Highly corrosion resistant siloxane-polymethyl methacrylate hybrid coatings

Siloxane-polymethyl methacrylate hybrid films were deposited on carbon steel substrates by dip-coating from a sol prepared by acid-catalyzed hydrolytic co-polycondensation of tetraethoxysilane (TEOS) and 3-methacryloxy propyl-trimethoxysilane (MPTS), followed by radical polymerization of methyl methacrylate (MMA). Structural properties of the hybrids were studied using ²⁹Si and ¹³C nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA), as a function of the MMA/MPTS ratio, which ranged between 2 and 10. The efficiency of corrosion protection of hybrid-coated carbon steel was investigated by XPS, potentiodynamic polarization curves and electrochemical impedance spectroscopy after immersion of the material in acidic and neutral saline aqueous solution. The NMR and TGA results indicate a high degree of polycondensation (84%) and elevated thermal stability of 410?°C for the hybrid film with a MMA/MPTS ratio of 8, exhibiting also and excellent adhesion to the substrate. The XPS analysis confirmed the variation of the MMA phase in the hybrid, and showed that no corrosion-induced changes had occurred after 18?days immersion of the coated steel in 3.5% NaCl solution. Potentiodynamic polarization curves have shown that the hybrid coating prepared using a TEOS/MPTS ratio of 8 yielded the best anti-corrosion performance. It acts as a very efficient corrosion barrier, increasing the total impedance by almost 6 orders of magnitude and reducing the current densities by 4 orders of magnitude, compared to the bare electrode. The obtained results are discussed based on the correlation of structural information with impedance data presented for both electrolytes in the form of electrical equivalent circuits.     

Synthesis and Photophysical Properties of Multichromophoric Carbonyl‐Bridged Triarylamines

The synthesis and photophysical properties of two novel multichromophoric compounds is presented. Their molecular design comprises a carbonyl‐bridged triarylamine core and either naphthalimides or 4‐(5‐hexyl‐2,2′‐bithiophene)naphthalimides as second chromophore in the periphery. The lateral chromophores are attached to the core via an amide linkage and a short alkyl spacer. The synthetic approach demonstrates a straightforward functionalization strategy for carbonyl‐bridged triarylamines. Steady‐state and time‐resolved spectroscopic investigations of these compounds, in combination with three reference compounds, provide clear evidence for energy transfer in both multichromophoric compounds. The direction of the energy transfer depends on the lateral chromophore used. Furthermore, the compound bearing the lateral 4‐(bithiophene)naphthaimides is capable of forming fluorescent gels at very low concentrations in the sub‐millimolar regime whilst retaining its energy transfer properties.     

Pattern formation by local amplification and lateral inhibition: Examples from biology and geology

This article provides an overview of current and prospected climate changes, their causes and implied threats, and of a possible route to keep the changes within a tolerable level. The global mean temperature has up to 2005 risen by almost 0.8°C, and the change expected by 2100 is as large as glacial-interglacial changes in the past, which were commonly spread out over 10000 years. As is well known, the principle actor is man-made CO₂, which, together with other anthropogenic gases, enhances the atmosphere’s greenhouse effect. The only man-made cooling agent appears to be atmospheric aerosols. Atmospheric CO₂ has now reached levels unprecedented during the past several million years. Principal threats are a greatly reduced biodiversity (species extinction), changes in the atmospheric precipitation pattern, more frequent weather extremes, and not the least, sea level rise. The expected precipitation pattern will enhance water scarcity in and around regions that suffer from water shortage already, affecting many countries. Sea level rise will act on a longer time scale. It is expected to amount to more than 50 cm by 2100, and over the coming centuries the potential rise is of the order of 10 m. A global-mean temperature increase of 2°C is often quoted as a safe limit, beyond which irreversible effects must be expected. To achieve that limit, a major, rapid, and coordinated international effort will be needed. Up to the year 2050, the man-made CO₂ releases must be reduced by at least 50%. This must be accompanied by a complete overhaul of the global energy supply toward depending increasingly on the Sun’s supply of energy, both directly and in converted form, such as wind energy. Much of the information and insight available today has been generated by the Intergovernmental Panel on Climate Change (IPCC), in particular its Fourth Assessment Report of 2007, which greatly advanced both public attention and political action.     

Dissociative and molecular oxygen chemisorption channels on reduced rutile TiO2(110): An STM and TPD study

High-resolution scanning tunneling microscopy (STM) and temperature-programmed desorption (TPD) were used to study the interaction of O₂ with reduced TiO₂(110)–(1 × 1) crystals. STM is the technique of choice to unravel the relation between vacancy and non-vacancy assisted O₂ dissociation channels as a function of temperature. It is revealed that the vacancy-assisted, first O₂ dissociation channel is preferred at low temperature (~ 120 K), whereas the non-vacancy assisted, second O₂ dissociation channel operates at temperatures higher than 150 K–180 K. Based on the STM results on the two dissociative O₂ interaction channels and the TPD data, a new comprehensive model of the O₂ chemisorption on reduced TiO₂(110) is proposed. The model explains the relations between the two dissociative and the molecular O₂ interaction channels. The experimental data are interpreted by considering the available charge in the near-surface region of reduced TiO₂(110) crystals, the kinetics of the two O₂ dissociation channels as well as the kinetics of the diffusion and reaction of Ti interstitials.     

Synthesis of oligonucleotides containing thiazole and thiazole N-oxide nucleobases

[reaction: see text] The thiazole C-nucleoside analogue was synthesized by the Hantzsch cyclization method to form the thiazole ring and was then converted to the thiazole N-oxide C-nucleoside analogue by peracid oxidation of the heterocycle nitrogen. Incorporation of the thiazole and thiazole N-oxide phosphoramidites into DNA was successful though significant deoxygenation of the N-oxide occurred during DNA assembly. The mechanism proposed for the reduction of the thiazole N-oxide to thiazole involves the formation of an N-oxide phosphite ester.     

Adsorbate-oxide interactions during the NO + CO reaction on MgO(100) supported Pd monolayer films

The potential energy diagram for the NO+CO reaction on 1, 2, and 3 monolayer (ML) Pd films supported by MgO(100) is calculated using density functional theory. Thin Pd films are generally found to be more reactive than thick films, with a notable exception for nitrogen adsorption on 2 ML Pd/MgO(100). For this system an attractive through-the-metal adsorbate-oxide interaction of 0.5 eV is identified. Nitrogen adsorption is consequently estimated to provide a thermodynamic driving force for the reconstruction of MgO(100) supported 3 ML (or thicker) Pd clusters into thinner Pd clusters.     

Collective states in highly symmetric atomic configurations and single-photon traps

We study correlated states in circular and linear-chain configurations of identical two-level atoms containing the energy of a single quasi-resonant photon in the form of a collective excitation, where the collective behavior is mediated by exchange of transverse photons between the atoms. For a circular atomic configuration containing N atoms, the collective energy eigenstates can be determined by group-theoretical means making use of the fact that the configuration possesses a cyclic symmetry group Z _N . For these circular configurations, the carrier spaces of the various irreducible representations of the symmetry group are at most two-dimensional, so that the effective Hamiltonian on the radiationless subspace of the system can be diagonalized analytically. As a consequence, the radiationless energy eigenstates carry a Z _N quantum number p = 0, 1, …, N, which is analogous to the angular momentum quantum number l = 0, 1, … carried by particles propagating in a central potential, such as a hydrogen-like system. Just as the hydrogen s states are the only electronic wave functions that can occupy the central region of the Coulomb potential, the quasi-particle corresponding to a collective excitation of the circular atomic sample can occupy the central atom only for vanishing Z _N quantum number p. When a central atom is present, the p = 0 state splits into two, showing level crossing at certain radii; in the regions between these radii, damped oscillations between two “ extreme” p = 0 states occur, where the excitation occupies either the outer atoms or the central atom only. For large numbers of atoms in a maximally subradiant state, a critical interatomic distance of λ/2 emerges both in the linear-chain and in the circular configuration of atoms. The spontaneous decay rate of the linear configuration exhibits a jumplike “critical” behavior for next-neighbor distances close to a half-wavelength. Furthermore, both the linear-chain and the circular configurations exhibit exponential photon trapping once the next-neighbor distance becomes less than a half-wavelength, with the suppression of spontaneous decay being particularly pronounced in the circular system. In this way, circular configurations containing sufficiently many atoms may be natural candidates for single-photon traps.     

Universal properties of two-dimensional boson droplets

We consider a system of N nonrelativistic bosons in two dimensions, interacting weakly via a short-range attractive potential. We show that for N large, but below some critical value, the properties of the N-boson bound state are universal. In particular, the ratio of the binding energies of (N+1)- and N-boson systems, B(N+1)/B(N), approaches a finite limit, approximately 8.567, at large N. We also confirm previous results that the three-body system has exactly two bound states. We find for the ground state B(0)(3)=16.522 688(1)B2 and for the excited state B(1)(3)=1.270 409 1(1)B2.