An internal language for autonomous categories

We present an internal language for symmetric monoidal closed (autonomous) categories analogous to the typed lambda calculus as an internal language for cartesian closed categories. The language we propose is the term assignment to the multiplicative fragment of Intuitionistic Linear Logic, which possesses exactly the right structure for an autonomous theory. We prove that this language is an internal language and show as an application the coherence theorem of Kelly and Mac Lane, which becomes straightforward to state and prove. Finally, we extend the language with the natural numbers and show that this corresponds to a weak Natural Numbers Object in an autonomous category.     

Stepwise hapticity changes in sequential one-electron redox reactions of indenyl-molybdenum complexes: combined electrochemical, ESR, X-ray, and theoretical studies.

Reduction of the dication [(eta5-Ind)(Cp)Mo[P(OMe)3]2]2+ (1(2+)) and oxidation of the neutral complex (eta3-Ind)(Cp)Mo[P(OMe)3]2 (1) proceed through a one-electron intermediate, 1+. The structures of 1(2+) and 1 have been determined by X-ray diffraction studies, which show the slip-fold distortion angle, Omega, of the indenyl ring increasing from 4.1 degrees in 1(2+) to 21.7 degrees in 1. Cyclic voltammetry and bulk electrolysis were employed to define the thermodynamics and heterogeneous charge-transfer kinetics of reactions 1(2+) + e(-) <==> 1+ and 1+ + e(-) <==> 1: DeltaE1/2 = 113 mV in CH3CN and 219 mV in CH2Cl2/0.1 M [NBu4][PF6]; k(s) = 0.4 cm x s(-1) for 1(2+)/1+ couple, 1.0 cm x s(-1) for 1+/1 couple in CH3CN. ESR spectra of 1+ displayed a surprisingly large hyperfine splitting (7.4 x 10(-4) x cm(-1)) from a single 1H nucleus, and spectra of the partially deuterated indenyl analogue confirmed assignment of a(H) to the H2 proton of the indenyl ring. The related eta5 18-electron complexes [(eta5-Ind)(Cp)Mo(dppe)]2+ (2(2+)) (dppe = diphenylphosphinoethane) and (eta5-Ind)(Cp)Mo(CN)2 (3) may also be reduced in two successive one-electron steps; ESR spectra of the radicals 2+ and 3- showed a similarly large a(H2) (8.7 x 10(-4) and 6.4 x 10(-4) x cm(-1), respectively). Molecular orbital calculations (density functional theory, DFT, and extended Hückel, EH) predict metal-indenyl bonding in 1+ that is approximately midway between that of the eta5 and eta3 hapticities (e.g., Omega = 11.4 degrees ). DFT results show that the large value of a(H2) arises from polarization of the indenyl-H2 by both inner-sphere orbitals and the singly occupied molecular orbital (SOMO) of 1+. The measured ks values are consistent with only minor inner-sphere reorganizational energies being necessary for the electron-transfer reactions, showing that a full eta5/eta3 hapticity change may require only small inner-sphere reorganization energies when concomitant with a pair of stepwise one-electron-transfer processes. The indenyl ligand in 1+ is best described as donating approximately four pi-electrons to Mo by combining a traditional eta3 linkage with two "half-strength" Mo-C bonds.     

Finding borders between coding and noncoding DNA regions by an entropic segmentation method

We present a new computational approach to finding borders between coding and noncoding DNA. This approach has two features: (i) DNA sequences are described by a 12-letter alphabet that captures the differential base composition at each codon position, and (ii) the search for the borders is carried out by means of an entropic segmentation method which uses only the general statistical properties of coding DNA. We find that this method is highly accurate in finding borders between coding and noncoding regions and requires no "prior training" on known data sets. Our results appear to be more accurate than those obtained with moving windows in the discrimination of coding from noncoding DNA.     

Structural modification of fullerene thin films by highly charged iron ions

In this paper, the results of structural modification of fullerene thin films bombarded by highly charged iron ions (Fe⁶⁺) are presented. The properties of as-deposited and irradiated fullerene thin films have been investigated by Raman spectroscopy, UV/Vis spectrophotometry and atomic force microscopy (AFM). The results of Raman spectroscopy have indicated structural changes of irradiated thin films depending on fluences. It was found that iron doped fullerene films are dominated by sp³ rather than sp² after bombardment which might be due to formation of nanodiamond structures. AFM analysis showed that the ion beam had destroyed the surface ordering. The optical band gap was found to be in the range of 0.6 to 1.4 eV for irradiated films by Fe⁶⁺ ions at the highest fluences. PACS 61.48.+c; 78.30.-j; 79.20.Rf     

Comprehensive liquid chromatography-ion-spray tandem mass spectrometry method for the identification and quantification of eight hydroxylated brominated diphenyl ethers in environmental matrices

We propose an instrumental method based on liquid chromatography coupled to negative ion-spray ionization (ISP(-)) tandem mass spectrometry (MS/MS), for the simultaneous analysis of eight hydroxylated brominated diphenyl ethers (OH-PBDEs) in four different environmental matrices (soil, fish, sludge and particulate matter). The reversed-phase chromatographic separation was performed on a 50 mm Xbridge C18 column, and the compounds were well resolved with a gradient consisting of a ternary mixture of 5 mMammonium acetate, methanol and acetonitrile. Detection was performed in the multiple reaction monitoring (MRM) mode using the [M - H](-) ion as base peak. The fragmentation pathways of the OH-PBDEs varied according to the hydroxyl substitution in the benzene rings and produced characteristic MRM transitions needed for resolving isomeric compounds. The method is acceptable for quantification in the high picogram per gram dry weight (dw) level for all matrices analyzed. Repeatability and reproducibility tested at 75 pg microl(-1) were below 10% using internal standard quantification. The ISP (-) enhancement due to matrix effects was in the 76-132% range and the highest values corresponded to sludge samples. The use of the proposed method based on LC-ISP(-)-MS/MS opens a new way to directly determine OH-PBDEs without the need of derivatization.     

CORM-3 reactivity toward proteins: the crystal structure of a Ru(II) dicarbonyl-lysozyme complex

CORM-3, [fac-Ru(CO)(3)Cl(κ(2)-H(2)NCH(2)CO(2))], is a well-known carbon monoxide releasing molecule (CORM) capable of delivering CO in vivo. Herein we show for the first time that the interactions of CORM-3 with proteins result in the loss of a chloride ion, glycinate, and one CO ligand. The rapid formation of stable adducts between the protein and the remaining cis-Ru(II)(CO)(2) fragments was confirmed by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES), Liquid-Chromatography Mass Spectrometry (LC-MS), Infrared Spectroscopy (IR), and X-ray crystallography. Three Ru coordination sites are observed in the structure of hen egg white lysozyme crystals soaked with CORM-3. The site with highest Ru occupancy (80%) shows a fac-[(His15)Ru(CO)(2)(H(2)O)(3)] structure.     

Topochemical polymerization of a diarylbutadiyne derivative in the gel and solid states

A diarylbutadiyne derivative was synthesized using a few steps and gelified in aromatic solvents. The gel prepared at low concentration is made of micrometers-long nanofibrils as shown by scanning electron microscopy. XRD of the dried gel shows sharp features, revealing a well-organized material. A topochemical reaction was performed on the dried gel, and a polydiacetylene presenting reversible thermochromism properties was obtained.     

Morphological, structural, and magnetic properties of Co nanoparticles in a silicon oxide matrix

We present a morphological, structural, and magnetic characterization of Co nanoparticles (mean diameter of 10.3 ± 1.8 nm) grown using a gas aggregation source and embedded in a silicon oxide matrix by sequential deposition of nanoparticles and silicon oxide. We show that the Co nanoparticles ??soft-land?? on the substrates and suffer a moderate oxidation in contact with the silicon oxide. Despite this moderate oxidation, it is found that, at room temperature, the magnetic volume of the resulting nanoparticles is below the superparamagnetic limit. The results presented in this article are compatible with the presence of an assembly of magnetically independent particles that also display a moderate exchange bias at low temperature.