Multidimensional LC x LC analysis of phenolic and flavone natural antioxidants with UV-electrochemical coulometric and MS detection

A comprehensive 2-D LC x LC system was developed for the separation of phenolic and flavone antioxidants, using a PEG-silica column in the first dimension and a C(18) column with porous-shell particles or a monolithic column in the second dimension. Combination of PEG and C18 or C8 stationary phase chemistries provide low selectivity correlations between the first dimension and the second dimension separation systems. This was evidenced by large differences in structural contributions to the retention by -COOH, -OH and other substituents on the basic phenol or flavone structure. Superficially porous columns with fused core particles or monolithic columns improve the resolution and speed of second dimension separation in comparison to a fully porous particle C(18) column. Increased peak capacity and high orthogonality in different 2-D setups was achieved by using gradients with matching profiles running in parallel in the two dimensions over the whole 2-D separation time range. Multi-dimensional set-up combining the LC x LC separation on-line with UV and multi-channel coulometric detection and off-line with MS/MS technique allowed positive peak identification. The Coularray software compensates for the effects of the baseline drift during the gradient elution and is compatible with parallel gradient comprehensive LC x LC technique. Furthermore, it provides significant improvement in the sensitivity and selectivity of detection in comparison to both UV and MS detection. The utility of these systems has been demonstrated in the analysis of beer samples.     

Modeling the effect of cell-associated polymeric fluid layers on force spectroscopy measurements. Part II: experimental results and comparison with model predictions

In this paper, experimentally obtained force curves on Staphylococcus aureus are compared with a previously developed model that incorporates hydrodynamic effects of extracellular polysaccharides together with the elastic response of the bacterium and cantilever. Force-displacement curves were predicted without any adjustable parameters. It is demonstrated that experimental results can be accurately described by our model, especially if viscoelastic effects of the extracellular polysaccharide layer are taken into account. Polysaccharide layer viscoelasticity was treated by means of a multimode Phan-Thien/Tanner (PTT) constitutive equation. Typical maximum relaxation times range from 0.2 to 2 s, whereas the corresponding zero-shear-rate viscosities are 6-9 Pa.s, based on published, steady-state rheological measurements on Staphylococcus aureus polysaccharide extracted from its native environment. The bacterial elastic constant is found to be in the range 0.02-0.4 N/m, corresponding to bacterial wall Young's moduli in the range of a few hundred MPa. Repeatability of measurements performed on different bacteria is found to be only fair, due to large individuum variability, whereas repetitions of measurements on the same bacterium showed high reproducibility. Improved force-indentation curve predictions are expected if transient rheological characterization of extracellular polysaccharides is available. More desirable however is the direct, in vivo rheological characterization of the extracellular polysaccharide. A model-based analysis of experimental force-indentation curves shows that appreciable further experimental improvements are still necessary to achieve this goal.     

High-performance liquid chromatography analysis of four Leuzea carthamoides flavonoids

A simple and sensitive high-performance liquid chromatography method for the determination of four Leuzea carthamoides flavonoids, namely eriodictyol, patuletin, eriodictyol-7-beta-glucopyranoside, and 6-hydroxykaempferol-7-O-(6"-O-acetyl-beta-D-glucopyranoside), is presented. Using this method, quantitative composition of flavonoids ranged from 0.011% to 0.574% in dried plant material was determined. This method could be used in the future for the quantitative evaluation of major phenolic compounds in L. carthamoides.     

Rapid analysis of multiple pesticide residues in fruit-based baby food using programmed temperature vaporiser injection-low-pressure gas chromatography-high-resolution time-of-flight mass spectrometry

A rapid method using programmed temperature vaporiser injection-low-pressure gas chromatography-high-resolution time-of-flight mass spectrometry (PTV-LP-GC-HR-TOF-MS) for the analysis of multiple pesticide residues in fruit-based baby food was developed. The fast and inexpensive buffered QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction method and "conventional" approach that employs ethyl acetate extraction followed by gel permeation chromatography (GPC) cleanup were employed for sample preparation. A PTV injector in solvent venting mode was used to reduce volume of acetonitrile and acetic acid (from the buffered QuEChERS extracts) that caused higher column bleed without their elimination. Otherwise, the time-to-digital converter would become saturated in HR-TOF-MS. For fast GC separation allowing analysis of 100 analytes within a 7 min runtime, both a high temperature programming rate and vacuum conditions in a megabore GC column were employed. The use of HR-TOF-MS allowed the unbiased identification and reliable quantification of target analytes through the application of a narrow mass window (0.02 Da) for extracting analyte ions and the availability of full spectral information even at very low levels. With only a few exceptions, the lowest calibration levels for the pesticides tested were 相似文献   

Functionalization of the methylene bridges of the calix[6]arene scaffold

The bromine atoms of the hexabromo calixarene derivative 3 were replaced by other groups under S(N)1 conditions, allowing the facile synthesis of calix[6]arene derivatives incorporating identical functionalities at all bridges. Heating at reflux a mixture of 3 and the appropriate alcohol incorporated primary and secondary alkoxy substituents. Hydride abstraction was observed when the reaction with EtOH and i-PrOH was conducted in hexafluoroisopropanol (HFIP). Solvolysis of 3 in TFE in the presence of strong nucleophiles (such as N3(-) and aniline) afforded the corresponding hexaazido and hexaanilino derivatives. Hydroxyl groups were incorporated into the calix[6]arene scaffold via acetolysis of 3, followed by LiAlH4 reduction of the hexaacetate derivative obtained. Friedel-Crafts alkylations in the absence of Lewis acids were conducted by heating at reflux a mixture of 3, HFIP, and a substituted benzene derivative (e.g, m-xylene, p-methyl anisole, mesitylene). The calix[6]arene bridges were alkylated by heating at reflux a mixture of 3 and 2,4-pentanedione in TFE or HFIP. In all cases the reaction proceeded with high diastereoselectivity, and the major isomer isolated was assigned to the rc5 (i.e., all-cis) form. NMR spectroscopy indicates that the conformation adopted by the macrocycle possesses 3-fold symmetry (a "pinched cone") that is rigid in the laboratory time scale in the mesityl-substituted derivative.     

Complexes derived from the copper(II)/succinamic acid/N,N′,N″-chelate tertiary reaction systems: Synthesis,structural and spectroscopic studies

The use of succinamic acid (H₂sucm) in Cu^II/N,N′,N″-donor [2,2′:6′,2″-terpyridine (terpy), 2,6-bis(3,5-dimethylpyrazol-1-yl)pyridine (dmbppy)] reaction mixtures yielded compounds [Cu(Hsucm)(terpy)]_n(ClO₄)_n (1), [Cu(Hsucm)(terpy)(MeOH)](ClO₄) (2), [Cu₂(Hsucm)₂(terpy)₂](ClO₄)₂ (3), [Cu(ClO₄)₂(terpy)(MeOH)] (4), [Cu(Hsucm)(dmbppy)]_n(NO₃)_n·3nH₂O (5^.3nH₂O), and [CuCl₂(dmbppy)]·H₂O (6·H₂O). The succinamate(−1) ligand exists in four different coordination modes in the structures of 1–3 and 5, i.e., the μ₂-κO:κO′:κO″ in 1 and 5 which involves asymmetric chelating coordination of the carboxylato group and ligation of the amide O-atom leading to 1D coordination polymers, the μ₂-κ²O:κO′ in 3 which involves asymmetric chelating and bridging coordination of the carboxylato group, and the asymmetric chelating mode in 2. The primary amide group, either coordinated in 1 and 5, or uncoordinated in 2 and 3, participate in hydrogen bonding interactions, leading to interesting crystal structures. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the Hsucm⁻ ligands. The thermal decomposition of complex 5·3nH₂O was monitored by TG/DTG and DTA measurements.     

Highly selective solid-state sensor for iodide based on the combined use of platinum (IV) phthalocyanine and solidified pyridinium ionic liquid

Journal of Solid State Electrochemistry - Solid-state iodide-selective electrodes based on the commercial screen-printed electrodes modified with readily available low-melting ionic material (ionic...     

Fluorescent Isoindole Crosslink (FlICk) Chemistry: A Rapid,User‐friendly Stapling Reaction

The stabilization of peptide secondary structure via stapling is a ubiquitous goal for creating new probes, imaging agents, and drugs. Inspired by indole‐derived crosslinks found in natural peptide toxins, we employed ortho‐phthalaldehydes to create isoindole staples, thus transforming inactive linear and monocyclic precursors into bioactive monocyclic and bicyclic products. Mild, metal‐free conditions give an array of macrocyclic α‐melanocyte‐stimulating hormone (α‐MSH) derivatives, of which several isoindole‐stapled α‐MSH analogues (K_i≈1 nm ) are found to be as potent as α‐MSH. Analogously, late‐stage intra‐annular isoindole stapling furnished a bicyclic peptide mimic of α‐amanitin that is cytotoxic to CHO cells (IC₅₀=70 μm ). Given its user‐friendliness, we have termed this approach FlICk (fluorescent isoindole crosslink) chemistry.