Band 6, Heft 3

The bottom-up construction and operation of machines and motors of molecular size is a topic of great interest in nanoscience, and a fascinating challenge of nanotechnology. Researchers in this field are stimulated and inspired by the outstanding progress of molecular biology that has begun to reveal the secrets of the natural nanomachines which constitute the material base of life. Like their macroscopic counterparts, nanoscale machines need energy to operate. Most molecular motors of the biological world are fueled by chemical reactions, but research in the last fifteen years has demonstrated that light energy can be used to power nanomachines by exploiting photochemical processes in appropriately designed artificial systems. As a matter of fact, light excitation exhibits several advantages with regard to the operation of the machine, and can also be used to monitor its state through spectroscopic methods. In this review we will illustrate the design principles at the basis of photochemically driven molecular machines, and we will describe a few examples based on rotaxane-type structures investigated in our laboratories.

9-Bromo-7,12-dihydroindolo[3,2-d][1]benzazepin-6-ylhydrazine was reacted with 2-acetylpyridine to give a Schiff base as a potential tridentate ligand. The reaction of this ligand with gallium chloride afforded complexes of 1:1 and 2:1 stoichiometry. The results of X-ray diffraction studies of the ligand and both gallium complexes are reported and compared with the data for a related gallium complex with a Schiff base obtained from 9-bromo-7,12-dihydroindolo[3,2-d][1]benzazepin-6-ylhydrazine and 2-hydroxybenzaldehyde.

Tetra-alkyl Phosphonium ionic liquids are phosphonium salts with melting points near room temperature. We report the NMR studies of water-trihexyl (tetradecyl) phosphonium chloride ionic liquid mixtures. The proton chemical shifts were used to investigate the intermolecular interactions in mixtures of ionic liquids and water. The OH chemical shifts were found to decrease as the water concentration in the ionic liquid increased, and their rate of change with temperature decreased with water concentration. The CH2 and CH3 chemical shifts were found to move downfield with the increase in temperature, and moved further downfield as water concentration was decreased. The interface of experimental data and the results of quantum calculations suggest a significant binding of phosphonium cations to chloride anion and water molecules. As well, the analysis of the data suggests a possible transformation from cationchloride-water configuration at low water concentrations to cation-water-water at higher water concentrations.

The Ugi reaction with formylphenylboronic acid derivatives as the carbonyl component proceeds to give the corresponding boron-containing dipeptide derivatives (Ugi products) in good yields.

N-Heterocyclic germylenes are known to exist in two structurally different forms, the planar Meller germylenes and the monoimino germylenes that feature an envelope structure. This essay reviews recent reports dealing with radical and cationic Meller type germylenes featuring the monoimino germylene structure, discusses their transformations and relationships, and asks the question whether indeed N-heterocyclic germylenes can be turned into Lewis acids.

Following the discovery of fullerenes (C60) and carbon nanotubes, it was shown that nanoparticles of inorganic layered compounds, like WS2 and MoS2, are unstable in the planar form and they form closed cage structures with polyhedral or nanotubular shapes. Although initially the method of synthesis for the formation of such closed caged structures and nanotubes involved starting from the respective oxides, it is now well established that the gas-phase synthetic route (using metal chlorides, carbonyls etc) provides an alternative which is suitable for the synthesis of very many closed caged structures and nanotubes hitherto unknown. Various issues with this method of synthesis, including its fundamentals, mechanism, and the properties of the inorganic fullerene-like structures produced are reviewed, together with some possible applications.

Xenbucin 1, an analgesic drug, was synthesized in 4 steps using two different routes. The biaryl fragment could successfully be produced via a Pd/C catalysed Suzuki coupling in water using sodium tetraphenylborate as a phenylation reagent. Overall yields of the routes were 36% and 59%, respectively.

The applications of linear-polarized IR-spectroscopy to oriented colloid suspensions in a nematic host are demonstrated with croconic and rhodizonic acids. The experimental IR vibrational assignments of the solid-state of both neutral compounds are presented. Assignments are supported by theoretical quantum chemical calculations and vibrational analysis at the DFT level of theoretical approximation with the 6-311++G** basis set.

The complexation energies of H3BNHnCl3−n (n= 3-0) complexes and the proton affinities of NHnCl3−n compounds have been computed at the G2(MP2) level of theory. G2(MP2) results show that the successive chlorine substitution on the ammonia decreases both the basicity of the NHnCl3−n ligands and the stability of H3BNHnCl3−n complexes. The findings are interpreted in terms of the rehybridisation of the nitrogen lone-pair orbital. The NBO partitioning scheme shows that the variation of the N-H and N-Cl bond lengths, upon complexation, is due to variation of “s” character in these bonds.

A one-pot multi-component reaction is developed for the efficient synthesis of 4,5-dibenzylidene octahydroacridines in high yields. The reaction is performed by the tandem reaction of three molar equivalent aromatic aldehydes with two molar equivalent 4-alkylcyclohexanone in the system of NH4OAc/HOAc under microwave irradiation.

Selected phenolic acids are determined by capillary zone electrophoresis and HPLC, each using UV detection. The optimised CZE background electrolyte contained 50 mM acetic acid, 95 mM 6-aminocaproic acid, 0.1% polyacrylamide, 1% polyvinylpyrrolidone, and 10% methanol. Twelve phenolic acids (gallic, p-hydroxybenzoic, 3,4-dihydroxybenzoic, vanillic, syringic, o-coumaric, p-coumaric, caffeic, sinapic, ferulic, salicylic and chlorogenic) were separated within 10 minutes. Chromatographic separation of these phenolic acids was carried out on an Eclipse XBD C8 column using a mobile phase gradient (acetonitrile / methanol / water / 0.1% phosphoric acid); all were separated within 25 minutes. Electrophoretic and chromatographic determinations of ferulic and chlorogenic acids were compared on barley, malt, and potato samples. The methods’ characteristics were: linearity (1–20 mg ml and 0.2–4 mg ml−1), accuracy (recovery 94 ± 5% and 96 ± 4%), intra-assay repeatability (4.1% and 3.5%), and detection limit (0.2 and 0.02 mg ml−1).

The kinetics of the esterification reaction between acetic acid and epichlorohydrin catalysed by Purolite A-520E strong basic anion exchange resin was studied. The effects of certain parameters such as stirring speed, particle diameter, temperature, catalyst amount and molar ratio between reactants were experimentally determined. It was found that the overall reaction rate is intrinsically kinetically controlled. The partial orders of reaction with respect to catalyst, acetic acid and epichlorohydrin were determined. A reaction mechanism is proposed. Based on chromatographic data and taking into account the partial orders of reaction, a more detailed kinetic model is suggested.

The paper reports on the dependence of the absorbance and luminescent intensity from pH of novel poly(oxyethylene phosphate) tris(β-diketonate) europium (III) complexes. The photophysical data obtained allow some preliminary assumptions about the nature of this phenomenon. Increase in luminescent efficiency is a consequence of enhanced efficiency of energy transfer caused by structural changes in complexes after water deprotonation. Remarkable change has been observed in photophysical properties of the polymer complexes by studying the fluorescent emission and excitation spectra and absorption recorded at various pH both in solution and in the solid state. Some of the complexes derivative of the dibenzoylmethane (DBM) show more than hundred times increase in the luminescence after alkalization. The pH value, at which the maximum luminescent efficiency appears, depends on the type of the fourth ligand. The difference between luminescent efficiency of the complexes in alkaline and neutral environment depends on the β-diketonate ligands and on polymer type as well.

Theoretical studies on the thermodynamic and kinetic properties of the reactions of scandium (I) ion with the sulfur-transfer reagent SCO via the C-O bond activation pathway have been carried out over the temperature range of 200-1200 K using the DFT/B3LYP method, general statistical thermodynamics, and Eyring transition state theory with Wigner correction. The relevant reactions include reaction 1 1Sc+ + SCO → 1IM1 → 1TS1 → 1IM2 (Step 1) → 1TS2 → 1IM3 → 1ScO+ + 1CS (Step 2), and reaction 2 3Sc+ + SCO → 3IM1 → CP → 1IM2 → 1TS2 → 1IM3 → 1ScO+ +1CS in which the spin multiplicity changes from the triplet state to the singlet state in the crossing region. It was concluded that the order of the equilibrium constants (K) and the reaction rate constants (k) are consistent with that of their corresponding exoergic energies, ΔE, and reaction barriers, respectively. Step 2 of reaction 1 is both thermodynamically and kinetically favored over the whole temperature range. Moreover, both Reaction 1 and reaction 2 are exothermic and spontaneous processes in which their entropy increases, and the magnitudes of their thermodynamic values all decrease with increasing temperature.

Three 2-(benzimidazol-2-yl)-3-hydroxychromone derivatives were synthesized. Their spectroscopic and fluorescent properties, due to excited state intramolecular proton transfer (ESIPT) from OH to carbonyl, were studied. Theoretical possibility of an alternative intramolecular H-bonding and experimental evidence for such behavior are discussed.

Reactive oxygen species (ROS) may generate different nucleoside/nucleotide radicals in a cell environment. In this study, the possibility of cyclic-2’-deoxyadenosines formation by a rearrangement of their free radicals was investigated. It seems that for cyclic-nucleosides formation, adoption of an O4’-exo conformation by the sugar moiety is necessary. However, this is the energetically unfavoured form of the 2-deoxyribose ring. Moreover, the creation of a O5’, C8 bond in purine deoxy-nucleosides/nucleotides leads to the termination of the DNA elongation process.

This paper reports on the results concerning the sol-gel preparation and characterization of Sr-substituted perovskite lanthanum cobaltates La1−xSrxCoO3−δ (x = 0.0, 0.25, 0.5 and 0.75). The metal ions, generated by dissolving starting materials in diluted acetic acid were complexed by 1,2-ethanediol to obtain the precursors for the non-substituted and Sr-substituted LaCoO3. The influence of the synthesis temperature, heating time and the amount of substituent on the phase purity of La1−xSrxCoO3−δ were investigated. The phase transformations, composition and micro-structural features in the gels and polycrystalline samples were studied by thermal analysis (TG/DTA), infrared spectroscopy (IR), powder X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM).

Water-soluble Mn3O4 nanocrystals have been prepared through thermal decomposition in a high temperature boiling solvent, 2-pyrrolidone. The final product was characterized with XRD, SEM, TEM, FTIR and Zeta Potential measurements. Average crystallite size was calculated as ∼15 nm using XRD peak broadening. TEM analysis revealed spherical nanoparticles with an average diameter of 14±0.4 nm. FTIR analysis indicated that 2-pyrrolidone coordinates with the Mn3O4 nanocrystals only via O from the carbonyl group, thus confining their growth and protecting their surfaces from interaction with neighboring particles.

The palladium(0) catalyzed amination of allylic acetates and carbonates derivatives from terpenic olefins was carried out under mild conditions. The reaction offers a very good method for the preparation of allylic amines and thus to provide a useful entry to new functionalized terpenic olefin products. The mechanism involving a formation of p-allyl-palladium intermediate complex is in good agreement with the results obtained with the optically active substrates, as well as via an analysis of the observed regio-and stereoselectivity.

A series of new dimeric surfactants, twin-tailed gemini surfactants, 2(12)-s-2(12), were successfully prepared and characterized, and their monolayer films investigated by the measurement of surface pressure-area (π-A) and surface pressure-time (π-t) isotherms at the air/water interface by a Langmuir film balance. Compared to their monomeric counterparts, their collapse pressure (γcollapse) is smaller, whilst all the molecular area parameters are larger. The limited area (Alimited) and the initial area (Ainitial) of these twin-tailed gemini surfactants change with increasing spacer length s, and the surface pressure decreases with increasing time. It was also found that the higher the initial surface pressure, the larger the attenuation.

Alumina-zirconia composite materials were produced with different acid ratios by the sol-gel method using aluminum isopropoxide and zirconium chloride. The composites were produced by changing acid/alkoxside ratio in alumina. The composite materials were calcinated at 600°C, 900°C and 1300°C. The effects of acid concentration and calcination temperature on the surface area and pore radius were determined from the nitrogen adsorption isotherm at 77 K. The density of the composites was also measured. The minimum density of produced material was recorded as 1.35 g cm−3 at an acid/alkoxside ratio of 0.2. The highest specific surface area and pore diameter of the lightest material are 191.86 m2 g−1 and 18.4 Ǻ, respectively. Although pore diameter and specific surface area are not changed at any of the experimental temperatures which were tested by decreasing acid/alkoxside ratio, the density is slightly increased. However, it was observed that the calcination temperature significantly affects the surface area and density of the material.

In the presented work, the conditions for cloud point extraction of iron from aqueous solutions using 7-iodo-8-hydroxyquinolin-5-sulphonic acid (Ferron) was investigated and optimized. The procedure is based on the separation of its ferron complex into the micellar media by adding the surfactant Triton X-114. After phase separation, the surfactant-rich phase was dissolved with 1.0 M HNO3 in methanol. Iron was determined by flame atomic absorption spectrometry. Optimization of the pH, ligand and surfactant quantities, incubation time, temperature, viscosity, sample volume, and interfering ions were investigated. The effects of the matrix ions were also examined. The detection limits for three times the standard deviations of the blank for iron was 0.4 ng m L-1, enrichment factor of 19.6 and preconcentration factor of 30 could be achieved. The validity of cloud point extraction was checked by employing real samples including soil, blood, spinach, milk, meat, liver and orange juice samples using the standard addition method, which gave satisfactory results.In the presented work, the conditions for cloud point extraction of iron from aqueous solutions using 7-iodo-8-hydroxyquinolin-5-sulphonic acid (Ferron) was investigated and optimized. The procedure is based on the separation of its ferron complex into the micellar media by adding the surfactant Triton X-114. After phase separation, the surfactant-rich phase was dissolved with 1.0 M HNO3 in methanol. Iron was determined by flame atomic absorption spectrometry. Optimization of the pH, ligand and surfactant quantities, incubation time, temperature, viscosity, sample volume, and interfering ions were investigated. The effects of the matrix ions were also examined. The detection limits for three times the standard deviations of the blank for iron was 0.4 ng m L−1, enrichment factor of 19.6 and preconcentration factor of 30 could be achieved. The validity of cloud point extraction was checked by employing real samples including soil, blood, spinach, milk, meat, liver and orange juice samples using the standard addition method, which gave satisfactory results.