Analysis of post-translational modification and characterization of the domain structure of dynamin A from Dictyostelium discoideum

The post-translational modifications of the 96 kDa protein dynamin A from Dictyostelium discoideum were analyzed using Q-TOF mass spectrometry. The accurate molecular mass of the intact protein revealed a covalent modification causing an additional mass of 42 Da. The modification could be identified as N-terminal acetylation by tandem mass spectrometry. Extracted ion chromatograms for the a(1) and b(1) ion of the tryptic T1 peptide were used to detect the acetylated peptide within 54 nanoelectrospray ionization tandem mass spectra. Owing to the accurate molecular mass of the intact protein, additional covalent modifications could be excluded. In addition to the covalent modification, the domain structure of dynamin A was determined by applying a combination of limited proteolysis, sodium dodecylsulfate polyacrylamide gel electrophoresis, automated tandem mass spectrometry and protein database searching.     

Chelatbildung mit N-unsubstituierten 1.2-Diiminliganden

Fe^II, Co^III, Ni^II, Pd^II, and Rh^III chelates with the N-unsubstituted 1-2-diimine ligands benzildiimine and 9.10-phenanthrenequinonediimine have been prepared. The compounds are characterised chemically, spectroscopically (uv, vis, ir) and polarographically. The results indicate remarkable π-back bonding in the chelates. The unusual magnetic moments of the Fe^II, Co^III and Rh^III chelates are caused by temperature-independent paramagnetism. Fe^II, Co^III, Ni^II and Cu^II chelates of the partially deprotonated phenanthrenequinone diimine are obtained.     

Dexamethasone Intravitreal Implant Is Active at the Molecular Level Eight Weeks after Implantation in Experimental Central Retinal Vein Occlusion

Central retinal vein occlusion (CRVO) is a visually disabling condition resulting from a thrombus in the major outflow vessel of the eye. The inflammatory response in CRVO is effectively treated with a dexamethasone (DEX) intravitreal implant. Uncovering the proteome changes following DEX implant intervention in CRVO may identify key proteins that mediate the beneficial effects of DEX. In six Göttingen minipigs, CRVO was induced in both eyes with an argon laser using a well-established experimental model. The right eyes were treated with a DEX intravitreal implant (Ozurdex, Allergan), while the left control eyes received a sham injection. Eight weeks after DEX intervention, retinal samples were collected and analyzed with tandem mass tag-based mass spectrometry. DEX implant intervention resulted in the upregulation of peptidyl-prolyl cis–trans isomerase FKBP5 (FKBP5) and ubiquilin-4. Immunohistochemistry showed expression of FKBP5 in the nuclei in all cellular layers of the retina. Cell adhesion molecule 3, tumor necrosis factor receptor superfamily member 16, and trans-1,2-dihydrobenzene-1,2-diol dehydrogenase were downregulated following DEX intervention. The upregulation of the corticosteroid-sensitive protein FKBP5 suggests that the implant remained active at the molecular level after eight weeks of treatment. Future studies may investigate if FKBP5 regulates the efficacy and duration of the DEX implant.     

Construction of Compactly Supported Shearlet Frames

Shearlet tight frames have been extensively studied in recent years due to their optimal approximation properties of cartoon-like images and their unified treatment of the continuum and digital settings. However, these studies only concerned shearlet tight frames generated by a band-limited shearlet, whereas for practical purposes compact support in spatial domain is crucial.     

Effect of viscosity of a liquid membrane containing oleyl alcohol on the pertraction of butyric acid

Solvent formulation is important in the optimization of the mass-transfer through supported liquid membranes (SLM) in pertraction and membrane extraction. Oleyl alcohol (OA) is frequently used as the solvent or diluent in the extraction of carboxylic acids. A disadvantage of OA is its relatively high viscosity of 28.32 mPa s at 25°C. This can be decreased by the application of a less viscous OA diluent, e.g. dodecane. The relationship between the ratio of the distribution coefficient of butyric acid (BA), D _F, and the viscosity of OA-dodecane solvents, µ, as extraction and transport characteristics, and the overall mass-transfer coefficient, K _p, through SLMs was analyzed. Dependence of the D _F/µ ratio on the OA concentration showed a maximum at the OA concentration of 15 mass % to 30 mass %. The OA concentration dependence of K _p for SLMs exhibited also a maximum at about 30 mass % and 20 mass % of OA at the BA concentration driving force of 0.12 kmol m^?3 and 0.3 kmol m^?3, respectively. Shifting of the maximum in K _p dependences towards lower OA concentrations by increasing the BA concentration driving force is in agreement with the D _F/µ ratio dependence. Using pure OA as the solvent or diluent is not preferable and a mixture of a low viscosity diluent with the OA concentration below 40 mass % should be used. The presented results show the potential of the D _F/µ ratio in the screening and formulation of solvents in extraction and SLM optimization.     

Exciton‐Vibrational Couplings in Homo‐ and Heterodimer Stacks of Perylene Bisimide Dyes within Cyclophanes: Studies on Absorption Properties and Theoretical Analysis

The optical properties of a series of three cyclophanes comprising either identical or different perylene bisimide (PBI) chromophores were studied by UV/Vis absorption spectroscopy and their distinctive spectral features were analyzed. All the investigated cyclophanes show significantly different absorption features with respect to the corresponding constituent PBI monomers indicating strong coupling interactions between the PBI units within the cyclophanes. DFT calculations suggest a π‐stacked arrangement of the PBI units at close van der Waals distance in the cyclophanes with rotational displacement. Simulations of the absorption spectra based on time‐dependent quantum mechanics properly reproduced the experimental spectra, revealing exciton‐vibrational coupling between the chromophores both in homo‐ and heterodimer stacks. The PBI cyclophane comprising two different PBI chromophores represents the first example of a PBI heterodimer stack for which the exciton coupling has been investigated. The quantum dynamics analysis reveals that exciton coupling in heteroaggregates is indeed of similar strength as for homoaggregates.     

Recurrence formulas for Macdonald polynomials of type <Emphasis Type="Italic">A</Emphasis>

We consider products of two Macdonald polynomials of type A, indexed by dominant weights which are respectively a multiple of the first fundamental weight and a weight having zero component on the kth fundamental weight. We give the explicit decomposition of any Macdonald polynomial of type A in terms of this basis.     

In situ detection of potassium atoms in high-temperature coal-combustion systems using near-infrared-diode lasers

Direct tunable diode laser absorption spectroscopy at 769.9 and 767.5 nm was used to measure potassium (K) atom concentrations in situ in the high temperature (up to 1650 K) flue gas of two different pulverized coal dust combustion systems (atmospheric or pressurized (12 bar)). Two laser types (Fabry-Pérot (FP) and vertical-cavity surface-emitting lasers (VCSEL)) were used for the spectrometer and characterized with respect to the magnitude and linearity of their static and dynamic wavelength tuning properties. The wide continuous current-induced tuning range of the VCSEL of 20 cm(-1) (compared to 1 cm(-1) for the FP) make this laser ideal for species monitoring in high pressure processes. Two VCSELs were time-multiplexed to realize the simultaneous detection of the potassium D1 and D2 lines. Several oxygen absorption lines in the A-band, which are in close spectral vicinity of the K lines, were detected simultaneously, showing the possibility of multi-species detection with one laser. Using the FP-DL for the atmospheric process and the VCSEL for the high pressure process, the pressure-dependent coefficients for spectral broadening as well as a shift of the K line in the flue gas were determined to be (0.18 +/- 0.01) and (-0.060 +/- 0.003) cm(-1) per atm (at 1540 K and 11.2 bar). The total width and shift of the D1 line (11.2 bar/1540 K) were 60 and -20 GHz, respectively. The K atom concentration was determined continuously for several days in both plants under various operation conditions. Typical concentrations in the atmospheric plant were around 2 microg m(-3) with a range of 50 ng m(-3)-30 microg m(-3). Averaging 100 scans for each concentration value, we achieved a time resolution of 1.7 s and a detection limit of 10 ng m(-3), which corresponds to a fractional absorption in the 10(-3)-10(-4) range. A strong anti-correlation with the oxygen concentration could be verified. At the 12 bar plant, the concentration was again typically around 2 microg m(-3) but K levels up to 60 microg m(-3) were observed. Here, a strong dependence of the K-signal on the type of fuel could be verified.