Stable associates of polyether oligomers with chlorine anion as revealed by the data of electrospray mass spectrometry and molecular dynamics

Zobnina, V. G.; Kosevich, M. V.; Chagovets, Vitaliy; Boryak, Oleg A.; Kulik, A. N.; Gömöry, Ágnes

doi:10.1134/s1061934811130107

Cited by 5 publications

(3 citation statements)

References 23 publications

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“…The above features, combined with quenching of the non-hydrogen-bonded water modes associated the Cl – -terminated surface, suggest a structural bias with CH 2 groups facing the halide-covered metal, while the ethereal O forms hydrogen bonds with the adjacent solvent. Further support for this interpretation is provided by an electrospray mass spectrometry study that indicates an association between Cl – and short-chain polyethers . Accompanying molecular dynamics simulations suggest that the halide is coordinated with −CH 2 – groups of the polymer to form quasi-cyclic structures, analogous to crown ether cationic complexes but with the polarity inverted.…”

Section: Resultsmentioning

confidence: 94%

“…Further support for this interpretation is provided by an electrospray mass spectrometry study that indicates an association between Cl − and short-chain polyethers. 95 Accompanying molecular dynamics simulations suggest that the halide is coordinated with −CH 2 − groups of the polymer to form quasi-cyclic structures, analogous to crown ether cationic complexes but with the polarity inverted.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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SEIRAS Study of Chloride-Mediated Polyether Adsorption on Cu

et al. 2018

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Surface-enhanced infrared absorption spectroscopy is used to examine the co-adsorption of a selection of polyethers with Cl– under conditions relevant to superconformal Cu electrodeposition in CuSO4–H2SO4 electrolytes. In 0.1 mol/L H2SO4, a potential-dependent mixed SO4 2––H3O+/H2O layer forms on weakly textured (111) Cu thin-film surfaces. With the addition of 1 mmol/L NaCl, the SO4 2––H3O+/H2O adlayer is displaced and rapidly replaced by an ordered halide layer that disrupts the adjacent solvent network, leading to an increase in non-hydrogen-bonded water that makes the interface more hydrophobic. The altered wetting behavior facilitates co-adsorption of polyethers, such as poly(ethylene glycols), polyoxamers, or polyoxamines. Interfacial water is displaced by co-adsorption of the hydrophobic polymer segments on the Cl–-terminated surface, while the hydrophilic ether oxygens are available for hydrogen bond formation with the solvent. The combined polyether–Cl– layer serves as an effective suppressor of the Cu electrodeposition reaction by limiting access of Cuaq 2+ to the underlying metal surface. This insight differs from previous work which suggested that polymer adsorption is mediated by Cu+–ether binding.

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Section: Resultsmentioning

confidence: 94%

Section: ■ Results and Discussionmentioning

confidence: 99%

SEIRAS Study of Chloride-Mediated Polyether Adsorption on Cu

et al. 2018

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show abstract

“…67,68 Although each of these ionization systems has its individual advantages and drawbacks, metal ions have been their main support in the analysis of various polymers by the formation of [M + anion] nÀ and [M + cation] n+ adducts, which led to the improvement of mass spectrometry performance for their analyses. [69][70][71][72][73][74][75][76][77][78][79] It was found that the type and the addition amount of metal salts have pronounced inuences.…”

Section: Metal Salt-assisted Different Ionization Systemsmentioning

confidence: 99%