An automated headspace solid-phase microextraction followed by gas chromatography–mass spectrometry method to determine macrocyclic musk fragrances in wastewater samples

A fully automated method has been developed for determining eight macrocyclic musk fragrances in wastewater samples. The method is based on headspace solid-phase microextraction (HS-SPME) followed by gas chromatography–mass spectrometry (GC-MS). Five different fibres (PDMS 7 μm, PDMS 30 μm, PDMS 100 μm, PDMS/DVB 65 μm and PA 85 μm) were tested. The best conditions were achieved when a PDMS/DVB 65 μm fibre was exposed for 45 min in the headspace of 10 mL water samples at 100 °C. Method detection limits were found in the low ng L^?1 range between 0.75 and 5 ng L^?1 depending on the target analytes. Moreover, under optimized conditions, the method gave good levels of intra-day and inter-day repeatabilities in wastewater samples with relative standard deviations (n?=?5, 1,000 ng L^?1) less than 9 and 14 %, respectively. The applicability of the method was tested with influent and effluent urban wastewater samples from different wastewater treatment plants (WWTPs). The analysis of influent urban wastewater revealed the presence of most of the target macrocyclic musks with, most notably, the maximum concentration of ambrettolide being obtained in WWTP A (4.36 μg L^?1) and WWTP B (12.29 μg L^?1), respectively. The analysis of effluent urban wastewater showed a decrease in target analyte concentrations, with exaltone and ambrettolide being the most abundant compounds with concentrations varying between below method quantification limit (<MQL) and 2.46 μg L^?1.

Cycloolefin Copolymers by Early and Late Transition Metal Catalysts

The complex [Pd(κ²‐P,O‐{2‐(2‐MeOC₆H₄)₂P}C₆H₄SO₃)Me(dmso)] ( 1 ) is investigated for the copolymerization of (E) with norbornene (N) and functionalized N derivatives affording P(E‐co‐N) in excellent yields. Copolymer molar masses are higher than those of PE and increase with N concentration. In addition, the complex [Ti(κ²‐N,O‐{2,6‐F₂C₆H₃N = C(Me)C(H) = C(CF₃)O})₂Cl₂] ( 2 ) is evaluated as catalyst for living E‐co‐N copolymerization upon activation with dried methylaluminoxane between 25 and 90 °C. Copolymerization at different [N]/[E] feed ratios affords stereoirregular alternating high molar mass P(E‐co‐N) with narrow molar mass distribution. P(E‐co‐N) living copolymerization is demonstrated by kinetics at 50 °C. Block copolymers are synthesized and fully characterized.

     

Asymmetric Synthesis of Highly Enantiomerically Enriched (S)(-)-β-Bisabolene

(S)-β-Bisabolene, (S)-1, was synthetized by a synthetic route in which (S)-4-methyl-3-cyclohexene carboxylic acid, (S)-10, which was the key intermediate, was prepared via a highly diastereoselective TiCl₄-catalyzed Diels-Alder reaction between isoprene and the acrylate of commercial (R)-pantolactone, followed by hydrolysis. Compound (S)-10 was then converted into ketone (S)-13 using two different procedures. The best one of these, as regards the degree of stereospecificity, involved the reaction of (S)-10 with 2 equiv of 4-methyl-3-penten-1-yllithium, 14, in the presence of CeCl₃, and gave (S)-13 having ca. 84% ee. The Zr-promoted methylenation of this ketone afforded highly enantiomerically enriched (S)-1.     

Simple Synthesis of Versatile Coumarin Scaffolds

We describe an approach using ring‐closing metathesis (RCM) to synthesize versatile coumarin derivatives that present appropriate substitutions both at the aromatic and at the α,β‐unsaturated lactone ring. The obtained compounds can be used as molecular scaffolds suitable for further diversifications through a combinatorial approach.     

Chiral bidiaziridines by a two-step domino aziridination of meso-α-diimines

Chiral racemic α-diimines, tested in aziridination reactions with NsONHCO₂Et, for the first time led to the synthesis of (±)-bidiaziridines, stereoselectively derived from the corresponding meso (E-s-trans-E)-α-diimines. Moreover, a minor bidiaziridine isomer, probably a meso form that was lost under classical work-up conditions, can be obtained by adding water to the crude mixtures at the end of amination reactions. The results definitively prove that the imine aziridination by carbamates is a two-step domino process. The structures of the compounds were determined using 2D NMR on purified bidiaziridines.     

Determination of 61 organic pollutants in drinking water by solid phase extraction followed by liquid and gas chromatography coupled to tandem mass spectrometry: an analytical strategy for a routine laboratory

A method for determination of 61 organic pollutants (polycyclic aromatic hydrocarbons and organochlorine, organophosphorous and organonitrogen pesticides) is proposed. It is based on solid phase extraction (SPE) and subsequent analysis of the extract by liquid and gas chromatography coupled to tandem mass spectrometry. Method validation yielded to the following values: limits of quantification, from 0.005 to 0.020?µg?L^?1; trueness, 95% to 113% and reproducibility (as percent relative standard deviation), 2% to 15%. Additionally, the method performed well in various proficiency tests.     

Easy Chemo-Enzymatic Synthesis of Human Milk Trisaccharides from a Common Selectively Protected Lactose Building Block

ABSTRACT

Three glycosyllactosides, contained in the neutral fraction of human milk oligosaccharides, were synthesised in a simple and straightforward manner through a sequence based on a chemo-enzymatic approach. Lipase catalysed regioselective 6'-O-acylation of benzyl β-lactoside, followed by the introduction of an isopropylidene group and acetylation afforded, depending on the reaction conditions, compounds 4a and 4b, which allow selective access to positions 3, 3' and 6'. Glycosylation with proper donors gave trisaccharides 6, 9 and 12.     

The Ligand‐Based Quintuple Bond‐Shortening Concept and Some of Its Limitations

Herein, the ligand‐based concept of shortening quintuple bonds and some of its limitations are reported. In dichromium–diguanidinato complexes, the length of the quintuple bond can be influenced by the substituent at the central carbon atom of the used ligand. The guanidinato ligand with a 2,6‐dimethylpiperidine backbone was found to be the optimal ligand. The reduction of its chromium(II) chloride–ate complex gave a quintuply bonded bimetallic complex with a Cr? Cr distance of 1.7056 (12) Å. Its metal–metal distance, the shortest observed in any stable compound yet, is of essentially the same length as that of the longest alkane C? C bond (1.704 (4) Å). Both molecules, the alkane and the Cr complex, are of remarkable stability. Furthermore, an unsupported Cr^I dimer with an effective bond order (EBO) of 1.25 between the two metal atoms, indicated by CASSCF/CASPT2 calculations, was isolated as a by‐product. The formation of this by‐product indicates that with a certain bulk of the guanidinato ligand, other coordination isomers become relevant. Over‐reduction takes place, and a chromium–arene sandwich complex structurally related to the classic dibenzene chromium complex was observed, even when bulkier substituents are introduced at the central carbon atom of the used guanidinato ligand.     

Epoxide Opening versus Silica Condensation during Sol–Gel Hybrid Biomaterial Synthesis

Hybrid organic–inorganic solids represent an important class of engineering materials, usually prepared by sol–gel processes by cross‐reaction between organic and inorganic precursors. The choice of the two components and control of the reaction conditions (especially pH value) allow the synthesis of hybrid materials with novel properties and functionalities. 3‐Glycidoxypropyltrimethoxysilane (GPTMS) is one of the most commonly used organic silanes for hybrid‐material fabrication. Herein, the reactivity of GPTMS in water at different pH values (pH 2–11) was deeply investigated for the first time by solution‐state multinuclear NMR spectroscopic and mass spectrometric analysis. The extent of the different and competing reactions that take place as a function of the pH value was elucidated. The NMR spectroscopic and mass spectrometric data clearly indicate that the pH value determines the kinetics of epoxide hydrolysis versus silicon condensation. Under slighly acidic conditions, the epoxy‐ring hydrolysis is kinetically more favourable than the formation of the silica network. In contrast, under basic conditions, silicon condensation is the main reaction that takes place. Full characterisation of the formed intermediates was carried out by using NMR spectroscopic and mass spectrometric analysis. These results indicate that strict control of the pH values allows tuning of the reactivity of the organic and inorganic moities, thus laying the foundations for the design and synthesis of sol–gel hybrid biomaterials with tuneable properties.