Search results for "CONST"

Spectrophotometric determination of binding constants between some aminocyclodextrins and nitrobenzene derivatives at various pH values

2002

Abstract The inclusion capacity of three modified cyclodextrins—namely mono-(6- N , N -dimethylamino-6-deoxy)- ( 3 ), mono-6-(2-aminoethyl)-amino-6-deoxy- ( 4 ) and mono-6-(2- N , N -dimethylaminoethyl)-amino-6-deoxy- ( 5 ) β-cyclodextrin, with six para -substituted nitrobenzenes ( A – F ) has been investigated at three different pH values. Molecular interactions in inclusion complexes have also been investigated by means of molecular mechanics (MM2/QD) models. The desolvation of the cyclodextrin is the most important factor in determining the binding ability of the various hosts. However, for a given host, electrostatic and van der Waals interactions and the formation of a hydrogen bond be…

Calorimetric investigation of the complex formation between surfactants and α-, β- and γ-cyclodextrins

1992

Abstract A calorimetric technique has been used to study complex formation between α-, β- and γ-cyclodextrins (αCD, βCD and γCD) and some surfactants (sodium dodecylsulphate (SDS), hexadecyl trimethylammonium bromide (CTAB) and p-(1,1,3,3-tetramethylbutyl) phenoxypoly(oxyethyleneglycol) (Triton X-100)). The experimental data indicate that some complexes (SDS-αCD, SDS-βCD and CTAB-αCD) are very stable and allow direct determination of their stoichiometry and molar enthalpy of complex formation. Those for other complexes closely fit a model based on an equilibrium reaction between surfactant, cyclodextrin and a single complex. According to the model, data analysis allows determination of the …

Binding properties of mono-(6-deoxy-6-amino)-β-cyclodextrin towards p-nitroaniline derivatives: a polarimetric study

2009

Abstract Polarimetry was used in order to investigate the formation of supramolecular complexes between mono-6-amino-β-cyclodextrin and various p-nitroaniline derivatives at two different pH values. Comparison with the behaviour of native β-cyclodextrin gave us the opportunity to consider the effect exerted by the presence of charged groups, having different solvation requirements, on the binding equilibrium. Data offer some support to the hypothesis of ‘dynamic co-inclusion’ of solvent molecules within the host–guest complex.

1984

Sedimentation coefficients of S of polystyrene covering a broad range of molecular weights M, are measured in toluene and 2-butanone in the semidilute regime. The results are compared with literature data using a plot of S · NA · η/(1 − νρ) = M · η/f versus concentration c, allowing experiments in different solvents of different density ρ and viscosity η to be compared (ν: partial specific volume of polymer; f: friction coefficient; NA: Avogadro number). According to scaling theory for concentrations higher than a critical concentration c, linear plots are to be expected. This is true for the theta-solvent cyclohexane, but for the theta-solvent cyclopentane as well as for the thermodynamica…

Species-Specific Aggregation Factor In Sponges.

1978

In dissociated single cells from the sponge Geodia cydonium, DNA synthesis is initiated after incubation with a homologous, soluble aggregation factor. During the DNA-initiation phase the cyclic AMP- and cyclic GMP levels vary drastically; the cyclic AMP content drops from 2.2 pmol/10(6) cells to 0.3 pmol/10(6) cells while the cyclic GMP content increases from 0.6 pmol to 3.7 pmol/10(6) cells. The activity of neither the adenylate cyclase nor of the guanylate cyclase isolated from cells which have been incubated for different periods of time with the aggregation factor, is changed. The soluble as well as the particulate enzyme activities were checked in vitro. The cyclic nucleotide receptor…

2003

Jerboa (Jaculus orientalis) is a deep hibernating rodent native to subdesert highlands. During hibernation, a high level of ketone bodies i.e. acetoacetate (AcAc) and D-3-hydroxybutyrate (BOH) are produced in liver, which are used in brain as energetic fuel. These compounds are bioconverted by mitochondrial D-3-hydroxybutyrate dehydrogenase (BDH) E.C. 1.1.1.30. Here we report, the function and the expression of BDH in terms of catalytic activities, kinetic parameters, levels of protein and mRNA in both tissues i.e brain and liver, in relation to the hibernating process. We found that: 1/ In euthemic jerboa the specific activity in liver is 2.4- and 6.4- fold higher than in brain, respective…

Formation rates and protonation constants of azo dyes in a sodium dodecylsulphate micellar solution.

1991

The effects of a sodium dodecylsulphate micellar solution on the coupling rates of several diazotizated arylamines with N-(1-naphthyl)-ethylenediamine and the shifts in the protonation constants of the corresponding azo dyes are quantitatively studied. Aniline, o-, m- and p-aminobenzoic acids, ethyl p-aminobenzoate and several sulphadrugs are used, and the relationships among the intensity of the effects and the molecular structure of the diazonium ions and the dyes are discussed. A single simplified procedure for the determination of all the substances at pH = 1.3 +/- 0.3, where coupling is quickly completed to directly produce the protonated form of the dyes, is established and applied to…

On the behaviour of the (Z)-Phenylhydrazones of some 5-alkyl-3-benzoyl-1,2,4-oxadiazoles in solution and in the gas phase: kinetic and spectrometric …

2008

Abstract Rate constants, k A,R , for the rearrangement of the ( Z )-phenylhydrazones ( 1a – e ) of a series of 5-alkyl-3-benzoyl-1,2,4-oxadiazoles substituted at C(5) with linear alkyl chains of different length (from C 4 up to C 12 ) into the relevant 4-acylamino-2,5-diphenyl-1,2,3-triazoles ( 2a – e ) have been measured in dioxan/water in the base-catalyzed region (pS + 10.5–12.6). For each substrate log  k A,R are linearly related to pS + . The significant decrease of the slopes of these straight lines (from 0.96 down to 0.78) upon increasing the length of the linear alkyl chain at C(5) and that of the reactivity (down to 14–26%) upon increasing the substrate concentration suggest a decr…

1983

The first dissociation constant of oligonuclear phenolic compounds consisting of one nitrophenol unit besides further alkyl phenol units (10 dinuclear, 15 trinuclear, 6 tetranuclear compounds, and 4 nitrophenols as model) was determined spectroscopically in water/methanol (50/50 by vol.) at 25°C. For the ortho-linked title compounds with the nitrophenol unit at the end of the molecule a decrease of pK1 is observed which becomes stronger with increasing chain length. The introduction of bulky groups in ortho-position of the dissociating phenolic unit, as well as at the opposite end of the molecule causes a further decrease of pK1. The lowest value is found for a p-nitrophenol unit in the mid…

Pressure dependence in the methyl vinyl ketone + OH and methacrolein + OH oxidation reactions: an electronic structure study.

2005

High-level electronic structure calculations were carried out for the study of the reaction pathways in the OH-initiated oxidations of methyl vinyl ketone (MVK) and methacrolein (MACR). For the two conformers of MVK (called synperiplanar and antiperiplanar), the addition channels of OH to the terminal and central carbon atom of the double bond dominate the overall rate constant, whereas the abstraction of the methyl hydrogen atoms has no significant kinetic role. In the case of MACR, only the antiperiplanar conformer is important in its reactivity. In addition, the lower Gibbs free energy barrier for MACR corresponds to the aldehydic hydrogen abstraction reaction, which will be somewhat mor…