Molecular dynamics study of temperature dehydration of a C12E6 spherical micelle

Hydration of a spherical micelles of C12E6 in solution is studied by molecular dynamics simulation. The interface is found to be separated in an inner part composed of water and hydrophobic and hydrophilic moieties and an outer part with hydrophilic moiety and water only. Hydration numbers in the inner and in the outer parts are in excellent agreement with experimental data from various different methods. Temperature dehydration occurs in the inner region only and is related to the presence of water molecules directly in contact with the hydrophobic core at low temperature.     

Identification and assay of wild-type and modified nucleoside mixtures by turbo ionspray ionization tandem mass spectrometry

A method is presented which allows the identification and assay of a nucleoside in the presence of other analogues and homologues. The method is based on the conventional multiple reaction monitoring approach performed on the [M + H]+ ions of wild-type and modified nucleosides produced by the turbo ionspray ionization method on a triple-quadrupole mass spectrometer. The accuracy of the quantitative determination relies on the evaluation of a response factor rho, which takes into account the kinetics of dissociation of the parent ions into the protonated [B + 2H]+ nucleobase ions. The evaluation of the absolute concentration of each analyte in the examined mixture does not require any previous chromatographic separation.     

Low-threshold quantum-cascade lasers at 3.5 THz (lambda = 85 microm)

Chirped-superlattice quantum-cascade lasers are reported that emit at lambda approximately 85 microm (3.6 THz), which is to the authors' knowledge the longest wavelength demonstrated so far with this technology. Collected peak output powers of 1.5 mW per facet were measured at liquid-helium temperature, and a maximum operating temperature of 45 K was reached. Record low-threshold-current densities of 95 and 115 A cm(-2) were observed in pulsed and continuous-wave operation, respectively. For the latter, output powers of a few hundred microwatts are estimated at low temperatures.     

Boosts in an Arbitrary Direction and Maximal Causal Velocities in a Deformed Minkowski Space

We discuss boosts in a deformed Minkowski space, i.e., a four-dimensional spacetime with metric coefficients depending on nonmetric coordinates (in particular on the energy). The general form of a boost in an arbitrary direction is derived in the case of space anisotropy. Two maximal trivector velocities are mathematically possible, an isotropic and an anisotropic one. However, only the anisotropic velocity has physical meaning, being invariant indeed under deformed boosts.     

Trinuclear and hexanuclear platinum clusters as building blocks for organometallic one-dimensional structures

The reaction between the new hexa- and trinuclear clusters [Pt6](CC-C6H4-CCH)2, (4) [[Pt6] = Pt6(CO)4(mu-PBu(t)2)4], and [Pt3]Cl, (6) [[Pt3] = Pt3(mu-PBu(t)2)3(CO)2], in CuI/Amine gives the thermally and air stable [Pt6](CC-C6H4-CC[Pt3])2 (7), where the cluster units are separated by conjugated 1,4-diethynylphenyl groups.     

Toward novel DNA binding metal complexes: structure and basic kinetic data of [M(9MeG)2(CH3OH)(CO)3]+(M = 99Tc,Re)

To study the interaction of the fac-[M(CO)(3)](+) moiety (M = (99m)Tc, (188)Re) with DNA bases, we reacted [M(OH(2))(3)(CO)(3)](+) with 9-methylguanine (9-MeG), guanosine (G), and 2-deoxyguanosine (2dG). Two bases bind to the metal center via the N7 atoms. X-ray structure analysis of [(99)Tc(CH(3)OH)(9-MeG)(2)(CO)(3)](+) (4) (monoclinic, I2/a, a = 28.7533(14) A, b = 8.0631(4) A, c = 32.3600(15) A, beta = 91.543(6) degrees, V = 7499.6(6) A(3), Z = 8) and [Re(OH(2))(9-MeG)(2)(CO)(3)](+) (7) (monoclinic, P2(1)/n, a = 12.2873(11) A, b = 16.0707(13) A, c = 14.1809(16) A, beta = 103.361(12) degrees, V = 2724.4(5) A(3), Z = 4) reveals that the two bases are in a head-to-tail (HT) orientation. Kinetic studies show that the rates of substitution of the purine bases are comparable to that of one of the active forms of cisplatin. The bis-substituted complexes are generally less stable than the platinum adducts, and metalation of the bases is reversible.     

New beta cis folded organocobalt derivatives with a salen-type ligand

The reduction of [Co(III)(tmsalen)py(2)](+)ClO(4)(-), where tmsalen = 4,4',7,7'-tetramethylsalen, with NaBH(4)/PdCl(2) in alkaline methanolic solution, followed by the oxidative addition of CH(2)ClI, leads to the expected trans organometallic dimeric species 1, [CH(2)ClCo(tmsalen)](2), provided that the product is recovered from the reaction mixture immediately after the completion of the reaction. If 1 is left for longer time in contact with the reaction mixture, the intramolecular reaction of the axial chloromethyl group with the equatorial chelate leads to the formation of the monocationic complex 2, containing a seven-membered ring. In this complex the novel tetradentate ligand coordinates Co in a cis fashion, the other two positions being occupied by one py and one water molecule. The resulting complex is chiral, even if the reaction product is a racemic compound. The unidentate ligands of 2 have been exchanged quantitatively for N-MeIm, and the resulting complex 3 still maintains the beta cis geometry. Therefore, 2 may be considered the precursor of a new class of organocobalt derivatives with a folded tetradentate ligand and two adjacent exchangeable sites. On the basis of the geometry of the tetradentate Schiff bases in complexes, where they adopt a planar geometry, it was suggested that there is a significant electron density delocalization involving the metal center over the two chemically equivalent moieties of Co(chel). Comparison of the geometry of the planar salicylaldiminate (sal) moiety with that of the cyclized methoxy-iminate one (imi) in 2 and 3 strongly supports that the delocalization, still present in sal, is essentially either lost or strongly reduced in imi.     

Functionalised enones as starting materials for the construction of aziridine scaffolds

alpha-Substituted beta-keto esters have been transformed by means of a straightforward procedure into aziridine-1,2-dicarboxylates, which have been efficiently converted into alkenyl aziridine-1,2-dicarboxylates through Wittig olefination reaction. The possibility of aziridine ring elaborations and the presence of an olefin function make these new molecules suitable scaffolds for further derivatisation into potential bioactive targets.     

Some noncoercive parabolic equations with lower order terms in divergence form

This paper deals with existence and regularity results for the problem $ \cases{u_t-\mathrm{div}(a(x,t,u )\nabla u)=-\mathrm{div}(u\,E) \qquad in \Omega\times (0,T),\cr u=0 \qquad on \partial \Omega\times (0,T), \cr u (0)= u_0 \qquad in \Omega ,\cr} $ under various assumptions on E and $ u_0 $. The main difculty in studying this problem is due to the presence of the term div(uE), which makes the differential operator non coercive on the "energy space" $ L^2 (0, T; H_0^1 (\Omega)) $.AMS Subject Classification: 35K10, 35K15, 35K65.