Molecular Weight Evaluation of Poly(dimethylsiloxane) on Solid Surfaces Using Silver Deposition/TOF-SIMS

Inoue, Masae; Murase, Atsushi; Sugiura, Motoyasu

doi:10.2116/analsci.20.1623

Cited by 12 publications

(9 citation statements)

References 29 publications

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“…Delcorte et al treated analytes including short peptide and polymers with alkali metal cations or metal salts to obtain ion signals through Lewis acid-base interactions: Weak bases (aromatic compounds) interact with weak acids (metal cations) to ionize them, whereas hard bases (peptides) ionize hard acids (alkali cations). Similarly to the use of matrix, the silver cationization method enabled the generation of quasimolecular ions from organic materials on solid surfaces (Xu, Proctor, & Hercules, 1995;Inoue, Murase, & Sugiura, 2004). The signal enhancement was also observed from carboxylic acid-terminated SAMs by replacing acidic hydrogen with the metal ion (Ag, Na, Cu, Tl, and Li) (Michel et al, 2000).…”

Section: B Matrix-enhanced Simsmentioning

confidence: 99%

Probing nanoparticles and nanoparticle‐conjugated biomolecules using time‐of‐flight secondary ion mass spectrometry

Kim

Shon

Shin

et al. 2014

Mass Spectrometry Reviews

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Bio-conjugated nanoparticles have emerged as novel molecular probes in nano-biotechnology and nanomedicine and chemical analyses of their surfaces have become challenges. The time-offlight (TOF) secondary ion mass spectrometry (SIMS) has been one of the most powerful surface characterization techniques for both nanoparticles and biomolecules. When combined with various nanoparticle-based signal enhancing strategies, TOF-SIMS can probe the functionalization of nanoparticles as well as their locations and interactions in biological systems. Especially, nanoparticle-based SIMS is an attractive approach for labelfree drug screening because signal-enhancing nanoparticles can be designed to directly measure the enzyme activity. The chemical-specific imaging analysis using SIMS is also well suited to screen nanoparticles and nanoparticle-biomolecule conjugates in complex environments. This review presents some recent applications of nanoparticle-based TOF-SIMS to the chemical analysis of complex biological systems.

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Section: B Matrix-enhanced Simsmentioning

confidence: 99%

Probing nanoparticles and nanoparticle‐conjugated biomolecules using time‐of‐flight secondary ion mass spectrometry

Kim

Shon

Shin

et al. 2014

Mass Spectrometry Reviews

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“…[4][5][6][7]9 There are also examples of direct molecular weight analysis by SIMS in the open literature. Molecular weight distributions of lower molecular weight polymers and oligomers have been determined directly by using special sample preparation through metal overlayers 11,12 or deposition on metals (most often silver) 10,[13][14][15][16][17][18] to enhance high mass ion yields or simply focus on smaller oligomers. 8,12 These experiments are reflective of the relatively new use of SIMS for polymer analysis at the time they were published and are not necessarily relatable or realistic for using SIMS as a surface analysis tool where it is necessary to avoid preparation methods that may alter the original surface chemistry.…”

Section: Introductionmentioning

confidence: 99%

Part I: Molecular weight characterization of linear polydimethyl siloxanes by secondary ion mass spectrometry

Pacholski

Vlasak

2020

Surface & Interface Analysis

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A correlation of SIMS ion intensities to the molecular weight of linear, trimethyl‐terminated polydimethyl siloxane (PDMS) has been developed by normalizing PDMS endgroup‐related signal to backbone‐related signal for a set of well‐characterized polymers with narrow molecular weight distributions. These initial experiments on thick PDMS films illustrate that PDMS molecular weight can be estimated using SIMS. A second paper describes the challenges in analyzing thin PDMS films on metal and polymer substrates. PDMS molecular weight determination is important to understanding surface‐related performance of materials using silicone additives across many different platforms including coefficient of friction, slip, mar, mold release, and nonstick properties as well as providing more specific characterization of surface contamination.

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“…Mass spectra of PDMS have been obtained for smaller mass ranges using electron ionization (EI) 8 and pyrolysis 9 methods. Much higher molecular weight samples have been analyzed using secondary ion time of flight mass spectrometry (SIMS-TOF), which has evaluated the molecular weight 10 and fragmentation pathway of PDMS 11 and other polysiloxanes. 12 In the examples above that used SIMS, silver was used as a substrate and so several Ag + adducts were observed.…”

Section: Introductionmentioning

confidence: 99%

Comparing the fragmentation chemistry of gas-phase adducts of poly(dimethylsiloxane) oligomers with metal and organic ions

2009

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Gas-phase ions of poly(dimethylsiloxane) oligomers were formed by electrospray ionization either by protonating them in solution with formic acid or by generating adducts of the oligomers with the metal ions Li + , Na + , K + , and Ag + as well as with the organic cations NH4 + , CH3CH2NH3 + , and protonated glycine, aspartic acid, and 1,2-diphenylethylamine. The collision-induced fragmentation of the oligomeric ions was strongly dependent on the nature of the charging species. Ag + adducts dissociated in a manner previously observed in secondary ion mass spectrometry experiments generating a series of linear and cyclic fragment ions, while Li + adducts fragmented to form two ions: an adduct of the metal ion with the oligomer end-group and one with the remaining oligomer. Na + and K + adducts simply dissociate to form the bare metal ion. The organic species, to varying extents, transfer the proton to the oligomer to form a protonated poly(siloxane) ion. These protonated oligomers then dissociate at very low laboratory-frame collision energy along the siloxane backbone by loss of a silanol. These backbone fragments can then lose a methyl group to form a second series of fragment ions. Suggestions for probable mechanistic pathways for these processes are presented.Résumé : On a observé la formation en phase gazeuse d'ions d'oligomères poly(diméthylsiloxane) lors de l'ionisation par électronébulisation d'oligomères protonés en solution avec de l'acide formique ou par la génération d'adduits des oligomè-res avec les ions métalliques Li + , Na + , K + et Ag + , les cations organiques NH 4 + , CH 3 CH 2 NH 2 + , ou les formes protonées de la glycine, de l'acide aspartique et de la 1,2-diphényléthylamine. La fragmentation induite par des collisions des ions oligomè-res dépend fortement de la nature des espèces utilisées pour les charger. Les adduits avec le Ag + se dissocient de la façon observée antérieurement lors d'expériences de spectrométrie de masse d'ions secondaires pour une série de fragments ioniques linéaires et cycliques alors que les adduits avec le Li + se fragmentent pour donner deux ions, un adduit de l'ion métal-lique avec la partie terminale de l'oligomère et un avec le reste de l'oligomère. Les adduits du Na + et du K + se dissocient simplement pour donner un ion métallique nu. Les espèces organiques transfèrent à des degrés variables le proton vers l'oligomère pour former un ion poly(siloxane) protoné. Sous l'influence d'énergie de collisions très faibles dans le cadre d'un laboratoire, les oligomères protonés se dissocient alors le long du squelette siloxane pour conduire à des pertes de silanol. Ces fragments de squelette peuvent alors perdre un groupe méthyle pour conduire à la formation d'une deuxième série de fragments ioniques. On présente des suggestions concernant les voies mécanistiques probables pour ces processus.Mots-clés : oligomères poly(diméthylsiloxane), acide aminé, bases, ions métalliques, spectrométrie de masse, dissociation induite par des collisions, voies de fragmentations.[Trad...

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Molecular Weight Evaluation of Poly(dimethylsiloxane) on Solid Surfaces Using Silver Deposition/TOF-SIMS

Cited by 12 publications

References 29 publications

Probing nanoparticles and nanoparticle‐conjugated biomolecules using time‐of‐flight secondary ion mass spectrometry

Probing nanoparticles and nanoparticle‐conjugated biomolecules using time‐of‐flight secondary ion mass spectrometry

Part I: Molecular weight characterization of linear polydimethyl siloxanes by secondary ion mass spectrometry

Comparing the fragmentation chemistry of gas-phase adducts of poly(dimethylsiloxane) oligomers with metal and organic ions

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