Gemini imidazolium amphiphiles for the synthesis, stabilization, and drug delivery from gold nanoparticles

Gold nanoparticles (AuNPs) are considered useful vehicles for medical therapy and diagnosis. Despite the progress made in this field, there is need to find direct, reliable, and versatile synthetic procedures for their preparation as well as new multifunctional coating agents. In this sense, we have explored the use of imidazolium amphiphiles to prepare new AuNPs designed for anion recognition and transport. Thus, in this work we describe (a) the synthesis, by a phase transfer method, of new gold nanoparticles using gemini-type surfactants as ligands based on imidazolium salts, those ligands acting as transfer agents into organic media and also as nanoparticle stabilizers, (b) the examination of their stability in solution, (c) the chemical and physical characterization of the nanoparticles, using a variety of techniques, including UV-visible spectroscopy (UV-vis), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), (d) toxicity data concerning both the imidazolium ligands and the imidazolium coated nanoparticles, (e) the assessment of their molecular recognition ability toward molecules of biological interest, such as anions and carboxylate containing model drugs, such as ibuprofen, (f) the study of their toxicity and those of their coating ligands, as well as their ability for cell internalization, and (g) the study of their ability for delivering anionic pharmaceuticals. The structurally governed triple role of those new gemini-type surfactants is responsible for the preparation, remarkable stability, and delivery properties of these functional AuNPs.     

Nondegenerate pi-donor/pi-acceptor [2]catenanes containing proton-ionizable 1H-1,2,4-triazole subunits: synthesis and spontaneous resolution

Chirality can hold the key to inducing directionality of motion in components of molecular devices. With this idea in mind, we describe here 1) the template-directed synthesis of two [2]catenanes wherein cyclobis(paraquat-p-phenylene) is interlocked with polyether macrocycles containing, in addition to one 3,5-bis(oxymethylene)-1H-1,2,4-triazole unit, either one 1,4-dioxybenzene or one 1,5-dioxynaphthalene ring system. We also report 2) the full characterization of both [2]catenanes by fast atom bombardment mass spectrometry (FABMS), X-ray crystallography, and dynamic (1)H NMR spectroscopy. We reveal 3) the fact that the [2]catenanes not only exist, both in the solution-state and in the solid-state, as strictly one of the two possible translational isomers, but that they also exhibit spontaneous resolution on crystallization leading to formation of homochiral crystals, as indicated by X-ray crystallography and circular dichroism (CD) experiments. Finally, we comment 4) on the chances of switching these catenanes chemically.     

Structural and thermal properties of a Bi nano-plane embedded in amorphous germanium

The synthesis by pulsed laser deposition of a bismuth nano-plane embedded in an amorphous germanium matrix is reported. The structural changes were studied by Raman spectroscopy as a function of temperature. Upon heating, the Bi nano-plane melts and, as the sample is cooled, it re-crystallizes at a temperature well below the melting point. The results show a broad melting–solidification hysteresis cycle (170 K) that is compared to the ones obtained earlier on nanoparticles. Furthermore, a metal-induced crystallization effect was also observed in the germanium matrix. PACS 81.15.Fg; 05.70.Fh; 78.30.En     

Unbounded Violations of Bipartite Bell Inequalities via Operator Space Theory

In this work we show that bipartite quantum states with local Hilbert space dimension n can violate a Bell inequality by a factor of order ${{\rm \Omega} \left(\frac{\sqrt{n}}{\log^2n} \right)}In this work we show that bipartite quantum states with local Hilbert space dimension n can violate a Bell inequality by a factor of order W (\frac?nlog²n ){{\rm \Omega} \left(\frac{\sqrt{n}}{\log^2n} \right)} when observables with n possible outcomes are used. A central tool in the analysis is a close relation between this problem and operator space theory and, in particular, the very recent noncommutative L _p embedding theory.     

A Composition Theorem for Multiple Summing Operators

We prove that the composition S(u₁, …, u_n) of a multilinear multiple 2-summing operator S with 2-summing linear operators u_j is nuclear, generalizing a linear result of Grothendieck.     

A microscopic view of physical and chemical activation in the synthesis of porous carbons

The nanostructure and porosity of activated carbon fibers (ACFs) prepared by physical activation with CO2 and by chemical activation with H3PO4 of the highly ordered polymer poly(m-phenylene isophthalamide) have been investigated and compared by means of scanning tunneling microscopy (STM), scanning electron microscopy (SEM), and gas adsorption measurements. In general terms, both types of activation led to porous carbons with similar nanometer-scale structure, which consisted of relatively ordered and homogeneous arrays of platelets below 10-nm wide, the porous structure being mainly comprised by the network of narrow trenches present between neighboring platelets. This similarity was attributed to the influence of the crystalline structure of the polymeric precursor, which should favor a homogeneous, uniform transformation of the polymer into the final carbon material. Such influence was only lost in chemical activation with the use of very large amounts of activating agent. A comparison of samples before and after physical activation allowed a direct identification of the local areas where gasification (activation) took place. For chemical activation, the STM measurements suggested that porosity was developed at a lower temperature than the highly cross-linked nanographitic structure of the final ACF. This result was discussed in terms of the thermal transformation mechanism of the precursor polymer into a carbonaceous solid in the presence of H3PO4.     

Turning light into a liquid via atomic coherence

We study a four-level atomic system with electromagnetically induced transparency with giant chi(3) and chi(5) susceptibilities of opposite signs. This system will allow us to obtain multidimensional solitons and light condensates with surface tension properties analogous to those of usual liquids.     

Solubility and Hydrolysis of La, Pr, Eu, Er, and Lu in 1 M NaCl Ionic Strength at 303 K

The pLn-pC _H diagrams obtained by a radiometric technique were used for the determination of the solubility and the first hydrolysis constants for La, Pr, Eu, Er, and Lu in 1 M NaCl ionic strength at 303 K. The saturation and unsaturation zones, and the borderline of precipitation were determined from these diagrams. The first hydrolysis constants were determined from pH titrations where no precipitation was found; these data were treated with the SUPERQUAD program. Fitting methods involving pLn versus pC _H and the average ligand number vs. pC _H were used to calculate both the first hydrolysis constants and the solubility products. The log K _sp values obtained for La, Pr, Eu, Er, and Lu were –19.53, –20.92, –22.24, –22.62, and –23.05 and the log* ₁ average values obtained were –8.87 ± 0.05, –8.54 ± 0.04, –8.34 ± 0.03, –8.16 ± 0.04, and –8.11 ± 0.03, respectively, under CO₂ free conditions. Finally, the results were compared with those found in the literature.