Mesoporous aluminum phosphite

High surface area pure mesoporous aluminum-phosphorus oxide-based derivatives have been synthesized through an S⁺I⁻ surfactant-assisted cooperative mechanism by means of a one-pot preparative procedure from aqueous solution and starting from aluminum atrane complexes and phosphoric and/or phosphorous acids. A soft chemical extraction procedure allows opening the pore system of the parent as-prepared materials by exchanging the surfactant without mesostructure collapse. The nature of the pore wall can be modulated from mesoporous aluminum phosphate (ALPO) up to total incorporation of phosphite entities (mesoporous aluminum phosphite), which results in a gradual evolution of the acidic properties of the final materials. While phosphate groups in ALPO act as network building blocks (bridging Al atoms), the phosphite entities become basically attached to the pore surface, what gives practically empty channels. The mesoporous nature of the final materials is confirmed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and N₂ adsorption–desorption isotherms. The materials present regular unimodal pore systems whose order decreases as the phosphite content increases. NMR spectroscopic results confirm the incorporation of oxo-phosphorus entities to the framework of these materials and also provide us useful information concerning the mechanism through which they are formed.     

Karyotypic similarity among Barycholos ternetzi and five species of the genus Eleutherodactylus from southeastern Brazil (Anura, Brachycephalidae)

Comparative cytogenetic analyses were carried out in six species of Brachycephalidae from southeastern Brazil. Barycholos ternetzi, Eleutherodactylus binotatus, Eleutherodactylus guentheri, Eleutherodactylus juipoca, Eleutherodactylus parvus and Eleutherodactylus sp. have 2n=22 karyotypes with a marked variation in the morphology of chromosome pairs 8, 10 and 11, which are of telocentric or metacentric types, resulting in FN=38, 40 and 44. Eleutherodactylus have a single chromosome pair bearing Ag-NOR, i.e. pair 1 in E. binotatus, pair 6 in E. guentheri and E. parvus, and pair 11 in E. juipoca and Eleutherodactylus sp. In contrast, B. ternetzi showed Ag-positive sites in the chromosome pairs 1, 4, 5, 9 and 11, and only one to three labelings per metaphase in each individual. Nevertheless, the main chromosome pair with Ag-NOR in the species seems to be the 11th, like in E. juipoca and Eleutherodactylus sp. The NOR site was confirmed by fluorescence in situ hybridization (FISH) technique in E. binotatus and in B. ternetzi, bearing 1p1p and 9p11p11p Ag-NOR pattern, respectively. All the species exhibited predominantly centromeric C-banding pattern, but interstitial bands have also been observed in some cases. In E. binotatus, there is an indication of geographical difference in the distribution of the interstitial C-bands. The fluorochromes GC-specific chromomycin A(3) (CMA(3)) and AT-specific 4',6-diamidino-2-phenylindole (DAPI), with distamycin A (DA) counterstaining, provided the molecular content of some repetitive regions in the karyotypes of the species. One male of E. binotatus presented an extensive heteromorphism, involving at least five different pairs, probably as a consequence of multiple reciprocal translocations. Such rearrangements might be responsible for the multivalent chain seen in the meiosis of this specimen, as well as in another male, although not exhibiting chromosome heteromorphism. The remaining males and those belonging to the other species have always shown 11 bivalents in diplotene and metaphase I cells. In all male specimens, metaphases II presented 11 chromosomes. Despite the observed discrepancies, the five species of Eleutherodactylus have a great uniformity in the 2n=22 karyotypes, suggesting an assemblage of species from southeastern and southern Brazil, in contrast to northern and northeastern assemblage which is characterized by higher diploid numbers. Undoubtedly, B. ternetzi could be included in that proposed assemblage, due to its karyotypic similarity with the Eleutherodactylus species, as evidenced in the present study. This fact strongly supports the close relationships of both genera, previously inferred on the basis of several characters shared by their species.     

ZnO nanoparticles embedded in UVM-7-like mesoporous silica materials: Synthesis and characterization

ZnO nanodomains embedded in bimodal mesoporous silica (UVM-7) materials with high Zn content (4≤Si/Zn≤30) have been synthesized by an one-pot surfactant-assisted procedure from a hydro alcoholic medium using a cationic surfactant (CTMABr=cetyltrimethylammonium bromide) as structural directing agent, and starting from molecular atrane complexes of Zn and Si as hydrolytic inorganic precursors. This chemical procedure allows optimizing the dispersion of the ZnO particles in the silica walls. The bimodal mesoporous nature of the final high surface area nano-sized materials is confirmed by XRD, TEM, and N₂ adsorption–desorption isotherms. The small intra-particle mesopore system is due to the supramolecular templating effect of the surfactant, while the large pores have their origin in the packing voids generated by aggregation of the primary nanometric mesoporous particles. A limited pore blocking and a high accessibility to the ZnO active nanoparticles have been achieved. The effects induced by the progressive incorporation of ZnO nanoparticles into the mesostructure have been examined, including a careful optical spectroscopic study (PL and UV–visible).     

Existence and stability of new nanoreactors: highly swollen hexagonal liquid crystals

We report the preparation of direct hexagonal liquid crystals, constituted of oil-swollen cylinders arranged on a triangular lattice in water. The volume ratio of oil over water, rho can be as large as 3.8. From the lattice parameter measured by small-angle X-ray scattering, we show that all the oil is indeed incorporated into the cylinders, thus allowing the diameter of the cylinders to be controlled over one decade range, provided that the ionic strength of the aqueous medium and rho are varied concomitantly. These hexagonal swollen liquid crystals (SLCs) have been first reported with sodium dodecyl sulfate as anionic surfactant, cyclohexane as solvent, 1-pentanol as co-surfactant, and sodium chloride as salt (Ramos, L.; Fabre, P. Langmuir 1997, 13, 13). The stability of these liquid crystals is investigated when the pH of the aqueous medium or the chemical nature of the components (salt and surfactant) is changed. We demonstrate that the range of stability is quite extended, rendering swollen hexagonal phases potentially useful for the fabrication of nanomaterials. As illustrations, we finally show that gelation of inorganic particles in the continuous aqueous medium of a SLC and polymerization within the oil-swollen cylinders of a SLC can be conducted without disrupting the hexagonal order of the system.     

A new method for fluoride determination by using fluorophores and dyes anchored onto MCM-41

A new colourimetric and fluorimetric method for fluoride determination in aqueous samples based on the specific reaction between fluoride and silica has been developed and applied on real samples.     

The thiosulfinyl group serves as a stereogenic center and shows diamagnetic anisotropy similar to that of the sulfinyl group

The pseudotetrahedral geometry of the thiosulfinyl group (>S=S) in the thionosulfite which was prepared by treatment of cis-3,4-di-tert-butylthiolane-3,4-diol with 1,1'-thiobisbenzimidazole is stable enough to allow the isolation of two diastereomers. X-ray crystallographic analysis revealed that the configuration of the >S=S group of the major diastereomer (45% isolated yield) is syn to the thiolane ring, while that of the minor diastereomer (10% isolated yield) is anti to the thiolane ring. 1H NMR spectrum analysis clarified that the shielding and deshielding zones of the >S=S group are similar to those of the >S=O group. Chemical properties of the >S=S group toward thermolysis, hydrolysis, and oxidation were clarified. The absorptions or bands in the UV/vis, IR, and Raman spectra, which originate from the >S=S group, were assigned on the basis of the B3LYP/6-31G* level calculations.     

First total synthesis of (±)-oxerine

Total synthesis of (±)-oxerine (1), a monoterpene alkaloid, starting from 3-bromopyridine (7) is described. The key reaction in this sequence is the samarium iodide (SmI₂)-mediated intramolecular cyclization of γ-ethynyl bromide (4).     

An analysis of thyroid function diagnosis using Bayesian-type and SOM-type neural networks

Thyroid function diagnosis is an important classification problem, and we made reanalysis of the human thyroid data, which had been analyzed by the multivariate analysis, by the two notable neural networks. One is the self-organizing map approach which clusters the patients and displays visually a characteristic of the distribution according to laboratory tests. We found that self-organizing map (SOM) consists of three well separated clusters corresponding to hyperthyroid, hypothyroid and normal, and more detailed information for patients is obtained from the position in the map. Besides, the missing value SOM which we had introduced to investigate QSAR problem turned out to be also useful in treating such classification problem. We estimated the classification rates of thyroid disease using Bayesian regularized neural network (BRNN) and found that its prediction accuracy is better than multivariate analysis. Automatic relevance determination (ARD) method of BRNN was surely verified to be effective by the direct calculation of classification rates using BRNN without ARD for all possible combinations of laboratory tests.     

Isomerization reactions of allylic alcohols into ketones with the Grubbs reagent

Allylic alcohols were isomerized into ketones by the action of the Grubbs reagent. Some model alcohols were prepared and tested under similar conditions to reveal that less substituted alkenes rearrange more easily. More hindered alcohols are stable under these conditions, however, the simple allylic alcohols tend to isomerize producing ethyl ketone and the corresponding degraded methyl ketone.     

Real-time optical monitoring system for dye colour and concentration

A system for real-time monitoring of a dye has been constructed which enables us to measure the concentration and fluctuations of the three base colours. The method is based on light attenuation theory and its principle requires three different lasers having the three base colours. The system consisted of a semiconductor laser and argon ion laser for light sources, a photodiode for a light detector and a personal computer for data processing. Detection sensitivity for the dye concentration was a few and the system can be applied for practical uses.