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Complexation
Kinds of Complexation Terms modified by Complexation Selected AbstractsA Study of Heavy Metal Complexation in Grape JuiceELECTROANALYSIS, Issue 5-6 2005Íńigo Salinas Abstract Differential pulse anodic stripping voltammetry, DPASV, has been used to monitor the initial stages of grape juice fermentation, focusing on Zn interactions with natural occurring ligands. Langmuir and Scatchard linearization methods have been employed. A 1,:,1 ratio has been found by either method; from Langmuir data analysis only one ligand population was found, while Scatchard approach gave rise to the detection of two ligand types. Both data analysis procedures led to the same total ligand concentration. When catechin was used as model ligand, a 1,:,1 ratio was found for Zn and also for Cu. [source] Study of the Complexation, Adsorption and Electrode Reaction Mechanisms of Chromium(VI) and (III) with DTPA Under Adsorptive Stripping Voltammetric ConditionsELECTROANALYSIS, Issue 19 2003Sylvia Sander Abstract The complexation of Cr(III) and Cr(VI) with diethylenetriaminepentaacetic acid (DTPA), the redox behavior of these complexes and their adsorption on the mercury electrode surface were investigated by a combination of electrochemical techniques and UV/vis spectroscopy. A homogenous two-step reaction was observed when mixing Cr(III), present as hexaquo complex, with DTPA. The first reaction product, the electroactive 1,:,1 complex, turns into an electroinactive form in the second step. The results indicate that the second reaction product is presumably a 1,:,2 Cr(III)/DTPA complex. The electroreduction of the DTPA-Cr(III) complex to Cr(II) was found to be diffusion rather than adsorption controlled. The Cr(III) ion, generated in-situ from Cr(VI) at the mercury electrode at about ,50,mV (vs. Ag|AgCl) (3,mol,L,1 KCl), was found to form instantly an electroactive and adsorbable complex with DTPA. By means of electrocapillary measurements its surface activity was shown to be 30 times higher than that of the complex built by homogenous reaction of DTPA with the hydrated Cr(III). Both components, DTPA and the in-situ built complex Cr(III) ion were found to adsorb on the mercury electrode. The effect of nitrate, used as catalytic oxidant in the voltammetric determination method, on the complexation reaction and on the adsorption processes was found to be negligible. The proposed complex structures and an overall reaction scheme are shown. [source] Binding of ciprofloxacin by humic substances: A molecular dynamics studyENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 1 2010Ludmilla Aristilde Abstract A comprehensive assessment of the potential impacts of antimicrobials released into the environment requires an understanding of their sequestration by natural particles. Of particular interest are the strong interactions of antimicrobials with natural organic matter (NOM), which are believed to reduce their bioavailability, retard their abiotic and biotic degradation, and facilitate their persistence in soils and aquatic sediments. Molecular dynamics (MD) relaxation studies of a widely used fluoroquinolone antibiotic, ciprofloxacin (Cipro), interacting with a model humic substance (HS) in a hydrated environment, were performed to elucidate the mechanisms of these interactions. Specifically, a zwitterionic Cipro molecule, the predominant species at circumneutral pH, was reacted either with protonated HS or deprotonated HS bearing Ca, Mg, or Fe(II) cations. The HS underwent conformational changes through rearrangements of its hydrophobic and hydrophilic regions and disruption of its intramolecular H-bonds to facilitate favorable intermolecular H-bonding interactions with Cipro. Complexation of the metal cations with HS carboxylates appeared to impede binding of the positively charged amino group of Cipro with these negatively charged HS complexation sites. On the other hand, an outer-sphere complex between Cipro and the HS-bound cation led to ternary Cipro,metal,HS complexes in the case of Mg,HS and Fe(II),HS, but no such bridging interaction occurred with Ca,HS. The results suggested that the ionic potential (valence/ionic radius) of the divalent cation may be a determining factor in the formation of the ternary complex, with high ionic potential favoring the bridging interaction. Environ. Toxicol. Chem. 2010;29:90,98. © 2009 SETAC [source] Chemical speciation and cellular deposition of lead in Sesbania drummondiiENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 9 2004Nilesh C. Sharma Abstract The internalized speciation of lead in roots and leaves of Sesbania drummondii, a lead hyperaccumulator, grown in lead nitrate solution was studied using x-ray absorption near-edge structure and extended x-ray absorption fine structure. Lead was predominantly present as lead acetate in both plant tissues. The other dominant forms of accumulation were lead,sulfur compounds. Whereas lead sulfate and sulfide were found in leaves, only lead sulfide was detected in root samples. These observations indicate that S. drummondii is able to biotransform lead nitrate in the nutrient solution to lead acetate and sulfate in its tissues. Complexation with acetate and sulfate may be a lead detoxification strategy in this plant. Transmission-electron microscopy revealed the pattern of lead distribution in and around the cells. Dense distributions of lead grains were detected in root cell walls and plasma membranes, whereas evidence for vacuolar transport of lead was noticed in the stem cells. [source] A TRLFS Study on the Complexation of CmIII and EuIII with 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine in Water/Methanol MixtureEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2010Sascha Trumm Abstract The complexation of CmIII and EuIII with 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPr-BTP) in water/methanol solution is studied. 1:3 complexes [M(nPr-BTP)3]3+ form from the solvated metal ions upon addition of ligand. The conditional stability constants are log,K = 14.4 and log,K = 11.9. For both metal ions the complexation reaction is both enthalpy and entropy driven. ,H is 10.1 kJ/mol more negative than ,H, whereas the entropy difference is small. The difference in ,G between the formation of the CmIII and EuIII complexes is in good agreement with nPr-BTP's selectivity in liquid-liquid extraction. [source] Long-Lived Luminescent Dendrimers with a [Ru(dpp)3]2+ -Type Core: Synthesis and Photophysical PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2009Uwe Hahn Abstract Metallodendrimers built around a [Ru(dpp)3]2+ -type core (dpp = 4,7-diphenyl-1,10-phenanthroline) were prepared containing peripheral phenyl moieties. The convergent synthesis of the ligands was accomplished by coupling dendritic branches with a focal amino function to the chelating phenanthroline precursor under the formation of sulfonamide linkages. Complexation of ruthenium ions afforded the corresponding metallodendrimers with up to 24 peripheral phenyl units in the case of the largest dendritic structure. The absorption spectra and luminescence properties of the four new dendrimers are reported. The dendritic effect is clearly visible, going from zero to second generation, as demonstrated by an elongation in the excited-state lifetime in aerated acetonitrile and improved emission quantum yields relative to the reference complex containing a [Ru(dpp)3]2+ core. Interestingly, the use of rigid and conjugated ruthenium-based cores results, for all dendritic structures, in luminescence lifetimes that are several microseconds long in deaerated solutions, even at room temperature.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Complexation of 2,6-Bis(3-pyrazolyl)pyridine,Bis(thiocyanato)iron(II) with a Bridging 4,4,-Bipyridine: A New Example of a Dinuclear Spin Crossover ComplexEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 7 2008Dalila Fedaoui Abstract Investigation of the coordination behavior of 2,6-bis(3-pyrazolyl)pyridine,bis(thiocyanato)iron(II) towards bridging ligands led to the discovery of a novel dinuclear complex showing spin-crossover. Chemical and structural characterization and a first report of physical properties are presented.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthesis, Complexation and Spectrofluorometric Studies of a New NS3 Anthracene-Containing Macrocyclic LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2006Abel Tamayo Abstract A new fluorescent device for detecting protons and metal ions, 11-(9-anthracenylmethyl)-1,4,7-trithia-11-azacyclotetradecane (L), has been synthesised. In addition, the photophysical properties of both the free and protonated species have been examined by absorption and fluorescence titrations of dichloromethane solutions of L with methanesulfonic acid. The coordinating properties of L toward PdII, ZnII, NiII and CoII have been studied both in solution and in the solid state. Different behaviours have been observed in the absorption and fluorescence titrations of L with the above-mentioned transition-metal ions. To evaluate whether these differences were due to the existence of equilibria between protonated and complexed species, such titrations have been repeated in the presence of an equivalent amount of acid. The structure of the [Pd(L)](BF4)2 complex has been solved by X-ray crystallography. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Monophosphanylcalix[6]arene Ligands: Synthesis Characterization, Complexation, and Their Use in CatalysisEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2006Yasushi Obora Abstract Novel phosphanylcalix[6]arenes having mono- O -diphenylphosphanylmethyl (3) and mono- O -(4-diphenylphosphanylphenyl)methyl substituents (5) have been synthesized. The structures of these monophosphanylcalix[6]arenes were determined by NMR spectroscopy, mass spectrometry, and X-ray crystal structure analysis. The X-ray structure reveals that 3 adopts a flattened 1,2,3-alternate conformation in the crystalline state, while the NMR spectra show that 3 and 5 have a cone conformation in solution. Structure optimization and energy calculations for 3 and 5 at the B3LYP/LANL2DZ-CONFLEX5/MMFF94s level of theory show that the cone conformation is slightly more stable than the 1,2,3-alternate conformation by 0.36 kcal,mol,1 for 3 and 0.96 kcal,mol,1 for 5. Complexation of 3 with [PtCl2(COD)] and [Rh(COD)2]BF4 gives cis -coordinated [PtCl2(3)2] and [Rh(COD)(3)2]BF4, respectively. The X-ray analysis of [PtCl2(3)2] shows that 3 adopts a cone conformation upon complexation. Combination of 3 and 5 with [Rh(COD)2]BF4 provides an active catalyst for the hydroformylation of a variety of terminal alkenes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Modulation of the Communication between Redox Centers in a Tris(ferrocene)-tren Ligand by Complexation of Lanthanide IonsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2003Marie Heitzmann The tripodal ligand L built on the tren platform and bearing three chemically equivalent ferrocene units was prepared and characterized. Electrochemical investigations indicate that electrostatic communication occurs between the three ferrocene groups in L, which leads to the observation of two distinct voltammetric waves. The electrochemical communication between the three ferrocene moieties is disrupted in 1:1 (L:M3+) type complexes formed between L and Y3+ or Eu3+ metal cations and their electrochemical response tends towards that of a single three-independent-electrons oxidation wave. Modulation of the electrochemical properties of L in the presence of lanthanide ions might be exploited with a view to their electrochemical sensing in organic and aqueous media. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Improved and Controlled Complexation of Paraquat Derivatives by the Formation of a Bis(m -phenylene)-26-Crown-8-Based Lariat EtherEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 29 2010Mingming Zhang Abstract A novel bis(m -phenylene)-26-crown-8-based lariat ether (i.e., 3b) was synthesized and characterized. It can bind paraquat derivatives more strongly than bis(m -phenylene)-26-crown-8 in solution. It forms pseudorotaxanes with two paraquat derivatives in the solid state. N -Methyl substitution was found to play an important role on the binding strength of lariat ether 3b. Furthermore, due to the introduction of two benzyloxy groups, its binding to paraquat derivatives can be switched off (and back on) by adding K+ (and then dibenzo-18-crown-6), and the disassociation percentage depends on the concentration of the added K+ ions. [source] Complexation and Dynamic Switching Properties of Fluorophore-Appended Resorcin[4]arene CavitandsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 5 2010Laura D. Shirtcliff Abstract Fluorophore-appended resorcin[4]arene-based cavitands having pyrene (2) and anthracene (3) moieties attached to the rims were prepared by short synthetic routes. Both undergo reversible temperature- and acid- (CF3COOD) induced vase,,,kite switching as evidenced by 1H NMR spectroscopy. The 1H NMR spectra also suggest that suitably sized solvents, such as [D8]toluene, efficiently solvate the cavity, reducing the conformational flexibility. In [D12]mesitylene, both cavitands undergo remarkably stable host-guest inclusion complexation with cycloalkanes. The larger cavity of 3 preferentially hosts cyclohexane, whereas the smaller cavity of 2 forms the most stable complex with cyclopentane. The propensity for the cavitands to facilitate ,,, stacking between the chromophores was confirmed by both 1H NMR and fluorescence spectroscopy. The interchromophoric interaction is strongly solvent-dependent: ,,, stacking between the pyrene moieties of 2 is not as efficient in [D8]toluene, as it solvates the inner cavity and prevents the two chromophores from approaching each other. Fluorescence studies revealed an unexpectedly large conformational flexibility of the cavitand structures both in the vase and kite forms, which was further confirmed by molecular dynamics simulations. Excimer formation is most preferred in [D12]mesitylene when the cavities are empty, whereas efficient solvation or guest binding in the interior spaces reduces the propensity for excimer formation. The observed high conformational flexibility of the cavitands in solution explains previous differences from the behavior of related systems in the solid state. This study shows that the rigid, perfect vase and kite geometries found for bridged resorcin[4]arene cavitands in the solid state are largely a result of crystal packing effects and that the conformational flexibility of the structures in solution is rather high. [source] Novel Promising Benzoazacrown Ethers as a Result of Ring Transformation of Benzocrown Ethers: Synthesis, Structure, and Complexation with Ca2+EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 16 2003Sergey P. Gromov Abstract A series of promising benzoazacrown ethers with the nitrogen atom conjugated with the benzene ring were synthesized using a novel synthetic procedure based on stepwise transformation of the macroheterocycle. The structures and spectral properties of the resulting benzoazacrown ethers and their complexes with Ca2+ were studied by X-ray diffraction and 1H, 13C, and 15N NMR spectroscopy including the 2D NOESY technique. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] PEI,PEG,Chitosan-Copolymer-Coated Iron Oxide Nanoparticles for Safe Gene Delivery: Synthesis, Complexation, and TransfectionADVANCED FUNCTIONAL MATERIALS, Issue 14 2009Forrest M. Kievit Abstract Gene therapy offers the potential of mediating disease through modification of specific cellular functions of target cells. However, effective transport of nucleic acids to target cells with minimal side effects remains a challenge despite the use of unique viral and non-viral delivery approaches. Here, a non-viral nanoparticle gene carrier that demonstrates effective gene delivery and transfection both in vitro and in vivo is presented. The nanoparticle system (NP,CP,PEI) is made of a superparamagnetic iron oxide nanoparticle (NP), which enables magnetic resonance imaging, coated with a novel copolymer (CP,PEI) comprised of short chain polyethylenimine (PEI) and poly(ethylene glycol) (PEG) grafted to the natural polysaccharide, chitosan (CP), which allows efficient loading and protection of the nucleic acids. The function of each component material in this nanoparticle system is illustrated by comparative studies of three nanoparticle systems of different surface chemistries, through material property characterization, DNA loading and transfection analyses, and toxicity assessment. Significantly, NP,CP,PEI demonstrates an innocuous toxic profile and a high level of expression of the delivered plasmid DNA in a C6 xenograft mouse model, making it a potential candidate for safe in vivo delivery of DNA for gene therapy. [source] Self-Assembling Peptide as a Potential Carrier for Hydrophobic Anticancer Drug Ellipticine: Complexation, Release and In Vitro DeliveryADVANCED FUNCTIONAL MATERIALS, Issue 1 2009Shan Yu Fung Abstract The self-assembling peptide EAK16-II is capable of stabilizing hydrophobic compounds to form microcrystal suspensions in aqueous solution. Here, the ability of this peptide to stabilize the hydrophobic anticancer agent ellipticine is investigated. The formation of peptide-ellipticine suspensions is monitored with time until equilibrium is reached. The equilibration time is found to be dependent on the peptide concentration. When the peptide concentration is close to its critical aggregation concentration, the equilibration time is minimal at 5,h. With different combinations of EAK16-II and ellipticine concentrations, two molecular states (protonated or cyrstalline) of ellipticine could be stabilized. These different states of ellipticine significantly affect the release kinetics of ellipticine from the peptide-ellipticine complex into the egg phosphatidylcholine vesicles, which are used to mimic cell membranes. The transfer rate of protonated ellipticine from the complex to the vesicles is much faster than that of crystalline ellipticine. This observation may also be related to the size of the resulting complexes as revealed from the scanning electron micrographs. In addition, the complexes with protonated ellipticine are found to have a better anticancer activity against two cancer cell lines, A549 and MCF-7. This work forms the basis for studies of the peptide-ellipticine suspensions in vitro and in vivo leading to future development of self-assembling peptide-based delivery of hydrophobic anticancer drugs. [source] Redox Properties of the Iron Complexes of Orally Active Iron Chelators CP20, CP502, CP509, and ICL670HELVETICA CHIMICA ACTA, Issue 12 2004Martin Merkofer Redox cycling of iron is a critical aspect of iron toxicity. Reduction of a low-molecular-weight iron(III)-complex followed by oxidation of the iron(II)-complex by hydrogen peroxide may yield the reactive hydroxyl radical (OH.) or an oxoiron(IV) species (the Fenton reaction). Complexation of iron by a ligand that shifts the electrode potential of the complex to either to far below ,350,mV (dioxygen/superoxide, pH=7) or to far above +320,mV (H2O2/HO., H2O pH=7) is essential for limitting Fenton reactivity. The oral chelating agents CP20, CP502, CP509, and ICL670 effectively remove iron from patients suffering from iron overload. We measured the electrode potentials of the iron(III) complexes of these drugs by cyclic voltammetry with a mercury electrode and determined the dependence on concentration, pH, and stoichiometry. The standard electrode potentials measured are ,620,mV, ,600,mV, ,535,mV, and ,535,mV with iron bound to CP20, ICL670, CP502, and CP509, respectively, but, at lower chelator concentrations, electrode potentials are significantly higher. [source] Poly(9,9-dioctylfluorene)-Based Conjugated Polyelectrolyte: Extended ,-Electron Conjugation Induced by Complexation with a Surfactant ZwitterionADVANCED MATERIALS, Issue 18 2010Giuseppina Pace We report on a conjugated polyelectrolyte (CPE) based on fluorene repeat units, which forms a supramolecular complex with a zwitterion surfactant. The complex self-assembles into multilamellar structures on solid substrates. The luminescence efficiency, low in the uncomplexed polymer, is strongly increased after complexation. This originates from the phase segregation between the aromatic backbone and ionic sides, reducing conformational defects and ionic dipole-induced quenching. [source] Acute cognitive effects of standardised Ginkgo biloba extract complexed with phosphatidylserineHUMAN PSYCHOPHARMACOLOGY: CLINICAL AND EXPERIMENTAL, Issue 4 2007D. O. Kennedy Abstract Recent data suggest that the complexation of standardised Ginkgo biloba extract (GBE) with soy-derived phospholipids enhances the bio-availablity of GBE's active components. The current study therefore aimed to assess the comparative cognitive and mood effects of a low dose of GBE and products complexing the same extract with either phosphatidylserine or phosphatidylcholine. The study utilised a placebo-controlled, multi-dose, double-blind, balanced-crossover design. Twenty-eight healthy young participants received 120,mg GBE, 120,mg GBE complexed with phosphatidylserine (VirtivaÔ), 120,mg GBE complexed with phosphatidylcholine and a matching placebo, on separate days 7 days apart. Cognitive performance was assessed using the Cognitive Drug Research (CDR) computerised test battery and Serial Subtraction tasks immediately prior to dosing and at 1, 2.5, 4 and 6,h thereafter. The primary outcome measures were the four aspects of cognitive performance, which have previously been derived by factor analysis of CDR subtests. Levels of terpenoids (bilobalide, ginkgolide A and ginkgolide B) were concomitantly assessed in plasma samples taken pre-dose and at 3 and 6.5,h post-dose. In keeping with previous research utilising the same methodology, 120,mg of GBE was not associated with markedly improved performance on the primary outcomes. However, administration of GBE complexed with phosphatidylserine resulted both in improved secondary memory performance and significantly increased speed of memory task performance across all of the post-dose testing sessions. Enhancement following GBE complexed with phosphatidylcholine was restricted to a modest improvement in secondary memory performance which was restricted to one post-dose time point. All three treatments were associated with improved calmness. There were no significant differences in post-dose levels of terpenoids between the Ginkgo containing treatments, although this latter finding may be attributable to methodological factors. Complexation with phosphatidylserine appears to potentiate the cognitive effects associated with a low dose of GBE. Further research is required to identify whether this effect is due to the complexation of the extracts, their mere combination, or the separate psychopharmacological actions of the two extracts. Copyright © 2007 John Wiley & Sons, Ltd. [source] A New Level of Hierarchical Structure Control by Use of Supramolecular Self-Assembled Dendronized Block Copolymers,ADVANCED MATERIALS, Issue 23 2008Chaoxu Li Complexation of dendronized block copolymers with sulfate alkyl tails forms unprecedented hierarchically ordered bulk structures, including rectangular-in-lamellar, tetragonal-in-lamellar, hexagonal-in-lamellar and lamellar-in-lamellar. These novel liquid-crystalline morphologies, which can be designed at low length scales in these systems, are expected to provide final materials with not only unprecedented structural complexity, but also tunable physical properties. [source] Complexation of 4-dimethylaminoazobenzene with various kinds of cyclodextrins: Effects of cyclodextrins on the thermal cis-to-trans isomerizationINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2002Yoshimi Sueishi On the basis of the change in electronic and induced circular dichroism spectra for complex formation, the complexation of 4-dimethylaminoazobenzene (DAAB) with four kinds of cyclodextrins (,- and ,-cyclodextrin (CD), heptakis(2,6-di- O -methyl)-,-cyclodextrin, and heptakis(2,3,6-tri- O -methyl)-,-cyclodextrin) was studied in methanol,water and dimethyl sulfoxide,water mixtures. It was found that the trans and cis isomers of DAAB form two different types of complex (inclusion and lid type) with CDs, depending on the kinds of CDs and solvents. Further, we have examined the effect of CDs on the thermal cis-to-trans isomerization of DAAB. The accelerated or decelerated effect on the thermal isomerization was observed upon adding CDs. The effects of CDs on the thermal isomerization are discussed in connection with the complexation of the cis-isomer of DAAB with CDs. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 481,487, 2002 [source] Complexation of C60 on a Cyclothiophene Monolayer Template,ADVANCED MATERIALS, Issue 4 2006E. Mena-Osteritz Highly ordered monolayers of macrocyclic oligothiophene C[12]T (see Figure) can be used as veritable templates to epitaxially grow 3D nanoarchitectures with C60 -fullerenes. Due to submolecularly resolved STM images, 1:1 complexes consisting of a ring-shaped p-type semiconductor (C[12]T) and a spherical n-type semiconductor (C60) can be investigated in terms of dynamics and complexation sites. [source] "Click" Polymer-Supported Palladium Nanoparticles as Highly Efficient Catalysts for Olefin Hydrogenation and Suzuki Coupling Reactions under Ambient ConditionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2009Cátia Ornelas Abstract Complexation of palladium(II) acetate [Pd(OAc)2] or dipotassium tetrachloropalladate [K2PdCl4] to "click" polymers functionalized with phenyl, ferrocenyl and sodium sulfonate groups gave polymeric palladium(II)-triazolyl complexes that were reduced to "click" polymer-stabilized palladium nanoparticles (PdNPs). Transmission electron microscopy (TEM) showed that reduction using sodium borohydride (NaBH4) produced PdNPs in the 1,3,nm range of diameters depending on the nature of the functional group, whereas slow reduction using methanol yielded PdNPs in the 22,25,nm range. The most active of these PdNPs (0.01% mol Pd), stabilized by poly(ferrocenyltriazolylmethyl)styrene, catalyzed the hydrogenation of styrene at 25,°C and 1 atm hydrogen, with turnover numbers (TONs) of 200,000. When stabilized by the water-soluble poly(sodium sulfonate-triazolylmethyl)styrene, the PdNPs (0.01% mol Pd) catalyze the Suzuki,Miyaura coupling between iodobenzene (PhI) and phenylboronic acid [PhB(OH)2] in water/ethanol (H2O/EtOH) at 25,°C with TONs of 8,200. This high catalytic activity is comparable to that obtained with "click" dendrimer-stabilized PdNPs under ambient conditions. [source] Complexation of sulfonamides with ,-cyclodextrin studied by experimental and theoretical methodsJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 7 2010Ariana Zoppi Abstract The complex formation between three structurally related sulfonamides (sulfadiazine (SDZ), sulfamerazine (SMR), and sulfamethazine (SMT)) and ,-cyclodextrin (,-CD) was studied, by exploring its structure affinity relationship. In all the cases, 1:1 stoichiometries were determined with different relative affinities found by phase solubility (SDZ:,-CD,>,SMR:,-CD,>,SMT:,-CD) and nuclear magnetic resonance (NMR) (SMT:,-CD,>,SMR:,-CD,>,SDZ:,-CD) studies. The spatial configurations determined by NMR were in agreement with those obtained by molecular modeling, showing that SDZ included its aniline ring into ,-CD, while SMR and SMT included the substituted pyrimidine ring. Energetic analyses demonstrated that hydrophobicity is the main driving force to complex formation. © 2010 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 99:3166,3176, 2010 [source] Complexation and chiral drug recognition of an amphiphilic phenothiazine derivative with , -cyclodextrinJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 4 2008Andrés Guerrero-Martínez Abstract Promethazine hydrochloride (PTZ) is an amphiphilic drug derived from the phenothiazine structure that possesses a charged aliphatic chain with a chiral carbon. In the presence of , -cyclodextrin (, -CD), this drug undergoes significant changes of its photophysical properties in aqueous solution. Fluorescence spectroscopy measurements show the formation of a 1:1 stoichiometry complex with quantum yield lower than that of the pure PTZ, and two fluorescence lifetimes, which can be assigned to the free and complexed forms of the drug. In addition, 1H NMR spectra, and 2D rotating-frame Overhauser enhancement spectroscopy (ROESY) were used to characterize the drug and the complex, and to determine the effects of the complexation on the aggregation. For the drug binary system, a noncooperative association process is observed, and in the presence of macrocycle, the chemical shifts reveal a chiral resolution of the drug enantiomers, with different stability constants of the complexes. , -CD modifies the aggregation of PTZ in an extension that confirms the formation of a 1:1 complex. ROE enhancements and molecular modeling strategies show the most likely structure of the complex in solution, in which one of the phenyl rings is buried into the CD cavity, with a slight inclusion of the aliphatic part. © 2007 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 97:1484,1498, 2008 [source] Mucoadhesive microspheres for nasal administration of an antiemetic drug, metoclopramide: in-vitro/ex-vivo studiesJOURNAL OF PHARMACY AND PHARMACOLOGY: AN INTERNATI ONAL JOURNAL OF PHARMACEUTICAL SCIENCE, Issue 3 2005Elisabetta Gavini Microparticulate delivery systems designed for the nasal administration of an antiemetic drug, metoclopramide hydrochloride, were prepared. Microspheres composed of sodium alginate, chitosan hydrochloride, or both, were obtained using a spray-drying method; some batches of drug-free microparticles were prepared as a comparison. The morphology, in-vitro swelling behaviour, mucoadhesive properties and drug release from microparticles were evaluated. Ex-vivo drug permeation tests were carried out using sheep nasal mucosa; permeation test of the drug solution was peformed as comparison. During ex-vivo permeation tests, transmission electron microscopy (TEM) analyses were carried out on the nasal mucosa to study the morphological changes of epithelial cells and tight junctions, while the change in microsphere morphology was examined using photostereo microscopy (PM). Spray-dried microparticles had a mean diameter (dvs) in the range of about 3,10 ,m. They showed good in-vitro mucoadhesive properties. In-vitro release profiles and swelling behaviour depended on their composition: the drug release occurred in 1,3 h. Ex-vivo studies showed that drug permeation through the mucosa from microparticles based on chitosan was higher than from those consisting of alginate alone. This can be related to the penetration enhancing properties of chitosan. Complexation of chitosan with alginate led to a control of the drug release. Microscopy observation of microspheres during the permeation tests revealed that microparticles swelled and gelled, maintaining their shape. TEM analyses of the mucosa after exposure to the microparticles consisting of alginate/chitosan showed opened tight junctions. This preliminary study shows that alginate/chitosan spray-dried microspheres have promising properties for use as mucoadhesive nasal carriers of an antiemetic drug. [source] Complexation of aminoglutethimide with native and modified cyclodextrinsJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 10 2009Michal Nowakowski Abstract Complexations of R(+) and RS(+/,)aminoglutethimide (AGT), the drug used in a treatment of breast and prostate cancer with native and modified cyclodextrins (, -CD, , -CD, , -CD, 2,6-di- O -methyl- , -CD (DM- , -CD), 2,3,6-tri- O -methyl- , -CD (TM- , -CD) and carboxymethyl- , -CD (CM- , -CD)) were studied. The stability constants were determined with UV,Vis spectrophotometric method at pH 9.0. The NMR data obtained for TM- , -CD suggest that the complexation of AGT is possible from both sides of CD molecule. This was confirmed by molecular dynamic simulations. Copyright © 2009 John Wiley & Sons, Ltd. [source] Synthesis of a new zirconium catalyst for ethylene polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2008Fabiana De C. Fim Abstract A novel complex dichlorobis(2-ethyl-3-hydroxy-4-pyrone)zirconium(IV) (ZrCl2(ethylpyrone)2) was synthesized. Complexation of the pyrone ligand to the zirconium was confirmed by UV, 1H and 13C-NMR, and electrochemical studies. NMR showed the presence of four isomers and density functional theory calculations indicated that the main isomer had a cis configuration. The catalyst was shown to be active in ethylene polymerization in the presence of the cocatalyst methylaluminoxane. The highest catalyst activity for the zirconium complex was achieved at Al/Zr = 2500, 70 °C and when a small concentration of catalyst was used (1 ,mol). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3830,3841, 2008 [source] First diphosphinoamine ligand bearing a polymerizable side chain: Complexation with copper(I)JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2005Ritu Ahuja Abstract A diphosphinoamine ligand with a polymerizable side chain, (PPh2)2NCH2C6H4CHCH2 (vbzpnp or 1), was synthesized. The ligand could be polymerized by anionic polymerization with n -butyllithium as the initiator. Polyvbzpnp was soluble in tetrahydrofuran and chloroform but was insoluble in methanol and was characterized with NMR, IR, and gel permeation chromatography. The number-average and weight-average molecular weights were 40,050 and 55,690, respectively, and the polydispersity index was 1.39. [Cu(CH3CN)4]ClO4 formed a bischelated complex with the monomer and produced [Cu(1)2]ClO4 (2), and CuCl formed a tetramer, Cu4(1)2Cl4 (3). All the compounds (1, 2, and 3) were characterized with single-crystal-structure determination, NMR, and IR spectroscopy. The addition of [Cu(CH3CN)4]ClO4 to polyvbzpnp resulted in an insoluble crosslinked polymer, which was characterized with solid-state 31P {1H} magic-angle-spinning NMR. The copolymerization of styrene and 1 produced a styrene,vbzpnp copolymer that was found to be soluble in common organic solvents. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3411,3420, 2005 [source] Protonatable Ionenes for Nucleic Acid ComplexationMACROMOLECULAR BIOSCIENCE, Issue 11 2009Sean M. Ramirez Abstract Novel tboc-protected ionenes with exceeding 30 kDa were prepared from the step-growth polymerization of tert- butyl bis[3-(dimethylamino)propyl]carbamate and 1,12-dibromododecane. The protected ionenes yielded pH-sensitive, protonatable ionenes with pKa,,,6.6 for the conjugate acid of the protonated secondary amine. Polyplexes of the protected and deprotected ionenes, whose cytotoxicity for endothelial cells was analyzed using the MTT assay, efficiently complex plasmid DNA. Polyplexes destabilized cellular membranes as revealed using the lactate dehydrogenase assay at high concentrations. The polyplexes were successfully transfected into HBMECs at mass ratios 2, 4, 8, 12, and 16 (polymer/DNA) at polyplex concentrations less than 10,µg,·,mL,1. [source] Effect of Polycarboxylate Blocks on the Amidase Activity of Trypsin through Complexation with PEG/Polycarboxylate Block IonomersMACROMOLECULAR BIOSCIENCE, Issue 3 2007Atsushi Harada Abstract The amidase reaction of trypsin, which is a member of the serine proteinase family, is accelerated by its complexation with block ionomers containing a polycarboxylate block, such as PEG-PAA, PEG-PGA, or PEG-PMA. PEG-PAA and PEG-PGA had similar effects, causing an increase in the kcat value and a shift in the pH profile to a lower pH region. On the other hand, PEG-PMA showed not only an increase in the kcat value, but also a decrease in the activation energy; however, there was no shift in the pH dependence of the initial reaction rate. Such differences might be induced by the difference in pKa values of the polycarboxylate block in block ionomers. [source] | ||||||||||||||||||||||||||||||||||||||||||||||