Hydration of drug-DNA complexes: Greater water uptake for adriamycin compared to daunomycin

Water is an integral part of DNA, and the conserved water molecules at the binding sites can modulate drug binding to DNA or protein. We report here that anthracycline antitumor antibiotics, adriamycin (AM) and daunomycin (DM), binding to DNA is accompanied by different hydration changes, with AM binding resulting in the uptake of about twice as many water molecules as DM. These results indicate that water is playing an important role in drug binding to DNA.

Daunomycin binding to detergent micelles: A model system for evaluating the hydrophobic contribution to drug-DNA interactions

The interaction of daunomycin with sodium dodecyl sulfate and Triton X-100 micelles was investigated as a model for the hydrophobic contribution to the free energy of DNA intercalation reactions. Measurements of visible absorbance, fluorescence lifetime, steady-state fluorescence emission intensity, and fluorescence anisotropy indicate that the anthraquinone ring partitions into the hydrophobic micelle interior. Fluorescence quenching experiments using both steady-state and lifetime measurements demonstrate reduced accessibility of daunomycin in sodium dodecyl sulfate micelles to the anionic quencher iodide and to the neutral quencher acrylamide. Quenching of daunomycin fluorescence by iodide in Triton X-100 micelles was similar to that seen with free daunomycin. Studies of the energetics of the interaction of daunomycin with micelles by fluorescence and absorbance titration methods and by isothermal titration calorimetry in the presence of excess micelles revealed that association with sodium dodecyl sulfate and Triton X-100 micelles is driven by a large negative enthalpy. Association of the drug with both types of micelles also has a favorable entropic contribution, which is larger in magnitude for Triton X-100 micelles than for sodium dodecyl sulfate micelles.

New HDPE/MCM41 nanocomposites with improved mechanical performance: synthesis and characterizatio

Ordered mesoporous silicas with a channel structure of well-defined geometries and dimensions at nanometer scale are excellent candidates to host intercalation reactions. In recent years, our research group has shown that mesoporous silicas of the M41S class combined with metallocene complexes give rise to excellent supported catalysts for ethylene polymerisation. Due to the support characteristics, the reaction is allowed to occur in the channels and in this way hybrid organic-inorganic materials can be prepared within a large range of nanofiller concentration. These HDPE/MCM-41 nanocomposites exhibit an improved mechanical performance and an easier degradability due to the additional role of MCM-41 as a promoter for PE degradation.

Síntese e caracterização de hidróxidos duplos a partir da lama vermelha

O resíduo do refino da bauxita, comumente conhecido como lama vermelha, tem mostrado ser capaz de ligar metais traços tais como o cobre, cádmio, zinco, cromo, níquel e chumbo sob condições apropriadas. A neutralização da lama vermelha é necessária porque essa lama é tipicamente cáustica, com pH em torno de 13. Muitas pesquisas têm sido desenvolvidas envolvendo a utilização da lama vermelha, porque contem uma série de elementos valiosos. Assim a utilização da lama vermelha como material de construção e como adsorvente é atrativa porque ela é utilizada em grande quantidade. Nada pode ser feito sem descartar componentes valiosos como titânio, zircônio e principalmente ferro. A síntese de hidrotalcita conectada com a reciclagem de soluções alcalinas representa uma maneira efetiva de uso dessa solução considerando a forte demanda por proteção ambiental no mundo. Os compostos tipo hidrotalcita, precipitados durante a neutralização da lama, também removem oxi-ânions de metais de transição através da combinação de intercalações e adsorção de espécies aniônicas na sua superfície externa. Os hidróxidos duplos lamelares (HDL) vêm sendo investigados à muitos anos como materiais hospedeiros para uma variedade de reações de intercalação de anions. A estrutura lamelar dos HDLs pode ser usada para controlar a adição ou remoção de uma variedade de espécies químicas, tanto orgânicas quanto inorgânicas. Isto é alcançado através de sua habilidade de adaptar a separação das lamelas de hidróxidos, e da reatividade da região interlamelar. O material resultante adsorve anions quando colocado em soluções e reverte a estrutura da hidrotalcita. Avanços significativos têm sido alcançados recentemente na caracterização desses materiais, incluindo estudos estruturais sobre o mecanismo de intercalação. O objetivo desse trabalho foi a síntese e caracterização de HDLs a partir da lama vermelha, e testar esses materiais como adsorventes de metais pesados.

Thermal behavior and decomposition of kaolinite-potassium acetate intercalation composite

A series of kaolinite-potassium acetate intercalation composite was prepared. The thermal behavior and decomposition of these composites were investigated by simultaneous differential scanning calorimetry-thermogravimetric analysis (DSC-TGA), X-ray diffraction (XRD) and Fourier-transformation infrared (FT-IR). The XRD pattern at room temperature indicated that intercalation of potassium acetate into kaolinite causes an increase of the basal spacing from 0.718 to 1.428nm. The peak intensity of the expanded phase of the composite decreased with heating above 300°C, and the basal spacing reduced to 1.19nm at 350°C and 0.718nm at 400°C. These were supported by DSC-TGA and FT-IR measurements, where the endothermic reactions are observed between 300 and 600°C. These reactions can be divided into two stages: 1) Removal of the intercalated molecules between 300-400°C. 2) Dehydroxylation of kaolinite between 400-600°C. Significant changes were observed in the infrared bands assigned to outer surface hydroxyl, inner surface hydroxyl, inner hydroxyl and hydrogen bands.

New insights into the molecular structure of kaolinite–methanol intercalation complexes

A series of kaolinite–methanol complexes with different basal spacings were synthesized using guest displacement reactions of the intercalation precursors kaolinite–N-methyformamide (Kaol–NMF), kaolinite–urea (Kaol–U), or kaolinite–dimethylsulfoxide (Kaol–DMSO), with methanol (Me). The interaction of methanol with kaolinite was examined using X-ray diffraction (XRD), infrared spectroscopy (IR), and nuclear magnetic resonance (NMR). Kaolinite (Kaol) initially intercalated with N-methyformamide (NMF), urea (U), or dimethylsulfoxide (DMSO) before subsequent reaction with Me formed final kaolinite–methanol (Kaol–Me) complexes characterized by basal spacing ranging between 8.6 Å and 9.6 Å, depending on the pre-intercalated reagent. Based on a comparative analysis of the three Kaol–Me displacement intercalation complexes, three types of Me intercalation products were suggested to have been present in the interlayer space of Kaol: (1) molecules grafted onto a kaolinite octahedral sheet in the form of a methoxy group (Al-O-C bond); (2) mobile Me and/or water molecules kept in the interlayer space via hydrogen bonds that could be partially removed during drying; and (3) a mixture of types 1 and 2, with the methoxy group (Al-O-C bond) grafted onto the Kaol sheet and mobile Me and/or water molecules coexisted in the system after the displacement reaction by Me. Various structural models that reflected four possible complexes of Kaol–Me were constructed for use in a complimentary computational study. Results from the calculation of the methanol kaolinite interaction indicate that the hydroxyl oxygen atom of methanol plays the dominant role in the stabilization and localization of the molecule intercalated in the interlayer space, and that water existing in the intercalated Kaol layer is inevitable.

Relationship between the continually expanded interlayer distance of layered silicates and excess intercalation of cationic surfactants

Excess intercalation of cationic surfactants into Na-montmorillonites (MMTs) was investigated in organically modified silicates (OMSs), synthesized with MMTs and octadecylammonium chloride (OAC) by systematically varying the surfactant loading level from 0.625 to 1, 1.25, 1.56, 2, and 2.5 with respect to the cation exchange capacity (CEC) of MMTs. Wide-angle X-ray diffraction and thermogravimetric analysis results indicated that the continuous increase of interlayer distances came from the entering of surfactants into the interlayer of MMTs. Excess surfactants were extracted with a Soxhlet apparatus, which showed two kinds of intercalation states of surfactants in the interlayer when the surfactant loading level was beyond the CEC. Fourier transform infrared spectroscopy and differential scanning calorimetry were used to explore the microstructures of OMSs. It was found that the surfactants arranged more orderly as the loading level increased and the excess surfactants piled up in the interlayer together with counterions, forming a sandwiched surfactant layer. On the basis of the results, the layer structures of OMSs and the mechanism by which the surfactants entered the interlayer were expounded: surfactant cations entered the interlayer through cation exchange reactions and were tightly attracted to the silicate platelet surfaces when the surfactant loading level was below the CEC;

Condensed phase combustion travelling waves with sequential exothermic or endothermic reactions

The one-dimensional propagation of a combustion wave through a premixed solid fuel for two-stage kinetics is studied. We re-examine the analysis of a single reaction travelling-wave and extend it to the case of two-stage reactions. We derive an expression for the travelling wave speed in the limit of large activation energy for both reactions. The analysis shows that when both reactions are exothermic, the wave structure is similar to the single reaction case. However, when the second reaction is endothermic, the wave structure can be significantly different from single reaction case. In particular, as might be expected, a travelling wave does not necessarily exist in this case. We establish conditions in the limiting large activation energy limit for the non-existence, and for monotonicity of the temperature profile in the travelling wave.

The effect of mechanochemical activation upon the intercalation of a high-defect kaolinite with formamide

The effect of mechanochemical activation upon the intercalation of formamide into a high-defect kaolinite has been studied using a combination of X-ray diffraction, thermal analysis, and DRIFT spectroscopy. X-ray diffraction shows that the intensity of the d(001) spacing decreases with grinding time and that the intercalated high-defect kaolinite expands to 10.2 A. The intensity of the peak of the expanded phase of the formamide-intercalated kaolinite decreases with grinding time. Thermal analysis reveals that the evolution temperature of the adsorbed formamide and loss of the inserting molecule increases with increased grinding time. The temperature of the dehydroxylation of the formamide-intercalated high-defect kaolinite decreases from 495 to 470oC with mechanochemical activation. Changes in the surface structure of the mechanochemically activated formamide-intercalated high-defect kaolinite were followed by DRIFT spectroscopy. Fundamentally the intensity of the high-defect kaolinite hydroxyl stretching bands decreases exponentially with grinding time and simultaneously the intensity of the bands attributed to the OH stretching vibrations of water increased. It is proposed that the mechanochemical activation of the high-defect kaolinite caused the conversion of the hydroxyls to water which coordinates the kaolinite surface. Significant changes in the infrared bands assigned to the hydroxyl deformation and amide stretching and bending modes were observed. The intensity decrease of these bands was exponentially related to the grinding time. The position of the amide C&unknown;O vibrational mode was found to be sensitive to grinding time. The effect of mechanochemical activation of the high-defect kaolinite reduces the capacity of the kaolinite to be intercalated with formamide.

Synthesis and Raman spectroscopic study of Mg/Al,Fe hydrotalcites with variable cationic ratios

Hydrotalcites of formula Mg6 (Fe,Al)2(OH)16(CO3).4H2O formed by intercalation with the carbonate anion as a function of divalent/trivalent cationic ratio have been successfully synthesised. The XRD patterns show variation in the d-spacing attributed to the size of the cation. Raman and infrared bands in the OH stretching region are assigned to (a) brucite layer OH stretching vibrations (b) water stretching bands and (c) water strongly hydrogen bonded to the carbonate anion. Multiple (CO3)2- symmetric stretching bands suggest that different types of (CO3)2- exist in the hydrotalcite interlayer. Increasing the cation ratio (Mg/Al,Fe) resulted in an increase in the combined intensity of the 2 Raman bands at around 3600 cm-1, attributed to Mg-OH stretching modes, and a shift of the overall band profile to higher wavenumbers. These observations are believed to be a result of the increase in magnesium in the structure. Raman spectroscopy shows a reduction in the symmetry of the carbonate, leading to the conclusion that the anions are bonded to the brucite-like hydroxyl surface and to the water in the interlayer. Water bending modes are identified in the infrared spectra at positions greater than 1630 cm-1, indicating the water is strongly hydrogen bonded to both the interlayer anions and the brucite-like surface.

Towards a cognitive-behavioural intervention for adult grief reactions

Published accounts of behavioural interventions for grief have relied on exposure and habituation to grief cues as the primary strategy. Such an approach is excessively narrow, since it does not adequately confront the challenges that are posed by a bereavement. Many people cope with a bereavement by themselves, and for those, intervention may well be counterproductive. A cognitive-behavioural intervention, following models for depression/anxiety, can assist vulnerable individuals obtain a more rapid or complete adjustment. The proposed approach differs from dynamic treatments by placing less emphasis on defensive behavior, insight, and interpretation and more emphasis on training of coping skills.

The psychological management of adult grief reactions

Despite the severe challenges which are posed by the loss of a close friend or relative, bereavement has a relatively benign outcome in most cases. While the majority of patients cope with bereavement, a significant minority develop problems. A behavioural approach may help the bereaved avoid adverse grief reactions.

Australian student reactions to U.S. tourism advertising : a test of advertising as public diplomacy

A study among Australian college students gauged their reactions to a television commercial produced for the U.S. Commerce Department to bolster sagging tourism numbers among international visitors. In addition to using traditional measures applied to tourism advertisements, the student also concluded items to measure attitudes toward the U.S. government and its people Pre- and post-viewing results indicated that while the Hollywood-movie-themed commercial was not well received by the Australian students as a tourism message, it did result in more favorable attitudes toward the U.S. government, though not the U.S. people. The findings lend partial support for the potential of tourism advertising efforts to exert a "bleed-over effect" in terms of their contributions to overall attitudes toward a country, regardless of whether viewers plan to visit the country whose travel advertisements they see.

Australian student reactions to US tourism advertising : a test of advertising as public diplomacy

A study among Australian college students gauged their reactions to a television commercial produced for the US Commerce Department to bolster sagging tourism numbers among international visitors. In additional to using traditional measures applied to tourism advertisements, the study also included items to measure attitudes toward the US government and its people. Pre- and post-viewing results indicated that although the Hollywood-movie-themes commercial was not well received by the Australian students as a tourism message, it did result in more favourable attitudes toward the US government, although not the US people. The findings lend partial support for the potential of tourism advertising efforts to exert a 'bleed-over effect' in terms of their contribution to overall attitudes toward a country, regardless of whether viewers plan to visit the country whose travel advertisements of which they see.