A “one pot” mass spectrometry technique for characterizing solution- and gas-phase photochemical reactions by electrospray mass spectrometry†

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Abstract

The characterization of new photochemical pathways is important to progress the understanding of emerging areas of light-triggered inorganic and organic chemistry. In this context, the development of platforms to perform routine characterization of photochemical reactions remains an important goal for photochemists. Here, we demonstrate a new instrument that can be used to characterise both solution-phase and gas-phase photochemical reactions through electrospray ionisation mass spectrometry (ESI-MS). The gas-phase photochemistry is studied by novel laser-interfaced mass spectrometry (LIMS), where the molecular species of interest is introduced to the gas-phase by ESI, mass-selected and then subjected to laser photodissociation in the ion-trap. On-line solution-phase photochemistry is initiated by LEDs prior to ESI-MS in the same instrument with ESI-MS again being used to monitor photoproducts. Two ruthenium metal carbonyls, [Ru(η ⁵-C ₅H ₅)(PPh ₃) ₂CO][PF ₆] and [Ru(η ⁵-C ₅H ₅)(dppe)CO][PF ₆] (dppe = 1,2-bis(diphenylphosphino)ethane) are studied using this methodology. We show that the gas-phase photofragmentation pathways observed for the ruthenium complexes via LIMS ( i.e. loss of CO + PPh ₃ ligands from [Ru(η ⁵-C ₅H ₅)(PPh ₃) ₂CO] ⁺ and loss of just CO from [Ru(η ⁵-C ₅H ₅)(dppe)CO] ⁺) mirror the solution-phase photochemistry at 3.4 eV. The advantages of performing the gas-phase and solution-phase photochemical characterisations in a single instrument are discussed.

Abstract

The solution and gas-phase dissociative photochemistry of two ruthenium half-sandwich complexes are analysed with electrospray ionisation mass spectrometry in a novel instrument.

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Visible light photocatalysis as a greener approach to photochemical synthesis.

Tehshik Yoon, Michael Ischay, Juana Du (2010)

Light can be considered an ideal reagent for environmentally friendly, 'green' chemical synthesis; unlike many conventional reagents, light is non-toxic, generates no waste, and can be obtained from renewable sources. Nevertheless, the need for high-energy ultraviolet radiation in most organic photochemical processes has limited both the practicality and environmental benefits of photochemical synthesis on industrially relevant scales. This perspective describes recent approaches to the use of metal polypyridyl photocatalysts in synthetic organic transformations. Given the remarkable photophysical properties of these complexes, these new transformations, which use Ru(bpy)(3)(2+) and related photocatalysts, can be conducted using almost any source of visible light, including both store-bought fluorescent light bulbs and ambient sunlight. Transition metal photocatalysis thus represents a promising strategy towards the development of practical, scalable industrial processes with great environmental benefits.

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The therapeutic potential of carbon monoxide.

Roberto Motterlini, Leo E. Otterbein (2010)

Carbon monoxide (CO) is increasingly being accepted as a cytoprotective and homeostatic molecule with important signalling capabilities in physiological and pathophysiological situations. The endogenous production of CO occurs through the activity of constitutive (haem oxygenase 2) and inducible (haem oxygenase 1) haem oxygenases, enzymes that are responsible for the catabolism of haem. Through the generation of its products, which in addition to CO includes the bile pigments biliverdin, bilirubin and ferrous iron, the haem oxygenase 1 system also has an obligatory role in the regulation of the stress response and in cell adaptation to injury. This Review provides an overview of the physiology of CO, summarizes the effects of CO gas and CO-releasing molecules in preclinical animal models of cardiovascular disease, inflammatory disorders and organ transplantation, and discusses the development and therapeutic options for the exploitation of this simple gaseous molecule.

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Solar synthesis: prospects in visible light photocatalysis.

Danielle M Schultz, Tehshik P Yoon (2014)

Chemists have long aspired to synthesize molecules the way that plants do-using sunlight to facilitate the construction of complex molecular architectures. Nevertheless, the use of visible light in photochemical synthesis is fundamentally challenging because organic molecules tend not to interact with the wavelengths of visible light that are most strongly emitted in the solar spectrum. Recent research has begun to leverage the ability of visible light-absorbing transition metal complexes to catalyze a broad range of synthetically valuable reactions. In this review, we highlight how an understanding of the mechanisms of photocatalytic activation available to these transition metal complexes, and of the general reactivity patterns of the intermediates accessible via visible light photocatalysis, has accelerated the development of this diverse suite of reactions.