Control Of Catalytic Activity Research Articles

Parts per Million of Propanol and Arsine as Responsible for the Poisoning of the Propylene Polymerization Reaction.

Polypropylene synthesis is a critical process in the plastics industry, where control of catalytic activity is essential to ensure the quality and performance of the final product. In this study, the effect of two inhibitors, propanol and arsine, on the properties of synthesized polypropylene was investigated. Experiments were conducted using a conventional catalyst to polymerize propylene, and different concentrations of propanol and arsine were incorporated into the process. The results revealed that the addition of propanol led to a significant decrease in the Melt Flow Index (MFI) of the resulting polypropylene. The reduction in the MFI was most notable at a concentration of 62.33 ppm propanol, suggesting that propanol acts as an effective inhibitor by slowing down the polymerization rate and thus reducing the fluidity of the molten polypropylene. On the other hand, introducing arsine as an inhibitor increased the MFI of polypropylene. The maximum increase in the MFI was observed at a concentration of 0.035 ppm arsine. This suggests that small amounts of arsine affect the MFI and Mw of the produced PP. Regarding the catalyst productivity, it was found that as the concentration of propanol in the sample increased (approximately seven ppm), there was a decrease in productivity from 45 TM/kg to 44 TM/kg. Starting from 10 ppm, productivity continued to decline, reaching its lowest point at 52 ppm, with only 35 MT/kg. In the case of arsine, changes in catalyst productivity were observed at lower concentrations than with propanol. Starting from about 0.006 ppm, productivity decreased, reaching 39 MT/kg at a concentration of 0.024 ppm and further decreasing to 36 TM/kg with 0.0036 ppm. Computational analysis supported the experimental findings, indicating that arsine adsorbs more stably to the catalyst with an energy of -60.8 Kcal/mol, compared to propanol (-46.17 Kcal/mol) and isobutyl (-33.13 Kcal/mol). Analyses of HOMO and LUMO orbitals, as well as reactivity descriptors, such as electronegativity, chemical potential, and nucleophilicity, shed light on the potential interactions and chemical reactions involving inhibitors. Generated maps of molecular electrostatic potential (MEP) illustrated the charge distribution within the studied molecules, further contributing to the understanding of their reactivity. The computational results supported the experimental findings and provided additional information on the molecular interactions between the inhibitors and the catalyst, shedding light on the possible modes of inhibition. Solubles in xylene values indicate that both propanol and arsine affect the polymer's morphology, which may have significant implications for its properties and final applications.

H2O Derivatives Mediate CO Activation in Fischer-Tropsch Synthesis: A Review.

The process of Fischer-Tropsch synthesis is commonly described as a series of reactions in which CO and H2 are dissociated and adsorbed on the metals and then rearranged to produce hydrocarbons and H2O. However, CO dissociation adsorption is regarded as the initial stage of Fischer-Tropsch synthesis and an essential factor in the control of catalytic activity. Several pathways have been proposed to activate CO, namely direct CO dissociation, activation hydrogenation, and activation by insertion into growing chains. In addition, H2O is considered an important by-product of Fischer-Tropsch synthesis reactions and has been shown to play a key role in regulating the distribution of Fischer-Tropsch synthesis products. The presence of H2O may influence the reaction rate, the product distribution, and the deactivation rate. Focus on H2O molecules and H2O-derivatives (H*, OH* and O*) can assist CO activation hydrogenation on Fe- and Co-based catalysts. In this work, the intermediates (C*, O*, HCO*, COH*, COH*, CH*, etc.) and reaction pathways were analyzed, and the H2O and H2O derivatives (H*, OH* and O*) on Fe- and Co-based catalysts and their role in the Fischer-Tropsch synthesis reaction process were reviewed.

Tuning Electrode Reactivity through Organometallic Complexes.

The use of molecularly modified electrodes in catalysis heralds a new paradigm in designing chemical transformations by allowing control of catalytic activity. Herein, we provide an overview of reported methods to develop electrodes functionalized with organometallic complexes and a summary of commonly used techniques for characterizing the electrode surface after immobilization. In addition, we highlight the implications of surface functionalization in catalysis to emphasize the key aspects that should be considered during the development and optimization of functionalized electrodes. Particularly, surface-molecule electronic coupling and electrostatic interactions within a hybrid system are discussed to present effective handles in tuning catalytic activity. We envision that this emerging type of hybrid catalytic system has the potential to combine the advantages of homogeneous catalysis and heterogeneous supports and could be applied to an expanded range of transformations beyond energy conversion.

Catalytic Three-Component Machinery: Control of Catalytic Activity by Machine Speed.

Three supramolecular slider-on-deck systems DS1-DS3 were obtained as two-component aggregates from the sliders S1-S3 and deck D with its three zinc porphyrin (ZnPor) binding sites. The binding of the two-footed slider to the deck varies with the donor qualities of and the steric hindrance at the pyridine/pyrimidine (pyr) feet, and was effected by two Npyr →ZnPor interactions. Accordingly, the sliders move over the three zinc porphyrins in the deck at different speeds, namely with 32.2, 220, and 440 kHz at room temperature. The addition of N-methylpyrrolidine as an organocatalyst to DS1-DS3 generates catalytic three-component machineries. By using a conjugate addition as a probe reaction, we observed a correlation between the operating speed of the slider-on-deck systems and the yields of the catalytic reaction. As the thermodynamic binding of the slider decreases, both the frequency of the sliding motion and the yield of the catalytic reaction increase.

Catalytic Activity Control via Crossover between Two Different Microstructures.

Metal nanocatalysts hold great promise for a wide range of heterogeneous catalytic reactions, while the optimization strategy of catalytic activity is largely restricted by particle size or shape control. Here, we demonstrate that a reversible microstructural control through the crossover between multiply twinned nanoparticle (MTP) and single crystal (SC) can be readily achieved by solvent post-treatment on gold nanoparticles (AuNPs). Polar solvents (e.g., water, methanol) direct the transformation from MTP to SC accompanied by the disappearance of twinning and stacking faults. A reverse transformation from SC to MTP is achieved in nonpolar solvent (e.g., toluene) mixed with thiol ligands. The transformation between two different microstructures is directly observed by in situ TEM and leads to a drastic modulation of catalytic activity toward the gas-phase selective oxidation of alcohols. On the basis of the combined experimental and theoretical investigations of alcohol chemisorption on these nanocatalysts, we propose that the exposure of {211}-like microfacets associated with twin boundaries and stack faults accounts for the strong chemisorption of alcohol molecules on MTP AuNPs and thus the exceptionally high catalytic activity.

Exploring pretreatment effects in Co/SiO2 Fischer-Tropsch catalysts: Different oxidizing gases applied to oxidation-reduction process

The influence of reduction-oxidation-reduction (ROR) pretreatment on 20% Co/SiO2 has been investigated using different oxidizing gases including water vapor and oxygen in the oxidation step. In this study, the evolution concerning the SiO2 structure and the cobalt phase and morphology is clearly elucidated at each step of reduction, oxidation and subsequent re-reduction. It is demonstrated that ROR treatment using both oxygen and water vapor decreases the average cobalt particle size. However, the catalytic performance affected in FTS is considerably different. ROR treatment in oxygen results in an increase in catalytic activity. In contrast, the water vapor applied in oxidation step obviously deactivates cobalt catalyst and enhances selectivity of methane. The resulting deactivation is ascribed to the promoted formation of irreducible cobalt silicate through the reaction between water vapor caused surface SiOH groups and oxidized cobalt (CoO) in spite of unchanged surface area and pore structure on SiO2. The characterization data reveals that the re-dispersion of cobalt particles occurs at oxidation step rather than the re-reduction step. In addition, the results indicate that the ROR treatment reducing the cobalt particle size depends on its initial size as no re-dispersion can be observed in the case of particles smaller than about 11nm. Furthermore, the water vapor shows more effective re-dispersion in cobalt particles compared with the use of oxygen. This study provides fundamental insights into the control of catalytic activity, product selectivity, and catalyst stability over supported cobalt catalysts by understanding the evolution of catalyst structure through ROR treatment in different chemical environment.

Double-channel emission from gold nanoparticles functionalized with a thermo-responsive copolymer ligand: preparation, optical properties and control of catalytic activity

Double-channel-emitting gold nanoparticles functionalized with a thermo-responsive copolymer ligand containing an episulfide group show a controllable thermo-responsive catalytic reduction performance for 4-nitrophenol.

Functional dichotomy in the 16S rRNA (m1A1408) methyltransferase family and control of catalytic activity via a novel tryptophan mediated loop reorganization.

Methylation of the bacterial small ribosomal subunit (16S) rRNA on the N1 position of A1408 confers exceptionally high-level resistance to a broad spectrum of aminoglycoside antibiotics. Here, we present a detailed structural and functional analysis of the Catenulisporales acidiphilia 16S rRNA (m1A1408) methyltransferase (‘CacKam’). The apo CacKam structure closely resembles other m1A1408 methyltransferases within its conserved SAM-binding fold but the region linking core β strands 6 and 7 (the ‘β6/7 linker’) has a unique, extended structure that partially occludes the putative 16S rRNA binding surface, and sequesters the conserved and functionally critical W203 outside of the CacKam active site. Substitution of conserved residues in the SAM binding pocket reveals a functional dichotomy in the 16S rRNA (m1A1408) methyltransferase family, with two apparently distinct molecular mechanisms coupling cosubstrate/ substrate binding to catalytic activity. Our results additionally suggest that CacKam exploits the W203-mediated remodeling of the β6/7 linker as a novel mechanism to control 30S substrate recognition and enzymatic turnover.

Sequence-Dependent pKaShift Induced by Molecular Self-Assembly: Insights from Computer Simulation

The control of catalytic activity using molecular self-assembly is of fundamental interest. Recent experiments (Muller et al., Angew. Chem., Int. Ed., 2009, 48, 922-925) have demonstrated that two sequence isomers of β-peptides show remarkably different activity as an amine catalyst for a retro-aldol cleavage reaction, a difference attributed to the ability of one of the sequences to form large aggregates. The self-assembly and catalytic activity of these two isomers are investigated using constant pH molecular dynamics (CPHMD), for an atomistic model of β-peptides in implicit solvent. Simulations show that the globally amphiphilic (GA) isomer, which experimentally has high activity, forms large aggregates, while the non-GA isomer forms aggregates that are at most three or four molecules in size. The pK(a) shift of the βK-residues is significantly higher in the GA isomers that make a large aggregate. Since the decrease in pK(a) of the side-chain ammonium group is the main driving force for amine catalysis, the calculations are consistent with experiment. We find that the buried βK residues become entirely deprotonated, and the pK(a) shift for other titratable βK residues is accompanied mainly by a clustering of solvent exposed βK residues. We conclude that simulations can be used to understand catalytic activity due to self-assembly.

Kinetic, mutagenic, and structural homology analysis of l-serine dehydratase from Legionella pneumophila

A structural database search has revealed that the same fold found in the allosteric substrate binding (ASB) domain of Mycobacterium tuberculosis D-3-phosphoglycerate dehydrogenase (PGDH) is found in l-serine dehydratase from Legionella pneumophila. The M. tuberculosis PGDH ASB domain functions in the control of catalytic activity. Bacterial l-serine dehydratases are 4Fe–4S proteins that convert l-serine to pyruvate and ammonia. Sequence homology reveals two types depending on whether their α and β domains are on the same (Type 2) or separate (Type 1) polypeptides. The α domains contain the catalytic iron–sulfur center while the β domains do not yet have a described function, but the structural homology with PGDH suggests a regulatory role. Type 1 β domains also contain additional sequence homologous to PGDH ACT domains. A continuous assay for l-serine dehydratase is used to demonstrate homotropic cooperativity, a broad pH range, and essential irreversibility. Product inhibition analysis reveals a Uni–Bi ordered mechanism with ammonia dissociating before pyruvate. l-Threonine is a poor substrate and l-cysteine and d-serine are competitive inhibitors with Ki values that differ by almost 10-fold from those reported for Escherichia colil-serine dehydratase. Mutagenesis identifies the three cysteine residues at the active site that anchor the iron–sulfur complex.

Hypothermia translocates nitric oxide synthase from cytosol to membrane in snail neurons

Neuronal nitric oxide (NO) levels are modulated through the control of catalytic activity of NO synthase (NOS). Although signals limiting excess NO synthesis are being extensively studied in the vertebrate nervous system, our knowledge is rather limited on the control of NOS in neurons of invertebrates. We have previously reported a transient inactivation of NOS in hibernating snails. In the present study, we aimed to understand the mechanism leading to blocked NO production during hypothermic periods of Helix pomatia. We have found that hypothermic challenge translocated NOS from the cytosol to the perinuclear endoplasmic reticulum, and that this cytosol to membrane trafficking was essential for inhibition of NO synthesis. Cold stress also downregulated NOS mRNA levels in snail neurons, although the amount of NOS protein remained unaffected in response to hypothermia. Our studies with cultured neurons and glia cells revealed that glia-neuron signaling may inhibit membrane binding and inactivation of NOS. We provide evidence that hypothermia keeps NO synthesis "hibernated" through subcellular redistribution of NOS.

Evaluation of Heterogeneous Metal−Organic Framework Organocatalysts Prepared by Postsynthetic Modification

A metal-organic framework (MOF) containing 2-amino-1,4-benzenedicarboxylate (NH(2)-BDC) as a building block is shown to undergo chemical modification with a set of cyclic anhydrides. The modification of the aluminum-based MOF known as MIL-53(Al)-NH(2) (MIL = Material Institut Lavoisier) by these reagents is demonstrated by using a variety of methods, including NMR and electrospray ionization mass spectrometry (ESI-MS), and the structural integrity of the modified MOFs has been confirmed by thermal gravimetric analysis (TGA) and powder X-ray diffraction (PXRD). Reaction with these cyclic anhydrides produces MOFs that display carboxylic acid functional groups within their pores. Furthermore, it is shown that maleic acid functionalized MIL-53(Al)-AMMal can act as a Brønsted acid catalyst and facilitate the methanolysis of several small epoxides. Experiments show that MIL-53(Al)-AMMal acts in a heterogeneous manner and is recyclable with consistent activity over at least three catalytic cycles. The findings presented here demonstrate several important features of covalent postsynthetic modification (PSM) on MOFs, including (1) facile introduction of catalytic functionality using simple organic reagents (e.g., anhydrides); (2) the ability to utilize and recycle organocatalytic MOFs; (3) control of catalytic activity through choice of functional group. The findings clearly illustrate that covalent postsynthetic modification represents a powerful means to access new MOF compounds that serve as organocatalytic materials.

Control of Catalytic Activity on Hydrosilylation Reaction by Polymer Bearing Sulfide Moieties

Control of Catalytic Activity on Hydrosilylation Reaction by Polymer Bearing Sulfide Moieties

Control of Catalytic Activity on Hydrosilylation Reaction by Sulfide Derivatives

Control of Catalytic Activity on Hydrosilylation Reaction by Sulfide Derivatives

Post-translational regulation of nitrate reductase: mechanism, physiological relevance and environmental triggers.

Assimilatory nitrate reductase (NR) of higher plants is a most interesting enzyme, both from its central function in plant primary metabolism and from the complex regulation of its expression and control of catalytic activity and degradation. Here, present knowledge about the mechanism of post-translational regulation of NR is summarized and the properties of the regulatory enzymes involved (protein kinases, protein phosphatases and 14-3-3-binding proteins) are described. It is shown that light and oxygen availability are the major external triggers for the rapid and reversible modulation of NR activity, and that sugars and/or sugar phosphates are the internal signals which regulate the protein kinase(s) and phosphatase. It is also demonstrated that stress factors like nitrate deficiency and salinity have remarkably little direct influence on the NR activation state. Further, changes in NR activity measured in vitro are not always associated with changes in nitrate reduction rates in vivo, suggesting that NR can be under strong substrate limitation. The degradation and half-life of the NR protein also appear to be affected by NR phosphorylation and 14-3-3 binding, as NR activation always correlates positively with its stability. However, it is not known whether the molecular form of NR in vivo affects its susceptibility to proteolytic degradation, or whether factors that affect the NR activation state also independently affect the activity or induction of the NR protease(s). A second and potentially important function of NR, the production of nitric oxide (NO) from nitrite is briefly described, but it remains to be determined whether NR produces NO for pathogen/stress signalling in vivo.

Heparanase expression in invasive trophoblasts and acute vascular damage.

Heparan sulfate proteoglycans play a pivotal role in tissue function, development, inflammation, and immunity. We have identified a novel cDNA encoding human heparanase, an enzyme thought to cleave heparan sulfate in physiology and disease, and have located the HEP gene on human chromosome 4q21. Monoclonal antibodies against human heparanase located the enzyme along invasive extravillous trophoblasts of human placenta and along endothelial cells in organ xenografts targeted by hyperacute rejection, both sites of heparan sulfate digestion. Heparanase deposition was evident in arterial walls in normal tissues; however, vascular heparan sulfate cleavage was coincident with heparanase enzyme during inflammatory episodes. These findings suggest that heparanase elaboration and control of catalytic activity may contribute to the development and pathogenesis of vascular disease and suggest that heparanase intervention might be a useful therapeutic target.

Development and Application of Latent Catalysts for Hydrosilylation Systems VIII1. Control of Catalytic Activity by Poly(1-phenylethylisocyanide)

Development and Application of Latent Catalysts for Hydrosilylation Systems VIII 1 . Control of Catalytic Activity by Poly(1-phenylethylisocyanide)

Temperature-Sensitive Dendritic Hosts: Synthesis, Characterization, and Control of Catalytic Activity

Temperature-Sensitive Dendritic Hosts: Synthesis, Characterization, and Control of Catalytic Activity

イミン誘導体によるヒドロシリル化反応における触媒活性の制御効果

ヒドロシリル化反応プロセスを制御する潜在性触媒の開発と応用を目的として、イミン類による白金触媒の活性の変化を評価した。その結果，イミン類により白金触媒の活性が良好に制御できることが明らかとなり，その際，イミン上の置換基の立体的および電子的な効果や添加量により活性制御効果が大きく変化することが分かった。また，同様の傾向はシリコーン樹脂の硬化反応系においても観察され，イミン化合物を添加した白金触媒系がヒドロシリル化反応において優れた熱潜在性触媒として作用することが示された。

Control of Catalytic Activity in Hydrosilylation by using Acetylene Derivatives

アセチレン誘導体存在下，ヒドロシリル化反応における白金触媒の活性制御を検討した。 その結果，アセチレン誘導体の立体的および電子的な効果により，触媒活性の制御能は大きく影響された。 また， 同様の傾向はシリコーン樹脂の硬化反応系においても観察された。 さらに，モノアセチレン類とジアセチレン類との制御能を比較した結果，ジアセチレン類は高い制御能を示した。 このことから，本系 におけるキレート効果の存在が示唆された。