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At least 73 records · Page 4Linked to original sources
PubMed2006

Cannizzaro-type disproportionation of aromatic aldehydes to amides and alcohols by using either a stoichiometric amount or a catalytic amount of lanthanide compounds.

Aromatic aldehydes can be directly converted to the corresponding amides and alcohols in good to excellent yields by the treatment of aromatic aldehydes with lithium amide LiN(SiMe3)2 in the presence of catalytic lanthanide chlorides LnCl3 or by the treatment of aromatic aldehydes with a stoichiometric amount of lanthanide amides [(Me3Si)2N]3Ln(mu-Cl)Li(THF)3 at ambient temperature. The effects of solvents, substitutents on the phenyl ring, and lanthanide metals on the reaction have been examined. The mechanism of the disproportionation reaction was proposed based on the experimental results.

Alcohols↗
PubMed2005

Computational evidence for a variable first shell coordination of the cadmium(II) ion in aqueous solution.

In this paper, we present a state-of-the-art 100 ns molecular dynamics simulation of a cadmium(II) aqueous solution that highlights a very flexible ion first coordination shell which transits between hexa- and heptahydrated complexes. From this investigation, a dynamical picture of the water exchange process emerges that takes place through an associative mechanism for the solvent substitution reaction. Our procedure starts from the generation of an effective two-body potential from quantum mechanical ab initio calculations in which the many-body ion-water terms are accounted for by the polarizable continuum method (PCM). This approach is computationally very efficient and has allowed us to carry out extremely long molecular dynamics simulations, indispensable to reproduce the dynamic properties of the cadmium(II) aqueous solution. Quantum mechanical ab initio calculations of the hexa- and heptahydrated complexes extracted from MD configurations have revealed stable minima for both clusters with the water molecules arranged in T(h)() and C(2) symmetries in the hexa- and heptahydrated complexes, respectively, with a slight energetic preference for the heptahydrated one. Finally, a comparison of the calculated hexa- and heptahydrated cluster IR and Raman spectra with the experimental data in the literature, has demonstrated that the IR spectroscopy is not able to distinguish between the two species, whereas the Raman spectrum of the Cd(2+)-(H(2)O)(7) cluster provides a better agreement with the experimental data.

Journal Article↗
PubMed1982

Freeze-substitution.

Freeze-substitution is a technique suitable for the preparation of unicellular and multi-cellular plant and animal specimens for conventional light microscopy, TEM and SEM. It is also widely used as a means of preparing animal and plant tissues for the localization of water soluble substances by analytical electron microscopy, autoradiography or visual detection of precipitates. The technical requirements of preparation, together with an evaluation of the procedures, are presented for various applications. Careful selection and evaluation of freezing technique, substitution solvent and regime are required for meaningful results.

Animals↗
PubMedDate not supplied

Rapid assay of cytotoxicity using Tetramitus flagellates.

A simple test for measuring cytotoxic agents has been developed using the flagellate phenotype of Tetramitus rostratus. The test measures dose-dependent inhibition of cell division by individual agents such as 4-nitroquinoline-N-oxide and other mutagens. Dose-response data are given also for mixtures including coal tar pitch condensate, centrifuged particles obtained from tap water, and water concentrates prepared with XAD-2 resin. Because Tetramitus flagellates have a gullet and are particle-feeders, the assay allows for cytotoxic measurements of whole particles without prior extraction or solvent substitution procedures. The cytotoxic activities observed may reflect genotoxic activity, since all chemicals that produced a positive response are genotoxic in other test systems.

4-Nitroquinoline-1-oxide↗
PubMed2006

Cryofixation methods for ultrastructural studies of Dictyostelium discoideum.

Cryopreservation methods, including rapid freezing, freeze-substitution, and low-temperature embedment, lead to superior ultrastructural preservation compared with traditional fixation procedures. This is particularly true for the multicellular stages of Dictyostelium discoideum, in which the hydrophobic sheath that surrounds the structures causes delayed penetration by the already slow-acting aqueous chemical fixatives, resulting in cell shape changes, loss of cell-cell contacts, and changes in cell-matrix interactions. The surface tension effects of traditional fixation methods can also result in disruption of the delicate structures. Depth of freezing is often greater than expected because of the relatively dehydrated state of the multicellular structures. Variations in freeze-substitution solvents and embedment media can be employed to allow for antigenic preservation. Commercial instruments exist for most of the procedures, but excellent results can be obtained using inexpensive hand-crafted apparatus.

Animals↗
PubMed1991

Avoiding gas bubble formation during freeze substitution.

Gas bubbles frequently are formed during freeze substitution, especially when tissues are warmed to room temperature. The problem arises largely from the extreme solubility of CO2 in the freeze substitution solvent. Gas bubbles may be minimized by briefly transferring the tissue to freshly chilled solvent before warming to room temperature.

Carbon Dioxide↗
PubMedDate not supplied

Platinum (II) complexes with stereochemically-defined thiepane dioxide diamine ligands as anticancer drugs.

Platinum (II) complexes are accredited with biological activities. New complexes with thiepane dioxide diamine as ligands, characterized by defined stereochemical features, a flexible 7-membered thiepane moiety and by C2 symmetry, were prepared. The complexes, related to the diamino cyclohexane family of platinum complexes, were soluble in dimethyl sulfoxide with the solvent substituting one chloride ion. These positively-charged complexes were tested against a human carcinoma cell line A431 and its cisplatin-resistant counterpart A431/Pt and were found to show: i) capability in bypassing cisplatin-resistance; ii) cytotoxicity comparable to that of oxaliplatin; iii) lower activity than cisplatin. In both cells lines, [PtCl(DACH)(DMSO)]+ was more cytotoxic than oxaliplatin. The best activity was shown by the platinum complexes with ligands which presented C2 symmetry.

Antineoplastic Agents↗
PubMedDate not supplied

Determination of the iodine value of oils and fats: summary of collaborative study.

Two collaborative studies were conducted using the Wijs method for determining the iodine value in a wide range of vegetable and animal oils and fats. The results obtained when using carbon tetrachloride were compared to those obtained when using a substitute solvent mixture of cyclohexane and glacial acetic acid. The values reported for the iodine values indicate that the cyclohexane and acetic acid mixture can be used in place of carbon tetrachloride without loss of precision. The method has been adopted first action by AOAC INTERNATIONAL as an IUPAC/AOCS/AOAC method.

Acetates↗
PubMed2003

Alkyl- and aryl-substituted corroles. 4. Solvent effects on the electrochemical and spectral properties of cobalt corroles.

Solvent effects on the electrochemistry and spectroscopic properties of alkyl- and aryl-substituted corroles in nonaqueous media are reported. The oxidation and reduction of six compounds containing zero to seven phenyl or substituted phenyl groups on the macrocycle were studied in four different nonaqueous solvents (CH(2)Cl(2), PhCN, THF, and pyridine) containing 0.1 M tetra-n-butylammonium perchlorate. Dimers were formed upon oxidation of all corroles in CH(2)Cl(2), but this was not the case in the other three solvents, where either monomers or dimers were formed upon oxidation depending upon the solvent Gutmann donor number and the number or location of aryl substituents on the macrocycle. The half-wave potentials were analyzed as a function of the number of aryl substituents on the macrocycle as well as the concentration of added pyridine to PhCN solutions of the compound, and these data were combined with data from the spectroelectrochemistry experiments to determine the stoichiometry of the species actually in solution after the first oxidation or first reduction of each compound. The results of these experiments indicate that reduction of the bispyridine adduct (Cor)Co(III)(py)(2) proceeds via the monopyridine complex (Cor)Co(III)(py) to give in each case the unligated cobalt(II) corrole [(Cor)Co(II)](-). In contrast, pyridine remains coordinated after electrooxidation, and the final product was characterized as [(Cor)Co(III)(py)(2)](+).

Journal Article↗
PubMed2004

Bone morphogenetic protein 2 accelerates osteointegration and remodelling of solvent-dehydrated bone substitutes.

INTRODUCTION: lt was the purpose of this study to investigate how bone morphogenetic protein 2 (BMP-2) influences remodelling and the biomechanics of solvent-dehydrated bone in the long run. Furthermore, the early influence of this growth factor on the substitute was investigated. MATERIALS AND METHODS: Using a weight-bearing animal model, solvent-dehydrated bone was implanted in the tibial head of merino sheep ( n=12) after being loaded with BMP-2 (100 microg/100 microl). At 4 weeks ( n=6) and 9 months ( n=6) after surgery, histomorphological, histomorphometrical and biomechanical investigations were performed. RESULTS: At 9 months after implantation of BMP-2-loaded specimens, the bone per tissue volume was high, with levels above those of physiological cancellous bone. The amount of remaining solvent-dehydrated bone was markedly decreased, and in contrast, the amount of newly formed bone was extremely high. The specimen degradation had already occurred within the first 4 weeks after implantation, showing no further impact throughout the 9-month period. Biomechanical investigations at 9 months after implantation demonstrated a yield strength which achieved levels at least equivalent to physiological cancellous bone. BMP-2 showed no significant impact on the biomechanical properties after 4 weeks, compared to specimens prior to implantation. CONCLUSION: BMP-2 predominantly has an impact on the early implant degradation as well as bone formation, which leads to an almost completed bone remodelling of the solvent-dehydrated specimen within the study period of 9 months.

Animals↗
PubMed2006

Relationship between structure and photoinitiating abilities of selected bromide salts of 2-oxo-2,3-dihydro-1H-imidazo[1,2-a]pyridine (IMP): influence of the solvent and the substitution in benzaldehyde on the course of its reaction with IMP.

2-Oxo-2,3-dihydro-1H-imidazo[1,2-a]pyridinium bromide and its C3-substituted derivatives have been synthesized and structurally characterized by X-ray crystallography and quantum chemical calculations. Their potential as photoinitiators for free-radical polymerization has been investigated experimentally and compared with theoretical results. It has been established that the course of the reaction that introduces the substituted benzylidene group to the imidazole ring is different in the protic and dipolar aprotic solvents, and also depends on the character of the substituent, as the energy change in the reaction favours either R1R2C=CHR3 or R1R2CH-CH(OCH3)R3 formation.

Journal Article↗
PubMed2007

Exploring the dynamics of calix[4]pyrrole: effect of solvent and fluorine substitution.

Molecular dynamics simulations show that calix[4]pyrrole (CP) and octafluorocalix[4]pyrrole (8F-CP) are extremely flexible molecules. CP mainly adopts the 1,3-alternate conformation in all the solvents, although the percentage of alternative conformations increases in polar solvents, especially those with good hydrogen-bonding acceptor properties. However, in the case of 8F-CP, the cone conformation is the most populated in some solvents. Transitions between conformers are common and fast, and both CP and 8F-CP can adopt the cone conformation needed for optimum interaction with anions more easily than would be predicted on the basis of previous gas-phase calculations. Furthermore, the present studies show that when a fluoride anion is specifically placed initially in close proximity to CP and 8F-CP in their respective 1,3-alternate conformations, an extremely fast change to the cone conformation is observed in both cases. The results suggest that preorganization does not represent a major impediment to anion-binding for either CP or 8F-CP, and that ion-induced conformational changes can follow different mechanisms depending on the solvent and the chemical substituents present on the calix[4]pyrrole beta-pyrrolic positions.

Calixarenes↗
PubMed2005

Can the absence of solvation of neutral reagents by ionic liquids be responsible for the high reactivity in base-assisted intramolecular nucleophilic substitutions in these solvents?

[reaction: see text] The kinetics of the rearrangement of the Z-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole (1a) into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole (2a) induced by amines have been studied in two room-temperature ionic liquids (IL-1, [BMIM][BF4] and IL-2, [BMIM][PF6]). The data collected show that the reaction occurs faster in ionic liquids than in other conventional solvents previously studied (both polar or apolar, protic or aprotic). Presumably, this could depend on their peculiar ability to minimize the strong substrate-solvent, amine-solvent and amine-amine interactions occurring in conventional solvents.

Journal Article↗
PubMed2006

Solvent tuning of the substitution behavior of a seven-coordinate iron(III) complex.

A detailed kinetic study of the substitution behavior of the seven-coordinate [Fe(dapsox)(L)2]ClO4 complex (H(2)dapsox = 2,6-diacetylpyridine-bis(semioxamazide), L = solvent or its deprotonated form) with thiocyanate as a function of the thiocyanate concentration, temperature, and pressure was undertaken in protic (EtOH and acidified EtOH and MeOH) and aprotic (DMSO) organic solvents. The lability and substitution mechanism depend strongly on the selected solvent (i.e., on solvolytic and protolytic processes). In the case of alcoholic solutions, substitution of both solvent molecules by thiocyanate could be observed, whereas in DMSO only one substitution step occurred. For both substitution steps, [Fe(dapsox)(L)2]ClO4 shows similar mechanistic behavior in methanol and ethanol, which is best reflected by the values of the activation volumes (MeOH DeltaV(I) = +15.0 +/- 0.3 cm(3) mol(-1), DeltaV(II) = +12.0 +/- 0.2 cm(3) mol(-1); EtOH DeltaV(I) = +15.8 +/- 0.7 cm(3) mol(-1), DeltaV(II) = +11.1 +/- 0.5 cm(3) mol(-1)). On the basis of the reported activation parameters, a dissociative (D) mechanism for the first substitution step and a D or dissociative interchange (I(d)) mechanism for the second substitution step are suggested for the reaction in MeOH and EtOH. This is consistent with the predominant existence of alcoxo [Fe(dapsox)(ROH)(OR)] species in alcoholic solutions. In comparison, the activation parameters for the substitution of the aqua-hydroxo [Fe(dapsox)(H2O)(OH)] complex by thiocyanate at pH 5.1 in MES were determined to be DeltaH = 72 +/- 3 kJ mol(-1), DeltaS = +38 +/- 11 J K(-1) mol(-1), and DeltaV = -3.0 +/- 0.1 cm(3) mol(-1), and the operation of a dissociative interchange mechanism was suggested, taking the effect of pressure on the employed buffer into account. The addition of triflic acid to the alcoholic solutions ([HOTf] = 10(-3) and 10(-2) M to MeOH and EtOH, respectively) resulted in a drastic changeover in mechanism for the first substitution step, for which an associative interchange (Ia) mechanism is suggested, on the basis of the activation parameters obtained for both the forward and reverse reactions and the corresponding volume profile. The second substitution step remained to proceed through an I(d) or D mechanism (acidified MeOH DeltaV(II) = +9.2 +/- 0.2 cm(3) mol(-1); acidified EtOH DeltaV(II) = +10.2 +/- 0.2 cm(3) mol(-1)). The first substitution reaction in DMSO was found to be slowed by several orders of magnitude and to follow an associative interchange mechanism (DeltaS = -50 +/- 9 J K(-1) mol(-1), DeltaV(I) = -1.0 +/- 0.5 cm(3) mol(-1)), making DMSO a suitable solvent for monitoring substitution processes that are extremely fast in aqueous solution.

Journal Article↗
PubMed2006

Coiled coils at the edge of configurational heterogeneity. Structural analyses of parallel and antiparallel homotetrameric coiled coils reveal configurational sensitivity to a single solvent-exposed amino acid substitution.

A detailed understanding of the mechanisms by which particular amino acid sequences can give rise to more than one folded structure, such as for proteins that undergo large conformational changes or misfolding, is a long-standing objective of protein chemistry. Here, we describe the crystal structures of a single coiled-coil peptide in distinct parallel and antiparallel tetrameric configurations and further describe the parallel or antiparallel crystal structures of several related peptide sequences; the antiparallel tetrameric assemblies represent the first crystal structures of GCN4-derived peptides exhibiting such a configuration. Intriguingly, substitution of a single solvent-exposed residue enabled the parallel coiled-coil tetramer GCN4-pLI to populate the antiparallel configuration, suggesting that the two configurations are close enough in energy for subtle sequence changes to have important structural consequences. We present a structural analysis of the small changes to the helix register and side-chain conformations that accommodate the two configurations and have supplemented these results using solution studies and a molecular dynamics energetic analysis using a replica exchange methodology. Considering the previous examples of structural nonspecificity in coiled-coil peptides, the findings reported here not only emphasize the predisposition of the coiled-coil motif to adopt multiple configurations but also call attention to the associated risk that observed crytstal structures may not represent the only (or even the major) species present in solution.

Amino Acid Sequence↗