Protein-Polyelectrolyte Complexes and Micellar Assemblies.

In this review, we highlight the recent progress in our understanding of the structure, properties and applications of protein-polyelectrolyte complexes in both bulk and micellar assemblies. Protein-polyelectrolyte complexes form the basis of the genetic code, enable facile protein purification, and have emerged as enterprising candidates for simulating protocellular environments and as efficient enzymatic bioreactors. Such complexes undergo self-assembly in bulk due to a combined influence of electrostatic interactions and entropy gains from counterion release. Diversifying the self-assembly by incorporation of block polyelectrolytes has further enabled fabrication of protein-polyelectrolyte complex micelles that are multifunctional carriers for therapeutic targeted delivery of proteins such as enzymes and antibodies. We discuss research efforts focused on the structure, properties and applications of protein-polyelectrolyte complexes in both bulk and micellar assemblies, along with the influences of amphoteric nature of proteins accompanying patchy distribution of charges leading to unique phenomena including multiple complexation windows and complexation on the wrong side of the isoelectric point

The remarkable amphoteric nature of defective UiO-66 in catalytic reactions

One of the major requirements in solid acid and base catalyzed reactions is that the reactants, intermediates or activated complexes cooperate with several functions of catalyst support. In this work the remarkable bifunctional behavior of the defective UiO-66(Zr) metal organic framework is shown for acid-base pair catalysis. The active site relies on the presence of coordinatively unsaturated zirconium sites, which may be tuned by removing framework linkers and by removal of water from the inorganic bricks using a dehydration treatment. To elucidate the amphoteric nature of defective UiO-66, the Oppenauer oxidation of primary alcohols has been theoretically investigated using density functional theory (DFT) and the periodic approach. The presence of acid and basic centers within molecular distances is shown to be crucial for determining the catalytic activity of the material. Hydrated and dehydrated bricks have a distinct influence on the acidity and basicity of the active sites. In any case both functions need to cooperate in a concerted way to enable the chemical transformation. Experimental results on UiO-66 materials of different defectivity support the theoretical observations made in this work

Thiacalix[4]arene derivatives bearing imidazole units : a ditopic hard/soft receptor for Na⁺ and K⁺/Ag⁺ with an allosteric effect and a reusable extractant for dichromate anions

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Two novel receptors 5,11,17,23-tetra-tert-butyl-25,27-bis[(ethoxycarbonyl)methoxy]-26,28-bis-[1-methyl-(imidazole)meth-oxy] -2,8,14,20-tetra-thiacalix[4]arene (L1) and 5,11,17,23-tetra-tert-butyl-25,27-bis-[(benzyl)methoxy] -26,28-bis-[1-methyl-(imidazole)-methoxy]-2,8,14,20-tetrathiacalix[4] arene (L2) possessing imidazole moieties based on thiacalix[4]arene in the 1,3-alternate conformation have been synthesized and characterized. The crystal structures of L1 and L2 have been determined. The binding behaviour towards Li + , Na + , K + and Ag + ions has been examined by 1 H NMR titration experiments in (CDCl 3 /CD 3 CN; 10:1, v/v) solution. The exclusive formation of mononuclear complexes of L1 with metal cations is of particular interest revealing a negative allosteric effect in the thiacalix[4]arene family. Liquid-liquid extraction experiments indicate that synthesized L2 can be utilized as an efficient reusable extractant for dichromate anion by controlling the pH of the aqueous solution

A new approach to immunoFET operation

A new method is presented for the detection of an immunological reaction taking place in a membrane, which covers the gate area of an ISFET. By stepwise changing the electrolyte concentration of the sample solution, a transient diffusion of ions through the membrane-protein layer occurs, resulting in a transient membrane potential, which is measured by the ISFET. The diffusion rate is determined by the immobile charge density in the amphoteric protein layer, which changes upon formation of antibody—antigen complexes. No membrane potential is induced at zero fixed charge density as occurs at a protein characteristic pH. Isoeletric points of embedded proteins can be determined by detecting the zero potential response.\ud \ud Up to now, the authors have studied the membrane adsorption of lysozyme, human serum albumin (HSA) and the immune reaction of HSA with the antibody anti-human serum albumin (αHSA). The influence of protein parameters on the amplitude of the transient can be described with an empirical equation. Assuming Langmuir behaviour, the protein concentration in the solution can well be correlated with the concentration in the membrane.\ud \ud This new detection method is unique concerning direct measurements of charge densities and isoelectric points of amphoteric macromolecules adsorbed in the membrane. The simple procedure of one incubation stage followed by one detection stage, without separate washing and labelling techniques, gives direct information about specific charge properties of the macromolecules to be studied

Assessing physical properties of amphoteric fluoroquinolones using phosphorescence spectroscopy

[EN] The self-association of fluoroquinolones (FQ) in water would play a relevant role in their translocations across lipid membranes. Triplet excited states of these drugs have been shown as reporters of FQ self-association using laser flash photolysis technique. A study using low-temperature phosphorescence technique was performed with quinolone derivatives such as enoxacin (ENX), norfloxacin (NFX), pefloxacin (PFX), ciprofloxacin (CPX, ofloxacin (OFX), nalidixic acid (NLA), pipemidic acid (PPA) and piromidic acid (PRA) to explore emission changes associated with self-associations and to shed some light on the triplet excited state energy (E-T) discrepancies described in the literature for most of these drugs. The emissions obtained at 77 K in buffered aqueous medium revealed that the amphoteric nature of the quinolones CPX, NFX, PFX, ENX, OFX and PPA must generate their self-associations because a redshift of their phosphorescence maxima is produced by FQ concentrations increases. Hence, this effect was not observed for NLA and PRA or when all quinolones were analysed using ethanol or ethylene glycol aqueous mixtures as glassed solvents. Interestingly, the presence of these organic mixtures produced a blue-shift in the phosphorescence emission maximum of each FQ. Additionally, laser flash photolysis experiments with PRA and the amphoteric quinolone PPA, compounds with the same skeleton but different peripheral substituent, confirm the expected correlations between the amphoteric nature of compounds and their self-associations in aqueous media because the excimer generation was only detected for PPA. Now, the discrepancies described in the literature for the ET of FQs can be understood considering that changes of medium polarity or proticity as well as the temperature can considerably modify their ET values. Thereby, low-temperature phosphorescence technique, is an effective way to detect molecular self-associations and surrounding changes in quinolones that opens the possibility to evaluate these effects in other drug families. (C) 2019 Elsevier B.V. All rights reserved.Financial support from Spanish government (grant CTQ2014-54729-C2-2-P) and the Generalitat Valenciana (PROMETEO program, 2017-075).Soldevila Serrano, S.; Bosca Mayans, F. (2020). Assessing physical properties of amphoteric fluoroquinolones using phosphorescence spectroscopy. Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy. 227:1-7. https://doi.org/10.1016/j.saa.2019.117569S17227Domagala, J. M., Hanna, L. D., Heifetz, C. L., Hutt, M. P., Mich, T. F., Sanchez, J. P., & Solomon, M. (1986). New structure-activity relationships of the quinolone antibacterials using the target enzyme. The development and application of a DNA gyrase assay. 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Seeking to Shed Some Light on the Binding of Fluoroquinolones to Albumins. The Journal of Physical Chemistry B, 116(11), 3504-3511. doi:10.1021/jp208930qCuquerella, M. C., Lhiaubet-Vallet, V., Miranda, M. A., & Bosca, F. (2017). Drug–DNA complexation as the key factor in photosensitized thymine dimerization. Physical Chemistry Chemical Physics, 19(7), 4951-4955. doi:10.1039/c6cp08485kAlfredson, T. V., Maki, A. H., & Waring, M. J. (1991). Optically detected triplet-state magnetic resonance studies of the DNA complexes of the bisquinoline analog of echinomycin. Biochemistry, 30(40), 9665-9675. doi:10.1021/bi00104a014Alfredson, T. V., & Maki, A. H. (1990). Phosphorescence and optically detected magnetic resonance studies of echinomycin-DNA complexes. Biochemistry, 29(38), 9052-9064. doi:10.1021/bi00490a024Li, J., Li, J., Shuang, S., & Dong, C. (2005). Study of the luminescence behavior of seven quinolones on a paper substrate. 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Evidence for Amphoteric Behavior of Ru on CdTe Surfaces

Modification of large grain p-CdTe by Ru is shown to reduce the sub-band-gap response and increase minority-carrier diffusion length from 0.67 to 0.92 µm. Contact potential difference (CPD) measurements on n- and p-CdTe show shifts in surface Fermi level in opposite directions corresponding to increase in barrier height in each case. The amphoteric nature of Ru on CdTe surfaces depending on conductivity type is thus inferred. The magnitudes of the changes in CPD are approximately equal to the increase of open circuit voltage V∞ observed in photoelectro-chemical cells

Co-planar spin-polarized light emitting diode

Studies of spin manipulation in semiconductors has benefited from the possibility to grow these materials in high quality on top of optically active III-V systems. The induced electroluminescence in these layered semiconductor heterostructures has been used for a reliable spin detection. In semiconductors with strong spin-orbit interaction, the sensitivity of vertical devices may be insufficient, however, because of the sepration of the spin aligner part and the spin detection region by one or more heterointerfaces and becuse of the short spin coherence length. Here we demostrate that higly sensitive spin detection can be achieved using a lateral arrangement of the spin polarized and optically active regions. Using our co-planar spin-polarized light emitting diodes we detect electrical field induced spin generation in a semiconductor heterojunction two-dimensional hole gas. The polarization results from spin asymmetric recombination of injected electrons with strongly SO coupled two-dimensional holes. The possibility to detect magnetized Co particles deposited on the co-planar diode structure is also demonstrated.Comment: 8 pages, 3 figure

Surface-acoustic-wave-driven luminescence from a lateral p-n junction

The authors report surface-acoustic-wave-driven luminescence from a lateral p-n junction formed by molecular beam epitaxy regrowth of a modulation doped GaAs/AlGaAs quantum well on a patterned GaAs substrate. Surface-acoustic-wave-driven transport is demonstrated by peaks in the electrical current and light emission from the GaAs quantum well at the resonant frequency of the transducer. This type of junction offers high carrier mobility and scalability. The demonstration of surface-acoustic-wave luminescence is a significant step towards single-photon applications in quantum computation and quantum cryptography.Comment: 4 pages, 3 figure