@article{VacogneSchlaad2017,
  author    = {Vacogne, Charlotte D. and Schlaad, Helmut},
  title     = {Controlled ring-opening polymerization of alpha-amino acid N-carboxyanhydrides in the presence of tertiary amines},
  series = {Polymer : the international journal for the science and technology of polymers},
  volume    = {124},
  journal   = {Polymer : the international journal for the science and technology of polymers},
  publisher = {Elsevier},
  address   = {Oxford},
  issn      = {0032-3861},
  doi       = {10.1016/j.polymer.2017.07.062},
  pages     = {203 -- 209},
  year      = {2017},
  abstract  = {The mechanism of the primary ammonium/tertiary amine-mediated ring-opening polymerization of gamma-benzyl-L-glutamate N-carboxyanhydride (BLG-NCA) was investigated. Kinetic analyses revealed that the normal amine mechanism (NAM) together with a dormant-active chain end equilibrium were responsible for the controlled nature of this polymerization pathway, but that the polymerization also proceeded via the activated monomer mechanism (AMM). Mixtures of primary amines (1 equiv) and tertiary amines (0-1.5 equiv) were therefore tested to confirm the co-existence of the NAM and AMM and determine the limits for a controlled polymerization. For tertiary amine molar fractions smaller than 0.8 equiv, the reaction times were greatly reduced (compared to primary amine-initiated polymerization) without compromising the control of the reaction. Hence, the polymerization of NCA can proceed in a controlled manner even when the AMM contributes to the overall chain growth mechanism. (C) 2017 Elsevier Ltd. All rights reserved.},
  language  = {en}
}
@article{LippoldEidnerKumkeetal.2017,
  author    = {Lippold, Holger and Eidner, Sascha and Kumke, Michael Uwe and Lippmann-Pipke, Johanna},
  title     = {Dynamics of metal-humate complexation equilibria as revealed by isotope exchange studies - a matter of concentration and time},
  series = {Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society},
  volume    = {197},
  journal   = {Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society},
  publisher = {Elsevier},
  address   = {Oxford},
  issn      = {0016-7037},
  doi       = {10.1016/j.gca.2016.10.019},
  pages     = {62 -- 70},
  year      = {2017},
  abstract  = {Complexation with dissolved humic matter can be crucial in controlling the mobility of toxic or radioactive contaminant metals. For speciation and transport modelling, a dynamic equilibrium process is commonly assumed, where association and dissociation run permanently. This is, however, questionable in view of reported observations of a growing resistance to dissociation over time. In this study, the isotope exchange principle was employed to gain direct insight into the dynamics of the complexation equilibrium, including kinetic inertisation phenomena. Terbium(III), an analogue of trivalent actinides, was used as a representative of higher-valent metals. Isotherms of binding to (flocculated) humic acid, determined by means of Tb-160 as a radiotracer, were found to be identical regardless of whether the radioisotope was introduced together with the bulk of stable Tb-159 or subsequently after pre-equilibration for up to 3 months. Consequently, there is a permanent exchange of free and humic-bound Tb since all available binding sites are occupied in the plateau region of the isotherm. The existence of a dynamic equilibrium was thus evidenced. There was no indication of an inertisation under these experimental conditions. If the small amount of Tb-160 was introduced prior to saturation with Tb-159, the expected partial desorption of Tb-160 occurred at much lower rates than observed for the equilibration process in the reverse procedure. In addition, the rates decreased with time of pre-equilibration. Inertisation phenomena are thus confined to the stronger sites of humic molecules (occupied at low metal concentrations). Analysing the time-dependent course of isotope exchange according to first-order kinetics indicated that up to 3 years are needed to attain equilibrium. Since, however, metal-humic interaction remains reversible, exchange of metals between humic carriers and mineral surfaces cannot be neglected on the long time scale to be considered in predictive transport models.},
  language  = {en}
}