Copolymer Fingerprints of Polystyrene-<i>block</i>-polyisoprene by MALDI-ToF-MS

Willemse, Robin X. E.; Staal, Bbp Bastiaan; Donkers, Ehd Ellen; Herk, AM Alex van

doi:10.1021/ma049471m

Cited by 54 publications

(72 citation statements)

References 33 publications

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“…As already mentioned by different authors [46][47], the fact that RAFT polymerization involves polymer chains of the same chain-length does introduce some new consequences compared to conventional free radical polymerization where short and long chains coexist (for instance concerning termination reactions). Such consequences are predominant at the beginning of the polymerization since the chain-length dependence of the rate constants is larger for shorter chains [48]. For our monomer/CTA pair where IR are well stabilized, the end of the induction period could be related to a chain-length dependence, especially concerning the addition and the fragmentation reactions.…”

Section: Influence Of the [Cta]/[aibn] Ratiomentioning

confidence: 82%

A detailed kinetic study of the RAFT polymerization of a bi-substituted acrylamide derivative: influence of experimental parameters

Favier

Charreyre

Pichot

2004

Polymer

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Section: Influence Of the [Cta]/[aibn] Ratiomentioning

confidence: 82%

A detailed kinetic study of the RAFT polymerization of a bi-substituted acrylamide derivative: influence of experimental parameters

Favier

Charreyre

Pichot

2004

Polymer

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“…[21,25,26] ) where MALDI could be applied for the analysis of copolymers, since the interpretation of copolymer MALDI spectra can be very difficult as a result of the presence of two distributions, namely a molecular weight and a chemical composition distribution. Nevertheless, we were able to investigate the synthesized block copolymers by MALDI-TOF MS utilizing a recently developed multiple layer spotting technique [20] in combination with a homemade program written in Visual Basic 6.0 [21] to result in a full copolymer characterization for polymer P1 as well as a good understanding of the other block copolymers. Figure 1A displays the MALDI-TOF MS spectra of the PEG macroinitiator as well as polymer P1.…”

Section: Resultsmentioning

confidence: 99%

“…Furthermore, we were able to calculate a complete copolymer fingerprint of polymer P1 (for details see ref. [21] ). Figure 1C shows this fingerprint clearly to reveal the maximum of both the PEO and PCL repeat units.…”

Section: Resultsmentioning

confidence: 99%

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PEO‐b‐PCL Block Copolymers: Synthesis, Detailed Characterization, and Selected Micellar Drug Encapsulation Behavior

Meier

Aerts

Staal

et al. 2005

Macromol. Rapid Commun.

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Summary: A series of poly(ethylene glycol)‐block‐poly(ε‐caprolactone) diblock copolymers was synthesized and fully characterized. In particular, MALDI‐TOF MS results revealed interesting new insights into their molecular architecture. Small and defined micelles could be prepared from these block copolymers. Utilizing a high‐throughput screening approach, it was observed that these micelles are able to encapsulate/solubilize different guest molecules (e.g. drugs) depending on the solubility of the guest in water. Furthermore, it could be proven that a guest is located within a micelle and that these micelles can be utilized as transport vehicles for the encapsulated guest molecules.PEO‐b‐PCL diblock copolymers can encapsulate small guest molecules in the core of the polymeric micelles.imagePEO‐b‐PCL diblock copolymers can encapsulate small guest molecules in the core of the polymeric micelles.

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“…This was first of all presented in a study of polystyrene-block-polyisoprene [69], as made via sequential anionic polymerization. This was first of all presented in a study of polystyrene-block-polyisoprene [69], as made via sequential anionic polymerization.…”

Section: Copolymerizationmentioning

confidence: 95%

Elucidation of Reaction Mechanisms: Conventional Radical Polymerization

Buback

Russell

Vana

2011

Mass Spectrometry in Polymer Chemistry

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It is often remarked that the molar mass distribution (MMD) of a polymer contains the entire history of its synthesis. It is because of this truism that those interested in the kinetics of polymerization are driven to understand polymer MMDs. As will be seen in this chapter, in the case of (conventional) radical polymerization (RP), this quest has been enormously advanced by the advent of large-molecule mass spectrometry (MS), for it is a characterization technique that furnishes hitherto unimaginable detail about the MMD of a polymer, and thus it may be used to elucidate or confirm the mechanisms of RP in many ways that simply were not previously possible.What is it that is so special about an MMD yielded by MS? It is not the distribution amount, for size exclusion chromatography (SEC) already makes a superior fist of measuring that, mostly through the use of refractive-index (RI) detection. Admittedly there can be issues with this, for example, that RI is molar mass dependent for oligomers [1]. However, such issues apply only in particular circumstances, and they pale beside the general uncertainty one must attach to polymer amounts as returned via MS: there is no doubt that SEC is a vastly superior technique in this respect. Rather, what is so special about MS is its delivery of the MMD variable, namely molar mass, M. The two important aspects here are mass accuracy and mass resolving powerFor many large-molecule studies, it is the mass accuracy of MS that is revolutionary. Indeed, the knee-jerk reaction of most RP workers would be that this is also the case in their field. In fact, the matter is not so straightforward. A good illustrative example of this is the pulsed-laser polymerization (PLP) method for measuring propagation rate coefficients, k p [3, 4], which requires knowledge of absolute values of M. By now an enormous quantity of accurate k p data has been yielded by this method, almost all of it through the use of SEC [5,6]. This evidences that for the study of RP kinetics and mechanisms, accurate SEC calibration is commonly possible, either directly through the use of standards, or indirectly through the additional use of Mark-Houwink parameters (so-called universal calibration). So, it is not this aspect alone that makes MS so useful.In fact what is so groundbreaking about MS for the study of RP mechanisms is its mass resolving power, that is, the ability of mass analyzers to separate and measure small differences in M, by now to well under 1-Dalton level with most instruments. As Barner-Kowollik et al. expressed it, this gives the power to visualize the individual polymer chains present in a given sample [7]. Thus, for example, polymer chains of identical degree of polymerization but with a different end group can be resolved, something of which SEC will never (in general) be capable. Because of the accurate determination of the M of the resolved species, their precise chemical composition may be deduced, and from this the mechanism of polymer formation can be inferred. Numerous examples of this ge...

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Copolymer Fingerprints of Polystyrene-block-polyisoprene by MALDI-ToF-MS

Cited by 54 publications

References 33 publications

A detailed kinetic study of the RAFT polymerization of a bi-substituted acrylamide derivative: influence of experimental parameters

A detailed kinetic study of the RAFT polymerization of a bi-substituted acrylamide derivative: influence of experimental parameters

PEO‐b‐PCL Block Copolymers: Synthesis, Detailed Characterization, and Selected Micellar Drug Encapsulation Behavior

Elucidation of Reaction Mechanisms: Conventional Radical Polymerization

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