@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} } @article{CouturierWischerhoffBerninetal.2016, author = {Couturier, Jean-Philippe and Wischerhoff, Erik and Bernin, Robert and Hettrich, Cornelia and Koetz, Joachim and Sutterlin, Martin and Tiersch, Brigitte and Laschewsky, Andre}, title = {Thermoresponsive Polymers and Inverse Opal Hydrogels for the Detection of Diols}, series = {Langmuir}, volume = {32}, journal = {Langmuir}, publisher = {American Chemical Society}, address = {Washington}, issn = {0743-7463}, doi = {10.1021/acs.langmuir.6b00803}, pages = {4333 -- 4345}, year = {2016}, abstract = {Responsive inverse opal hydrogels functionalized by boroxole moieties were synthesized and explored as sensor platforms for various low molar mass as well as polymeric diols and polyols, including saccharides, glycopolymers and catechols, by exploiting the diol induced modulation of their structural color. The underlying thermoresponsive water-soluble copolymers and hydrogels exhibit a coil-to-globule or volume phase transition, respectively, of the LCST-type. They were prepared from oligoethylene oxide methacrylate (macro)monomers and functionalized via copolymerization to bear benzoboroxole moieties. The resulting copolymers represent weak polyacids, which can bind specifically to diols within an appropriate pH window. Due to the resulting modulation of the overall hydrophilicity of the systems and the consequent shift of their phase transition temperature, the usefulness of such systems for indicating the presence of catechols, saccharides, and glycopolymers was studied, exploiting the diol/polyol induced shifts of the soluble polymers' cloud point, or the induced changes of the hydrogels' swelling. In particular, the increased acidity of benzoboroxoles compared to standard phenylboronic acids allowed performing the studies in PBS buffer (phosphate buffered saline) at the physiologically relevant pH of 7.4. The inverse opals constructed of these thermo- and analyte-responsive hydrogels enabled following the binding of specific diols by the induced shift of the optical stop band. Their highly porous structure enabled the facile and specific optical detection of not only low molar mass but also of high molar mass diol/polyol analytes such as glycopolymers. Accordingly, such thermoresponsive inverse opal systems functionalized with recognition units represent attractive and promising platforms for the facile sensing of even rather big analytes by simple optical means, or even by the bare eye.}, language = {en} } @misc{WilkensSuetterlinWelleretal.2014, author = {Wilkens, Martin and S{\"u}tterlin, Sabine and Weller, Nina and Horn-Conrad, Antje and Kampe, Heike and Eckardt, Barbara and G{\"o}rlich, Petra and J{\"a}ger, Sophie and Zimmermann, Matthias and Mitsch, Wolfgang}, title = {Portal Wissen = Zeit}, number = {02/2014}, organization = {Universit{\"a}t Potsdam, Referat f{\"u}r Presse- und {\"O}ffentlichkeitsarbeit}, issn = {2194-4237}, doi = {10.25932/publishup-44084}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-440842}, pages = {99}, year = {2014}, abstract = {„Was ist also 'Zeit'?" seufzt Augustinus von Hippo im 11. Buch seiner „Confessiones" melancholisch, und f{\"a}hrt fort „Wenn mich niemand danach fragt, weiß ich es; will ich einem Fragenden es erkl{\"a}ren, weiß ich es nicht." Auch heute, 1584 Jahre nach Augustinus, erscheint 'Zeit' immer noch r{\"a}tselhaft. Abhandlungen {\"u}ber das Wesen der Zeit f{\"u}llen Bibliotheken. Oder eben dieses Heft. Wesensfragen sind den modernen Wissenschaften allerdings fremd. Zeit ist - zumindest in der Physik - unproblematisch. „Time is defined so that Motion looks simple" erk{\"a}rt man kurz und trocken, und verabschiedet sich damit vom Augustinischen R{\"a}tsel oder der Newtonschen Vorstellung einer absoluten Zeit, deren mathematischen Fluss man durch irdische Instrumente eh immer nur n{\"a}herungsweise erfassen kann. In der Alltagssprache, selbst in den Wissenschaften, reden wir zwar weiterhin vom Fluss der Zeit, aber Zeit ist schon lange keine nat{\"u}rliche Gegebenheit mehr. Zeit ist vielmehr ein konventioneller Ordnungsparameter f{\"u}r {\"A}nderung und Bewegung. Geordnet werden Prozesse, indem eine Klasse von Prozessen als Z{\"a}hlsystem dient, um andere Prozesse mit ihnen zu vergleichen und anhand der tempor{\"a}ren Kategorien „vorher", „w{\"a}hrend" und „nachher" anzuordnen. Zu Galileis Zeiten galt der eigene Pulsschlag als Zeitstandard f{\"u}r den Flug von Kanonenkugeln. Mit zunehmender Verfeinerung der Untersuchungsmethoden erschien das zu unpraktisch: Die Weg-Zeit-Diagramme frei fliegender Kanonenkugeln erweisen sich in diesem Standard ziemlich verwackelt, schlecht reproduzierbar, und keineswegs „simpel". Heutzutage greift man zu C{\"a}sium-Atomen. Demnach dauert ein Prozess eine Sekunde, wenn ein 133Cs-Atom genau 9 192 631 770 Schwingungen zwischen zwei sogenannten Hyperfeinzust{\"a}nden des Grundzustands vollf{\"u}hrt hat. Und ein Meter ist die Entfernung, die Licht im Vakuum in exakt 1/299 792 458 Sekunden zur{\"u}cklegt. Gl{\"u}cklicherweise sind diese Daten im General Positioning System GPS hart kodiert, so dass der Nutzer sie nicht jedes Mal aufs Neue eingeben muss, wenn er wissen will, wo er ist. Aber schon morgen muss er sich vielleicht ein Applet runterladen, weil der Zeitstandard durch raffinierte {\"U}berg{\"a}nge in Ytterbium ersetzt wurde. Der konventionelle Charakter des Zeitbegriffs sollte nicht dazu verf{\"u}hren zu glauben, alles sei irgendwie relativ und daher willk{\"u}rlich. Die Beziehung eines Pulsschlags zu einer Atomuhr ist absolut, und genauso real, wie die Beziehung einer Sanduhr zum Lauf der Sonne. Die exakten Wissenschaften sind Beziehungswissenschaften. Sie handeln nicht vom Ding an sich, was Newton und Kant noch getr{\"a}umt haben, sondern von Beziehungen - worauf schon Leibniz und sp{\"a}ter Mach hingewiesen haben. Kein Wunder, dass sich f{\"u}r andere Wissenschaften der physikalische Zeit-Standard als ziemlich unpraktisch erweist. Der Psychologie der Zeitwahrnehmung entnehmen wir - und jeder wird das best{\"a}tigen k{\"o}nnen - dass das gef{\"u}hlte Alter durchaus verschieden ist vom physikalischen Alter. Je {\"a}lter man ist, desto k{\"u}rzer erscheinen einem die Jahre. Unter der einfachen Annahme, dass die gef{\"u}hlte Dauer umgekehrt proportional zum physikalischen Alter ist, und man als Zwanzigj{\"a}hriger ein physikalisches Jahr auch psychologisch als ein Jahr empfindet, ergibt sich der erstaunliche Befund, dass man mit 90 Jahren 90 Jahre ist. Und - bei einer angenommenen Lebenserwartung von 90 Jahren - mit 20 (bzw. 40) physikalischen Jahren bereits 67 (bzw. 82) Prozent seiner gef{\"u}hlten Lebenszeit hinter sich hat. Bevor man angesichts der „Relativit{\"a}t von Zeit" selbst in Melancholie versinkt, vielleicht die Fortsetzung des Eingangszitats von Augustinus: „Aber zuversichtlich behaupte ich zu wissen, dass es vergangene Zeit nicht g{\"a}be, wenn nichts verginge, und nicht k{\"u}nftige Zeit, wenn nichts herank{\"a}me, und nicht gegenw{\"a}rtige Zeit wenn nichts seiend w{\"a}re." Tja - oder mit Bob Dylan „The times they're a changing". Ich w{\"u}nsche Ihnen eine spannende Zeit bei der Lekt{\"u}re dieser Ausgabe. Prof. Dr. Martin Wilkens Professor f{\"u}r Quantenoptik}, language = {de} } @misc{WilkensSuetterlinKampeetal.2014, author = {Wilkens, Martin and S{\"u}tterlin, Sabine and Kampe, Heike and Eckardt, Barbara and J{\"a}ger, Sophie and Zimmermann, Matthias}, title = {Portal Wissen = Time}, number = {02/2014}, organization = {University of Potsdam, Press and Public Relations Department}, issn = {2198-9974}, doi = {10.25932/publishup-44149}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-441497}, pages = {55}, year = {2014}, abstract = {"What then is time?", Augustine of Hippo sighs melancholically in Book XI of "Confessions" and continues, "If no one asks me, I know; if I want to explain it to a questioner, I don't know." Even today, 1584 years after Augustine, time still appears mysterious. Treatises about the essence of time fill whole libraries - and this magazine. However, questions of essence are alien to modern sciences. Time is - at least in physics - unproblematic: "Time is defined so that motion looks simple", briefly and prosaically phrased, waves goodbye to Augustine's riddle and to the Newtonian concept of absolute time, whose mathematical flow can only be approximately recorded with earthly instruments anyway. In our everyday language and even in science we still speak of the flow of time but time has not been a natural condition for quite a while now. It is rather a conventional order parameter for change and movement. Processes are arranged by using a class of processes as a counting system in order to compare other processes and to organize them with the help of the temporary categories "before", "during", and "after". During Galileo's time one's own pulse was seen as the time standard for the flight of cannon balls. More sophisticated examination methods later made this seem too impractical. The distance-time diagrams of free-flying cannon balls turned out to be rather imprecise, difficult to replicate, and in no way "simple". Nowadays, we use cesium atoms. A process is said to take one second when a caesium-133 atom completes 9,192,631,770 periods of the radiation corresponding to the transition between two hyperfine levels of the ground state. A meter is the length of the path travelled by light in a vacuum in exactly 1/299,792,458 of a second. Fortunately, these data are hard-coded in the Global Positioning System GPS so users do not have to reenter them each time they want to know where they are. In the future, however, they might have to download an app because the time standard has been replaced by sophisticated transitions to ytterbium. The conventional character of the time concept should not tempt us to believe that everything is somehow relative and, as a result, arbitrary. The relation of one's own pulse to an atomic clock is absolute and as real as the relation of an hourglass to the path of the sun. The exact sciences are relational sciences. They are not about the thing-initself as Newton and Kant dreamt, but rather about relations as Leibniz and, later, Mach pointed out. It is not surprising that the physical time standard turned out to be rather impractical for other scientists. The psychology of time perception tells us - and you will all agree - that the perceived age is quite different from the physical age. The older we get the shorter the years seem. If we simply assume that perceived duration is inversely related to physical age and that a 20-year old also perceives a physical year as a psychological one, we come to the surprising discovery that at 90 years we are 90 years old. With an assumed life expectancy of 90 years, 67\% (or 82\%) of your felt lifetime is behind you at the age of 20 (or 40) physical years. Before we start to wallow in melancholy in the face of the "relativity of time", let me again quote Augustine. "But at any rate this much I dare affirm I know: that if nothing passed there would be no past time; if nothing were approaching, there would be no future time; if nothing were, there would be no present time." Well, - or as Bob Dylan sings "The times they are a-changin". I wish you an exciting time reading this issue. Prof. Martin Wilkens Professor of Quantum Optics}, language = {en} } @article{CouturierSuetterlinLaschewskyetal.2015, author = {Couturier, Jean-Philippe and S{\"u}tterlin, Martin and Laschewsky, Andr{\´e} and Hettrich, Cornelia and Wischerhoff, Erik}, title = {Responsive Inverse Opal Hydrogels for the Sensing of Macromolecules}, series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, volume = {54}, journal = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, number = {22}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1433-7851}, doi = {10.1002/anie.201500674}, pages = {6641 -- 6644}, year = {2015}, abstract = {Dual responsive inverse opal hydrogels were designed as autonomous sensor systems for (bio)macromolecules, exploiting the analyte-induced modulation of the opal's structural color. The systems that are based on oligo(ethylene glycol) macromonomers additionally incorporate comonomers with various recognition units. They combine a coil-to-globule collapse transition of the LCST type with sensitivity of the transition temperature toward molecular recognition processes. This enables the specific detection of macromolecular analytes, such as glycopolymers and proteins, by simple optical methods. While the inverse opal structure assists the effective diffusion even of large analytes into the photonic crystal, the stimulus responsiveness gives rise to strong shifts of the optical Bragg peak of more than 100nm upon analyte binding at a given temperature. The systems' design provides a versatile platform for the development of easy-to-use, fast, and low-cost sensors for pathogens.}, language = {en} } @misc{CommingesFrascaSuetterlinetal.2014, author = {Comminges, Cl{\´e}ment and Frasca, Stefano and S{\"u}tterlin, Martin and Wischerhoff, Erik and Laschewsky, Andr{\´e} and Wollenberger, Ursula}, title = {Surface modification with thermoresponsive polymer brushes for a switchable electrochemical sensor}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-99471}, year = {2014}, abstract = {Elaboration of switchable surfaces represents an interesting way for the development of a new generation of electrochemical sensors. In this paper, a method for growing thermoresponsive polymer brushes from a gold surface pre-modified with polyethyleneimine (PEI), subsequent layer-by-layer polyelectrolyte assembly and adsorption of a charged macroinitiator is described. We propose an easy method for monitoring the coil-to-globule phase transition of the polymer brush using an electrochemical quartz crystal microbalance with dissipation (E-QCM-D). The surface of these polymer modified electrodes shows reversible switching from the swollen to the collapsed state with temperature. As demonstrated from E-QCM-D measurements using an original signal processing method, the switch is operating in three reversible steps related to different interfacial viscosities. Moreover, it is shown that the one electron oxidation of ferrocene carboxylic acid is dramatically affected by the change from the swollen to the collapsed state of the polymer brush, showing a spectacular 86\% decrease of the charge transfer resistance between the two states.}, language = {en} }