A new sensitive method for the quantification of glyoxal and methylglyoxal in snow and ice by stir bar sorptive extraction and liquid desorption-HPLC-ESI-MS

In this study, the development of a new sensitive method for the analysis of alpha-dicarbonyls glyoxal (G) and methylglyoxal (MG) in environmental ice and snow is presented. Stir bar sorptive extraction with in situ derivatization and liquid desorption (SBSE-LD) was used for sample extraction, enrichment, and derivatization. Measurements were carried out using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). As part of the method development, SBSE-LD parameters such as extraction time, derivatization reagent, desorption time and solvent, and the effect of NaCl addition on the SBSE efficiency as well as measurement parameters of HPLC-ESI-MS/MS were evaluated. Calibration was performed in the range of 1–60 ng/mL using spiked ultrapure water samples, thus incorporating the complete SBSE and derivatization process. 4-Fluorobenzaldehyde was applied as internal standard. Inter-batch precision was <12 % RSD. Recoveries were determined by means of spiked snow samples and were 78.9 ± 5.6 % for G and 82.7 ± 7.5 % for MG, respectively. Instrumental detection limits of 0.242 and 0.213 ng/mL for G and MG were achieved using the multiple reaction monitoring mode. Relative detection limits referred to a sample volume of 15 mL were 0.016 ng/mL for G and 0.014 ng/mL for MG. The optimized method was applied for the analysis of snow samples from Mount Hohenpeissenberg (close to the Meteorological Observatory Hohenpeissenberg, Germany) and samples from an ice core from Upper Grenzgletscher (Monte Rosa massif, Switzerland). Resulting concentrations were 0.085–16.3 ng/mL for G and 0.126–3.6 ng/mL for MG. Concentrations of G and MG in snow were 1–2 orders of magnitude higher than in ice core samples. The described method represents a simple, green, and sensitive analytical approach to measure G and MG in aqueous environmental samples.

Nota exacta de las missas, i, aniversaris se celebran en la Igl[esi]a Parr[oquia]l de Sn. Andreu de Vallgorguina per la Casa del Más Pujadas de dita Parroquia [Manuscrito]

Alcance y contenido: "Misas y Aniversaris deuhers celebrarse en la Igla. Parr[oqui]al de St. Andreu de Vallgorguina per los passats, o difunts de Casa Pujadas de dita Parr[oqui]a; distribuhidas, y distribuhits per los dotze mesos del any."

A Highly Efficient Solvent-Free Asymmetric Direct Aldol Reaction Organocatalyzed by Recoverable (s)-Binam-L-Prolinamides. ESI-MS Evidence of the Enamine-Iminium Formation

Recoverable (Sa)-binam-l-prolinamide in combination with benzoic acid is used as catalysts in the direct aldol reaction between cycloalkyl, alkyl, and α-functionalized ketones and aldehydes under solvent-free reaction conditions. Three different methods are assayed: simple conventional magnetic stirring, magnetic stirring after previous dissolution in THF and evaporation, and ball mill technique. These procedures allow one to reduce not only the amount of required ketone to 2 equiv but also the reaction time to give the aldol products with regio-, diastereo-, and enantioselectivities comparable to those in organic or aqueous solvents. Generally anti-isomers are mainly obtained with enantioselectivities up to 97%. The reaction can be carried out under these conditions also using aldehydes as nucleophiles, yielding after in situ reduction of the aldol products the corresponding chiral 1,3-diols with moderate to high enantioselectivities mainly as anti-isomers. The aldol reaction has been studied by the use of positive ESI-MS technique, providing the evidence of the formation of the corresponding enamine−iminium intermediates.

Akty, otnosi︠a︡shchīesi︠a︡ k istorīi i︠u︡zhnoĭ i zapadnoĭ Rossīi.

Mode of access: Internet.

Ezhemi͡esi͡achny ̆bi͡ulletenʹ po gorodu Moskvi͡e. Bulletin statistique mensuel de la ville de Moscou.

Summary at end of each year.

Gramoty i drugīe istoricheskīe dokumenty XVIII stoli͡etīi͡a, otnosi͡ashchīesi͡a k Gruzīi /

Documents in Russian and Georgian.

Materīaly istorīi drevneĭ Rossīi khrani͡a︡shchīesi͡a︡ v Kopengageni͡e︡: 1326-1690 gg.

Mode of access: Internet.

Akty, otnosi͡a︡shchīesi͡a︡ do i͡u︡ridicheskago byta drevneĭ Rossīi /

Each sheet entitled: Kalac̮ov, N. V. Akty, otnosjaščiesja do juridičeskago byta... (R-10,146). Moskva, 1857-

Pushkin : dokumenty Gosudarstvennago i S.-Peterburgskago glavnago arkhivov Ministerstva inostrannykh di͡e︡l, otnosi͡a︡shchīesi͡a︡ k sluzhbi͡e︡ ego 1831-1837 gg. S semʹi͡u︡ snimkami s avtografov Pushkina i odnim snimkom s podlinnago svidi͡e︡telʹstva ob okonchanīi im kursa v Imperatorskom t͡s︡arskoselʹskom lit͡s︡ei͡e︡ /

Includes bibliographical references.

Taxonomy of Australian Funnel-web spiders using rp-HPLC/ESI-MS profiling techniques

The complex nature of venom from spider species offers a unique natural source of potential pharmacological tools and therapeutic leads. The increased interest in spider venom molecules requires reproducible and precise identification methods. The current taxonomy of the Australian Funnel-web spiders is incomplete, and therefore, accurate identification of these spiders is difficult. Here, we present a study of venom from numerous morphologically similar specimens of the Hadronyche infensa species group collected from a variety of geographic locations in southeast Queensland. Analysis of the crude venoms using online reversed-phase high performance liquid chromatography/electrospray ionisation mass spectrometry (rp-HPLC/ESI-MS) revealed that the venom profiles provide a useful means of specimen identification, from the species level to species variants. Tables defining the descriptor molecules for each group of specimens were constructed and provided a quick reference of the relationship between one specimen and another. The study revealed that the morphologically similar specimens from the southeast Queensland region are a number of different species/species variants. Furthermore, the study supports aspects of the current taxonomy with respect to the H. infensa species group. Analysis of Australian Funnel-web spider venom by rp-HPLC/ESI-MS provides a rapid and accurate method of species/species variant identification. (c) 2006 Elsevier Ltd. All rights reserved.