Solid Lipid Nanoparticles (SLNs): Preparation and Properties of Calix[4]resorcinarene Derived Systems.

Solid Lipid Nanoparticles (SLNs) have been prepared fromc-2,c-8,c-14,c-20-tetraundecyl-4,6,10,12,16,18,22,24-octahydroxyresorc[4]areneas colloidal suspensions. Photon Correlation Spectroscopy studies revealed aparticle hydrodynamic diameter of 150 nm. Non-contact mode Atomic ForceMicroscopy allows observation of the particles as slightly flattened sphericalobjects of 236 (±40) nm diameter and 145 (±40) nm height. Thestudy of the preparation parameters showed that shear force does not affectthe hydrodynamic size of the SLNs. In contrast, the viscosity and the pH ofthe aqueous phase, the amphiphile concentration in the organic phase and thevolume of organic phase used, all lead to variation in the size of the particles.In term of post preparation parameters only the ionic strength has been shownto affect significantly the particle size; while the pH of the storing solution,microwave, ultrasonic and thermal treatments do not. Short and long-termstability studies have been performed to measure the effect of the ionic strengthon the stability of the particles. The use of carbohydrate cryoprotectants does notallow re-dispersion of the colloidal suspension after freeze-drying.     

Monitoring the packet gap of real-time packet traffic

Real-time packet traffic is characterized by a strict deadline on the end-to-end time delay and an upper bound on the information loss. Due to the high correlation among consecutive packets, the individual packet loss does not well characterize the performance of real-time packet sessions. An additional measure of packet loss is necessary to adequately assess the quality of each real-time connection. The additional measure considered here is the average number of consecutively lost packets, also called the average packet gap. We derive a closed form for the average packet gap for the multiclassG/G/m/B queueing system in equilibrium and show that it only depends on the loss behavior of two consecutive packets. This result considerably simplifies the monitoring process of real-time packet traffic sessions. If the packet loss process is markovian, the consecutive packet loss has a geometric distribution.     

On the number of conjugacy classes of a finite solvable group II

We prove that a finite solvable group G has at least (49p+1)/60 conjugacy classes whenever p is a prime such that p² divides the order of G. We also construct an infinite family of finite solvable groups, where this bound is attained.     

Efficient synthesis of 2- and 3-substituted-2,3-dihydro [1,4]dioxino[2,3-b]pyridine derivatives

A versatile new approach for the synthesis in three steps of 2-substituted-2,3-dihydro[1,4]dioxino[2,3-b]pyridines B via a Smiles rearrangement using easily available reagents is described. A study illustrating the influence of experimental conditions on the progress of the reaction is reported.     

Sodium-23 Nuclear Magnetic Resonance Spectroscopy

With the availability of Fourier transform spectrometers, ²³Na-NMR spectroscopy has become an important tool. It affords direct insight into solvation and ion pairing phenomena, both in organic and in bio-inorganic systems. Monitoring the chemical shifts and linewidths of ²³Na signals gives access to binding constants, reorientational correlation times and the microdynamics of the sodium coordination shell. The binding of other cations can also be studied by ²³Na-NMR spectroscopy, in competition experiments.     

Enhancement of phosphoprotein analysis using a fluorescent affinity tag and mass spectrometry

A fluorescent affinity tag (FAT) was synthesized and was utilized to selectively modify phosphorylated serine and threonine residues via beta-elimination and Michael addition chemistries in a 'one-step' reaction. This labeling technique was used for covalent modification of both phosphoproteins and phosphopeptides, allowing identification of these molecular species by fluorescence imaging after solution- or gel-based separation methods. In addition to the strong fluorescence of the rhodamine tag, a commercially available antibody can be used to enrich low-abundance post-labeled phosphopeptides present in complex mixtures. Application of this methodology to phosphorylation-site mapping has been evaluated for a phosphoprotein standard, bovine beta-casein. Initial results demonstrated low femtomole detection limits after fluorescence image analysis of FAT-labeled proteins or peptides.     

Investigating bidentate and tridentate carbamoylmethylphosphine oxide ligand interactions with rare-Earth elements using electrospray ionization quadrupole ion trap mass spectrometry

Electrospray ionization (ESI) quadrupole ion trap mass spectrometry (QIT-MS) and collisionally activated dissociation (CAD) were used to evaluate the rare-earth binding properties of two hydrophobic carbamoylmethylphosphine oxide (CMPO) ligands, the normal bidentate variety, (t-BuC6H4)2P(O)CH2C(O)N(i-Bu)2 (A), a new potentially tridentate extractant, (t-BuC6H4)2P(O)CH[CH2C(O)N(i-Bu)2]C(O)N(i-Bu)2 (B), and tributyl phosphate. The mass spectral results obtained from analysis of 1% HNO3/methanol solution containing the ligands and dissolved lanthanide salts reveal that the favorable stoichiometries of the ligand/metal/nitrate complexes are 2:1:2 for the bidentate ligand A, 1:1:2 for the tridentate ligand B, and 3:1:2 for the monodentate tributyl phosphate. These observed stoichiometries correlate with the number of available binding sites on each ligand as well as with potential steric effects. Energy-variable collisionally activated dissociation experiments showed that for the 2:1:2 complexes involving ligand A or B, as the ionic radius of the bound metal decreased, the removal of nitric acid required less energy and resulted in less extensive spontaneous solvent coordination. This experimental trend suggests that, as the ionic radius of the lanthanide ion decreases, a pair of the carbamoylmethylphosphine ligands is able to more completely solvate the bound metal ion thereby weakening the nitrate-metal interaction.     

Direct Clay-Catalyzed Friedel-Crafts Arylation and Chlorination of the Hydrocarbon Adamantane

Multiple chlorinations and arylations at the tertiary positions of adamantane are promoted by FeCl₃-doped K10 montmorillonite in CCl₄ or in aromatic solvents. The process, remarkably easy to implement, can be tailored to selective formation of monosubstituted 1-adamantyl derivatives or 1,3-disubstituted adamantanes. The process achieves alkylation at the meta- and para-positions of toluene leading to a purely statistical distribution and displays no substrate specificity in competition experiments between toluene and benzene.