Estudo da síntese da zeólita MCM-71

A new kind of material, denominated MCM-71, was synthesized and characterized by several complementary techniques: X Ray Diffractometry, textural analysis by nitrogen adsorption, Scanning electronic microscopy and infrared spectroscopy. MCM-71 zeolite was successfully synthesized by hydrothermal synthesis in the presence of triethanolamine. Mordenite phase as impurity was not detected, otherwise quartz was observed. The MCM-71 sample obtained presented a BET surface area of 20 m²/g in the as synthesized form and of 85 m²/g in protonic form. By SEM was observed crystals with rectangular shape with average size of 2 x 0,2 x 0,05 µm and this crystals were agglomerated in spherical particles with average diameter between 14 and 24 µm.

Immobilization of laccase on hybrid layered double hydroxide

Crystals of Mg/Al layered double hydroxide were synthesized by alkaline precipitation and treated in an aqueous solution of glutamic acid. The glutamate ions were not intercalated into the interlayer space, but were detected in the material by Fourier transform infrared spectroscopy, suggesting that only the external surfaces of crystals were modified with glutamate ions. The resulting hybrid material was tested as a support for immobilization of the enzyme laccase (Myceliophthora thermophila). The immobilized enzyme preparation was characterized by electronic paramagnetic resonance spectroscopy and by assays of catalytic activity. The activity of the immobilized laccase was 97% of the activity in the free enzyme. Layered double hydroxide is a suitable support for use in remediation of soil studies.

Quiralidade em moléculas e cristais

The present contribution describes some concepts of stereochemistry and chirality in molecules and crystals. This paper also reports on the development of a simple and fast experiment to prepare and recognize conglomerate and true racemate of tartaric acid produced by mechanic mixture of commercial enantiomers and recristalization. Optical activity and melting point of mixtures are also used in the analysis.

Tecnologia de nanocristais em fármacos

The use of poorly water soluble molecules in pharmaceutical area has grown. Since these molecules exhibit low oral bioavailability, they are not used in intravenous administrations. Therefore, it is necessary to develop their new formulations with the aim to increase their oral bioavailabilities as to enable intravenous applications. One of the few possibilities in achieving this is a nanonization process that can produce crystals smaller than 1 μm by high pressure homogenization and without use of organic solvents. This mini-review describes technical aspects of the nanocrystal production, morphological aspects (polymorphisms), the market relevance of the nanocrystals products that are already in clinical phase or at the market, as well as, perspectives for the near future.

Crescimento de cristais de rubi e safira pelo método do fluxo

This work reports the growth of corundum crystals by the flux method. The main objective was the evaluation of versatility, effectiveness and real possibilities of the flux method to the synthesis and doping of monocrystals with impurities of particular interest. In this work the chosen impurities were i) Cr and ii) Fe and Ti, aiming the synthesis of rubies and sapphires, respectively. The crystals were grown by heating a mixture of Al2O3:Cr or Al2O3:Fe:Ti and flux (MoO3). The maximum crystal size obtained was 1.0 mm, all transparent, presenting well developed faces, bipiramidal hexagonal shape, and showing a typical red (ruby) and/or light blue (sapphire) color. EDX and XPD experiments were performed in order to characterize some of the synthesized crystals. All crystallized specimens presented the α-alumina atomic structure.

Desenvolvimento de microcélula eletroquímica para estudos de microrregiões

The construction and optimization of a device that can be applied to electrochemical studies in flat micro regions are described. This was developed as an attempt to study small regions of metallic samples, whose properties may differ completely from its macroscopic behavior and for studies in highly resistive medium. Some results were obtained for individual grains of polycrystalline samples, welded regions, pure copper, platinum, glassy carbon, single crystals of Cu-Zn-Al alloy, and steel in biodiesel without electrolyte intentionally added. The device showed to be useful for the proposed purpose, allowing to be automated and has potential possibilities of other applications.

Caracterización de cristales líquidos por microscopía óptica en sistemas surfactante polietoxilado-alcano-agua

The phase behavior of an alcohol polyethoxylated surfactant with decane and dodecane oil phase varying the water proportion from 5 to 90% to determine compositions in which the formation of liquid crystals and microemulsions ocurred was investigated. Pseudoternary phase diagrams were built to represent the regions of liquid crystals, biphases and microemulsions. Polarized light optical microscopy was used for the analysis and characterization of the separate phases. The micrographs obtained showed characteristics of hexagonal and lamellar phases of liquid crystal, isotropic phases, microemulsions and vesicles. This study is important to propose hypothesis regarding the factors determining the formation and stability of phases composed by surfactant/oil/water systems.

Síntese de cristais líquidos derivados do nitroazobenzeno: uma proposta de síntese multi-etapas aplicada às aulas de química orgânica experimental

We describe a synthetic route consisting of five steps from aniline to obtain liquid crystal compounds derived from nitroazobenzene. Syntheses were performed during the second half of the semester in organic chemistry laboratory classes. Students characterized the liquid crystal phase by the standard melting point techniques, differential scanning calorimetry and polarized optical microscopy. These experiments allow undergraduate students to explore fundamentally important reactions in Organic Chemistry, as well as modern concepts in Chemistry such as self-assembly and self-organization, nanostructured materials and molecular electronics.

Caracterização mecânica e estrutural de um dispositivo PDLC baseado em hidrogéis de PAAm e cristal líquido liotrópico LP/DeOH/H2O

In this work, a novel device based on polyacrylamide (PAAm) hydrogels and KL - DeOH - H2O lyotropic liquid crystal (LLC), with potential for application as Polymer Dispersed Liquid Crystals (PDLC), was proposed and its properties characterized. The confinement of LLC promoted significant changes in spectroscopic, morphological, optical, hydrophilic, structural and mechanical properties due to the interaction between the LLC-PAAm matrix and entropic parameter changes. The mechanical and structural properties can be controlled by adjusting AAm, temperature and presence of LLC, which can be useful for technological applications of these systems in optical devices.

REAÇÃO DE CONDENSAÇÃO DO GLICEROL COM COMPOSTOS CARBONÍLICOS. SÍNTESE, CARACTERIZAÇÃO E APLICAÇÃO EM CRISTAIS LÍQUIDOS

Condensation reactions of glycerol with aldehydes and ketones were performed under thermal heating and microwave irradiation regimes. Homogeneous and heterogeneous catalysts were tested in both conditions. A silica sulfated (SiO2-SO3H) heterogeneous catalyst demonstrated the best performance relative to a selectivity of >95% in favor of 5-membered ketals. For acetals, preference in favor of 5-membered or 6-membered functional groups depends on the nature of the catalyst. Homogenous catalysts favor the more stable 6-membered acetals, whereas heterogeneous catalysts favor the less stable 5-membered acetals. However, the isomer ratios in the acetalization reaction are too low, and hence the reaction cannot be used in a synthetic plan for functional materials. Ketalization processes mediated by SiO2-SO3H show a high selectivity in favor of a 5-membered ring (1,3-dioxolane). The scope of condensation was tested with different ketones. A mechanism for heterogeneous catalysis related to the selectivity in the cyclization process is presented herein. Solketal, a commercial product, was also obtained by a condensation reaction of glycerol and propanone, and showed a high selectivity in favor of 1,3-dioxolane. It was transformed to potential allylic and chiral intermediates. A mesogenic core was connected to the organic framework of glycerol to produce a monomer liquid crystal material with a stable smectic-C mesophase.

RESSONÂNCIA MAGNÉTICA NUCLEAR DE SUBSTÂNCIAS ORGANOFLUORADAS: UM DESAFIO NO ENSINO DE ESPECTROSCOPIA

Nuclear magnetic resonance is a technique that is widely used for elucidating and characterizing organic substances. Organofluorine substances have applications in many areas from drugs to liquid crystals, but their NMR spectra are often challenging due to fluoride coupling with other nuclei. For this reason, NMR spectra of this class of substances are not commonly covered in undergraduate and graduate chemistry courses and related fields. Thus, the aim of this work was the presentation and discussion of 1H, 13C, and 19F NMR spectra of eleven organofluorine substances which, in the case of 1H and 13C nuclei, showed classic patterns of first-order coupling and the effects of the fluorine nucleus in different chemical and magnetic environments. In addition, the observation of long distance coupling constants was possible through the use of apodization functions in the processing of the spectra. It is expected that the examples presented herein can be utilized and discussed in undergraduate and graduate NMR spectroscopy disciplines and thus improve the teaching and future research of organofluorine compounds.

MÉTODOS SELETIVOS DE FLUORAÇÃO DE MOLÉCULAS ORGÂNICAS

Presently, the world depends on a wide variety of new materials based on organofluorine compounds. These compounds can be used as surfactants, high resistance polymers, liquid crystals, agrochemicals, radiopharmaceuticals for positron emission tomography, and drugs. However, the selective formation of C–F bonds remains a challenge. This study reviews our knowledge of organofluorine compounds and describes conventional and modern selective fluorination methods for obtaining these compounds. Here, we highlight the most common fluorination reagents and describe the fluorination reactions. This review is organized by the type of fluorine transfer: nucleophilic, electrophilic, and enzymatic

Crystal structures of 5-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Zn(II)

The crystal and molecular structures of [bis(5-chloro-2-methoxybenzoate)tetraaquamanganese(II)], [pentaaqua(5-chloro-2-methoxybenzoato)cobalt(II)] (5-chloro-2-methoxybenzoate), [pentaaqua(5-chloro-2-methoxybenzoato)nickel(II)] (5-chloro-2-methoxybenzoate) and [aquabis(5-chloro-2-methoxybenzoate)zinc(II)] monohydrate were determined by a single-crystal X-ray analysis. Mn(H2O)4L2 (where L = C8H6ClO3) crystallizes in the monoclinic system, space group P21/c. [Co(H2O)5L]L and [Ni(H2O)5L]L both are isostructural, space group P212121. The crystals of [Zn(H2O)L2] H2O are monoclinic, space group Pc. Mn(II) ion is positioned at the crystallographic symmetry center. Mn(II) and Co(II) ions adopt the distorted octahedral coordination but Zn(II) tetrahedral one.The carboxylate groups in the complexes with M(II) cations function as monodentate, bidentate and/or free COO-groups. The ligands exist in the crystals as aquaanions. The complexes of 5-chloro-2-methoxybenzoates with Mn(II), Co(II) and Zn(II) form bilayer structure.

Histochemical aspects of reserves mobilization of Caesalpinia peltophoroides (Leguminosae) seeds during germination and seedlings early growth

The objective of this study was to investigate reserve mobilization in Caesalpinia peltophoroides seeds during germination and initial seedling growth. The variation in these compounds was analyzed from the pre-germination period (0 to 5 days after sowing - DAS) to the total cotyledon senescence and abscission at 35 DAS. For this histochemical tests were made on cotyledons fixed in FAA50 or included in glycol-metacrylate. To follow the mobilization of the main reserve compounds, sudan III was used to detect total lipids, xylidine Ponceau to detect total proteins, lugol to detect starch and polarized light to visualize the crystals. The lipids, present in a great quantity in the cotyledon, gradually decreased in the period studied. A greater quantity of starch was observed on the 10th DAS than in the previous periods and it was totally consumed by 30 DAS. The distribution pattern and the morphology of the protein material were very modified by 10 DAS, a period during which it was intensely consumed, remaining only parietally fragments distributed, that practically disappeared at 25 DAS. The calcium oxalate druses were not consumed during the period studied, there was only crystal agglutination.