From arm-shaped layers to a new type of polythreaded array: a two fold interpenetrated three-dimensional network with a rutile topology

The self-assembly based on 2D motifs with side arms leads to the formation of a new type of polythreaded network which exhibits a 2-fold interpenetrated 3D array if H-bonds are taken into account.     

Mechanochemical preparation of hydrogen-bonded adducts between the diamine 1,4-diazabicyclo[2.2.2]octane and dicarboxylic acids of variable chain length: an X-ray diffraction and solid-state NMR study

Mechanical mixing of solid dicarboxylic acids of variable chain length HOOC(CH(2))(n)COOH (n = 1-7) with solid 1,4-diazabicyclo[2.2.2]octane generates the corresponding salts or co-crystals of the formula [N(CH(2)CH(2))(3)N]-H-[OOC(CH(2))(n)COOH] (n=1-7). Preparation of the same systems from solution has been instrumental for a full characterization of the mechanochemical products by means of single-crystal and powder-diffraction X-ray analyses, as well as by solid-state NMR. The acid-base adducts, whether involving proton transfer from the COOH group to the N-acceptor, that is having ((-))O...H-N((+)) interactions, or the formation of neutral O-H...N hydrogen bonds, show a melting point alternation phenomenon analogous to that shown by the neutral carboxylic acids. The carbon chemical shift tensors of the COOH group obtained from the sideband intensity of low speed spinning NMR spectra provide a reliable criterion for assigning the protonation state of the adducts.     

Multivalent recognition of bis- and tris-Zn-porphyrins by N-methylimidazole functionalized gold nanoparticles

N-Methylimidazole-functionalized gold nanoparticles behave as multivalent ligands for porphyrin arrays with an increase in binding strength of up to three order of magnitude with respect to a monovalent system.     

Pore formation by 6-ketocholestanol in phospholipid monolayers and its interpretation by a general nucleation-and-growth model accounting for the sigmoidal shape of voltage-clamp curves of ion channels

6-Ketocholestanol (KC), a steroid that differs from cholesterol mainly by the presence of a carbonyl group, forms pores inside a dioleoylphosphatidylcholine monolayer self-assembled on mercury by a mechanism similar to that of channel-forming peptides and proteins. The potential steps responsible for pore formation by KC molecules give rise to potentiostatic charge vs time curves whose sigmoidal shape and potential dependence can be quantitatively interpreted on the basis of a mechanism of nucleation and growth of KC clusters. Pore formation by KC allows the penetration of thallous ions across the otherwise impermeable phosphatidylcholine monolayer, while pore disruption taking place at more negative potentials causes a drop in thallous ion permeation. Pore disruption is also accounted for by a mechanism of nucleation and growth of holes inside the KC clusters. The kinetic model of nucleation and growth is general, and accounts quantitatively for the sigmoidal shape and potential dependence of the classical Hodgkin-Huxley voltage-clamp curves of potassium channels in squid giant axon,(1) using a minimum number of free parameters.     

Nickel nanostructured materials from liquid phase photodeposition

Liquid Phase Photo-Deposition (LPPD) technique has been used to obtain both colloidal particles and thin films of metallic and chloride nickel from solutions of only precursor Ni(acac)₂ (acac=2,4-pentandionato). Metallic nickel was obtained from ethanol solutions by direct nickel(II) photoreduction at 254 nm and by acetone sensitised reaction at 300 nm. In this latter process the rate was higher than in the first one. NiCl₂ was formed from CCl₄ solution by a solvent-initiated reaction. TEM analysis, performed on colloidal particles of nickel, showed that their dimensions are in the range 2–4 nm. The films did not present carbon contamination and were characterized by AFM, XPS and GIXRD. Metallic films consisted of particles of 20–40 nm that are the result of the aggregation of smaller crystallites (4–5 nm). Larger agglomerations (around 200 nm) have been observed for NiCl₂ films.     

A novel simplified synthesis of acivicin

This report describes an efficient synthesis of the natural isomer of acivicin, which is the only one provided with a noteworthy biological activity. The present procedure allowed the synthesis of (+)-1 in just five steps with a 34% overall yield. Due to the easy separation of the two diastereomers and to the availability of the starting material at low cost, the present procedure can be scaled-up to gram quantities.     

Long-term operation of a domestic wastewater treatment plant with membrane filtration

Possibilities of membrane technology and the use of membrane processes in wastewater treatment were investigated. The main focus was the monitoring of the starting phase of a domestic wastewater treatment plant. Experimental part of the study was realized at the municipal wastewater treatment plant (WWTP) Devínska Nová Ves — Bratislava during the period from February 2005 to September 2006. The system was stable without any external chemical treatment of the membrane modules and the permeate quality was very high. Observed decrease of COD and BOD₅ values ranged between 91 % and 98 %. The process of nitrification was very successful considering its high efficiency (> 95 %). Presented at the 34th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 21–25 May 2007.     

A New Indirect Electroanalytical Method to Monitor the Contamination of Natural Waters with 4‐Nitrophenol Using Multiwall Carbon Nanotubes

The electrochemical detection of the hazardous pollutant 4‐nitrophenol (4‐NP) at low potentials, in order to avoid matrix interferences, is an important research challenge. This study describes the development, electrochemical characterization and utilization of a multiwall carbon nanotube (MWCNT) film electrode for the quantitative determination of 4‐NP in natural water. Electrochemical impedance spectroscopy measurements showed that the modified surface exhibits a decrease of ca. 13 times in the charge transfer resistance when compared with a bare glassy carbon (GC) surface. Voltammetric experiments showed the possibility to oxidize a hydroxylamine layer (produced by the electrochemical reduction of 4‐NP on the GC/MWNCT surface) in a potential region which is approximately 700 mV less positive than that needed to oxidize 4‐NP, thus minimizing the interference of matrix components. The limit of detection for 4‐NP obtained using square‐wave voltammetry (0.12 μmol L^?1) was lower than the value advised by EPA. A natural water sample from a dam located in São Carlos (Brazil) was spiked with 4‐NP and analyzed by the standard addition method using the GC/MWCNT electrode, without any further purification step. The recovery procedure yielded a value of 96.5% for such sample, thus confirming the suitability of the developed method to determine 4‐NP in natural water samples. The electrochemical determination was compared with that obtained by HPLC with UV‐vis detection.