Induced-fit in the gas phase: conformational effects on the enantioselectivity of chiral tetra-amide macrocycles

The structure, stability, and reactivity of proton-bound diastereomeric [M x H x A]+ complexes between some amino acid derivatives (A) and several chiral tetra-amide macrocycles (M) have been investigated in the gas phase by ESI-FT-ICR and ESI-ITMS-CID mass spectrometry. The displacement of the A guest from the diastereomeric [M x H x A]+ complexes by reaction with the 2-aminobutane enantiomers (B) exhibits a distinct enantioselectivity with regards to the leaving amino acid A and, to a minor extent, to the amine reactant B. The emerging selectivity picture, discussed in the light of molecular mechanics calculations, provides compelling evidence that the most stable conformers of the selected chiral tetra-amide macrocycles M may acquire in the gas phase a different conformation by induced fit on complexation with some representative amino acid derivatives A. This leads to the coexistence in the gas phase of stable diastereomeric [M x H x A]+ eq-eq and ax-ax structures, in proportions depending on the configuration of A and M and characterized by different stability and reactivity toward the 2-aminobutane enantiomers. The enantioselectivity of the gas-phase A-to-B displacement in the diastereomeric [M x H x A]+ complexes essentially reflects the free energy gap between the homo- and heterochiral [M x H x A]+ complexes, except when the tetra-amidic host presents an additional macrocycle generated by a decamethylene chain. In this case, the measured enantioselectivity mostly reflects the stability difference between the relevant diastereomeric transition structures.     

Monosolvation of R-1-phenyl-2,2,2-trifluoroethanol with amines: configurational effects on the excitation, ionization, and fragmentation of diastereomeric complexes

Wavelength and mass selected resonant two-photon ionization spectra of molecular clusters between R-1-phenyl-2,2,2-trifluoroethanol (FER) and methylamine (M) or the enantiomers of 2-aminobutane (AR and AS) were recorded after supersonic molecular beam expansion and analyzed with the aid of ab initio molecular orbital calculations. The experimental results agree with theoretical calculations pointing to the predominance of the two most stable conformers of monosolvated FER whose CF3 group establishes intense NH...F interactions with the selected amines so as to orient them away from the aromatic ring. This reduces the enantioselectivity of FER toward the 2-aminobutane enantiomers as compared to that exhibited by the R-1-phenylethanol (ER) analogue, where obviously NH...F interactions are absent.     

广义Bethe树上奇偶马尔可夫链场上的若干极限性质

通过构造两个非负鞅证明了一个强极限定理,然后把它应用到本文所定义的广义Bethe树上的奇偶马尔可夫链场上,从而获得了此马氏链场上的一类强极限定理.     

Dissymmetry effects on the laser spectroscopy of supersonically expanded rare gas/chiral arene heteroclusters

The R2PI-TOF spectra of supersonically expanded rare gas/chiral arene heteroclusters have been rationalized in terms of the distortion of the pi-electron density reflecting the different dipole and quadrupole momenta induced in the rare gas atoms by interaction with the opposite pi-faces of the chiral arene itself.     

The valence electronic structure and conformational flexibility of epichlorohydrin

The electronic structure of epichlorohydrin is investigated in the whole valence region by a combined experimental and theoretical study. The issue of controversial assignments of the molecular electronic structure is here addressed. Photoelectron spectra (PES) and Threshold Photoelectron spectra (TPES) of room temperature molecules in the gas phase are recorded. Geometries and energies of the stable conformers due to internal rotation of the C-C-C-Cl dihedral angle, gauche-II (g-II), gauche-I (g-I), and cis, are calculated, and the effect of the conformational flexibility on the photoionization energetics is studied by DFT and 2h-1p Configuration Interaction (CI) methods. Strong breakdown of the Koopmans Theorem (KT) is obtained for the four outermost ionizations, which are further investigated by higher level ab initio calculations. The full assignment of the spectrum is put on a firm basis by the combination of experimental and theoretical results. The orbital composition from correlated calculations is found closer to the DFT orbitals, which are then used to analyze the electronic structure of the molecule. The Highest Occupied Molecular Orbital (HOMO) and HOMO--2 are n(O)/n(Cl) mixed orbitals. The nature of each valence MO is generally preserved in all the conformers, although the magnitude of the n(O)/n(Cl) mixing in HOMO and HOMO--2 varies to some extent with the C-C-C-Cl dihedral angle. The low energy part of the HOMO PE band is predicted to be substantially affected by the conformational flexibility, as experimentally observed in the spectra. The rest of the spectrum is described in terms of the dominant conformer g-II, and a good agreement between experiment and theory is found. The inner-valence PE spectrum is characterized by satellite structures, due to electron correlation effects, which are interpreted by means of 2h-1p CI calculations.     

Preparation and characterization of ZnO particles embedded in organic–inorganic planar waveguide by sol–gel route

Hybrid organic–inorganic waveguides based on ZnO-(3-glycidoxypropil)trimethoxisilane (GPTS) have been fabricated by sol–gel route. A transparent sol of ZnO was added to the GPTS host and the resulting sol was deposited on silica substrates by spin coating technique. Waveguides with different molar composition (100?x)GPTS?xZnO (x = 10, 20, 30) were investigated by different diagnostic techniques. Morphological measurements were carried out by means of an AFM apparatus, and a roughness of few nanometers was estimated for all the waveguides. Optical properties such as refractive index, thickness, number of propagating modes and attenuation coefficient were measured at 632.8, 543.5, 1319 and 1542 nm by the prism coupling technique as a function of the ZnO content. Photoluminescence measurements, upon excitation at 325 nm, showed a large luminescence band in the region between 350 and 600 nm with a main peak centered at about 380 nm, due to the presence of ZnO nanoparticles.     

Gas-phase reactions of free phenylium cations with C3H6 hydrocarbons

Free, unsolvated phenylium ions formed by the spontaneous β decay of a constituent atom of multitritiated benzene have been allowed to react with gaseous propene and cyclopropane in the pressure range from 10 to 700 torr. Phenylium ions attack efficiently both the C-H and the C-C bonds of cyclopropane, yielding respectively tritiated cyclopropylbenzene and indane as the major products. Selective attack of phenylium ions on the π bond of propene is suggested by the composition of tritiated products, isomeric phenylpropenes and isopropylbenzene. The different behavior of propene and cyclopropane toward gaseous phenylium ions is consistent with the results of related radiolytic investigations concerning gaseous systems at nearly atmospheric pressure. The reactivity pattern of the isomeric C₃H₆ hydrocarbons toward gaseous phenylium ions is discussed and compared with pertinent mass spectrometric data.     

A multidimensional knapsack model for asset-backed securitization

Securitization is a financial operation which allows a financial institution to transform financial assets, for instance mortgage assets or lease contracts, into marketable securities. We focus the analysis on a real case of a bank for the leasing. Once the securitization characteristics, such as size and times of the operation, have been defined, the profit for the financial institution—Italease Bank for the Leasing in our case—depends on how the financial assets to use in the securitization are selected. We show that the selection problem can be modelled as a multidimensional knapsack problem (MDKP). Some formal arguments suggest that there may exist a prevailing constraint in the MDKP. Such an idea is used in the design of some simple heuristics which turn out to be very effective.