Langmuir-Blodgett films of a clay mineral and ruthenium(II) complexes with a noncentrosymmetric structure

Mono- and multilayers of amphiphilic [Ru(phen)(2)(dcC12bpy)](2+) (phen = 1,10-phenanthroline, dcC12bpy = 4,4'-caboxyl-2,2'-bipyridyl didodecyl ester) hybridized with a clay mineral have been prepared by a modified Langmuir-Blodgett method, and their structures and properties have been investigated. Formation of a hybrid monolayer of the Ru(II) complex cations and the clay platelets at an air-clay suspension interface was confirmed by surface pressure-molecular area (pi-A) isotherm measurement and atomic force microscopic (AFM) observation. Multilayers were fabricated by depositing the hybrid monolayers onto glass substrates. The absorbance at 492 nm due to the Ru(II) complex cation in the multilayer increased linearly with the increase in the layer number, indicating layer-by-layer deposition of the hybrid monolayers. Because no increase in the second-harmonic generation (SHG) signal from the multilayers against the layer number was observed, the orientation of the Ru(II) complex cations in the layer would be disturbed. The hydrophilic surface of the transferred hybrid monolayer can be converted to a hydrophobic surface by dipping it in an aqueous solution of octadecylammonium chloride (ODAH(+)Cl(-)). The multilayers modified with ODAH(+) showed a quadratic relation between the SHG intensity and the layer number. This means that the Ru(II) complex cations in the multilayer are successfully oriented in a noncentrosymmetric way by the conversion of the surface property. Both a racemic mixture and an enantiomer of the Ru(II) complex cations were employed to examine the chiral effect on the film properties. The chiral contribution to the SHG signal was enhanced in the multilayer modified with ODAH(+).     

Fabrication of high performance thin films from metal fluorocomplex aqueous solution by the liquid phase deposition

The hetro-structured oxide thin films from metal fluorocomplex solution have been prepared by the liquid phase deposition (LPD) method. The Pt/Nb₂O₅ and Au/Nb₂O₅ composite films can be prepared from a mixed solution of niobium source, H₃BO₃, Pt(NH₃)₄Cl₂ and HAuCl₄ aqueous solutions under the ambient temperature and atmosphere. In the case of Au/SiO₂ composite film, (NH₄)₂SiF₆ solution is used as a mother solution. The Pt and Au ionic species are deposited in Nb₂O₅ and SiO₂ matrices. They are reduced to their metallic state after treatment above 200 °C. The size of dispersed particles can be controlled by heat treatment temperature. It is also clear that, gold nanoparticles are also found to interact with SiO₂, although the interaction is smaller than that with Nb₂O₅ showing the size of Au nanoparticles remain smaller in Nb₂O₅ that in SiO₂.     

Negative ion mass spectra of chlorine-containing molecules

The negative ion mass spectra of chlorine-containing molecules have been measured using a double focusing mass spectrometer with a photographic plate detector. The formulae of the negative ions not previously assigned using an electron multiplier detector have now been assigned.     

Novel method to control release of lipophilic drugs with high potency from silicone

Silicone has been utilized as a carrier material for sustained release system of lipophilic drugs. Extensive studies revealed that drug release rate is influenced by factors such as physicochemical properties of the drug and additives.(1-5)) When a lipophilic drug is highly potent at low concentrations, the drug release rate should be strictly controlled so as to avoid side effects. In this study, using vitamin D(3) (VD(3)) as an example of such drugs, we investigated novel method to suppress initial burst and to modify drug release rate from silicone matrix. As a result, it was found that (a). addition of human serum albumin (HSA) suppressed initial burst and enhanced release rate in the later stage, resulting constant release of VD(3), (b). covering a matrix formulation with a membrane of low diffusivity (core-rod formulation) suppressed initial burst and released drug in a constant rate, and (3) using materials for which the drug has high affinity as dissolution solvent (reservoir formulation), the drug release rate was reduced.     

Metal-dependent regioselective oxidative coupling of 5,10,15-triarylporphyrins with DDQ-Sc(OTf)3 and formation of an oxo-quinoidal porphyrin

[reaction: see text] Regioselectivity of the oxidative coupling of 5,10,15-triarylporphyrin metal complexes with DDQ-Sc(OTf)(3) was dependent on the central metal and meso-aryl substituent. Oxo-quinoidal porphyrin was obtained from Ni(II) porphyrin under the same conditions.     

Stereocontrolled approaches to 9(0)-methanoprostacyclin

A stable PGI₂ analog (methanoprostacyclin $\text{2}$) was synthesized starting from 5-norbornene-2,3-dicarboxylic anhydride.     

Molecule-Responsive Fluorescent Sensors of α-Helix Peptides Bearing α-Cyclodextrin, Pyrene and Nitrobenzene Units in Their Side Chains

-Helix peptides bearing one unit of -cyclodextrin (-CD), one unit of pyrene and one unit of nitrobenzene (NB) in their side chains have been designed and synthesized as novel molecule-responsive devices.In both the CD-peptides, -PR17 and -PL17, the NB unit is separated from the CD unit by two turns of the helix. Two reference peptides (PL17, and -P17,) have also been synthesized. The circular dichroism studies in the peptide absorption region (200–250 nm)of -PR17 and -PL17 suggestthat the CD-peptides form stable-helixstructures (83–77%), which was destabilized by accommodating guest molecules (e.g., n-pentanol) into the CD cavity. It suggests that formation of intramolecular host–guest(CD–NB) complex stabilized thehelical structure and exogenous guest molecule excluded the appending NB moiety from inside to outside of the CD cavity, thereby causing destabilization of the helical structure and increasing the random coil content. The ICD spectra of the peptides in the pyrene and nitrobenzene absorption region (250–40 nm) suggest that NB forms inclusion complex with CD. The fluorescence studies revealed that the fluorescence of the pyrene unit is quenched by the NB unit in -PR17 and -PL17. The fluorescence intensity increases with increasing guest concentration for the CD-peptides.This guest-responsiveenhancement in the fluorescence intensity can be explained in terms of increased distance between the pyrene and NB moieties, which is caused by exclusion of the NB moiety from the CD cavity by guest accommodation. Using the guest-responsive fluorescence quenching properties of the CD-peptides, we have obtained binding constants for various short chain alkanols. -PL17 has higher binding affinity to the guest molecules than its isomer, -PR17, indicating that the location of functional groups on the peptide scaffold is important in molecule detection.     

The microenvironment in polymer solids with added plasticizers. An attempt to measure the size and distribution of free volume in poly(methyl methacrylate) solids

Various amounts of n-alkylbenzenes (C_n: C₆H₅-C_nH_2n+1 (n = 3-16)) were doped into poly(methyl methacrylate) (PMMA) films, and the emission and thermal properties of each film were measured in detail together with their solid-state ¹³C NMR spectra. The aim of the present work was to estimate the size distribution of free volume in amorphous regions of polymer solids heavily doped with plasticizers by using C_n as models of a plasticizer. The excimer fluorescence yields of C_n in PMMA were found to depend on both the amount of C_n and the length of the alkyl chains of C_n, although the fluorescence spectra of all of the C_ns in dilute fluid solution were almost the same. The quantitative analysis showed: (1) C_n with n ? 12 induces a phase separation in PMMA, in which almost all of the C_n molecules are in a separated phase, and thus they cannot penetrate regions in which PMMA chains are aggregated. This means that C_n with n ? 12 cannot enlarge the space between PMMA chains. (2) Smaller C_n (n < 11) can enter free volumes between PMMA chains that correspond to their molecular size, but they can enlarge them only to a limited extent. Thus, the amount by which plasticization can increase the free volume of PMMA is limited by the size of the dopant and the inherent free volume of the polymer matrix. (3) The efficiency of excimer formation was found to reveal the maximum amount of C_n that could fit in the free volume of PMMA. Thus our fluorescence measurements showed that PMMA solids that were plasticized to their limit had a free volume that was larger than the volume occupied by all the conformers of C₅ and smaller than the volume occupied by almost all the conformers of C₁₂. In conclusion, we were able to obtain information on plasticization and to demonstrate a method of monitoring microenvironments in polymer solids after they have been doped with plasticizers.     

Total Synthesis of Natural PI-091, a New Platelet Aggregation Inhibitor of Microbial Origin

The total synthesis of a new platelet aggregation-inhibiting gamma-lactam PI-091 (1) gave a 1:1 diastereomeric mixture at the gamma-ketal carbon. The high-yielding aldol reaction of an appropriately protected 1,3,4-trihydroxy-4-methyldecan-2-one 42, prepared from D-glucose, with the kinetically generated enolate of 3-methyl-2-butanone provided 43. The resulting diastereomeric mixture of the aldol adduct 43 was converted to a 2,4-alkylated furan 45 via an intramolecular ketalization followed by dehydration. The addition of a singlet oxygen to the alpha-trimethylsilylated furan 48derived from 45 under photochemical conditions efficiently provided an alpha,gamma-dialkylated gamma-hydroxy gamma-lactone 47. The transformation of methyl ketal 52 prepared from 47 into gamma-hydroxy gamma-lactam 53 was achieved by exposure to liquid ammonia in MeOH. The total synthesis of 1 was achieved from 52 through the Dess-Martin periodinane oxidation of the secondary hydroxy group in the side chain. The present total synthesis revealed that the stereogenic carbon center in the side chain in natural 1 is S.     

Pi-face-selective Diels-Alder reactions of 3,4-di-tert-butylthiophene 1-oxide and 1-imide and formation of 1,2-thiazetidines

3,4-Di-tert-butylthiophene 1-oxide (1a) reacted with a series of electron-deficient alkenic dienophiles at its syn-pi-face relating to the S=O bond to give [4+2] adducts in excellent yields. The 1-oxide 1a also reacted even with angle-strained dienophiles acenaphthylene and norbornene at its syn-pi-face to afford [4+2] adducts; in the latter case, norbornene reacted exclusively at its exo-pi-face. The oxide 1a reacted with dimethyl acetylenedicarboxylate to produce dimethyl 4,5-di-tert-butylphthalate in high yield with spontaneous extrusion of SO from the initial adduct even at room temperature. Similarly, 3,4-di-tert-butylthiophene 1-(p-toluenesulfonyl)imide (3a) reacted with alkenic dienophiles at its syn-pi-face relating to the S=N bond to give [4+2] adducts in good yields. The reaction of 3a with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) afforded a 1,2-thiazetidine 12a, the first example of S-unoxidized 1,2-thiazetidine, in good yield, through rearrangement of the initial [4+2] adduct. The molecular structure of 12a is discussed on the basis of the X-ray crystallographic analysis. Comparison of the foregoing reactions leads to the conclusion that the 1-oxide 1a is more reactive as a diene than the 1-imide 3a, which is more reactive than 3,4-di-tert-butylthiophene 1,1-dioxide. The origin of the syn-pi-face selectivities of 1a and 3a in Diels-Alder reactions is discussed in terms of the orbital mixing rule and steric effect and also based on B3LYP/6-31G(d) calculations.