Molecular modeling of polymer-clay nanocomposite precursors: Lysine in montmorillonite interlayers

The layered structure of clays with interlayer cations leads to unique chemical and mechanical properties, which have been capitalized on in the field of polymer/layered silicate nanocomposites. Hydrophilic silica surfaces can become organophilic with the inclusion of alkylammonium cations, which improve the wetting characteristics of the polymer matrix. In fact, the molecular level interactions of amino acids, either natural or non-natural, with clay surfaces are at the heart of fields of study as diverse as nanocomposites fabrication, drug delivery, bio-remediation of soils and catalysis of biological polymers, to name a few. The ubiquity of these systems and the potential uses to which they could be put suggests the necessity of a deeper understanding of the interplay of bonds, conformations, and configurations between the molecules and the hosts. The interactions of the amino acid lysine with sodium montmorillonite were studied using theoretical molecular modeling methods. The interlayer spacing of montmorillonite was increased by incorporating water molecules and allowing the system to evolve with molecular mechanics. Care was taken to retain the sodium cations in the interlayer. The initial amino acid conformation was obtained surrounding the molecule with numerous discrete water molecules and minimizing the system at the semi empirical level. The optimized amino acid was then placed in the interlayer space in a series of initial positions. Molecular mechanics calculations were performed and the final positions were analyzed. The results tended to indicate the preponderance of configurations which included surface-sodium-amino acid complexes with a variety of spatial arrangements. These results were compared with molecular dynamics calculations of similar systems from the literature.     

Mercury determination in urine samples by gold nanostructured screen-printed carbon electrodes after vortex-assisted ionic liquid dispersive liquid–liquid microextraction

A novel approach is presented to determine mercury in urine samples, employing vortex-assisted ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction to prepare samples, and screen-printed electrodes modified with gold nanoparticles for voltammetric analysis. Mercury was extracted directly from non-digested urine samples in a water-immiscible ionic liquid, being back-extracted into an acidic aqueous solution. Subsequently, it was determined using gold nanoparticle-modified screen-printed electrodes. Under optimized microextraction conditions, standard addition calibration was applied to urine samples containing 5, 10 and 15 μg L⁻¹ of mercury. Standard addition calibration curves using standards between 0 and 20 μg L⁻¹ gave a high level of linearity with correlation coefficients ranging from 0.990 to 0.999 (N = 5). The limit of detection was empirical and statistically evaluated, obtaining values that ranged from 0.5 to 1.5 μg L⁻¹, and from 1.1 to 1.3 μg L⁻¹, respectively, which are significantly lower than the threshold level established by the World Health Organization for normal mercury content in urine (i.e., 10–20 μg L⁻¹). A certified reference material (REC-8848/Level II) was analyzed to assess method accuracy finding 87% and 3 μg L⁻¹ as the recovery (trueness) and standard deviation values, respectively. Finally, the method was used to analyze spiked urine samples, obtaining good agreement between spiked and found concentrations (recovery ranged from 97 to 100%).     

A general and regioselective synthesis of cyclopentenone derivatives through nickel(0)-mediated [3 + 2] cyclization of alkenyl Fischer carbene complexes and internal alkynes

A broad range of substituted 2-cyclopentenone derivatives 3-6 are synthesized by the nickel(0)-mediated [3 + 2] cyclization reaction of chromium alkenyl(methoxy)carbene complexes 1 and internal alkynes 2. The reaction takes place with complete regioselectivity with both unactivated alkynes and activated alkynes (electron-withdrawing and electron-donating substituted alkynes). Representative cycloadducts containing boron and tin substituents are further demonstrated to be active partners in classical Pd-catalyzed C-C coupling processes to allow the production of 2-aryl- and 2-alkynyl-substituted cyclopentenones 9-13.     

Solid-phase synthesis of novel trimers containing a phenylstatine core and analysis by high-resolution magic angle spinning

Here we describe a multistep solid-phase synthetic approach for the addition of amino acid residues to both the C- and N-termini of a phenylstatine core, yielding a library aimed at the development of structure-activity relationships in the S2 and S2' regions of the aspartyl proteases. Optimization of the synthetic strategy was performed on the basis of the in situ analysis of the compounds bound to the solid support through high-resolution magic angle spinning NMR Spectroscopy (HR-MAS NMR).     

Physical-Mechanical Behavior and Water-Barrier Properties of Biopolymers-Clay Nanocomposites

The preparation and characterization of biodegradable films based on starch-PVA-nanoclay by solvent casting are reported in this study. The films were prepared with a relation of 3:2 of starch:PVA and nanoclay (0.5, 1.0, and 1.5% w/v), and glycerol as plasticizer. The nanoclays before being incorporated in the filmogenic solution of starch-PVA were dispersed in two ways: by magnetic stirring and by sonication. The SEM results suggest that the sonication of nanoclay is necessary to reach a good dispersion along the polymeric matrix. FTIR results of films with 1.0 and 1.5% w/v of sonicated nanoclay suggest a strong interaction of hydrogen bond with the polymeric matrix of starch-PVA. However, the properties of WVP, tensile strength, percentage of elongation at break, and Young’s modulus improved to the film with sonicated nanoclay at 0.5% w/v, while in films with 1.0 and 1.5% w/w these properties were even worse than in film without nanoclay. Nanoclay concentrations higher than 1.0 w/v saturate the polymer matrix, affecting the physicochemical properties. Accordingly, the successful incorporation of nanoclays at 0.5% w/v into the matrix starch-PVA suggests that this film is a good candidate for use as biodegradable packaging.     

In Situ Incorporation of Praziquantel in Polymer Microparticles through Suspension Polymerization for Treatment of Schistosomiasis

Schistosomiasis is one of the major public health problems worldwide. Even though this is a common illness among preschool children in poor countries, treatment is carried out mainly through the administration of praziquantel tablets, which has some disadvantages, such as the strong bitter taste. As an alternative to overcome this problem, the development of new encapsulated praziquantel formulations is demanded. For this reason, suspension polymerizations are carried out for the in situ encapsulation of praziquantel into polymer microparticles, using methyl methacrylate (MMA) and cationic compounds (diethylaminoethyl methacrylate, DEAEMA, and dimethylaminoethyl methacrylate, DMAEMA) as comonomers. This technique allows for the preparation of polymer microparticles with high encapsulation efficiencies (>90%) with characteristic sizes ranging from 0.5 to 1500 µm. Drug release profiles show that praziquantel is released from poly(methyl methacrylate) microparticles slowly due to the existence of strong diffusional resistance. On the other hand, the addition of cationic comonomers renders polymer particles sensitive to pH variations, allowing for faster release of praziquantel in acidic environments, as found in the stomach.     

Identification of potential trypanothione reductase inhibitors among commercially available $$\upbeta $$-carboline derivatives using chemical space,lead-like and drug-like filters,pharmacophore models and molecular docking

American trypanosomiasis or Chagas disease caused by the protozoan Trypanosoma cruzi (T. cruzi) is an important endemic trypanosomiasis in Central and South America. This disease was considered to be a priority in the global plan to combat neglected tropical diseases, 2008–2015, which indicates that there is an urgent need to develop more effective drugs. The development of new chemotherapeutic agents against Chagas disease can be related to an important biochemical feature of T. cruzi: its redox defense system. This system is based on trypanothione (\(N^{1}\),\(N^{8}\)-bis(glutathyonil)spermidine) and trypanothione reductase (TR), which are rather unique to trypanosomes and completely absent in mammalian cells. In this regard, tricyclic compounds have been studied extensively due to their ability to inhibit the T. cruzi TR. However, synthetic derivatives of natural products, such as \(\upbeta \)-carboline derivatives (\(\upbeta \)-CDs), as potential TR inhibitors, has received little attention. This study presents an analysis of the structural and physicochemical properties of commercially available \(\upbeta \)-CDs in relation to compounds tested against T. cruzi in previously reported enzymatic assays and shows that \(\upbeta \)-CDs cover chemical space that has not been considered for the design of TR inhibitors. Moreover, this study presents a ligand-based approach to discover potential TR inhibitors among commercially available \(\upbeta \)-CDs, which could lead to the generation of promising \(\upbeta \)-CD candidates.     

Cyclic oligomers (macroaldonolactones) from a protected d-galactonic acid monomer

Dicyclohexylcarbodiimide-promoted self-condensation of 2,3:4,5-di-O-isopropylidene-d-galactonic acid (3) led to the macrocyclic oligomeric cyclo[(2,3:4,5-di-O-isopropylidene-(1→6)-d-galactonate)₂] (4) and cyclo[(2,3:4,5-di-O-isopropylidene-(1→6)-d-galactonate)₃] (5), having, respectively, 14- and 21-membered rings. The macrocycles 4 and 5 were also synthesized by cyclization of the respective linear dimer 11 and trimer 14 ω-hydroxy acids precursors prepared by stepwise additions of 3. Compounds 4 and 5 are biomaterials that may be described as macrolactone-cyclodextrins.     

Investigations by various analytical techniques to the correct classification of archaeological finds and delineation of technological features: Late Roman lamps from Egnatia: From imports to local production

Late Roman oil lamps from the archaeological site of Egnatia (Fasano, Brindisi, Italy) were characterized from physical–chemical, mineralogical and morphological points of view. Atomic Spectroscopy, Scanning Electron Microscopy and X-Ray Diffraction analyses were carried out on ceramic body and coatings with the aim of identifying the provenance of lamps, in order to arrive at a correct archaeological classification of finds and to outline their technological features.The analytical results show that the finds differ in raw materials and in production technology. The statistical multivariate treatment of compositional data of ceramic bodies groups the objects into two macro clusters and, according to a study of their different petrographic features and by a comparison with coeval pottery whose provenance is already known, suggests one group to have been imported from North Africa and the other to have been locally produced. Moreover, chemical results and in-depth archaeological analyses allow us to split the imported lamps into two subgroups, hypothesizing the first group to originate from central Tunisia and the second from the north of the same country.The analytical characterisation of finds, by different complementary techniques, has allowed us to identify the raw materials and the technological solutions used by the ancient potters from Egnatia to produce lamps. The potters made lamps which had an external appearance very similar to that of African prototypes, but which were nevertheless different as they employed the locally available materials.     

Speciation of mercury by ionic liquid-based single-drop microextraction combined with high-performance liquid chromatography-photodiode array detection

Room temperature ionic liquids can be considered as environmentally benign solvents with unique physicochemical properties. Ionic liquids can be used as extractant phases in SDME, being compatible with chromatographic systems. A single-drop microextraction method was developed for separation and preconcentration of mercury species (MeHg⁺, EtHg⁺, PhHg⁺ and Hg²⁺), which relies on the formation of the corresponding dithizonates and microextraction of these neutral chelates onto a microdrop of an ionic liquid. Afterwards, the separation and determination were carried out by high-performance liquid chromatography with a photodiode array detector. Variables affecting the formation and extraction of mercury dithizonates were optimized. The optimum conditions found were: microextraction time, 20 min; stirring rate, 900 rpm; pH, 11; ionic liquid type, 1-hexyl-3-methylimidazolium hexafluorophosphate ([C₆MIM][PF₆]); drop volume, 4 μL; and no sodium chloride addition. Limits of detection were between 1.0 and 22.8 μg L⁻¹ for the four species of mercury, while the repeatability of the method, expressed as relative standard deviation, was between 3.7 and 11.6% (n = 8). The method was finally applied to the determination of mercury species in different water samples.