Polarized near-edge x-ray-absorption fine structure spectroscopy of C60-functionalized 11-amino-1-undecane thiol self-assembled monolayer: molecular orientation and evidence for C60 aggregation

Near-edge x-ray-absorption fine structure (NEXAFS) spectroscopy was adopted to probe the unoccupied electronic states of C60 anchored onto an organized assembly of 11-amino-1-undecane thiol on Au(111). The polarization dependence of the intensity of pi* resonance associated with C60 pi network revealed the self-assembled monolayer (SAM) system to be oriented with an average molecular tilt angle of 57 degrees with respect to the surface normal. Invoking the absence of solid-state band dispersion effects and in comparison to solid C60 and /or 1-ML C60/Au(111), the electronic structure of the resulting assembly was found dominated by spectral position shift and linewidth and intensity changes of the lowest unoccupied molecular orbital (LUMO), LUMO+1, and LUMO+2 orbitals. The latter implied hybridization between N Pz of -NH2 group of thiolate SAM and pi levels of C60, resulting in a nucleophilic addition with a change in the symmetry of C60 from Ih to C1 in the SAM. Occurrence of a new feature at 285.3 eV in the NEXAFS spectrum, assigned previously to pi* graphitic LUMO, signified the formation of aggregated clusters, (C60)n of C60 monomer. Low tunneling current scanning tunneling microscopy confirmed them to be spherical and stable aggregates with n approximately 5.     

Silver nanoparticles dispersed within amphiphilic star-block copolymers as templates for plasmon band materials

Formation of silver nanoparticles has been developed based on a template technique. Amphiphilic star-block copolymers employed as single molecule template, utilizing the coordination of Ag⁺ ions with carboxyl groups in the core of the star-block copolymer. Silver nanoparticles have been prepared by the addition of chemical reductant, e.g., NaBH₄. The solution of the resultant nanosphere composites showed yellow due to the surface plasmon resonance. These composites were soluble in organic solvents, because hydrophobic corona of the star-block copolymer protected the fabricated silver nanoparticles from aggregation.     

Second-derivative spectrophotometric study on the interactions of chlorpromazine and triflupromazine with bovine serum albumin

The second-derivative spectra of chlorpromazine (CPZ) or triflupromazine (TFZ) in buffer solutions (pH 7.4) containing various amounts of BSA (the reference solutions contained the same amount of BSA) showed derivative isosbestic points. The residual background signals derived from incomplete suppression of BSA signals can be entirely eliminated in the second-derivative spectra and BSA has spectrophotometrically one kind of binding site for CPZ or TFZ. The fractions of the drugs bound to BSA were calculated from the derivative intensity differences (ΔD values) of CPZ or TFZ before and after the addition of BSA. Scatchard plot experiments suggested that the binding of the drugs to BSA could be explained as a partition like non-specific binding model. The association constants (K) of CPZ or TFZ with BSA were calculated from the ΔD values according to the non-specific binding model by a nonlinear least-squares method. The K values were almost constant for all of the drug concentrations studied, and good reproducibility was obtained. The fractions predicted by the K values were in good coincidence to the observed values. These results confirm the usefulness of the proposed derivative method which does not need any separation procedures.     

Orientation control of perovskite thin films on glass substrates by the application of a seed layer prepared from oxide nanosheets

Orientation control of perovskite compounds was investigated by the application of a seed layer prepared from oxide nanosheets. An aqueous suspension of oxide nanosheets was prepared by the exfoliation of a layered compound of KCa₂Nb₃O₁₀ oxide grains. A seed layer composed of (TBA)Ca₂Nb₃O₁₀ nanosheets (TBA = tetrabutylammonium) was formed on a glass substrate by simply dip coating it in the suspension. Two kinds of perovskite compounds, LaNiO₃ (LNO) and Pb(Zr,Ti)O₃ (PZT) with a preferred orientation of (00l) were successfully grown on this seeded glass substrate. In this study, the relation between lattice mismatch and electrical properties is investigated. A large, oriented PZT film with a size of 5 ×4 cm shows an improved P-E hysteresis behavior by use of this orientation control.     

Palladium catalyzed synthesis of tertiary allylamines. Utilization of α-nitro olefins as allylic nitro compounds

Reaction of α-nitro olefins with secondary amines in the presence of palladium(O) catalyst affords allylic amines.     

Thermal degradation of poly[(tetramethyl-p-silphenylene) siloxane]

For the purpose of studying the mechanism of thermal degradation of poly[(tetramethyl-p-silphenylene) Siloxane] (poly TMPS) a series of polymers with silphenylene and siloxane bonds in the main chain were prepared and subjected to thermogravimetry (TG) and pyrolysis study. Analyses of products from poly TMPS degradation (in vacuum at a constant temperature) by gas chromatography (GC), infrared (IR), nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry (GC–MS) revealed that degradation occurs at the silphenylene bonds. The TG curves obtained in He for heating rates of 1,2,2.5,7.5, and 10°C/min were analyzed by the Ozawa method; activation energies of 39 ± 1 and 45 ± 2 kcal/mol were obtained respectively for the initial cleavage of the methyl side group and the later-stage scission of the main-chain silphenylene bond which leads to a major weight loss. The results agree with those obtained for other structurally similar polymers.     

Structure changes on polymer blends by means of phase growth on microheterophase surface

We have studied the structural changes on poly(2-hydroxyethyl methacrylate) (PHEMA)/polystyrene (PS) blends by means of phase growth of microheterophase pattern on a template surface composed of poly[2-hydroxyethyl methacrylate (HEMA)-g-styrene (S)] graft copolymer (lamellar shape). The PS macromonomer was synthesized by free radical polymerization of S monomer initiated by a functional initiator [2,2'-azobis(2-(2-imidazolin-2-yl)propane: VA-061] in the presence of a degradative chain transfer agent, followed by an end-capping reaction with p-chloromethylstyrene (CMS). Poly(HEMA-g-S) graft copolymers were prepared by free radical copolymerization of these vinylbenzyl-terminated PS macromonomers with HEMA comonomer.     

EFFECTS OF N-PHENYLIMIDE S-23142 AND N-METHYL MESOPORPHYRIN IX ON THE SYNTHESIS OF THE PHYTOCHROME CHROMOPHORE IN PEA EMBRYONIC AXES

Abstract Treatment of imbibed embryonic axes taken from seeds of Pisum sativum with N-phenylimide S-23142, a herbicide that has been suggested to inhibit protoporphyrin synthesis, or with N -methyl mesoporphyrin IX, an inhibitor of the iron chelatase for heme, resulted in a significant decrease in the amount of spectrophotometrically detectable phytochromc in the axes in both cases. However, the amount of immunochemically detectable phytochrome was not affected by either treatment. If S-23142 inhibits the synthesis of protoporphyrin IX in pea, it appears that the conversion of protoporphyrinogen IX to protoporphyrin IX is involved in the biosynthesis of the phytochrome chromophore. The conversion of protoporphyrin IX to heme (Fe-protoporpbyrin) also appears to be a step in the biosynthesis of the chromophore, since N -methyl mesoporphyrin IX prevented the synthesis of spectrophotometrically detectable phytochrome but did not affect the magnesium chelatase activity required for the synthesis of chlorophyll in pea embryonic axes. The results suggest that protoporphyrinogen IX, protoporphyrin IX and heme are intermediates in the biogenesis of the phytochromc chromophore. The pathway to phytochromobilin might become fixed after protoporphyrin IX, being directed toward the Fe branch for heme rather than to the Mg branch for chlorophyll.