LAYERED DOUBLE HYDROXIDES: NANOMATERIALS FOR APPLICATIONS IN AGRICULTURE

The current research aims to introduce Layered Double Hydroxides (LDH) as nanomaterials to be used in agriculture, with particular reference to its use as storage and slow release matrix of nutrients and agrochemicals for plant growing. Structural characteristics, main properties, synthesis methods and characterization of LDH were covered in this study. Moreover, some literature data have been reported to demonstrate their potential for storage and slow release of nitrate, phosphate, agrochemicals, besides as being used as adsorbent for the wastewater treatment. This research aims to expand, in near future, the investigation field on these materials, with application in agriculture, increasing the interface between chemistry and agronomy.

Models for the estimation of thermodynamic properties of layered double hydroxides: application to the study of their anion exchange characteristics

Several models for the estimation of thermodynamic properties of layered double hydroxides (LDHs) are presented. The predicted thermodynamic quantities calculated by the proposed models agree with experimental thermodynamic data. A thermodynamic study of the anion exchange process on LDHs is also made using the described models. Tables for the prediction of monovalent anion exchange selectivities on LDHs are provided. Reasonable agreement is found between the predicted and the experimental monovalent anion exchange selectivities.

Review of the synthesis of layered double hydroxides: a thermodynamic approach

The synthesis of layered double hydroxides (LDHs) by hydrothermal-LDH reconstruction and coprecipitation methods is reviewed using a thermodynamic approach. A mixture model was used for the estimation of the thermodynamics of formation of LDHs. The synthesis and solubility of LDHs are discussed in terms of standard molar Gibbs free energy change of reaction. Data for numerous divalent and trivalent metals as well as for some monovalent and tetravalent metals that may be part of the LDH structure have been compiled. Good agreement is found between theoretical and experimental data. Diagrams and tables for the prediction of possible new LDH materials are provided.

Nickel incorporation in Fe(II, III) hydroxysulfate Green Rust: effect on crystal lattice spacing and oxidation products

Ni(II)-Fe(II)-Fe(III) layered double hydroxides (LDH) or Ni-containing sulfate green rust (GR2) samples were prepared from Ni(II), Fe(II) and Fe(III) sulfate salts and analyzed with X ray diffraction. Nickel is readily incorporated in the GR2 structure and forms a solid solution between GR2 and a Ni(II)-Fe(III) LDH. There is a correlation between the unit cell a-value and the fraction of Ni(II) incorporated into the Ni(II)-GR2 structure. Since there is strong evidence that the divalent/trivalent cation ratio in GR2 is fixed at 2, it is possible in principle to determine the extent of divalent cation substitution for Fe(II) in GR2 from the unit cell a-value. Oxidation forms a mixture of minerals but the LDH structure is retained if at least 20 % of the divalent cations in the initial solution are Ni(II). It appears that Ni(II) is incorporated in a stable LDH structure. This may be important for two reasons, first for understanding the formation of LDHs, which are anion exchangers, in the natural environment. Secondly, this is important for understanding the fate of transition metals in the environment, particularly in the presence of reduced Fe compounds.

Hidróxidos duplos lamelares: síntese, estrutura, propriedades e aplicações

The layered double hydroxides, known as anionic clays and represented by the general formula [M2+1-x M3+x (OH) 2]x+ Am-x/m·nH 2O, are a group of materials which are of much interest currently. They present a variety of potential applications as adsorbents, catalysts and catalyst support, ion-exchangers, antacids and as a polymer stabilizer. It is possible to obtain a broad variety of layered double hydroxides (LDHs), depending on the identity and ratio of the cations M2+ and M3+, as well as the interlamelar anion. The aim of this review is to give out some information about this class of materials, concerning to the synthesis, characterization, properties and applications.

Materiales laminares pilareados: preparación y propiedades

The structure of several types of layered materials will be described. These include clays, layered double hydroxides, group IV metal phosphates and other layered materials. The preparation of the pillared materials and pillaring agents will be presented along with a description of the properties and applications of the products.

Intercalação e funcionalização da brucita com ácidos carboxílicos

Brucite (Mg(OH)2) is a structural model of several natural layered minerals as well as of synthetic layered double hydroxides (LDH). Exchange reaction studies of these compounds are well documented in the literature but surface chemical modifications, especially for brucite, are quite rare. We report the behaviour of brucite in reaction with succinic and benzoic acid in different solvents and temperatures. The compounds were analysed through X-ray diffraction (XRD) and infrared spectroscopy (FTIR). The surfaces of brucite crystals were grafted producing expansions, attributed to the arrangement of the grafted species between the layers.

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.

Hidróxidos duplos lamelares: nanopartículas inorgânicas para armazenamento e liberação de espécies de interesse biológico e terapêutico

Studies about the inorganic nanoparticles applying for non-viral release of biological and therapeutic species have been intensified nowadays. This work reviews the preparation strategies and application of layered double hydroxides (LDH) as carriers for storing, carrying and control delivery of intercalated species as drugs and DNA for gene therapy. LDH show low toxicity, biocompatibility, high anion exchange capacity, surface sites for functionalization, and a suitable equilibrium between chemical stability and biodegradability. LDH can increase the intercalated species stability and promote its sub-cellular uptake for biomedical purposes. Concerning the healthy field, LDH have been evaluated for clinical diagnosis as a biosensor component.

Hidróxidos duplos lamelares à base de escória de alto forno

Hydrotalcite like compounds (HT) were prepared by co-precipitation (Mg/Al = 3.5), using an acid solution with blast furnace slag and MgCl2.6H2O and aqueous solutions of NaOH. The following synthesis variables were investigated: temperature (30 and 45 ºC) and pH (9 and 12). Depending of the temperature two systems were observed: Mg-Al-CO3 (T = 30 ºC); Mg-Al-Cl-CO3 (T = 45 ºC). An increase in the pH of synthesis and Mg2+ concentration produced HTs well-crystallized and with greater values of all cell parameters. The study showed the potentiality of BFS in the synthesis of well-crystallized LDHs without the presence of other crystalline phases.

Comparação estrutural entre amostras de materiais tipo hidrotalcita obtidas a partir de diferentes rotas de síntese

Three samples of hydrotalcite-like materials (HTC) were synthesized and their structural characteristics were compared with two HTCs obtained commercially. Thermal analyses, FT-IR, PXRD and textural analyses were used to investigate the structural differences between commercial and synthetic samples. Particularly, the memory effect was observed at temperature higher than 600 ºC. The Rietveld refinements were obtained with expressive accuracy and the statistical parameters of goodness of fit are quite satisfactory. In conclusion, the procedures adopted in synthesis of HTC produced crystalline materials with high surface area materials.

Alkaline earth layered benzoates as reusable heterogeneous catalysts for the methyl esterification of benzoic acid

This paper describes the synthesis and characterization of layered barium, calcium and strontium benzoates and evaluates the potential of these materials as catalysts in the synthesis of methyl benzoate. The methyl esterification of benzoic acid was investigated, where the effects of temperature, alcohol:acid molar ratio and amount of catalyst were evaluated. Ester conversions of 65 to 70% were achieved for all the catalysts under the best reaction conditions. The possibility of recycling these metallic benzoates was also demonstrated, evidenced by unaltered catalytic activity for three consecutive reaction cycles.

Análise citológica e cariométrica da ação da colchina sôbre a espermatogênese dos hemípteros

The action of colchicine upon the spermatogenesis of Triatoma infestans, (Hemipt. Heteroptera), has been studied and the different categories of giant spermatids that appear during the treatment have been compared with the nuclear volumes of the whole series of normal spermatogenetic stages. The following facts have been ascertained: 1) 4 hours after the treatment the gonial mitotic metaphases, and the 1st. and 2nd. metaphases of meiosis are stopped. The prophasic stages of meiosis and diakynesis appear to be normal. After 9 days of treatment, all the tetrads are broken in the meiotic metaphases and the cells appear with 44 and 22 chromosomes respectively, scattered in the cytoplasm. 2) At 9 days, practically all spermatogenetic stages have disappeared except for a few cysts of spermatogonia, and practically the whole testicle is full of cysts of spermatozoa and spermatid, with some large zones of necrosis with pycnotic nuclei. The spermatids appear to be of different sizes and the statistical analysis of the nuclear volumes gives a polymodal hystogram with 4 modes, whose volumes are in the ratio of 1:2:4:8. Ripe spermatozoa seem to have a certain volume variability, that has not been possible to analyse quantitatively. All these facts confirm what DOOLEY found in the colchicinized Orthoptera testicle. 3) The caryometric analysis conducted statistically on the normal stages of the spermatogenesis (resting spermatogonia, gonial prophases, leptotene, "confused stage", diakynesis, and spermatid) revealed the following facts: a) Considering the volume of the resting, spermatogonia as 1, their mitotic prophases have a volume of 2. Some rare prophases appear to have a volume of 4 and probably belong to tetraployd spermatogonia normally present in the testicle of Hemiptera. b) The first spermatocyte at the beginning of the auxocitary growth (leptotene) has a volume of 2, which is equal to that of them gonial prophase. It grows further during the "confused stage" and reduplicates, reaching thus the volume of 4. Diakynesis has a rather variable nuclear volume and it is higher than volume 4. This is probably of physico-chemical nature and not a growth increase. c) The spermatid at the beginning of the spermiogenetic process has a volume of 1 which is very constant and homogeneous. 4) These results can be summarized concluding that the meiotic process begins from a spermatogonium at the end of his mitotic interphasic growth (vol. 2) and instead of entering into the mitotic prophase transforms itself into the leptotene spermatocyte. During the diplotene ("confused stage") the volume of the nucleus doubles once more and reaches volume 4. In consequence of the two successive meiotic divisions the spermatid, although having an haploid number of chromosomes, has a nuclear volume of 1, just like the diploid spermatogonium. The interpretation of this strange result probably comes from the existence of the "tertiary split" in the chromosomes of the haploid set, that has been illustrated in the Hemiptera by HUGUES SCHRADER and in Orthoptera by MICKEY and co-workers. The tertiary split indicates that the chromosomes of the haploid set are constituted from almost two chromonemata, and this double constitution corresponds to the double cycle of reduplication that takes place during the spermatogenesis starting from the resting gonia. In Triatoma infestans the tertiary split appears in the chromosomes in the 1st. and 2nd. metaphases and in the diakynesis. In the blocked metaphases at the 9th. day of colchicinization some of the 44 elements scattered in the cytoplasm, show, when properly oriented, the split very clearly. Some new and strange facts revealed by SCHRADER and LEUCHTEMBERGER in Arvelius suggest the possibility of other interpretations of the rhythmic growth in special cases. There appears the necessity of more knowledge about the multiple or simple constitution of the chromosomes in somatic and spermatogonial mitosis.

Differentation of the fat body cells in the precocius adults of Schistocerca gregaria: regulation of polyploidy by juvenile hormone

Precocious adults from 2nd and 3rd instar larvae of the desert locust Schistocerca gregaria were used to assess the competence of their fat body to synthesize DNA in response to a juvenile hormone analog (JHA), hydoprene. Autoradiographic studies show that JHA stimulates DNA synthesis since a significant proportion of the fat body nuclei are labelled after treatment with 100 or 200 µg of JHA. Maximum DNA synthesis occurs 24 h after treatment with 100 µg of JHA. The nuclear ploidy classes of the precocious adults from 3rd larvae are similar to those of 1-d-old normal adults, but treatemnt of these precociuos adults with µg of JHA doubles the DNA content resulting in enhanced ploidy classes which resemble those of 10-d-old normal females. In the precocious adults that emerged from 2nd instar larvae the ploidy classes are higher than those of 1-d-old normal adults, and treatment of these precocious adults with JHA results in a further increase in the DNA content of the fat body nuclei leading to the formation of high percentages of 16C and 32C nuclei. The results of these studies suggest that any model on the mode of action of JH should recognize this phenomenon of JH-induced polyploidization in the fat body nuclei.