<i>Operando</i> acoustic analysis: a valuable method for investigating reaction mechanisms in mechanochemistry

Leroy, César; Mittelette, Sébastien; Félix, Gautier; Fabregue, Nicolas; Špačková, Jessica; Gaveau, Philippe; Métro, Thomas‐Xavier; Laurencin, Danielle

doi:10.1039/d2sc01496c

Cited by 12 publications

(12 citation statements)

References 33 publications

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“…The jar was closed, sealed with parafilm, and subjected to grinding for 5 min in the mixer mill operated at 25 Hz. Although the exact change in temperature inside the jar during this milling process could not be measured, it is expected to be small under such conditions (less than ∼25 °C). , …”

Section: Methodsmentioning

confidence: 99%

“…Although the exact change in temperature inside the jar during this milling process could not be measured, it is expected to be small under such conditions (less than ∼25 °C). 67 , 68 …”

Section: Methodsmentioning

confidence: 99%

“…Although the exact change in temperature inside the jar during this milling process could not be measured, it is expected to be small under such conditions (less than ∼25 °C). 67,68 Three types of experiments were performed: (1) milling with the sample being collected directly after the reaction, abbreviated as COM-BM; (2) milling followed by an additional aging step, during which the sample was left in the closed grinding jar for 72 h at room temperature, abbreviated as COM-BM-AGED; and (3) milling with no PTFE ball and sample collection straight after the reaction, abbreviated as COM-SHAKE. The given abbreviations used herein were modified further in this manuscript by adding -2 H, - 17 O, or - 18 O at the end to indicate the enriched nuclei in the material (Scheme 1).…”

Section: ■ Introductionmentioning

confidence: 99%

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First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution ¹⁷O and ²H NMR Analyses

et al. 2022

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Calcium oxalate minerals of the general formula CaC 2 O 4 . x H 2 O are widely present in nature and usually associated with pathological calcifications, constituting up to 70–80% of the mineral component of renal calculi. The monohydrate phase (CaC 2 O 4 . H 2 O, COM) is the most stable form, accounting for the majority of the hydrated calcium oxalates found. These mineral phases have been studied extensively via X-ray diffraction and IR spectroscopy and, to a lesser extent, using 1 H, 13 C, and 43 Ca solid-state NMR spectroscopy. However, several aspects of their structure and reactivity are still unclear, such as the evolution from low- to high-temperature COM structures (LT-COM and HT-COM, respectively) and the involvement of water molecules in this phase transition. Here, we report for the first time a 17 O and 2 H solid-state NMR investigation of the local structure and dynamics of water in the COM phase. A new procedure for the selective 17 O- and 2 H-isotopic enrichment of water molecules within the COM mineral is presented using mechanochemistry, which employs only microliter quantities of enriched water and leads to exchange yields up to ∼30%. 17 O NMR allows both crystallographically inequivalent water molecules in the LT-COM structure to be resolved, while 2 H NMR studies provide unambiguous evidence that these water molecules are undergoing different types of motions at high temperatures without exchanging with one another. Dynamics appear to be essential for water molecules in these structures, which have not been accounted for in previous structural studies on the HT-COM structure due to lack of available tools, highlighting the importance of such NMR investigations for refining the overall knowledge on biologically relevant minerals like calcium oxalates.

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Section: Methodsmentioning

confidence: 99%

“…Although the exact change in temperature inside the jar during this milling process could not be measured, it is expected to be small under such conditions (less than ∼25 °C). 67 , 68 …”

Section: Methodsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution ¹⁷O and ²H NMR Analyses

et al. 2022

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“…Changes in rheology and chemical composition of the mechanochemical reaction mixture can also be reflected in the sound generated by the motion and collisions of milling media in the operating ball mill. The value of the acoustic effect for monitoring mechanochemical reactions was recently demonstrated by Leroy and co-workers, who followed the evolution of sound in the milling reaction of terephthalic acid (H 2 ta ) and dabco, yielding the salt [ dabco H 2 + ][ ta 2– ]. Microphone recording data were used to generate an audio frequency spectrogram, which enabled monitoring of the Fourier transform of the audio signal with respect to time.…”

Section: In Situ Monitoring Of Milling Reactionsmentioning

confidence: 99%

Section: In Situ Monitoring Of Milling Reactionsmentioning

confidence: 99%

Methods for Monitoring Milling Reactions and Mechanistic Studies of Mechanochemistry: A Primer

Julien

Friščić

2022

Crystal Growth & Design

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Mechanochemistry by ball milling is garnering significant attention as an efficient and versatile means of chemical synthesis which minimizes the need for solvents and reduces the amount of energy required to conduct many molecular transformations. Understanding milling reactions often requires monitoring the reaction of solid forms, with little or ideally no disruption of the milling process. Herein, we provide a broad but succinct summary of how different ex situ and the more recently developed in situ techniques have been applied to monitor mechanochemical reactions, revealing reaction pathways and the mechanisms driving different solid-state molecular and materials transformations by milling. The rapidly evolving field of monitoring milling reactions has already revolutionized our understanding of mechanochemical reactions, revealing complex self-assembled phases as intermediates in catalytic and other types of synthesis through ball milling. The multitude of recently reported techniques for investigating ball milling reactions, many of which are touched upon in this summary, promise to dramatically increase the pace of mechanochemical reaction development and the understanding of solid-state chemistry.

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Terahertz-Raman spectroscopy for in situ benchtop monitoring of changes to extended, supramolecular structure in milling mechanochemistry

Borchers,

Topić,

Arhangelskis

et al. 2024

Chem

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Operando acoustic analysis: a valuable method for investigating reaction mechanisms in mechanochemistry

Abstract: We present a new operando approach for following reactions taking place in mechanochemistry, relying on the analysis of the evolution of the sound during milling. We show that differences in...

Cited by 12 publications

References 33 publications

First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution ¹⁷O and ²H NMR Analyses

First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution ¹⁷O and ²H NMR Analyses

Methods for Monitoring Milling Reactions and Mechanistic Studies of Mechanochemistry: A Primer

Terahertz-Raman spectroscopy for in situ benchtop monitoring of changes to extended, supramolecular structure in milling mechanochemistry

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Operando acoustic analysis: a valuable method for investigating reaction mechanisms in mechanochemistry

Abstract: We present a new operando approach for following reactions taking place in mechanochemistry, relying on the analysis of the evolution of the sound during milling. We show that differences in...

Cited by 12 publications

References 33 publications

First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution 17O and 2H NMR Analyses

First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution 17O and 2H NMR Analyses

Methods for Monitoring Milling Reactions and Mechanistic Studies of Mechanochemistry: A Primer

Terahertz-Raman spectroscopy for in situ benchtop monitoring of changes to extended, supramolecular structure in milling mechanochemistry

Contact Info

Product

Resources

About

First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution ¹⁷O and ²H NMR Analyses

First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution ¹⁷O and ²H NMR Analyses