Cytotoxic Activity and Structure–Activity Relationship of Triazole‐Containing Bis(Aryl Ether) Macrocycles

Cancer continues to be a worldwide health problem. Certain macrocyclic molecules have become attractive therapeutic alternatives for this disease because of their efficacy and, frequently, their novel mechanisms of action. Herein, we report the synthesis of a series of 20‐, 21‐, and 22‐membered macrocycles containing triazole and bis(aryl ether) moieties. The compounds were prepared by a multicomponent approach from readily available commercial substrates. Notably, some of the compounds displayed interesting cytotoxicity against cancer (PC‐3) and breast (MCF‐7) cell lines, especially those bearing an aliphatic or a trifluoromethyl substituent on the N‐phenyl moiety (IC₅₀<13 μm ). Additionally, some of the compounds were able to induce apoptosis relative to the solvent control; in particular, (Z)‐N‐cyclohexyl‐7‐oxo‐6‐[4‐(trifluoromethyl)phenyl]‐1¹H‐3,10‐dioxa‐6‐aza‐1(4,1)‐triazola‐4(1,3),9(1,4)‐dibenzenacyclotridecaphane‐5‐carboxamide ( 12 f ) was the most potent in this regard (22.7 % of apoptosis).     

An apparatus for in situ spectroscopy of radiation damage of polymers by bombardment with high-energy heavy ions

A new target station providing Fourier transform infrared (FT-IR) spectroscopy and residual gas analysis (RGA) for in situ observation of ion-induced changes in polymers has been installed at the GSI Helmholtz Centre for Heavy Ion Research. The installations as well as first in situ measurements at room temperature are presented here. A foil of polyimide Kapton HN(?) was irradiated with 1.1 GeV Au ions. During irradiation several in situ FT-IR spectra were recorded. Simultaneously outgassing degradation products were detected with the RGA. In the IR spectra nearly all bands decrease due to the degradation of the molecular structure. In the region from 3000 to 2700 cm(-1) vibration bands of saturated hydrocarbons not reported in literature so far became visible. The outgassing experiments show a mixture of C(2)H(4), CO, and N(2) as the main outgassing components of polyimide. The ability to combine both analytical methods and the opportunity to measure a whole fluence series within a single experiment show the efficiency of the new setup.     

A new synthetic route to molecularly imprinted ORMOSIL: Characterization and evaluation

A new strategy for synthesis of molecularly imprinted organically modified silica (MIORMOSIL) has been described. The MIORMOSIL was prepared by reacting vinyl acetate and 3-(trimethoxysilyl) propyl methacrylate, followed by condensation and hydrolysis with tetraethyl orthosilicate in the presence of caffeine. The ORMOSIL was characterized by SEM, FTIR, ²⁹Si MAS NMR, ¹³C MAS NMR, TGA, nitrogen adsorption/desorption and tested to extract analyte from coffee samples. The percentage recovery of caffeine 88 ± 5% (n = 9), limits of detection and quantification, 5.14 × 10^–4 and 1.71 × 10^?3 mmolL^?1 respectively, were achieved. Cross reactivity studies for theophylline and theobromine showed high recovery (77% and 82% respectively).

Abbreviations: HMIP: Molecularly Imprinted ORMOSIL; HNIP: non imprinted ORMOSIL; TMSPM: 3-(Trimethoxysilyl)propylmethacrylate     

Effect of montmorillonite clay addition on the morphological and physical properties of Jatropha curcas L. and Glycine max L. protein concentrate films

Protein concentrates from jatropha (JPC) and soy seeds (SPC) were obtained by solubilization and acid precipitation of proteins. JPC and SPC films were prepared by the casting method, using two different montmorillonite (MMT) clay concentrations and plasticized with glycerol. Film properties were evaluated by scanning electron microscopy, transmission electron microscopy, X‐ray diffraction (XRD), Fourier transform infrared spectroscopy, thermogravimetric analysis, tensile properties, water retention, and water vapor transmission rate (WVRT). Typical tactoid microcomposite structures were found to be heterogeneously dispersed in the films containing MMT. A small XRD peak was found in films with MMT. Slight improvements in thermal stability and tensile strength were observed in the films with MMT. Reductions in water retention and WVRT were obtained when MMT was added into the films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44459.     

Hybrid networks based on epoxidized camelina oil

Lately, renewable resources received great attention in the macromolecular compounds area, regarding the design of the monomers and polymers with different applications. In this study the capacity of several modified vegetable oil-based monomers to build competitive hybrid networks was investigate, taking into account thermal and mechanical behavior of the designed materials. In order to synthesize such competitive nanocomposites, the selected renewable raw material, camelina oil, was employed due to the non-toxicity and biodegradability behavior. General properties of epoxidized camelina oil-based materials were improved by loading of different types of organic-inorganic hybrid compounds – polyhedral oligomeric silsesquioxane (POSS) bearing one (POSS1Ep) or eight (POSS8Ep) epoxy rings on the cages. In order to identify the chemical changes occurring after the thermal curing reactions, FT-IR spectrometry was employed. The new synthesized nanocomposites based on epoxidized camelina oil (ECO) were characterized by dynamic mechanical analyze and thermogravimetric analyze. The morphology of the ECO-based materials was investigate by scanning electron microscopy and supplementary information regarding the presence of the POSS compounds were establish by energy dispersive X-ray analysis and X-ray photoelectron spectroscopy. The smooth materials without any separation phase indicates a well dispersion of the Si–O–Si cages within the organic matrix and the incorporation of this hybrid compounds into the ECO network demonstrates to be a well strategy to improve the thermal and mechanical properties, simultaneously.     

Quantification of fecal coliform inputs to aquatic systems through soil leaching

In order to assess the fecal contamination of rivers in the Seine watershed through soil leaching, 78 small streams located in rural areas were sampled upstream from any wastewater outfall. Culturable fecal coliforms (FC) and beta-D-glucuronidase activity (specific of Escherichia coli) were measured in the samples. Data showed a significant correlation between both estimates of fecal contamination. In the two different areas of the Seine river watershed investigated, most of the small streams were significantly contaminated by fecal bacteria. In general, the streams flowing through areas partly or fully covered with pastures were more contaminated than those flowing through forest and cultivated areas. Rainfall increased the suspended solid content of small streams as well as their fecal contamination, as an important fraction of FC was adsorbed on particles. Calculations showed that, at a large watershed scale, the input of FC in rivers through soil leaching was very low when compared to the input through the discharge of treated domestic wastewater but this could not be true at local scale.     

Interaction between manufactured gold nanoparticles and naturally occurring organic macromolecules

The increasing exploitation of nanomaterials into many consumer and other products is raising concerns as these nanomaterials are likely to be released into the environment. Due to our lack of knowledge about the environmental chemistry, transport and ecotoxicology of nanomaterials, it is of paramount importance to study how natural aquatic colloids can interact with manufactured gold nanoparticles as these interactions will determine their environmental fate and behaviour. In this context, our work aims to quantify the effect of naturally occurring riverine macromolecules--International Humic Substances Society (IHSS) Suwannee River Humic Acid Standard (SRHA)--on citrate- and acrylate-stabilized gold nanoparticles. The influence of SRHA on the stability of the gold colloids was studied as a function of pH by UV-visible absorption spectroscopy, dynamic light scattering (DLS) and transmission electron microscopy (TEM). At high ionic strengths (0.1 M), extensive and rapid aggregation occurred, while more subtle effects were observed at lower ionic strength values. Evidence was found that SRHA enhances particle stability at extreme pH values (ionic strength<0.01 M) by substituting and/or over-coating the original stabilizer on the gold nanoparticle surface, thus affecting surface charge and chemistry. These findings have important implications for the fate and behaviour of nanoparticles in the environment and their ecotoxicity.