Express Method for Determination of Low Value of Trans-membrane Potential of Living Cells with Fluorescence Probe: Application on Haemocytes at Immune Responses

The method for measurement of trans-membrane potential of cell membrane was evaluated for the case of low potential value using fluorescence probe 4-(4-dimethylaminostyryl)-1-methylpyridinium, DSM. The method is based on comparative titration of cells with probe in buffers containing Na(+) or K(+). The apparent trans-membrane potential obtained with this way is a result of K(+)-Na(+) pump activity. The presented approach allowed measuring the low value of potential with 1-2?mV of accuracy without additional calibration procedures. The method was applied for investigation of potential of cell membrane of haemocytes of Galleria mellonella larvae. The value of potential of intact insect's haemocytes was found in the range from -10 to -20?mV. The change of potential value of haemocytes was investigated under model immune response and natural envenomation and parasitizing. The obtained deviations of cell membrane potential were in good correlation with changes of activity of main immune reactions, described in literature and obtained by us earlier.     

High-order above-threshold ionization of heteronuclear diatomic molecules by a strong laser field with arbitrary polarization

The molecular strong-field approximation is applied to calculate angle-resolved photoelectron spectra in the process of high-order above-threshold ionization of carbon-monoxide molecules by an elliptically polarized laser field. The theory is formulated to include the Stark shift of the initial bound state of the valence electron. It is shown that the angle-resolved photoelectron spectra of aligned CO molecules exhibit pronounced minima which can be explained by destructive interference of two partial T-matrix contributions. The dependence of contributing partial amplitudes on the laser field ellipticity is analyzed in detail.     

Fast Detection Allows Analysis of the Electronic Structure of Metalloprotein by X-ray Emission Spectroscopy at Room Temperature

The paradigm of "detection-before-destruction" was tested for a metalloprotein complex exposed at room temperature to the high x-ray flux typical of third generation synchrotron sources. Following the progression of the x-ray induced damage by Mn Kβ x-ray emission spectroscopy, we demonstrated the feasibility of collecting room temperature data on the electronic structure of native Photosystem II, a trans-membrane metalloprotein complex containing a Mn(4)Ca cluster. The determined non-damaging observation timeframe (about 100 milliseconds using continuous monochromatic beam, deposited dose 1*10(7) photons/μm(2) or 1.3*10(4) Gy, and 66 microseconds in pulsed mode using pink beam, deposited dose 4*10(7) photons/μm(2) or 4.2*10(4) Gy) is sufficient for the analysis of this protein's electron dynamics and catalytic mechanism at room temperature. Reported time frames are expected to be representative for other metalloproteins. The described instrumentation, based on the short working distance dispersive spectrometer, and experimental methodology is broadly applicable to time-resolved x-ray emission analysis at synchrotron and x-ray free-electron laser light sources.     

Light harvesting architectures for electron beam evaporated solid phase crystallized Si thin film solar cells: Statistical and periodic approaches

The fabrication of light trapping architectures for electron beam (e-beam) evaporated polycrystalline Si thin film solar cells is investigated based on tailored self-organized light scattering silica nanospheres and 2 dimensional periodic nanoimprinted structures on glass. A microscopic analysis reveals a unique correlation between the microstructure of high-rate e-beam evaporated Si and the substrate topography. These features provide the basis for the design of nanostructured Si that complies with its distinctive growth characteristics. A layer of self-organized nanospheres embedded in a sol–gel matrix and an anti-reflection coating is found to be an e-beam compatible light trapping approach for poly-Si solar cells, contributing to an increase of 50% in current collection. We developed a preparation process for arrays of equidistant free-standing Si crystals with remarkable optical absorption characteristics based on a nanoimprinted glass substrate by selectively etching e-beam evaporated Si. This periodic approach opens design possibilities for effective three-dimensional architectures for advanced photon management.     

Proteins and polyelectrolytes: A charged relationship

We review the interaction of charged polymeric systems with proteins. In solutions of low ionic strength there are many examples of proteins attracted to polyelectrolytes even if both systems carry the same overall charge. This attractive interaction is widespread, having been observed for single polyelectrolyte chains as well as for polyelectrolytes grafted to surfaces (polyelectrolyte brushes) and charged polymeric networks. In all cases, adding salt weakens the interaction considerably. We discuss the suggestion that the attractive force at low salinity originates from the asymmetry of interaction between charged polymer segments and charged patches on the surface of the protein globule. This can be explained if the attractive force is mainly due to a counterion release force, i.e., the polyelectrolyte chains become the multivalent counterions for the patches of opposite charge localized on the surface of the proteins. We review a selection of simple models that lead to semi-quantitative estimates of this force as the function of salt concentration.     

Cooperative Al(salen)-pyridinium catalysts for the asymmetric synthesis of trans-configured β-lactones by [2+2]-cyclocondensation of acylbromides and aldehydes: investigation of pyridinium substituent effects

The trans-selective catalytic asymmetric formation of β-lactones constitutes an attractive surrogate for anti-aldol additions. Recently, we have reported the first catalyst which is capable of forming trans-β-lactones with high enantioselectivity from aliphatic (and aromatic) aldehyde substrates by cyclocondensation with acyl bromides. In that previous study the concepts of Lewis acid and organic aprotic ion pair catalysis were combined in a salen-type catalyst molecule. Since a pyridinium residue on the salen periphery is essential for high trans- and enantioselectivity, we were interested in the question of whether substituents on the pyridinium rings could be used to further improve the catalyst efficiency, as they might have a significant impact on the effective charges within the heterocycles. In the present study we have thus compared a small library of aluminum salen/bispyridinium catalysts mainly differing in the substituents on the pyridinium residues. As one result of these studies a new catalyst was identified which offers slightly superior stereoselectivity as compared to the previously reported best catalyst. NBO calculations have revealed that the higher stereoselectivity can arguably not be explained by the variation of the effective charge.     

Dynamics of the sputtering of water from ice films by collisions with energetic xenon atoms

The flow of energy from the impact site of a heavy, translationally energetic xenon atom on an ice surface leads to several non-equilibrium events. The central focus of this paper is on the collision-induced desorption (sputtering) of water molecules into the gas-phase from the ice surface. Sputtering is strongly activated with respect to xenon translational energy, and a threshold for desorption was observed. To best understand these results, we discuss our findings in the context of other sputtering studies of molecular solids. The sputtering yield is quite small; differential measurements of the energy of xenon scattered from ice surfaces show that the ice efficiently accommodates the collisional energy. These results are important as they quantitatively elucidate the dynamics of such sputtering events, with implications for energetic non-equilibrium processes at interfaces.     

Polyketide proofreading by an acyltransferase-like enzyme

Trans-acyltransferase polyketide synthases (trans-AT PKSs) are an important group of bacterial enzymes producing bioactive polyketides. One difference from textbook PKSs is the presence of one or more free-standing AT-like enzymes. While one homolog loads the PKS with malonyl units, the function of the second copy (AT2) was unknown. We studied the two ATs PedC and PedD involved in pederin biosynthesis in an uncultivated symbiont. PedD displayed malonyl- but not acetyltransferase activity toward various acyl carrier proteins (ACPs). In contrast, the AT2 PedC efficiently hydrolyzed acyl units bound to N-acetylcysteamine or ACP. It accepted substrates with various chain lengths and functionalizations but did not cleave malonyl-ACP. These data are consistent with the role of PedC in?PKS proofreading, suggesting a similar function for other AT2 homologs and providing strategies for?polyketide titer improvement and biosynthetic investigations.