TY - THES A1 - Steeples, Elliot T1 - Amino acid-derived imidazolium salts: platform molecules for N-Heterocyclic carbene metal complexes and organosilica materials T1 - Imidazolium-Salze aus Aminosäure: Bausteine für N-Heterozyklische-Carben Metallkomplexe und Organosilicamaterialien N2 - In the interest of producing functional catalysts from sustainable building-blocks, 1, 3-dicarboxylate imidazolium salts derived from amino acids were successfully modified to be suitable as N-Heterocyclic carbene (NHC) ligands within metal complexes. Complexes of Ag(I), Pd(II), and Ir(I) were successfully produced using known procedures using ligands derived from glycine, alanine, β-alanine and phenylalanine. The complexes were characterized in solid state using X-Ray crystallography, which allowed for the steric and electronic comparison of these ligands to well-known NHC ligands within analogous metal complexes. The palladium complexes were tested as catalysts for aqueous-phase Suzuki-Miyaura cross-coupling. Water-solubility could be induced via ester hydrolysis of the N-bound groups in the presence of base. The mono-NHC–Pd complexes were seen to be highly active in the coupling of aryl bromides with phenylboronic acid; the active catalyst of which was determined to be mostly Pd(0) nanoparticles. Kinetic studies determined that reaction proceeds quickly in the coupling of bromoacetophenone, for both pre-hydrolyzed and in-situ hydrolysis catalyst dissolution. The catalyst could also be recycled for an extra run by simply re-using the aqueous layer. The imidazolium salts were also used to produce organosilica hybrid materials. This was attempted via two methods: by post-grafting onto a commercial organosilica, and co-condensation of the corresponding organosilane. The co-condensation technique harbours potential for the production of solid-support catalysts. N2 - Um Katalysatoren aus nachhaltigen Chemikalien herzustellen, wurden 1,3-Dicarbonsäure-Imidazolium-Salze, welche aus Aminosäuren synthetisiert wurden als N-heterozyklische-Carben-Liganden (NHC) in Metallkomplexen modifiziert. Liganden aus Glycin, Alanin, β-Alanin und Phenylalanin wurden wiederum genutzt, um Metallkomplexe aus Silber(I), Palladium(II) und Iridium(I) darzustellen. Alle Komplexverbindungen wurden mit Röntgenkristallographie charakterisiert. Die Palladiumkomplexe wurden als Katalysatoren in der Suzuki-Miyaura Reaktion eingesetzt. Durch zusätzliche Hydrolyse der Ester-Gruppen konnte eine gute Wasserlöslichkeit erreicht werden. Die hohe Aktivität der Mono-NHC–Palladium-Komplexe konnte bei der Kupplung von Arylbromiden mit Phenylboronsäuren aufgezeigt werden. Die aktive Spezies wurde hauptsächlich Pd(0) Nanopartikeln zugeschrieben. Nach erfolgreichem Recycling konnte der Katalysator noch einmal wiederverwendet werden. Die Imidazolium-Salze wurden ebenfalls herangezogen, um Organosilicamaterialien zu synthetisieren. Die Herstellung wurde durch zwei Methoden erreicht. Zum einen durch nachträgliches Aufbringen auf kommerzielle Siliziummaterialien, sowie durch Co-Kondensation auf das entsprechende Organosilan. Diese Co-Kondensation birgt Potential zur Herstellung von festen Trägerkatalysatoren. KW - synthesis KW - Synthese KW - sustainable chemistry KW - nachhaltige Chemie KW - organometallics KW - Metallorganischen KW - water KW - Wasser Y1 - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-101861 ER - TY - GEN A1 - Steeples, Elliot A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Esposito, Davide T1 - Amino acid-derived N-heterocyclic carbene palladium complexes for aqueous phase Suzuki–Miyaura couplings N2 - In this work, three ligands produced from amino acids were synthesized and used to produce five bis- and PEPPSI-type palladium–NHC complexes using a novel synthesis route from sustainable starting materials. Three of these complexes were used as precatalysts in the aqueous-phase Suzuki–Miyaura coupling of various substrates displaying high activity. TEM and mercury poisoning experiments provide evidence for Pd-nanoparticle formation stabilized in water. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 319 KW - transition-metal-complexes KW - imidazolium salts KW - green chemistry KW - water KW - catalysts KW - nhc KW - hydrogenation KW - isomerization KW - nanoparticles KW - precatalysts Y1 - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-394488 SP - 4922 EP - 4930 ER - TY - GEN A1 - Block, Inga A1 - Günter, Christina A1 - Rodrigues, Alysson Duarte A1 - Paasch, Silvia A1 - Hesemann, Peter A1 - Taubert, Andreas T1 - Carbon Adsorbents from Spent Coffee for Removal of Methylene Blue and Methyl Orange from Water T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Activated carbons (ACs) were prepared from dried spent coffee (SCD), a biological waste product, to produce adsorbents for methylene blue (MB) and methyl orange (MO) from aqueous solution. Pre-pyrolysis activation of SCD was achieved via treatment of the SCD with aqueous sodium hydroxide solutions at 90 °C. Pyrolysis of the pretreated SCD at 500 °C for 1 h produced powders with typical characteristics of AC suitable and effective for dye adsorption. As an alternative to the rather harsh base treatment, calcium carbonate powder, a very common and abundant resource, was also studied as an activator. Mixtures of SCD and CaCO3 (1:1 w/w) yielded effective ACs for MO and MB removal upon pyrolysis needing only small amounts of AC to clear the solutions. A selectivity of the adsorption process toward anionic (MO) or cationic (MB) dyes was not observed. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1155 KW - water KW - spent coffee KW - dye adsorption KW - methylene blue KW - methyl orange KW - calcium carbonate KW - activated carbon KW - water treatment KW - dye removal Y1 - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-521653 SN - 1866-8372 IS - 14 ER - TY - JOUR A1 - Block, Inga A1 - Günter, Christina A1 - Rodrigues, Alysson Duarte A1 - Paasch, Silvia A1 - Hesemann, Peter A1 - Taubert, Andreas T1 - Carbon Adsorbents from Spent Coffee for Removal of Methylene Blue and Methyl Orange from Water JF - Materials N2 - Activated carbons (ACs) were prepared from dried spent coffee (SCD), a biological waste product, to produce adsorbents for methylene blue (MB) and methyl orange (MO) from aqueous solution. Pre-pyrolysis activation of SCD was achieved via treatment of the SCD with aqueous sodium hydroxide solutions at 90 °C. Pyrolysis of the pretreated SCD at 500 °C for 1 h produced powders with typical characteristics of AC suitable and effective for dye adsorption. As an alternative to the rather harsh base treatment, calcium carbonate powder, a very common and abundant resource, was also studied as an activator. Mixtures of SCD and CaCO3 (1:1 w/w) yielded effective ACs for MO and MB removal upon pyrolysis needing only small amounts of AC to clear the solutions. A selectivity of the adsorption process toward anionic (MO) or cationic (MB) dyes was not observed. KW - water KW - spent coffee KW - dye adsorption KW - methylene blue KW - methyl orange KW - calcium carbonate KW - activated carbon KW - water treatment KW - dye removal Y1 - 2021 U6 - https://doi.org/10.3390/ma14143996 SN - 1996-1944 VL - 14 IS - 14 PB - MDPI CY - Basel ER - TY - JOUR A1 - Pietzsch, Annette A1 - Niskanen, Johannes A1 - Vaz da Cruz, Vinicius A1 - Büchner, Robby A1 - Eckert, Sebastian A1 - Fondell, Mattis A1 - Jay, Raphael Martin A1 - Lu, Xingye A1 - McNally, Daniel A1 - Schmitt, Thorsten A1 - Föhlisch, Alexander T1 - Cuts through the manifold of molecular H2O potential energy surfaces in liquid water at ambient conditions JF - Proceedings of the National Academy of Sciences of the United States of America N2 - The fluctuating hydrogen bridge bonded network of liquid water at ambient conditions entails a varied ensemble of the underlying constituting H2O molecular moieties. This is mirrored in a manifold of the H2O molecular potentials. Subnatural line width resonant inelastic X-ray scattering allowed us to quantify the manifold of molecular potential energy surfaces along the H2O symmetric normal mode and the local asymmetric O-H bond coordinate up to 1 and 1.5 angstrom, respectively. The comparison of the single H2O molecular potentials and spectroscopic signatures with the ambient conditions liquid phase H2O molecular potentials is done on various levels. In the gas phase, first principles, Morse potentials, and stepwise harmonic potential reconstruction have been employed and benchmarked. In the liquid phase the determination of the potential energy manifold along the local asymmetric O-H bond coordinate from resonant inelastic X-ray scattering via the bound state oxygen ls to 4a(1) resonance is treated within these frameworks. The potential energy surface manifold along the symmetric stretch from resonant inelastic X-ray scattering via the oxygen 1 s to 2b(2) resonance is based on stepwise harmonic reconstruction. We find in liquid water at ambient conditions H2O molecular potentials ranging from the weak interaction limit to strongly distorted potentials which are put into perspective to established parameters, i.e., intermolecular O-H, H-H, and O-O correlation lengths from neutron scattering. KW - water KW - potential ene rgy surface KW - RIXS Y1 - 2022 U6 - https://doi.org/10.1073/pnas.2118101119 SN - 1091-6490 VL - 119 IS - 28 PB - National Acad. of Sciences CY - Washington, DC ER - TY - BOOK A1 - Bahouth, Chadi T1 - Der Konflikt um Wasser in Israel und Palästina BT - Konfliktstoff trotz Friedensquells – die vergebene Chance einer nachhaltigen und gerechten Lösung N2 - Wasser ist rar im Nahen Osten. Die knappe Ressource wird immer häufiger zum Gegenstand politischer Konflikte in der ohnehin instabilen Region. Der Konflikt zwischen Israel und Palästina gilt als eines der gravierendsten Beispiele für diese Entwicklung: Wasser als umkämpftes Menschenrecht, Wasser als strategisches Mittel der Besetzungspolitik und Wasser als Gegenstand langwieriger Verhandlungen. Der Wasserkonflikt ist so alt wie der Nahostkonflikt selbst. Sogar mit Beginn des Oslo-Prozesses 1993 hat es weder einen grundlegenden Wandel im Wasserkonflikt, noch in der Aussicht auf Veränderung der Wasserknappheit gegeben. Immerhin können die Palästinenser in der momentanen Situation ihre eigene Wasserversorgung dort selbst verwalten, wo es ihnen laut der Übereinkünfte erlaubt ist. Jedoch ist diese Freiheit eine sehr begrenzte und eine endgültige Klärung dieses Streitpunktes wurde, zusammen mit Jerusalem, den Flüchtlingen, den Siedlungen und der Staatsbildung auf die Endstatusverhandlungen verschoben. Chadi Bahouth, Absolvent des Otto-Suhr-Instituts der Freien Universität Berlin, untersucht in seiner Doktorarbeit die Gründe für die ungelöste Wasserfrage. Er analysiert die historische und rechtliche Chronologie des Konfliktes, bietet Lösungsvorschläge für die Wasserkrise an und erklärt, warum die Region dennoch für Generationen nicht zur Ruhe kommen wird. N2 - Water is rare at the Middle East and becomes more and more a matter of political conflicts in the already instable region. The conflict between Israel and Palestine is a serious noticeable example of this development: water as a hard-fought human right, water as a strategic mean of the politics of occupation and water as a matter of protracted negotiations. The battles for water are as old as the Middle East conflict itself. Even with the beginning of the Oslo-Process in 1993 there has not been a fundamental change containing the water conflict. After all, the Palestinians in the actual situation can administrate their own water supply, where they are allowed to concern the accords. But this freedom is strictly confined and a clarification of the controversial subject, together with Jerusalem, the refugees, the settlements and the building of the state were adjusted to the negotiations of the permanent status. Chadi Bahouth, alumnus of the Otto-Suhr-Institute (Free University Berlin), inspects in his doctoral thesis the reasons for the unsolved water politics. He analyses the historical and judicial chronology of the conflict, offers proposals for solution and explains, why the region will not be steadied for generations, nevertheless. T3 - Horizonte 21 : Umwelt · Energie · Sicherheit - 2 KW - Nahostkonflikt KW - Israel KW - Palästina KW - Wasser KW - Friedensprozess KW - Middle-East Conflict KW - Israel KW - Palestine KW - water KW - peace process Y1 - 2010 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-40747 SN - 978-3-86956-035-9 PB - Universitätsverlag Potsdam CY - Potsdam ER - TY - JOUR A1 - Lehr, Christian A1 - Lischeid, Gunnar T1 - Efficient screening of groundwater head monitoring data for anthropogenic effects and measurement errors JF - Hydrology and Earth System Sciences N2 - Groundwater levels are monitored by environmental agencies to support the sustainable use of groundwater resources. For this purpose continuous and spatially comprehensive monitoring in high spatial and temporal resolution is desired. This leads to large datasets that have to be checked for quality and analysed to distinguish local anthropogenic influences from natural variability of the groundwater level dynamics at each well. Both technical problems with the measurements as well as local anthropogenic influences can lead to local anomalies in the hydrographs. We suggest a fast and efficient screening method for the identification of well-specific peculiarities in hydrographs of groundwater head monitoring networks. The only information required is a set of time series of groundwater heads all measured at the same instants of time. For each well of the monitoring network a reference hydrograph is calculated, describing expected "normal" behaviour at the respective well as is typical for the monitored region. The reference hydrograph is calculated by multiple linear regression of the observed hydrograph with the "stable" principal components (PCs) of a principal component analysis of all groundwater head series of the network as predictor variables. The stable PCs are those PCs which were found in a random subsampling procedure to be rather insensitive to the specific selection of the analysed observation wells, i.e. complete series, and to the specific selection of measurement dates. Hence they can be considered to be representative for the monitored region in the respective period. The residuals of the reference hydrograph describe local deviations from the normal behaviour. Peculiarities in the residuals allow the data to be checked for measurement errors and the wells with a possible anthropogenic influence to be identified. The approach was tested with 141 groundwater head time series from the state authority groundwater monitoring network in northeastern Germany covering the period from 1993 to 2013 at an approximately weekly frequency of measurement. KW - streamflow variability KW - principal components KW - united states KW - time-seriesa KW - water KW - network KW - nonstationarity KW - fluctuations KW - rotation Y1 - 2020 U6 - https://doi.org/10.5194/hess-24-501-2020 SN - 1027-5606 SN - 1607-7938 VL - 24 IS - 2 SP - 501 EP - 513 PB - Copernicus CY - Göttingen ER - TY - GEN A1 - Lehr, Christian A1 - Lischeid, Gunnar T1 - Efficient screening of groundwater head monitoring data for anthropogenic effects and measurement errors T2 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Groundwater levels are monitored by environmental agencies to support the sustainable use of groundwater resources. For this purpose continuous and spatially comprehensive monitoring in high spatial and temporal resolution is desired. This leads to large datasets that have to be checked for quality and analysed to distinguish local anthropogenic influences from natural variability of the groundwater level dynamics at each well. Both technical problems with the measurements as well as local anthropogenic influences can lead to local anomalies in the hydrographs. We suggest a fast and efficient screening method for the identification of well-specific peculiarities in hydrographs of groundwater head monitoring networks. The only information required is a set of time series of groundwater heads all measured at the same instants of time. For each well of the monitoring network a reference hydrograph is calculated, describing expected “normal” behaviour at the respective well as is typical for the monitored region. The reference hydrograph is calculated by multiple linear regression of the observed hydrograph with the “stable” principal components (PCs) of a principal component analysis of all groundwater head series of the network as predictor variables. The stable PCs are those PCs which were found in a random subsampling procedure to be rather insensitive to the specific selection of the analysed observation wells, i.e. complete series, and to the specific selection of measurement dates. Hence they can be considered to be representative for the monitored region in the respective period. The residuals of the reference hydrograph describe local deviations from the normal behaviour. Peculiarities in the residuals allow the data to be checked for measurement errors and the wells with a possible anthropogenic influence to be identified. The approach was tested with 141 groundwater head time series from the state authority groundwater monitoring network in northeastern Germany covering the period from 1993 to 2013 at an approximately weekly frequency of measurement. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1424 KW - streamflow variability KW - principal components KW - united states KW - time-series KW - water KW - network KW - nonstationarity KW - fluctuations KW - rotation Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-511992 SN - 1866-8372 IS - 2 ER - TY - THES A1 - Sinn, Cornelia G. T1 - Ion binding to polymers and lipid membranes in aqueous solutions : Ionenbindung an Polymeren und Lipidmembranen in wässrigen Lösungen N2 - Ziel dieser Arbeit ist die Untersuchung der Ionenbindung an Polymeren und Lipidmembranen in wässrigen Lösungen. Im ersten Teil dieser Arbeit wurde der Einfluss verschiedener anorganischer Salze und Polyelektrolyte auf die Struktur des Wassers mit Hilfe Isothermer Mikrotitrationskalorimetrie (ITC) erforscht. Die Verdünnungswärme der Salze wurde als Maß für die Fähigkeit der Ionen, die geordnete Struktur des Wassers zu stabilisieren oder zu zerstören, verwendet. Die Verdünnungswärmen konnten auf Hofmeister Effekte zurückgeführt werden. Im Anschluss daran wurde die Bindung von Ca2+ an Natrium- Poly(acrylsäure) (NaPAA) untersucht. Mit Hilfe von ITC und einer Ca2+- selektiven Elektrode wurde die Reaktionsenthalpie und Bindungsisotherme gemessen. Es wurde gezeigt, dass die Binding von Ca2+ - Ionen an NaPAA stark endotherm und daher entropiegetrieben ist. Anschließend wurde die Bindung von Ca2+ an die eindimensionale Polymerkette mit der an ein Lipidvesikel mit denselben funktioniellen Gruppen verglichen. Es wurde beobachtet, dass die Ionenbindung –wie auch im Fall des Polymers- endotherm ist. Ein Vergleich der Ca2+- Bindung an die Lipidmembran mit der an das Polymer konnte zeigen, dass das Ion schwächer an die Membran bindet. Im Zusammenhang mit diesen Experimenten wurde auch beobachtet, dass Ca2+ nicht nur an geladene, sondern auch an zwitterionische Lipidvesikel bindet. Schließlich wurde die Wechselwirkung zweier Salze, KCl and NaCl, mit einem neutralen Polymergel, PNIPAAM, und dem geladenen Polymer PAA untersucht. Mit Hilfe von Kalorimetrie und einer kaliumselektiven Elektrode wurde beobachtet, dass die Ionen mit beiden Polymeren wechselwirken, unabhängig davon, ob diese Ladungen tragen, oder nicht. N2 - The goal of this work was to study the binding of ions to polymers and lipid bilayer membranes in aqueous solutions. In the first part of this work, the influence of various inorganic salts and polyelectrolytes on the structure of water was studied using Isothermal Titration Calorimetry (ITC). The heat of dilution of the salts was used as a scale of water structure making and breaking of the ions. The heats of dilution could be attributed to the Hofmeister Series. Following this, the binding of Ca2+ to poly(sodium acrylate) (NaPAA) was studied. ITC and a Ca2+ Ion Selective Electrode were used to measure the reaction enthalpy and binding isotherm. Binding of Ca2+ ions to PAA, was found to be highly endothermic and therefore solely driven by entropy. We then compared the binding of ions to the one-dimensional PAA polymer chain to the binding to lipid vesicles with the same functional groups. As for the polymer, Ca2+ binding was found to be endothermic. Binding of calcium to the lipid bilayer was found to be weaker than to the polymer. In the context of these experiments, it was shown that Ca2+ not only binds to charged but also to zwitterionic lipid vesicles. Finally, we studied the interaction of two salts, KCl and NaCl, to a neutral polymer gel, PNIPAAM, and to the ionic polymer PAA. Combining calorimetry and a potassium selective electrode we observed that the ions interact with both polymers, whether containing charges or not. T2 - Ion binding to polymers and lipid membranes in aqueous solutions : Ionenbindung an Polymeren und Lipidmembranen in wässrigen Lösungen KW - Ionen KW - Bindung KW - Salz KW - Wasser KW - Struktur KW - Hofmeister KW - Polyelektrolyt KW - Isotherme Titrationskalorimetrie KW - ionenselektive Elektrode KW - Vesikel KW - Calcium KW - Micr KW - ions KW - binding KW - salt KW - water KW - structure KW - Hofmeister KW - polyelectrolyte KW - Isothermal Titration Calorimetry KW - ion selective electrode KW - vesicle KW - calcium KW - micro Y1 - 2004 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-0001778 ER - TY - JOUR A1 - Guzman, Diego A. A1 - Samprogna Mohor, Guilherme A1 - Mendiondo, Eduardo Mario T1 - Multi-year index-based insurance for adapting Water Utility Companies to hydrological drought BT - case study of a water supply system of the Sao Paulo metropolitan region, Brazil JF - Water N2 - The sustainability of water utility companies is threatened by non-stationary drivers, such as climate and anthropogenic changes. To cope with potential economic losses, instruments such as insurance are useful for planning scenarios and mitigating impacts, but data limitations and risk uncertainties affect premium estimation and, consequently, business sustainability. This research estimated the possible economic impacts of business interruption to the Sao Paulo Water Utility Company derived from hydrological drought and how this could be mitigated with an insurance scheme. Multi-year insurance (MYI) was proposed through a set of "change" drivers: the climate driver, through forcing the water evaluation and planning system (WEAP) hydrological tool; the anthropogenic driver, through water demand projections; and the economic driver, associated with recent water price policies adopted by the utility company during water scarcity periods. In our study case, the evaluated indices showed that MYI contracts that cover only longer droughts, regardless of the magnitude, offer better financial performance than contracts that cover all events (in terms of drought duration). Moreover, through MYI contracts, we demonstrate solvency for the insurance fund in the long term and an annual average actuarially fair premium close to the total expected revenue reduction. KW - multi-year insurance KW - climate change KW - hydrological drought KW - water KW - security and economy Y1 - 2020 U6 - https://doi.org/10.3390/w12112954 SN - 2073-4441 VL - 12 IS - 11 PB - MDPI CY - Basel ER -