@misc{AlbrechtCummingKreuderetal.1986, author = {Albrecht, O. and Cumming, W. and Kreuder, W. and Laschewsky, Andr{\´e} and Ringsdorf, Helmut}, title = {Monolayers of rod-shaped and disc-shaped liquid crystalline compounds at the air-water interface}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-17124}, year = {1986}, abstract = {Calamitic (rod-shaped) and discotic (disc-shaped) thermotropic liquid crystalline (LC) compounds were spread at the air-water interface, and their ability to form monolayers was studied. The calamitic LCs investigated were found to form monolayers which behave analogously to conventional amphiphiles such as fatty acids. The spreading of the discotic LCs produced monolayers as well, but with a behaviour different from classical amphiphiles. The areas occupied per molecule are too small to allow the contact of all hydrophilic groups with the water surface and the packing of all hydrophobic chains. Various molecular arrangements of the discotics at the water surface to fit the spreading data are discussed.}, language = {en} } @misc{KortPeterKoopmanschap1983, author = {Kort, C. A. D. de and Peter, Martin G. and Koopmanschap, A. B.}, title = {Binding and degradation of juvenile hormone III by haemolymph proteins of the Colorado potato beetle: a re-examination}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-16777}, year = {1983}, abstract = {The haemolymph of the adult Colorado potato beetle, Lepinotarsa decemlineata Say, contains a high molecular weight (MW > 200,000) JH-III specific binding protein. The Kd value of the protein for racemic JH-III is 1.3 ± 0.2 × 10-7 M. It has a lower affinity for racemic JH-I and it does not bind JH-III-diol or JH-III-acid. The binding protein does discriminate between the enantiomers of synthetic, racemic JH-III as was determined by stereochemical anaysis of the bound and the free JH-III. Incubation of racemic JH-III with crude haemolymph results in preferential formation of (10S)-JH-III-acid, the unnatural configuration. The JH-esterase present in L. decemlineata haemolymph is not enantioselective. It is concluded that the most important function of the binding protein is that of a specific carrier, protecting the natural hormone against degradation by esterases. The carrier does not protect JH-I as efficiently as the lower homologue.}, language = {en} } @phdthesis{Imranulhaq2008, author = {Imran ul-haq, Muhammad}, title = {Synthesis of fluorinated polymers in supercritical carbon dioxide (scCO₂)}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-19868}, school = {Universit{\"a}t Potsdam}, year = {2008}, abstract = {For the first time stabilizer-free vinylidene fluoride (VDF) polymerizations were carried out in homogeneous phase with supercritical CO₂. Polymerizations were carried out at 140°C, 1500 bar and were initiated with di-tert-butyl peroxide (DTBP). In-line FT-NIR (Fourier Transform- Near Infrared) spectroscopy showed that complete monomer conversion may be obtained. Molecular weights were determined via size-exclusion chromatography (SEC) and polymer end group analysis by 1H-NMR spectroscopy. The number average molecular weights were below 104 g∙mol-1 and polydispersities ranged from 3.1 to 5.7 depending on DTBP and VDF concentration. To allow for isothermal reactions high CO₂ contents ranging from 61 to 83 wt.\% were used. The high-temperature, high-pressure conditions were required for homogeneous phase polymerization. These conditions did not alter the amount of defects in VDF chaining. Scanning electron microscopy (SEM) indicated that regular stack-type particles were obtained upon expansion of the homogeneous polymerization mixture. To reduce the required amount of initiator, further VDF polymerizations using chain transfer agents (CTAs) to control molecular weights were carried out in homogeneous phase with supercritical carbon dioxide (scCO₂) at 120 °C and 1500 bar. Using perfluorinated hexyl iodide as CTA, polymers of low polydispersity ranging from 1.5 to 1.2 at the highest iodide concentration of 0.25 mol·L-1 were obtained. Electrospray ionization- mass spectroscopy (ESI-MS) indicates the absence of initiator derived end groups, supporting livingness of the system. The "livingness" is based on the labile C-I bond. However, due to the weakness of the C-I bond perfluorinated hexyl iodide also contributes to initiation. To allow for kinetic analyses of VDF polymerizations the CTA should not contribute to initiation. Therefore, additional CTAs were applied: BrCCl3, C6F13Br and C6F13H. It was found that C6F13H does not contribute to initiation. At 120°C and 1500 bar kp/kt0.5~ 0.64 (L·mol-1·s-1)0.5 was derived. The chain transfer constant (CT) at 120°C has been determined to be 8·10-1, 9·10-2 and 2·10-4 for C6F13I, C6F13Br and C6F13H, respectively. These CT values are associated with the bond energy of the C-X bond. Moreover, the labile C-I bond allows for functionalization of the polymer to triazole end groups applying click reactions. After substitution of the iodide end group by an azide group 1,3 dipolar cycloadditions with alkynes yield polymers with 1,2,3 triazole end groups. Using symmetrical alkynes the reactions may be carried out in the absence of any catalyst. This end-functionalized poly (vinylidene fluoride) (PVDF) has higher thermal stability as compared to the normal PVDF. PVDF samples from homogeneous phase polymerizations in supercritical CO₂ and subsequent expansion to ambient conditions were analyzed with respect to polymer end groups, crystallinity, type of polymorphs and morphology. Upon expansion the polymer was obtained as white powder. Scanning electron microscopy (SEM) showed that DTBP derived polymer end groups led to stack-type particles whereas sponge- or rose-type particles were obtained in case of CTA fragments as end groups. Fourier-Transform Infrared spectroscopy and wide angle X-ray diffraction indicated that the type of polymorph, α or β crystal phase was significantly affected by the type of end group. The content of β-phase material, which is responsible for piezoelectricity of PVDF, is the highest for polymer with DTBP-derived end groups. In addition, the crystallinity of the material, as determined via differential scanning calorimetry is affected by the end groups and polymer molecular weights. For example, crystallinity ranges from around 26 \% for DTBP-derived end groups to a maximum of 62 \% for end groups originating from perfluorinated hexyl iodide for polymers with Mn ~2200 g·mol-1. Expansion of the homogeneous polymerization mixture results in particle formation by a non-optimized RESS (Rapid Expansion from Supercritical Solution) process. Thus, it was tested how polymer end groups affect the particles size distribution obtained from RESS process under controlled conditions (T = 50°C and P = 200 bar). In all RESS experiments, small primary PVDF with diameters less than 100 nm without the use of liquid solvents, surfactants, or other additives were produced. A strong correlation between particle size and particle size distribution with polymer end groups and molecular weight of the original material was observed. The smallest particles were found for RESS of PVDF with Mn~ 4000 g·mol-1 and PFHI (C6F13I) - derived end groups.}, language = {en} } @misc{FrimmelKumke1998, author = {Frimmel, Fritz Hartmann and Kumke, Michael Uwe}, title = {Optische Parameter zur Stoffcharakterisierung vom Trinkwasser bis zum Abwasser}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-13088}, year = {1998}, abstract = {Die Anwendung von optischen Parametern zur Stoffcharakterisierung wird diskutiert. Dabei ist der Schwerpunkt der Diskussion auf absorptions- und fluoreszenzspektroskopische Methoden gesetzt. Beide Methoden k{\"o}nnen schnell und zuverl{\"a}ssig - auch im on-line Betrieb - eingesetzt werden. Der Beitrag soll einen {\"U}berblick {\"u}ber die grundlegenden M{\"o}glichkeiten der Anwendung beider Methoden geben.}, language = {de} } @misc{LoehmannsroebenBeckHildebrandtetal.2006, author = {L{\"o}hmannsr{\"o}ben, Hans-Gerd and Beck, Michael and Hildebrandt, Niko and Schm{\"a}lzlin, Elmar and van Dongen, Joost T.}, title = {New challenges in biophotonics : laser-based fluoroimmuno analysis and in-vivo optical oxygen monitoring}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-10120}, year = {2006}, abstract = {Two examples of our biophotonic research utilizing nanoparticles are presented, namely laser-based fluoroimmuno analysis and in-vivo optical oxygen monitoring. Results of the work include significantly enhanced sensitivity of a homogeneous fluorescence immunoassay and markedly improved spatial resolution of oxygen gradients in root nodules of a legume species.}, subject = {Sauerstoff}, language = {en} } @misc{NiederkruegerSalbBecketal.2006, author = {Niederkr{\"u}ger, Matthias and Salb, Christian and Beck, Michael and Hildebrandt, Niko and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Marowsky, Gerd}, title = {Improvement of a fluorescence immunoassay with a compact diode-pumped solid state laser at 315 nm}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-10150}, year = {2006}, abstract = {We demonstrate the improvement of fluorescence immunoassay (FIA) diagnostics in deploying a newly developed compact diode-pumped solid state (DPSS) laser with emission at 315 nm. The laser is based on the quasi-three-level transition in Nd:YAG at 946 nm. The pulsed operation is either realized by an active Q-switch using an electro-optical device or by introduction of a Cr4+:YAG saturable absorber as passive Q-switch element. By extra-cavity second harmonic generation in different nonlinear crystal media we obtained blue light at 473 nm. Subsequent mixing of the fundamental and the second harmonic in a β-barium-borate crystal provided pulsed emission at 315 nm with up to 20 μJ maximum pulse energy and 17 ns pulse duration. Substitution of a nitrogen laser in a FIA diagnostics system by the DPSS laser succeeded in considerable improvement of the detection limit. Despite significantly lower pulse energies (7 μJ DPSS laser versus 150 μJ nitrogen laser), in preliminary investigations the limit of detection was reduced by a factor of three for a typical FIA.}, subject = {Immunoassay}, language = {en} } @misc{KaafaraniWexStrehmeletal.2002, author = {Kaafarani, Bilal R. and Wex, Brigitte and Strehmel, Bernd and Neckers, Douglas C.}, title = {Structural concept for fluorinated Y-enynes with solvatochromic properties}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-13168}, year = {2002}, abstract = {An approach to the development of fluorescent probes to follow polymerizations in situ using fluorinated cross-conjugated enediynes (Y-enynes) is reported. Different substitution patterns in the Y-enynes result in distinct solvatochromic behavior. β,β-Bis(phenylethynyl)pentafluorostyrene 7, which bears no donor substituents and only fluorine at the styrene moiety, shows no solvatochromism. Donor substituted β,β-bis(3,4,5-trimethoxyphenylethynyl) pentafluorostyrene 8 and β,β-bis(4-butyl-2,3,5,6-tetrafluorophenylethynyl)-3,4,5-trimethoxystyrene 9 exhibit solvatochromism upon change of solvent polarity. Y-enyne 8 showed the largest solvatochromic shift (94 nm bathochromic shift) upon changing solvent from cyclohexane to acetonitrile. A smaller solvatochromic response (44 nm bathochromic shift) was observed for 9. Lippert-Mataga treatment of 8 and 9 yields slopes of -10,800 and -6,400 cm -1, respectively. This corresponds to a change in dipole moment of 9.6 and 6.9 D, respectively. The solvatochromic behavior in 8 and 9 supports the formation of an intramolecular charge transfer (ICT) state. The low fluorescence quantum yields are caused by competitive double bond rotation. The fluorescence decay time of 9 decreases in methyltetrahydrofuran from 2.1 ns at 77 K to 0.11 ns at 200 K. Efficient single bond rotation in 9 was frozen at -50 °C in a configuration in which the trimethoxyphenyl ring is perpendicular to the fluorinated rings. 7-9 are photostable compounds. The X-ray structure of 7 shows it is not planar and that its conjugation is distorted. Y-enyne 7 stacks in the solid state showing coulombic, actetylene-arene, and fluorine-π interactions.}, language = {en} } @misc{DoscheMicklerLoehmannsroebenetal.2007, author = {Dosche, Carsten and Mickler, Wulfhard and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Agenet, Nicolas and Vollhardt, K. Peter C.}, title = {Photoinduced electron transfer in [N]phenylenes}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12463}, year = {2007}, abstract = {First studies of electron transfer in [N]phenylenes were performed in bimolecular quenching reactions of angular [3]- and triangular [4]phenylene with various electron acceptors. The relation between the quenching rate constants kq and the free energy change of the electron transfer (ΔG0CS ) could be described by the Rehm-Weller equation. From the experimental results, a reorganization energy λ of 0.7 eV was derived. Intramolecular electron transfer reactions were studied in an [N]phenylene bichomophore and a corresponding reference compound. Fluorescence lifetime and quantum yield of the bichromophor display a characteristic dependence on the solvent polarity, whereas the corresponding values of the reference compound remain constant. From the results, a nearly isoenergonic ΔG0CS can be determined. As the triplet quantum yield is nearly independent of the polarity, charge recombination leads to the population of the triplet state.}, language = {en} } @misc{PeterBoldtNiedersteinetal.1990, author = {Peter, Martin G. and Boldt, Peter C. and Niederstein, Yvonne and Peter-Katalinić, Jasna}, title = {Synthesen von Galactose-Cluster-haltigen Steroid-Derivaten}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-16783}, year = {1990}, abstract = {The synthesis of galactose clusters that are linked to a steroid moiety by a peptide-like spacer unit is described. The galactose cluster is obtained by Koenigs-Knorr glycosylation of TRIS-Gly-Fmoc (2b) under Helferich conditions. Peptide and ester bonds are formed after activation of carboxylic acids as diphenylthiophene dioxide (TDO) esters. 6a is synthesized in a convergent way by coupling of (Ac4Gal)3-TRIS-Gly (3e) with cholesteryl TDO succinate (5b). Coupling of (Ac4Gal)3-TRIS-Gly hydrogen succinate (3f) with Gly-O-Chol (5d) by means of EEDQ yields 6d. Reaction of (Ac4Gal)3-TRIS-Gly-SUCC-O-TDO (3g) with 25-hydroxycholesterol leads in a linear sequence to the oxysterol derivative 6f. Selective cleavage of the acetyl groups from galactose units yields the known compound 6b and the new derivatives 6e and 6g.}, language = {de} } @misc{PeterAndersenHartmannetal.1992, author = {Peter, Martin G. and Andersen, Svend Olav and Hartmann, Rudolf and Miessner, Merle and Roepstorff, Peter}, title = {Catecholamine-protein conjugates : isolation of 4-phenylphenoxazin-2-ones from oxidative coupling of N-acetyldopamine with alipathic amino acids}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-17571}, year = {1992}, abstract = {4-Phenylphenoxazinones were isolated after biomimetic oxidation, using diphenoloxidases of insect cuticle, mushroom tyrosinase, or after autoxidation of N-acetyldopamine (Image ) in the presence of β-alanine, β-alanine methyl ester or N-acetyl-L-lysine. They are formed presumably by addition of 2-aminoalkyl-5-alkylphenols to the o-quinone of biphenyltetrol which, in turn, arises from oxidative coupling of. The structures of present the first examples for the assembly of reasonably stable intermediates in the rather complex process of chemical modifications of aliphatic amino acid residues by o-quinones.}, language = {en} }