The Dissociation of Anilinium Ions in Aqueous Dimethylsulfoxide

1972 ◽  
Vol 50 (4) ◽  
pp. 474-478 ◽  
Author(s):  
Keith Yates ◽  
Graeme Welch
Keyword(s):  
Aqueous Solution ◽  
Solvent System ◽  
Ionization Mechanism ◽  
Normal Order ◽  
Aqueous Dimethylsulfoxide

The pKa values often substituted primary anilines and six substituted tertiary anilines have been determined in 70% DMSO–water. The ΔpKa values relative to those in aqueous solution indicate that DMSO is about 2 log units stronger as a base than H2O. The normal order of basicity (tertiary > primary) is inverted in this solvent system and the Hammett ρ values for the two series provide evidence for a different ionization mechanism than that in water.

scholarly journals Extraction of Reduced Wool Proteins by Solutions of Salts

1969 ◽  
Vol 22 (4) ◽  
pp. 1081 ◽  
Author(s):  
JA Maclaren ◽  
DJ Kilpatrick
Keyword(s):  
Aqueous Solution ◽  
Solvent System ◽  
Disulphide Bonds ◽  
Wool Proteins

It has been shown earlier that the disulphide bonds in wool fibres are reduced specifically and almost quantitatively in aqueous solution using toluene-w-thiol (Maclaren 1962) or tributyl phosphine (Sweetman and Maclaren 1966; Maclaren, Kilpatrick, and Kirkpatrick 1968). The next step was to find a suitable solvent system to extract the proteins from the reduced fibre.

The H− acidity function for dimethylformamide–water

1970 ◽  
Vol 48 (21) ◽  
pp. 3354-3357 ◽  
Author(s):  
E. Buncel ◽  
E. A. Symons ◽  
Douglas Dolman ◽  
Ross Stewart
Keyword(s):  
Solvent System ◽  
Tetramethylammonium Hydroxide ◽  
Acidity Function ◽  
Hydroxide Ion ◽  
Indicator Method ◽  
Aqueous Dimethylsulfoxide

The H− acidity function has been determined for N,N-dimethylformamide–water mixtures containing tetramethylammonium hydroxide by the Hammett indicator method. Basicity in the aqueous dimethylformamide system exceeds that in aqueous tetramethylenesulfone but is slightly less than in aqueous dimethylsulfoxide, at equivalent molar compositions of solvent and base. However, the basic aqueous dimethylformamide solvent system is only of limited utility as a result of reaction of hydroxide ion with the dimethylformamide.

scholarly journals Solvent kinetic isotope effects of human placental alkaline phosphatase in reverse micelles

1998 ◽  
Vol 330 (1) ◽  
pp. 267-275 ◽  
Author(s):  
Ter-Mei HUANG ◽  
Hui-Chih HUNG ◽  
Tsu-Chung CHANG ◽  
Gu-Gang CHANG
Keyword(s):  
Aqueous Solution ◽  
Isotope Effect ◽  
Reverse Micelles ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Solvent System ◽  
Placental Alkaline Phosphatase ◽  
K Value ◽  
Kinetic Isotope ◽  
Human Placental Alkaline Phosphatase

Human placental alkaline phosphatase was embedded in a reverse micellar system prepared by dissolving the surfactant sodium bis(2-ethylhexyl) sulphosuccinate (Aerosol-OT) in 2,2,4-trimethylpentane. This microemulsion system provides a convenient instrumental tool to study the possible kinetic properties of the membranous enzyme in an immobilized form. The pL (pH/p2H) dependence of hydrolysis of 4-nitrophenyl phosphate has been examined over a pL range of 8.5-12.5 in both aqueous and reverse micellar systems. Profiles of log V versus pL were Ha-bell shaped in the acidic region but reached a plateau in the basic region in which two pKa values of 9.01-9.71 and 9.86-10.48, respectively, were observed in reverse micelles. However, only one pKa value of 9.78-10.27 in aqueous solution was detected. Profiles of log V/K versus pL were bell-shaped in the acidic region. However, they were wave-shaped in the basic region in which a residue of pKa 9.10-9.44 in aqueous solution and 8.07-8.78 in reverse micelles must be dehydronated for the reaction to reach an optimum. The V/K value shifted to a lower value upon dehydronation of a pKa value of 9.80-10.62 in aqueous solution and 11.23-12.17 in reverse micelles. Solvent kinetic isotope effects were measured at three pL values. At pL 9.5, the observed isotope effect was a product of equilibrium isotope effect and a kinetic isotope effect; at pL 10.4, the log V/K value was identical in water and deuterium. The deuterium kinetic isotope effect on V/K was 1.14 in an aqueous solution and 1.16 in reverse micelles. At pL 11.0 at which the log V values reached a plateau in either solvent system, the deuterium kinetic isotope effect on V was 2.08 in an aqueous solution and 0.62 in reverse micelles. Results from a proton inventory experiment suggested that a hydron transfer step is involved in the transition state of the catalytic reaction. The isotopic fractionation factor (ϕ) for deuterium for the transition state (ϕT) increased when the pH of the solution was raised. At pL 11.0, the ϕT was 1.07 in reverse micelles, which corresponds to the inverse-isotope effect of the reaction in this solvent system. Normal viscosity effects on kcat and kcat/Km were observed in aqueous solution, corresponding to a diffusional controlled physical step as the rate-limiting step. We propose that the rate-limiting step of the hydrolytic reaction changes from phosphate releasing in aqueous solution to a covalent phosphorylation or dephosphorylation step in reverse micelles.

scholarly journals Catalytic Hydrolysis of Phosphate Monoester by Supramolecular Complexes Formed by the Self-Assembly of a Hydrophobic Bis(Zn2+-cyclen) Complex, Copper, and Barbital Units That Are Functionalized with Amino Acids in a Two-Phase Solvent System

Micromachines ◽  
2019 ◽  
Vol 10 (7) ◽  
pp. 452
Author(s):  
Yuya Miyazawa ◽  
Akib Bin Rahman ◽  
Yutaka Saga ◽  
Hiroki Imafuku ◽  
Yosuke Hisamatsu ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Amino Acids ◽  
Active Site ◽  
Self Assembly ◽  
Hydrolytic Activity ◽  
Solvent System ◽  
Supramolecular Complexes ◽  
Artificial System ◽  
Two Phase ◽  
Hydrolysis Of

We previously reported on the preparation of supramolecular complexes by the 2:2:2 assembly of a dinuclear Zn2+-cyclen (cyclen = 1,4,7,10-tetraazacyclododecane) complex having a 2,2′-bipyridyl linker equipped with 0~2 long alkyl chains (Zn2L1~Zn2L3), 5,5-diethylbarbituric acid (Bar) derivatives, and a copper(II) ion (Cu2+) in aqueous solution and two-phase solvent systems and their phosphatase activities for the hydrolysis of mono(4-nitrophenyl) phosphate (MNP). These supermolecules contain Cu2(μ-OH)2 core that mimics the active site of alkaline phosphatase (AP), and one of the ethyl groups of the barbital moiety is located in close proximity to the Cu2(μ-OH)2 core. The generally accepted knowledge that the amino acids around the metal center in the active site of AP play important roles in its hydrolytic activity inspired us to modify the side chain of Bar with various functional groups in an attempt to mimic the active site of AP in the artificial system, especially in two-phase solvent system. In this paper, we report on the design and synthesis of new supramolecular complexes that are prepared by the combined use of bis(Zn2+-cyclen) complexes (Zn2L1, Zn2L2, and Zn2L3), Cu2+, and Bar derivatives containing amino acid residues. We present successful formation of these artificial AP mimics with respect to the kinetics of the MNP hydrolysis obeying Michaelis–Menten scheme in aqueous solution and a two-phase solvent system and to the mode of the product inhibition by inorganic phosphate.

scholarly journals Glycerin/NaOH Aqueous Solution as a Green Solvent System for Dissolution of Cellulose

Polymers ◽  
2020 ◽  
Vol 12 (8) ◽  
pp. 1735
Author(s):  
Ke Li ◽  
Huiyu Yang ◽  
Lang Jiang ◽  
Xin Liu ◽  
Peng Lang ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Solvent System ◽  
Industrial Applications ◽  
Degree Of Polymerization ◽  
Green Solvent ◽  
Mixed Aqueous Solution ◽  
Before And After ◽  
Solvent Systems ◽  
The Difference ◽  
Ubbelohde Viscometer

Dissolving cellulose in water-based green solvent systems is highly desired for further industrial applications. The green solvent glycerin—which contains hydrogen-bonding acceptors—was used together with NaOH and water to dissolve cellulose. This mixed aqueous solution of NaOH and glycerin was employed as the new green solvent system for three celluloses with different degree of polymerization. FTIR (Fourier-transform infrared), XRD (X-ray diffractometer) and TGA (thermogravimetric analysis) were used to characterize the difference between cellulose before and after regenerated by HCl. A UbbeloHde viscometer was used to measure the molecule weight of three different kinds of cellulose with the polymerization degree of 550, 600 and 1120. This solvent system is useful to dissolve cellulose with averaged molecule weight up to 2.08 × 105 g/mol.

Sign in / Sign up

Export Citation Format

Share Document