Emergence of Highly Enantioselective Catalytic Activity in a Helical Polymer Mediated by Deracemization of Racemic Pendants

Rare-earth phosphates are of particular interest because of their catalytic properties associated with the hydrolysis of many aromatic chlorides in the petroleum industry. Lanthanum phosphates (LaPO4) which have been doped with small amounts of copper have shown increased catalytic activity (1). However the physical and chemical characteristics of the samples leading to good catalytic activity are not known.Many catalysts are amorphous and thus do not easily lend themselves to methods of investigation which would include electron microscopy. However, the LaPO4, crystals are quite suitable samples for high resolution techniques.The samples used were obtained from William L. Kehl of Gulf Research and Development Company. The electron microscopy was carried out on a JEOL JEM-100B which had been modified for high resolution microscopy (2). Standard high resolution techniques were employed. Three different sample types were observed: 669A-1-5-7 (poor catalyst), H-L-2 (good catalyst) and 27-011 (good catalyst).

Electron Microscopy and image analysis of nucleo-protein complexes

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100168177 ◽

1994 ◽

Vol 52 ◽

pp. 88-89

Author(s):

E. H. Egelman ◽

X. Yu

Keyword(s):

Electron Microscopy ◽

Image Analysis ◽

Normal Cell ◽

Genetic Recombination ◽

Protein Complexes ◽

Chromosomal Rearrangements ◽

Reca Protein ◽

E Coli ◽

Helical Polymer ◽

Specific Protease

The RecA protein of E. coli has been shown to mediate genetic recombination, regulate its own synthesis, control the expression of other genes, act as a specific protease, form a helical polymer and have an ATPase activity, among other observed properties. The unusual filament formed by the RecA protein on DNA has not previously been shown to exist outside of bacteria. Within this filament, the 36 Å pitch of B-form DNA is extended to about 95 Å, the pitch of the RecA helix. We have now establishedthat similar nucleo-protein complexes are formed by bacteriophage and yeast proteins, and availableevidence suggests that this structure is universal across all of biology, including humans. Thus, understanding the function of the RecA protein will reveal basic mechanisms, in existence inall organisms, that are at the foundation of general genetic recombination and repair.Recombination at this moment is assuming an importance far greater than just pure biology. The association between chromosomal rearrangements and neoplasms has become stronger and stronger, and these rearrangements are most likely products of the recombinatory apparatus of the normal cell. Further, damage to DNA appears to be a major cause of cancer.

The design and catalytic performance of molybdenum active sites on an MCM-41 framework for the aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran

Catalysis Science & Technology ◽

10.1039/c8cy02291g ◽

2019 ◽

Vol 9 (3) ◽

pp. 811-821 ◽

Cited By ~ 7

Author(s):

Zhao-Meng Wang ◽

Li-Juan Liu ◽

Bo Xiang ◽

Yue Wang ◽

Ya-Jing Lyu ◽

...

Keyword(s):

Catalytic Activity ◽

Active Sites ◽

Aerobic Oxidation ◽

Catalytic Performance ◽

Mcm 41

The catalytic activity decreases as –(SiO)3Mo(OH)(O) > –(SiO)2Mo(O)2 > –(O)4–MoO.

Prolonged Expression of Procoagulant Activity of Human Platelets Degranulated by Thrombin

Thrombosis and Haemostasis ◽

10.1055/s-0038-1649855 ◽

1995 ◽

Vol 74 (03) ◽

pp. 958-961 ◽

Cited By ~ 6

Author(s):

Raelene L Kinlough-Rathbone ◽

Dennis W Perry

Keyword(s):

Catalytic Activity ◽

Thrombus Formation ◽

Annexin V ◽

Human Platelets ◽

Procoagulant Activity ◽

Prothrombinase Complex ◽

Arterial Thrombus ◽

Flowing Blood

SummaryPlatelets are exposed to thrombin when they take part in arterial thrombus formation, and they may return to the circulation when they are freed by fibrinolysis and dislodged by flowing blood. Thrombin causes the expression of procoagulant activity on platelets, and if this activity persists, the recirculating platelets may contribute to subsequent thrombosis. We have developed techniques to degranulate human platelets by treatment with thrombin, and recover them as single, discrete platelets that aggregate in response to both weak and strong agonists. In the present study we examined the duration of procoagulant activity on the surface of thrombin-degranulated platelets by two methods: a prothrombinase assay, and the binding of 125I-labeled annexin. Control platelets generated 0.9 ± 0.4 U thrombin per 107 platelets in 15 min. Suspensions of thrombin-degranulated platelets formed 5.4 ± 0.1 U thrombin per 107 platelets in this time. Binding of 125I-annexin V was also greater with thrombin-treated platelets than with control platelets (controls: 1.7 ±0.1 ng annexin/107 platelets; thrombin-degranulated platelets: 6.8 ± 0.2 ng annexin/107 platelets). With thrombin-degranulated platelets, increased procoagulant activity and annexin binding persisted for at least 4 h after degranulation and resuspension, indicating that the catalytic activity for the prothrombinase complex is not reversed during this time. These platelets maintained their ability to aggregate for 4 h, even in response to the weak agonist, ADP. Thus, platelets that have taken part in thrombus formation and returned to the circulation may contribute to the promotion of further thrombotic events because of the persistence of procoagulant activity on their surface.

Enhanced catalytic activity of low-Pt content nanocatalysts supported on hollow carbon spheres for the ORR in alkaline media

MRS Advances ◽

10.1557/adv.2020.370 ◽

2020 ◽

Vol 5 (57-58) ◽

pp. 2961-2972

Author(s):

P.C. Meléndez-González ◽

E. Garza-Duran ◽

J.C. Martínez-Loyola ◽

P. Quintana-Owen ◽

I.L. Alonso-Lemus ◽

...

Keyword(s):

Catalytic Activity ◽

Anion Exchange ◽

Average Particle Size ◽

Synthesis Method ◽

Alkaline Media ◽

High Catalytic Activity ◽

Average Particle ◽

Carbon Spheres ◽

Hollow Carbon ◽

Hollow Carbon Spheres

In this work, low-Pt content nanocatalysts (≈ 5 wt. %) supported on Hollow Carbon Spheres (HCS) were synthesized by two routes: i) colloidal conventional polyol, and ii) surfactant-free Bromide Anion Exchange (BAE). The nanocatalysts were labelled as Pt/HCS-P and Pt/HCS-B for polyol and BAE, respectively. The physicochemical characterization of the nanocatalysts showed that by following both methods, a good control of chemical composition was achieved, obtaining in addition well dispersed nanoparticles of less than 3 nm TEM average particle size (d) on the HCS. Pt/HCS-B contained more Pt0 species than Pt/HCS-P, an effect of the synthesis method. In addition, the structure of the HCS remains more ordered after BAE synthesis, compared to polyol. Regarding the catalytic activity for the Oxygen Reduction Reaction (ORR) in 0.5 M KOH, Pt/HCS-P and Pt/HCS-B showed a similar performance in terms of current density (j) at 0.9 V vs. RHE than the benchmark commercial 20 wt. % Pt/C. However, Pt/HCS-P and Pt/HCS-B demonstrated a 6 and 5-fold increase in mass catalytic activity compared to Pt/C, respectively. A positive effect of the high specific surface area of the HCS and its interactions with metal nanoparticles and electrolyte, which promoted the mass transfer, increased the performance of Pt/HCS-P and Pt/HCS-B. The high catalytic activity showed by Pt/HCS-B and Pt/HCS-P for the ORR, even with a low-Pt content, make them promising cathode nanocatalysts for Anion Exchange Membrane Fuel Cells (AEMFC).

Catalytic Activity of Binary and Triple Systems Based on Redox Inactive Metal Compound, LiSt and Additives of Monodentate Ligands-Modifiers: DMF, HMPA and PhOH, in Selective Ethylbenzene Oxidation with Dioxygen

Chemistry & Chemical Technology ◽

10.23939/chcht10.03.259 ◽

2016 ◽

Vol 10 (3) ◽

pp. 259-270

Author(s):

Ludmila Matienko ◽

◽

Larisa Mosolova ◽

Vladimir Binyukov ◽

Gennady Zaikov ◽

...

Keyword(s):

Catalytic Activity ◽

Triple System ◽

Metal Compound ◽

Ethylbenzene Oxidation ◽

Catalytic Systems ◽

Triple Systems ◽

Lithium Compound ◽

Mechanism Of Catalysis ◽

Monodentate Ligands

Mechanism of catalysis with binary and triple catalytic systems based on redox inactive metal (lithium) compound {LiSt+L2} and {LiSt+L2+PhOH} (L2=DMF or HMPA), in the selective ethylbenzene oxidation by dioxygen into -phenylethyl hydroperoxide is researched. The results are compared with catalysis by nickel-lithium triple system {NiII(acac)2+LiSt+PhOH} in selective ethylbenzene oxidation to PEH. The role of H-bonding in mechanism of catalysis is discussed. The possibility of the stable supramolecular nanostructures formation on the basis of triple systems, {LiSt+L2+PhOH}, due to intermolecular H-bonds, is researched with the AFM method.

Hierarchically porous Co3O4spheres with tunable shell structure and enhanced catalytic activity

Manufacture Engineering and Environment Engineering ◽

10.2495/meee130041 ◽

2013 ◽

Author(s):

Li Liang

Keyword(s):

Catalytic Activity ◽

Shell Structure ◽

Hierarchically Porous

SuFExable Polymers with Helical Structures Derived from Thionyl Tetrafluoride (SOF4)

10.26434/chemrxiv.10005758 ◽

2019 ◽

Author(s):

Suhua Li ◽

Gencheng Li ◽

Bing Gao ◽

Sidharam P. Pujari ◽

Xiaoyan Chen ◽

...

Keyword(s):

Functional Polymers ◽

Polymer Chains ◽

New Materials ◽

Helical Structures ◽

Polymer Backbone ◽

Silyl Ethers ◽

Helical Polymer ◽

Key Characteristics ◽

Post Modification ◽

Individual Polymer

The first SuFEx click chemistry synthesis of SOF4-derived copolymers based upon the polymerization of bis(iminosulfur oxydifluorides) and bis(aryl silyl ethers) is described. This novel class of SuFEx polymer presents two key characteristics: First, the newly created [-N=S(=O)F-O-] polymer backbone linkages are themselves SuFExable and primed to undergo further high-yielding and precise SuFEx-based post-modification with phenols or amines to yield branched functional polymers. Second, studies of individual polymer chains of several of these new materials indicate the presence of helical polymer structures, which itself suggests a preferential approach of new monomers onto the growing polymer chain upon the formation of the stereogenic linking moiety.

Ordered Intermetallic Nanoparticles with High Catalytic Activity Prepared by an Electrochemically Induced Phase Transformation

10.26434/chemrxiv.8289812 ◽

2019 ◽

Author(s):

Du Sun ◽

yunfei wang ◽

Kenneth Livi ◽

chuhong wang ◽

ruichun luo ◽

...

Keyword(s):

Catalytic Activity ◽

Diffusion Mechanism ◽

Reduction Reaction ◽

Atomic Scale ◽

High Catalytic Activity ◽

Ambient Conditions ◽

Magnetic Devices ◽

Disordered Alloys ◽

Ordered Intermetallic ◽

Intermetallic Nanoparticles

<div> The synthesis of alloys with long range atomic scale ordering (ordered intermetallics) is an emerging field of nanochemistry. Ordered intermetallic nanoparticles are useful for a wide variety of applications such as catalysis, superconductors, and magnetic devices. However, the preparation of nanostructured ordered intermetallics is challenging in comparison to disordered alloys, hindering progress in materials development. We report a process for converting colloidally synthesized ordered intermetallic PdBi2 to ordered intermetallic Pd3Bi nanoparticles under ambient conditions by an electrochemically induced phase transition. The low melting point of PdBi2 corresponds to low vacancy formation energies which enables the facile removal of the Bi from the surface, while simultaneously enabling interdiffusion of the constituent atoms via a vacancy diffusion mechanism under ambient conditions. The resulting phase-converted ordered intermetallic Pd3Bi exhibits 11x and 3.5x higher mass activty and high methanol tolerance for the oxygen reduction reaction compared to Pt/C and Pd/C, respectively,which is the highest reported for a Pd-based catalyst, to the best of our knowledge. These results establish a key development in the synthesis of noble metal rich ordered intermetallic phases with high catalytic activity, and sets forth guidelines for the design of ordered intermetallic compounds under ambient conditions. </div>

Directed Evolution of P450 Fatty Acid Decarboxylases via High-Throughput Screening Towards Improved Catalytic Activity

10.26434/chemrxiv.9791162 ◽

2019 ◽

Author(s):

Huifang Xu ◽

Weinan Liang ◽

Linlin Ning ◽

Yuanyuan Jiang ◽

Wenxia Yang ◽

...

Keyword(s):

Catalytic Activity ◽

Fatty Acid ◽

Directed Evolution ◽

High Throughput ◽

High Throughput Screening ◽

Colorimetric Detection ◽

Screening Method ◽

Random Mutagenesis ◽

Direct Production ◽

Consumption Activity

P450 fatty acid decarboxylases (FADCs) have recently been attracting considerable attention owing to their one-step direct production of industrially important 1-alkenes from biologically abundant feedstock free fatty acids under mild conditions. However, attempts to improve the catalytic activity of FADCs have met with little success. Protein engineering has been limited to selected residues and small mutant libraries due to lack of an effective high-throughput screening (HTS) method. Here, we devise a catalase-deficient Escherichia coli host strain and report an HTS approach based on colorimetric detection of H2O2-consumption activity of FADCs. Directed evolution enabled by this method has led to effective identification for the first time of improved FADC variants for medium-chain 1-alkene production from both DNA shuffling and random mutagenesis libraries. Advantageously, this screening method can be extended to other enzymes that stoichiometrically utilize H2O2 as co-substrate.