Efficient Regioselective Ring Opening of Activated Aziridine-2-Carboxylates with [18F]Fluoride

Aziridines can undergo a range of ring-opening reactions with nucleophiles. The regio- and stereochemistry of the products depend on the substituents on the aziridine. Aziridine ring-opening reactions have rarely been used in radiosynthesis. Herein we report the ring opening of activated aziridine-2-carboxylates with [¹⁸F]fluoride. The aziridine was activated for nucleophilic attack by substitution of various groups on the aziridine nitrogen atom. Fluorine-18 radiolabelling was followed by ester hydrolysis and removal of the activation group. Totally regioselective ring opening and subsequent deprotection was achieved with tert-butyloxycarbonyl- and carboxybenzyl-activated aziridines to give α-[¹⁸F]fluoro-β-alanine in good radiochemical yield.     

Biogas Production from N-Methylmorpholine-N-oxide (NMMO) Pretreated Forest Residues

Lignocellulosic biomass represents a great potential for biogas production. However, a suitable pretreatment is needed to improve their digestibility. This study investigates the effects of an organic solvent, N-Methylmorpholine-N-oxide (NMMO) at temperatures of 120 and 90 °C, NMMO concentrations of 75 and 85 % and treatment times of 3 and 15 h on the methane yield. The long-term effects of the treatment were determined by a semicontinuous experiment. The best results were obtained using 75 % NMMO at 120 °C for 15 h, resulting in 141 % increase in the methane production. These conditions led to a decrease by 9 % and an increase by 8 % in the lignin and in the carbohydrate content, respectively. During the continuous digestion experiments, a specific biogas production rate of 92 NmL/gVS/day was achieved while the corresponding rate from the untreated sample was 53 NmL/gVS/day. The operation conditions were set at 4.4 gVS/L/day organic loading rate (OLR) and hydraulic retention time (HRT) of 20 days in both cases. NMMO pretreatment has substantially improved the digestibility of forest residues. The present study shows the possibilities of this pretreatment method; however, an economic and technical assessment of its industrial use needs to be performed in the future.     

Laser-printed lithium-sulphur micro-electrodes for Li/S batteries

A novel path for the preparation of electrodes for lithium-sulphur cells was developed using a very fast laser-printing setup for the direct and dry i.e., solvent-free transfer of electrode materials onto the current collectors. Model electrodes could be prepared at very small dimensions enabling these batteries to be used even in portable small devices. The initial specific charge was remarkably high at about 1300 A h kg^?1 (relating to the active material content of the electrode) with a loss of specific charge of about 75% after about 400 cycles at 1C. In addition, the dry transfer technique has highly beneficial effects on the environmental sustainability and, therefore, supports the concept of the use of “green” power storage.     

Improved Synthesis,Structure, and Solution Characterization of the Cyclic 48-Tungsto-8-Arsenate(V), [H4As8W48O184]36−

We report on an improved synthesis and structural characterization of the cyclic 48-tungsto–8-arsenate(V) [H₄As₈W₄₈O₁₈₄]^36? (1). The mixed lithium–potassium salt of this polyanion, K_26.5Li_9.5[H₄As₈W₄₈O₁₈₄]·90H₂O (KLi-1), has been studied in the solid state by IR, single-crystal X-ray diffraction, and elemental analysis, and in solution by ¹⁸³W NMR spectroscopy.     

Aggressive dereplication using UHPLC–DAD–QTOF: screening extracts for up to 3000 fungal secondary metabolites

In natural-product drug discovery, finding new compounds is the main task, and thus fast dereplication of known compounds is essential. This is usually performed by manual liquid chromatography-ultraviolet (LC-UV) or visible light-mass spectroscopy (Vis-MS) interpretation of detected peaks, often assisted by automated identification of previously identified compounds. We used a 15 min high-performance liquid chromatography–diode array detection (UHPLC–DAD)–high-resolution MS method (electrospray ionization (ESI)⁺ or ESI^?), followed by 10–60 s of automated data analysis for up to 3000 relevant elemental compositions. By overlaying automatically generated extracted-ion chromatograms from detected compounds on the base peak chromatogram, all major potentially novel peaks could be visualized. Peaks corresponding to compounds available as reference standards, previously identified compounds, and major contaminants from solvents, media, filters etc. were labeled to differentiate these from compounds only identified by elemental composition. This enabled fast manual evaluation of both known peaks and potential novel-compound peaks, by manual verification of: the adduct pattern, UV–Vis, retention time compared with log D, co-identified biosynthetic related compounds, and elution order. System performance, including adduct patterns, in-source fragmentation, and ion-cooler bias, was investigated on reference standards, and the overall method was used on extracts of Aspergillus carbonarius and Penicillium melanoconidium, revealing new nitrogen-containing biomarkers for both species.     

Determination of aminopolycarboxylic acids at ultra-trace levels by means of online coupling ion exchange chromatography and inductively coupled plasma-mass spectrometry with indirect detection via their Pd-complexes

A new indirect IC-ICP-MS method for the determination of aminopolycarboxylic acids in water samples is described. It is based on the addition of an excess of Pd(II) to water samples. The analytes are forced into very strong and negatively charged palladium complexes, separated by ion exchange chromatography and detected by their palladium content, utilizing an on-line coupled ICP-MS. This method is suitable to determine the concentration of 8 aminopolycarboxylic acids (nitrilotriacetic acid (NTA), (2-carboxyethyl) iminodiacetic acid (β-ADA), methylglycinediacetic acid (MGDA), 2-hydroxyethyl) ethylenediamine triacetic acid (HEDTA), diethylene triamine pentaacetic acid (DTPA), ethylendiamine tetraacetic acid (EDTA), 1,3-diaminopropane tetraacetic acid (1,3-PDTA) and 1,2-diaminopropane tetraacetic acid (1,2-PDTA) at the ng kg⁻¹ level. The method is faster and easier than the established gas chromatography (GC)-method ISO 16588:2002 [1] and up to two orders of magnitude more sensitive than the ion pair chromatography based method of DIN 38413-8. Analytic performance is superior to ISO 16588:2002 and the comparability is good.