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.     

Organotin and tin(IV) derivatives of dimethyldithioarsinic acid

Organotin derivatives of dimethyldithioarsinic (dithocacodylic) acid have been obtained from the appropriate organotin chloride and the sodium salt of the latter. Tin(IV) chloride and NaS₂AsMe₂ · 2 H₂O yielded only two products, namely Cl₂Sn(S₂AsMe₂)₂ and Sn (S₂AsMe₂)₄, regardless of the reagent ratio. Spectroscopic characterization of the compounds (infrared and¹H NMR) provides structural information suggesting that the dimethyldithioarsinato group behaves as monodentate (or anisobidentate) ligand in Me₂Sn(S₂AsMe₂)₂, Bu₂Sn-(S₂AsMe₂)₂ and Cy₃Sn(S₂AsMe₂), as bidentate in Ph₂Sn(S₂AsMe₂)₂, Ph₃Sn(S₂AsMe₂) and Cl₂As(S₂AsMe₂)₂, whereas Sn(S₂AsMe₂)₄ contains both mono- and bidentate ligands, presumably in a six-coordinate structure.     

Resolution enhancement in multidimensional solid-state NMR spectroscopy of proteins using spin-state selection

We show that the resolution of homonuclear multidimensional solid-state NMR correlation experiments can be significantly improved using transition selection and spin-state-selective polarization transfer techniques. The selection and transfer of single states allow the removal of the J-coupling contribution from the line width in both the direct and indirect spectral dimensions. This is demonstrated with a new spin-state-selective CO-Calpha correlation experiment, applied to a microcrystalline 85-residue protein. With this new sequence, all four components of the CO-Calpha cross-peaks are separated into different spectra, obtained by linear combination of four recorded data sets. Line narrowing of up to 44% was obtained on the protein sample for the spin-state-selective CO-Calpha spectrum compared to a standard spin-diffusion experiment. The new technique also allows an easy distinction between "direct" and "relayed" transfer cross-peaks.     

Synthesis and characterization of thiophene‐substituted N‐phenyl maleimide polymers by photoinduced radical polymerization

Two types of novel functionalized N‐[4‐(4′‐hydroxyphenyloxycarbonyl)phenyl]maleimide and N‐(4‐{[2‐(3‐thienyl)acetyl]oxyphenyl}oxycarbonylphenyl)maleimide (MIThi) were synthesized starting from 4‐maleimido benzoic acid. Photoinduced radical homopolymerization of MIThi and its copolymerization with styrene were performed at room temperature to give linear polymers containing pendant thienyl moieties using ω,ω‐dimethoxy‐ω‐phenylacetophenone as an initiator. Copolymers' compositions and the equilibrium constant (K) for electron donor–acceptor complex formation suggest an alternating nature of the copolymerization. The monomer reactivity ratios and Alfrey–Price Q,e values were also determined. The thermal behavior of the new synthesized monomers and polymers was investigated by differential scanning calorimetry and thermogravimetric analysis. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 995–1004, 2002     

Sol–Gel SiO2-ZrO2 Coatings for Optical Applications

SiO₂-ZrO₂ based nanostructured multilayers films have been prepared by sol–gel processing from metallorganic precursors by low temperature inorganic polymerization reactions. Simultaneous gelation of both precursors was realized. Homogeneous and transparent films were obtained at room temperature by dip- and spin-coating on glass and silicon wafer substrates. Samples with successively deposited layers (1–3 layers) and successive thermal treatments have been also studied. Each deposited layer was thermally treated for 1 h at 300°C. The coatings were characterized by XRD, spectroellipsometry (SE), UV-VIS spectroscopy and AFM methods. The influence of substrates, number of coatings and number of thermal treatments on the optical and structural properties of the films was established. The thickness of three deposited SiO₂-ZrO₂ layers is about 496 nm on glass substrates and 413 nm on the silicon wafer substrate. The films deposited on glass are more porous than those deposited on silicon. The properties of optical waveguide prepared from SiO₂-ZrO₂ layers on silicon substrates will be discussed.     

Stereochemistry of cyclobutanone resulted from cycloadditions of t-butylcyanoketene to bicyclo[2.2.1]heptene derivatives, as evidence for a π2s+π2a reaction mode

The stereochemistry of the cyclobutanones 1-7, resulted from the reaction of t-butylcyanoketene with bicyclo[2.2.1]heptene, bicyclo[2.2.1]heptadiene, 1,4 - dihydro - 1,4 - methanonaphthalene, 1,4 - dihydro - 9 - (1 - methylethylidene) - 1,4 - methanonaphthalene, 1,4 - dihydro - 1,4 - epoxynaphthalene, l,4,4a,8b - tetrahydro - 1,4 - methanobiphenylene (l,4,4a,8b) and 1,4,4a,8b - tetrahydro - 1,4 - methanobiphenylene(1,4,4aβ,8bβ) was established as having the cyclobutanone ring exo and the t-Bu group in the configuration. These findings represent a stereochemical argument in favour of a _π2_s + _π2_a reaction mode of t-butylcyanoketene to the above mentioned bicyclo[2.2.1]heptene derivatives. Observations regarding preservation of the original configurations of alkenes as well as the geometrical distorsion of the cyclobutanones are shortly discussed.     

Light Energy Collection in a Porphyrin–Imide–Corrole Ensemble

An assembly consisting of three units, that is, a meso‐substituted corrole ( C3 ), 1,8 naphthaleneimide ( NIE ), and a Zn porphyrin ( ZnP ), has been synthesized. NIE is connected to C3 through a 1,3‐phenylene bridge and to the ZnP unit through a direct C? C bond. The convergent synthetic strategy includes the preparation of a trans‐A₂B‐corrole possessing the imide unit, followed by Sonogashira coupling with a meso‐substituted A₃B‐porphyrin. The photophysical processes in the resulting triad ZnP-NIE-C3 are examined and compared with those of the corresponding C3-NIE dyad and the constituent reference models C3 , NIE , and ZnP . Excitation of the NIE unit in C3-NIE leads to a fast energy transfer of 98 % efficiency to C3 with a rate k_en=7.5×10¹⁰ s^?1, whereas excitation of the corrole unit leads to a reactivity of the excited state identical to that of the model C3 , with a deactivation rate to the ground state k=2.5×10⁸ s^?1. Energy transfer to C3 and to ZnP moieties follows excitation of NIE in the triad ZnP-NIE-C3 . The rates are k_en=7.5×10¹⁰ s^?1 and k_en=2.5×10¹⁰ s^?1 for the sensitization of the C3 and ZnP unit, respectively. The light energy transferred from NIE to Zn porphyrin unit is ultimately funneled to the corrole component, which is the final recipient of the excitation energy absorbed by the different components of the array. The latter process occurs with a rate k_en=3.4×10⁹ s^?1 and 89 % efficiency. Energy transfer processes take place in all cases by a Förster (dipole–dipole) mechanism. The theory predicts quite satisfactorily the rate for the ZnP/C3 couple, where components are separated by about 23 Å, but results in calculated rates that are one to two orders of magnitude higher for the couples NIE/ZnP (D/A) and NIE/C3, which are separated by distances of about 14 and 10 Å, respectively.     

New symmetric azomethinic dimer: the influence of structural heterogeneity on the liquid crystalline behaviour

The paper deals with the study of the thermotropic liquid crystalline properties of a new azomethinic symmetric dimer and some of its structural heterogeneous mixtures with one of its reagents. Their thermotropic behaviour was monitored by polarised light microscopy, differential scanning microscopy and variable temperature X-ray diffraction measurements. The influence of the structural heterogeneity on the mesomorphic behaviour was established and some similarities with the mesomorphic behaviour of the polydisperse polymers were underlined.     

Synergistic effect between TiO2 sol–gel and Degussa P25 in dye photodegradation

The TiO₂ powders were synthesized by versatile and low cost sol–gel process using HNO₃ and titanium tetra-isopropoxide (volumetric ratio of 4:1) following by the hydrolysis reaction. The powders show the two polymorphs of TiO₂: 96 % anatase and 4 % brookite, due to acidic condition (pH = 3). Thin films of titanium oxide were obtained by dip-coating, using the sol–gel of titanium oxide mixed with commercial Degussa P25 into a weight ratio 1:1 or 1:1.5, to enhance the synergistic effect of anatase/rutile ratio aiming at increasing the efficiency of the TiO₂ photocatalyst in dyes degradation. The thin film surface (charge and morphology) was controlled by polymer (poly-ethylene glycol) and surfactant (Sodium dodecyl sulphate, Triton X100) addition. The titanium oxide was characterized by particle size analyzer, contact angle measurements, X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The photocatalytic properties of powders and coatings were evaluated based on the degradation efficiency of two reference dyes (methyl orange and methylene blue). The results outline that poly(ethylene glycol) and films morphologies are the most influential factors that affecting the photocatalytic activity.