@article{FudickarLinker2020, author = {Fudickar, Werner and Linker, Torsten}, title = {Structural motives controlling the binding affinity of 9,10-bis(methylpyridinium)anthracenes towards DNA}, series = {Bioorganic \& medicinal chemistry : a Tetrahedron publication for the rapid dissemination of full original research papers and critical reviews on biomolecular chemistry, medicinal chemistry and related disciplines}, volume = {28}, journal = {Bioorganic \& medicinal chemistry : a Tetrahedron publication for the rapid dissemination of full original research papers and critical reviews on biomolecular chemistry, medicinal chemistry and related disciplines}, number = {8}, publisher = {Elsevier}, address = {Oxford}, issn = {0968-0896}, doi = {10.1016/j.bmc.2020.115432}, pages = {7}, year = {2020}, abstract = {In the search of new DNA groove binding agents a series of substituted 9,10-methylpyridiniumanthracenes have been synthesized and their interactions with DNA have been studied by UV/vis absorption, CD and fluorescence spectroscopy. A minor groove binding mode is confirmed by DNA melting studies, strong CD effects, the dependence of the binding affinity on ionic strength, and the differentiation between AT and GC base pairs. No binding occurs to GC sequences. Binding constants to calf thymus DNA (ct-DNA) and poly(dA:dT) in the range between 1 x 10(4) and 3 x 10(5) M-1 have been determined. The binding strength decreases with the size of substituents attached at the anthracene site. Variation of the substitution pattern of the charged groups shows that methyl groups in meta position cause slightly stronger binding than methyl groups in para position. In contrast, with these groups in ortho position, no binding interaction has been observed. The strongest binding is achieved with an expansion of the peripheral heterocycle from pyridine to quinoline. Molecular modeling reveals the pivotal role of the substitution pattern: Anthracenes with para and meta pyridines align along the minor grooves. On the other hand, the ortho derivative adopts no groove-alignment.}, language = {en} } @article{Hermanns2021, author = {Hermanns, Jolanda}, title = {The task navigator following the STRAKNAP concept}, series = {Journal of chemical education / Division of Chemical Education, Inc., American Chemical Society}, volume = {98}, journal = {Journal of chemical education / Division of Chemical Education, Inc., American Chemical Society}, number = {4}, publisher = {American Chemical Society}, address = {Washington}, issn = {0021-9584}, doi = {10.1021/acs.jchemed.0c01162}, pages = {1077 -- 1087}, year = {2021}, abstract = {Educational Scaffolding was first mentioned in 1976 by Wood et al. Several examples for scaffolding in chemistry are also known from the literature. As written scaffolds, stepped supporting tools to support students while solving problems in organic chemistry were developed, applied, and evaluated. Although the students rated the tool as very helpful, a think-aloud study showed that the support given by this scaffold was not sufficient. As a further development of stepped supporting tools, task navigators were therefore developed, applied, and evaluated. This new scaffold gives tips on strategy, knowledge, and application of knowledge after the STRAKNAP concept. The evaluation of this tool shows that the students rated the tool as being very helpful. A think-aloud study showed that the scaffold supports the students while they solve a problem. Because of the stepwise construction of the task navigators and the providing of the knowledge needed for the application, the students can solve parts of the task successfully even if they do not solve all parts correctly; the students can always start from scratch. When students use the tool regularly, their knowledge of organic chemistry increases compared to students who did not use the tool at all. The task navigator is not only a scaffold for the content of the task but also for the development of methodological competences on the field of strategies and applying knowledge.}, language = {en} } @article{KruegerBramborgKellingetal.2021, author = {Kr{\"u}ger, Tobias and Bramborg, Andrea and Kelling, Alexandra and Sperlich, Eric and Linker, Torsten}, title = {Birch Reduction of Arenes as an Easy Entry to γ-Spirolactones}, series = {European journal of organic chemistry}, volume = {2021}, journal = {European journal of organic chemistry}, number = {46}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-193X}, doi = {10.1002/ejoc.202101018}, pages = {6383 -- 6391}, year = {2021}, abstract = {A convenient method for the synthesis of γ-spirolactones in only 2-3 steps is described. Birch reduction of inexpensive and commercially available aromatic carboxylic acids in the presence of ethylene oxide affords hydroxy acids, which undergo direct lactonization during work-up. Suitable precursors are methyl-substituted benzoic acids, naphthoic, and dicarboxylic acids. Subsequent hydrogenation proceeds smoothly with Pd/C as catalyst and saturated γ-spirolactones are isolated in excellent yields and stereoselectivities. Thus, up to 3 new stereogenic centers can be constructed as sole diastereomers from achiral benzoic acids. Furthermore, it is possible to control the degree of saturation with Raney nickel or Wilkinson's catalyst to obtain products with 1 double bond. Overall, more than 30 new γ-spirolactones have been synthesized in analytically pure form.}, language = {en} } @article{KruegerKellingSchildeetal.2016, author = {Kr{\"u}ger, Tobias and Kelling, Alexandra and Schilde, Uwe and Linker, Torsten}, title = {Simple Synthesis of gamma-Spirolactams by Birch Reduction of Benzoic Acids}, series = {European journal of organic chemistry}, journal = {European journal of organic chemistry}, number = {6}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-193X}, doi = {10.1002/ejoc.201601650}, pages = {1074 -- 1077}, year = {2016}, abstract = {A convenient synthesis of gamma-spirolactams in only two steps was developed. Birch reduction of benzoic acids and immediate alkylation with chloroacetonitrile afforded cyclohexadienes in high yields. The products could be isolated by crystallization on a large scale in analytically pure form. Subsequent hydrogenation with platinum(IV) oxide as the catalyst reduced the nitrile functionality and the double bonds in the same step with excellent stereoselectivity. The relative configurations were determined unequivocally by X-ray analyses. Direct cyclization of the intermediary formed amino acids afforded the desired gamma-spirolactams in excellent overall yields. The procedure is characterized by few steps, cheap reagents, and can be performed on a large scale, interesting for industrial processes.}, language = {en} } @phdthesis{Kuhrts, author = {Kuhrts, Lucas}, title = {The effect of Polycations on the Formation of Magnetite Nanoparticles}, address = {Potsdam}, school = {Universit{\"a}t Potsdam}, pages = {VIII, 99}, abstract = {Nanoparticles of magnetite (Fe3O4) are envisioned to find used in diverse applications, ranging from magnetic data storage, inks, ferrofluids as well as in magnetic resonance imaging, drug delivery, and hyperthermia cancer treatment. Their magnetic properties strongly depend on their size and morphology, two properties that can be synthetically controlled. Achieving appropriate control under soft chemical conditions has so far remained a challenging endeavor. One proven way of exerting this desired control has been using a biomimetic approach that emulates the proteome of magnetotactic bacteria by adding poly-L-arginine in the co- precipitation of ferrous and ferric chloride. The objective of the work presented here is to understand the impact of this polycation on the formation mechanism of magnetite and, through rational design, to enhance the control we can exert on magnetite nanoparticle size and morphology. We developed a SAXS setup to temporally and structurally resolve the formation of magnetite in the presence of poly-L-arginine in situ. Using analytical scattering models, we were able to separate the scattering contribution of a low-density 5 nm iron structure from the contribution of the growing nanoparticles. We identified that the low-density iron structure is a metastable precursor to the magnetite particles and that it is electrostatically stabilized by poly-L-arginine. In a process analogous to biomineralization, the presence of the charged macromolecule thus shifts the reaction mechanism from a thermodynamically controlled one to a kinetically controlled one. We identify this shift in reactions mechanism as the cornerstone of the proposed mechanism and as the crucial step in the paradigm of this extraordinary nanoparticle morphology and size control. Based on SAXS data, theoretical considerations suggest that an observed morphological transition between spherical, solid, and sub-structured mesocrystalline magnetite nanoparticles is induced through a pH-driven change in the wettability of the nanoparticle surface. With these results, we further demonstrate that SAXS can be an invaluable tool for investigating nanoparticle formation. We were able to change particle morphology from spherically solid particles to sub-structured mesocrystals merely by changing the precipitation pH. Improving the synthesis sustainability by substituting poly-L-arginine with renewable, polysaccharide-based polycations produced at the metric ton scale, we demonstrated that the ability to alter the reaction mechanism of magnetite can be generically attributed to the presence of polycations. Through meticulous analysis and the understanding of the formation mechanism, we were able to exert precise control over particle size and morphology, by adapting crucial synthesis parameters. We were thus able to grow mesocrystals up to 200 nm and solid nanocrystals of 100 nm by adding virtually any strong polycation. We further found a way to produce stable single domain magnetite at only slightly increased alkalinity, as magnetotactic bacteria do it. Thus through the understanding of the biological system, the consecutive biomimetic synthesis of magnetite and the following understanding of the mechanism involved in the in vitro synthesis, we managed to improve the synthetic control over the co-precipitation of magnetite, coming close biomineralization of magnetite in magnetotactic bacteria. Polyanions, in both natural as well as in synthetic systems, have been in the spotlight of recent research, yet our work shows the pivotal influence polycations have on the nucleation of magnetite. This work will contribute significantly to our ability to tailor magnetite nanoparticle size and morphology; in addition, we presume it will provide us with a model system for studying biomineralization of magnetite in vitro, putting the spotlight on the important influence of polycations, which have not had the scientific attention they deserve.}, language = {en} } @article{PolleyWernerBalderasValadezetal.2022, author = {Polley, Nabarun and Werner, Peter and Balderas-Valadez, Ruth Fabiola and Pacholski, Claudia}, title = {Bottom, top, or in between}, series = {Advanced materials interfaces}, volume = {9}, journal = {Advanced materials interfaces}, number = {15}, publisher = {Wiley}, address = {Hoboken}, issn = {2196-7350}, doi = {10.1002/admi.202102312}, pages = {10}, year = {2022}, abstract = {Attractive label-free plasmonic optical fiber sensors can be developed by cleverly choosing the arrangement of plasmonic nanostructures and other building blocks. Here, the final response depends very much on the alignment and position (stacking) of the individual elements. In this work, three different types of fiber optic sensing geometries fabricated by simple layer-by-layer stacking are presented, consisting of stimulus-sensitive poly-N-isopropylacrylamide (polyNIPAM) microgel arrays and plasmonic nanohole arrays (NHAs), namely NHA/polyNIPAM, polyNIPAM/NHA, polyNIPAM/NHA/polyNIPAM. Their optical response to a representative stimulus, namely temperature, is investigated. NHA/polyNIPAM monitors the volume phase transition of polyNIPAM microgels through changes in the spectral position and the amplitude of the reflection minimum of plasmonic NHA. In contrast, polyNIPAM/NHA shows a more complex response to the swelling and collapse of polyNIPAM microgels in their reflectance spectra. The most pronounced changes in optical response are observed by monitoring the amplitude of the reflectance minimum of this sensor during heating/cooling cycles. Finally, the triple stack of polyNIPAM/NHA/polyNIPAM at the end of a optical fiber tip combines the advantages of the NHA/polyNIPAM, polyNIPAM/NHA double stacks for optical sensing. The unique layer-by-layer stacking of microgel and nanostructure is customizable and can be easily adopted for other applications.}, language = {en} } @misc{PacholskiAgarwalBalderasValadez2016, author = {Pacholski, Claudia and Agarwal, Vivechana and Balderas-Valadez, Ruth Fabiola}, title = {Fabrication of porous silicon-based optical sensors using metal-assisted chemical etching}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-394426}, pages = {21430 -- 21434}, year = {2016}, abstract = {Optical biosensors based on porous silicon were fabricated by metal assisted chemical etching. Thereby double layered porous silicon structures were obtained consisting of porous pillars with large pores on top of a porous silicon layer with smaller pores. These structures showed a similar sensing performance in comparison to electrochemically produced porous silicon interferometric sensors.}, language = {en} } @article{BalderasValadezAntunezOliveMendezetal.2017, author = {Balderas-Valadez, Ruth Fabiola and Antunez, E. E. and Olive-Mendez, Sion Federico and Pacholski, Claudia and Campos-Alvarez, Jose and Bokhimi, Xim and Agarwal, V.}, title = {Porous silicon pillar and bilayer structure as a nucleation center for the formation of aligned vanadium pentoxide nanorods}, series = {Ceramics International}, volume = {43}, journal = {Ceramics International}, publisher = {Elsevier}, address = {Oxford}, issn = {0272-8842}, doi = {10.1016/j.ceramint.2017.03.114}, pages = {8023 -- 8030}, year = {2017}, abstract = {Porous silicon single layer (PSM), bilayer (PSB) and pillar (PSP) structures have been evaluated as nucleation centers for vanadium pentoxide (V2O5) crystals. Deposition of vanadium precursor over different substrates (drop casting technique), followed by annealing treatment under Ar-H-2 (5\% H-2) atmosphere, induced crystallization of vanadium oxide. With respect to c-Si/SiO2 substrate, V2O5 nanorods with relatively large aspect ratio were formed over and within PSP structures. On the other hand, pores in PSM and PSB were found to be filled with relatively smaller crystals. Additionally, PSB provided a nucleation substrate capable to align the nanocrystals in a preferential orientation, while V2O5 crystals grown on PSP were found to be randomly aligned around the nanoporous pillar microstructure. Nanorods and nanocrystals were identified as V2O5 by temperature-controlled XRD measurements and evidence of their crystalline nature was observed via transmission electron microscopy. A careful analysis of electronic microscopy images allows the identification of the facets composing the ends of the crystals and its corresponding surface free energy has been evaluated employing the Wulff theorem. Such high surface area composite structures have potential applications as cathode material in Lithium-ion batteries.}, language = {en} } @article{BalderasValadezSchuermannPacholski2019, author = {Balderas-Valadez, Ruth Fabiola and Sch{\"u}rmann, Robin Mathis and Pacholski, Claudia}, title = {One Spot-Two Sensors: Porous Silicon Interferometers in Combination With Gold Nanostructures Showing Localized Surface Plasmon Resonance}, series = {Frontiers in chemistry}, volume = {7}, journal = {Frontiers in chemistry}, publisher = {Frontiers Research Foundation}, address = {Lausanne}, issn = {2296-2646}, doi = {10.3389/fchem.2019.00593}, pages = {12}, year = {2019}, abstract = {Sensors composed of a porous silicon monolayer covered with a film of nanostructured gold layer, which provide two optical signal transduction methods, are fabricated and thoroughly characterized concerning their sensing performance. For this purpose, silicon substrates were electrochemically etched in order to obtain porous silicon monolayers, which were subsequently immersed in gold salt solution facilitating the formation of a porous gold nanoparticle layer on top of the porous silicon. The deposition process was monitored by reflectance spectroscopy, and the appearance of a dip in the interference pattern of the porous silicon layer was observed. This dip can be assigned to the absorption of light by the deposited gold nanostructures leading to localized surface plasmon resonance. The bulk sensitivity of these sensors was determined by recording reflectance spectra in media having different refractive indices and compared to sensors exclusively based on porous silicon or gold nanostructures. A thorough analysis of resulting shifts of the different optical signals in the reflectance spectra on the wavelength scale indicated that the optical response of the porous silicon sensor is not influenced by the presence of a gold nanostructure on top. Moreover, the adsorption of thiol-terminated polystyrene to the sensor surface was solely detected by changes in the position of the dip in the reflectance spectrum, which is assigned to localized surface plasmon resonance in the gold nanostructures. The interference pattern resulting from the porous silicon layer is not shifted to longer wavelengths by the adsorption indicating the independence of the optical response of the two nanostructures, namely porous silicon and nanostructured gold layer, to refractive index changes and pointing to the successful realization of two sensors in one spot.}, language = {en} } @article{NeffeZhangHommesSchattmannetal.2021, author = {Neffe, Axel T. and Zhang, Quanchao and Hommes-Schattmann, Paul J. and Lendlein, Andreas}, title = {Ethylene oxide sterilization of electrospun poly(L-lactide)/poly(D-lactide) core/shell nanofibers}, series = {MRS advances}, volume = {6}, journal = {MRS advances}, number = {33}, publisher = {Springer}, address = {Cham}, issn = {2059-8521}, doi = {10.1557/s43580-021-00058-5}, pages = {786 -- 789}, year = {2021}, abstract = {The application of polymers in medicine requires sterilization while retaining material structure and properties. This demands detailed analysis, which we show exemplarily for the sterilization of PLLA/PDLA core-shell nanofibers with ethylene oxide (EtO). The electrospun patch was exposed to EtO gas (6 vol\% in CO2, 1.7 bar) for 3 h at 45 degrees C and 75\% rel. humidity, followed by degassing under pressure/vacuum cycles for 12 h. GC-MS analysis showed that no residual EtO was retained. Fiber diameters (similar to 520 +/- 130 nm) of the patches remained constant as observed by electron microscopy. Young's modulus slightly increased and the elongation at break slightly decreased, determined at 37 degrees C. No changes were detected in H-1-NMR spectra, in molar mass distribution (GPC) or in crystallinity measured for annealed samples with comparable thermal history (Wide Angle X-Ray Scattering). Altogether, EtO emerged as suitable sterilization method for polylactide nanofibers with core-shell morphology.}, language = {en} } @phdthesis{Bilkay2012, author = {Bilkay, Taybet}, title = {Thiophen und Benzodithiophen basierte organische Halbleiter f{\"u}r aus L{\"o}sung prozessierbare Feldeffekttransistoren}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-66164}, school = {Universit{\"a}t Potsdam}, year = {2012}, abstract = {Diese Arbeit befasst sich mit der Synthese und Charakterisierung von organol{\"o}slichen Thiophen und Benzodithiophen basierten Materialien und ihrer Anwendung als aktive lochleitende Halbleiterschichten in Feldeffekttransistoren. Im ersten Teil der Arbeit wird durch eine gezielte Modifikation des Thiophengrundger{\"u}stes eine neue Comonomer-Einheit f{\"u}r die Synthese von Thiophen basierten Copolymeren erfolgreich dargestellt. Die hydrophoben Hexylgruppen in der 3-Position des Thiophens werden teilweise durch hydrophile 3,6-Dioxaheptylgruppen ersetzt. {\"U}ber die Grignard-Metathese nach McCullough werden statistische Copolymere mit unterschiedlichen molaren Anteilen vom hydrophoben Hexyl- und hydrophilem 3,6-Dioxaheptylgruppen 1:1 (P-1), 1:2 (P-2) und 2:1 (P-3) erfolgreich hergestellt. Auch die Synthese eines definierten Blockcopolymers BP-1 durch sequentielle Addition der Comonomere wird realisiert. Optische und elektrochemische Eigenschaften der neuartigen Copolymere sind vergleichbar mit P3HT. Mit allen Copolymeren wird ein charakteristisches Transistorverhalten in einem Top-Gate/Bottom-Kontakt-Aufbau erhalten. Dabei werden mit P-1 als die aktive Halbleiterschicht im Bauteil, PMMA als Dielektrikum und Silber als Gate-Elektrode Mobilit{\"a}ten von bis zu 10-2 cm2/Vs erzielt. Als Folge der optimierten Grenzfl{\"a}che zwischen Dielektrikum und Halbleiter wird eine Verbesserung der Luftstabilit{\"a}t der Transistoren {\"u}ber mehrere Monate festgestellt. Im zweiten Teil der Arbeit werden Benzodithiophen basierte organische Materialien hergestellt. F{\"u}r die Synthese der neuartigen Benzodithiophen-Derivate wird die Schl{\"u}sselverbindung TIPS-BDT in guter Ausbeute dargestellt. Die Difunktionalisierung von TIPS-BDT in den 2,6-Positionen {\"u}ber eine elektrophile Substitution liefert die gew{\"u}nschten Dibrom- und Distannylmonomere. Zun{\"a}chst werden {\"u}ber die Stille-Reaktion alternierende Copolymere mit alkylierten Fluoren- und Chinoxalin-Einheiten realisiert. Alle Copolymere zeichnen sich durch eine gute L{\"o}slichkeit in g{\"a}ngigen organischen L{\"o}sungsmitteln, hohe thermische Stabilit{\"a}t und durch gute Filmbildungseigenschaften aus. Des Weiteren sind alle Copolymere mit HOMO Lagen h{\"o}her als -6.3 eV, verglichen mit den Thiophen basierten Copolymeren (P-1 bis P-3), sehr oxidationsstabil. Diese Copolymere zeigen amorphes Verhalten in den Halbleiterschichten in OFETs auf und es werden Mobilit{\"a}ten bis zu 10-4 cm2/Vs erreicht. Eine Abh{\"a}ngigkeit der Bauteil-Leistung von dem Zinngehalt-Rest im Polymer wird nachgewiesen. Ein Zinngehalt von {\"u}ber 0.6 \% kann enormen Einfluss auf die Mobilit{\"a}t aus{\"u}ben, da die funktionellen SnMe3-Gruppen als Fallenzust{\"a}nde wirken k{\"o}nnen. Alternativ wird das alternierende TIPS-BDT/Fluoren-Copolymer P-5-Stille nach der Suzuki-Methode polymerisiert. Mit P-5-Suzuki als die aktive organische Halbleiterschicht im OFET wird die h{\"o}chste Mobilit{\"a}t von 10-2 cm2/Vs erzielt. Diese Mobilit{\"a}t ist somit um zwei Gr{\"o}ßenordnungen h{\"o}her als bei P-5-Stille, da die Fallenzust{\"a}nde in diesem Fall minimiert werden und folglich der Ladungstransport verbessert wird. Sowohl das Homopolymer P-12 als auch das Copolymer mit dem aromatischen Akzeptor Benzothiadiazol P-9 f{\"u}hren zu schwerl{\"o}slichen Polymeren. Aus diesem Grund werden einerseits Terpolymere aus TIPS-BDT/Fluoren/BTD-Einheiten P-10 und P-11 aufgebaut und andererseits wird versucht die TIPS-BDT-Einheit in die Seitenkette des Styrols einzubringen. Mit der Einf{\"u}hrung von BTD in die Hauptpolymerkette werden insbesondere die Absorptions- und die elektrochemischen Eigenschaften beeinflusst. Im Vergleich zu dem TIPS-BDT/Fluoren-Copolymer reicht die Absorption bis in den sichtbaren Bereich und die LUMO Lage wird zu niederen Werten verschoben. Eine Verbesserung der Leistung in den Bauteilen wird jedoch nicht festgestellt. Die erfolgreiche erstmalige Synthese von TIPS-BDT als Seitenkettenpolymer an Styrol P-13 f{\"u}hrt zu einem l{\"o}slichen und amorphen Polymer mit vergleichbaren Mobilit{\"a}ten von Styrol basierten Polymeren (µ = 10-5 cm2/Vs) im OFET. Ein weiteres Ziel dieser Arbeit ist die Synthese von niedermolekularen organol{\"o}slichen Benzodithiophen-Derivaten. {\"U}ber Suzuki- und Stille-Reaktionen ist es erstmals m{\"o}glich, verschiedenartige Aromaten {\"u}ber eine σ-Bindung an TIPS-BDT in den 2,6-Positionen zu kn{\"u}pfen. Die UV/VIS-Untersuchungen zeigen, dass die Absorption durch die Verl{\"a}ngerung der π-Konjugationsl{\"a}nge zu h{\"o}heren Wellenl{\"a}ngen verschoben wird. Dar{\"u}ber hinaus ist es m{\"o}glich, thermisch vernetzbare Gruppen wie Allyloxy in das Molek{\"u}lger{\"u}st einzubauen. Das Einf{\"u}hren von F-Atomen in das Molek{\"u}lger{\"u}st resultiert in einer verst{\"a}rkten Packungsordnung im Fluorbenzen funktionalisiertem TIPS-BDT (SM-4) im Festk{\"o}rper mit sehr guten elektronischen Eigenschaften im OFET, wobei Mobilit{\"a}ten bis zu 0.09 cm2/Vs erreicht werden.}, language = {de} } @phdthesis{Bomm2012, author = {Bomm, Jana}, title = {Von Gold Plasmonen und Exzitonen : Synthese, Charakterisierung und Applikationen von Gold Nanopartikeln}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-66402}, school = {Universit{\"a}t Potsdam}, year = {2012}, abstract = {In dieser Arbeit wurden sph{\"a}rische Gold Nanopartikel (NP) mit einem Durchmesser gr{\"o}ßer ~ 2 nm, Gold Quantenpunkte (QDs) mit einem Durchmesser kleiner ~ 2 nm sowie Gold Nanost{\"a}bchen (NRs) unterschiedlicher L{\"a}nge hergestellt und optisch charakterisiert. Zudem wurden zwei neue Synthesevarianten f{\"u}r die Herstellung thermosensitiver Gold QDs entwickelt werden. Sph{\"a}rische Gold NP zeigen eine Plasmonenbande bei ~ 520 nm, die auf die kollektive Oszillation von Elektronen zur{\"u}ckzuf{\"u}hren ist. Gold NRs weisen aufgrund ihrer anisotropen Form zwei Plasmonenbanden auf, eine transversale Plasmonenbande bei ~ 520 nm und eine longitudinale Plasmonenbande, die vom L{\"a}nge-zu-Durchmesser-Verh{\"a}ltnis der Gold NRs abh{\"a}ngig ist. Gold QDs besitzen keine Plasmonenbande, da ihre Elektronen Quantenbeschr{\"a}nkungen unterliegen. Gold QDs zeigen jedoch aufgrund diskreter Energieniveaus und einer Bandl{\"u}cke Photolumineszenz (PL). Die synthetisierten Gold QDs besitzen eine Breitbandlumineszenz im Bereich von ~ 500-800 nm, wobei die Lumineszenz-eigenschaften (Emissionspeak, Quantenausbeute, Lebenszeiten) stark von den Herstellungs-bedingungen und den Oberfl{\"a}chenliganden abh{\"a}ngen. Die PL in Gold QDs ist ein sehr komplexes Ph{\"a}nomen und r{\"u}hrt vermutlich von Singulett- und Triplett-Zust{\"a}nden her. Gold NRs und Gold QDs konnten in verschiedene Polymere wie bspw. Cellulosetriacetat eingearbeitet werden. Polymernanokomposite mit Gold NRs wurden erstmals unter definierten Bedingungen mechanisch gezogen, um Filme mit optisch anisotropen (richtungsabh{\"a}ngigen) Eigenschaften zu erhalten. Zudem wurde das Temperaturverhalten von Gold NRs und Gold QDs untersucht. Es konnte gezeigt werden, dass eine lokale Variation der Gr{\"o}ße und Form von Gold NRs in Polymernanokompositen durch Temperaturerh{\"o}hung auf 225-250 °C erzielt werden kann. Es zeigte sich, dass die PL der Gold QDs stark temperaturabh{\"a}ngig ist, wodurch die PL QY der Proben beim Abk{\"u}hlen (-7 °C) auf knapp 30 \% verdoppelt und beim Erhitzen auf 70 °C nahezu vollst{\"a}ndig gel{\"o}scht werden konnte. Es konnte demonstriert werden, dass die L{\"a}nge der Alkylkette des Oberfl{\"a}chenliganden einen Einfluss auf die Temperaturstabilit{\"a}t der Gold QDs hat. Zudem wurden verschiedene neuartige und optisch anisotrope Sicherheitslabels mit Gold NRs sowie thermosensitive Sicherheitslabel mit Gold QDs entwickelt. Ebenso scheinen Gold NRs und QDs f{\"u}r die und die Optoelektronik (bspw. Datenspeicherung) und die Medizin (bspw. Krebsdiagnostik bzw. -therapie) von großem Interesse zu sein.}, language = {de} } @phdthesis{Matthes2013, author = {Matthes, Annika}, title = {Die Dehydro-Diels-Alder-Reaktion (DDA-Reaktion) als neue Methode zur Darstellung von Naphthalenophanen}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-65264}, school = {Universit{\"a}t Potsdam}, year = {2013}, abstract = {Die Dissertation beschreibt die Herstellung von ringf{\"o}rmigen Verbindungen (Naphthalenophanen) mit Hilfe der Dehydro-Diels-Alder-Reaktion, wobei immer Enantiomerenpaare auftreten. Es wird der diastereoselektive Aufbau von Naphthalenophanen und der enantiomeren reine Aufbau von Biarylen untersucht. Desweiteren werden die physikalischen Eigenschaften der erhaltenen Verbindungen, wie die Phosphoreszenz, Trennbarkeit der entstehenden Enantiomere und die Ringspannung beschrieben.}, language = {de} } @phdthesis{Santan2013, author = {Santan, Harshal Diliprao}, title = {Synthesis and characterization of thermosensitive hydrogels derived from polysaccharides}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-69793}, school = {Universit{\"a}t Potsdam}, year = {2013}, abstract = {In this work, thermosensitive hydrogels having tunable thermo-mechanical properties were synthesized. Generally the thermal transition of thermosensitive hydrogels is based on either a lower critical solution temperature (LCST) or critical micelle concentration/ temperature (CMC/ CMT). The temperature dependent transition from sol to gel with large volume change may be seen in the former type of thermosensitive hydrogels and is negligible in CMC/ CMT dependent systems. The change in volume leads to exclusion of water molecules, resulting in shrinking and stiffening of system above the transition temperature. The volume change can be undesired when cells are to be incorporated in the system. The gelation in the latter case is mainly driven by micelle formation above the transition temperature and further colloidal packing of micelles around the gelation temperature. As the gelation mainly depends on concentration of polymer, such a system could undergo fast dissolution upon addition of solvent. Here, it was envisioned to realize a thermosensitive gel based on two components, one responsible for a change in mechanical properties by formation of reversible netpoints upon heating without volume change, and second component conferring degradability on demand. As first component, an ABA triblockcopolymer (here: Poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) (PEPE) with thermosensitive properties, whose sol-gel transition on the molecular level is based on micellization and colloidal jamming of the formed micelles was chosen, while for the additional macromolecular component crosslinking the formed micelles biopolymers were employed. The synthesis of the hydrogels was performed in two ways, either by physical mixing of compounds showing electrostatic interactions, or by covalent coupling of the components. Biopolymers (here: the polysaccharides hyaluronic acid, chondroitin sulphate, or pectin, as well as the protein gelatin) were employed as additional macromolecular crosslinker to simultaneously incorporate an enzyme responsiveness into the systems. In order to have strong ionic/electrostatic interactions between PEPE and polysaccharides, PEPE was aminated to yield predominantly mono- or di-substituted PEPEs. The systems based on aminated PEPE physically mixed with HA showed an enhancement in the mechanical properties such as, elastic modulus (G′) and viscous modulus (G′′) and a decrease of the gelation temperature (Tgel) compared to the PEPE at same concentration. Furthermore, by varying the amount of aminated PEPE in the composition, the Tgel of the system could be tailored to 27-36 °C. The physical mixtures of HA with di-amino PEPE (HA·di-PEPE) showed higher elastic moduli G′ and stability towards dissolution compared to the physical mixtures of HA with mono-amino PEPE (HA·mono-PEPE). This indicates a strong influence of electrostatic interaction between -COOH groups of HA and -NH2 groups of PEPE. The physical properties of HA with di-amino PEPE (HA·di-PEPE) compare beneficially with the physical properties of the human vitreous body, the systems are highly transparent, and have a comparable refractive index and viscosity. Therefore,this material was tested for a potential biological application and was shown to be non-cytotoxic in eluate and direct contact tests. The materials will in the future be investigated in further studies as vitreous body substitutes. In addition, enzymatic degradation of these hydrogels was performed using hyaluronidase to specifically degrade the HA. During the degradation of these hydrogels, increase in the Tgel was observed along with decrease in the mechanical properties. The aminated PEPE were further utilised in the covalent coupling to Pectin and chondroitin sulphate by using EDC as a coupling agent. Here, it was possible to adjust the Tgel (28-33 °C) by varying the grafting density of PEPE to the biopolymer. The grafting of PEPE to Pectin enhanced the thermal stability of the hydrogel. The Pec-g-PEPE hydrogels were degradable by enzymes with slight increase in Tgel and decrease in G′ during the degradation time. The covalent coupling of aminated PEPE to HA was performed by DMTMM as a coupling agent. This method of coupling was observed to be more efficient compared to EDC mediated coupling. Moreover, the purification of the final product was performed by ultrafiltration technique, which efficiently removed the unreacted PEPE from the final product, which was not sufficiently achieved by dialysis. Interestingly, the final products of these reaction were in a gel state and showed enhancement in the mechanical properties at very low concentrations (2.5 wt\%) near body temperature. In these hydrogels the resulting increase in mechanical properties was due to the combined effect of micelle packing (physical interactions) by PEPE and covalent netpoints between PEPE and HA. PEPE alone or the physical mixtures of the same components were not able to show thermosensitive behavior at concentrations below 16 wt\%. These thermosensitive hydrogels also showed on demand solubilisation by enzymatic degradation. The concept of thermosensitivity was introduced to 3D architectured porous hydrogels, by covalently grafting the PEPE to gelatin and crosslinking with LDI as a crosslinker. Here, the grafted PEPE resulted in a decrease in the helix formation in gelatin chains and after fixing the gelatin chains by crosslinking, the system showed an enhancement in the mechanical properties upon heating (34-42 °C) which was reversible upon cooling. A possible explanation of the reversible changes in mechanical properties is the strong physical interactions between micelles formed by PEPE being covalently linked to gelatin. Above the transition temperature, the local properties were evaluated by AFM indentation of pore walls in which an increase in elastic modulus (E) at higher temperature (37 °C) was observed. The water uptake of these thermosensitive architectured porous hydrogels was also influenced by PEPE and temperature (25 °C and 37 °C), showing lower water up take at higher temperature and vice versa. In addition, due to the lower water uptake at high temperature, the rate of hydrolytic degradation of these systems was found to be decreased when compared to pure gelatin architectured porous hydrogels. Such temperature sensitive architectured porous hydrogels could be important for e.g. stem cell culturing, cell differentiation and guided cell migration, etc. Altogether, it was possible to demonstrate that the crosslinking of micelles by a macromolecular crosslinker increased the shear moduli, viscosity, and stability towards dissolution of CMC-based gels. This effect could be likewise be realized by covalent or non-covalent mechanisms such as, micelle interactions, physical interactions of gelatin chains and physical interactions between gelatin chains and micelles. Moreover, the covalent grafting of PEPE will create additional net-points which also influence the mechanical properties of thermosensitive architectured porous hydrogels. Overall, the physical and chemical interactions and reversible physical interactions in such thermosensitive architectured porous hydrogels gave a control over the mechanical properties of such complex system. The hydrogels showing change of mechanical properties without a sol-gel transition or volume change are especially interesting for further study with cell proliferation and differentiation.}, language = {en} } @misc{Metzke2013, type = {Master Thesis}, author = {Metzke, Sarah}, title = {Synthesis and characterization of transition metal nitrides and carbides for catalysis and electrochemistry application}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-69835}, school = {Universit{\"a}t Potsdam}, year = {2013}, abstract = {It was the goal of this work to explore two different synthesis pathways using green chemistry. The first part of this thesis is focusing on the use of the urea-glass route towards single phase manganese nitride and manganese nitride/oxide nano-composites embedded in carbon, while the second part of the thesis is focusing on the use of the "saccharide route" (namely cellulose, sucrose, glucose and lignin) towards metal (Ni0), metal alloy (Pd0.9Ni0.1, Pd0.5Ni0.5, Fe0.5Ni0.5, Cu0.5Ni0.5 and W0.15Ni0.85) and ternary carbide (Mn0.75Fe2.25C) nanoparticles embedded in carbon. In the interest of battery application, MnN0.43 nanoparticles surrounded by a graphitic shell and embedded in carbon with a high surface area (79 m^2/g) were synthesized, following a previously set route.The comparison of the material characteristics before and after the discharge showed no remarkable difference in terms of composition and just slight differences in the morphological point of view, meaning the particles are stable but agglomerate. The graphitic shell is contributing to the resistance of the material and leads to a fine cyclic stability over 140 cycles of 230 mAh/g after the first charge/discharge and coulombic efficiencies close to 100\%. Due to the low voltage towards Li/Li+ and the low polarization, it might be an attractive anode material for lithium ion batteries. However, the capacity is still noticeably lower than the theoretical value for MnN0.43. A mixture of MnN0.43 and MnO nanoparticles embedded in carbon (surface area 93 m^2/g) was able to improve the cyclic stability to over 160 cycles giving a capacity of 811 mAh/g, which is considerably higher than the capacity of the conventional material graphite (372 mAh/g). This nano-composite seems to agglomerate less during the process of discharge. Interestingly, although the capacity is much higher than of the single phase manganese nitride, the nano-composite seems to only contain MnN0.43 nanoparticles after the process of discharge with no oxide phase to be found. Concerning catalysis application, different metal, metal alloy, and metal carbide nanoparticles were synthesized using the saccharide route. At first, systems that were already investigated before, being Pd0.9Ni0.1, Pd0.5Ni0.5, Fe0.5Ni0.5 and Mn0.75Fe2.25C using cellulose as the carbon source were prepared and tested in an alkylation reaction of toluene with benzylchloride. Unexpectedly, the metal alloys did not show any catalytic activity, but the ternary carbide Mn0.75Fe2.25C showed fine catalytic activity of 98\% conversion after 9 hour reaction time (110 °C). In a second step, the saccharide route was modified towards other carbon sources and carbon to metal ratios in order to improve the homogeneity of the samples and accessibility of the particle surfaces. The used carbon sources sucrose and glucose are similar in their basic structure of carbohydrates, but reducing the (polymeric) chain length. Indeed, the cellulose could be successfully replaced by sucrose and glucose. A lower carbon to metal ratio was found to influence the size, homogeneity and accessibility (as evidenced by TEM) of the samples. Since sucrose is an aliment, glucose is the better choice as a carbon source. Using glucose, the synthesis of Cu0.5Ni0.5 and W0.15Ni0.85 nano-composites was also possible, although the later was never obtained as pure phase. These alloy nano-composites were tested, along with nickel0 nanoparticles also prepared with glucose and on their catalytic activity towards the reduction of phenylacetylene. The results obtained let believe that any (poly) saccharide, including lignin, could be used as carbon source. The nickel0 nano-composites prepared with lignin as a carbon source were tested along with those prepared with cellulose and sucrose for their catalytic activity in the transfer hydrogenation of nitrobenzene (results compared with exposed nickel nanoparticles and nickel supported on carbon) leading to very promising results. Based on the urea-glass route and the saccharide route, simple equipment and transition metals, it was possible to have a one-pot synthesize with scale-up possibilities towards new material that can be applied in catalysis and battery systems.}, language = {en} } @phdthesis{Suetterlin2013, author = {S{\"u}tterlin, Martin}, title = {New inverse hydogel opals as protein responsive sensors}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-70179}, school = {Universit{\"a}t Potsdam}, year = {2013}, abstract = {In this work, the development of temperature- and protein-responsive sensor materials based on biocompatible, inverse hydrogel opals (IHOs) is presented. With these materials, large biomolecules can be specifically recognised and the binding event visualised. The preparation of the IHOs was performed with a template process, for which monodisperse silica particles were vertically deposited onto glass slides as the first step. The obtained colloidal crystals with a thickness of 5 μm displayed opalescent reflections because of the uniform alignment of the colloids. As a second step, the template was embedded in a matrix consisting of biocompatible, thermoresponsive hydrogels. The comonomers were selected from the family of oligo(ethylene glycol)methacrylates. The monomer solution was injected into a polymerisation mould, which contained the colloidal crystals as a template. The space in-between the template particles was filled with the monomer solution and the hydrogel was cured via UV-polymerisation. The particles were chemically etched, which resulted in a porous inner structure. The uniform alignment of the pores and therefore the opalescent reflection were maintained, so these system were denoted as inverse hydrogel opals. A pore diameter of several hundred nanometres as well as interconnections between the pores should facilitate a diffusion of bigger (bio)molecules, which was always a challenge in the presented systems until now. The copolymer composition was chosen to result in a hydrogel collapse over 35 °C. All hydrogels showed pronounced swelling in water below the critical temperature. The incorporation of a reactive monomer with hydroxyl groups ensured a potential coupling group for the introduction of recognition units for analytes, e.g. proteins. As a test system, biotin as a recognition unit for avidin was coupled to the IHO via polymer-analogous Steglich esterification. The amount of accessible biotin was quantified with a colorimetric binding assay. When avidin was added to the biotinylated IHO, the wavelength of the opalescent reflection was significantly shifted and therefore the binding event was visualised. This effect is based on the change in swelling behaviour of the hydrogel after binding of the hydrophilic avidin, which is amplified by the thermoresponsive nature of the hydrogel. A swelling or shrinking of the pores induces a change in distance of the crystal planes, which are responsible for the colour of the reflection. With these findings, the possibility of creating sensor materials or additional biomolecules in the size range of avidin is given.}, language = {en} } @phdthesis{Audoersch2016, author = {Aud{\"o}rsch, Stephan}, title = {Die Synthese von (2Z,4E)-Diencarbons{\"a}ureestern und ihre Anwendung in der Totalsynthese von Polyacetylenen}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-92366}, school = {Universit{\"a}t Potsdam}, pages = {139}, year = {2016}, abstract = {Z,E-Diene sind ein h{\"a}ufig auftretendes Strukturmerkmal in Naturstoffen. Aus diesem Grund ist die einfache Darstellung dieser Struktureinheit von großen Interesse in der organischen Chemie. Das erste Ziel der vorliegenden Arbeit war daher die Weiterentwicklung der Ringschlussmetathese-/ baseninduzierten Ring{\"o}ffnungs-/ Veresterungssequenz (RBRV-Sequenz) zur Synthese von (2Z,4E)-Diencarbons{\"a}ureethylestern ausgehend von Butenoaten. Dazu wurde zun{\"a}chst die RBRV-Sequenz optimiert. Diese aus drei Schritten bestehende Sequenz konnte in einem Eintopf-Verfahren angewendet werden. Die Ringschlussmetathese gelang mit einer Katalysatorbeladung von 1 mol\% des GRUBBS-Katalysators der zweiten Generation in Dichlormethan. F{\"u}r die baseninduzierte Ring{\"o}ffnung des β,γ-unges{\"a}ttigten δ Valerolactons wurde NaHMDS verwendet. Die Alkylierung der Carboxylatspezies gelang mit dem MEERWEIN-Reagenz. Die Anwendbarkeit der Sequenz wurde f{\"u}r verschiedene Substrate demonstriert. Die Erweiterung der Methode auf α-substituierte Butenoate unterlag starken Einschr{\"a}nkungen. So konnte der Zugang f{\"u}r α Hydroxyderivate realisiert werden. Bei der Anwendung der RBRV-Sequenz auf die α-substituierten Butenoate wurde festgestellt, dass diese sich nur in moderaten Ausbeuten umsetzen ließen und zudem nicht selektiv zu den (2E,4E)-konfigurierten α-substituierten-Dienestern reagierten. Der Einsatz von Eninen unter den Standardbedingungen der RBRV-Sequenz gelang nicht. Erst nach Modifizierung der Sequenz (h{\"o}here Katalysatorbeladung, Wechsel des L{\"o}sungsmittels) konnten die [3]Dendralen-Produkte in geringen Ausbeuten erhalten werden. Im zweiten Teil der Arbeit wurde der Einsatz von (2Z,4E)-Diencarbons{\"a}ureethylestern in der Totalsynthese von Naturstoffen untersucht. Dazu wurden zun{\"a}chst die Transformationsm{\"o}glichkeiten der Ester gepr{\"u}ft. Es konnte gezeigt werden, dass sich (2Z,4E)-Diencarbons{\"a}ureethylester insbesondere zur Synthese von (2Z,4E)-Aldehyden sowie zum Aufbau der (3Z,5E)-Dien-1-in-Struktur eignen. Anhand dieser Ergebnisse wurde im Anschluss die RBRV-Sequenz in der Totalsynthese eingesetzt. Dazu wurde zun{\"a}chst der (2Z,4E)-Dienester Microsphaerodiolin in seiner ersten Totalsynthese auf drei verschiedene Routen hergestellt. Im Anschluss wurden sechs verschiedene Polyacetylene mit einer (3Z,5E)-Dien-1-in-Einheit hergestellt. Schl{\"u}sselschritte in ihrer Synthese waren immer die RBRV-Sequenz zum Aufbau der Z,E-Dien-Einheit, die Transformation des Esters in ein terminales Alkin sowie die CADIOT-CHODKIEWICZ-Kupplung zum Aufbau unsymmetrischer Polyine. Alle sechs Polyacetylene wurden zum ersten Mal in einer Totalsynthese synthetisiert. Drei Polyacetylene wurden ausgehend von (S)-Butantriol enantiomerenrein dargestellt. Anhand ihrer Drehwerte konnte eine Revision der von YAO und Mitarbeitern vorgenommen Zuordnung der Absolutkonfiguration der Naturstoffe vorgenommen werden.}, language = {de} } @phdthesis{Pape2016, author = {Pape, Simon}, title = {Entwicklung und Evaluierung von Methoden zur Synthese neuartiger Additive f{\"u}r die außenstromlose Nickel-Phosphor-Abscheidung}, school = {Universit{\"a}t Potsdam}, pages = {223}, year = {2016}, language = {de} } @misc{SchmidtHauke2013, author = {Schmidt, Bernd and Hauke, Sylvia}, title = {Cross metathesis of allyl alcohols}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-95037}, pages = {4194 -- 4206}, year = {2013}, abstract = {Under standard conditions the cross metathesis of allyl alcohols and methyl acrylate is accompanied by the formation of ketones, resulting from uncontrolled and undesired double bond isomerization. By conducting the CM in the presence of phenol, the catalyst loading and the reaction time required for quantiative conversion can be reduced, and isomerization can be suppressed. On the other hand, consecutive isomerization can be deliberately promoted by evaporating excess methyl acrylate after completing cross metathesis and by adding a base or silane as chemical triggers.}, language = {en} } @misc{CherstvyMetzler2013, author = {Cherstvy, Andrey G. and Metzler, Ralf}, title = {Population splitting, trapping, and non-ergodicity in heterogeneous diffusion processes}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-94468}, pages = {20220 -- 20235}, year = {2013}, abstract = {We consider diffusion processes with a spatially varying diffusivity giving rise to anomalous diffusion. Such heterogeneous diffusion processes are analysed for the cases of exponential, power-law, and logarithmic dependencies of the diffusion coefficient on the particle position. Combining analytical approaches with stochastic simulations, we show that the functional form of the space-dependent diffusion coefficient and the initial conditions of the diffusing particles are vital for their statistical and ergodic properties. In all three cases a weak ergodicity breaking between the time and ensemble averaged mean squared displacements is observed. We also demonstrate a population splitting of the time averaged traces into fast and slow diffusers for the case of exponential variation of the diffusivity as well as a particle trapping in the case of the logarithmic diffusivity. Our analysis is complemented by the quantitative study of the space coverage, the diffusive spreading of the probability density, as well as the survival probability.}, language = {en} }