Metal‐Ion‐Binding Analogs of Ribonucleosides: Preparation and Formation of Ternary Pd2+ and Hg2+ Complexes with Natural Pyrimidine Nucleosides

Four metal‐ion‐binding nucleosides, viz. 2,6‐bis(1‐methylhydrazinyl)‐9‐(β‐D ‐ribofuranosyl)‐9H‐purine ( 2a ) and its N‐acetylated derivative, 2b , 2,4‐bis(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)‐5‐(β‐D ‐ribofuranosyl)pyrimidine ( 3 ), and 2,4‐bis(1‐methylhydrazinyl)‐5‐(β‐D ‐ribofuranosyl)pyrimidine ( 4 ) have been synthesized. The ability of these nucleosides and the previously prepared 2,6‐bis(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)‐9‐(β‐D ‐ribofuranosyl)‐9H‐purine to form Pd²⁺‐ and Hg²⁺‐mediated complexes with uridine has been studied by ¹H‐NMR spectroscopy. To obtain additional support for the interpretation of the NMR data, comparative measurements on the ternary‐complex formation between pyridine‐2,6‐dicarboxamide ( 5 ), pyrimidine nucleosides, and K₂PdCl₄ were carried out.     

Covalently Palladated Oligonucleotides Through Oxidative Addition of Pd0

An 11-mer oligonucleotide incorporating a central (2-iodobenzoylamino)methyl residue has been synthesized and palladated by oxidative addition of Pd₂(dba)₃. UV melting profiles of the duplexes formed by the palladated oligonucleotide with its natural complements were biphasic and the higher melting temperatures (T_m) exhibited considerable hysteresis. CD spectra, in turn, resembled those of canonical B-type double helices. Two-step denaturation, with the “low-T_m” melting involving only canonical base pairs and the “high-T_m” melting involving also dissociation of a Pd^II-mediated base pair, appears the most likely explanation for the observed UV melting profiles. As the latter step in all cases takes place at a higher temperature than denaturation of natural duplexes of the same length, the putative Pd^II-mediated base pairs are stabilizing.     

New method of determining the young’s Modulus of (Ga,Mn)As nanowhiskers with a scanning electron microscope

Arrays of (Ga,Mn)As nanowhiskers have been grown by molecular-beam epitaxy. The scanning electron microscopy study of the surface morphology of the samples has revealed the appearance of mechanical vibrations of individual nanowhiskers. To describe the vibrations, a model has been developed for the determination of the Young’s modulus of (Ga,Mn)As nanowhiskers.     

Intramolecular Participation of Amino Groups in the Cleavage and Isomerization of Ribonucleoside 3′‐Phosphodiesters: The Role in Stabilization of the Phosphorane Intermediate

A dinucleoside‐3′,5′‐phosphodiester model, 5′‐amino‐4′‐aminomethyl‐5′‐deoxyuridylyl‐3′,5′‐thymidine, incorporating two aminomethyl functions in the 4′‐position of the 3′‐linked nucleoside has been prepared and its hydrolytic reactions studied over a wide pH range. The amino functions were found to accelerate the cleavage and isomerization of the phosphodiester linkage in both protonated and neutral form. When present in protonated form, the cleavage of the 3′,5′‐phosphodiester linkage and its isomerization to a 2′,5′‐linkage are pH‐independent and 50–80 times as fast as the corresponding reactions of uridylyl‐3′,5′‐uridine (3′,5′‐UpU). The cleavage of the resulting 2′,5′‐isomer is also accelerated, albeit less than with the 3′,5′‐isomer, whereas isomerization back to the 3′,5′‐diester is not enhanced. When the amino groups are deprotonated, the cleavage reactions of both isomers are again pH‐independent and up to 1000‐fold faster than the pH‐independent cleavage of UpU. Interestingly, the 2′‐ to 3′‐isomerization is now much faster than its reverse reaction. The mechanisms of these reactions are discussed. The rate accelerations are largely accounted for by electrostatic and hydrogen‐bonding interactions of the protonated amino groups with the phosphorane intermediate.     

Kinetics of bioconjugate nanoparticle label binding in a sandwich-type immunoassay

Nanoparticle labels have enhanced the performance of diagnostic, screening, and other measurement applications and hold further promise for more sensitive, precise, and cost-effective assay technologies. Nevertheless, a clear view of the biomolecular interactions on the molecular level is missing. Controlling the ratio of molecular recognition over undesired nonspecific adhesion is the key to improve biosensing with nanoparticles. To improve this ratio with an aim to disallow nonspecific binding, a more detailed perspective into the kinetic differences between the cases is needed. We present the application of two novel methods to determine complex binding kinetics of bioconjugate nanoparticles, interferometry, and force spectroscopy. Force spectroscopy is an atomic force microscopy technique and optical interferometry is a direct method to monitor reaction kinetics in second-hour timescale, both having steadily increasing importance in nanomedicine. The combination is perfectly suited for this purpose, due to the high sensitivity to detect binding events and the ability to investigate biological samples under physiological conditions. We have attached a single biofunctionalized nanoparticle to the outer tip apex and studied the binding behavior of the nanoparticle in a sandwich-type immunoassay using dynamic force spectroscopy in millisecond timescale. Utilization of the two novel methods allowed characterization of binding kinetics in a time range spanning from 50 ms to 4 h. These experiments allowed detection and demonstration of differences between specific and nonspecific binding. Most importantly, nonspecific binding of a nanoparticle was reduced at contact times below 100 ms with the solid-phase surface.

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Figure A single biofunctionalized nanoparticle was attached to the outer tip apex and the binding behavior of the nanoparticle in a sandwich-type immunoassay, A) without analyte, B) with analyte and C) saturating analyte concentration, was recorded using dynamic force spectroscopy in millisecond timescale. The setting allowed measurement of the association speed of nonspecific binding.

     

A synthesis of crambescidin 359

A potentially biomimetic synthesis of the guanidine-containing marine natural product crambescidin 359 via a double Michael addition of guanidine to a suitably functionalised bis-enone is reported.     

Carrier dynamics in strain-induced InGaAsP/InP quantum dots

Carrier dynamics of strain-induced InGaAsP/InP quantum dots (QDs) is investigated. In this structure, self-assembled InAs islands on the surface act as stressors and create a lateral confinement potential in the near surface InGaAsP/InP quantum well. Photoluminescence (PL) measurements reveal that decreasing the distance from the QD to the surface significantly diminishes the QD–PL intensity, presumably due to surface states of the InAs islands. Moreover, time-resolved measurements show a faster decay of the QD–PL with decreasing distance. To analyze the carrier dynamics, rate equation model is applied and surface state-related transitions are taken into account. The model is found to agree with measurements, and thus provides a possible explanation for the observed temporal behavior of the carriers.     

GaN/GaAs(1 0 0) superlattices grown by metalorganic vapor phase epitaxy using dimethylhydrazine precursor

Superlattices of cubic gallium nitride (GaN) and gallium arsenide (GaAs) were grown on GaAs(1 0 0) substrates using metalorganic vapor phase epitaxy (MOVPE) with dimethylhydrazine (DMHy) as nitrogen source. Structures grown at low temperatures with varying layer thicknesses were characterized using high resolution X-ray diffraction and atomic force microscopy. Several growth modes of GaAs on GaN were observed: step-edge, layer-by-layer 2D, and 3D island growth. A two-temperature growth process was found to yield good crystal quality and atomically flat surfaces. The results suggest that MOVPE-grown thin GaN layers may be applicable to novel GaAs heterostructure devices.     

Sets in Abelian groups with distinct sums of pairs

A subset S={s₁,…,sk} of an Abelian group G is called an St-set of size k if all sums of t different elements in S are distinct. Let s(G) denote the cardinality of the largest S₂-set in G. Let v(k) denote the order of the smallest Abelian group for which s(G)?k. In this article, bounds for s(G) are developed and v(k) is determined for k?15 by computing s(G) for Abelian groups of order up to 183 using exhaustive backtrack search with isomorph rejection.