Pyridine-based lanthanide complexes combining MRI and NIR luminescence activities

A series of novel triazole derivative pyridine-based polyamino-polycarboxylate ligands has been synthesized for lanthanide complexation. This versatile platform of chelating agents combines advantageous properties for both magnetic resonance (MR) and optical imaging applications of the corresponding Gd(3+) and near-infrared luminescent lanthanide complexes. The thermodynamic stability constants of the Ln(3+) complexes, as assessed by pH potentiometric measurements, are in the range log K(LnL)=17-19, with a high selectivity for lanthanides over Ca(2+), Cu(2+), and Zn(2+). The complexes are bishydrated, an important advantage to obtain high relaxivities for the Gd(3+) chelates. The water exchange of the Gd(3+) complexes (k(ex)(298)=7.7-9.3×10(6) s(-1)) is faster than that of clinically used magnetic resonance imaging (MRI) contrast agents and proceeds through a dissociatively activated mechanism, as evidenced by the positive activation volumes (ΔV(≠)=7.2-8.8 cm(3) mol(-1)). The new triazole ligands allow a considerable shift towards lower excitation energies of the luminescent lanthanide complexes as compared to the parent pyridinic complex, which is a significant advantage in the perspective of biological applications. In addition, they provide increased epsilon values resulting in a larger number of emitted photons and better detection sensitivity. The most conjugated system PheTPy, bearing a phenyl-triazole pendant on the pyridine ring, is particularly promising as it displays the lowest excitation and triplet-state energies associated with good quantum yields for both Nd(3+) and Yb(3+) complexes. Cellular and in vivo toxicity studies in mice evidenced the non-toxicity and the safe use of such bishydrated complexes in animal experiments. Overall, these pyridinic ligands constitute a highly versatile platform for the simultaneous optimization of both MRI and optical properties of the Gd(3+) and the luminescent lanthanide complexes, respectively.     

Strong reciprocity, social structure, and the evolution of fair allocations in a simulated ultimatum game

Cooperation has long been an enigma in the life and social sciences. A possible explanation for the phenomenon is the recently developed idea of strong reciprocity in which agents altruistically reward those that cooperate and altruistically punish those that do not. The acts are altruistic in the sense that when agents punish or reward they incur a cost but receive no material benefit. Both experimentalists and modelers have focused primarily on third-party altruistic punishment mechanisms yet rarely discuss how they establish a cost for punishing. In this study I used agent-based modelling to test the ability of altruistic punishment to elicit fair allocations in a simulated ultimatum game. In particular I simulated agents with the ability to punish neighbors whose offers were deemed too low while systematically varying the ratio of costs between punisher and punishee. Despite several studies in which strong reciprocity is shown to induce cooperation, altruistic punishment failed to evolve fair allocations in these simulations. However, outcomes were highly dependant on the spatial structure of agents in the simulations and fair allocations did evolve in a linearly structured population even in the absence of punishment. As the number of immediate neighbors increased, mean offers fell but still remained significantly greater than that predicted by standard economic theory. Only when social structure was removed, and agents could interact with any other agent in the population, did offers in the simulated ultimatum game match theoretical expectations.

A strategy to protect and sensitize near-infrared luminescent Nd3+ and Yb3+: organic tropolonate ligands for the sensitization of Ln(3+)-doped NaYF4 nanocrystals

A strategy to sensitize and protect near-infrared (NIR) emitting Nd3+ and Yb3+ is presented. Combining protection provided by the inorganic matrix of NaYF4 nanocrystals and sensitization from tropolonate ligands capped on their surface, the lanthanide cation centered luminescence was observed through the ligand excitation. The extended lanthanide luminescence lifetimes indicate the success of this strategy.     

Duplex‐Selective Ruthenium‐Based DNA Intercalators

We report the design and synthesis of small molecules that exhibit enhanced luminescence in the presence of duplex rather than single‐stranded DNA. The local environment presented by a well‐known [Ru(dipyrido[3,2‐a:2′,3′‐c]phenazine)L₂]²⁺‐based DNA intercalator was modified by functionalizing the bipyridine ligands with esters and carboxylic acids. By systematically varying the number and charge of the pendant groups, it was determined that decreasing the electrostatic interaction between the intercalator and the anionic DNA backbone reduced single‐strand interactions and translated to better duplex specificity. In studying this class of complexes, a single Ru^II complex emerged that selectively luminesces in the presence of duplex DNA with little to no background from interacting with single‐stranded DNA. This complex shows promise as a new dye capable of selectively staining double‐ versus single‐stranded DNA in gel electrophoresis, which cannot be done with conventional SYBR dyes.     

Cation radicals. XXVIII. Isolation and some reactions of dibenzodioxin cation radical perchlorate

Preparation and isolation of dibenzodioxin cation radical perchlorate ( 2 ) by oxidation of dibenzodioxin in ethyl acetate-lithium perchlorate at a platinum anode has been achieved. Reasonably pure 2 in amounts of 150–200 mg. were obtained reliably and reproducibly. Reaction of 2 with both nitrite and nitrate ions gave 2-nitrodibenzodioxin ( 3 ). Reaction of 2 with pyridine gave N-(2-dibenzodioxinyl)pyridinium perchlorate ( 4 ). Reaction with water gave, as anticipated, the stoichiometric amount of dibenzodioxin. Reaction with ammonia, propylamine, t-butylamine, and cyanide ion also gave dibenzodioxin with no evidence that nucleophilic substitution had occurred. It is believed that the formation of 3 and 4 represent the first examples of nucleophilic substitution into dibenzodioxin via its cation radical.     

Polynuclear SmIII Polyamidoamine‐Based Dendrimer: A Single Probe for Combined Visible and Near‐Infrared Live‐Cell Imaging

We report herein the synthesis of a luminescent polynuclear dendritic structure (Sm^III‐G3P‐2,3Nap) in which eight Sm^III ions are sensitized by thirty‐two 2,3‐naphthalimide chromophores. Upon a single excitation wavelength, the dendrimer complex exhibits two types of emission in the visible and in the near‐infrared (NIR) ranges. Sm^III‐G3P‐2,3Nap was non‐cytotoxic after 24 h of incubation and up to 2.5 μM . The ability of the Sm^III‐based probe to be taken up by cells was confirmed by confocal microscopy. Epifluorescence microscopy validated Sm^III‐G3P‐2,3Nap as a versatile probe, capable of performing interchangeably in the visible or NIR for live‐cell imaging. As both emissions are obtained from a single complex, the cytotoxicity and biodistribution are inherently the same. The possibility for discriminating the sharp Sm^III signals from autofluorescence in two spectral ranges increases the reliability of analysis and reduces the probability of artifacts and instrumental errors.