Vinylic MIDA Boronates: New Building Blocks for the Synthesis of Aza‐Heterocycles

A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif.     

Approximations for Markovian multi-class queues with preemptive priorities

We discuss the approximation of performance measures in multi-class M/M/k queues with preemptive priorities for large problem instances (many classes and servers) using class aggregation and server reduction. We compared our approximations to exact and simulation results and found that our approach yields small-to-moderate approximation errors.     

Comparative study of photodynamic properties of 13,15-N-cycloimide derivatives of chlorin p6

Comparative study of 13,15-[N-(2-hydroxyethyl)]cycloimide chlorin p6 (2), 13,15-(N-acetoxy)cycloimide chlorin p6 (3), 13,15-(N-hydroxy)cycloimide chlorin p6 methyl ester (4) and 13,15-(N-methoxy)cycloimide chlorin p6 methyl ester (5) together with the previously investigated 13,15-[N-(3-hydroxypropyl)]cycloimide chlorin p6 (1) was performed. The dependence of the key photodynamic properties of 1-5 on the introduced substituents was analyzed. The photoinduced cell-killing activity of 4 is 100- and 280-fold higher than that of chlorin p6 and Photogem, respectively, as estimated on A549 human lung adenocarcinoma cells. The activity is reduced eight times in the order 4 > 5 > 1 > 2 > 3. The intracellular accumulation of 1-5 occurs in cytoplasm in a monomeric form bound to the lipids of cellular membranes. This form of 1, 2, 3, 4 and 5 is characterized by the high quantum yield of singlet oxygen generation, which depends on the introduced substituents, 0.66, 0.59, 0.35, 0.51 and 0.73, respectively. The photostability is two-fold less for 1 and four-fold less for 2, 3 and 5 than for 4. The rates of cellular uptake and efflux of 1-5 vary widely, thus providing the way to optimize the pharmacological properties of the photosensitizer (PS) using the respective substituents. Modifying the substituents, 1-5 were targeted to different cellular organelles. The enhanced accumulation in the Golgi apparatus and mitochondria complemented with diffuse staining of intracellular membranous structures is a property of 1-4. Compound 5 accumulates selectively in the lipid droplets and stains weakly perinuclear structures. Temperature-sensitive mechanisms of transport are responsible for the 1-4 uptake. Diffusion can play a role in the internalization of 5 but not of 1-4. Endocytosis via caveolae, clathrin-dependent and adenosine triphosphate-dependent pathways are not noticeably involved in the 1-5 internalization. Independently from their intracellular localization 1, 4 and 5 are highly efficient near-IR PS, which induce predominantly an apoptotic type of cell death under conditions providing ca 50% level of phototoxicity and necrosis at the 100% level of phototoxicity.     

Surface and porosity of nanocrystalline boehmite xerogels

Boehmite xerogels are prepared by hydrolysis of Al(OC4H9)3 followed by peptization with HNO3 (H+/Al = 0, 0.07, 0.2). XRD and TEM show that these gels are made of nanosized crystals (5-9 nm in width and 3 nm thick). According to the amount of acid, no significant differences are found in size and shape, but only in the spatial arrangement of the crystallites. Nitrogen adsorption-desorption isotherms of nonpeptized gels are of type IV, whereas isotherms of peptized gels are of type I. These isotherms are analyzed by the t-plot method. The majority of pore volume results from intercrystalline mesopores, but the peptized gels also contain intercrystalline micropores. The particle packing is very dense for the gel peptized with H+/Al = 0.2 (porosity = 0.26), but it is less dense in non-peptized gel (porosity = 0.44). Heating these gels under vacuum creates, from 250 degrees C onwards, an intracrystalline microporosity resulting from the conversion of boehmite into transition alumina. But heating also causes intercrystalline micropores collapsing. The specific surface area increases up to a limit temperature (300 degrees C for nonpeptized gels and 400 degrees C for peptized) beyond which sintering of the particles begins and the surface decreases. The PSD are calculated assuming a cylindrical pore geometry and using the corrected Kelvin equation proposed by Kruk et al. Peptized xerogels give a monomodal distribution with a maximum near 2 nm and no pores are larger than 6 nm. Nonpeptized gels have a bimodal distribution with a narrow peak near to 2 nm and a broad unsymmetrical peak with a maximum at 4 nm. Heating in air above 400 degrees C has a strong effect on the porosity. As the temperature increases, there is a broadening of the distribution and a marked decrease of small pores (below 3 nm). However, even after treatment at 800 degrees C, micropores are still present.     

Time-resolved ultraviolet laser-induced breakdown spectroscopy for organic material analysis

Ultraviolet pulses (266 nm) delivered by a quadrupled Nd:YAG laser were used to analyze organic samples with laser-induced breakdown spectroscopy (LIBS). We present characteristics of the spectra obtained from organic samples with special attentions on the emissions of organic elements, O and N, and molecular bonds CN. The choice of these atomic or molecular species is justified on one hand, by the importance of these species to specify organic or biological materials; and on the other hand by the possible interferences with ambient air when laser ablation takes place in the atmosphere. Time-resolved LIBS was used to determine the time-evolution of line intensity emitted from these species. We demonstrate different kinetic behaviors corresponding to different origins of emitters: native atomic or molecular species directly vaporized from the sample or those generated through dissociation or recombination due to interaction between laser-induced plasma and air molecules. Our results show the ability of time-resolved UV-LIBS for detection and identification of native atomic or molecular species from an organic sample.     

Relevant synthesis parameters for the sequential catalytic growth of carbon nanotubes

Sequential catalytic growth provides an efficient tool for the synthesis of carbon nanotubes periodically inserted with catalyst nanoparticles. Several synthesis parameters were found crucial in order to induce this particular growth mechanism. The presence of phosphorus is required to form metal phosphide particles active for the formation of carbon nanotubes with a matchstick morphology. The metal composition (Ni/Fe ratio) and the carbon supply have no influence on the nanofilament type but strongly affect the nanotube yield. The synthesis temperature induces important changes on both the nanofilament type and yield, which are correlated with important transformations of the catalyst layer in terms of composition, particle size, and physical state.     

Ring-fused cyclobutanes via cycloisomerization of alkylidenecyclopropane acylsilanes

A novel Lewis acid-catalyzed cycloisomerization of alkylidenecyclopropane acylsilanes is disclosed. The readily available starting materials participate in tandem Prins addition/ring expansion/1,2-silyl shift to grant access to bicyclo[4.2.0]octanes and bicyclo[3.2.0]heptanes, which are common motifs in terpenoid natural products. Notably, the transformation relies on the ability of acylsilanes to act sequentially as acceptors and donors on the same carbon atom.

A novel Lewis acid-catalyzed cycloisomerization of alkylidenecyclopropane acylsilanes is disclosed that involves tandem Prins addition/ring expansion/1,2-silyl shift to grant access to bicyclo[4.2.0]octanes and bicyclo[3.2.0]heptanes.