Wormlike reverse micelles in lecithin/bile salt/water mixtures in oil

Knowing the ability of water and bile salts to promote the reverse wormlike micelle growth in lecithin/water or lecithin/bile salt mixtures in oil, this work was aimed at elucidating the association properties of the three solutes lecithin, water and the bile salt (BS) sodium deoxycholate in cyclohexane. By systematically changing the fraction of the two additives (i.e.: water and BS) we could identify a region at low additive/lecithin molar ratios where stable wormlike micelle dispersions were formed. Small angle X-ray scattering and oscillatory rheology measurements demonstrated that the ability of bile salt and water to transform the originally spherical lecithin reverse micelles into wormlike micelles and thereby impart to the sample viscoelastic properties is preserved in the three-solute mixture. The results suggest that reverse micelle including both bile salt and water are formed in this system. Reasonably the two primers interact with the same region of the lecithin headgroups and are complementary in altering the packing parameter of the amphiphile to values suitable for the formation of cylindrical aggregates

Physiology and physical chemistry of bile acids

Bile acids (BAs) are facial amphiphiles synthesized in the body of all vertebrates. They undergo the enterohepatic circulation: they are produced in the liver, stored in the gallbladder, released in the intestine, taken into the bloodstream and lastly re-absorbed in the liver. During this pathway, BAs are modified in their molecular structure by the action of enzymes and bacteria. Such transformations allow them to acquire the chemical–physical properties needed for fulling several activities including metabolic regulation, antimicrobial functions and solubilization of lipids in digestion. The versatility of BAs in the physiological functions has inspired their use in many bioapplications, making them important tools for active molecule delivery, metabolic disease treatments and emulsification processes in food and drug industries. Moreover, moving over the borders of the biological field, BAs have been largely investigated as building blocks for the construction of supramolecular aggregates having peculiar structural, mechanical, chemical and optical properties. The review starts with a biological analysis of the BAs functions before progressively switching to a general overview of BAs in pharmacology and medicine applications. Lastly the focus moves to the BAs use in material science

Anthracyclines gels: Chemical structure and functional behaviour

Anthracyclines are a family of antibiotics often used in cancer chemotherapy. Daunorubicin (DA) was the first isolated from a strain of Streptomyces peucetius back in 1960 and still in use for the treatment of several malignancies together with the even more frequently used analogue Doxorubicin (DX, also called Adriamycin) and its semisynthetic derivative Epirubicyn (EPI). Despite their extremely close chemical formula (Figure 1), their properties when in solution are enormously different. In fact, whereas the increase of the ionic strength induces the formation of a gel with DX1-3, in the case of the related EPI and DA molecules what is observed are only the well-known self-association phenomena documented in the literature from decades4. Please click Additional Files below to see the full abstract

Colorimetric transition of polydiacetylene/cyclodextrin supramolecular assemblies and implications as colorimetric sensors for food phenolic antioxidants

Molecular self-assembly has significant potential in the field of sensing. Polydiacetylenes (PDAs) are conjugated polymers possessing peculiar optical properties obtained by photopolymerization of self-assembled diacetylene monomers. Herein, the blue-to-red phase transition upon either thermal stimulus or interaction with cyclodextrins (CDs) of two PDAs, bearing either carboxylic (PCDA) or amino (PCDA-NH2) polar heads, is investigated to develop a colorimetric sensor for food phenolic antioxidants. The change in the PDA polar head does not affect significantly thermo-chromatic transition. Upon thermal stimulus, in both PDAs, color transition occurs straightforward between two distinct stable states and does not involve the disordering of the PDA crystal phase, as revealed by UV-vis spectroscopy and SAXS analysis. Contrarily, PDA/alpha-CD interaction is influenced by intermolecular forces among PDA polar heads and is more efficient for PCDA. alpha-CDs presumably cause changes in both PDA backbone conformation and local environment surrounding the individual PDA chains. The PCDA/alpha-CD assemblies are investigated as colorimetric sensors for the detection of Tyrosol (Ty) and caffeic acid (CAF), by using the principle of competitive inclusion complex formation. The system results to be more sensitive to CAF than Ty and may permit the determination of CAF in concentration ranges suitable for different food products

Conformational disorder analysis of the conditionally disordered protein CP12 from Arabidopsis thaliana in its different redox states

CP12 is a redox-dependent conditionally disordered protein universally distributed in oxygenic photosynthetic organisms. It is primarily known as a light-dependent redox switch regulating the reductive step of the metabolic phase of photosynthesis. In the present study, a small angle X-ray scattering (SAXS) analysis of recombinant Arabidopsis CP12 (AtCP12) in a reduced and oxidized form confirmed the highly disordered nature of this regulatory protein. However, it clearly pointed out a decrease in the average size and a lower level of conformational disorder upon oxidation. We compared the experimental data with the theoretical profiles of pools of conformers generated with different assumptions and show that the reduced form is fully disordered, whereas the oxidized form is better described by conformers comprising both the circular motif around the C-terminal disulfide bond detected in previous structural analysis and the N-terminal disulfide bond. Despite the fact that disulfide bridges are usually thought to confer rigidity to protein structures, in the oxidized AtCP12, their presence coexists with a disordered nature. Our results rule out the existence of significant amounts of structured and compact conformations of free AtCP12 in a solution, even in its oxidized form, thereby highlighting the importance of recruiting partner proteins to complete its structured final folding

Development and Validation of a LiDAR Scanner for 3D Evaluation of Soil Vegetal Coverage

Water and wind erosion are serious problems due to the loss of soil productivity. The coverage of soil, by means of cover crops or crops residues, is an effective tool to prevent wind and water erosion. The soil coverage could curb wind on the surface, avoid water runoff and reduce direct soil evaporation. Residue spatial distribution is the main factor to successful soil protection. The current work presents details of a prototype, design and validation as a measuring instrument to sense the height of vegetal crop residues based on a short-ranged laser distance sensor (LiDAR) and a computer numerical control (CNC) mechanism. The results obtained in this work showed a high level of confidence to estimate the height and composition of soil vegetal coverage.Fil: Micheletto, Matías Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Investigaciones en Ingeniería Eléctrica "Alfredo Desages". Universidad Nacional del Sur. Departamento de Ingeniería Eléctrica y de Computadoras. Instituto de Investigaciones en Ingeniería Eléctrica "Alfredo Desages"; ArgentinaFil: Zubiaga, Luciano. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Instituto Nacional de Tecnología Agropecuaria. Centro Regional Buenos Aires Sur. Estación Experimental Agropecuaria Hilario Ascasubi; ArgentinaFil: Santos, Rodrigo Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Ciencias e Ingeniería de la Computación. Universidad Nacional del Sur. Departamento de Ciencias e Ingeniería de la Computación. Instituto de Ciencias e Ingeniería de la Computación; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Eléctrica y de Computadoras; ArgentinaFil: Galantini, Juan Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Centro de Recursos Naturales Renovables de la Zona Semiárida. Universidad Nacional del Sur. Centro de Recursos Naturales Renovables de la Zona Semiárida; Argentina. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas; ArgentinaFil: Cantamutto, Miguel Ángel. Instituto Nacional de Tecnología Agropecuaria. Centro Regional Buenos Aires Sur. Estación Experimental Agropecuaria Hilario Ascasubi; ArgentinaFil: Orozco, Javier Dario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Ciencias e Ingeniería de la Computación. Universidad Nacional del Sur. Departamento de Ciencias e Ingeniería de la Computación. Instituto de Ciencias e Ingeniería de la Computación; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Eléctrica y de Computadoras; Argentin

Synthesis and Complexation of Polytopic Adamantane-Based Probes

The 9th International Electronic Conference on Synthetic Organic Chemistry session Supramolecular ChemistryThe authors thank the Ministerio de Ciencia y Tecnología (Project MAT2001-2911) and Xunta de Galicia (PGIDIT02PXIC26202PN) for financial support. V. H. Soto thanks AECI (Beca Mutis)/University of Costa Rica for a research scholarshi

Synthesis and Characterization of a Thermoresponsive Copolymer with an LCST–UCST-like Behavior and Exhibiting Crystallization

In this work, the diblock copolymer methoxy-poly(ethylene glycol)-block-poly(ε-caprolactone) (MPEG–b-PCL) was synthesized with a block composition that allows this polymer in aqueous media to possess both an upper critical solution temperature (UCST) and a lower critical solution temperature (LCST) over a limited temperature interval. The value of the UCST, associated with crystallization of the PCL-block, depended on heating (H) or cooling (C) of the sample and was found to be CPUCSTH = 32 °C and CPUCSTC = 23 °C, respectively. The LCST was not affected by the heating or cooling scans; assumed a value of 52 °C (CPLCSTH = CPLCSTC). At intermediate temperatures (e.g., 45 °C), dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (cryo-TEM) showed that the solution consisted of a large population of spherical core–shell particles and some self-assembled rodlike objects. At low temperatures (below 32 °C), differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS) in combination with SAXS disclosed the formation of crystals with a cylindrical core–shell structure. Cryo-TEM supported a thread-like appearance of the self-assembled polymer chains. At temperatures above 52 °C, incipient phase separation took place and large aggregation complexes of amorphous morphology were formed. This work provides insight into the intricate interplay between UCST and LCST and the type of structures formed at these conditions in aqueous solutions of MPEG–b-PCL diblock copolymers.publishedVersio

Synthesis, characterization and self aggregation of a new neo-pentylamide cholic derivative (Na-n-penC)

The 10th International Electronic Conference on Synthetic Organic Chemistry session Supramolecular ChemistryThe self-aggregation in aqueous solution of a new neo-pentyl amide of the 3-β-amino derivative of cholic acid (Na-n-penC) has been investigated in aqueous solution by surface tension and steady state-fluorescence spectroscopy of pyrene (used as a probe). The nature of the agregates was determined by transmission electron microscopy (TEM) revealing that vesicles are formed. The structure of the compound in the solid state was resolved by X-ray spectroscopy. The synthesis of the compound is also give

Complexation of adamantyl derivatives by a β–cyclodextrin dimer.

The 13th International Electronic Conference on Synthetic Organic Chemistry session Polymer and Supramolecular ChemistryThe binding constants, standard molar enthalpy, Gibbs free energy, and entropy changes were determined for the formation of complexes between adamantyl derivatives and a β-cyclodextrin dimer. It is concluded that, within experimental error, the two cyclodextrin residues in the dimer behave independent to each other when complexing the adamantyl derivativesThe authors from USC thank the Ministerio de Ciencia y Tecnología (Project MAT2004-04606) and Xunta de Galicia (PGIDIT05PXIC26201PN) for financial suppor