@article{ZhuSchulzBrumaetal.1996, author = {Zhu, Shigen and Schulz, Burkhard and Bruma, Maria and Brehmer, Ludwig}, title = {Comparative study of the thermal properties of related aromatic polyhydrazides and poly(1,3,4-oxadiazole)s}, issn = {1042-7147}, doi = {10.1002/(SICI)1099-1581(199612)7:12<879::AID-PAT600>3.0.CO;2-X}, year = {1996}, language = {en} } @article{TurhanSaracGencturketal.2012, author = {Turhan, Metehan C. and Sarac, A. Sezai and Gencturk, Asli and Gilsing, Hans-Detlev and Faltz, Heike and Schulz, Burkhard}, title = {Electrochemical impedance characterization and potential dependence of poly[3,4-(2,2-dibutylpropylenedioxy)thiophene] nanostructures on single carbon fiber microelectrode}, series = {Synthetic metals : the journal of electronic polymers and electronic molecular materials}, volume = {162}, journal = {Synthetic metals : the journal of electronic polymers and electronic molecular materials}, number = {5-6}, publisher = {Elsevier}, address = {Lausanne}, issn = {0379-6779}, doi = {10.1016/j.synthmet.2012.01.012}, pages = {511 -- 515}, year = {2012}, abstract = {The electropolymerization of 3,4-(2,2-dibutylpropylenedioxy)thiophene (ProDOT-Bu-2) onto single carbon fiber microelectrode (SCFME) was conducted in acetonitrile (ACN) containing sodium perchlorate (NaClO4) as electrolyte and investigated by cyclic voltammetry (CV). The nanostructured films of poly[3,4-(2,2-dibutyl-propyleneclioxy)thiophene] (PProDOT-Bu-2) which were depositing showed complete reversible redox behavior in monomer-free electrolyte solution. The capacitive behavior of the films was investigated by electrochemical impedance spectroscopy (EIS) at applied potentials from 0.1 V to 1.3 V. The analysis by equivalent circuit modeling revealed an applied potential around 0.4V to be most suitable for the system PProDOT-Bu-2/SCFME as a double layer supercapacitor component inducing a double layer capacitance C-d, value of 62 mFcm(-2).}, language = {en} } @article{TarazonaMachatschekSchulzetal.2019, author = {Tarazona, Natalia A. and Machatschek, Rainhard Gabriel and Schulz, Burkhard and Auxiliadora Prieto Jim{\´e}nez, M. and Lendlein, Andreas}, title = {Molecular Insights into the Physical Adsorption of Amphiphilic Protein PhaF onto Copolyester Surfaces}, series = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, volume = {20}, journal = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, number = {9}, publisher = {American Chemical Society}, address = {Washington}, issn = {1525-7797}, doi = {10.1021/acs.biomac.9b00069}, pages = {3242 -- 3252}, year = {2019}, abstract = {Phasins are amphiphilic proteins located at the polymer-cytoplasm interface of bacterial polyhydroxyalkanoates (PHA). The immobilization of phasins on biomaterial surfaces is a promising way to enhance the hydrophilicity and supply cell- directing elements in bioinstructing processes. Optimizing the physical adsorption of phasins requires deep insights into molecular processes during polymer-protein interactions to preserve their structural conformation while optimizing surface coverage. Here, the assembly, organization, and stability of phasin PhaF from Pseudomonas putida at interfaces is disclosed. The Langmuir technique, combined with in situ microscopy and spectroscopic methods, revealed that PhaF forms stable and robust monolayers at different temperatures, with an almost flat orientation of its alpha-helix at the air-water interface. PhaF adsorption onto preformed monolayers of poly[(3-R-hydroxyoctanoate)-co-(3-R-hydroxyhexanoate)] (PHOHHx), yields stable mixed layers below pi = similar to 15.7 mN/m. Further insertion induces a molecular reorganization. PHOHHx with strong surface hydrophobicity is a more adequate substrate for PhaF adsorption than the less hydrophobic poly[(rac-lactide)-co-glycolide] (PLGA). The observed orientation of the main axis of the protein in relation to copolyester interfaces ensures the best exposure of the hydrophobic residues, providing a suitable coating strategy for polymer functionalization.}, language = {en} } @article{TanneJeoungPengetal.2015, author = {Tanne, Johannes and Jeoung, Jae-Hun and Peng, Lei and Yarman, Aysu and Dietzel, Birgit and Schulz, Burkhard and Schad, Daniel and Dobbek, Holger and Wollenberger, Ursula and Bier, Frank Fabian and Scheller, Frieder W.}, title = {Direct Electron Transfer and Bioelectrocatalysis by a Hexameric, Heme Protein at Nanostructured Electrodes}, series = {Electroanalysis : an international journal devoted to fundamental and practical aspects of electroanalysis}, volume = {27}, journal = {Electroanalysis : an international journal devoted to fundamental and practical aspects of electroanalysis}, number = {10}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1040-0397}, doi = {10.1002/elan.201500231}, pages = {2262 -- 2267}, year = {2015}, abstract = {A nanohybrid consisting of poly(3-aminobenzenesulfonic acid-co-aniline) and multiwalled carbon nanotubes [MWCNT-P(ABS-A)]) on a gold electrode was used to immobilize the hexameric tyrosine-coordinated heme protein (HTHP). The enzyme showed direct electron transfer between the heme group of the protein and the nanostructured surface. Desorption of the noncovalently bound heme from the protein could be excluded by control measurements with adsorbed hemin on aminohexanthiol-modified electrodes. The nanostructuring and the optimised charge characteristics resulted in a higher protein coverage as compared with MUA/MU modified electrodes. The adsorbed enzyme shows catalytic activity for the cathodic H2O2 reduction and oxidation of NADH.}, language = {en} } @article{SchuermannKochImperiaetal.1999, author = {Sch{\"u}rmann, H. and Koch, Norbert and Imperia, Paolo and Schrader, Sigurd and Jandke, M. and Strohriegl, P. and Schulz, Burkhard and Leising, G. and Brehmer, Ludwig}, title = {Ultraviolet photoelectron spectroscopic study of heterocyclic model compounds for electroluminescent devices}, year = {1999}, language = {en} } @article{SchoeneSchulzRichauetal.2014, author = {Sch{\"o}ne, Anne-Christin and Schulz, Burkhard and Richau, Klaus and Kratz, Karl and Lendlein, Andreas}, title = {Characterization of Langmuir films prepared from copolyesterurethanes based on oligo(omega-pentadecalactone) and oligo(epsilon-caprolactone)segments}, series = {Macromolecular chemistry and physics}, volume = {215}, journal = {Macromolecular chemistry and physics}, number = {24}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1352}, doi = {10.1002/macp.201400377}, pages = {2437 -- 2445}, year = {2014}, abstract = {A series of multiblock copolymers (PDLCL) synthesized from oligo(omega-pentadecalactone) diol (OPDL) and oligo(epsilon-caprolactone) diol (OCL), which are linked by 2,2(4), 4-trimethyl-hexamethylene diisocyanate (TMDI), is investigated by the Langmuir monolayer technique at the air-water interface. Brewster angle microscopy (BAM) and spectroscopic ellipsometry are employed to characterize the polymer film morphologies in situ. PDLCL containing >= 40 wt\% OCL segments form homogeneous Langmuir monofilms after spreading. The film elasticity modulus decreases with increasing amounts of OPDL segments in the copolymer. In contrast, the OCL-free polyesterurethane OPDL-TMDI cannot be spread to monomolecular films on the water surface properly, and movable slabs are observed by BAM even at low surface pressures. The results of the in situ morphological characterization clearly show that essential information concerning the reliability of Langmuir monolayer degradation (LMD) experiments cannot be obtained from the evaluation of the pi-A isotherms only. Consequently, in situ morphological characterization turns out to be indispensable for characterization of Langmuir layers before LMD experiments.}, language = {en} } @article{SchoeneSchulzLendlein2016, author = {Sch{\"o}ne, Anne-Christin and Schulz, Burkhard and Lendlein, Andreas}, title = {Stimuli Responsive and Multifunctional Polymers: Progress in Materials and Applications}, series = {Macromolecular rapid communications}, volume = {37}, journal = {Macromolecular rapid communications}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201600650}, pages = {1856 -- 1859}, year = {2016}, language = {en} } @article{SchoeneRichauKratzetal.2015, author = {Sch{\"o}ne, Anne-Christin and Richau, Klaus and Kratz, Karl and Schulz, Burkhard and Lendlein, Andreas}, title = {Influence of Diurethane Linkers on the Langmuir Layer Behavior of Oligo[(rac-lactide)-co-glycolide]-based Polyesterurethanes}, series = {Macromolecular rapid communications}, volume = {36}, journal = {Macromolecular rapid communications}, number = {21}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201500316}, pages = {1910 -- 1915}, year = {2015}, abstract = {Three oligo[(rac-lactide)-co-glycolide] based polyesterurethanes (OLGA-PUs) containing different diurethane linkers are investigated by the Langmuir monolayer technique and compared to poly[(rac-lactide)-co-glycolide] (PLGA) to elucidate the influence of the diurethane junction units on hydrophilicity and packing motifs of these polymers at the air-water interface. The presence of diurethane linkers does not manifest itself in the Langmuir layer behavior both in compression and expansion experiments when monomolecular films of OLGA-PUs are spread on the water surface. However, the linker retard the evolution of morphological structures at intermediate compression level under isobaric conditions (with a surface pressure greater than 11 mN m(-1)) compared to the PLGA, independent on the chemical structure of the diurethane moiety. The layer thicknesses of both OLGA-PU and PLGA films decrease in the high compression state with decreasing surface pressure, as deduced from ellipsometric data. All films must be described with the effective medium approximation as water swollen layers.}, language = {en} } @article{SchoeneKratzSchulzetal.2016, author = {Sch{\"o}ne, Anne-Christin and Kratz, Karl and Schulz, Burkhard and Lendlein, Andreas}, title = {The relevance of hydrophobic segments in multiblock copolyesterurethanes for their enzymatic degradation at the air-water interface}, series = {Polymer : the international journal for the science and technology of polymers}, volume = {102}, journal = {Polymer : the international journal for the science and technology of polymers}, publisher = {Elsevier}, address = {Oxford}, issn = {0032-3861}, doi = {10.1016/j.polymer.2016.09.001}, pages = {92 -- 98}, year = {2016}, abstract = {The interplay of an enzyme with a multiblock copolymer PDLCL containing two segments of different hydrophilicity and degradability is explored in thin films at the air-water interface. The enzymatic degradation was studied in homogenous Langmuir monolayers, which are formed when containing more than 40 wt\% oligo(epsilon-caprolactone) (OCL). Enzymatic degradation rates were significantly reduced with increasing content of hydrophobic oligo(omega-pentadecalactone) (OPDL). The apparent deceleration of the enzymatic process is caused by smaller portion of water-soluble degradation fragments formed from degradable OCL fragments. Beside the film degradation, a second competing process occurs after adding lipase from Pseudomonas cepacia into the subphase, namely the enrichment of the lipase molecules in the polymeric monolayer. The incorporation of the lipase into the Langmuir film is experimentally revealed by concurrent surface area enlargement and by Brewster angle microscopy (BAM). Aside from the ability to provide information about the degradation behavior of polymers, the Langmuir monolayer degradation (LMD) approach enables to investigate polymer-enzyme interactions for non-degradable polymers. (C) 2016 Elsevier Ltd. All rights reserved.}, language = {en} } @article{SchoeneKratzSchulzetal.2016, author = {Sch{\"o}ne, Anne-Christin and Kratz, Karl and Schulz, Burkhard and Lendlein, Andreas}, title = {Polymer architecture versus chemical structure as adjusting tools for the enzymatic degradation of oligo(epsilon-caprolactone) based films at the air-water interface}, series = {Polymer Degradation and Stability}, volume = {131}, journal = {Polymer Degradation and Stability}, publisher = {Elsevier}, address = {Oxford}, issn = {0141-3910}, doi = {10.1016/j.polymdegradstab.2016.07.010}, pages = {114 -- 121}, year = {2016}, abstract = {The enzymatic degradation of oligo(epsilon-caprolactone) (OCL) based films at the air-water interface is investigated by Langmuir monolayer degradation (LMD) experiments to elucidate the influence of the molecular architecture and of the chemical structure on the chain scission process. For that purpose, the interactions of 2D monolayers of two star-shaped poly(epsilon-caprolactone)s (PCLs) and three linear OCL based copolyesterurethanes (P(OCL-U)) with the lipase from Pseudomonas cepacia are evaluated in comparison to linear OCL. While the architecture of star-shaped PCL Langmuir layers slightly influences their degradability compared to OCL films, significantly retarded degradations are observed for P(OCL-U) films containing urethane junction units derived from 2, 2 (4), 4-trimethyl hexamethylene diisocyanate (TMDI), hexamethylene diisocyanate (HDI) or lysine ethyl ester diisocyanate (LDI). The enzymatic degradation of the OCL based 2D structures is related to the presence of hydrophilic groups within the macromolecules rather than to the packing density of the film or to the molecular weight. The results reveal that the LMD technique allows the parallel analysis of both the film/enzyme interactions and the degradation process on the molecular level. (C) 2016 Elsevier Ltd. All rights reserved.}, language = {en} } @article{SchulzStillerZetzscheetal.1995, author = {Schulz, Burkhard and Stiller, Burkhard and Zetzsche, Thomas and Knochenhauer, Gerald and Dietel, Reinhard and Brehmer, Ludwig}, title = {Characterization of 2,5-di(p-tolyl-1,3,4- oxadiazole) crystals by IR-spectroscopy and atomic force microscopy}, year = {1995}, language = {en} } @article{SchulzStillerZetzscheetal.1994, author = {Schulz, Burkhard and Stiller, Burkhard and Zetzsche, Thomas and Knochenhauer, Gerald and Dietel, Reinhard and Brehmer, Ludwig}, title = {Crystal structure of 2,5-Di(4- methoxycarbonyl-phenyl)-1,3,4-oxadiazole characterized by AFM and IR- spectroscopy}, year = {1994}, language = {en} } @article{SchulzStillerZetzscheetal.1997, author = {Schulz, Burkhard and Stiller, Burkhard and Zetzsche, Thomas and Knochenhauer, Gerald and Brehmer, Ludwig}, title = {Characterization of crystals based on 1,3,4-oxadiazoles by atomic force microscopy}, year = {1997}, abstract = {The surface structures of crystals based on aromatic oxadiazoles were investigated by AFM. The crystal structure for 2,5-di(p-tolyl)-1,3,4-oxadiazole (DTO) differs from that of 2,5-di (4-methoxycarbonyl-phenyl)-1,3,4- oxadiazole (DMPO). In DMPO all molecules show parallel orientation to the surface in such a way that the surface is formed as well as by the nitrogen atoms of the heterocyclic rings and the methyl groups of the ester substituents. By contrast, the oxadiazole molecules in DTO crystals are oriented perpendicular to the crystal surface. The experimental data are interpreted by molecular modelling. It is shown that there is a difference between molecular structure of the surface, as detected by AFM, and the bulk structure determined by X-ray diffraction.}, language = {en} } @article{SchulzOrgzallDiezetal.2010, author = {Schulz, Burkhard and Orgzall, Ingo and Diez, Isabel and Dietzel, Birgit and Tauer, Klaus}, title = {Template mediated formation of shaped polypyrrole particles}, issn = {0927-7757}, doi = {10.1016/j.colsurfa.2009.11.034}, year = {2010}, abstract = {The formation of different micro- and nanostructures during the chemical synthesis of polypyrrole is reviewed shortly based on the conceptions of hard- and soft-templating models. Contrary to other models that emphasize the role of micelles it is found here that during the oxidative polymerization of pyrole using sulfonic acid dopants a crystalline hard template is found in the first steps of the reaction before the addition of the oxidant. This template is formed by a complex consisting of 2,5-bis(pyrrole-2-yl)pyrrolidine and the sulfonic acid anion. The acid catalyzed formation of this specific tripyrrole is discussed. (C) 2009 Elsevier B.V. All rights reserved.}, language = {en} } @article{SchulzKnochenhauerBrehmeretal.1995, author = {Schulz, Burkhard and Knochenhauer, Gerald and Brehmer, Ludwig and Janietz, Silvia}, title = {Stuctures and properties of aromatic poly(1,3,4-oxadiazole)s}, year = {1995}, language = {en} } @article{SchulzKnochenhauerBrehmeretal.1994, author = {Schulz, Burkhard and Knochenhauer, Gerald and Brehmer, Ludwig and Janietz, Silvia}, title = {Stuctures and properties of aromatic poly(1,3,4-oxadiazole)s}, year = {1994}, language = {en} } @article{SchulzKaminorzBrehmer1997, author = {Schulz, Burkhard and Kaminorz, Yvette and Brehmer, Ludwig}, title = {New aromatic poly(1,3,4-oxadiazole)s for light emitting diodes}, year = {1997}, abstract = {New aromatic poly(1,3,4-oxadiazole)s were synthesized having excellent film forming properties due to their solubility in common organic solvents. The investigated new polyoxadiazoles can be used as emission material in single layer LED. The poly- oxadiazoles show an emission in the range of blue to yellow light. The external quantum efficiency as well as the turn-on voltage of the devices are influenced when blends of the polyoxadiazole with hole transport materials are used.}, language = {en} } @article{SchulzJanietz1994, author = {Schulz, Burkhard and Janietz, Silvia}, title = {Electrochemical studies on thin films of poly(arylene 1,3,4-oxadiazole)s}, year = {1994}, language = {en} } @article{SchulzJanietz1995, author = {Schulz, Burkhard and Janietz, Silvia}, title = {Preparation and characterization of thin films containing aromatic poly(1,3,4- oxadiazole)s}, year = {1995}, language = {en} } @article{SchulzDietzelOrgzalletal.2009, author = {Schulz, Burkhard and Dietzel, Birgit and Orgzall, Ingo and Diez, Isabel and Xu, Chenggang}, title = {Aspects of morphology control during the oxidative synthesis of electrically conducting polymers}, issn = {0954-0083}, doi = {10.1177/0954008309339933}, year = {2009}, abstract = {The formation of micro- and nanostructures during the oxidative polymerization of polypyrrole and polyaniline is investigated using different sulfonic acid dopants. Rod- or tube-like structures are found in polypyrrole as well as in polyaniline without addition of further compounds to the initial reaction mixture of monomer, dopant and oxidant. In these cases, always a crystalline precursor complex composed of a dopand molecule and the pure monomer (aniline) or a trimeric moiety (pyrrole) serves as in-situ template. In most cases the surface of the growing polymer is covered by secondary structures with much smaller sizes so that a hierarchical order of structures at different length scales results. Corresponding model considerations for the polymerization process are outlined. Additionally, unusual structures like platelets, frames, rings, or ribbons are observed in the polypyrrole synthesis in the presence of fluorosurfactants.}, language = {en} } @article{SchulzBrumaBrehmer1997, author = {Schulz, Burkhard and Bruma, Maria and Brehmer, Ludwig}, title = {Aromatic poly(1,3,4-oxadiazole)s as advanced materials}, year = {1997}, abstract = {Poly(1,3,4-oxadiazole)s have been the focus of considerable interest with regard to the- production of high- performance materials, particularly owing to their high thermal stability in oxidative atmosphere and specific properties determined by the structure of 1,3,4-oxadiazole ring, which, from the spectral and electronic points of view, is similar to a p-phenylene structure.[1] Besides their excellent resistance to high temperature, polyoxadiazoles have many desirable characteristics, such as good hydrolytic stability, high glass transition temperatures, low dielectric constants, and tough mechanical properties. Some polyoxadiazoles have semiconductive properties, other structures can be electrochemically doped and thus made conductive, and other have liquid-crystalline properties, which make them very attractive for a wide range of high-performance applications. They exhibit excellent fiber- and film-forming capabilities, thus being considered for use as heat-resistant reinforcing fibers for advanced composite materials, highly resistant fabrics for the filtration of hot gases, special membranes for gas separation or reverse osmosis, precursors for highly oriented graphite fibers, films, and blocks to be used in the construction of electronic instruments based on X-rays, neutron beams, or a-particles, or in the construction of nuclear reactor walls. Since they were first reported in 1961,[2] a wide variety of polymers containing 1,3,4-oxadiazole rings have been synthesized, and their preparation, characterization, and physico-mechanical properties have been periodically reviewed .[3-8] This article will present a general overview of this class of polymers and will refer to the work carried out by different researchers in the last ten years with the emphasis on the potential uses of such polymers as advanced materials.}, language = {en} } @article{SchulzBrehmerKnochenhauer1995, author = {Schulz, Burkhard and Brehmer, Ludwig and Knochenhauer, Gerald}, title = {Supramolecular structures of aromatic 1,3,4-oxadiazole solids}, year = {1995}, language = {en} } @article{SchulzBrehmerDietzeletal.1995, author = {Schulz, Burkhard and Brehmer, Ludwig and Dietzel, Birgit and Zetzsche, Thomas}, title = {Preparation and characterization of ordered thin films based on aromatic poly(1,3,4-oxadiazole)s}, year = {1995}, language = {en} } @article{SchulzBrehmer1995, author = {Schulz, Burkhard and Brehmer, Ludwig}, title = {Preparation and characterization of ordered thin films based on aromatic poly(1,3,4-oxadiazole)s}, year = {1995}, language = {en} } @article{Schulz1994, author = {Schulz, Burkhard}, title = {New aspects of the solid-state structures and electrochemical properties of aromatic Poly(1,3,4- Oxadiazole)s}, year = {1994}, language = {en} } @article{Schulz1995, author = {Schulz, Burkhard}, title = {Structure and properties of thin polyoxadiazole films}, year = {1995}, language = {en} } @article{SavaSzesztayBrumaetal.1997, author = {Sava, Ion and Szesztay, Marta and Bruma, Maria and Mercer, Frank W. and Schulz, Burkhard}, title = {Compared properties of aromatic polyamides containing silicon in the chain}, year = {1997}, abstract = {Two series of aromatic polyamides incorporating silicon together with phenylquinoxaline or with hexafluoroisopropylidene groups have been synthesized and their properties have been characterized and compared with those of related polymers. These polymers are easily soluble in polar amidic solvents such as N-rnethyl-2-pyrrolidinone and dimethylformamide, and in tetrahydrofuran, and can be cast into thin, transparent films from solution. The polyamides have weight- and number-average molecular weights in the range of 10000-40000 and 3000-6000, respectively, and polydispersities in the range of 3-10. They show glass transition temperatures in the range of 236 °C-275 °C and decomposition temperatures above 400 °C. The polymer films have low dielectric constants in the range of 3.26-3.68, and good mechanical properties (tensile strength 74-100 MPa, tensile modulus 180-386 MPa), thus being comparable with other high performance dielectrics.}, language = {en} } @article{SavaSchulzZhuetal.1995, author = {Sava, Ion and Schulz, Burkhard and Zhu, Shigen and Bruma, Maria}, title = {Synthesis and characterization of new silicon-containing poly(arylene-1,3,4-oxadiazole)s}, issn = {0954-0083}, doi = {10.1088/0954-0083/7/4/011}, year = {1995}, language = {en} } @article{SavaBrumaSchulzetal.1997, author = {Sava, Ion and Bruma, Maria and Schulz, Burkhard and Mercer, Frank W. and Belomoina, Nataliya}, title = {Synthesis and Properties of Silicon-containing Polyamides}, year = {1997}, abstract = {A series of aromatic polyamides incorporating silicon together with phenylquinoxaline or with hexafluoroisopropylidene groups has been synthesized by solution polycondensation of a silicon-containing diacid chloride with aromatic diamines having phenylquinoxaline rings or hexafluoroisopropylidene groups. These polymers are easily soluble in polar aprotic solvents, such as N-methylpyrrolidinone and dimethylformamide, and in tetrahydrofurane, and can be solution-cast into thin, transparent films having low dielectric constant, in the range of 3.26 to 3.68. These polymers show high thermal stability with decomposition temperature being above 400 °C and glass transition temperature in the range of 236 °C to 275 °C.}, language = {en} } @article{SavaBrumaSchulzetal.2005, author = {Sava, Ion and Bruma, Maria and Schulz, Burkhard and K{\"o}pnick, Thomas}, title = {Comparison of properties of silicon-containing poly(amide-imide)s}, issn = {0954-0083}, year = {2005}, abstract = {New silicon-containing poly(amide-imide)s have been synthesized by direct polycondensation of various aromatic diamines with a dicarboxylic acid containing the dimethylsilylene group and preformed in-tide cycles. These polymers are easily soluble in polar amidic solvents such as N-methylpyrrolidinone (NMP) or dimethylformamide (DMF) and can be cast into thin flexible films or coatings from such solutions. They show high thermal stability, with initial decomposition temperature being above 400 C and glass transition temperature in the range of 220-270 degrees C. Very thin polymer films deposited by spincoating technique onto silicon wafers showed a smooth, pinhole-free surface in atomic force microscopy investigations}, language = {en} } @article{SaretiaMachatschekSchulzetal.2019, author = {Saretia, Shivam and Machatschek, Rainhard Gabriel and Schulz, Burkhard and Lendlein, Andreas}, title = {Reversible 2D networks of oligo(epsilon-caprolactone) at the air-water interface}, series = {Biomedical Materials}, volume = {14}, journal = {Biomedical Materials}, number = {3}, publisher = {IOP Publ. Ltd.}, address = {Bristol}, issn = {1748-6041}, doi = {10.1088/1748-605X/ab0cef}, pages = {10}, year = {2019}, abstract = {Hydroxyl terminated oligo(epsilon-caprolactone) (OCL) monolayers were reversibly cross-linked forming two dimensional networks (2D) at the air-water interface. The equilibrium reaction with glyoxal as the cross-linker is pH-sensitive. Pronounced contraction in the area of the prepared 2DOCL films in dependence of surface pressure and time revealed the process of the reaction. Cross-linking inhibited crystallization and retarded enzymatic degradation of the OCLfilm. Altering the subphase pH led to a cleavage of the covalent acetal cross-links. The reversibility of the covalent acetal cross-links was proved by observing an identical isotherm as non-cross-linked sample. Besides as model systems, these customizable reversible OCL2D networks are intended for use as pHresponsive drug delivery systems or functionalized cell culture substrates.}, language = {en} } @article{SarauliXuDietzeletal.2012, author = {Sarauli, David and Xu, Chenggang and Dietzel, Birgit and Stiba, Konstanze and Leimk{\"u}hler, Silke and Schulz, Burkhard and Lisdat, Fred}, title = {Thin films of substituted polyanilines interactions with biomolecular systems}, series = {Soft matter}, volume = {8}, journal = {Soft matter}, number = {14}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1744-683X}, doi = {10.1039/c2sm07261k}, pages = {3848 -- 3855}, year = {2012}, abstract = {We use substituted polyanilines for the construction of new polymer electrodes for interaction studies with the redox protein cytochrome c (cyt c) and the enzyme sulfite oxidase (SO). For these purposes four different polyaniline copolymers are chemically synthesized. Three of them are copolymers, containing 2-methoxyaniline-5-sulfonic acid with variable ratios of aniline; the fourth copolymer consists of 3-amino-benzoic acid and aniline. The results show that all polymers are suitable for being immobilized as thin stable films on gold wire and indium tin oxide (ITO) electrode surfaces from DMSO solution. This can be demonstrated by cyclic voltammetry and UV-Vis spectroscopy measurements. Moreover, cyt c can be electrochemically detected not only in solution, but also immobilized on top of the polymer films. Furthermore, the appearance of a significant catalytic current has been demonstrated for the sulfonated polyanilines, when the polymer-coated protein electrode is being measured upon addition of sulfite oxidase, confirming the establishment of a bioanalytical signal chain. Best results have been obtained for the polymer with highest sulfonation grade. The redox switching of the polymer by the enzymatic reaction can also be analyzed by following the spectral properties of the polymer electrode.}, language = {en} } @article{SarauliXuDietzeletal.2013, author = {Sarauli, David and Xu, Chenggang and Dietzel, Birgit and Schulz, Burkhard and Lisdat, Fred}, title = {Differently substituted sulfonated polyanilines - the role of polymer compositions in electron transfer with pyrroloquinoline quinone-dependent glucose dehydrogenase}, series = {Acta biomaterialia}, volume = {9}, journal = {Acta biomaterialia}, number = {9}, publisher = {Elsevier}, address = {Oxford}, issn = {1742-7061}, doi = {10.1016/j.actbio.2013.06.008}, pages = {8290 -- 8298}, year = {2013}, abstract = {Sulfonated polyanilines have become promising building blocks in the construction of biosensors, and therefore we use here differently substituted polymer forms to investigate the role of their structural composition and properties in achieving a direct electron transfer with the redox enzyme pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH). To this end, new copolymers containing different ratios of 2-methoxyaniline-5-sulfonic acid (MAS), 3-aminobenzenesulfonic acid (ABS) and 3-aminobenzoic acid (AB) units have been chemically synthesized. All polymers have been studied with respect to their ability to react directly with PQQ-GDH. This interaction has been monitored initially in solution, and subsequently on electrode surfaces. The results show that only copolymers with MAS and aniline units can directly react with PQQ-GDH in solution; the background can be mainly ascribed to the emeraldine salt redox state of the polymer, allowing rather easy reduction. However, when polymers and the enzyme are immobilized on the surface of carbon nanotube-containing electrodes, direct bioelectrocatalysis is also feasible in the case of copolymers composed of ABS/AB and MAS/AB units, existing initially in pernigraniline base form. This verifies that a productive interaction of the enzyme with differently substituted polymers is feasible when the electrode potential can be used to drive the reaction towards the oxidation of the substrate-reduced enzyme. These results clearly demonstrate that enzyme electrodes based on sulfonated polyanilines and direct bioelectrocatalysis can be successfully constructed.}, language = {en} } @article{SarauliXuDietzeletal.2014, author = {Sarauli, David and Xu, Chenggang and Dietzel, Birgit and Schulz, Burkhard and Lisdat, Fred}, title = {A multilayered sulfonated polyaniline network with entrapped pyrroloquinoline quinone-dependent glucose dehydrogenase: tunable direct bioelectrocatalysis}, series = {Journal of materials chemistry : B, Materials for biology and medicine}, volume = {2}, journal = {Journal of materials chemistry : B, Materials for biology and medicine}, number = {21}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2050-750X}, doi = {10.1039/c4tb00336e}, pages = {3196 -- 3203}, year = {2014}, abstract = {A feasible approach to construct multilayer films of sulfonated polyanilines - PMSA1 and PABMSA1 containing different ratios of aniline, 2-methoxyaniline-5-sulfonic acid (MAS) and 3-aminobenzoic acid (AB), with the entrapped redox enzyme pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH) on Au and ITO electrode surfaces, is described. The formation of layers has been followed and confirmed by electrochemical impedance spectroscopy (EIS), which demonstrates that the multilayer assembly can be achieved in a progressive and uniform manner. The gold and ITO electrodes subsequently modified with PMSA1:PQQ-GDH and PABMSA1 films are studied by cyclic voltammetry (CV) and UV-Vis spectroscopy which show a significant direct bioelectrocatalytical response to the oxidation of the substrate glucose without any additional mediator. This response correlates linearly with the number of deposited layers. Furthermore, the constructed polymer/enzyme multilayer system exhibits a rather good long-term stability, since the catalytic current response is maintained for more than 60\% of the initial value even after two weeks of storage. This verifies that a productive interaction of the enzyme embedded in the film of substituted polyaniline can be used as a basis for the construction of bioelectronic units, which are useful as indicators for processes liberating glucose and allowing optical and electrochemical transduction.}, language = {en} } @article{SarauliPetersXuetal.2014, author = {Sarauli, David and Peters, Kristina and Xu, Chenggang and Schulz, Burkhard and Fattakhova-Rohlfing, Dina and Lisdat, Fred}, title = {3D-Electrode architectures for enhanced direct bioelectrocatalysis of pyrroloquinoline quinone-dependent glucose dehydrogenase}, series = {ACS applied materials \& interfaces}, volume = {6}, journal = {ACS applied materials \& interfaces}, number = {20}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/am5046026}, pages = {17887 -- 17893}, year = {2014}, abstract = {We report on the fabrication of a complex electrode architecture for efficient direct bioelectrocatalysis. In the developed procedure, the redox enzyme pyrroloquinoline quinone-dependent glucose dehydrogenase entrapped in a sulfonated polyaniline [poly(2-methoxyaniline-5-sulfonic acid)-co-aniline] was immobilized on macroporous indium tin oxide (macroITO) electrodes. The use of the 3D-conducting scaffold with a large surface area in combination with the conductive polymer enables immobilization of large amounts of enzyme and its efficient communication with the electrode, leading to enhanced direct bioelectrocatalysis. In the presence of glucose, the fabricated bioelectrodes show an exceptionally high direct bioelectrocatalytical response without any additional mediator. The catalytic current is increased more than 200-fold compared to planar ITO electrodes. Together with a high long-term stability (the current response is maintained for >90\% of the initial value even after 2 weeks of storage), the transparent 3D macroITO structure with a conductive polymer represents a valuable basis for the construction of highly efficient bioelectronic units, which are useful as indicators for processes liberating glucose and allowing optical and electrochemical transduction.}, language = {en} } @article{SarauliBorowskiPetersetal.2016, author = {Sarauli, David and Borowski, Anja and Peters, Kristina and Schulz, Burkhard and Fattakhova-Rohlfing, Dina and Leimk{\"u}hler, Silke and Lisdat, Fred}, title = {Investigation of the pH-Dependent Impact of Sulfonated Polyaniline on Bioelectrocatalytic Activity of Xanthine Dehydrogenase}, series = {ACS catalysis}, volume = {6}, journal = {ACS catalysis}, publisher = {American Chemical Society}, address = {Washington}, issn = {2155-5435}, doi = {10.1021/acscatal.6b02011}, pages = {7152 -- 7159}, year = {2016}, abstract = {We report on the pH-dependent bioelectrocatalytic activity of the redox enzyme xanthine dehydrogenase (XDH) in the presence of sulfonated polyaniline PMSA1 (poly(2-methoxyaniline-5-sulfonic acid)-co-aniline). Ultraviolet-visible (UV-vis) spectroscopic measurements with both components in solution reveal electron transfer from the hypoxanthine (HX)-reduced enzyme to the polymer. The enzyme shows bioelectrocatalytic activity on indium tin oxide (ITO) electrodes, when the polymer is present. Depending on solution pH, different processes can be identified. It can be demonstrated that not only product-based communication with the electrode but also efficient polymer-supported bioelectrocatalysis occur. Interestingly, substrate dependent catalytic currents can be obtained in acidic and neutral solutions, although the highest activity of XDH with natural reaction partners is in the alkaline region. Furthermore, operation of the enzyme electrode without addition of the natural cofactor of XDH is feasible. Finally, macroporous ITO electrodes have been used as an immobilization platform for the fabrication of HX-sensitive electrodes. The study shows that the efficient polymer/enzyme interaction can be advantageously combined with the open structure of an electrode material of controlled pore size, resulting in good processability, stability, and defined signal transfer in the presence of a substrate.}, language = {en} } @article{SaracGencturkGilsingetal.2009, author = {Sarac, A. Sezai and Gencturk, Asli and Gilsing, Hans-Detlev and Schulz, Burkhard and Turhan, C. Metehan}, title = {Effect of electrolyte on the electropolymerization of 2,2-dibutyl-3,4-propylenedioxythiophene on carbon fiber microelectrodes}, issn = {1533-4880}, doi = {10.1166/Jnn.2009.027}, year = {2009}, abstract = {Electrocoating of 2,2 dibutylpropylene dioxythiophene on carbon fiber microelectrodes (CFMEs) in different electrolytes in acetonitrile was performed, and surface morphology and electrochemical impedance spectroscopic investigation has been carried out. Impedance spectra showed the typical form of Z(IM) versus Z(RE) for transmission- line at frequencies 10 Hz, with transition to almost pure capacitive behaviour down to 10 mHz (the lower limit of frequency scan).}, language = {en} } @article{RottkeSchulzRichauetal.2016, author = {Rottke, Falko O. and Schulz, Burkhard and Richau, Klaus and Kratz, Karl and Lendlein, Andreas}, title = {An ellipsometric approach towards the description of inhomogeneous polymer-based Langmuir layers}, series = {Beilstein journal of nanotechnology}, volume = {7}, journal = {Beilstein journal of nanotechnology}, publisher = {Beilstein-Institut zur F{\~A}\Prderung der Chemischen Wissenschaften}, address = {Frankfurt, Main}, issn = {2190-4286}, doi = {10.3762/bjnano.7.107}, pages = {1156 -- 1165}, year = {2016}, abstract = {The applicability of nulling-based ellipsometric mapping as a complementary method next to Brewster angle microscopy (BAM) and imaging ellipsometry (IE) is presented for the characterization of ultrathin films at the air-water interface. First, the methodology is demonstrated for a vertically nonmoving Langmuir layer of star-shaped, 4-arm poly(omega-pentadecalactone) (PPDL-D4). Using nulling-based ellipsometric mapping, PPDL-D4-based inhomogeneously structured morphologies with a vertical dimension in the lower nm range could be mapped. In addition to the identification of these structures, the differentiation between a monolayer and bare water was possible. Second, the potential and limitations of this method were verified by applying it to more versatile Langmuir layers of telechelic poly[(rac-lactide)-co-glycolide]-diol (PLGA). All ellipsometric maps were converted into thickness maps by introduction of the refractive index that was derived from independent ellipsometric experiments, and the result was additionally evaluated in terms of the root mean square roughness, R-q. Thereby, a three-dimensional view into the layers was enabled and morphological inhomogeneity could be quantified.}, language = {en} } @article{RossbergRottkeSchulzetal.2016, author = {Rossberg, Joana and Rottke, Falko O. and Schulz, Burkhard and Lendlein, Andreas}, title = {Enzymatic Degradation of Oligo(epsilon-caprolactone)s End-Capped with Phenylboronic Acid Derivatives at the Air-Water Interface}, series = {Macromolecular rapid communications}, volume = {37}, journal = {Macromolecular rapid communications}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201600471}, pages = {1966 -- 1971}, year = {2016}, abstract = {The influence of terminal functionalization of oligo(epsilon-caprolactone)s (OCL) with phenylboronic acid pinacol ester or phenylboronic acid on the enzymatic degradation behavior at the air-water interface is investigated by the Langmuir monolayer degradation technique. While the unsubstituted OCL immediately degrades after injection of the enzyme lipase from Pseudomonas cepacia, enzyme molecules are incorporated into the films based on end-capped OCL before degradation. This incorporation of enzymes does not inhibit or suppress the film degradation, but retards it significantly. A specific binding of lipase to the polymer monolayer allows studying the enzymatic activity of bound proteins and the influence on the degradation process. The functionalization of a macromolecule with phenyl boronic acid groups is an approach to investigate their interactions with diol-containing biomolecules like sugars and to monitor their specified impact on the enzymatic degradation behavior at the air-water interface.}, language = {en} } @article{ReicheZetzscheHelmsetal.1997, author = {Reiche, J{\"u}rgen and Zetzsche, Thomas and Helms, Andreas and Freydank, Anke-Christine and Knochenhauer, Gerald and Schulz, Burkhard and Brehmer, Ludwig}, title = {Organized molecular films of oxadiazole compounds formed by vacuum deposition}, year = {1997}, language = {en} } @article{ReicheSchulzKnochenhaueretal.1997, author = {Reiche, J{\"u}rgen and Schulz, Burkhard and Knochenhauer, Gerald and Dietzel, Birgit and Freydank, Anke-Christine and Zetzsche, Thomas and Brehmer, Ludwig}, title = {Supramolecular structures formed from heterocyclic aromatic molecules}, year = {1997}, abstract = {This paper describes the formation and structure investigation of Langmuir monolayers and Langmuir-Blodgett multilayers formed from amphiphilic derivatives of 2,5-diphenyl-1,3,4-oxadiazole. The 2,5-diphenyl-1,3,4-oxadiazole group as a functional unit with interesting physical and chemical properties is maintained, while the head group, the length of the alkyl chain and the structure of the coupling unit between aromatic and aliphatic part of these linear short-chain amphiphiles is systematically varied in order to explore the influence of this change on the film forming properties and the stability of Langmuir and Langmuir-Blodgett films. Molecular mechanics simulations are shown by these systematic variations to be suitable for the prediction of optimal chemical structures allowing for a stable stratified molecular packing. The combination of a detailed structure investigation of the multilayers based on scanning force microscopy and X-ray data with molecular mechanics simulations yields an insight into the packing of the molecules and the intermolecular interactions.}, language = {en} } @article{ReicheFreydankHelmsetal.1999, author = {Reiche, J{\"u}rgen and Freydank, Anke-Christine and Helms, Andreas and Geue, Thomas and Schulz, Burkhard and Brehmer, Ludwig and Stiller, Burkhard and Knochenhauer, Gerald}, title = {Vacuum deposition films of oxadiazole compounds : formation and structure investigation}, year = {1999}, abstract = {The search for alternative routes of organic thin film formation is stimulated by the outstanding properties of these films in such fields as nonlinear optics, photonic data processing and molecular electronics. The formation of highly ordered multilayer structures by thermal vacuum deposition (VD) of organic compounds is an essential step toward the application of supramolecular organic architectures in technical systems. The VD of an amphiphilic substituted 2,5- diphenylene-1,3,4-oxadiazole 1 onto silicon substrates at defined temperature was used for the formation of ultrathin films. The structural data obtained for the VD-films of oxadiazole 1 by means of X-ray reflectivity, X-ray grazing incidence diffraction and atomic force microscopy (AFM) investigations indicate the formation of well ordered oxadiazole multilayers. The structure of the VD-multilayers is compared with that of Langmuir-Blodgett (LB) films and thermally treated LB-multilayers prepared from the same compound.}, language = {en} } @article{OrgzallLorenzMikatetal.1998, author = {Orgzall, Ingo and Lorenz, Bernd and Mikat, J{\"u}rgen E. R. and Reck, G{\"u}nter and Knochenhauer, Gerald and Schulz, Burkhard}, title = {Phase transition in 1,3,4-oxadiazole crystals under high pressure}, year = {1998}, language = {en} } @article{OrgzallLorenzMikatetal.1999, author = {Orgzall, Ingo and Lorenz, Bernd and Mikat, J{\"u}rgen E. R. and Reck, G{\"u}nter and Knochenhauer, Gerald and Schulz, Burkhard}, title = {Phase transition in 1,3,4-oxadiazole crystals under high pressure}, year = {1999}, abstract = {Crystalline 2,5-di(4-nitrophenyl)-1,3,4-oxadiazole (DNO) has been investigated at pressures up to 5 GPa using Raman and optical spectroscopy as well as energy dispersive X-ray techniques. At ambient pressure DNO shows an orthorhombic unit cell (a = 0.5448 nm, b = 1.2758 nm, c = 1.9720 nm, density 1.513 g cm-3) with an appropriate space group Pbcn. From Raman spectroscopic investigations three phase transitions have been detected at 0.88, 1.28, and 2.2 GPa, respectively. These transitions have also been confirmed by absorption spectroscopy and X-ray measurements. Molecular modeling simulations have considerably contributed to the interpretation of the X-ray diffractograms. In general, the nearly flat structure of the oxadiazole molecule is preserved during the transitions. All subsequent structures are characterized by a stack-like arrangement of the DNO molecules. Only the mutual position of these molecular stacks changes due to the transformations so that this process may be described as a topotactical reaction. Phases II and III show a monoclinic symmetry with space group P21/c with cell parameters a = 1.990 nm, b = 0.500 nm, c = 1.240 nm, ß = 91.7°, density 1.681 g cm-3 (phase II, determined at 1. 1 GPa) and a = 1.890 nm, b = 0.510 nm, C = 1.242 nm, ß = 89.0°, density 1.733 g cm-3 (phase 111, determined at 2.0 GPa), respectively. The high-pressure phase IV stable at least up to 5 GPa shows again an orthorhombic structure with space group Pccn with corresponding cell parameters at 2.9 GPa: a = 0.465 nm, b = 1.920 nm, c = 1.230 nm and density 1.857 g cm-3 . For the first phase a blue pressure shift of the onset of absorption by about 0.032 eV GPa has been observed that may be explained by pressure influences on the electronic conjugation of the molecule. In the intermediate and high-pressure phases II-IV the onset of absorption shifts to increased wavelengths due to larger intermolecular interactions and enhanced excitation delocalization with decreasing intermolecular spacing.}, language = {en} } @article{OrgzallLorenzMikatetal.1997, author = {Orgzall, Ingo and Lorenz, Bernd and Mikat, J{\"u}rgen E. R. and Dietel, Reinhard and Knochenhauer, Gerald and Schulz, Burkhard}, title = {Raman and IR spectroscopic investigation of aromatic 1,3,4-oxadiazole polymers and oligomers}, year = {1997}, abstract = {The molecular structure of poly(p-phenylene-1,3,4-oxadiazole) (POD) is investigated using i.r. and Raman spectroscopy. Both methods reveal characteristic differences for the a- and b-POD forms that are most obvious in the spectral region between 1500 and 1650 cm-1. The spectra for dimer and tetramer compounds already show the same features as found for longer chains. Based on molecular modelling calculations these differences are assigned to cis and trans conformations of the main chain segments. High pressure measurements show a linear shift of the Raman lines and support the result of the thermodynamic stability of the trans conformation.}, language = {en} } @article{OrgzallFrancoSchulz2006, author = {Orgzall, Ingo and Franco, Olga and Schulz, Burkhard}, title = {High pressure structural investigations of 2,5-di(4-pyridyl)-1,3,4-oxadiazole - importance of strain studies for the description of intermolecular interactions}, doi = {10.1088/0953-8984/18/23/001}, year = {2006}, abstract = {Results of a high pressure x-ray study of 2,5-di(4-pyridyl)-1,3,4-oxadiazole up to 2.5 GPa are presented and discussed. Parameters for the Murnaghan equation of state are derived. The bulk modulus amounts to K-0 = 4.6 +/- 0.3 GPa and its pressure derivative to K-0' = 7.4 +/- 0.6. These values are comparable to values of other diphenyl-1,3,4- oxadiazoles. The anisotropy of the compression is analysed using the strain tensor and discussed based on the anisotropy of the intermolecular interactions}, language = {en} } @article{OrgzallFrancoRecketal.2005, author = {Orgzall, Ingo and Franco, Olga and Reck, Guenter and Schulz, Burkhard}, title = {High-pressure studies on fluorine substituted 2,5-di(phenyl)-1,3,4-oxadiazoles}, issn = {0022-2860}, year = {2005}, abstract = {Results are presented from structural and high-pressure investigations on four differently but symmetrically fluorine substituted 2,5di(phenyl)-1,3,4-oxadiazoles. The substitution pattern includes the para-, meta-, or ortho- substitution and the fully fluorinated 2,5-bis(pentafluorophenyl)-1,3,4-oxadiazole. The crystal structure depends on the molecular structure and results in a different high-pressure behavior. Parameters for the Murnaghan equation of state (EOS) are determined for every compound and the anisotropic pressure response of the crystal lattice is discussed. Although the EOS parameters, bulk modulus K. and its pressure derivative K'(o) are of the same order of magnitude for all four compounds, the anisotropy of strain is noticeably different. (c) 2005 Elsevier B.V. All rights reserved}, language = {en} } @article{OkatovaLavrenkoFedotovetal.1995, author = {Okatova, Olga V. and Lavrenko, Peter N. and Fedotov, Y. A. and Schulz, Burkhard}, title = {Polyelectrolyte behavior of some new polyheteroarylene derivatives in sulfuric acid}, year = {1995}, language = {en} } @article{OkatovaAndreevaSchulzetal.1999, author = {Okatova, Olga V. and Andreeva, Katharina A. and Schulz, Burkhard and Lavrenko, Peter N.}, title = {Degradation of poly(m-phenylene oxadiazole) in concentrated sulfuric acid}, year = {1999}, language = {en} } @article{OkatovaAndreevaSchulz1996, author = {Okatova, Olga V. and Andreeva, Katharina A. and Schulz, Burkhard}, title = {Thermal hydrolytic degradation of polyoxadiazole derivatives}, year = {1996}, language = {en} }