An altered mechanism of hydrolysis for a metal-complexed phosphate diester

Isotope effects in the nucleophile and in the leaving group were measured to gain information about the mechanism and transition state of the hydrolysis of methyl p-nitrophenyl phosphate complexed to a dinuclear cobalt complex. The complexed diester undergoes hydrolysis about 1011 times faster than the corresponding uncomplexed diester. The kinetic isotope effects indicate that this rate acceleration is accompanied by a change in mechanism. A large inverse 18O isotope effect in the bridging hydroxide nucleophile (0.937 +/- 0.002) suggests that nucleophilic attack occurs before the rate-determining step. Large isotope effects in the nitrophenyl leaving group (18Olg = 1.029 +/- 0.002, 15N = 1.0026 +/- 0.0002) indicate significant fission of the P-O ester bond in the transition state of the rate-determining step. The data indicate that in contrast to uncomplexed diesters, which undergo hydrolysis by a concerted mechanism, the reaction of the complexed diester likely proceeds via an addition-elimination mechanism. The rate-limiting step is expulsion of the p-nitrophenyl leaving group from the intermediate, which proceeds by a late transition state with extensive bond fission to the leaving group. This represents a substantial change in mechanism from the hydrolysis of uncomplexed aryl phosphate diesters.     

Strong oscillations in molecular valence photoemission intensities

Photoemission from the two outermost ionizations [highest occupied molecular orbitals (HOMO and HOMO-1)] of Mg(eta(5)-C(5)H(5))(2) has been studied with synchrotron radiation in the gas phase. Strong oscillations in the HOMO-1/HOMO ratio, qualitatively similar to those well-known for fullerenes, are found. Excellent agreement with the experimental ratio is provided by accurate cross section calculations both at the density-functional theory and time-dependent density-functional theory level, indicating that a many electron response has a minor role for this effect. A comparison with the calculated values for other metal sandwich compounds indicate that the presence of oscillations is a widespread phenomenon, and a potential source of interesting information on the structural and electronic properties of the target molecule.     

R.F. (280 MHz) EPR imaging of extended samples: Apparatus and preliminary results

This paper presents the preliminary results obtained using an Electron Paramagnetic Resonance imaging apparatus operating at 280 MHz. The acquisition technique and the procedure used to obtain the spin density spatial localization are presented and specimen images of extended samples are given. The accuracy of the images and the spatial resolution are also discussed.     

Torsion Structure in Riemann-Cartan Manifold and Dislocation

The U(1) gauge structure of torsion and dislocation in three dimensional Riemann-Cartan manifold have been studied. The local topological structure of dislocation have been presented by so-called topological method in which the quantum number is by Hopf indices and Brouwer degree. Furthermore, the relationship between the dislocation lines and Wilson lines of the U(1) gauge theory is discussed by using the Chern-Simons theory.     

Evidence for a kaon-bound state K(-)pp produced in K(-) absorption reactions at rest

We have searched for a deeply bound kaonic state by using the FINUDA spectrometer installed at the e(+)e(-) collider DAPhiNE. Almost monochromatic K(-)'s produced through the decay of phi(1020) mesons are used to observe K(-) absorption reactions stopped on very thin nuclear targets. Taking this unique advantage, we have succeeded to detect a kaon-bound state K(-)pp through its two-body decay into a Lambda hyperon and a proton. The binding energy and the decay width are determined from the invariant-mass distribution as 115(+6)(-5)(stat)(+3)(-4)(syst) MeV and 67(+14)(-11)(stat)(+2)(-3)(syst) MeV, respectively.     

An open volume, high isolation, radio frequency surface coil system for pulsed magnetic resonance

We present an open volume, high isolation, RF system suitable for pulsed NMR and EPR spectrometers with reduced dead time. It comprises a set of three RF surface coils disposed with mutually parallel RF fields and a double-channel receiver (RX). Theoretical and experimental results obtained with a prototype operating at about 100 MHz are reported. Each surface RF coil (diameter 5.5 cm) was tuned to f₀ = 100.00 ± 0.01 MHz when isolated. Because of the mutual coupling and the geometry of the RF coils, only two resonances at f₁ = 97.94 MHz and f₂ = 101.85 MHz were observed. We show they are associated with two different RF field spatial distributions. In continuous mode (CW) operation the isolation between the TX coil and one of the RX coils (single-channel) was about −10 dB. By setting the double-channel RF assembly in subtraction mode the isolation values at f₁ or f₂ could be optimised to about −75 dB. Following a TX RF pulse (5 μs duration) an exponential decay with time constant of about 600 ns was observed. The isolation with single-channel RX coil was about −11 dB and it increased to about −47 dB with the double-channel RX in subtraction mode. Similar results were obtained with the RF pulse frequency selected to f₂ and also with shorter (500 ns) RF pulses. The above geometrical parameters and operating frequency of the RF assembly were selected as a model for potential applications in solid state NMR and in free radical EPR spectroscopy and imaging.     

Semiconductor Quantum Dots as Components of Photoactive Supramolecular Architectures

Luminescent quantum dots (QDs) are colloidal semiconductor nanocrystals consisting of an inorganic core covered by a molecular layer of organic surfactants. Although QDs have been known for more than thirty years, they are still attracting the interest of researchers because of their unique size-tunable optical and electrical properties arising from quantum confinement. Moreover, the controlled decoration of the QD surface with suitable molecular species enables the rational design of inorganic-organic multicomponent architectures that can show a vast array of functionalities. This minireview highlights the recent progress in the use of surface-modified QDs – in particular, those based on cadmium chalcogenides – as supramolecular platforms for light-related applications such as optical sensing, triplet photosensitization, photocatalysis and phototherapy.