Confined water in aqueous solutions of imidazolium-based ionic liquids (ILs) associated with acetate and imidazolate anions react reversibly with CO2 to yield bicarbonate. Three types of CO2 sorption in these “IL aqueous solutions” were observed: physical, CO2-imidazolium adduct generation, and bicarbonate formation (up to 1.9 molbicarbonate mol−1 of IL), resulting in a 10:1 (molar ratio) total absorption of CO2 relative to imidazolate anions in the presence of water 1:1000 (IL/water). These sorption values are higher than the classical alkanol amines or even alkaline aqueous solutions under similar experimental conditions.

The incorporation of small amount of highly anisotropic nanoparticles into liquid crystalline hydroxypropylcellulose (LC-HPC) matrix improves its response when is exposed to humidity gradients due to an anisotropic increment of order in the structure. Dispersed nanoparticles give rise to faster order/disorder transitions when exposed to moisture as it is qualitatively observed and quantified by stress-time measurements. The presence of carbon nanotubes derives in a improvement of the mechanical properties of LC-HPC thin films.

Cellulose and its derivatives, such as hydroxypropylcellulose (HPC) have been studied for a long time but they are still not well understood particularly in liquid crystalline solutions. These systems can be at the origin of networks with properties similar to liquid crystalline (LC) elastomers. The films produced from LC solutions can be manipulated by the action of moisture allowing for instance the development of a soft motor (Geng et al., 2013) driven by humidity. Cellulose nanocrystals (CNC), which combine cellulose properties with the specific characteristics of nanoscale materials, have been mainly studied for their potential as a reinforcing agent. Suspensions of CNC can also self-order originating a liquid-crystalline chiral nematic phases. Considering the liquid crystalline features that both LC-HPC and CNC can acquire, we prepared LC-HPC/CNC solutions with different CNC contents (1,2 and 5 wt.%). The effect of the CNC into the LC-HPC matrix was determined by coupling rheology and NMR spectroscopy - Rheo-NMR a technique tailored to analyse orientational order in sheared systems. (C) 2015 Elsevier Ltd. All rights reserved.

Pullulan, a neutral polysaccharide, was chemically modified in order to obtain two charged derivatives: reaction with SO3.DMF complex afforded a sulfate derivative (SP), while reaction with glycidyltrimethylammonium chloride gave a quaternary ammonium salt (AP). The presence of the charged groups was confirmed by FTIR. Assessment of the positions where the reaction took place was based on 1H- and 13C NMR (COSY, HSQC-TOCSY, HSQC-DEPT, and HMBC) experiments. Estimation of the degree of substitution (DS) was made from elemental analysis data, and further confirmed by NMR peak areas in the case of AP. These new derivatives showed the capability to condense with each other, forming nanoparticles with the ability to associate a model protein (BSA) and displaying adequate size for drug delivery applications, therefore making them good candidates for the production of pullulan-based nanocarriers by polyelectrolyte complexation.

Chromonic liquid crystals (CLC) are lyotropic phases formed by discotic mesogens in water. Simple chiral dopants such as amino acids have been reported to turn chromonic liquid crystals into their cholesteric counterparts. Here we report a chirality amplification effect in the nematic phase of a 9 wt% disodium cromoglycate (DSCG) lyotropic liquid crystal (LLC) upon doping with a water-soluble codeine derivative. The transition on cooling the isotropic to the nematic phase showed the presence of homochiral spindle-shaped droplets (tactoids). NMR DOSY experiments on a triple gradient probe revealed a small degree of diffusion anisotropy for the alkaloid embedded in the liquid crystal structure. These results in combination with XRD, CD and POM experiments agree with a supramolecular aggregation model based on simple columnar stacks.

{Fungal stains affect documents and artworks on paper all over the world, diminishing their chemical stability and compromising their readability. The present paper studies the suitability of agarose and gellan gum hydrogels to remove fungal stains from paper, using paper impregnated with alizarin as a model system to simulate the most common colorant molecules produced by fungi - polyketide quinones. The effect of pH variation on the efficacy of the gels was evaluated by UV spectrometry. The results show that the cleaning efficacy of the gels greatly depends on the gel matrix, the colorant molecules, and the pH balance of the process.}

Calculations of deuterium NMR spectra were performed using a model of slow motions based on the collective modes present in liquid crystalline systems and evaluated within the Landau de Gennes free energy expansion on the order parameter tensor. Simulations obtained with this model are applied to the case of deuterium NMR spectra collected in static and rotating samples of organosiloxane tetrapodes exhibiting uniaxial and biaxial nematic phases. The analysis of the slow motions influence on deuterium NMR spectra shows that molecular motions within a time-scale of the order of magnitude of NMR observation times are particularly effective on modulating the NMR line-shape in the case of the liquid crystalline system investigated.

Core shell nanoparticles (NPs) formed by superparamagnetic iron oxide NPs (SPIONs) coated with inorganic or organically modified (ORMOSIL) sol gel silica exhibited promising properties as negative contrast agents (CA) for MRI applications. The potentiality of these new core shell NPs as negative CA for MRI is demonstrated and quantified. The longitudinal and transverse relaxivities of NPs with three different coating compositions were studied at a 7 T magnetic field: silica (TEOS), (3-aminopropyl) triethoxysilane (APTES) and (3-glycidoxypropyl) methyldiethoxysilane (GPTMS). Clearly, it was found that the core shell NPs efficiency as CA was strongly depend on the SPIONs coating. All the three core shell NPs studied presented a very small effect on the longitudinal relaxation time but a pronounced one on the transverse relaxation time, leading to a very high transverse longitudinal relaxivities ratio, decisive for their efficiency as negative CA for MRI The effect of the core shell NPs on the MRI contrast enhancement is obtained and quantified in a set of MRI of agar phantoms obtained at 7 T magnetic field and with a imaging gradient field of 1.6 T/m. The core shell NPs were tested in Zebra-fish (Danio rerio) animal model. Zebra-fish MRI were obtained with animals injected with the three core shell NPs and the contrast enhancement validated. (C) 2015 Elsevier B.V. All rights reserved.

The preorganization and cooperation mechanism of imide‐based ionic liquids reported in a recent Communication was evocated to rationalize the extremely high gravimetric CO2 capture displayed by these fluids. An analysis of the reported spectroscopic evidences together with additional experiments led to the proposition of an alternative, simpler, and feasible mechanism involving the formation of bicarbonate.

Gum arabic (GA) is a hydrophilic composite polysaccharide derived from exudates of Acacia senegal and Acacia seyal trees. It is biocompatible, possesses emulsifying and stabilizing properties and has been explored as coating agent of nanomaterials for biomedical applications, namely magnetic nanoparticles (MNPs). Previous studies focused on the adsorption of GA onto MNPs produced by co-precipitation methods. In this work, MNPs produced by a thermal decomposition method, known to produce uniform particles with better crystalline properties, were used for the covalent coupling of GA through its free amine groups, which increases the stability of the coating layer. The MNPs were produced by thermal decomposition of Fe(acac)3 in organic solvent and, after ligand-exchange with meso-2,3-dimercaptosuccinic acid (DMSA), GA coating was achieved by the establishment of a covalent bond between DMSA and GA moieties. Clusters of several magnetic cores entrapped in a shell of GA were obtained, with good colloidal stability and promising magnetic relaxation properties (r2 /r1 ratio of 350). HCT116 colorectal carcinoma cell line was used for in vitro cytotoxicity evaluation and cell-labeling efficiency studies. We show that, upon administration at the respective IC50 , GA coating enhances MNP cellular uptake by 19 times compared to particles bearing only DMSA moieties. Accordingly, in vitro MR images of cells incubated with increasing concentrations of GA-coated MNP present dose-dependent contrast enhancement. The obtained results suggest that the GA magnetic nanosystem could be used as a MRI contrast agent for cell-labeling applications.

We carry out a detailed deuterium nuclear magnetic resonance (NMR) study of local nematic ordering in polydomain nematic elastomers. This system has a close analogy to the random-anisotropy spin glass. We find that, in spite of the quadrupolar nematic symmetry in three dimensions requiring a first-order transition, the order parameter in the quenched "nematic glass" emerges via a continuous phase transition. In addition to this remarkable effect, by a careful analysis of the NMR line shape, we deduce that the local director fluctuations grow in a critical manner around the transition point. This could become an essential experimental evidence for the quenched disorder changing the order of discontinuous transition.

Lopinavir (LPV) is currently used in combination with ritonavir for the clinical management of HIV infections due to its limited oral bioavailability. Herein, we report the application of an in silico method to study cyclodextrin (CyD) host-guest molecular interaction with LPV for the rational selection of the best CyD for developing a CyD based LPV delivery system. The predicted CyD, a (2-hydroxy)propyl-gamma derivative with high degree of substitution (HP17-γ-CyD) was synthesized and comparatively evaluated with γ-CyD and the commercially available HP-γ-CyD. All complexes were prepared by supercritical assisted spray drying (SASD) and co-evaporation (CoEva) at molar ratios (1:1 and 1:2); and afterwards fully characterized. Results indicate a higher LPV amorphization and solubilization ability of HP17-γ-CyD. The SASD processing technology also enhanced LPV solubilization and release from complexes. The application of in silico methodologies is a feasible approach for the rational and/or deductive development of CyD drug delivery systems.