Thermodynamic Differences Between Deuterated and Protonated Polystyrenes Evaluated Using Reversed Phase Liquid Chromatography

Kayillo, Sindy; Shalliker, R. Andrew; Dennis, Gary R.

doi:10.1002/macp.200500207

Cited by 11 publications

(8 citation statements)

References 15 publications

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“…The differences in thermal properties between protonated and perdeuterated PHO may have also been influenced by the substitution of hydrogens by deuterons. While it has generally been assumed that deuteration of polymer chains has no effect on their thermodynamics, recent work by Kayillo et al and others have shown that these properties are sensitive to deuteration. , The vibrational states of protonated and deuterated molecules are significantly different as they depend on the mass of their nuclei . Due to its larger mass, the vibrational amplitude for deuterium is smaller than that for its protonated analogues, resulting in lower molar volumes and bond polarizability.…”

Section: Resultsmentioning

confidence: 99%

Biosynthesis and Characterization of Deuterated Polyhydroxyoctanoate

et al. 2006

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The synthesis of a polyhydroxyalkanoate with medium chain length alkyl substituents by Pseudomonas oleovoranswas investigated using protonated and deuterated forms of octanoic acid in a minimal salts medium. Cultivation with deuterated octanoic acid resulted in a reduced rate of polymer accumulation compared to that with its protonated counterpart (107 and 207 mg of polymer L(-1) of medium h(-1) of cultivation, respectively). Nuclear magnetic resonance and gas chromatography coupled mass spectrometry of the derivatized polymer was used to establish the extent and distribution of deuterium in the biopolymer. A partially deuterated heteropolymer with 3-hydroxyoctanoic acid as the main constituent was produced. Deuteration is an important tool for contrast variation studies using neutron scattering, but predicates that the deuterated polymer is otherwise comparable in its physiochemical and material properties to its protonated counterpart. In studies reported here, the deuterated biopolymer exhibited an additional diffraction maximum at 7.55 A and slight differences in its melting point (60 and 55 degrees C) and glass transition temperature (-39 and -36 degrees C) when compared to its protonated equivalent. While significant differences between the protonated and deuterated biopolymers were determined, our results support the use of this deuterated polyhydroxyalkanoate in its application in investigations using analytical neutron scattering techniques.

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Section: Resultsmentioning

confidence: 99%

Biosynthesis and Characterization of Deuterated Polyhydroxyoctanoate

et al. 2006

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“…Like small molecules, deuterated polymers are retained less than their hydrogenous counterparts in RPLC separation. Kayillo et al reported on the deuterium isotope effect in the RPLC retention of polystyrene (PS) oligomer. , They found the same trend as that observed for polybutadiene: the deuterated PS was retained less. In this study, we examined the retention of deuterated PS (d-PS) relative to hydrogenous PS (h-PS) in normal phase (NP) LC as well as in RPLC.…”

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confidence: 63%

Isotopic Effect in the Separation of Polystyrene by Normal Phase and Reversed Phase Liquid Chromatography

2010

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The retention behavior of deuterated polystyrene (d-PS) and normal hydrogenous polystyrene (h-PS) was investigated in normal phase (NP) and reversed phase (RP) liquid chromatography (LC). It was found that d-PS was retained slightly longer than h-PS in NPLC (bare silica column and tetrahydrofuran (THF)/n-hexane mixed mobile phase) while in RPLC (C18-bonded silica column and THF/methanol mixed mobile phase) h-PS was retained longer than d-PS. The retention behaviors are interpreted in terms of the thermodynamic variables associated with LC separations. The different retention behavior of deuterated polymers from that of hydrogenous polymers could allow separation of partially deuterated polymers according to the deuterium content, such as for copolymers in LC characterization.

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“…Perny et al reported a discernible isotope effect in the temperature gradient interaction chromatography (TGIC) retention of polybutadiene . Kayillo et al reported on the deuterium isotope effect in the reversed phase liquid chromatography (RPLC) retention of styrene oligomer and also noticed a significant deuteration effect. , Like small molecules, the retention times for deuterated polymers are shorter than their protiated counterparts under most chromatographic conditions. The retention behavior of D-PS and H-PS was later investigated in normal phase (NP) and RPLC by Kim and co-workers .…”

Section: Main Applications Of Deuterationmentioning

confidence: 99%

Deuteration and Polymers: Rich History with Great Potential

Jakowski

et al. 2021

Macromolecules

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Deuterium, a stable hydrogen isotope, has been playing important roles in many scientific areas, including polymer science. The developments of deuteration science and polymer science have been interwoven for the past 60 years. The unique characteristics of the scattering lengths for hydrogen isotopes (protium and deuterium) result in the dramatic differences of scattering length densities for protiated and deuterated compounds omnipresent in polymers, rendering neutron scattering a powerful tool for the investigation of polymeric structures and dynamics that are inaccessible to other tools. While the role of deuteration in neutron scattering of polymeric materials can hardly be overstated, it has also enabled the addressing of many questions using other approaches, such as NMR and vibrational spectra. In this Perspective, we provide a brief account of deuterium in the synthesis, properties, and application of various polymers. We also offer an outlook of the potentials in this ever-evolving and exciting area.

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Thermodynamic Differences Between Deuterated and Protonated Polystyrenes Evaluated Using Reversed Phase Liquid Chromatography

Cited by 11 publications

References 15 publications

Biosynthesis and Characterization of Deuterated Polyhydroxyoctanoate

Biosynthesis and Characterization of Deuterated Polyhydroxyoctanoate

Isotopic Effect in the Separation of Polystyrene by Normal Phase and Reversed Phase Liquid Chromatography

Deuteration and Polymers: Rich History with Great Potential

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