Julien Furrer - Academia.edu (original) (raw)
Papers by Julien Furrer
JBIC Journal of Biological Inorganic Chemistry
Amino acid dhbq 2,5-Dihydroxy-1,4-benzoquinonato dhnq 5,8-Dihydroxy-1,4-naphthoquinonato DOSY Dif... more Amino acid dhbq 2,5-Dihydroxy-1,4-benzoquinonato dhnq 5,8-Dihydroxy-1,4-naphthoquinonato DOSY Diffusion-ordered spectroscopy ESI Electrospray ionization oxa Oxalato tpt 2,4,6-Tri(pyridin-4-yl)-1,3,5-triazine
JBIC Journal of Biological Inorganic Chemistry
A new series of cationic dinuclear p-cymene ruthenium complexes bridged by three thiophenolato li... more A new series of cationic dinuclear p-cymene ruthenium complexes bridged by three thiophenolato ligands containing various substituents mainly in meta and ortho positions, [(Z 6 -p-MeC 6 H 4 Pr i ) 2 Ru 2 (m 2 -SR) 3 ] + (R = 3-C 6 H 4 Me: 1; R = 3-C 6 H 4 OMe: 2; R = 3-C 6 H 4 OEt: 3; R = 3-C 6 H 4 CF 3 : 4; R = 3-C 6 H 4 NH 2 : 5; R = 3-C 6 H 4 Cl: 6; R = 2-C 6 H 4 Me: 7; R = 2-C 6 H 4 OMe: 8; R = 2-C 6 H 4 Pr i : 9; R = 2-C 6 H 4 CF 3 : 10; R = npt: 11 (npt = 2-naphthyl); R = mco: 12 (mco = 4-methylcoumarinyl); R = 3,5-C 6 H 3 Me 2 : 13; R = 3,5-C 6 H 3 (CF 3 ) 2 : 14; R = 3,5-C 6 H 3 Cl 2 :
JBIC Journal of Biological Inorganic Chemistry
Chemical Communications
Norbornapeptides (bicyclo[2.2.1]heptapeptides) and related bicyclic homodetic peptides were prepa... more Norbornapeptides (bicyclo[2.2.1]heptapeptides) and related bicyclic homodetic peptides were prepared by solid-phase peptide synthesis using an orthogonal protection scheme. These conformationally rigid peptides cover an almost pristine area of peptide topological space and adopt globular shapes similar to those of short α-helical peptides.
Chembiochem, 2003
Hsp90 is one of the most abundant chaperone proteins in the cytosol. In an ATP-dependent manner i... more Hsp90 is one of the most abundant chaperone proteins in the cytosol. In an ATP-dependent manner it plays an essential role in the folding and activation of a range of client proteins involved in signal transduction and cell cycle regulation. We used NMR shift perturbation experiments to obtain information on the structural implications of the binding of AMP-PNP (adenylyl-imidodiphosphate-a non-hydrolysable ATP analogue), ADP and the inhibitors radicicol and geldanamycin. Analysis of 1 H, 15 N correlation spectra showed a specific pattern of chemical shift perturbations at N210 (ATP binding domain of Hsp90, residues 1 ± 210) upon ligand binding. This can be interpreted qualitatively either as a consequence of direct ligand interactions or of ligand-induced conformational changes within the protein. All ligands show specific interactions in the binding site, which is known from the crystal structure of the N-terminal domain of Hsp90. For AMP-PNP and ADP, additional shift perturbations of residues outside the binding pocket were observed and can be regarded as a result of conformational rearrangement upon binding. According to the crystal structures, these regions are the first a-helix and the ™ATP-lid∫ ranging from amino acids 85 to 110. The N-terminal domain is therefore not a passive nucleotide-binding site, as suggested by X-ray crystallography, but responds to the binding of ATP in a dynamic way with specific structural changes required for the progression of the ATPase cycle.
PloS one, 2015
1H high resolution magic angle spinning (HR-MAS) NMR spectroscopy was applied in combination with... more 1H high resolution magic angle spinning (HR-MAS) NMR spectroscopy was applied in combination with multivariate statistical analyses to study the metabolic response of whole cells to the treatment with a hexacationic ruthenium metallaprism [1]6+ as potential anticancer drug. Human ovarian cancer cells (A2780), the corresponding cisplatin resistant cells (A2780cisR), and human embryonic kidney cells (HEK-293) were each incubated for 24 h and 72 h with [1]6+ and compared to untreated cells. Different responses were obtained depending on the cell type and incubation time. Most pronounced changes were found for lipids, choline containing compounds, glutamate and glutathione, nucleotide sugars, lactate, and some amino acids. Possible contributions of these metabolites to physiologic processes are discussed. The time-dependent metabolic response patterns suggest that A2780 cells on one hand and HEK-293 cells and A2780cisR cells on the other hand may follow different cell death pathways and...
Advances in Chemistry, 2014
This review article covers the synthetic strategies, structural aspects, and host-guest propertie... more This review article covers the synthetic strategies, structural aspects, and host-guest properties of ruthenium metalla-assemblies, with a special focus on their use as drug delivery vectors. The two-dimensional metalla-rectangles show interesting host-guest possibilities but seem less appropriate for being used as drug carriers. On the other hand, metalla-prisms allow encapsulation and possible targeted release of bioactive molecules and consequently show some potential as drug delivery vectors. The reactivity of these metalla-prisms can be fine-tuned to allow a fine control of the guest's release. The larger metalla-cubes can be used to stabilize the formation of G-quadruplex DNA and can be used to encapsulate and release photoactive molecules such as porphins. These metalla-assemblies demonstrate great prospective in photodynamic therapy.
![Research paper thumbnail of Cationic triruthenium(III) oxo complexes of the type [Ru3O(OAc)6L3]+ containing imidazole, pyrazole, thiazole and oxazole ligands: Synthesis, molecular structure, and cytotoxicity](https://attachments.academia-assets.com/39297607/thumbnails/1.jpg)
](Inorganica Chimica Acta, 2014
The cationic complexes [Ru 3 O(OAc) 6 L 3 ] + [1: L = imidazole (imz), 2: L = pyrazole (pyz), 3: ... more The cationic complexes [Ru 3 O(OAc) 6 L 3 ] + [1: L = imidazole (imz), 2: L = pyrazole (pyz), 3: L = thiazole (taz), 4: L = oxazole (oxz), 5: L = benzimidazole (biz), 6: L = benzopyrazole (bpz), 7: L = benzothiazole (btz) and 8: L = benzoxazole (boz)] were synthesized by reaction of the precursor [Ru 3 O(OAc) 6 (MeOH) 3 ] + with the corresponding heterocycle and isolated as the triflate salts. In all complexes, the heterocycle is coordinated to ruthenium by the p-bonded nitrogen atom. The single-crystal X-ray structure analysis of [4][CF 3-SO 3 ] shows the typical triruthenium l 3 -oxo core, in which the three ruthenium atoms are pairwise bridged by two acetato ligands and N-coordinated by an oxazole ligand. The in vitro anticancer activity of 1-7 was studied with human lung cancer cells A549, the only active complex being the benzothiazole derivative 7 (IC 50 = 49 lM).
European Journal of Inorganic Chemistry, 2014
Journal of Organometallic Chemistry, 2015
A new series of cationic dinuclear arene ruthenium complexes bridged by three thiophenolato ligan... more A new series of cationic dinuclear arene ruthenium complexes bridged by three thiophenolato ligands, [(h 6 -arene) 2 Ru 2 (m 2 -SR) 3 ] þ with arene ¼ indane, R ¼ met: 1 (met ¼ 4-methylphenyl); R ¼ mco: 4 (mco ¼ 4-methylcoumarin-7-yl); arene ¼ biphenyl, R ¼ met: 2; R ¼ mco: 5; arene ¼ 1,2,3,4tetrahydronaphthalene, R ¼ met: 3; R ¼ mco: 6, have been prepared from the reaction of the neutral precursor [(h 6 -arene)Ru(m 2 -Cl)Cl] 2 and the corresponding thiophenol RSH. All cationic complexes have been isolated as chloride salts and fully characterized by spectroscopic and analytical methods. The molecular structure of 1, solved by X-ray structure analysis of a single crystal of the chloride salt, shows the two ruthenium atoms adopting a pseudo-octahedral geometry without metalemetal bond in accordance with the noble gas rule. All complexes are stable in H 2 O at 37 C, but only 1 remains soluble in a 100 mM aqueous NaCl solution, while significant percentages (30e60 %) of 2e6 precipitate as chloride salts under these conditions. The 4-methylphenylthiolato complexes (R ¼ met) are highly cytotoxic towards human ovarian cancer cells, the IC 50 values being in the sub-micromolar range, while the 4-methylcoumarin-7-yl thiolato complexes (R ¼ mco) are only slightly cytotoxic. Complexes 1 and 3
Journal of the Electrochemical Society, 2014
A multi-functionalized suppressor additive (IBDGE) for copper electroplating has been synthesized... more A multi-functionalized suppressor additive (IBDGE) for copper electroplating has been synthesized by co-polymerizing imidazole and 1,4-butanediol diglycidyl ether (BDGE). This new co-polymer contains ether, hydroxyl and imidazolium functionalities that are common functional groups in polyalkylene glycol (PAG) suppressors and state-of-the-art leveler additives such as the polymerizate of imidazole and epichlorohydrin (IMEP). Electrochemical studies reveal a synergistic suppression effect of these functional groups with respect to the copper electroplating. In addition, this polymer demonstrates a variety of interactions with bis-(sodium-sulfopropyl)disulfide (SPS). Firstly, the ether part of the polymer interacts antagonistically with SPS which is typical for PAG polymers. Secondly, the IMEP-like part of the polymer interacts antagonistically or synergistically with the SPS similar to the IMEP polymer. Because of this, temporal instabilities appear in the galvanostatic copper plating in the form of oscillations in the potential/time transient measurements. An N-shaped negative differential resistance (N-NDR) is visible in polarization measurements. Overall, this new polymer acts as an efficient suppressor additive rather than as a leveler additive. Fill-experiments on Damascene test-structures demonstrate a successful superfill. The quality of the resulting copper deposit was analyzed on blanket wafers by Secondary Ion Mass Spectroscopy (SIMS) experiments.
Journal of the Electrochemical Society, 2013
Galvanostatic potential/time transient measurements confirm TBPS (3,3-thiobis-1-propanesulfonic a... more Galvanostatic potential/time transient measurements confirm TBPS (3,3-thiobis-1-propanesulfonic acid, as received) as accelerant for copper electrodeposition. In-situ STM data reveal, however, identical structure motifs on single crystalline Cu(100) model substrates when exposed to TBPS containing electrolytes as previously reported for MPS (3-mercapto-1-propanesulfonic acid) and SPS (bis(3-sulfopropyl)disulfide). In all three cases MPS is found as chemisorbed species on the copper. In the present paper we discuss two hypotheses rationalizing both the accelerating effect of the TBPS (as received) on the copper electrodeposition and the appearance of MPS on the copper surface. The first possibility proposes that low levels of MPS and SPS are present in raw TBPS as origin for the observed acceleration. A second scenario suggests the formation of MPS as a result of the asymmetric TBPS decomposition. The latter hypothesis will be discussed on the basis of DFT calculations.
Iranian journal of pharmaceutical research : IJPR, 2014
Phytochemical investigation of a dichloromethane-methanol (1:1) extract of the fruit pericarp of ... more Phytochemical investigation of a dichloromethane-methanol (1:1) extract of the fruit pericarp of Omphalocarpum procerum which exhibited antiplasmodial activity during preliminary screening led to the isolation of the new fatty ester triterpenoid 3β-hexadecanoyloxy-28-hydroxyolean-12-en-11-one (1), together with five known compounds 2-6. The structure of the new compound as well as those of the known compounds was established by means of spectroscopic methods and by comparison with previously reported data. Compounds 1- 4 were evaluated in-vitro for their cytotoxicity against L6 cell lines and antiprotozoal activities against Plasmodium falciparum, Leishmania donovani, Trypanosoma brucei rhodesiense and Trypanosoma cruzi (species responsible for human malaria, visceral leishmaniasis, African trypanosomiasis and Chagas disease, respectively). The tested compounds showed weak to moderate antiprotozoal activity and, no significant effect was detected regarding their cytotoxic potency.
JBIC Journal of Biological Inorganic Chemistry, 2014
Amino acid dhbq 2,5-Dihydroxy-1,4-benzoquinonato dhnq 5,8-Dihydroxy-1,4-naphthoquinonato DOSY Dif... more Amino acid dhbq 2,5-Dihydroxy-1,4-benzoquinonato dhnq 5,8-Dihydroxy-1,4-naphthoquinonato DOSY Diffusion-ordered spectroscopy ESI Electrospray ionization oxa Oxalato tpt 2,4,6-Tri(pyridin-4-yl)-1,3,5-triazine
Org. Biomol. Chem., 2014
Interactions between three hexacationic arene ruthenium metallaprisms, ([(pcymene) Ru 6 (tpt) 2 (... more Interactions between three hexacationic arene ruthenium metallaprisms, ([(pcymene) Ru 6 (tpt) 2 (dhnq) 3 ] 6+ , [(p-cymene) 6 Ru 6 (tpt) 2 (dhbq) 3 ] 6+ and [(pcymene) 6 Ru 6 (tpt) 2 (oxa) 3 ] 6+ , and a series of human proteins including human serum albumin, transferrin, cytochrome c, myoglobin and ubiquitin have been studied using NMR spectroscopy, mass spectrometry and circular dichroism spectroscopy. All data suggest that no covalent adducts are formed between the proteins and the metallaprisms.
Med. Chem. Commun., 2015
In order to improve the water-solubility of dinuclear thiolato-bridged arene ruthenium complexes,... more In order to improve the water-solubility of dinuclear thiolato-bridged arene ruthenium complexes, a new series was synthesized by conjugation to octaarginine, octalysine, and cyclo[Lys-Arg-Gly-Asp-D-Phe] using the chloroacetyl thioether (ClAc) ligation, resulting in cytotoxic conjugates against A2780 human ovarian cancer cells (IC 50 = 2 -8 µ µ µ µM) and against the cisplatin resistant line A2780cisR (IC 50 = 7 -15 µ µ µ µM). These metal complexes represent, to the best of our knowledge, the most cytotoxic ruthenium bioconjugates reported so far.
![Research paper thumbnail of Encapsulation of Triphenylene Derivatives in the Hexanuclear Arene Ruthenium Metallo-Prismatic Cage [Ru6(p-PriC6H4Me)6(tpt)2(dhbq)3]6+ (tpt = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine, dhbq = 2,5-dihydroxy-1,4-benzoquinonato)](https://attachments.academia-assets.com/39297599/thumbnails/1.jpg)
](Zeitschrift für anorganische und allgemeine Chemie, 2008
A large cationic triangular metallo-prism, [Ru 6 (p-Pr i C 6 H 4 Me) 6 (tpt) 2 (dhbq) 3 ] 6ϩ (1) ... more A large cationic triangular metallo-prism, [Ru 6 (p-Pr i C 6 H 4 Me) 6 (tpt) 2 (dhbq) 3 ] 6ϩ (1) 6ϩ , incorporating p-cymene ruthenium building blocks, bridged by 2,5-dihydroxy-1,4-benzoquinonato (dhbq) ligands, and connected by two 2,4,6-tri(pyridin-4yl)-1,3,5-triazine (tpt) subunits, allows the permanent encapsulation of the triphenylene derivatives hexahydroxytriphenylene, C 18 H 6 (OH) 6 and hexamethoxytriphenylene, C 18 H 6 (OMe) 6 . These two cationic carceplex systems [C 18 H 6 (OH) 6 ʚ1] 6ϩ and 1349 [C 18 H 6 (OMe) 6 ʚ1] 6ϩ have been isolated as their triflate salts. The molecular structure of these systems has been established by onedimensional 1 H ROESY NMR experiments as well as by the singlecrystal structure analysis of [C 18 H 6 (OMe) 6 ʚ1][O 3 SCF 3 ] 6 .
JBIC Journal of Biological Inorganic Chemistry
Amino acid dhbq 2,5-Dihydroxy-1,4-benzoquinonato dhnq 5,8-Dihydroxy-1,4-naphthoquinonato DOSY Dif... more Amino acid dhbq 2,5-Dihydroxy-1,4-benzoquinonato dhnq 5,8-Dihydroxy-1,4-naphthoquinonato DOSY Diffusion-ordered spectroscopy ESI Electrospray ionization oxa Oxalato tpt 2,4,6-Tri(pyridin-4-yl)-1,3,5-triazine
JBIC Journal of Biological Inorganic Chemistry
A new series of cationic dinuclear p-cymene ruthenium complexes bridged by three thiophenolato li... more A new series of cationic dinuclear p-cymene ruthenium complexes bridged by three thiophenolato ligands containing various substituents mainly in meta and ortho positions, [(Z 6 -p-MeC 6 H 4 Pr i ) 2 Ru 2 (m 2 -SR) 3 ] + (R = 3-C 6 H 4 Me: 1; R = 3-C 6 H 4 OMe: 2; R = 3-C 6 H 4 OEt: 3; R = 3-C 6 H 4 CF 3 : 4; R = 3-C 6 H 4 NH 2 : 5; R = 3-C 6 H 4 Cl: 6; R = 2-C 6 H 4 Me: 7; R = 2-C 6 H 4 OMe: 8; R = 2-C 6 H 4 Pr i : 9; R = 2-C 6 H 4 CF 3 : 10; R = npt: 11 (npt = 2-naphthyl); R = mco: 12 (mco = 4-methylcoumarinyl); R = 3,5-C 6 H 3 Me 2 : 13; R = 3,5-C 6 H 3 (CF 3 ) 2 : 14; R = 3,5-C 6 H 3 Cl 2 :
JBIC Journal of Biological Inorganic Chemistry
Chemical Communications
Norbornapeptides (bicyclo[2.2.1]heptapeptides) and related bicyclic homodetic peptides were prepa... more Norbornapeptides (bicyclo[2.2.1]heptapeptides) and related bicyclic homodetic peptides were prepared by solid-phase peptide synthesis using an orthogonal protection scheme. These conformationally rigid peptides cover an almost pristine area of peptide topological space and adopt globular shapes similar to those of short α-helical peptides.
Chembiochem, 2003
Hsp90 is one of the most abundant chaperone proteins in the cytosol. In an ATP-dependent manner i... more Hsp90 is one of the most abundant chaperone proteins in the cytosol. In an ATP-dependent manner it plays an essential role in the folding and activation of a range of client proteins involved in signal transduction and cell cycle regulation. We used NMR shift perturbation experiments to obtain information on the structural implications of the binding of AMP-PNP (adenylyl-imidodiphosphate-a non-hydrolysable ATP analogue), ADP and the inhibitors radicicol and geldanamycin. Analysis of 1 H, 15 N correlation spectra showed a specific pattern of chemical shift perturbations at N210 (ATP binding domain of Hsp90, residues 1 ± 210) upon ligand binding. This can be interpreted qualitatively either as a consequence of direct ligand interactions or of ligand-induced conformational changes within the protein. All ligands show specific interactions in the binding site, which is known from the crystal structure of the N-terminal domain of Hsp90. For AMP-PNP and ADP, additional shift perturbations of residues outside the binding pocket were observed and can be regarded as a result of conformational rearrangement upon binding. According to the crystal structures, these regions are the first a-helix and the ™ATP-lid∫ ranging from amino acids 85 to 110. The N-terminal domain is therefore not a passive nucleotide-binding site, as suggested by X-ray crystallography, but responds to the binding of ATP in a dynamic way with specific structural changes required for the progression of the ATPase cycle.
PloS one, 2015
1H high resolution magic angle spinning (HR-MAS) NMR spectroscopy was applied in combination with... more 1H high resolution magic angle spinning (HR-MAS) NMR spectroscopy was applied in combination with multivariate statistical analyses to study the metabolic response of whole cells to the treatment with a hexacationic ruthenium metallaprism [1]6+ as potential anticancer drug. Human ovarian cancer cells (A2780), the corresponding cisplatin resistant cells (A2780cisR), and human embryonic kidney cells (HEK-293) were each incubated for 24 h and 72 h with [1]6+ and compared to untreated cells. Different responses were obtained depending on the cell type and incubation time. Most pronounced changes were found for lipids, choline containing compounds, glutamate and glutathione, nucleotide sugars, lactate, and some amino acids. Possible contributions of these metabolites to physiologic processes are discussed. The time-dependent metabolic response patterns suggest that A2780 cells on one hand and HEK-293 cells and A2780cisR cells on the other hand may follow different cell death pathways and...
Advances in Chemistry, 2014
This review article covers the synthetic strategies, structural aspects, and host-guest propertie... more This review article covers the synthetic strategies, structural aspects, and host-guest properties of ruthenium metalla-assemblies, with a special focus on their use as drug delivery vectors. The two-dimensional metalla-rectangles show interesting host-guest possibilities but seem less appropriate for being used as drug carriers. On the other hand, metalla-prisms allow encapsulation and possible targeted release of bioactive molecules and consequently show some potential as drug delivery vectors. The reactivity of these metalla-prisms can be fine-tuned to allow a fine control of the guest's release. The larger metalla-cubes can be used to stabilize the formation of G-quadruplex DNA and can be used to encapsulate and release photoactive molecules such as porphins. These metalla-assemblies demonstrate great prospective in photodynamic therapy.
Inorganica Chimica Acta, 2014
The cationic complexes [Ru 3 O(OAc) 6 L 3 ] + [1: L = imidazole (imz), 2: L = pyrazole (pyz), 3: ... more The cationic complexes [Ru 3 O(OAc) 6 L 3 ] + [1: L = imidazole (imz), 2: L = pyrazole (pyz), 3: L = thiazole (taz), 4: L = oxazole (oxz), 5: L = benzimidazole (biz), 6: L = benzopyrazole (bpz), 7: L = benzothiazole (btz) and 8: L = benzoxazole (boz)] were synthesized by reaction of the precursor [Ru 3 O(OAc) 6 (MeOH) 3 ] + with the corresponding heterocycle and isolated as the triflate salts. In all complexes, the heterocycle is coordinated to ruthenium by the p-bonded nitrogen atom. The single-crystal X-ray structure analysis of [4][CF 3-SO 3 ] shows the typical triruthenium l 3 -oxo core, in which the three ruthenium atoms are pairwise bridged by two acetato ligands and N-coordinated by an oxazole ligand. The in vitro anticancer activity of 1-7 was studied with human lung cancer cells A549, the only active complex being the benzothiazole derivative 7 (IC 50 = 49 lM).
European Journal of Inorganic Chemistry, 2014
Journal of Organometallic Chemistry, 2015
A new series of cationic dinuclear arene ruthenium complexes bridged by three thiophenolato ligan... more A new series of cationic dinuclear arene ruthenium complexes bridged by three thiophenolato ligands, [(h 6 -arene) 2 Ru 2 (m 2 -SR) 3 ] þ with arene ¼ indane, R ¼ met: 1 (met ¼ 4-methylphenyl); R ¼ mco: 4 (mco ¼ 4-methylcoumarin-7-yl); arene ¼ biphenyl, R ¼ met: 2; R ¼ mco: 5; arene ¼ 1,2,3,4tetrahydronaphthalene, R ¼ met: 3; R ¼ mco: 6, have been prepared from the reaction of the neutral precursor [(h 6 -arene)Ru(m 2 -Cl)Cl] 2 and the corresponding thiophenol RSH. All cationic complexes have been isolated as chloride salts and fully characterized by spectroscopic and analytical methods. The molecular structure of 1, solved by X-ray structure analysis of a single crystal of the chloride salt, shows the two ruthenium atoms adopting a pseudo-octahedral geometry without metalemetal bond in accordance with the noble gas rule. All complexes are stable in H 2 O at 37 C, but only 1 remains soluble in a 100 mM aqueous NaCl solution, while significant percentages (30e60 %) of 2e6 precipitate as chloride salts under these conditions. The 4-methylphenylthiolato complexes (R ¼ met) are highly cytotoxic towards human ovarian cancer cells, the IC 50 values being in the sub-micromolar range, while the 4-methylcoumarin-7-yl thiolato complexes (R ¼ mco) are only slightly cytotoxic. Complexes 1 and 3
Journal of the Electrochemical Society, 2014
A multi-functionalized suppressor additive (IBDGE) for copper electroplating has been synthesized... more A multi-functionalized suppressor additive (IBDGE) for copper electroplating has been synthesized by co-polymerizing imidazole and 1,4-butanediol diglycidyl ether (BDGE). This new co-polymer contains ether, hydroxyl and imidazolium functionalities that are common functional groups in polyalkylene glycol (PAG) suppressors and state-of-the-art leveler additives such as the polymerizate of imidazole and epichlorohydrin (IMEP). Electrochemical studies reveal a synergistic suppression effect of these functional groups with respect to the copper electroplating. In addition, this polymer demonstrates a variety of interactions with bis-(sodium-sulfopropyl)disulfide (SPS). Firstly, the ether part of the polymer interacts antagonistically with SPS which is typical for PAG polymers. Secondly, the IMEP-like part of the polymer interacts antagonistically or synergistically with the SPS similar to the IMEP polymer. Because of this, temporal instabilities appear in the galvanostatic copper plating in the form of oscillations in the potential/time transient measurements. An N-shaped negative differential resistance (N-NDR) is visible in polarization measurements. Overall, this new polymer acts as an efficient suppressor additive rather than as a leveler additive. Fill-experiments on Damascene test-structures demonstrate a successful superfill. The quality of the resulting copper deposit was analyzed on blanket wafers by Secondary Ion Mass Spectroscopy (SIMS) experiments.
Journal of the Electrochemical Society, 2013
Galvanostatic potential/time transient measurements confirm TBPS (3,3-thiobis-1-propanesulfonic a... more Galvanostatic potential/time transient measurements confirm TBPS (3,3-thiobis-1-propanesulfonic acid, as received) as accelerant for copper electrodeposition. In-situ STM data reveal, however, identical structure motifs on single crystalline Cu(100) model substrates when exposed to TBPS containing electrolytes as previously reported for MPS (3-mercapto-1-propanesulfonic acid) and SPS (bis(3-sulfopropyl)disulfide). In all three cases MPS is found as chemisorbed species on the copper. In the present paper we discuss two hypotheses rationalizing both the accelerating effect of the TBPS (as received) on the copper electrodeposition and the appearance of MPS on the copper surface. The first possibility proposes that low levels of MPS and SPS are present in raw TBPS as origin for the observed acceleration. A second scenario suggests the formation of MPS as a result of the asymmetric TBPS decomposition. The latter hypothesis will be discussed on the basis of DFT calculations.
Iranian journal of pharmaceutical research : IJPR, 2014
Phytochemical investigation of a dichloromethane-methanol (1:1) extract of the fruit pericarp of ... more Phytochemical investigation of a dichloromethane-methanol (1:1) extract of the fruit pericarp of Omphalocarpum procerum which exhibited antiplasmodial activity during preliminary screening led to the isolation of the new fatty ester triterpenoid 3β-hexadecanoyloxy-28-hydroxyolean-12-en-11-one (1), together with five known compounds 2-6. The structure of the new compound as well as those of the known compounds was established by means of spectroscopic methods and by comparison with previously reported data. Compounds 1- 4 were evaluated in-vitro for their cytotoxicity against L6 cell lines and antiprotozoal activities against Plasmodium falciparum, Leishmania donovani, Trypanosoma brucei rhodesiense and Trypanosoma cruzi (species responsible for human malaria, visceral leishmaniasis, African trypanosomiasis and Chagas disease, respectively). The tested compounds showed weak to moderate antiprotozoal activity and, no significant effect was detected regarding their cytotoxic potency.
JBIC Journal of Biological Inorganic Chemistry, 2014
Amino acid dhbq 2,5-Dihydroxy-1,4-benzoquinonato dhnq 5,8-Dihydroxy-1,4-naphthoquinonato DOSY Dif... more Amino acid dhbq 2,5-Dihydroxy-1,4-benzoquinonato dhnq 5,8-Dihydroxy-1,4-naphthoquinonato DOSY Diffusion-ordered spectroscopy ESI Electrospray ionization oxa Oxalato tpt 2,4,6-Tri(pyridin-4-yl)-1,3,5-triazine
Org. Biomol. Chem., 2014
Interactions between three hexacationic arene ruthenium metallaprisms, ([(pcymene) Ru 6 (tpt) 2 (... more Interactions between three hexacationic arene ruthenium metallaprisms, ([(pcymene) Ru 6 (tpt) 2 (dhnq) 3 ] 6+ , [(p-cymene) 6 Ru 6 (tpt) 2 (dhbq) 3 ] 6+ and [(pcymene) 6 Ru 6 (tpt) 2 (oxa) 3 ] 6+ , and a series of human proteins including human serum albumin, transferrin, cytochrome c, myoglobin and ubiquitin have been studied using NMR spectroscopy, mass spectrometry and circular dichroism spectroscopy. All data suggest that no covalent adducts are formed between the proteins and the metallaprisms.
Med. Chem. Commun., 2015
In order to improve the water-solubility of dinuclear thiolato-bridged arene ruthenium complexes,... more In order to improve the water-solubility of dinuclear thiolato-bridged arene ruthenium complexes, a new series was synthesized by conjugation to octaarginine, octalysine, and cyclo[Lys-Arg-Gly-Asp-D-Phe] using the chloroacetyl thioether (ClAc) ligation, resulting in cytotoxic conjugates against A2780 human ovarian cancer cells (IC 50 = 2 -8 µ µ µ µM) and against the cisplatin resistant line A2780cisR (IC 50 = 7 -15 µ µ µ µM). These metal complexes represent, to the best of our knowledge, the most cytotoxic ruthenium bioconjugates reported so far.
Zeitschrift für anorganische und allgemeine Chemie, 2008
A large cationic triangular metallo-prism, [Ru 6 (p-Pr i C 6 H 4 Me) 6 (tpt) 2 (dhbq) 3 ] 6ϩ (1) ... more A large cationic triangular metallo-prism, [Ru 6 (p-Pr i C 6 H 4 Me) 6 (tpt) 2 (dhbq) 3 ] 6ϩ (1) 6ϩ , incorporating p-cymene ruthenium building blocks, bridged by 2,5-dihydroxy-1,4-benzoquinonato (dhbq) ligands, and connected by two 2,4,6-tri(pyridin-4yl)-1,3,5-triazine (tpt) subunits, allows the permanent encapsulation of the triphenylene derivatives hexahydroxytriphenylene, C 18 H 6 (OH) 6 and hexamethoxytriphenylene, C 18 H 6 (OMe) 6 . These two cationic carceplex systems [C 18 H 6 (OH) 6 ʚ1] 6ϩ and 1349 [C 18 H 6 (OMe) 6 ʚ1] 6ϩ have been isolated as their triflate salts. The molecular structure of these systems has been established by onedimensional 1 H ROESY NMR experiments as well as by the singlecrystal structure analysis of [C 18 H 6 (OMe) 6 ʚ1][O 3 SCF 3 ] 6 .