The protonation thermodynamics of cyclodextrin-containing polymers for drug inclusion

A poly(amido-amine), PAA, bearing β-CD units in the side chain was synthesized by a polyaddition reaction of 1,4-bis-acryloyl-piperazine with 6-monodeoxy-6-monoamino-β-cyclodextrin (β-CD-NH₂). Unlike the simple β-CD-NH₂ with a greater basicity constant (log K = 8.60), the polymer revealed an unusual polyelectrolyte behaviour with a lower basicity constant (log K° = 6.29) of the tertiary nitrogen atom, that is strongly dependent on the degree of protonation α of the whole macromolecule. It follows the modified Henderson–Hasselbalch equation with n = 1.75, in a wide α-range. The greater (?46.1 kJ/mol) and the lower (?27.6 kJ/mol) enthalpy (ΔH°) changes of the compounds were in line with the protonation of a primary or a tertiary nitrogen atom. The calorimetric data suggested that the PAA protonation destroyed a packing structure formed by two rigid β-CD side chains interacting head-to-head. The UV spectrophotometric data showed that the PAA exhibits affinity towards the l-ascorbic acid at low pH (pH 2.46) with an isosbestic point at 241 nm and a slight blue shift of the maximum absorption of the ascorbic acid (244 nm) on PAA additions.     

Sorbent trapping solid-phase microextraction of fragrance allergens in indoor air

Exposure to fragrance substances is exponentially increasing in our daily life due to the enhanced use of scented products. Some fragrances are known to be important sensitizers, inhalation being an important exposure pathway in indoor environments. A simple and sensitive method based on solid-phase enrichment and solid-phase microextraction (SPME) followed by gas chromatography–mass spectrometry (GC–MS) has been developed for the analysis of 24 volatile fragrance allergens in indoor air. Suspected allergens present in the air (0.2 m³) were adsorbed onto a very small quantity of florisil (25 mg) and then transferred to a SPME fiber in the headspace mode (HS). To the best of our knowledge, this paper describes the first application of SPME for the determination of these compounds in air samples. The experimental parameters affecting the microextraction process have been optimized using a multifactor experimental design strategy. Accuracy, linearity, precision and detection limits (LODs) were evaluated to assess the performance of the proposed method. External calibration, using spiked sorbent standards, and not requiring the complete sampling process (only the SPME step), demonstrated to be suitable for the quantification of all suspected allergens. Recovery studies were performed at three concentration levels (0.04, 1.00 and 50 μg m⁻³), obtaining quantitative recoveries (≥85%) in most cases. LOD values at the low ng m⁻³ level were achieved for all the target compounds. The application of the method to daily home air samples demonstrated the ubiquity of this kind of fragrance ingredients in quotidian indoor environments, finding 18 of the 24 considered compounds in concentrations ranging from 0.01 to 56 μg m⁻³. Benzyl alcohol, linalool, citronellol, ionone and lilial were found in most analyzed samples.     

A new type of entanglement involving one-dimensional ribbons of rings catenated to a three-dimensional network in the nanoporous structure of [Co(bix)2(H2O)2](SO4).7H2O [bix = 1,4-bis(imidazol-1-ylmethyl)benzene

Co(II) sulfate reacts with the flexible ligand 1,4-bis(imidazol-1-ylmethyl)benzene (bix) to yield the coordination network [Co(bix)2(H2O)2](SO4).7H2O, containing polymeric ribbons of rings which penetrate and catenate a 3D single frame of the CdSO4 topology, to produce an open-channel entangled architecture with nanoporous behaviour.     

From arm-shaped layers to a new type of polythreaded array: a two fold interpenetrated three-dimensional network with a rutile topology

The self-assembly based on 2D motifs with side arms leads to the formation of a new type of polythreaded network which exhibits a 2-fold interpenetrated 3D array if H-bonds are taken into account.     

Role of secondary structure in the asymmetric acylation reaction catalyzed by peptides based on chiral C alpha-tetrasubstituted alpha-amino acids

In a recent series of papers, Miller and co-workers were able to show that His(pi-Me)-based, terminally protected peptides are potent catalysts of the asymmetric acyl transfer reaction, useful for the kinetic resolution of alcohols. In a structure-supporting solvent, one of the most active compounds, an Aib-containing tetrapeptide, is folded in a doubly intramolecularly H-bonded beta-hairpin motif incorporating a type-II' beta-turn conformation. In this work, we have expanded the study of the Miller tetrapeptide by examining a set of analogues and shorter sequences (dipeptide amides), characterized by chiral C(alpha)-tetrasubstituted alpha-amino acids of diverging bulkiness and optical configuration. Peptide synthesis in solution, conformational analysis by FT-IR absorption and (1)H NMR techniques, and screening of catalytic activity as well have been performed. Our results confirm the close relationship between the beta-hairpin 3D-structure and the catalytic activity of the peptides. A tetrapeptide analogue slightly more selective than the Miller compound has been found. However, the terminally protected, industrially more appealing, dipeptide amides are poorly effective.     

Simultaneous determination of the urinary metabolites of benzene, toluene, xylene and styrene using high-performance liquid chromatography/hybrid quadrupole time-of-flight mass spectrometry

A simple and rapid method using reversed-phase liquid chromatography/tandem mass spectrometry (LC/MS/MS) for the simultaneous determination of the urinary metabolites of benzene, toluene, xylene and styrene in human urine specimens and standard solutions is described. A hybrid quadrupole/time-of-flight (QqTOF) mass spectrometer was compared for the determination of metabolite of aromatic solvents in urine samples. The metabolites selected were: trans,trans-muconic acid, hippuric acid, o-, m- and p-methylhippuric acid and phenylglyoxylic acid. The compounds were well separated from each other on narrow-bore 1-mm i.d. reversed-phase LC C-18 columns. Average recoveries for loading 100 microL of urine samples varied from 88-110% and the quantification limits were less than 30 ng/mL for each analyte (3 ng/mL for trans,trans-muconic acid). The qualitative information obtained (mass accuracy, resolution and full-scan spectra) with the QqTOF mass spectrometer allows a secure identification of analytes in biological matrices.     

Solid-state versus solution preparation of two crystal forms of [HN(CH2CH2)3NH][OOC(CH2)COOH]2. Polymorphs or hydrogen bond isomers?

The reaction of [N(CH2CH2)3N] with malonic acid [HOOC(CH2)COOH] in the molar 1:2 ratio yields two different crystal forms of the salt [HN(CH2CH2)3NH][OOC(CH2)COOH]2 depending on the preparation technique and crystallization speed: form I, containing malonate anions with intramolecular hydrogen bonds, is obtained by solid-state co-grinding or by rapid crystallization, whereas form II containing intermolecular hydrogen bonds is obtained by slow crystallization. Form I and II do not interconvert, and form I undergoes an order-disorder phase transition on cooling.     

Phase transfer of CdS nanocrystals mediated by heptamine β-cyclodextrin

A fundamental and systematic study on the fabrication of a supramolecularly assembled nanostructure of an organic ligand-capped CdS nanocrystal (NC) and multiple heptamine β-cyclodextrin ((NH(2))(7)βCD) molecules in aqueous solution has been here reported. The functionalization process of presynthesized hydrophobic CdS NCs by means of (NH(2))(7)βCD has been extensively investigated by using different spectroscopic and structural techniques, as a function of different experimental parameters, such as the composition and the concentration of CD, the concentration of CdS NCs, the nature of the NC surface capping ligand (oleic acid and octylamine), and the organic solvent. The formation of a complex based on the direct coordination of the (NH(2))(7)βCD amine groups at the NC surface has been demonstrated and found responsible for the CdS NC phase transfer process. The amine functional group in (NH(2))(7)βCD and the appropriate combination of pristine capping agent coordinating the NC surface and a suitable solvent have been found decisive for the success of the CdS NC phase transfer process. Furthermore, a layer-by-layer assembly experiment has indicated that the obtained (NH(2))(7)βCD functionalized CdS NCs are still able to perform the host-guest chemistry. Thus, they offer a model of a nanoparticle-based material with molecular receptors, useful for bio applications.     

Capillary flooding of wood with microemulsions from Winsor I systems

A new approach based on microemulsions formulated with at least 85% water and minority components consisting of oil (limonene) and surfactant (anionic and nonionic) is demonstrated for the first time to be effective for flooding wood's complex capillary structure. The formulation of the microemulsion was based on phase behavior scans of Surfactant-Oil-Water systems (SOWs) and the construction of pseudo-ternary diagrams to localize thermodynamically stable one-phase emulsion systems with different composition, salinity and water-to-oil ratios. Wicking and fluid penetration isotherms followed different kinetic regimes and indicated enhanced performance relative to that of the base fluids (water, oil or surfactant solutions). The key properties of microemulsions to effectively penetrate the solid structure are discussed; microemulsion formulation and resultant viscosity are found to have a determining effect in the extent of fluid uptake. The solubilization of cell wall components is observed after microemulsion impregnation. Thus, the microemulsion can be tuned not only to effectively penetrate the void spaces but also to solubilize hydrophobic and hydrophilic components. The concept proposed in this research is expected to open opportunities in fluid sorption in fiber systems for biomass pretreatment, and delivery of hydrophilic or lipophilic moieties in porous, lignocellulosics.