Adsorption of crude oil on anhydrous and hydrophobized vermiculite

This publication reports the adsorption of crude oil on vermiculite samples, expanded and hydrophobized with carnauba (Copernícia Cerífera) wax. The adsorption studies were performed by using columns filled with the vermiculite matrices and by dispersion of the vermiculite samples in an oil-water (50 ppm of oil) emulsion. The hydrate vermiculite exhibits a very low adsorption capacity against crude oil. On the other hand, anhydrous (expanded) and hydrophobized matrices show a high adsorption capacity. The 10% hydrophobized matrix show a 50% increased adsorption capacity, in comparison with the expanded one. For adsorption performed in the water-oil emulsion, saturation of the solid hydrophobized matrix is achieved after 60 min. The hydrophobized samples exhibit adsorption factors in the 0.7-1.0 range.     

Purpurin-18 in combination with light leads to apoptosis or necrosis in HL60 leukemia cells

Photodynamic therapy (PDT), a cancer treatment using a photosensitizer and visible light, has been shown to induce apoptosis or necrosis. We report here that Purpurin-18 (Pu18) in combination with light induces rapid apoptotic cell death in the human leukemia cell line (HL60) at low doses and necrosis at higher concentrations. Cells treated with Pu18 and light under apoptotic conditions exhibited DNA laddering and an increase in both cellular content of subdiploid DNA and externalization of phosphatidylserine (PS), indicating DNA fragmentation and loss of membrane phospholipid asymmetry. In the absence of light activation, Pu18 at nanomolar concentrations had no detectable cytotoxic effect. Caspase-3 activity was increased even after 1 h from treatment with low doses of Pu18 and light. The PS exposure and nuclear features of apoptosis were prevented by treatment of cells before illumination with caspase inhibitors benzyloxycarbonyl-Val-Ala-Asp-fluoromethylketone (Z-VAD-FMK) and benzyloxycarbonyl-Asp-Glu-Val-Asp-fluoromethylketone (Z-DEVD-FMK). Conversely, the caspase-1 inhibitor, acetyl-Tyr-Val-Ala-Asp-aldehyde (Ac-YVAD-CHO) failed to suppress the apoptosis. No protective effect of the three caspase inhibitors was observed when the cells were exposed to necrotic concentrations of Pu18 and light. Our results show that caspase-3, but not caspase-1, is involved in the signaling of apoptotic events in PDT with Pu18-induced apoptosis of HL60 cells. Moreover, both the time course of PS exposure and the effect of caspase inhibitors on it indicate that it is regulated in the same manner as DNA fragmentation.     

Tailored pump-probe transient spectroscopy with time-dependent density-functional theory: controlling absorption spectra

Recent advances in laser technology allow us to follow electronic motion at its natural time-scale with ultra-fast time resolution, leading the way towards attosecond physics experiments of extreme precision. In this work, we assess the use of tailored pumps in order to enhance (or reduce) some given features of the probe absorption (for example, absorption in the visible range of otherwise transparent samples). This type of manipulation of the system response could be helpful for its full characterization, since it would allow us to visualize transitions that are dark when using unshaped pulses. In order to investigate these possibilities, we perform first a theoretical analysis of the non-equilibrium response function in this context, aided by one simple numerical model of the hydrogen atom. Then, we proceed to investigate the feasibility of using time-dependent density-functional theory as a means to implement, theoretically, this absorption-optimization idea, for more complex atoms or molecules. We conclude that the proposed idea could in principle be brought to the laboratory: tailored pump pulses can excite systems into light-absorbing states. However, we also highlight the severe numerical and theoretical difficulties posed by the problem: large-scale non-equilibrium quantum dynamics are cumbersome, even with TDDFT, and the shortcomings of state-of-the-art TDDFT functionals may still be serious for these out-of-equilibrium situations.     

Preparation,characterization, and structure of zirconium fluoride alkylamino-N,N-bis methylphosphonates: a new design for layered zirconium diphosphonates with a poorly hindered interlayer region

This paper reports the preparation and characterization of the homologous series of layered zirconium fluoride n-alkylamino-N,N-bis methylphosphonates, of general formula ZrF(O(3)PCH(2))(2)NHC(n)H(2n+1) (n = 1, 2, 3, 4, 5, 6, 8, 9, 10), in which the two phosphonic groups of each diphosphonate building block participate in the assembly of a single lamella, because they are joined to zirconium atoms belonging to the same layer. The crystal structure of one of the series of these zirconium diphosphonates, ZrF(O(3)PCH(2))(2)NHC(5)H(11), has been solved "ab initio" by X-ray powder diffraction data. The structure is monoclinic, space group P2(1)/c. The zwitterionic character of the diphosphonate moiety is a distinctive feature which acts as a structure-orienting factor, generating a layer framework which is different from the other structures known for zirconium phosphates and phosphonates. This compound undergoes a phase transition at 117 degrees C which involves a rearrangement of the interlayer alkyl chains. The structure of the high-temperature phase has been refined by the Rietveld method. Because only one organic residue is associated with two phosphonate tetrahedra, a poorly hindered interlayer region is formed, and alkyl chains bonded to adjacent layers are interdigitated. Preliminary experiments have shown that these compounds are able to intercalate organic molecules, such as n-alkanols, from very dilute water solutions.     

Enhancement of shake-up structure in alkali-metal-ion exchanged forms of α-Zr(HPO4)2 by sputtering

Mg Kα ESCA spectra of several α-Zr(PO₄)₂M₂ compounds (M = Li⁺, Na⁺, K⁺, Cs⁺) have been obtained. Satellite structure is observed at ～7–8 eV from the main P 2s peak (corresponding to ～15–16 eV from the main Zr 3d_{$\text{5}\text{2}$} peak). The intensity of the satellite depends on the counter-ion intercalated. For a given counter-ion it is strongly increased by sputtering, the rate of increase being also dependent on the counter-ion. This observation is interpreted mainly in terms of electron-defect formation similar to that involved in the formation of colour centres by radiation damage, and subsequent charge-transfer shake-up of the trapped electrons to the electron-deficient phosphorus or Zr(IV) centres.     

Completion of L-fuzzy relations

It is shown that the category $\text{L}\text{?}$ of complete L-similarities on L-sets is a full reflective subcategory of $\text{R}$(L) (L-fuzzy graphs); $\text{L}\text{?}$ is equivalent to $\text{Lh}$ (L)(sheaves on L). Connections with other known “fuzzy” categories are also studied.     

Interaction of NO with nanosized Ru-, Pd-, and Pt-Doped SnO2: electron paramagnetic resonance, Mössbauer, and electrical investigation

The mechanism of NO interaction with nanosized Ru(Pd,Pt)-doped SnO(2) was studied by electron paramagnetic resonance, M?ssbauer, and electric resistance measurements. Three steps were proposed for the reaction between the semiconductor oxide and the gaseous component: (i) the formation of bielectronic oxygen vacancies (V(o)) in SnO(2); (ii) their single-ionization (V(o)(*)) with injection of electrons into the SnO(2) conduction band; (iii) the subsequent transfer of electrons from V(o)(*) to [Ru(Pd,Pt)](4+). The last process induces the formation of further oxygen vacancies which reduce the transition metal centers to lower oxidation states; the redox processes is enhanced and the electrical resistance in transition metal-doped SnO(2) is stronger modified with respect to the undoped material.     

One-pot synthesis of cyanuric acid-bridged porphyrin-porphyrin dyads

Stepwise amination of cyanuric chloride (1) with 5-(4-aminophenyl)-10,15,20-triphenylporphyrin (2) and/or its zinc(II) complex (3) enables the synthesis of porphyrin-porphyrin dyads with predetermined free base-free base forms or free base-zinc and zinc-zinc metalation states. Furthermore, the use of aminopropyl-silanized silica gel as a scavenger for unwanted byproducts allowed the one-pot synthesis of title porphyrin compounds in high yield and purity with minimum use of preparative column chromatography.