Kinetic preference for interaction of cisplatin with the G-C-rich wobble basepair region in both tRNAAla and MhAla

The anticancer active complex cisplatin interacts preferentially with the common, G-C rich, wobble base pair region of both tRNA(Ala) and Mh(Ala) in a reaction that at pH 6.3 is rate limited by the acid hydrolysis of the metal complex.     

Wigner-Ville distribution for pulse propagation in random media: pulsed plane wave

The time-frequency Wigner-Ville distribution for a pulsed plane-wave signal propagating in a continuous random medium is found, based on the previously derived modal series expression for the two-frequency coherence function. The theory can address propagation in any homogeneous isotropic random medium, but closed-form expressions are specifically derived for a general power-law medium. Two alternative formulations are presented: a modal-wavefront approach wherein each mode is asymptotically transformed to the time domain and a collective approach wherein the mode series is summed collectively and then transformed to the time domain using pole contributions. The physical interpretation of these two different representations in the time-frequency domain as either a superposition of localized wavefronts or collective excitations is established, and their applications to the calculation of local moments are considered.     

Modal theory for the two-frequency mutual coherence function in random media: general theory and plane wave solution: I

In this paper, the modal expansion theory is presented as a new analytical approach together with the resulting new physical parameters. In particular, the features of an arbitrary power-law structure function are investigated. The exact expression for the Gaussian spectrum is rederived. An approximate analytical expression for the two-frequency coherence function evaluated at equal positions for the Kolmogorov spectrum is presented and comparison with the numerical solution in the literature exhibits a remarkable agreement. As a result of the modal decomposition, general properties for a transversally homogeneous and isotropic medium are demonstrated, such as the exponential decay of the amplitude of the solution and the linear phase behaviour at large propagation distances.     

On-Chip Neo-Glycopeptide Synthesis for Multivalent Glycan Presentation

Single glycan–protein interactions are often weak, such that glycan binding partners commonly utilize multiple, spatially defined binding sites to enhance binding avidity and specificity. Current array technologies usually neglect defined multivalent display. Laser-based array synthesis technology allows for flexible and rapid on-surface synthesis of different peptides. By combining this technique with click chemistry, neo-glycopeptides were produced directly on a functionalized glass slide in the microarray format. Density and spatial distribution of carbohydrates can be tuned, resulting in well-defined glycan structures for multivalent display. The two lectins concanavalin A and langerin were probed with different glycans on multivalent scaffolds, revealing strong spacing-, density-, and ligand-dependent binding. In addition, we could also measure the surface dissociation constant. This approach allows for a rapid generation, screening, and optimization of a multitude of multivalent scaffolds for glycan binding.     

Through-Space Polar-π Interactions in 2,6-Diarylthiophenols

Molecular recognition between polar groups and aromatic molecules is fundamentally important to rational drug design. Although it has been well established that many polar functionalities interact with electron-rich aromatic residues through energetically favorable polar-π interactions, there is a limited understanding of the association between thiols and aromatic systems. Herein we report physical-organic chemistry studies on 2,6-diarylthiophenols that possess the central thiophenol ring and two flanking aromatic rings with tunable electronic properties caused by substituents at distant para position. Hammett analysis revealed that pK_a values and proton affinities correlate well with Hammett sigma values of substituents. Additional energy decomposition analysis supported the conclusion that both through-space SH-π interactions and S⁻-π interactions contribute to intramolecular stabilization of 2,6-diarylthiophenols.     

Gold-Catalyzed C(sp2)−C(sp) Coupling by Alkynylation through Oxidative Addition of Bromoalkynes

A gold(I)-catalyzed cascade cyclization–alkynylation of allenoates using alkynyl bromide to generate β-alkynyl-γ-butenolides was investigated. Whereas alkynyl iodides afforded significant amounts of the homo-coupling of two lactone units, alkynyl bromides led to a selective reaction, and a broad functional group tolerance was observed. Under the optimized reaction conditions, it was possible to directly synthesize a large range of β-alkynyl-γ-butenolides in moderate to good yields without the need for any external oxidant.