Theoretical study on the mechanism for the excited-state double proton transfer process of an asymmetric Schiff base ligand

Excited-state double proton transfer (ESDPT) in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol (HYDRAVH₂) ligand was studied by the density functional theory and time-dependent density functional theory method. The analysis of frontier molecular orbitals, infrared spectra, and non-covalent interactions have cross-validated that the asymmetric structure has an influence on the proton transfer, which makes the proton transfer ability of the two hydrogen protons different. The potential energy surfaces in both S₀ and S₁ states were scanned with varying O-H bond lengths. The results of potential energy surface analysis adequately proved that the HYDRAVH₂ can undergo the ESDPT process in the S₁ state and the double proton transfer process is a stepwise proton transfer mechanism. Our work can pave the way towards the design and synthesis of new molecules.     

NEW WAVELET BASES FOR NON－HOMOGENEOUS SYMBOLIC SPACE OpS1,1^m AND RELATED KERNEL－DISTRIBUTION SPACES

This paper constructs several classes of new wavelet bases, which are unconditional bases for related operator spaces. Using these bases, the author analyzes non-homogeneous symbolic space OpSm1,1 and two related kernel-distribution spaces, and characterizes them in two wavelet coefficients spaces. Besides, some properties for singular integral operators are studied.     

Numerical approximation of generalized Newtonian fluids using Powell–Sabin–Heindl elements: I. theoretical estimates

In this paper we consider the numerical approximation of steady and unsteady generalized Newtonian fluid flows using divergence free finite elements generated by the Powell–Sabin–Heindl elements. We derive a priori and a posteriori finite element error estimates and prove convergence of the method of successive approximations for the steady flow case. A priori error estimates of unsteady flows are also considered. These results provide a theoretical foundation and supporting numerical studies are to be provided in Part II. Copyright © 2003 John Wiley & Sons, Ltd.     

A constructive characterization of the split closure of a mixed integer linear program

Two independent proofs of the polyhedrality of the split closure of mixed integer linear program have been previously presented. Unfortunately neither of these proofs is constructive. In this paper, we present a constructive version of this proof. We also show that split cuts dominate a family of inequalities introduced by Köppe and Weismantel.     

Chemical reactivity of hypervalent silicon compounds: The local hard and soft acids and bases principle viewpoint

The silicon atom may increase its coordination number to values greater than four, to form pentacoordinated compounds. It has been observed experimentally that, in general, pentacoordinated compounds show greater reactivity than tetracoordinated compounds. In this work, density functional theory is used to calculate the global softness and the condensed softness of the silicon atom for SiH _n F_4−n and SiH _n F _5−n ¹⁻ . The values obtained show that the global and condensed softness are greater in the pentacoordinated compounds than in the tetracoordinated compounds, a result that explains the enhanced reactivity. If the results are analysed through a local version of the hard and soft acids and bases principle, it is possible to suggest that in nucleophilic substitution reactions, soft nucleophiles preferably react with SiH _n F _5−n ¹⁻ , and hard nucleophiles with SiH _n F_4−n .     

Catalytic Hydrosilylation of Furan, Thiophene, and Pyridine Aldimines

The addition of hydrosilanes (HSiEt₃, HSiMe₂Ph, H₂SiPh₂) to the CH=N bond of heterocyclic azomethines has been studied in the presence of monovalent complexes of rhodium and palladium. The effect on the reaction of the CF₃ group of the aldimines, which were obtained from O-, S-, and N-heteroaromatic aldehydes and 2-trifluoromethylaniline, has been clarified, as were other regularities of the processes being studied. A series of corresponding furans, thiophenes, and pyridine amines has been synthesized.     

Pseudoaffinity, de Boor algorithm, and blossoms

In order to ensure existence of a de Boor algorithm (hence of a B-spline basis) in a given spline space with (n+1)-dimensional sections, it is important to be able to generate each spline by restriction to the diagonal of a symmetric function of n variables supposed to be pseudoaffine w.r. to each variable. We proved that a way to obtain these three properties (symmetry, n-pseudoaffinity, diagonal property) is to suppose the existence of blossoms on the set of admissible n-tuples, given that blossoms are defined in a geometric way by means of intersections of osculating flats. In the present paper, we examine the converse: do symmetry, n-pseudoaffinity, and diagonal property imply existence of blossoms?     

On the local structure of doubly laced crystals

Let g be a Lie algebra all of whose regular subalgebras of rank 2 are type A₁×A₁, A₂, or C₂, and let B be a crystal graph corresponding to a representation of g. We explicitly describe the local structure of B, confirming a conjecture of Stembridge.     

Overloaded elution band profiles of ionizable compounds in reversed‐phase liquid chromatography: Influence of the competition between the neutral and the ionic species

The parameters that affect the shape of the band profiles of acido‐basic compounds under moderately overloaded conditions (sample size less than 500 nmol for a conventional column) in RPLC are discussed. Only analytes that have a single pK_a are considered. In the buffer mobile phase used for their elution, their dissociation may, under certain conditions, cause a significant pH perturbation during the passage of the band. Two consecutive injections (3.3 and 10 μL) of each one of three sample solutions (0.5, 5, and 50 mM) of ten compounds were injected on five C₁₈‐bonded packing materials, including the 5 μm Xterra‐C₁₈ (121 Å), 5 μm Gemini‐C₁₈ (110 Å), 5 μm Luna‐C₁₈(2) (93 Å), 3.5 μm Extend‐C₁₈ (80 Å), and 2.7 μm Halo‐C₁₈ (90 Å). The mobile phase was an aqueous solution of methanol buffered at a constant _W^WpH of 6, with a phosphate buffer. The total concentration of the phosphate groups was constant at 50 mM. The methanol concentration was adjusted to keep all the retention factors between 1 and 10. The compounds injected were phenol, caffeine, 3‐phenyl 1‐propanol, 2‐phenyl butyric acid, amphetamine, aniline, benzylamine, p‐toluidine, procainamidium chloride, and propranololium chloride. Depending on the relative values of the analyte pK_a and the buffer solution pH, these analytes elute as the neutral, the cationic, or the anionic species. The influence of structural parameters such as the charge, the size, and the hydrophobicity of the analytes on the shape of its overloaded band profile is discussed. Simple but general rules predict these shapes. An original adsorption model is proposed that accounts for the unusual peak shapes observed when the analyte is partially dissociated in the buffer solution during its elution.