Layer-by-layer self-assembled polyelectrolyte multilayers with embedded liposomes: immobilized submicronic reactors for mineralization

The development of chemical reactions in nanospaces is of paramount importance for the development of active nanodevices, particularly in nanofluidics. It has been shown in a previous paper that phospholipid vesicles can be incorporated without spontaneous bilayer rupture into poly-L-glutamic acid/poly(allylamine) (PGA/PAH) multilayered polyelectrolyte films. The aim of the present study was to use such a system as an "embedded submicronic reactor" able to trigger precipitation of calcium phosphates within closed spaces through an enzymatic reaction, the enzyme also being encapsulated in the vesicle interior. To this aim, large unilamellar vesicles (LUVs) were produced containing calcium ions as active ions in the mineralization process, spermine as an activator of crystal growth, and alkaline phosphatase as a catalyst to convert phosphate esters into phosphates. After stabilization by adding a layer of poly-(D-lysine), these vesicles were embedded in a (PGA-PAH)n film. A paranitrophenyl phosphate containing solution was then put in contact with this film. It is shown by means of infrared spectroscopy in the attenuated total reflection mode that, consecutively to this contact, calcium phosphates are growing inside the embedded vesicles. By using scanning near-field fluorescence microscopy, it is demonstrated that the alkaline phosphatase enzymes are most probably located inside the vesicles after their embedding. In addition, atomic force microscopy was used to show, after chemical removal of the organic top layer of the film, that the inorganic platelets produced after the precipitation reaction are localized in volumes of similar size and shape as that of the vesicles into which the phosphate ester hydrolysis and subsequent precipitation reaction did occur.     

Robust Optimal Stopping-Time Control for Nonlinear Systems

Abstract. We formulate a robust optimal stopping-time problem for a state-space system and give the connection between various notions of lower value function for the associated games (and storage function for the associated dissipative system) with solutions of the appropriate variational inequality (VI) (the analogue of the Hamilton—Jacobi—Bellman—Isaacs equation for this setting). We show that the stopping-time rule can be obtained by solving the VI in the viscosity sense and a positive definite supersolution of the VI can be used for stability analysis.     

{N‐[2‐(η5‐Cyclopentadienyl)ethyl]‐4‐toluenesulfonamido‐N,O}(tetrahydrofuran‐O)bis(trifluoromethanesulfonato‐O)titanium(II)

The title compound, [Ti(CF₃O₃S)₂(C₁₄H₁₅NO₂S)(C₄H₈O)], contains a unique ligand system in which the Ti ion is bound to the N and O atoms of a 2‐p‐toluene­sulfon­amide ligand, which is linked by an ethyl group to a coordinated cyclo­penta­diene moiety. The distorted octahedral geometry about the Ti ion is completed by two tri­fluoro­methane­sulfonate ligands and a tetra­hydro­furan mol­ecule. Comparison with related compounds shows that both the Ti—N and Ti—O bonds of the sulfon­amide, although longer than normal values, indicate significant bonding interactions.     

Probing the structures of gas-phase rhodium cluster cations by far-infrared spectroscopy

The geometric structures of small cationic rhodium clusters Rh(n)(+) (n = 6-12) are investigated by comparison of experimental far-infrared multiple photon dissociation spectra with spectra calculated using density functional theory. The clusters are found to favor structures based on octahedral and tetrahedral motifs for most of the sizes considered, in contrast to previous theoretical predictions that rhodium clusters should favor cubic motifs. Our findings highlight the need for further development of theoretical and computational methods to treat these high-spin transition metal clusters.     

Thermal‐ and Light‐Induced Spin Crossover in a Guest‐Dependent Dinuclear Iron(II) System

We previously reported the dinuclear material [Fe^II₂(ddpp)₂(NCS)₄] ? 4 CH₂Cl₂ ( 1? 4 CH₂Cl₂; ddpp=2,5‐di(2′,2′′‐dipyridylamino)pyridine) and its partially desolvated analogue ( 1? CH₂Cl₂), which undergo two‐ and one‐step spin‐crossover (SCO) transitions, respectively. Here, we manipulate the type and degree of solvation in this system and find that either a one‐ or two‐step spin transition can be specifically targeted. The chloroform clathrate 1? 4 CHCl₃ undergoes a relatively abrupt one‐step SCO, in which the two equivalent Fe^II sites within the dinuclear molecule crossover simultaneously. Partial desolvation of 1? 4 CHCl₃ to form 1? 3 CHCl₃ and 1? CHCl₃ occurs through single‐crystal‐to‐single‐crystal processes (monoclinic C2/c to P2₁/n to P2₁/n) in which the two equivalent Fe^II sites become inequivalent sites within the dinuclear molecule of each phase. Both 1? 3 CHCl₃ and 1? CHCl₃ undergo one‐step spin transitions, with the former having a significantly higher SCO temperature than 1? 4 CHCl₃ and the latter, and each has a broader SCO transition than 1? 4 CHCl₃, attributable to the overlap of two SCO steps in each case. Further magnetic manipulation can be carried out on these materials through reversibly resolvating the partially desolvated material with chloroform to produce the original one‐step SCO, or with dichloromethane to produce a two‐step SCO reminiscent of that seen for 1? 4 CH₂Cl₂. Furthermore, we investigate the light‐induced excited spin state trapping (LIESST) effect on 1? 4 CH₂Cl₂ and 1? CH₂Cl₂ and observe partial LIESST activity for the former and no activity for the latter.     

Impedance spectroscopy measurements to study physio-chemical processes in lime-based composites

The conduction and dielectric behaviour of two different grades of natural hydraulic lime is presented over the frequency range 1 Hz–1 MHz, with measurements taken over the initial six months after gauging with water. Samples containing embedded electrodes were exposed to both a natural atmosphere (20°C and 65% relative humidity) and a natural atmosphere with a carbon dioxide concentration maintained at 400 ppm which was used to accelerate the carbonation process. A decrease in relative dielectric permittivity and rise in conductivity, with increasing frequency, was observed at all stages over the time-scale presented. When plotted in the complex plane, the impedance featured a bulk response comprising two depressed semicircles and a low frequency spur, the latter being associated with the electrode/sample interface. The complex impedance plot, together with the application of an equivalent circuit model, indicated a dual arc feature with carbonation and hydration contributing to bulk impedance response. This study demonstrates the applicability of electrical property measurements to monitor the combined processes of hydration and carbonation in this group of materials.     

Beta–neutrino correlation experiments on laser trapped 38mK, 37K

Laser trapping and cooling techniques are now being applied to the study of nuclear β-decay at several labs. A magneto-optical trap (MOT) provides a localized source of atoms suspended in space, so the low-energy recoiling nuclei can freely escape and be detected in coincidence with the β. This allows reconstruction of the neutrino momentum, and the deduction of the β-v correlation in a more direct fashion than previously possible. In addition, the nuclei can be polarized by atomic techniques, opening a new class of spin correlation measurements to test the degree to which parity is maximally violated in the weak interaction. Our present experiment has detected several hundred thousand recoil-β⁺ coincidences from the 0⁺ → 0⁺ pure Fermi decay of ^38mK, produced at the on-line isotope separators TISOL and ISAC at TRIUMF. Our goal is to set constraints on non-Standard Model scalar bosons competitive with high-energy colliders and more conventional β-v correlation experiments. This revised version was published online in August 2006 with corrections to the Cover Date.