Synthesis and Evaluation of α-Methylidene-γ-butyrolactone bearing flavone and xanthone moieties

In a search for inhibitors of platelet aggregation, a number of α-methylidene-γ-butyrolactones 5 and 6 bearing flavone or xanthone moieties, respectively, were synthesized and evaluated for their antiplatelet activity against thrombin(Thr)-, arachidonic-acid(AA)-, collagen(Col)?, and platelet-activating-factor(PAF)-induced aggregation in washed rabbit platelets. These compounds were synthesized from 7-hydroxyflavone ( 1 ) or 3-hydroxyxanthone ( 2 ) via O-alkylation (→ 3 and 4 , resp.) and Reformatsky-type condensation (Scheme). Most of the flavone-containing α-methylidene-γ-butyrolactones 5a – d showed potent antiplatelet effects on AA- and Col-induced aggregation, while xanthone derivatives 6c – e were found to have the same pharmacological profile than aspirin in which only AA-induced aggregation was inhibited (Table 1). However, 6c – e were approximately three to ten times more potent than aspirin (Table 2). For the vasorelaxing effects, 5a was the only compound which exhibited significant inhibitory activity on the high-K⁺ medium, Ca²⁺-induced vasoconstriction (Table3). Both 5a and 6a , with an aliphatic Me substituent at C(γ) of the lactone, were active against norepinephrine-induced phasic and tonic constrictions while their γ-aryl-substituted counterparts 5b – f and 6b – f were inactive.     

Synthesis and Evaluation of 2-{[(2-Oxo-1H-quinolin-8-yl)oxy]methyl}-Substituted α-Methylidene-γ-butyrolactones

O-Alkylation of 8-hydroxy-1H-quinolin-2-one ( 1 ) afforded 8-(2-oxopropoxy)-1H-quinolin-2-one ( 2 ) which was immediately cyclized to form the tricyclic 2,3-dihydro-3-hydroxy-3-methyl-5H-pyrido[1,2,3-de][1,4]benzoxazine,-5-one ( 3). The Reformatsky-type condensation of 3 furnished antiplatelet 8-[(2,3,4,5-tetrahydro-2-methyl-4-methylidene-5-oxofuran-2-yl)melhoxy]-1H-quinolin-2-one ( 4 ). Its counterparts 7a – f , Ph-substituted at C(2) of the furan ring, were obtained from 1 via alkylation and the Reformatsky-type condensation. Although compound 4 was less active against platelet aggregation than 7a – f , it was the only compound which exhibited significant inhibitory activity on high-K⁺ medium, Ca²⁺-induced vasoconstriction and was more active than most of its Ph-substituted counterparts against norepinephrine-induced vasoconstrictions.     

Three New Cadinene Derivatives from Xenia Puerto‐Galerae

Chromatographic investigation of an acetone extract of the octocoral Xenia puerto‐galerae afforded three new cadinene sesquiterpenes; 8‐epi‐xenitorin A ( 1 ), 10‐epi‐xenitorin C ( 2 ), and 7‐isopropenyl‐4,10‐dimethyl‐2,3,4,5‐tetrahydronaphthalene ( 3 ), in addition to four known cadinene analogs ( 4 , 11–13 ) and six xenicanes ( 5–10 ). The structures were elucidated through spectroscopic analysis, especially 2D NMR. A biogenetic pathway of 1–3 and analogs was proposed.     

Positive exchange bias in a Ni80Fe20/NixFe1−xO thin-film bilayer

We have measured positive exchange bias in a Ni₈₀Fe₂₀/Ni_xFe_1−xO thin-film nanocrystallite system. A series of solid solution Ni_xFe_1−xO 40 nm thick films capped with 25 nm thick Ni₈₀Fe₂₀ were deposited using a range of %O₂/Ar bombardment energies (i.e. End-Hall voltages). Proper tuning of the deposition conditions results in a Ni₈₀Fe₂₀/Ni_xFe_1−xO (30%O₂/Ar) based bilayer that exhibits a positive exchange bias loop shift of H_ex∼60 Oe at 150 K.     

Variation of molecular stacking with different length of alkyl chain: synthesis, structure determination, and mesogenic study of N,N-disubstituted aminophenylazo-(4)-p-alkylbenzenes

To help understand the influence of polarity and length of the terminal alkyl chain of a molecule on the molecular stacking of a liquid crystal and on its mesogenic behaviour, four new aminophenylazo-(4)-p-alkylbenzenes were prepared and one of them was further studied by single crystal structure determination. The molecular stacking based on this crystallographic data was established, and compared with that of two previously reported homologues. The mesogenic behaviour of this series of compounds was also investigated.     

Using fuzzy integral for evaluating subjectively perceived travel costs in a traffic assignment model

A good traffic assignment model can be a powerful tool to describe the characteristics of traffic behavior in a road network. The traffic assignment results often play an important role in transportation planning, e.g., an optimal and economical network design. Many traditional traffic assignment models rely heavily on the travel cost function established by Wardrop’s principles; however, the Wardrop’s travel cost function has been proven to be weak for explaining the uncertainty and interactivity of traffic among links. This study tries to construct a traffic assignment model that is different from Wardrop’s in many aspects. First, it considers the cross-effect among the links. Second, a fuzzy travel cost function is established based on the possibility concept instead of precise calculation of traffic volumes. Third, the techniques of fuzzy measure and fuzzy integral are applied to calculate the subjectively perceived travel costs during traffic assignment. Furthermore, in order to validate our model, a detailed network with 22 nodes and 36 links is used to illustrate it. Study results show that our model explains more interactivity and uncertainty of traffic among links when compared with the traditional model of Wardrop’s.     

Mass-analyzed threshold ionization spectroscopy of deuterium-substituted isotopomers of o-fluoroaniline and m-fluoroaniline cations

We applied the resonant two-photon ionization and mass-analyzed threshold ionization techniques to record the vibronic and cation spectra of deuterium-substituted isotopomers of o-fluoroaniline (OFA) and m-fluoroaniline (MFA). The origins of the S₁ ← S₀ electronic transitions and adiabatic ionization energies of these isotopomers were precisely determined.     

Wind identification along a flight trajectory,part 3: 2D-dynamic approach

This paper deals with the identification of the wind profile along a flight trajectory by means of a two-dimensional dynamic approach. In this approach, the wind velocity components are computed as the difference between the inertial velocity components and the airspeed components. The airspeed profile as well as the nominal thrust, drag, and lift profiles are obtained from the available DFDR measurements. The actual values of the thrust, drag, and lift are assumed to be proportional to the respective nominal values via multiplicative parameters, called the thrust, drag, and lift factors. The thrust, drag, and lift factors plus the inertial velocity components at impact are determined by matching the flight trajectory computed from DFDR data with the flight trajectory available from ATCR data. This leads to a least-square problem which is solved analytically under the additional requirement of closeness of the multiplicative factors to unity. Application of the 2D-dynamic approach to the case of Flight Delta 191 shows that, with reference to the last 180 sec before impact, the values of the multiplicative factors were 1.09, 0.84, and 0.89; this implies that the actual values of the thrust, drag, and lift were 9% above, 16% below, and 11% below their respective nominal values. For the last 60 sec before impact, the aircraft was subject to severe windshear, characterized by a horizontal wind velocity difference of 123 fps and a vertical wind velocity difference of 80 fps. The 2D-dynamic approach is applicable to the analysis of windshear accidents in take-off or landing, especially for the case of older-generation, shorter-range aircraft which do not carry the extensive instrumentation of newer-generation, longer-range aircraft. The same methodology can be extended to the investigation of aircraft accidents originating from causes other than windshear (e.g., icing, incorrect flap position, engine malfunction), above all if its precision is further increased by combining the 2D-dynamic approach and the 2D-kinematic approach.     

Photostability of amino acids: internal conversion versus dissociation

Photodissociation dynamics for various tryptophan chromophores was studied at 193 or 248 nm using multimass ion imaging techniques. The competition between internal conversion to the ground electronic state and dissociation from the repulsive excited state reveals size-dependent photostability for these amino acid chromophores. As the size of chromophore increases, internal conversion to the ground state becomes the major nonradiative process. For tryptophan and larger chromophores, dissociation directly from the repulsive state is completely quenched.     

Computational study of reaction pathways for the formation of indium nitride from trimethylindium with HN3: comparison of the reaction with NH3 and that on TiO2 rutile (110) surface

The reactions of trimethylindium (TMIn) with HN3 and NH3 are relevant to the chemical vapor deposition of indium nitride thin film. The mechanisms and energetics of these reactions in the gas phase have been investigated by density functional theory and ab initio calculations using the CCSD(T)/Lanl2dz//B3LYP/Lanl2dz and CCSD(T)/Lanl2dz//MP2/Lanl2dz methods. The results of both methods are in good agreement for the optimized geometries and relative energies. These results suggest that the reaction with HN3 forms a new stable product, dimethylindiumnitride, CH3-In=N-CH3 via another stable In(CH3)2N3 (dimethylindium azide, DMInA) intermediate. DMInA may undergo unimolecular decomposition to form CH3InNCH3 by two main possible pathways: (1) a stepwise decomposition process through N2 elimination followed by CH3 migration from In to the remaining N atom and (2) a concerted process involving the concurrent CH3 migration and N2 elimination directly giving N2+CH3InNCH3. The reaction of TMIn with NH3 forms a most stable product DMInNH2 following the initial association and CH4-elimination reaction. The required energy barrier for the elimination of the second CH4 molecule from DMInNH2 is 74.2 kcal/mol. Using these reactions, we predict the heats of formation at 0 K for all the products and finally for InN which is 123+/-1 kcal/mol predicted by the two methods. The gas-phase reaction of HN3 with TMIn is compared with that occurring on rutile TiO2 (110). The most noticeable difference is the high endothermicity of the gas-phase reaction for InN production (53 kcal/mol) and the contrasting large exothermicity (195 kcal/mol) released by the low-barrier Langmuir-Hinshelwood type processes following the adsorption of TMIn and HN3 on the surface producing a horizontally adsorbed InN(a), Ti-NIn-O(a), and other products, CH4(g)+N2(g)+2CH3O(a) [J. Phys. Chem. B 2006, 110, 2263].