The Contribution of the Activation Entropy to the Gas-Phase Stability of Modified Nucleic Acid Duplexes

Tricyclo-DNA (tcDNA) is a sugar-modified analogue of DNA currently tested for the treatment of Duchenne muscular dystrophy in an antisense approach. Tandem mass spectrometry plays a key role in modern medical diagnostics and has become a widespread technique for the structure elucidation and quantification of antisense oligonucleotides. Herein, mechanistic aspects of the fragmentation of tcDNA are discussed, which lay the basis for reliable sequencing and quantification of the antisense oligonucleotide. Excellent selectivity of tcDNA for complementary RNA is demonstrated in direct competition experiments. Moreover, the kinetic stability and fragmentation pattern of matched and mismatched tcDNA heteroduplexes were investigated and compared with non-modified DNA and RNA duplexes. Although the separation of the constituting strands is the entropy-favored fragmentation pathway of all nucleic acid duplexes, it was found to be only a minor pathway of tcDNA duplexes. The modified hybrid duplexes preferentially undergo neutral base loss and backbone cleavage. This difference is due to the low activation entropy for the strand dissociation of modified duplexes that arises from the conformational constraint of the tc-sugar-moiety. The low activation entropy results in a relatively high free activation enthalpy for the dissociation comparable to the free activation enthalpy of the alternative reaction pathway, the release of a nucleobase. The gas-phase behavior of tcDNA duplexes illustrates the impact of the activation entropy on the fragmentation kinetics and suggests that tandem mass spectrometric experiments are not suited to determine the relative stability of different types of nucleic acid duplexes.

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All-optical noninvasive control of unstable steady states in a semiconductor laser

All-optical noninvasive control of a multisection semiconductor laser by means of time-delayed feedback from an external Fabry-Perot cavity is realized experimentally. A theoretical analysis, in both a generic model as well as a device-specific simulation, points out the role of the optical phase. Using phase-dependent feedback we demonstrate stabilization of the continuous-wave laser output and noninvasive suppression of intensity pulsations.     

Low latency localization of multiple sound sources in reverberant environments

Sound source localization algorithms determine the physical position of a sound source in respect to a listener. For practical applications, a localization algorithm design has to take into account real world conditions like multiple active sources, reverberation, and noise. The application can impose additional constraints on the algorithm, e.g., a requirement for low latency. This work defines the most important constraints for practical applications, introduces an algorithm, which tries to fulfill all requirements as good as possible, and compares it to state-of-the-art sound source localization approaches.     

The quadrupole moment of the 535 keV state of 133La

The quadrupole moment of the 535 keV $\text{3}\text{2}{}^{\mathrm{?}}$ state of ¹³³La has been derived from a time-differential perturbed angular correlation measurement in an environment of La metal. The effective electric gradient is known from a nuclear quadrupole resonance measurement with the ground state of ¹³⁹La. The result Q = 0.35 ± 0.03 b does not confirm a proposed shape isomerism.     

Novel peripherally functionalized seco-porphyrazines: synthesis, characterization and spectroscopic evaluation

Co-macrocyclizations of 2,3-dipropylmaleonitrile and 2,3-di-(4-(methoxycarbonyl)phenyl)maleonitrile, respectively, with N,N′-dibenzyl-N,N′-di-(11-tetrahydropyranyloxy-3,6,9-trioxo-undecyl))maleonitrile and N,N,N′,N′-tetramethylmaleonitrile were used to prepare derivatives of the 4,5-diamino-porphyrazine systems including the zinc(II) complexes. Subsequent oxidation of the macrocycles with potassium permanganate gave the corresponding seco-porphyrazines. These were shown to be efficient sensitizers for the production of singlet oxygen (Φ_Δ=0.15-0.57) by the determination of their photophysical properties.