Carbon Dioxide Microbubble Bursting Ionization Mass Spectrometry

Aerosols generated by bubble bursting have been proved to promote the extraction of analytes and have ultrahigh electric fields at their water–air interfaces. This study presented a simple and efficient ionization method, carbon dioxide microbubble bursting ionization (CDMBI), without the presence of an exogenous electric field (namely, zero voltage), by simulating the interfacial chemistries of sea spray aerosols. In CDMBI, microbubbles are generated in situ by continuous input of carbon dioxide into an aqueous solution containing low-concentration analytes. The microbubbles extract low- and high-polarity analytes as they pass through the aqueous solution. Upon reaching the water–air interface, these microbubbles burst to produce charged aerosol microdroplets with an average diameter of 260 μm (8.1–10.4 nL in volume), which are immediately transferred to a mass spectrometer for the detection and identification of extracted analytes. The above analytical process occurs every 4.2 s with a stable total ion chromatogram (relative standard deviation: 9.4%) recorded. CDMBI mass spectrometry (CDMBI-MS) can detect surface-active organic compounds in aerosol microdroplets, such as perfluorooctanoic acid, free fatty acids epoxidized by bubble bursting, sterols, and lecithins in soybean and egg, with the limit of detection reaching the level of fg/mL. In addition, coupling CDMBI-MS with an exogenous voltage yields relatively weak gains in ionization efficiency and sensitivity of analysis. The results suggested that CDMBI can simultaneously accomplish both bubbling extraction and microbubble bursting ionization. The mechanism of CDMBI involves bubbling extraction, proton transfer, inlet ionization, and electrospray-like ionization. Overall, CDMBI-MS can work in both positive and negative ion modes without necessarily needing an exogenous high electric field for ionization and quickly detect trace surface-active analytes in aqueous solutions

Generating Electrospray Ionization on Ballpoint Tips

In this study, we report a simple and economical ballpoint electrospray ionization mass spectrometry (BP-ESI-MS) technique. This combines a small ballpoint tip with a syringe pump for the direct loading and ionization of various samples in different phases (including solution, semisolid, and solid) and allows for additional applications in surface analysis. The tiny metal ball on the ballpoint tip exhibits a larger surface for ionization than that of a conventional sharp tip end, resulting in higher ionization efficiency and less sample consumption. The adamant properties of the ballpoint tip allow sampling by simply penetrating or scraping various surfaces, such as a fruit peel, paper, or fabric. Complex samples, such as fine herbal powders and small solid samples, could be stored in the hollow space in the ballpoint socket and subsequently extracted online, which greatly facilitated MS analysis with little to no sample preparation. Positive ion mode was attempted, and various compounds, including amino acids, carbohydrates, flavonoids, and alkaloids, were detected from different types of samples. The results demonstrated that the special and excellent physical characteristics of ballpoint tips allowed for fast and convenient sampling and ionization for mass spectrometry analysis by the BP-ESI-MS method

Nickel-Catalyzed Reductive Three-Component Cross-Coupling of Butadiene with Aldehydes and Alkenyl Triflates/Bromides: Access to Skipped Dienes

A regio- and stereoselective nickel-catalyzed reductive three-component cross-coupling of 1,3-butadiene with aldehydes and alkenyl triflates or bromides was realized. This protocol afforded a convenient approach to the synthesis of skipped diene compounds bearing various functionals and heterocyclic groups. The utility of this reaction was also demonstrated by scale-up preparation and diverse transformations

Enantioselective Ir-Catalyzed Allyl Alkylation/Semipinacol Rearrangement

The semipinacol rearrangement is a powerful and versatile method for constructing all-carbon quaternary stereocenters. The development of catalytic asymmetric semipinacol rearrangements using multifunctionalizable electrophiles remains highly sought-after in organic synthesis. In this study, a catalytic enantioselective allylic cation-induced semipinacol rearrangement reaction was presented that enables the simultaneous construction of two skipped chiral carbon centers. Chiral Ir(I)-(P,olefin) and Sc(OTf)3 catalysts cooperatively initiate the asymmetric allylic alkylation of alkenyl cyclobutanols with allylic alcohols, triggering ring expansion of the cyclobutanol moiety through a stereoselective 1,2-alkyl migration. The reaction afforded a range of cyclopentanones bearing an α-quaternary carbon that is adjacent to a chiral allyl scaffold. The products were applied to synthesize enantioenriched fused tricyclopentanoids bearing four stereogenic carbon centers