A novel approach to the synthesis of 6-amino-7-hydroxy-flavone

A novel approach to the synthesis of 6-amino-7-hydroxyflavone (1) is described. Reaction in acetone of 2',4'-dihydroxy-5'-nitroacetophenone and benzoyl chloride in the presence of potassium carbonate affords 3-benzoyl-7-hydroxy-6-nitroflavone, which is cleaved in 5% ethanolic potassium hydroxide to give 1-(2,4-dihydroxy-5-nitrophenyl)-3- phenyl-1,3-propanedione. The 1,3-diketone thus formed is then transformed into 7-hydroxy- 6-nitroflavone, followed by reduction to afford the title compound.     

A Class of k-Quantum Nonlinear Coherent States and Some of Their Properties

A class of k-quantum nonlinear coherent states, i.e., the k eigenstates of the powers B ^k (k 3) of the annihilation operator of f-oscillators, is obtained and its completeness is investigated. An alternative method to construct them is proposed. We introduce a new kind of higher-order squeezing and sub-Poissonian distribution. The quantum statistical properties of the k states are studied. The result shows that all of the eigenstates can be generated by a linear superposition of k Roy-type nonlinear coherent states. These states may form a complete Hilbert space, and the M-th order [M = (n + 1/2)k; n = 0,1, ...] squeezing effects exist in all of the k states when k is even. There is the sub-Poissonian distribution in all of the states.     

Highly selective asymmetric hydrogenation using a three hindered quadrant bisphosphine rhodium catalyst

A concise synthesis of both enantiomers of ligand 2 and rhodium complex 5 is presented. The crux of the synthesis is a chiral HPLC separation of the enantiomers of 4. Rhodium complex 5 possesses three hindered quadrants in the steric environment within which a substrate binds. Evidence is presented that this configuration leads to high enantioselectivity (>99% ee) for rhodium-catalyzed asymmetric hydrogenation of alpha-acetamido dehydroamino acids, 6a-e. High enantioselectivities are also reported for the hydrogenation of a substrate precursor, 8, of pharmaceutical candidate, pregabalin. Advantages for large-scale hydrogenation of 8 using catalyst 5a vs Rh-Me-DuPhos are discussed.     

Isospin-dependent relativistic microscopic optical potential in the Dirac Brueckner-Hartree-Fock method

There is growing evidence to suggest that the binding energy of nucleon in nuclear matter comes from a cancellation between large Lorentz scalar and vector potentials[1,2]. The relativistic approach has been of a great success in describing not only the ground state properties of stable nuclei, but also those of exotic nuclei. In the relativistic frame, the spin-orbit coupling can be deduced automatically, which is usually given by hand in the non-relativistic approach. The relativistic method…     

Fabrication of alternating polycation and albumin multilayer coating onto stainless steel by electrostatic layer-by-layer adsorption

Multilayer films consisting of polyethylenimine (PEI) and albumin were successfully prepared on biomedical 316L stainless steel surface via electrostatic self-assembly of the PEI and albumin. The process of electrostatic self-assembly of PEI/albumin was monitored by125I radiolabeling, electrochemical impedance spectroscopy (EIS) and atomic force microscopy (AFM). The EIS data revealed that the multilayer coating was stable in Tris-HCl (pH 7.35) buffer solution for 21 days. 125I radiolabeling experiments indicated that less than 10% albumin was eluted by PBS in 45 days. Static platelet adhesion experiments indicated that the PEI/albumin deposited on stainless steel could resist platelet adhesion effectively. Such an easy processing and shape-independent method may have good potential for surface modification of cardiovascular devices.     

Effect of sodium sulfide on Ni-containing carbon monoxide dehydrogenases

The structure of the active-site C-cluster in CO dehydrogenase from Carboxydothermus hydrogenoformans includes a mu(2)-sulfide ion bridged to the Ni and unique Fe, whereas the same cluster in enzymes from Rhodospirillum rubrum (CODH(Rr)) and Moorella thermoacetica (CODH(Mt)) lack this ion. This difference was investigated by exploring the effects of sodium sulfide on activity and spectral properties. Sulfide partially inhibited the CO oxidation activity of CODH(Rr) and generated a lag prior to steady-state. CODH(Mt) was inhibited similarly but without a lag. Adding sulfide to CODH(Mt) in the C(red1) state caused the g(av) = 1.82 EPR signal to decline and new features to appear, including one with g = 1.95, 1.85 and (1.70 or 1.62). Removing sulfide caused the g(av) = 1.82 signal to reappear and activity to recover. Sulfide did not affect the g(av) = 1.86 signal from the C(red2) state. A model was developed in which sulfide binds reversibly to C(red1), inhibiting catalysis. Reducing this adduct causes sulfide to dissociate, C(red2) to develop, and activity to recover. Using this model, apparent K(I) values are 40 +/- 10 nM for CODH(Rr) and 60 +/- 30 microM for CODH(Mt). Effects of sulfide are analogous to those of other anions, including the substrate hydroxyl group, suggesting that these ions also bridge the Ni and unique Fe. This proposed arrangement raises the possibility that CO binding labilizes the bridging hydroxyl and increases its nucleophilic tendency toward attacking Ni-bound carbonyl.     

Giant extended pi-conjugated dendrimers containing the 10,15-dihydro-5H-diindeno[1,2-a;1',2'-c]fluorene chromophore: synthesis, NMR behaviors, optical properties, and electroluminescence

This paper reports the facile synthetic strategy of a series of novel pi-conjugated dendrimers (G0 and G1) based on 10,15-dihydro-5H-diindeno[1,2-a;1',2'-c]fluorene (truxene) in which the benzene cores are generated "in-situ" from acetyl aromatics by the acid-promoted cyclotrimerizations. The unique NMR behaviors, physical properties, and electroluminescence device applications are also presented. Besides the purity, the structure, and the confirmation of the successful formation and isolation of desired compounds by clear assignments of every molecule by (1)H and (13)C and 2D NMR characterizations, several astonishing NMR behaviors have been observed in various solvents. For 1, chemical shift values belonging to H-2' of hexyl substituents move to the most upfield; however, such chemical shift values move from 0.48 to 0.85 ppm when pyridine-d(5) or benzene-d(6) is used as solvent. Our dendrimers as the emissive layers in organic light-emitting diodes gave blue-green light with an external quantum efficiency up to 0.16% both for G0 and for G1 in nitrogen, respectively, which exhibit unique electroluminescence spectra in comparison with their corresponding photoluminescence ones.     

A new synthesis of lysergic acid

[reaction: see text] (+/-)-Lysergic acid has been synthesized via an economical 8-step route from 4-bromoindole and isocinchomeronic acid without the need to protect the indole during the synthesis. Initial efforts to form the simpler 3-acylindole derivatives first and then cyclize these were unsuccessful in the cyclization step.     

Stereoselective total synthesis of antitumor macrolide (+)-rhizoxin D

[structure: see text] A convergent, stereoselective total synthesis of the macrolide antitumor agent rhizoxin D is described. (+)-DIPCl-promoted asymmetric aldol reaction, Evans-Tishchenko 1,3-diol synthesis, modified Julia coupling, and Horner-Wadsworth-Emmons reactions are featured.     

Kp,q-factorization of complete bipartite graphs

Let K_(m,n) be a complete bipartite graph with two partite sets having m and nvertices, respectively. A K_(p,q)-factorization of K_(m,n) is a set of edge-disjoint K_(p,q)-factorsof K_(m,n) which partition the set of edges of K_(m,n). When p=i and q is a prime number,Wang, in his paper "On K_(1,k)-factorizations of a complete bipartite graph" (Discrete Math,1994, 126; 359-364), investigated the K_(1,q)-factorization of K_(m,n) and gave a sufficientcondition for such a factorization to exist. In the paper "K_(1,k)-factorizations of completebipartite graphs" (Discrete Math, 2002, 259: 301-306), Du and Wang extended Wang'sresult to the case that q is any positive integer In this paper, we give a sufficient conditionfor K_(m,n) to have a K_(p,q)-factorization. As a special case, it is shown that the Martin's BACconjecture is true when p: q=k: (k+1) for any positive integer k.