True Catalysis Research Articles

Quantifying Catalysis at the Origin of Life.

The construction of hypothetical environments to produce organic molecules such as metabolic intermediates or amino acids is the subject of ongoing research into the emergence of life. Experiments specifically focused on an anabolic approach typically rely on a mineral catalyst to facilitate the supply of organics that may have produced prebiotic building blocks for life. Alternatively to a true catalytic system, a mineral could be sacrificially oxidized in the production of organics, necessitating the emergent 'life' to turn to virgin materials for each iteration of metabolic processes. The aim of this perspective is to view the current 'metabolism-first' literature through the lens of materials chemistry to evaluate the need for higher catalytic activity and materials analyses. While many elegant studies have detailed the production of chemical building blocks under geologically plausible and biologically relevant conditions, few appear to do so with sub-stoichiometric amounts of metals or minerals. Moving toward sub-stoichiometric metals with rigorous materials analyses is necessary to demonstrate the viability of an elusive cornerstone of the 'metabolism-first' hypotheses: catalysis. We emphasize that future work should aim to demonstrate decreased catalyst loading, increased productivity, and/or rigorous materials analyses for evidence of true catalysis.

Chitosan bead containing metal–organic framework encapsulated heteropolyacid as an efficient catalyst for cascade condensation reaction

Using cyclodextrin and chitosan that are bio-based compounds, a novel bi-functional catalytic composite is designed, in which metal–organic framework encapsulated phosphomolybdic acid was incorporated in a dual chitosan-cyclodextrin nanosponge bead. The composite was characterized via XRD, TGA, ICP, BET, NH3-TPD, FTIR, FE-SEM/EDS, elemental mapping analysis and its catalytic activity was examined in alcohol oxidation and cascade alcohol oxidation–Knoevenagel condensation reaction. It was found that the designed catalyst that possess both acidic feature and redox potential could promote both reactions in aqueous media at 55 °C and various substrates with different electronic features could tolerate the aforementioned reactions to furnish the products in 75–95% yield. Furthermore, the catalyst could be readily recovered and recycled for five runs with slight loss of the catalytic activity. Notably, in this composite the synergism between the components led to high catalytic activity, which was superior to each component. In fact, the amino groups on the chitosan served as catalysts, while cyclodextrin nanosponge mainly acted as a phase transfer agent. Moreover, measurement of phosphomolybdic acid leaching showed that its incorporation in metal–organic framework and bead structure could suppress its leaching, which is considered a drawback for this compound. Other merits of this bi-functional catalyst were its simplicity, use of bio-based compounds and true catalysis, which was proved via hot filtration.

Metal Cation-Driven Dynamic Covalent Formation of Imine and Hydrazone Ligands Displaying Synergistic Co-catalysis and Auxiliary Amine Effects.

Optimizing C=N bond formation and C/N component exchange has major significance in Dynamic Covalent Chemistry (DCC). Imine and hydrazone generation from their aldehyde, amine and hydrazine components showed large accelerations in presence of AgOTf or Zn(OTf)2 , up to 104 for the Zn(II)-(p-anisidine)imine complex. Zn(OTf)2 and auxiliary p-anisidine together accelerated 630 times the formation of the Zn(II)-hydrazone complex, revealing a strong synergistic effect, traced to very fast initial formation of the reactive Zn(II)-imine complex presenting a C=N bond metallo-activated towards reaction with the hydrazine component. Reactions involving more entities showed kinetically faster and thermodynamically simpler outputs due to dynamic competition within a mixture of higher complexity. Catalytic amounts of metal salts and auxiliary amine gave similar marked rate accelerations and turnover, indicating true catalysis. The synergistic effect achieved by combining metallo- and organo-catalysis points to a powerful co-catalysis strategy of bond-formation in DCC through interconnected chemical transformations.

Post-modified polymer with imidazole groups as an efficient and reusable heterogeneous catalyst for organophosphate degradation

In this work, the commercial polymer poly(ethylene-alt-maleic anhydride) was used as a platform for the preparation of an imidazole-rich polymeric catalyst (PEIIm) designed for organophosphate degradation. The catalyst was prepared at gram-scale using simple and cost-effective steps and was characterized by 1H NMR, IR, CHN and TGA. PEIIm showed higher activity than the free imidazole towards the degradation of diethyl 2,4-dinitrophenylphosphate, an organophosphate model, and was recovered by centrifugation and reused without loss of activity. Importantly, experiments performed under excess of substrate demonstrate that true catalysis takes place. Solvent kinetic isotope effect indicates that the pendant imidazole groups attack the phosphorus atom to form a phosphorylated polymeric intermediate that is rapidly hydrolyzed, allowing for the catalyst regeneration. PEIIm was also employed in the degradation of toxic pesticide ethyl paraoxon, resulting in a reduction in its half-life from 780 days to 25 days at 25 °C, pH 8.0.

Micelle-catalyzed domain swapping in the GlpG rhomboid protease cytoplasmic domain.

Three-dimensional domain swapping is a mode of self-interaction that can give rise to altered functional states and has been identified as the trigger event in some protein deposition diseases, yet rates of interconversion between oligomeric states are usually slow, with the requirement for transient disruption of an extensive network of interactions giving rise to a large kinetic barrier. Here we demonstrate that the cytoplasmic domain of the Escherichia coli GlpG rhomboid protease undergoes slow dimerization via domain swapping and that micromolar concentrations of micelles can be used to enhance monomer-dimer exchange rates by more than 1000-fold. Detergents bearing a phosphocholine headgroup are shown to be true catalysts, with hexadecylphosphocholine reducing the 26 kcal/mol free energy barrier by >11 kcal/mol while preserving the 5 kcal/mol difference between monomer and dimer states. Catalysis involves the formation of a micelle-bound intermediate with a partially unfolded structure that is primed for domain swapping. Taken together, these results are the first to demonstrate true catalysis for domain swapping, by using micelles that work in a chaperonin-like fashion to unfold a kinetically trapped state and allow access to the domain-swapped form.

Alkaline Degradation of the Organophosphorus Pesticide Fenitrothion as Mediated by Cationic C12, C14, C16, and C18 Surfactants

The effect of varying surfactant chain length (C12, C14, C16, C18) on the alkaline hydrolysis of the organophosphorus pesticide fenitrothion was determined for the following series of inert counterion cationic surfactants: dodecyltrimethylammonium bromide (DTABr), tetradecyltrimethylammonium bromide (TTABr), hexadecyltrimethylammonium bromide (CTABr), and octadecyltrimethylammonium bromide (OTABr). Plots of kobs versus [surfactant] at constant [KOH] showed saturation behavior at low total [Br-], and (constrained) S-shaped curvature was observed at high total [Br-]. kobs values increased with increasing surfactant chain length but decreased with added KBr. For systems exhibiting saturation behavior, further analysis of the results using the PPIE treatment as modified to account for HO-/Br- exchange allowed the evaluation of substrate binding constants, KS, and micellar rate constants, k2m. The binding constants increased with chain length (hydrophobicity), but ionic strength had no effect on KS. Meanwhile, because of the increased KS values as the surfactant chain length increased, the rate enhancements observed for fenitrothion degradation correspondingly increased. However, rate enhancements decreased with ionic strength because reactive counterions could not compete against the bromide anion for micellar binding sites. Low k2m/k2w ratios revealed that the observed rate enhancements were due to the so-called concentration effect rather than true catalysis. Finally, where the PPIE model failed (displaying S-shaped curvature), our results support the intervention of sphere-to-rod transitions that are favored at high ionic strength (>0.01 M Br-) and lower temperatures as the cause of the S-shaped curvature.

Micellar Catalyzed Degradation of Fenitrothion, an Organophosphorus Pesticide, in Solution and Soils

We report on a study of the decomposition of fenitrothion (an organophosphorus pesticide that is a persistent contaminant in soils and groundwater) as catalyzed by cetyltrimethylammonium (CTA+) micelles. The CTA micelles were associated with two types of counterions: (1) inert counterions (e.g. CTABr) and (2) reactive counterions (e.g. CTAOH). The reactive counterion surfactants used were hydroxide anion (HO-) as a normal nucleophile and hydroperoxide anion (HOO-) and the anion of pyruvaldehyde oxime (MINA-) as two alpha-nucleophiles. The reactivity order followed: CTABr < CTAOH < CTAMINA << CTAOOH. Treatment of the rate data using the Pseudo-Phase Ion Exchange (PPIE) model of micellar catalysis showed the ratio k2M/k2w to be less than unity for all the surfactants employed. Rather than arising from a "true catalysis", we attributed the observed rate enhancements to a "concentration effect", where both pesticide and nucleophile were incorporated into the small micellar phase volume. Furthermore, the CTAOOH/CTAOH pair gave an alpha-effect of 57, showing that the alpha-effect can play an important role in micellar systems. We further investigated the effectiveness of reactive counterion surfactants in decontaminating selected environmental solids that were spiked with 27 ppb fenitrothion. The solids were as follows: the clay mineral montmorillonite and SO-1 and S0-2 soils (obtained from the Canadian Certified Reference Materials Project). The reactive counterion surfactant solutions significantly enhanced the rate of fenitrothion degradation in the spiked solids over that obtained when the spiked solid was placed in contact with either 0.02 M KOH or water. The rate enhancements followed the order CTAOOH >> CTAMINA approximately CTAOH > KOH >> water. We conclude that reactive counterion surfactants, especially with alpha-nucleophiles, hold great potential in terms of remediating soils contaminated by toxic organophosphorus esters.

Catalysis of carcinogen-detoxification by DNA: Comparison of enantiomeric diol epoxides

The interactions of the (+)- and (-)-enantiomers of 7r,8t-dihydroxy-9t,10t-oxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BPDE-I) with purified DNA have been studied in vitro. These compounds are formed by cellular metabolism of the potent environmental carcinogen benzo[a]pyrene, and the (+)-enantiomer is thought to be the ultimate carcinogenic metabolite. Non-covalent, intercalative binding was measured spectrophotometrically, hydrolysis was measured spectrofluorometrically and covalent binding was detected by liquid scintillation counting. No significant differences were found in the association constants for intercalative binding or in the ability of DNA to catalyse the hydrolysis of the two enantiomers. Covalent DNA binding was 4.5-fold higher for the (+)-enantiomer. When DNA was pretreated with a molar equivalent of the (-)-enantiomer, its subsequent ability to enhance the rate of BPDE-I hydrolysis and to bind covalently to (+)-BPDE-I was unimpaired. This suggests that the participation of the DNA in the hydrolysis reaction does not alter the DNA and therefore that the rate-enhancement is true catalysis.

Catalysts for initiating the hydrogen-oxygen reaction at 78 °K

Catalysts for initiating reaction of hydrogen with oxygen in gas mixtures at temperatures down to 78 °K (−195 °C) were sought. A rising-temperature reactor was used for detecting onset of reaction. The platinum metals, especially iridium, platinum, and ruthenium, were the most active. With high concentrations of iridium on an alumina support, reaction initiation was observed at −195 °C for a helium stream containing 3% hydrogen and 1% oxygen. Best results were obtained when the catalyst had been preheated in hydrogen and cooled in a hydrogen environment before being contacted with oxygen-containing gas. The initiation is interpreted to be the result of transient phenomena which occur when a hydrogen-oxygen mixture contacts an active catalyst. Chemisorption of oxygen and formation of some water, along with water adsorption on the support, serve to raise the temperature to a point where true catalysis can proceed.

La théorie de la catalyse vue d'ensemble et essai de synthèse

THE definition of the word 'catalyst' used to have a quite precise meaning in chemistry, whether catalysis occurred in heterogeneous or homogeneous systems. In recent years 'catalysis' has come to include a tremendous variety of chemical reactions which, strictly speaking, do not involve true catalysis at all. In a similar way, the term 'negative catalysis' did duty until such time that the mechanism of the retardation and inhibition of chemical reactions was more fully understood, when it became abundantly plain that the inhibitor was almost invariably chemically destroyed in the inhibitory reaction. This extension of the meaning of the term has therefore led to the belief that a systematic treatment of the mechanism of chemical reactions is most easily accomplished by treating reactions as catalytic processes. La theorie de la catalyse vue d'ensemble et essai de synthese Par Prof. Jacques Metadier. (Actualites scientifiques et industrielles, 1005.) Pp. 101. (Paris: Hermann et Cie., 1946.) 200 francs.