Gold-Nanoparticle-Decorated Metal-Organic Frameworks for Anticancer Therapy

Confinement of Au nanoparticles (NPs) within the porous materials with few nanometers (2-3 nm) has been a well established research area in the past decades in heterogeneous catalysis mainly due to the unique behaviour of Au NPs than its bulk counterpart. In this aspect, Au NPs encapsulated within the pore volumes of metal−organic frameworks (MOFs) have been intensively explored as heterogeneous solid catalysts for wide range of reactions. In recent years, Au NPs confined within the porous MOFs along with the photosensitizer or drug have been effectively used for the treatment of tumor cells through the generation of reactive oxygen species via cascade reactions. This work highlights the benefits of MOFs pores in the preparation of nanomedicine with high efficiency by assembling Au NPs, photosensitizer/drug with the combination of laser either for imaging or treatment of tumor cells. Further, the existing literature is grouped based on the nature of porous materials employed in the preparation of nanomedicine. The final section comments on our view on future developments in the field.     

Synthesis,characterization and rheological properties of multiblock associative copolymers by RAFT technique

Polymer Bulletin - Preparation of associating multiblock copolymer electrolytes mediated by radical addition–fragmentation chain transfer (RAFT) technique has been evaluated and reported in...     

Synthesis and characterization of nanocomposites of thermoplastic polyurethane with both graphene and graphene nanoribbon fillers

Thermoplastic polyurethane (TPU) nanocomposites containing graphene and graphene nanoribbons were obtained by polymerizing 1,4-butanediol with two diisocyanates (namely, 1,6-hexane diisocyanate or isophorone diisocyanate), in which the nanofillers were previously dispersed. Raman spectroscopy and Transmission Electron Microscopy demonstrated the formation of few-layer graphene and graphene nanoribbons dispersed in the monomers. At variance to the methods commonly reported in literature, that used in this work consists of the direct exfoliation of graphite without any chemical manipulation. Apart from the obvious cost and ease advantages, the so-obtained graphene does not contain any carboxy or alkoxy groups formed during the exfoliation process, which, at variance, are typically present in the most commonly reported methods. This finding paves the way toward the large-scale production of graphene and its nanoribbons, which are considered even more interesting than graphene itself for many potential applications. The obtained nanocomposites show a peculiar thermal and rheological behavior due to the presence of the nanofillers and to their reinforcing or plasticizing effect exerted on the TPU matrices.     

The Anti-Inflammatory Effects of the Methanolic Extract and Fractions from Davilla elliptica St. Hil. (Dilleniaceae) on Bothrops jararaca Envenomation

Inflammation and haemorrhage are the main characteristics of tissue injury in botropic envenomation. Although some studies have shown that anti-venom prevents systemic reactions, it is not efficient in preventing tissue injury at the site of the bite. Therefore, this work was undertaken to investigate the anti-inflammatory effects of the methanolic extract and fractions from D. elliptica and to evaluate the role of matrix metalloproteinases (MMPs) in this process. Effects of the extract and fractions from D. elliptica were evaluated using a carrageenan-induced paw oedema model in rats, and leukocyte rolling was visualized by intravital. The quantification of MMPs activities (MMP-2 and MMP-9) extracted from the dermis of mice treated with extract and fractions alone or incubated with venom was determined by zymographic analyses. Our results show that intraperitoneal (i.p.) injection of fractions significantly reduced paw oedema after the carrageenan challenge. Treatment with the tannins fraction also resulted in considerable inhibition of the rolling of leukocytes and this fraction was able to decrease the activation of MMP-9. These results confirmed the anti-inflammatory activity of the methanolic extract and tannins fraction of D. elliptica and showed that the dermonecrosis properties of B. jararaca venom might be mediated through the inhibition of MMP-9 activity.     

Structural Determinants of the Selectivity of 3‐Benzyluracil‐1‐acetic Acids toward Human Enzymes Aldose Reductase and AKR1B10

The human enzymes aldose reductase (AR) and AKR1B10 have been thoroughly explored in terms of their roles in diabetes, inflammatory disorders, and cancer. In this study we identified two new lead compounds, 2‐(3‐(4‐chloro‐3‐nitrobenzyl)‐2,4‐dioxo‐3,4‐dihydropyrimidin‐1(2H)‐yl)acetic acid (JF0048, 3 ) and 2‐(2,4‐dioxo‐3‐(2,3,4,5‐tetrabromo‐6‐methoxybenzyl)‐3,4‐dihydropyrimidin‐1(2H)‐yl)acetic acid (JF0049, 4 ), which selectively target these enzymes. Although 3 and 4 share the 3‐benzyluracil‐1‐acetic acid scaffold, they have different substituents in their aryl moieties. Inhibition studies along with thermodynamic and structural characterizations of both enzymes revealed that the chloronitrobenzyl moiety of compound 3 can open the AR specificity pocket but not that of the AKR1B10 cognate. In contrast, the larger atoms at the ortho and/or meta positions of compound 4 prevent the AR specificity pocket from opening due to steric hindrance and provide a tighter fit to the AKR1B10 inhibitor binding pocket, probably enhanced by the displacement of a disordered water molecule trapped in a hydrophobic subpocket, creating an enthalpic signature. Furthermore, this selectivity also occurs in the cell, which enables the development of a more efficient drug design strategy: compound 3 prevents sorbitol accumulation in human retinal ARPE‐19 cells, whereas 4 stops proliferation in human lung cancer NCI‐H460 cells.     

Synthesis and characterization of the polyols by air oxidation of soybean oil and its effect on the morphology and dynamic mechanical properties of poly(vinyl chloride) blends

The use of natural additives, with low toxicity and good compatibility, for PVC is becoming increasingly attractive. In this study, soybean oil additives were prepared by air oxidation reactions and blending with PVC. The oxidation reaction produced a significant increase in the number of hydroxyl groups in soybean oil; however, this kind of reaction results in the formation of a heterogeneous structure due to free radical reactions in the medium. The oxidized soybean oil improved the compatibility with PVC due to an increase in the number of polar groups, such as hydroxyls, and thus a reduction in the amount of atactic polymer was observed. Furthermore, an increase in the molecular weight of the oxidized oil, as well as large amounts of polar groups contributes to reducing the migration of oil in the PVC. Regarding the crystallinity of PVC, the use of pure and oxidized soybean oil causes small changes in the crystalline phase of the polymer. Oxidized soybean oil has great potential for usage as a secondary plasticizer for PVC. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42102.     

Effects of composition and furnace temperature on (Ni,Co) (Cr,Al)2O4 pigments synthesized by solution combustion route

The effects of composition and furnace temperature on Ni_1‐ΨCo_ΨCr_2?2ΨAl_2ΨO₄ (0≤Ψ≤1) pigments prepared by Solution Combustion Synthesis were studied. As‐synthesized samples showed spinel‐like spongy structure, very easy to grind. However, important differences on crystallinity, crystal size, and microstructure were observed depending on composition and furnace temperature. All pigments developed intense tones, covering a wide color palette because of composition influence, although little effect was observed with furnace temperature. Stable crystalline structures, suitable grain size, and high resistance against synthesizing variables and ceramic glazes make SCS pigments perfect candidates to be used in the ceramic ink‐jet decoration.     

On the steady‐state drop size distribution in stirred vessels. Part I: Effect of dispersed phase viscosity

Previous studies on emulsification have used the maximum drop size (d_max) or Sauter mean diameter ( ) to investigate the effect of viscosity on the drop size distribution (DSD), however, these parameters fall short for highly polydispersed emulsions. In this investigation (Part I), the steady‐state DSD of dilute emulsions is studied using of silicon oils with viscosities varying across six orders of magnitude at different stirring speeds. Different emulsification regimes were identified; our modeling and analysis is centered on the intermediate viscosity range where interfacial cohesive stresses can be considered negligible and drop size increases with viscosity. The bimodal frequency distributions by volume were well described using two log‐normal density functions. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3293–3302, 2018     

Characterisation of surface oxidation of nickel-titanium alloy by ion-beam and electrochemical techniques

The passivating effects produced on Ni₄₉Ti₅₁ (at.%) shape memory alloy by electropolishing in methanol-sulphuric acid electrolyte or thermal treatment in air are investigated with ion-beam techniques (secondary ion mass spectrometry (SIMS) and mass resolved ion scattering spectrometry (MARISS)) and electrochemical techniques (polarisation curves, photocurrent spectroscopy and impedance). Electropolishing produces a limited passivation due to formation of a thin layer of amorphous TiO₂, which causes only a slight hindrance to the oxygen evolution reaction. Thermal treatment in air at 450 °C causes a more substantial passivation due to formation of a thick oxide layer, estimated at about 80 nm for a 16 h treatment on the basis of weight increase, disregarding roughness. Data indicate that the film produced by thermal oxidation has probably a duplex structure, with a porous outer layer with inclusions of Ni species and a compact inner layer, in contact with the substrate, consisting of (essentially) nickel free TiO₂ rutile.     

Preliminary study of the anticancer applications of mesoporous materials functionalized with the natural product betulinic acid

Dehydrated MCM-41 (S1) was functionalized under nitrogen with 3-chloropropyltriethoxysilane (CPTS) and 3-aminopropyltriethoxysilane (APTS) by grafting in toluene at 80 °C over 48 h to give the corresponding materials S2 and S3, respectively. Subsequently, S2 and S3 were suspended in methanol and reacted in a nitrogen atmosphere with betulinic acid (BA) for 48 h at 65 °C (in the presence of the triethylamine of S2) to give the BA-functionalized materials S4 and S5. All materials studied were characterized by powder X-ray diffraction, X-ray fluorescence, nitrogen gas sorption, multinuclear MAS NMR spectroscopy, thermogravimetry, UV spectroscopy, IR, SEM, and TEM. To study the release of BA, S4 and S5 were suspended in solutions simulating various body pH conditions (pH 7.4, 5.5, and 3.0). Results of the quantification of BA release by HPLC for S4 show a pH-dependent and very slow BA release following a logarithmic tendency, while S5 behaves differently, also pH-dependent but, in this case, fast release of BA which requires only days for total release of the therapeutic compound. In addition, the cytotoxic activity of all synthesized materials against various cancer cell lines was studied. The results show the absence of an antiproliferative effect on the surfaces without BA S1-S3, while an antiproliferative effect was observed with S4 and S5 and was attributed to the release of BA in the medium.