time-of-Flight Secondary Ion Mass Spectroscopy (ToF-SIMS) show a redistribution of Ti impurities within the first hundred nanometers and superficial concentration up to 1 × 1021 cm−3. Raman spectroscopy of these Ti supersaturated, and regrown GaAs samples shows a sharp crystalline peak and tensile strain due to the Ti lattice incorporation. Scanning Transmission Electron Microscopy (STEM) and high-resolution Transmission Electron Microscopy (TEM) images show a good GaAs crystallinity after the PLM process. Energy-Dispersive X-ray Spectroscopy (EDS) reveals an enhanced Ti signal inside bubble-like structures and an appearance of interface oxide layer with all processed samples.Authors would like to acknowledge C.A.I. de Tecnicas Físicas of the Universidad Complutense de Madrid for ion implantation, and the technical. This work was partially supported by the Project MADRIDPV2 (Grant No. P20138/EMT-4308) funded by the Comunidad Autonoma de Madrid with the support of FEDER funds, by the Spanish MINECO (Ministerio de Economía y Competitividad) under grants PID2020-116508RB-I00, PID2020-117498RB-I00 and RTI2018-096498-B-I00. One of the authors (S. Algaidy) would also like to acknowledge financial support from Ministry of Education in the Kingdom of Saudi Arabia. D.Caudevilla would also like to acknowledge a grant (PRE2018-083798), financed by MICINN and European Social Fund. F. Perez-Zenteno would like to acknowledge financial support Mexico grant program CONACyT under grant 786327. The authors would like to also acknowledge the services of CAI de Espectroscopia of UCM, (INA-LMA) de Universidad de Zaragoza and C.A.C.T.I de Universidad de Vigo for Raman, FIB-SEM and SIMS, respectivelyPeer reviewe

Network Structure of Vertebrate Scavenger Assemblages at the Global Scale: Drivers and Ecosystem Functioning Implications

The organization of ecological assemblages has important implications for ecosystem functioning, but little is known about how scavenger communities organize at the global scale. Here, we test four hypotheses on the factors affecting the network structure of terrestrial vertebrate scavenger assemblages and its implications on ecosystem functioning. We expect scavenger assemblages to be more nested (i.e. structured): 1) in species‐rich and productive regions, as nestedness has been linked to high competition for carrion resources, and 2) regions with low human impact, because the most efficient carrion consumers that promote nestedness are large vertebrate scavengers, which are especially sensitive to human persecution. 3) We also expect climatic conditions to affect assemblage structure, because some scavenger assemblages have been shown to be more nested in colder months. Finally, 4) we expect more organized assemblages to be more efficient in the consumption of the resource. We first analyzed the relationship between the nestedness of the scavenger assemblages and climatic variables (i.e. temperature, precipitation, temperature variability and precipitation variability), ecosystem productivity and biomass (i.e. NDVI) and degree of human impact (i.e. human footprint) using 53 study sites in 22 countries across five continents. Then, we related structure (i.e. nestedness) with its function (i.e. carrion consumption rate). We found a more nested structure for scavenger assemblages in regions with higher NDVI values and lower human footprint. Moreover, more organized assemblages were more efficient in the consumption of carrion. However, our results did not support the prediction that the structure of the scavenger assemblages is directly related to climate. Our findings suggest that the nested structure of vertebrate scavenger assemblages affects its functionality and is driven by anthropogenic disturbance and ecosystem productivity worldwide. Disarray of scavenger assemblage structure by anthropogenic disturbance may lead to decreases in functionality of the terrestrial ecosystems via loss of key species and trophic facilitation processes

Singlet oxygen production from excited singlet and triplet states of anthracene derivatives in acetonitrile

The efficiencies of singlet oxygen production from the singlet and triplet states of a series of anthracene derivatives in acetonitrile are reported. For anthracene and for all of the anthracene meso derivatives studied, the efficiency of singlet oxygen production from triplet states quenched by oxygen, ∫ΔT, is found to be unity, with the exception of 9-methoxyanthracene, where the value drops to one-third. The efficiencies of singlet oxygen production from excited singlet states quenched by oxygen, ∫ΔS in acetonitrile as solvent, are lower than in cyclohexane and vary from zero to one-half. In addition, the fractions of singlet states quenched by oxygen which yield triplet states, with or without singlet oxygen production, ∫TO2, for anthracene and 9-methyl-, 9-phenyl-, and 9,10-dichloroanthracene were measured and the values were found to vary from 0.57 to 0.83. Kinetic considerations allow the determination of estimates of this fraction for the other derivatives. For anthracene deri

Rate Constants for Reactions in Viscous Media: Correlation between the Viscosity of the Solvent and the Rate Constant of the Diffusion-Controlled Reactions

The kinetics of the quenching of excited pyrene by several molecules in a variety of hydrocarbon solvents and in a diol are reported. The rate constants for reaction of the excited pyrene are, for the most part, diffusion-controlled and considerably faster than those calculated by use of the Smoluchowski and Stokes—Einstein equations. Measurements of the diffusion constants of the reactants and direct use of the Smoluchowski equation does predict rate constants that are in agreement with those measured. Application of the Stokes—Einstein equation shows that this equation does not calculate the correct diffusion constant for the reactants in the media studied. A free volume theory with transition-state concepts suggests that the diffusion constants of reactants in the liquids used vary as the increase of the square root of the bulk viscosity. This is in very good agreement with the experimental findings. A discussion of what the data mean for diffusion-controlled reactions involving el

PHOTOCHEMISTRY OF 1‐PYRENYLDIAZOMETHANE

Photoexcitation of 1‐pyrenyldiazomethane (1) leads to carbenes which attach to various molecules, e.g. surfactants, polymers, hydroxylated surfaces. This provides a convenient method of labelling these compounds with pyrene for probe studies of complex structures and surfaces. Photophysical and photochemical studies of the various events resulting from the photoexcitation of 1, show that the quantum yield for disappearance of 1 and of carbene formation is low (∼ 5%) and that other processes lead to relaxation of excited 1, in particular fluorescence and intersystem crossing. The mechanism involves a mixing of low lying π‐π* states of the pyrene chromaphore with diazo n‐π+ states, and is discussed in the light of other similar systems and the present studies. Copyright © 1991, Wiley Blackwell. All rights reserve

Structural Modifications of Deoxycholic Acid to Obtain Three Known Brassinosteroid Analogues and Full NMR Spectroscopic Characterization

An improved synthesis route for obtaining known brassinosteroid analogues, i.e., methyl 2α,3α-dihydroxy-6-oxo-5α-cholan-24-oate (11), methyl 3α-hydroxy-6-oxo-7-oxa-5α-cholan-24-oate (15) and methyl 3α-hydroxy-6-oxa-7-oxo-5α-cholan-24-oate (16), from hyodeoxycholic acid (4) maintaining the native side chain is described. In the alternative procedure, the di-oxidized product 6, obtained in the oxidation of methyl hyodeoxycholate 5, was converted almost quantitatively into the target monoketone 7 by stereoselective reduction with NaBH4, increasing the overall yield of this synthetic route to 96.8%. The complete 1H- and 13C-NMR assignments for all compounds synthesized in this work have been made by 1D and 2D heteronuclear correlation gs-HSQC and gs-HMBC techniques. Thus, it was possible to update the spectroscopic information of 1H-NMR and to accomplish a complete assignment of all 13C-NMR signals for analogues 5–16, which were previously reported only in partial form