Filtern
Erscheinungsjahr
- 2024 (207)
- 2023 (1287)
- 2022 (2385)
- 2021 (2423)
- 2020 (2818)
- 2019 (2590)
- 2018 (2819)
- 2017 (2525)
- 2016 (2358)
- 2015 (2172)
- 2014 (1892)
- 2013 (2109)
- 2012 (1999)
- 2011 (2047)
- 2010 (1445)
- 2009 (1835)
- 2008 (1363)
- 2007 (1396)
- 2006 (1807)
- 2005 (1956)
- 2004 (2021)
- 2003 (1553)
- 2002 (1354)
- 2001 (1425)
- 2000 (1686)
- 1999 (1852)
- 1998 (1690)
- 1997 (1541)
- 1996 (1557)
- 1995 (1473)
- 1994 (1031)
- 1993 (405)
- 1992 (255)
- 1991 (169)
- 1990 (16)
- 1989 (28)
- 1988 (22)
- 1987 (23)
- 1986 (16)
- 1985 (12)
- 1984 (15)
- 1983 (31)
- 1982 (10)
- 1981 (9)
- 1980 (10)
- 1979 (15)
- 1978 (9)
- 1977 (12)
- 1976 (7)
- 1975 (3)
- 1974 (2)
- 1973 (2)
- 1972 (2)
- 1971 (2)
- 1970 (1)
- 1958 (1)
Dokumenttyp
- Wissenschaftlicher Artikel (35754)
- Dissertation (6485)
- Monographie/Sammelband (5550)
- Postprint (3296)
- Rezension (2291)
- Teil eines Buches (Kapitel) (1066)
- Sonstiges (911)
- Preprint (567)
- Konferenzveröffentlichung (539)
- Ausgabe (Heft) zu einer Zeitschrift (525)
Sprache
- Englisch (30690)
- Deutsch (26048)
- Spanisch (363)
- Französisch (330)
- Italienisch (115)
- Russisch (112)
- Mehrsprachig (66)
- Hebräisch (36)
- Portugiesisch (25)
- Polnisch (24)
Schlagworte
- Germany (202)
- climate change (183)
- Deutschland (142)
- machine learning (82)
- European Union (79)
- diffusion (78)
- Sprachtherapie (77)
- morphology (74)
- Logopädie (73)
- Migration (73)
Institut
- Institut für Biochemie und Biologie (5448)
- Institut für Physik und Astronomie (5424)
- Institut für Geowissenschaften (3648)
- Institut für Chemie (3481)
- Wirtschaftswissenschaften (2645)
- Historisches Institut (2511)
- Department Psychologie (2346)
- Institut für Mathematik (2145)
- Institut für Romanistik (2108)
- Sozialwissenschaften (1883)
Liquid crystalline side group polymers with azo-chromophores and fluorinated tails of varying length
(1996)
Quo vadis, Mindanao?
(2017)
Collagen is the most abundant protein in mammals. In many tissues, collagen molecules assemble to form a hierarchical structure. In the smallest supramolecular unit, named fibril, each molecule is displaced in the axial direction with respect to its neighbors. This staggering creates a periodic gap and overlap regions, where the gap regions exhibit 20% less density. These fibril-forming collagens play an essential role in the strength of connective tissues. Despite much effort, directed at understanding collagen function and regulation, the influence of the chemical environment on the local structural and mechanical properties remains poorly understood. Recent studies, aimed at elucidating the effect of osmotic pressure, showed that collagen contracts upon water removal. This observation highlights the importance of water for the stabilization and mechanics of the collagen molecule.
Using collagen mimetic peptides (CMPs), which fold into triple helical structures reminiscent of natural collagen, the primary goal of this work was to investigate the effect of the osmotic pressure on specific collagen-mimetic sequences. CMPs were used as the model system as they provide sequence control, which is essential for discriminating local from global structural changes and for relating the observed effects to existing knowledge about the full-length collagen molecule. Of specific interest was the structure of individual collagen triple helices as well as their organization into self-assembled higher order structures. These key structural features were monitored with infrared spectroscopy (IR) and synchrotron X-ray scattering, while varying the osmotic pressure. For controlling the osmotic pressure, CMP powder samples were incubated in air of defined relative humidity, ranging from dry conditions to highly “humid”. In addition, to obtain more biologically relevant conditions, the CMPs were measured in ultrapure water and in solutions containing small molecule osmolytes.
Using the sequences (Pro-Pro-Gly)10, (Pro-Hyp-Gly)10 and (Hyp-Hyp-Gly)10, it was shown that CMPs with different degrees of proline hydroxylation (Hyp = hydroxyproline) exhibit a sequence-specific response to osmotic pressure. IR spectroscopy revealed that osmotic pressure changes affect the strength of the triple helix stabilizing, interchain hydrogen bond and that the extent of this change depends on the degree of hydroxylation. X-ray scattering experiments further showed that changes in osmotic pressure affect both the molecular length as well as the higher order organization of CMPs. Starting from a pseudo-hexagonal packing in the dry state, all three CMPs showed isotropic swelling when increasing the water content to approximately 1.2 water molecules per amino acid, again to different extents depending on the degree of hydroxylation. When increasing the water content further, this pseudo-hexagonal arrangement breaks down. In the fully hydrated state, each CMP is characterized by its own specific and more complex packing geometry.
While these changes in the lateral packing arrangement suggest swelling upon hydration, an overall decrease of the molecular length (i.e. contraction) was observed in the axial direction. Also for this structural feature, a strong dependency on the specific amino acid sequence was found. Interestingly, the observed contraction is the opposite of what has been reported for natural collagen. As (Pro-Pro-Gly)n, (Pro-Hyp-Gly)n and (Hyp-Hyp-Gly)n repeat units are found in collagen with a relatively high abundance, this suggests that other collagen sequence fragments need to respond to hydration in the opposite way to obtain a net elongation of the full-length collagen molecule.
To test this hypothesis, sequences predicted to be sensitive to osmotic pressure were considered. One such sequence, consisting of two repeat units (Ala-Arg-Gly-Ser-Asp-Gly), was inserted as a guest into a (Pro-Pro-Gly) host. When compared to the canonical CMP sequences investigated earlier, the lateral helix packing follows a similar trend with increasing hydration; however, the host-guest CMP axially elongates with increasing water content. This behavior is more similar to what has been found for natural collagen and suggests that different sequences do determine the molecular length of collagen sequences differently. Interestingly, the canonical sequences are more abundant in the overlap region while the guest sequence is found in the gap region. This allows to speculate that sequences in the gap and overlap regions possess a specifically fine-tuned local response to osmotic pressure changes. Clearly, more experiments with additional sequences are needed to confirm this.
In conclusion, the results obtained in this work indicate a highly sequence specific interaction between collagen and water. Osmotic pressure-induced conformational changes mostly originate from local geometries and bonding patterns and affect both the structure of individual triple helices as well as higher order assemblies. One key remaining question is how these conformational changes affect the local mechanical properties of the collagen molecule. As a first step, the stiffness (persistence length) of full-length collagen was determined using atomic force microscopy. In the future, experimental strategies need to be developed that allow for investigating the mechanical properties of specific collagen sequences, e.g. performing single-molecule force spectroscopy of CMPs.
Photon Density Wave (PDW) spectroscopy was applied for temperature dependent monitoring of melting and crystallization of milk fat within homogenized fresh milk. As an in-line process analytical technique, PDW spectroscopy quantifies continuously the optical properties of turbid material, providing an insight into its structural processes. Here, the measured absorption coefficients reflect temperature as well as fat content of milk and the reduced scattering coefficients probe physical changes of the light scattering fat droplets and casein micelles. Thermal processing reveals breakpoints within the temperature trend of the reduced scattering coefficient of fat containing milk. Found at 16 degrees C and 24 degrees C while cooling and heating, respectively, they are associated to the phase transitions of milk fat. Continuous isothermal measurement of the optical coefficients showed that the crystallization process requires several hours. The strongly changing reduced scattering coefficient implies that the thermal history of milk will have a major impact on any method based on light scattering as quantitative analytical technique.
This dissertation was carried out as part of the international and interdisciplinary graduate school StRATEGy. This group has set itself the goal of investigating geological processes that take place on different temporal and spatial scales and have shaped the southern central Andes. This study focuses on claystones and carbonates of the Yacoraite Fm. that were deposited between Maastricht and Dan in the Cretaceous Salta Rift Basin. The former rift basin is located in northwest Argentina and is divided into the sub-basins Tres Cruces, Metán-Alemanía and Lomas de Olmedo. The overall motivation for this study was to gain new knowledge about the evolution of marine and lacustrine conditions during the Yacoraite Fm. Deposit in the Tres Cruces and Metán-Alemanía sub-basins. Other important aspects that were examined within the scope of this dissertation are the conversion of organic matter from Yacoraite Fm. into oil and its genetic relationship to selected oils produced and natural oil spills. The results of my study show that the Yacoraite Fm. began to be deposited under marine conditions and that a lacustrine environment developed by the end of the deposition in the Tres Cruces and Metán-Alemanía Basins. In general, the kerogen of Yacoraite Fm. consists mainly of the kerogen types II, III and II / III mixtures. Kerogen type III is mainly found in samples from the Yacoraite Fm., whose TOC values are low. Due to the adsorption of hydrocarbons on the mineral surfaces (mineral matrix effect), the content of type III kerogen with Rock-Eval pyrolysis in these samples could be overestimated. Investigations using organic petrography show that the organic particles of Yacoraite Fm. mainly consist of alginites and some vitrinite-like particles. The pyrolysis GC of the rock samples showed that the Yacoraite Fm. generates low-sulfur oils with a predominantly low-wax, paraffinic-naphthenic-aromatic composition and paraffinic wax-rich oils. Small proportions of paraffinic, low-wax oils and a gas condensate-generating facies are also predicted. Here, too, mineral matrix effects were taken into account, which can lead to a quantitative overestimation of the gas-forming character.
The results of an additional 1D tank modeling carried out show that the beginning (10% TR) of the oil genesis took place between ≈10 Ma and ≈4 Ma. Most of the oil (from ≈50% to 65%) was generated prior to the development of structural traps formed during the Plio-Pleistocene Diaguita deformation phase. Only ≈10% of the total oil generated was formed and potentially trapped after the formation of structural traps. Important factors in the risk assessment of this petroleum system, which can determine the small amounts of generated and migrated oil, are the generally low TOC contents and the variable thickness of the Yacoraite Fm. Additional risks are associated with a low density of information about potentially existing reservoir structures and the quality of the overburden.
Two sesquiterpenes, corymbolone and mustakone, isolated from the chloroform extract of the rhizomes of Cyperus articulatus, exhibited significant anti-plasmodial properties. Mustakone was approximately ten times more active than corymbolone against the sensitive strains of the Plasmodium falciparum.
A new precursor route for the preparation of bulk oxides and thin films of bismuth vanadates is proposed. The method involves the thermal treatment under air and mild conditions of hybrid organic-inorganic precursors, made from a zwitterionic salt-free polymer matrix and selected inorganic species. Monoclinic BiVO4 was obtained in the form of bulk oxide by calcination of the powdered homogeneous hybrid materials at 600 degrees C, from precursors containing Bi and V in stoichiometric amounts. In the same way, thermodiffractometry studies performed on a hybrid material exhibiting a Bi/ V molar ratio of 2 revealed that the ionic conductor gamma-Bi4V2O11 phase can be stabilized under very soft thermal conditions (300 degrees C). Additionally, thin films of yellow monoclinic BiVO4 were for the first time fabricated, by thermal treatment of the same hybrid polymeric precursors deposited on quartz substrates by spin coating, using a layer- by-layer technique. The presence of the target phase at the surface of the plates was confirmed by X-ray diffraction as well as UV-vis measurements
Homopolymers were prepared from diallylammonium monomers bearing 4-methylcoumarin and 4-cyanobiphenyl as fluorescent and mesogenic side groups, as well as their copolymers with diallyldimethylammonium chloride (DADMAC). Organic-inorganic hybrid films were electrostatically self-assembled via the layer-by-layer technique on silicon wafers and quartz plates from the chromophore-bearing polymers and an exfoliated synthetic hectorite. Photophysical studies performed in solution as well as in the self-assembled films demonstrated only a weak tendency for aggregation of the chromophores in the macromolecules. Moreover, assemblies made from the polymers carrying the cyanobiphenyl mesogen were found to exhibit a pronounced internal order
An unconventional but easily accessible precursor route involving the thermal treatment of hybrid precursors containing an ampholytic polymer matrix is developed to prepare multimetallic oxides of catalytic interest such as transition metal molybdates. A copolymer of diallyldimethylammonium chloride and a functionalized maleamic acid bearing an amine group suited for cation complexation was designed, synthesized and used as a matrix to stabilize inorganic species generated in solution from Ni(NO3)(2)center dot 6H(2)O, Co(NO3)(2)center dot 6H(2)O and/or Mn(NO3)(2)center dot 4H(2)O together with (NH4)(6)Mo(7)O(24)center dot 4H(2)O. UV-vis-NIR as well as C-13-NMR studies suggest that the interactions between the cations and the polymer in solution are mainly electrostatic. Only minor complexation interactions take place under certain conditions. Homogeneous hybrid blends were prepared from these solutions. The presence of a complexing amine group in addition to the charged betaine moieties in the polymer permits stabilization of more than stoichiometric amounts of the metal species in the blends. XRD measurements suggest that the homogeneity in the solid state can be kept up to about 1.5 mol of each metal that is incorporated ( anionic as well as cationic) per mol of repeat units of the copolymer. The blends were calcined under air at 600 degrees C to produce the simple as well as mixed nickel, cobalt and manganese molybdates. Characterization of the final phases by XRD and Raman spectroscopy indicates that the alpha- as well as the beta-molybdate phases can be prepared, and that the mixed structures are solid solutions of the simple NiMoO4, MnMoO4 and CoMoO4. If the precursors engaged are homogeneous, the pH of the precursor solution, the amount of metal that is incorporated in the matrix, and the nature of the polymer matrix seem to exert only a minor influence on the nature of the final phase, which demonstrates the versatility and facile applicability of the method