TY - JOUR A1 - Yalcinkaya, Hacer A1 - Bressel, Katharina A1 - Lindner, Peter A1 - Gradzielski, Michael T1 - Controlled formation of vesicles with added styrene and their fixation by polymerization JF - Journal of colloid and interface science N2 - Hypothesis: An effective way for fixating vesicle structures is the insertion of monomers and cross-linking agents into their bilayer, and their subsequent polymerization can lead to the formation of polymeric nanocapsules. Particularly attractive here are vesicle systems that form spontaneously well-defined small vesicles, as obtaining such small nanocapsules with sizes below 100 nm is still challenging. Experiments: A spontaneously forming well-defined vesicle system composed of the surfactants TDMAO (tetradecyldimethylamine oxide), Pluronic L35, and LiPFOS (lithium perfluorooctylsulfonate) mixture was used as template for fixation by polymerization. Therefore, styrene monomer was incorporated into the vesicle bilayer and ultimately these structures were fixated by UV induced radical polymerization. Structural alteration of the vesicles upon loading with monomer and the cross-linker as well as the effect of subsequent polymerization in the membrane were investigated in detail by turbidity measurements, dynamic and static light scattering, (DLS, SLS), and small angle neutron scattering (SANS). Findings: The analysis showed the changes on vesicle structures due to the monomer loading, and that these structures can become permanently fixed by the polymerization process. The potential of this approach to produce well-defined nanocapsules starting from a self-assembled system and following polymerization is critically evaluated. (C) 2018 Elsevier Inc. All rights reserved. KW - Template reaction KW - Zwitterionic surfactant KW - Anionic surfactant KW - Styrene KW - Vesicle KW - Small angle neutron scattering KW - Polymerization Y1 - 2018 U6 - https://doi.org/10.1016/j.jcis.2018.07.097 SN - 0021-9797 SN - 1095-7103 VL - 531 SP - 672 EP - 680 PB - Elsevier CY - San Diego ER - TY - JOUR A1 - Scholz, Robert A1 - Lindner, Steven A1 - Loncaric, Ivor A1 - Tremblay, Jean Christophe A1 - Juaristi, J. A1 - Alducin, Maite A1 - Saalfrank, Peter T1 - Vibrational response and motion of carbon monoxide on Cu(100) driven by femtosecond laser pulses: Molecular dynamics with electronic friction JF - Physical review : B, Condensed matter and materials physics N2 - Carbon monoxide on copper surfaces continues to be a fascinating, rich microlab for many questions evolving in surface science. Recently, hot-electron mediated, femtosecond-laser pulse induced dynamics of CO molecules on Cu(100) were the focus of experiments [Inoue et al., Phys. Rev. Lett. 117, 186101 (2016)] and theory [Novko et al., Phys. Rev. Lett. 122, 016806 (2019)], unraveling details of the vibrational nonequilibrium dynamics on ultrashort (subpicoseconds) timescales. In the present work, full-dimensional time-resolved hot-electron driven dynamics are studied by molecular dynamics with electronic friction (MDEF). Dissipation is included by a friction term in a Langevin equation which describes the coupling of molecular degrees of freedom to electron-hole pairs in the copper surface, calculated from gradient-corrected density functional theory (DFT) via a local density friction approximation (LDFA). Relaxation due to surface phonons is included by a generalized Langevin oscillator model. The hot-electron induced excitation is described via a time-dependent electronic temperature, the latter derived from an improved two-temperature model. Our parameter-free simulations on a precomputed potential energy surface allow for excellent statistics, and the observed trends are confirmed by on-the-fly ab initio molecular dynamics with electronic friction (AIMDEF) calculations. By computing time-resolved frequency maps for selected molecular vibrations, instantaneous frequencies, probability distributions, and correlation functions, we gain microscopic insight into hot-electron driven dynamics and we can relate the time evolution of vibrational internal CO stretch-mode frequencies to measured data, notably an observed redshift. Quantitatively, the latter is found to be larger in MDEF than in experiment and possible reasons are discussed for this observation. In our model, in addition we observe the excitation and time evolution of large-amplitude low-frequency modes, lateral CO surface diffusion, and molecular desorption. Effects of surface atom motion and of the laser fluence are also discussed. Y1 - 2019 U6 - https://doi.org/10.1103/PhysRevB.100.245431 SN - 2469-9950 SN - 2469-9969 VL - 100 IS - 24 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Lotze-Campen, Hermann A1 - Verburg, Peter H. A1 - Popp, Alexander A1 - Lindner, Marcus A1 - Verkerk, Pieter J. A1 - Moiseyev, Alexander A1 - Schrammeijer, Elizabeth A1 - Helming, John A1 - Tabeau, Andrzej A1 - Schulp, Catharina J. E. A1 - van der Zanden, Emma H. A1 - Lavalle, Carlo A1 - Batista e Silva, Filipe A1 - Walz, Ariane A1 - Bodirsky, Benjamin Leon T1 - A cross-scale impact assessment of European nature protection policies under contrasting future socio-economic pathways JF - Regional environmental change N2 - Protection of natural or semi-natural ecosystems is an important part of societal strategies for maintaining biodiversity, ecosystem services, and achieving overall sustainable development. The assessment of multiple emerging land use trade-offs is complicated by the fact that land use changes occur and have consequences at local, regional, and even global scale. Outcomes also depend on the underlying socio-economic trends. We apply a coupled, multi-scale modelling system to assess an increase in nature protection areas as a key policy option in the European Union (EU). The main goal of the analysis is to understand the interactions between policy-induced land use changes across different scales and sectors under two contrasting future socio-economic pathways. We demonstrate how complementary insights into land system change can be gained by coupling land use models for agriculture, forestry, and urban areas for Europe, in connection with other world regions. The simulated policy case of nature protection shows how the allocation of a certain share of total available land to newly protected areas, with specific management restrictions imposed, may have a range of impacts on different land-based sectors until the year 2040. Agricultural land in Europe is slightly reduced, which is partly compensated for by higher management intensity. As a consequence of higher costs, total calorie supply per capita is reduced within the EU. While wood harvest is projected to decrease, carbon sequestration rates increase in European forests. At the same time, imports of industrial roundwood from other world regions are expected to increase. Some of the aggregate effects of nature protection have very different implications at the local to regional scale in different parts of Europe. Due to nature protection measures, agricultural production is shifted from more productive land in Europe to on average less productive land in other parts of the world. This increases, at the global level, the allocation of land resources for agriculture, leading to a decrease in tropical forest areas, reduced carbon stocks, and higher greenhouse gas emissions outside of Europe. The integrated modelling framework provides a method to assess the land use effects of a single policy option while accounting for the trade-offs between locations, and between regional, European, and global scales. KW - Land use change KW - Integrated modelling KW - Cross-scale interaction KW - Nature protection KW - Impact assessment Y1 - 2017 U6 - https://doi.org/10.1007/s10113-017-1167-8 SN - 1436-3798 SN - 1436-378X VL - 18 IS - 3 SP - 751 EP - 762 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - Rietze, Clemens A1 - Titov, Evgenii A1 - Lindner, Steven A1 - Saalfrank, Peter T1 - Thermal isomerization of azobenzenes: on the performance of Eyring transition state theory JF - Journal of physics : Condensed matter N2 - The thermal Z -> E (back-) isomerization of azobenzenes is a prototypical reaction occurring in molecular switches. It has been studied for decades, yet its kinetics is not fully understood. In this paper, quantum chemical calculations are performed to model the kinetics of an experimental benchmark system, where a modified azobenzene (AzoBiPyB) is embedded in a metal-organic framework (MOF). The molecule can be switched thermally from cis to trans, under solvent-free conditions. We critically test the validity of Eyring transition state theory for this reaction. As previously found for other azobenzenes (albeit in solution), good agreement between theory and experiment emerges for activation energies and activation free energies, already at a comparatively simple level of theory, B3LYP/6-31G* including dispersion corrections. However, theoretical Arrhenius prefactors and activation entropies are in qualitiative disagreement with experiment. Several factors are discussed that may have an influence on activation entropies, among them dynamical and geometric constraints (imposed by the MOF). For a simpler model-Z -> E isomerization in azobenzene-a systematic test of quantum chemical methods from both density functional theory and wavefunction theory is carried out in the context of Eyring theory. Also, the effect of anharmonicities on activation entropies is discussed for this model system. Our work highlights capabilities and shortcomings of Eyring transition state theory and quantum chemical methods, when applied for the Z -> E (back-) isomerization of azobenzenes under solvent-free conditions. KW - thermal isomerization Y1 - 2017 U6 - https://doi.org/10.1088/1361-648X/aa75bd SN - 0953-8984 SN - 1361-648X VL - 29 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Kramer, Koen A1 - Bouriaud, Laura A1 - Feindt, Peter H. A1 - van Wassenaer, Lan A1 - Glanemann, Nicole A1 - Hanewinkel, Marc A1 - van der Heide, Martijn A1 - Hengeveld, Geerten M. A1 - Hoogstra, Marjanke A1 - Ingram, Verina A1 - Levermann, Anders A1 - Lindner, Marcus A1 - Mátyás, Csaba A1 - Mohren, Frits A1 - Muys, Bart A1 - Nabuurs, Gert-Jan A1 - Palahi, Marc A1 - Polman, Nico A1 - Reyer, Christopher P. O. A1 - Schulze, Ernst-Detlef A1 - Seidl, Rupert A1 - de Vries, Wim A1 - Werners, Saskia E. A1 - Winkel, Georg A1 - Yousefpour, Rasoul T1 - Perspective Roadmap to develop a stress test for forest ecosystem services supply JF - One Earth N2 - Forests play a key role in a bio-based economy by providing renewable materials, mitigating climate change, and accommodating biodiversity. However, forests experience massive increases in stresses in their ecological and socioeconomic environments, threatening forest ecosystem services supply. Alleviating those stresses is hampered by conflicting and disconnected governance arrangements, competing interests and claims, and rapid changes in technology and social demands. Identifying which stresses threaten forest ecosystem services supply and which factors hamper their alleviation requires stakeholders' perceptions. Stakeholder-oriented stress tests for the supply of forest ecosystem services are therefore necessary but are not yet available. This perspective presents a roadmap to develop a stress test tailored to multiple stakeholders' needs and demands across spatial scales. We provide the Cascade and Resilience Rosetta, with accompanying performance- and resilience indicators, as tools to facilitate development of the stress test. The application of the stress test will facilitate the transition toward a bio-based economy in which healthy and diverse forests provide sustainable and resilient ecosystem services. Y1 - 2022 U6 - https://doi.org/10.1016/j.oneear.2021.12.009 SN - 2590-3330 SN - 2590-3322 VL - 5 IS - 1 SP - 25 EP - 34 PB - Elsevier CY - Amsterdam ER -