Monitoring pH-dependent conformational changes in aqueous solutions of poly(methacrylic acid)-b-polydimethylsiloxane copolymer based on fluorescence spectra of pyrene and 1,3-bis(1-pyrenyl)propane

Aqueous solutions of poly(methacrylic acid)-b-polydimethylsiloxane copolymer (PMA-b-PDMS), and reference solutions of PMA homopolymer, were studied as a function of pH using fluorescent probes: pyrene (P) and 1,3-bis(1-pyrenyl)propane (P3P). In both polymers the conformational transition of PMA chains at pH>5 was reflected in the sharp increase of the intensity ratio of the first to the third vibronic band in emission spectra of P; an excimer emission appeared for P3P, as well as for P if the probe concentration was higher than its solubility limit in water. The excimer to monomer intensity ratio of both probes is a sensitive indicator of the conformational transitions of polymer chains, but P3P is significantly more sensitive compared to pyrene. The data clearly indicated that the presence of PDMS blocks markedly facilitated the transition, even though the ratio of dimethylsiloxane to methacrylic acid units in the copolymer was low, 1:34. The absence of the P3P excimer emission at pH≈3 was rationalized by assuming that clustering of sections of PMA chains around pyrene moieties imposes an extended conformation of the probe molecule.     

Anticoagulant, Antioxidant and Antitumor Activities of Heterofucans from the Seaweed Dictyopteris delicatula

In the present study, six families of sulfated polysaccharides were obtained from seaweed Dictyopteris delicatula by proteolytic digestion, followed by acetone fractionation and molecular sieving on Sephadex G-100. Chemical analyses demonstrated that all polysaccharides contain heterofucans composed mainly of fucose, xylose, glucose, galactose, uronic acid, and sulfate. The fucans F0.5v and F0.7v at 1.0 mg/mL showed high ferric chelating activity (～45%), whereas fucans F1.3v (0.5 mg/mL) showed considerable reducing power, about 53.2% of the activity of vitamin C. The fucan F1.5v presented the most prominent anticoagulant activity. The best antiproliferative activity was found with fucans F1.3v and F0.7v. However, F1.3v activity was much higher than F0.7v inhibiting almost 100% of HeLa cell proliferation. These fucans have been selected for further studies on structural characterization as well as in vivo experiments, which are already in progress.     

Dye-labelled polymer chains at specific sites: Synthesis by living/controlled polymerization

Dye-labelled polymer chains are extremely useful in many fields, such as optical imaging, signal amplification in biological diagnostics, light-harvesting and photochromic materials as well as in fluorescence studies about intra- and inter-molecular polymer chain associations, conformations and dynamics of polymer chains. However, in many cases, it is particularly useful that the dye is localized at a specific site, such as the chain-end or the junction between blocks. With the development of living/controlled polymerization techniques, end- and junction-functionalized polymers can be prepared with controlled molecular weights from a huge variety of monomers. This review highlights the state of the art in the strategies leading to one and only one precisely localized dye per polymer chain. Such dye can be introduced at three different steps of the polymerization: i) at the very beginning via the initiator or a chain transfer agent, ii) during polymerization via a functional monomer or a quencher, or iii) after polymerization via covalent binding of a dye-derivative.     

Chain packing versus chain mobility in semialiphatic BTDA-based copolyimides

A series of partially aliphatic copolyimides derived from 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 4,4′-diaminodiphenylmethane (DDM) and 1,6-diaminohexane (DAH) was synthesized. Solubility tests and structural characteristics, evaluated by wide-angle X-ray diffraction measurements (WAXD) did not vary steadily with the content of the flexible segment. On the dynamic mechanical analysis (DMA) the evolution of the secondary relaxations (γ and β) suggested an increased chain tightness as more aliphatic component is included. The onset temperature of α-relaxation decreased regularly with the content of aliphatic sequence. During the α-relaxation the trend of E′, E″ and tan δ with temperature, and at multiple frequencies, evidenced the overlapping of phenomena. The increased mobility determines the formation of oriented structures that behave as constraints. Simultaneously, as the flexible content (DAH segment) is more important, orientation relaxations take place with increasing temperature. The equilibrium between stiffening and flowing makes the polyimides with high aliphatic content behave like elastomers.     

Methodology to evaluate variations in piezoelectric constants after aging process

ABSTRACT

Piezoelectric ceramic properties change with time. Detected aging effects for PZT ceramics are; the difference in the value of the dielectric constants diminishes, whereas dielectric losses and elastic stiffness increases. In this work, an optimisation technique based on adjusting a finite element model to reproduce the complex impedance curves of a resonant piezoceramic disk is analysed aiming to detect changes due to aging. This technique allows estimating all material parameters, both their real and imaginary parts. The optimisation uses the constitutive equations of the piezoelectric effect in the linear regime. The evolution of elastic, piezoelectric and dielectric constants is evaluated after 5 years of aging. To compute the ten complex parameters, the piezoelectric model is adjusted to minimise the difference between finite element simulations and the experimental data. Results presented here, show that the proposed technique is sensitive enough to detect changes in the individual parameters due to aging process.     

Organosoluble asymmetric aromatic polyamides bearing pendent phenoxy groups

This study focuses on the synthesis and characterization of new polyamides based on an aromatic asymmetric diamine‐containing phenoxy‐substituted benzophenone segment. Low‐temperature solution polycondensation reactions of this diamine with various aromatic diacid chlorides containing ether, hexafluoroisopropylidene or diphenylsilane groups resulted in polyamides with molecular weights in the range 102 900–113 200 g mol^?1. The structures of these monomers and the corresponding polymers were fully confirmed using elemental analysis and infrared and NMR spectroscopy. All polyamides were easily soluble at room temperature in polar aprotic solvents and even in less polar solvents such as tetrahydrofuran. The polymers showed excellent thermal stability, up to 385 °C, and displayed glass transition temperatures in the range 225–256 °C. All the polymers presented blue florescence upon irradiation with UV light and thus show promise for applications in electroluminescent devices. Copyright © 2011 Society of Chemical Industry     

Synthesis of poly(urethane-urea) varnish bearing azobenzene chromophoric pendants

A new diol with azoaromatic pendant was prepared by N-phenyl-4-amido-3,4-dichloromaleimide with 2-mercaptoethanol in the presence of NaOH, and used to obtain photosensible poly(urethane-urea) varnish. A poly(urethane-urea) varnish bearing azobenzene chromophores, based on a poly(ethylene adipate)diol (average molecular weight—2000), 4,4′-dibenzyldiisocyanate, diethylene glycol, trimethylolpropane, and afore-mentioned diol, were prepared and characterized. The polymers were characterized by FTIR spectroscopy, thermal analysis (DMA, DSC, and TGA), and the photochromic behavior by UV irradiation of thin films was discussed.     

ACE2, the Receptor that Enables Infection by SARS-CoV-2: Biochemistry,Structure, Allostery and Evaluation of the Potential Development of ACE2 Modulators

Angiotensin converting enzyme 2 (ACE2) is the human receptor that interacts with the spike protein of coronaviruses, including the one that produced the 2020 coronavirus pandemic (COVID-19). Thus, ACE2 is a potential target for drugs that disrupt the interaction of human cells with SARS-CoV-2 to abolish infection. There is also interest in drugs that inhibit or activate ACE2, that is, for cardiovascular disorders or colitis. Compounds binding at alternative sites could allosterically affect the interaction with the spike protein. Herein, we review biochemical, chemical biology, and structural information on ACE2, including the recent cryoEM structures of full-length ACE2. We conclude that ACE2 is very dynamic and that allosteric drugs could be developed to target ACE2. At the time of the 2020 pandemic, we suggest that available ACE2 inhibitors or activators in advanced development should be tested for their ability to allosterically displace the interaction between ACE2 and the spike protein.     

Synthesis,Computational Studies and Assessment of in Vitro Activity of Squalene Derivatives as Carbonic Anhydrase Inhibitors

We report novel molecules incorporating the nontoxic squalene scaffold and different carbonic anhydrase inhibitors (CAIs). Potent inhibitory action, in the low-nanomolar range, was detected against isoforms hCA II for sulfonamide derivatives, which proved to be selective against this isoform over the tumor-associate hCA IX and XII isoforms. On the other hand, coumarin derivatives showed weak potency but high selectivity against the tumor-associated isoform CA IX. These compounds are interesting candidates for preclinical evaluation in glaucoma or various tumors in which the two enzymes are involved. In addition, an in silico study of inhibitor-bound hCA II revealed extensive interactions with the hydrophobic pocket of the active site and provided molecular insights into the binding properties of these new inhibitors.