π-Selective stationary phases: (III) Influence of the propyl phenyl ligand density on the aromatic and methylene selectivity of aromatic compounds in reversed phase liquid chromatography

The retention characteristics of phenyl type stationary phases for reversed phase high performance liquid chromatography are still largely unknown. This paper explores the retention process of these types of stationary phases by examining the retention behaviour of linear PAHs and n-alkylbenzenes on a series of propyl phenyl stationary phases that have changes in their ligand density (1.23, 1.31, 1.97, 2.50 μmol m⁻²). The aromatic and methylene selectivities increased with increasing ligand density until a point where a plateau was observed, overall the propyl phenyl phases had a higher degree of aromatic selectivity than methylene selectivity indicating that these columns are suitable for separations involving aromatic compounds. Also, retention characteristics relating to the size of the solute molecule were observed to be influenced by the ligand density. It is likely that the changing retention characteristics are caused by the different topologies of the stationary phases at different ligand densities. At high ligand densities, the partition coefficient became constant.

Anti-metastatic and differential effects on protein expression of epigallocatechin-3-gallate in HCCLM6 hepatocellular carcinoma cells

Hepatocellular carcinoma (HCC) is the fifth most common cancer worldwide and the third highest cause of cancer-related mortality in humans. Epigallocatechin-3-gallate (EGCG) has been shown to inhibit the metastatic activity of certain cancer cells. The aim of this study was to determine the effects and molecular mechanism(s) of action of EGCG in human HCC cells. A migration and invasion assay for the metastatic behavior of HCCLM6 cells was performed. The anti-metastatic effects of EGCG were investigated by RT-PCR and gelatin zymography. A total cellular protein profile was obtained using 2-dimensional gel electrophoresis (2-DE), followed by matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF-MS) analyses of proteins with significant differences in expression following treatment with EGCG. The results revealed that EGCG induced apoptosis and inhibited the metastasis of HCCLM6 cells. The anti-metastatic effects of EGCG were associated with the inhibition of matrix metalloproteinase (MMP)-2 and MMP-9 activity. The expression levels of far upstream element (FUSE) binding protein 1 (FUBP1), heat shock protein beta 1 (HSPB1), heat shock 60 kDa protein 1 (chaperonin) (CH60) and nucleophosmin (NPM) proteins, which are associated with metastasis, were significantly altered in the EGCG-treated HCCLM6 cells. The data from the present study suggest that EGCG has potential as a therapeutic agent for the treatment of HCC.

Physicochemical properties of N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide for sodium metal battery applications.

The physicochemical properties of a range of NaNTf2 (or NaTFSI) salt concentrations in N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (or C3mpyrFSI) ionic liquid were investigated by DSC, conductivity, cyclic voltammetry and diffusivity studies. Cyclic voltammetry indicated a stable sodium plating behavior with a current of 5 mA cm(-2) at 25 °C to 20 mA cm(-2) at 100 °C, along with high reversibility identifying this electrolyte as a possible candidate for sodium-ion or sodium metal battery applications. (23)Na NMR chemical shifts and spectral linewidths (FWHM) indicate a complex coordination of the Na(+) ion which is dependent on both temperature and salt concentration with an apparently stronger coordination to the NTf2 anion upon increasing the NaNTf2 concentration. Temperature dependent PFG-NMR diffusion measurements show that both FSI and NTf2 have a comparable behaviour although the smaller FSI anion is more diffusive.

Epigallocatechin-3-gallate induces the apoptosis of hepatocellular carcinoma LM6 cells but not non-cancerous liver cells

Epigallocatechin-3-gallate (EGCG) is a constituent of green tea and has been associated with anticancer activity. In the present study, the inhibitory effect of EGCG on human hepatocellular cancer cells was examined by cell viability assay, in vitro apoptosis assay and cell cycle analysis. In addition, gene expression was measured to elucidate the molecular mechanisms of action of EGCG by mitochondrial membrane potential (MMP) determination and western blot analysis. We demonstrated that EGCG induced apoptosis, decreased mitochondrial membrane potential and promoted G0/G1 phase cell cycle arrest of HCCLM6 cells but not that of non-cancerous liver cells (HL-7702). The EGCG-induced apoptosis of HCCLM6 cells was associated with a significant decrease in Bcl-2 and NF-κB expression. In addition, the expression of Bax, p53, caspase-9 and caspase-3 increased, and cytochrome c was released. These results suggest that EGCG inhibits the progression of cancer through cytocidal activity and that it is a potential therapeutic compound for hepatocellular carcinoma (HCC).

Physical properties of high Li-ion content N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide based ionic liquid electrolytes

Electrolytes based on bis(fluorosulfonyl)imide (FSI) with a range of LiFSI salt concentrations were characterized using physical property measurements, as well as NMR, FT-IR and Raman spectroscopy. Different from the behavior at lower concentrations, the FSI electrolyte containing 1 : 1 salt to IL mole ratio showed less deviation from the KCl line in the Walden plot, suggesting greater ionic dissociation. Diffusion measurements show higher mobility of lithium ions compared to the other ions, which suggests that the partial conductivity of Li(+) is higher at this higher composition. Changes in the FT-IR and Raman peaks indicate that the cis-FSI conformation is preferred with increasing Li salt concentration.

Inhibitory Effect of Gallic Acid and Its Esters on 2,2 '-Azobis(2-amidinopropane)hydrochloride (AAPH)-Induced Hemolysis and Depletion of Intracellular Glutathione in Erythrocytes

The protective effect of gallic acid and its esters, methyl, propyl, and lauryl gallate, against 2,2'-azobis(2-amidinopropane)hydrochloride (AAPH)-induced hemolysis and depletion of intracellular glutathione (GSH) in erythrocytes was studied. The inhibition of hemolysis was dose-dependent, and the esters were significantly more effective than gallic acid. Gallic acid and its esters were compared with regard to their reactivity to free radicals, using the DPPH and AAPH/pyranine free-cell assays, and no significant difference was obtained. Gallic acid and its esters not only failed to inhibit the depletion of intracellular GSH in erythrocytes induced by AAPH but exacerbated it. Similarly, the oxidation of GSH by AAPH or horseradish peroxidase/H(2)O(2) in cell-free systems was exacerbated by gallic acid or gallates. This property could be involved in the recent findings on proapoptotic and pro-oxidant activities of gallates in tumor cells. We provide evidence that lipophilicity and not only radical scavenger potency is an important factor regarding the efficiency of antihemolytic substances.

Nanoparticles of octakis [3-(3-amino-1,2,4-triazole)propyl] octasilsesquioxane as ligands for Cu(II), Ni(II), Cd(II), Zn(II), and Fe(III) in aqueous solution

Nanoparticles of octakis[3-(3-amino-1,2,4-triazole)propyl]octasilsesquioxane (ATZ-SSQ) were tested as ligands, for transition-metal ions in aqueous solution with a special attention to sorption isotherms, ligand-metal interaction, and determination of metal ions in natural waters. The adsorption potential of the material ATZ-SSQ was compared with related [3(3-amino-1,2,4-triazole)propyl]silica gel (ATZ-SG). The adsorption was performed using a batchwise process and both organofunctionalized surfaces showed the ability to adsorb the metal ions from aqueous solution. The Langmuir model was used to simulate the sorption isotherms. The results suggest that the sorption of these metals on ATZ-SSQ and ATZ-SG occurs mainly by surface complexation. The equilibrium condition is reached at time lower than 3 min for ATZ-SSQ, while for ATZ-SG is only reached at time of 25 min. The maximum metal ion uptake values for ATZ-SSQ were higher than the corresponding values achieved with the ATZ-SG. In order to obtain more information on the ligand-metal interaction of the complexes on the surface of the ATZ-SSQ nanomaterial, ESR study with various degrees of copper loadings was carried out. The ATZ-SSQ was tested for the determination (in flow using a column technique) of the metal ions present in natural waters. (C) 2007 Elsevier B.V. All rights reserved.

Characterization and catalytic activity of 2,6-dichlorophenyl substituted iron(III) porphyrin supported on silica gel and imidazole propyl gel

In this work we have made use of the study of the interaction between Fe(TDCPP)(+) and the axial ligands OH- and imidazole in order to help characterize the heterogenized catalysts Fe(TDCPP)SG and Fe(TDCPP)IPG through UV-VIS and EPR spectroscopies and thus, better understand their different catalytic activity in the oxidation of cyclohexane by PhIO. We have found out that in Fe(TDCPP)SG (containing 1.2 X 10(-6) mol Fe(TDCPP)(+)/g of support), the FeP bis-coordinates to silica gel through Fe-O coordination and it is high-spin (FeP)-P-III species. In Fe(TDCPP)IPG 1 (containing 1.1 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-4) mol imidazole/g of support), the FeP is bis-ligated to imidazole propyl gel through Fe-imidazole coordination and using NO as a paramagnetic probe, we present evidence that Fe(TDCPP)(+) is present as a mixture of low-spin (FeP)-P-III and (FeP)-P-II species. This catalyst led to a relative low yield of cyclohexanol (25%) because the bis-coordination of the (FeP)-P-III to the support partially blocks the reaction between Fe(TDCPP)(+) and PhIO, thus leading to the formation of only a small amount of the active species Fe-IV(OP+, while the (FeP)-P-II species do not react with the oxygen donor. Increasing the amount of Fe(TDCPP)(+) and decreasing the amount of imidazole in the support led to the obtention of high-spin (FeP)-P-III EPR signals in the spectra of Fe(TDCPP)IPG 5 (containing 4.4 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-5) mol imidazole/g of IPG), together with low-spin (FeP)-P-III species. This latter catalyst led to better cyclohexanol yields (67%) than Fe(TDCPP)IPG 1. Fe(TDCPP)IPG 5 was further used in a study of the optimization of its catalytic activity and in recycling experiments in the optimized conditions. Recycling oxidation reactions of Fe(TDCPP)IPG 5 led to a total turnover number of 201 and total cyclohexanol yield of 201%, which could not be attained with Fe(TDCPP)Cl in homogeneous solution (turnover = 96) due to the difficulty in recovering and reusing it.

Study of the catalytical intermediates of metalloporphyrins supported on imidazole propyl gel

In this work, the catalytic intermediates for Fe(TPP)(+), Fe(TDCPP)(+), Fe(TFPP)(+), Mn(TPP)(+) and Mn(TDCPP)(+) supported on imidazole propyl gel with PhIO were studied by UV-Vis spectrophotometry. For Fe(TPP)+ and Fe(TFPP)+ the study was also monitored by EPR spectroscopy. The active catalytic intermediate observed for FeP-IPG is the ore-iron (IV) porphyrin pi cation radical Fe-IV(O)P.+, which is evidenced by a decrease in the intensity of the Sorer band. The total re-establishment of the initial Soret band intensity for Fe(TDCPP)IPG and Fe(TFPP)IPG at the end of the reaction shows that they were completely recovered, There are advantages in following the reactions of PNO with unsubstituted Fe(TPP)(+) and Mn(TPP)(+) on IPG by UV-Vis, since they were slower and allowed to 'see' the intermediate species without spectral interference from the recovered catalyst, since they are only partially recovered. With Fe(TPP)IPG, a band at 580 nm was detected at the beginning of the reaction, indicating the possible formation of a Fe-OIPh intermediate. Supporting Mn(TPP)(+) on IPG leads to a shift of band V from 478 nm to 488 nm. In the reaction of MnP-IPG with PhIO, we observed the disappearance of the band in 488 nm and the appearance of a band in 412 nm, which corresponds to the active catalytic intermediate Mn-V(O)P as the main component, as is expected for a more efficient system. The recovery of supported catalysts observed in these experiments was further proved with the possibility of their successive recyclings in cyclohexane oxidation reactions by PhIO.

Preconcentration and determination of mercury(II) at a chemically modified electrode containing 3-(2-thioimidazolyl)propyl silica gel

A mercury-sensitive chemically modified graphite paste electrode was constructed by incorporating modified silica gel into a conventional graphite paste electrode. The functional group attached to the (3-chloropropyl) silica gel surface was 2-mercaptoimidazole, giving a new product denoted by 3-(2-thioimidazolyl)propyl silica gel, which is able to complex mercury ions. Mercury was chemically adsorbed on the modified graphite paste electrode containing 3-(2-thioimidazolyl)propyl silica (TIPSG GPE) by immersion in a Hg(II) solution, and the resultant surface was characterized by cyclic and differential pulse anodic stripping voltammetry. One cathodic peak at 0.1 V and other anodic peak at 0.34 V were observed on scanning the potential from -0.1 to 0.8 V (0.01 M KNO3; ν = 2.0 mV s-1 νs. Ag/AgCl). The anodic peak at 0.34 V show an excellent sensitivity for Hg(II) ions in the presence of several foreign ions. A calibration graph covering the concentration range from 0.02 to 2 mg L-1 was obtained. The detection limit was estimated to be 5 μg L-1. The precision for six determinations of 0.05 and 0.26 mg L-1 Hg(II) was 3.0 and 2.5% (relative standard deviation), respectively. The method can be used to determine the concentration of mercury(II) in natural waters contaminated by this metal. 2005 © The Japan Society for Analytical Chemistry.

Study of adsorption and preconcentration by using a new silica organomodified with [3-(2,2′-dipyridylamine)propyl] groups

In this work, a silica surface chemically modified with [3-(2,2′-dipyridylamine)propyl] groups, named [3-(2,2′- dipyridylamine)propyl]silica (Si-Pr-DPA) was prepared, characterized, and evaluated for its heavy metal adsorption characteristics from aqueous solution. To our knowledge, we are the first authors who have reported the present modification. The material was characterized using infrared spectroscopy, SEM, and NMR 29Si and 13C solid state. Batch and column experiments were conducted to investigate for heavy metal removal from dilute aqueous solution by sorption onto Si-Pr-DPA. From a number of studies the affinity of various metal ions for the Si-Pr-DPA sorbent was determined to follow the order Fe(III) > Cr(III) >> Cu(II) > Cd(II) > Pb(II) > Ni(II). Two standard reference materials were used for checking the accuracy and precision of the method. The proposed method was successfully applied to the analysis of environmental samples. This ligand material has great advantage for adsorption of transition-metal ions from aqueous medium due to its high degree of organofunctionalization associated with the large adsorption capacity, reutilization possibility, and rapidity in reaching the equilibrium. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, structure, and thermal stability of poly(methyl methacrylate)-co- poly(3-tri(methoxysilyil)propyl methacrylate)/ montmorillonite nanocomposites

The structure and the thermodegradation behavior of both poly(methyl methacrylate)-co-poly(3-tri(methoxysilyil)propyl methacrylate) polymer modified with silyl groups and of intercalated poly(methyl methacrylate)-co-poly(3- tri(methoxysilyil)propyl methacrylate)/Cloisite 15A™ nanocomposite have been in situ probed. The structural feature were comparatively studied by Fourier transform infrared spectroscopy (FTIR), 13C and 29Si nuclear magnetic resonance (NMR), and small angle X-ray scattering (SAXS) measurements. The intercalation of polymer in the interlayer galleries was evidenced by the increment of the basal distance from 31 to 45 Å. The variation of this interlayer distance as function of temperature was followed by in situ SAXS. Pristine polymer decomposition pathway depends on the atmosphere, presenting two steps under air and three under N2. The nanocomposites are more stable than polymer, and this thermal improvement is proportional to the clay loading. The experimental results indicate that clay nanoparticles play several different roles in polymer stabilization, among them, diffusion barrier, charring, and suppression of degradation steps by chemical reactions between polymer and clay. Charring is atmosphere dependent, occurring more pronounced under air. © 2012 Society of Plastics Engineers.