Angular polycyclic thiophenes containing two thiophene rings. Part II

The syntheses of naphtho[1,2–6:7,6-b′]bisbenzo[b]thiophene ( 4 ), naphtho[1,2–6:7,8-b′]bisbenzo[b]thiophene ( 5 ), naphtho[2,1-b:7,6-b′]bisbenzo[b]thiophene ( 8 ), naphtho[2,1-b:7,8-b′]bisbenzo[b]thiophene ( 9 ), naphtho-[1,2–6:5,6-b′]bisbenzo[b]thiophene ( 14 ), naphtho[1,2–6:6,5-b]bisbenzo[b]thiophene ( 17 ) and naphtho[2,1–6:-6,5-b′]bisbenzo[b]thiophene ( 23 ) are reported.     

Mechanism of charge–transfer polymerization. II. Propagation mechanism of the polymerization of N-vinylcarbazole with organic electron acceptors

Copolymerizations of N-vinylcarbazole with both isobutyl vinyl ether and N-vinyl-pyrrolidone initiated by some organic electron acceptors have been investigated for the purpose of elucidating the propagation mechanism in the charge-transfer polymerization. Copolymerizations of the same system catalyzed by authentic cationic catalysts have also been made for comparison. The results indicate that the propagation mechanism of the charge-transfer polymerization studied is catio ie.     

Probing the electronic structures of ternary perovskite and pyrochlore oxides containing Sn(4+) or Sb(5+)

Experimental and computational studies were performed to understand the electronic structure of ternary perovskites (ASnO(3), A = Ca, Sr, Ba, Cd), pyrochlores (RE(2)Sn(2)O(7), RE = Y, La, Lu; Cd(2)Sb(2)O(7)), and defect pyrochlore oxides (Ag(2)Sb(2)O(6)) containing the main group ions Sn(4+) and Sb(5+). In all compounds, the lowest energy states in the conduction band arise primarily from the antibonding Sn/Sb 5s-O 2p interaction. In the alkaline-earth stannate perovskites (BaSnO(3), SrSnO(3), and CaSnO(3)) the conduction bandwidth decreases strongly in response to the octahedral tilting distortion triggered by the decreasing size of the alkaline-earth cation. This in turn leads to a corresponding increase in the band gap from 3.1 eV in BaSnO(3) to 4.4 eV in CaSnO(3). The band gap of CdSnO(3) is relatively small (3.0 eV) considering the large octahedral tilting distortion. The origin of this apparent anomaly is the mixing between the empty Cd 5s orbitals and the antibonding Sn 5s-O 2p states. This mixing leads to a widening of the conduction band and a corresponding decrease in the band gap. The participation of the normally inert A-site cation in the electronic structure near the Fermi level can be considered an inductive effect, as it utilizes substitution on the A-site to directly modify the electronic structure of the SnO(3)(2)(-) framework. While the pyrochlore structure is more complicated, the energy level and width of the lowest energy conduction band can be analyzed in a manner similar to that utilized on the perovskite structure. The Sn-O-Sn and Sb-O-Sb bonds are highly distorted from linear geometry in pyrochlore, leading to a relatively narrow conduction band and a wide band gap. In Cd(2)Sb(2)O(7) and Ag(2)Sb(2)O(6) the Cd(2+) and Ag(+) ions exhibit a strong inductive effect that widens the conduction band and lowers the band gap significantly, very similar to the effect observed in the perovskite form of CdSnO(3).     

Synthesis and spectroscopic studies of non-heme diiron(III) species with a terminal hydroperoxide ligand: models for hemerythrin

Two compounds, [Fe2(mu-OH)(mu-Ph4DBA)(TMEDA)2(OTf)] (4) and [Fe2(mu-OH)(mu-Ph4DBA)(DPE)2(OTf)] (7), where Ph4DBA(2-) is the dinucleating bis(carboxylate) ligand dibenzofuran-4,6-bis(diphenylacetate), have been prepared as synthetic models for the dioxygen-binding non-heme diiron protein hemerythrin (Hr). X-ray crystallography reveals that, in the solid state, these compounds contain the asymmetric coordination environment found at the diiron center in the reduced form of the protein, deoxyHr. M?ssbauer spectra of the models (4, delta = 1.21(2), DeltaE(Q) = 2.87(2) mm s(-1); 7, delta(av) = 1.23(1), DeltaE(Qav) = 2.79(1) mm s(-1)) and deoxyHr (delta = 1.19, DeltaE(Q) = 2.81 mm s(-1)) are also in good agreement. Oxygenation of the diiron(II) complexes dissolved in CH2Cl2 containing 3 equiv of N-MeIm (4) or neat EtCN (7) at -78 degrees C affords a red-orange solution with optical bands at 336 nm (7300 M(-1) cm(-1)) and 470 nm (2600 M(-1) cm(-1)) for 4 and at 334 nm (6400 M(-1) cm(-1)) and 484 nm (2350 M(-1) cm(-1)) for 7. These spectra are remarkably similar to that of oxyHr, 330 nm (6800 M(-1) cm(-1)) and 500 nm (2200 M(-1) cm(-1)). The electron paramagnetic resonance (EPR) spectrum of the cryoreduced, mixed-valence dioxygen adduct of 7 displays properties consistent with a (mu-oxo)diiron(II,III) core. An investigation of 7 and its dioxygen-bound adduct by extended X-ray absorption fine structure (EXAFS) spectroscopy indicates that the oxidized species contains a (mu-oxo)diiron(III) core with iron-ligand distances in agreement with those expected for oxide, carboxylate, and amine/hydroperoxide donor atoms. The analogous cobalt complex [Co2(mu-OH)(mu-Ph4DBA)(TMEDA)2(OTf)] (6) was synthesized and structurally characterized, but it was unreactive toward dioxygen.     

SERS and FT-IR studies of CO adsorbed on underpotential deposited Ag/Pt electrodes

CO adsorbed on UPD and OPD (under- and overpotential deposited) Ag layers on a Pt electrode surface was studied by SERS and IRRAS in conjunction with cyclic voltammetry. Electrochemical activation of a uniform UPD Ag adlayer produced Ag clusters on the Pt electrode as well as bare Pt sites. The strong adsorption of CO on the UPD Ag/Pt electrode compared with a bulk Ag electrode is explained by the influence of the substrate Pt atoms. The degree of electron back-donation to CO increases the degree of lower frequency shifts of CO on the electrodes in the order Pt electrodes < monolayer Ag/Pt < multilayer Ag/Pt.     

Analysis of organotin compounds by grignard derivatization and gas chromatography-ion trap tandem mass spectrometry

The determination of organotin compounds in water using gas chromatography-tandem mass spectrometry (GC-MS-MS) is described. Several organotin derivatives were synthesized by the reaction of organotin chlorides with Grignard reagents such as methyl-, propyl- and pentylmagnesium halides. After the optimization of the GC-MS-MS conditions, several derivatizations with the Grignard reagents were compared by evaluating the molar responses and volatilities of the derivatives and derivatization yields. As a result, the derivatizing reagent of choice is pentylmagnesium bromide. Calibration curves for the mono-, di- and tributyltins and mono-, di- and triphenyltins with pentylmagnesium bromide were linear in the range of 0.5-100 pg of Sn. The instrumental detection limits of six organotins ranged from 0.20 to 0.35 pg of Sn. The recovery tests from water samples (500 ml) were performed by using sodium diethyldithiocarbamate (DDTC) as a complexing reagent. Except for monophenyltin, the absolute recoveries of organotins from pure water at 200 ng of Sn/l were satisfactory. The recoveries calibrated by surrogate compounds (perdeuterated organotin chlorides) ranged from 71 to 109%. The method detection limits ranged from 0.26 to 0.84 pg of Sn (500-ml sample). This method was applied to the recovery of organotins from river water and seawater. The calibrated recoveries were between 90 and 122%.     

Modes of conformational changes of proteins adsorbed on a planar hydrophobic polymer surface reflecting their adsorption behaviors

Infrared spectra of hen egg white lysozyme and bovine serum albumin (BSA) adsorbed on a solid poly tris(trimethylsiloxy)silylstyrene (pTSS) surface in D2O solution were measured using attenuated total reflection (ATR) Fourier transform infrared spectroscopy. From the area and shape of the amide I' band of each spectrum, the adsorption amount and the secondary structure were determined simultaneously, as a function of adsorption time. We could show that the average conformation for all the adsorbed lysozyme molecules was solely determined by the adsorption time, and independent of the bulk concentration, while the adsorption amount increased with the bulk concentration as well as the adsorption time. These results suggest that lysozyme molecules form discrete assemblies on the surface, and that the surface assemblies grow over several hours to have a definite architecture independent of the adsorption amount. As for BSA, the extent of the conformational change was solely determined by the adsorption amount, regardless of the bulk concentration and the adsorption time. These differences in the adsorption properties of lysozyme and BSA may reflect differences in their conformational stabilities.     

Broad spectrum and mode of action of an antibiotic produced byScytonema sp. TISTR 8208 in a seaweed-type bioreactor

A photobioreactor was constructed using anchored polyurethane foam strips (1 x 1 x 40 cm) fixed onto a stainless-steel ring to prevent flotation, as a biomass support material (BSM). This type of reactor was named a seaweed-type bioreactor. A filamentous cyanobacterium, Scytonema sp. TISTR 8208, which produces a novel cyclic dodecapeptide antibiotic, was immobilized in seaweed-type photobioreactor and cultivated with air containing 5% CO₂ sparged at a gas flow rate of 250 mL/min under illumination at a light intensity of 200 μmol photon m^-2s^-1. The antibiotic produced in the seaweed-type photobioreactor was purified by HPLC and examined regarding its spectrum and mode of action. The antibiotic effectively inhibited the growth of Gram-positive bacteria, pathogenic yeasts, and filamentous fungi, but it had only a weak effect on Gram-negative bacteria. Scanning electron micrograph analysis showed that the most characteristic change was swelling of the cells after exposure to the antibiotic. The antibiotic seems to alter the conformation of the microbial cell membrane, thereby changing its permeability, leading to osmotic shock.     

Synthesis of polyanionic glycopolymers for the facile assembly of glycosyl arrays

Polyanionic glycopolymers were synthesized aiming at establishing a simple process for assembling glycosyl arrays. The synthetic glycopolymers carry the key carbohydrate epitopes of α-d-galactobioside (Gb₂), β-lactoside, and α-d-mannopyranoside, each of which serves as a ligand of bacterial toxins and adhesion proteins. The Gb₂ epitope, prepared from penta-O-acetyl-d-galactopyranose, was coupled with poly(ethylene-alt-maleic anhydride) in a polymer reaction to afford a Gb₂-embedded glycopolymer having also carboxylate (COO⁻) polyanions at the side chain. The polyanionic glycopolymer was then applied to a preparation of sugar-coated gold electrodes, which involves an alternating layer-by-layer adsorption based on electrostatic interactions. The presence of the Gb₂-coat on the surface was evidenced by Fourier transform infrared reflection absorption spectroscopy. The Gb₂-coated glyco-chip was stable in 10 mM HEPES buffer containing 150 mM NaCl aq. Other glycopolymers carrying the β-lactoside and α-d-mannopyranoside epitopes were applied to the same assembling process. The derived glycosyl arrays will be useful for detecting Shiga toxins, other pathogenic toxins and viruses when applied as glyco-chips for surface plasmon resonance or quartz crystal microbalance technique.     

Regulation of geometry around the ruthenium center of bis(2-pyridinecarboxylato) complexes by the nitrosyl moiety: syntheses, structures, and theoretical studies

cis-[Ru(NO)Cl(pyca)(2)] (pyca = 2-pyridinecarboxylato), in which the two pyridyl nitrogen atoms of the two pyca ligands coordinate at the trans position to each other and the two carboxylic oxygen atoms at the trans position to the nitrosyl ligand and the chloro ligand, respectively (type I shown as in Chart 1), reacted with NaOCH(3) to generate cis-[Ru(NO)(OCH(3))(pyca)(2)] (type I). The geometry of this complex was confirmed to be the same as the starting complex by X-ray crystallography: C(13.5)H(13)N(3)O(6.5)Ru; monoclinic, P2(1)/n; a = 8.120(1), b = 16.650(1), c = 11.510(1) A; beta = 99.07(1) degrees; V = 1536.7(2) A(3); Z = 4. The cis-trans geometrical change reaction occurred in the reactions of cis-[Ru(NO)(OCH(3))(pyca)(2)] (type I) in water and alcohol (ROH, R = CH(3), C(2)H(5)) to form [[trans-Ru(NO)(pyca)(2)](2)(H(3)O(2))](+) (type V) and trans-[Ru(NO)(OR)(pyca)(2)] (type V). The reactions of the trans-form complexes, trans-[Ru(NO)(H(2)O)(pyca)(2)](+) (type V) and trans-[Ru(NO)(OCH(3))(pyca)(2)] (type V), with Cl(-) in hydrochloric acid solution afforded the cis-form complex, cis-[Ru(NO)Cl(pyca)(2)] (type I). The favorable geometry of [Ru(NO)X(pyca)(2)](n)(+) depended on the nature of the coexisting ligand X. This conclusion was confirmed by theoretical, synthetic, and structural studies. The mono-pyca-containing nitrosylruthenium complex (C(2)H(5))(4)N[Ru(NO)Cl(3)(pyca)] was synthesized by the reaction of [Ru(NO)Cl(5)](2)(-) with Hpyca and characterized by X-ray structural analysis: C(14)H(24)N(3)O(3)Cl(3)Ru; triclinic, Ponemacr;, a = 7.631(1), b = 9.669(1), c = 13.627(1) A; alpha = 83.05(2), beta = 82.23(1), gamma = 81.94(1) degrees; V = 981.1(1) A(3); Z = 2. The type II complex of cis-[Ru(NO)Cl(pyca)(2)] was synthesized by the reaction of [Ru(NO)Cl(3)(pyca)](-) or [Ru(NO)Cl(5)](2)(-) with Hpyca and isolated by column chromatography. The structure was determined by X-ray structural analysis: C(12)H(8)N(3)O(5)ClRu; monoclinic, P2(1)/n; a = 10.010(1), b = 13.280(1), c = 11.335(1) A; beta = 113.45(1) degrees; V = 1382.4(2) A(3); Z = 4.