자료유형  

 학위논문

Control Number  

0016932673

International Standard Book Number  

9798379836641

Dewey Decimal Classification Number  

545

Main Entry-Personal Name  

Chen, Xingshuo.

Publication, Distribution, etc. (Imprint  

[S.l.] : Purdue University., 2021

Publication, Distribution, etc. (Imprint  

Ann Arbor : ProQuest Dissertations & Theses, 2021

Physical Description  

1 online resource(98 p.)

General Note  

Source: Dissertations Abstracts International, Volume: 85-01, Section: B.

General Note  

Advisor: Cooks, R. Graham.

Dissertation Note  

Thesis (Ph.D.)--Purdue University, 2021.

Restrictions on Access Note  

This item must not be sold to any third party vendors.

Summary, Etc.  

요약Mass spectrometry-based techniques have been widely used in reaction monitoring due to their high sensitivity and ability to offer structure information by tandem mass spectrometry. We applied nano-electrospray mass spectrometry (nanoESI-MS) to simultaneously monitor precatalysts, catalytic intermediates, reagents, and products of palladium catalyzed Suzuki-Miyaura cross-coupling reactions. A set of Pd cluster ions related to the monoligated Pd (0) active catalyst is detected, and its deconvoluted isotopic distribution reveals contributions from two neutral molecules. One is assigned to the generally accepted Pd (0) active catalyst, seen in MS as the protonated molecule, while the other is suggested to correspond to a deactivated form of Pd catalyst. Oxidative stress testing of the synthetic model catalyst XPhos Pd cyclo-octadiene, performed using oxygen and Fe(III), supported this assignment. Thus, the make-up of the monoligated set of Pd (0) ions appears to indicate the oxidation state of the system. The formation and removal of the oxidative addition intermediate during the catalytic cycle was monitored to provide information on the progress of the transmetalation step.Recently, microdroplets created by ambient ionization source have been used as reaction vessels to accelerate organic reactions. Field desorption mass spectrometry under ambient conditions is applied to study solution-phase organic reactions in micro-volumes. Compared to nanoelectrospray, it is noteworthy that radical cations and formation of radical cation products are observed. Three reactions, the hydrazone formation by phenyl hydrazine and indoline-2,3-dione, the Katritzky reaction between a pyrylium salt and anisidine, and the Hantzsch synthesis of 1,4- dihydropyridine, were investigated by this system and reaction acceleration was observed to different extents. The increase in rate relative to that for the corresponding bulk reactions is attributed to solvent evaporation which increases concentration, and to the increase of surface-tovolume ratio with enhanced interfacial reaction rate constants. Later work in this thesis describes explicit solvent calculations to study the energies and structures of the hydrazone formation reaction from phenylhydrazine and indoline-2,3-dione in acidic methanol with density functional tight binding (DFTB) methods. Additionally, the thesis covers MS based methods for determination of isoaspartate and aspartate in peptide by gas-phase chemistry and detection of Snitrosoglutathione in exhaled breath condensate sample.

Subject Added Entry-Topical Term  

Mass spectrometry.

Subject Added Entry-Topical Term  

Acids.

Subject Added Entry-Topical Term  

Reagents.

Subject Added Entry-Topical Term  

Oxidation.

Subject Added Entry-Topical Term  

Palladium.

Subject Added Entry-Topical Term  

Ions.

Subject Added Entry-Topical Term  

Solvents.

Subject Added Entry-Topical Term  

Scientific imaging.

Subject Added Entry-Topical Term  

Gas flow.

Subject Added Entry-Topical Term  

Thin films.

Subject Added Entry-Topical Term  

Analytical chemistry.

Subject Added Entry-Topical Term  

Chemistry.

Subject Added Entry-Topical Term  

Condensed matter physics.

Subject Added Entry-Topical Term  

Materials science.

Subject Added Entry-Topical Term  

Physics.

Added Entry-Corporate Name  

Purdue University.

Host Item Entry  

Dissertations Abstracts International. 85-01B.

Host Item Entry  

Dissertation Abstract International

Electronic Location and Access  

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Control Number  

joongbu:643311