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PubMed1992

Thromboxane in the pathogenesis of glomerular injury in diabetes.

The present study examined the role of thromboxane (TX) in the initiation and progression of glomerular injury in diabetic rats, as reflected by albuminuria and glomerular histology. Urinary thromboxane and albumin excretion (UTX and UAlb) were elevated by four months after induction of diabetes in the moderately hyperglycemic (200 to 400 mg/dl glucose) streptozotocin diabetic rat (SDR) compared to age-matched control rats. UTX and UAlb both increased progressively in SDR over the seven month period of study. Glomerular TX production, glomerular volume, fractional and absolute mesangial volume and glomerular basement membrane (GBM) width were also increased after seven months in SDR compared to control. Treatment of SDR with a thromboxane synthetase inhibitor (TXI) 4' (imidazol-l-yl) acetophenone (100 mg/kg/day) for seven months beginning at the time of induction of diabetes prevented the increases in UTX, UAlb, glomerular TX production, glomerular volume and mesangial volume and attenuated, but did not prevent, GBM thickening. When the same dose of the TXI was begun five months after induction of diabetes and continued for two months, UTX and ex vivo glomerular TX production were reduced by only 60% compared to untreated SDR and remained higher than corresponding values in control rats. Delayed treatment with the TXI alone did not alter UAlb compared to untreated SDR. By contrast, treatment of five month albuminuric SDR for only two months with the TXI plus the TX receptor antagonist (TXRA) Bay U3405 (5 mg/kg/day) prevented a further increase in UAlb, and reduced fractional albumin clearance and mesangial volume compared to values in untreated SDR. Combined treatment with the TXI and TXRA had no effect on GBM width or glomerular volume compared to values in untreated SDR. The results support roles for TX in the initiation of, and for TX and/or endoperoxides in the progression of glomerular injury in SDR.

Albuminuria↗
PubMed2002

Redox/ROS regulation of lipopolysaccharide-induced mitogen-activated protein kinase (MAPK) activation and MAPK-mediated TNF-alpha biosynthesis.

Redox and ROS regulation of MAPK-mediated TNF-alpha biosynthesis is not well characterized. It was hypothesized that the involvement of the MAPK pathway in regulating LPS-mediated TNF-alpha secretion is redox-dependent, NF-kappaB-sensitive and attenuated by N-acetyl-L-cysteine (NAC) and other antioxidants. In alveolar epithelial cells, LPS induced a time- and dose-dependent phosphorylation of MAPK(p38). This was associated with the activation of MAPK-activated protein kinase, which phosphorylated the small heat-shock protein, Hsp27. MAPK(p38) inhibition (SB-203580) abrogated LPS-induced TNF-alpha production. MAPK(ERK) blockade (PD-98059) attenuated TNF-alpha secretion, an effect synergistically amplified in the presence of SB-203580. Regulation of NF-kappaB by selective inhibitors revealed that this pathway is partially involved in regulating LPS-mediated TNF-alpha secretion. Whereas the proteasome inhibitor, MG-132, had no effect on LPS-mediated TNF-alpha production, CAPE, sulfasalazine and SN-50, a cell-permeant NF-kappaB inhibitor, attenuated but did not abrogate TNF-alpha biosynthesis. LPS up-regulated ROS, an effect abrogated by 4'-hydroxy-3'-methoxy-acetophenone and NAC, which reduced TNF-alpha secretion, induced the accumulation of GSH, reduced the concentration of GSSG, and blockaded the phosphorylation/activation of MAPK(p38) pathway. ROS induced MAPK(p38) phosphorylation and selective antioxidants, including the permeant GSH precursor, gamma-GCE, reduced ROS-dependent MAPK(p38) phosphorylation. These results indicate that the MAPK pathway and MAPK-mediated regulation of TNF-alpha production is redox-dependent, GSH-mediated and requires, at least in part, a NF-kappaB/ROS-sensitive mechanism.

Acetylcysteine↗
PubMed2000

Measurement of styrene-7,8-oxide and other oxidation products of styrene in air.

Styrene-7,8-oxide (SO) is generated at low concentrations from the oxidation of styrene during the processing of reinforced plastics. Since exposure to SO has important health implications, we developed air sampling and analytical methods to measure low levels of airborne SO in the presence of styrene and its other oxidation products, namely phenylacetaldehyde (PAA) and acetophenone (AP). Both active and passive air monitors were used. The active sampling method, which employed adsorption on Tenax, was suitable for measuring SO, PAA and AP but had limited capacity for styrene due to breakthrough. The passive monitor employed a carbon adsorbent and was suitable for measurement of styrene and SO but not PAA and AP due to poor recovery. After sampling, the analytes were extracted from the adsorbents with ethyl acetate and measured by gas chromatography with flame ionization detection or mass spectrometry. By maintaining the injection port at 70 degrees C, the thermal rearrangement of SO to PAA was minimized. Recovery of styrene and SO from the passive monitor depended upon loading and was corrected by linearization of the Freundlich isotherm. The limits of detection for SO, PAA, and AP were 0.2 ppb using the active monitor, and for SO was 1 ppb using the passive monitor. The sampling precision for SO (RSD from personal measurements) was 5.0% for the passive monitor and was 13.4% for the active monitor over a range of exposures from 5-150 ppb. The corresponding precision for styrene was 5.3% for the passive monitor for levels ranging from 1.2 to 104 ppm. Measurements of 235 personal exposures with the active monitor in 12 facilities manufacturing fiberglass-reinforced plastics (FRP) showed that levels of AP and PAA were below 7.8 ppb and 5 ppb, respectively. In contrast, SO averaged 30.4 ppb (SE=2.4) in these FRP facilities, ranging from below 0.2 ppb to 190 ppb. The active monitor was also used to detect airborne SO at levels of approximately equals 1 ppb in one facility manufacturing styrene butadiene rubber, suggesting that SO is generally present during the polymerization of styrene. Personal passive monitoring in the 12 FRP facilities (n = 657) revealed mean concentrations of styrene ranging between 1.8 and 55.4 ppm, and for SO between 1.7 and 62.6 ppb. The ratio of the mean styrene level to the mean SO level varied between 449:1 and 1,635:1 among the 12 FRP facilities.

Air Pollutants↗
PubMed2003

Two-photon photoacoustic calorimetry and the absolute measurement of molar absorption coefficients of transient species in solution.

The theory of two-photon photoacoustic calorimetry (PAC) is developed for the case of a homogeneously irradiated volume and it is shown that the laser-intensity dependence of the photoacoustic signals can be used to determine the molar absorption coefficient of transient species. The application of the method is illustrated via the measurement of the absorption coefficients of benzophenone and acetophenone triplets using a front-face PAC cell. The very high sensitivity exhibited by this cell strongly recommends the inclusion of laser-intensity dependence studies in the procedure for measuring heat depositions. Only extrapolation to zero laser intensity can afford reliable enthalpies of formation for very short-lived species.

Journal Article↗
PubMed2003

Ship-in-a-bottle synthesis of 2,4,6-triphenylthiapyrylium cations encapsulated in zeolites Y and beta: a novel robust photocatalyst.

The 2,4,6-triphenylthiapyrylium ion has been obtained imprisoned inside the supercages of the tridirectional, large pore zeolites Y and beta via ship-in-a-bottle synthesis from chalcone and acetophenone in the presence of hydrogen sulfide. The resulting solids are efficient and robust photocatalysts that are able to degrade phenol and aniline in water with a higher efficiency than the P-25 TiO(2) standard. Preliminary tests have shown that these encapsulated dye materials are also efficient photocatalysts for the oxidative degradation of malodorous sulfur-containing molecules.

Journal Article↗
PubMed2004

Solvent-free reactions of C60 with active methylene compounds, either with or without carbon tetrabromide, in the presence of bases under high-speed vibration milling conditions.

Solvent-free reactions of C(60) with active methylene compounds, either with or without carbon tetrabromide (CBr(4)), in the presence of a base under high-speed vibration milling (HSVM) conditions were investigated. The reaction of C(60) with diethyl bromomalonate was conducted under HSVM conditions in the presence of piperidine, triethylamine or Na(2)CO(3) to afford cyclopropane derivative. In the presence of CBr(4), methanofullerenes, and could be obtained by the direct reaction of C(60) with diethyl malonate, dimethyl malonate, ethyl acetoacetate and ethyl cyanoacetate, respectively, with the aid of 1,8-diazabicyclo[5,4,0]undec-7-ene, piperidine, triethylamine or Na(2)CO(3). More interestingly, 1,4-bisadducts and were produced by the reaction of C(60) with diethyl malonate and dimethyl malonate in the presence of piperidine, triethylamine or Na(2)CO(3) under HSVM conditions. On the other hand, dihydrofuran-fused C(60) derivatives, and were obtained from the reaction of C(60) with ethyl acetoacetate, 2,4-pentanedione and 5,5-dimethyl-1,3-cyclohexanedione with the aid of a base. Under the same conditions, less activated aryl methyl ketones such as 2-acetylpyridine, 2-acetylpyrazine and acetophenone provided monocarbonylated methanofullerene derivatives, and. Except for the Bingel reactions, all other reactions under the HSVM conditions are considered to proceed according to a single-electron-transfer mechanism.

Journal Article↗
PubMed2004

Photochemical reaction mechanisms of 2-nitrobenzyl compounds: 2-nitrobenzyl alcohols form 2-nitroso hydrates by dual proton transfer.

Irradiation of 2-nitrobenzyl alcohol (1, R = H) and 1-(2-nitrophenyl)ethanol (1, R = Me) in various solvents yields 2-nitroso benzaldehyde (4, R = H) and 2-nitroso acetophenone (4 R = Me), respectively, with quantum yields of about 60%. The mechanism of this reaction, known since 1918, was investigated using laser flash photolysis, time-resolved infrared spectroscopy (TRIR), and 18O-labeling experiments. The primary aci-nitro photoproducts 2 react by two competing paths. The balance between the two depends on the reaction medium. Reaction via hydrated nitroso compounds 3 formed by proton transfer prevails in aprotic solvents and in aqueous acid and base. In water, pH 3-8, the classical mechanism of cyclization to benzisoxazolidine intermediates 5, followed by ring opening to carbonyl hydrates 6, predominates. The transient intermediates 3 and 6 were identified by TRIR. Potential energy surfaces for these reactions were mapped by density functional calculations.

Benzyl Alcohols↗
PubMed2004

Stoichiometric reactions of methylparathion with a palladium aryl oxime metallacycle.

The reaction of [Pd(3)(OAc)(6)] with (E)-acetophenone oxime and pyridine in CHCl(3) under reflux affords the metallacycle [Pd(OAc)[C,N-(C(6)H(4)C(CH(3))=NOH)-2](py)] (1) as a yellow air-stable complex. The same reaction carried out at room temperature in the absence of pyridine affords the trinuclear oximato complex [Pd(mu-(E)-ON=C(CH(3))Ph)(mu-OAc)](3) (2), which can be converted into 1 upon heating in the presence of pyridine. As indicated by (1)H and (31)P NMR spectroscopy, complex 1 reacts with methylparathion in acetone-d(6)-D(2)O solutions to afford [Pd(SP(=O)(OCH(3))(2))[C,N-(C(6)H(4)C(CH(3))=NOH)-2](py)] (3) and [Pd(mu-SP(=O)(OCH(3))(2))[C,N-(C(6)H(4)C(CH(3))=NOH)-2]](2) (4) as well as free p-nitrophenol. Compounds 1-4 have been characterized by single-crystal X-ray analysis, NMR and EA. Compounds 1 and 3 are mononuclear complexes with the acetate and dimethylthiophosphate ligand, respectively, trans from the phenyl group. Compound 2 is a trinuclear complex whose structure can be derived from that of [Pd(3)(OAc)(6)] by replacing three of the acetate ligands on one side of Pd(3) plane by three N,O-coordinated oximate ligands. Complex 4 is a dinuclear complex in which the two square-planar palladium moieties are linked by the sulfur atoms of the bridging dimethylthiophosphate ligands.

Journal Article↗
PubMed2004

Phosphaallyl complexes of Ru(II) derived from dicyclohexylvinylphosphine (DCVP).

The complexes [(eta5-RC5H4)Ru(CH3CN)3]PF6(R = H, CH3) react with DCVP (DCVP = Cy2PCH=CH2) at room temperature to produce the phosphaallyl complexes [(eta5-C5H5)Ru(eta1-DCVP)(eta3-DCVP)]PF6 and [(eta5-MeC5H4)Ru(eta1-DCVP)(eta3-DCVP)]PF6. Both compounds react with a variety of two-electron donor ligands displacing the coordinated vinyl moiety. In contrast, we failed to prepare the phosphaallyl complexes [(eta5-C5Me5)Ru(eta1-DCVP)(eta3-DCVP)]PF6, [(eta5-MeC5H4)Ru(CO)(eta3-DCVP)]PF6 and [(eta5-C5Me5)Ru(CO)(eta3-DPVP)]PF6(DPVP = Ph2PCH=CH2). The compounds [(eta5-MeC5H4)Ru(CO)(CH3CN)(DPVP)]PF6 and [(eta5-C5Me5)Ru(CO)(CH3CN)(DPVP)]PF6 react with DMPP (3,4-dimethyl-1-phenylphosphole) to undergo [4 + 2] Diels-Alder cycloaddition reactions at elevated temperature. Attempts at ruthenium catalyzed hydration of phenylacetylene produced neither acetophenone nor phenylacetaldehyde but rather dimers and trimers of phenylacetylene. The structures of the complexes described herein have been deduced from elemental analyses, infrared spectroscopy, 1H, 13C{1H}, 31P{1H} NMR spectroscopy and in several cases by X-ray crystallography.

Journal Article↗
PubMed2005

Insertion reactions of hydridonitrosyltetrakis(trimethylphosphine) tungsten(0).

[W(H)(NO)(PMe3)4] (1) was prepared by the reaction of [W(Cl)(NO)(PMe3)4] with NaBH4 in the presence of PMe3. The insertion of acetophenone, benzophenone and acetone into the W-H bond of 1 afforded the corresponding alkoxide complexes [W(NO)(PMe3)4(OCHR1R2)](R1 = R2 = Me (2); R1 = Me, R2 = Ph (3); R1 = R2 = Ph (4)), which were however thermally unstable. Insertion of CO2 into the W-H bond of yields the formato-O complex trans-W(NO)(OCHO)(PMe3)4 (5). Reaction of trans-W(NO)(H)(PMe3)4 with CO led to the formation of mer-W(CO)(NO)(H)(PMe3)3 (6) and not the formyl complex W(NO)(CHO)(PMe3)4. Insertion of Fe(CO)(5), Re2(CO)10 and Mn2(CO)10 into trans-W(NO)(H)(PMe3)4 resulted in the formation of trans-W(NO)(PMe3)4(mu-OCH)Fe(CO)4 (7), trans-W(NO)(PMe3)4(mu-OCH)Re2(CO)9 (8) and trans-W(NO)(PMe3)4(mu-OCH)Mn2(CO)9 (9). For Re2(CO)10, an equilibrium was established and the thermodynamic data of the equilibrium reaction have been determined by a variable-temperature NMR experiments (K(298K)= 104 L mol(-1), DeltaH=-37 kJ mol(-1), DeltaS =-86 J K(-1) mol(-1)). Both compounds 7 and 8 were separated in analytically pure form. Complex 9 decomposed slowly into some yet unidentified compounds at room temperature. Insertion of imines into the W-H bond of 1 was also additionally studied. For the reactions of the imines PhCH=NPh, Ph(Me)C=NPh, C6H5CH=NCH2C6H5, and (C6H5)2C=NH with only decomposition products were observed. However, the insertion of C10H7N=CHC6H5 into the W-H bond of led to loss of one PMe3 ligand and at the same time a strong agostic interaction (C17-H...W), which was followed by an oxidative addition of the C-H bond to the tungsten center giving the complex [W(NO)(H)(PMe3)3(C10H6NCH2Ph)] (10). The structures of compounds 1, 4, 7, 8 and 10 were studied by single-crystal X-ray diffraction.

Journal Article↗
PubMed2005

Reducing ability of supramolecular C60 dianion toward C=O, C=C and N-N bonds.

Different from C60 dianion which readily reacts with electrophiles, supramolecular C60 dianion (2) generated from gamma-cyclodextrin-bicapped C60 (1) and NaBH4 (or diborate) in DMSO-H2O (9:1, v/v) is able to reduce N-N+, C=C-EWG and C=O bonds to provide the respective dihydro derivatives; 1-mediated reduction of acetophenone with NaBH4 in the presence of (Me2N)2CH2 and EtONa gives turn over frequency (TOF)/h of 400.

Journal Article↗
PubMed2005

Easy synthesis of beta-O-4 type lignin related polymers.

The beta-O-4 structure is the most abundant substructure in lignin. Lignin related polymers composed of only the beta-O-4 structure were prepared using simple aromatic compounds as starting materials. Acetophenone derivatives were brominated, polymerized in the presence of K2CO3 and reduced with NaBH4 to give the lignin related polymers. These are linear polymers which resemble natural lignins in their structures, although they do not have a gamma-hydroxymethyl group. The number average degree of polymerization (DPn) was determined with peracetate of the polymers by gel permeation chromatography. The DPn of guaiacyl type polymers ranged from 15.2-21.4, where the value for the syringyl type was 11.3 and for the p-hydroxyphenyl type 16.9. The Guaiacyl type polymer was very soluble in usual lignin solvents such as 1, 4-dioxane-water (96 : 4, v/v) and DMSO, but only slightly soluble in acetone-water (9 : 1, v/v).

Acetylation↗
PubMed2005

Hydride transfer reactivity of tetrakis(trimethylphosphine)(hydrido)(nitrosyl)molybdenum(0).

The tetrakis(trimethylphosphine) molybdenum nitrosyl hydrido complex trans-Mo(PMe(3))(4)(H)(NO) (2) and the related deuteride complex trans-Mo(PMe(3))(4)(D)(NO) (2a) were prepared from trans-Mo(PMe(3))(4)(Cl)(NO) (1). From (2)H T(1 min) measurements and solid-state (2)H NMR the bond ionicities of 2a could be determined and were found to be 80.0% and 75.3%, respectively, indicating a very polar Mo--D bond. The enhanced hydridicity of 2 is reflected in its very high propensity to undergo hydride transfer reactions. 2 was thus reacted with acetone, acetophenone, and benzophenone to afford the corresponding alkoxide complexes trans-Mo(NO)(PMe(3))(4)(OCHR'R'') (R' = R'' = Me (3); R' = Me, R'' = Ph (4); R' = R'' = Ph (5)). The reaction of 2 with CO(2) led to the formation of the formato-O-complex Mo(NO)(OCHO)(PMe(3))(4) (6). The reaction of with HOSO(2)CF(3) produced the anion coordinated complex Mo(NO)(PMe(3))(4)(OSO(2)CF(3)) (7), and the reaction with [H(Et(2)O)(2)][BAr(F)(4)] with an excess of PMe(3) produced the pentakis(trimethylphosphine) coordinated compound [Mo(NO)(PMe(3))(5)][BAr(F)(4)] (8). Imine insertions into the Mo-H bond of 2 were also accomplished. PhCH[double bond, length as m-dash]NPh (N-benzylideneaniline) and C(10)H(7)CH=NPh (N-1-naphthylideneaniline) afforded the amido compounds Mo(NO)(PMe(3))(4)[NR'(CH(2)R'')] (R' = R'' = Ph (9), R' = Ph, R'' = naphthyl (11)). 9 could not be obtained in pure form, however, its structure was assigned by spectroscopic means. At room temperature 11 reacted further to lose one PMe(3) forming 12 (Mo(NO)PMe(3))(3)[N(Ph)CH(2)C(10)H(6))]) with agostic stabilization. In a subsequent step oxidative addition of the agostic naphthyl C-H bond to the molybdenum centre occurred. Then hydrogen migration took place giving the chelate amine complex Mo(NO)(PMe(3))(3)[NH(Ph)(CH(2)C(10)H(6))] (15). The insertion reaction of 2 with C(10)H(7)N=CHPh led to formation of the agostic compound Mo(NO)(PMe(3))(3)[N(CH(2)Ph)(C(10)H(7))] (10). Based on the knowledge of facile formation of agostic compounds the catalytic hydrogenation of C(10)H(7)N=CHPh and PhN=CHC(10)H(7) with 2 (5 mol%) was tested. The best conversion rates were obtained in the presence of an excess of PMe(3), which were 18.4% and 100% for C(10)H(7)N=CHPh and PhN=CHC(10)H(7), respectively.

Journal Article↗
PubMed2006

Asymmetric induction during electron transfer mediated photoreduction of carbonyl compounds: role of zeolites.

Photochemistry of 17 aryl alkyl ketones included within cation exchanged zeolites has been examined. In solution five of the 17 ketones undergo intramolecular hydrogen abstraction reaction even in the presence of a chiral amine and the rest are photoreduced to the corresponding alcohol. Within zeolites all 17 ketones yielded in presence of a chiral amine, the corresponding alcohol as the major product. When a chiral amine was used as the coadsorbent within alkali ion exchanged zeolites, enantiomerically enriched alcohol was formed in all cases. The best chiral induction was obtained with phenyl cyclohexyl ketone (enantiomeric excess: 68%). 1H-13C Cross Polarization Magic Angle Spinning (CP-MAS) experiments, with a model ketone (perdeuterated acetophenone) and chiral amine (pseudoephedrine) included within MY zeolites, suggested that the cation brings the reactant and the chiral amine closer. The role of the cation in such a process is also revealed by the computation results. The results presented here highlight the importance of a supramolecular structure in forcing a closer interaction between a reactant and a chiral inductor that could be used to achieve asymmetric induction in photoproducts.

Journal Article↗
PubMed2006

Triruthenium carbonyl clusters derived from chiral aminooxazolines: synthesis and catalytic activity.

Treatment of [Ru3(CO)12] with the chiral aminooxazolines (+)-2-amino-(4R)-phenyl-2-oxazoline (H2amphox), (+)-2-amino-(4R,5S)-indanyl-2-oxazoline (H2aminox) and (+)-2-(2-anilinyl)-(4R,5S)-indanyl-2-oxazoline (H2aninox) in THF at reflux temperature, affords the complexes [Ru3(mu-H)(mu3-kappa2-Hox-N,N)(CO)9] (H2ox = H2amphox, 1; H2aminox, 2) and [Ru3(mu-H)(mu-kappa2-Haninox-N,N)(CO)9] (3). In all cases, the activation of an N-H bond has occurred and the resulting amido fragment spans an edge of the metal triangle, while the N atom of the oxazoline ring is attached to the remaining metal atom (as in 1 and 2), or to one of the metal atoms of the bridged edge (as in 3). The use of 1-3 as catalyst precursors in the asymmetric hydrogen-transfer reduction of acetophenone and in the asymmetric cycloaddition of cyclopentadiene and acroleine is reported.

Journal Article↗
PubMed2006

Photochemical synthesis of benzoyl spiro[2.2]pentanes.

In the present study, we describe the photochemical behaviour of 2-mesyloxy phenyl ketones 8 and 12 bearing a cyclopropane moiety in the side-chain. Irradiation of 8 and 12 leads to the corresponding benzoyl spiro[2.2]pentanes as a consequence of an initial gamma-H-shift, subsequent elimination of MsOH (accompanied by a spin-center shift) and cyclization of the resulting 1,3-diradicals. In contrast, a corresponding phenyl ketone without a mesyloxy group in the 2-position, and thus a potential reactant of the "classical" Norrish-Yang reaction, shows no photochemical reaction. By means of quantum chemical calculations we discovered that in the presence of a mesyloxy group the activation barrier for the photochemical gamma-H-shift is substantially decreased. Furthermore, a photoinduced skeletal rearrangement of benzoyl spiro[2.2]pentane to 2-cyclobutylidene-acetophenone could be observed. Compared to the common methods used to synthesize spiro[2.2]pentanes, the photochemical preparation of benzoyl spiro[2.2]pentane presented herein is the first example where a bond between the spiro atom and an adjacent atom is formed.

Cyclization↗