MNDO studies on five-membered 1,3-heterocyclic systems. Part I. The acidity of the azolium cations

The technique of energy partitioning in the MNDO SCF-MO method has been used to understand the main electronic factors which determine the acidity order of the azolium cations. It is found that the greater acidity of thiazolium cation relative to the imidazolium one can be ascribed to a substantial stabilization of the one-center energy term associated to the sulphur atom in the conjugate base, suggesting a higher effective electronegativity of this atom.     

A rotational study of laser ablated thiourea

A laser ablation device in combination with a molecular beam Fourier-transform microwave spectrometer has allowed the observation of the rotational spectrum of solid thiourea for the first time. The sensitivity reached in the experiment allowed the observation of the isotopomers (34)S, (13)C, and (15)N in their natural abundance. The spectrum of D(4)-thiourea was also analyzed from an enriched sample. The complicated hyperfine structure arising from the presence of two (14)N quadrupolar nuclei has been fully resolved and analyzed. The substitution r(s) structure has been derived from the experimental moments of inertia. Thiourea in gas phase presents a planar heavy atom skeleton. Experimental inertial defect values and high-level ab initio calculations reveal that the amino groups hydrogen atoms lie out-of-plane with a C(2) symmetry configuration and are involved in large amplitude inversion motions.     

New approach to sulfonated diphosphine complexes: synthesis and amphoteric behaviour of zwitterionic [Mn+(CO4{(PPh2)2C(H)SO3-}

Oxidation of the thioketone residue in the complex [Mn(CO)4{(PPh2)2C=S}]+ (2) with hydrogen peroxide affords the sulfonate derivative [Mn(CO)4{(PPh2)2C(H)SO3}] (3), which shows amphoteric behaviour in reversible acid-base processes, and is easily chlorinated to give [Mn(CO)4{(PPh2)2C(Cl)SO3}] (8).     

On sub-harmonic bifurcations

Under fairly general hypotheses, we investigate by elementary methods the structure of the p-periodic orbits of a family $h_u$ of transformations near $(u_0,x_0)$ when $h_{u_0}(x_0)=x_0$ and $\mathrm{d}{h}_{u_0}(x_0)$ has a simple eigenvalue which is a primitive p-th root of unity. To cite this article: M. Chaperon et al., C. R. Acad. Sci. Paris, Ser. I 340 (2005).     

The Dynamics of the Energy of a Kähler Class

The energy of a Kähler class, on a compact complex manifold (M,J) of Kähler type, is the infimum of the squared L²-norm of the scalar curvature over all Kähler metrics representing the class. We study general properties of this functional, and define its gradient flow over all Kähler classes represented by metrics of fixed volume. When besides the trivial holomorphic vector field of (M,J), all others have no zeroes, we extend it to a flow over all cohomology classes of fixed top cup product. We prove that the dynamical system in this space defined by the said flow does not have periodic orbits, that its only fixed points are critical classes of a suitably defined extension of the energy function, and that along solution curves in the Kähler cone the energy is a monotone function. If the Kähler cone is forward invariant under the flow, solutions to the flow equation converge to a critical point of the class energy function. We show that this is always the case when the manifold has a signed first Chern class. We characterize the forward stability of the Kähler cone in terms of the value of a suitable time dependent form over irreducible subvarieties of (M,J). We use this result to draw several geometric conclusions, including the determination of optimal dimension dependent bounds for the squared L²-norm of the scalar curvature functional.Acknowledgement We would like to thank Nicholas Buchdahl for helpful conversations leading us to several improvements of an earlier version of the article, including the correction of two improper assertions.     

Influence of the carbon nanotube probe tilt angle on the effective probe stiffness and image quality in tapping-mode atomic force microscopy

Previous studies have shown that when using carbon nanotubes (CNTs) as tapping-mode AFM probes, their tilt angle with respect to vertical (denoted phi) must be close to 0 degrees to obtain high-quality images and that very poor images are obtained for phi > 30 degrees . Here we present a quantitative theoretical investigation of the effect of phi on tapping-mode AFM imaging for single-wall and multiwall nanotube (SWNT and MWNT, respectively) probes of diameters 3.4-5.5 nm and aspect ratio 7.5, which have been found ideal for imaging via TEM. Using molecular and classical dynamics, we investigate the effect of phi on CNT probe stiffness (quantified through the maximum gradient of the tip-sample interaction force) and show that it decreases linearly with increasing phi, becoming negligible at around phi approximately 40 degrees , thus confirming the conclusions of previous studies. We find that MWNT probe stiffness is proportional to the number of walls, but that the difference in stiffness between SWNTs and MWNTs also decreases linearly with increasing phi and becomes negligible at around phi approximately 40 degrees . The simulated cross-sectional scans of a sample SWNT using two different values of phi show that the image can be distorted and shifted laterally when phi is large, in some cases giving measured heights appreciably greater than the sample dimensions. We show analytically that the tip-sample forces that occur during imaging can be significantly lower when CNT probes are used instead of conventional probes, even in the absence of buckling, and that they can be further reduced by increasing phi. On the basis of this result, we propose the design of free-standing kinked probes for the characterization of sensitive samples, whereby the probe approaches the sample at a vertical orientation and possesses a tilted section that regulates the tip-sample interaction forces.     

A Mesoscopic Simulation Approach for Modeling Intracellular Reactions

Reactions in the intracellular medium occur in a highly organized and heterogenous environment rendering invalid modeling approaches based on the law of mass action or its stochastic counter-part. This has led to the recent development of a variety of stochastic microscopic approaches based on lattice-gas automata or Brownian dynamics. The main disadvantage of these methods is that they are computationally intensive. We propose a mesoscopic method which permits the efficient simulation of reactions occurring in the complex geometries typical of intracellular environments. This approach is used to model the transport of a substrate through a pore in a semi-permeable membrane, in which its Michaelis–Menten enzyme is embedded. We find that the temporal evolution of the substrate is a sensitive function of the spatial heterogeneity of the environment. The spatial organization and heterogeneities of the intracellular medium seem to be playing an important role in the regulation of biochemical reactions.     

Synthesis, characterization, and structure of a new N-nitrosamine of cyclam (1,4,8,11-tetraazacyclotetradecane)

A novel N-nitrosamine of cyclam has been synthesized. The N-N bond lengths values, as determined from the X-ray crystal structure, fall in the 1.318(2) and 1.320(2) Å range, smaller than the ones expected for the N-N single bond. The N-NO bond angles are in the 115.0(1)° and 114.8(1)° range. The νNO, νNN, and δN-NO vibrational modes were observed in the infrared spectrum at 1454, 1139, and 555 cm⁻¹, respectively. The photolysis of the cyclam(NO)₄ compound gives rise to the nitrosyl release through an heterolytic cleavage of the N-NO bonds, as indicated by the appearance of the νNO⁺ band at 2228 cm⁻¹ at the expense of decreasing the νNO, νNN, and δN-NO bands.     

Determination of carbohydrazide at trace and subtrace levels

We developed three analytical methods for the determination of carbohydrazide at different concentration levels. One involves the volumetric titration of the analyte with bromate ion and dead-stop end-point detection, and is applicable to concentrations above 10 mg/l., so it can be used for standardizing carbohydrazide solutions. A second, spectrophotometric method is based on the reduction of FE(III) and measurement of the absorbance of the Fe(II)-ferrozine complex, and features an applicability range of 25-700,mug/l. carbohydrazide. The third method uses differential pulse polarography and the oxidation of carbohydrazide in a basic medium at a dropping mercury electrode to determine the analyte. This last method is the most sensitive of the three and also that offering the widest determination range: from 4 to 3000 mug/l. carbohydrazide.     

A flexible and versatile strategy for the covalent immobilization of chiral catalysts based on pyridinebis(oxazoline) ligands

[reaction: see text] Flexible and versatile methods have been developed for the immobilization of chiral pyridinebis(oxazoline) ligands by covalent bonding to a solid support, either by grafting or by polymerization. Different spacers can easily be introduced to modulate the support-ligand distance and the electronic properties of the chiral ligand. As an example, 2,6-bis[(S)-4-isopropyloxazolin-2-yl]pyridine has been immobilized on polystyrene resins, both on a Merrifield-type resin by grafting and on supports prepared by polymerization of 4-vinyl-substituted ligands. The corresponding Ru complexes have been tested as catalysts in the cyclopropanation reaction between styrene and ethyl diazoacetate. The catalytic activity, the enantioselectivity, and the recyclability are strongly dependent on the catalyst preparation method and the total exclusion of oxygen and moisture in the filtration process. Under such optimized conditions, yields over 60% with up to 90% ee can be obtained in four successive reactions-the best cyclopropanation results described to date for a chiral solid ruthenium catalyst.