Flash photolytic generation and study of p-quinone methide in aqueous solution. An estimate of rate and equilibrium constants for heterolysis of the carbon-bromine bond in p-hydroxybenzyl bromide

Flash photolysis of p-hydroxybenzyl acetate in aqueous perchloric acid solution and formic acid, acetic acid, biphosphate ion, and tris(hydroxymethyl)methylammonium ion buffers produced p-quinone methide as a short-lived species that underwent hydration to p-hydroxybenzyl alcohol in hydronium ion catalyzed (k(H(+)) = 5.28 x 10(4) M(-1) s(-1)) and uncatalyzed (k(uc) = 3.33 s(-1)) processes. The inverse nature of the solvent isotope effect on the hydronium ion-catalyzed reaction, k(H(+))/k(D(+)) = 0.41, indicates that this process occurs by rapid and reversible protonation of the quinone methide on its carbonyl carbon atom, followed by rate-determining capture of the p-hydroxybenzyl carbocation so produced by water, while the magnitude of the rate constant on the uncatalyzed process indicates that this reaction occurs by simple nucleophilic addition of water to the methylene group of the quinone methide. p-Quinone methide also underwent hydronium ion-catalyzed and uncatalyzed nucleophilic addition reactions with chloride ion, bromide ion, thiocyanate ion, and thiourea. The solvent isotope effects on the hydronium ion-catalyzed processes again indicate that these reactions occurred by preequilibrium mechanisms involving a p-hydroxybenzyl carbocation intermediate, and assignment of a diffusion-controlled value to the rate constant for reaction of this cation with thiocyanate ion led to K(SH) = 110 M as the acidity constant of oxygen-protonated p-quinone methide. In a certain perchloric acid concentration range, the bromide ion reaction became biphasic, and least-squares analysis of the kinetic data using a double-exponential function provided k(Br(-)) = 3.8 x 10(8) M(-1) s(-1) as the rate constant for nucleophilic capture of the p-hydroxybenzyl carbocation by bromide ion, k(ionz) = 8.5 x 10(2) s(-1) for ionization of the carbon-bromine bond of p-hydroxybenzyl bromide, and K = 4.5 x 10(5) M(-1) as the equilibrium constant for the carbocation-bromide ion combination reaction, all in aqueous solution at 25 degrees C. Comparisons are made of the reactivity of p-quinone methide with p-quinone alpha,alpha-bis(trifluoromethyl)methide as well as p-quinone methide with o-quinone methide.     

A unique reaction pathway of fluorine-substituted ethyl groups on Cu(111): successive alpha,alpha-fluoride elimination

Fluorine-substituted ethyl groups on Cu(111) were generated by thermal scission of the C-I bond in the adsorbed C2F5I. Temperature-programmed reaction spectrometry observed a novel pathway resulting in the evolution of C4F6 above 400 K. Among the various isomers, this product was identified as hexafluro-2-butyne. Although abstraction of two fluorine atoms from the starting Cu-CF2CF3 was required, Cu-CCF3 (trifluoroethylidyne) was favored over Cu-CF=CF2 (trifluorovinyl) as the intermediate because this ethyl-ethylidyne-butyne pathway was suppressed on a Cu(100) surface devoid of the key threefold hollow binding sites for ethylidyne. Once formed, perfluoroethylidyne readily coupled to afford a tightly surface-bound hexafluoro-2-butyne up to 400 K. Therefore, the C-F bonds adjacent to the metal were found to be more susceptible to the bond activation, leading the chemisorbed perfluoroethyl to eliminate two F atoms successively from the alpha-carbon. This preference for alpha-elimination rather than beta-elimination (the most favorable route in hydrocarbons) may be quite general for metal surface-mediated reactions involving fluorinated alkyl groups.     

Synthesis,Antiproliferative, and Antiplatelet Activities of Oxime‐Containing 3,4‐Dihydroquinolin‐2(1H)‐One Derivatives

Some oxime‐containing 3,4‐dihydroquinolin‐2(1H)‐one derivatives were synthesized and evaluated for their antiplatelet and antiproliferative activities. These compounds were synthesized via alkylation of hydroxyl precursors followed by the reaction with NH₂OH. The preliminary assays indicated that (Z)‐7‐[2‐(4‐fluorophenyl)‐2‐(hydroxyimino)ethoxy]‐3,4‐dihydroquinolin‐2(1H)‐one (13c) is the most active against U46619 induced platelet aggregation with an IC₅₀ value of 3.51 μM. For the inhibition of AA‐induced aggregation, (E)‐6‐[2‐(hydroxyimino)propoxy]‐3,4‐dihydroquinolin‐2(1H)‐one (15 ) is the most potent with an IC₅₀ value of 1.85 μM. These oxime‐containing 3,4‐dihydroquinolin‐2(1H)‐one derivatives were inactive against thrombin induced platelet aggregation with an IC₅₀ value of greater than 26.78 μM. For the antiproliferative activity, most of these oxime‐containing 3,4‐dihydroquinolin‐2(1H)‐one derivatives were inactive while (Z)‐7‐[2‐(hydroxyimino)‐2‐(naphthalen‐2‐yl)ethoxy]‐3,4‐dihydroquinolin‐2(1H)‐one (13a) exhibited only marginal activities with GI₅₀ value of 7.63, 7.34 and 6.36 μM against the growth of NPC‐TW01, NCI‐H661, and Jurkat respectively.     

Synthesis and computational oxidation mechanism study of novel organosoluble aramids with high modulus by low‐temperature solution polycondensation

A series of highly organosoluble polyamides with high modulus having propeller‐shaped triarylamine were synthesized using aromatic diacid chlorides by low‐temperature solution polycondensation. The polyamide films had strong, tough, flexible, and amorphous properties. These polymers revealed electrochromic characteristics both in the visible range and near‐infrared (NIR) region, with a color change from pale yellowish at its neutral state to green and blue at its oxidized state at applied potentials ranging from 0.00 to 1.35 V. Cyclic voltammetry (CV) of the polymer films cast onto an indium tin oxide (ITO)‐coated glass substrate exhibited two reversible redox couples at potentials of 0.80–0.87 V and 1.19–1.25 V, respectively, vs. Ag/Ag⁺ in acetonitrile solution. From the combination of the experimental and computational study, we proposed an oxidation mechanism based on molecular orbital (MO) theory, which well explains the CV experimental result. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and structural characterization of two cobalt phosphites: 1-D (H3NC6H4NH3)Co(HPO3)2 and 2-D (NH4)2Co2(HPo3)3

Two new cobalt phosphites, (H₃NC₆H₄NH₃)Co(HPO₃)₂ (1) and (NH₄)₂Co₂(HPO₃)₃ (2), have been synthesized and characterized by single-crystal X-ray diffraction. All the cobalt atoms of 1 are in tetrahedral CoO₄ coordination. The structure of 1 comprises twisted square chains of four-rings, which contain alternating vertex-shared CoO₄ tetrahedra and HPO₃ groups. These chains are interlinked with trans-1,4-diaminocyclohexane cations by hydrogen bonds. The 2-D structure of 2 comprises anionic complex sheets with ammonium cations present between them. An anionic complex sheet contains three-deck phosphite units, which are interconnected by Co₂O₉ to form complex layers. Magnetic susceptibility measurements of 1 and 2 showed that they have a weak antiferromagnetic interaction.     

Anion‐Directed Copper(II) Metallocages,Coordination Chain,and Complex Double Salt: Structures,Magnetic Properties,EPR Spectra,and Density Functional Study

A series of Cu^II metallo‐assemblies showing anion‐directed structural variations, including five metallocages [(G^n?)?{Cu₂(Hdpma)₄}]^(8?n)+(A^?)_8?n (G^n?=NO₃^?, ClO₄^?, SiF₆^2?, BF₄^?, SO₄^2?; A^?=NO₃^?, ClO₄^?, BF₄^?, CH₃SO₄^?; Hdpma=bis(3‐pyridylmethyl)ammonium cation), a complex double salt, namely, (H₃dpma)₄(CuCl₄)₅Cl₂, and a coordination chain, namely, [Cu₂(dpma)(OAc)₄], are reported. The influence of the anion can be explained by its coordinating ability, the affinity of which for the Cu^II center interferes significantly with metallocage formation, and its shape, which offers host–guest recognition ability to engage in weak metal–anion coordination and hydrogen bonding to the organic ligand, which are responsible for metallocage templation. EPR studies of these metallocages in the powder phase at room temperature and 77 K showed a trend of the g values (g_||>2.10>g_⊥>2.00) indicating a ‐based ground state with square‐pyramidal geometry for the Cu^II centers. The magnetism of these metallocages can be interpreted as the result of a combination of relatively small magnetic coupling integrals and a substantial contribution of temperature‐independent paramagnetism (TIP). The weak magnetic interaction is corroborated by the results of DFT calculations and the EPR spectra. Availability of the low‐lying state for spin population was confirmed by a magnetization study, which revealed a magnetic moment approaching 2Nβ, which would explain the presence of the larger TIP term.     

Chlorinated briarane-type diterpenoids from the gorgonian coral Ellisella robusta (Ellisellidae)

Four chlorinated metabolites featuring briarane carbon skeletons have been isolated from the gorgonian coral Ellisella robusta, which was collected off the coast of southern Taiwan: two new natural products, robustolides D (1) and E (2), and two known metabolites, robustolides F (3) and G (4). The structures of metabolites 1–4 were determined by spectroscopic methods, using 1D and 2D NMR in particular. The structures and absolute stereochemistry of robustolides D (1), F (3), and G (4) were directly established by X-ray diffraction analysis. Robustolide D (1) is the first metabolite of briarane-related natural products found to possess two halogen atoms.     

Detection of antinuclear antibodies by a colloidal gold modified optical fiber: comparison with ELISA

A fiberoptic evanescent-wave sensor has been developed for the measurement of antinuclear antibodies in sera from patients and healthy individuals. The sensor was constructed on the basis of modification of the unclad portion of an optical fiber with self-assembled gold colloids, where the colloidal gold surface was further functionalized with extractable nuclear antigens. Results show that detection of antinuclear antibodies by this sensor agrees quantitatively with the clinically accepted enzyme-linked immunosorbent assay (ELISA) method. This sensing platform has the following advantages: label-free and real-time detection capability, simple to construct and use, highly sensitive, and does not require a secondary antibody. The sensitivity of this platform is at least an order of magnitude higher than that of the ELISA method and thus may lead to a new direction in recognition of immune response. Biomolecular binding of antinuclear antibodies (ANA) with extractable nuclear antigens (ENA)-functionalized gold nanoparticles results in a change of surface plasmon absorption. When light propagates in an optical fiber by multiple total internal reflection, such a change in signal can be significantly enhanced.     

Synthesis of 5‐Radioiodoarabinosyl Uridine Analog for Probing the HSV‐1 Thymidine Kinase Gene

Tumor cells transduced with herpes simplex virus thymidine kinase gene have been intensively applied to the field of positron emission tomography via imaging of its substrate. As a pilot synthesis approach, a facile preparation of 5‐[¹²⁵I] iodoarabinosyl uridine starting from commercially available uridine is reported herein.