Impact of Titanium in Controlling Silver Particle Size on Enhancement of Catalytic Performance of AgMoO3/Ti-HMS for Direct Epoxidation of Propylene.

In this work, direct gas-phase epoxidation of propylene (DPO) to propylene oxide by molecular oxygen has been studied by using Ag-MoO3 supported on titanium-containing hexagonal mesoporous silica (Ti-HMS n ) of different Si/Ti molar ratios. The promotion effect of NaCl on the synthesized catalysts has also been investigated. Among the studied supports, the hexagonal mesoporous silica (HMS) with a Si/Ti ratio of 10 was the most suitable one for production of propylene oxide (PO). The optimal performance of the AgMo/Ti-HMS10 catalyst in DPO exhibited a selectivity to PO of 43.2% with a propylene conversion of 14.1%, at 400 °C, 0.1 MPa, and a space velocity of 12,000 h-1. The catalyst verified good stability over at least 20 h on stream. Only 2.7% PO selectivity with a propylene conversion of 10.1% was achieved over the AgMo/HMS sample. The incorporation of Ti into the HMS frame could optimize the particle size distribution of Ag, producing Ag nanoparticles with an average size of 6.8 nm compared with that of Ag/HMS (24.3 nm). The in situ Raman spectrum of AgMo/Ti-HMS10 heated in a stream of C3H6/He at 400 °C showed new bands at 616, 390, and 210 cm-1, characteristic of the Ag x Mo y O z intermediate phase. The obtained results suggested that this formed AgMo/Ti-HMS10 phase could most likely be relevant for selective epoxidation of propylene. However, during the reaction of C3H6 with AgMo/HMS, the formation of this intermediate was hardly detected. On the other hand, the hydrogen temperature-programmed reduction measurements indicated improved reducibility of MoO3 in the AgMo/Ti-HMS10 catalyst, which acknowledged the role of Mo6+ in gaining electrons from silver to form positively charged Ag. This could reduce the effective charge of the adsorbed oxygen on silver sites and in turn favor the epoxidation path of propylene rather than the combustion route. Also, during the reaction of C3H6 with NaAgMo/Ti-HMS10 at 400 °C, two new Raman bands were detected at 277 and 350 cm-1, characteristic of Ag2MoO4.

Synthesis and antiproliferative activity of monocationic arylthiophene derivatives.

Eleven compounds of substituted 4-(5-arylthiophen-2-yl)benzamidines 4a-k were synthesized from their corresponding mononitriles via treatment with lithium trimethylsilylamide and subsequent de-protection with ethanol/hydrogen chloride. In vitro antiproliferative activities of the new monocationic arylthiophenes were evaluated against 60 human cell lines at NCI, USA. This class of compounds displayed promising submicromolar antiproliferative activities with the most potent compound being 4i (GI50 and TGI of 0.20 and 0.37 µM, respectively). On the other hand, most of the tested compounds exhibited LC50 at concentrations much higher than those they had GI50 at; ∼10× (for 4b) up to 228× (for 4e) which indicates lower lethality and efficient growth inhibition. Cancer cell lines, HCC-2998 colon, SNB-75 CNS, MDA-MB-435 melanoma, and MCF-7 breast cancer were the most responsive, with GI50s of 0.156, 0.165, 0.163, and 0.168 µM, respectively. The p-chlorophenyl derivatives 4e and 4i discerned themselves with GI50 values at 0.36 and 0.20 µM, respectively, and LC50 values at ∼83 and 36 µM, respectively, but safe to RBCs at 1000 µM. The cytotoxic activity data of these compounds in two normal cell lines; WI38 and WISH proved that they are very safe on normal cells. The plausible mechanism of action of the tested monocations was examined by evaluating their antioxidant power, nuclease-like DNA degradation aptitude and tyrosine kinase (TK) inhibition activities. The tested monocations showed potent activity in all assays. Compounds 4e and 4i caused 88 and 98%, respectively, inhibition in TK activity at 1 µM and the IC50 for 4i was 13 nM. The tested monocations have selective anticancer activity without insulting normal cells most probably due to inhibition of the key enzyme TK at nanomolar concentrations.

Partial charge transfer contribution to the solvent isotope effect and photosensitized generation of singlet oxygen, O2(1Δg), by substituted ruthenium(II) bipyridyl complexes in aqueous media.

The efficiency of singlet oxygen photosensitized by some ruthenium(ii) bipyridyl complex ions in aqueous media is reported in this study. Measurements were carried out in H2O and D2O. The effect of the deuterium isotope on the lifetime of (3)MLCT excited states of these complexes is studied in H2O and D2O. The deuterium isotope effect was discussed in terms of the vibronic coupling to the solvent in addition to the charge transfer to the solvent mechanism due to their dependence on the oxidation potential of the sensitizer. Quenching rate constants, kq, for quenching of the (3)MLCT states of these ruthenium complex ions by molecular oxygen were found to be in the range of (2.08-3.84) × 10(9) M(-1) s(-1) in H2O and (1.69-3.48) × 10(9) M(-1) s(-1) in D2O. The efficiency of singlet oxygen, O2((1)Δg), production as a result of the (3)MLCT quenching by oxygen, f, is reported in D2O and found to be in the range 0.25-0.56. It has been found that the lifetime of the excited state is longer in D2O, τ, than in H2O, τ, which was related to partial charge transfer to the solvent in addition to the vibronic coupling mechanism. Mechanisms by which the excited states of these ruthenium complexes are quenched by molecular oxygen that shows the competition between charge transfer, non-charge transfer deactivation channels or energy transfer assisted charge transfer deactivation mechanisms are reported.

Synthesis, characterization and biological studies of some novel thieno[2,3-d]pyrimidines.

Several 2-unsubstituted thieno[2,3-d]pyrimidines have been prepared from 2-aminothiophene-3-carboxylic acid esters and their carbonitrile analogs. Some triazolo-thienopyrimidine and 2-thioxothienopyrimidine representatives have also been synthesized using thermal and microwave (MW) irradiation techniques. Structures of the prepared compounds were elucidated on the basis of IR, NMR, 2D NMR and mass spectral data. The biological activity of some selected synthesized compounds was also examined.

Biological activity of a phloroglucinol glucoside derivative from Conyza aegyptiaca.

The phloroglucinol glucoside derivative [2,4-dihydroxy-6-(beta-D-glucopyranosyloxy)phenyl]-butan-1-one (1), roseoside (2), and kaempferol-3-O-beta-D-glucopyranoside (3) were isolated from the aerial parts of Conyza aegyptiaca (L.). To the best of our knowledge, this is the first isolation of compounds 1-3 from C. aegyptiaca. Their structures were determined by spectroscopic techniques including, IR, HR-EIMS, and extensive 500 MHz 1D- and 2D-NMR analyses (1H, 13C NMR, DEPT, 1H-1H COSY, HMQC and HMBC experiments). The antioxidant activity of 1, using the DPPH assay, was investigated; in addition, 1 was investigated against different types of cell lines, including Hep-G2, HCT-116, and RAW 264.7 for its cytotoxic effects. Also, this is the first report on the activity of 1.

Fluorescence enhancement of 1-napthol-5-sulfonate by forming inclusion complex with beta-cyclodextrin in aqueous solution.

Fluorescence enhancement of 1-naphthol-5-sulfonate (1N5S) upon inclusion in beta-cyclodextrin is studied by spectrophotometry and spectrofluorimetery techniques. The spectral shifts were only observed in the emission spectra in different solvents and were found to be directly correlated to the solvent's hydrogen-bond donor strength (alpha). Spectral changes in the absorption spectra upon the addition of beta-cyclodextrin to 1N5S in aqueous medium were too small to allow for the determination of the binding constant. On the other hand; fluorescence measurements show that the emission of both the anionic and neutral forms of 1N5S increase upon the addition of beta-cyclodextrin with an increase in the quantum yield by about 60%. Fluorescence measurements show 1:1 inclusion of 1N5S in the beta-cyclodextrin cavity with an association constant of 88+/-10M(-1). (1)H NMR studies are used to confirm the inclusion and to provide information on the geometry of 1N5S inside the cavity of beta-cyclodextrin.

Spectrophotometric and electrical studies of charge transfer complexes of 2-amino-1,3,4-thiadiazole with pi-acceptors.

Charge transfer (CT) complexes formed between 2-amino-1,3,4-thiadiazole as donor and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), p-chloranil (p-CHL), o-chloranil (o-CHL), p-bromanil (BRL) and chloranilic acid (CHA) as acceptors, have been studied spectrophotometrically. Benesi-Hildebrand and Job continuous variation methods were applied to the determination of association constant (K), molar extinction coefficients (epsilon), dipole moment and stoichiometric ratio, respectively. The solid CT complexes have been synthesized and characterized by different spectral methods. The spectral changes reveal that the CT interaction depends on the type of the acceptors. The magnetic properties of the various complexes were also investigated. The electrical properties for the solid CT complexes are measured from which the activation energies are calculated.

Spectroscopic studies of inclusion complexes of 1-naphthol-4-sulfonate with beta-cyclodextrin in aqueous solution.

The photophysical properties of 1-naphthol-4-sulfonate (1N4S) in some solvents and in aqueous beta-cyclodextrin solution have been investigated. The effect of beta-cyclodextrin on the fluorescence quantum yield and on the proton transfer is examined. Fluorescence measurements show 1:1 inclusion of 1N4S in the beta-cyclodextrin cavity with an association constant of 108M(-1). NMR studies are used to study the inclusion phenomena and to provide information on the geometry of 1N4S inside the cavity of beta-cyclodextrin.

A new heterocyclic glucoside from the fruits of Xanthium pungens.

A new thiazinedione glucoside, 7-(beta-D-glucopyranosyloxymethyl)-8,8-dimethyl-4,8-dihydrobenzo[1,4]thiazine-3,5-dione (1) and named xanthiside, was isolated from the methanol extract of the fruits of Xanthium pungens. Its structure was determined by spectroscopic techniques including, IR, CIMS, high-resolution-EIMS, and extensive 400 MHz one- and two-dimensional NMR-analysis (1H, 13C-NMR, DEPT, 1H-1H COSY, HMQC, COLOC, and NOE experiments).

Diterpenoid quinones from rosemary (Rosmarinus officinalis L.).

Two new abietane-type diterpenoid o-quinones, 7beta-methoxyabieta-8,13-diene-11,12-dione-(20,6beta)-olide (rosmaquinone A) (1) and 7alpha-methoxyabieta-8,13-diene-11,12-dione-(20,6beta)-olide (rosmaquinone B) (2), together with six known compounds were isolated from the aerial parts of Rosmarinus officinalis L. The structures of the new compounds were determined by extensive spectroscopic analysis, including IR, UV, HR-EIMS, 1D and 2D 400 MHz NMR data (1H, 13C NMR, DEPT, 1H-1H COSY, HMQC, HMBC and NOEs).

(E)-2-(2-adamantylidene)-3-(1-ferrocenylethylidene)succinic anhydride.

The title compound, [Fe(C(5)H(5))(C(21)H(21)O(3))], was obtained from successive Stobbe condensations between ketones and dimethyl succinate. The succinic anhydride five-membered ring is distorted significantly from planarity, with the butadiene moiety being twisted by 49.3 (2) degrees from planarity and the C atoms at the succinic anhydride end of the alkene bonds showing significant pyramidalization. The cyclopentadiene rings of the ferrocenyl moiety adopt an almost eclipsed conformation.