Role of the leaving group in the base-catalysed hydrolysis of pseudo-esters

The relative insensitivity of the rate of hydrolysis of γ-pseudo-esters to the leaving group compared to that of the normal esters emphasises that the conjugative ability is an important factor in determining the rate of hydrolysis of esters

Studies on nucleotide pyrophosphatase I. Partial purification and properties of a sheep liver enzyme that catalyzes the hydrolysis of dinucleotides

A partially purified sheep liver enzyme that hydrolyzed dinucleotides at the pyrophosphate bond was obtained by solubilizing the 18,000g sediment with n-butanol and fractionating the solubilized enzyme with acetone. The enzyme activity when measured using FAD as substrate, (FAD → FMN + AMP), was optimal at pH 9.7 and temperatures between 30 °–36 ° and at 60 °. The rate of release of FMN with time occurred with an initial lag of 30 sec, a linear increase for 1 min, and a subsequent irregular rate. In the presence of orthophosphate (Pi; 10 μImage ), FMN was released at an uniformly continuous and enhanced rate. 32Pi was not incorporated into the substrate or products. Sodium arsenate counteracted the effects of Pi. The apparent Km and Vmax were 0.133 mImage and 100 units; and 0.133 mImage and 200 units, in the absence and presence of Pi, respectively. The temperature optimum was 42 ° in the presence of Pi.Negative cooperative interactions observed at low concentrations of FAD were abolished by the addition of Pi. The inhibition by AMP was sigmoid and Pi abolished this sigmoidal response. The enzyme hydrolyzed in addition to FAD, NAD+ and NADP+. Nucleoside triphosphates were potent inhibitors of the enzyme activity. The partial inhibition of the enzyme by o-phenanthroline and by p-hydroxymercuribenzoate could be reversed by Fe2+ ions and by reduced glutathione, respectively.

Aspects of tautomerism. 7. Study of keto participation in alkaline hydrolysis of normal esters of .gamma.-keto acids

Study of the alkaline hydrolysis of a number of variously substituted normal o-benzoylbenzoic esters has been reported. Although carbonyl-assisted hydrolysis is the general rule, in compounds containing strongly electron-donating groups, the ester function is directly attacked. The cause of rate enhancement in carbonyl-assisted hydrolysis and in greater detail the case of 6-substituted derivatives are discussed. It is shown that the carbonyl-assisted hydrolyses are characterized by decreased sensitivity to leaving-group structure. The implications of this result are pointed out.

Lipid hydrolysis in mackerel (Rastrelliger kanagurta) during frozen storage

The hydrolytic changes in the lipids of mackerel (Rastrelliger kanagurta) during storage at -l8°C were studied with a view to understand the factors involved in the formation of free fatty acids. Only the phosphorylated fraction did undergo hydrolysis at an appreciable rate. It was found that the free fatty acid production was mainly associated with the phospholipid hydrolysis. As regards the triglycerides and unsaponifiable matter, there was no significant change in levels during frozen storage.

Study on the hydrolysis/precipitation behavior of Keggin Al-13 and Al-30 polymers in polyaluminum solutions

The hydrolysis/precipitation behaviors of Al3+, Al-13 and Al-30 under conditions typical for flocculation in water treatment were investigated by studying the particulates' size development, charge characteristics, chemical species and speciation transformation of coagulant hydrolysis precipitates. The optimal pH conditions for hydrolysis precipitates formation for AlCl3, PAC(A113) and PAC(A130) were 6.5-7.5, 8.5-9.5, and 7.5-9.5, respectively. The precipitates' formation rate increased with the increase in dosage, and the relative rates were AlCl3 >> PAC(A130) > PACA113. The precipitates' size increased when the dosage increased from 50 mu M to 200 mu M, but it decreased when the dosage increased to 800 AM. The Zeta potential of coagulant hydrolysis precipitates decreased with the increase in pH for the three coagulants. The isoelectric points of the freshly formed precipitates for AlCl3, PAC(A113) and PAC(A130) were 7.3, 9.6 and 9.2, respectively. The Zeta potentials of AlCl3 hydrolysis precipitates were lower than those of PAC(A113) and PAC(A130) when pH > 5.0. The Zeta potential of PAC(A130) hydrolysis precipitates was higher than that of PACA113 at the acidic side, but lower at the alkaline side. The dosage had no obvious effect on the Zeta potential of hydrolysis precipitates under fixed pH conditions. The increase in Zeta potential with the increase in dosage under uncontrolled pH conditions was due to the pH depression caused by coagulant addition. Al-Ferron research indicated that the hydrolysis precipitates of AlCl3 were composed of amorphous AI(OH)3 precipitates, but those of PACA113 and PACA130 were composed of aggregates of Al-13 and Al-30, respectively. Al3+ was the most un-stable species in coagulants, and its hydrolysis was remarkably influenced by solution pH. Al-13 and Al-30 species were very stable, and solution pH and aging had little effect on the chemical species of their hydrolysis products. The research method involving coagulant hydrolysis precipitates based on Al-Ferron reaction kinetics was studied in detail. The Al species classification based on complex reaction kinetic of hydrolysis precipitates and Ferron reagent was different from that measured in a conventional coagulant assay using the Al--Ferron method. The chemical composition of Al-a, Al-b and Al-c depended on coagulant and solution pH. The Al-b measured in the current case was different from Keggin Al-13, and the high Alb content in the AlCl3 hydrolysis precipitates could not used as testimony that most of the Al3+ Was converted to highly charged Al-13 species during AlCl3 coagulation.

Kinetic Model Study on Enzymatic Hydrolysis of Cellulose Using Artificial Neural Networks

Enzymatic hydrolysis of cellulose was highly complex because of the unclear enzymatic mechanism and many factors that affect the heterogeneous system. Therefore, it is difficult to build a theoretical model to study cellulose hydrolysis by cellulase. Artificial neural network (ANN) was used to simulate and predict this enzymatic reaction and compared with the response surface model (RSM). The independent variables were cellulase amount X-1, substrate concentration X-2, and reaction time X-3, and the response variables were reducing sugar concentration Y-1 and transformation rate of the raw material Y-2. The experimental results showed that ANN was much more suitable for studying the kinetics of the enzymatic hydrolysis than RSM. During the simulation process, relative errors produced by the ANN model were apparently smaller than that by RSM except one and the central experimental points. During the prediction process, values produced by the ANN model were much closer to the experimental values than that produced by RSM. These showed that ANN is a persuasive tool that can be used for studying the kinetics of cellulose hydrolysis catalyzed by cellulase.

Studies on the stability of polyazamacrocycle-Eu (Tb) by potentiometry and its catalytic hydrolysis on phosphate diester

The stability constants and species distributions of complexes of two lanthanide ions, Eu (III) and Tb(III), with a macrocyclic ligand, 3,6, 9, 17 20, 23-hexaazo-29, 30-dihydroxy-13, 27-dimethyl-tricylco-[23,3,1,1(11,15)] triaconta-1 (28) 11,13,15 (30), 25 26-hexane (BDBPH), in 1: 1 and 2: 1 system, were determined potentiometrically in 50% ethanol solution, at 35.0 degrees C and I = 0.100 mol/L (KCl). The two metal ions could form deprotonated mono- or dinuclear complexes with BDBPH with high stability after the three protons of the ligand completely neutralized. At higher pH values, Eu(M) could not form hydroxo complexes with BDBPH, while Tb(III) could form hydroxo complexes in the types of M2L(OH) M2L(OH)(2) and M2L (OH)(2). The kinetic study on the hydrolysis reaction of his (4-nitrophenyl) phosphate (BNPP) catalyzed by Tb-BDBPH system (2:1) was carried out in aqueous solution (pH 7.0 similar to 10.0) at 35 degrees C with I = 0.1000 mol/L (KCl). The second-order rate constant k(BNPP) (2.3 x 10(-3) (mol/L)(-1)center dot s(-1)) was determined. The dinuclear monohydroxo species, L-Tb-2-OH, is kinetically active species.

Kinetic Analysis of Ester Hydrolysis

A two-week multi-step experiment that introduces students to mechanistic organic chemistry and substituent effects. A simple preparation of differentially substituted para-nitrophenyl benzoates is followed by ester hydrolysis with monitoring by UV-Vis spectroscopy to provide rate data for the reaction.

Neighboring Group-Controlled Hydrolysis: Towards “Designer” Drug Release Biomaterials

To give the first demonstration of neighboring group-controlled drug delivery rates, a series of novel, polymerizable ester drug conjugates was synthesized and fully characterized. The monomers are suitable for copolymerization in biomaterials where control of drug release rate is critical to prophylaxis or obviation of infection. The incorporation of neighboring group moieties differing in nucleophilicity, geometry, and steric bulk in the conjugates allowed the rate of ester hydrolysis, and hence drug liberation, to be rationally and widely controlled. Solutions (2.5 x 10-5 mol dm-3) of ester conjugates of nalidixic acid incorporating pyridyl, amino, and phenyl neighboring groups hydrolyzed according to first-order kinetics, with rate constants between 3.00 ( 0.12 10-5 s -1 (fastest) and 4.50 ( 0.31 10- 6 s-1 (slowest). The hydrolysis was characterized using UV-visible spectroscopy. When copolymerized with poly(methyl methacrylate), free drug was shown to elute from the resulting materials, with the rate of release being controlled by the nature of the conjugate, as in solution. The controlled molecular architecture demonstrated by this system offers an attractive class of drug conjugate for the delivery of drugs from polymeric biomaterials such as bone cements in terms of both sustained, prolonged drug release and minimization of mechanical compromise as a result of release. We consider these results to be the rationale for the development of 'designer' drug release biomaterials, where the rate of required release can be controlled by predetermined molecular architecture.

Dilute acid hydrolysis of cellulose and cellulosic bio-waste using a microwave reactor system

The dilute acid hydrolysis of grass and cellulose with phosphoric acid was undertaken in a microwave reactor system. The experimental data and reaction kinetic analysis indicate that this is a potential process for cellulose and hemi-cellulose hydrolysis, due to a rapid hydrolysis reaction at moderate temperatures. The optimum conditions for grass hydrolysis were found to be 2.5% phosphoric acid at a temperature of 175 degrees C. It was found that sugar degradation occurred at acid concentrations greater than 2.5% (v/v) and temperatures greater than 175 degrees C. In a further series of experiments, the kinetics of dilute acid hydrolysis of cellulose was investigated varying phosphoric acid concentration and reaction temperatures. The experimental data indicate that the use of microwave technology can successfully facilitate dilute acid hydrolysis of cellulose allowing high yields of glucose in short reaction times. The optimum conditions gave a yield of 90% glucose. A pseudo-homogeneous consecutive first order reaction was assumed and the reaction rate constants were calculated as: k(1) = 0.0813 s(-1); k(2) = 0.0075 s(-1), which compare favourably with reaction rate constants found in conventional non-microwave reaction systems. The kinetic analysis would indicate that the primary advantages of employing microwave heating were to: achieve a high rate constant at moderate temperatures: and to prevent 'hot spot' formation within the reactor, which would have cause localised degradation of glucose.

Kinetic model for the hydrolysis of lignocellulosic biomass in the ionic liquid, 1-ethyl-3-methyl-imidazolium chloride†

The kinetics of the acid-catalysed hydrolysis of cellobiose in the ionic liquid 1-ethyl-3-methylimidazolium chloride, [C(2)mim]Cl, was studied as a model for general lignocellulosic biomass hydrolysis in ionic liquid systems. The results show that the rate of the two competing reactions, polysaccharide hydrolysis and sugar decomposition, vary with acid strength, and that for acids with an aqueous pK(a) below approximately zero, the hydrolysis reaction is significantly faster than the degradation of glucose, thus allowing hydrolysis to be performed with a high selectivity in glucose. In tests with soluble cellulose, hemicellulose (xylan), and lignocellulosic biomass (Miscanthus grass), comparable hydrolysis rates were observed with bond scission occurring randomly along the biopolymer chains, in contrast to end-group hydrolysis observed with aqueous acids.

Dilute acid hydrolysis of Lignocellulosic biomass

The overall aim of this work was to establish the optimum conditions for acid hydrolysis of hemicellulosic biomass in the form of potato peel. The hydrolysis reaction was undertaken in a 1l high pressure pilot batch reactor using dilute phosphoric acid. Analysis of the decomposition rate of hemicellulosic biomass (namely Cellulose, Hemicellulose and lignin) was undertaken using HPLC of the reaction products namely, 5 and 6 carbon sugars. Process parameters investigated included, reactor temperature (from 135 degrees C to 200 degrees C) and acid concentration (from 2.5% (w/w) to 10% (w/w)). Analysis of the reactor products indicated that high conversion of cellulose to glucose was apparent although arabinose conversion was quite low due to thermally un-stability. However, an overall sugar yield is 82.5% was achieved under optimum conditions. This optimum yield was obtained at 135 degrees C and 10% (w/w) acid concentration. 55.2 g sugar/100 g dry potato peel is produced after a time of 8 min. The work indicates that the use of potato peel may be a feasible option as a feed material for the production of sugars for biofuel synthesis, due its low cost and high sugar yields. (C) 2009 Elsevier B.V. All rights reserved.

Acid-catalyzed hydrolysis of cellulose and cellulosic waste using a microwave reactor system

A microwave reactor system was investigated as a potential technique to maximize sugar yield for the hydrolysis of municipal solid waste for ethanol production. Specifically, dilute acid hydrolysis of a-cellulose and waste cellulosic biomass (grass clippings) with phosphoric acid was undertaken within the microwave reactor system. The experimental data and reaction kinetic analysis indicate that the use of a microwave reactor system can successfully facilitate dilute acid hydrolysis of cellulose and waste cellulosic biomass, producing high yields of total sugars in short reaction times. The maximum yield of reducing sugars was obtained at 7.5% (w/v) phosphoric acid and 160 degrees C, corresponding to 60% of the theoretical total sugars, with a reaction time of 5 min. When using a very low acid concentration (0.4% w/v) for the hydrolysis in the microwave reactor, it was found that 10 g of total sugars/100 g dry mass was produced, which is significant considering the low acid concentration. When hydrolyzing grass clippings using the microwave reactor, the optimum conditions were an acid concentration of 2.5% (w/v), 175 degrees C with a 15 min reaction time, giving 18 g/100 g dry mass of total sugars, with xylose being the sugar with the highest yield. It was observed that pentose sugars were more easily formed but also more easily degraded, these being significantly affected by increases in acid concentration and temperature. Kinetic modeling of the data indicated that the use of microwave heating may account for an increase in reaction rate constant, k(1), found in this study in comparison with conventional systems described in the literature.

Alkaline hydrolysis of trinitrotoluene, TNT

The kinetics of the alkaline hydrolysis of trinitrotoluene, TNT, in an aqueous solution is a possible approach to destroying the active agent in unwanted munitions. The kinetics are shown to have a rapid initial step, step A, in which a highly coloured species, X (lambda(max) = 450 nm) is formed via an equilibrium reaction: TNT + OH- double left right arrow X. The bimolecular rate constant for the forward part of this equilibrium process, k(1), is: 0.099 +/- 0.004, 0.32 +/- 0.02 and 1.27 +/- 0.05 dm(3) mol(-1) s(-1), at 25, 40 and 60degreesC, respectively. The activation energy for the forward process is 60 kJ mol(-1). The first-order rate constant for the reverse of this process, k(-1), is: (5.3 +/- 2.6) x 10(-4), (1.2 +/- 1.0) x 10(-3) and (7.7 +/- 2.9) x 10(-3) s(-1) at 25, 40 and 60degreesC, respectively. The activation energy for the overall equilibrium process (k(1)/k(-1)) is ca. -5 kJ mol(-1). The subsequent alkaline hydrolysis of X to form the final product P, i.e. step B, is much slower than step A and appears to comprise two processes coupled in series, i.e. steps B1 (X +2OH(-) --> Z) and B2 (Z+OH- --> P). At 25degreesC, Step B1 appears rate determining throughout the decay process. At 45 degreesC and, more so, at 60degreesC, step B appears increasingly biphasic with increasing alkaline concentrations, as step B2 begins to compete with step B1 for position as the rate determining step. The trimolecular rate constant for step B1 is: 0.017 +/- 0.001, 0.0085 +/- 0.0002 and 0.0011 +/- 0.0001 dm(6) mol(-2) s(-1) at 25, 40 and 60degreesC, respectively, and the process has an activation energy of 64 kJ mol(-1). The transition from uniform kinetics, described by step B1, to mixed kinetics, described by steps B1 and B2, as the reaction temperature and alkali concentration are increased most likely occurs because (a) step B2 has a lower activation energy than B1, although it was not possible to measure the former parameter, and (b) step B2 has a lower (1st) order dependence upon [OH-] compared with that of step B1 (2nd). The bimolecular rate constant for step B2 is 0.0035 +/- 0.03 dm(3) mol(-1) s(-1) at 60degreesC. A brief NMR study of the initial hydrolysis product in water, acetone and chloroform, coupled with UV/visible spectra, provides evidence that species X is a Meisenheimer complex.

Rate acceleration of the Baylis-Hillman reaction in polar solvents (water and formamide). Dominant role of hydrogen bonding, not hydrophobic effects, is implicated

A substantial acceleration of the Baylis-Hillman reaction between cyclohexenone and benzaldehyde has been observed when the reaction is conducted in water. Several different amine catalysts were tested, and as with reactions conducted in the absence of solvent, 3-hydroxyquinuclidine was found to be the optimum catalyst in terms of rate. The reaction has been extended to other aldehyde electrophiles including pivaldehyde. Attempts to extend this work to acrylates was only partially successful as rapid hydrolysis of methyl and ethyl acrylates occurred under the base-catalyzed and water-promoted conditions. However, tert-butyl acrylates were sufficiently stable to couple with relatively reactive electrophiles. Further studies on the use of polar solvents revealed that formamide also provided significant acceleration and the use of 5 equiv of formamide (optimum amount) gave faster rates than reactions conducted in water. Using formamide, further acceleration was achieved in the presence of Yb(OTf)(3) (5 mol %). The scope of the new conditions was tested with a range of Michael acceptors and benzaldehyde and with a range of electrophiles and ethyl acrylate. The origin of the rate acceleration is discussed.