Formation of paramagnetic mononuclear iron nitrosyl complexes from diamagnetic di- and tetranuclear iron-sulphur nitrosyls: characterisation by EPR spectroscopy and study of thiolate and nitrosyl ligand exchange reactions

The diamagnetic Roussin esters Fe₂(SR)₂(NO)₄ readily underwent exchange with thiols R′SH to yield Fe₂(SR′)₂(NO)₄: the exchange was faster in polar, coordinating solvents where paramagnetic, mononuclear complexes of types [Fe(NO)₂(solvent)₂]⁺ and Fe(NO) ₂(SR)(solvent) were formed. With the corresponding thiolate anions RS^-, the esters Fe₂(SR)₂(NO)₄ formed the mononuclear complexes [Fe(SR)₂(NO)₂]^-, which were fully characterised by EPR spectroscopy for R = H, Me, Et, i-Pr, t-Bu and PhCH₂: assignments of hyperfine couplings were confirmed by use of ¹⁵N. With Fe₂(SR)₂(NO)₄ and a different set of thiolate anion, R′S ^-, in excess, thiol exchange occurred to give [Fe(SR′)₂(NO)₂]^-. A mechanism for formation of Fe₂(SR′)₂(NO)₄ from Fe₂(SR)₂(NO)₄ has been proposed. The paramagnetic mononuclear complexes [Fe(SR)₂(NO)₂] were also readily formed from the diamagnetic clusters [Fe₄S₃(NO)₇]^- and Fe₄S₄(NO)₄, together with [Fe(SR)₃(NO)]^-, and additionally from [Fe(CO)₃NO]^-. [Fe(SMe)₂(NO)₂]^-. was found to be a precursor of isolable Fe₂(SMe)₂(NO)₄, and [Fe(SH)₂ (NO)₂]^- to be the common precursor of both Roussin′s red anion [Fe₂S₂(NO)₄]^- and Roussin's black anion [Fe₄S₃ (NO)₇]^- interconvertible by appropriate adjustment of pH. The nitrosyl groups in these complexes were freely labile, and mononitrosyliron and dinitrosyliron fragments were readily interconvertible: FE(NO) fragments were favoured by the dimethyldithiocarbamate ligand (Me₂NCS ₂) and Fe(NO)₂ fragments by thiolate ligands, RS^-, regardless of the origin of the Fe(NO)_x(x = 1,2) fragment: both mono- and dinitrosyliron complexes persisted with [(i-PrO)₂S₂]^- as ligand. Isotopic labelling showed the occurrence of rapid exchange of nitrogen between nitrosyl ligands and added nitrite in Fe(NO)(S₂CNMe₂)₂ and [Fe(SR)₂(NO)₂]^-     

Chromatography of xanthines on ion-exchange resins.

Short columns of a 4% crosslinked cation-exchange resin gave good chromatography of xanthines, including caffeine, theophylline and hypoxanthine, and related polar aromatic compounds. Elution volumes and sequences can be modified by changing pH, solvent composition and resin counter-ion. A macroporous cation-exchange resin showed exaggerated counter-ion effects. A method is described for determining caffeine and theophylline in blood serum, using the 4% crosslinked resin with aqueous sodium phosphate eluent of pH 7.5; the temperature was 65 degrees. Detection limits are 10 ng and less.     

A faster,more stable method for computing the pth roots of positive definite matrices

An accelerated, more stable generalization of Newton's method for finding matrix pth roots is developed in a form suitable for finding the positive definite pth root of a positive definite matrix. Numerical examples are given and compared with the corresponding Newton iterates.     

Information and Distinguishability of Ensembles of Identical Quantum States

We consider a fixed quantum measurement performed over n identical copies of quantum states. Using a rigorous notion of distinguishability based on Shannon’s 12th theorem, we show that in the case of a single qubit, the number of distinguishable states is , where (α₁,α₂) is the angle interval from which the states are chosen. In the general case of an N-dimensional Hilbert space and an area Ω of the domain on the unit sphere from which the states are chosen, the number of distinguishable states is . The optimal distribution is uniform over the domain in Cartesian coordinates.     

Synthesis and characterisation of cis-dioxomolybdenum(VI) complexes of N-substituted 3-hydroxy-2-pyridinones

The butoxy- and methoxy-derivatives (HLc, and HLb, respectively) of 1-[(ethoxycarbonyl)methyl]-3-hydroxy-2-(1H)-pyridinone, HLa, were synthesized by transesterification and the mononuclear complexes [MoO2(L(a-c))2] were obtained by the reaction of the ligands with molybdenyl acetylacetonate. The three complexes were fully characterized by (1)H and (13)C NMR spectroscopy, mass spectrometry and elemental analyses. A variable temperature NMR study showed that the N-substituents do not have a significant influence on the racemisation process of the complexes. The comparison of the crystal structure of [MoO2(Lb)2] with [MoO2(La)2] confirmed that an additional methylene group does not affect the immediate coordination environment of the molybdenum centre. The methoxy-derivative HLb was also found to produce a dinuclear complex of composition [(MoO2(Lb)O)2], the structure of which was determined by X-ray diffraction.     

Strong Bragg gratings photoinduced by 633-nm illumination in evaporated As2Se3 thin films

Bragg gratings are used in several photonic devices to reflect, and thus to isolate, specific wavelengths of light. Gratings can be photoinduced in chalcogenide glasses by illumination of bandgap light in an interference pattern. We used holographic interferometry to create Bragg gratings in amorphous As2Se3 thin films with a period of 0.56 microm by illumination with 633-nm light. The quality of the gratings was tested in real time, and refractive-index modulations as high as 0.037 were measured. These gratings were found to be stable over a period of several months if they were kept in the dark.     

Use of floating electrodes in transient isotachophoresis to increase the sensitivity of detection

We report a protocol for on-chip electrophoretic sample loading and sample component separation in which each operation requires simultaneous control of the potential of only two electrodes: during the sample-loading phase, the potentials at the ends of the separation channel are electrically floating; during electrophoresis of the sample mixture down the separation channel, the potentials at the ends of the sample-introduction channel are floating. This method, which we call "floating-stacking," avoids the dispersion/distortion of the sample plug that is commonly associated with simultaneous electrical control of only two electrodes in a crossed-channel or offset-double-tee injection system. Further, when this floating loading/separation is done in the presence of back-transient-isotachophoresis, sample loss from the plug of material being injected is minimal and a significant concentration increase--up to 13x--of the sample components in the separated bands occurs relative to the commonly used "pinch-and-pull-back" technique (which requires simultaneous electrical control of four electrodes).     

Yttrium polyoxometalates. Synthesis and characterization of a carbonate-encapsulated sandwich-type complex

Reaction of A-alpha-PW(9)O(34)(9)(-) with YCl(3) in an aqueous Na(2)CO(3) solution produces a dianion-encapsulated A-type sandwich polyoxometalate, (YOH(2))(3)(CO(3))(A-alpha-PW(9)O(34))(2)(11)(-). The X-ray structure of this complex reveals that three Y(III) ions are sandwiched between two A-alpha-PW(9)O(34)(9)(-) moieties and that a carbonate dianion is encapsulated in the same plane as the three Y(III) atoms. The oxygen atoms of the CO(3)(2)(-) are sitting at the midpoints of the sides of the triangle formed by the three Y(III) ions. (31)P and (13)C NMR studies confirm that this complex is significantly more stable than the analogous A-type sandwich polyoxometalates containing divalent metals.