Flow systems exploiting in-line prior assays

An expert sequential injection system involving a prior assay is proposed for spectrophotometric determination of phosphate and eventually zinc in soil extracts. The result of phosphate determination is the basis for a concentration-oriented decision regarding to the need or not for zinc determination. Zinc was only determined if a threshold value (peak height corresponding to 5.0 mg l⁻¹ P) was surpassed. The methods involved formation of molybdenum blue and the Rhodamine 6G/ammonium thiocyanate/Zn²⁺ ternary complex. Variations in the threshold value were < 2% during 4 h operating periods, false responses were not verified, and the analytical time was reduced in about 30%. Precise results (R.S.D. <3% P and < 1% Zn) in agreement with spectrophotometry and flame atomic absorption spectrometry were obtained. The innovation permits faster information processing, as well as a reduction in the number of measurements, number of analytical steps, laboratorial time, and consumption of sample and reagents, thus waste generation.     

Electron–Electron interaction energy in homonuclear diatomic molecules

The derivative of the electron–electron potential energy U_ee with respect to internuclear separation R is studied for light homonuclear diatomic molecules at equilibrium. It is readily related to nuclear–nuclear potential energy U_nn, the force constant K, and the electron–nuclear potential energy U_en. An approximate expression, based on the simplest form of density functional theory, is then used to eliminate dU_en/dR|_Re. The result thus obtained for dU_ee/dR|_Re transcends an earlier proposal of Kryachko by including a term 2/3R_eK, with K the force constant. Numerical tests at SCF–RHF level are presented for nine homonuclear diatomic molecules.     

Aromatic substitution in the complexes formed upon addition of gaseous arenium ions to proelectrophiles. A FT-ICR study

Experiments based on FT-ICR mass spectrometry provide conclusive evidence for the operation of an alternative mechanism of electrophilic aromatic substitution occurring within the complex formed upon addition of gaseous arenium ions to a variety of proelectrophiles, including alkyl halides, alcohols, epoxides, esters and diazoalkanes. The factors affecting the efficiency of the unconventional substitution are examined in the light of the kinetic results of the FT-ICR experiments.     

Peptide backbone folding induced by the C(alpha)-tetrasubstituted cyclic alpha-amino acids 4-amino-1,2-dithiolane-4-carboxylic acid (Adt) and 1-aminocyclopentane-1-carboxylic acid (Ac5c). A joint computational and experimental study

The conformational study of a new group of synthetic peptides containing 4-amino-1,2-dithiolane-4-carboxylic acid (Adt), a cysteine-related achiral residue, has been carried out through a joint application of computational and experimental methodologies. Molecular Dynamics simulations clearly suggest the tendency of this molecule to adopt a gamma-turn conformation in vacuum and help in analyzing the complex and crucial conformational behaviour of the dithiolane ring which appears to preferentially adopt a C(S)-like structure. Electronic structure calculations carried out in solution using the Density Functional Theory also indicate the preservation of the gamma-like folding in apolar solvents and the helix-like one in more polar solvents. A comparison with the achiral 1-aminocycloalkane-1-carboxylic acid (Ac5c) has been carried out using the same computational tools. NMR and IR data on dipeptide derivatives containing the Adt or Ac5c residue show that in chloroform solution all the models prefer a gamma-turn structure, centered at the cyclic residue, stabilized by an intramolecular H-bond, whereas in a more polar solvent, i.e. dimethyl sulfoxide, this folding is not maintained. The experimental conformational studies, extended to N-Boc protected tripeptides, clearly indicate the remarkable tendency of both the five-membered C(alpha)-tetrasubstituted cyclic amino acids Adt and Ac5c to induce the gamma-turn structure also in models able to adopt the beta-bend conformation.     

Parameter dependence and outcome dependence in dynamical models for state vector reduction

We apply the distinction between parameter independence and outcome independence to the linear and nonlinear models of a recent nonrelativistic theory of continuous state vector reduction. We show that in the nonlinear model there is a set of realizations of the stochastic process that drives the state vector reduction for which parameter independence is violated for parallel spin components in the EPR-Bohm setup. Such a set has an appreciable probability of occurrence ( 1/2). On the other hand, the linear model exhibits only extremely small parameter dependence effects. We investigate some specific features of the models and we recall that, as has been pointed out recently, if one wants to be able to speak of definite outcomes (or equivalently of possessed objective elements of reality) at finite times, one has to slightly change the criteria for their attribution to physical systems. The concluding section is devoted to a detailed discussion of the difficulties which one meets when one tries to take, as a starting point for the formulation of a relativistic theory, a nonrelativistic scheme which exhibits parameter dependence. Here we derive a theorem which identifies the precise sense in which the occurrence of parameter dependence forbids a genuinely relativistic generalization. Finally we show how the appreciable parameter dependence of the nonlinear model gives rise to problems with relativity, while the extremely weak parameter dependence of the linear model does not give rise to any difficulty, provided one takes into account the appropriate criteria for the attribution of definite outcomes.Work supported in part by the Trieste Section of the INFN.     

Computational study of the reaction of N(2D) atoms with CH2F radicals: an example of a barrier-free reaction involving very high internal energies

The singlet potential-energy surface for the N(2D)+CH2F(2A') reaction has been studied employing both second-order M?ller-Plesset and density-functional theories. The energies of the involved species have been refined using the Gaussian-2, complete basis set, and coupled-cluster singles and doubles (triples) methods. The reaction proceeds through the formation of an initial intermediate, which does not involve any activation barrier. Based on the energy profile for the singlet potential-energy surface, the preferred product should be the most exothermic one, namely, HCN+HF, followed by HNC+HF and FCN+H2. This result seems in contradiction with a computational study of the kinetics of the title reaction in terms of the statistical theories, which leads to the prediction that the production of HNC+HF should be the dominant channel. Consequently, a limited molecular-dynamics study has been carried out, concluding that in fact the system behaves in a nonstatistical way. According to the molecular-dynamics study, the most exothermic channel, HCN+HF, should be the dominant one. An analysis of the possible role of the singlet surface in the reaction of N(4S) with CH2F(2A') has also been carried out. The computational study shows that the microcanonical coefficients for the nonadiabatic channels are much smaller than the competing adiabatic ones. Therefore, the reaction of N(4S) with CH2F(2A') should proceed on the triplet surface without spin change.