Influence of Polarization of Exciting X-Radiation on Sensitivity of Energy Dispersive X-Ray Fluorescence Trace Analysis at Rocks and Soils

The application of polarized X-rays in energy dispersive X-ray fluorescence analysis (EDXRF) is prooved to be one method for improvement the sensitivity of trace analysis at rock- and soil-samples. The use of a high power X-ray tube in connection with an amorphous Barkla-scattering target for polarization makes possible the increase of peak-to-background ratios in a wide energy range (5 keV < E < 40 keV) in comparison to direct excitation. The influence of the polarization on the peak-to-background ratios at trace analysis at geological samples will be shown.     

Binding of hairpin polyamides to DNA studied by fluorescence correlation spectroscopy for DNA nanoarchitectures

We have recently constructed a “DNA strut” consisting of two DNA-binding hairpin polyamides of Dervan-type connected via a long flexible linker and were able to show that this strut can be used to sequence-selectively connect DNA helices. This approach provides a second structural element (besides the Watson–Crick base pairing) for the assembly of higher-order DNA nanoarchitectures from smaller DNA building blocks. Since none of the existing analytical techniques for studying this kind of system were found suitable for detection and quantification of the formation of the resulting complexes, we chose fluorescence correlation spectroscopy (FCS). In the present study we show that FCS allowed us in a versatile and fast way to investigate the binding of Dervan polyamides to DNA. In particular it also shows its power in the quantitative detection of the formation of multimeric complexes and the in investigation of binding under nonphysiological conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Light-activatable molecular beacons with a caged loop sequence

We have synthesized molecular beacons with caged nucleobases in the loop region. These constructs remain non-fluorescent in the presence of their target RNA but can be fully activated by light (366 or 405 nm) in vitro and in HEK293 cells. We suggest that this technology will be useful for single molecule RNA tracking in living cells.     

Double-Pullback Transitions and Coalgebraic Loose Semantics for Graph Transformation Systems

The classical algebraic approach to graph transformation is a mathematical theory based on categorical techniques with several interesting applications in computer science. In this paper, a new semantics of graph transformation systems (in the algebraic, double-pushout (DPO) approach) is proposed in order to make them suitable for the specification of concurrent and reactive systems. Classically, a graph transformation system comes with a fixed behavioral interpretation. Firstly, all transformation steps are intended to be completely specified by the rules of the system, that is, there is an implicit frame condition: it is assumed that there is a complete control about the evolution of the system. Hence, the interaction between the system and its (possibly unknown) environment, which is essential in a reactive system, cannot be modeled explicitly. Secondly, each sequence of transformation steps represents a legal computation of the system, and this makes it difficult to model systems with control. The first issue is addressed by providing graph transformation rules with a loose semantics, allowing for unspecified effects which are interpreted as activities of the environment. This is formalized by the notion of double-pullback transitions, which replace (and generalize) the well-known double-pushout diagrams by allowing for spontaneous changes in the context of a rule application. Two characterizations of double-pullback transitions are provided: the first one describes them in terms of extended direct DPO derivations, and the second one as incomplete views of parallel or amalgamated derivations. The issue of constraining the behavior of a system to transformation sequences satisfying certain properties is addressed instead by introducing a general notion of logic of behavioral constraints, which includes instances like start graphs, application and consistency conditions, and temporal logic constraints. The loose semantics of a system with restricted behavior is defined as a category of coalgebras over a suitable functor. Such category has a final object which includes all finite and infinite transition sequences satisfying the constraints.     

Proton-Transfer Dynamics of Photoacidic Merocyanines in Aqueous Solution

Photoacids attract increasing scientific attention, as they are valuable tools to spatiotemporally control proton-release reactions and pH values of solutions. We present the first time-resolved spectroscopic study of the excited state and proton-release dynamics of prominent merocyanine representatives. Femtosecond transient absorption measurements of a pyridine merocyanine with two distinct protonation sites revealed dissimilar proton-release mechanisms: one site acts as a photoacid generator as its pK_a value is modulated in the ground state after photoisomerization, while the other functions as an excited state photoacid which releases its proton within 1.1 ps. With a pK_a drop of 8.7 units to −5.5 upon excitation, the latter phenolic site is regarded a super-photoacid. The 6-nitro derivative exhibits only a phenolic site with similar, yet slightly less photoacidic characteristics and both compounds transfer their proton to methanol and ethanol. In contrast, for the related 6,8-dinitro compound an intramolecular proton transfer to the ortho-nitro group is suggested that is involved in a rapid relaxation into the ground state.     

Über Leucin aus Kaseïn

Ohne Zusammenfassung     

Über Gelatine,II

Ohne Zusammenfassung     

Ein neues Herzgift, das Vernonin

Ohne Zusammenfassung     

A ribozyme for the aldol reaction

Directed in vitro evolution can create RNA catalysts for a variety of organic reactions, supporting the "RNA world" hypothesis, which proposes that metabolic transformations in early life were catalyzed by RNA molecules rather than proteins. Among the most fundamental carbon-carbon bond-forming reactions in nature is the aldol reaction, mainly catalyzed by aldolases that utilize either an enamine mechanism (class I) or a Zn(2+) cofactor (class II). We report on isolation of a Zn(2+)-dependent ribozyme that catalyzes an aldol reaction at its own modified 5' end with a 4300-fold rate enhancement over the uncatalyzed background reaction. The ribozyme can also act as an intermolecular catalyst that transfers a biotinylated benzaldehyde derivative to the aldol donor substrate, coupled to an external hexameric RNA oligonucleotide, supporting the existence of RNA-originated biosynthetic pathways for metabolic sugar precursors and other biomolecules.