1825-45-2Relevant academic research and scientific papers
Manifesto for the routine use of NMR for the liquid product analysis of aqueous CO2 reduction: From comprehensive chemical shift data to formaldehyde quantification in water
Boutin, Etienne,Chatterjee, Tamal,Robert, Marc
, p. 4257 - 4265 (2020)
CO2 reduction research is at a critical turnaround since it has the potential to partially or even substantially fulfil future clean energy needs. CO2-to-CO electrochemical conversion is getting closer from industrial implementation requirements. Efforts are now more and more directed to obtain highly reduced products such as methanol, methane, ethylene, ethanol, etc., most of them being liquids. Gas-phase products (e.g., CO, CH4) are typically detected and quantified by well-defined gas chromatography (GC and GC/MS) protocols. On the other hand, NMR, GC-MS, HPLC have been used for the liquid phase characterization, but no routine technique has yet been established, mainly due to lack of versatility of a single technique. Additionally, except NMR and GC-MS, classical techniques cannot distinguish 13C from 12C products, although it is a mandatory step to assess products origin. Herein, we show the efficiency and applicability of 1H NMR as routine technique for liquid phase products analysis and we address two previous shortcomings. We first established a comprehensive 1H and 13C NMR chemical shifts list for all 12CO2 and 13CO2 reduction products in water ranging from C1 to C3. Then we overcame the difficulty of identifying aqueous formaldehyde intermediate by 1H NMR through an efficient chemical trapping step, along with isotopic signature study. Formaldehyde can be reliably quantified in water with a concentration as low as 50 μM.
Cosmetic or dermatological topical compositions comprising dendritic polyesters
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, (2008/06/13)
The present invention relates to cosmetic or dermatological compositions capable of being applied to the skin, the keratinous fibers, the nails, the semimucous membranes and/or the mucous membranes, and which includes a dendritic polyester polymer having terminal hydroxyl functional groups or the combination of such a polymer with a film-forming polymer. It also relates to methods of cosmetic or dermatological treatment using these compositions as well as the use of the compositions for the preparation of dermatological or cosmetic compositions.
The reversible enolization and hydration of pyruvate: Possible roles of keto, enol, and hydrated pyruvate in lactate dehydrogenase catalysis
Esposito,Lukas,Meany,Pocker
, p. 1108 - 1117 (2007/10/03)
The reversible enolization and hydration of pyruvic acid and pyruvate anion were monitored using spectrophotometric methods at several temperatures. Widely varying values for the equilibrium constant for the enolization of pyruvic acid and pyruvate ion appear in the literature. To accurately determine the position of equilibrium for the enolization reaction, we have developed a method that gives consistent results in which purified samples of sodium pyruvate are first "titrated" with triiodide ion to remove any triiodide-scavenging impurities such as those resulting from aldol condensation reactions. After reequilibration to allow the regeneration of enol pyruvate, the addition of small quantities of triiodide result in an initial burst in the decrease of absorbance at 353 nm, followed by the much slower zero-order decrease due to the formation of new enol pyvuvate molecules. The absorbance change during the burst phase of the reaction is proportional to the enol concentration plus that of any triiodide-scavenging impurity which may be present in the original pyruvate solution. Thus, as the quantity of triiodide used in the pretreatment stage of the experiments is increased, these burst absorbance changes, ΔA, decrease until a constant value of ΔA is reached. Accordingly, this final ΔA value is proportional to enol pyruvate (or enol pyruvic acid) in the absence of triiodide-scavenging impurity, allowing the accurate and reproducible determinations of Kenol. The equilibrium constants for both pyruvate and pyruvic acid are relatively temperature insensitive and, typically, Kenol (pyruvate anion) = 2.6 × 10-5 and Kenol (pyruvic acid) = 7.8 × 10-5 at 25.0°C. The zero-order phase of the reaction of triiodide ion may be used to calculate rate constants for enolization. The hydration and dehydration of pyruvic acid were followed directly by following absorbance changes in the peak at 340 nm due to the keto group. The thermodynamic and kinetic results reported in this paper are used to help determine whether the observed "substrate" inhibition of the lactate dehydrogenase catalyzed reduction of pyruvate is actually caused by keto, hydrated, or enol pyruvate.
Keto-enol equilibria in the pyruvic acid system: Determination of the Keto-enol equilibrium constants of pyruvic acid and pyruvate anion and the acidity constant of pyruvate enol in aqueous solution
Chiang,Kresge,Pruszynski
, p. 3103 - 3107 (2007/10/02)
Keto-enol equilibrium constants for the pyruvic acid system in aqueous solution at 25°C were determined by Meyer halogen titration and also by another method that evaluates these constants as ratios of enolization to ketonization rate constants, KE = kE/kK. Measurements by each method were made in both acidic and basic solution, and enol required for the ketonization rate measurements was supplied by hydrolysis of a silyl derivative and also by an equilibrated DMSO solution in which the enol content is greater than it is in water. The various methods gave nicely consistent results, which nevertheless differed between acidic and basic solutions, in accord with the different states of ionization of pyruvic acid in the two media; the values obtained were pKE = 3.21 for pyruvic acid in the carboxylic acid form and pKE = 5.03 for the pyruvate ion. The latter gives a free energy change for the ketonization of pyruvate enol that is 47% of the free energy liberated by the hydrolysis of the high-energy molecule, phosphoenolpyruvate; this shows that nearly half of the high energy content of this molecule resides in its masked enol function. An acidity constant for ionization of the enol hydroxyl group of pyruvate enol, pKaE = 11.55, was also determined, and this, when combined with pKE for this species, gives pKaK = 16.58 as the acidity constant of the pyruvate ion ionizing as a carbon acid.
The Hydration of Aliphatic Aldehydes and Pyruvic Acid in Mixed Solvents
Knoche, Wilhelm,Lopez-Quintela, M. Arturo,Weiffen, Joachim
, p. 1047 - 1050 (2007/10/02)
In water/dioxane mixtures and aqueous electrolyte solutions the hydration reaction has been studied.The formation of the gem-diol of aliphatic aldehydes is associated with the binding of 3 water molecules to the carbonyl group, whereas for pyruvic acid 6 or 7 water molecules are involved in this reaction.Rate and equilibrium constants of the reactions have been determined.The hydration equilibria may be used to measure conveniently the local water activity in the aqueous and non-aqueous regions of micellar solutions and microemulsions.The reaction rate indicates the local proton activity in these system. - Keywords: Chemical Kinetics / Solutions / Surfaces / Thermodynamics
REVERSIBLE HYDRATION OF CARBONYL COMPOUNDS IN AQUEOUS SOLUTION - 2. THE KINETICS OF THE KETO/GEM-DIOL TRANSITION.
Buschmann,Dutkiewicz,Knoche
, p. 129 - 141 (2007/10/02)
The kinetics of hydration of 17 different carbonyl compounds have been studied in acidic solution. The reactions have been found to acid-catalyzed. For the aliphatic aldehydes propanal to hexanal the rate constants are k//0 equals (3. 5 plus or minus 1) multiplied by 10** minus **3 s** minus **1 and k//H equals (450 plus or minus 30) dm**3 mol** minus **1 s** minus **1 and for alpha -keto acids they are in the ranges k//0 equals (0. 13 to 0. 40) s** minus **1 and k//H equals (1 to 6) dm**3 mol** minus **1. For halogenated acetones the rate constants depend strongly on the substituents. The large negative value for the reaction entropy DELTA S**0 approximately equal to minus 70 J mol** minus **1 K** minus **1 indicates that three water molecules are involved in the hydration process.
