TY - JOUR A1 - Zühlke, Martin A1 - Riebe, Daniel A1 - Beitz, Toralf A1 - Löhmannsröben, Hans-Gerd A1 - Zenichowski, Karl A1 - Diener, Marc A1 - Linscheid, Michael W. T1 - An electrospray ionization-ion mobility spectrometer as detector for high-performance liquid chromatography JF - European journal of mass spectrometry N2 - The application of electrospray ionization (ESI) ion mobility (IM) spectrometry on the detection end of a high-performance liquid chromatograph has been a subject of study for some time. So far, this method has been limited to low flow rates or has required splitting of the liquid flow. This work presents a novel concept of an ESI source facilitating the stable operation of the spectrometer at flow rates between 10 mu L min(-1) and 1500 mu L min(-1) without flow splitting, advancing the T-cylinder design developed by Kurnin and co-workers. Flow rates eight times faster than previously reported were achieved because of a more efficient dispersion of the liquid at increased electrospray voltages combined with nebulization by a sheath gas. Imaging revealed the spray operation to be in a rotationally symmetric multijet-mode. The novel ESI-IM spectrometer tolerates high water contents (<= 90%) and electrolyte concentrations up to 10 mM, meeting another condition required of high-performance liquid chromatography (HPLC) detectors. Limits of detection of 50 nM for promazine in the positive mode and 1 mu M for 1,3-dinitrobenzene in the negative mode were established. Three mixtures of reduced complexity (five surfactants, four neuroleptics, and two isomers) were separated in the millisecond regime in stand-alone operation of the spectrometer. Separations of two more complex mixtures (five neuroleptics and 13 pesticides) demonstrate the application of the spectrometer as an HPLC detector. The examples illustrate the advantages of the spectrometer over the established diode array detector, in terms of additional IM separation of substances not fully separated in the retention time domain as well as identification of substances based on their characteristic IMs. KW - ESI KW - IMS KW - HPLC KW - spray imaging KW - neuroleptics KW - pesticides KW - surfactants Y1 - 2015 U6 - https://doi.org/10.1255/ejms.1367 SN - 1469-0667 SN - 1751-6838 VL - 21 IS - 3 SP - 391 EP - 402 PB - WeltTrends CY - Sussex ER - TY - JOUR A1 - Zou, Hua A1 - Schlaad, Helmut T1 - Thermoresponsive PNIPAM/Silica Nanoparticles by Direct Photopolymerization in Aqueous Media JF - Journal of polymer science : A, Polymer chemistry N2 - This article presents a simple and facile method to fabricate thermoresponsive polymer-grafted silica particles by direct surface-initiated photopolymerization of N-isopropylacrylamide (NIPAM). This method is based on silica particles bearing thiol functionalities, which are transformed into thiyl radicals by irradiation with UV light to initiate the polymerization of NIPAM in aqueous media at room temperature. The photopolymerization of NIPAM could be applied to smaller thiol-functionalized particles (approximate to 48 nm) as well as to larger particles (approximate to 692 nm). Hollow poly(NIPAM) capsules could be formed after etching away the silica cores from the composite particles. It is possible to produce tailor-made composite particles or capsules for particular applications by extending this approach to other vinyl monomers. (c) 2015 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 2015, 53, 1260-1267 KW - nanocomposites KW - nanoparticles KW - photopolymerization KW - silica nanoparticles KW - surface-initiated photopolymerization KW - thermoresponsive KW - thiol Y1 - 2015 U6 - https://doi.org/10.1002/pola.27593 SN - 0887-624X SN - 1099-0518 VL - 53 IS - 10 SP - 1260 EP - 1267 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Zhong, Qi A1 - Metwalli, Ezzeldin A1 - Rawolle, Monika A1 - Kaune, Gunar A1 - Bivigou Koumba, Achille Mayelle A1 - Laschewsky, André A1 - Papadakis, Christine M. A1 - Cubitt, Robert A1 - Müller-Buschbaum, Peter T1 - Rehydration of Thermoresponsive Poly(monomethoxydiethylene glycol acrylate) Films Probed in Situ by Real-Time Neutron Reflectivity JF - Macromolecules : a publication of the American Chemical Society N2 - The rehydration of thermoresponsive poly(monomethoxydiethylene glycol acrylate) (PMDEGA) films exhibiting a lower critical solution temperature (LCST) type demixing phase transition in aqueous environments, induced by a decrease in temperature, is investigated in situ with real-time neutron reflectivity. Two different starting conditions (collapsed versus partially swollen chain conformation) are compared. In one experiment, the temperature is reduced from above the demixing temperature to well below the demixing temperature. In a second experiment, the starting temperature is below the demixing temperature, but within the transition regime, and reduced to the same final temperature. In both cases, the observed rehydration process can be divided into three stages: first condensation of water from the surrounding atmosphere, then absorption of water by the PMDEGA film and evaporation of excess water, and finally, rearrangement of the PMDEGA chains. The final rehydrated film is thicker and contains more absorbed water as compared with the initially swollen film at the same temperature well below the demixing temperature. Y1 - 2015 U6 - https://doi.org/10.1021/acs.macromol.5b00645 SN - 0024-9297 SN - 1520-5835 VL - 48 IS - 11 SP - 3604 EP - 3612 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Zhang, Quanchao A1 - Sauter, Tilman A1 - Fang, Liang A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Shape-Memory Capability of Copolyetheresterurethane Microparticles Prepared via Electrospraying JF - Macromolecular materials and engineering N2 - Multifunctional thermo-responsive and degradable microparticles exhibiting a shapememory effect (SME) have attracted widespread interest in biomedicine as switchable delivery vehicles or microactuators. In this work almost spherical solid microparticles with an average diameter of 3.9 +/- 0.9 mm are prepared via electrospraying of a copolyetheresterurethane named PDC, which is composed of crystallizable oligo(p-dioxanone) (OPDO) hard and oligo(e-caprolactone) (OCL) switching segments. The PDC microparticles are programmed via compression at different pressures and their shapememory capability is explored by off-line and online heating experiments. When a low programming pressure of 0.2 MPa is applied a pronounced thermally-induced shape-memory effect is achieved with a shape recovery ratio about 80%, while a high programming pressure of 100 MPa resulted in a weak shape-memory performance. Finally, it is demonstrated that an array of PDC microparticles deposited on a polypropylene (PP) substrate can be successfully programmed into a smart temporary film, which disintegrates upon heating to 60 degrees C. KW - biomaterials KW - microparticles KW - processing KW - stimuli-sensitive polymers KW - shape-memory effect Y1 - 2015 U6 - https://doi.org/10.1002/mame.201400267 SN - 1438-7492 SN - 1439-2054 VL - 300 IS - 5 SP - 522 EP - 530 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Zerball, Maximilian A1 - Laschewsky, André A1 - von Klitzing, Regine T1 - Swelling of Polyelectrolyte Multilayers: The Relation Between, Surface and Bulk Characteristics JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - The odd even effect, i.e., the influence of the outermost layer of polyelectrolyte multilayers (PEMs) on their swelling behavior, is investigated. For that purpose poly(styrene sodium sulfonate) (PSS)/poly(diallyl-dimethylammonium chloride) (PDADMAC) polyelectrolyte multilayers are studied in air with 1% relative humidity (RH), 30% RH, 95% RH, and in liquid water by ellipsometry, atomic force microscopy (AFM), and X-ray reflectometry (XRR). Since the total amount of water uptake in swollen PEMs is divided into two fractions, the void water and the swelling water, a correct evaluation of the odd even effect is only possible if both fractions are examined separately. In order to allow measuring samples over a larger thickness regime the investigation of a larger amount of samples is required. Therefore, the concept of separating void water from swelling water using neutron reflectometry is for the first time transferred to ellipsometry. The subsequent analysis of swelling water, void water, and roughness revealed the existence of two types of odd even effects: an odd even effect which addresses only the surface of the PEM (surface-odd even effect) and an odd even effect which addresses also the bulk of the PEM (bulk-odd even effect). The appearance of both effects is dependent on the environment; the surface-odd even effect is only detectable in humid air while the bulk-odd even effect is only detectable in liquid water. The bulk-odd even effect is related to the osmotic pressure between the PEM and the surrounding water. A correlation between the amount of void water and both odd even effects is not found. The amount of void water is independent of the terminated layer and the thickness of PEMs. Y1 - 2015 U6 - https://doi.org/10.1021/acs.jpcb.5b04350 SN - 1520-6106 VL - 119 IS - 35 SP - 11879 EP - 11886 PB - American Chemical Society CY - Washington ER - TY - THES A1 - Yuan, Jiayin T1 - Poly(Ionic Liquid)s BT - innovative polyelectrolytes for materials applications Y1 - 2015 ER - TY - JOUR A1 - Yan, Wan A1 - Fang, Liang A1 - Nöchel, Ulrich A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Influence of deformation temperature on structural variation and shape-memory effect of a thermoplastic semi-crystalline multiblock copolymer JF - eXPRESS polymer letters N2 - A multiblock copolymer termed as PCL-PIBMD, consisting of crystallizable poly(epsilon-caprolactone) (PCL) segments and crystallizable poly(3S-isobutyl-morpholine-2,5-dione) (PIBMD) segments, has been reported as a material showing a thermally-induced shape-memory effect. While PIBMD crystalline domains act as netpoints to determine the permanent shape, both PCL crystalline domains and PIBMD amorphous domains, which have similar transition temperatures (T-trans) can act as switching domains. In this work, the influence of the deformation temperature (T-deform = 50 or 20 degrees C), which was above or below T-trans, on the structural changes of PCL-PIBMD during uniaxial deformation and the shapememory properties were investigated. Furthermore, the relative contribution of crystalline PCL and PIBMD amorphous phases to the fixation of the temporary shape were distinguished by a toluene vapor treatment approach. The results indicated that at 50 degrees C, both PCL and PIBMD amorphous phases can be orientated during deformation, resulting in thermally-induced crystals of PCL domains and joint contribution to the switching domains. In contrast at 20 degrees C, the temporary shape was mainly fixed by PCL crystals generated via strain-induced crystallization. KW - biodegradable polymers KW - shape-memory polymer KW - multiblock copolymer KW - polydepsipeptide Y1 - 2015 U6 - https://doi.org/10.3144/expresspolymlett.2015.58 SN - 1788-618X VL - 9 IS - 7 SP - 624 EP - 635 PB - Budapest University of Technology and Economics, Department of Polymer Engineering CY - Budapest ER - TY - JOUR A1 - Wu, Lei A1 - Glebe, Ulrich A1 - Böker, Alexander T1 - Surface-initiated controlled radical polymerizations from silica nanoparticles, gold nanocrystals, and bionanoparticles JF - Polymer Chemistry N2 - In recent years, core/shell nanohybrids containing a nanoparticle core and a distinct surrounding shell of polymer brushes have received extensive attention in nanoelectronics, nanophotonics, catalysis, nanopatterning, drug delivery, biosensing, and many others. From the large variety of existing polymerization methods on the one hand and strategies for grafting onto nanoparticle surfaces on the other hand, the combination of grafting-from with controlled radical polymerization (CRP) techniques has turned out to be the best suited for synthesizing these well-defined core/shell nanohybrids and is known as surface-initiated CRP. Most common among these are surface-initiated atom transfer radical polymerization (ATRP), surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, and surface-initiated nitroxide-mediated polymerization (NMP). This review highlights the state of the art of growing polymers from nanoparticles using surface-initiated CRP techniques. We focus on mechanistic aspects, synthetic procedures, and the formation of complex architectures as well as novel properties. From the vast number of examples of nanoparticle/polymer hybrids formed by surface-initiated CRP techniques, we present nanohybrid formation from the particularly important and most studied silica nanoparticles, gold nanocrystals, and proteins which can be regarded as bionanoparticles. Y1 - 2015 U6 - https://doi.org/10.1039/c5py00525f SN - 1759-9954 SN - 1759-9962 VL - 6 IS - 29 SP - 5143 EP - 5184 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Wirth, Jonas A1 - Hatter, Nino A1 - Drost, Robert A1 - Umbach, Tobias R. A1 - Barja, Sara A1 - Zastrow, Matthias A1 - Rück-Braun, Karola A1 - Pascual, Jose Ignacio A1 - Saalfrank, Peter A1 - Franke, Katharina J. T1 - Diarylethene Molecules on a Ag(111) Surface: Stability and Electron-Induced Switching JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - Diarylethene derivatives are photochromic molecular switches, undergoing a ring-opening/-closing reaction by illumination with light. The symmetry of the closed form is determined by the WoodWard Hoffinann rules according to which the reaction proceeds by corirotatory rotation -in that case. Here, we show by a cOrnbined approach of scanning tunneling microscopy (STM) and density functional theory (DFT) calculations that the Open isomer of 4,4'-(4,4'-(perfluorocydopent-1-ene-1,2-diyl)bis(5-methyl-thiophent-4,2,4-dipyridine) (PDTE) retains its open form upon adsorption on a Ag(111) surface. It caribe switched into a closed form, which we identify as the digrotatOly cydization product, by controlled manipulation 'With the STM tip, Evidence of an electric-field dependent switching-process 'is interpreted on the basis of a Simple electroStatic Model, which suggests that the reaction proceedS via an "upright" intermediate state. This pathway thus strongly differs from the switching reaction in solution. Y1 - 2015 U6 - https://doi.org/10.1021/jp5122036 SN - 1932-7447 VL - 119 IS - 9 SP - 4874 EP - 4883 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Wessig, Pablo A1 - Merkel, Roswitha A1 - Mueller, Peter T1 - Articulated rods - a novel class of molecular rods based on oligospiroketals (OSK) JF - Beilstein journal of organic chemistry N2 - We developed a new type of molecular rods consisting of two (or more) rigid units linked by a flexible joint. Consequently we called these constructs articulated rods (ARs). The syntheses of ARs were carried out by a flexible and modular approach providing access to a number of compounds with various functionalizations in terminal positions. First applications were presented with pyrene, cinnamoyl and anthracenyl labelled ARs. KW - articulated rods KW - click chemistry KW - molecular rods KW - oligospiroketals KW - pyrene excimer Y1 - 2015 U6 - https://doi.org/10.3762/bjoc.11.11 SN - 1860-5397 VL - 11 SP - 74 EP - 84 PB - Beilstein-Institut zur Förderung der Chemischen Wissenschaften CY - Frankfurt, Main ER -