Crystal structure of a seven-coordinate cobalt(II) complex with a new polyfunctional hydrazonic ligand, [Co(H4dapis)(OH2)2]Cl2·9/2H2O

A seven-coordinate cobalt(II) complex has been synthesized with a new hydrazonic ligand, H₄dapis, and its crystal structure determined by X-ray diffraction methods and refined toR 0.0564 for 2763 independent reflections. The structure consists of [Co(H₄dapis)(OH₂)2] cations, Cl anions, and lattice H₂O molecules interlinked by hydrogen bonds. The cobalt atom has a distorted pentagonal bipyramidal environment with two axial H₂O molecules and the H₄dapis ligand forming the basal plane.     

Binding modes identification through molecular dynamic simulations: A case study with carnosine enantiomers and the Teicoplanin A2‐2‐based chiral stationary phase

In the present study, an in silico methodology able to define the binding modes adopted by carnosine enantiomers in the setting of the chiral recognition process is described. The inter‐ and intramolecular forces involved in the enantioseparation process with the Teicoplanin A2‐2 chiral selector and carnosine as model compound are successfully identified. This approach fully rationalizes, at a molecular level, the (S) < (R) enantiomeric elution order obtained under reversed‐phase conditions. Consistent explanations were achieved by managing molecular dynamics results with advanced techniques of data analysis. As a result, the time‐dependent identification of all the interactions simultaneously occurring in the chiral selector‐enantiomeric analyte binding process was obtained. Accordingly, it was found that only (R)‐carnosine is able to engage a stabilizing charge–charge interaction through its ionized imidazole ring with the carboxylate counter‐part on the chiral selector. Instead, (S)‐carnosine establishes intramolecular contacts between its ionized functional groups, that limit its conformational freedom and impair the association with the chiral selector unit.     

Sorptive tape extraction in the analysis of the volatile fraction emitted from biological solid matrices

Sorptive tape extraction (STE) is a recent sorption-based sampling technique in which a flexible polydimethylsiloxane (PDMS) tape is used to recover analytes at the surface of a solid matrix by direct contact as well as from the headspace in equilibrium with it. Solutes thus enriched on the inert PDMS material can be recovered either by solvent desorption or by thermo-desorption. The concentration capability of both direct contact and headspace STE was evaluated by sampling (a) aromatic plants to study the reaction of a vegetable matrix submitted to stress, and (b) fruits at the surface of the pulp or inside the pulp; the composition of the volatile fraction released from the skin when a perfume is sprayed on the back of the hand was also studied. The concentration capability of direct contact and headspace STE was compared to that of HSSE with a 20 microL PDMS twister and HS-SPME with a PDMS 100 microm fibre, by determining the relative abundances (RA) of the characterizing components of the aromatic plants under investigation. Repeatability and influence of tape surface on STE recovery were also evaluated.     

Reliability of fibres in solid-phase microextraction for routine analysis of the headspace of aromatic and medicinal plants

This article evaluates the HS-SPME recovery repeatability, intermediate precision and their performance over time when applied to HS-SPME sampling for quality control of medicinal and aromatic plants. Experiments were carried out on two sets of fibres coated with two different coatings and belonging to different lots (i.e 100 microm polydimethylsyloxane (PDMS) and Carboxen/divinylbenzene/PDMS 50/30 microm, l: 1 cm (CAR/DVB/PDMS)) and on chamomile (Matricaria chamomilla L.), sage (Salvia lavandulifolia Vahl.) and a standard solution containing 3-hexanol, isoamyl acetate, 1,8-cineole and menthol in diisobutyl phthalate. The performance of each set of fibres was evaluated by determining a group of complementary statistical parameters including: (i) repeatability of the absolute areas of each marker from each matrix with each fibre; (ii) intra-fibre repeatability of the total absolute areas of the markers of each matrix obtained with each fibre of each set; (iii) inter-fibre intermediate precision of the total absolute areas of the markers of each matrix obtained with all fibres of each set; and (iv) analysis of variance by one-way ANOVA with Fisher and Tukey tests. The influence of the number of analyses on fibre effectiveness (fibre life-time) was studied by linear regression analysis (LRA). The results proved that HS-SPME can successfully be used for routine control analysis of aromatic ad medicinal plants since both types of fibres showed good repeatability and intermediate precision of analytes recovery and consistency over time. Unlike data previously reported by other authors, CAR/DVB/PDMS coated fibres gave better results than those coated with PDMS. The fibre-life seemed mainly to be influenced by the number and conditions of samplings and nature of the matrix investigated.     

Dielectric study on Zn1−x Mg x O ceramic materials prepared by the solid-state route

The present work investigates the structural and dielectric properties of Zn_1?x Mg _x O composites prepared by the standard sintering method at 1200 °C during 24 h and doped with different weight percentages of MgO (x = 0–40 %). For this purpose, the scanning electron microscopy (SEM) was used to study the effect of the magnesium’s proportion on the morphology and crystallinity of the obtained samples. The SEM observations have shown rougher surfaces of the samples covered by grains having prismatic shapes and different sizes. The dielectric properties of the ceramics were investigated by spectroscopic impedance at different temperatures and frequencies, thus showing a frequency-dependent dispersion of the permittivity constants and dielectric losses. From these measurements, the relaxation processes were identified and their activation energies extracted. Dielectric responses were correlated with the microstructure and chemical composition of the ZnMgO composites. The mechanisms of ac conductivity are controlled by the polaron hopping and the electron tunneling models. Concerning the tunneling model, two types corresponding to the overlapping large polaron tunneling model for the composites Zn_0.9Mg_0.1O and Zn_0.8Mg_0.2O and the small polaron tunneling model for the composites Zn_0.64Mg_0.36O (in the frequency range 1.7 × 10⁴ Hz–1 MHz) and Zn_0.6Mg_0.4O were observed. Besides, one type of hopping model corresponding to the correlated barrier hopping for the composites ZnO and Zn_0.64Mg_0.36O (in the frequency range 6 × 10²–1.7 × 10⁴ Hz) was noted.     

Enhanced wavefront reconstruction by random phase modulation with a phase diffuser

A phase retrieval technique for enhanced wavefront reconstruction using random phase modulation and a phase diffuser is proposed. The speckle field generated is sampled at multiple axially displaced planes and the speckle patterns are used in an iterative algorithm based on the optical wave propagation in free space. The presentation of this technique is carried out using two setups. In the first setup, a diffuser plate is placed at the image plane of a metallic test object. The benefit of randomizing the phase of the object wave is the enhanced intensity recording due to high dynamic range of the diffusely scattered beam. The use of demagnification optics will also allow the investigations of relatively large objects. In the second setup, a transparent object is illuminated using a wavefront with random phase and constant amplitude by positioning the phase diffuser close to the object. The benefit of phase-only modulation is the increased resolution of the phase structures of the transparent test objects.     

High-resolution quantitative phase microscopic imaging in deep UV with phase retrieval

High-resolution three-dimensional (3D) microscopic imaging requires the use of short wavelengths. Quantitative 3D imaging techniques, such as digital holographic microscopy, require interference between the object beam and a known reference background for the extraction of phase information. At shorter wavelengths, due to short coherence lengths, it may be difficult to implement a two-beam off-axis setup. Thus, a single-beam technique, which provides complete phase information, may be better suited for short wavelengths. This Letter describes the development of a quantitative microscopy technique at 193 nm using multiple intensity samplings and phase retrieval.     

Copper catalysis in the construction of indole and benzo[b]furan rings

This perspective reports on some of the main copper-catalyzed routes to the construction of the pyrrole and furan rings incorporated into the indole and benzo[b]furan systems, respectively. The first part illustrates the synthesis of indoles through cyclizations of 2-alkynylanilid(n)es, preformed or generated in situ, and cyclizations via intramolecular N-arylation, N-vinylation, and C-C bond forming reactions. The second part illustrates the synthesis of benzo[b]furans through cyclizations of preformed 2-alkynylphenols, domino synthesis of 2-alkynylphenols/cyclization processes, and cyclizations via intramolecular O-arylation reactions.     

Continuous flow organometallic catalysis: new wind in old sails

Organometallic catalysis is a powerful tool for chemical synthesis, and the field still evolves at a high pace continuously improving efficiencies and opening up new possibilities. However, despite increasing use in specialty and fine chemical production issues of catalyst recovery still hamper broader application and prevent tapping the full potential of this technology on industrial scale. Even though scientists have tackled this problem for decades practicable methods remained scarce. In this contribution we analyse the major challenges of performing organometallic catalysis in continuous flow from a conceptual point of view, and exemplify for recently developed concepts based on near- and supercritical fluids how the integration of molecular and engineering principles can offer new solutions to this persistent problem.     

Synthesis of Selectively Permodified γ–Cyclodextrins. A New Set of Chiral Stationary Phases in Capillary GC

ABSTRACT

Two pairs of new chiral selectors, derived from octakis(6-O-t-butyldimethylsilyl)- and octakis(6-O-t-hexyldimethylsilyl)-γ-cyclodextrin, were synthesized with inverse substitution patterns at the secondary positions. 2-O-methyl-3-O-acetyl- and 2-O-acetyl-3-O-methyl derivatives are suggested as useful models to further investigate the effect of substituents at C-2 and C-3 on the efficiency of enantio-separation using gas chromatography.