Synthesis, characterization, spectroscopic, and electrochemiluminescence properties of a solvatochromic azacrown-containing cyanoruthenate(II): potential applications in separation and indirect photometric detection of cations and amino acids in HPLC.

A new anionic ruthenium(II) complex, (Et4N)[Ru(tpyA18C6)(CN)3] (tpyA18C6=N-[4'-(2,2':6',2''-terpyridyl)]-1,4,7,10,13-pentaoxa-16-azacyclohexadodecane), has been synthesized and characterized. The complex was found to show pronounced solvatochromic behavior and, when dissolved in solution, changed its color from purple to yellow when the solvent system was varied from pure acetonitrile to pure water. Its absorption and emission energies in various solvents showed a linear dependence of the Gutman's acceptor number.

Oxidation chemistry of poly(ethylene glycol)-supported carbonylruthenium(II) and dioxoruthenium(VI) meso-tetrakis(pentafluorophenyl)porphyrin.

[Ru(II)(F(20)-tpp)(CO)] (1, F(20)-tpp=meso-tetrakis(pentafluorophenyl)porphyrinato dianion) was covalently attached to poly(ethylene glycol) (PEG) through the reaction of 1 with PEG and sodium hydride in DMF. The water-soluble PEG-supported ruthenium porphyrin (PEG-1) is an efficient catalyst for 2,6-Cl(2)pyNO oxidation and PhI==NTs aziridination/amidation of hydrocarbons, and intramolecular amidation of sulfamate esters with PhI(OAc)(2). Oxidation of PEG-1 by m-CPBA in CH(2)Cl(2), dioxane, or water afforded a water-soluble PEG-supported dioxoruthenium(VI) porphyrin (PEG-2), which could react with hydrocarbons to give oxidation products in up to 80 % yield.

Dioxiranes generated in situ from pyruvates and oxone as environmentally friendly oxidizing agents for disinfection.

Dioxiranes generated in situ from pyruvates (alpha-keto esters) and Oxone have been found to be environmentally friendly oxidizing agents for disinfection. These oxidizing agents were highly effective for destruction of various strains of bacteria, fungi, and bacterial endospores in a wide temperature range with exceptional stability. Notably, by using an aqueous solution of methyl pyruvate (1a) and Oxone/NaHCO3, complete destruction of bacteria such as Staphylococcus aureus and fungus Penicillium corylophilum was achieved within 5 min at 20 degrees C at neutral pH.

EFA6A enhances glioma cell invasion through ADP ribosylation factor 6/extracellular signal-regulated kinase signaling.

EFA6A, or Pleckstrin and Sec7 domain protein, is a member of guanine nucleotide exchange factors for ADP ribosylation factor 6 (ARF6). Whereas EFA6A is specifically expressed in the brain, little is known about its function in glial cells or glioma. Here we show that elevated EFA6A expression is detectable in both low-grade and high-grade human glioma tissues samples.

Activation of insulin-like growth factor I receptor-mediated pathway by ginsenoside Rg1.

Ginsenoside Rg1, an active ingredient in ginseng, was previously shown to be a novel class of potent phytoestrogen. The present study aims at investigating the molecular mechanisms involved in mediating its actions in human breast cancer (MCF-7) cells. Rg1 (1 pM) stimulates cell proliferation (P<0.

Enantiomeric separation and quantification of ephedrine-type alkaloids in herbal materials by comprehensive two-dimensional gas chromatography.

The separation of ephedrine-type alkaloids and their enantiomers in raw herbs and commercial herbal products was investigated by carrying out enantioselective separation in the first-dimension column (containing beta-cyclodextrin as the chiral selector) of a comprehensive two-dimensional gas chromatography (GC x GC) system, whereas a polar polyethylene glycol capillary column was used for separation in the second dimension. Naturally occurring ephedrine-type alkaloids and their synthetic analogues (enantiomeric counterparts) were adequately resolved from each other, as well as from potential interference species in the sample matrix using GC x GC, whereas single column GC analysis was unable to separate all the alkaloids of interest. Detection limits in the order of 0.

Trans influence of boryl ligands and comparison with C, SI, and SN ligands.

In this paper, the trans influence of boryl ligands, together with that of other ligands commonly believed to have a strong trans influence, has been investigated theoretically via density functional theory (DFT) calculations on a series of square-planar platinum(II) complexes of the form trans-[PtL(Cl)(PMe3)2]. The following order of trans influence has been obtained: -BMe2>-SiMe3>-BH2>-SnMe3 approximately >-Bpin>> approximately -Bcat approximately -BCl2 approximately -BBr2 approximately -SiH3>-CH2CH3>-CH=CH2>-H approximately -Me>-C6H5>-SiCl3>-SnCl3>-CCH. Natural bond order analyses have been used to understand how the substituents at the boron center affect the trans-influence properties of the boryl ligands.

Imido transfer from bis(imido)ruthenium(VI) porphyrins to hydrocarbons: effect of imido substituents, C-H bond dissociation energies, and Ru(VI/V) reduction potentials.

[Ru(VI)(TMP)(NSO2R)2] (SO2R = Ms, Ts, Bs, Cs, Ns; R = p-C6H4OMe, p-C6H4Me, C6H5, p-C6H4Cl, p-C6H4NO2, respectively) and [Ru(VI)(Por)(NTs)2] (Por = 2,6-Cl2TPP, F20-TPP) were prepared by the reactions of [Ru(II)(Por)(CO)] with PhI=NSO2R in CH2Cl2. These complexes exhibit reversible Ru(VI/V) couple with E(1/2) = -0.41 to -0.

Silver nanoparticles fabricated in Hepes buffer exhibit cytoprotective activities toward HIV-1 infected cells.

Silver nanoparticles fabricated in Hepes buffer exhibit potent cytoprotective and post-infected anti-HIV-1 activities toward Hut/CCR5 cells.

Alkene cis-dihydroxylation by [(Me3tacn)(CF3CO2)RuVI O2)]ClO4(Me(3)tacn = 1,4,7-Trimethyl-1,4,7-triazacyclononane): structural characterization of [3 + 2] cycloadducts and kinetic studies.

cis-Dioxoruthenium(VI) complex [(Me(3)tacn)(CF(3)CO(2))Ru(VI)O(2)]ClO(4) (1, Me(3)tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) reacted with alkenes in aqueous tert-butyl alcohol to afford cis-1,2-diols in excellent yields under ambient conditions. When the reactions of 1 with alkenes were conducted in acetonitrile, oxidative C=C cleavage reaction prevailed giving carbonyl products in >90% yields without any cis-diol formation. The alkene cis-dihydroxylation and C=C cleavage reactions proceed via the formation of a [3 + 2] cycloadduct between 1 and alkenes, analogous to the related reactions with alkynes [Che et al.

Gold(III) compound is a novel chemocytotoxic agent for hepatocellular carcinoma.

Recently, a series of gold(III) meso-tetraarylporphyrins that are stable against demetallation in physiological conditions have been synthesized. In the present study, the antitumor effects of one of these compounds, gold(III) meso-tetraarylporphyrin 1a (gold-1a) was investigated in an orthotopic rat hepatocellular carcinoma (HCC) model as well as using a HCC cell line. The rat HCC model was induced by injection of rat hepatoma cells, McA-RH7777, into the left lobe of the liver.

Water soluble luminescent platinum terpyridine complexes with glycosylated acetylide and arylacetylide ligands: photoluminescent properties and cytotoxicities.

Platinum(II) terpyridine complexes with glycosylated acetylide and arylacetylide ligands bind to DNA with binding constants approximately 10(5) mol(-1) dm(3); the glycosylated arylacetylide complexes exhibit emission at lambda(max) approximately 620 nm in water and are up to approximately 100-times higher in potency than the clinical cisplatin drug in killing cancer cells.

Hydrocarbon oxidation by beta-halogenated dioxoruthenium(VI) porphyrin complexes: effect of reduction potential (RuVI/V) and C-H bond-dissociation energy on rate constants.

beta-Halogenated dioxoruthenium(VI) porphyrin complexes [Ru(VI)(F(28)-tpp)O(2)] [F(28)-tpp=2,3,7,8,12,13, 17,18-octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato(2-)] and [Ru(VI)(beta-Br(8)-tmp)O(2)] [beta-Br(8)-tmp=2,3,7,8,12,13,17,18-octabromo-5,10,15,20- tetrakis(2,4,6-trimethylphenyl)porphyrinato(2-)] were prepared from reactions of [Ru(II)(por)(CO)] [por=porphyrinato(2-)] with m-chloroperoxybenzoic acid in CH(2)Cl(2). Reactions of [Ru(VI)(por)O(2)] with excess PPh(3) in CH(2)Cl(2) gave [Ru(II)(F(20)-tpp)(PPh(3))(2)] [F(20)-tpp=5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato(2-)] and [Ru(II)(F(28)-tpp)(PPh(3))(2)]. The structures of [Ru(II)(por)(CO)(H(2)O)] and [Ru(II)(por)(PPh(3))(2)] (por=F(20)-tpp, F(28)-tpp) were determined by X-ray crystallography, revealing the effect of beta-fluorination of the porphyrin ligand on the coordination of axial ligands to ruthenium atom.

Highly cytotoxic iron(II) complexes with pentadentate pyridyl ligands as a new class of anti-tumor agents.

The iron(II) complexes and with pentadentate pyridyl ligands are stable under physiological conditions and exhibit higher cytotoxicities toward a series of human carcinoma cell lines than cisplatin; can significantly increase intracellular oxidant levels, cleave supercoiled plasmid DNA in vitro without addition of a reductant and induce apoptotic cell death in human cervical epithelioid carcinoma cells (HeLa) as observed in flow cytometric studies.

Fluorescent anion sensor derived from cholic acid: the use of flexible side chain.

[structure: see text] The fluorescent photoinduced electron transfer (PET) chemosensors 1-3 were synthesized from cholic acid. 1 and 2 containing amidothiourea groups as anion receptive sites demonstrated much higher affinity toward anions than 3 containing traditional thiourea H-bond donating group. Comparative studies on their binding affinity toward carboxylates, dihydrogen phosphate, and halides revealed that the amidothiourea moiety on the C17 side chain could work cooperatively with H-bond donating groups on C7 and C12 to bind spherical halogen anions.

Fluorescein-labeled beta-lactamase mutant for high-throughput screening of bacterial beta-lactamases against beta-lactam antibiotics.

The increasing emergence of new bacterial beta-lactamases that can efficiently hydrolyze beta-lactam antibiotics to clinically inactive carboxylic acids has created an intractable problem in the treatment of bacterial infections, and it is highly desirable to develop a useful tool that can rapidly screen bacteria for beta-lactamases against a variety of antibiotic candidates in a high-throughput manner. This paper describes the use of a fluorescein-labeled beta-lactamase mutant (E166Cf) as a convenient fluorescent tool to screen beta-lactamases, including the Bacillus cereus beta-lactamase I (PenPC), B. cereus beta-lactamase II, Bacillus licheniformis PenP, Escherichia coli TEM-1, and Enterobacter cloacae P99 against various beta-lactam antibiotics (penicillin G, penicillin V, ampicillin, cefuroxime, cefoxitin, moxalactam, cephaloridine), using a 96-well microplate reader.

Catalytic asymmetric alkynylation of alpha-imino ester: a versatile approach to optically active unnatural alpha-amino acid derivatives.

The catalytic asymmetric introduction of alkynyl functionality to alpha-amino acid derivatives was realized by the direct addition of terminal alkynes to alpha-imino ester in the presence of chiral Cu(I) complex under mild reaction conditions. Owing to the rich chemistry to which alkyne can be subjected, the present system provides a remarkably versatile tool for the construction of optically active alpha-amino acid derivatives. Good yields and enantiomeric excess values were achieved with an array of terminal alkynes and challenging, biologically active, unnatural alpha-amino acid derivatives could be conveniently obtained.

Activities of fresh juice of Scutellaria barbata and warmed water extract of Radix Sophorae Tonkinensis on anti-proliferation and apoptosis of human cancer cell lines.

The possible antiproliferative and apoptotic inducing potentials of fresh juice prepared from Scutellaria barbata (SBJ) and warmed water extract of Radix Sophorae Tonkinensis (RSTE) have been tested on a series of cancer cell lines, including HepG2 hepatoblastoma, Hep3B hepatocellular carcinoma, MDA-MB231 breast carcinoma, A549 lung cancer and KG-1 acute myelogenous leukaemia in vitro. Both SBJ and RSTE were able to inhibit the growth of cancer cell lines and induce apoptosis. Further analysis of the action of RSTE on HepG2 cells suggested that the activity of the central machinery of apoptosis, caspase 3, was significantly elevated.

Physiologically stable vanadium(IV) porphyrins as a new class of anti-HIV agents.

The water soluble oxovanadium(IV) tetraarylporphyrin has demonstrated excellent solution stability against glutathione reduction and high potency (5 microM, 97% inhibition) in inhibiting HIV-1 replication in Hut/CCR5 cells.

Proteomic analysis of a preneoplastic phenotype in ovarian surface epithelial cells derived from prophylactic oophorectomies.

Objective: To study the pattern of protein expression associated with a predisposition to develop ovarian cancer.

Methods: Prophylactic oophorectomy is used to prevent ovarian carcinoma in high-risk populations who have a strong family history of breast/ovarian cancer. In ovarian specimens of these women, the ovarian surface epithelium (OSE), which is tissue of origin of epithelial ovarian cancer, often shows altered morphology, growth patterns and differentiation features that are believed to be preneoplastic.

Chiral osmium complexes with sterically bulky Schiff-base ligands. Crystal structures of Os(IV) derivatives and the reactivity and catalytic cyclopropanation of alkenes with EDA.

The syntheses and reactivities of sterically encumbered trans-dioxoosmium(VI) complexes containing Schiff-base ligands bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamine (H2tBu-salch) and bis(3,5-dibromosalicylidene)-1,2-cyclohexane-diamine (H2Br-salch) are described. Reactions of [Os(VI)tBu-salch)O2] (1a) and [Os(VI)(Br-salch)O2] (1b) with PPh(3), p-X-arylamines (X = NO2, CN), N2H4 x H2O, Ph2NNH2, SOCl2, CF3CO2H, Br2, and I2 under reducing conditions gave [Os(II)(Br-salch)(OPPh3)2] (2), [Os(IV)(Br-salch)(p-X-C6H4NH)2] (3), [mu-O-{Os(IV)(tBu-salch)(p-NO2C6H4NH)}2] (4), [Os(II)(Br-salch)(N2)(H2O)] (5), [Os(IV)(tBu-salch)(OH)(Cl)] (6), [Os(IV)(tBu-salch)(OH)2] (7), [Os(IV)(tBu-salch)Cl2] (8), [Os(IV)(tBu-salch)(CF3CO2)2] (9), [Os(IV)(tBu-salch)Br2] (10), and [Os(IV)(tBu-salch)I2] (11), respectively. X-ray crystal structure determinations of [Os(IV)(Br-salch)(p-NO2C6H4NH)2] (3a), [Os(IV)(Br-salch)(p-CNC6H4NH)2] (3b), 6, 8, 9, and 11 reveal the Os-N(amido) distances to be 1.

Tuning the reactivity of dioxoruthenium(VI) porphyrins toward an arylimine by altering porphyrin substituents.

Reaction of dioxoruthenium(VI) porphyrins [Ru(VI)(Por)O2] with arylimine HN=CPh2 in dichloromethane afforded bis(methyleneamido)ruthenium(IV) porphyrins [Ru(IV)(Por)(N=CPh2)2] for Por = 4-Cl-TPP and TMP; (methyleneamido)hydroxoruthenium(IV) porphyrins [Ru(IV)(Por)(N=CPh2)(OH)] for Por = TPP and TTP; and bis(arylimine)ruthenium(II) porphyrins [Ru(II)(Por)(HN=CPh2)2] for Por = 3,5-Cl2TPP and 3,5-(CF3)2TPP. In dichloromethane solution exposed to air, complex [Ru(II)(3,5-Cl2TPP)(HN=CPh2)2] underwent oxidative deprotonation to form [Ru(IV)(3,5-Cl2TPP)(N=CPh2)2]. The new ruthenium porphyrins were identified by 1H NMR, UV-vis, IR, and mass spectroscopy, along with elemental analysis.

Metalloporphyrin-catalyzed diastereoselective epoxidation of allyl-substituted alkenes.

By using [Mn(2,6-Cl(2)TPP)Cl] (1) as a catalyst and Oxone/H(2)O(2) as an oxidant, we have developed an efficient method for erythro-selective epoxidation of acyclic allyl-substituted alkenes, including allylic alcohols, amines, and esters. Up to 9:1 erythro selectivities for terminal allyllic alkenes could be achieved, which are significantly higher than that achieved using m-CPBA as an oxidant. In addition, the synthetic utilities of this epoxidation method were highlighted in stereoselective synthesis of key anti-HIV drug intermediates and epoxidation of glycals.