Structure and surface coverage of water-based stearate coatings on calcium carbonate nanoparticles

In a preceding paper it was found that, during coating with solutions of a stearin salt in water, whatever the concentration used, a considerable part of the PCC surface remains free, indicating the development of an incomplete monolayer. This was explained by assuming a micelle adsorption mechanism as the dominating process in water, resulting in the formation of a multilayer structure composed of an inner incomplete chemisorbed monolayer and one or more physically adsorbed layers. This model predicted a physisorbed layer in which polar groups are oriented outwards of the particles, resulting in a hydrophilic surface, and contrary to experimental evidence. In this paper we propose that during the drying stage the physisorbed calcium stearate layers undergo a complex rearrangement leading to a hydrophobic coating with the aliphatic tails oriented outwards of the particles. The results of XRD measurements proved that the physisorbed stearate layer is crystalline, while DSC model experiments indicated that the layer goes through phase transitions during heat treatment. The proposed model matched with IGC measurements, showing a clear dependence of the specific component of surface energy on the amount of absorbed stearin. The agreement with values obtained for solvent and dry-coated particles support the proposed rearrangement of alkanoate molecules in the coating.     

Synthesis,characterization and X-ray studies of new chiral five-six-membered ring, [4.3.0] heterobicyclic system of monomeric boronates

Nine new boronates, six of them chiral, with five-six-membered ring heterobicycles were prepared by reaction of the Schiff bases and phenyl boronic acid. The boronates were fully characterized by spectroscopic techniques, NMR ¹H, ¹³C, ¹¹B, Infrared spectroscopy, mass spectrometry and elemental analysis. The reaction showed high diasteroselectivity, only in the case of compound 4c, containing a methyl substituent in the aliphatic moiety, the induction is low giving a 2:1 mixture of two diatereoisomers. The results showed that the preferred stereochemistry in the heterocycles is that where all substituents in the five membered ring and the phenyl group attached to boron atom are on the same side.     

A new flow injection preconcentration method based on multiwalled carbon nanotubes for the ETA-AAS determination of Cd in urine

A new flow injection (FIA) procedure for the preconcentration of cadmium in urine using multiwalled carbon nanotubes (MWCNT) as sorbent and posterior electrothermal atomization atomic absorption spectrometry (ETA-AAS) Cd determination has been developed. Cadmium was retained in a column filled with previously oxidized MWCNTs and it was quantitatively eluted with a nitric acid solution. The parameters influencing the adsorption-elution process such as pH of the sample solution, amount of sorbent and flow rates of sample as well as eluent solutions have been studied. Cd concentration in the eluent was measured by ETA-AAS under the optimized conditions obtained. The results indicated the elimination of urine matrix effect as a consequence of the preconcentration process performed. Total recovery of cadmium from urine at pH 7.2 using a column with 45 mg of MWCNTs as sorbent and employing a HNO₃ 0.5 mol L⁻¹ solution for elution was attained. The detection limit obtained was 0.010 μg L⁻¹ and the preconcentration factor achieved was 3.4. The method showed adequate precision (RSD: 3.4-9.8%) and accuracy (mean recovery: 97.4-100%). The developed method was applied for the determination of cadmium in real urine samples from healthy people (in the range of 0.14-2.94 μg L⁻¹) with satisfactory results.     

(Oligo)thienyl-imidazo-benzocrown ether derivatives: synthesis, photophysical studies and evaluation of their chemosensory properties

A series of novel (oligo)thienyl-imidazo-benzocrown ethers were synthesised through a simple method and evaluated as fluorimetric chemosensors for transition metal cations. Interaction with Ni²⁺, Pd²⁺, and Hg²⁺ in ACN/DMSO solution (99:1) was studied by absorption and emission spectroscopy. Chemoselectivity studies in the presence of Na⁺ were also carried out and a fluorescence enhancement upon chelation (CHEF) effect was observed following Hg²⁺ complexation. Considering that most systems using fluorescence spectroscopy for detecting Hg²⁺ are based on the complexation enhancement of the fluorescence quenching (CHEQ) effect, the present work represents one of the few examples for sensing of Hg²⁺ based on a CHEF effect.     

Imidazo-benzo-15-crown-5 ethers bearing arylthienyl and bithienyl moieties as novel fluorescent chemosensors for Pd and Cu

Novel fluorescent ionophores bearing imidazo-arylthienyl or imidazo-bithienyl π-conjugated bridges functionalized with one or two fused benzo-15-crown-5 ethers as receptor units are reported. The sensing ability of the compounds in the presence of metallic cations (Li⁺, Na⁺, K⁺, Ca²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Pd²⁺, and Hg²⁺) and fluoride ion was studied in MeCN/DMSO solutions by absorption and emission spectroscopy. The experimental results indicate that all compounds could act as selective fluorimetric sensors for Cu²⁺ and Pd²⁺ and also for the fluoride ion, in the case of the bis-substituted crown ether derivatives.     

Botrylactone: new interest in an old molecule—review of its absolute configuration and related compounds

The absolute configuration of botrylactone, a unique compound with an interesting polyketide lactone skeleton with two oxirane bridges previously isolated from Botrytis cinerea and described as a powerful antibiotic, has been reviewed on the basis of sign of the optical rotation, NOE experiments and NMR method. The isolation of 7-deoxybotrylactone and 5-hydroxy-7-(4-hydroxydec-2(3)-enoyl) botrylactone enables us to characterize an intriguing new family of compounds with this interesting polyketide skeleton. A common biosynthetic origin with botcinin derivatives is proposed.     

A unique bicyclic monosaccharide from the Bradyrhizobium lipopolysaccharide and its role in the molecular interaction with plants

Sugar coat: The nitrogen-fixing soil bacterium Bradyrhizobium sp. BTAi1 is coated with a unique lipopolysaccharide that does not induce innate immune responses in its host plant Aeschynomene indica or in different plant families. The chemical nature of the monosaccharide forming the polymer (see picture) is unprecedented in nature, which helps to avoid "harmful" recognition by its symbiotic host.     

NHC/iron cooperative catalysis: aerobic oxidative esterification of aldehydes with phenols

An NHC/iron cooperative catalytic system mediates the aerobic oxidative esterification of aldehydes with phenols. The use of equimolar amounts of reactants led to good to excellent isolated yields of esters.     

Synthesis, biological evaluation and structural characterization of novel glycopeptide analogues of nociceptin N/OFQ

To examine if the biological activity of the N/OFQ peptide, which is the native ligand of the pain-related and viable drug target NOP receptor, could be modulated by glycosylation and if such effects could be conformationally related, we have synthesized three N/OFQ glycopeptide analogues, namely: [Thr(5)-O-α-D-GalNAc-N/OFQ] (glycopeptide 1), [Ser(10)-O-α-D-GalNAc]-N/OFQ (glycopeptide 2) and [Ser(10)-O-β-D-GlcNAc]-N/OFQ] (glycopeptide 3). They were tested for biological activity in competition binding assays using the zebrafish animal model in which glycopeptide 2 exhibited a slightly improved binding affinity, whereas glycopeptide 1 showed a remarkably reduced binding affinity compared to the parent compound and glycopeptide 3. The structural analysis of these glycopeptides and the parent N/OFQ peptide by NMR and circular dichroism indicated that their aqueous solutions are mainly populated by random coil conformers. However, in membrane mimic environments a certain proportion of the molecules of all these peptides exist as α-helix structures. Interestingly, under these experimental conditions, glycopeptide 1 (glycosylated at Thr-5) exhibited a population of folded hairpin-like geometries. From these facts it is tempting to speculate that nociceptin analogues showing linear helical structures are more complementary and thus interact more efficiently with the native NOP receptor than folded structures, since glycopeptide 1 showed a significantly reduced binding affinity for the NOP receptor.