Synthesis of N-alkylated amino acids using fluorous-tagged hydroxylamines

The development of a new fluorous-tagged ammonia-equivalent for the synthesis of N-alkylated amino acids is described. The required building blocks were readily accessed in high yield and purity using F-SPE purification technique. Coupling of the fluorous-tagged hydroxylamines with a selection of boronic acids and glyoxalic acid gave the desired N-alkylated amino acids. Subsequent removal of the fluorous tag via catalytic hydrogenation was investigated using a number of different catalysts and solvents. A more robust de-tagging procedure involves the transformation of the amino acid to the corresponding methyl ester followed by a Mo(CH₃CN)₃(CO)₃ mediated N-O bond cleavage.     

Determination of steroid hormones in blood by GC–MS/MS

This paper presents the development, optimization and validation of a methodology to determine nine key steroid hormones (viz. pregnenolone, progesterone, dehydroepiandrosterone, androstenedione, testosterone, dihydrotestosterone, estrone, 17α-estradiol and 17β-estradiol) expressed in the steroidogenesis in biological fluids. The analytical method allows for the determination of steroid hormones in blood plasma and serum down to 0.08–0.16 ng/mL for estrogens, 0.20–0.36 ng/mL for androgens and 0.36–0.43 ng/mL for progestagens. These limits of detection were obtainable using a two-step solid-phase clean-up for fractionation and elimination of interfering lipids (fatty acids, phospholipids, glycerides and sterols) from the steroid hormones. The accuracy of the method was 50–112% in the range 0.10 to 2.00 ng/mL.     

Local orbitals by minimizing powers of the orbital variance

It is demonstrated that a set of local orthonormal Hartree-Fock (HF) molecular orbitals can be obtained for both the occupied and virtual orbital spaces by minimizing powers of the orbital variance using the trust-region algorithm. For a power exponent equal to one, the Boys localization function is obtained. For increasing power exponents, the penalty for delocalized orbitals is increased and smaller maximum orbital spreads are encountered. Calculations on superbenzene, C(60), and a fragment of the titin protein show that for a power exponent equal to one, delocalized outlier orbitals may be encountered. These disappear when the exponent is larger than one. For a small penalty, the occupied orbitals are more local than the virtual ones. When the penalty is increased, the locality of the occupied and virtual orbitals becomes similar. In fact, when increasing the cardinal number for Dunning's correlation consistent basis sets, it is seen that for larger penalties, the virtual orbitals become more local than the occupied ones. We also show that the local virtual HF orbitals are significantly more local than the redundant projected atomic orbitals, which often have been used to span the virtual orbital space in local correlated wave function calculations. Our local molecular orbitals thus appear to be a good candidate for local correlation methods.     

Damped response theory description of two-photon absorption

Damped response theory is applied to the calculation of two-photon absorption (TPA) spectra, which are determined directly, at each frequency, from a modified damped cubic response function. The TPA spectrum may therefore be evaluated for selected frequency ranges, making the damped TPA approach attractive for calculations on large molecules with a high density of states, where the calculation of TPA using standard theory is more problematic. Damped response theory can also be applied to the case of intermediate state resonances, where the standard TPA expression is divergent. Both exact damped response theory and its application within density functional theory are discussed. The latter is implemented using an atomic-orbital based density matrix formulation, which makes the approach especially suitable for studies on large systems. A test preliminary study is presented for the TPA spectrum of R-(+)-1,1'-bi(2-naphtol).     

Variational response-function formulation of vibrational circular dichroism

The atomic axial tensor (AAT) of vibrational circular dichroism is expressed as the frequency derivative at zero frequency of a linear response function for operators referencing a nuclear displacement and a magnetic field. This is used in the density matrix-based quasienergy derivative Lagrangian approach of Thorvaldsen et al. [J. Chem. Phys., 2008, 129, 214108] to express the AAT in a form where the need to solve response equations for the nuclear displacements is removed, significantly reducing the computation cost compared to existing formulations. The density matrix-based quasienergy derivative Lagrangian approach also allows us straightforwardly to use London atomic orbitals to remove the gauge-origin dependence and to account for the atomic orbitals' dependence on the nuclear coordinates. The formalism is entirely based on atomic-orbital density and integral matrices and therefore amenable to linear scaling for sufficiently sparse matrices and given a linearly scaling response solver.     

Thin noble metal films on Si (111) investigated by optical second-harmonic generation and photoemission

Thin noble metal films (Ag, Au and Cu) on Si (111) have been investigated by optical second-harmonic generation (SHG) in combination with synchrotron radiation photoemission spectroscopy. The valence band spectra of Ag films show a quantization of the sp-band in the 4-eV energy range from the Fermi level down to the onset of the d-bands. For Cu and Au the corresponding energy range is much narrower and quantization effects are less visible. Quantization effects in SHG are observed as oscillations in the signal as a function of film thickness. The oscillations are strongest for Ag and less pronounced for Cu, in agreement with valence band photoemission spectra. In the case of Au, a reacted layer floating on top of the Au film masks the observation of quantum well levels by photoemission. However, SHG shows a well-developed quantization of levels in the Au film below the reacted layer. For Ag films, the relation between film thickness and photon energy of the SHG resonances indicates different types of resonances, some of which involve both quantum well and substrate states. Received: 16 October 2001 / Revised version: 14 March 2002 / Published online: 29 May 2002     

Dynamical approach to complex regional economic growth based on Keynesian model for China

The paper addresses the problem of complex regional economic growth by using nonlinear Keynesian model with focusing on direct foreign investments effects. We investigate the dynamics of the model for the broad range of parameters which, in particular, contains the parameter values obtained recently by econometric analysis of the data for economic growth in China. For the single-region model we give conditions for which the dynamics of the model will be chaotic or regular. The parameters which prevent the economic stagnation are indicated. Further, we consider the model for two regions with a common trade as a coupling factor. The conditions are given for the two trading systems to exhibit chaotic synchronization, in-phase and out-of-phase behavior.     

Chemistry of chloroethylenes on Cu(100): bonding and reactions

The bonding and reactions of chloroethylenes (vinyl chloride, trans- and cis-dichloroethylene, trichloroethylene) on a Cu(100) surface have been investigated by temperature-programmed desorption and reaction, near-edge X-ray absorption fine structure (NEXAFS) studies and measurements of changes of the surface work function. The monolayer molecules adsorb molecularly intact at 95 K via π coordination. The molecules orient with their molecular planes parallel to the surface with little increase (<0.02 Å) in the C---C bond distance compared with the gas phase values. The degree of thermal dissociation increases with the extent of halogenation, and no chlorine is present in the hydrocarbon reaction products liberated from the surface. Both cis- and trans-1.2-chloroethylene produce acetylene and a small amount of benzene, while dissociation of trichloroethylene generates acetylene and deposits a carbon residue on the surface. Vinyl chloride desorbs from Cu(100) without reaction.     

Kohlenwasserstoffe

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