Structural requirements of choline derivatives for 'conversion' of pneumococcal amidase. A new single-step procedure for purification of this autolysin.

PubMed

Sanz, J M; Lopez, R; Garcia, J L

1988-05-23

Tertiary amines appear to be the minimal structure needed to convert in vitro the inactive form (E-form) of pneumococcal amidase to the catalytic active form (C-form). Diethylethanolamine was one of the compounds that converted the E-form, a finding that has been used successfully to develop an affinity chromatography system in DEAE-cellulose for the rapid and efficient purification of lytic enzymes of pneumococcus and its bacteriophages.

Effects of copper-precursors on the catalytic activity of Cu/graphene catalysts for the selective catalytic oxidation of ammonia

NASA Astrophysics Data System (ADS)

Li, Jingying; Tang, Xiaolong; Yi, Honghong; Yu, Qingjun; Gao, Fengyu; Zhang, Runcao; Li, Chenlu; Chu, Chao

2017-08-01

Different copper-precursors were used to prepare Cu/graphene catalysts by an impregnation method. XRD, Raman spectra, TEM, BET, XPS, H2-TPR, NH3-TPD, DRIFTS and catalytic activity test were used to characterize and study the effect of precursors on the catalytic activity of Cu/graphene catalysts for NH3-SCO reaction. The large specific surface area of Cu/graphene catalysts and high dispersion of the metal particles on the graphene caused the well catalytic activity of NH3-SCO reaction. Compared to Cu/GE(AC), Cu/GE(N) showed better catalytic performance, and the complete NH3 removal efficiency was obtained at 250 °C with N2 selectivity of 85%. The copper-precursors had influence on the distribution of surface Cu species and further affected the catalytic activity of Cu/GE catalysts. The more amount of surface Cu species and highly dispersed CuO particles on the graphene surface formed by using copper nitrate as precursor could significantly improve the reducibility of catalysts and enhance NH3 adsorption, thereby improving the catalytic activity of Cu/graphene catalyst.

In vitro evolution of a ribozyme that contains 5-bromouridine

NASA Technical Reports Server (NTRS)

Dai, X.; Joyce, G. F.; Bada, J. L. (Principal Investigator)

2000-01-01

The Tetrahymena group I ribozyme was modified by replacing all 99 component uridine residues with 5-bromouridine. This resulted in a 13-fold reduction in catalytic efficiency in the RNA-catalyzed phosphoester-transfer reaction compared to the behavior of the unmodified ribozyme. A population of 10(13) variant ribozymes was constructed, each containing 5-bromouridine in place of uridine. Five successive 'generations' of in vitro evolution were carried out, selecting for improved phosphoester transferase activity. The evolved molecules exhibited a 27-fold increase in catalytic efficiency compared to the wild-type bromouridine-containing ribozyme, even exceeding that of the wild-type ribozyme in the non-brominated form. Three specific mutations were found to be responsible for this altered behavior. These mutations enhanced activity in the context of 5-bromouridine, but were detrimental in the context of unmodified uridine. The evolved RNAs not only tolerated but came to exploit the presence of the nucleotide analogue in carrying out their catalytic function.

Characterization of C-terminally engineered laccases.

PubMed

Liu, Yingli; Cusano, Angela Maria; Wallace, Erin C; Mekmouche, Yasmina; Ullah, Sana; Robert, Viviane; Tron, Thierry

2014-08-01

Extremities of proteins are potent sites for functionalization. Carboxy terminus variants of the Trametes sp. strain C30 LAC3 laccase were generated and produced in Saccharomyces cerevisiae. A variant deleted of the last 13 residues (CΔ) and its 6 His tagged counterpart (CΔ6H) were found active enzymes. The production of CΔ6H resulted in the synthesis of a unusually high proportion of highly glycosylated forms of the enzyme therefore allowing the additional purification of a hyper-glycosylated form of CΔ6H noted CΔ6Hh. Properties of CΔ, CΔ6H and CΔ6Hh were compared. Globally, LAC3 catalytic efficiency was moderately affected by terminal modifications except in CΔ for which the kcat/KM ratio decreased 4 fold (with syringaldazine as substrate) and 10 fold (with ABTS as substrate) respectively. The catalytic parameters kcat and KM of CΔ6H and CΔ6Hh were found to be strictly comparable revealing that over glycosylation does not affect the enzyme catalytic efficiency. To the contrary, in vitro deglycosylation of laccase drastically reduced its activity. So, despite a complex glycosylated pattern observed for some of the variant enzymes, terminal sequences of laccases appear to be appropriate sites for the functionalization/immobilization of laccase. Copyright © 2014 Elsevier B.V. All rights reserved.

Preparation and photo-catalytic activities of FeOOH/ZnO/MMT composite

NASA Astrophysics Data System (ADS)

Zhou, Yao; Liu, Fusheng; Yu, Shitao

2015-11-01

Montmorillonite (MMT) was used as the carrier for synthesis of FeOOH and FeOOH/ZnO nano-material. FeOOH and FeOOH/ZnO were synthesized by the aqueous solutions of Fe(NO3)3-HNO3 and Zn(NO3)2-NaOH/Fe(NO3)3-HNO3 with the carrier of montmorillonite respectively. Transmission electron-microscopy (TEM) and X-ray diffraction (XRD) were used to study the morphology form and structure of the nano-materials. TEM was also used to demonstrate that FeOOH/ZnO can be formed with the appropriate interface. According to UV-vis absorption spectra, FeOOH/ZnO has a better response to visible light than FeOOH and ZnO, which indicates there is some coupling effect between FeOOH and ZnO. Pentachlorophenol (PCP) was used as a representative organic pollutant to evaluate the photo-catalytic efficiency of the FeOOH/ZnO and FeOOH catalysts in visible light (λ > 400 nm). The photo-catalytic efficiency of FeOOH/ZnO/MMT is better than FeOOH/MMT. According to FTIR, changes of pH and TOC, the degradation mechanism was also discussed. PCP was degraded to aromatic ketone and chloro-hydrocarbon compounds and then to H2O, CO2 and HCl.

Efficient catalytic decomposition of formic acid for the selective generation of H2 and H/D exchange with a water-soluble rhodium complex in aqueous solution.

PubMed

Fukuzumi, Shunichi; Kobayashi, Takeshi; Suenobu, Tomoyoshi

2008-01-01

Formic acid (HCOOH) decomposes efficiently to afford H2 and CO2 selectively in the presence of a catalytic amount of a water-soluble rhodium aqua complex, [Rh(III)(Cp*)(bpy)(H2O)]2+ (Cp*=pentamethylcyclopentadienyl, bpy=2,2'-bipyridine) in aqueous solution at 298 K. No CO was produced in this catalytic decomposition of HCOOH. The decomposition rate reached a maximum value at pH 3.8. No deterioration of the catalyst was observed during the catalytic decomposition of HCOOH, and the catalytic activity remained the same for the repeated addition of HCOOH. The rhodium-hydride complex was detected as the catalytic active species that undergoes efficient H/D exchange with water. When the catalytic decomposition of HCOOH was performed in D2O, D2 was produced selectively. Such an efficient H/D exchange and the observation of a deuterium kinetic isotope effect in the catalytic decomposition of DCOOH in H2O provide valuable mechanistic insight into this efficient and selective decomposition process.

Retraction: Gold nanoparticles immobilized on electrospun titanium dioxide nanofibers for catalytic reduction of 4-nitrophenol.

PubMed

Cavusoglu, Halit; Buyukbekar, Burak Zafer; Sakalak, Huseyin; Kohsakowski, Sebastian

2017-02-13

This study involves the preparation and catalytic properties of anatase titanium dioxide nanofibers (TiO2 NFs) supported gold nanoparticles (Au NPs) using a model reaction based on the reduction of 4-nitrophenol (NP) into 4-aminophenol (AP) by sodium borohydride (NaBH4). The fabrication of surfactant-free Au NPs was performed using pulsed laser ablation in liquid (PLAL) technique. The TiO2 NFs were fabricated by a combination of electrospinning and calcination process using a solution containing poly(vinyl pyrolidone)(PVP) and titanium isopropoxide. The adsorption efficiency of laser-generated surfactant-free Au NPs to TiO2 NF supports as a function of pH was analyzed. Our results show that the electrostatic interaction mainly controls the adsorption of the nanoparticles. Au NPs/TiO2 NFs composite exhibited good catalytic activity for the reduction of 4-NP to 4-AP. The unique combination of these materials leads to the development of highly efficient catalysts. Our heterostructured nanocatalysts possibly form an efficient path to fabricate various metal NP/metal-oxide supported catalysts. Thus the applications of PLAL-noble metal NPs can widely broaden. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pineapple stem bromelain immobilized on different supports: catalytic properties in model wine.

PubMed

Ilaria, Benucci; Marco, Esti; Katia, Liburdi; Maria Vittoria, Garzillo Anna

2012-01-01

Bromelain from pineapple stem has been covalently immobilized on different supports to select the more efficient biocatalyst that should be applied toward unstable proteins in real white wine. In this preliminary study, catalytic properties of different immobilized bromelain forms were compared under wine-like conditions, against a synthetic substrate (Bz-Phe-Val-Arg-pNA).Covalent immobilization affected protease kinetic properties, even if all immobilized forms presented both a better substrate affinity and higher half-life (with the exception of a few procedures) with respect to the free enzyme. Stem bromelain was successfully immobilized on chitosan beads without glutaraldehyde thus yielding a food-safe and promising biocatalyst for unstable real wine future application. Copyright © 2012 American Institute of Chemical Engineers (AIChE).

Hydrogen and carbon nanotube production via catalytic decomposition of methane

NASA Astrophysics Data System (ADS)

Deniz, Cansu; Karatepe, Nilgün

2013-09-01

The future energy demand is expected to increase significantly due to an increasing world population and demands for higher standards of living and better air quality. Hydrogen is considered as an energy carrier because of its high conversion efficiency and low pollutant emissions. It can be produced from various sources and transformed into electricity and other energy forms with a low pollution. The catalytic decomposition of hydrocarbon has been seen as a really useful method for production of pure hydrogen and for the environmental concern. The objective of this study was to assess the impact of catalyst composition and processing parameters on COx-free hydrogen production and to produce an available solid form of co-product carbon as carbon nanotubes via catalytic decomposition of methane. The optimum experimental conditions for methane decomposition have been investigated. Fe, Co and Ni are used as catalysts (nano materials) over different substrates as SiO2 and MgO to produce hydrogen at optimum temperatures.

Platinum-coated non-noble metal-noble metal core-shell electrocatalysts

DOEpatents

Adzic, Radoslav; Zhang, Junliang; Mo, Yibo; Vukmirovic, Miomir

2015-04-14

Core-shell particles encapsulated by a thin film of a catalytically active metal are described. The particles are preferably nanoparticles comprising a non-noble core with a noble metal shell which preferably do not include Pt. The non-noble metal-noble metal core-shell nanoparticles are encapsulated by a catalytically active metal which is preferably Pt. The core-shell nanoparticles are preferably formed by prolonged elevated-temperature annealing of nanoparticle alloys in an inert environment. This causes the noble metal component to surface segregate and form an atomically thin shell. The Pt overlayer is formed by a process involving the underpotential deposition of a monolayer of a non-noble metal followed by immersion in a solution comprising a Pt salt. A thin Pt layer forms via the galvanic displacement of non-noble surface atoms by more noble Pt atoms in the salt. The overall process is a robust and cost-efficient method for forming Pt-coated non-noble metal-noble metal core-shell nanoparticles.

Catalytic reactive separation system for energy-efficient production of cumene

DOEpatents

Buelna, Genoveva [Nuevo Laredo, MX; Nenoff, Tina M [Albuquerque, NM

2009-07-28

The present invention relates to an atmospheric pressure, reactive separation column packed with a solid acid zeolite catalyst for producing cumene from the reaction of benzene with propylene. Use of this un-pressurized column, where simultaneous reaction and partial separation occur during cumene production, allow separation of un-reacted, excess benzene from other products as they form. This high-yielding, energy-efficient system allows for one-step processing of cumene, with reduced need for product purification. Reacting propylene and benzene in the presence of beta zeolite catalysts generated a selectivity greater than 85% for catalytic separation reactions at a reaction temperature of 115 degrees C and at ambient pressure. Simultaneously, up to 76% of un-reacted benzene was separated from the product; which could be recycled back to the reactor for re-use.

Method to monitor HC-SCR catalyst NOx reduction performance for lean exhaust applications

DOEpatents

Viola, Michael B [Macomb Township, MI; Schmieg, Steven J [Troy, MI; Sloane, Thompson M [Oxford, MI; Hilden, David L [Shelby Township, MI; Mulawa, Patricia A [Clinton Township, MI; Lee, Jong H [Rochester Hills, MI; Cheng, Shi-Wai S [Troy, MI

2012-05-29

A method for initiating a regeneration mode in selective catalytic reduction device utilizing hydrocarbons as a reductant includes monitoring a temperature within the aftertreatment system, monitoring a fuel dosing rate to the selective catalytic reduction device, monitoring an initial conversion efficiency, selecting a determined equation to estimate changes in a conversion efficiency of the selective catalytic reduction device based upon the monitored temperature and the monitored fuel dosing rate, estimating changes in the conversion efficiency based upon the determined equation and the initial conversion efficiency, and initiating a regeneration mode for the selective catalytic reduction device based upon the estimated changes in conversion efficiency.

Phosphate forms an unusual tripodal complex with the Fe–Mn center of sweet potato purple acid phosphatase

PubMed Central

Schenk, Gerhard; Gahan, Lawrence R.; Carrington, Lyle E.; Mitić, Nataša; Valizadeh, Mohsen; Hamilton, Susan E.; de Jersey, John; Guddat, Luke W.

2005-01-01

Purple acid phosphatases (PAPs) are a family of binuclear metalloenzymes that catalyze the hydrolysis of phosphoric acid esters and anhydrides. A PAP in sweet potato has a unique, strongly antiferromagnetically coupled Fe(III)–Mn(II) center and is distinguished from other PAPs by its increased catalytic efficiency for a range of activated and unactivated phosphate esters, its strict requirement for Mn(II), and the presence of a μ-oxo bridge at pH 4.90. This enzyme displays maximum catalytic efficiency (kcat/Km) at pH 4.5, whereas its catalytic rate constant (kcat) is maximal at near-neutral pH, and, in contrast to other PAPs, its catalytic parameters are not dependent on the pKa of the leaving group. The crystal structure of the phosphate-bound Fe(III)–Mn(II) PAP has been determined to 2.5-Å resolution (final Rfree value of 0.256). Structural comparisons of the active site of sweet potato, red kidney bean, and mammalian PAPs show several amino acid substitutions in the sweet potato enzyme that can account for its increased catalytic efficiency. The phosphate molecule binds in an unusual tripodal mode to the two metal ions, with two of the phosphate oxygen atoms binding to Fe(III) and Mn(II), a third oxygen atom bridging the two metal ions, and the fourth oxygen pointing toward the substrate binding pocket. This binding mode is unique among the known structures in this family but is reminiscent of phosphate binding to urease and of sulfate binding to λ protein phosphatase. The structure and kinetics support the hypothesis that the bridging oxygen atom initiates hydrolysis. PMID:15625111

Enhanced photocatalytic hydrogen production from an MCM-41-immobilized photosensitizer-[Fe-Fe] hydrogenase mimic dyad.

PubMed

Wang, Wen; Yu, Tianjun; Zeng, Yi; Chen, Jinping; Yang, Guoqiang; Li, Yi

2014-11-01

A covalently linked photosensitizer-catalytic center dyad Ps-Hy, consisting of two bis(2-phenylpyridine)(2,2'-bipyridine)iridium(iii) chromophores (Ps) and a diiron hydrogenase mimic (Hy) was constructed by using click reaction. Ps-Hy was incorporated into K(+)-exchanged molecular sieve MCM-41 to form a composite (Ps-Hy@MCM-41), which has been successfully applied to the photochemical production of hydrogen. The catalytic activity of Ps-Hy@MCM-41 is ∼3-fold higher as compared with that of Ps-Hy in the absence of MCM-41. The incorporation of Ps-Hy into MCM-41 stabilizes the catalyst, and consequently, advances the photocatalysis. The present study provides a potential strategy for improving catalytic efficiency of artificial photosynthesis systems using mesoporous molecular sieves.

Prereduction of Metal Oxides via Carbon Plasma Treatment for Efficient and Stable Electrocatalytic Hydrogen Evolution.

PubMed

Zhang, Yongqi; Ouyang, Bo; Xu, Kun; Xia, Xinhui; Zhang, Zheng; Rawat, Rajdeep Singh; Fan, Hong Jin

2018-04-01

Prereduction of transition metal oxides is a feasible and efficient strategy to enhance their catalytic activity for hydrogen evolution. Unfortunately, the prereduction via the common H 2 annealing method is unstable for nanomaterials during the hydrogen evolution process. Here, using NiMoO 4 nanowire arrays as the example, it is demonstrated that carbon plasma (C-plasma) treatment can greatly enhance both the catalytic activity and the long-term stability of transition metal oxides for hydrogen evolution. The C-plasma treatment has two functions at the same time: it induces partial surface reduction of the NiMoO 4 nanowire to form Ni 4 Mo nanoclusters, and simultaneously deposits a thin graphitic carbon shell. As a result, the C-plasma treated NiMoO 4 can maintain its array morphology, chemical composition, and catalytic activity during long-term intermittent hydrogen evolution process. This work may pave a new way for simultaneous activation and stabilization of transition metal oxide-based electrocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Green and facile synthesis of fibrous Ag/cotton composites and their catalytic properties for 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Li, Ziyu; Jia, Zhigang; Ni, Tao; Li, Shengbiao

2017-12-01

Natural cotton, featuring abundant oxygen-containing functional groups, has been utilized as a reductant to synthesize Ag nanoparticles on its surface. Through the facile and environment-friendly reduction process, the fibrous Ag/cotton composite (FAC) was conveniently synthesized. Various characterization techniques including XRD, XPS, TEM, SEM, EDS and FT-IR had been utilized to study the material microstructure and surface properties. The resulting FAC exhibited favorable activity on the catalytic reduction of 4-nitrophenol with high reaction rate. Moreover, the fibrous Ag/cotton composites were capable to form a desirable catalytic mat for catalyzing and simultaneous product separation. Reactants passing through the mat could be catalytically transformed to product, which is of great significance for water treatment. Such catalyst (FAC) was thus expected to have the potential as a highly efficient, cost-effective and eco-friendly catalyst for industrial applications. More importantly, this newly developed synthetic methodology could serve as a general tool to design and synthesize other metal/biomass composites catalysts for a wider range of catalytic applications.

Facile synthesis of polypyrrole functionalized nickel foam with catalytic activity comparable to Pt for the poly-generation of hydrogen and electricity

NASA Astrophysics Data System (ADS)

Tang, Tiantian; Li, Kan; Shen, Zhemin; Sun, Tonghua; Wang, Yalin; Jia, Jinping

2016-01-01

Polypyrrole functionalized nickel foam is facilely prepared through the potentiostatic electrodeposition. The PPy-functionalized Ni foam functions as a hydrogen-evolution cathode in a rotating disk photocatalytic fuel cell, in which hydrogen energy and electric power are generated by consuming organic wastes. The PPy-functionalized Ni foam cathode exhibits stable catalytic activities after thirteen continuous runs. Compared with net or plate structure, the Ni foam with a unique three-dimensional reticulate structure is conducive to the electrodeposition of PPy. Compared with Pt-group electrode, PPy-coated Ni foam shows a satisfactory catalytic performance for the H2 evolution. The combination of PPy and Ni forms a synergistic effect for the rapid trapping and removal of proton from solution and the catalytic reduction of proton to hydrogen. The PPy-functionalized Ni foam could be applied in photocatalytic and photoelectrochemical generation of H2. In all, we report a low cost, high efficient and earth abundant PPy-functionalized Ni foam with a satisfactory catalytic activities comparable to Pt for the practical application of poly-generation of hydrogen and electricity.

Rational design of a carboxylic esterase RhEst1 based on computational analysis of substrate binding

DOE PAGES

Chen, Qi; Luan, Zheng -Jiao; Yu, Hui -Lei; ...

2015-10-31

A new carboxylic esterase RhEst1 which catalyzes the hydrolysis of (S)-(+)-2,2-dimethylcyclopropanecarboxylate (S-DmCpCe), the key chiral building block of cilastatin, was identified and subsequently crystallized in our previous work. Mutant RhEst 1A147I/V148F/G254A was found to show a 5-fold increase in the catalytic activity. In this work, molecular dynamic simulations were performed to elucidate the molecular determinant of the enzyme activity. Our simulations show that the substrate binds much more strongly in the A147I/V148F/G254A mutant than in wild type, with more hydrogen bonds formed between the substrate and the catalytic triad and the oxyanion hole. The OH group of the catalytic residuemore » Ser101 in the mutant is better positioned to initiate the nucleophilic attack on S-DmCpCe. Interestingly, the "170-179" loop which is involved in shaping the catalytic sites and facilitating the product release shows remarkable dynamic differences in the two systems. Based on the simulation results, six residues were identified as potential "hot-spots" for further experimental testing. Consequently, the G126S and R133L mutants show higher catalytic efficiency as compared with the wild type. In conclusion, this work provides molecular-level insights into the substrate binding mechanism of carboxylic esterase RhEst1, facilitating future experimental efforts toward developing more efficient RhEst1 variants for industrial applications.« less

Development of a para-orthohydrogen catalytic converter for a solid hydrogen cooler

NASA Technical Reports Server (NTRS)

Nast, T. C.; Hsu, I. C.

1984-01-01

Design features of a tested catalytic converter for altering vented cryogenic parahydrogen used as a coolant on spacecraft into a para-ortho equilibrium for channeling to other cooling functions are described. The hydrogen is expected to be stored in either liquid or solid form. A high surface area Ni-on-Si catalyst was selected for tests at an operating pressure of 2 torr at a ratio of 1000 gr catalyst for a gr/sec hydrogen flow. Cylindrical and radial flow geometries were tried and measurements centered on the converter efficiencies at different operating temperatures when the converter was placed in the vent line of the H2 cooler. Efficiencies ranging from 10-100 percent were obtained for varying flow rates. Further testing is necessary to characterize the converter performance under a wider range of operating temperatures and environments.

Cellular localization and detergent dependent oligomerization of rice allene oxide synthase-1.

PubMed

Yoeun, Sereyvath; Kim, Jeong-Il; Han, Oksoo

2015-01-01

Allene oxide synthase-1 from Oryza sativa (OsAOS1) localizes to the chloroplast, but lacks a putative chloroplast targeting sequence typically found in dicot AOS. Here, kinetic parameters and the oligomerization state/subunit composition of OsAOS1 were characterized in vitro in the absence or presence of detergent micelles. The catalytic efficiency (k(cat)/K(m)) of OsAOS1 reached a maximum near the critical micelle concentration for polyoxyethylene 10 tridecyl ether. Native gel analysis showed that OsAOS1 exists as a multimer in the absence of detergent micelles. The multimeric form of OsAOS1 was stably cross-linked in the absence of detergents, while only monomeric OsAOS1 was detected in the presence of detergent micelles. Gel filtration analysis indicated that the oligomeric state of OsAOS1 depends strongly on the detergents and that the monomer becomes the predominant form in the presence of detergent micelles. These data suggest that the detergent-dependent oligomeric state of OsAOS1 is an important factor for the regulation of its catalytic efficiency.

High-density defects on PdAg nanowire networks as catalytic hot spots for efficient dehydrogenation of formic acid and reduction of nitrate.

PubMed

Liu, Hu; Yu, Yongsheng; Yang, Weiwei; Lei, Wenjuan; Gao, Manyi; Guo, Shaojun

2017-07-13

Controlling the surface defects of nanocrystals is a new way of tuning/boosting their catalytic properties. Herein, we report networked PdAg nanowires (NWs) with high-density defects as catalytic hot spots for efficient catalytic dehydrogenation of formic acid (FA) and catalytic reduction of nitrates. The networked PdAg NWs exhibit composition-dependent catalytic activity for the dehydrogenation reaction of FA without any additive, with Pd 5 Ag 5 NWs exhibiting the highest activity. They also show good durability, reflected by the retention of their initial activity during the dehydrogenation reaction of FA even after five cycles. Their initial TOF is 419 h -1 at 60 °C in water solution, much higher than those of the most Pd-based catalysts with a support. Moreover, they can efficiently reduce nitrates to alleviate nitrate pollution in water (conversion yield >99%). This strategy opens up a new green synthetic technique to design support-free heterogeneous catalysts with high-density defects as catalytic hot spots for efficient dehydrogenation catalysis of FA to meet the requirement of fuel cell applications and catalytic reduction of nitrates in water polluted with nitrates.

Self-sensitization of tetracycline degradation with simulated solar light catalyzed by ZnO@montmorillonite

NASA Astrophysics Data System (ADS)

Zyoud, Ahed; Jondi, Waheed; AlDaqqah, Najat; Asaad, Sara; Qamhieh, Naser; Hajamohideen, AbdulRazack; Helal, Muath H. S.; Kwon, Hansang; Hilal, Hikmat S.

2017-12-01

Zinc oxide (ZnO) nano-particles were chemically deposited onto montmorillonite (MONT) clay particles. The composite ZnO@MONT was then characterized and used as a catalyst for photo-degradation of aqueous tetracycline. Unlike earlier studies, solar simulated light can be effectively used in this work. The composite shows high efficiency as adsorbent and as a photo-degradation catalyst. Both adsorbed and dissolved tetracycline molecules undergo mineralization under the photo-catalytic conditions, and up to 94% of the contaminant gross amount is completely mineralized. Other forms of ZnO particles, commercial ZnO and synthetic ZnO particles were examined in separate experiments. The ZnO@MONT is superior to both pristine counterparts. The ability of tetracycline to sensitize the supported ZnO particles, to solar simulated light, before being photo-degraded itself, is discussed here for the first time. In addition to enhanced catalytic activity of the ZnO@MONT, the composite can be efficiently recovered and reused with no significant loss of efficiency.

Oxygen Reduction Reaction for Generating H2 O2 through a Piezo-Catalytic Process over Bismuth Oxychloride.

PubMed

Shao, Dengkui; Zhang, Ling; Sun, Songmei; Wang, Wenzhong

2018-02-09

Oxygen reduction reaction (ORR) for generating H 2 O 2 through green pathways have gained much attention in recent years. Herein, we introduce a piezo-catalytic approach to obtain H 2 O 2 over bismuth oxychloride (BiOCl) through an ORR pathway. The piezoelectric response of BiOCl was directly characterized by piezoresponse force microscopy (PFM). The BiOCl exhibits efficient catalytic performance for generating H 2 O 2 (28 μmol h -1 ) only from O 2 and H 2 O, which is above the average level of H 2 O 2 produced by solar-to-chemical processes. A piezo-catalytic mechanism was proposed: with ultrasonic waves, an alternating electric field will be generated over BiOCl, which can drive charge carriers (electrons) to interact with O 2 and H 2 O, then to form H 2 O 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic reduction of organic dyes at gold nanoparticles impregnated silica materials: influence of functional groups and surfactants

NASA Astrophysics Data System (ADS)

Azad, Uday Pratap; Ganesan, Vellaichamy; Pal, Manas

2011-09-01

Gold nanoparticles (Au NPs) in three different silica based sol-gel matrixes with and without surfactants are prepared. They are characterized by UV-vis absorbance and transmission electron microscopic (TEM) studies. The size and shape of Au NPs varied with the organo-functional group present in the sol-gel matrix. In the presence of mercaptopropyl functionalized organo-silica, large sized (200-280 nm) spherical Au NPs are formed whereas in the presence of aminopropyl functionalized organo-silica small sized (5-15 nm) Au NPs are formed inside the tube like organo-silica. Further, it is found that Au NPs act as efficient catalyst for the reduction of organic dyes. The catalytic rate constant is evaluated from the decrease in absorbance of the dye molecules. Presence of cationic or anionic surfactants greatly influences the catalytic reaction. The other factors like hydrophobicity of the organic dyes, complex formation of the dyes with anionic surfactants, repulsion between dyes and cationic surfactant, adsorption of dyes on the Au NPs also play important role on the reaction rate.

Lindqvist Polyoxoniobate Ion-Assisted Electrodeposition of Cobalt and Nickel Water Oxidation Catalysts.

PubMed

Liu, YuPing; Guo, Si-Xuan; Ding, Liang; Ohlin, C André; Bond, Alan M; Zhang, Jie

2015-08-05

A method has been developed for the efficient electrodeposition of cobalt and nickel nanostructures with the assistance of the Lindqvist ion [Nb6O19](8-). Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma optical emission spectrometry, and a range of electrochemical techniques have been used to characterize the morphology, composition, catalytic water oxidation activity and stability of the films in alkaline solution. SEM images show that films consisting of nanoparticles with diameters of ca. 30 to 40 nm are formed after 40-50 potential cycles of deposition. Nb and Co/Ni are detected in the films by EDX. ICP-MS results show an elemental ratio of 1:1 for Co:Nb and 1:3 for Ni:Nb, respectively. Raman spectra reveal the presence of both [Nb6O19](8-) and Co(OH)2/Ni(OH)2. The films exhibit excellent stability and efficiency for electrocatalytic water oxidation in alkaline solution. Turnover frequencies of 12.9 and 13.2 s(-1) were determined by rotating ring disk electrode voltammetry at an overpotential of 480 mV for Co and Ni films, respectively. Fourier transformed large amplitude alternating current (FTAC) voltammetry reveals an additional underlying oxidation process for Co under catalytic turnover conditions, which indicates that a Co(IV) species is involved in the efficient catalytic water oxidation reactions. FTAC voltammetric data also suggest that the Ni films undergoes a clear phase transformation upon aging in aqueous 1 M NaOH and the electrogenerated higher oxidation state Ni from β-NiOOH is the more active form of the catalyst.

Catalytic immunoglobulin gene delivery in a mouse model of Alzheimer's disease: prophylactic and therapeutic applications.

PubMed

Kou, Jinghong; Yang, Junling; Lim, Jeong-Eun; Pattanayak, Abhinandan; Song, Min; Planque, Stephanie; Paul, Sudhir; Fukuchi, Ken-Ichiro

2015-02-01

Accumulation of amyloid beta-peptide (Aβ) in the brain is hypothesized to be a causal event leading to dementia in Alzheimer's disease (AD). Aβ vaccination removes Aβ deposits from the brain. Aβ immunotherapy, however, may cause T cell- and/or Fc-receptor-mediated brain inflammation and relocate parenchymal Aβ deposits to blood vessels leading to cerebral hemorrhages. Because catalytic antibodies do not form stable immune complexes and Aβ fragments produced by catalytic antibodies are less likely to form aggregates, Aβ-specific catalytic antibodies may have safer therapeutic profiles than reversibly-binding anti-Aβ antibodies. Additionally, catalytic antibodies may remove Aβ more efficiently than binding antibodies because a single catalytic antibody can hydrolyze thousands of Aβ molecules. We previously isolated Aβ-specific catalytic antibody, IgVL5D3, with strong Aβ-hydrolyzing activity. Here, we evaluated the prophylactic and therapeutic efficacy of brain-targeted IgVL5D3 gene delivery via recombinant adeno-associated virus serotype 9 (rAAV9) in an AD mouse model. One single injection of rAAV9-IgVL5D3 into the right ventricle of AD model mice yielded widespread, high expression of IgVL5D3 in the unilateral hemisphere. IgVL5D3 expression was readily detectable in the contralateral hemisphere but to a much lesser extent. IgVL5D3 expression was also confirmed in the cerebrospinal fluid. Prophylactic and therapeutic injection of rAAV9-IgVL5D3 reduced Aβ load in the ipsilateral hippocampus of AD model mice. No evidence of hemorrhages, increased vascular amyloid deposits, increased proinflammatory cytokines, or infiltrating T-cells in the brains was found in the experimental animals. AAV9-mediated anti-Aβ catalytic antibody brain delivery can be prophylactic and therapeutic options for AD.

HETERODIMERIZATION OF PROPYLENE AND VINYLARENES: FUNCTIONAL GROUP COMPATIBILITY IN A HIGHLY EFFICIENT NI-CATALYZED CARBON-CARBON BOND-FORMING REACTION. (R826120)

EPA Science Inventory

Abstract

Unlike heterodimerization reactions of ethylene and vinylarenes, no such synthetically useful reactions using propylene are known. We find that propylene reacts with various vinylarenes in the presence of catalytic amounts of [(allyl)NiBr]₂, triphen...

Efficient oxidation of alcohols to carbonyl compounds with molecular oxygen catalyzed by N-hydroxyphthalimide combined with a Co species

PubMed

Iwahama; Yoshino; Keitoku; Sakaguchi; Ishii

2000-10-06

Highly efficient catalytic oxidation of alcohols with molecular oxygen by N-hydroxyphthalimide (NHPI) combined with a Co species was developed. The oxidation of 2-octanol in the presence of catalytic amounts of NHPI and Co(OAc)2 under atmospheric dioxygen in AcOEt at 70 degrees C gave 2-octanone in 93% yield. The oxidation was significantly enhanced by adding a small amount of benzoic acid to proceed smoothly even at room temperature. Primary alcohols were oxidized by NHPI in the absence of any metal catalyst to form the corresponding carboxylic acids in good yields. In the oxidation of terminal vic-diols such as 1,2-butanediol, carbon-carbon bond cleavage was induced to give one carbon less carboxylic acids such as propionic acid, while internal vic-diols were selectively oxidized to 1,2-diketones.

Naturally occurring alkaline amino acids function as efficient catalysts on Knoevenagel condensation at physiological pH: a mechanistic elucidation.

PubMed

Li, Weina; Fedosov, Sergey; Tan, Tianwei; Xu, Xuebing; Guo, Zheng

2014-05-01

To maintain biological functions, thousands of different reactions take place in human body at physiological pH (7.0) and mild conditions, which is associated with health and disease. Therefore, to examine the catalytic function of the intrinsically occurring molecules, such as amino acids at neutral pH, is of fundamental interests. Natural basic α-amino acid of L-lysine, L-arginine, and L-histidine neutralized to physiological pH as salts were investigated for their ability to catalyze Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate. Compared with their free base forms, although neutralized alkaline amino acid salts reduced the catalytic activity markedly, they were still capable to perform an efficient catalysis at physiological pH as porcine pancreatic lipase (PPL), one of the best enzymes that catalyze Knoevenagel condensation. In agreement with the fact that the three basic amino acids were well neutralized, stronger basic amino acid Arg and Lys showed more obvious variation in NH bend peak from the FTIR spectroscopy study. Study of ethanol/water system and quantitative kinetic analysis suggested that the microenvironment in the vicinity of amino acid salts and protonability/deprotonability of the amine moiety may determine their catalytic activity and mechanism. The kinetic study of best approximation suggested that the random binding might be the most probable catalytic mechanism for the neutralized alkaline amino acid salt-catalyzed Knoevenagel condensation.

Three-Dimensional Array of TiN@Pt3Cu Nanowires as an Efficient Porous Electrode for the Lithium-Oxygen Battery.

PubMed

Luo, Wen-Bin; Pham, Thien Viet; Guo, Hai-Peng; Liu, Hua-Kun; Dou, Shi-Xue

2017-02-28

The nonaqueous lithium-oxygen battery is a promising candidate as a next-generation energy storage system because of its potentially high energy density (up to 2-3 kW kg -1 ), exceeding that of any other existing energy storage system for storing sustainable and clean energy to reduce greenhouse gas emissions and the consumption of nonrenewable fossil fuels. To achieve high round-trip efficiency and satisfactory cycling stability, the air electrode structure and the electrocatalysts play important roles. Here, a 3D array composed of one-dimensional TiN@Pt 3 Cu nanowires was synthesized and employed as a whole porous air electrode in a lithium-oxygen battery. The TiN nanowire was primarily used as an air electrode frame and catalyst support to provide a high electronic conductivity network because of the high-orientation one-dimensional crystalline structure. Meanwhile, deposited icosahedral Pt 3 Cu nanocrystals exhibit highly efficient catalytic activity owing to the abundant {111} active lattice facets and multiple twin boundaries. This porous air electrode comprises a one-dimensional TiN@Pt 3 Cu nanowire array that demonstrates excellent energy conversion efficiency and rate performance in full discharge and charge modes. The discharge capacity is up to 4600 mAh g -1 along with an 84% conversion efficiency at a current density of 0.2 mA cm -2 , and when the current density increased to 0.8 mA cm -2 , the discharge capacity is still greater than 3500 mAh g -1 together with a nearly 70% efficiency. This designed array is a promising bifunctional porous air electrode for lithium-oxygen batteries, forming a continuous conductive and high catalytic activity network to facilitate rapid gas and electrolyte diffusion and catalytic reaction throughout the whole energy conversion process.

Rational design of a carboxylic esterase RhEst1 based on computational analysis of substrate binding.

PubMed

Chen, Qi; Luan, Zheng-Jiao; Yu, Hui-Lei; Cheng, Xiaolin; Xu, Jian-He

2015-11-01

A new carboxylic esterase RhEst1 which catalyzes the hydrolysis of (S)-(+)-2,2-dimethylcyclopropanecarboxylate (S-DmCpCe), the key chiral building block of cilastatin, was identified and subsequently crystallized in our previous work. Mutant RhEst1A147I/V148F/G254A was found to show a 5-fold increase in the catalytic activity. In this work, molecular dynamic simulations were performed to elucidate the molecular determinant of the enzyme activity. Our simulations show that the substrate binds much more strongly in the A147I/V148F/G254A mutant than in wild type, with more hydrogen bonds formed between the substrate and the catalytic triad and the oxyanion hole. The OH group of the catalytic residue Ser101 in the mutant is better positioned to initiate the nucleophilic attack on S-DmCpCe. Interestingly, the "170-179" loop which is involved in shaping the catalytic sites and facilitating the product release shows remarkable dynamic differences in the two systems. Based on the simulation results, six residues were identified as potential "hot-spots" for further experimental testing. Consequently, the G126S and R133L mutants show higher catalytic efficiency as compared with the wild type. This work provides molecular-level insights into the substrate binding mechanism of carboxylic esterase RhEst1, facilitating future experimental efforts toward developing more efficient RhEst1 variants for industrial applications. Copyright © 2015 Elsevier Inc. All rights reserved.

Method of producing pyrolysis gases from carbon-containing materials

DOEpatents

Mudge, Lyle K.; Brown, Michael D.; Wilcox, Wayne A.; Baker, Eddie G.

1989-01-01

A gasification process of improved efficiency is disclosed. A dual bed reactor system is used in which carbon-containing feedstock materials are first treated in a gasification reactor to form pyrolysis gases. The pyrolysis gases are then directed into a catalytic reactor for the destruction of residual tars/oils in the gases. Temperatures are maintained within the catalytic reactor at a level sufficient to crack the tars/oils in the gases, while avoiding thermal breakdown of the catalysts. In order to minimize problems associated with the deposition of carbon-containing materials on the catalysts during cracking, a gaseous oxidizing agent preferably consisting of air, oxygen, steam, and/or mixtures thereof is introduced into the catalytic reactor at a high flow rate in a direction perpendicular to the longitudinal axis of the reactor. This oxidizes any carbon deposits on the catalysts, which would normally cause catalyst deactivation.

Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan

NASA Astrophysics Data System (ADS)

Huang, Guan; Liu, Yao; Cai, Jing Li; Chen, Xiang Feng; Zhao, Shu Kai; Guo, Yong An; Wei, Su Juan; Li, Xu

2017-04-01

This study investigates how ligands modulate metalloporphyrin activity with the goal of producing a practical biomimetic catalyst for use in the chemical industry. We immobilized iron porphyrinate [iron-tetrakis-(4-sulfonatophenyl)-porphyrin; Fe(III) (TPPS)] on powdered chitosan (pd-CTS) to form an immobilized catalyst Fe(III) (TPPS)/pd-CTS, which was characterized using modern spectroscopic techniques and used for catalytic oxidation of cyclohexane with O2. Amino coordination to iron porphyrin in Fe(III) (TPPS)/pd-CTS altered the electron cloud density around the iron cation, probably by reducing the activation energy of Fe(III) (TPPS) and raising the reactivity of the iron ion catalytic center, thereby improving the catalytic efficiency. One milligram of Fe(III) (TPPS) catalyst can be reused three times for the oxidation reaction to yield an average of 22.9 mol% of cyclohexanone and cyclohexanol.

Oligomerization triggered by foldon: a simple method to enhance the catalytic efficiency of lichenase and xylanase.

PubMed

Wang, Xinzhe; Ge, Huihua; Zhang, Dandan; Wu, Shuyu; Zhang, Guangya

2017-07-03

Effective and simple methods that lead to higher enzymatic efficiencies are highly sough. Here we proposed a foldon-triggered trimerization of the target enzymes with significantly improved catalytic performances by fusing a foldon domain at the C-terminus of the enzymes via elastin-like polypeptides (ELPs). The foldon domain comprises 27 residues and can forms trimers with high stability. Lichenase and xylanase can hydrolyze lichenan and xylan to produce value added products and biofuels, and they have great potentials as biotechnological tools in various industrial applications. We took them as the examples and compared the kinetic parameters of the engineered trimeric enzymes to those of the monomeric and wild type ones. When compared with the monomeric ones, the catalytic efficiency (k cat /K m ) of the trimeric lichenase and xylanase increased 4.2- and 3.9- fold. The catalytic constant (k cat ) of the trimeric lichenase and xylanase increased 1.8- fold and 5.0- fold than their corresponding wild-type counterparts. Also, the specific activities of trimeric lichenase and xylanase increased by 149% and 94% than those of the monomeric ones. Besides, the recovery of the lichenase and xylanase activities increased by 12.4% and 6.1% during the purification process using ELPs as the non-chromatographic tag. The possible reason is the foldon domain can reduce the transition temperature of the ELPs. The trimeric lichenase and xylanase induced by foldon have advantages in the catalytic performances. Besides, they were easier to purify with increased purification fold and decreased the loss of activities compared to their corresponding monomeric ones. Trimerizing of the target enzymes triggered by the foldon domain could improve their activities and facilitate the purification, which represents a simple and effective enzyme-engineering tool. It should have exciting potentials both in industrial and laboratory scales.

Biomimetic catalytic transformation of toxic α-oxoaldehydes to high-value chiral α-hydroxythioesters using artificial glyoxalase I

NASA Astrophysics Data System (ADS)

Park, Sang Yeon; Hwang, In-Soo; Lee, Hyun-Ju; Song, Choong Eui

2017-04-01

Glyoxalase I plays a critical role in the enzymatic defence against glycation by catalysing the isomerization of hemithioacetal, formed spontaneously from cytotoxic α-oxoaldehydes and glutathione, to (S)-α-hydroxyacylglutathione derivatives. Upon the hydrolysis of the thioesters catalysed by glyoxalase II, inert (S)-α-hydroxy acids, that is, lactic acid, are then produced. Herein, we demonstrate highly enantioselective glyoxalase I mimic catalytic isomerization of in-situ-generated hemithioacetals, providing facile access to both enantiomers of α-hydroxy thioesters. Owing to the flexibility of thioesters, a family of optically pure α-hydroxyamides, which are highly important drug candidates in the pharmaceutical industry, were prepared without any coupling reagents. Similar to real enzymes, the enforced proximity of the catalyst and substrates by the chiral cage in situ formed by the incorporation of potassium salt can enhance the reactivity and efficiently transfer the stereochemical information.

Catalytic decomposition of gaseous 1,2-dichlorobenzene over CuOx/TiO₂ and CuOx/TiO₂-CNTs catalysts: Mechanism and PCDD/Fs formation.

PubMed

Wang, Qiu-lin; Huang, Qun-xing; Wu, Hui-fan; Lu, Sheng-yong; Wu, Hai-long; Li, Xiao-dong; Yan, Jian-hua

2016-02-01

Gaseous 1,2-dichlorobenzene (1,2-DCBz) was catalytically decomposed in a fixed-bed catalytic reactor using composite copper-based titanium oxide (CuOx/TiO2) catalysts with different copper ratios. Carbon nanotubes (CNTs) were introduced to produce novel CuOx/TiO2-CNTs catalysts by the sol-gel method. The catalytic performances of CuOx/TiO2 and CuOx/TiO2-CNTs on 1,2-DCBz oxidative destruction under different temperatures (150-350 °C) were experimentally examined and the correlation between catalyst structure and catalytic activity was characterized and the role of oxygen in catalytic reaction was discussed. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) generation during 1,2-DCBz catalytic oxidation by CuOx/TiO2-CNTs composite catalyst was also examined. Results indicate that the 1,2-DCBz destruction/removal efficiencies of CuOx (4 wt%)/TiO2 catalyst at 150 °C and 350 °C with a GHSV of 3400 h(-1) are 59% and 94% respectively and low-temperature (150 °C) catalytic activity of CuOx/TiO2 on 1,2-DCBz oxidation can be improved from 59 to 77% when CNTs are introduced. Furthermore, oxygen either in catalyst or from reaction atmosphere is indispensible in reaction. The former is offered to activate and oxidize the 1,2-DCBz adsorbed on catalyst, thus can be generally consumed during reaction and the oxygen content in catalyst is observed lost from 39.9 to 35.0 wt% after reacting under inert atmosphere; the latter may replenish the vacancy in catalyst created by the consumed oxygen thus extends the catalyst life and raises the destruction/removal efficiency. The introduction of CNTs also increases the Cu(2+)/Cu(+) ratio, chemisorbed oxygen concentration and surface lattice oxygen binding energy which are closely related with catalytic activity. PCDD/Fs is confirmed to be formed when 1,2-DCBz catalytically oxidized by CuOx/TiO2-CNTs composite catalyst with sufficient oxygen (21%), proper temperature (350 °C) and high concentration of 1,2-DCBz feed (120 ppm). Copyright © 2015 Elsevier Ltd. All rights reserved.

Structure-guided systems-level engineering of oxidation-prone methionine residues in catalytic domain of an alkaline α-amylase from Alkalimonas amylolytica for significant improvement of both oxidative stability and catalytic efficiency.

PubMed

Yang, Haiquan; Liu, Long; Shin, Hyun-dong; Li, Jianghua; Du, Guocheng; Chen, Jian

2013-01-01

High oxidative stability and catalytic efficiency are required for the alkaline α-amylases to keep the enzymatic performance under the harsh conditions in detergent industries. In this work, we attempted to significantly improve both the oxidative stability and catalytic efficiency of an alkaline α-amylase from Alkalimonas amylolytica by engineering the five oxidation-prone methionine residues around the catalytic domain via a systematic approach. Specifically, based on the tertiary structure analysis, five methionines (Met 145, Met 214, Met 229, Met 247 and Met 317) were individually substituted with oxidation-resistant threonine, isoleucine and alaline, respectively. Among the created 15 mutants, 7 mutants M145A, M145I, M214A, M229A, M229T, M247T and M317I showed significantly enhanced oxidative stability or catalytic efficiency. In previous work, we found that the replacement of M247 with leucine could significantly improve the oxidative stability. Thus, these 8 positive mutants (M145A, M145I, M214A, M229A, M229T, M247T, M247L and M317I) were used to conduct the second round of combinational mutations. Among the constructed 85 mutants (25 two-point mutants, 36 three-point mutants, 16 four-point mutants and 8 five-point mutants), the mutant M145I-214A-229T-247T-317I showed a 5.4-fold increase in oxidative stability and a 3.0-fold increase in catalytic efficiency. Interestingly, the specific activity, alkaline stability and thermal stability of this mutant were also increased. The increase of salt bridge and hydrogen bonds around the catalytic domain contributed to the significantly improved catalytic efficiency and stability, as revealed by the three-dimensional structure model of wild-type alkaline α-amylase and its mutant M145I-214A-229T-247T-317I. With the significantly improved oxidative stability and catalytic efficiency, the mutant M145I-214A-229T-247T-317I has a great potential as a detergent additive, and this structure-guided systems engineering strategy may be useful for the protein engineering of the other microbial enzymes to fulfill industrial requirements.

Improvement of activity and stability of chloroperoxidase by chemical modification

PubMed Central

Liu, Jian-Zhong; Wang, Min

2007-01-01

Background Enzymes show relative instability in solvents or at elevated temperature and lower activity in organic solvent than in water. These limit the industrial applications of enzymes. Results In order to improve the activity and stability of chloroperoxidase, chloroperoxidase was modified by citraconic anhydride, maleic anhydride or phthalic anhydride. The catalytic activities, thermostabilities and organic solvent tolerances of native and modified enzymes were compared. In aqueous buffer, modified chloroperoxidases showed similar Km values and greater catalytic efficiencies kcat/Km for both sulfoxidation and oxidation of phenol compared to native chloroperoxidase. Of these modified chloroperoxidases, citraconic anhydride-modified chloroperoxidase showed the greatest catalytic efficiency in aqueous buffer. These modifications of chloroperoxidase increased their catalytic efficiencies for sulfoxidation by 12%~26% and catalytic efficiencies for phenol oxidation by 7%~53% in aqueous buffer. However, in organic solvent (DMF), modified chloroperoxidases had lower Km values and higher catalytic efficiencies kcat/Km than native chloroperoxidase. These modifications also improved their thermostabilities by 1~2-fold and solvent tolerances of DMF. CD studies show that these modifications did not change the secondary structure of chloroperoxidase. Fluorescence spectra proved that these modifications changed the environment of tryptophan. Conclusion Chemical modification of epsilon-amino groups of lysine residues of chloroperoxidase using citraconic anhydride, maleic anhydride or phthalic anhydride is a simple and powerful method to enhance catalytic properties of enzyme. The improvements of the activity and stability of chloroperoxidase are related to side chain reorientations of aromatics upon both modifications. PMID:17511866

Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts

DOE PAGES

Zugic, Branko; Wang, Lucun; Heine, Christian; ...

2016-12-19

Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver–gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changesmore » occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Finally, our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.« less

Demonstration of catalytic combustion with residual fuel

NASA Technical Reports Server (NTRS)

Dodds, W. J.; Ekstedt, E. E.

1981-01-01

An experimental program was conducted to demonstrate catalytic combustion of a residual fuel oil. Three catalytic reactors, including a baseline configuration and two backup configurations based on baseline test results, were operated on No. 6 fuel oil. All reactors were multielement configurations consisting of ceramic honeycomb catalyzed with palladium on stabilized alumina. Stable operation on residual oil was demonstrated with the baseline configuration at a reactor inlet temperature of about 825 K (1025 F). At low inlet temperature, operation was precluded by apparent plugging of the catalytic reactor with residual oil. Reduced plugging tendency was demonstrated in the backup reactors by increasing the size of the catalyst channels at the reactor inlet, but plugging still occurred at inlet temperature below 725 K (845 F). Operation at the original design inlet temperature of 589 K (600 F) could not be demonstrated. Combustion efficiency above 99.5% was obtained with less than 5% reactor pressure drop. Thermally formed NO sub x levels were very low (less than 0.5 g NO2/kg fuel) but nearly 100% conversion of fuel-bound nitrogen to NO sub x was observed.

Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zugic, Branko; Wang, Lucun; Heine, Christian

Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver–gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changesmore » occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Finally, our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.« less

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

DOE PAGES

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; ...

2017-11-14

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4, Ln(OTf) 3, In(OTf) 3, Al(OTf) 3] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt %more » of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.« less

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4, Ln(OTf) 3, In(OTf) 3, Al(OTf) 3] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt %more » of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.« less

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

PubMed

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

2018-01-10

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Engineered disulfide bonds increase active-site local stability and reduce catalytic activity of a cold-adapted alkaline phosphatase.

PubMed

Asgeirsson, Bjarni; Adalbjörnsson, Björn Vidar; Gylfason, Gudjón Andri

2007-06-01

Alkaline phosphatase is an extracellular enzyme that is membrane-bound in eukaryotes but resides in the periplasmic space of bacteria. It normally carries four cysteine residues that form two disulfide bonds, for instance in the APs of Escherichia coli and vertebrates. An AP variant from a Vibrio sp. has only one cysteine residue. This cysteine is second next to the nucleophilic serine in the active site. We have individually modified seven residues to cysteine that are on two loops predicted to be within a 5 A radius. Four of them formed a disulfide bond to the endogenous cysteine. Thermal stability was monitored by circular dichroism and activity measurements. Global stability was similar to the wild-type enzyme. However, a significant increase in heat-stability was observed for the disulfide-containing variants using activity as a measure, together with a large reduction in catalytic rates (k(cat)) and a general decrease in Km values. The results suggest that a high degree of mobility near the active site and in the helix carrying the endogenous cysteine is essential for full catalytic efficiency in the cold-adapted AP.

How low does iron go? Chasing the active species in fe-catalyzed cross-coupling reactions.

PubMed

Bedford, Robin B

2015-05-19

The catalytic cross-coupling reactions of organic halides or related substrates with organometallic nucleophiles form the cornerstone of many carbon-carbon bond-forming processes. While palladium-based catalysts typically mediate such reactions, there are increasing concerns about the long-term sustainability of palladium in synthesis. This is due to the high cost of palladium, coupled with its low natural abundance, environmentally deleterious extraction (∼6 g of metal are produced per ton of ore), toxicity, and competition for its use from the automotive and consumer electronics sectors. Therefore, there is a growing interest in replacing palladium-based catalysts with those incorporating more earth-abundant elements. With its low cost, high natural abundance, and low toxicity, iron makes a particularly appealing alternative, and accordingly, the development of iron-catalyzed cross-coupling is undergoing explosive growth. However, our understanding of the mechanisms that underpin the iron-based catalytic cycles is still very much in its infancy. Mechanistic insight into catalytic reactions is not only academically important but also allows us to maximize the efficiency of processes or even to develop entirely new transformations. Key to the development of robust mechanistic models for cross-coupling is knowing the lowest oxidation state in the cycle. Once this is established, we can explore subsequent redox processes and build the catalytic manifold. Until we know with confidence what the lowest oxidation state is, any cycles proposed are largely just guesswork. To date, Fe(-II), Fe(-I), Fe(0), Fe(I), and Fe(II) have been proposed as contenders for the lowest-oxidation-state species in the cycle in iron-catalyzed cross-coupling; the aim of this Account is to pull together the various pieces of evidence in support, or otherwise, of each of these suggestions in turn. There currently exists no direct evidence that oxidation states below Fe(0) are active in the catalytic cycle. Meanwhile, the reactivity required of the lowest-oxidation-state species has been observed with model compounds in higher oxidation states, implying that there is no need to invoke such low oxidation states. While subzero-valent complexes do indeed act as effective precatalysts, it is important to recognize that this tells us that they are efficiently converted to an active catalyst but says nothing about the oxidation states of the species in the catalytic cycle. Zero-valent heterogeneous iron nanoparticles can be formed under typical catalytic conditions, but there is no evidence to suggest that homogeneous Fe(0) complexes can be produced under comparable conditions. It seems likely that the zero-valent nanoparticles act as a reservoir for soluble higher-oxidation-state species. Fe(II) complexes can certainly be formed under catalytically relevant conditions, and when bulky nucleophilic coupling partners are exploited, potential intermediates can be isolated. However, the bulky reagents act as poor proxies for most nucleophiles used in cross-coupling, as they give Fe(II) organometallic intermediates that are kinetically stabilized with respect to reductive elimination. When more realistic substrates are exploited, reduction or disproportionation to Fe(I) is widely observed, and while it still has not been conclusively proved, this oxidation state currently represents a likely candidate for the lowest one active in many iron-catalyzed cross-coupling processes.

The canonical methionine 392 of matrix metalloproteinase 2 (gelatinase A) is not required for catalytic efficiency or structural integrity: probing the role of the methionine-turn in the metzincin metalloprotease superfamily.

PubMed

Butler, Georgina S; Tam, Eric M; Overall, Christopher M

2004-04-09

Matrix metalloproteinases (MMPs) are an important family of extracellular proteases that process a variety of biologically significant molecules. MMPs are members of the metzincin superfamily of >770 zinc endopeptidases, which includes astacins, serralysins, adamalysins, leishmanolysins, and snapalysins. Metzincins are characterized by an absolutely conserved methionine residue COOH-terminal to the third histidine in the consensus sequence HEXXHXXGXX(H/D), where the histidine residues chelate a catalytic zinc ion. The canonical methionine is part of a tight 1,4-beta-turn that loops the polypeptide chain beneath the catalytic zinc ion, forming a hydrophobic floor to the Zn(2+) ion binding site. The role of this methionine is uncertain, but its absolute conservation indicates an essential catalytic or structural function. To investigate this hypothesis, we replaced Met-392 that forms the Met-turn of human MMP-2 (gelatinase A) by site-directed mutagenesis. The catalytic competence of leucine and serine mutants was assessed. (M392L)MMP-2 and (M392S)MMP-2 cleaved the physiological substrates gelatin, native type I collagen, and the chemokine monocyte chemoattractant protein-3 with similar efficiency to wild-type MMP-2. These mutants also cleaved two quenched fluorescent peptide substrates with a k(cat)/K(m) comparable to wild-type MMP-2 and underwent 4-aminophenylmercuric acetate-induced autoactivation with similar kinetics. (M392L)MMP-2 and (M392S)MMP-2 were inhibited by tissue inhibitor of metalloproteinases (TIMP)-1, -2, and -4 and by the zinc chelators 1,10-phenanthroline and a synthetic hydroxamate inhibitor, Batimastat, similar to the wild-type protein, indicating an unaltered active site topography. A tryptic susceptibility assay also suggested that (M392L)MMP-2 and (M392S)MMP-2 were correctly folded. These results challenge the dogma that this methionine residue and the Met-turn, which are absolutely conserved in all of the subfamilies of the metzincins, play an essential role in catalysis or active site structure.

Two Oxidation Sites for Low Redox Potential Substrates

PubMed Central

Morales, María; Mate, María J.; Romero, Antonio; Martínez, María Jesús; Martínez, Ángel T.; Ruiz-Dueñas, Francisco J.

2012-01-01

Versatile peroxidase shares with manganese peroxidase and lignin peroxidase the ability to oxidize Mn2+ and high redox potential aromatic compounds, respectively. Moreover, it is also able to oxidize phenols (and low redox potential dyes) at two catalytic sites, as shown by biphasic kinetics. A high efficiency site (with 2,6-dimethoxyphenol and p-hydroquinone catalytic efficiencies of ∼70 and ∼700 s−1 mm−1, respectively) was localized at the same exposed Trp-164 responsible for high redox potential substrate oxidation (as shown by activity loss in the W164S variant). The second site, characterized by low catalytic efficiency (∼3 and ∼50 s−1 mm−1 for 2,6-dimethoxyphenol and p-hydroquinone, respectively) was localized at the main heme access channel. Steady-state and transient-state kinetics for oxidation of phenols and dyes at the latter site were improved when side chains of residues forming the heme channel edge were removed in single and multiple variants. Among them, the E140G/K176G, E140G/P141G/K176G, and E140G/W164S/K176G variants attained catalytic efficiencies for oxidation of 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) at the heme channel similar to those of the exposed tryptophan site. The heme channel enlargement shown by x-ray diffraction of the E140G, P141G, K176G, and E140G/K176G variants would allow a better substrate accommodation near the heme, as revealed by the up to 26-fold lower Km values (compared with native VP). The resulting interactions were shown by the x-ray structure of the E140G-guaiacol complex, which includes two H-bonds of the substrate with Arg-43 and Pro-139 in the distal heme pocket (at the end of the heme channel) and several hydrophobic interactions with other residues and the heme cofactor. PMID:23071108

Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

DOEpatents

Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

2012-04-10

A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

DOEpatents

Cortright, Randy D.; Dumesic, James A.

2013-04-02

A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

DOEpatents

Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

2011-01-18

A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

It's a Clean Machine

NASA Technical Reports Server (NTRS)

1998-01-01

Under an SBIR (Small Business Innovative Research) from Lewis Research Center, Precision Combustion, Inc. (PCI) developed the Advanced Technology Catalytic Combustor. The research proved the viability of efficient, cost-effective catalytic reduction of gas turbine nitrogen oxide emissions along with fuel efficiency. PCI has signed agreements with Westinghouse, other gas turbine manufacturers, including Capstone Turbine Corporation to develop a catalytic combustor for their hybrid electric vehicle.

Silver-Catalyzed Cyclopropanation of Alkenes Using N-Nosylhydrazones as Diazo Surrogates.

PubMed

Liu, Zhaohong; Zhang, Xinyu; Zanoni, Giuseppe; Bi, Xihe

2017-12-15

An efficient silver-catalyzed [2 + 1] cyclopropanation of sterically hindered internal alkenes with diazo compounds in which room-temperature-decomposable N-nosylhydrazones are used as diazo surrogates is reported. The unexpected unique catalytic activity of silver was ascribed to its dual role as a Lewis acid activating alkene substrates and as a transition metal forming silver carbenoids. A wide range of internal alkenes, including challenging diarylethenes, were suitable for this protocol, thereby affording a variety of cyclopropanes with high efficiency in a stereoselective manner under mild conditions.

Catalytic activation of carbon-carbon bonds in cyclopentanones.

PubMed

Xia, Ying; Lu, Gang; Liu, Peng; Dong, Guangbin

2016-11-24

In the chemical industry, molecules of interest are based primarily on carbon skeletons. When synthesizing such molecules, the activation of carbon-carbon single bonds (C-C bonds) in simple substrates is strategically important: it offers a way of disconnecting such inert bonds, forming more active linkages (for example, between carbon and a transition metal) and eventually producing more versatile scaffolds. The challenge in achieving such activation is the kinetic inertness of C-C bonds and the relative weakness of newly formed carbon-metal bonds. The most common tactic starts with a three- or four-membered carbon-ring system, in which strain release provides a crucial thermodynamic driving force. However, broadly useful methods that are based on catalytic activation of unstrained C-C bonds have proven elusive, because the cleavage process is much less energetically favourable. Here we report a general approach to the catalytic activation of C-C bonds in simple cyclopentanones and some cyclohexanones. The key to our success is the combination of a rhodium pre-catalyst, an N-heterocyclic carbene ligand and an amino-pyridine co-catalyst. When an aryl group is present in the C3 position of cyclopentanone, the less strained C-C bond can be activated; this is followed by activation of a carbon-hydrogen bond in the aryl group, leading to efficient synthesis of functionalized α-tetralones-a common structural motif and versatile building block in organic synthesis. Furthermore, this method can substantially enhance the efficiency of the enantioselective synthesis of some natural products of terpenoids. Density functional theory calculations reveal a mechanism involving an intriguing rhodium-bridged bicyclic intermediate.

Highly efficient catalytic systems based on Pd-coated microbeads

NASA Astrophysics Data System (ADS)

Lim, Jin Hyun; Cho, Ahyoung; Lee, Seung Hwan; Park, Bumkyo; Kang, Dong Woo; Koo, Chong Min; Yu, Taekyung; Park, Bum Jun

2018-01-01

The efficiency of two prototype catalysis systems using palladium (Pd)-coated microparticles was investigated with regard to the recovery and recyclability of the catalytic particles. One such system was the interface-adsorption method, in which polymer particles coated with Pd nanoparticles strongly and irreversibly attach to the oil-water interface. Due to the irreversible adsorption of the catalytic particles to the interface, particle loss was completely prevented while mixing the aqueous solution and while collecting the products. The other system was based on the magnetic field-associated particle recovery method. The use of polymeric microparticles containing Pd nanoparticles and magnetite nanoparticles accelerated the sedimentation of the particles in the aqueous phase by applying a strong magnetic field, consequently suppressing drainage of the particles from the reactor along the product stream. Upon multiple runs of the catalytic reactions, it was found that conversion does not change significantly, demonstrating the excellent recyclability and performance efficiency in the catalytic processes.

Mechanism of Ribonuclease III Catalytic Regulation by Serine Phosphorylation

NASA Astrophysics Data System (ADS)

Gone, Swapna; Alfonso-Prieto, Mercedes; Paudyal, Samridhdi; Nicholson, Allen W.

2016-05-01

Ribonuclease III (RNase III) is a conserved, gene-regulatory bacterial endonuclease that cleaves double-helical structures in diverse coding and noncoding RNAs. RNase III is subject to multiple levels of control, reflective of its global regulatory functions. Escherichia coli (Ec) RNase III catalytic activity is known to increase during bacteriophage T7 infection, reflecting the expression of the phage-encoded protein kinase, T7PK. However, the mechanism of catalytic enhancement is unknown. This study shows that Ec-RNase III is phosphorylated on serine in vitro by purified T7PK, and identifies the targets as Ser33 and Ser34 in the N-terminal catalytic domain. Kinetic experiments reveal a 5-fold increase in kcat and a 1.4-fold decrease in Km following phosphorylation, providing a 7.4-fold increase in catalytic efficiency. Phosphorylation does not change the rate of substrate cleavage under single-turnover conditions, indicating that phosphorylation enhances product release, which also is the rate-limiting step in the steady-state. Molecular dynamics simulations provide a mechanism for facilitated product release, in which the Ser33 phosphomonoester forms a salt bridge with the Arg95 guanidinium group, thereby weakening RNase III engagement of product. The simulations also show why glutamic acid substitution at either serine does not confer enhancement, thus underscoring the specific requirement for a phosphomonoester.

A comparative evaluation on the emission characteristics of ceramic and metallic catalytic converter in internal combustion engine

NASA Astrophysics Data System (ADS)

Leman, A. M.; Jajuli, Afiqah; Rahman, Fakhrurrazi; Feriyanto, Dafit; Zakaria, Supaat

2017-09-01

Enforcement of a stricter regulation on exhaust emission by many countries has led to utilization of catalytic converter to reduce the harmful pollutant emission. Ceramic and metallic catalytic converters are the most common type of catalytic converter used. The purpose of this study is to evaluate the performance of the ceramic and metallic catalytic converter on its conversion efficiency using experimental measurement. Both catalysts were placed on a modified exhaust system equipped with a Mitshubishi 4G93 single cylinder petrol engine that was tested on an eddy current dynamometer under steady state conditions for several engine speeds. The experimental results show that the metallic catalytic converter reduced a higher percentage of CO up to 98.6% reduction emissions while ceramic catalytic converter had a better reduction efficiency of HC up to 85.4% and 87.2% reduction of NOx.

Bio-production of Baccatin III, an Important Precursor of Paclitaxel by a Cost-Effective Approach.

PubMed

Lin, Shu-Ling; Wei, Tao; Lin, Jun-Fang; Guo, Li-Qiong; Wu, Guang-Pei; Wei, Jun-Bin; Huang, Jia-Jun; Ouyang, Ping-Lan

2018-07-01

Natural production of anti-cancer drug taxol from Taxus has proved to be environmentally unsustainable and economically unfeasible. Currently, bioengineering the biosynthetic pathway of taxol is an attractive alternative production approach. 10-deacetylbaccatin III-10-O-acetyl transferase (DBAT) was previously characterized as an acyltransferase, using 10-deacetylbaccatin III (10-DAB) and acetyl CoA as natural substrates, to form baccatin III in the taxol biosynthesis. Here, we report that other than the natural acetyl CoA (Ac-CoA) substrate, DBAT can also utilize vinyl acetate (VA), which is commercially available at very low cost, acylate quickly and irreversibly, as acetyl donor in the acyl transfer reaction to produce baccatin III. Furthermore, mutants were prepared via a semi-rational design in this work. A double mutant, I43S/D390R was constructed to combine the positive effects of the different single mutations on catalytic activity, and its catalytic efficiency towards 10-DAB and VA was successfully improved by 3.30-fold, compared to that of wild-type DBAT, while 2.99-fold higher than the catalytic efficiency of WT DBAT towards 10-DAB and Ac-CoA. These findings can provide a promising economically and environmentally friendly method for exploring novel acyl donors to engineer natural product pathways.

Purification and characterization of Taenia crassiceps cysticerci thioredoxin: insight into thioredoxin-glutathione-reductase (TGR) substrate recognition.

PubMed

Martínez-González, J J; Guevara-Flores, A; Rendón, J L; Sosa-Peinado, A; Del Arenal Mena, I P

2015-04-01

Thioredoxin (Trx) is an oxidoreductase central to redox homeostasis in cells and is involved in the regulation of protein activity through thiol/disulfide exchanges. Based on these facts, our goal was to purify and characterize cytosolic thioredoxin from Taenia crassiceps cysticerci, as well as to study its behavior as a substrate of thioredoxin-glutathione reductase (TGR). The enzyme was purified >133-fold with a total yield of 9.7%. A molecular mass of 11.7kDa and a pI of 4.84 were measured. Native electrophoresis was used to identify the oxidized and reduced forms of the monomer as well as the presence of a homodimer. In addition to the catalytic site cysteines, cysticerci thioredoxin contains Cys28 and Cys65 residues conserved in previously sequenced cestode thioredoxins. The following kinetic parameters were obtained for the substrate of TGR: a Km of 3.1μM, a kcat of 10s(-1) and a catalytic efficiency of 3.2×10(6)M(-1)s(-1). The negative patch around the α3-helix of Trx is involved in the interaction with TGR and suggests variable specificity and catalytic efficiency of the reductase toward thioredoxins of different origins. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Method of realizing catalytic processes under unsteady state conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noskov, A.S.; Lakhmostov, V.S.; Matros, Yu.S.

1988-07-01

The operation of a system with the catalyst bed divided into three parts was investigated theoretically and experimentally. The conditions under which the system will efficiently convert a reaction mixture with a low inlet temperature in an unsteady state regime are determined. Calculations were performed for the industrially typical process of afterburning CO on a copper-chrome catalyst in the form of Raschig rings. A flow sheet of the unit with the catalyst divided into three is shown with temperature profiles along the bed at various moments in time. The method can be used for processing large volumes of gaseous wastesmore » on very active catalysts and for catalytic reactions with optimum temperature profiles close to those presented.« less

Efficient utilization of renewable feedstocks: the role of catalysis and process design

NASA Astrophysics Data System (ADS)

Palkovits, Regina; Delidovich, Irina

2017-11-01

Renewable carbon feedstocks such as biomass and CO2 present an important element of future circular economy. Especially biomass as highly functionalized feedstock provides manifold opportunities for the transformation into attractive platform chemicals. However, this change of the resources requires a paradigm shift in refinery design. Fossil feedstocks are processed in gas phase at elevated temperature. In contrast, biorefineries are based on processes in polar solvents at moderate conditions to selectively deoxygenate the polar, often thermally instable and high-boiling molecules. Here, challenges of catalytic deoxygenation, novel strategies for separation and opportunities provided at the interface to biotechnology are discussed in form of showcases. This article is part of a discussion meeting issue 'Providing sustainable catalytic solutions for a rapidly changing world'.

[FeFe]-Hydrogenases: recent developments and future perspectives.

PubMed

Wittkamp, F; Senger, M; Stripp, S T; Apfel, U-P

2018-06-08

[FeFe]-Hydrogenases are the most efficient enzymes for catalytic hydrogen turnover. Their H2 production efficiency is hitherto unrivalled. However, functional details of the catalytic machinery and possible modes of application are discussed controversially. The incorporation of synthetically modified cofactors and utilization of semi-artificial enzymes only recently allowed us to shed light on key steps of the catalytic cycle. Herein, we summarize the essential findings regarding the redox chemistry of [FeFe]-hydrogenases and discuss their catalytic hydrogen turnover. We furthermore will give an outlook on potential research activities and exploit the utilization of synthetic cofactor mimics.

Precise localization of metal nanoparticles in dendrimer nanosnakes or inner periphery and consequences in catalysis

NASA Astrophysics Data System (ADS)

Liu, Xiang; Gregurec, Danijela; Irigoyen, Joseba; Martinez, Angel; Moya, Sergio; Ciganda, Roberto; Hermange, Philippe; Ruiz, Jaime; Astruc, Didier

2016-10-01

Understanding the relationship between the location of nanoparticles (NPs) in an organic matrix and their catalytic performances is essential for catalyst design. Here we show that catalytic activities of Au, Ag and CuNPs stabilized by dendrimers using coordination to intradendritic triazoles, galvanic replacement or stabilization outside dendrimers strongly depends on their location. AgNPs are found at the inner click dendrimer periphery, whereas CuNPs and AuNPs are encapsulated in click dendrimer nanosnakes. AuNPs and AgNPs formed by galvanic replacement are larger than precursors and only partly encapsulated. AuNPs are all the better 4-nitrophenol reduction catalysts as they are less sterically inhibited by the dendrimer interior, whereas on the contrary CuNPs are all the better alkyne azide cycloaddition catalysts as they are better protected from aerobic oxidation inside dendrimers. This work highlights the role of the location in macromolecules on the catalytic efficiency of metal nanoparticles and rationalizes optimization in catalyst engineering.

Green synthesis of silver nanoparticles by waste tea extract and degradation of organic dye in the absence and presence of H2O2

NASA Astrophysics Data System (ADS)

Qing, Weixia; Chen, Kui; Wang, Yong; Liu, Xiuhua; Lu, Minghua

2017-11-01

The silver nanoparticles (AgNPs) had been successfully synthesized by using an aqueous extract of waste tea as a stabilizing and reducing agent. The green synthesized AgNPs were characterized by ultraviolet visible (UV-vis) spectroscopy, Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and zeta potential. The work focused on the degradation of methylene blue (MB) and ethyl violet (EV) in aqueous solution with AgNPs as catalyst in the absence and presence of H2O2. The AgNPs exhibit fast, efficient and stable catalytic activity in the degradation of cationic organic dyes, but it is no catalytic degradation of anionic organic dyes at room temperature. The kinetics of dyes degradation with AgNPs follows the pseudo-second-order model. Meanwhile, the AgNPs also show better antimicrobial activity against pathogenic bacteria. The formed highly catalytic active AgNPs can be used as catalyst in industries and water purification.

Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis

NASA Astrophysics Data System (ADS)

Nguyen, Thach T.; Koh, Ming Joo; Mann, Tyler J.; Schrock, Richard R.; Hoveyda, Amir H.

2017-12-01

Catalytic cross-metathesis is a central transformation in chemistry, yet corresponding methods for the stereoselective generation of acyclic trisubstituted alkenes in either the E or the Z isomeric forms are not known. The key problems are a lack of chemoselectivity—namely, the preponderance of side reactions involving only the less hindered starting alkene, resulting in homo-metathesis by-products—and the formation of short-lived methylidene complexes. By contrast, in catalytic cross-coupling, substrates are more distinct and homocoupling is less of a problem. Here we show that through cross-metathesis reactions involving E- or Z-trisubstituted alkenes, which are easily prepared from commercially available starting materials by cross-coupling reactions, many desirable and otherwise difficult-to-access linear E- or Z-trisubstituted alkenes can be synthesized efficiently and in exceptional stereoisomeric purity (up to 98 per cent E or 95 per cent Z). The utility of the strategy is demonstrated by the concise stereoselective syntheses of biologically active compounds, such as the antifungal indiacen B and the anti-inflammatory coibacin D.

Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis.

PubMed

Nguyen, Thach T; Koh, Ming Joo; Mann, Tyler J; Schrock, Richard R; Hoveyda, Amir H

2017-12-20

Catalytic cross-metathesis is a central transformation in chemistry, yet corresponding methods for the stereoselective generation of acyclic trisubstituted alkenes in either the E or the Z isomeric forms are not known. The key problems are a lack of chemoselectivity-namely, the preponderance of side reactions involving only the less hindered starting alkene, resulting in homo-metathesis by-products-and the formation of short-lived methylidene complexes. By contrast, in catalytic cross-coupling, substrates are more distinct and homocoupling is less of a problem. Here we show that through cross-metathesis reactions involving E- or Z-trisubstituted alkenes, which are easily prepared from commercially available starting materials by cross-coupling reactions, many desirable and otherwise difficult-to-access linear E- or Z-trisubstituted alkenes can be synthesized efficiently and in exceptional stereoisomeric purity (up to 98 per cent E or 95 per cent Z). The utility of the strategy is demonstrated by the concise stereoselective syntheses of biologically active compounds, such as the antifungal indiacen B and the anti-inflammatory coibacin D.

A PEG/copper(i) halide cluster as an eco-friendly catalytic system for C-N bond formation.

PubMed

Li, Cheng-An; Ji, Wei; Qu, Jian; Jing, Su; Gao, Fei; Zhu, Dun-Ru

2018-05-22

The catalytic activities of eight copper(i) halide clusters assembled from copper(i) halide and ferrocenyltelluroethers, 1-8, were investigated in C-N formation under various conditions. A catalytic procedure using poly(ethylene glycol) (PEG-400) as a greener alternative organic solvent has been developed. The PEG-400/5 system can achieve 99% targeted yield with a mild reaction temperature and short reaction time. After the isolation of the products by extraction with diethyl ether, this PEG-400/cluster system could be easily recycled. Spectroscopic studies elucidate a stepwise mechanism: firstly, proton-coupled electron transfer (PCET) involving the transfer of an electron from Cu+ and a proton from imidazole results in the formation of a labile penta-coordinated Cu2+ and aryl radical; the following effective electron transfer from the ferrocene unit reduces Cu2+ and forms the target product; finally, the ferrocenium unit is reduced by the I- anion. The merits of this eco-friendly synthesis are the efficient utilization of reagents and easy recyclability.

Water-medium and solvent-free organic reactions over a bifunctional catalyst with Au nanoparticles covalently bonded to HS/SO3H functionalized periodic mesoporous organosilica.

PubMed

Zhu, Feng-Xia; Wang, Wei; Li, He-Xing

2011-08-03

An operationally simple approach for the preparation of a new class of bifunctional Au nanoparticle-acid catalysts has been developed. In situ reduction of Au(3+) with HS-functionalized periodic mesoporous organosilicas (PMOs) creates robust, fine Au nanoparticles and concomitantly produces a sulfonic acid moiety strongly bonded to PMOs. Characterizations of the nanostructures reveal that Au nanoparticles are formed with uniformed, narrow size distribution around 1-2 nm, which is very critical for essential catalytic activities. Moreover, the Au nanoparticles are mainly attached onto the pore surface rather than onto the outer surface with ordered mesoporous channels, allowing for maximal exposure to reaction substrates while minimizing Au nanoparticle leaching. Their higher S(BET), V(P), and D(P) than either the Au-HS-PMO(Et) or the Au/SO(3)H-PMO(Et) render the catalyst with comparably even higher catalytic efficiency than its homogeneous counterparts. Furthermore, the unique amphiphilic compartment of the Au-HS/SO(3)H-PMO(Et) nanostructures enables organic reactions to proceed efficiently in a pure aqueous solution without using any organic solvents or even without water. As demonstrated experimentally, remarkably, the unique bifunctional Au-HS/SO(3)H-PMO(Et) catalyst displays higher efficiencies in promoting water-medium alkyne hydration, intramolecular hydroamination, styrene oxidation, and three-component coupling reactions and even the solvent-free alkyne hydration process than its homogeneous catalysts. The robust catalyst can be easily recycled and used repetitively at least 10 times without loss of catalytic efficiency. These features render the catalyst particularly attractive in the practice of organic synthesis in an environmentally friendly manner.

Defect-rich Ni-Ti layered double hydroxide as a highly efficient support for Au nanoparticles in base-free and solvent-free selective oxidation of benzyl alcohol.

PubMed

Liu, Mengran; Fan, Guoli; Yu, Jiaying; Yang, Lan; Li, Feng

2018-04-17

Tuning the surface properties of supported metal catalysts is of vital importance for governing their catalytic performances in nanocatalysis. Here, we report highly dispersed nanometric gold nanoparticles (NPs) supported on Ni-Ti layered double hydroxides (NiTi-LDHs), which were employed in solvent-free and base-free selective oxidation of benzyl alcohol. A series of characterization techniques demonstrated that defect-rich NiTi-LDHs could efficiently stabilize Au NPs and decrease surface electron density of Au NPs. The as-formed Au/NiTi-LDH catalyst with a Ni/Ti molar ratio of 3 : 1 and an Au loading of 0.71 wt% yielded the highest turnover frequency value of ∼4981 h-1 at 120 °C among tested Au/NiTi-LDH catalysts with different Ni/Ti molar ratios, along with a high benzaldehyde selectivity of 98%. High catalytic efficiency of the catalyst was mainly correlated with surface cooperation between unique defects (i.e. defective Ti3+ species and oxygen vacancies) and abundant hydroxyl groups on the brucite-like layers of the NiTi-LDH support, which could lead to the preferential adsorption and activation of an alcohol hydroxyl moiety in benzyl alcohol and oxygen molecule, as well as the formation of more electron-deficient Ni3+ and Au0 species on the catalyst surface. Furthermore, the present Au/NiTi-LDH catalyst tolerated the oxidation of a wide variety of substrate structures into the corresponding aldehydes, acids or ketones. Our primary results illustrate that defect-rich NiTi-LDHs are promising supports which can efficiently modify surface structure and electronic properties of supported metal catalysts and consequently improve their catalytic performances.

Boosting the catalytic performance of MoSx cocatalysts over CdS nanoparticles for photocatalytic H2 evolution by Co doping via a facile photochemical route

NASA Astrophysics Data System (ADS)

Lei, Yonggang; Hou, Jianhua; Wang, Fang; Ma, Xiaohua; Jin, Zhiliang; Xu, Jing; Min, Shixiong

2017-10-01

Low-crystalline or amorphous molybdenum sulfides (MoSx), bearing abundant unsaturated active sites, have been identified as efficient catalysts for electrocatalytic and photocatalytic H2 evolution reactions, however, their intrinsic activity is still low and need to be further improved for large-scale applications. In this paper, we report that low-crystalline MoSx doped with Co (Co-MoSx) as efficient cocatalysts could be loaded on CdS nanoparticles through a facile and controllable photochemical reduction method and showed high performances in catalyzing H2 evolution under visible light irradiation (≥420 nm). The photochemical loading of Co-MoSx was accomplished by using an in-situ formed molecular complex precursor and photogenerated electrons on CdS as reductants under mild conditions. The optimized CdS/Co-MoSx (Co:Mo = 1:4, 2 mol% loading) photocatalyst exhibited a catalytic H2 evolution rate of 535 μmol h-1, which is 1.8 times higher than that of CdS/MoSx, and an apparent quantum efficiency (AQE) of 23.5% was achieved over CdS/Co-MoSx photocatalyst at 420 nm. Co-MoSx catalyst also shows a long-term stability without noticeable activity degradation. Notably, Co-MoSx cocatalyst was found more efficient than that of noble metals in catalyzing photocatalytic H2 evolution on CdS. The formation of CoMoS phase, the enhanced electrocatalytic activity as well as reduced electron transfer resistance due to the doping effects of Co ions, account for the enhanced catalytic activity of this Co-MoSx cocatalyst.

Synthesis of ZnO-Pt nanoflowers and their photocatalytic applications.

PubMed

Yuan, Jiaquan; Choo, Eugene Shi Guang; Tang, Xiaosheng; Sheng, Yang; Ding, Jun; Xue, Junmin

2010-05-07

The photocatalytic behaviors of ZnO nanoparticles have been intensively studied recently. However, the photocatalytic efficiency of pure ZnO nanoparticles always suffers from the quick recombination of photoexcited electrons and holes. In order to suppress the electron-hole recombination and then raise the photocatalytic efficiency of ZnO, metal nanoparticles have been combined with ZnO to form ZnO-metal heterostructures. In this work, the feasibility of synthesizing ZnO-Pt composite nanoflowers for optimized catalytic properties was studied. Three different Pt nanocrystals, i.e. cubic Pt nanocrystals enclosed by {100} facets, octahedral Pt nanocrystals enclosed by {111} facets, and truncated octahedral Pt nanocrystals enclosed by both {111} and {100} facets, were selected as seeds for epitaxial growth of ZnO. A ZnO-Pt flowerlike nanostructure was formed by selective growth of ZnO nanolobes at {111} facets of the truncated octahedral Pt nanocrystals. The resultant nanoflowers had well defined ZnO-Pt interfaces and exposed Pt {100} facets, as confirmed by transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) measurements. The photocatalytic behaviors of the resultant ZnO-Pt nanoflowers were demonstrated in the photodegradation of ethyl violet. In comparison with the commercial TiO(2) photocatalyst P25, the ZnO-Pt flowerlike nanostructures showed improved catalytic efficiency. Notable ferromagnetism of the obtained ZnO-Pt flowerlike nanostructures was also observed. It is believed that the ZnO-Pt interface played an important role in the enlarged magnetic coercivity of the ZnO-Pt nanoflowers.

AMP-forming acetyl-CoA synthetases in Archaea show unexpected diversity in substrate utilization

PubMed Central

Ingram-Smith, Cheryl; Smith, Kerry S.

2007-01-01

Adenosine monophosphate (AMP)-forming acetyl-CoA synthetase (ACS; acetate:CoA ligase (AMP-forming), EC 6.2.1.1) is a key enzyme for conversion of acetate to acetyl-CoA, an essential intermediate at the junction of anabolic and catabolic pathways. Phylogenetic analysis of putative short and medium chain acyl-CoA synthetase sequences indicates that the ACSs form a distinct clade from other acyl-CoA synthetases. Within this clade, the archaeal ACSs are not monophyletic and fall into three groups composed of both bacterial and archaeal sequences. Kinetic analysis of two archaeal enzymes, an ACS from Methanothermobacter thermautotrophicus (designated as MT-ACS1) and an ACS from Archaeoglobus fulgidus (designated as AF-ACS2), revealed that these enzymes have very different properties. MT-ACS1 has nearly 11-fold higher affinity and 14-fold higher catalytic efficiency with acetate than with propionate, a property shared by most ACSs. However, AF-ACS2 has only 2.3-fold higher affinity and catalytic efficiency with acetate than with propionate. This enzyme has an affinity for propionate that is almost identical to that of MT-ACS1 for acetate and nearly tenfold higher than the affinity of MT-ACS1 for propionate. Furthermore, MT-ACS1 is limited to acetate and propionate as acyl substrates, whereas AF-ACS2 can also utilize longer straight and branched chain acyl substrates. Phylogenetic analysis, sequence alignment and structural modeling suggest a molecular basis for the altered substrate preference and expanded substrate range of AF-ACS2 versus MT-ACS1. PMID:17350930

Heat Transfer to Surfaces of Finite Catalytic Activity in Frozen Dissociated Hypersonic Flow

NASA Technical Reports Server (NTRS)

Chung, Paul M.; Anderson, Aemer D.

1961-01-01

The heat transfer due to catalytic recombination of a partially dissociated diatomic gas along the surfaces of two-dimensional and axisymmetric bodies with finite catalytic efficiencies is studied analytically. An integral method is employed resulting in simple yet relatively complete solutions for the particular configurations considered. A closed form solution is derived which enables one to calculate atom mass-fraction distribution, therefore catalytic heat transfer distribution, along the surface of a flat plate in frozen compressible flow with and without transpiration. Numerical calculations are made to determine the atom mass-fraction distribution along an axisymmetric conical body with spherical nose in frozen hypersonic compressible flow. A simple solution based on a local similarity concept is found to be in good agreement with these numerical calculations. The conditions are given for which the local similarity solution is expected to be satisfactory. The limitations on the practical application of the analysis to the flight of the blunt bodies in the atmosphere are discussed. The use of boundary-layer theory and the assumption of frozen flow restrict application of the analysis to altitudes between about 150,000 and 250,000 feet.

Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water

PubMed Central

Zhang, Ruifeng; Huang, Tinglin; Wen, Gang; Chen, Yongpan; Cao, Xin; Zhang, Beibei

2017-01-01

An iron-manganese co-oxide filter film (MeOx) has been proven to be a good catalyst for the chemical catalytic oxidation of ammonium in groundwater. Compared with groundwater, surface water is generally used more widely and has characteristics that make ammonium removal more difficult. In this study, MeOx was used to remove ammonium from surface water. It indicated that the average ammonium removal efficiency of MeOx was greater than 90%, even though the water quality changed dramatically and the water temperature was reduced to about 6–8 °C. Then, through inactivating microorganisms, it showed that the removal capability of MeOx included both biological (accounted for about 41.05%) and chemical catalytic oxidation and chemical catalytic oxidation (accounted for about 58.95%). The investigation of the characterizations suggested that MeOx was formed by abiotic ways and the main elements on the surface of MeOx were distributed homogenously. The analysis of the catalytic oxidation process indicated that ammonia nitrogen may interact with MeOx as both ammonia molecules and ammonium ions and the active species of O2 were possibly •O and O2−. PMID:28753939

Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water.

PubMed

Zhang, Ruifeng; Huang, Tinglin; Wen, Gang; Chen, Yongpan; Cao, Xin; Zhang, Beibei

2017-07-19

An iron-manganese co-oxide filter film (MeO x ) has been proven to be a good catalyst for the chemical catalytic oxidation of ammonium in groundwater. Compared with groundwater, surface water is generally used more widely and has characteristics that make ammonium removal more difficult. In this study, MeO x was used to remove ammonium from surface water. It indicated that the average ammonium removal efficiency of MeO x was greater than 90%, even though the water quality changed dramatically and the water temperature was reduced to about 6-8 °C. Then, through inactivating microorganisms, it showed that the removal capability of MeO x included both biological (accounted for about 41.05%) and chemical catalytic oxidation and chemical catalytic oxidation (accounted for about 58.95%). The investigation of the characterizations suggested that MeO x was formed by abiotic ways and the main elements on the surface of MeO x were distributed homogenously. The analysis of the catalytic oxidation process indicated that ammonia nitrogen may interact with MeO x as both ammonia molecules and ammonium ions and the active species of O₂ were possibly • O and O₂ - .

Asymmetric photoredox transition-metal catalysis activated by visible light.

PubMed

Huo, Haohua; Shen, Xiaodong; Wang, Chuanyong; Zhang, Lilu; Röse, Philipp; Chen, Liang-An; Harms, Klaus; Marsch, Michael; Hilt, Gerhard; Meggers, Eric

2014-11-06

Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest. Photoredox catalysis provides the opportunity to generate highly reactive radical ion intermediates with often unusual or unconventional reactivities under surprisingly mild reaction conditions. In such systems, photoactivated sensitizers initiate a single electron transfer from (or to) a closed-shell organic molecule to produce radical cations or radical anions whose reactivities are then exploited for interesting or unusual chemical transformations. However, the high reactivity of photoexcited substrates, intermediate radical ions or radicals, and the low activation barriers for follow-up reactions provide significant hurdles for the development of efficient catalytic photochemical processes that work under stereochemical control and provide chiral molecules in an asymmetric fashion. Here we report a highly efficient asymmetric catalyst that uses visible light for the necessary molecular activation, thereby combining asymmetric catalysis and photocatalysis. We show that a chiral iridium complex can serve as a sensitizer for photoredox catalysis and at the same time provide very effective asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles. This new asymmetric photoredox catalyst, in which the metal centre simultaneously serves as the exclusive source of chirality, the catalytically active Lewis acid centre, and the photoredox centre, offers new opportunities for the 'green' synthesis of non-racemic chiral molecules.

Asymmetric photoredox transition-metal catalysis activated by visible light

NASA Astrophysics Data System (ADS)

Huo, Haohua; Shen, Xiaodong; Wang, Chuanyong; Zhang, Lilu; Röse, Philipp; Chen, Liang-An; Harms, Klaus; Marsch, Michael; Hilt, Gerhard; Meggers, Eric

2014-11-01

Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest. Photoredox catalysis provides the opportunity to generate highly reactive radical ion intermediates with often unusual or unconventional reactivities under surprisingly mild reaction conditions. In such systems, photoactivated sensitizers initiate a single electron transfer from (or to) a closed-shell organic molecule to produce radical cations or radical anions whose reactivities are then exploited for interesting or unusual chemical transformations. However, the high reactivity of photoexcited substrates, intermediate radical ions or radicals, and the low activation barriers for follow-up reactions provide significant hurdles for the development of efficient catalytic photochemical processes that work under stereochemical control and provide chiral molecules in an asymmetric fashion. Here we report a highly efficient asymmetric catalyst that uses visible light for the necessary molecular activation, thereby combining asymmetric catalysis and photocatalysis. We show that a chiral iridium complex can serve as a sensitizer for photoredox catalysis and at the same time provide very effective asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles. This new asymmetric photoredox catalyst, in which the metal centre simultaneously serves as the exclusive source of chirality, the catalytically active Lewis acid centre, and the photoredox centre, offers new opportunities for the `green' synthesis of non-racemic chiral molecules.

THE EFFECT OF SULFUR ON METHANE PARTIAL OXIDATION AND REFORMING PROCESSES FOR LEAN NOX TRAP CATALYSIS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parks, II, James E; Ponnusamy, Senthil

2006-01-01

Lean NOx trap catalysis has demonstrated the ability to reduce NOx emissions from lean natural gas reciprocating engines by >90%. The technology operates in a cyclic fashion where NOx is trapped on the catalyst during lean operation and released and reduced to N2 under rich exhaust conditions; the rich cleansing operation of the cycle is referred to as "regeneration" since the catalyst is reactivated for more NOx trapping after NOx purge. Creating the rich exhaust conditions for regeneration can be accomplished by catalytic partial oxidation of methane in the exhaust system. Furthermore, catalytic reforming of partial oxidation exhaust can enablemore » increased quantities of H2 which is an excellent reductant for lean NOx trap regeneration. It is critical to maintain clean and efficient partial oxidation and reforming processes to keep the lean NOx trap functioning properly and to reduce extra fuel consumption from the regeneration process. Although most exhaust constituents do not impede partial oxidation and reforming, some exhaust constituents may negatively affect the catalysts and result in loss of catalytic efficiency. Of particular concern are common catalyst poisons sulfur, zinc, and phosphorous. These poisons form in the exhaust through combustion of fuel and oil, and although they are present at low concentrations, they can accumulate to significant levels over the life of an engine system. In the work presented here, the effects of sulfur on the partial oxidation and reforming catalytic processes were studied to determine any durability limitations on the production of reductants for lean NOx trap catalyst regeneration.« less

Water oxidation by a nickel-glycine catalyst.

PubMed

Wang, Dong; Ghirlanda, Giovanna; Allen, James P

2014-07-23

The utilization of solar energy requires an efficient means for its storage as chemical energy. In bioinspired artificial photosynthesis, light energy can be used to drive water oxidation, but catalysts that produce molecular oxygen from water are needed to avoid excessive driving potentials. In this paper, we demonstrate the utility of a novel complex utilizing earth-abundant Ni in combination with glycine as an efficient catalyst with a modest overpotential of 0.475 ± 0.005 V at a current density of 1 mA/cm(2) at pH 11. Catalysis requires the presence of the amine moiety with the glycine most likely coordinating the Ni in a 4:1 molar ratio. The production of molecular oxygen at a high potential is verified by measurement of the change in oxygen concentration, yielding a Faradaic efficiency of 60 ± 5%. The catalytic species is most likely a heterogeneous Ni-hydroxide formed by electrochemical oxidation. This Ni species can achieve a current density of 4 mA/cm(2) that persists for at least 10 h. Based upon the observed pH dependence of the current amplitude and oxidation/reduction peaks, the catalytic mechanism is an electron-proton coupled process.

The Performance of Chrome-Coated Copper as Metallic Catalytic Converter to Reduce Exhaust Gas Emissions from Spark-Ignition Engine

NASA Astrophysics Data System (ADS)

Warju; Harto, S. P.; Soenarto

2018-01-01

One of the automotive technologies to reduce exhaust gas emissions from the spark-ignition engine (SIE) is by using a catalytic converter. The aims of this research are firstly to conduct a metallic catalytic converter, secondly to find out to what extend chrome-coated copper plate (Cu+Cr) as a catalyst is efficient. To measure the concentration of carbon monoxide (CO) and hydrocarbon (HC) on the frame there are two conditions required. First is when the standard condition, and second is when Cu+Cr metallic catalytic converter is applied using exhaust gas analyzer. Exhaust gas emissions from SIE are measured by using SNI 19-7118.1-2005. The testing of CO and HC emissions were conducted with variable speed to find the trend of exhaust gas emissions from idle speed to high speed. This experiment results in the fact that the use of Cu+Cr metallic catalytic converter can reduce the production of CO and HC of a four-stroke gasoline engine. The reduction of CO and HC emission are 95,35% and 79,28%. Using active metal catalyst in form of metallic catalytic converter, it is gained an optimum effective surface of a catalyst which finally is able to decrease the amount of CO and HC emission significantly in every spinning happened in the engine. Finally, this technology can be applied to the spark ignition engine both car and motorcycle to support blue sky program in Indonesia.

Catalytic activation of carbon–carbon bonds in cyclopentanones

PubMed Central

Xia, Ying; Lu, Gang; Liu, Peng; Dong, Guangbin

2017-01-01

In the chemical industry, molecules of interest are based primarily on carbon skeletons. When synthesizing such molecules, the activation of carbon–carbon single bonds (C–C bonds) in simple substrates is strategically important: it offers a way of disconnecting such inert bonds, forming more active linkages (for example, between carbon and a transition metal) and eventually producing more versatile scaffolds1–13. The challenge in achieving such activation is the kinetic inertness of C–C bonds and the relative weakness of newly formed carbon–metal bonds6,14. The most common tactic starts with a three- or four-membered carbon-ring system9–13, in which strain release provides a crucial thermodynamic driving force. However, broadly useful methods that are based on catalytic activation of unstrained C–C bonds have proven elusive, because the cleavage process is much less energetically favourable. Here we report a general approach to the catalytic activation of C–C bonds in simple cyclopentanones and some cyclohexanones. The key to our success is the combination of a rhodium pre-catalyst, an N-heterocyclic carbene ligand and an amino-pyridine co-catalyst. When an aryl group is present in the C3 position of cyclopentanone, the less strained C–C bond can be activated; this is followed by activation of a carbon–hydrogen bond in the aryl group, leading to efficient synthesis of functionalized α-tetralones—a common structural motif and versatile building block in organic synthesis. Furthermore, this method can substantially enhance the efficiency of the enantioselective synthesis of some natural products of terpenoids. Density functional theory calculations reveal a mechanism involving an intriguing rhodium-bridged bicyclic intermediate. PMID:27806379

Advanced treatment of biologically pretreated coal chemical industry wastewater using the catalytic ozonation process combined with a gas-liquid-solid internal circulating fluidized bed reactor.

PubMed

Li, Zhipeng; Liu, Feng; You, Hong; Ding, Yi; Yao, Jie; Jin, Chao

2018-04-01

This paper investigated the performance of the combined system of catalytic ozonation and the gas-liquid-solid internal circulating fluidized bed reactor for the advanced treatment of biologically pretreated coal chemical industry wastewater (CCIW). The results indicated that with ozonation alone for 60min, the removal efficiency of chemical oxygen demand (COD) could reach 34%. The introduction of activated carbon, pumice, γ-Al 2 O 3 carriers improved the removal performance of COD, and the removal efficiency was increased by 8.6%, 4.2%, 2%, respectively. Supported with Mn, the catalytic performance of activated carbon and γ-Al 2 O 3 were improved significantly with COD removal efficiencies of 46.5% and 41.3%, respectively; however, the promotion effect of pumice supported with Mn was insignificant. Activated carbon supported with Mn had the best catalytic performance. The catalytic ozonation combined system of MnO X /activated carbon could keep ozone concentration at a lower level in the liquid phase, and promote the transfer of ozone from the gas phase to the liquid phase to improve ozonation efficiency.

A general method for the catalytic nazarov cyclization of heteroaromatic compounds.

PubMed

Malona, John A; Colbourne, Jessica M; Frontier, Alison J

2006-11-23

A general, catalytic method for efficient Nazarov cyclization of systems containing heteroaromatic components has been developed. Scandium triflate was identified as the most reactive promoter, and it was found that addition of lithium perchlorate was necessary for synthetically useful catalytic cyclizations. The method was used to synthesize a range of cyclopentanone-fused heteroaromatic systems in 36-97% yield, and the reactivity trends observed demonstrate the impact of polarization on cyclization efficiency. [reaction: see text].

Silver nanocluster catalytic microreactors for water purification

NASA Astrophysics Data System (ADS)

Da Silva, B.; Habibi, M.; Ognier, S.; Schelcher, G.; Mostafavi-Amjad, J.; Khalesifard, H. R. M.; Tatoulian, M.; Bonn, D.

2016-07-01

A new method for the elaboration of a novel type of catalytic microsystem with a high specific area catalyst is developed. A silver nanocluster catalytic microreactor was elaborated by doping a soda-lime glass with a silver salt. By applying a high power laser beam to the glass, silver nanoclusters are obtained at one of the surfaces which were characterized by BET measurements and AFM. A microfluidic chip was obtained by sealing the silver coated glass with a NOA 81 microchannel. The catalytic activity of the silver nanoclusters was then tested for the efficiency of water purification by using catalytic ozonation to oxidize an organic pollutant. The silver nanoclusters were found to be very stable in the microreactor and efficiently oxidized the pollutant, in spite of the very short residence times in the microchannel. This opens the way to study catalytic reactions in microchannels without the need of introducing the catalyst as a powder or manufacturing complex packed bed microreactors.

General Catalytic Enantioselective Access to Monohalomethyl and Trifluoromethyl Cyclopropanes.

PubMed

Huang, Wei-Sheng; Schlinquer, Claire; Poisson, Thomas; Pannecoucke, Xavier; Charette, André B; Jubault, Philippe

2018-05-29

An efficient catalytic enantioselective access to chiral functionalized trifluoromethyl cyclopropanes from two classes of diazo compounds and alpha-trifluoromethyl styrenes using Rh2((S)-BTPCP)4 as a catalyst is described. This method provides an efficient and practical strategy for the synthesis of highly functionalized CF3-cyclopropanes with excellent diastereoselectivities (up to 20:1) and enantioselectivities (up to 99% ee). The depicted methodology represents up to date the most efficient catalytic enantioselective method to access highly decorated chiral CF3-cyclopropanes. Extension to chiral monohalomethyl cyclopropanes in high ee is also reported. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper-catalyzed oxidative dimerizations of 3-N-hydroxy-aminoprop-1-enes to form 1,4-dihydroxy-2,3-diaminocyclohexanes with C2  symmetry.

PubMed

Ghorpade, Satish; Liu, Rai-Shung

2014-11-17

This work describes the one-step construction of complex and important molecular frameworks through copper-catalyzed oxidations of cheap tertiary amines. Copper-catalyzed aerobic oxidations of N-hydroxyaminopropenes to form C2 -symmetric N- and O-functionalized cyclohexanes are described. Such catalytic oxidations proceed with remarkable stereocontrol and high efficiency. Reductive cleavage of the two NO bonds of these products delivers 1,4-dihydroxy-2,3-diaminocyclohexanes, which are important skeletons of several bioactive molecules. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interrogating heterobimetallic co-catalytic responses for the electrocatalytic reduction of CO2 using supramolecular assembly.

PubMed

Machan, Charles W; Kubiak, Clifford P

2016-10-12

The use of hydrogen-bonding interactions to direct the non-covalent assembly of a heterobimetallic supramolecular system with Re and Mn bipyridine-based electrocatalysts is reported. Under catalytic conditions, the formation of hydrogen bonds generates a catalyst system which passes ∼10% more current than the individual current responses of the respective Re and Mn complexes for the reduction of CO 2 to CO and H 2 O. Infrared spectroelectrochemical studies indicate that the Re and Mn metal centers interact during the reduction mechanism, even forming heterobimetallic bonds under reducing conditions in the absence of substrate. These findings demonstrate that non-covalent assembly is a powerful method for generating new co-catalyst systems with greater reactivity and efficiency for transformations of interest.

Molecular Evolution of Human PON to Design Enhanced Catalytic Efficiency for Hydrolysis of Nerve Agents

DTIC Science & Technology

2011-12-01

8   C.   Catalytic activity of evolved variants with GA ................................................................. 11   D...several variants of rePON1 with enhanced activity towards a racemic mixture of CMP-Coumarin by screening ‘neutral drift’ libraries of rePON1 (e.g. 1G3, 2G9...22. The most active variant was 3B3, which had ~250-fold higher catalytic efficiency (kcat/Km 20x106 M-1min-1) compared to the wild-type-like

Palladium Nanoparticle-Loaded Cellulose Paper: A Highly Efficient, Robust, and Recyclable Self-Assembled Composite Catalytic System.

PubMed

Zheng, Guangchao; Kaefer, Katharina; Mourdikoudis, Stefanos; Polavarapu, Lakshminarayana; Vaz, Belén; Cartmell, Samantha E; Bouleghlimat, Azzedine; Buurma, Niklaas J; Yate, Luis; de Lera, Ángel R; Liz-Marzán, Luis M; Pastoriza-Santos, Isabel; Pérez-Juste, Jorge

2015-01-15

We present a novel strategy based on the immobilization of palladium nanoparticles (Pd NPs) on filter paper for development of a catalytic system with high efficiency and recyclability. Oleylamine-capped Pd nanoparticles, dispersed in an organic solvent, strongly adsorb on cellulose filter paper, which shows a great ability to wick fluids due to its microfiber structure. Strong van der Waals forces and hydrophobic interactions between the particles and the substrate lead to nanoparticle immobilization, with no desorption upon further immersion in any solvent. The prepared Pd NP-loaded paper substrates were tested for several model reactions such as the oxidative homocoupling of arylboronic acids, the Suzuki cross-coupling reaction, and nitro-to-amine reduction, and they display efficient catalytic activity and excellent recyclability and reusability. This approach of using NP-loaded paper substrates as reusable catalysts is expected to open doors for new types of catalytic support for practical applications.

Catalytic asymmetric epoxidation of alpha,beta-unsaturated amides: efficient synthesis of beta-aryl alpha-hydroxy amides using a one-pot tandem catalytic asymmetric epoxidation-Pd-catalyzed epoxide opening process.

PubMed

Nemoto, Tetsuhiro; Kakei, Hiroyuki; Gnanadesikan, Vijay; Tosaki, Shin-Ya; Ohshima, Takashi; Shibasaki, Masakatsu

2002-12-11

The catalytic asymmetric epoxidation of alpha,beta-unsaturated amides using Sm-BINOL-Ph3As=O complex was succeeded. Using 5-10 mol % of the asymmetric catalyst, a variety of amides were epoxidized efficiently, yielding the corresponding alpha,beta-epoxy amides in up to 99% yield and in more than 99% ee. Moreover, the novel one-pot tandem process, one-pot tandem catalytic asymmetric epoxidation-Pd-catalyzed epoxide opening process, was developed. This method was successfully utilized for the efficient synthesis of beta-aryl alpha-hydroxy amides, including beta-aryllactyl-leucine methyl esters. Interestingly, it was found that beneficial modifications on the Pd catalyst were achieved by the constituents of the first epoxidation, producing a more suitable catalyst for the Pd-catalyzed epoxide opening reaction in terms of chemoselectivity.

ZIF-67 incorporated with carbon derived from pomelo peels: A highly efficient bifunctional catalyst for oxygen reduction/evolution reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hao; Yin, Feng-Xiang; Chen, Biao-Hua

Developing carbon catalyst materials using natural, abundant and renewable resources as precursors plays an increasingly important role in clean energy generation and environmental protection. In this work, N-doped pomelo-peel-derived carbon (NPC) materials were prepared using a widely available food waste-pomelo peels and melamine. The synthetic NPC exhibits well-defined porosities and a highly doped-N content (e.g. 6.38 at% for NPC-2), therefore affords excellent oxygen reduction reaction (ORR) catalytic activities in alkaline electrolytes. NPC was further integrated with ZIF-67 to form ZIF-67@NPC hybrids through solvothermal reactions. The hybrid catalysts show substantially enhanced ORR catalytic activities comparable to that of commercial 20 wamore » Pt/C. Furthermore, the catalysts also exhibit excellent oxygen evolution reaction (OER) catalytic activities. Among all prepared ZIF-67@NPC hybrids, the optimal composition with ZIF-67 to NPC ratio of 2:1 exhibits the best ORR and OER bifunctional catalytic performance and the smallest Delta E (E-OER@10 mA cm(-2)-E-ORR@-1 mA cm(-2)) value of 0.79 V. The catalyst also demonstrated desirable 4-electron transfer pathways and superior catalytic stabilities. The Co-N-4 in ZIF-67, electrochemical active surface area, and the strong interactions between ZIF-67 and NPC are attributed as the main contributors to the bifunctional catalytic activities. These factors act synergistically, resulting in substantially enhanced bifunctional catalytic activities and stabilities; consequently, this hybrid catalyst is among the best of the reported bifunctional electrocatalysts and is promising for use in metal-air batteries and fuel cells. (C) 2016 Elsevier B.V. All rights reserved.« less

New Metamaterials with Combined Subnano - and Mesoscale Topology for High-efficiency Catalytic Combustion Chambers of Innovative Gas Turbine Engines

NASA Astrophysics Data System (ADS)

Knysh, Yu A.; Xanthopoulou, G. G.

2018-01-01

The object of the study is a catalytic combustion chamber that provides a highly efficient combustion process through the use of effects: heat recovery from combustion, microvortex heat transfer, catalytic reaction and acoustic resonance. High efficiency is provided by a complex of related technologies: technologies for combustion products heat transfer (recuperation) to initial mixture, catalytic processes technology, technology for calculating effective combustion processes based on microvortex matrices, technology for designing metamaterials structures and technology for obtaining the required topology product by laser fusion of metal powder compositions. The mesoscale level structure provides combustion process with the use of a microvortex effect with a high intensity of heat and mass transfer. High surface area (extremely high area-to-volume ratio) created due to nanoscale periodic structure and ensures catalytic reactions efficiency. Produced metamaterial is the first multiscale product of new concept which due to combination of different scale level periodic topologies provides qualitatively new set of product properties. This research is aimed at solving simultaneously two global problems of the present: ensure environmental safety of transport systems and power industry, as well as the economy and rational use of energy resources, providing humanity with energy now and in the foreseeable future.

Active site loop dynamics of a class IIa fructose 1,6-bisphosphate aldolase from M. tuberculosis

PubMed Central

Pegan, Scott D.; Rukseree, Kamolchanok; Capodagli, Glenn C.; Baker, Erica A; Krasnykh, Olga; Franzblau, Scott G; Mesecar, Andrew D

2014-01-01

Class II fructose 1,6-bisphosphate aldolases (FBA; E.C. 4.1.2.13) comprise one of two families of aldolases. Instead of forming a Schiff-base intermediate using an ε-amino group of a lysine side chain, class II FBAs utilize Zn(II) to stabilize a proposed hydroxyenolate intermediate (HEI) in the reversible cleavage of fructose 1,6-bisphosphate forming glyceraldehyde 3-phosphate and dihydroxyacetone phosphate (DHAP). As class II FBAs has been shown to be essential in pathogenic bacteria, focus has been placed on these enzymes as potential antibacterial targets. Although structural studies on class II FBAs from Mycobacterium tuberculosis (MtFBA), other bacteria and protozoa have been reported, the structure of the active site loop responsible for catalyzing the protonation/deprotonation steps of the reaction for class II FBAs has not yet been observed. We therefore utilized the potent class II FBA inhibitor phosphoglycolohydroxamate (PGH) as a mimic of the HEI/DHAP bound form of the enzyme and determined the X-ray structure of MtFBA-PGH complex to 1.58 Å. Remarkably, we are able to observe well-defined electron density for the previously elusive active site loop of MtFBA trapped in a catalytically competent orientation. Utilization of this structural information plus site-directed mutagenesis and kinetic studies conducted on a series of residues within the active-site loop revealed that E169 facilitates a water mediated deprotonation/protonation step of the MtFBA reaction mechanism. Also, secondary isotope effects on MtFBA and catalytically relevant mutants were used to probe the effect of loop flexibility on catalytic efficiency. Additionally, we also reveal the structure of MtFBA in its holoenzyme form. PMID:23298222

Active site loop dynamics of a class IIa fructose 1,6-bisphosphate aldolase from Mycobacterium tuberculosis.

PubMed

Pegan, Scott D; Rukseree, Kamolchanok; Capodagli, Glenn C; Baker, Erica A; Krasnykh, Olga; Franzblau, Scott G; Mesecar, Andrew D

2013-02-05

Class II fructose 1,6-bisphosphate aldolases (FBAs, EC 4.1.2.13) comprise one of two families of aldolases. Instead of forming a Schiff base intermediate using an ε-amino group of a lysine side chain, class II FBAs utilize Zn(II) to stabilize a proposed hydroxyenolate intermediate (HEI) in the reversible cleavage of fructose 1,6-bisphosphate, forming glyceraldehyde 3-phosphate and dihydroxyacetone phosphate (DHAP). As class II FBAs have been shown to be essential in pathogenic bacteria, focus has been placed on these enzymes as potential antibacterial targets. Although structural studies of class II FBAs from Mycobacterium tuberculosis (MtFBA), other bacteria, and protozoa have been reported, the structure of the active site loop responsible for catalyzing the protonation-deprotonation steps of the reaction for class II FBAs has not yet been observed. We therefore utilized the potent class II FBA inhibitor phosphoglycolohydroxamate (PGH) as a mimic of the HEI- and DHAP-bound form of the enzyme and determined the X-ray structure of the MtFBA-PGH complex to 1.58 Å. Remarkably, we are able to observe well-defined electron density for the previously elusive active site loop of MtFBA trapped in a catalytically competent orientation. Utilization of this structural information and site-directed mutagenesis and kinetic studies conducted on a series of residues within the active site loop revealed that E169 facilitates a water-mediated deprotonation-protonation step of the MtFBA reaction mechanism. Also, solvent isotope effects on MtFBA and catalytically relevant mutants were used to probe the effect of loop flexibility on catalytic efficiency. Additionally, we also reveal the structure of MtFBA in its holoenzyme form.

Active Site Loop Dynamics of a Class IIa Fructose 1,6-Bisphosphate Aldolase from Mycobacterium tuberculosis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pegan, Scott D.; Rukseree, Kamolchanok; Capodagli, Glenn C.

The class II fructose 1,6-bisphosphate aldolases (FBAs, EC 4.1.2.13) comprises one of two families of aldolases. Instead of forming a Schiff base intermediate using an ε-amino group of a lysine side chain, class II FBAs utilize Zn(II) to stabilize a proposed hydroxyenolate intermediate (HEI) in the reversible cleavage of fructose 1,6-bisphosphate, forming glyceraldehyde 3-phosphate and dihydroxyacetone phosphate (DHAP). As class II FBAs have been shown to be essential in pathogenic bacteria, focus has been placed on these enzymes as potential antibacterial targets. Although structural studies of class II FBAs from Mycobacterium tuberculosis (MtFBA), other bacteria, and protozoa have been reported,more » the structure of the active site loop responsible for catalyzing the protonation–deprotonation steps of the reaction for class II FBAs has not yet been observed. We therefore utilized the potent class II FBA inhibitor phosphoglycolohydroxamate (PGH) as a mimic of the HEI- and DHAP-bound form of the enzyme and determined the X-ray structure of the MtFBA–PGH complex to 1.58 Å. Remarkably, we are able to observe well-defined electron density for the previously elusive active site loop of MtFBA trapped in a catalytically competent orientation. Utilization of this structural information and site-directed mutagenesis and kinetic studies conducted on a series of residues within the active site loop revealed that E169 facilitates a water-mediated deprotonation–protonation step of the MtFBA reaction mechanism. Furthermore, solvent isotope effects on MtFBA and catalytically relevant mutants were used to probe the effect of loop flexibility on catalytic efficiency. Additionally, we also reveal the structure of MtFBA in its holoenzyme form.« less

Polyvinylpyrrolidone (PVP)-Capped Pt Nanocubes with Superior Peroxidase-Like Activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Haihang; Liu, Yuzi; Chhabra, Ashima

2016-12-21

Peroxidase mimics of inorganic nanoparticles are expected to circumvent the inherent issues of natural peroxidases, providing enhanced performance in important applications such as diagnosis and imaging. Despite the report of a variety of peroxidase mimics in the past decade, very limited progress has been made on improving their catalytic efficiency. The catalytic efficiencies of most previously reported mimics are only up to one order of magnitude higher than those of natural peroxidases. In this work, we demonstrate a type of highly efficient peroxidase mimic – polyvinylpyrrolidone (PVP)-capped Pt nanocubes of sub-10 nm in size. These PVP-capped Pt cubes are ~200-foldmore » more active than the natural counterparts and exhibit a record-high specific catalytic efficiency. In addition to the superior efficiency, the new mimic shows several other promising features, including excellent stabilities, well-controlled uniformity in both size and shape, controllable sizes, and facile and scalable production.« less

Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading

DOE PAGES

Iisa, Kristiina; Robichaud, David J.; Watson, Michael J.; ...

2017-11-24

Partial deoxygenation of bio-oil by catalytic fast pyrolysis with subsequent coupling and hydrotreating can lead to improved economics and will aid commercial deployment of pyrolytic conversion of biomass technologies. Biomass pyrolysis efficiently depolymerizes and deconstructs solid plant matter into carbonaceous molecules that, upon catalytic upgrading, can be used for fuels and chemicals. Upgrading strategies include catalytic deoxygenation of the vapors before they are condensed (in situ and ex situ catalytic fast pyrolysis), or hydrotreating following condensation of the bio-oil. In general, deoxygenation carbon efficiencies, one of the most important cost drivers, are typically higher for hydrotreating when compared to catalyticmore » fast pyrolysis alone. However, using catalytic fast pyrolysis as the primary conversion step can benefit the entire process chain by: (1) reducing the reactivity of the bio-oil, thereby mitigating issues with aging and transport and eliminating need for multi-stage hydroprocessing configurations; (2) producing a bio-oil that can be fractionated through distillation, which could lead to more efficient use of hydrogen during hydrotreating and facilitate integration in existing petroleum refineries; and (3) allowing for the separation of the aqueous phase. In this perspective, we investigate in detail a combination of these approaches, where some oxygen is removed during catalytic fast pyrolysis and the remainder removed by downstream hydrotreating, accompanied by carbon–carbon coupling reactions in either the vapor or liquid phase to maximize carbon efficiency toward value-driven products (e.g. fuels or chemicals). The economic impact of partial deoxygenation by catalytic fast pyrolysis will be explored in the context of an integrated two-stage process. In conclusion, improving the overall pyrolysis-based biorefinery economics by inclusion of production of high-value co-products will be examined.« less

Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iisa, Kristiina; Robichaud, David J.; Watson, Michael J.

Partial deoxygenation of bio-oil by catalytic fast pyrolysis with subsequent coupling and hydrotreating can lead to improved economics and will aid commercial deployment of pyrolytic conversion of biomass technologies. Biomass pyrolysis efficiently depolymerizes and deconstructs solid plant matter into carbonaceous molecules that, upon catalytic upgrading, can be used for fuels and chemicals. Upgrading strategies include catalytic deoxygenation of the vapors before they are condensed (in situ and ex situ catalytic fast pyrolysis), or hydrotreating following condensation of the bio-oil. In general, deoxygenation carbon efficiencies, one of the most important cost drivers, are typically higher for hydrotreating when compared to catalyticmore » fast pyrolysis alone. However, using catalytic fast pyrolysis as the primary conversion step can benefit the entire process chain by: (1) reducing the reactivity of the bio-oil, thereby mitigating issues with aging and transport and eliminating need for multi-stage hydroprocessing configurations; (2) producing a bio-oil that can be fractionated through distillation, which could lead to more efficient use of hydrogen during hydrotreating and facilitate integration in existing petroleum refineries; and (3) allowing for the separation of the aqueous phase. In this perspective, we investigate in detail a combination of these approaches, where some oxygen is removed during catalytic fast pyrolysis and the remainder removed by downstream hydrotreating, accompanied by carbon–carbon coupling reactions in either the vapor or liquid phase to maximize carbon efficiency toward value-driven products (e.g. fuels or chemicals). The economic impact of partial deoxygenation by catalytic fast pyrolysis will be explored in the context of an integrated two-stage process. In conclusion, improving the overall pyrolysis-based biorefinery economics by inclusion of production of high-value co-products will be examined.« less

Virtual screening of mandelate racemase mutants with enhanced activity based on binding energy in the transition state.

PubMed

Gu, Jiali; Liu, Min; Guo, Fei; Xie, Wenping; Lu, Wenqiang; Ye, Lidan; Chen, Zhirong; Yuan, Shenfeng; Yu, Hongwei

2014-02-05

Mandelate racemase (MR) is a promising candidate for the dynamic kinetic resolution of racemates. However, the poor activity of MR towards most of its non-natural substrates limits its widespread application. In this work, a virtual screening method based on the binding energy in the transition state was established to assist in the screening of MR mutants with enhanced catalytic efficiency. Using R-3-chloromandelic acid as a model substrate, a total of 53 mutants were constructed based on rational design in the two rounds of screening. The number of mutants for experimental validation was brought down to 17 by the virtual screening method, among which 14 variants turned out to possess improved catalytic efficiency. The variant V26I/Y54V showed 5.2-fold higher catalytic efficiency (k(cat)/K(m)) towards R-3-chloromandelic acid than that observed for the wild-type enzyme. Using this strategy, mutants were successfully obtained for two other substrates, R-mandelamide and R-2-naphthylglycolate (V26I and V29L, respectively), both with a 2-fold improvement in catalytic efficiency. These results demonstrated that this method could effectively predict the trend of mutational effects on catalysis. Analysis from the energetic and structural assays indicated that the enhanced interactions between the active sites and the substrate in the transition state led to improved catalytic efficiency. It was concluded that this virtual screening method based on the binding energy in the transition state was beneficial in enzyme rational redesign and helped to better understand the catalytic properties of the enzyme. Copyright © 2013 Elsevier Inc. All rights reserved.

Substituting Tyr138 in the active site loop of human phenylalanine hydroxylase affects catalysis and substrate activation.

PubMed

Leandro, João; Stokka, Anne J; Teigen, Knut; Andersen, Ole A; Flatmark, Torgeir

2017-07-01

Mammalian phenylalanine hydroxylase (PAH) is a key enzyme in l-phenylalanine (l-Phe) metabolism and is active as a homotetramer. Biochemical and biophysical work has demonstrated that it cycles between two states with a variably low and a high activity, and that the substrate l-Phe is the key player in this transition. X-ray structures of the catalytic domain have shown mobility of a partially intrinsically disordered Tyr 138 -loop to the active site in the presence of l-Phe. The mechanism by which the loop dynamics are coupled to substrate binding at the active site in tetrameric PAH is not fully understood. We have here conducted functional studies of four Tyr 138 point mutants. A high linear correlation ( r 2 = 0.99) was observed between their effects on the catalytic efficiency of the catalytic domain dimers and the corresponding effect on the catalytic efficiency of substrate-activated full-length tetramers. In the tetramers, a correlation ( r 2 = 0.96) was also observed between the increase in catalytic efficiency (activation) and the global conformational change (surface plasmon resonance signal response) at the same l-Phe concentration. The new data support a similar functional importance of the Tyr 138 -loop in the catalytic domain and the full-length enzyme homotetramer.

Enhanced rates of enzymatic saccharification and catalytic synthesis of biofuel substrates in gelatinized cellulose generated by trifluoroacetic acid

DOE PAGES

Shiga, Tânia M.; Xiao, Weihua; Yang, Haibing; ...

2017-12-27

The crystallinity of cellulose is a principal factor limiting the efficient hydrolysis of biomass to fermentable sugars or direct catalytic conversion to biofuel components. We evaluated the impact of TFA-induced gelatinization of crystalline cellulose on enhancement of enzymatic digestion and catalytic conversion to biofuel substrates. Low-temperature swelling of cotton linter cellulose in TFA at subzero temperatures followed by gentle heating to 55 degrees C dissolves the microfibril structure and forms composites of crystalline and amorphous gels upon addition of ethanol. The extent of gelatinization of crystalline cellulose was determined by reduction of birefringence in darkfield microscopy, loss of X-ray diffractability,more » and loss of resistance to acid hydrolysis. Upon freeze-drying, an additional degree of crystallinity returned as mostly cellulose II. Both enzymatic digestion with a commercial cellulase cocktail and maleic acid/AlCl3-catalyzed conversion to 5-hydroxymethylfurfural and levulinic acid were markedly enhanced with the low-temperature swollen cellulose. Only small improvements in rates and extent of hydrolysis and catalytic conversion were achieved upon heating to fully dissolve cellulose. Low-temperature swelling of cellulose in TFA substantially reduces recalcitrance of crystalline cellulose to both enzymatic digestion and catalytic conversion. In a closed system to prevent loss of fluorohydrocarbons, the relative ease of recovery and regeneration of TFA by distillation makes it a potentially useful agent in large-scale deconstruction of biomass, not only for enzymatic depolymerization but also for enhancing rates of catalytic conversion to biofuel components and useful bio-products.« less

Enhanced rates of enzymatic saccharification and catalytic synthesis of biofuel substrates in gelatinized cellulose generated by trifluoroacetic acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shiga, Tânia M.; Xiao, Weihua; Yang, Haibing

The crystallinity of cellulose is a principal factor limiting the efficient hydrolysis of biomass to fermentable sugars or direct catalytic conversion to biofuel components. We evaluated the impact of TFA-induced gelatinization of crystalline cellulose on enhancement of enzymatic digestion and catalytic conversion to biofuel substrates. Low-temperature swelling of cotton linter cellulose in TFA at subzero temperatures followed by gentle heating to 55 degrees C dissolves the microfibril structure and forms composites of crystalline and amorphous gels upon addition of ethanol. The extent of gelatinization of crystalline cellulose was determined by reduction of birefringence in darkfield microscopy, loss of X-ray diffractability,more » and loss of resistance to acid hydrolysis. Upon freeze-drying, an additional degree of crystallinity returned as mostly cellulose II. Both enzymatic digestion with a commercial cellulase cocktail and maleic acid/AlCl3-catalyzed conversion to 5-hydroxymethylfurfural and levulinic acid were markedly enhanced with the low-temperature swollen cellulose. Only small improvements in rates and extent of hydrolysis and catalytic conversion were achieved upon heating to fully dissolve cellulose. Low-temperature swelling of cellulose in TFA substantially reduces recalcitrance of crystalline cellulose to both enzymatic digestion and catalytic conversion. In a closed system to prevent loss of fluorohydrocarbons, the relative ease of recovery and regeneration of TFA by distillation makes it a potentially useful agent in large-scale deconstruction of biomass, not only for enzymatic depolymerization but also for enhancing rates of catalytic conversion to biofuel components and useful bio-products.« less

Removal of disinfection by-products from contaminated water using a synthetic goethite catalyst via catalytic ozonation and a biofiltration system.

PubMed

Wang, Yu-Hsiang; Chen, Kuan-Chung

2014-09-10

The effects of synthetic goethite (α-FeOOH) used as the catalyst in catalytic ozonation for the degradation of disinfection by-product (DBP) precursors are investigated. A biofiltration column applied following the catalytic ozonation process is used to evaluate the efficiency of removing DBP precursors via biotreatment. Ozone can rapidly react with aromatic compounds and oxidize organic compounds, resulting in a decrease in the fluorescence intensity of dissolved organic matter (DOM). In addition, catalytic ozonation can break down large organic molecules, which causes a blue shift in the emission-excitation matrix spectra. Water treated with catalytic ozonation is composed of low-molecular structures, including soluble microbial products (SMPs) and other aromatic proteins (APs). The DOM in SMPs and APs is removed by subsequent biofiltration. Catalytic ozonation has a higher removal efficiency for dissolved organic carbon and higher ultraviolet absorbance at 254 nm compared to those of ozonation without a catalyst. The use of catalytic ozonation and subsequent biofiltration leads to a lower DBP formation potential during chlorination compared to that obtained using ozonation and catalytic ozonation alone. Regarding DBP species during chlorination, the bromine incorporation factor (BIF) of trihalomethanes and haloacetic acids increases with increasing catalyst dosage in catalytic ozonation. Moreover, the highest BIF is obtained for catalytic ozonation and subsequent biofiltration.

Removal of Disinfection By-Products from Contaminated Water Using a Synthetic Goethite Catalyst via Catalytic Ozonation and a Biofiltration System·

PubMed Central

Wang, Yu-Hsiang; Chen, Kuan-Chung

2014-01-01

The effects of synthetic goethite (α-FeOOH) used as the catalyst in catalytic ozonation for the degradation of disinfection by-product (DBP) precursors are investigated. A biofiltration column applied following the catalytic ozonation process is used to evaluate the efficiency of removing DBP precursors via biotreatment. Ozone can rapidly react with aromatic compounds and oxidize organic compounds, resulting in a decrease in the fluorescence intensity of dissolved organic matter (DOM). In addition, catalytic ozonation can break down large organic molecules, which causes a blue shift in the emission-excitation matrix spectra. Water treated with catalytic ozonation is composed of low-molecular structures, including soluble microbial products (SMPs) and other aromatic proteins (APs). The DOM in SMPs and APs is removed by subsequent biofiltration. Catalytic ozonation has a higher removal efficiency for dissolved organic carbon and higher ultraviolet absorbance at 254 nm compared to those of ozonation without a catalyst. The use of catalytic ozonation and subsequent biofiltration leads to a lower DBP formation potential during chlorination compared to that obtained using ozonation and catalytic ozonation alone. Regarding DBP species during chlorination, the bromine incorporation factor (BIF) of trihalomethanes and haloacetic acids increases with increasing catalyst dosage in catalytic ozonation. Moreover, the highest BIF is obtained for catalytic ozonation and subsequent biofiltration. PMID:25211774

Efficient Decarbonylation of Furfural to Furan Catalyzed by Zirconia-Supported Palladium Clusters with Low Atomicity.

PubMed

Ishida, Tamao; Kume, Kurumi; Kinjo, Kota; Honma, Tetsuo; Nakada, Kengo; Ohashi, Hironori; Yokoyama, Takushi; Hamasaki, Akiyuki; Murayama, Haruno; Izawa, Yusuke; Utsunomiya, Masaru; Tokunaga, Makoto

2016-12-20

Decarbonylation of furfural to furan was efficiently catalyzed by ZrO 2 -supported Pd clusters in the liquid phase under a N 2 atmosphere without additives. Although Pd/C and Pd/Al 2 O 3 have frequently been used for decarbonylation, Pd/ZrO 2 exhibited superior catalytic performance compared with these conventional catalysts. Transmission electron microscopy and X-ray absorption fine structure measurements revealed that the size of the Pd particles decreased with an increase in the specific surface area of ZrO 2 . ZrO 2 with a high surface area immobilized Pd as clusters consisting of several (three to five) Pd atoms, whereas Pd aggregated to form nanoparticles on other supports such as carbon and Al 2 O 3 despite their high surface areas. The catalytic activity of Pd/ZrO 2 was enhanced with a decrease in particle size, and the smallest Pd/ZrO 2 was the most active catalyst for decarbonylation. When CeO 2 was used as the support, a decrease in Pd particle size with an increase in surface area was also observed. Single Pd atoms were deposited on CeO 2 with a high surface area, with a strong interaction through the formation of a Pd-O-Ce bond, which led to a lower catalytic activity than that of Pd/ZrO 2 . This result suggests that zero-valent small Pd clusters consisting of more than one Pd atom are the active species for the decarbonylation reaction. Recycling tests proved that Pd/ZrO 2 maintained its catalytic activity until its sixth use. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

NADP-dependent malate dehydrogenase (decarboxylating) from sugar cane leaves. Kinetic properties of different oligomeric structures.

PubMed

Iglesias, A A; Andreo, C S

1990-09-24

NADP-dependent malate dehydrogenase (decarboxylating) from sugar cane leaves was inhibited by increasing the ionic strength in the assay medium. The inhibitory effect was higher at pH 7.0 than 8.0, with median inhibitory concentrations (IC50) of 89 mM and 160 mM respectively, for inhibition by NaCl. Gel-filtration experiments indicated that the enzyme dissociated into dimers and monomers when exposed to high ionic strength (0.3 M NaCl). By using the enzyme-dilution approach in the absence and presence of 0.3 M NaCl, the kinetic properties of each oligomeric species of the protein was determined at pH 7.0 and 8.0. Tetrameric, dimeric and monomeric structures were shown to be active but with different V and Km values. The catalytic efficiency of the oligomers was tetramer greater than dimer greater than monomer, and each quaternary structure exhibited higher activity at pH 8.0 than 7.0. Dissociation constants for the equilibria between the different oligomeric forms of the enzyme were determined. It was established that Kd values were affected by pH and Mg2+ levels in the medium. Results suggest that the distinct catalytic properties of the different oligomeric forms of NADP-dependent malate dehydrogenase and changes in their equilibrium could be the molecular basis for an efficient physiological regulation of the decarboxylation step of C4 metabolism.

Chaperones are necessary for the expression of catalytically active potato apyrases in prokaryotic cells.

PubMed

Porowińska, Dorota; Czarnecka, Joanna; Komoszyński, Michał

2014-07-01

NTPDases (nucleoside triphosphate diphosphohydrolases) (also called in plants apyrases) hydrolyze nucleoside 5'-tri- and/or diphosphate bonds producing nucleosides di or monophosphate and inorganic phosphate. For years, studies have been carried out to use both plant and animal enzymes for medicine. Therefore, there is a need to develop an efficient method for the quick production of large amounts of homogeneous proteins with high catalytic activity. Expression of proteins in prokaryotic cells is the most common way for the protein production. The aim of our study was to develop a method of expression of potato apyrase (StAPY4, 5, and 6) genes in bacterial cells under conditions that allowed the production of catalytically active form of these enzymes. Apyrase 4 and 6 were overexpressed in BL21-CodonPlus (DE3) bacteria strain but they were accumulated in inclusion bodies, regardless of the culture conditions and induction method. Co-expression of potato apyrases with molecular chaperones allowed the expression of catalytically active apyrase 5. However, its high nucleotidase activity could be toxic for bacteria and is therefore synthesized in small amounts in cells. Our studies show that each protein requires other conditions for maturation and even small differences in amino acid sequence can essentially affect protein folding regardless of presence of chaperones.

Insights into the molecular mechanism of dehalogenation catalyzed by D-2-haloacid dehalogenase from crystal structures.

PubMed

Wang, Yayue; Feng, Yanbin; Cao, Xupeng; Liu, Yinghui; Xue, Song

2018-01-23

D-2-haloacid dehalogenases (D-DEXs) catalyse the hydrolytic dehalogenation of D-2-haloacids, releasing halide ions and producing the corresponding 2-hydroxyacids. A structure-guided elucidation of the catalytic mechanism of this dehalogenation reaction has not been reported yet. Here, we report the catalytic mechanism of a D-DEX, HadD AJ1 from Pseudomonas putida AJ1/23, which was elucidated by X-ray crystallographic analysis and the H 2 18 O incorporation experiment. HadD AJ1 is an α-helical hydrolase that forms a homotetramer with its monomer including two structurally axisymmetric repeats. The product-bound complex structure was trapped with L-lactic acid in the active site, which is framed by the structurally related helices between two repeats. Site-directed mutagenesis confirmed the importance of the residues lining the binding pocket in stabilizing the enzyme-substrate complex. Asp205 acts as a key catalytic residue and is responsible for activating a water molecule along with Asn131. Then, the hydroxyl group of the water molecule directly attacks the C2 atom of the substrate to release the halogen ion instead of forming an enzyme-substrate ester intermediate as observed in L-2-haloacid dehalogenases. The newly revealed structural and mechanistic information on D-DEX may inspire structure-based mutagenesis to engineer highly efficient haloacid dehalogenases.

Synthesis and visible-light-induced catalytic activity of Ag2S-coupled TiO2 nanoparticles and nanowires

NASA Astrophysics Data System (ADS)

Xie, Yi; Heo, Sung Hwan; Kim, Yong Nam; Yoo, Seung Hwa; Cho, Sung Oh

2010-01-01

We present the synthesis and visible-light-induced catalytic activity of Ag2S-coupled TiO2 nanoparticles (NPs) and TiO2 nanowires (NWs). Through a simple wet chemical process from a mixture of peroxo titanic acid (PTA) solution, thiourea and AgAc, a composite of Ag2S NPs and TiO2 NPs with sizes of less than 7 nm was formed. When the NP composite was further treated with NaOH solution followed by annealing at ambient conditions, a new nanocomposite material comprising Ag2S NPs on TiO2 NWs was created. Due to the coupling with such a low bandgap material as Ag2S, the TiO2 nanocomposites could have a visible-light absorption capability much higher than that of pure TiO2. As a result, the synthesized Ag2S/TiO2 nanocomposites exhibited much higher catalytic efficiency for the decomposition of methyl orange than commercial TiO2 (Degussa P25, Germany) under visible light.

Synthesis of a Ni2P/Ni12P5 bi-phase nanocomposite for the efficient catalytic reduction of 4-nitrophenol based on the unique n-n heterojunction effects.

PubMed

Tian, Feng-Yu; Hou, Dongfang; Zhang, Wei-Min; Qiao, Xiu-Qing; Li, Dong-Sheng

2017-10-24

A novel heterostructure catalyst of Ni 2 P/Ni 12 P 5 has been fabricated through a simple solvothermal method by modifying the molar ratio of the initial raw materials. The products are characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). It is found that the two phases, Ni 2 P and Ni 12 P 5 , are interlaced with one another in the as-formed nanocomposite, resulting in more interfaces. The bi-phase catalyst exhibits a markedly enhanced catalytic activity in the reduction of 4-nitrophenol, as compared to that of single Ni 2 P or Ni 12 P 5 . The enhanced catalytic activity can be attributed to the unique n-n series effects, which result in the increased ease of electron transfer over the Ni 2 P/Ni 12 P 5 bi-phase catalyst.

Multienzyme kinetics and sequential metabolism.

PubMed

Wienkers, Larry C; Rock, Brooke

2014-01-01

Enzymes are the catalysts of biological systems and are extremely efficient. A typical enzyme accelerates the rate of a reaction by factors of at least a million compared to the rate of the same reaction in the absence of the enzyme. In contrast to traditional catalytic enzymes, the family of cytochrome P450 (CYP) enzymes are catalytically promiscuous, and thus they possess remarkable versatility in substrates. The great diversity of reactions catalyzed by CYP enzymes appears to be based on two unique properties of these heme proteins, the ability of their iron to exist under multiple oxidation states with different reactivities and a flexible active site that can accommodate a wide variety of substrates. Herein is a discussion of two distinct types of kinetics observed with CYP enzymes. The first example is of CYP complex kinetic profiles when multiple CYP enzymes form the sample product. The second is sequential metabolism, in other words, the formation of multiple products from one CYP enzyme. Given the degree of CYP enzyme promiscuity, it is hardly surprising that there is also a high degree of complex kinetic profiles generated during the catalytic cycle.

Dynamics of the active site loops in catalyzing aminoacylation reaction in seryl and histidyl tRNA synthetases.

PubMed

Dutta, Saheb; Kundu, Soumya; Saha, Amrita; Nandi, Nilashis

2018-03-01

Aminoacylation reaction is the first step of protein biosynthesis. The catalytic reorganization at the active site of aminoacyl tRNA synthetases (aaRSs) is driven by the loop motions. There remain lacunae of understanding concerning the catalytic loop dynamics in aaRSs. We analyzed the functional loop dynamics in seryl tRNA synthetase from Methanopyrus kandleri ( mk SerRS) and histidyl tRNA synthetases from Thermus thermophilus ( tt HisRS), respectively, using molecular dynamics. Results confirm that the motif 2 loop and other active site loops are flexible spots within the catalytic domain. Catalytic residues of the loops form a network of interaction with the substrates to form a reactive state. The loops undergo transitions between closed state and open state and the relaxation of the constituent residues occurs in femtosecond to nanosecond time scale. Order parameters are higher for constituent catalytic residues which form a specific network of interaction with the substrates to form a reactive state compared to the Gly residues within the loop. The development of interaction is supported from mutation studies where the catalytic domain with mutated loop exhibits unfavorable binding energy with the substrates. During the open-close motion of the loops, the catalytic residues make relaxation by ultrafast librational motion as well as fast diffusive motion and subsequently relax rather slowly via slower diffusive motion. The Gly residues act as a hinge to facilitate the loop closing and opening by their faster relaxation behavior. The role of bound water is analyzed by comparing implicit solvent-based and explicit solvent-based simulations. Loops fail to form catalytically competent geometry in absence of water. The present result, for the first time reveals the nature of the active site loop dynamics in aaRS and their influence on catalysis.

Metal-organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations.

PubMed

Chughtai, Adeel H; Ahmad, Nazir; Younus, Hussein A; Laypkov, A; Verpoort, Francis

2015-10-07

Novel catalytic materials are highly demanded to perform a variety of catalytic organic reactions. MOFs combine the benefits of heterogeneous catalysis like easy post reaction separation, catalyst reusability, high stability and homogeneous catalysis such as high efficiency, selectivity, controllability and mild reaction conditions. The possible organization of active centers like metallic nodes, organic linkers, and their chemical synthetic functionalization on the nanoscale shows potential to build up MOFs particularly modified for catalytic challenges. In this review, we have summarized the recent research progress in heterogeneous catalysis by MOFs and their catalytic behavior in various organic reactions, highlighting the key features of MOFs as catalysts based on the active sites in the framework. Examples of their post functionalization, inclusion of active guest species and metal nanoparticles have been discussed. Finally, the use of MOFs as catalysts for asymmetric heterogeneous catalysis and stability of MOFs has been presented as separate sections.

Advanced treatment of biologically pretreated coal gasification wastewater by a novel integration of heterogeneous catalytic ozonation and biological process.

PubMed

Zhuang, Haifeng; Han, Hongjun; Jia, Shengyong; Hou, Baolin; Zhao, Qian

2014-08-01

Advanced treatment of biologically pretreated coal gasification wastewater (CGW) was investigated employing heterogeneous catalytic ozonation integrated with anoxic moving bed biofilm reactor (ANMBBR) and biological aerated filter (BAF) process. The results indicated that catalytic ozonation with the prepared catalyst (i.e. MnOx/SBAC, sewage sludge was converted into sludge based activated carbon (SBAC) which loaded manganese oxides) significantly enhanced performance of pollutants removal by generated hydroxyl radicals. The effluent of catalytic ozonation process was more biodegradable and less toxic than that in ozonation alone. Meanwhile, ANMBBR-BAF showed efficient capacity of pollutants removal in treatment of the effluent of catalytic ozonation at a shorter reaction time, allowing the discharge limits to be met. Therefore, the integrated process with efficient, economical and sustainable advantages was suitable for advanced treatment of real biologically pretreated CGW. Copyright © 2014 Elsevier Ltd. All rights reserved.

Fabrication of reduced graphene oxide/macrocyclic cobalt complex nanocomposites as counter electrodes for Pt-free dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Tsai, Chih-Hung; Shih, Chun-Jyun; Wang, Wun-Shiuan; Chi, Wen-Feng; Huang, Wei-Chih; Hu, Yu-Chung; Yu, Yuan-Hsiang

2018-03-01

In this study, macrocyclic Co complexes were successfully grafted onto graphene oxide (GO) to produce GO/Co nanocomposites with a large surface area, high electrical conductivity, and excellent catalytic properties. The novel GO/Co nanocomposites were applied as counter electrodes for Pt-free dye-sensitized solar cells (DSSCs). Various ratios of macrocyclic Co complexes were used as the reductant to react with the GO, with which the surface functional groups of the GO were reduced and the macrocyclic ligand of the Co complexes underwent oxidative dehydrogenation, after which the conjugated macrocyclic Co systems were grafted onto the surface of the reduced GO to form GO/Co nanocomposites. The surface morphology, material structure, and composition of the GO/Co composites and their influences on the power-conversion efficiency of DSSC devices were comprehensively investigated. The results showed that the GO/Co (1:10) counter electrode (CE) exhibited an optimal power conversion efficiency of 7.48%, which was higher than that of the Pt CE. The GO/Co (1:10) CE exhibited superior electric conductivity, catalytic capacity, and redox capacity. Because GO/Co (1:10) CEs are more efficient and cheaper than Pt CEs, they could potentially be used as a replacement for Pt electrodes.

Charge transfer mechanism in titanium-doped microporous silica for photocatalytic water-splitting applications

DOE PAGES

Sapp, Wendi; Koodali, Ranjit; Kilin, Dmitri

2016-02-29

Solar energy conversion into chemical form is possible using artificial means. One example of a highly-efficient fuel is solar energy used to split water into oxygen and hydrogen. Efficient photocatalytic water-splitting remains an open challenge for researchers across the globe. Despite significant progress, several aspects of the reaction, including the charge transfer mechanism, are not fully clear. Density functional theory combined with density matrix equations of motion were used to identify and characterize the charge transfer mechanism involved in the dissociation of water. A simulated porous silica substrate, using periodic boundary conditions, with Ti 4+ ions embedded on the innermore » pore wall was found to contain electron and hole trap states that could facilitate a chemical reaction. A trap state was located within the silica substrate that lengthened relaxation time, which may favor a chemical reaction. A chemical reaction would have to occur within the window of photoexcitation; therefore, the existence of a trapping state may encourage a chemical reaction. Furthermore, this provides evidence that the silica substrate plays an integral part in the electron/hole dynamics of the system, leading to the conclusion that both components (photoactive materials and support) of heterogeneous catalytic systems are important in optimization of catalytic efficiency.« less

Allene formation by gold catalyzed cross-coupling of masked carbenes and vinylidenes

PubMed Central

Lavallo, Vincent; Frey, Guido D.; Kousar, Shazia; Donnadieu, Bruno; Bertrand, Guy

2007-01-01

Addition of a sterically demanding cyclic (alkyl)(amino)carbene (CAAC) to AuCl(SMe2) followed by treatment with [Et3Si(Tol)]+[B(C6F5)4]− in toluene affords the isolable [(CAAC)Au(η2-toluene)]+[B(C6F5)4]− complex. This cationic Au(I) complex efficiently mediates the catalytic coupling of enamines and terminal alkynes to yield allenes and not propargyl amines as observed with other catalysts. Mono-, di-, and tri-substituted enamines can be used, as well as aryl-, alkyl-, and trimethylsilyl-substituted terminal alkynes. The reaction tolerates sterically hindered substrates and is diastereoselective. This general catalytic protocol directly couples two unsaturated carbon centers to form the three-carbon allenic core. The reaction most probably proceeds through an unprecedented “carbene/vinylidene cross-coupling.” PMID:17698808

Cellulosic Biomass Sugars to Advantage Jet Fuel: Catalytic Conversion of Corn Stover to Energy Dense, Low Freeze Point Paraffins and Naphthenes: Cooperative Research and Development Final Report, CRADA Number CRD-12-462

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elander, Rick

NREL will provide scientific and engineering support to Virent Energy Systems in three technical areas: Process Development/Biomass Deconstruction; Catalyst Fundamentals; and Technoeconomic Analysis. The overarching objective of this project is to develop the first fully integrated process that can convert a lignocellulosic feedstock (e.g., corn stover) efficiently and cost effectively to a mix of hydrocarbons ideally suited for blending into jet fuel. The proposed project will investigate the integration of Virent Energy System’s novel aqueous phase reforming (APR) catalytic conversion technology (BioForming®) with deconstruction technologies being investigated by NREL at the 1-500L scale. Corn stover was chosen as a representativemore » large volume, sustainable feedstock.« less

Chemically-modified cellulose paper as a microstructured catalytic reactor.

PubMed

Koga, Hirotaka; Kitaoka, Takuya; Isogai, Akira

2015-01-15

We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

Controlled evolution of an RNA enzyme

NASA Technical Reports Server (NTRS)

Joyce, G. F.

1991-01-01

It is generally thought that prior to the origin of protein synthesis, life on earth was based on self-replicating RNA molecules. This idea has become especially popular recently due to the discovery of catalytic RNA (ribozymes). RNA has both genotypic and phenotypic properties, suggesting that it is capable of undergoing Darwinian evolution. RNA evolution is likely to have played a critical role in the early history of life on earth, and thus is important in considering the possibility of life elsewhere in the solar system. We have constructed an RNA-based evolving system in the laboratory, combining amplification and mutation of an RNA genotype with selection of a corresponding RNA phenotype. This system serves as a functional model of a primitive organism. It can also be used as a tool to explore the catalytic potential of RNA. By altering the selection constraints, we are attempting to modify the substrate specificity of an existing ribozyme in order to develop ribozymes with novel catalytic function. In this way, we hope to gain a better understanding of RNA's catalytic versatility and to assess its suitability for the role of primordial catalyst. All of the RNA enzymes that are known to exist in contemporary biology carry out cleavage/ligation reactions involving RNA substrates. The Tetrahymena ribozyme, for example, catalyzes phosphoester transfer between a guanosine containing and an oligopyrimidine containing substrate. We tested the ability of mutant forms of the Tetrahymena ribozyme to carry out a comparable reaction using DNA, rather than RNA substrate. An ensemble of structural variants of the ribozyme was prepared and tested for their ability to specifically cleave d(GGCCCTCT-A3TA3TA) at the phosphodiester bond following the sequence CCCTCT. We recovered a mutant form of the enzyme that cleaves DNA more efficiently than does the wild-type. Beginning with this selected mutant we have now scattered random mutations throughout the ribozyme and have begun an evolutionary search to further expand the catalytic repertoire of RNA.

New Insights into the Role of T3 Loop in Determining Catalytic Efficiency of GH28 Endo-Polygalacturonases

PubMed Central

Tu, Tao; Meng, Kun; Luo, Huiying; Turunen, Ossi; Zhang, Lujia; Cheng, Yanli; Su, Xiaoyun; Ma, Rui; Shi, Pengjun; Wang, Yaru; Yang, Peilong; Yao, Bin

2015-01-01

Intramolecular mobility and conformational changes of flexible loops have important roles in the structural and functional integrity of proteins. The Achaetomium sp. Xz8 endo-polygalacturonase (PG8fn) of glycoside hydrolase (GH) family 28 is distinguished for its high catalytic activity (28,000 U/mg). Structure modeling indicated that PG8fn has a flexible T3 loop that folds partly above the substrate in the active site, and forms a hydrogen bond to the substrate by a highly conserved residue Asn94 in the active site cleft. Our research investigates the catalytic roles of Asn94 in T3 loop which is located above the catalytic residues on one side of the substrate. Molecular dynamics simulation performed on the mutant N94A revealed the loss of the hydrogen bond formed by the hydroxyl group at O34 of pentagalacturonic acid and the crucial ND2 of Asn94 and the consequent detachment and rotation of the substrate away from the active site, and that on N94Q caused the substrate to drift away from its place due to the longer side chain. In line with the simulations, site-directed mutagenesis at this site showed that this position is very sensitive to amino acid substitutions. Except for the altered K m values from 0.32 (wild type PG8fn) to 0.75–4.74 mg/ml, all mutants displayed remarkably lowered k cat (~3–20,000 fold) and k cat/K m (~8–187,500 fold) values and significantly increased △(△G) values (5.92–33.47 kJ/mol). Taken together, Asn94 in the GH28 T3 loop has a critical role in positioning the substrate in a correct way close to the catalytic residues. PMID:26327390

Switchable Hydrolase Based on Reversible Formation of Supramolecular Catalytic Site Using a Self-Assembling Peptide.

PubMed

Zhang, Chunqiu; Shafi, Ramim; Lampel, Ayala; MacPherson, Douglas; Pappas, Charalampos G; Narang, Vishal; Wang, Tong; Maldarelli, Charles; Ulijn, Rein V

2017-11-13

The reversible regulation of catalytic activity is a feature found in natural enzymes which is not commonly observed in artificial catalytic systems. Here, we fabricate an artificial hydrolase with pH-switchable activity, achieved by introducing a catalytic histidine residue at the terminus of a pH-responsive peptide. The peptide exhibits a conformational transition from random coil to β-sheet by changing the pH from acidic to alkaline. The β-sheet self-assembles to form long fibrils with the hydrophobic edge and histidine residues extending in an ordered array as the catalytic microenvironment, which shows significant esterase activity. Catalytic activity can be reversible switched by pH-induced assembly/disassembly of the fibrils into random coils. At higher concentrations, the peptide forms a hydrogel which is also catalytically active and maintains its reversible (de-)activation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coordinated activities of wild-type plus mutant EZH2 drive tumor-associated hypertrimethylation of lysine 27 on histone H3 (H3K27) in human B-cell lymphomas.

PubMed

Sneeringer, Christopher J; Scott, Margaret Porter; Kuntz, Kevin W; Knutson, Sarah K; Pollock, Roy M; Richon, Victoria M; Copeland, Robert A

2010-12-07

EZH2, the catalytic subunit of the PRC2 complex, catalyzes the mono- through trimethylation of lysine 27 on histone H3 (H3K27). Histone H3K27 trimethylation is a mechanism for suppressing transcription of specific genes that are proximal to the site of histone modification. Point mutations of the EZH2 gene (Tyr641) have been reported to be linked to subsets of human B-cell lymphoma. The mutant allele is always found associated with a wild-type allele (heterozygous) in disease cells, and the mutations were reported to ablate the enzymatic activity of the PRC2 complex for methylating an unmodified peptide substrate. Here we demonstrate that the WT enzyme displays greatest catalytic efficiency (k(cat)/K) for the zero to monomethylation reaction of H3K27 and diminished efficiency for subsequent (mono- to di- and di- to trimethylation) reactions. In stark contrast, the disease-associated Y641 mutations display very limited ability to perform the first methylation reaction, but have enhanced catalytic efficiency for the subsequent reactions, relative to the WT enzyme. These results imply that the malignant phenotype of disease requires the combined activities of a H3K27 monomethylating enzyme (PRC2 containing WT EZH2 or EZH1) together with the mutant PRC2s for augmented conversion of H3K27 to the trimethylated form. To our knowledge, this is the first example of a human disease that is dependent on the coordinated activities of normal and disease-associated mutant enzymatic function.

Graphene as a thin-film catalyst booster: graphene-catalyst interface plays a critical role.

PubMed

Chae, Sieun; Jin Choi, Won; Sang Chae, Soo; Jang, Seunghun; Chang, Hyunju; Lee, Tae Il; Kim, Youn Sang; Lee, Jeong-O

2017-12-08

Due to its extreme thinness, graphene can transmit some surface properties of its underlying substrate, a phenomenon referred to as graphene transparency. Here we demonstrate the application of the transparency of graphene as a protector of thin-film catalysts and a booster of their catalytic efficiency. The photocatalytic degradation of dye molecules by ZnO thin films was chosen as a model system. A ZnO thin film coated with monolayer graphene showed greater catalytic efficiency and long-term stability than did bare ZnO. Interestingly, we found the catalytic efficiency of the graphene-coated ZnO thin film to depend critically on the nature of the bottom ZnO layer; graphene transferred to a relatively rough, sputter-coated ZnO thin film showed rather poor catalytic degradation of the dye molecules while a smooth sol-gel-synthesized ZnO covered with monolayer graphene showed enhanced catalytic degradation. Based on a systematic investigation of the interface between graphene and ZnO thin films, we concluded the transparency of graphene to be critically dependent on its interface with a supporting substrate. Graphene supported on an atomically flat substrate was found to efficiently transmit the properties of the substrate, but graphene suspended on a substrate with a rough nanoscale topography was completely opaque to the substrate properties. Our experimental observations revealed the morphology of the substrate to be a key factor affecting the transparency of graphene, and should be taken into account in order to optimally apply graphene as a protector of catalytic thin films and a booster of their catalysis.

Formation of alcohol conversion catalysts

DOEpatents

Wachs, Israel E.; Cai, Yeping

2001-01-01

The method of the present invention involves a composition containing an intimate mixture of (a) metal oxide support particles and (b) a catalytically active metal oxide from Groups VA, VIA, or VIIA, its method of manufacture, and its method of use for converting alcohols to aldehydes. During the conversion process, catalytically active metal oxide from the discrete catalytic metal oxide particles migrates to the oxide support particles and forms a monolayer of catalytically active metal oxide on the oxide support particle to form a catalyst composition having a higher specific activity than the admixed particle composition.

Carbon nanotube aerogel-CoS2 hybrid catalytic counter electrodes for enhanced photovoltaic performance dye-sensitized solar cells.

PubMed

Liu, Tao; Mai, Xianmin; Chen, Haijun; Ren, Jing; Liu, Zheting; Li, Yingxiang; Gao, Lina; Wang, Ning; Zhang, Jiaoxia; He, Hongcai; Guo, Zhanhu

2018-03-01

The carbon nanotube aerogel (CNA) with an ultra-low density, three-dimensional network nanostructure, superior electronic conductivity and large surface area is being widely employed as a catalytic electrode and catalytic support. Impressively, dye-sensitized solar cells (DSSCs) assembled with a CNA counter electrode (CE) achieved a maximum power conversion efficiency (PCE) of 8.28%, which exceeded that of the conventional platinum (Pt)-based DSSC (7.20%) under the same conditions. Furthermore, highly dispersed CoS 2 nanoparticles endowed with excellent intrinsic catalytic activity were hydrothermally incorporated to form a CNA-supported CoS 2 (CNA-CoS 2 ) CE, which was due to the large number of catalytically active sites and sufficient connections between CoS 2 and the CNA. The electrocatalytic ability and stability were systematically evaluated by cyclic voltammetry (CV), electrochemical impedance spectra (EIS) and Tafel polarization, which confirmed that the resultant CNA-CoS 2 hybrid CE exhibited a remarkably higher electrocatalytic activity toward I 3 - reduction, and faster ion diffusion and electron transfer than the pure CNA CE. Such cost-effective DSSCs assembled with an optimized CNA-CoS 2 CE yielded an enhanced PCE of 8.92%, comparable to that of the cell fabricated with the CNA-Pt hybrid CE reported in our published literature (9.04%). These results indicate that the CNA-CoS 2 CE can be considered as a promising candidate for Pt-free CEs used in low-cost and high-performance DSSCs.

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric

Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalyticmore » system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.« less

Silica-Protection-Assisted Encapsulation of Cu2 O Nanocubes into a Metal-Organic Framework (ZIF-8) To Provide a Composite Catalyst.

PubMed

Li, Bo; Ma, Jian-Gong; Cheng, Peng

2018-06-04

The integration of metal/metal oxide nanoparticles (NPs) into metal-organic frameworks (MOFs) to form composite materials has attracted great interest due to the broad range of applications. However, to date, it has not been possible to encapsulate metastable NPs with high catalytic activity into MOFs, due to their instability during the preparation process. For the first time, we have successfully developed a template protection-sacrifice (TPS) method to encapsulate metastable NPs such as Cu 2 O into MOFs. SiO 2 was used as both a protective shell for Cu 2 O nanocubes and a sacrificial template for forming a yolk-shell structure. The obtained Cu 2 O@ZIF-8 composite exhibits excellent cycle stability in the catalytic hydrogenation of 4-nitrophenol with high activity. This is the first report of a Cu 2 O@MOF-type composite material. The TPS method provides an efficient strategy for encapsulating unstable active metal/metal oxide NPs into MOFs or maybe other porous materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An alternative synthetic approach for efficient catalytic conversion of syngas to ethanol.

PubMed

Yue, Hairong; Ma, Xinbin; Gong, Jinlong

2014-05-20

Ethanol is an attractive end product and a versatile feedstock because a widespread market exists for its commercial use as a fuel additive or a potential substitute for gasoline. Currently, ethanol is produced primarily by fermentation of biomass-derived sugars, particularly those containing six carbons, but coproducts 5-carbon sugars and lignin remain unusable. Another major process for commercial production of ethanol is hydration of ethylene over solid acidic catalysts, yet not sustainable considering the depletion of fossil fuels. Catalytic conversion of synthetic gas (CO + H2) could produce ethanol in large quantities. However, the direct catalytic conversion of synthetic gas to ethanol remains challenging, and no commercial process exists as of today although the research has been ongoing for the past 90 years, since such the process suffers from low yield and poor selectivity due to slow kinetics of the initial C-C bond formation and fast chain growth of the C2 intermediates. This Account describes recent developments in an alternative approach for the synthesis of ethanol via synthetic gas. This process is an integrated technology consisting of the coupling of CO with methanol to form dimethyl oxalate and the subsequent hydrogenation to yield ethanol. The byproduct of the second step (methanol) can be separated and used in circulation as the feedstock for the coupling step. The coupling reaction of carbon monoxide for producing dimethyl oxalate takes place under moderate reaction conditions with high selectivity (∼95%), which ideally leads to a self-closing, nonwaste, catalytic cycling process. This Account also summarizes the progress on the development of copper-based catalysts for the hydrogenation reaction with remarkable efficiencies and stability. The unique lamellar structure and the cooperative effect between surface Cu(0) and Cu(+) species are responsible for the activity of the catalyst with high yield of ethanol (∼91%). The understanding of nature of valence states of Cu could also guide the rational design of Cu-based catalysts for other similar reactions, particularly for hydrogenation catalytic systems. In addition, by regulating the reaction condition and the surface structure of the catalysts, the products in the hydrogenation steps, such as ethanol, methyl glycolate, and ethylene glycol, could be tuned efficiently. This synthetic approach enables a more sustainable ethanol, methyl glycolate, and ethylene glycol synthesis in industry and greatly reduces the dependence on petroleum resources and the emission of the greenhouse gas.

Catalytic Oxidation of Hydroquinone in Aqueous Solution over Bimetallic PdCo Catalyst Supported on Carbon: Effect of Interferents and Electrochemical Measurement.

PubMed

Ye, Weichun; Shi, Xuezhao; Zhang, Yane; Hong, Chenghui; Wang, Chunming; Budzianowski, Wojciech M; Xue, Desheng

2016-02-10

Palladium-cobalt alloy nanoparticles were synthesized and dispersed on carbon black support, aiming to have a less expensive catalyst. Catalytic behaviors of PdCo/C catalyst for the oxidation of hydroquinone (HQ) with H2O2 in aqueous solution were evaluated using high-performance liquid chromatography (HPLC). The results revealed that PdCo/C catalyst had better catalytic activity than an equal amount of commercial Pd/C and Co/C catalysts because of the d-band hybridization between Pd and Co. The effects of pH value, solvent, and various interferents including inorganic and organic compounds on the efficiency of HQ oxidation were further investigated. Furthermore, on the basis of mixed potential theory, comprehensive electrochemical measurements such as the open-circuit potential-time (OCP-t) technique and Tafel plot were efficient to assess the catalytic activity of the catalyst, and the results obtained were consistent with those of HPLC measurements. The efficient HQ oxidation was closely associated with the catalytic activity of PdCo nanoparticles because they accelerated the electron-transfer process and facilitated the generation of OH radicals.

Expanding the substrate scope of chitooligosaccharide oxidase from Fusarium graminearum by structure-inspired mutagenesis.

PubMed

Ferrari, Alessandro R; Lee, Misun; Fraaije, Marco W

2015-06-01

Chitooligosaccharide oxidase from Fusarium graminearum (ChitO) oxidizes N-acetyl-D-glucosamine (GlcNAc) and its oligomers with high efficiency at the C1-hydroxyl moiety while it shows poor or no activity with other carbohydrates. By sequence and structural comparison with other known carbohydrate oxidases (glucooligosaccharide oxidase from Acremonium strictum and lactose oxidase from Microdochium nivale) eleven mutants were designed to redirect the catalytic scope of ChitO for improved oxidation of lactose, cellobiose and maltose. The catalytic properties of the most interesting mutants were further improved by combining single mutations. This has resulted in the creation of a set of ChitO variants that display totally different substrate tolerances. One ChitO variant shows a dramatic improvement in catalytic efficiency towards oxidation of glucose, cellobiose, lactose, and maltose. We also describe a ChitO variant with the highest catalytic efficiency in GlcNAc oxidation so far reported in the literature. © 2015 Wiley Periodicals, Inc.

Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

DOEpatents

Chen, Wei-Fu; Iyer, Shweta; Iyer, Shilpa; Sasaki, Kotaro; Muckerman, James T.; Fujita, Etsuko

2017-02-28

A catalytic composition from earth-abundant transition metal salts and biomass is disclosed. A calcined catalytic composition formed from soybean powder and ammonium molybdate is specifically exemplified herein. Methods for making the catalytic composition are disclosed as are electrodes for hydrogen evolution reactions comprising the catalytic composition.

Integration of Photothermal Effect and Heat Insulation to Efficiently Reduce Reaction Temperature of CO2 Hydrogenation.

PubMed

Zhang, Wenbo; Wang, Liangbing; Wang, Kaiwen; Khan, Munir Ullah; Wang, Menglin; Li, Hongliang; Zeng, Jie

2017-02-01

The photothermal effect is applied in CO 2 hydrogenation to reduce the reaction temperature under illumination by encapsulating Pt nanocubes and Au nanocages into a zeolitic imidazolate framework (ZIF-8). Under illumination, the heat generated by the photothermal effect of Au nanocages is mainly insulated in the ZIF-8 to form a localized high-temperature region, thereby improving the catalytic activity of Pt nanocubes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enantioselective Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds.

PubMed

Hari, Durga Prasad; Waser, Jerome

2017-06-28

Enantioselective catalytic methods allowing the addition of both a nucleophile and an electrophile onto diazo compounds give a fast access into important building blocks. Herein, we report the highly enantioselective oxyalkynylation of diazo compounds using ethynylbenziodoxol-(on)e reagents and a simple copper bisoxazoline catalyst. The obtained α-benzoyloxy propargylic esters are useful building blocks, which are difficult to synthesize in enantiopure form using other methods. The obtained products could be efficiently transformed into vicinal diols and α-hydroxy propargylic esters without loss in enantiopurity.

Improvement of the catalytic performance of a Bispora antennata cellulase by replacing the N-terminal semi-barrel structure.

PubMed

Zheng, Fei; Huang, Huoqing; Wang, Xiaoyu; Tu, Tao; Liu, Qiong; Meng, Kun; Wang, Yuan; Su, Xiaoyun; Xie, Xiangming; Luo, Huiying

2016-10-01

The aim of this work was to study the contribution of the N-terminal structure to cellulase catalytic performance. A wild-type cellulase (BaCel5) of glycosyl hydrolase (GH) family 5 from Bispora antennata and two hybrid enzymes (BaCel5(127) and BaCel5(167)) with replacement of the N-terminal (βα)3 (127 residues) or (βα)4 (167 residues)-barrel with the corresponding sequences of TeEgl5A from Talaromyces emersonii were produced in Pichia pastoris and biochemically characterized. BaCel5 exhibited optimal activity at pH 5.0 and 50°C but had low catalytic efficiency (25.4±0.8mLs(-1)mg(-1)). In contrast, BaCel5(127) and BaCel5(167) showed similar enzymatic properties but improved catalytic performance. When using CMC-Na, barley β-glucan, lichenan, and cellooligosaccharides as substrates, BaCel5(127) and BaCel5(167) had increased specific activities and catalytic efficiencies by ∼1.8-6.7-fold and ∼1.0-4.7-fold, respectively. The catalytic efficiency of BaCel5(167) was even higher than that of parental proteins. The underlying mechanism was analyzed by molecular docking and molecular dynamic simulation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Coupling catalytic hydrolysis and oxidation on Mn/TiO2-Al2O3 for HCN removal

NASA Astrophysics Data System (ADS)

Wang, Langlang; Wang, Xueqian; Cheng, Jinhuan; Ning, Ping; Lin, Yilong

2018-05-01

The manganese-modified titania-alumina (Mn/TiO2-Al2O3) catalyst synthesized by sol-gol method was used to remove hydrogen cyanide (HCN) from simulated flue gas. Further, effects of the mass ratios of Ti/Al, Mn loading, calcination temperature, and relative humidity on HCN conversion efficiency and catalytic activity were systematically investigated. The results indicated that the Mn/TiO2-Al2O3 catalyst exhibited significantly enhanced HCN removal efficiency, and the maximum yield of N2 increased to 68.02% without the participation of water vapor. When water vapor was added into the flue gas, the yield of N2 decreased and the formation of NOx was also inhibited. The XRD and XPS results indicated that Mn was mainly present in the form of Mn2+, Mn3+, and Mn4+ on the surface of catalyst and chemisorbed oxygen played a major role in the HCN catalytic oxidation process. The results of DSC-TGA analysis and H2-TPR indicated that the catalyst also exhibited a good thermal and chemical stability. NH3-TPD and CO2-TPD indicated that the surface of the catalyst mainly contained acidic sites. During the reaction, part of NH3 was adsorbed by Brönsted and Lewis acid sites. NH3 adsorbed on Lewis acid sites participated in NH3-SCR, which reduced the amount of NOx produced and resulted in a high N2 yield.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buckpitt, Alan, E-mail: arbuckpitt@ucdavis.edu; Morin, Dexter; Murphy, Shannon

Naphthalene produces species and cell selective injury to respiratory tract epithelial cells of rodents. In these studies we determined the apparent K{sub m}, V{sub max}, and catalytic efficiency (V{sub max}/K{sub m}) for naphthalene metabolism in microsomal preparations from subcompartments of the respiratory tract of rodents and non-human primates. In tissues with high substrate turnover, major metabolites were derived directly from naphthalene oxide with smaller amounts from conjugates of diol epoxide, diepoxide, and 1,2- and 1,4-naphthoquinones. In some tissues, different enzymes with dissimilar K{sub m} and V{sub max} appeared to metabolize naphthalene. The rank order of V{sub max} (rat olfactory epitheliummore » > mouse olfactory epithelium > murine airways ≫ rat airways) correlated well with tissue susceptibility to naphthalene. The V{sub max} in monkey alveolar subcompartment was 2% that in rat nasal olfactory epithelium. Rates of metabolism in nasal compartments of the monkey were low. The catalytic efficiencies of microsomes from known susceptible tissues/subcompartments are 10 and 250 fold higher than in rat airway and monkey alveolar subcompartments, respectively. Although the strong correlations between catalytic efficiencies and tissue susceptibility suggest that non-human primate tissues are unlikely to generate metabolites at a rate sufficient to produce cellular injury, other studies showing high levels of formation of protein adducts support the need for additional studies. - Highlights: • Naphthalene is metabolized with high catalytic efficiency in susceptible tissue. • Naphthalene is metabolized at low catalytic efficiency in non-susceptible tissue. • Respiratory tissues of the non human primate metabolize naphthalene slowly.« less

Tension-Enhanced Hydrogen Evolution Reaction on Vanadium Disulfide Monolayer

NASA Astrophysics Data System (ADS)

Pan, Hui

2016-02-01

Water electrolysis is an efficient way for hydrogen production. Finding efficient, cheap, and eco-friendly electrocatalysts is essential to the development of this technology. In the work, we present a first-principles study on the effects of tension on the hydrogen evolution reaction of a novel electrocatalyst, vanadium disulfide (VS2) monolayer. Two electrocatalytic processes, individual and collective processes, are investigated. We show that the catalytic ability of VS2 monolayer at higher hydrogen coverage can be efficiently improved by escalating tension. We find that the individual process is easier to occur in a wide range of hydrogen coverage and the collective process is possible at a certain hydrogen coverage under the same tension. The best hydrogen evolution reaction with near-zero Gibbs free energy can be achieved by tuning tension. We further show that the change of catalytic activity with tension and hydrogen coverage is induced by the change of free carrier density around the Fermi level, that is, higher carrier density, better catalytic performance. It is expected that tension can be a simple way to improve the catalytic activity, leading to the design of novel electrocatalysts for efficient hydrogen production from water electrolysis.

Removal of elemental mercury by TiO₂doped with WO₃ and V₂O₅ for their photo- and thermo-catalytic removal mechanisms.

PubMed

Shen, Huazhen; Ie, Iau-Ren; Yuan, Chung-Shin; Hung, Chung-Hsuang; Chen, Wei-Hsiang

2016-03-01

The catalytic removal of Hg(0) was investigated to ascertain whether the catalysts could simultaneously possess both thermo- and photo-catalytic reactivity. The immobilized V2O5/TiO2 and WO3/TiO2 catalysts were synthesized by sol-gel method and then coated on the surface of glass beads for catalytic removal of Hg(0). They were also characterized by SEM, BET, XRD, UV-visible, and XPS analysis, and their catalytic reactivity was tested under 100-160 °C under the near-UV irradiation. The results indicated that V2O5/TiO2 solely possessed the thermo-catalytic reactivity while WO3/TiO2 only had photo-catalytic reactivity. Although the synthesis catalytic reactivity has not been found for these catalysts up to date, but compared with TiO2, the removal efficiencies of Hg(0) at 140 and 160 °C were enhanced; particularly, the efficiency was improved from 20 % at 160 °C by TiO2 to nearly 90 % by WO3/TiO2 under the same operating conditions. The effects of doping amount of V2O5 and WO3 were also investigated, and the results showed that 10 % V2O5 and 5 % WO3/TiO2 were the best immobilized catalysts for thermo- and photo-catalytic reactivity, respectively. The effect of different influent concentrations of Hg(0) was demonstrated that the highest concentration of Hg(0) led to the best removal efficiencies for V2O5/TiO2 and WO3/TiO2 at 140 and 160 °C, because high Hg(0) concentration increased the mass transfer rate of Hg(0) toward the surface of catalysts and drove the reaction to proceed. At last, the effect of single gas component on the removal of Hg(0) was also investigated.

Investigation of hybrid plasma-catalytic removal of acetone over CuO/γ-Al2O3 catalysts using response surface method.

PubMed

Zhu, Xinbo; Tu, Xin; Mei, Danhua; Zheng, Chenghang; Zhou, Jinsong; Gao, Xiang; Luo, Zhongyang; Ni, Mingjiang; Cen, Kefa

2016-07-01

In this work, plasma-catalytic removal of low concentrations of acetone over CuO/γ-Al2O3 catalysts was carried out in a cylindrical dielectric barrier discharge (DBD) reactor. The combination of plasma and the CuO/γ-Al2O3 catalysts significantly enhanced the removal efficiency of acetone compared to the plasma process using the pure γ-Al2O3 support, with the 5.0 wt% CuO/γ-Al2O3 catalyst exhibiting the best acetone removal efficiency of 67.9%. Catalyst characterization was carried out to understand the effect the catalyst properties had on the activity of the CuO/γ-Al2O3 catalysts in the plasma-catalytic reaction. The results indicated that the formation of surface oxygen species on the surface of the catalysts was crucial for the oxidation of acetone in the plasma-catalytic reaction. The effects that various operating parameters (discharge power, flow rate and initial concentration of acetone) and the interactions between these parameters had on the performance of the plasma-catalytic removal of acetone over the 5.0 wt% CuO/γ-Al2O3 catalyst were investigated using central composite design (CCD). The significance of the independent variables and their interactions were evaluated by means of the Analysis of Variance (ANOVA). The results showed that the gas flow rate was the most significant factor affecting the removal efficiency of acetone, whilst the initial concentration of acetone played the most important role in determining the energy efficiency of the plasma-catalytic process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Engineering of Helicobacter pylori L-asparaginase: characterization of two functionally distinct groups of mutants.

PubMed

Maggi, Maristella; Chiarelli, Laurent R; Valentini, Giovanna; Scotti, Claudia

2015-01-01

Bacterial L-asparaginases have been used as anti-cancer drugs for over 4 decades though presenting, along with their therapeutic efficacy, several side effects due to their bacterial origin and, seemingly, to their secondary glutaminase activity. Helicobacter pylori type II L-asparaginase possesses interesting features, among which a reduced catalytic efficiency for L-GLN, compared to the drugs presently used in therapy. In the present study, we describe some enzyme variants with catalytic and in vitro cytotoxic activities different from the wild type enzyme. Particularly, replacements on catalytic threonines (T16D and T95E) deplete the enzyme of both its catalytic activities, once more underlining the essential role of such residues. One serendipitous mutant, M121C/T169M, had a preserved efficiency vs L-asparagine but was completely unable to carry out L-glutamine hydrolysis. Interestingly, this variant did not exert any cytotoxic effect on HL-60 cells. The M121C and T169M single mutants had reduced catalytic activities (nearly 2.5- to 4-fold vs wild type enzyme, respectively). Mutant Q63E, endowed with a similar catalytic efficiency versus asparagine and halved glutaminase efficiency with respect to the wild type enzyme, was able to exert a cytotoxic effect comparable to, or higher than, the one of the wild type enzyme when similar asparaginase units were used. These findings may be relevant to determine the role of glutaminase activity of L-asparaginase in the anti-proliferative effect of the drug and to shed light on how to engineer the best asparaginase/glutaminase combination for an ever improved, patients-tailored therapy.

Engineering of Helicobacter pylori L-Asparaginase: Characterization of Two Functionally Distinct Groups of Mutants

PubMed Central

Maggi, Maristella; Chiarelli, Laurent R.; Valentini, Giovanna; Scotti, Claudia

2015-01-01

Bacterial L-asparaginases have been used as anti-cancer drugs for over 4 decades though presenting, along with their therapeutic efficacy, several side effects due to their bacterial origin and, seemingly, to their secondary glutaminase activity. Helicobacter pylori type II L-asparaginase possesses interesting features, among which a reduced catalytic efficiency for L-GLN, compared to the drugs presently used in therapy. In the present study, we describe some enzyme variants with catalytic and in vitro cytotoxic activities different from the wild type enzyme. Particularly, replacements on catalytic threonines (T16D and T95E) deplete the enzyme of both its catalytic activities, once more underlining the essential role of such residues. One serendipitous mutant, M121C/T169M, had a preserved efficiency vs L-asparagine but was completely unable to carry out L-glutamine hydrolysis. Interestingly, this variant did not exert any cytotoxic effect on HL-60 cells. The M121C and T169M single mutants had reduced catalytic activities (nearly 2.5- to 4-fold vs wild type enzyme, respectively). Mutant Q63E, endowed with a similar catalytic efficiency versus asparagine and halved glutaminase efficiency with respect to the wild type enzyme, was able to exert a cytotoxic effect comparable to, or higher than, the one of the wild type enzyme when similar asparaginase units were used. These findings may be relevant to determine the role of glutaminase activity of L-asparaginase in the anti-proliferative effect of the drug and to shed light on how to engineer the best asparaginase/glutaminase combination for an ever improved, patients-tailored therapy. PMID:25664771

Experimentally Dissecting the Origins of Peroxiredoxin Catalysis.

PubMed

Nelson, Kimberly J; Perkins, Arden; Van Swearingen, Amanda E D; Hartman, Steven; Brereton, Andrew E; Parsonage, Derek; Salsbury, Freddie R; Karplus, P Andrew; Poole, Leslie B

2018-03-01

Peroxiredoxins (Prxs) are ubiquitous cysteine-based peroxidases involved in oxidant defense and signal transduction. Despite much study, the precise roles of conserved residues remain poorly defined. In this study, we carried out extensive functional and structural characterization of 10 variants of such residues in a model decameric bacterial Prx. Three active site proximal mutations of Salmonella typhimurium AhpC, T43V, R119A, and E49Q, lowered catalytic efficiency with hydrogen peroxide by 4-5 orders of magnitude, but did not affect reactivity toward their reductant, AhpF. pK a values of the peroxidatic cysteine were also shifted up by 1-1.3 pH units for these and a decamer disruption mutant, T77I. Except for the decamer-stabilizing T77V, all mutations destabilized decamers in the reduced form. In the oxidized form, three mutants-T77V, T43A, and T43S-exhibited stabilized decamers and were more efficiently reduced by AhpF than wild-type AhpC. Crystal structures of most mutants were solved and many showed alterations in stability of the fully folded active site loop. This is the first study of Prx mutants to comprehensively assess the effects of mutations on catalytic activities, the active site cysteine pK a , and the protein structure and oligomeric status. The Arg119 side chain must be properly situated for efficient catalysis, but for other debilitating variants, the functional defects could be explained by structural perturbations and/or associated decamer destabilization rather than direct effects. This underscores the importance of our comprehensive approach. A remarkable new finding was the preference of the reductant for decamers. Antioxid. Redox Signal. 28, 521-536.

Enhanced DNA Sensing via Catalytic Aggregation of Gold Nanoparticles

PubMed Central

Huttanus, Herbert M.; Graugnard, Elton; Yurke, Bernard; Knowlton, William B.; Kuang, Wan; Hughes, William L.; Lee, Jeunghoon

2014-01-01

A catalytic colorimetric detection scheme that incorporates a DNA-based hybridization chain reaction into gold nanoparticles was designed and tested. While direct aggregation forms an inter-particle linkage from only ones target DNA strand, the catalytic aggregation forms multiple linkages from a single target DNA strand. Gold nanoparticles were functionalized with thiol-modified DNA strands capable of undergoing hybridization chain reactions. The changes in their absorption spectra were measured at different times and target concentrations and compared against direct aggregation. Catalytic aggregation showed a multifold increase in sensitivity at low target concentrations when compared to direct aggregation. Gel electrophoresis was performed to compare DNA hybridization reactions in catalytic and direct aggregation schemes, and the product formation was confirmed in the catalytic aggregation scheme at low levels of target concentrations. The catalytic aggregation scheme also showed high target specificity. This application of a DNA reaction network to gold nanoparticle-based colorimetric detection enables highly-sensitive, field-deployable, colorimetric readout systems capable of detecting a variety of biomolecules. PMID:23891867

Study of removal of ammonia from urine vapor by dual catalyst

NASA Technical Reports Server (NTRS)

Budininkas, P.

1976-01-01

The feasibility of ammonia removal from urine vapor by a low temperature dual-catalyst system was investigated. The process is based on the initial catalytic oxidation of ammonia present in urine vapor to nitrogen and nitrous oxide, followed by a catalytic decomposition of the nitrous oxide formed into its elements. The most active catalysts for the oxidation of ammonia and for the decomposition of N2O, identified in screening tests, were then combined into dual catalyst systems and tested to establish their overall efficiencies for the removal of ammonia from artificial gas mixtures. Dual catalyst systems capable of ammonia removal from the artificial gas mixtures were then tested with the actual urine vapor produced by boiling untreated urine. A suitable dual catalyst bed arrangement was found that achieved the removal of ammonia and organic carbon, and recovered water of good quality from urine vapor.

Insights into cellulosome assembly and dynamics: from dissection to reconstruction of the supramolecular enzyme complex.

PubMed

Smith, Steven P; Bayer, Edward A

2013-10-01

Cellulosomes are multi-enzyme complexes produced by anaerobic bacteria for the efficient deconstruction of plant cell wall polysaccharides. The assembly of enzymatic subunits onto a central non-catalytic scaffoldin subunit is mediated by a highly specific interaction between the enzyme-bearing dockerin modules and the resident cohesin modules of the scaffoldin, which affords their catalytic activities to work synergistically. The scaffoldin also imparts substrate-binding and bacterial-anchoring properties, the latter of which involves a second cohesin-dockerin interaction. Recent structure-function studies reveal an ever-growing array of unique and increasingly complex cohesin-dockerin complexes and cellulosomal enzymes with novel activities. A 'build' approach involving multimodular cellulosomal segments has provided a structural model of an organized yet conformationally dynamic supramolecular assembly with the potential to form higher order structures. Copyright © 2013. Published by Elsevier Ltd.

A peptide affinity reagent for isolating an intact and catalytically active multi-protein complex from mammalian cells.

PubMed

Saathoff, Hinnerk; Brofelth, Mattias; Trinh, Anne; Parker, Benjamin L; Ryan, Daniel P; Low, Jason K K; Webb, Sarah R; Silva, Ana P G; Mackay, Joel P; Shepherd, Nicholas E

2015-03-01

We have developed an approach for directly isolating an intact multi-protein chromatin remodeling complex from mammalian cell extracts using synthetic peptide affinity reagent 4. FOG1(1-15), a short peptide sequence known to target subunits of the nucleosome remodeling and deacetylase (NuRD) complex, was joined via a 35-atom hydrophilic linker to the StreptagII peptide. Loading this peptide onto Streptactin beads enabled capture of the intact NuRD complex from MEL cell nuclear extract. Gentle biotin elution yielded the desired intact complex free of significant contaminants and in a form that was catalytically competent in a nucleosome remodeling assay. The efficiency of 4 in isolating the NuRD complex was comparable to other reported methods utilising recombinantly produced GST-FOG1(1-45). Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

The different paths and potential risks of photo(-electro)-catalytic degradation for rhodamine B in water by graphene/TiO2 membrane.

PubMed

Ren, Miao; Liu, Haiyang; Qu, Jiao; Zhang, Yanan; Ma, Ying; Yuan, Xing

2018-03-07

The graphene (GR)/TiO 2 membrane was prepared by the sol-gel method and coated on the indium tin oxide (ITO) conductive glass, which showed high and stable photo(-electro)-catalytic activities to rhodamine B (Rh-B) in water. Characterization results showed that the GR was dispersed and wrapped in the needle-like TiO 2 . With GR/TiO 2 membrane and simulated sunlight irradiation, the removal efficiency of Rh-B (10 mg l -1 and pH at 5.4) arrived at 87.6% within 300 min. However, the higher removal efficiency for Rh-B reached to 97.8% by the photo-electro-catalytic degradation with the applied voltage 4 v for 30 min. The ·OH that generated in the photo-catalytic degradation process were responsible for Rh-B decomposition. The ·O 2 - played the significant role in the photo-electro-catalytic degradation of Rh-B. Furthermore, the decarboxylation was also occurred in the photo-electro-catalytic degradation for the Rh-B in water except for the deethylation and hydroxylation in the photo-catalytic degradation. In addition, the toxicities of the intermediates were calculated using the ECOSAR program and the EPIWIN software. The results indicated that the toxicities of intermediates from photo-electro-catalytic degradation for the Rh-B were higher than photo-catalytic degradation, due to the generation of decarboxylate.

Influence of active site location on catalytic activity in de novo-designed zinc metalloenzymes.

PubMed

Zastrow, Melissa L; Pecoraro, Vincent L

2013-04-17

While metalloprotein design has now yielded a number of successful metal-bound and even catalytically active constructs, the question of where to put a metal site along a linear, repetitive sequence has not been thoroughly addressed. Often several possibilities in a given sequence may exist that would appear equivalent but may in fact differ for metal affinity, substrate access, or protein dynamics. We present a systematic variation of active site location for a hydrolytically active ZnHis3O site contained within a de novo-designed three-stranded coiled coil. We find that the maximal rate, substrate access, and metal-binding affinity are dependent on the selected position, while catalytic efficiency for p-nitrophenyl acetate hydrolysis can be retained regardless of the location of the active site. This achievement demonstrates how efficient, tailor-made enzymes which control rate, pKa, substrate and solvent access (and selectivity), and metal-binding affinity may be realized. These findings may be applied to the more advanced de novo design of constructs containing secondary interactions, such as hydrogen-bonding channels. We are now confident that changes to location for accommodating such channels can be achieved without location-dependent loss of catalytic efficiency. These findings bring us closer to our ultimate goal of incorporating the secondary interactions we believe will be necessary in order to improve both active site properties and the catalytic efficiency to be competitive with the native enzyme, carbonic anhydrase.

Surface Catalytic Efficiency of Advanced Carbon Carbon Candidate Thermal Protection Materials for SSTO Vehicles

NASA Technical Reports Server (NTRS)

Stewart, David A.

1996-01-01

The catalytic efficiency (atom recombination coefficients) for advanced ceramic thermal protection systems was calculated using arc-jet data. Coefficients for both oxygen and nitrogen atom recombination on the surfaces of these systems were obtained to temperatures of 1650 K. Optical and chemical stability of the candidate systems to the high energy hypersonic flow was also demonstrated during these tests.

Very Green Photosynthesis of Gold Nanoparticles by a Living Aquatic Plant: Photoreduction of AuIII by the Seaweed Ulva armoricana.

PubMed

Mukhoro, Ofhani C; Roos, Wiets D; Jaffer, Mohammed; Bolton, John J; Stillman, Martin J; Beukes, Denzil R; Antunes, Edith

2018-02-01

Light-assisted in vivo synthesis of gold nanoparticles (NPs) from aqueous solutions of dilute Au III salts by a living green marine seaweed (Ulva armoricana) is reported for the first time. NPs synthesised using typical procedures have many associated environmental hazards. The reported methods involve green, nontoxic, eco-friendly synthetic procedures. The formation of AuNPs was extremely rapid (≈15 min) following illumination of the living U. armoricana, while the rate of NP formation in the dark was very slow (over 2 weeks). The properties of the AuNPs formed were confirmed using a battery of spectroscopic techniques. U. armoricana were found to be very efficient in Au 0 uptake, and this, together with the rapid formation of AuNPs under illumination, indicated that the seaweed remained living during NP formation. The TEM images supported this, revealing that the thylakoid membranes and cell structure remained intact. The AuNPs formed on the surface of U. armoricana thallus, along the cell walls and in the chloroplasts. Without further workup, the dried, U. armoricana-supported AuNPs were efficient in the catalytic reduction of 4-nitrophenol, demonstrating the completely green cycle of AuNP formation and catalytic activity. The results mean that an aquatic plant growing in water rich in gold salts could bio-accumulate AuNPs from its aquatic environment, simply with the activation of sunlight. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Generating carbyne equivalents with photoredox catalysis

NASA Astrophysics Data System (ADS)

Wang, Zhaofeng; Herraiz, Ana G.; Del Hoyo, Ana M.; Suero, Marcos G.

2018-02-01

Carbon has the unique ability to bind four atoms and form stable tetravalent structures that are prevalent in nature. The lack of one or two valences leads to a set of species—carbocations, carbanions, radicals and carbenes—that is fundamental to our understanding of chemical reactivity. In contrast, the carbyne—a monovalent carbon with three non-bonded electrons—is a relatively unexplored reactive intermediate; the design of reactions involving a carbyne is limited by challenges associated with controlling its extreme reactivity and the lack of efficient sources. Given the innate ability of carbynes to form three new covalent bonds sequentially, we anticipated that a catalytic method of generating carbynes or related stabilized species would allow what we term an ‘assembly point’ disconnection approach for the construction of chiral centres. Here we describe a catalytic strategy that generates diazomethyl radicals as direct equivalents of carbyne species using visible-light photoredox catalysis. The ability of these carbyne equivalents to induce site-selective carbon-hydrogen bond cleavage in aromatic rings enables a useful diazomethylation reaction, which underpins sequencing control for the late-stage assembly-point functionalization of medically relevant agents. Our strategy provides an efficient route to libraries of potentially bioactive molecules through the installation of tailored chiral centres at carbon-hydrogen bonds, while complementing current translational late-stage functionalization processes. Furthermore, we exploit the dual radical and carbene character of the generated carbyne equivalent in the direct transformation of abundant chemical feedstocks into valuable chiral molecules.

WOR5, a Novel Tungsten-Containing Aldehyde Oxidoreductase from Pyrococcus furiosus with a Broad Substrate Specificity

PubMed Central

Bevers, Loes E.; Bol, Emile; Hagedoorn, Peter-Leon; Hagen, Wilfred R.

2005-01-01

WOR5 is the fifth and last member of the family of tungsten-containing oxidoreductases purified from the hyperthermophilic archaeon Pyrococcus furiosus. It is a homodimeric protein (subunit, 65 kDa) that contains one [4Fe-4S] cluster and one tungstobispterin cofactor per subunit. It has a broad substrate specificity with a high affinity for several substituted and nonsubstituted aliphatic and aromatic aldehydes with various chain lengths. The highest catalytic efficiency of WOR5 is found for the oxidation of hexanal (Vmax = 15.6 U/mg, Km = 0.18 mM at 60°C). Hexanal-incubated enzyme exhibits S = 1/2 electron paramagnetic resonance signals from [4Fe-4S]1+ (g values of 2.08, 1.93, and 1.87) and W5+ (g values of 1.977, 1.906, and 1.855). Cyclic voltammetry of ferredoxin and WOR5 on an activated glassy carbon electrode shows a catalytic wave upon addition of hexanal, suggesting that ferredoxin can be a physiological redox partner. The combination of WOR5, formaldehyde oxidoreductase, and aldehyde oxidoreductase forms an efficient catalyst for the oxidation of a broad range of aldehydes in P. furiosus. PMID:16199576

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering.

PubMed

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-09-21

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal-air batteries. Herein, we report the novel system of nickel-aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles.

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering

PubMed Central

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-01-01

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal−air batteries. Herein, we report the novel system of nickel−aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles. PMID:27650532

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering

NASA Astrophysics Data System (ADS)

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-09-01

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal-air batteries. Herein, we report the novel system of nickel-aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles.

Highly enhanced electrochemical activity of Ni foam electrodes decorated with nitrogen-doped carbon nanotubes for non-aqueous redox flow batteries

NASA Astrophysics Data System (ADS)

Lee, Jungkuk; Park, Min-Sik; Kim, Ki Jae

2017-02-01

Nitrogen-doped carbon nanotubes (NCNTs) are directly grown on the surface of a three-dimensional (3D) Ni foam substrate by floating catalytic chemical vapor deposition (FCCVD). The electrochemical properties of the 3D NCNT-Ni foam are thoroughly examined as a potential electrode for non-aqueous redox flow batteries (RFBs). During synthesis, nitrogen atoms can be successfully doped onto the carbon nanotube (CNT) lattices by forming an abundance of nitrogen-based functional groups. The 3D NCNT-Ni foam electrode exhibits excellent electrochemical activities toward the redox reactions of [Fe (bpy)3]2+/3+ (in anolyte) and [Co(bpy)3]+/2+ (in catholyte), which are mainly attributed to the hierarchical 3D structure of the NCNT-Ni foam electrode and the catalytic effect of nitrogen atoms doped onto the CNTs; this leads to faster mass transfer and charge transfer during operation. As a result, the RFB cell assembled with 3D NCNT-Ni foam electrodes exhibits a high energy efficiency of 80.4% in the first cycle; this performance is maintained up to the 50th cycle without efficiency loss.

Metal-Organic Framework-Templated Porous Carbon for Highly Efficient Catalysis: The Critical Role of Pyrrolic Nitrogen Species.

PubMed

Huang, Gang; Yang, Li; Ma, Xiao; Jiang, Jun; Yu, Shu-Hong; Jiang, Hai-Long

2016-03-01

Metal-free catalysts are of great importance and alternative candidates to conventional metal-based catalysts for many reactions. Herein, several types of metal-organic frameworks have been exploited as templates/precursors to afford porous carbon materials with various nitrogen dopant forms and contents, degrees of graphitization, porosities, and surface areas. Amongst these materials, the PCN-224-templated porous carbon material optimized by pyrolysis at 700 °C (denoted as PCN-224-700) is composed of amorphous carbon coated with well-defined graphene layers, offering a high surface area, hierarchical pores, and high nitrogen content (mainly, pyrrolic nitrogen species). Remarkably, as a metal-free catalyst, PCN-224-700 exhibits a low activation energy and superior activity to most metallic catalysts in the catalytic reduction of 4-nitrophenol to 4-aminophenol. Theoretical investigations suggest that the content and type of the nitrogen dopant play crucial roles in determining the catalytic performance and that the pyrrolic nitrogen species makes the dominant contribution to this activity, which explains the excellent efficiency of the PCN-224-700 catalyst well. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A graded catalytic–protective layer for an efficient and stable water-splitting photocathode

DOE PAGES

Gu, Jing; Aguiar, Jeffery A.; Ferrere, Suzanne; ...

2017-01-09

Achieving solar-to-hydrogen efficiencies above 15% is key for the commercial success of photoelectrochemical water splitting devices. While tandem cells can reach those efficiencies, increasing the catalytic activity and long-term stability remains a significant challenge. We show that annealing a bilayer of amorphous titanium dioxide (TiO x) and molybdenum sulfide (MoS x) deposited onto GaInP 2 results in a photocathode with high catalytic activity (current density of 11 mA/cm -2 at 0 V vs. the reversible hydrogen electrode under 1 sun illumination) and stability (retention of 80% of initial photocurrent density over a 20 h durability test) for the hydrogen evolutionmore » reaction. Microscopy and spectroscopy reveal that annealing results in a graded MoS x/MoO x/TiO 2 layer that retains much of the high catalytic activity of amorphous MoS x but with stability similar to crystalline MoS 2. These findings demonstrate the potential of utilizing a hybridized, heterogeneous surface layer as a cost-effective catalytic and protective interface for solar hydrogen production.« less

Cellulose microfibril structure: inspirations from plant diversity

NASA Astrophysics Data System (ADS)

Roberts, A. W.

2018-03-01

Cellulose microfibrils are synthesized at the plasma membrane by cellulose synthase catalytic subunits that associate to form cellulose synthesis complexes. Variation in the organization of these complexes underlies the variation in cellulose microfibril structure among diverse organisms. However, little is known about how the catalytic subunits interact to form complexes with different morphologies. We are using an evolutionary approach to investigate the roles of different catalytic subunit isoforms in organisms that have rosette-type cellulose synthesis complexes.

Highly reusability surface loaded metal particles magnetic catalyst microspheres (MCM-MPs) for treatment of dye-contaminated water

NASA Astrophysics Data System (ADS)

Liu, Ying; Zhang, Kun; Yin, Xiaoshuang; Yang, Wenzhong; Zhu, Hongjun

2016-04-01

The metal-deposited magnetic catalyst microspheres (MCM-MPs) were successfully synthesized by one facile, high yield and controllable approach. Here, the bare magnetic microspheres were firstly synthesized according to the solvothermal method. Then silica shell were coated on the surface of the magnetic microspheres via sol-gel method, and subsequently with surface modifying with amino in the purpose to form SiO2-NH2 shell. Thus, metal particles were easily adsorbed into the SiO2-NH2 shell and in-situ reduced by NaBH4 solution. All the obtained products (MCM-Cu, MCM-Ag, MCM-Pd) which were monodisperse and constitutionally stable were exhibited high magnetization and excellent catalytic activity towards dyes solution reduction. The catalytic rate ratio of MCM-Pd: MCM-Cu: MCM-Ag could be 10:3:1. Besides, some special coordination compound Cu2(OH)3Br had been generated in the in-situ reduced process of MCM-Cu, which produced superior cyclical stability (>20 times) than that of MCM-Ag and MCM-Pd. In all, those highly reusability and great catalytic efficiency of MCM-MPs show promising and great potential for treatment of dye-contaminated water.

Rubisco small subunits from the unicellular green alga Chlamydomonas complement Rubisco-deficient mutants of Arabidopsis.

PubMed

Atkinson, Nicky; Leitão, Nuno; Orr, Douglas J; Meyer, Moritz T; Carmo-Silva, Elizabete; Griffiths, Howard; Smith, Alison M; McCormick, Alistair J

2017-04-01

Introducing components of algal carbon concentrating mechanisms (CCMs) into higher plant chloroplasts could increase photosynthetic productivity. A key component is the Rubisco-containing pyrenoid that is needed to minimise CO 2 retro-diffusion for CCM operating efficiency. Rubisco in Arabidopsis was re-engineered to incorporate sequence elements that are thought to be essential for recruitment of Rubisco to the pyrenoid, namely the algal Rubisco small subunit (SSU, encoded by rbcS) or only the surface-exposed algal SSU α-helices. Leaves of Arabidopsis rbcs mutants expressing 'pyrenoid-competent' chimeric Arabidopsis SSUs containing the SSU α-helices from Chlamydomonas reinhardtii can form hybrid Rubisco complexes with catalytic properties similar to those of native Rubisco, suggesting that the α-helices are catalytically neutral. The growth and photosynthetic performance of complemented Arabidopsis rbcs mutants producing near wild-type levels of the hybrid Rubisco were similar to those of wild-type controls. Arabidopsis rbcs mutants expressing a Chlamydomonas SSU differed from wild-type plants with respect to Rubisco catalysis, photosynthesis and growth. This confirms a role for the SSU in influencing Rubisco catalytic properties. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

[Studies on photo-electron-chemical catalytic degradation of the malachite green].

PubMed

Li, Ming-yu; Diao, Zeng-hui; Song, Lin; Wang, Xin-le; Zhang, Yuan-ming

2010-07-01

A novel two-compartment photo-electro-chemical catalytic reactor was designed. The TiO2/Ti thin film electrode thermally formed was used as photo-anode, and graphite as cathode and a saturated calomel electrode (SCE) as the reference electrode in the reactor. The anode compartment and cathode compartment were connected with the ionic exchange membrane in this reactor. Effects of initial pH, initial concentration of malachite green and connective modes between the anode compartment and cathode compartment on the decolorization efficiency of malachite green were investigated. The degradation dynamics of malachite green was studied. Based on the change of UV-visible light spectrum, the degradation process of malachite green was discussed. The experimental results showed that, during the time of 120 min, the decolouring ratio of the malachite green was 97.7% when initial concentration of malachite green is 30 mg x L(-1) and initial pH is 3.0. The catalytic degradation of malachite green was a pseudo-first order reaction. In the degradation process of malachite green the azo bond cleavage and the conjugated system of malachite green were attacked by hydroxyl radical. Simultaneity, the aromatic ring was oxidized. Finally, malachite green was degraded into other small molecular compounds.

Efficient low-temperature soot combustion by bimetallic Ag-Cu/SBA-15 catalysts.

PubMed

Wen, Zhaojun; Duan, Xinping; Hu, Menglin; Cao, Yanning; Ye, Linmin; Jiang, Lilong; Yuan, Youzhu

2018-02-01

In this study, the effects of copper (Cu) additive on the catalytic performance of Ag/SBA-15 in complete soot combustion were investigated. The soot combustion performance of bimetallic Ag-Cu/SBA-15 catalysts was higher than that of monometallic Ag and Cu catalysts. The optimum catalytic performance was acquired with the 5Ag 1 -Cu 0.1 /SBA-15 catalyst, on which the soot combustion starts at T ig =225°C with a T 50 =285°C. The temperature for 50% of soot combustion was lower than that of conventional Ag-based catalysts to more than 50°C (Aneggi et al., 2009). Physicochemical characterizations of the catalysts indicated that addition of Cu into Ag could form smaller bimetallic Ag-Cu nanolloy particles, downsizing the mean particle size from 3.7nm in monometallic catalyst to 2.6nm in bimetallic Ag-Cu catalyst. Further experiments revealed that Ag and Cu species elicited synergistic effects, subsequently increasing the content of surface active oxygen species. As a result, the structure modifications of Ag by the addition of Cu strongly intensified the catalytic performance. Copyright © 2017. Published by Elsevier B.V.

Catalytic four-electron reduction of O2 via rate-determining proton-coupled electron transfer to a dinuclear cobalt-μ-1,2-peroxo complex.

PubMed

Fukuzumi, Shunichi; Mandal, Sukanta; Mase, Kentaro; Ohkubo, Kei; Park, Hyejin; Benet-Buchholz, Jordi; Nam, Wonwoo; Llobet, Antoni

2012-06-20

Four-electron reduction of O(2) by octamethylferrocene (Me(8)Fc) occurs efficiently with a dinuclear cobalt-μ-1,2-peroxo complex, 1, in the presence of trifluoroacetic acid in acetonitrile. Kinetic investigations of the overall catalytic reaction and each step in the catalytic cycle showed that proton-coupled electron transfer from Me(8)Fc to 1 is the rate-determining step in the catalytic cycle.

Design and Stereoselective Preparation of a New Class of Chiral Olefin Metathesis Catalysts and Application to Enantioselective Synthesis of Quebrachamine: Catalyst Development Inspired by Natural Product Synthesis

PubMed Central

Sattely, Elizabeth S.; Meek, Simon J.; Malcolmson, Steven J.; Schrock, Richard R.; Hoveyda, Amir H.

2010-01-01

A total synthesis of the Aspidosperma alkaloid quebrachamine in racemic form is first described. A key catalytic ring-closing metathesis of an achiral triene is used to establish the all-carbon quaternary stereogenic center and the tetracyclic structure of the natural product; the catalytic transformation proceeds with reasonable efficiency through the use of existing achiral Ru or Mo catalysts. Ru- or Mo-based chiral olefin metathesis catalysts have proven to be inefficient and entirely nonselective in cases where the desired product is observed. In the present study, the synthesis route thus serves as a platform for the discovery of new olefin metathesis catalysts that allow for efficient completion of an enantioselective synthesis of quebrachamine. Accordingly, on the basis of mechanistic principles, stereogenic-at-Mo complexes bearing only monodentate ligands have been designed. The new catalysts provide significantly higher levels of activity than observed with the previously reported Ru- or Mo-based complexes. Enantiomerically enriched chiral alkylidenes are generated through diastereoselective reactions involving achiral Mo-based bispyrrolides and enantiomerically pure silyl-protected binaphthols. Such chiral catalysts initiate the key enantioselective ring-closing metathesis step in the total synthesis of quebrachamine efficiently (1 mol % loading, 22 °C, 1 h, >98% conversion, 84% yield) and with high selectivity (98:2 er, 96% ee). PMID:19113867

Catalytic stereoselective synthesis of highly substituted indanones via tandem Nazarov cyclization and electrophilic fluorination trapping.

PubMed

Nie, Jing; Zhu, Hong-Wei; Cui, Han-Feng; Hua, Ming-Qing; Ma, Jun-An

2007-08-02

A new catalytic stereoselective tandem transformation via Nazarov cyclization/electrophilic fluorination has been accomplished. This sequence is efficiently catalyzed by a Cu(II) complex to afford fluorine-containing 1-indanone derivatives with two new stereocenters with high diastereoselectivity (trans/cis up to 49/1). Three examples of catalytic enantioselective tandem transformation are presented.

Steam reformer with catalytic combustor

DOEpatents

Voecks, Gerald E.

1990-03-20

A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

Steam reformer with catalytic combustor

NASA Technical Reports Server (NTRS)

Voecks, Gerald E. (Inventor)

1990-01-01

A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

Pd-MnO2 nanoparticles/TiO2 nanotube arrays (NTAs) photo-electrodes photo-catalytic properties and their ability of degrading Rhodamine B under visible light.

PubMed

Thabit, Mohamed; Liu, Huiling; Zhang, Jian; Wang, Bing

2017-10-01

Pd-MnO 2 /TiO 2 nanotube arrays (NTAs) photo-electrodes were successfully fabricated via anodization and electro deposition subsequently; the obtained Pd-MnO 2 /TiO 2 NTAs photo electrodes were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and characterized accordingly. Moreover, the light harvesting and absorption properties were investigated via ultraviolet-visible diffuse reflectance spectrum (DRS); photo degradation efficiency was investigated via analyzing the photo catalytic degradation of Rhodamine B under visible illumination (xenon light). The performed analyses illustrated that Pd-MnO 2 codoped particles were successfully deposited onto the surface of the TiO 2 nanotube arrays; DRS results showed significant improvement in visible light absorption which was between 400 and 700nm. Finally, the photo catalytic degradation efficiency results of the designated organic pollutant (Rhodamine B) illustrated a superior photocatalytic (PC) efficiency of approximately 95% compared to the bare TiO 2 NTAs, which only exhibited a photo catalytic degradation efficiency of approximately 61%, thus it indicated the significant enhancement of the light absorption properties of fabricated photo electrodes and their yield of OH radicals. Copyright © 2017. Published by Elsevier B.V.

An efficient system for selectively altering genetic information within mRNAs

PubMed Central

Montiel-González, Maria Fernanda; Vallecillo-Viejo, Isabel C.; Rosenthal, Joshua J. C.

2016-01-01

Site-directed RNA editing (SDRE) is a strategy to precisely alter genetic information within mRNAs. By linking the catalytic domain of the RNA editing enzyme ADAR to an antisense guide RNA, specific adenosines can be converted to inosines, biological mimics for guanosine. Previously, we showed that a genetically encoded iteration of SDRE could target adenosines expressed in human cells, but not efficiently. Here we developed a reporter assay to quantify editing, and used it to improve our strategy. By enhancing the linkage between ADAR's catalytic domain and the guide RNA, and by introducing a mutation in the catalytic domain, the efficiency of converting a UAG premature termination codon (PTC) to tryptophan (UGG) was improved from ∼11 % to ∼70 %. Other PTCs were edited, but less efficiently. Numerous off-target edits were identified in the targeted mRNA, but not in randomly selected endogenous messages. Off-target edits could be eliminated by reducing the amount of guide RNA with a reduction in on-target editing. The catalytic rate of SDRE was compared with those for human ADARs on various substrates and found to be within an order of magnitude of most. These data underscore the promise of site-directed RNA editing as a therapeutic or experimental tool. PMID:27557710

Catalytic Exhaust Gas Recirculation-Loop Reforming for High Efficiency in a Stoichiometric Spark-Ignited Engine through Thermochemical Recuperation and Dilution Limit Extension, Part 2: Engine Performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, Yan; Szybist, James P.; Pihl, Josh A.

This is the second part of a two-part investigation of on-board catalytic fuel reforming to increase the brake efficiency of a multicylinder, stoichiometric spark-ignited (SI) engine. In Part 1 of the investigation, we analytically and experimentally characterized the energetics and kinetics of a candidate reforming catalyst over a range of reforming equivalence ratios and oxygen concentration conditions to identify the best conditions for efficient reforming. In the present part of our investigation, we studied an engine strategy that combined exhaust gas recirculation (EGR)–loop reforming with dilution limit extension of the combustion. In our experiments, we found that, under an enginemore » operating condition of 2000 rpm and brake mean effective pressure (4 bar), catalytic EGR reforming made it possible to sustain stable combustion with a volumetric equivalent of 45%–55% EGR. Under this same operating condition with stoichiometric engine exhaust (and no reforming), we were only able to sustain stable combustion with EGR under 25%. In conclusion, these results indicate that multicylinder gasoline engine efficiency can be increased substantially with catalytic reforming combined with and higher EGR operation, resulting in a decrease of more than 8% in fuel consumption, compared to baseline operation.« less

Catalytic Exhaust Gas Recirculation-Loop Reforming for High Efficiency in a Stoichiometric Spark-Ignited Engine through Thermochemical Recuperation and Dilution Limit Extension, Part 2: Engine Performance

DOE PAGES

Chang, Yan; Szybist, James P.; Pihl, Josh A.; ...

2018-01-17

This is the second part of a two-part investigation of on-board catalytic fuel reforming to increase the brake efficiency of a multicylinder, stoichiometric spark-ignited (SI) engine. In Part 1 of the investigation, we analytically and experimentally characterized the energetics and kinetics of a candidate reforming catalyst over a range of reforming equivalence ratios and oxygen concentration conditions to identify the best conditions for efficient reforming. In the present part of our investigation, we studied an engine strategy that combined exhaust gas recirculation (EGR)–loop reforming with dilution limit extension of the combustion. In our experiments, we found that, under an enginemore » operating condition of 2000 rpm and brake mean effective pressure (4 bar), catalytic EGR reforming made it possible to sustain stable combustion with a volumetric equivalent of 45%–55% EGR. Under this same operating condition with stoichiometric engine exhaust (and no reforming), we were only able to sustain stable combustion with EGR under 25%. In conclusion, these results indicate that multicylinder gasoline engine efficiency can be increased substantially with catalytic reforming combined with and higher EGR operation, resulting in a decrease of more than 8% in fuel consumption, compared to baseline operation.« less

Conformational changes of a chemically modified HRP: formation of a molten globule like structure at pH 5

PubMed Central

Bamdad, Kourosh; Ranjbar, Bijan; Naderi-Manesh, Hossein; Sadeghi, Mehdi

2014-01-01

Horseradish peroxidase is an all alpha-helical enzyme, which widely used in biochemistry applications mainly because of its ability to enhance the weak signals of target molecules. This monomeric heme-containing plant peroxidase is also used as a reagent for the organic synthesis, biotransformation, chemiluminescent assays, immunoassays, bioremediation, and treatment of wastewaters as well. Accordingly, enhancing stability and catalytic activity of this protein for biotechnological uses has been one of the important issues in the field of biological investigations in recent years. In this study, pH-induced structural alterations of native (HRP), and modified (MHRP) forms of Horseradish peroxidase have been investigated. Based on the results, dramatic loss of the tertiary structure and also the enzymatic activity for both forms of enzymes recorded at pH values lower than 6 and higher than 8. Ellipticiy measurements, however, indicated very slight variations in the secondary structure for MHRP at pH 5. Spectroscopic analysis also indicated that melting of the tertiary structure of MHRP at pH 5 starts at around 45 °C, which is associated to the pKa of His 42 that has a serious role in keeping of the heme prostethic group in its native position through natural hydrogen bond network in the enzyme structure. According to our data, a molten globule like structure of a chemically modified form of Horseradish peroxidase at pH 5 with initial steps of conformational transition in tertiary structure with almost no changes in the secondary structure has been detected. Despite of some conformational changes in the tertiary structure of MHRP at pH 5, this modified form still keeps its catalytic activity to some extent besides enhanced thermal stability. These findings also indicated that a molten globular state does not necessarily preclude efficient catalytic activity. PMID:26417287

Carbohydrates as efficient catalysts for the hydration of α-amino nitriles.

PubMed

Chitale, Sampada; Derasp, Joshua S; Hussain, Bashir; Tanveer, Kashif; Beauchemin, André M

2016-11-01

Directed hydration of α-amino nitriles was achieved under mild conditions using simple carbohydrates as catalysts exploiting temporary intramolecularity. A broadly applicable procedure using both formaldehyde and NaOH as catalysts efficiently hydrated a variety of primary and secondary susbtrates, and allowed the hydration of enantiopure substrates to proceed without racemization. This work also provides a rare comparison of the catalytic activity of carbohydrates, and shows that the simple aldehydes at the basis of chemical evolution are efficient organocatalysts mimicking the function of hydratase enzymes. Optimal catalytic efficiency was observed with destabilized aldehydes, and with difficult substrates only simple carbohydrates such as formaldehyde and glycolaldehyde proved reliable.

Composite ceria-coated aerogels and methods of making the same

DOEpatents

Eyring, Edward M; Ernst, Richard D; Turpin, Gregory C; Dunn, Brian C

2013-05-07

Ceria-coated aerogels can include an aerogel support material having a stabilized ceria coating thereon. The ceria coating can be formed by solution or vapor deposition of alcogels or aerogels. Additional catalytic metal species can also be incorporated into the coating to form multi-metallic compounds having improved catalytic activity. Further, the ceria coated aerogels retain high surface areas at elevated temperatures. Thus, improvements in catalytic activity and thermal stability can be achieved using these ceria-coated composite aerogels.

The DUSP–Ubl domain of USP4 enhances its catalytic efficiency by promoting ubiquitin exchange

PubMed Central

Clerici, Marcello; Luna-Vargas, Mark P. A.; Faesen, Alex C.; Sixma, Titia K.

2014-01-01

Ubiquitin-specific protease USP4 is emerging as an important regulator of cellular pathways, including the TGF-β response, NF-κB signalling and splicing, with possible roles in cancer. Here we show that USP4 has its catalytic triad arranged in a productive conformation. Nevertheless, it requires its N-terminal DUSP–Ubl domain to achieve full catalytic turnover. Pre-steady-state kinetics measurements reveal that USP4 catalytic domain activity is strongly inhibited by slow dissociation of ubiquitin after substrate hydrolysis. The DUSP–Ubl domain is able to enhance ubiquitin dissociation, hence promoting efficient turnover. In a mechanism that requires all USP4 domains, binding of the DUSP–Ubl domain promotes a change of a switching loop near the active site. This ‘allosteric regulation of product discharge’ provides a novel way of regulating deubiquitinating enzymes that may have relevance for other enzyme classes. PMID:25404403

Homogeneous Catalysis for Sustainable Hydrogen Storage in Formic Acid and Alcohols.

PubMed

Sordakis, Katerina; Tang, Conghui; Vogt, Lydia K; Junge, Henrik; Dyson, Paul J; Beller, Matthias; Laurenczy, Gábor

2018-01-24

Hydrogen gas is a storable form of chemical energy that could complement intermittent renewable energy conversion. One of the main disadvantages of hydrogen gas arises from its low density, and therefore, efficient handling and storage methods are key factors that need to be addressed to realize a hydrogen-based economy. Storage systems based on liquids, in particular, formic acid and alcohols, are highly attractive hydrogen carriers as they can be made from CO 2 or other renewable materials, they can be used in stationary power storage units such as hydrogen filling stations, and they can be used directly as transportation fuels. However, to bring about a paradigm change in our energy infrastructure, efficient catalytic processes that release the hydrogen from these molecules, as well as catalysts that regenerate these molecules from CO 2 and hydrogen, are required. In this review, we describe the considerable progress that has been made in homogeneous catalysis for these critical reactions, namely, the hydrogenation of CO 2 to formic acid and methanol and the reverse dehydrogenation reactions. The dehydrogenation of higher alcohols available from renewable feedstocks is also described. Key structural features of the catalysts are analyzed, as is the role of additives, which are required in many systems. Particular attention is paid to advances in sustainable catalytic processes, especially to additive-free processes and catalysts based on Earth-abundant metal ions. Mechanistic information is also presented, and it is hoped that this review not only provides an account of the state of the art in the field but also offers insights into how superior catalytic systems can be obtained in the future.

Role of aspartate 400, arginine 262, and arginine 401 in the catalytic mechanism of human coproporphyrinogen oxidase

PubMed Central

Stephenson, Jason R.; Stacey, Julie A.; Morgenthaler, Justin B.; Friesen, Jon A.; Lash, Timothy D.; Jones, Marjorie A.

2007-01-01

Coproporphyrinogen oxidase (CPO) is the sixth enzyme in the heme biosynthetic pathway, catalyzing two sequential oxidative decarboxylations of propionate moieties on coproporphyrinogen-III forming protoporphyrinogen-IX through a monovinyl intermediate, harderoporphyrinogen. Site-directed mutagenesis studies were carried out on three invariant amino acids, aspartate 400, arginine 262, and arginine 401, to determine residue contribution to substrate binding and/or catalysis by human recombinant CPO. Kinetic analyses were performed on mutant enzymes incubated with three substrates, coproporphyrinogen-III, harderoporphyrinogen, or mesoporphyrinogen-VI, in order to determine catalytic ability to perform the first and/or second oxidative decarboxylation. When Asp400 was mutated to alanine no divinyl product was detected, but the production of a small amount of monovinyl product suggested the Km value for coproporphyrinogen-III did not change significantly compared to the wild-type enzyme. Upon mutation of Arg262 to alanine, CPO was again a poor catalyst for the production of a divinyl product, with a catalytic efficiency <0.01% compared to wild-type, including a 15-fold higher Km for coproporphyrinogen-III. The efficiency of divinyl product formation for mutant enzyme Arg401Ala was ∼3% compared to wild-type CPO, with a threefold increase in the Km value for coproporphyrinogen-III. These data suggest Asp400, Arg262, and Arg401 are active site amino acids critical for substrate binding and/or catalysis. Possible roles for arginine 262 and 401 include coordination of carboxylate groups of coproporphyrinogen-III, while aspartate 400 may initiate deprotonation of substrate, resulting in an oxidative decarboxylation. PMID:17242372

Role of aspartate 400, arginine 262, and arginine 401 in the catalytic mechanism of human coproporphyrinogen oxidase.

PubMed

Stephenson, Jason R; Stacey, Julie A; Morgenthaler, Justin B; Friesen, Jon A; Lash, Timothy D; Jones, Marjorie A

2007-03-01

Coproporphyrinogen oxidase (CPO) is the sixth enzyme in the heme biosynthetic pathway, catalyzing two sequential oxidative decarboxylations of propionate moieties on coproporphyrinogen-III forming protoporphyrinogen-IX through a monovinyl intermediate, harderoporphyrinogen. Site-directed mutagenesis studies were carried out on three invariant amino acids, aspartate 400, arginine 262, and arginine 401, to determine residue contribution to substrate binding and/or catalysis by human recombinant CPO. Kinetic analyses were performed on mutant enzymes incubated with three substrates, coproporphyrinogen-III, harderoporphyrinogen, or mesoporphyrinogen-VI, in order to determine catalytic ability to perform the first and/or second oxidative decarboxylation. When Asp400 was mutated to alanine no divinyl product was detected, but the production of a small amount of monovinyl product suggested the K(m) value for coproporphyrinogen-III did not change significantly compared to the wild-type enzyme. Upon mutation of Arg262 to alanine, CPO was again a poor catalyst for the production of a divinyl product, with a catalytic efficiency <0.01% compared to wild-type, including a 15-fold higher K(m) for coproporphyrinogen-III. The efficiency of divinyl product formation for mutant enzyme Arg401Ala was approximately 3% compared to wild-type CPO, with a threefold increase in the K(m) value for coproporphyrinogen-III. These data suggest Asp400, Arg262, and Arg401 are active site amino acids critical for substrate binding and/or catalysis. Possible roles for arginine 262 and 401 include coordination of carboxylate groups of coproporphyrinogen-III, while aspartate 400 may initiate deprotonation of substrate, resulting in an oxidative decarboxylation.

Silver/iron oxide/graphitic carbon composites as bacteriostatic catalysts for enhancing oxygen reduction in microbial fuel cells

NASA Astrophysics Data System (ADS)

Ma, Ming; You, Shijie; Gong, Xiaobo; Dai, Ying; Zou, Jinlong; Fu, Honggang

2015-06-01

Biofilms from anode heterotrophic bacteria are inevitably formed over cathodic catalytic sites, limiting the performances of single-chamber microbial fuel cells (MFCs). Graphitic carbon (GC) - based nano silver/iron oxide (AgNPs/Fe3O4/GC) composites are prepared from waste pomelo skin and used as antibacterial oxygen reduction catalysts for MFCs. AgNPs and Fe3O4 are introduced in situ into the composites by one-step carbothermal reduction, enhancing their conductivity and catalytic activity. To investigate the effects of Fe species on the antibacterial and catalytic properties, AgNPs/Fe3O4/GC is washed with sulfuric acid (1 mol L-1) for 0.5 h, 1 h, and 5 h and marked as AgNPs/Fe3O4/GC-x (x = 0.5 h, 1 h and 5 h, respectively). A maximum power density of 1712 ± 35 mW m-2 is obtained by AgNPs/Fe3O4/GC-1 h, which declines by 4.12% after 17 cycles. Under catalysis of all AgNP-containing catalysts, oxygen reduction reaction (ORR) proceeds via the 4e- pathway, and no toxic effects to anode microorganisms result from inhibiting the cathodic biofilm overgrowth. With the exception of AgNPs/Fe3O4/GC-5 h, the AgNPs-containing composites exhibit remarkable power output and coulombic efficiency through lowering proton transfer resistance and air-cathode biofouling. This study provides a perspective for the practical application of MFCs using these efficient antibacterial ORR catalysts.

Au-HKUST-1 Composite Nanocapsules: Synthesis with a Coordination Replication Strategy and Catalysis on CO Oxidation.

PubMed

Liu, Yongxin; Zhang, Jiali; Song, Lingxiao; Xu, Wenyuan; Guo, Zanru; Yang, Xiaomin; Wu, Xiaoxin; Chen, Xi

2016-09-07

A novel coordination replication of Cu2O redox-template strategy is reported to efficiently fabricate Au-HKUST-1 composite nanocapsule, with a HKUST-1 sandwich shell and an embedded Au nanoparticles layer. The novel synthesis procedure involves forming Au nanoparticles on the surface of Cu2O, transforming partial Cu2O into HKUST-1 shell via coordination replication, and removing the residual Cu2O by acid. The as-prepared Au-HKUST-1 composite nanocapsules displayed high catalytic activity on CO oxidation.

Biomass energy production. Citations from the International Aerospace Abstracts data base

NASA Technical Reports Server (NTRS)

Moore, P. W.

1980-01-01

These 210 citations from the international literature describe the production and/or utilization of most forms of biomass as a source of energy, fuel, food, and chemical intermediates or feedstocks. Biomass conversion by incineration, gasification, pyrolysis, hydrolysis, anaerobic digestion, or fermentation, as well as by catalytic, photosynthetic, chemosynthetic, and bio-electrochemical means are among the conversion processes considered. Discussions include biomass plantation and material productivity, transportation and equipment requirements, effects, comparisons of means and efficiencies of utilization and conversion, assessments of limitations, and evaluations of economic potential.

Partial oxidation of alkanes by dioxiranes formed in situ at low temperature.

PubMed

Yacob, Sara; Caulfield, Michael J; Barckholtz, Timothy A

2018-01-13

Partial oxidation catalysts capable of efficiently operating at low temperatures may limit the over-oxidation of alkane substrates and thereby improve selectivity. This work focuses on examining alkane oxidation using completely metal-free organocatalysts, dioxiranes. The dioxiranes employed here are synthesized by oxidation of a ketone using a terminal oxidant, such as hydrogen peroxide. Our work generates the dioxirane in situ , so that the process can be catalytic with respect to the ketone. To date, we have demonstrated selective partial oxidation of adamantane using ketone catalysts resulting in yields upwards of 60% towards 1-adamantanol with greater than 99% selectivity. Furthermore, we have demonstrated that changing the electrophilic character of the ketone R groups to contain more electron-donating ligands facilitates the dioxirane ring formation and improves overall oxidation yields. Isotopic labelling studies using H 2 18 O 2 show the preferential incorporation of an 18 O label into the parent ketone, providing evidence for a dioxirane intermediate formed in situ The isotopic labelling studies, along with solvent effect studies, suggest the formation of peracetic acid as a reactive intermediate.This article is part of a discussion meeting issue 'Providing sustainable catalytic solutions for a rapidly changing world'. © 2017 The Author(s).

Solution structures and backbone dynamics of Escherichia coli rhodanese PspE in its sulfur-free and persulfide-intermediate forms: implications for the catalytic mechanism of rhodanese.

PubMed

Li, Hongwei; Yang, Fan; Kang, Xue; Xia, Bin; Jin, Changwen

2008-04-15

Rhodanese catalyzes the sulfur-transfer reaction that transfers sulfur from thiosulfate to cyanide by a double-displacement mechanism, in which an active cysteine residue plays a central role. Previous studies indicated that the phage-shock protein E (PspE) from Escherichia coli is a rhodanese composed of a single active domain and is the only accessible rhodanese among the three single-domain rhodaneses in E. coli. To understand the catalytic mechanism of rhodanese at the molecular level, we determined the solution structures of the sulfur-free and persulfide-intermediate forms of PspE by nuclear magnetic resonance (NMR) spectroscopy and identified the active site by NMR titration experiments. To obtain further insights into the catalytic mechanism, we studied backbone dynamics by NMR relaxation experiments. Our results demonstrated that the overall structures in both sulfur-free and persulfide-intermediate forms are highly similar, suggesting that no significant conformational changes occurred during the catalytic reaction. However, the backbone dynamics revealed that the motional properties of PspE in its sulfur-free form are different from the persulfide-intermediate state. The conformational exchanges are largely enhanced in the persulfide-intermediate form of PspE, especially around the active site. The present structural and biochemical studies in combination with backbone dynamics provide further insights in understanding the catalytic mechanism of rhodanese.

Solid strong base K-Pt/NaY zeolite nano-catalytic system for completed elimination of formaldehyde at room temperature

NASA Astrophysics Data System (ADS)

Song, Shaoqing; Wu, Xi; Lu, Changhai; Wen, Meicheng; Le, Zhanggao; Jiang, Shujuan

2018-06-01

Solid strong base nano-catalytic system of K-modification NaY zeolite supported 0.08% Pt (K-Pt/NaY) were constructed for eliminating HCHO at room temperature. In the catalytic process, activation energy over K-Pt/NaY nano-catalytic system was greatly decreased along with the enhanced reaction rate. Characterization and catalytic tests revealed the surface electron structure of K-Pt/NaY was improved, as reflected by the enhanced HCHO adsorption capability, high sbnd OH concentration, and low-temperature reducibility. Therefore, the optimal K-Pt/NaY showed high catalytic efficiency and strong H2O tolerance for HCHO elimination by directly promoting the reaction between active sbnd OH and formate species. These results may suggest a new way for probing the advanced solid strong base nano-catalytic system for the catalytic elimination of indoor HCHO.

Supported catalysts using nanoparticles as the support material

DOEpatents

Wong, Michael S.; Wachs, Israel E.; Knowles, William V.

2010-11-02

A process for making a porous catalyst, comprises a) providing an aqueous solution containing a nanoparticle precursor, b) forming a composition containing nanoparticles, c) adding a first catalytic component or precursor thereof and a pore-forming agent to the composition containing nanoparticles and allowing the first catalytic component, the pore-forming agent, and the nanoparticles form an organic-inorganic structure, d) removing water from the organic-inorganic structure; and e) removing the pore-forming agent from the organic-inorganic structure so as to yield a porous catalyst.

Mutant form C115H of Clostridium sporogenes methionine γ-lyase efficiently cleaves S-Alk(en)yl-l-cysteine sulfoxides to antibacterial thiosulfinates.

PubMed

Kulikova, Vitalia V; Anufrieva, Natalya V; Revtovich, Svetlana V; Chernov, Alexander S; Telegin, Georgii B; Morozova, Elena A; Demidkina, Tatyana V

2016-10-01

Pyridoxal 5'-phosphate-dependent methionine γ-lyase (MGL) catalyzes the β-elimination reaction of S-alk(en)yl-l-cysteine sulfoxides to thiosulfinates, which possess antimicrobial activity. Partial inactivation of the enzyme in the course of the reaction occurs due to oxidation of active site cysteine 115 conserved in bacterial MGLs. In this work, the C115H mutant form of Clostridium sporogenes MGL was prepared and the steady-state kinetic parameters of the enzyme were determined. The substitution results in an increase in the catalytic efficiency of the mutant form towards S-substituted l-cysteine sulfoxides compared to the wild type enzyme. We used a sulfoxide/enzyme system to generate antibacterial activity in situ. Two-component systems composed of the mutant enzyme and three S-substituted l-cysteine sulfoxides were demonstrated to be effective against Gram-positive and Gram-negative bacteria and three clinical isolates from mice. © 2016 IUBMB Life, 68(10):830-835, 2016. © 2016 International Union of Biochemistry and Molecular Biology.

Inhibition of human papillomavirus expression using DNAzymes.

PubMed

Benítez-Hess, María Luisa; Reyes-Gutiérrez, Pablo; Alvarez-Salas, Luis Marat

2011-01-01

Deoxyribozymes (DXZs) are catalytic oligodeoxynucleotides capable of performing diverse functions including the specific cleavage of a target RNA. These molecules represent a new type of therapeutic oligonucleotides combining the efficiency of ribozymes and the intracellular endurance and simplicity of modified antisense oligonucleotides. Commonly used DXZs include the 8-17 and 10-23 motifs, which have been engineered to destroy disease-associated genes with remarkable efficiency. Targeting DXZs to disease-associated transcripts requires extensive biochemical testing to establish target RNA accessibility, catalytic efficiency, and nuclease sensibility. The usage of modified nucleotides to render nuclease-resistance DXZs must be counterweighted against deleterious consequences on catalytic activity. Further intracellular testing is required to establish the effect of microenvironmental conditions on DXZ activity and off-target issues. Application of modified DXZs to cervical cancer results in specific growth inhibition, cell death, and apoptosis. Thus, DXZs represent a highly effective antisense moiety with minimal secondary effects.

Fuel cell with interdigitated porous flow-field

DOEpatents

Wilson, Mahlon S.

1997-01-01

A polymer electrolyte membrane (PEM) fuel cell is formed with an improved system for distributing gaseous reactants to the membrane surface. A PEM fuel cell has an ionic transport membrane with opposed catalytic surfaces formed thereon and separates gaseous reactants that undergo reactions at the catalytic surfaces of the membrane. The fuel cell may also include a thin gas diffusion layer having first and second sides with a first side contacting at least one of the catalytic surfaces. A macroporous flow-field with interdigitated inlet and outlet reactant channels contacts the second side of the thin gas diffusion layer for distributing one of the gaseous reactants over the thin gas diffusion layer for transport to an adjacent one of the catalytic surfaces of the membrane. The porous flow field may be formed from a hydrophilic material and provides uniform support across the backside of the electrode assembly to facilitate the use of thin backing layers.

Fuel cell with interdigitated porous flow-field

DOEpatents

Wilson, M.S.

1997-06-24

A polymer electrolyte membrane (PEM) fuel cell is formed with an improved system for distributing gaseous reactants to the membrane surface. A PEM fuel cell has an ionic transport membrane with opposed catalytic surfaces formed thereon and separates gaseous reactants that undergo reactions at the catalytic surfaces of the membrane. The fuel cell may also include a thin gas diffusion layer having first and second sides with a first side contacting at least one of the catalytic surfaces. A macroporous flow-field with interdigitated inlet and outlet reactant channels contacts the second side of the thin gas diffusion layer for distributing one of the gaseous reactants over the thin gas diffusion layer for transport to an adjacent one of the catalytic surfaces of the membrane. The porous flow field may be formed from a hydrophilic material and provides uniform support across the backside of the electrode assembly to facilitate the use of thin backing layers. 9 figs.

Application of BiFeO3-based on nickel foam composites with a highly efficient catalytic activity and easily recyclable in Fenton-like process under microwave irradiation

NASA Astrophysics Data System (ADS)

Li, Shuo; Zhang, Guangshan; Zheng, Heshan; Zheng, Yongjie; Wang, Peng

2018-05-01

In this study, BiFeO3 (BFO) powders decorated on nickel foam (NF) with a high catalytic activity are prepared via a one-step microwave-assisted hydrothermal method. The factors that influence the degradation of bisphenol A (BPA) with BFO/NFs as catalysts are optimized to improve the catalytic activity in a microwave-enhanced Fenton-like process. BFO/NF exhibit a superior catalytic activity with a high BPA removal ratio (98.4%) and TOC removal ratio (69.5%) within 5 min. Results indicate that NF significantly affect the improvement of the catalytic activity of BFO because it served as a source of hydroxyl radicals (•OH) during degradation. The amount of •OH generated by BFO/NF is approximately 1.65-fold higher than that by pure BFO. After six reaction cycles, the stability and reusability of •OH remain high. These findings provide new insights into the synthesis of composites on heterogeneous catalysts with high efficiency and easy recyclability for water treatment applications.

Removal of ethylene from air stream by adsorption and plasma-catalytic oxidation using silver-based bimetallic catalysts supported on zeolite.

PubMed

Trinh, Quang Hung; Lee, Sang Baek; Mok, Young Sun

2015-03-21

Dynamic adsorption of ethylene on 13X zeolite-supported Ag and Ag-M(x)O(y) (M: Co, Cu, Mn, and Fe), and plasma-catalytic oxidation of the adsorbed ethylene were investigated. The experimental results showed that the incorporation of Ag into zeolite afforded a marked enhancement in the adsorptivity for ethylene. The addition of transition metal oxides was found to have a positive influence on the ethylene adsorption, except Fe(x)O(y). The presence of the additional metal oxides, however, appeared to somewhat interrupt the diffusion of ozone into the zeolite micro-pores, leading to a decrease in the plasma-catalytic oxidation efficiency of the ethylene adsorbed there. Among the second additional metal oxides, Fe(x)O(y) was able to reduce the emission of ozone during the plasma-catalytic oxidation stage while keeping a high effectiveness for the oxidative removal of the adsorbed ethylene. The periodical treatment consisting of adsorption followed by plasma-catalytic oxidation may be a promising energy-efficient ethylene abatement method. Copyright © 2014 Elsevier B.V. All rights reserved.

The Crystal Structure of a hCA VII Variant Provides Insights into the Molecular Determinants Responsible for Its Catalytic Behavior.

PubMed

Buonanno, Martina; Di Fiore, Anna; Langella, Emma; D'Ambrosio, Katia; Supuran, Claudiu T; Monti, Simona Maria; De Simone, Giuseppina

2018-05-24

Although important progress has been achieved in understanding the catalytic mechanism of Carbonic Anhydrases, a detailed picture of all factors influencing the catalytic efficiency of the various human isoforms is still missing. In this paper we report a detailed structural study and theoretical pKa calculations on a hCA VII variant. The obtained data were compared with those already known for another thoroughly investigated cytosolic isoform, hCA II. Our structural studies show that in hCA VII the network of ordered water molecules, which connects the zinc bound solvent molecule to the proton shuttle His64, is altered compared to hCA II, causing a reduction of the catalytic efficiency. Theoretical calculations suggest that changes in solvent network are related to the difference in pKa of the proton shuttle in the two enzymes. The residue that plays a major role in determining the diverse pKa values of the proton shuttle is the one in position four, namely His for hCA II and Gly for hCA VII. This residue is located on the protein surface, outside of the active site cavity. These findings are in agreement with our previous studies that highlighted the importance of histidines on the protein surface of hCA II (among which His4) as crucial residues for the high catalytic efficiency of this isoform.

Method for recovering catalytic elements from fuel cell membrane electrode assemblies

DOEpatents

Shore, Lawrence [Edison, NJ; Matlin, Ramail [Berkeley Heights, NJ; Heinz, Robert [Ludwigshafen, DE

2012-06-26

A method for recovering catalytic elements from a fuel cell membrane electrode assembly is provided. The method includes converting the membrane electrode assembly into a particulate material, wetting the particulate material, forming a slurry comprising the wetted particulate material and an acid leachate adapted to dissolve at least one of the catalytic elements into a soluble catalytic element salt, separating the slurry into a depleted particulate material and a supernatant containing the catalytic element salt, and washing the depleted particulate material to remove any catalytic element salt retained within pores in the depleted particulate material.

Construction and in vivo assembly of a catalytically proficient and hyperthermostable de novo enzyme.

PubMed

Watkins, Daniel W; Jenkins, Jonathan M X; Grayson, Katie J; Wood, Nicola; Steventon, Jack W; Le Vay, Kristian K; Goodwin, Matthew I; Mullen, Anna S; Bailey, Henry J; Crump, Matthew P; MacMillan, Fraser; Mulholland, Adrian J; Cameron, Gus; Sessions, Richard B; Mann, Stephen; Anderson, J L Ross

2017-08-25

Although catalytic mechanisms in natural enzymes are well understood, achieving the diverse palette of reaction chemistries in re-engineered native proteins has proved challenging. Wholesale modification of natural enzymes is potentially compromised by their intrinsic complexity, which often obscures the underlying principles governing biocatalytic efficiency. The maquette approach can circumvent this complexity by combining a robust de novo designed chassis with a design process that avoids atomistic mimicry of natural proteins. Here, we apply this method to the construction of a highly efficient, promiscuous, and thermostable artificial enzyme that catalyzes a diverse array of substrate oxidations coupled to the reduction of H 2 O 2 . The maquette exhibits kinetics that match and even surpass those of certain natural peroxidases, retains its activity at elevated temperature and in the presence of organic solvents, and provides a simple platform for interrogating catalytic intermediates common to natural heme-containing enzymes.Catalytic mechanisms of enzymes are well understood, but achieving diverse reaction chemistries in re-engineered proteins can be difficult. Here the authors show a highly efficient and thermostable artificial enzyme that catalyzes a diverse array of substrate oxidations coupled to the reduction of H 2 O 2 .

One Electron-Initiated Two-Electron Oxidation of Water by Aluminum Porphyrins with Earth's Most Abundant Metal.

PubMed

Kuttassery, Fazalurahman; Mathew, Siby; Sagawa, Shogo; Remello, Sebastian Nybin; Thomas, Arun; Yamamoto, Daisuke; Onuki, Satomi; Nabetani, Yu; Tachibana, Hiroshi; Inoue, Haruo

2017-05-09

We report herein a new molecular catalyst for efficient water splitting, aluminum porphyrins (tetra-methylpyridiniumylporphyrinatealuminum: AlTMPyP), containing earth's most abundant metal as the central ion. One-electron oxidation of the aluminum porphyrin initiates the two-electron oxidation of water to form hydrogen peroxide as the primary reaction product with the lowest known overpotential (97 mV). The aluminum-peroxo complex was detected by a cold-spray ionization mass-spectrometry in high-resolution MS (HRMS) mode and the structure of the intermediate species was further confirmed using laser Raman spectroscopy, indicating the hydroperoxy complex of AlTMPyP to be the key intermediate in the reaction. The two-electron oxidation of water to form hydrogen peroxide was essentially quantitative, with a Faradaic efficiency of 99 %. The catalytic reaction was found to be highly efficient, with a turnover frequency up to ∼2×10 4  s -1 . A reaction mechanism is proposed involving oxygen-oxygen bond formation by the attack of a hydroxide ion on the oxyl-radical-like axial ligand oxygen atom in the one-electron-oxidized form of AlTMPyP(O - ) 2 , followed by a second electron transfer to the electrode. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transcriptomic characterization of Caecomyces churrovis: a novel, non-rhizoid-forming lignocellulolytic anaerobic fungus

DOE PAGES

Henske, John K.; Gilmore, Sean P.; Knop, Doriv; ...

2017-12-20

Anaerobic gut fungi are the primary colonizers of plant material in the rumen microbiome, but are poorly studied due to a lack of characterized isolates. While most genera of gut fungi form extensive rhizoidal networks, which likely participate in mechanical disruption of plant cell walls, fungi within the Caecomyces genus do not possess these rhizoids. Here, we describe a novel fungal isolate, Caecomyces churrovis, which forms spherical sporangia with a limited rhizoidal network yet secretes a diverse set of carbohydrate active enzymes (CAZymes) for plant cell wall hydrolysis. Despite lacking an extensive rhizoidal system, C. churrovis is capable of growthmore » on fibrous substrates like switchgrass, reed canary grass, and corn stover, although faster growth is observed on soluble sugars. Gut fungi have been shown to use enzyme complexes (fungal cellulosomes) in which CAZymes bind to non-catalytic scaffoldins to improve biomass degradation efficiency. However, transcriptomic analysis and enzyme activity assays reveal that C. churrovis relies more on free enzymes compared to other gut fungal isolates. Only 15% of CAZyme transcripts contain non-catalytic dockerin domains in C. churrovis, compared to 30% in rhizoid-forming fungi. Furthermore, C. churrovis is enriched in GH43 enzymes that provide complementary hemicellulose degrading activities, suggesting that a wider variety of these activities are required to degrade plant biomass in the absence of an extensive fungal rhizoid network. In conclusion, molecular characterization of a non-rhizoid-forming anaerobic fungus fills a gap in understanding the roles of CAZyme abundance and associated degradation mechanisms during lignocellulose breakdown within the rumen microbiome.« less

Transcriptomic characterization of Caecomyces churrovis: a novel, non-rhizoid-forming lignocellulolytic anaerobic fungus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henske, John K.; Gilmore, Sean P.; Knop, Doriv

Anaerobic gut fungi are the primary colonizers of plant material in the rumen microbiome, but are poorly studied due to a lack of characterized isolates. While most genera of gut fungi form extensive rhizoidal networks, which likely participate in mechanical disruption of plant cell walls, fungi within the Caecomyces genus do not possess these rhizoids. Here, we describe a novel fungal isolate, Caecomyces churrovis, which forms spherical sporangia with a limited rhizoidal network yet secretes a diverse set of carbohydrate active enzymes (CAZymes) for plant cell wall hydrolysis. Despite lacking an extensive rhizoidal system, C. churrovis is capable of growthmore » on fibrous substrates like switchgrass, reed canary grass, and corn stover, although faster growth is observed on soluble sugars. Gut fungi have been shown to use enzyme complexes (fungal cellulosomes) in which CAZymes bind to non-catalytic scaffoldins to improve biomass degradation efficiency. However, transcriptomic analysis and enzyme activity assays reveal that C. churrovis relies more on free enzymes compared to other gut fungal isolates. Only 15% of CAZyme transcripts contain non-catalytic dockerin domains in C. churrovis, compared to 30% in rhizoid-forming fungi. Furthermore, C. churrovis is enriched in GH43 enzymes that provide complementary hemicellulose degrading activities, suggesting that a wider variety of these activities are required to degrade plant biomass in the absence of an extensive fungal rhizoid network. In conclusion, molecular characterization of a non-rhizoid-forming anaerobic fungus fills a gap in understanding the roles of CAZyme abundance and associated degradation mechanisms during lignocellulose breakdown within the rumen microbiome.« less

Transcriptomic characterization of Caecomyces churrovis: a novel, non-rhizoid-forming lignocellulolytic anaerobic fungus.

PubMed

Henske, John K; Gilmore, Sean P; Knop, Doriv; Cunningham, Francis J; Sexton, Jessica A; Smallwood, Chuck R; Shutthanandan, Vaithiyalingam; Evans, James E; Theodorou, Michael K; O'Malley, Michelle A

2017-01-01

Anaerobic gut fungi are the primary colonizers of plant material in the rumen microbiome, but are poorly studied due to a lack of characterized isolates. While most genera of gut fungi form extensive rhizoidal networks, which likely participate in mechanical disruption of plant cell walls, fungi within the Caecomyces genus do not possess these rhizoids. Here, we describe a novel fungal isolate, Caecomyces churrovis , which forms spherical sporangia with a limited rhizoidal network yet secretes a diverse set of carbohydrate active enzymes (CAZymes) for plant cell wall hydrolysis. Despite lacking an extensive rhizoidal system, C. churrovis is capable of growth on fibrous substrates like switchgrass, reed canary grass, and corn stover, although faster growth is observed on soluble sugars. Gut fungi have been shown to use enzyme complexes (fungal cellulosomes) in which CAZymes bind to non-catalytic scaffoldins to improve biomass degradation efficiency. However, transcriptomic analysis and enzyme activity assays reveal that C. churrovis relies more on free enzymes compared to other gut fungal isolates. Only 15% of CAZyme transcripts contain non-catalytic dockerin domains in C. churrovis , compared to 30% in rhizoid-forming fungi. Furthermore, C. churrovis is enriched in GH43 enzymes that provide complementary hemicellulose degrading activities, suggesting that a wider variety of these activities are required to degrade plant biomass in the absence of an extensive fungal rhizoid network. Overall, molecular characterization of a non-rhizoid-forming anaerobic fungus fills a gap in understanding the roles of CAZyme abundance and associated degradation mechanisms during lignocellulose breakdown within the rumen microbiome.

Efficient decomposition of formaldehyde at room temperature over Pt/honeycomb ceramics with ultra-low Pt content.

PubMed

Nie, Longhui; Zheng, Yingqiu; Yu, Jiaguo

2014-09-14

Pt/honeycomb ceramic (Pt/HC) catalysts with ultra-low Pt content (0.005-0.055 wt%) were for the first time prepared by an impregnation of honeycomb ceramics with Pt precursor and NaBH4-reduction combined method. The microstructures, morphologies and textural properties of the resulting samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The obtained Pt/HC catalysts were used for catalytic oxidative decomposition of formaldehyde (HCHO) at room temperature. It was found that the as-prepared Pt/HC catalysts can efficiently decompose HCHO in air into CO2 and H2O at room temperature. The catalytic activity of the Pt/HC catalysts increases with increasing the Pt loading in the range of 0.005-0.013 wt%, and the further increase of the Pt loading does not obviously improve catalytic activity. From the viewpoint of cost and catalytic performance, 0.013 wt% Pt loading is the optimal Pt loading amount, and the Pt/HC catalyst with 0.013 wt% Pt loading also exhibited good catalytic stability. Considering practical applications, this work will provide new insights into the low-cost and large-scale fabrication of advanced catalytic materials for indoor air purification.

Engineering New Catalysts for In-Process Elimination of Tars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Felix, Larry G.

2012-09-30

The key objective of this project was to develop a new and more efficient methodology for engineering and economically producing optimized robust catalysts for the reduction or elimination of tars in biomass gasification. Whereas current catalyst technology typically disposes thin layers of catalytically-active material onto rigid supports via wet chemistry-based methods, this project investigated novel thermal methods for directly incorporating catalytically active materials onto robust supports as well as novel approaches for incorporating catalytically active materials on and/or within an otherwise inert refractory support material which is then subsequently formed and processed to create a catalytically-active material on all exposedmore » surfaces. Specifically, the focus of this engineered catalyst development was on materials which were derived from, or otherwise related to, olivine-like minerals, due to the inherent attrition resistance and moderate catalytic properties exhibited by natural olivine when used in a fluidized bed biomass gasifier. Task 1 of this project successfully demonstrated the direct thermal impregnation of catalytically-active materials onto an olivine substrate, with the production of a Ni-olivine catalyst. Nickel and nickel oxide were thermally impregnated onto an olivine substrate and when reduced were shown to demonstrate improved catalytic activity over the baseline olivine material and equal the tar-decomposing performance of Ni-olivine catalysts prepared by conventional wet impregnation. Task 2 involved coordination with our subcontracted project partners to further develop and characterize catalyst formulations and to optimize activity and production methods. Within this task, several significant new materials were developed. NexTech Materials developed a sintered ceramic nickel-magnesium-silicate catalyst that demonstrated superb catalytic activity and high resistance to deactivation by H2S. Alfred University developed both supported and integrated (bulk) catalysts via a glass-ceramic processing route which were shown to exhibit excellent catalytic activity and superior resistance to attrition deactivation. With the discovery of these active, robust, glass-based catalysts, and with the permission of the project officer, the investigation of waste-based materials as originally proposed for Task 3 and pilot-scale testing proposed in Task 5 were deferred indefinitely in favor of further investigation of the glass-ceramic based catalyst materials. This choice was justified in part because during FY 2006 and through FY 2007, funding restrictions imposed by congressional budget choices significantly reduced funding for DOE biomass-related projects. Funding for this project was limited to what had been authorized which slowed the pace of project work at GTI so that our project partners could continue in their work. Thereafter, project work was allowed to resume and with restored funding, the project continued and concentrated on the development and testing of glass-ceramic catalysts in bulk or supported formats. Work concluded with a final development devoted to increasing the surface area of glass-ceramic catalysts in the form of microspheres. Following that development, project reporting was completed and the project was concluded.« less

Catalytic fast pyrolysis of lignocellulosic biomass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Changjun; Wang, Huamin; Karim, Ayman M.

2014-11-21

Increasing energy demand, especially in the transportation sector, and soaring CO2 emissions necessitate the exploitation of renewable sources of energy. Despite the large variety of new energy Q3 carriers, liquid hydrocarbon still appears to be the most attractive and feasible form of transportation fuel taking into account the energy density, stability and existing infrastructure. Biomass is an abundant, renewable source of energy; however, utilizing it in a cost-effective way is still a substantial challenge. Lignocellulose is composed of three major biopolymers, namely cellulose, hemicellulose and lignin. Fast pyrolysis of biomass is recognized as an efficient and feasible process to selectivelymore » convert lignocellulose into a liquid fuel—bio-oil. However bio-oil from fast pyrolysis contains a large amount of oxygen, distributed in hundreds of oxygenates. These oxygenates are the cause of many negative properties, such as low heating values, high corrosiveness, high viscosity, and instability; they also greatly Q4 limit the application of bio-oil particularly as transportation fuel. Hydrocarbons derived from biomass are most attractive because of their high energy density and compatibility with the existing infrastructure. Thus, converting lignocellulose into transportation fuels via catalytic fast pyrolysis has attracted much attention. Many studies related to catalytic fast pyrolysis of biomass have been published. The main challenge of this process is the development of active and stable catalysts that can deal with a large variety of decomposition intermediates from lignocellulose. This review starts with the current understanding of the chemistry in fast pyrolysis of lignocellulose and focuses on the development of catalysts in catalytic fast pyrolysis. Recent progress in the experimental studies on catalytic fast pyrolysis of biomass is also summarized with the emphasis on bio-oil yields and quality.« less

[PEG-chitosan branched copolymers to improve the biocatalytic properties of Erwinia carotovora recombinant L-asparaginase].

PubMed

Kudryashova, E V; Suhoverkov, K V; Sokolov, N N

2015-01-01

A new approach to the regulation of catalytic properties of medically relevant enzymes has been proposed using the novel recombinant preparation of L-asparaginase from Erwinia carotovora (EwA), a promising antitumor agent. New branched co-polymers of different composition based on chitosan modified with polyethylene glycol (PEG) molecules, designated as PEG-chitosan, have been synthesized. PEG-chitosan copolymers were further conjugated with EwA. In order to optimize the catalytic properties of asparaginase two types of conjugates differing in their architecture have been synthesized: (1) crown-type conjugates were synthesized by reductive amination reaction between the reducing end of the PEG-chitosan copolymer and enzyme amino groups; (2) multipoint-conjugates were synthesized using the reaction of multipoint amide bond formation between PEG-chitosan amino groups and carboxyl groups of the enzyme in the presence of the Woodward's reagent. The structure and composition of these conjugates were determined by IR spectroscopy. The content of the copolymers in the conjugates was controlled by the characteristic absorption band of C-O-C bonds in the PEG structure at the frequency of 1089 cm-1. The study of catalytic characteristics of EwA preparations by conductometry showed that at physiological pH values the enzyme conjugates with PEG-chitosan with optimized structure and the optimal composition demonstrated 5-8-fold higher catalytic efficiency (kcat/Km) than the native enzyme. To certain extent, this can be attributed to favorable shift of pH-optima in result of positively charged amino-groups introduction in the vicinity of the active site. The proposed approach, chito-pegylation, is effective for regulating the catalytic and pharmacokinetic properties of asparaginase, and is promising for the development of prolonged action dosage forms for other enzyme therapeutics.

Transition Metal Catalyzed Hydroarylation of Multiple Bonds: Exploration of Second Generation Ruthenium Catalysts and Extension to Copper Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

T. Brent Gunnoe

2011-02-17

Catalysts provide foundational technology for the development of new materials and can enhance the efficiency of routes to known materials. New catalyst technologies offer the possibility of reducing energy and raw material consumption as well as enabling chemical processes with a lower environmental impact. The rising demand and expense of fossil resources has strained national and global economies and has increased the importance of accessing more efficient catalytic processes for the conversion of hydrocarbons to useful products. The goals of the research are to develop and understand single-site homogeneous catalysts for the conversion of readily available hydrocarbons into useful materials.more » A detailed understanding of these catalytic reactions could lead to the development of catalysts with improved activity, longevity and selectivity. Such transformations could reduce the environmental impact of hydrocarbon functionalization, conserve energy and valuable fossil resources and provide new technologies for the production of liquid fuels. This project is a collaborative effort that incorporates both experimental and computational studies to understand the details of transition metal catalyzed C-H activation and C-C bond forming reactions with olefins. Accomplishments of the current funding period include: (1) We have completed and published studies of C-H activation and catalytic olefin hydroarylation by TpRu{l_brace}P(pyr){sub 3}{r_brace}(NCMe)R (pyr = N-pyrrolyl) complexes. While these systems efficiently initiate stoichiometric benzene C-H activation, catalytic olefin hydroarylation is hindered by inhibition of olefin coordination, which is a result of the steric bulk of the P(pyr){sub 3} ligand. (2) We have extended our studies of catalytic olefin hydroarylation by TpRu(L)(NCMe)Ph systems to L = P(OCH{sub 2}){sub 3}CEt. Thus, we have now completed detailed mechanistic studies of four systems with L = CO, PMe{sub 3}, P(pyr){sub 3} and P(OCH{sub 2}){sub 3}CEt, which has provided a comprehensive understanding of the impact of steric and electronic parameters of 'L' on the catalytic hydroarylation of olefins. (3) We have completed and published a detailed mechanistic study of stoichiometric aromatic C-H activation by TpRu(L)(NCMe)Ph (L = CO or PMe{sub 3}). These efforts have probed the impact of functionality para to the site of C-H activation for benzene substrates and have allowed us to develop a detailed model of the transition state for the C-H activation process. These results have led us to conclude that the C-H bond cleavage occurs by a {sigma}-bond metathesis process in which the C-H transfer is best viewed as an intramolecular proton transfer. (4) We have completed studies of Ru complexes possessing the N-heterocyclic carbene IMes (IMes = 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene). One of these systems is a unique four-coordinate Ru(II) complex that catalyzes the oxidative hydrophenylation of ethylene (in low yields) to produce styrene and ethane (utilizing ethylene as the hydrogen acceptor) as well as the hydrogenation of olefins, aldehydes and ketones. These results provide a map for the preparation of catalysts that are selective for oxidative olefin hydroarylation. (5) The ability of TpRu(PMe{sub 3})(NCMe)R systems to activate sp{sup 3} C-H bonds has been demonstrated including extension to subsequent C-C bond forming steps. These results open the door to the development of catalysts for the functionalization of more inert C-H bonds. (6) We have discovered that Pt(II) complexes supported by simple nitrogen-based ligands serve as catalysts for the hydroarylation of olefins. Given the extensive studies of Pt-based catalytic C-H activation, we believe these results will provide an entry point into an array of possible catalysts for hydrocarbon functionalization.« less

Biochemical and Structural Analysis of an Eis Family Aminoglycoside Acetyltransferase from Bacillus anthracis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Green, Keith D.; Biswas, Tapan; Chang, Changsoo

Proteins from the enhanced intracellular survival (Eis) family are versatile acetyltransferases that acetylate amines at multiple positions of several aminoglycosides (AGs). Their upregulation confers drug resistance. Homologues of Eis are present in diverse bacteria, including many pathogens. Eis from Mycobacterium tuberculosis (Eis_Mtb) has been well characterized. In this study, we explored the AG specificity and catalytic efficiency of the Eis family protein from Bacillus anthracis (Eis_Ban). Kinetic analysis of specificity and catalytic efficiency of acetylation of six AGs indicates that Eis_Ban displays significant differences from Eis_Mtb in both substrate binding and catalytic efficiency. The number of acetylated amines was alsomore » different for several AGs, indicating a distinct regiospecificity of Eis_Ban. Furthermore, most recently identified inhibitors of Eis_Mtb did not inhibit Eis_Ban, underscoring the differences between these two enzymes. To explain these differences, we determined an Eis_Ban crystal structure. The comparison of the crystal structures of Eis_Ban and Eis_Mtb demonstrates that critical residues lining their respective substrate binding pockets differ substantially, explaining their distinct specificities. Our results suggest that acetyltransferases of the Eis family evolved divergently to garner distinct specificities while conserving catalytic efficiency, possibly to counter distinct chemical challenges. The unique specificity features of these enzymes can be utilized as tools for developing AGs with novel modifications and help guide specific AG treatments to avoid Eis-mediated resistance.« less

Improved catalytic efficiency, thermophilicity, anti-salt and detergent tolerance of keratinase KerSMD by partially truncation of PPC domain

PubMed Central

Fang, Zhen; Zhang, Juan; Du, Guocheng; Chen, Jian

2016-01-01

The keratinase from Stenotrophomonas maltophilia (KerSMD) is known for its high activity and pH stability in keratin degradation. However, catalytic efficiency and detergent tolerability need to be improved in order to be used for industrial application. In this work, we obtained several keratinase variants with enhanced catalytic efficiency, thermophilicity, and anti-salt and detergent tolerability by partially truncating the PPC domain of KerSMD. The variants all showed improved catalytic efficiency to synthetic substrate AAPF, with the V355 variant having the highest kcat /Km value of 143.6 s−1 mM−1. The truncation of keratinase had little effect on alkaline stability but obviously decreased collagenase activity, developing its potential application in leather treatment. The variants V380, V370, and V355 were thermophilic, with a 1.7-fold enhancement of keratinlytic activity at 60 °C when compared to the wild type. The entire truncation of PPC domain obtained the variant V355 with improved tolerance to alkalinity, salt, chaotropic agents, and detergents. The V355 variant showed more than a 40% improvement in activity under 15% (w/v) NaCl or 4% (w/v) SDS solution, showing excellent stability under harsh washing and unhairing conditions. Our work investigated how protein engineering affects the function of PPC domain of KerSMD. PMID:27298079

Improved catalytic efficiency, thermophilicity, anti-salt and detergent tolerance of keratinase KerSMD by partially truncation of PPC domain.

PubMed

Fang, Zhen; Zhang, Juan; Du, Guocheng; Chen, Jian

2016-06-14

The keratinase from Stenotrophomonas maltophilia (KerSMD) is known for its high activity and pH stability in keratin degradation. However, catalytic efficiency and detergent tolerability need to be improved in order to be used for industrial application. In this work, we obtained several keratinase variants with enhanced catalytic efficiency, thermophilicity, and anti-salt and detergent tolerability by partially truncating the PPC domain of KerSMD. The variants all showed improved catalytic efficiency to synthetic substrate AAPF, with the V355 variant having the highest kcat /Km value of 143.6 s(-1) mM(-1). The truncation of keratinase had little effect on alkaline stability but obviously decreased collagenase activity, developing its potential application in leather treatment. The variants V380, V370, and V355 were thermophilic, with a 1.7-fold enhancement of keratinlytic activity at 60 °C when compared to the wild type. The entire truncation of PPC domain obtained the variant V355 with improved tolerance to alkalinity, salt, chaotropic agents, and detergents. The V355 variant showed more than a 40% improvement in activity under 15% (w/v) NaCl or 4% (w/v) SDS solution, showing excellent stability under harsh washing and unhairing conditions. Our work investigated how protein engineering affects the function of PPC domain of KerSMD.

A high-throughput assay for DNA topoisomerases and other enzymes, based on DNA triplex formation.

PubMed

Burrell, Matthew R; Burton, Nicolas P; Maxwell, Anthony

2010-01-01

We have developed a rapid, high-throughput assay for measuring the catalytic activity (DNA supercoiling or relaxation) of topoisomerase enzymes that is also capable of monitoring the activity of other enzymes that alter the topology of DNA. The assay utilises intermolecular triplex formation to resolve supercoiled and relaxed forms of DNA, the principle being the greater efficiency of a negatively supercoiled plasmid to form an intermolecular triplex with an immobilised oligonucleotide than the relaxed form. The assay provides a number of advantages over the standard gel-based methods, including greater speed of analysis, reduced sample handling, better quantitation and improved reliability and accuracy of output data. The assay is performed in microtitre plates and can be adapted to high-throughput screening of libraries of potential inhibitors of topoisomerases including bacterial DNA gyrase.

Process to convert biomass and refuse derived fuel to ethers and/or alcohols

DOEpatents

Diebold, James P.; Scahill, John W.; Chum, Helena L.; Evans, Robert J.; Rejai, Bahman; Bain, Richard L.; Overend, Ralph P.

1996-01-01

A process for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols.

Process for catalytically oxidizing cycloolefins, particularly cyclohexene

DOEpatents

Mizuno, Noritaka; Lyon, David K.; Finke, Richard G.

1993-01-01

This invention is a process for catalytically oxidizing cycloolefins, particularly cyclohexenes, to form a variety of oxygenates. The catalyst used in the process is a covalently bonded iridium-heteropolyanion species. The process uses the catalyst in conjunction with a gaseous oxygen containing gas to form 2-cyclohexen-1-ol and also 2-cyclohexen-1-one.

Molecular mechanisms of isocitrate dehydrogenase 1 (IDH1) mutations identified in tumors: The role of size and hydrophobicity at residue 132 on catalytic efficiency

PubMed Central

Avellaneda Matteo, Diego; Grunseth, Adam J.; Gonzalez, Eric R.; Anselmo, Stacy L.; Kennedy, Madison A.; Moman, Precious; Scott, David A.; Hoang, An; Sohl, Christal D.

2017-01-01

Isocitrate dehydrogenase 1 (IDH1) catalyzes the reversible NADP+-dependent conversion of isocitrate (ICT) to α-ketoglutarate (αKG) in the cytosol and peroxisomes. Mutations in IDH1 have been implicated in >80% of lower grade gliomas and secondary glioblastomas and primarily affect residue 132, which helps coordinate substrate binding. However, other mutations found in the active site have also been identified in tumors. IDH1 mutations typically result in a loss of catalytic activity, but many also can catalyze a new reaction, the NADPH-dependent reduction of αKG to d-2-hydroxyglutarate (D2HG). D2HG is a proposed oncometabolite that can competitively inhibit αKG-dependent enzymes. Some kinetic parameters have been reported for several IDH1 mutations, and there is evidence that mutant IDH1 enzymes vary widely in their ability to produce D2HG. We report that most IDH1 mutations identified in tumors are severely deficient in catalyzing the normal oxidation reaction, but that D2HG production efficiency varies among mutant enzymes up to ∼640-fold. Common IDH1 mutations have moderate catalytic efficiencies for D2HG production, whereas rarer mutations exhibit either very low or very high efficiencies. We then designed a series of experimental IDH1 mutants to understand the features that support D2HG production. We show that this new catalytic activity observed in tumors is supported by mutations at residue 132 that have a smaller van der Waals volume and are more hydrophobic. We report that one mutation can support both the normal and neomorphic reactions. These studies illuminate catalytic features of mutations found in the majority of patients with lower grade gliomas. PMID:28330869

Ultrasensitive detection of nucleic acids by template enhanced hybridization followed by rolling circle amplification and catalytic hairpin assembly.

PubMed

Song, Weiling; Zhang, Qiao; Sun, Wenbo

2015-02-11

An ultrasensitive protocol for fluorescent detection of DNA is designed by combining the template enhanced hybridization process (TEHP) with Rolling Circle Amplification (RCA) and Catalytic Hairpin Assembly (CHA), showing a remarkable amplification efficiency.

Characterization of nicotinamidases: steady state kinetic parameters, classwide inhibition by nicotinaldehydes, and catalytic mechanism.

PubMed

French, Jarrod B; Cen, Yana; Vrablik, Tracy L; Xu, Ping; Allen, Eleanor; Hanna-Rose, Wendy; Sauve, Anthony A

2010-12-14

Nicotinamidases are metabolic enzymes that hydrolyze nicotinamide to nicotinic acid. These enzymes are widely distributed across biology, with examples found encoded in the genomes of Mycobacteria, Archaea, Eubacteria, Protozoa, yeast, and invertebrates, but there are none found in mammals. Although recent structural work has improved our understanding of these enzymes, their catalytic mechanism is still not well understood. Recent data show that nicotinamidases are required for the growth and virulence of several pathogenic microbes. The enzymes of Saccharomyces cerevisiae, Drosophila melanogaster, and Caenorhabditis elegans regulate life span in their respective organisms, consistent with proposed roles in the regulation of NAD(+) metabolism and organismal aging. In this work, the steady state kinetic parameters of nicotinamidase enzymes from C. elegans, Sa. cerevisiae, Streptococcus pneumoniae (a pathogen responsible for human pneumonia), Borrelia burgdorferi (the pathogen that causes Lyme disease), and Plasmodium falciparum (responsible for most human malaria) are reported. Nicotinamidases are generally efficient catalysts with steady state k(cat) values typically exceeding 1 s(-1). The K(m) values for nicotinamide are low and in the range of 2 -110 μM. Nicotinaldehyde was determined to be a potent competitive inhibitor of these enzymes, binding in the low micromolar to low nanomolar range for all nicotinamidases tested. A variety of nicotinaldehyde derivatives were synthesized and evaluated as inhibitors in kinetic assays. Inhibitions are consistent with reaction of the universally conserved catalytic Cys on each enzyme with the aldehyde carbonyl carbon to form a thiohemiacetal complex that is stabilized by a conserved oxyanion hole. The S. pneumoniae nicotinamidase can catalyze exchange of (18)O into the carboxy oxygens of nicotinic acid with H(2)(18)O. The collected data, along with kinetic analysis of several mutants, allowed us to propose a catalytic mechanism that explains nicotinamidase and nicotinic acid (18)O exchange chemistry for the S. pneumoniae enzyme involving key catalytic residues, a catalytic transition metal ion, and the intermediacy of a thioester intermediate.

Test results of low NO(x) catalytic combustors for gas turbines

NASA Astrophysics Data System (ADS)

Ozawa, Y.; Hirano, J.; Sato, M.; Saiga, M.; Watanabe, S.

1994-07-01

Catalytic combustion is an ultralow NO(x) combustion method, so it is expected that this method will be applied to a gas turbine combustor. However, it is difficult to develop a catalytic combustor because catalytic reliability at high temperature is still insufficient. To overcome this difficulty, we designed a catalytic combust gas at a combustion temperature of 1300 C while keeping the catalytic temperature below 1000 C. After performing preliminary tests using LPG, we designed two types of combustor for natural gas with a capacity equivalent to one combustor used in a 20 MW class multican-type gas turbine. Combustion tests were conducted at atmospheric pressure using natural gas. As a result, it was confirmed that a combustor in which catalytic combustor segments were arranged alternately with premixing nozzles could achieve low NO(x) and high combustion efficiency in the range from 1000 C to 1300 C of the combustor exit gas temperature.

Facile one-pot synthesis of cellulose nanocrystal-supported hollow CuFe2O4 nanoparticles as efficient catalyst for 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Zhang, Sufeng; Zhao, Dongyan; Hou, Chen; Liang, Chen; Li, Hao

2018-06-01

A facile and efficient one-pot method for the synthesis of well-dispersed hollow CuFe2O4 nanoparticles (H-CuFe2O4 NPs) in the presence of cellulose nanocrystals (CNC) as the support was described. Based on the one-pot solvothermal condition control, magnetic H-CuFe2O4 NPs were in-situ grown on the CNC surface uniformly. TEM images indicated good dispersity of H-CuFe2O4 NPs with uniform size of 300 nm. The catalytic activity of H-CuFe2O4/CNC was tested in the catalytic reduction of 4-nitrophenol (4-NP) in aqueous solution. Compared with most CNC-based ferrite catalysts, H-CuFe2O4/CNC catalyst exhibited an excellent catalytic activity toward the reduction of 4-NP. The catalytic performance of H-CuFe2O4/CNC catalyst was remarkably enhanced with the rate constant of 3.24 s-1 g-1, which was higher than H-CuFe2O4 NPs (0.50 s-1 g-1). The high catalytic activity was attributed to the introduction of CNC and the special hollow mesostructure of H-CuFe2O4 NPs. In addition, the H-CuFe2O4/CNC catalyst promised good conversion efficiency without significant decrease even after 10 cycles, confirming relatively high stability. Because of its environmental sustainability and magnetic separability, H-CuFe2O4/CNC catalyst was shown to indicate that the ferrite nanoparticles supported on CNC were acted as a promising catalyst and exhibited potential applications in numerous ferrite based catalytic reactions.

Monitoring of TiO2-catalytic UV-LED photo-oxidation of cyanide contained in mine wastewater and leachate.

PubMed

Kim, Seong Hee; Lee, Sang Woo; Lee, Gye Min; Lee, Byung-Tae; Yun, Seong-Taek; Kim, Soon-Oh

2016-01-01

A photo-oxidation process using UV-LEDs and TiO2 was studied for removal of cyanide contained in mine wastewater and leachates. This study focused on monitoring of a TiO2-catalyzed LED photo-oxidation process, particularly emphasizing the effects of TiO2 form and light source on the efficiency of cyanide removal. The generation of hydroxyl radicals was also examined during the process to evaluate the mechanism of the photo-catalytic process. The apparent removal efficiency of UV-LEDs was lower than that achieved using a UV-lamp, but cyanide removal in response to irradiation as well as consumption of electrical energy was observed to be higher for UV-LEDs than for UV-lamps. The Degussa P25 TiO2 showed the highest performance of the TiO2 photo-catalysts tested. The experimental results indicate that hydroxyl radicals oxidize cyanide to OCN(-), NO2(-), NO3(-), HCO3(-), and CO3(2-), which have lower toxicity than cyanide. In addition, the overall efficacy of the process appeared to be significantly affected by diverse operational parameters, such as the mixing ratio of anatase and rutile, the type of gas injected, and the number of UV-LEDs used. Copyright © 2015 Elsevier Ltd. All rights reserved.

Controllable fabrication of Pt nanocatalyst supported on N-doped carbon containing nickel nanoparticles for ethanol oxidation.

PubMed

Yu, Jianguo; Dai, Tangming; Cao, Yuechao; Qu, Yuning; Li, Yao; Li, Juan; Zhao, Yongnan; Gao, Haiyan

2018-08-15

In this paper, platinum nanoparticles were deposited on a carbon carrier with the partly graphitized carbon and the highly dispersive carbon-coated nickel particles. An efficient electron transfer structure can be fabricated by controlling the contents of the deposited platinum. The high resolution transmission electron microscopy images of Pt 2 /Ni@C N-doped sample prove the electron transfer channel from Pt (1 1 1) crystal planes to graphite (1 0 0) or Ni (1 1 1) crystal planes due to these linked together crystal planes. The Pt 3 /Ni@C N-doped with low Pt contents cannot form the electron transfer structure and the Pt 1 /Ni@C N-doped with high Pt contents show an obvious aggregation of Pt nanoparticles. The electrochemical tests of all the catalysts show that the Pt 2 /Ni@C N-doped sample presents the highest catalytic activity, the strongest CO tolerance and the best catalytic stability. The high performance is attributed to the efficient electronic transport structure of the Pt 2 /Ni@C N-doped sample and the synergistic effect between Pt and Ni nanoparticles. This paper provides a promising method for enhancing the conductivity of electrode material. Copyright © 2018 Elsevier Inc. All rights reserved.

Bioinspired catalytic generation of high-valent cobalt-oxo species by the axially coordinated CoPc on pyridine-functionalized MWCNTs for the elimination of organic contaminants

NASA Astrophysics Data System (ADS)

Li, Nan; Wang, Ying; Wu, Chenren; Lu, Wangyang; Pei, Kemei; Chen, Wenxing

2018-03-01

Enzymes have always been a source of inspiration for the design and improvement of catalysts. Many examples are occurring in heme/non-heme metalloenzymes with the generation of active high-valent metal-oxo intermediates that are controlled by the surrounding amino acids/protein and axial residue ligands, facilitating the efficient oxidation of substrates in biochemical processes. Here, the high-valent cobalt-oxo species have been formed during the heterolysis of H2O2 activated by the bioinspired catalyst, axially coordinated cobalt phthalocyanine (CoPc) on pyridine-functionalized multi-walled carbon nanotubes (MWCNTs-Py), characterized by ultraviolet-visible and X-ray photoelectron spectroscopy. Formation process of the active cobalt-oxo species has been further confirmed by electrospray ionization mass spectrometry analysis and the results from the density functional theory (B3LYP/6-311G) calculations. Such high-valent cobalt-oxo species exhibit high reactivity and enough persistence for the oxidation of the target substrate, C.I. Acid Red 1. The oxidation products are nearly biodegradable small molecules identified by ultra-performance liquid chromatography/high-definition mass spectrometry. This strategy provides a foundation on developing efficient and persistent catalytic system, in particular oxidation processes based on the complex catalysts with N4 macrocycle structures.

Pulsed discharge plasma induced Fenton-like reactions for the enhancement of the degradation of 4-chlorophenol in water.

PubMed

Hao, Xiaolong; Zhou, Minghua; Xin, Qing; Lei, Lecheng

2007-02-01

To sufficiently utilize chemically active species and enhance the degradation rate and removal efficiency of toxic and biorefractory organic pollutant para-chlorophenol (para-CP), the introductions of iron metal ions (Fe2+/Fe3+) into either pulsed discharge plasma (PDP) process or the PDP process with TiO2 photo-catalyst were tentatively performed. The experimental results showed that under the same experimental condition, the degradation rate and removal efficiency of para-CP were greatly enhanced by the introduction of iron ions (Fe2+/Fe3+) into the PDP process. Moreover, when iron ions and TiO2 were added together in the PDP process, the degradation rate and removal energy of para-CP further improved. The possible mechanism was discussed that the obvious promoting effects were attributed to ferrous ions via plasma induced Fenton-like reactions by UV light irradiation excited and hydrogen peroxide formed in pulsed electrical discharge, resulting in a larger amount of hydroxyl radicals produced from the residual hydrogen peroxide. In addition, the regeneration of ferric ions to ferrous ions facilitates the progress of plasma induced Fenton-like reactions by photo-catalytic reduction of UV light, photo-catalytic reduction on TiO2 surface and electron transfer of quinone intermediates, i.e. 1,4-hydroquinone and 1,4-benzoquinone.

Electrochemical reduction of CO2 to CO over Zn in propylene carbonate/tetrabutylammonium perchlorate

NASA Astrophysics Data System (ADS)

Shen, Feng-xia; Shi, Jin; Chen, Tian-you; Shi, Feng; Li, Qing-yuan; Zhen, Jian-zheng; Li, Yun-fei; Dai, Yong-nian; Yang, Bin; Qu, Tao

2018-02-01

Developing low cost and high efficient electrode for carbon dioxide (CO2) reduction in organic media is essential for practical application. Zn is a cheap metal and has high catalytic effects on CO2 reduction to carbon monoxide (CO) in aqueous solution. However, little attention has been given to investigate the performance of Zn in organic media for CO2 reduction. In present work, we have conducted CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate on Zn due to that propylene carbonate is a widely used industrial absorber, and tetrabutylammonium perchlorate is a commonly used organic supporting electrolyte. In addition, because electrochemical reduction of CO2 to CO naturally produces H2O, we have discussed water effects on CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate+6.8 wt % H2O. Our experiment results reveal that the faradaic efficiency for CO formation reaches to 83%, and the current density remains stable at 6.72 mA/cm2 at voltage -2.3 V for 4 h. Interestingly, Zn presents higher catalytic activity than Ag, and slightly lower than Au. X-ray photoelectron spectroscopy results confirm that no poisonous species is formed and absorbed on the cathode, which is an important advantage in practical application.

Improvement of thermostability and halostability of β-1,3-1,4-glucanase by substituting hydrophobic residue for Lys48.

PubMed

Lee, Jong Min; Moon, Soo Young; Kim, Yu-Ri; Kim, Kang Woong; Lee, Bong-Joo; Kong, In-Soo

2017-01-01

The aim of this study was to improve the stability of β-1,3-1,4-glucanase by substituting hydrophobic residue for specific amino acid. The results indicated that the catalytic efficiency, thermostability and halostability were enhanced simultaneously by replacement of Lys48 with Ala (K48A) or Leu (K48L). Comparison of kinetic parameters revealed that catalytic efficiency of mutants is enhanced as a result of the increase in substrate affinity. A great improvement in thermostability and halostability was observed. The half-lives of mutants significantly increased (up to ∼7-fold) at 60-70°C. Moreover, relative enzymatic activities of mutants were observed more than 80% even in the presence of 30% NaCl, and half-lives were increased to 3-fold that of wild-type. Based on above results, when applied to ionic liquid, mutants were more active and stable compared to wild-type. These were the results from improvement of protein functions by the substitution of hydrophobic single residue in adjacent with forming carbohydrate binding cavity. Therefore, this report could be helpful for improvement of the enzyme property and for biotechnological application as well. Copyright © 2016 Elsevier B.V. All rights reserved.

Surface-immobilized DNAzyme-type biocatalysis

NASA Astrophysics Data System (ADS)

Stefan, Loic; Lavergne, Thomas; Spinelli, Nicolas; Defrancq, Eric; Monchaud, David

2014-02-01

The structure of the double helix of deoxyribonucleic acid (DNA, also called duplex-DNA) was elucidated sixty years ago by Watson, Crick, Wilkins and Franklin. Since then, DNA has continued to hold a fascination for researchers in diverse fields including medicine and nanobiotechnology. Nature has indeed excelled in diversifying the use of DNA: beyond its canonical role of repository of genetic information, DNA could also act as a nanofactory able to perform some complex catalytic tasks in an enzyme-mimicking manner. The catalytic capability of DNA was termed DNAzyme; in this context, a peculiar DNA structure, a quadruple helix also named quadruplex-DNA, has recently garnered considerable interest since its autonomous catalytic proficiency relies on its higher-order folding that makes it suitable to interact efficiently with hemin, a natural cofactor of many enzymes. Quadruplexes have thus been widely studied for their hemoprotein-like properties, chiefly peroxidase-like activity, i.e., their ability to perform hemin-mediated catalytic oxidation reactions. Recent literature is replete with applications of quadruplex-based peroxidase-mimicking DNAzyme systems. Herein, we take a further leap along the road to biochemical applications, assessing the actual efficiency of catalytic quadruplexes for the detection of picomolar levels of surface-bound analytes in an enzyme-linked immunosorbent (ELISA)-type assay. To this end, we exploit an innovative strategy based on the functionalization of DNA by a multitasking platform named RAFT (for regioselectivity addressable functionalized template), whose versatility enables the grafting of DNA whatever its nature (duplex-DNA, quadruplex-DNA, etc.). We demonstrate that the resulting biotinylated RAFT/quadruplex systems indeed acquire catalytic properties that allow for efficient luminescent detection of picomoles of surface-bound streptavidin. We also highlight some of the pitfalls that have to be faced during optimization, notably demonstrating that highly optimized experimental conditions can make DNA pre-catalysts catalytically competent whatever their secondary structures.

Engineered stabilization and structural analysis of the autoinhibited conformation of PDE4

DOE PAGES

Cedervall, Peder; Aulabaugh, Ann; Geoghegan, Kieran F.; ...

2015-03-09

Phosphodiesterase 4 (PDE4) is an essential contributor to intracellular signaling and an important drug target. The four members of this enzyme family (PDE4A to -D) are functional dimers in which each subunit contains two upstream conserved regions (UCR), UCR1 and -2, which precede the C-terminal catalytic domain. Alternative promoters, transcriptional start sites, and mRNA splicing lead to the existence of over 25 variants of PDE4, broadly classified as long, short, and supershort forms. We report the X-ray crystal structure of long form PDE4B containing UCR1, UCR2, and the catalytic domain, crystallized as a dimer in which a disulfide bond cross-linksmore » cysteines engineered into UCR2 and the catalytic domain. Biochemical and mass spectrometric analyses showed that the UCR2-catalytic domain interaction occurs in trans, and established that this interaction regulates the catalytic activity of PDE4. By elucidating the key structural determinants of dimerization, we show that only long forms of PDE4 can be regulated by this mechanism. The results also provide a structural basis for the long-standing observation of high- and low-affinity binding sites for the prototypic inhibitor rolipram.« less

Highly efficient and recyclable basic mesoporous zeolite catalyzed condensation, hydroxylation, and cycloaddition reactions.

PubMed

Sarmah, Bhaskar; Satpati, Biswarup; Srivastava, Rajendra

2017-05-01

Crystalline mesoporous ZSM-5 zeolite was prepared in the presence of 1,4-diazabicyclo[2.2.2]octane derived multi-cationic structure directing agent. The calcined form of the mesoprous zeolite was treated with NH 4 OH to obtain basic mesoporous ZSM-5. Catalyst was characterized by the complementary combination of X-ray diffraction, N 2 -adsorption, electron microscopes, and temperature programme desorption techniques. Catalytic activity of the basic mesoporous ZSM-5 was systematically assessed using Knoevenagel condensation reaction for the synthesis a wide range of substituted styrene. Applications of the catalyst were investigated in the benzamide hydroxylation for the synthesis of carbinolamides and one-pot, multi-component condensation reaction for the synthesis of naphthopyrans. Finally, the catalyst was evaluated in the cycloaddition of CO 2 to epoxide for the synthesis of cyclic carbonates. Recycling study shows that no significant decrease in the catalytic activity was observed after five recycles. Copyright © 2017. Published by Elsevier Inc.

Pt-like Hydrogen Evolution Electrocatalysis on PANI/CoP Hybrid Nanowires by Weakening the Shackles of Hydrogen Ions on the Surfaces of Catalysts.

PubMed

Feng, Jin-Xian; Tong, Si-Yao; Tong, Ye-Xiang; Li, Gao-Ren

2018-04-18

The search for high active, stable, and cost-efficient hydrogen evolution reaction (HER) electrocatalysts for water electrolysis has attracted great interest. The coordinated water molecules in the hydronium ions will obviously reduce the positive charge density of H + and hamper the ability of H + to receive electrons from the cathode, leading to large overpotential of HER on nonprecious metal catalysts. Here we realize Pt-like hydrogen evolution electrocatalysis on polyaniline (PANI) nanodots (NDs)-decorated CoP hybrid nanowires (HNWs) supported on carbon fibers (CFs) (PANI/CoP HNWs-CFs) as PANI can effectively capture H + from hydronium ions to form protonated amine groups that have higher positive charge density than those of hydronium ions and can be electro-reduced easily. The PANI/CoP HNWs-CFs as low-cost electrocatalysts show excellent catalytic performance toward HER in acidic solution, such as super high catalytic activity, small Tafel slope, and superior stability.

A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation

NASA Astrophysics Data System (ADS)

Garrison Kinney, R.; Tjutrins, Jevgenijs; Torres, Gerardo M.; Liu, Nina Jiabao; Kulkarni, Omkar; Arndtsen, Bruce A.

2018-02-01

The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.

Peptide B12: emerging trends at the interface of inorganic chemistry, chemical biology and medicine.

PubMed

Zelder, Felix; Zhou, Kai; Sonnay, Marjorie

2013-01-28

The sophisticated and efficient delivery of vitamin B(12) ("B(12)") into cells offers promise for B(12)-bioconjugates in medicinal diagnosis and therapy. It is therefore surprising that rather little attention is presently paid to an alternative strategy in drug design: the development of structurally perfect, but catalytically inactive semi-artificial B(12) surrogates. Vitamin B(12) cofactors catalyse important biological transformations and are indispensible for humans and most other forms of life. This strong metabolic dependency exhibits enormous medicinal opportunities. Inhibitors of B(12) dependent enzymes are potential suppressors of fast proliferating cancer cells. This perspective article focuses on the design and study of backbone modified B(12) derivatives, particularly on peptide B(12) derivatives. Peptide B(12) is a recently introduced class of biomimetic cobalamins bearing an artificial peptide backbone with adjustable coordination and redox-properties. Pioneering biological studies demonstrated reduced catalytic activity, combined with inhibitory potential that is encouraging for future efforts in turning natural cofactors into new anti-proliferative agents.

A Janus cobalt-based catalytic material for electro-splitting of water

NASA Astrophysics Data System (ADS)

Cobo, Saioa; Heidkamp, Jonathan; Jacques, Pierre-André; Fize, Jennifer; Fourmond, Vincent; Guetaz, Laure; Jousselme, Bruno; Ivanova, Valentina; Dau, Holger; Palacin, Serge; Fontecave, Marc; Artero, Vincent

2012-09-01

The future of energy supply depends on innovative breakthroughs regarding the design of cheap, sustainable and efficient systems for the conversion and storage of renewable energy sources. The production of hydrogen through water splitting seems a promising and appealing solution. We found that a robust nanoparticulate electrocatalytic material, H2-CoCat, can be electrochemically prepared from cobalt salts in a phosphate buffer. This material consists of metallic cobalt coated with a cobalt-oxo/hydroxo-phosphate layer in contact with the electrolyte and mediates H2 evolution from neutral aqueous buffer at modest overpotentials. Remarkably, it can be converted on anodic equilibration into the previously described amorphous cobalt oxide film (O2-CoCat or CoPi) catalysing O2 evolution. The switch between the two catalytic forms is fully reversible and corresponds to a local interconversion between two morphologies and compositions at the surface of the electrode. After deposition, the noble-metal-free coating thus functions as a robust, bifunctional and switchable catalyst.

Structural and Functional Insights into the Catalytic Inactivity of the Major Fraction of Buffalo Milk Xanthine Oxidoreductase

PubMed Central

Gadave, Kaustubh S.; Panda, Santanu; Singh, Surender; Kalra, Shalini; Malakar, Dhruba; Mohanty, Ashok K.; Kaushik, Jai K.

2014-01-01

Background Xanthine oxidoreductase (XOR) existing in two interconvertible forms, xanthine dehydrogenase (XDH) and xanthine oxidase (XO), catabolises xanthine to uric acid that is further broken down to antioxidative agent allantoin. XOR also produces free radicals serving as second messenger and microbicidal agent. Large variation in the XO activity has been observed among various species. Both hypo and hyper activity of XOR leads to pathophysiological conditions. Given the important nutritional role of buffalo milk in human health especially in south Asia, it is crucial to understand the functional properties of buffalo XOR and the underlying structural basis of variations in comparison to other species. Methods and Findings Buffalo XO activity of 0.75 U/mg was almost half of cattle XO activity. Enzymatic efficiency (k cat/K m) of 0.11 sec−1 µM−1 of buffalo XO was 8–10 times smaller than that of cattle XO. Buffalo XOR also showed lower antibacterial activity than cattle XOR. A CD value (Δε430 nm) of 46,000 M−1 cm−1 suggested occupancy of 77.4% at Fe/S I centre. Buffalo XOR contained 0.31 molybdenum atom/subunit of which 48% existed in active sulfo form. The active form of XO in buffalo was only 16% in comparison to ∼30% in cattle. Sequencing revealed 97.4% similarity between buffalo and cattle XOR. FAD domain was least conserved, while metal binding domains (Fe/S and Molybdenum) were highly conserved. Homology modelling of buffalo XOR showed several variations occurring in clusters, especially close to FAD binding pocket which could affect NAD+ entry in the FAD centre. The difference in XO activity seems to be originating from cofactor deficiency, especially molybdenum. Conclusion A major fraction of buffalo milk XOR exists in a catalytically inactive form due to high content of demolybdo and desulfo forms. Lower Fe/S content and structural factors might be contributing to lower enzymatic efficiency of buffalo XOR in a minor way. PMID:24498153

In situ synthesis and catalytic application of reduced graphene oxide supported cobalt nanowires

NASA Astrophysics Data System (ADS)

Xu, Zhiqiang; Long, Qin; Deng, Yi; Liao, Li

2018-05-01

Controlled synthesis of magnetic nanocomposite with outstanding catalytic performances is a promising strategy in catalyst industry. We proposed a novel concept for fabrication of reduced graphene oxide-supported cobalt nanowires (RGO/Co-NWs) nanocomposite as high-efficient magnetic catalyst. Unlike the majority of experiments necessitating harsh synthesis conditions such as high-pressure, high-temperature and expensive template, here the RGO/Co-NWs were successfully prepared in aqueous solution under mild conditions with the assistance of external magnetic field. The synthetic process was facile and external magnetic force was adopted to induce the unidirectional self-assembly of cobalt crystals on graphene oxide to form RGO/Co-NWs. The possible formation mechanism laid on the fact that the dipole magnetic moments of the nanoparticles were aligned along the magnetic induction lines with the external magnetic field direction resulting in the formation of nanowires elongating in the direction of the magnetization axis. Simultaneously, a series of controlled reactions were conducted to illuminate the effect of graphene oxide, external magnetic field and PVP on the morphology and size of RGO/Co-NWs in the present approach. More importantly, the nanocomposite exhibited a high catalytic performance towards ammonia borane. Hence the novel nanocomposite holds a great potential for technological applications such as catalyst industry.

Occurrence of dead core in catalytic particles containing immobilized enzymes: analysis for the Michaelis-Menten kinetics and assessment of numerical methods.

PubMed

Pereira, Félix Monteiro; Oliveira, Samuel Conceição

2016-11-01

In this article, the occurrence of dead core in catalytic particles containing immobilized enzymes is analyzed for the Michaelis-Menten kinetics. An assessment of numerical methods is performed to solve the boundary value problem generated by the mathematical modeling of diffusion and reaction processes under steady state and isothermal conditions. Two classes of numerical methods were employed: shooting and collocation. The shooting method used the ode function from Scilab software. The collocation methods included: that implemented by the bvode function of Scilab, the orthogonal collocation, and the orthogonal collocation on finite elements. The methods were validated for simplified forms of the Michaelis-Menten equation (zero-order and first-order kinetics), for which analytical solutions are available. Among the methods covered in this article, the orthogonal collocation on finite elements proved to be the most robust and efficient method to solve the boundary value problem concerning Michaelis-Menten kinetics. For this enzyme kinetics, it was found that the dead core can occur when verified certain conditions of diffusion-reaction within the catalytic particle. The application of the concepts and methods presented in this study will allow for a more generalized analysis and more accurate designs of heterogeneous enzymatic reactors.

One-Pot Green Synthesis of Ag-Decorated SnO2 Microsphere: an Efficient and Reusable Catalyst for Reduction of 4-Nitrophenol.

PubMed

Hu, Min; Zhang, Zhenwei; Luo, Chenkun; Qiao, Xiuqing

2017-12-01

In this paper, hierarchical Ag-decorated SnO 2 microspheres were synthesized by a facile one-pot hydrothermal method. The resulting composites were characterized by XRD, SEM, TEM, XPS, BET, and FTIR analysis. The catalytic performances of the samples were evaluated with the reduction of 4-nitrophenol to 4-aminophenol by potassium borohydride (KBH 4 ) as a model reaction. Time-dependent experiments indicated that the hierarchical microspheres assembled from SnO 2 and Ag nanoparticles can be formed when the react time is less than 10 h. With the increase of hydrothermal time, SnO 2 nanoparticles will self-assemble into SnO 2 nanosheets and Ag nanoparticles decorated SnO 2 nanosheets were obtained. When evaluated as catalyst, the obtained Ag-decorated SnO 2 microsphere prepared for 36 h exhibited excellent catalytic performance with normalized rate constant (κ nor ) of 6.20 min -1 g -1 L, which is much better than that of some previous reported catalysts. Moreover, this Ag-decorated SnO 2 microsphere demonstrates good reusability after the first five cycles. In addition, we speculate the formation mechanism of the hierarchical Ag-decorated SnO 2 microsphere and discussed the possible origin of the excellent catalytic activity.

Identifying the Atomic-Level Effects of Metal Composition on the Structure and Catalytic Activity of Peptide-Templated Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Merrill, Nicholas A.; McKee, Erik M.; Merino, Kyle C.

2015-10-12

Bioinspired approaches for the formation of metallic nanomaterials have been extensively employed for a diverse range of applications including diagnostics and catalysis. These materials can often be used under sustainable conditions; however, it is challenging to control the material size, morphology, and composition simultaneously. Here we have employed the R5 peptide, which forms a 3D scaffold to direct the size and linear shape of bimetallic PdAu nanomaterials for catalysis. The materials were prepared at varying Pd:Au ratios to probe optimal compositions to achieve maximal catalytic efficiency. These materials were extensively characterized at the atomic level using transmission electron microscopy, extendedmore » X-ray absorption fine structure spectroscopy, and atomic pair distribution function analysis derived from high-energy X-ray diffraction patterns to provide highly resolved structural information. The results confirmed PdAu alloy formation, but also demonstrated that significant surface structural disorder was present. The catalytic activity of the materials was studied for olefin hydrogenation, which demonstrated enhanced reactivity from the bimetallic structures.These results present a pathway to the bioinspired production of multimetallic materials with enhanced properties, which can be assessed via a suite of characterization methods to fully ascertain structure/function relationships.« less

Enhanced Catalytic Reduction of 4-Nitrophenol Driven by Fe3O4-Au Magnetic Nanocomposite Interface Engineering: From Facile Preparation to Recyclable Application

PubMed Central

Chen, Yue; Zhang, Yuanyuan; Kou, Qiangwei; Liu, Yang; Han, Donglai; Wang, Dandan; Sun, Yantao; Zhang, Yongjun; Wang, Yaxin; Lu, Ziyang; Chen, Lei; Yang, Jinghai; Xing, Scott Guozhong

2018-01-01

In this work, we report the enhanced catalytic reduction of 4-nitrophenol driven by Fe3O4-Au magnetic nanocomposite interface engineering. A facile solvothermal method is employed for Fe3O4 hollow microspheres and Fe3O4-Au magnetic nanocomposite synthesis via a seed deposition process. Complementary structural, chemical composition and valence state studies validate that the as-obtained samples are formed in a pure magnetite phase. A series of characterizations including conventional scanning/transmission electron microscopy (SEM/TEM), Mössbauer spectroscopy, magnetic testing and elemental mapping is conducted to unveil the structural and physical characteristics of the developed Fe3O4-Au magnetic nanocomposites. By adjusting the quantity of Au seeds coating on the polyethyleneimine-dithiocarbamates (PEI-DTC)-modified surfaces of Fe3O4 hollow microspheres, the correlation between the amount of Au seeds and the catalytic ability of Fe3O4-Au magnetic nanocomposites for 4-nitrophenol (4-NP) is investigated systematically. Importantly, bearing remarkable recyclable features, our developed Fe3O4-Au magnetic nanocomposites can be readily separated with a magnet. Such Fe3O4-Au magnetic nanocomposites shine the light on highly efficient catalysts for 4-NP reduction at the mass production level. PMID:29789457

Hydrothermal conversion of xylose, glucose, and cellulose under the catalysis of transition metal sulfates.

PubMed

Cao, Xuefei; Peng, Xinwen; Sun, Shaoni; Zhong, Linxin; Chen, Wei; Wang, Sha; Sun, Run-Cang

2015-03-15

Hydrothermal conversion (HTC) is an important thermochemical process to upgrade low-cost biomass into valuable chemicals or fuels. As compared with non-catalytic HTC, catalytic HTC shows high energy efficiency on biomass upgradation. In this work, the catalytic performances of various transition metal sulfates (Mn(2+), Fe(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), and Zn(2+)) in the HTCs of xylose, glucose, and cellulose under different conditions were explored. Among these catalysts, Zn(2+) and Ni(2+) showed obvious effects on the conversions of xylose, glucose, and cellulose into lactic acid, while Cu(2+) and Fe(3+), which could significantly accelerate the hydrolysis of cellulose into glucose at 200°C, displayed high efficiency on converting glucose and cellulose into levulinic acid and formic acid at high temperature. Additionally, significant positive correlative relationships among xylose, glucose, and cellulose degradations were observed. This study is helpful for screening appropriate catalysts for biomass upgradation through catalytic HTC of monosaccharide. Copyright © 2014 Elsevier Ltd. All rights reserved.

Iron doped fibrous-structured silica nanospheres as efficient catalyst for catalytic ozonation of sulfamethazine.

PubMed

Bai, Zhiyong; Wang, Jianlong; Yang, Qi

2018-04-01

Sulfonamide antibiotics are ubiquitous pollutants in aquatic environments due to their large production and extensive application. In this paper, the iron doped fibrous-structured silica (KCC-1) nanospheres (Fe-KCC-1) was prepared, characterized, and applied as a catalyst for catalytic ozonation of sulfamethazine (SMT). The effects of ozone dosage, catalyst dosage, and initial concentration of SMT were examined. The experimental results showed that Fe-KCC-1 had large surface area (464.56 m2 g -1 ) and iron particles were well dispersed on the catalyst. The catalyst had high catalytic performance especially for the mineralization of SMT, with mineralization ratio of about 40% in a wide pH range. With addition of Fe-KCC-1, the ozone utilization increased nearly two times than single ozonation. The enhancement of SMT degradation was mainly due to the surface reaction, and the increased mineralization of SMT was due to radical mechanism. Fe-KCC-1 was an efficient catalyst for SMT degradation in catalytic ozonation system.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, Jing; Aguiar, Jeffery A.; Ferrere, Suzanne

Achieving solar-to-hydrogen efficiencies above 15% is key for the commercial success of photoelectrochemical water splitting devices. While tandem cells can reach those efficiencies, increasing the catalytic activity and long-term stability remains a significant challenge. We show that annealing a bilayer of amorphous titanium dioxide (TiO x) and molybdenum sulfide (MoS x) deposited onto GaInP 2 results in a photocathode with high catalytic activity (current density of 11 mA/cm -2 at 0 V vs. the reversible hydrogen electrode under 1 sun illumination) and stability (retention of 80% of initial photocurrent density over a 20 h durability test) for the hydrogen evolutionmore » reaction. Microscopy and spectroscopy reveal that annealing results in a graded MoS x/MoO x/TiO 2 layer that retains much of the high catalytic activity of amorphous MoS x but with stability similar to crystalline MoS 2. These findings demonstrate the potential of utilizing a hybridized, heterogeneous surface layer as a cost-effective catalytic and protective interface for solar hydrogen production.« less

Analytic Corrections to CFD Heating Predictions Accounting for Changes in Surface Catalysis. Part II

NASA Technical Reports Server (NTRS)

Gnoffo, Peter A.; Inger, George R.

1996-01-01

A new approach for combining the insight afforded by integral boundary-layer analysis with comprehensive (but time intensive) computational fluid dynamic (CFD) flowfield solutions of the thin-layer Navier-Stokes equations is described. The approach extracts CFD derived quantities at the wall and at the boundary layer edge for inclusion in a post-processing boundary-layer analysis. It allows a designer at a work-station to address two questions, given a single CFD solution. (1) How much does the heating change for a thermal protection system (TPS) with different catalytic properties than was used in the original CFD solution? (2) How does the heating change at the interface of two different TPS materials with an abrupt change in catalytic efficiency? The answer to the second question is particularly important, because abrupt changes from low to high catalytic efficiency can lead to localized increase in heating which exceeds the usually conservative estimate provided by a fully catalytic wall assumption. Capabilities of this approach for application to Reusable Launch Vehicle (RLV) design are demonstrated. If the definition of surface catalysis is uncertain early in the design process, results show that fully catalytic wall boundary conditions provide the best baseline for CFD design points.

Redox-inactive metal ions promoted the catalytic reactivity of non-heme manganese complexes towards oxygen atom transfer.

PubMed

Choe, Cholho; Yang, Ling; Lv, Zhanao; Mo, Wanling; Chen, Zhuqi; Li, Guangxin; Yin, Guochuan

2015-05-21

Redox-inactive metal ions can modulate the reactivity of redox-active metal ions in a variety of biological and chemical oxidations. Many synthetic models have been developed to help address the elusive roles of these redox-inactive metal ions. Using a non-heme manganese(II) complex as the model, the influence of redox-inactive metal ions as a Lewis acid on its catalytic efficiency in oxygen atom transfer was investigated. In the absence of redox-inactive metal ions, the manganese(II) catalyst is very sluggish, for example, in cyclooctene epoxidation, providing only 9.9% conversion with 4.1% yield of epoxide. However, addition of 2 equiv. of Al(3+) to the manganese(II) catalyst sharply improves the epoxidation, providing up to 97.8% conversion with 91.4% yield of epoxide. EPR studies of the manganese(II) catalyst in the presence of an oxidant reveal a 16-line hyperfine structure centered at g = 2.0, clearly indicating the formation of a mixed valent di-μ-oxo-bridged diamond core, Mn(III)-(μ-O)2-Mn(IV). The presence of a Lewis acid like Al(3+) causes the dissociation of this diamond Mn(III)-(μ-O)2-Mn(IV) core to form monomeric manganese(iv) species which is responsible for improved epoxidation efficiency. This promotional effect has also been observed in other manganese complexes bearing various non-heme ligands. The findings presented here have provided a promising strategy to explore the catalytic reactivity of some di-μ-oxo-bridged complexes by adding non-redox metal ions to in situ dissociate those dimeric cores and may also provide clues to understand the mechanism of methane monooxygenase which has a similar diiron diamond core as the intermediate.

Catalytic degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nano-Fe2O3 activated peroxymonosulfate: Influential factors and mechanism determination.

PubMed

Jaafarzadeh, Nematollah; Ghanbari, Farshid; Ahmadi, Mehdi

2017-02-01

2,4-Dichlorophenoxyacetic acid (2,4-D) is one of the most applicable herbicides in the world. Therefore, its residue in aquatic environment threatens the human health and ecosystems. In this study, Fe 2 O 3 (hematite) nanoparticles (HNPs) were synthesized, and the characteristics of the obtained HNPs were determined using X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) technique, and particle size analyzer (PSA). The catalytic activity of HNPs was evaluated for the activation of peroxymonosulfate (PMS) for the degradation of 2,4-D. The effects of the operating parameters were studied for the PMS/HNPs system. The results showed that the acidic condition provided higher efficiency, while overdosing of PMS had a scavenging effect. The PMS/HNPs showed high efficiency in comparison with the homogeneous forms of iron (Fe 2+ and Fe 3+ ). Reusability of HNPs was studied in five consequent usages. The presence of the anions (chloride, nitrate, and hydrogen phosphate) reduced the 2,4-D degradation. Moreover, the catalytic activity of HNPs was also investigated in the presence of other oxidants. UV irradiation increased the function of PMS/HNPs and its mechanism was described. The order of 2,4-D removal for the oxidants was PMS > persulfate > H 2 O 2  > percarbonate. A total of 29.7% of 2,4-D chlorine content was released during the destruction of 2,4-D. The quenching study showed that sulfate radical was the major agent in the degradation of 2,4-D. Copyright © 2016 Elsevier Ltd. All rights reserved.

Exploring the Influence of Domain Architecture on the Catalytic Function of Diterpene Synthases.

PubMed

Pemberton, Travis A; Chen, Mengbin; Harris, Golda G; Chou, Wayne K W; Duan, Lian; Köksal, Mustafa; Genshaft, Alex S; Cane, David E; Christianson, David W

2017-04-11

Terpenoid synthases catalyze isoprenoid cyclization reactions underlying the generation of more than 80,000 natural products. Such dramatic chemodiversity belies the fact that these enzymes generally consist of only three domain folds designated as α, β, and γ. Catalysis by class I terpenoid synthases occurs exclusively in the α domain, which is found with α, αα, αβ, and αβγ domain architectures. Here, we explore the influence of domain architecture on catalysis by taxadiene synthase from Taxus brevifolia (TbTS, αβγ), fusicoccadiene synthase from Phomopsis amygdali (PaFS, (αα) 6 ), and ophiobolin F synthase from Aspergillus clavatus (AcOS, αα). We show that the cyclization fidelity and catalytic efficiency of the α domain of TbTS are severely compromised by deletion of the βγ domains; however, retention of the β domain preserves significant cyclization fidelity. In PaFS, we previously demonstrated that one α domain similarly influences catalysis by the other α domain [ Chen , M. , Chou , W. K. W. , Toyomasu , T. , Cane , D. E. , and Christianson , D. W. ( 2016 ) ACS Chem. Biol. 11 , 889 - 899 ]. Here, we show that the hexameric quaternary structure of PaFS enables cluster channeling. We also show that the α domains of PaFS and AcOS can be swapped so as to make functional chimeric αα synthases. Notably, both cyclization fidelity and catalytic efficiency are altered in all chimeric synthases. Twelve newly formed and uncharacterized C 20 diterpene products and three C 25 sesterterpene products are generated by these chimeras. Thus, engineered αβγ and αα terpenoid cyclases promise to generate chemodiversity in the greater family of terpenoid natural products.

Silica, Alumina and Clay Catalyzed Peptide Bond Formation: Enhanced Efficiency of Alumina Catalyst

NASA Astrophysics Data System (ADS)

Bujdák, Juraj; Rode, Bernd M.

1999-10-01

Catalytic efficiencies of clay (hectorite), silica and alumina were tested in peptide bond formation reactions of glycine (Gly), alanine (Ala), proline (Pro), valine (Val) and leucine (Leu). The reactions were performed as drying/wetting (hectorite) and temperature fluctuation (silica and alumina) experiments at 85 °C. The reactivity of amino acids decreased in order Gly > Ala > Pro ~ Val ~ Leu. The highest catalytic efficiency was observed for alumina, the only catalyst producing oligopeptides in all investigated reaction systems. The peptide bond formation on alumina is probably catalyzed by the same sites and via similar reaction mechanisms as some alumina-catalyzed dehydration reactions used in industrial chemistry.

Process to convert biomass and refuse derived fuel to ethers and/or alcohols

DOEpatents

Diebold, J.P.; Scahill, J.W.; Chum, H.L.; Evans, R.J.; Rejai, B.; Bain, R.L.; Overend, R.P.

1996-04-02

A process is described for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols. 35 figs.

Natrolite zeolite supported copper nanoparticles as an efficient heterogeneous catalyst for the 1,3-diploar cycloaddition and cyanation of aryl iodides under ligand-free conditions.

PubMed

Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Khalaj, Mehdi

2015-09-01

In this paper, we report the preparation of Natrolite zeolite supported copper nanoparticles as a heterogeneous catalyst for 1,3-diploar cycloaddition and synthesis aryl nitriles from aryl iodides under ligand-free conditions. The catalyst was characterized using XRD, SEM, TEM, EDS and TG-DTA. The experimental procedure is simple, the products are formed in high yields and the catalyst can be recycled and reused several times without any significant loss of catalytic activity. Copyright © 2015 Elsevier Inc. All rights reserved.

Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons

DOEpatents

Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2011-02-01

Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

Enhanced adsorption and catalytic oxidation of ciprofloxacin by an Ag/AgCl@N-doped activated carbon composite

NASA Astrophysics Data System (ADS)

Nekouei, Farzin; Nekouei, Shahram; Noorizadeh, Hossein

2018-03-01

In this study, we synthesized a new nanocomposite catalyst comprising Ag/AgCl@N-doped activated carbon (Ag/AgCl@N-AC) and demonstrated its high efficiency during the enhanced adsorptive removal and catalytic oxidation of ciprofloxacin (CIP) with peroxymonosulfate (PMS) and persulfate (PS) as oxidants in aqueous solution. The efficiency of the new nanocomposite was compared with those of both pristine AC and N-AC under the same conditions. Furthermore, the effects of oxidants on the catalytic oxidation of CIP were assessed using PMS and PS. We found that the degradation efficiency of CIP with Ag/AgCl@N-AC was higher when using PS as an oxidant, whereas the use of PMS obtained relatively better results with both AC and N-AC. The adsorption processes for AC, N-AC, and Ag/AgCl@N-AC were dominated not only by electrostatic attraction but also by π-π interactions, which had higher impacts on the adsorption processes than the specific surface area.

Molecular characterization of a thermophilic endo-polygalacturonase from Thielavia arenaria XZ7 with high catalytic efficiency and application potential in the food and feed industries.

PubMed

Tu, Tao; Meng, Kun; Huang, Huoqing; Luo, Huiying; Bai, Yingguo; Ma, Rui; Su, Xiaoyun; Shi, Pengjun; Yang, Peilong; Wang, Yaru; Yao, Bin

2014-12-31

Thermophilic endo-polygalacturonases with high catalytic efficiency are of great interest in the food and feed industries. This study identified an endo-polygalacturonase gene (pg7fn) of glycoside hydrolase family 28 in the thermophilic fungus Thielavia arenaria XZ7. Recombinant PG7fn produced in Pichia pastoris is distinguished from other enzyme counterparts by its high functional temperature (60 °C) and specific activity (34382 ± 351 U/mg toward polygalacturonic acid). The enzyme exhibited good pH stability (pH 3.0-8.0) and resistance to pepsin and trypsin digestion and had a significant effect on disaggregation of soybean meal. Addition of 1 U/g PG7fn increased the pectin bioavailability by 19.33%. The excellent properties described above make PG7fn valuable for applications in the food and feed industries. Furthermore, a comparative study showed that N-glycosylation improved the thermostability and catalytic efficiency of PG7fn.

Improvement in the thermostability of chitosanase from Bacillus ehimensis by introducing artificial disulfide bonds.

PubMed

Sheng, Jun; Ji, Xiaofeng; Zheng, Yuan; Wang, Zhipeng; Sun, Mi

2016-10-01

To determine the effects of artificial disulfide bridges on the thermostability and catalytic efficiency of chitosanase EAG1. Five artificial disulfide bridges were designed based on the structural information derived from the three-dimensional (3-D) model of chitosanase EAG1. Two beneficial mutants (G113C/D116C, A207C-L286C) were located in the flexible surface loop region, whereas the similar substitutions introduced in α-helices regions had a negligible effect. Mut5, the most active mutant, had a longer half-life at 50 °C (from 10.5 to 69.3 min) and a 200 % higher catalytic efficiency (K cat/K m) than that of the original EAG1. The contribution of disulfide bridges to enzyme thermostability is mainly dependent on its location within the polypeptide chain. Strategical placement of a disulfide bridge in flexible regions provides a rigid support and creation of a protected microenvironment, which is effective in improving enzyme's thermostability and catalytic efficiency.

3D Flower-like β-MnO2/Reduced Graphene Oxide Nanocomposites for Catalytic Ozonation of Dichloroacetic Acid

NASA Astrophysics Data System (ADS)

Li, Gang; Li, Kezheng; Liu, Aijuan; Yang, Ping; Du, Yukou; Zhu, Mingshan

2017-03-01

Considering the potential use of manganese oxide based nanocomposite in catalytic ozonation of water contaminant, we report unique three-dimensional (3D) nanoarchitectures composed of β-MnO2 and reduced graphene oxide (RGO) for catalytic ozonation of dichloroacetic acid (DCAA) from drinking water. The catalytic results show that the 3D β-MnO2/RGO nanocomposites (FMOG) can be used as efficient and stable ozonation catalysts to eliminate DCAA from water. The probable mechanism of catalytic ozonation was also proposed by detecting intermediates using gas chromatography-mass spectrometry. This result likely paves a facile avenue and initiates new opportunities for the exploration of heterogeneous catalysts for the removal of disinfection by-products from drinking water.

Highly efficient conversion of terpenoid biomass to jet-fuel range cycloalkanes in a biphasic tandem catalytic process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Xiaokun; Li, Teng; Tang, Kan

2017-06-12

The demand for bio-jet fuels to reduce carbon emissions is increasing substantially in the aviation sector, while the scarcity of high-density jet fuel components limits the use of bio-jet fuels in high-performance aircrafts compared with conventional jet fuels. In this paper, we report a novel biphasic tandem catalytic process (biTCP) for synthesizing cycloalkanes from renewable terpenoid biomass, such as 1,8-cineole. Multistep tandem reactions, including C–O ring opening by hydrolysis, dehydration, and hydrogenation, were carried out in the “one-pot” biTCP. 1,8-Cineole was efficiently converted to p-menthane at high yields (>99%) in the biTCP under mild reaction conditions. Finally, the catalytic reactionmore » mechanism is discussed.« less

Cleave and couple: toward fully sustainable catalytic conversion of lignocellulose to value added building blocks and fuels.

PubMed

Sun, Zhuohua; Barta, Katalin

2018-06-21

The structural complexity of lignocellulose offers unique opportunities for the development of entirely new, energy efficient and waste-free pathways in order to obtain valuable bio-based building blocks. Such sustainable catalytic methods - specifically tailored to address the efficient conversion of abundant renewable starting materials - are necessary to successfully compete, in the future, with fossil-based multi-step processes. In this contribution we give a summary of recent developments in this field and describe our "cleave and couple" strategy, where "cleave" refers to the catalytic deconstruction of lignocellulose to aromatic and aliphatic alcohol intermediates, and "couple" involves the development of novel, sustainable transformations for the formation of C-C and C-N bonds in order to obtain a range of attractive products from lignocellulose.

Comparative effects of MTBE and ethanol additions into gasoline on exhaust emissions

NASA Astrophysics Data System (ADS)

Song, Chong-Lin; Zhang, Wen-Mei; Pei, Yi-Qiang; Fan, Guo-Liang; Xu, Guan-Peng

The effects of the additives of ethanol (EA) and methyl tert-butyl ether (MTBE) in various blend ratios into the gasoline fuel on the exhaust emissions and the catalytic conversion efficiencies were investigated in an EFI gasoline engine. The regulated exhaust emissions (CO, THC and NO X) and the unregulated exhaust emissions (benzene, formaldehyde, acetaldehyde, unburned EA and MTBE) before and after the three-way catalytic converter were measured. The experimental results showed that EA brought about generally lower regulated engine-out emissions than MTBE did. But, the comparison of the unregulated engine-out emissions between both additives was different. Concretely, the effect of EA on benzene emission was worse than that of MTBE on the whole, which was a contrast with formaldehyde emission. The difference in the acetaldehyde comparison depended much on the engine operating conditions, especially the engine speed. Both EA and MTBE were identified in the engine exhaust gases only when they were added to the fuel, and their volume fraction increased with blend ratios. The catalytic conversion efficiencies of the regulated emissions for the EA blends were in general lower than those for MTBE blends, especially at the low and high engine speeds. There was little difference in the catalytic conversion efficiencies for both benzene and formaldehyde, while distinct difference for acetaldehyde.

Measurement of total polychlorinated biphenyls (PCBs) in catalytic combustion effluents using a simple HPLC procedure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perera, S.P.; Jefferies, T.M.

1995-05-01

The production, use and toxicity of Polychlorinated biphenyls (PCBs) has been discussed in detail and increasing concern has been shown by the scientific community and by the public about the effectiveness of thermal incineration as an environmentally satisfactory means of destroying polychlorinated biphenyls. Therefore, a greater need for alternative, more efficient, low energy processes such as catalytic combustion, has been discussed. This paper is part of research to investigate the catalytic combustion of Aroclor 1242 in a packed bed reactor using chromia on an alumina support and other oxidation catalysts. It was essential for these studies to be able tomore » determine the PCB destruction efficiencies of the catalytic processes examined. The high efficiency of capillary GC columns permits the resolution of an Aroclor into a chromatogram consisting mainly of individual PCB congeners. The chromatogram may typically contain 50-150 peaks. Quantification requires each peak to be identified and individual response factors assigned before the amount of each congener present may be calculated. Response factors vary and the high cost of purchasing all individual PCB standards was prohibitive. A commonly adopted alternative method is to measure only the 6 or 7 individual PCB congeners available as a commercial mixture and convert the answer into a value for an Aroclor, not an accurate measure of the destruction efficiency of PCBs. This paper describes a simple quantitative HPLC method that measures all PCBs as a single peak. 14 refs., 3 figs., 1 tab.« less

Refining cocoon to prepare (N, S, and Fe) ternary-doped porous carbon aerogel as efficient catalyst for the oxygen reduction reaction in alkaline medium

NASA Astrophysics Data System (ADS)

Li, Changqing; Sun, Fengzhan; Lin, Yuqing

2018-04-01

Various advanced sulfur doped Fe-N-C non-noble metal catalysts of oxygen reduction reaction (ORR) have been recently designed and reported with excellent catalytic activity. Herein, we refined cocoon with several steps to form silk fibroin solution, treated with iron salt to prepare an easy available, heteroatom (N, S, and Fe) ternary-doped, porous carbon aerogel (HDCA). Heteroatom existed in organic compounds in silk fibroin endow active site for ORR of the resultant carbon frameworks. Moreover, the amino acids presented in silk fibroin acted as ligands, functioning with Fe ions to form FeNx coordination compounds, which also served as active sites towards ORR. The synthesized HDCA electrocatalysts, especially HDCA-800 (obtained at 800 °C) displayed excellent catalytic activity with onsets, half-wave potential of 0.94 V, 0.79 V and higher limited current density of 3.80 mA cm-2 through a near four-electron reduction pathway with an average electron transferred number of 3.86, making them promising alternatives for state-of-the-art ORR electrocatalysts in fuel cell field. The porous structure with synergistic effect of N and S heteroatom doping has been proposed to play a key role in facilitating the desired ORR reaction.

Institute for Atom-Efficient Chemical Transformations Energy Frontier

Science.gov Websites

Synthesis Search Argonne ... Search Argonne Home > Institute for Atom-Efficient Chemical Transformations Synthesis Characterization Computational Studies Evaluation and Mechanisms/Catalytic Experimentation Using

Method of fabricating a catalytic structure

DOEpatents

Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2009-09-22

A precursor to a catalytic structure comprising zinc oxide and copper oxide. The zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide. The copper oxide is reduced to copper, producing the catalytic structure. The catalytic structure is fabricated by a hydrothermal process. A reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent is formed. The reaction mixture is heated under confined volume conditions to produce the precursor. The copper oxide in the precursor is reduced to copper. A method of hydrogenating a carbon oxide using the catalytic structure is also disclosed, as is a system that includes the catalytic structure.

Radiation/Catalytic Augmented Combustion.

DTIC Science & Technology

1982-05-01

enhanced combustion processes, utilizing pulsed and continuous VUV light- serces . Similarly, the catalytic technique has provided efficient combustion...tures we had a pl /cx LiF lens with a focal length of 200 nm, and a MgF2 window 2 nmn in thickness. Although these materials are considered to be among

Catalytic epoxidation activity of keplerate polyoxomolybdate nanoball toward aqueous suspension of olefins under mild aerobic conditions.

PubMed

Rezaeifard, Abdolreza; Haddad, Reza; Jafarpour, Maasoumeh; Hakimi, Mohammad

2013-07-10

Catalytic efficiency of a sphere-shaped nanosized polyoxomolybdate {Mo132} in the aerobic epoxidation of olefins in water at ambient temperature and pressure in the absence of reducing agent is exploited which resulted good-to-high yields and desired selectivity.

Study of the Performances of a Thermoelectric Generator Based on a Catalytic Meso-Scale H₂/C₃H₈ Fueled Combustor.

PubMed

Abedi, Hossein; Merotto, Laura; Fanciulli, Carlo; Donde, Roberto; De Luliis, Silvana; Passaretti, Francesca

2017-03-01

In this work the thermoelectric generator (TEG) based on catalytic combustion already developed in our lab has been further investigated and improved. The system made of two thermoelectric (TE) modules coupled with a catalytic combustor has been used in this work to obtain higher overall efficiency by adding hydrogen to the fuel mixture. Since implementation of hydrogen as a fuel has shown low and stable combustion temperature in literature, it is expected to achieve good overall efficiency of TEG. Moreover, hydrogen can be used to improve the system inducing self-ignition. Focus of the present work is the implementation of different mixture proportions, varying the amount of hydrogen, and the investigation of their effects on the overall efficiency. The overall TEG efficiency, has been evaluated by parallel characterization of thermoelectric modules and exhaust gases composition. The system performances have been characterized using different mixtures: the results indicate that addition of H₂ to the fuel contribute to increase the chemical and overall TEG efficiency respect to previous work, producing up to 5.92 W of electrical power. Finally, the effects of H₂ for on self-ignition conditions have been investigated finding the minimum H₂ amount for different gas flow rates.

Thiolate-bridged dinuclear ruthenium and iron complexes as robust and efficient catalysts toward oxidation of molecular dihydrogen in protic solvents.

PubMed

Yuki, Masahiro; Sakata, Ken; Hirao, Yoshifumi; Nonoyama, Nobuaki; Nakajima, Kazunari; Nishibayashi, Yoshiaki

2015-04-01

Thiolate-bridged dinuclear ruthenium and iron complexes are found to work as efficient catalysts toward oxidation of molecular dihydrogen in protic solvents such as water and methanol under ambient reaction conditions. Heterolytic cleavage of the coordinated molecular dihydrogen at the dinuclear complexes and the sequential oxidation of the produced hydride complexes are involved as key steps to promote the present catalytic reaction. The catalytic activity of the dinuclear complexes toward the chemical oxidation of molecular dihydrogen achieves up to 10000 TON (turnover number), and electrooxidation of molecular dihydrogen proceeds quite rapidly. The result of the density functional theory (DFT) calculation on the reaction pathway indicates that a synergistic effect between the two ruthenium atoms plays an important role to realize the catalytic oxidation of molecular dihydrogen efficiently. The present dinuclear ruthenium complex is found to work as an efficient organometallic anode catalyst for the fuel cell. It is noteworthy that the present dinuclear complex worked not only as an effective catalyst toward chemical and electrochemical oxidation of molecular dihydrogen but also as a good anode catalyst for the fuel cell. We consider that the result described in this paper provides useful and valuable information to develop highly efficient and low-cost transition metal complexes as anode catalysts in the fuel cell.

Hydrogen Recombination and Dimer Formation on Graphite from Ab Initio Molecular Dynamics Simulations.

PubMed

Casolo, S; Tantardini, G F; Martinazzo, R

2016-07-14

We studied Eley-Rideal molecular hydrogen formation on graphite using ab initio molecular dynamics, in the energy range relevant for the chemistry of the interstellar medium and for terrestrial experiments employing cold plasma (0.02-1 eV). We found substantial projectile steering effects that prevent dimer formation at low energies, thereby ruling out any catalytic synthetic pathways that form hydrogen molecules. Ortho and para dimers do form efficiently thanks to preferential sticking, but only at energies that are too high to be relevant for the chemistry of the interstellar medium. Computed reaction cross sections and ro-vibrational product populations are in good agreement with available experimental data and capable of generating adsorbate configurations similar to those observed with scanning tunneling microscopy techniques.

Mononuclear ruthenium polypyridine complexes that catalyze water oxidation

DOE PAGES

Tong, Lianpeng; Thummel, Randolph P.

2016-08-05

Over the past decade, significant advances have been made in the development of molecular water oxidation catalysts (WOCs) in the context of developing a system that would accomplish artificial photosynthesis. Mononuclear ruthenium complexes with polypyridine ligands have drawn considerable attention in this regard, due to their high catalytic activity and relatively simple structure. In this perspective review, we will discuss mononuclear Ru polypyridine WOCs by organizing them into four groups according to their ligand environments. Each group will be discussed with regard to three fundamental questions: first, how does the catalyst initiate O–O bond formation? Second, which step in themore » catalytic cycle is rate-determining? Third, how efficient is the catalyst according to the specific descriptors such as turnover frequency? All discussion is based on the high-valent ruthenium intermediates that are proposed in the catalytic cycle according to experimental observation and theoretical simulation. Two fundamental mechanisms are set forth. An acid–base mechanism that involves the attack of a water molecule on the oxo of a high valent Ru=O species to form the O–O bond. Subsequent steps lead to dissociation of O 2 and rehydration of the metal center. A second mechanism involves the formation of a Ru–O˙ radical species, two of which then couple to form a Ru–O–O–Ru species that can release O 2 afterwards. The acid–base mechanism appears to be more common and mechanistic differences could result from variation directly related to polypyridine ligand structures. Thus, understanding how electronic, steric, and conformational properties can effect catalyst performance will lead to the rational design of more effective WOCs with not only ruthenium but also other transition metals.« less

Nitroxides protect horseradish peroxidase from H2O2-induced inactivation and modulate its catalase-like activity.

PubMed

Samuni, Amram; Maimon, Eric; Goldstein, Sara

2017-08-01

Horseradish peroxidase (HRP) catalyzes H 2 O 2 dismutation while undergoing heme inactivation. The mechanism underlying this process has not been fully elucidated. The effects of nitroxides, which protect metmyoglobin and methemoglobin against H 2 O 2 -induced inactivation, have been investigated. HRP reaction with H 2 O 2 was studied by following H 2 O 2 depletion, O 2 evolution and heme spectral changes. Nitroxide concentration was followed by EPR spectroscopy, and its reactions with the oxidized heme species were studied using stopped-flow. Nitroxide protects HRP against H 2 O 2 -induced inactivation. The rate of H 2 O 2 dismutation in the presence of nitroxide obeys zero-order kinetics and increases as [nitroxide] increases. Nitroxide acts catalytically since its oxidized form is readily reduced to the nitroxide mainly by H 2 O 2 . The nitroxide efficacy follows the order 2,2,6,6-tetramethyl-piperidine-N-oxyl (TPO)>4-OH-TPO>3-carbamoyl proxyl>4-oxo-TPO, which correlates with the order of the rate constants of nitroxide reactions with compounds I, II, and III. Nitroxide catalytically protects HRP against inactivation induced by H 2 O 2 while modulating its catalase-like activity. The protective role of nitroxide at μM concentrations is attributed to its efficient oxidation by P940, which is the precursor of the inactivated form P670. Modeling the dismutation kinetics in the presence of nitroxide adequately fits the experimental data. In the absence of nitroxide the simulation fits the observed kinetics only if it does not include the formation of a Michaelis-Menten complex. Nitroxides catalytically protect heme proteins against inactivation induced by H 2 O 2 revealing an additional role played by nitroxide antioxidants in vivo. Copyright © 2017 Elsevier B.V. All rights reserved.

Pressure- and heat-induced inactivation of butyrylcholinesterase: evidence for multiple intermediates and the remnant inactivation process.

PubMed Central

Weingand-Ziade, A; Ribes, F; Renault, F; Masson, P

2001-01-01

The inactivation process of native (N) human butyrylcholinesterase (BuChE) by pressure and/or heat was found to be multi-step. It led to irreversible formation of an active intermediate (I) state and a denatured state. This series-inactivation process was described by expanding the Lumry-Eyring [Lumry, R. and Eyring, H. (1954) J. Phys. Chem. 58, 110-120] model. The intermediate state (I) was found to have a K(m) identical with that of the native state and a turnover rate (k(cat)) twofold higher than that of the native state with butyrylthiocholine as the substrate. The increased catalytic efficiency (k(cat)/K(m)) of I can be explained by a conformational change in the active-site gorge and/or restructuring of the water-molecule network in the active-site pocket, making the catalytic steps faster. However, a pressure/heat-induced covalent modification of native BuChE, affecting the catalytic machinery, cannot be ruled out. The inactivation process of BuChE induced by the combined action of pressure and heat was found to continue after interruption of pressure/temperature treatment. This secondary inactivation process was termed 'remnant inactivation'. We hypothesized that N and I were in equilibrium with populated metastable N' and I' states. The N' and I' states can either return to the active forms, N and I, or develop into inactive forms, N(')(in) and I(')(in). Both active N' and I' intermediate states displayed different rates of remnant inactivation depending on the pressure and temperature pretreatments and on the storage temperature. A first-order deactivation model describing the kinetics of the remnant inactivation of BuChE is proposed. PMID:11368776

Clean catalytic combustor program

NASA Technical Reports Server (NTRS)

Ekstedt, E. E.; Lyon, T. F.; Sabla, P. E.; Dodds, W. J.

1983-01-01

A combustor program was conducted to evolve and to identify the technology needed for, and to establish the credibility of, using combustors with catalytic reactors in modern high-pressure-ratio aircraft turbine engines. Two selected catalytic combustor concepts were designed, fabricated, and evaluated. The combustors were sized for use in the NASA/General Electric Energy Efficient Engine (E3). One of the combustor designs was a basic parallel-staged double-annular combustor. The second design was also a parallel-staged combustor but employed reverse flow cannular catalytic reactors. Subcomponent tests of fuel injection systems and of catalytic reactors for use in the combustion system were also conducted. Very low-level pollutant emissions and excellent combustor performance were achieved. However, it was obvious from these tests that extensive development of fuel/air preparation systems and considerable advancement in the steady-state operating temperature capability of catalytic reactor materials will be required prior to the consideration of catalytic combustion systems for use in high-pressure-ratio aircraft turbine engines.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong, Yongchun; Hensley, Alyssa; McEwen, Jean-Sabin

Catalytic fast pyrolysis is the most promising approach for biofuel production, due to its simple process and versatility to handle lignocellulosic biomass feedstocks with varying and complex compositions. Compared with in situ catalytic fast pyrolysis, ex situ catalytic pyrolysis has the flexibility of optimizing the pyrolysis step and catalytic process individually to improve the quality of pyrolysis oil (stability, oxygen content, acid number, etc.) and to maximize the carbon efficiency in the conversion of biomass to pyrolysis oil. Hydrodeoxygenation is one of the key catalytic functions in ex situ catalytic fast pyrolysis. Recently, Fe-based catalysts have been reported to exhibitmore » superior catalytic properties in hydrodeoxygenation of model compounds in pyrolysis oil, which potentially makes the ex situ pyrolysis of biomass commercially viable due to the abundance and low cost of Fe. Here, we briefly summarize the recent progress on Fe-based catalysts for hydrodeoxygenation of biomass, and provide perspectives on how to further improve Fe-based catalysts (activity and stability) for their potential applications in the emerging area of biomass conversion.« less

Recent Developments in Hydrogen Evolving Molecular Cobalt(II)-Polypyridyl Catalysts

PubMed Central

Queyriaux, N.; Jane, R. T.; Massin, J.; Artero, V.; Chavarot-Kerlidou, M.

2015-01-01

The search for efficient noble metal-free hydrogen-evolving catalysts is the subject of intense research activity. A new family of molecular cobalt(II)-polypyridyl catalysts has recently emerged. These catalysts prove more robust under reductive conditions than other cobalt-based systems and display high activities under fully aqueous conditions. This review discusses the design, characterization, and evaluation of these catalysts for electrocatalytic and light-driven hydrogen production. Mechanistic considerations are addressed and structure-catalytic activity relationships identified in order to guide the future design of more efficient catalytic systems. PMID:26688590

Method and apparatus for a catalytic firebox reactor

DOEpatents

Smith, Lance L.; Etemad, Shahrokh; Ulkarim, Hasan; Castaldi, Marco J.; Pfefferle, William C.

2001-01-01

A catalytic firebox reactor employing an exothermic catalytic reaction channel and multiple cooling conduits for creating a partially reacted fuel/oxidant mixture. An oxidation catalyst is deposited on the walls forming the boundary between the multiple cooling conduits and the exothermic catalytic reaction channel, on the side of the walls facing the exothermic catalytic reaction channel. This configuration allows the oxidation catalyst to be backside cooled by any fluid passing through the cooling conduits. The heat of reaction is added to both the fluid in the exothermic catalytic reaction channel and the fluid passing through the cooling conduits. After discharge of the fluids from the exothermic catalytic reaction channel, the fluids mix to create a single combined flow. A further innovation in the reactor incorporates geometric changes in the exothermic catalytic reaction channel to provide streamwise variation of the velocity of the fluids in the reactor.

Systems including catalysts in porous zeolite materials within a reactor for use in synthesizing hydrocarbons

DOEpatents

Rolllins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2012-07-24

Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

Green technology for conversion of renewable hydrocarbon based on plasma-catalytic approach

NASA Astrophysics Data System (ADS)

Fedirchyk, Igor; Nedybaliuk, Oleg; Chernyak, Valeriy; Demchina, Valentina

2016-09-01

The ability to convert renewable biomass into fuels and chemicals is one of the most important steps on our path to green technology and sustainable development. However, the complex composition of biomass poses a major problem for established conversion technologies. The high temperature of thermochemical biomass conversion often leads to the appearance of undesirable byproducts and waste. The catalytic conversion has reduced yield and feedstock range. Plasma-catalytic reforming technology opens a new path for biomass conversion by replacing feedstock-specific catalysts with free radicals generated in the plasma. We studied the plasma-catalytic conversion of several renewable hydrocarbons using the air plasma created by rotating gliding discharge. We found that plasma-catalytic hydrocarbon conversion can be conducted at significantly lower temperatures (500 K) than during the thermochemical ( 1000 K) and catalytic (800 K) conversion. By using gas chromatography, we determined conversion products and found that conversion efficiency of plasma-catalytic conversion reaches over 85%. We used obtained data to determine the energy yield of hydrogen in case of plasma-catalytic reforming of ethanol and compared it with other plasma-based hydrogen-generating systems.

Time-dependent 31P saturation transfer in the phosphoglucomutase reaction. Characterization of the spin system for the Cd(II) enzyme and evaluation of rate constants for the transfer process.

PubMed

Post, C B; Ray, W J; Gorenstein, D G

1989-01-24

Time-dependent 31P saturation-transfer studies were conducted with the Cd2+-activated form of muscle phosphoglucomutase to probe the origin of the 100-fold difference between its catalytic efficiency (in terms of kcat) and that of the more efficient Mg2+-activated enzyme. The present paper describes the equilibrium mixture of phosphoglucomutase and its substrate/product pair when the concentration of the Cd2+ enzyme approaches that of the substrate and how the nine-spin 31P NMR system provided by this mixture was treated. It shows that the presence of abortive complexes is not a significant factor in the reduced activity of the Cd2+ enzyme since the complex of the dephosphoenzyme and glucose 1,6-bisphosphate, which accounts for a large majority of the enzyme present at equilibrium, is catalytically competent. It also shows that rate constants for saturation transfer obtained at three different ratios of enzyme to free substrate are mutually compatible. These constants, which were measured at chemical equilibrium, can be used to provide a quantitative kinetic rationale for the reduced steady-state activity elicited by Cd2+ relative to Mg2+ [cf. Ray, W.J., Post, C.B., & Puvathingal, J.M. (1989) Biochemistry (following paper in this issue)]. They also provide minimal estimates of 350 and 150 s-1 for the rate constants describing (PO3-) transfer from the Cd2+ phosphoenzyme to the 6-position of bound glucose 1-phosphate and to the 1-position of bound glucose 6-phosphate, respectively. These minimal estimates are compared with analogous estimates for the Mg2+ and Li+ forms of the enzyme in the accompanying paper.

Chitosan-microreactor: a versatile approach for heterogeneous organic synthesis in microfluidics.

PubMed

Basavaraju, K C; Sharma, Siddharth; Singh, Ajay K; Im, Do Jin; Kim, Dong-Pyo

2014-07-01

Microreactors have been proven to be efficient tools for a variety of homogeneous organic transformations due to their mixing efficiency, which results in very fast reactions, better heat and mass transfer, and simple scale-up. However, in heterogeneous catalytic reactions each catalyst needs an individual substrate as support. Herein, a versatile approach to immobilize metal catalysts on chitosan as a common substrate is presented. Chitosan, accommodating many metal catalysts, is grafted onto the microchannel surface as nanobrush. The versatility, catalytic efficiency, and stability/durability of the microreactor are demonstrated for a number of organic transformations involving various metal compounds as catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of an azanoradamantane-type nitroxyl radical catalyst for class-selective oxidation of alcohols.

PubMed

Doi, Ryusuke; Shibuya, Masatoshi; Murayama, Tsukasa; Yamamoto, Yoshihiko; Iwabuchi, Yoshiharu

2015-01-02

The development of 1,5-dimethyl-9-azanoradamantane N-oxyl (DMN-AZADO; 1,5-dimethyl-Nor-AZADO, 2) as an efficient catalyst for the selective oxidation of primary alcohols in the presence of secondary alcohols is described. The compact and rigid structure of the azanoradamantane nucleus confers potent catalytic ability to DMN-AZADO (2). A variety of hindered primary alcohols such as neopentyl primary alcohols were efficiently oxidized by DMN-AZADO (2) to the corresponding aldehydes, whereas secondary alcohols remained intact. DMN-AZADO (2) also has high catalytic efficiency for one-pot oxidation from primary alcohols to the corresponding carboxylic acids in the presence of secondary alcohols and for oxidative lactonization from diols.

Catalytic degradation of the nerve agent VX by water-swelled polystyrene-supported ammonium fluorides.

PubMed

Marciano, Daniele; Goldvaser, Michael; Columbus, Ishay; Zafrani, Yossi

2011-10-21

The catalytic degradation of the nerve agent VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate) by water-swelled polymer-supported ammonium fluorides is described. VX (0.06-0.53 mol/mol F(-)) is rapidly degraded (t(1/2) ∼ 10-30 min) to form the "G-analogue" (O-ethyl methylphosphonofluoridate), which hydrolyzes (t(1/2) ∼ 1-1.5 h) to the nontoxic EMPA (ethyl methylphosphonic acid). The toxic desethyl-VX is not formed. The catalytic effect of fluoride is maintained even when 6 equiv of VX are loaded. GB (O-isopropyl methylphosphonofluoridate) and desethyl-VX agents are also degraded under these conditions.

Catalytic oxidation of VOCs over Mn/TiO2/activated carbon under 185 nm VUV irradiation.

PubMed

Shu, Yajie; Xu, Yin; Huang, Haibao; Ji, Jian; Liang, Shimin; Wu, Muyan; Leung, Dennis Y C

2018-06-04

Volatile organic compounds (VOCs) are regarded as the major contributors to air pollution, and should be strictly regulated. Photocatalytic oxidation (PCO) is of great interest for the removal of VOCs owing to its strong oxidation capability. However, its application is greatly limited by catalytic deactivation. Vacuum Ultraviolet (VUV) irradiation provides a novel way to improve the photocatalytic activity while much O 3 will be generated which may cause secondary pollution. In this study, a multi-functional catalyst of Mn/TiO 2 /activated carbon (AC) was developed to eliminate and utilize O 3 , as well as enhance catalytic oxidation of VOC degradation via ozone-assisted catalytic oxidation (OZCO). The results indicate that Mn modified TiO 2 /AC (i.e. 0.1%Mn/20%TiO 2 /AC) achieved a toluene removal efficiency of nearly 86% with 100% elimination rate of O 3 . With the help of Mn/TiO 2 /AC catalyst, O 3 was catalytically decomposed and transformed into active species of O ( 1 D) and OH, thus enhancing toluene removal. The combination of VUV irradiation with multi-functional catalyst provides a novel and efficient way for the degradation of VOCs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Systems analysis of electricity production from coal using fuel cells

NASA Technical Reports Server (NTRS)

Fleming, D. K.

1983-01-01

Gasifiers, heat transfer, gas stability, quench, water-gas shift reaction, reforming-methanation, other catalytic reactions, compressors and expanders, acid-gas removal, the fuel cell, and catalytic combustors are described. System pressure drops, efficiency of rotating power equipment, heat exchangers, chemical reactions, steam systems, and the fuel cell subsystems are discussed.

Influence and efficiency of catalytic stripper in organic carbon removal from laboratory generated soot aerosols

EPA Science Inventory

A catalytic stripper (CS) is a device used to remove the semi-volatile, typically organic carbon, fraction by passing raw or diluted exhaust over an oxidation catalyst heated to 300˚C. The oxidation catalyst used in this study is a commercially available diesel oxidation ca...

Mechanistic exploration of the catalytic cycles for the CO oxidation by O2 over FeO(1-3) application of the energetic span model.

PubMed

Wang, Huan-Jiang; Wang, Yong-Cheng

2014-06-01

Carbon monoxide (CO) and oxygen (O2) catalyzed by small neutral iron oxide clusters (FeO(1-3)) was investigated at the density functional level of theory using the Becke-Perdew-Wang functional (BPW91). Three reaction pathways along with singlet, triplet and quintet states were calculated for ascertaining the presence of some spin inversion during the catalytic cycle. The catalytic cycle was found to be "two state reactivity" resulting from the crossing among the multistate energetic profiles. The Landau-Zener equation was used to calculate the thermally-averaged spin transition probabilities for the non-adiabatic surface crossing reaction. In order to predict the efficiency of catalyst the energetic span model developed by Kozuch was implemented, whereas this model is not suitable for handling the diabatic reaction, this feature we must take into consideration. To this end, a kinetic assessment is carried out with an expansion of the energetic span model, including the spin-crossing effects. This approximation enables one to measure the efficiency of catalytic cycle including spin-crossing effects by quantum mechanical computation.

Spatial decoupling of light absorption and catalytic activity of Ni-Mo-loaded high-aspect-ratio silicon microwire photocathodes

NASA Astrophysics Data System (ADS)

Vijselaar, Wouter; Westerik, Pieter; Veerbeek, Janneke; Tiggelaar, Roald M.; Berenschot, Erwin; Tas, Niels R.; Gardeniers, Han; Huskens, Jurriaan

2018-03-01

A solar-driven photoelectrochemical cell provides a promising approach to enable the large-scale conversion and storage of solar energy, but requires the use of Earth-abundant materials. Earth-abundant catalysts for the hydrogen evolution reaction, for example nickel-molybdenum (Ni-Mo), are generally opaque and require high mass loading to obtain high catalytic activity, which in turn leads to parasitic light absorption for the underlying photoabsorber (for example silicon), thus limiting production of hydrogen. Here, we show the fabrication of a highly efficient photocathode by spatially and functionally decoupling light absorption and catalytic activity. Varying the fraction of catalyst coverage over the microwires, and the pitch between the microwires, makes it possible to deconvolute the contributions of catalytic activity and light absorption to the overall device performance. This approach provided a silicon microwire photocathode that exhibited a near-ideal short-circuit photocurrent density of 35.5 mA cm-2, a photovoltage of 495 mV and a fill factor of 62% under AM 1.5G illumination, resulting in an ideal regenerative cell efficiency of 10.8%.

Bottom-Up Catalytic Approach towards Nitrogen-Enriched Mesoporous Carbons/Sulfur Composites for Superior Li-S Cathodes

PubMed Central

Sun, Fugen; Wang, Jitong; Chen, Huichao; Qiao, Wenming; Ling, Licheng; Long, Donghui

2013-01-01

We demonstrate a sustainable and efficient approach to produce high performance sulfur/carbon composite cathodes via a bottom-up catalytic approach. The selective oxidation of H2S by a nitrogen-enriched mesoporous carbon catalyst can produce elemental sulfur as a by-product which in-situ deposit onto the carbon framework. Due to the metal-free catalytic characteristic and high catalytic selectivity, the resulting sulfur/carbon composites have almost no impurities that thus can be used as cathode materials with compromising battery performance. The layer-by-layer sulfur deposition allows atomic sulfur binding strongly with carbon framework, providing efficient immobilization of sulfur. The nitrogen atoms doped on the carbon framework can increase the surface interactions with polysulfides, leading to the improvement in the trapping of polysulfides. Thus, the composites exhibit a reversible capacity of 939 mAh g−1 after 100 cycles at 0.2 C and an excellent rate capability of 527 mAh g−1 at 5 C after 70 cycles. PMID:24084754

Nano-array based monolithic catalysts: Concept, rational materials design and tunable catalytic performance

DOE PAGES

Ren, Zheng; Guo, Yanbing; Gao, Pu-Xian

2015-03-20

Monolithic catalysts, also known as structured catalysts, represent an important catalyst configuration widely used in automotive, chemical, and energy industries. However, several issues associated with washcoat based monolithic catalyst preparation are ever present, such as compromised materials utilization efficiency due to a less-than-ideal wash coating process, difficulty in precise and optimum microstructure control and lack of structure-property correlation. Here, in this mini-review, we introduce the concept of nano-array catalyst, a new type of monolithic catalyst featuring high catalyst utilization efficiency, good thermal/mechanical robustness, and catalytic performance tunability. A comprehensive overview is presented with detailed discussion of the strategies for nano-arraymore » catalyst preparation and rational catalytic activity adjustment enabled by the well-defined nano-array geometry. Specifically their scalable fabrication processes are reviewed in conjunction with discussion of their various catalytic oxidation reaction performances at low temperature. Finally, we hope this review will serve as a timely and useful research guide for rational design and utilization of the new type of monolithic catalysts.« less

Heterogeneous organocatalysis at work: functionalization of hollow periodic mesoporous organosilica spheres with MacMillan catalyst.

PubMed

Shi, Jiao Yi; Wang, Chang An; Li, Zhi Jun; Wang, Qiong; Zhang, Yuan; Wang, Wei

2011-05-23

We report a new method for the synthesis of hollow-structured phenylene-bridged periodic mesoporous organosilica (PMO) spheres with a uniform particle size of 100-200 nm using α-Fe(2)O(3) as a hard template. Based on this method, the hollow-structured phenylene PMO could be easily functionalized with MacMillan catalyst (H-PhPMO-Mac) by a co-condensation process and a "click chemistry" post-modification. The synthesized H-PhPMO-Mac catalyst has been found to exhibit high catalytic activity (98% yield, 81% enantiomeric excess (ee) for endo and 81% ee for exo) in asymmetric Diels-Alder reactions with water as solvent. The catalyst could be reused for at least seven runs without a significant loss of catalytic activity. Our results have also indicated that hollow-structured PMO spheres exhibit higher catalytic efficiency than solid (non-hollow) PMO spheres, and that catalysts prepared by the co-condensation process and "click chemistry" post-modification exhibit higher catalytic efficiency than those prepared by a grafting method. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analytic corrections to CFD heating predictions accounting for changes in surface catalysis

NASA Technical Reports Server (NTRS)

Gnoffo, Peter A.; Inger, George R.

1996-01-01

Integral boundary-layer solution techniques applicable to the problem of determining aerodynamic heating rates of hypersonic vehicles in the vicinity of stagnation points and windward centerlines are briefly summarized. A new approach for combining the insight afforded by integral boundary-layer analysis with comprehensive (but time intensive) computational fluid dynamic (CFD) flowfield solutions of the thin-layer Navier-Stokes equations is described. The approach extracts CFD derived quantities at the wall and at the boundary layer edge for inclusion in a post-processing boundary-layer analysis. It allows a designer at a workstation to address two questions, given a single CFD solution. (1) How much does the heating change for a thermal protection system with different catalytic properties than was used in the original CFD solution? (2) How does the heating change at the interface of two different TPS materials with an abrupt change in catalytic efficiency? The answer to the second question is particularly important, because abrupt changes from low to high catalytic efficiency can lead to localized increase in heating which exceeds the usually conservative estimate provided by a fully catalytic wall assumption.

Improvement of enzyme activity of β-1,3-1,4-glucanase from Paenibacillus sp. X4 by error-prone PCR and structural insights of mutated residues.

PubMed

Baek, Seung Cheol; Ho, Thien-Hoang; Lee, Hyun Woo; Jung, Won Kyeong; Gang, Hyo-Seung; Kang, Lin-Woo; Kim, Hoon

2017-05-01

β-1,3-1,4-Glucanase (BGlc8H) from Paenibacillus sp. X4 was mutated by error-prone PCR or truncated using termination primers to improve its enzyme properties. The crystal structure of BGlc8H was determined at a resolution of 1.8 Å to study the possible roles of mutated residues and truncated regions of the enzyme. In mutation experiments, three clones of EP 2-6, 2-10, and 5-28 were finally selected that exhibited higher specific activities than the wild type when measured using their crude extracts. Enzyme variants of BG 2-6 , BG 2-10 , and BG 5-28 were mutated at two, two, and six amino acid residues, respectively. These enzymes were purified homogeneously by Hi-Trap Q and CHT-II chromatography. Specific activity of BG 5-28 was 2.11-fold higher than that of wild-type BG wt , whereas those of BG 2-6 and BG 2-10 were 0.93- and 1.19-fold that of the wild type, respectively. The optimum pH values and temperatures of the variants were nearly the same as those of BG wt (pH 5.0 and 40 °C, respectively). However, the half-life of the enzyme activity and catalytic efficiency (k cat /K m ) of BG 5-28 were 1.92- and 2.12-fold greater than those of BG wt at 40 °C, respectively. The catalytic efficiency of BG 5-28 increased to 3.09-fold that of BG wt at 60 °C. These increases in the thermostability and catalytic efficiency of BG 5-28 might be useful for the hydrolysis of β-glucans to produce fermentable sugars. Of the six mutated residues of BG 5-28 , five residues were present in mature BGlc8H protein, and two of them were located in the core scaffold of BGlc8H and the remaining three residues were in the substrate-binding pocket forming loop regions. In truncation experiments, three forms of C-terminal truncated BGlc8H were made, which comprised 360, 286, and 215 amino acid residues instead of the 409 residues of the wild type. No enzyme activity was observed for these truncated enzymes, suggesting the complete scaffold of the α 6 /α 6 -double-barrel structure is essential for enzyme activity.

Catalytic Enantioselective Olefin Metathesis in Natural Product Synthesis. Chiral Metal-Based Complexes that Deliver High Enantioselectivity and More

PubMed Central

Malcolmson, Steven J.; Meek, Simon J.; Zhugralin, Adil R.

2012-01-01

Chiral olefin metathesis catalysts enable chemists to access enantiomerically enriched small molecules with high efficiency; synthesis schemes involving such complexes can be substantially more concise than those that would involve enantiomerically pure substrates and achiral Mo alkylidenes or Ru-based carbenes. The scope of research towards design and development of chiral catalysts is not limited to discovery of complexes that are merely the chiral versions of the related achiral variants. A chiral olefin metathesis catalyst, in addition to furnishing products of high enantiomeric purity, can offer levels of efficiency, product selectivity and/or olefin stereoselectivity that are unavailable through the achiral variants. Such positive attributes of chiral catalysts (whether utilized in racemic or enantiomerically enriched form) should be considered as general, applicable to other classes of transformations. PMID:19967680

Co(II)-Doped Cd-MOF as an Efficient Water Oxidation Catalyst: Doubly Interpenetrated Boron Nitride Network with the Encapsulation of Free Ligand Containing Pyridine Moieties.

PubMed

Maity, Kartik; Bhunia, Kousik; Pradhan, Debabrata; Biradha, Kumar

2017-11-01

Development of an efficient and inexpensive water oxidation electrocatalyst using the earth-abundant elements is still far to go. Herein, a novel strategy has been demonstrated for developing the OER electrocatalyst by doping Co(II) in to a three-dimensional Cd-based MOF that contains a naked pyridine moieties in the form of uncoordinated ligand. Electrochemically active CoCd-MOF was resulted through the doping of Co(II) into the inactive Cd-MOF. CoCd-MOF exhibited very high catalytic activity in water oxidation reaction. An overpotential of 353 mV is required to produce an anodic current density of 1 mA/cm 2 under alkaline conditions. Further, the CoCd-MOF exhibits remarkable recyclability over 1000 cycles.

Fusion of an oligopeptide to the N terminus of an alkaline α-amylase from Alkalimonas amylolytica simultaneously improves the enzyme's catalytic efficiency, thermal stability, and resistance to oxidation.

PubMed

Yang, Haiquan; Lu, Xinyao; Liu, Long; Li, Jianghua; Shin, Hyun-dong; Chen, Rachel R; Du, Guocheng; Chen, Jian

2013-05-01

In this study, we constructed and expressed six fusion proteins composed of oligopeptides attached to the N terminus of the alkaline α-amylase (AmyK) from Alkalimonas amylolytica. The oligopeptides had various effects on the functional and structural characteristics of AmyK. AmyK-p1, the fusion protein containing peptide 1 (AEAEAKAKAEAEAKAK), exhibited improved specific activity, catalytic efficiency, alkaline stability, thermal stability, and oxidative stability compared with AmyK. Compared with AmyK, the specific activity and catalytic constant (kcat) of AmyK-p1 were increased by 4.1-fold and 3.5-fold, respectively. The following properties were also improved in AmyK-p1 compared with AmyK: kcat/Km increased from 1.8 liter/(g·min) to 9.7 liter/(g·min), stable pH range was extended from 7.0 to 11.0 to 7.0 to 12.0, optimal temperature increased from 50°C to 55°C, and the half-life at 60°C increased by ∼2-fold. Moreover, AmyK-p1 showed improved resistance to oxidation and retained 54% of its activity after incubation with H2O2, compared with 20% activity retained by AmyK. Finally, AmyK-p1 was more compatible than AmyK with the commercial solid detergents tested. The mechanisms responsible for these changes were analyzed by comparing the three-dimensional (3-D) structural models of AmyK and AmyK-p1. The significantly enhanced catalytic efficiency and stability of AmyK-p1 suggests its potential as a detergent ingredient. In addition, the oligopeptide fusion strategy described here may be useful for improving the catalytic efficiency and stability of other industrial enzymes.

Fusion of an Oligopeptide to the N Terminus of an Alkaline α-Amylase from Alkalimonas amylolytica Simultaneously Improves the Enzyme's Catalytic Efficiency, Thermal Stability, and Resistance to Oxidation

PubMed Central

Yang, Haiquan; Lu, Xinyao; Li, Jianghua; Shin, Hyun-dong; Chen, Rachel R.; Du, Guocheng

2013-01-01

In this study, we constructed and expressed six fusion proteins composed of oligopeptides attached to the N terminus of the alkaline α-amylase (AmyK) from Alkalimonas amylolytica. The oligopeptides had various effects on the functional and structural characteristics of AmyK. AmyK-p1, the fusion protein containing peptide 1 (AEAEAKAKAEAEAKAK), exhibited improved specific activity, catalytic efficiency, alkaline stability, thermal stability, and oxidative stability compared with AmyK. Compared with AmyK, the specific activity and catalytic constant (kcat) of AmyK-p1 were increased by 4.1-fold and 3.5-fold, respectively. The following properties were also improved in AmyK-p1 compared with AmyK: kcat/Km increased from 1.8 liter/(g·min) to 9.7 liter/(g·min), stable pH range was extended from 7.0 to 11.0 to 7.0 to 12.0, optimal temperature increased from 50°C to 55°C, and the half-life at 60°C increased by ∼2-fold. Moreover, AmyK-p1 showed improved resistance to oxidation and retained 54% of its activity after incubation with H2O2, compared with 20% activity retained by AmyK. Finally, AmyK-p1 was more compatible than AmyK with the commercial solid detergents tested. The mechanisms responsible for these changes were analyzed by comparing the three-dimensional (3-D) structural models of AmyK and AmyK-p1. The significantly enhanced catalytic efficiency and stability of AmyK-p1 suggests its potential as a detergent ingredient. In addition, the oligopeptide fusion strategy described here may be useful for improving the catalytic efficiency and stability of other industrial enzymes. PMID:23455344

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maiti, Tushar K.; Permaul, Michelle; Boudreaux, David A.

Ubiquitin carboxy-terminal hydrolase L5 (UCHL5) is a proteasome-associated deubiquitinating enzyme, which, along with RPN11 and USP14, is known to carry out deubiquitination on proteasome. As a member of the ubiquitin carboxy-terminal hydrolase (UCH) family, UCHL5 is unusual because, unlike UCHL1 and UCHL3, it can process polyubiquitin chain. However, it does so only when it is bound to the proteasome; in its free form, it is capable of releasing only relatively small leaving groups from the C-terminus of ubiquitin. Such a behavior might suggest at least two catalytically distinct forms of the enzyme, an apo form incapable of chain processing activity,more » and a proteasome-induced activated form capable of cleaving polyubiquitin chain. Through the crystal structure analysis of two truncated constructs representing the catalytic domain (UCH domain) of this enzyme, we were able to visualize a state of this enzyme that we interpret as its inactive form, because the catalytic cysteine appears to be in an unproductive orientation. While this work was in progress, the structure of a different construct representing the UCH domain was reported; however, in that work the structure reported was that of an inactive mutant [catalytic Cys to Ala; Nishio K et al. (2009) Biochem Biophys Res Commun390, 855-860], which precluded the observation that we are reporting here. Additionally, our structures reveal conformationally dynamic parts of the enzyme that may play a role in the structural transition to the more active form.« less

Effects of interaction with gene carrier polyethyleneimines on conformation and enzymatic activity of pig heart lactate dehydrogenase.

PubMed

Wang, Fan; Mo, Junyong; Huang, Aimin; Zhang, Min; Ma, Lin

2018-06-15

Polyethyleneimine (PEI) has long been considered as "golden standard" for polymeric gene delivery carrier, however also induces cytotoxicity. To make a further insight into the molecular basis of PEI cytotoxicity, fluorescence, absorption and circular dichroism spectroscopy were conducted to investigate the influence of PEI (average molecular weight 25,000 and 1800 Da) on the conformation of pig heart lactate dehydrogenase (LDH) and its catalytic efficiency. Zeta-potential measurement and isothermal titration calorimetry were used to reveal the interaction between PEI and LDH. PEI was found to bind onto the surface of LDH predominantly via hydrophobic interaction, inducing a more compact conformation and an increased surface hydrophobicity of the enzyme. The conformational change of LDH induced by PEI binding had little influence on the complex formation between LDH and reduced nicotinamide adenine dinucleotide (NADH, the co-enzyme). However, the nonspecific binding of PEI on the surface of LDH retarded the turnover of the enzyme. Meanwhile, the large quantity of amine groups on the polymer chain made PEI subject to form complexes with NADH and pyruvate (the substrate) via hydrogen bond and electrostatic interaction, which greatly reduced the binding efficient of LDH. The polymer size played an important role in PEI-LDH interaction. The smaller size of lower molecular weight PEI facilitated the close contact with LDH and consequential reduction of the turnover number of the enzyme. However, higher molecular weight PEI was more favorable for competitive binding with NADH and pyruvate and generally decreased the catalytic efficient of LDH. Copyright © 2018. Published by Elsevier B.V.

Catalytic efficiency is a better predictor of arsenic toxicity to soil alkaline phosphatase.

PubMed

Wang, Ziquan; Tian, Haixia; Lu, Guannan; Zhao, Yiming; Yang, Rui; Megharaj, Mallavarapu; He, Wenxiang

2018-02-01

Arsenic (As) is an inhibitor of phosphatase, however, in the complex soil system, the substrate concentration effect and the mechanism of As inhibition of soil alkaline phosphatase (ALP) and its kinetics has not been adequately studied. In this work, we investigated soil ALP activity in response to As pollution at different substrate concentrations in various types of soils and explored the inhibition mechanism using the enzyme kinetics. The results showed that As inhibition of soil ALP activity was substrate concentration-dependent. Increasing substrate concentration decreased inhibition rate, suggesting reduced toxicity. This dependency was due to the competitive inhibition mechanism of As to soil ALP. The kinetic parameters, maximum reaction velocity (V max ) and Michaelis constant (K m ) in unpolluted soils were 0.012-0.267mMh -1 and 1.34-3.79mM respectively. The competitive inhibition constant (K ic ) was 0.17-0.70mM, which was lower than K m , suggesting higher enzyme affinity for As than for substrate. The ecological doses, ED 10 and ED 50 (concentration of As that results in 10% and 50% inhibition on enzyme parameter) for inhibition of catalytic efficiency (V max /K m ) were lower than those for inhibition of enzyme activity at different substrate concentrations. This suggests that the integrated kinetic parameter, catalytic efficiency is substrate concentration independent and more sensitive to As than ALP activity. Thus, catalytic efficiency was proposed as a more reliable indicator than ALP activity for risk assessment of As pollution. Copyright © 2017 Elsevier Inc. All rights reserved.

Improving the reversibility of thermal denaturation and catalytic efficiency of Bacillus licheniformis α-amylase through stabilizing a long loop in domain B.

PubMed

Li, Zhu; Duan, Xuguo; Chen, Sheng; Wu, Jing

2017-01-01

The reversibility of thermal denaturation and catalytic efficiency of Bacillus licheniformis α-amylase were improved through site-directed mutagenesis. By using multiple sequence alignment and PoPMuSiC algorithm, Ser187 and Asn188, which located within a long loop in Domain B of Bacillus licheniformis α-amylase, were selected for mutation. In addition, Ala269, which is adjacent to Ser187 and Asn188, was also investigated. Seven mutants carrying the mutations S187D, N188T, N188S, A269K, A269K/S187D, S187D/N188T, and A269K/S187D/N188T were generated and characterized. The most thermostable mutant, A269K/S187D/N188T, exhibited a 9-fold improvement in half-life at 95°C and pH 5.5, compared with that of the wild-type enzyme. Mutant A269K/S187D/N188T also exhibited improved catalytic efficiency. The catalytic efficiency of mutant A269K/S187D/N188T reached 5.87×103±0.17 g·L-1·s-1 at pH 5.5, which is 1.84-fold larger than the corresponding value determined for the wild-type enzyme. Furthermore, the structure analysis showed that immobilization of the loop containing Ser187 and Asn188 plays a significant role in developing the properties of Bacillus licheniformis α-amylase.

Improving the reversibility of thermal denaturation and catalytic efficiency of Bacillus licheniformis α-amylase through stabilizing a long loop in domain B

PubMed Central

Li, Zhu; Duan, Xuguo; Chen, Sheng; Wu, Jing

2017-01-01

The reversibility of thermal denaturation and catalytic efficiency of Bacillus licheniformis α-amylase were improved through site-directed mutagenesis. By using multiple sequence alignment and PoPMuSiC algorithm, Ser187 and Asn188, which located within a long loop in Domain B of Bacillus licheniformis α-amylase, were selected for mutation. In addition, Ala269, which is adjacent to Ser187 and Asn188, was also investigated. Seven mutants carrying the mutations S187D, N188T, N188S, A269K, A269K/S187D, S187D/N188T, and A269K/S187D/N188T were generated and characterized. The most thermostable mutant, A269K/S187D/N188T, exhibited a 9-fold improvement in half-life at 95°C and pH 5.5, compared with that of the wild-type enzyme. Mutant A269K/S187D/N188T also exhibited improved catalytic efficiency. The catalytic efficiency of mutant A269K/S187D/N188T reached 5.87×103±0.17 g·L-1·s-1 at pH 5.5, which is 1.84-fold larger than the corresponding value determined for the wild-type enzyme. Furthermore, the structure analysis showed that immobilization of the loop containing Ser187 and Asn188 plays a significant role in developing the properties of Bacillus licheniformis α-amylase. PMID:28253342

Treatment of hazardous landfill leachate using Fenton process followed by a combined (UASB/DHS) system.

PubMed

Ismail, Sherif; Tawfik, Ahmed

2016-01-01

Fenton process for pre-treatment of hazardous landfill leachate (HLL) was investigated. Total, particulate and soluble chemical oxygen demand (CODt, CODp and CODs) removal efficiency amounted to 67%, 47% and 64%, respectively, at pH value of 3.5, molar ratio (H2O2/Fe(2+)) of 5, H2O2 dosage of 25 ml/L and contact time of 15 min. Various treatment scenarios were attempted and focused on studying the effect of pre-catalytic oxidation process on the performance of up-flow anaerobic sludge blanket (UASB), UASB/down-flow hanging sponge (DHS) and DHS system. The results obtained indicated that pre-catalytic oxidation process improved the CODt removal efficiency in the UASB reactor by a value of 51.4%. Overall removal efficiencies of CODt, CODs and CODp were 80 ± 6%, 80 ± 7% and 78 ± 16% for UASB/DHS treating pre-catalytic oxidation effluent, respectively. The removal efficiencies of CODt, CODs and CODp were, respectively, decreased to 54 ± 2%, 49 ± 2% and 71 ± 16% for UASB/DHS system without pre-treatment. However, the results for the combined process (UASB/DHS) system is almost similar to those obtained for UASB reactor treating pre-catalytic oxidation effluent. The DHS system achieved average removal efficiencies of 52 ± 4% for CODt, 51 ± 4% for CODs and 52 ± 15% for CODp. A higher COD fractions removal was obtained when HLL was pre-treated by Fenton reagent. The combined processes provided a removal efficiency of 85 ± 1% for CODt, 85 ± 1% for CODs and 83 ± 8% for CODp. The DHS system is not only effective for organics degradation but also for ammonia oxidation. Almost complete ammonia (NH4-N) removal (92 ± 3.6%) was occurred and the nitrate production amounted to 37 ± 6 mg/L in the treated effluent. This study strongly recommends applying Fenton process followed by DHS system for treatment of HLL.

Process for forming a homogeneous oxide solid phase of catalytically active material

DOEpatents

Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

1995-01-01

A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

Crystal-defect-induced facet-dependent electrocatalytic activity of 3D gold nanoflowers for the selective nanomolar detection of ascorbic acid.

PubMed

De, Sandip Kumar; Mondal, Subrata; Sen, Pintu; Pal, Uttam; Pathak, Biswarup; Rawat, Kuber Singh; Bardhan, Munmun; Bhattacharya, Maireyee; Satpati, Biswarup; De, Amitabha; Senapati, Dulal

2018-06-14

Understanding and exploring the decisive factors responsible for superlative catalytic efficiency is necessary to formulate active electrode materials for improved electrocatalysis and high-throughput sensing. This research demonstrates the ability of bud-shaped gold nanoflowers (AuNFs), intermediates in the bud-to-blossom gold nanoflower synthesis, to offer remarkable electrocatalytic efficiency in the oxidation of ascorbic acid (AA) at nanomolar concentrations. Multicomponent sensing in a single potential sweep is measured using differential pulse voltammetry while the kinetic parameters are estimated using electrochemical impedance spectroscopy. The outstanding catalytic activity of bud-structured AuNF [iAuNFp(Bud)/iGCp ≅ 100] compared with other bud-to-blossom intermediate nanostructures is explained by studying their structural transitions, charge distributions, crystalline patterns, and intrinsic irregularities/defects. Detailed microscopic analysis shows that density of crystal defects, such as edges, terraces, steps, ledges, kinks, and dislocation, plays a major role in producing the high catalytic efficiency. An associated ab initio simulation provides necessary support for the projected role of different crystal facets as selective catalytic sites. Density functional theory corroborates the appearance of inter- and intra-molecular hydrogen bonding within AA molecules to control the resultant fingerprint peak potentials at variable concentrations. Bud-structured AuNF facilitates AA detection at nanomolar levels in a multicomponent pathological sample.

One molecule of ionic liquid and tert-alcohol on a polystyrene-support as catalysts for efficient nucleophilic substitution including fluorination.

PubMed

Shinde, Sandip S; Patil, Sunil N

2014-12-07

The tert-alcohol and ionic liquid solvents in one molecule [mim-(t)OH][OMs] was immobilized on polystyrene and reported to be a highly efficient catalyst in aliphatic nucleophilic substitution using alkali metal salts. Herein, we investigated the catalytic activity of a new structurally modified polymer-supported tert-alcohol functionalized imidazolium salt catalyst in nucleophilic substitution of 2-(3-methanesulfonyloxypropyoxy)naphthalene as a model substrate with various metal nucleophiles. The tert-alcohol moiety of the ionic liquid with a hexyl chain distance from polystyrene had a better catalytic activity compared to the other resin which lacked an alkyl linker and tert-alcohol moiety. We found that the maximum [mim-(t)OH][OMs] loading had the best catalytic efficacy among the tested polystyrene-based ionic liquids (PSILs) in nucleophilic fluorination. The catalytic efficiency of the PS[him-(t)OH][OMs] as a phase transfer catalyst (PTC) was determined by carrying out various nucleophilic substitutions using the corresponding alkali metal salts from the third to sixth periodic in CH3CN or tert-BuOH media. The scope of this protocol with primary and secondary polar substrates containing many heteroatoms is also reported. This PS[him-(t)OH][OMs] catalyst not only enhances the reactivity of alkali metal salts and reduces the formation of by-products but also affords high yield with easy isolation.

Endogenous Catalytic Generation of O2 Bubbles for In Situ Ultrasound-Guided High Intensity Focused Ultrasound Ablation.

PubMed

Liu, Tianzhi; Zhang, Nan; Wang, Zhigang; Wu, Meiying; Chen, Yu; Ma, Ming; Chen, Hangrong; Shi, Jianlin

2017-09-26

High intensity focused ultrasound (HIFU) surgery generally suffers from poor precision and low efficiency in clinical application, especially for cancer therapy. Herein, a multiscale hybrid catalytic nanoreactor (catalase@MONs, abbreviated as C@M) has been developed as a tumor-sensitive contrast and synergistic agent (C&SA) for ultrasound-guided HIFU cancer surgery, by integrating dendritic-structured mesoporous organosilica nanoparticles (MONs) and catalase immobilized in the large open pore channels of MONs. Such a hybrid nanoreactor exhibited sensitive catalytic activity toward H 2 O 2 , facilitating the continuous O 2 gas generation in a relatively mild manner even if incubated with 10 μM H 2 O 2 , which finally led to enhanced ablation in the tissue-mimicking PAA gel model after HIFU exposure mainly resulting from intensified cavitation effect. The C@M nanoparticles could be accumulated within the H 2 O 2 -enriched tumor region through enhanced permeability and retention effect, enabling durable contrast enhancement of ultrasound imaging, and highly efficient tumor ablation under relatively low power of HIFU exposure in vivo. Very different from the traditional perfluorocarbon-based C&SA, such an on-demand catalytic nanoreactor could realize the accurate positioning of tumor without HIFU prestimulation and efficient HIFU ablation with a much safer power output, which is highly desired in clinical HIFU application.

Quantitative methylene blue decolourisation assays as rapid screening tools for assessing the efficiency of catalytic reactions.

PubMed

Kruid, Jan; Fogel, Ronen; Limson, Janice Leigh

2017-05-01

Identifying the most efficient oxidation process to achieve maximum removal of a target pollutant compound forms the subject of much research. There exists a need to develop rapid screening tools to support research in this area. In this work we report on the development of a quantitative assay as a means for identifying catalysts capable of decolourising methylene blue through the generation of oxidising species from hydrogen peroxide. Here, a previously described methylene blue test strip method was repurposed as a quantitative, aqueous-based spectrophotometric assay. From amongst a selection of metal salts and metallophthalocyanine complexes, monitoring of the decolourisation of the cationic dye methylene blue (via Fenton-like and non-Fenton oxidation reactions) by the assay identified the following to be suitable oxidation catalysts: CuSO 4 (a Fenton-like catalyst), iron(II)phthalocyanine (a non-Fenton oxidation catalyst), as well as manganese(II) phthalocyanine. The applicability of the method was examined for the removal of bisphenol A (BPA), as measured by HPLC, during parallel oxidation experiments. The order of catalytic activity was identified as FePc > MnPc > CuSO 4 for both BPA and MB. The quantitative MB decolourisation assay may offer a rapid method for screening a wide range of potential catalysts for oxidation processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Platinum-Coated Hollow Graphene Nanocages as Cathode Used in Lithium-Oxygen Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Feng; Xing, Yi; Zeng, Xiaoqiao

2016-08-31

One of the formidable challenges facing aprotic lithium-oxygen (Li-O-2) batteries is the high charge overpotential, which induces the formation of byproducts, loss in efficiency, and poor cycling performance. Herein, the synthesis of the ultrasmall Pt-coated hollow graphene nano cages as cathode in Li-O-2 batteries is reported. The charge voltage plateau can reduce to 3.2 V at the current density of 100 mA g(-1), even maintain below 3.5 V when the current density increased to 500 mA g(-1). The unique hollow graphene nanocages matrix can not only provide numerous nanoscale tri-phase regions as active sites for efficient oxygen reduction, but alsomore » offer sufficient amount of mesoscale pores for rapid oxygen diffusion. Furthermore, with strong atomic-level oxygen absorption into its subsurface, ultrasmall Pt catalytically serves as the nucleation site for Li2O2 growth. The Li2O2 is subsequently induced into a favorable form with small size and amorphous state, decomposed more easily during recharge. Meanwhile, the conductive hollow graphene substrate can enhance the catalytic activity of noble metal Pt catalysts due to the graphene-metal interfacial interaction. Benefiting from the above synergistic effects between the hollow graphene nanocages and the nanosized Pt catalysts, the ultrasmall Pt-decorated graphene nanocage cathode exhibits enhanced electrochemical performances.« less

Preparation of a magnetic N-Fe/AC catalyst for aqueous pharmaceutical treatment in heterogeneous sonication system.

PubMed

Zhang, Nan; Zhao, He; Zhang, Guangming; Chong, Shan; Liu, Yucan; Sun, Liyan; Chang, Huazhen; Huang, Ting

2017-02-01

High efficiency and facile separation are desirable for catalysts used in water treatment. In this study, a magnetic catalyst (nitrogen doped iron/activated carbon) was prepared and used for pharmaceutical wastewater treatment. The catalyst was characterized using BET, SEM, XRD, VSM and XPS. Results showed that iron and nitrogen were successfully loaded and doped, magnetic Fe 2 N was formed, large amount of active surface oxygen and Fe(II) were detected, and the catalyst could be easily separated from water. Diclofenac was then degraded using the catalyst in ultrasound system. The catalyst showed high catalytic activity with 95% diclofenac removal. Analysis showed that ·OH attack of diclofenac was a main pathway, and then ·OH generation mechanism was clarified. The effects of catalyst dosage, sonication time, ultrasonic density, initial pH, and inorganic anions on diclofenac degradation were studied. Sulfate anion enhanced the degradation of diclofenac. Mechanism in the catalytic ultrasonic process was analyzed and reactions were clarified. Large quantity of oxidants was generated on the catalyst surface, including ·OH, O 2 - , O - and HO 2 ·, which degraded diclofenac efficiently. In the solution and interior of cavitation bubbles, ·OH and "hot spot" effects contributed to the degradation of diclofenac. Reuse of the catalyst was further investigated to enhance its economy, and the catalyst maintained activity after seven uses. Copyright © 2016 Elsevier Ltd. All rights reserved.

In situ characterization of catalytic activity of graphene stabilized small-sized Pd nanoparticles for CO oxidation

NASA Astrophysics Data System (ADS)

Mao, Bao-Hua; Liu, Chang-Hai; Gao, Xu; Chang, Rui; Liu, Zhi; Wang, Sui-Dong

2013-10-01

The room-temperature ionic liquid assisted sputtering method is utilized to achieve the Pd-nanoparticle (NP)-graphene hybrid. The supported Pd NPs possess uniformly small sizes of 1-2 nm, which create huge surface area with ultralow Pd consumption and high NP stability. The Pd-NP-graphene hybrid is in situ characterized by the ambient pressure X-ray photoelectron spectroscopy using synchrotron radiation, and the results demonstrate high catalytic activity of the hybrid for CO oxidation. The catalytic behavior is reproducible for several catalytic cycles. The present simple and clean approach is promising to produce metal-NP-based high-efficiency catalysts for CO oxidation.

Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide

NASA Astrophysics Data System (ADS)

Cabán-Acevedo, Miguel; Stone, Michael L.; Schmidt, J. R.; Thomas, Joseph G.; Ding, Qi; Chang, Hung-Chih; Tsai, Meng-Lin; He-Hau, Jr.; Jin, Song

2015-12-01

The scalable and sustainable production of hydrogen fuel through water splitting demands efficient and robust Earth-abundant catalysts for the hydrogen evolution reaction (HER). Building on promising metal compounds with high HER catalytic activity, such as pyrite structure cobalt disulphide (CoS2), and substituting non-metal elements to tune the hydrogen adsorption free energy could lead to further improvements in catalytic activity. Here we present a combined theoretical and experimental study to establish ternary pyrite-type cobalt phosphosulphide (CoPS) as a high-performance Earth-abundant catalyst for electrochemical and photoelectrochemical hydrogen production. Nanostructured CoPS electrodes achieved a geometrical catalytic current density of 10 mA cm-2 at overpotentials as low as 48 mV, with outstanding long-term operational stability. Integrated photocathodes of CoPS on n+-p-p+ silicon micropyramids achieved photocurrents up to 35 mA cm-2 at 0 V versus the reversible hydrogen electrode (RHE), onset photovoltages as high as 450 mV versus RHE, and the most efficient solar-driven hydrogen generation from Earth-abundant systems.

Reduced Graphene Oxide-Immobilized Tris(bipyridine)ruthenium(II) Complex for Efficient Visible-Light-Driven Reductive Dehalogenation Reaction.

PubMed

Li, Xiaoyan; Hao, Zhongkai; Zhang, Fang; Li, Hexing

2016-05-18

A sodium benzenesulfonate (PhSO3Na)-functionalized reduced graphene oxide was synthesized via a two-step aryl diazonium coupling and subsequent NaCl ion-exchange procedure, which was used as a support to immobilize tris(bipyridine)ruthenium(II) complex (Ru(bpy)3Cl2) by coordination reaction. This elaborated Ru(bpy)3-rGO catalyst exhibited excellent catalytic efficiency in visible-light-driven reductive dehalogenation reactions under mild conditions, even for ary chloride. Meanwhile, it showed the comparable reactivity with the corresponding homogeneous Ru(bpy)3Cl2 catalyst. This high catalytic performance could be attributed to the unique two-dimensional sheet-like structure of Ru(bpy)3-rGO, which efficiently diminished diffusion resistance of the reactants. Meanwhile, the nonconjugated PhSO3Na-linkage between Ru(II) complex and the support and the very low electrical conductivity of the catalyst inhibited energy/electron transfer from Ru(II) complex to rGO support, resulting in the decreased support-induced quenching effect. Furthermore, it could be easily recycled at least five times without significant loss of catalytic reactivity.

Crystal Structure and Catalytic Mechanism of 7-Hydroxymethyl Chlorophyll a Reductase*

PubMed Central

Wang, Xiao; Liu, Lin

2016-01-01

7-Hydroxymethyl chlorophyll a reductase (HCAR) catalyzes the second half-reaction in chlorophyll b to chlorophyll a conversion. HCAR is required for the degradation of light-harvesting complexes and is necessary for efficient photosynthesis by balancing the chlorophyll a/b ratio. Reduction of the hydroxymethyl group uses redox cofactors [4Fe-4S] cluster and FAD to transfer electrons and is difficult because of the strong carbon-oxygen bond. Here, we report the crystal structure of Arabidopsis HCAR at 2.7-Å resolution and reveal that two [4Fe-4S]clusters and one FAD within a very short distance form a consecutive electron pathway to the substrate pocket. In vitro kinetic analysis confirms the ferredoxin-dependent electron transport chain, thus supporting a proton-activated electron transfer mechanism. HCAR resembles a partial reconstruction of an archaeal F420-reducing [NiFe] hydrogenase, which suggests a common mode of efficient proton-coupled electron transfer through conserved cofactor arrangements. Furthermore, the trimeric form of HCAR provides a biological clue of its interaction with light-harvesting complex II. PMID:27072131

Detection of damaged DNA bases by DNA glycosylase enzymes.

PubMed

Friedman, Joshua I; Stivers, James T

2010-06-22

A fundamental and shared process in all forms of life is the use of DNA glycosylase enzymes to excise rare damaged bases from genomic DNA. Without such enzymes, the highly ordered primary sequences of genes would rapidly deteriorate. Recent structural and biophysical studies are beginning to reveal a fascinating multistep mechanism for damaged base detection that begins with short-range sliding of the glycosylase along the DNA chain in a distinct conformation we call the search complex (SC). Sliding is frequently punctuated by the formation of a transient "interrogation" complex (IC) where the enzyme extrahelically inspects both normal and damaged bases in an exosite pocket that is distant from the active site. When normal bases are presented in the exosite, the IC rapidly collapses back to the SC, while a damaged base will efficiently partition forward into the active site to form the catalytically competent excision complex (EC). Here we review the unique problems associated with enzymatic detection of rare damaged DNA bases in the genome and emphasize how each complex must have specific dynamic properties that are tuned to optimize the rate and efficiency of damage site location.

Rationale behind the near-ideal catalysis of Candida antarctica lipase A (CAL-A) for highly concentrating ω-3 polyunsaturated fatty acids into monoacylglycerols.

PubMed

He, Yongjin; Li, Jingbo; Kodali, Sitharam; Chen, Bilian; Guo, Zheng

2017-03-15

Dramatic decline in the quality and quantity of ω-3 PUFAs from marine resource demands new environmental-friendly technology to produce high quality ω-3 PUFAs concentrates in a better bioavailable form. Accordingly this work demonstrated an exceptionally highly efficient non-aqueous approach that non-regiospecific and non ω-3 PUFAs preferential Candida antarctica lipase A (CAL-A), functioning as a near-ideal biocatalyst, is capable to directly concentrate ω-3 PUFAs from 20% to 30% in oils to up to >90% in monoacylglycerols form through one step reaction. The rationale behind the experimental observation is justified and the catalytic property and specificity of an ideal enzyme tackling this task are defined. High selectivity and efficiency, excellent reusability of biocatalyst, general applicability for concentrating ω-3 PUFAs from both fish and microalgae oils, simple process for product recovery (e.g. by short path distillation), make this novel approach a highly industrially relevant and with potential application in food and drug industries. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fluorescent aptasensor for detection of four tetracycline veterinary drugs in milk based on catalytic hairpin assembly reaction and displacement of G-quadruplex.

PubMed

Zhou, Chen; Zou, Haimin; Sun, Chengjun; Ren, Dongxia; Xiong, Wei; Li, Yongxin

2018-05-01

Based on a novel signal amplification strategy by catalytic hairpin assembly and displacement of G-quadruplex DNA, an enzyme-free, non-label fluorescent aptasensing approach was established for sensitive detection of four tetracycline veterinary drugs in milk. The network consisted of a pair of partially complementary DNA hairpins (HP1 and HP2). The DNA aptamer of four tetracycline veterinary drugs was located at the sticky end of the HP1. The ring region of HP1 rich in G and C could form a stable G-quadruplex structure, which could emit specific fluorescence signal after binding with the fluorescent dye and N-methylmesoporphyrin IX (NMM). When presented in the system, the target analytes would be repeatedly used to trigger a recycling procedure between the hairpins, generating numerous HP1-HP2 duplex complexes and displacing G-quadruplex DNA. Thus, the sensitive detection of target analytes was achieved in a wide linear range (0-1000 μg/L) with the detection limit of 4.6 μg/L. Moreover, this proposed method showed high discrimination efficiency towards target analytes against other common mismatched veterinary drugs, and could be successfully applied to the analysis of milk samples. Graphical abstract Schematic of target analyte detection based on catalytic hairpin assembly reaction and displacement of G-quadruplex.

E2 superfamily of ubiquitin-conjugating enzymes: constitutively active or activated through phosphorylation in the catalytic cleft.

PubMed

Valimberti, Ilaria; Tiberti, Matteo; Lambrughi, Matteo; Sarcevic, Boris; Papaleo, Elena

2015-10-14

Protein phosphorylation is a modification that offers a dynamic and reversible mechanism to regulate the majority of cellular processes. Numerous diseases are associated with aberrant regulation of phosphorylation-induced switches. Phosphorylation is emerging as a mechanism to modulate ubiquitination by regulating key enzymes in this pathway. The molecular mechanisms underpinning how phosphorylation regulates ubiquitinating enzymes, however, are elusive. Here, we show the high conservation of a functional site in E2 ubiquitin-conjugating enzymes. In catalytically active E2s, this site contains aspartate or a phosphorylatable serine and we refer to it as the conserved E2 serine/aspartate (CES/D) site. Molecular simulations of substrate-bound and -unbound forms of wild type, mutant and phosphorylated E2s, provide atomistic insight into the role of the CES/D residue for optimal E2 activity. Both the size and charge of the side group at the site play a central role in aligning the substrate lysine toward E2 catalytic cysteine to control ubiquitination efficiency. The CES/D site contributes to the fingerprint of the E2 superfamily. We propose that E2 enzymes can be divided into constitutively active or regulated families. E2s characterized by an aspartate at the CES/D site signify constitutively active E2s, whereas those containing a serine can be regulated by phosphorylation.

Selenoglutathione Diselenide: Unique Redox Reactions in the GPx-Like Catalytic Cycle and Repairing of Disulfide Bonds in Scrambled Protein.

PubMed

Shimodaira, Shingo; Asano, Yuki; Arai, Kenta; Iwaoka, Michio

2017-10-24

Selenoglutathione (GSeH) is a selenium analogue of naturally abundant glutathione (GSH). In this study, this water-soluble small tripeptide was synthesized in a high yield (up to 98%) as an oxidized diselenide form, i.e., GSeSeG (1), by liquid-phase peptide synthesis (LPPS). Obtained 1 was applied to the investigation of the glutathione peroxidase (GPx)-like catalytic cycle. The important intermediates, i.e., GSe - and GSeSG, besides GSeO 2 H were characterized by 77 Se NMR spectroscopy. Thiol exchange of GSeSG with various thiols, such as cysteine and dithiothreitol, was found to promote the conversion to GSe - significantly. In addition, disproportionation of GSeSR to 1 and RSSR, which would be initiated by heterolytic cleavage of the Se-S bond and catalyzed by the generated selenolate, was observed. On the basis of these redox behaviors, it was proposed that the heterolytic cleavage of the Se-S bond can be facilitated by the interaction between the Se atom and an amino or aromatic group, which is present at the GPx active site. On the other hand, when a catalytic amount of 1 was reacted with scrambled 4S species of RNase A in the presence of NADPH and glutathione reductase, native protein was efficiently regenerated, suggesting a potential use of 1 to repair misfolded proteins through reduction of the non-native SS bonds.

Bi2S3microspheres grown on graphene sheets as low-cost counter-electrode materials for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Li, Guang; Chen, Xiaoshuang; Gao, Guandao

2014-02-01

In this work, we synthesized 3D Bi2S3 microspheres comprised of nanorods grown along the (211) facet on graphene sheets by a solvothermal route, and investigated its catalytic activities through I-V curves and conversion efficiency tests as the CE in DSSCs. Although the (211) facet has a large band gap for a Bi2S3 semiconductor, owing to the introduction of graphene into the system, its short-circuit current density, open-circuit voltage, fill factor, and efficiency were Jsc = 12.2 mA cm-2, Voc = 0.75 V, FF = 0.60, and η = 5.5%, respectively. By integrating it with graphene sheets, our material achieved the conversion efficiency of 5.5%, which is almost triple the best conversion efficiency value of the DSSCs with (211)-faceted 3D Bi2S3 without graphene (1.9%) reported in the latest literature. Since this conversion-efficient 3D material grown on the graphene sheets significantly improves its catalytic properties, it paves the way for designing and applying low-cost Pt-free CE materials in DSSC from inorganic nanostructures.In this work, we synthesized 3D Bi2S3 microspheres comprised of nanorods grown along the (211) facet on graphene sheets by a solvothermal route, and investigated its catalytic activities through I-V curves and conversion efficiency tests as the CE in DSSCs. Although the (211) facet has a large band gap for a Bi2S3 semiconductor, owing to the introduction of graphene into the system, its short-circuit current density, open-circuit voltage, fill factor, and efficiency were Jsc = 12.2 mA cm-2, Voc = 0.75 V, FF = 0.60, and η = 5.5%, respectively. By integrating it with graphene sheets, our material achieved the conversion efficiency of 5.5%, which is almost triple the best conversion efficiency value of the DSSCs with (211)-faceted 3D Bi2S3 without graphene (1.9%) reported in the latest literature. Since this conversion-efficient 3D material grown on the graphene sheets significantly improves its catalytic properties, it paves the way for designing and applying low-cost Pt-free CE materials in DSSC from inorganic nanostructures. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr06093d

New La(III) complex immobilized on 3-aminopropyl-functionalized silica as an efficient and reusable catalyst for hydrolysis of phosphate ester bonds.

PubMed

Muxel, Alfredo A; Neves, Ademir; Camargo, Maryene A; Bortoluzzi, Adailton J; Szpoganicz, Bruno; Castellano, Eduardo E; Castilho, Nathalia; Bortolotto, Tiago; Terenzi, Hernán

2014-03-17

Described herein is the synthesis, structure, and monoesterase and diesterase activities of a new mononuclear [La(III)(L(1))(NO3)2] (1) complex (H2L(1) = 2-bis[{(2-pyridylmethyl)-aminomethyl}-6-[N-(2-pyridylmethyl) aminomethyl)])-4-methyl-6-formylphenol) in the hydrolysis of 2,4-bis(dinitrophenyl)phosphate (2,4-BDNPP). When covalently linked to 3-aminopropyl-functionalized silica, 1 undergoes disproportionation to form a dinuclear species (APS-1), whose catalytic efficiency is increased when compared to the homogeneous reaction due to second coordination sphere effects which increase the substrate to complex association constant. The anchored catalyst APS-1 can be recovered and reused for subsequent hydrolysis reactions (five times) with only a slight loss in activity. In the presence of DNA, we suggest that 1 is also converted into the dinuclear active species as observed with APS-1, and both were shown to be efficient in DNA cleavage.

Dual properties of a hydrogen oxidation Ni-catalyst entrapped within a polymer promote self-defense against oxygen.

PubMed

Oughli, Alaa A; Ruff, Adrian; Boralugodage, Nilusha Priyadarshani; Rodríguez-Maciá, Patricia; Plumeré, Nicolas; Lubitz, Wolfgang; Shaw, Wendy J; Schuhmann, Wolfgang; Rüdiger, Olaf

2018-02-28

The Ni(P 2 N 2 ) 2 catalysts are among the most efficient non-noble-metal based molecular catalysts for H 2 cycling. However, these catalysts are O 2 sensitive and lack long term stability under operating conditions. Here, we show that in a redox silent polymer matrix the catalyst is dispersed into two functionally different reaction layers. Close to the electrode surface is the "active" layer where the catalyst oxidizes H 2 and exchanges electrons with the electrode generating a current. At the outer film boundary, insulation of the catalyst from the electrode forms a "protection" layer in which H 2 is used by the catalyst to convert O 2 to H 2 O, thereby providing the "active" layer with a barrier against O 2 . This simple but efficient polymer-based electrode design solves one of the biggest limitations of these otherwise very efficient catalysts enhancing its stability for catalytic H 2 oxidation as well as O 2 tolerance.

Fe Isolated Single Atoms on S, N Codoped Carbon by Copolymer Pyrolysis Strategy for Highly Efficient Oxygen Reduction Reaction.

PubMed

Li, Qiheng; Chen, Wenxing; Xiao, Hai; Gong, Yue; Li, Zhi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Cheong, Weng-Chon; Shen, Rongan; Fu, Ninghua; Gu, Lin; Zhuang, Zhongbin; Chen, Chen; Wang, Dingsheng; Peng, Qing; Li, Jun; Li, Yadong

2018-06-01

Heteroatom-doped Fe-NC catalyst has emerged as one of the most promising candidates to replace noble metal-based catalysts for highly efficient oxygen reduction reaction (ORR). However, delicate controls over their structure parameters to optimize the catalytic efficiency and molecular-level understandings of the catalytic mechanism are still challenging. Herein, a novel pyrrole-thiophene copolymer pyrolysis strategy to synthesize Fe-isolated single atoms on sulfur and nitrogen-codoped carbon (Fe-ISA/SNC) with controllable S, N doping is rationally designed. The catalytic efficiency of Fe-ISA/SNC shows a volcano-type curve with the increase of sulfur doping. The optimized Fe-ISA/SNC exhibits a half-wave potential of 0.896 V (vs reversible hydrogen electrode (RHE)), which is more positive than those of Fe-isolated single atoms on nitrogen codoped carbon (Fe-ISA/NC, 0.839 V), commercial Pt/C (0.841 V), and most reported nonprecious metal catalysts. Fe-ISA/SNC is methanol tolerable and shows negligible activity decay in alkaline condition during 15 000 voltage cycles. X-ray absorption fine structure analysis and density functional theory calculations reveal that the incorporated sulfur engineers the charges on N atoms surrounding the Fe reactive center. The enriched charge facilitates the rate-limiting reductive release of OH* and therefore improved the overall ORR efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Protein-protein interactions and substrate channeling in orthologous and chimeric aldolase-dehydrogenase complexes.

PubMed

Baker, Perrin; Hillis, Colleen; Carere, Jason; Seah, Stephen Y K

2012-03-06

Bacterial aldolase-dehydrogenase complexes catalyze the last steps in the meta cleavage pathway of aromatic hydrocarbon degradation. The aldolase (TTHB246) and dehydrogenase (TTHB247) from Thermus thermophilus were separately expressed and purified from recombinant Escherichia coli. The aldolase forms a dimer, while the dehydrogenase is a monomer; these enzymes can form a stable tetrameric complex in vitro, consisting of two aldolase and two dehydrogenase subunits. Upon complex formation, the K(m) value of 4-hydroxy-2-oxopentanoate, the substrate of TTHB246, is decreased 4-fold while the K(m) of acetaldehyde, the substrate of TTHB247, is increased 3-fold. The k(cat) values of each enzyme were reduced by ~2-fold when they were in a complex. The half-life of TTHB247 at 50 °C increased by ~4-fold when it was in a complex with TTHB246. The acetaldehyde product from TTHB246 could be efficiently channelled directly to TTHB247, but the channeling efficiency for the larger propionaldehyde was ~40% lower. A single A324G substitution in TTHB246 increased the channeling efficiency of propionaldehyde to a value comparable to that of acetaldehyde. Stable and catalytically competent chimeric complexes could be formed between the T. thermophilus enzymes and the orthologous aldolase (BphI) and dehydrogenase (BphJ) from the biphenyl degradation pathway of Burkholderia xenovorans LB400. However, channeling efficiencies for acetaldehyde in these chimeric complexes were ~10%. Structural and sequence analysis suggests that interacting residues in the interface of the aldolase-dehydrogenase complex are highly conserved among homologues, but coevolution of partner enzymes is required to fine-tune this interaction to allow for efficient substrate channeling.

A catalytic tethering strategy: simple aldehydes catalyze intermolecular alkene hydroaminations.

PubMed

MacDonald, Melissa J; Schipper, Derek J; Ng, Peter J; Moran, Joseph; Beauchemin, André M

2011-12-21

Herein we describe a catalytic tethering strategy in which simple aldehyde precatalysts enable, through temporary intramolecularity, room-temperature intermolecular hydroamination reactivity and the synthesis of vicinal diamines. The catalyst allows the formation of a mixed aminal from an allylic amine and a hydroxylamine, resulting in a facile intramolecular hydroamination event. The promising enantioselectivities obtained with a chiral aldehyde also highlight the potential of this catalytic tethering approach in asymmetric catalysis and demonstrate that efficient enantioinduction relying only on temporary intramolecularity is possible. © 2011 American Chemical Society

Low and medium heating value coal gas catalytic combustor characterization

NASA Technical Reports Server (NTRS)

Schwab, J. A.

1982-01-01

Catalytic combustion with both low and medium heating value coal gases obtained from an operating gasifier was demonstrated. A practical operating range for efficient operation was determined, and also to identify potential problem areas were identified for consideration during stationary gas turbine engine design. The test rig consists of fuel injectors, a fuel-air premixing section, a catalytic reactor with thermocouple instrumentation and a single point, water cooled sample probe. The test rig included inlet and outlet transition pieces and was designed for installation into an existing test loop.

Catalytic, hollow, refractory spheres, conversions with them

NASA Technical Reports Server (NTRS)

Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

1989-01-01

Improved, heterogeneous, refractory catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitable formed of a shell (12) of refractory such as alumina having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be itself catalytic or a catalytically active material coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Catalytic, hollow, refractory spheres

NASA Technical Reports Server (NTRS)

Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

1987-01-01

Improved, heterogeneous, refractory catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitable formed of a shell (12) of refractory such as alumina having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be itself catalytic or a catalytically active material coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Cloning, preparation and preliminary crystallographic studies of penicillin V acylase autoproteolytic processing mutants

PubMed Central

Chandra, P. Manish; Brannigan, James A.; Prabhune, Asmita; Pundle, Archana; Turkenburg, Johan P.; Dodson, G. Guy; Suresh, C. G.

2005-01-01

The crystallization of three catalytically inactive mutants of penicillin V acylase (PVA) from Bacillus sphaericus in precursor and processed forms is reported. The mutant proteins crystallize in different primitive monoclinic space groups that are distinct from the crystal forms for the native enzyme. Directed mutants and clone constructs were designed to study the post-translational autoproteolytic processing of PVA. The catalytically inactive mutants will provide three-dimensional structures of precursor PVA forms, plus open a route to the study of enzyme–substrate complexes for this industrially important enzyme. PMID:16508111

40 CFR 63.1576 - What records must I keep, in what form, and for how long?

Code of Federal Regulations, 2010 CFR

2010-07-01

... Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Notifications, Reports, and Records... keep records required by Tables 6, 7, 13, and 14 of this subpart (for catalytic cracking units); Tables...

40 CFR 63.1576 - What records must I keep, in what form, and for how long?

Code of Federal Regulations, 2011 CFR

2011-07-01

... Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Notifications, Reports, and Records... keep records required by Tables 6, 7, 13, and 14 of this subpart (for catalytic cracking units); Tables...

The catalytic cycle of nitrous oxide reductase - The enzyme that catalyzes the last step of denitrification.

PubMed

Carreira, Cíntia; Pauleta, Sofia R; Moura, Isabel

2017-12-01

The reduction of the potent greenhouse gas nitrous oxide requires a catalyst to overcome the large activation energy barrier of this reaction. Its biological decomposition to the inert dinitrogen can be accomplished by denitrifiers through nitrous oxide reductase, the enzyme that catalyzes the last step of the denitrification, a pathway of the biogeochemical nitrogen cycle. Nitrous oxide reductase is a multicopper enzyme containing a mixed valence CuA center that can accept electrons from small electron shuttle proteins, triggering electron flow to the catalytic sulfide-bridged tetranuclear copper "CuZ center". This enzyme has been isolated with its catalytic center in two forms, CuZ*(4Cu1S) and CuZ(4Cu2S), proven to be spectroscopic and structurally different. In the last decades, it has been a challenge to characterize the properties of this complex enzyme, due to the different oxidation states observed for each of its centers and the heterogeneity of its preparations. The substrate binding site in those two "CuZ center" forms and which is the active form of the enzyme is still a matter of debate. However, in the last years the application of different spectroscopies, together with theoretical calculations have been useful in answering these questions and in identifying intermediate species of the catalytic cycle. An overview of the spectroscopic, kinetics and structural properties of the two forms of the catalytic "CuZ center" is given here, together with the current knowledge on nitrous oxide reduction mechanism by nitrous oxide reductase and its intermediate species. Copyright © 2017 Elsevier Inc. All rights reserved.

Novel catalytic effects of Mn3O4 for all vanadium redox flow batteries.

PubMed

Kim, Ki Jae; Park, Min-Sik; Kim, Jae-Hun; Hwang, Uk; Lee, Nam Jin; Jeong, Goojin; Kim, Young-Jun

2012-06-04

A new approach for enhancing the electrochemical performance of carbon felt electrodes by employing non-precious metal oxides is designed. The outstanding electro-catalytic activity and mechanical stability of Mn(3)O(4) are advantageous in facilitating the redox reaction of vanadium ions, leading to efficient operation of a vanadium redox flow battery.

Heterogeneous Catalysis: A Central Science for a Sustainable Future.

PubMed

Friend, Cynthia M; Xu, Bingjun

2017-03-21

Developing active, selective, and energy efficient heterogeneous catalytic processes is key to a sustainable future because heterogeneous catalysis is at the center of the chemicals and energy industries. The design, testing, and implementation of robust and selective heterogeneous catalytic processes based on insights from fundamental studies could have a tremendous positive impact on the world.

IN SITU DESTRUCTION OF CHLORINATED HYDROCARBON COMPOUNDS IN GROUNDWATER USING CATALYTIC REDUCTIVE REDUCTIVE DEHALOGENATION IN A REACTIVE WELL: TESTING AND OPERATIONAL EXPERIENCES. (R825421)

EPA Science Inventory

A groundwater treatment technology based on catalytic reductive
dehalogenation has been developed to efficiently destroy chlorinated
hydrocarbons in situ using a reactive well approach. The treatment process
utilizes dissolved H₂ as an electron donor, in...

Novel combination of zero-valent Cu and Ag nanoparticles @ cellulose acetate nanocomposite for the reduction of 4-nitro phenol.

PubMed

Khan, Farman Ullah; Asimullah; Khan, Sher Bahadar; Kamal, Tahseen; Asiri, Abdullah M; Khan, Ihsan Ullah; Akhtar, Kalsoom

2017-09-01

A very simple and low-cost procedure has been adopted to synthesize efficient copper (Cu), silver (Ag) and copper-silver (Cu-Ag) mixed nanoparticles on the surface of pure cellulose acetate (CA) and cellulose acetate-copper oxide nanocomposite (CA-CuO). All nanoparticles loaded onto CA and CA-CuO presented excellent catalytic ability, but Cu-Ag nanoparticles loaded onto CA-CuO (Cu 0 -Ag 0 /CA-CuO) exhibited outstanding catalytic efficiency to convert 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) in the presence of NaBH 4 . Additionally, the Cu 0 -Ag 0 /CA-CuO can be easily recovered by removing the sheet from the reaction media, and can be recycled several times, maintaining high catalytic ability for four cycles. Copyright © 2017 Elsevier B.V. All rights reserved.

Rapid bursts and slow declines: on the possible evolutionary trajectories of enzymes

PubMed Central

Newton, Matilda S.; Arcus, Vickery L.; Patrick, Wayne M.

2015-01-01

The evolution of enzymes is often viewed as following a smooth and steady trajectory, from barely functional primordial catalysts to the highly active and specific enzymes that we observe today. In this review, we summarize experimental data that suggest a different reality. Modern examples, such as the emergence of enzymes that hydrolyse human-made pesticides, demonstrate that evolution can be extraordinarily rapid. Experiments to infer and resurrect ancient sequences suggest that some of the first organisms present on the Earth are likely to have possessed highly active enzymes. Reconciling these observations, we argue that rapid bursts of strong selection for increased catalytic efficiency are interspersed with much longer periods in which the catalytic power of an enzyme erodes, through neutral drift and selection for other properties such as cellular energy efficiency or regulation. Thus, many enzymes may have already passed their catalytic peaks. PMID:25926697

Installing hydrolytic activity into a completely de novo protein framework

NASA Astrophysics Data System (ADS)

Burton, Antony J.; Thomson, Andrew R.; Dawson, William M.; Brady, R. Leo; Woolfson, Derek N.

2016-09-01

The design of enzyme-like catalysts tests our understanding of sequence-to-structure/function relationships in proteins. Here we install hydrolytic activity predictably into a completely de novo and thermostable α-helical barrel, which comprises seven helices arranged around an accessible channel. We show that the lumen of the barrel accepts 21 mutations to functional polar residues. The resulting variant, which has cysteine-histidine-glutamic acid triads on each helix, hydrolyses p-nitrophenyl acetate with catalytic efficiencies that match the most-efficient redesigned hydrolases based on natural protein scaffolds. This is the first report of a functional catalytic triad engineered into a de novo protein framework. The flexibility of our system also allows the facile incorporation of unnatural side chains to improve activity and probe the catalytic mechanism. Such a predictable and robust construction of truly de novo biocatalysts holds promise for applications in chemical and biochemical synthesis.

Highly Efficient Catalysis of Azo Dyes Using Recyclable Silver Nanoparticles Immobilized on Tannic Acid-Grafted Eggshell Membrane

NASA Astrophysics Data System (ADS)

Liu, Xiaojing; Liang, Miao; Liu, Mingyue; Su, Rongxin; Wang, Mengfan; Qi, Wei; He, Zhimin

2016-10-01

In this study, a facile one-step synthesis of a novel nanocomposite catalytic film was developed based on silver nanoparticles (AgNPs) immobilized in tannic acid-modified eggshell membrane (Tan-ESM). Tannic acid, as a typical plant polyphenol from oak wood, was first grafted onto ESM fibers to serve as both the reductant and the stabilizer during the synthesis of AgNPs. The morphology, constitution, and thermal stability of the resulting AgNPs@Tan-ESM composites were fully characterized to explain the excellent catalytic efficiency of AgNPs@Tan-ESM composites. These composite catalysts were applied to the degradation of azo dyes which exhibited the high catalytic activity toward Congo red and methyl orange according to the kinetic curves. More importantly, they can be easily recovered and reused for many times because of their good stability.

Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures as efficient bicatalysts for oxygen reduction and evolution reactions

NASA Astrophysics Data System (ADS)

Qi, Chunling; Zhang, Li; Xu, Guancheng; Sun, Zhipeng; Zhao, Aihua; Jia, Dianzeng

2018-01-01

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play crucial roles in efficient energy conversion and storage solutions. Here, Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures (denoted as Co@Co3O4/NCs) are prepared via a simple two-step and in situ approach by carbonization and subsequent oxidation of Co-MOF containing high contents of carbon and nitrogen. When evaluated as electrocatalyst towards both ORR and OER in a KOH electrolyte solution, the as-fabricated Co@Co3O4/NC-2 exhibits similar ORR catalytic activity to the commercial Pt/C catalyst, but superior stability and good methanol tolerance. Furthermore, the as-fabricated catalysts also show promising catalytic activity for OER. The effective catalytic activities originate from the synergistic effects between well wrapped Co@Co3O4 nanoparticles and nitrogen doped carbon structures.

Correction: β-Amyrin synthase from Euphorbia tirucalli L. functional analyses of the highly conserved aromatic residues Phe413, Tyr259 and Trp257 disclose the importance of the appropriate steric bulk, and cation-π and CH-π interactions for the efficient catalytic action of the polyolefin cyclization cascade.

PubMed

Ito, Ryousuke; Nakada, Chika; Hoshino, Tsutomu

2017-01-18

Correction for 'β-Amyrin synthase from Euphorbia tirucalli L. functional analyses of the highly conserved aromatic residues Phe413, Tyr259 and Trp257 disclose the importance of the appropriate steric bulk, and cation-π and CH-π interactions for the efficient catalytic action of the polyolefin cyclization cascade' by Ryousuke Ito et al., Org. Biomol. Chem., 2017, 15, 177-188.

Ultrasonic activated efficient synthesis of chromenes using amino-silane modified Fe3O4 nanoparticles: A versatile integration of high catalytic activity and facile recovery

NASA Astrophysics Data System (ADS)

Safari, Javad; Zarnegar, Zohre

2014-08-01

An efficient synthesis of 2-amino-4H-chromenes is achieved by one pot three component coupling reaction of aldehyde, malononitrile, and resorcinol using amino-silane modified Fe3O4 nanoparticles (MNPs-NH2) heterogeneous nanocatalyst under sonic condition. The attractive advantages of the present process are mild reaction conditions, short reaction times, easy isolation of products, good yields and simple operational procedures. Combination of the advantages of ultrasonic irradiation and magnetic nanoparticles provides important methodology to carry out catalytic transformations.

Responses of soil hydrolase kinetics to nitrogen and phosphorus additions in Chinese fir plantations of subtropical China

NASA Astrophysics Data System (ADS)

Zhang, X.; Zhang, C.; Yang, Y.; Wang, H.; Chen, F.; Fu, X.; Fang, X.; Sun, X.

2016-12-01

Nitrogen (N) deposition and low soil phosphorus (P) content aggravate the P limitation in subtropical forest soils. However, the responses of soil organic matter related hydrolyase kinetics to N and P additions in subtropical plantations are still not clear. We tested the hypothesis that P application can improve the potential maximum activities of soil carbon (C) and N related hydrolayase but substrate demand (Km) may tradeoff the catalytic efficiency of the enzymes. Thirty 20m×20m plots were established in November 2011 and six different treatments were randomly distributed with five replicates in the Chinese fir plantations in subtropical China. The ongoing treatments are control (CK, no N and P application), low N addition (N1:50 kg N ha-1 yr-1), high N addition (N2: 100 kg N ha-1 yr-1), P addition (P: 50 kg P ha-1 yr-1), low N andP addition (N1P: 50 kg N ha-1 yr-1 and 50 kg P ha-1 yr-1) and high N and P addition (N2P: 100 kg N ha-1yr-1and 50 kg P ha-1 yr-1). Soil enzyme kinetic parameters for b-1,4-glucosidase (βG), β-1,4-N-acetylglucosaminidase (NAG), and acid phosphatase (aP) were measured in November 2015. The substrate affinities (Km) of βG and NAG were not affected by N or /and P additions. However, the substrate affinities of aP were decreased by N additions (N1, N2) with higher Km values than the other treatments. N additions (N1, N2) or higher N combined P additions (N2P) increased Vmax and catalytic efficiencies for βG, while with P addition treatments (N1P, N2P, and P) decreased Vmax and catalytic efficiencies for aP. The effects of N combined P treatments (N1P and N2P) on kinetic parameters (Vmax, Km) and catalytic efficiencies for AP were similar to P treatment, indicating that P had stronger effects on organic phosphorus hydrolysis than N in the research site. The N additions (N1 and N2) did not affect the catalytic efficiencies for NAG despite of their positive responses to Vmax for NAG compared with CK. The catalytic efficiencies of aP and NAG were negatively correlated with soil TP and available P contents, and both the enzyme kinetics for aP exhibited strong negative correlations with TP and available P contents. However, the Vmax for BG and NAG were positively correlated with SOC contents, but were negatively correlated with soil pH.

Molecular Self-Assembly Strategy for Generating Catalytic Hybrid Polypeptides

PubMed Central

Ikezoe, Yasuhiro; Pike, Douglas H.; Nanda, Vikas; Matsui, Hiroshi

2016-01-01

Recently, catalytic peptides were introduced that mimicked protease activities and showed promising selectivity of products even in organic solvents where protease cannot perform well. However, their catalytic efficiency was extremely low compared to natural enzyme counterparts presumably due to the lack of stable tertiary fold. We hypothesized that assembling these peptides along with simple hydrophobic pockets, mimicking enzyme active sites, could enhance the catalytic activity. Here we fused the sequence of catalytic peptide CP4, capable of protease and esterase-like activities, into a short amyloidogenic peptide fragment of Aβ. When the fused CP4-Aβ construct assembled into antiparallel β-sheets and amyloid fibrils, a 4.0-fold increase in the hydrolysis rate of p-nitrophenyl acetate (p-NPA) compared to neat CP4 peptide was observed. The enhanced catalytic activity of CP4-Aβ assembly could be explained both by pre-organization of a catalytically competent Ser-His-acid triad and hydrophobic stabilization of a bound substrate between the triad and p-NPA, indicating that a design strategy for self-assembled peptides is important to accomplish the desired functionality. PMID:27116246

Molecular self-assembly strategy for generating catalytic hybrid polypeptides

DOE PAGES

Maeda, Yoshiaki; Fang, Justin; Ikezoe, Yasuhiro; ...

2016-04-26

Recently, catalytic peptides were introduced that mimicked protease activities and showed promising selectivity of products even in organic solvents where protease cannot perform well. However, their catalytic efficiency was extremely low compared to natural enzyme counterparts presumably due to the lack of stable tertiary fold. We hypothesized that assembling these peptides along with simple hydrophobic pockets, mimicking enzyme active sites, could enhance the catalytic activity. Here we fused the sequence of catalytic peptide CP4, capable of protease and esterase-like activities, into a short amyloidogenic peptide fragment of Aβ. When the fused CP4-Aβ construct assembled into antiparallel β- sheets and amyloidmore » fibrils, a 4.0-fold increase in the hydrolysis rate of p-nitrophenyl acetate (p-NPA) compared to neat CP4 peptide was observed. Furthermore, the enhanced catalytic activity of CP4-Aβ assembly could be explained both by pre-organization of a catalytically competent Ser-His-acid triad and hydrophobic stabilization of a bound substrate between the triad and p-NPA, indicating that a design strategy for self-assembled peptides is important to accomplish the desired functionality.« less

Development and assessment of photo-catalytic membranes for water purification using solar radiation

NASA Astrophysics Data System (ADS)

Coto, M.; Troughton, S. C.; Duan, J.; Kumar, R. V.; Clyne, T. W.

2018-03-01

This paper describes a novel set-up for characterization of the performance of membranes designed for purification of water. It involves a recirculatory system, with continuous monitoring of the concentration in the water of a representative pollutant (Methylene Blue). Pressures, flow rates and temperatures are also measured. Results, in the form of rate constants for reduction in pollutant concentration, are presented for three different types of membrane, all of which incorporate relatively high surface areas of titania and have permeability values in a range making them suitable for this type of processing (∼10-11 m2). These results are rationalized in terms of the surface areas of the membranes, and the likely water flow characteristics within them. It is concluded that all of the titania surfaces within them have similar efficiencies for photo-catalytic oxidation of pollutants, but there are significant differences in the ways that the water is exposed to these surfaces, and hence in the pollutant oxidation rates. These points are relevant to the optimization of membrane design for this purpose.

Incorporating nitrogen atoms into cobalt nanosheets as a strategy to boost catalytic activity toward CO2 hydrogenation

NASA Astrophysics Data System (ADS)

Wang, Liangbing; Zhang, Wenbo; Zheng, Xusheng; Chen, Yizhen; Wu, Wenlong; Qiu, Jianxiang; Zhao, Xiangchen; Zhao, Xiao; Dai, Yizhou; Zeng, Jie

2017-11-01

Hydrogenation of CO2 into fuels and useful chemicals could help to reduce reliance on fossil fuels. Although great progress has been made over the past decades to improve the activity of catalysts for CO2 hydrogenation, more efficient catalysts, especially those based on non-noble metals, are desired. Here we incorporate N atoms into Co nanosheets to boost the catalytic activity toward CO2 hydrogenation. For the hydrogenation of CO2, Co4N nanosheets exhibited a turnover frequency of 25.6 h-1 in a slurry reactor under 32 bar pressure at 150 °C, which was 64 times that of Co nanosheets. The activation energy for Co4N nanosheets was 43.3 kJ mol-1, less than half of that for Co nanosheets. Mechanistic studies revealed that Co4N nanosheets were reconstructed into Co4NHx, wherein the amido-hydrogen atoms directly interacted with the CO2 to form HCOO* intermediates. In addition, the adsorbed H2O* activated amido-hydrogen atoms via the interaction of hydrogen bonds.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thi, Trinh Cham, E-mail: s1240009@jaist.ac.jp; Koyama, Koichi; Ohdaira, Keisuke

We improve the passivation property of n-type crystalline silicon (c-Si) surface passivated with a catalytic chemical vapor deposited (Cat-CVD) Si nitride (SiN{sub x}) film by inserting a phosphorous (P)-doped layer formed by exposing c-Si surface to P radicals generated by the catalytic cracking of PH{sub 3} molecules (Cat-doping). An extremely low surface recombination velocity (SRV) of 2 cm/s can be achieved for 2.5 Ω cm n-type (100) floating-zone Si wafers passivated with SiN{sub x}/P Cat-doped layers, both prepared in Cat-CVD systems. Compared with the case of only SiN{sub x} passivated layers, SRV decreases from 5 cm/s to 2 cm/s. The decrease in SRVmore » is the result of field effect created by activated P atoms (donors) in a shallow P Cat-doped layer. Annealing process plays an important role in improving the passivation quality of SiN{sub x} films. The outstanding results obtained imply that SiN{sub x}/P Cat-doped layers can be used as promising passivation layers in high-efficiency n-type c-Si solar cells.« less

Conjugated polymers nanostructured as smart interfaces for controlling the catalytic properties of enzymes.

PubMed

Barbosa, Camila Gouveia; Caseli, Luciano; Péres, Laura Oliveira

2016-08-15

The search for new molecular architectures to improve the efficiency of enzymes entrapped in ultrathin films is useful to enhance the effectiveness of biosensors. In this present work, conjugated polymers, based on thiophene and fluorine, were investigated to verify their suitability as matrices for the immobilization of urease. The copolymer poly[(9,9-dioctylfluorene)-co-thiophene], PDOF-co-Th was spread on the air-water interface forming stable Langmuir monolayers as determined by surface pressure-area isotherms, polarization-modulation reflection-absorption infrared spectroscopy (PM-IRRAS), and Brewster angle microscopy (BAM). Urease was incorporated in the floating monolayers being further transferred to solid supports as mixed Langmuir-Blodgett (LB) films. These films were then characterized with transfer ratio, fluorescence spectroscopy, PM-IRRAS and atomic force microscopy, confirming the co-transfer of the enzyme as well as its structuring in β-sheets. The catalytic activity was detected for urease, with a lower reaction rate than that encountered for the homogeneous environment. This was attributed to conformational constraints imposed to the biomacromolecule entrapped in the polymeric matrix. Copyright © 2016 Elsevier Inc. All rights reserved.

In Situ Fabrication and Reactivation of Highly Selective and Stable Ag Catalysts for Electrochemical CO2 Conversion.

PubMed

Ma, Ming; Liu, Kai; Shen, Jie; Kas, Recep; Smith, Wilson A

2018-06-08

In this work, the highly selective and stable electrocatalytic reduction of CO 2 to CO on nanostructured Ag electrocatalysts is presented. The Ag electrocatalysts are synthesized by the electroreduction of Ag 2 CO 3 formed by in situ anodic-etching of Ag foil in a KHCO 3 electrolyte. After 3 min of this etching treatment, the Ag 2 CO 3 -derived nanostructured Ag electrocatalysts are capable of producing CO with up to 92% Faradaic efficiency at an overpotential as low as 290 mV, which surpasses all of the reported Ag catalysts at identical conditions to date. In addition, the anodic-etched Ag retained ∼90% catalytic selectivity in the electroreduction of CO 2 to CO for more than 100 h. The Ag 2 CO 3 -derived Ag is able to facilitate the activation of CO 2 via reduction of the activation energy barrier of the initial electron transfer and provide an increased number of active sites, resulting in the dramatically improved catalytic activity for the reduction of CO 2 to CO.

The Clk/Sty protein kinase phosphorylates SR splicing factors and regulates their intranuclear distribution.

PubMed Central

Colwill, K; Pawson, T; Andrews, B; Prasad, J; Manley, J L; Bell, J C; Duncan, P I

1996-01-01

Mammalian Clk/Sty is the prototype for a family of dual specificity kinases (termed LAMMER kinases) that have been conserved in evolution, but whose physiological substrates are unknown. In a yeast two-hybrid screen, the Clk/Sty kinase specifically interacted with RNA binding proteins, particularly members of the serine/arginine-rich (SR) family of splicing factors. Clk/Sty itself has an serine/arginine-rich non-catalytic N-terminal region which is important for its association with SR splicing factors. In vitro, Clk/Sty efficiently phosphorylated the SR family member ASF/SF2 on serine residues located within its serine/arginine-rich region (the RS domain). Tryptic phosphopeptide mapping demonstrated that the sites on ASF/SF2 phosphorylated in vitro overlap with those phosphorylated in vivo. Immunofluorescence studies showed that a catalytically inactive form of Clk/Sty co-localized with SR proteins in nuclear speckles. Overexpression of the active Clk/Sty kinase caused a redistribution of SR proteins within the nucleus. These results suggest that Clk/Sty kinase directly regulates the activity and compartmentalization of SR splicing factors. Images PMID:8617202

Comparison and Analysis of Zinc and Cobalt-Based Systems as Catalytic Entities for the Hydration of Carbon Dioxide

PubMed Central

Lau, Edmond Y.; Wong, Sergio E.; Baker, Sarah E.; Bearinger, Jane P.; Koziol, Lucas; Valdez, Carlos A.; Satcher, Joseph H.; Aines, Roger D.; Lightstone, Felice C.

2013-01-01

In nature, the zinc metalloenzyme carbonic anhydrase II (CAII) efficiently catalyzes the conversion of carbon dioxide (CO2) to bicarbonate under physiological conditions. Many research efforts have been directed towards the development of small molecule mimetics that can facilitate this process and thus have a beneficial environmental impact, but these efforts have met very limited success. Herein, we undertook quantum mechanical calculations of four mimetics, 1,5,9-triazacyclododedacane, 1,4,7,10-tetraazacyclododedacane, tris(4,5-dimethyl-2-imidazolyl)phosphine, and tris(2-benzimidazolylmethyl)amine, in their complexed form either with the Zn2+ or the Co2+ ion and studied their reaction coordinate for CO2 hydration. These calculations demonstrated that the ability of the complex to maintain a tetrahedral geometry and bind bicarbonate in a unidentate manner were vital for the hydration reaction to proceed favorably. Furthermore, these calculations show that the catalytic activity of the examined zinc complexes was insensitive to coordination states for zinc, while coordination states above four were found to have an unfavorable effect on product release for the cobalt counterparts. PMID:23840420

Effect of alginate microencapsulation on the catalytic efficiency and in vitro enzyme-prodrug therapeutic efficacy of cytosine deaminase and of recombinant E. coli expressing cytosine deaminase.

PubMed

Funaro, Michael G; Nemani, Krishnamurthy V; Chen, Zhihang; Bhujwalla, Zaver M; Griswold, Karl E; Gimi, Barjor

2016-02-01

Cytosine deaminase (CD) catalyses the enzymatic conversion of the non-toxic prodrug 5-fluorocytosine (5-FC) to the potent chemotherapeutic form, 5-fluorouracil (5-FU). Intratumoral delivery of CD localises chemotherapy dose while reducing systemic toxicity. Encapsulation in biocompatible microcapsules immunoisolates CD and protects it from degradation. We report on the effect of alginate encapsulation on the catalytic and functional activity of isolated CD and recombinant E. coli engineered to express CD (E. coli(CD)). Alginate microcapsules containing either CD or Escherichia coli(CD) were prepared using ionotropic gelation. Conversion of 5-FC to 5-FU was quantitated in unencapsulated and encapsulated CD/E. coli(CD) using spectrophotometry, with a slower rate of conversion observed following encapsulation. Both encapsulated CD/5-FC and E. coli(CD)/5-FC resulted in cell kill and reduced proliferation of 9 L rat glioma cells, which was comparable to direct 5-FU treatment. Our results show that encapsulation preserves the therapeutic potential of CD and E. coli(CD) is equally effective for enzyme-prodrug therapy.

Site-specific deposition of single gold nanoparticles by individual growth in electrohydrodynamically-printed attoliter droplet reactors.

PubMed

Schneider, Julian; Rohner, Patrik; Galliker, Patrick; Raja, Shyamprasad N; Pan, Ying; Tiwari, Manish K; Poulikakos, Dimos

2015-06-07

Gold nanoparticles with unique electronic, optical and catalytic properties can be efficiently synthesized in colloidal suspensions and are of broad scientific and technical interest and utility. However, their orderly integration on functional surfaces and devices remains a challenge. Here we show that single gold nanoparticles can be directly grown in individually printed, stabilized metal-salt ink attoliter droplets, using a nanoscale electrohydrodynamic printing method with a stable high-frequency dripping mode. This enables controllable sessile droplet nanoreactor formation and sustenance on non-wetting substrates, despite simultaneous rapid evaporation. The single gold nanoparticles can be formed inside such reactors in situ or by subsequent thermal annealing and plasma ashing. With this non-contact technique, single particles with diameters tunable in the range of 5-35 nm and with narrow size distribution, high yield and alignment accuracy are generated on demand and patterned into arbitrary arrays. The nanoparticles feature good catalytic activity as shown by the exemplary growth of silicon nanowires from the nanoparticles and the etching of nanoholes by the printed nanoparticles.

Comparison and analysis of zinc and cobalt-based systems as catalytic entities for the hydration of carbon dioxide

DOE PAGES

Lau, E. Y.; Wong, S. E.; Baker, S. E.; ...

2013-06-20

In nature, the zinc metalloenzyme carbonic anhydrase II (CAII) efficiently catalyzes the conversion of carbon dioxide (CO 2) to bicarbonate under physiological conditions. Efforts have been directed towards the development of small molecule mimetics that can facilitate this process and thus have a beneficial environmental impact, but these efforts have met very limited success. Herein, we undertook quantum mechanical calculations of four mimetics, 1,5,9-triazacyclododedacane, 1,4,7,10-tetraazacyclododedacane, tris(4,5-dimethyl-2-imidazolyl)phosphine, and tris(2-benzimidazolylmethyl)amine, in their complexed form either with the Zn 2+ or the Co 2+ ion and studied their reaction coordinate for CO 2 hydration. These calculations demonstrated that the ability of the complexmore » to maintain a tetrahedral geometry and bind bicarbonate in a unidentate manner were vital for the hydration reaction to proceed favorably. Moreover, these calculations show that the catalytic activity of the examined zinc complexes was insensitive to coordination states for zinc, while coordination states above four were found to have an unfavorable effect on product release for the cobalt counterparts.« less

In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures.

PubMed

Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

2014-04-14

Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of Mo species with Species, which is from the carbothermal reduction of sodium sulfate. Due to the excellent graphene "painting" on MoS2 atomic layers, the significantly shortened lithium ion diffusion distance and the markedly enhanced electronic conductivity, these multilayered graphene/MoS2 heterostructures exhibit high specific capacity, unprecedented rate performance and outstanding cycling stability, especially at a high current density, when used as an anode material for lithium batteries. This work provides a simple but efficient route for the controlled fabrication of large-area multilayered graphene/metal sulfide heterostructures with promising applications in battery manufacture, electronics or catalysis.

In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures

PubMed Central

Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

2014-01-01

Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of Mo species with S pecies, which is from the carbothermal reduction of sodium sulfate. Due to the excellent graphene “painting” on MoS2 atomic layers, the significantly shortened lithium ion diffusion distance and the markedly enhanced electronic conductivity, these multilayered graphene/MoS2 heterostructures exhibit high specific capacity, unprecedented rate performance and outstanding cycling stability, especially at a high current density, when used as an anode material for lithium batteries. This work provides a simple but efficient route for the controlled fabrication of large-area multilayered graphene/metal sulfide heterostructures with promising applications in battery manufacture, electronics or catalysis. PMID:24728289

In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures

NASA Astrophysics Data System (ADS)

Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

2014-04-01

Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of Mo species with S pecies, which is from the carbothermal reduction of sodium sulfate. Due to the excellent graphene ``painting'' on MoS2 atomic layers, the significantly shortened lithium ion diffusion distance and the markedly enhanced electronic conductivity, these multilayered graphene/MoS2 heterostructures exhibit high specific capacity, unprecedented rate performance and outstanding cycling stability, especially at a high current density, when used as an anode material for lithium batteries. This work provides a simple but efficient route for the controlled fabrication of large-area multilayered graphene/metal sulfide heterostructures with promising applications in battery manufacture, electronics or catalysis.

Influence of surface phenomena in oxidative desulfurization with WOx/ZrO2 catalysts

NASA Astrophysics Data System (ADS)

Torres-García, E.; Canizal, G.; Velumani, S.; Ramírez-Verduzco, L. F.; Murrieta-Guevara, F.; Ascencio, J. A.

2004-12-01

Oil refinery related catalysis, particularly hydro desulfurization is viewed as a mature technology, but still we view that more efforts have to be made to boost the efficiency of the existing catalysts. So in this article we report the use of WOx/ZrO2 catalysts for the oxidation of dibenzothiophene (DBT) as a more effective material in nanometer scales. The WOx/ZrO2 samples were prepared by solid impregnation of ZrO2-x(OH)2x with ammonium metatungstate solution maintaining the pH at 10. Detailed structural and surface morphological analyses were carried out using Raman spectroscopy and Atomic force microscopy. In order to understand the catalytic activity which is largely influenced by the surface morphology, an interpretation based on the experimental results is given. The results showed an important correlation between the catalytic efficiency with the morphology of the surface which is identified as arrays of planes with steps of around 10 nm with the structures showing faceting with a preferential angle of 90°. It was established that when the number of W atoms in the surface increase the catalytic efficiency also increases. Thus we conclude that the material efficiency as a catalyst is directly related with the surface structure.

Analysis of in vitro evolution reveals the underlying distribution of catalytic activity among random sequences.

PubMed

Pressman, Abe; Moretti, Janina E; Campbell, Gregory W; Müller, Ulrich F; Chen, Irene A

2017-08-21

The emergence of catalytic RNA is believed to have been a key event during the origin of life. Understanding how catalytic activity is distributed across random sequences is fundamental to estimating the probability that catalytic sequences would emerge. Here, we analyze the in vitro evolution of triphosphorylating ribozymes and translate their fitnesses into absolute estimates of catalytic activity for hundreds of ribozyme families. The analysis efficiently identified highly active ribozymes and estimated catalytic activity with good accuracy. The evolutionary dynamics follow Fisher's Fundamental Theorem of Natural Selection and a corollary, permitting retrospective inference of the distribution of fitness and activity in the random sequence pool for the first time. The frequency distribution of rate constants appears to be log-normal, with a surprisingly steep dropoff at higher activity, consistent with a mechanism for the emergence of activity as the product of many independent contributions. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Surface Structure Dependent Electrocatalytic Activity of Co3O4 Anchored on Graphene Sheets toward Oxygen Reduction Reaction

PubMed Central

Xiao, Junwu; Kuang, Qin; Yang, Shihe; Xiao, Fei; Wang, Shuai; Guo, Lin

2013-01-01

Catalytic activity is primarily a surface phenomenon, however, little is known about Co3O4 nanocrystals in terms of the relationship between the oxygen reduction reaction (ORR) catalytic activity and surface structure, especially when dispersed on a highly conducting support to improve the electrical conductivity and so to enhance the catalytic activity. Herein, we report a controllable synthesis of Co3O4 nanorods (NR), nanocubes (NC) and nano-octahedrons (OC) with the different exposed nanocrystalline surfaces ({110}, {100}, and {111}), uniformly anchored on graphene sheets, which has allowed us to investigate the effects of the surface structure on the ORR activity. Results show that the catalytically active sites for ORR should be the surface Co2+ ions, whereas the surface Co3+ ions catalyze CO oxidation, and the catalytic ability is closely related to the density of the catalytically active sites. These results underscore the importance of morphological control in the design of highly efficient ORR catalysts. PMID:23892418

Predicting Catalytic Activity of Nanoparticles by a DFT-Aided Machine-Learning Algorithm.

PubMed

Jinnouchi, Ryosuke; Asahi, Ryoji

2017-09-07

Catalytic activities are often dominated by a few specific surface sites, and designing active sites is the key to realize high-performance heterogeneous catalysts. The great triumphs of modern surface science lead to reproduce catalytic reaction rates by modeling the arrangement of surface atoms with well-defined single-crystal surfaces. However, this method has limitations in the case for highly inhomogeneous atomic configurations such as on alloy nanoparticles with atomic-scale defects, where the arrangement cannot be decomposed into single crystals. Here, we propose a universal machine-learning scheme using a local similarity kernel, which allows interrogation of catalytic activities based on local atomic configurations. We then apply it to direct NO decomposition on RhAu alloy nanoparticles. The proposed method can efficiently predict energetics of catalytic reactions on nanoparticles using DFT data on single crystals, and its combination with kinetic analysis can provide detailed information on structures of active sites and size- and composition-dependent catalytic activities.

Advanced catalytic combustors for low pollutant emissions, phase 1

NASA Technical Reports Server (NTRS)

Dodds, W. J.

1979-01-01

The feasibility of employing the known attractive and distinguishing features of catalytic combustion technology to reduce nitric oxide emissions from gas turbine engines during subsonic, stratospheric cruise operation was investigated. Six conceptual combustor designs employing catalytic combustion were defined and evaluated for their potential to meet specific emissions and performance goals. Based on these evaluations, two parallel-staged, fixed-geometry designs were identified as the most promising concepts. Additional design studies were conducted to produce detailed preliminary designs of these two combustors. Results indicate that cruise nitric oxide emissions can be reduced by an order of magnitude relative to current technology levels by the use of catalytic combustion. Also, these combustors have the potential for operating over the EPA landing-takeoff cycle and at cruise with a low pressure drop, high combustion efficiency and with a very low overall level of emission pollutants. The use of catalytic combustion, however, requires advanced technology generation in order to obtain the time-temperature catalytic reactor performance and durability required for practical aircraft engine combustors.

VUV photo-oxidation of gaseous benzene combined with ozone-assisted catalytic oxidation: Effect on transition metal catalyst

NASA Astrophysics Data System (ADS)

Huang, Haibao; Lu, Haoxian; Zhan, Yujie; Liu, Gaoyuan; Feng, Qiuyu; Huang, Huiling; Wu, Muyan; Ye, Xinguo

2017-01-01

Volatile organic compounds (VOCs) cause the major air pollution concern. In this study, a series of ZSM-5 supported transition metals were prepared by impregnation method. They were combined with vacuum UV (VUV) photo-oxidation in a continuous-flow packed-bed reactor and used for the degradation of benzene, a typical toxic VOCs. Compared with VUV photo-oxidation alone, the introduction of catalysts can greatly enhance benzene oxidation under the help of O3, the by-products from VUV irradiation, via ozone-assisted catalytic oxidation (OZCO). The catalytic activity of transition metals towards benzene oxidation followed the order: Mn > Co > Cu > Ni > Fe. Mn achieved the best catalytic activity due to the strongest capability for O3 catalytic decomposition and utilization. Benzene and O3 removal efficiency reached as high as 97% and 100% after 360 min, respectively. O3 was catalytically decomposed, generating highly reactive oxidants such as rad OH and rad O for benzene oxidation.

Patterned structures of graphene and graphitic carbon and methods for their manufacture

DOEpatents

Polsky, Ronen; Xiao, Xiaoyin; Burckel, David Bruce; Wheeler, David R.; Brozik, Susan M.; Beechem, Thomas Edwin

2017-01-03

A patterned graphene or graphitic body is produced by providing a three-dimensionally patterned carbonaceous body; coating the body with a catalytic metal whereby is formed a coating having an inner surface proximal the body and an outer surface distal the body; and annealing the coated body under time and temperature conditions effective to form a graphene or graphitic layer on the outer surface of the catalytic metal coating.

Patterned structures of graphene and graphitic carbon and methods for their manufacture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polsky, Ronen; Xiao, Xiaoyin; Burckel, David Bruce

A patterned graphene or graphitic body is produced by providing a three-dimensionally patterned carbonaceous body; coating the body with a catalytic metal whereby is formed a coating having an inner surface proximal the body and an outer surface distal the body; and annealing the coated body under time and temperature conditions effective to form a graphene or graphitic layer on the outer surface of the catalytic metal coating.

In situ formed catalytically active ruthenium nanocatalyst in room temperature dehydrogenation/dehydrocoupling of ammonia-borane from Ru(cod)(cot) precatalyst.

PubMed

Zahmakiran, Mehmet; Ayvalı, Tuğçe; Philippot, Karine

2012-03-20

The development of simply prepared and effective catalytic materials for dehydrocoupling/dehydrogenation of ammonia-borane (AB; NH(3)BH(3)) under mild conditions remains a challenge in the field of hydrogen economy and material science. Reported herein is the discovery of in situ generated ruthenium nanocatalyst as a new catalytic system for this important reaction. They are formed in situ during the dehydrogenation of AB in THF at 25 °C in the absence of any stabilizing agent starting with homogeneous Ru(cod)(cot) precatalyst (cod = 1,5-η(2)-cyclooctadiene; cot = 1,3,5-η(3)-cyclooctatriene). The preliminary characterization of the reaction solutions and the products was done by using ICP-OES, ATR-IR, TEM, XPS, ZC-TEM, GC, EA, and (11)B, (15)N, and (1)H NMR, which reveal that ruthenium nanocatalyst is generated in situ during the dehydrogenation of AB from homogeneous Ru(cod)(cot) precatalyst and B-N polymers formed at the initial stage of the catalytic reaction take part in the stabilization of this ruthenium nanocatalyst. Moreover, following the recently updated approach (Bayram, E.; et al. J. Am. Chem. Soc.2011, 133, 18889) by performing Hg(0), CS(2) poisoning experiments, nanofiltration, time-dependent TEM analyses, and kinetic investigation of active catalyst formation to distinguish single metal or in the present case subnanometer Ru(n) cluster-based catalysis from polymetallic Ru(0)(n) nanoparticle catalysis reveals that in situ formed Ru(n) clusters (not Ru(0)(n) nanoparticles) are kinetically dominant catalytically active species in our catalytic system. The resulting ruthenium catalyst provides 120 total turnovers over 5 h with an initial turnover frequency (TOF) value of 35 h(-1) at room temperature with the generation of more than 1.0 equiv H(2) at the complete conversion of AB to polyaminoborane (PAB; [NH(2)BH(2)](n)) and polyborazylene (PB; [NHBH](n)) units.

Catalytic molecularly imprinted polymer membranes: development of the biomimetic sensor for phenols detection.

PubMed

Sergeyeva, T A; Slinchenko, O A; Gorbach, L A; Matyushov, V F; Brovko, O O; Piletsky, S A; Sergeeva, L M; Elska, G V

2010-02-05

Portable biomimetic sensor devices for the express control of phenols content in water were developed. The synthetic binding sites mimicking active site of the enzyme tyrosinase were formed in the structure of free-standing molecularly imprinted polymer membranes. Molecularly imprinted polymer membranes with the catalytic activity were obtained by co-polymerization of the complex Cu(II)-catechol-urocanic acid ethyl ester with (tri)ethyleneglycoldimethacrylate, and oligourethaneacrylate. Addition of the elastic component oligourethaneacrylate provided formation of the highly cross-linked polymer with the catalytic activity in a form of thin, flexible, and mechanically stable membrane. High accessibility of the artificial catalytic sites for the interaction with the analyzed phenol molecules was achieved due to addition of linear polymer (polyethyleneglycol Mw 20,000) to the initial monomer mixture before the polymerization. As a result, typical semi-interpenetrating polymer networks (semi-IPNs) were formed. The cross-linked component of the semi-IPN was represented by the highly cross-linked catalytic molecularly imprinted polymer, while the linear one was represented by polyethyleneglycol Mw 20,000. Extraction of the linear polymer from the fully formed semi-IPN resulted in formation of large pores in the membranes' structure. Concentration of phenols in the analyzed samples was detected using universal portable device oxymeter with the oxygen electrode in a close contact with the catalytic molecularly imprinted polymer membrane as a transducer. The detection limit of phenols detection using the developed sensor system based on polymers-biomimics with the optimized composition comprised 0.063 mM, while the linear range of the sensor comprised 0.063-1 mM. The working characteristics of the portable sensor devices were investigated. Storage stability of sensor systems at room temperature comprised 12 months (87%). As compared to traditional methods of phenols detection the developed sensor system is characterized by simplicity of operation, compactness, and low cost. Copyright 2009 Elsevier B.V. All rights reserved.

The amyloid architecture provides a scaffold for enzyme-like catalysts.

PubMed

Al-Garawi, Z S; McIntosh, B A; Neill-Hall, D; Hatimy, A A; Sweet, S M; Bagley, M C; Serpell, L C

2017-08-03

Natural biological enzymes possess catalytic sites that are generally surrounded by a large three-dimensional scaffold. However, the proportion of the protein molecule that participates in the catalytic reaction is relatively small. The generation of artificial or miniature enzymes has long been a focus of research because enzyme mimetics can be produced with high activity at low cost. These enzymes aim to mimic the active sites without the additional architecture contributed by the protein chain. Previous work has shown that amyloidogenic peptides are able to self-assemble to create an active site that is capable of binding zinc and catalysing an esterase reaction. Here, we describe the structural characterisation of a set of designed peptides that form an amyloid-like architecture and reveal that their capability to mimic carbonic anhydrase and serve as enzyme-like catalysts is related to their ability to self-assemble. These amyloid fibril structures can bind the metal ion Zn 2+ via a three-dimensional arrangement of His residues created by the amyloid architecture. Our results suggest that the catalytic efficiency of amyloid-like assembly is not only zinc-dependent but also depends on an active centre created by the peptides which is, in turn, dependent on the ordered architecture. These fibrils have good esterase activity, and they may serve as good models for the evolution of modern-day enzymes. Furthermore, they may be useful in designing self-assembling fibrils for applications as metal ion catalysts. This study also demonstrates that the ligands surrounding the catalytic site affect the affinity of the zinc-binding site to bind the substrate contributing to the enzymatic activity of the assembled peptides.

Identification of novel inhibitors of the SARS coronavirus main protease 3CLpro.

PubMed

Bacha, Usman; Barrila, Jennifer; Velazquez-Campoy, Adrian; Leavitt, Stephanie A; Freire, Ernesto

2004-05-04

SARS (severe acute respiratory syndrome) is caused by a newly discovered coronavirus. A key enzyme for the maturation of this virus and, therefore, a target for drug development is the main protease 3CL(pro) (also termed SARS-CoV 3CL(pro)). We have cloned and expressed in Escherichia coli the full-length SARS-CoV 3CL(pro) as well as a truncated form containing only the catalytic domains. The recombinant proteins have been characterized enzymatically using a fluorescently labeled substrate; their structural stability in solution has been determined by differential scanning calorimetry, and novel inhibitors have been discovered. Expression of the catalytic region alone yields a protein with a reduced catalytic efficiency consistent with the proposed regulatory role of the alpha-helical domain. Differential scanning calorimetry indicates that the alpha-helical domain does not contribute to the structural stability of the catalytic domains. Analysis of the active site cavity reveals the presence of subsites that can be targeted with specific chemical functionalities. In particular, a cluster of serine residues (Ser139, Ser144, and Ser147) was identified near the active site cavity and was susceptible to being targeted by compounds containing boronic acid. This cluster is highly conserved in similar proteases from other coronaviruses, defining an attractive target for drug development. It was found that bifunctional aryl boronic acid compounds were particularly effective at inhibiting the protease, with inhibition constants as strong as 40 nM. Isothermal titration microcalorimetric experiments indicate that these inhibitors bind reversibly to 3CL(pro) in an enthalpically favorable fashion, implying that they establish strong interactions with the protease molecule, thus defining attractive molecular scaffolds for further optimization.

Magnetic heterogeneous catalytic ozonation: a new removal method for phenol in industrial wastewater

PubMed Central

2014-01-01

In this study, a new strategy in catalytic ozonation removal method for degradation of phenol from industrial wastewater was investigated. Magnetic carbon nano composite as a novel catalyst was synthesized, characterized and then used in the catalytic ozonation process (COP) and compared with the single ozonation process (SOP). The influential parameters were all investigated. The results showed that the removal efficiency of phenol and COD (chemical oxygen demand) in COP (98.5%, 69.8%) was higher than those of SOP (78.7%, 50.5%) and the highest catalytic potential was achieved at optimal neutral pH. First order modeling demonstrated that the reactions were dependent on the concentration of catalyst, with kinetic constants varying from 0.023 1/min (catalyst = 0 g/L) to 0.071 1/min (catalyst = 4 g/L), whereby the optimum dosage of catalyst was found to be 2 g/L. Furthermore, the catalytic properties of the catalyst remained almost unchanged after 5-time reuse. The results regarding the biodegradability of the effluent showed that a 5-min reaction time in COP reduced the concentrations of phenol and COD to the acceptable levels for the efficient post-treatment in the SBR in a 4-h cycle period. Finally, this combined system is proven to be a technically effective method for treating phenolic contaminants. PMID:24572145

Molecular ligand modulation of palladium nanocatalysts for highly efficient and robust heterogeneous oxidation of cyclohexenone to phenol

DOE PAGES

Xue, Teng; Lin, Zhaoyang; Chiu, Chin-Yi; ...

2017-01-06

Metallic nanoparticles are emerging as an exciting class of heterogeneous catalysts with the potential advantages of exceptional activity, stability, recyclability, and easier separation than homogeneous catalysts. The traditional colloid nanoparticle syntheses usually involve strong surface binding ligands that could passivate the surface active sites and result in poor catalytic activity. The subsequent removal of surface ligands could reactivate the surface but often leads to metal ion leaching and/or severe Ostwald ripening with diminished catalytic activity or poor stability. Molecular ligand engineering represents a powerful strategy for the design of homogeneous molecular catalysts but is insufficiently explored for nanoparticle catalysts tomore » date. We report a systematic investigation on molecular ligand modulation of palladium (Pd) nanoparticle catalysts. Our studies show that β-functional groups of butyric acid ligand on Pd nanoparticles can significantly modulate the catalytic reaction process to modify the catalytic activity and stability for important aerobic reactions. With a β-hydroxybutyric acid ligand, the Pd nanoparticle catalysts exhibit exceptional catalytic activity and stability with an unsaturated turnover number (TON) >3000 for dehydrogenative oxidation of cyclohexenone to phenol, greatly exceeding that of homogeneous Pd(II) catalysts (TON, ~30). This study presents a systematic investigation of molecular ligand modulation of nanoparticle catalysts and could open up a new pathway toward the design and construction of highly efficient and robust heterogeneous catalysts through molecular ligand engineering.« less

Co and Fe-catalysts supported on sepiolite: effects of preparation conditions on their catalytic behaviors in high temperature gas flow treatment of dye.

PubMed

Lin, Xiangfeng; Fang, Jian; Chen, Menglin; Huang, Zhi; Su, Chengyuan

2016-08-01

An efficient adsorbent/catalyst Co and Fe-catalysts loaded on sepiolite (Co-Fe/sepiolite) was successfully prepared for high temperature gas flow catalytic reaction by a simple impregnation method. The impact of preparation conditions (such as pH value of impregnation solution, impregnation time, calcination temperature, and time) on catalytic activity was studied. We found that the catalytic activity of Co-Fe/sepiolite was strongly influenced by all the investigated parameters. The regeneration efficiency (RE) was used to evaluate the catalytic activity. The RE is more noticeable at pH 5.0 of impregnation solution, impregnation time 18 h, calcination temperature 650 °C, and calcination time 3 h. This Co-Fe/sepiolite has great adsorption capacity in absorbing dye. It is used for an adsorbent to adsorb dye from wastewater solution under dynamic adsorption and saturated with dye, then regenerated with high temperature gas flow for adsorption/oxidation cycles. The Co-Fe/sepiolite acts as a catalyst to degrade the dye during regeneration under high temperature gas flow. Hence, the Co-Fe/sepiolite is not only an adsorbent but also a catalyst. The Co-Fe/sepiolite is more stable than sepiolite when applied in the treatment of plant's wastewater. The Co-Fe/sepiolite can be reused in adsorption-regeneration cycle. The results indicate the usability of the proposed combined process, dye adsorption on Co-Fe/sepiolite followed by the catalytic oxidation in high temperature gas flow.

A spontaneous change in the oxidation states of Pd/WO3 toward an active phase during catalytic cycles of CO oxidation

NASA Astrophysics Data System (ADS)

Jeon, Byungwook; Kim, Ansoon; Lee, Young-Ahn; Seo, Hyungtak; Kim, Yu Kwon

2017-11-01

CO oxidation over Pd/WO3 films prepared on a glass substrate has been examined at the substrate temperature of 150 - 250 °C and pressures less than 1 Torr with a stoichiometric mixture of CO and O2. Under the given reaction condition, the chemical states of the Pd/WO3 film gradually change into the most catalytically active form with the highest saturation reaction rate regardless of the initial oxidation states. The measured CO oxidation rate over the Pd/WO3 is strongly dependent on the chemical states of Pd and W. Either metallic Pd or fully oxidized PdO phase is not as catalytically active as the active form with mixed metallic Pd and thin PdO layers supported on WO3 with partially reduced W5+ state which is spontaneously obtained during the catalytic reaction cycles. Our results indicate that the facile oxygen transfer between Pd and WO3 layers not only facilitate the spontaneous changes into the active form, but also act as a promotional role in CO oxidation over the Pd layer.

Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides

PubMed Central

Strieter, Eric R.; Bhayana, Brijesh; Buchwald, Stephen L.

2009-01-01

The copper-catalyzed N-arylation of amides, i.e., the Goldberg reaction, is an efficient method for the construction of products relevant to both industry and academic settings. Herein, we present mechanistic details concerning the catalytic and stoichiometric N-arylation of amides. In the context of the catalytic reaction, our findings reveal the importance of chelating diamine ligands in controlling the concentration of the active catalytic species. The consistency between the catalytic and stoichiometric results suggest that the activation of aryl halides occurs through a 1,2-diamine-ligated copper(I) amidate complex. Kinetic studies on the stoichiometric N-arylation of aryl iodides using 1,2-diamine ligated Cu(I) amidates also provide insights into the mechanism of aryl halide activation. PMID:19072233

Catalytic bismetallative multicomponent coupling reactions: scope, applications, and mechanisms

PubMed Central

Cho, Hee Yeon

2014-01-01

Catalytic reactions have played an indispensable role in organic chemistry for the last several decades. In particular, catalytic multicomponent reactions have attracted a lot of attention due to their efficiency and expediency towards complex molecule synthesis. The presence of bismetallic reagents (e.g. B–B, Si–Si, B–Si, Si–Sn, etc.) in this process renders the products enriched with various functional groups and multiple stereocenters. For this reason, catalytic bismetallative coupling is considered an effective method to generate the functional and stereochemical complexity of simple hydrocarbon substrates. This review highlights key developments of transition-metal catalyzed bismetallative reactions involving multiple π components. Specifically, it will highlight the scope, synthetic applications, and proposed mechanistic pathways of this process. PMID:24736839

Gold nanoparticle-catalyzed environmentally benign deoxygenation of epoxides to alkenes.

PubMed

Noujima, Akifumi; Mitsudome, Takato; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi

2011-09-28

We have developed a highly efficient and green catalytic deoxygenation of epoxides to alkenes using gold nanoparticles (NPs) supported on hydrotalcite [HT: Mg(6)Al(2)CO(3)(OH)(16)] (Au/HT) with alcohols, CO/H(2)O or H(2) as the reducing reagent. Various epoxides were selectively converted to the corresponding alkenes. Among the novel metal NPs on HT, Au/HT was found to exhibit outstanding catalytic activity for the deoxygenation reaction. Moreover, Au/HT can be separated from the reaction mixture and reused with retention of its catalytic activity and selectivity. The high catalytic performance of Au/HT was attributed to the selective formation of Au-hydride species by the cooperative effect between Au NPs and HT.

Catalytic efficiency and thermostability improvement of Suc2 invertase through rational site-directed mutagenesis.

PubMed

Mohandesi, Nooshin; Haghbeen, Kamahldin; Ranaei, Omid; Arab, Seyed Shahriar; Hassani, Sorour

2017-01-01

Engineering of invertases has come to attention because of increasing demand for possible applications of invertases in various industrial processes. Due to the known physicochemical properties, invertases from micro-organisms such as Saccharomyces cerevisiae carrying SUC2 gene are considered as primary models. To improve thermostability and catalytic efficiency of SUC2 invertase (SInv), six influential residues with Relative Solvent Accessibility<5% were selected through multiple-sequence alignments, molecular modelling, structural and computational analyses. Consequently, SInv and 5 mutants including three mutants with single point substitution [Mut1=P152V, Mut2=S85V and Mut3=K153F)], one mutant with two points [Mut4=S305V-N463V] and one mutant with three points [Mut5=S85V-K153F-T271V] were developed via site-directed mutagenesis and produced using Pichia pastoris as the host. Physicochemical studies on these enzymes indicated that the selected amino acids which were located in the active site region mainly influenced catalytic efficiency. The best improvement belonged to Mut1 (54% increase in K cat /K m ) and Mut3 exhibited the worst effect (90% increase in K m ). These results suggest that Pro152 and Lys153 play key role in preparation of the right substrate lodging in the active site of SInv. The best thermostability improvement (16%) was observed for Mut4 in which two hydrophilic residues located on the loops, far from the active site, were replaced by Valines. These results suggest that tactful simultaneous substitution of influential hydrophilic residues in both active site region and peripheral loops with hydrophobic amino acids could result in more thermostable invertases with enhanced catalytic efficiency. Copyright © 2016 Elsevier Inc. All rights reserved.

Transition States and transition state analogue interactions with enzymes.

PubMed

Schramm, Vern L

2015-04-21

Enzymatic transition states have lifetimes of a few femtoseconds (fs). Computational analysis of enzyme motions leading to transition state formation suggests that local catalytic site motions on the fs time scale provide the mechanism to locate transition states. An experimental test of protein fs motion and its relation to transition state formation can be provided by isotopically heavy proteins. Heavy enzymes have predictable mass-altered bond vibration states without altered electrostatic properties, according to the Born-Oppenheimer approximation. On-enzyme chemistry is slowed in most heavy proteins, consistent with altered protein bond frequencies slowing the search for the transition state. In other heavy enzymes, structural changes involved in reactant binding and release are also influenced. Slow protein motions associated with substrate binding and catalytic site preorganization are essential to allow the subsequent fs motions to locate the transition state and to facilitate the efficient release of products. In the catalytically competent geometry, local groups move in stochastic atomic motion on the fs time scale, within transition state-accessible conformations created by slower protein motions. The fs time scale for the transition state motions does not permit thermodynamic equilibrium between the transition state and stable enzyme states. Isotopically heavy enzymes provide a diagnostic tool for fast coupled protein motions to transition state formation and mass-dependent conformational changes. The binding of transition state analogue inhibitors is the opposite in catalytic time scale to formation of the transition state but is related by similar geometries of the enzyme-transition state and enzyme-inhibitor interactions. While enzymatic transition states have lifetimes as short as 10(-15) s, transition state analogues can bind tightly to enzymes with release rates greater than 10(3) s. Tight-binding transition state analogues stabilize the rare but evolved enzymatic geometry to form the transition state. Evolution to efficient catalysis optimized this geometry and its stabilization by a transition state mimic results in tight binding. Release rates of transition state analogues are orders of magnitude slower than product release in normal catalytic function. During catalysis, product release is facilitated by altered chemistry. Compared to the weak associations found in Michaelis complexes, transition state analogues involve strong interactions related to those in the transition state. Optimum binding of transition state analogues occurs when the complex retains the system motions intrinsic to transition state formation. Conserved dynamic motion retains the entropic components of inhibitor complexes, improving the thermodynamics of analogue binding.

Diesel particulate abatement via wall-flow traps based on perovskite catalysts.

PubMed

Fino, Debora; Russo, Nunzio; Saracco, Guido; Specchia, Vito

2003-01-01

It is probably redundant to stress how extensive are nowadays the attempts to reduce the diesel particulate emissions from automotive and stationary sources. The present paper looks into a technology relied on a catalytic trap based on a SiC wall-flow monolith lined with suitable catalysts for the sake of promoting a more complete and faster regeneration after particulate capture. All the major steps of the catalytic filter preparation are dealt with, including: the synthesis and choice of the proper catalyst and trap materials, the development of an in situ catalyst deposition technique, the bench testing of the derived catalytic wall-flow. The best catalyst selected was the perovskite La0.9K0.1Cr0.9O3-delta. The filtration efficiency and the pressure drop of the catalytic and non-catalytic monoliths were evaluated on a diesel engine bench under various operating conditions.

Catalytic oxidation of waste materials

NASA Technical Reports Server (NTRS)

Jagow, R. B.

1977-01-01

Aqueous stream of human waste is mixed with soluble ruthenium salts and is introduced into reactor at temperature where ruthenium black catalyst forms on internal surfaces of reactor. This provides catalytically active surface to convert oxidizable wastes into breakdown products such as water and carbon dioxide.

Catalytic Ketone Hydrodeoxygenation Mediated by Highly Electrophilic Phosphonium Cations.

PubMed

Mehta, Meera; Holthausen, Michael H; Mallov, Ian; Pérez, Manuel; Qu, Zheng-Wang; Grimme, Stefan; Stephan, Douglas W

2015-07-06

Ketones are efficiently deoxygenated in the presence of silane using highly electrophilic phosphonium cation (EPC) salts as catalysts, thus affording the corresponding alkane and siloxane. The influence of distinct substitution patterns on the catalytic effectiveness of several EPCs was evaluated. The deoxygenation mechanism was probed by DFT methods. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

40 CFR Table 27 to Subpart Uuu of... - Continuous Compliance With Inorganic HAP Emission Limits for Catalytic Reforming Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... percent by weight or to a concentration of 30 ppmv (dry basis), corrected to 3 percent oxygen. Maintaining...), corrected to 3 percent oxygen. 2. Each existing cyclic or continuous catalytic reforming unit Reduce... to 3 percent oxygen Maintaining a 97 percent HCl control efficiency or an HCl concentration no more...

40 CFR Table 27 to Subpart Uuu of... - Continuous Compliance With Inorganic HAP Emission Limits for Catalytic Reforming Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... oxygen. Maintaining a 92 percent HCl emission reduction or an HCl concentration no more than 30 ppmv (dry basis), corrected to 3 percent oxygen. 2. Each existing cyclic or continuous catalytic reforming unit...), corrected to 3 percent oxygen Maintaining a 97 percent HCl control efficiency or an HCl concentration no...

40 CFR Table 27 to Subpart Uuu of... - Continuous Compliance With Inorganic HAP Emission Limits for Catalytic Reforming Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... percent by weight or to a concentration of 30 ppmv (dry basis), corrected to 3 percent oxygen. Maintaining...), corrected to 3 percent oxygen. 2. Each existing cyclic or continuous catalytic reforming unit Reduce... to 3 percent oxygen Maintaining a 97 percent HCl control efficiency or an HCl concentration no more...

40 CFR Table 27 to Subpart Uuu of... - Continuous Compliance With Inorganic HAP Emission Limits for Catalytic Reforming Units

Code of Federal Regulations, 2012 CFR

2012-07-01

... oxygen. Maintaining a 92 percent HCl emission reduction or an HCl concentration no more than 30 ppmv (dry basis), corrected to 3 percent oxygen. 2. Each existing cyclic or continuous catalytic reforming unit...), corrected to 3 percent oxygen Maintaining a 97 percent HCl control efficiency or an HCl concentration no...

In situ catalytic hydrogenation of model compounds and biomass-derived phenolic compounds for bio-oil upgrading

Treesearch

Junfeng Feng; Zhongzhi Yang; Chung-yun Hse; Qiuli Su; Kui Wang; Jianchun Jiang; Junming Xu

2017-01-01

The renewable phenolic compounds produced by directional liquefaction of biomass are a mixture of complete fragments decomposed from native lignin. These compounds are unstable and difficult to use directly as biofuel. Here, we report an efficient in situ catalytic hydrogenation method that can convert phenolic compounds into saturated cyclohexanes. The process has...

A Triazole-Containing Metal-Organic Framework as a Highly Effective and Substrate Size-Dependent Catalyst for CO2 Conversion.

PubMed

Li, Pei-Zhou; Wang, Xiao-Jun; Liu, Jia; Lim, Jie Sheng; Zou, Ruqiang; Zhao, Yanli

2016-02-24

A highly porous metal-organic framework (MOF) incorporating both exposed metal sites and nitrogen-rich triazole groups was successfully constructed via solvothermal assembly of a clicked octcarboxylate ligand and Cu(II) ions, which presents a high affinity toward CO2 molecules clearly verified by gas adsorption and Raman spectral detection. The constructed MOF featuring CO2-adsorbing property and exposed Lewis-acid metal sites could serve as an excellent catalyst for CO2-based chemical fixation. Catalytic activity of the MOF was confirmed by remarkably high efficiency on CO2 cycloaddition with small epoxides. When extending the substrates to larger ones, its activity showed a sharp decrease. These observations reveal that MOF-catalyzed CO2 cycloaddition of small substrates was carried out within the framework, while large ones cannot easily enter into the porous framework for catalytic reactions. Thus, the synthesized MOF exhibits high catalytic selectivity to different substrates on account of the confinement of the pore diameter. The high efficiency and size-dependent selectivity toward small epoxides on catalytic CO2 cycloaddition make this MOF a promising heterogeneous catalyst for carbon fixation.

Conversion of CO2 into cyclic carbonates by a Co(ii) metal-organic framework and the improvement of catalytic activity via nanocrystallization.

PubMed

Ji, Xiao-He; Zhu, Ning-Ning; Ma, Jian-Gong; Cheng, Peng

2018-02-06

The Co(ii) metal-organic framework (MOF) {[Co(μ 3 -L)(H 2 O)]·0.5H 2 O} n (1, H 2 L = thiazolidine 2,4-dicarboxylic acid) with rich Lewis acid sites was used as a catalyst for the conversion of CO 2 and propylene oxide into propylene carbonate with a yield of up to 98% under 50 °C and 1 atm. 1 exhibited excellent reusability, which could be regenerated easily for at least five runs without a decrease in the yield. Importantly, we synthesized two types of nano-crystals (N1 and N2) of 1 with polyvinylpyrrolidone (PVP) and hexadecyltrimethylammonium bromide (CTAB) as surfactants, respectively, and investigated their catalytic properties in comparison with that of 1 in the powder phase. A significant enhancement in both catalytic efficiency and product yield was observed when 1 was nano-crystallized. This is the first investigation about the relationship between the morphology and the catalytic parameters of MOFs. The results showed a strategy for efficiently applying MOFs as catalysts towards CO 2 conversion, which could also be used in other MOF-catalyzed processes.

Highly stable CuO incorporated TiO(2) catalyst for photo-catalytic hydrogen production from H(2)O.

PubMed

Bandara, J; Udawatta, C P K; Rajapakse, C S K

2005-11-01

A CuO incorporated TiO(2) catalyst was found to be an active photo-catalyst for the reduction of H(2)O under sacrificial conditions. The catalytic activity originates from the photogeneration of excited electrons in the conduction bands of both TiO(2) and CuO resulting in a build-up of excess electrons in the conduction band of CuO. Consequently, the accumulation of excess electrons in CuO causes a negative shift in the Fermi level of CuO. The efficient inter-particle charge transfer leads to a higher catalytic activity and the formation of highly reduced states of TiO(2)/CuO, which are stable even under oxygen saturated condition. Negative shift in the Fermi level of CuO of the catalyst TiO(2)/CuO gains the required over-voltage necessary for efficient water reduction reaction. The function of CuO is to help the charge separation and to act as a water reduction site. The amount of CuO and crystalline structure were found to be crucial for the catalytic activity and the optimum CuO loading was ca. approximately 5-10%(w/w).

Promiscuity in the Enzymatic Catalysis of Phosphate and Sulfate Transfer

PubMed Central

2016-01-01

The enzymes that facilitate phosphate and sulfate hydrolysis are among the most proficient natural catalysts known to date. Interestingly, a large number of these enzymes are promiscuous catalysts that exhibit both phosphatase and sulfatase activities in the same active site and, on top of that, have also been demonstrated to efficiently catalyze the hydrolysis of other additional substrates with varying degrees of efficiency. Understanding the factors that underlie such multifunctionality is crucial both for understanding functional evolution in enzyme superfamilies and for the development of artificial enzymes. In this Current Topic, we have primarily focused on the structural and mechanistic basis for catalytic promiscuity among enzymes that facilitate both phosphoryl and sulfuryl transfer in the same active site, while comparing this to how catalytic promiscuity manifests in other promiscuous phosphatases. We have also drawn on the large number of experimental and computational studies of selected model systems in the literature to explore the different features driving the catalytic promiscuity of such enzymes. Finally, on the basis of this comparative analysis, we probe the plausible origins and determinants of catalytic promiscuity in enzymes that catalyze phosphoryl and sulfuryl transfer. PMID:27187273

Theoretical investigation of the electron transfer dynamics and photodegradation pathways in a hydrogen-evolving ruthenium-palladium photocatalyst.

PubMed

Staniszewska, Magdalena; Kupfer, Stephan; Guthmuller, Julien

2018-05-16

Time-dependent density functional theory calculations combined with the Marcus theory of electron transfer (ET) were applied on the molecular photocatalyst [(tbbpy)2Ru(tpphz)PdCl2]2+ in order to elucidate the light-induced relaxation pathways populated upon excitation in the longer wavelength range of its absorption spectrum. The computational results show that after the initial excitation, metal (Ru) to ligand (tpphz) charge transfer (MLCT) triplet states are energetically accessible, but that an ET toward the catalytic center (PdCl2) from these states is a slow process, with estimated time constants above 1 ns. Instead, the calculations predict that low-lying Pd-centered states are efficiently populated - associated to an energy transfer toward the catalytic center. Thus, it is postulated that these states lead to the dissociation of a Cl- and are consequently responsible for the experimentally observed degradation of the catalytic center. Following dissociation, it is shown that the ET rates from the MLCT states to the charge separated states are significantly increased (i.e. 10^5-10^6 times larger). This demonstrates that alteration of the catalytic center generates efficient charge separation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal oxide composite enabled nanotextured Si photoanode for efficient solar driven water oxidation.

PubMed

Sun, Ke; Pang, Xiaolu; Shen, Shaohua; Qian, Xueqiang; Cheung, Justin S; Wang, Deli

2013-05-08

We present a study of a transition metal oxide composite modified n-Si photoanode for efficient and stable water oxidation. This sputter-coated composite functions as a protective coating to prevent Si from photodecomposition, a Schottky heterojunction, a hole conducting layer for efficient charge separation and transportation, and an electrocatalyst to reduce the reaction overpotential. The formation of mixed-valence oxides composed of Ni and Ru effectively modifies the optical, electrical, and catalytic properties of the coating material, as well as the interfaces with Si. The successful application of this oxide composite on nanotextured Si demonstrates improved conversion efficiency due to enhanced catalytic activity, minimized reflection, and increased surface reaction sites. Although the coated nanotextured Si shows a noticeable degradation from 500 cycles of operation, the oxide composite provides a simple method to enable unstable photoanode materials for solar fuel conversion.

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

NASA Astrophysics Data System (ADS)

Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

2013-05-01

Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

PubMed Central

Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

2013-01-01

Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

Mild Deoxygenation of Sulfoxides over Plasmonic Molybdenum Oxide Hybrid with Dramatic Activity Enhancement under Visible Light.

PubMed

Kuwahara, Yasutaka; Yoshimura, Yukihiro; Haematsu, Kohei; Yamashita, Hiromi

2018-06-17

Harvesting solar light to boost commercially important organic synthesis still remains a challenge. Coupling of conventional noble metal catalysts with plasmonic oxide materials which exhibit intense plasmon absorption in the visible light region is a promising option for efficient solar energy utilization in catalysis. Herein we for the first time demonstrate that plasmonic hydrogen molybdenum bronze coupled with Pt nanoparticles (Pt/H x MoO 3-y ) shows a high catalytic performance in the deoxygenation of sulfoxides with 1 atm H 2 at room temperature, with dramatic activity enhancement under visible light irradiation relative to dark condition. The plasmonic molybdenum oxide hybrids with strong plasmon resonance peaks pinning at around 556 nm are obtained via a facile H-spillover process. Pt/H x MoO 3-y hybrid provides excellent selectivity for the deoxygenation of various sulfoxides as well as pyridine N-oxides, in which drastically improved catalytic efficiencies are obtained under the irradiation of visible light. Comprehensive analyses reveal that oxygen vacancies massively introduced via a H-spillover process are the main active sites, and reversible redox property of Mo atoms and strong plasmonic absorption play key roles in this reaction. The catalytic system works under extremely mild conditions and can boost the reaction by the assist of visible light, offering an ultimately greener protocol to produce sulfides from sulfoxides. Our findings may open up a new strategy for designing plasmon-based catalytic systems that can harness visible light efficiently.

A general strategy for the evolution of bond-forming enzymes using yeast display

PubMed Central

Chen, Irwin; Dorr, Brent M.; Liu, David R.

2011-01-01

The ability to routinely generate efficient protein catalysts of bond-forming reactions chosen by researchers, rather than nature, is a long-standing goal of the molecular life sciences. Here, we describe a directed evolution strategy for enzymes that catalyze, in principle, any bond-forming reaction. The system integrates yeast display, enzyme-mediated bioconjugation, and fluorescence-activated cell sorting to isolate cells expressing proteins that catalyze the coupling of two substrates chosen by the researcher. We validated the system using model screens for Staphylococcus aureus sortase A–catalyzed transpeptidation activity, resulting in enrichment factors of 6,000-fold after a single round of screening. We applied the system to evolve sortase A for improved catalytic activity. After eight rounds of screening, we isolated variants of sortase A with up to a 140-fold increase in LPETG-coupling activity compared with the starting wild-type enzyme. An evolved sortase variant enabled much more efficient labeling of LPETG-tagged human CD154 expressed on the surface of HeLa cells compared with wild-type sortase. Because the method developed here does not rely on any particular screenable or selectable property of the substrates or product, it represents a powerful alternative to existing enzyme evolution methods. PMID:21697512

Transition metal catalysis in the generation of petroleum and natural gas. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mango, F.D.

1997-01-21

This project originated on the premise that natural gas could be formed catalytically in the earth rather than thermally as commonly believed. The intention was to test this hypothetical view and to explore generally the role of sedimentary metals in the generation of light hydrocarbons (C1 - C9). We showed the metalliferous source rocks are indeed catalytic in the generation of natural gas. Various metal compounds in the pure state show the same levels of catalytic activity as sedimentary rocks and the products are identical. Nickel is particularly active among the early transition metals and is projected to remain catalyticallymore » robust at all stages of catagenesis. Nickel oxide promotes the formation of n-alkanes in addition to natural gas (NG), demonstrating the full scope of the hypothetical catalytic process: The composition of catalytic gas duplicates the entire range of natural gas, from so-called wet gas to dry gas (60 to 95+ wt % methane), while gas generated thermally is consistently depleted in methane (10 to 60 wt % methane). These results support the view that metal catalysis is a major pathway through which natural gas is formed in the earth.« less

Transition metal catalysis in the generation of petroleum and natural gas. Final report, September 1, 1992--October 31, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mango, F.D.

1997-01-21

This project originated on the premise that natural gas could be formed catalytically in the earth rather than thermally as commonly believed. The intention was to test this hypothetical view and to explore generally the role of sedimentary metals in the generation of light hydrocarbons (C1 - C9). We showed the metalliferous source rocks are indeed catalytic in the generation of natural gas. Various metal compounds in the pure state show the same levels of catalytic activity as sedimentary rocks and the products are identical. Nickel is particularly active among the early transition metals and is projected to remain catalyticallymore » robust at all stages of catagenesis. Nickel oxide promotes the formation of n-alkanes in addition to natural gas (NG), demonstrating the full scope of the hypothetical catalytic process. The composition of catalytic gas duplicates the entire range of natural gas, from so-called wet gas to dry gas (60 to 95+ wt % methane), while gas generated thermally is consistently depleted in methane (10 to 60 wt % methane). These results support the view that metal catalysis is a major pathway through which natural gas is formed in the earth.« less

Nanofibrous electrocatalysts

DOEpatents

Liu, Di Jia; Shui, Jianglan; Chen, Chen

2016-05-24

A nanofibrous catalyst and method of manufacture. A precursor solution of a transition metal based material is formed into a plurality of interconnected nanofibers by electro-spinning the precursor solution with the nanofibers converted to a catalytically active material by a heat treatment. Selected subsequent treatments can enhance catalytic activity.

Growth of aragonite calcium carbonate nanorods in the biomimetic anodic aluminum oxide template

NASA Astrophysics Data System (ADS)

Lee, Inho; Han, Haksoo; Lee, Sang-Yup

2010-04-01

In this study, a biomimetic template was prepared and applied for growing calcium carbonate (CaCO 3) nanorods whose shape and polymorphism were controlled. A biomimetic template was prepared by adsorbing catalytic dipeptides into the pores of an anodic aluminum oxide (AAO) membrane. Using this peptide-adsorbed template, mineralization and aggregation of CaCO 3 was carried out to form large nanorods in the pores. The nanorods were aragonite and had a structure similar to nanoneedle assembly. This aragonite nanorod formation was driven by both the AAO template and catalytic function of dipeptides. The AAO membrane pores promoted generation of aragonite polymorph and guided nanorod formation by guiding the nanorod growth. The catalytic dipeptides promoted the aggregation and further dehydration of calcium species to form large nanorods. Functions of the AAO template and catalytic dipeptides were verified through several control experiments. This biomimetic approach makes possible the production of functional inorganic materials with controlled shapes and crystalline structures.

Reversible Regulation of Catalytic Activity of Gold Nanoparticles with DNA Nanomachines

NASA Astrophysics Data System (ADS)

Zhou, Peipei; Jia, Sisi; Pan, Dun; Wang, Lihua; Gao, Jimin; Lu, Jianxin; Shi, Jiye; Tang, Zisheng; Liu, Huajie

2015-09-01

Reversible catalysis regulation has gained much attention and traditional strategies utilized reversible ligand coordination for switching catalyst’s conformations. However, it remains challenging to regulate the catalytic activity of metal nanoparticle-based catalysts. Herein, we report a new DNA nanomachine-driven reversible nano-shield strategy for circumventing this problem. The basic idea is based on the fact that the conformational change of surface-attached DNA nanomachines will cause the variation of the exposed surface active area on metal nanoparticles. As a proof-of-concept study, we immobilized G-rich DNA strands on gold nanoparticles (AuNPs) which have glucose oxidase (GOx) like activity. Through the reversible conformational change of the G-rich DNA between a flexible single-stranded form and a compact G-quadruplex form, the catalytic activity of AuNPs has been regulated reversibly for several cycles. This strategy is reliable and robust, which demonstrated the possibility of reversibly adjusting catalytic activity with external surface coverage switching, rather than coordination interactions.

Design of biomimetic catalysts by molecular imprinting in synthetic polymers: the role of transition state stabilization.

PubMed

Wulff, Günter; Liu, Junqiu

2012-02-21

The impressive efficiency and selectivity of biological catalysts has engendered a long-standing effort to understand the details of enzyme action. It is widely accepted that enzymes accelerate reactions through their steric and electronic complementarity to the reactants in the rate-determining transition states. Thus, tight binding to the transition state of a reactant (rather than to the corresponding substrate) lowers the activation energy of the reaction, providing strong catalytic activity. Debates concerning the fundamentals of enzyme catalysis continue, however, and non-natural enzyme mimics offer important additional insight in this area. Molecular structures that mimic enzymes through the design of a predetermined binding site that stabilizes the transition state of a desired reaction are invaluable in this regard. Catalytic antibodies, which can be quite active when raised against stable transition state analogues of the corresponding reaction, represent particularly successful examples. Recently, synthetic chemistry has begun to match nature's ability to produce antibody-like binding sites with high affinities for the transition state. Thus, synthetic, molecularly imprinted polymers have been engineered to provide enzyme-like specificity and activity, and they now represent a powerful tool for creating highly efficient catalysts. In this Account, we review recent efforts to develop enzyme models through the concept of transition state stabilization. In particular, models for carboxypeptidase A were prepared through the molecular imprinting of synthetic polymers. On the basis of successful experiments with phosphonic esters as templates to arrange amidinium groups in the active site, the method was further improved by combining the concept of transition state stabilization with the introduction of special catalytic moieties, such as metal ions in a defined orientation in the active site. In this way, the imprinted polymers were able to provide both an electrostatic stabilization for the transition state through the amidinium group as well as a synergism of transition state recognition and metal ion catalysis. The result was an excellent catalyst for carbonate hydrolysis. These enzyme mimics represent the most active catalysts ever prepared through the molecular imprinting strategy. Their catalytic activity, catalytic efficiency, and catalytic proficiency clearly surpass those of the corresponding catalytic antibodies. The active structures in natural enzymes evolve within soluble proteins, typically by the refining of the folding of one polypeptide chain. To incorporate these characteristics into synthetic polymers, we used the concept of transition state stabilization to develop soluble, nanosized carboxypeptidase A models using a new polymerization method we term the "post-dilution polymerization method". With this methodology, we were able to prepare soluble, highly cross-linked, single-molecule nanoparticles. These particles have controlled molecular weights (39 kDa, for example) and, on average, one catalytically active site per particle. Our strategies have made it possible to obtain efficient new enzyme models and further advance the structural and functional analogy with natural enzymes. Moreover, this bioinspired design based on molecular imprinting in synthetic polymers offers further support for the concept of transition state stabilization in catalysis.

Practical synthesis of Shi's diester fructose derivative for catalytic asymmetric epoxidation of alkenes.

PubMed

Nieto, N; Molas, P; Benet-Buchholz, J; Vidal-Ferran, A

2005-11-25

[reaction: see text] A practical synthesis of Shi's diester 3 for catalytic asymmetric epoxidations has been developed. The catalyst has been prepared in multigram quantities from D-fructose in four steps with a 66% overall yield. Efficiency, cost, and selectivity aspects of the reagents involved for its preparation have been taken care of during its preparation. The workup procedures have been simplified to the bare minimum, rendering a very practical preparation method. The well-known high efficiency of this catalyst 3 in the epoxidation of alpha,beta-unsaturated carbonyl compounds has also proved to be high in unfunctionalized alkenes.

A General, Concise Strategy that Enables Collective Total Syntheses of over 50 Protoberberine and Five Aporhoeadane Alkaloids within Four to Eight Steps.

PubMed

Zhou, Shiqiang; Tong, Rongbiao

2016-05-17

A concise, catalytic, and general strategy that allowed efficient total syntheses of 22 natural 13-methylprotoberberines within four steps for each molecule is reported. This synthesis represents the most efficient and shortest route to date, featuring three catalytic processes: CuI-catalyzed redox-A(3) reaction, Pd-catalyzed reductive carbocyclization, and PtO2 -catalyzed hydrogenation. Importantly, this new strategy to the tetracyclic framework has also been applied to the collective concise syntheses of >30 natural protoberberines (without 13-methyl group) and five aporhoeadane alkaloids. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic cartridge SO.sub.3 decomposer

DOEpatents

Galloway, Terry R.

1982-01-01

A catalytic cartridge internally heated is utilized as a SO.sub.3 decomposer for thermochemical hydrogen production. The cartridge has two embodiments, a cross-flow cartridge and an axial flow cartridge. In the cross-flow cartridge, SO.sub.3 gas is flowed through a chamber and incident normally to a catalyst coated tube extending through the chamber, the catalyst coated tube being internally heated. In the axial-flow cartridge, SO.sub.3 gas is flowed through the annular space between concentric inner and outer cylindrical walls, the inner cylindrical wall being coated by a catalyst and being internally heated. The modular cartridge decomposer provides high thermal efficiency, high conversion efficiency, and increased safety.

Synthesis of Ureas from CO2.

PubMed

Wang, Hua; Xin, Zhuo; Li, Yuehui

2017-04-01

Ureas are an important class of bioactive organic compounds in organic chemistry and exist widely in natural products, agricultural pesticides, uron herbicides, pharmaceuticals. Even though urea itself has been synthesized from CO 2 and ammonia for a long time, the selective and efficient synthesis of substituted ureas is still challenging due to the difficulty of dehydration processes. Efficient and economic fixation of CO 2 is of great importance in solving the problems of resource shortages, environmental issues, global warming, etc. During recent decades, chemists have developed different catalytic systems to synthesize ureas from CO 2 and amines. Herein, we focus on catalytic synthesis of ureas using CO 2 and amines.

Few-layer MoSe₂ possessing high catalytic activity towards iodide/tri-iodide redox shuttles.

PubMed

Lee, Lawrence Tien Lin; He, Jian; Wang, Baohua; Ma, Yaping; Wong, King Young; Li, Quan; Xiao, Xudong; Chen, Tao

2014-02-14

Due to the two-dimensional confinement of electrons, single- and few-layer MoSe₂ nanostructures exhibit unusual optical and electrical properties and have found wide applications in catalytic hydrogen evolution reaction, field effect transistor, electrochemical intercalation, and so on. Here we present a new application in dye-sensitized solar cell as catalyst for the reduction of I₃(-) to I(-) at the counter electrode. The few-layer MoSe₂ is fabricated by surface selenization of Mo-coated soda-lime glass. Our results show that the few-layer MoSe₂ displays high catalytic efficiency for the regeneration of I(-) species, which in turn yields a photovoltaic energy conversion efficiency of 9.00%, while the identical photoanode coupling with "champion" electrode based on Pt nanoparticles on FTO glass generates efficiency only 8.68%. Thus, a Pt- and FTO-free counter electrode outperforming the best conventional combination is obtained. In this electrode, Mo film is found to significantly decrease the sheet resistance of the counter electrode, contributing to the excellent device performance. Since all of the elements in the electrode are of high abundance ratios, this type of electrode is promising for the fabrication of large area devices at low materials cost.

Understanding product specificity of protein lysine methyltransferases from QM/MM molecular dynamics and free energy simulations: the effects of mutation on SET7/9 beyond the Tyr/Phe switch.

PubMed

Yao, Jianzhuang; Chu, Yuzhuo; An, Ran; Guo, Hong

2012-02-27

The results of hybrid quantum mechanical/molecular mechanical (QM/MM) free energy (potential of mean force) simulations for methyl-transfer processes in SET7/9 and its Y245A mutant are compared to address the question concerning the change of the product specificity as well as catalytic efficiency due to the mutation. One of the key questions is whether or not the free energy profiles of methyl transfers may be used to predict the change of the product specificity as a result of the mutations for the residues that are not located at the Tyr/Phe switch position. The simulations show that while the wild-type SET7/9 is a monomethylase, the Y245→A mutation increases the ability of the enzyme to add more methyl groups on the target lysine (i.e., acting as a trimethylase). However, the first methyl-transfer process seems to become less efficient in the mutant compared to that in wild-type. All these results are consistent with experimental observations concerning the effects of the mutation on the product specificity and catalytic efficiency. Thus, the previous suggestion that the energetics of the methyl-transfer reactions may determine the product specificity, at least in some cases, is confirmed by the present work. Moreover, the dynamic information of the reactant complexes obtained from the QM/MM molecular dynamics simulations shows that the ability of the reactant complexes to form the reactive transition-state-like configurations may be used as an important indicator for the prediction of the product specificity of PKMTs, consistent with previous computational studies.

Purifier-integrated methanol reformer for fuel cell vehicles

NASA Astrophysics Data System (ADS)

Han, Jaesung; Kim, Il-soo; Choi, Keun-Sup

We developed a compact, 3-kW, purifier-integrated modular reformer which becomes the building block of full-scale 30-kW or 50-kW methanol fuel processors for fuel cell vehicles. Our proprietary technologies regarding hydrogen purification by composite metal membrane and catalytic combustion by washcoated wire-mesh catalyst were combined with the conventional methanol steam-reforming technology, resulting in higher conversion, excellent quality of product hydrogen, and better thermal efficiency than any other systems using preferential oxidation. In this system, steam reforming, hydrogen purification, and catalytic combustion all take place in a single reactor so that the whole system is compact and easy to operate. Hydrogen from the module is ultrahigh pure (99.9999% or better), hence there is no power degradation of PEMFC stack due to contamination by CO. Also, since only pure hydrogen is supplied to the anode of the PEMFC stack, 100% hydrogen utilization is possible in the stack. The module produces 2.3 Nm 3/h of hydrogen, which is equivalent to 3 kW when PEMFC has 43% efficiency. Thermal efficiency (HHV of product H 2/HHV of MeOH in) of the module is 89% and the power density of the module is 0.77 kW/l. This work was conducted in cooperation with Hyundai Motor Company in the form of a Korean national project. Currently the module is under test with an actual fuel cell stack in order to verify its performance. Sooner or later a full-scale 30-kW system will be constructed by connecting these modules in series and parallel and will serve as the fuel processor for the Korean first fuel cell hybrid vehicle.

Orion EFT-1 Catalytic Tile Experiment Overview and Flight Measurements

NASA Technical Reports Server (NTRS)

Salazar, Giovanni; Amar, Adam; Hyatt, Andrew; Rezin, Marc D.

2016-01-01

This paper describes the design and results of a surface catalysis flight experiment flown on the Orion Multipurpose Crew Vehicle during Exploration Flight Test 1 (EFT1). Similar to previous Space Shuttle catalytic tile experiments, the present test consisted of a highly catalytic coating applied to an instrumented TPS tile. However, the present catalytic tile experiment contained significantly more instrumentation in order to better resolve the heating overshoot caused by the change in surface catalytic efficiency at the interface between two distinct materials. In addition to collecting data with unprecedented spatial resolution of the "overshoot" phenomenon, the experiment was also designed to prove if such a catalytic overshoot would be seen in turbulent flow in high enthalpy regimes. A detailed discussion of the results obtained during EFT1 is presented, as well as the challenges associated with data interpretation of this experiment. Results of material testing carried out in support of this flight experiment are also shown. Finally, an inverse heat conduction technique is employed to reconstruct the flight environments at locations upstream and along the catalytic coating. The data and analysis presented in this work will greatly contribute to our understanding of the catalytic "overshoot" phenomenon, and have a significant impact on the design of future spacecraft.

Treated carbon fibers with improved performance for electrochemical and chemical applications

DOEpatents

Chu, X.; Kinoshita, Kimio

1999-02-23

A treated mesophase carbon fiber is disclosed having a high density of exposed edges on the fiber surface, and a method is described for making such a treated fiber. A carbon electrode is also described which is constructed from such treated mesophase carbon fibers. The resulting electrode, formed from such treated flexible carbon fibers, is characterized by a high density of active sites formed from such exposed edges, low corrosion, and good mechanical strength, and may be fabricated into various shapes. The treated mesophase carbon fibers of the invention are formed by first loading the surface of the mesophase carbon fiber with catalytic metal particles to form catalytic etch sites on a hard carbon shell of the fiber. The carbon fiber is then subject to an etch step wherein portions of the hard carbon shell or skin are selectively removed adjacent the catalytic metal particles adhering to the carbon shell. This exposes the underlying radial edges of the graphite-like layers within the carbon shell of the mesophase carbon fiber, which exposed radial edges then act as active sites of a carbon electrode subsequently formed from the treated mesophase carbon fibers. 14 figs.

Treated carbon fibers with improved performance for electrochemical and chemical applications

DOEpatents

Chu, Xi; Kinoshita, Kimio

1999-01-01

A treated mesophase carbon fiber is disclosed having a high density of exposed edges on the fiber surface, and a method of making such a treated fiber. A carbon electrode is also described which is constructed from such treated mesophase carbon fibers. The resulting electrode, formed from such treated flexible carbon fibers, is characterized by a high density of active sites formed from such exposed edges, low corrosion, and good mechanical strength, and may be fabricated into various shapes. The treated mesophase carbon fibers of the invention are formed by first loading the surface of the mesophase carbon fiber with catalytic metal particles to form catalytic etch sites on a hard carbon shell of the fiber. The carbon fiber is then subject to an etch step wherein portions of the hard carbon shell or skin are selectively removed adjacent the catalytic metal particles adhering to the carbon shell. This exposes the underlying radial edges of the graphite-like layers within the carbon shell of the mesophase carbon fiber, which exposed radial edges then act as active sites of a carbon electrode subsequently formed from the treated mesophase carbon fibers.

Catalytic asymmetric nitro-Mannich reactions with a Yb/K heterobimetallic catalyst.

PubMed

Nitabaru, Tatsuya; Kumagai, Naoya; Shibasaki, Masakatsu

2010-03-04

A catalytic asymmetric nitro-Mannich (aza-Henry) reaction with rare earth metal/alkali metal heterobimetallic catalysts is described. A Yb/K heterobimetallic catalyst assembled by an amide-based ligand promoted the asymmetric nitro-Mannich reaction to afford enantioenriched anti-b-nitroamines in up to 86% ee. Facile reduction of the nitro functionality allowed for efficient access to optically active 1,2-diamines.

Polarizing the Nazarov cyclization: efficient catalysis under mild conditions.

PubMed

He, Wei; Sun, Xiufeng; Frontier, Alison J

2003-11-26

Substituted divinyl ketones were studied in the Nazarov cyclization. alpha-Carbomethoxy divinyl ketones underwent efficient Nazarov cyclization with catalytic copper triflate (2 mol %) to give a single cyclopentenone regio- and stereoisomer. The efficiency of the cyclizations correlated with the ability of the substituents to favorably polarize the pi-system of the cationic intermediate.

Catalytic enantioselective addition of Grignard reagents to aromatic silyl ketimines

NASA Astrophysics Data System (ADS)

Rong, Jiawei; Collados, Juan F.; Ortiz, Pablo; Jumde, Ravindra P.; Otten, Edwin; Harutyunyan, Syuzanna R.

2016-12-01

α-Chiral amines are of significant importance in medicinal chemistry, asymmetric synthesis and material science, but methods for their efficient synthesis are scarce. In particular, the synthesis of α-chiral amines with the challenging tetrasubstituted carbon stereocentre is a long-standing problem and catalytic asymmetric additions of organometallic reagents to ketimines that would give direct access to these molecules are underdeveloped. Here we report a highly enantioselective catalytic synthesis of N-sulfonyl protected α-chiral silyl amines via the addition of inexpensive, easy to handle and readily available Grignard reagents to silyl ketimines. The key to this success was our ability to suppress any unselective background addition reactions and side reduction pathway, through the identification of an inexpensive, chiral Cu-complex as the catalytically active structure.

Catalytic Upgrading of Thermochemical Intermediates to Hydrocarbons: Conversion of Lignocellulosic Feedstocks to Aromatic Fuels and High Value Chemicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cortright, Randy; Rozmiarek, Bob; Van Straten, Matt

The principal objective of this project was to develop a fully integrated catalytic process that efficiently converts lignocellulosic feedstocks (e.g. bagasse, corn stover, and loblolly pine) into aromatic-rich fuels and chemicals. Virent led this effort with key feedstock support from Iowa State University. Within this project, Virent leveraged knowledge of catalytic processing of sugars and biomass to investigate two liquefaction technologies (Reductive Catalytic Liquefaction (USA Patent No. 9,212,320, 2015) and Solvolysis (USA Patent No. 9,157,030, 2015) (USA Patent No. 9,157,031, 2015)) that take advantage of proprietary catalysts at temperatures less than 300°C in the presence of unique solvent molecules generatedmore » in-situ within the liquefaction processes.« less

Carbon Dioxide Reduction Systems

NASA Technical Reports Server (NTRS)

Burghardt, Stanley I.; Chandler, Horace W.; Taylor, T. I.; Walden, George

1961-01-01

The Methoxy system for regenerating oxygen from carbon dioxide was studied. Experiments indicate that the reaction between carbon dioxide and hydrogen can be carried out with ease in an efficient manner and with excellent heat conservation. A small reactor capable of handling the C02 expired by three men has been built and operated. The decomposition of methane by therma1,arc and catalytic processes was studied. Both the arc and catalytic processes gave encouraging results with over 90 percent of the methane being decomposed to carbon and hydrogen in some of the catalytic processes. Control of the carbon deposition in both the catalytic and arc processes is of great importance to prevent catalyst deactivation and short circuiting of electrical equipment. Sensitive analytical techniques have been developed for all of the components present in the reactor effluent streams.

Oxidative Dehydrogenation on Nanocarbon: Insights into the Reaction Mechanism and Kinetics via in Situ Experimental Methods.

PubMed

Qi, Wei; Yan, Pengqiang; Su, Dang Sheng

2018-03-20

Sustainable and environmentally benign catalytic processes are vital for the future to supply the world population with clean energy and industrial products. The replacement of conventional metal or metal oxide catalysts with earth abundant and renewable nonmetallic materials has attracted considerable research interests in the field of catalysis and material science. The stable and efficient catalytic performance of nanocarbon materials was discovered at the end of last century, and these materials are considered as potential alternatives for conventional metal-based catalysts. With its rapid development in the past 20 years, the research field of carbon catalysis has been experiencing a smooth transition from the discovery of novel nanocarbon materials or related new reaction systems to the atomistic-level mechanistic understanding on the catalytic process and the subsequent rational design of the practical catalytic reaction systems. In this Account, we summarize the recent progress in the kinetic and mechanistic studies on nanocarbon catalyzed alkane oxidative dehydrogenation (ODH) reactions. The paper attempts to extract general concepts and basic regularities for carbon catalytic process directing us on the way for rational design of novel efficient metal-free catalysts. The nature of the active sites for ODH reactions has been revealed through microcalorimetric analysis, ambient pressure X-ray photoelectron spectroscopy (XPS) measurement, and in situ chemical titration strategies. The detailed kinetic analysis and in situ catalyst structure characterization suggests that carbon catalyzed ODH reactions involve the redox cycles of the ketonic carbonyl-hydroxyl pairs, and the key physicochemical parameters (activation energy, reaction order, and rate/equilibrium constants, etc.) of the carbon catalytic systems are proposed and compared with conventional transition metal oxide catalysts. The proposal of the intrinsic catalytic activity (TOF) provides the possibility for the fair comparisons of different nanocarbon catalysts and the consequent structure-function relation regularity. Surface modification and heteroatom doping are proved as the most effective strategies to adjust the catalytic property (activity and product selectivity etc.) of the nanocarbon catalysts. Nanocarbon is actually a proper candidate platform helping us to understand the classical catalytic reaction mechanism better, since there is no lattice oxygen and all the catalytic process happens on nanocarbon surface. This Account also exhibits the importance of the in situ structural characterizations for heterogeneous nanocarbon catalysis. The research strategy and methods proposed for carbon catalysts may also shed light on other complicated catalytic systems or fields concerning the applications of nonmetallic materials, such as energy storage and environment protection etc.

Magnetic nanoparticles entrapped in siliceous mesocellular foam: a new catalyst support.

PubMed

Lee, Su Seong; Riduan, Siti Nurhanna; Erathodiyil, Nandanan; Lim, Jaehong; Cheong, Jian Liang; Cha, Junhoe; Han, Yu; Ying, Jackie Y

2012-06-11

γ-Fe(2)O(3) nanoparticles were formed inside the cage-like pores of mesocellular foam (MCF). These magnetic nanoparticles showed a uniform size distribution that could be easily controlled by the MCF pore size, as well as by the hydrocarbon chain length used for MCF surface modification. Throughout the entrapment process, the pore structure and surface area of the MCF remained intact. The resulting magnetic MCF facilitated the immobilization of biocatalysts, homogeneous catalysts, and nanoclusters. Moreover, the MCF allowed for facile catalyst recovery by using a simple magnet. The supported catalysts exhibited excellent catalytic efficiencies that were comparable to their homogeneous counterparts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transesterification of diethyl oxalate with phenol over sol-gel MoO(3)/TiO(2) catalysts.

PubMed

Kotbagi, Trupti; Nguyen, Duy Luan; Lancelot, Christine; Lamonier, Carole; Thavornprasert, Kaew-Arpha; Wenli, Zhu; Capron, Mickaël; Jalowiecki-Duhamel, Louise; Umbarkar, Shubhangi; Dongare, Mohan; Dumeignil, Franck

2012-08-01

The transesterification of diethyl oxalate (DEO) with phenol to form diphenyl oxalate (DPO) has been carried out in the liquid phase over very efficient MoO(3)/TiO(2) solid-acid sol-gel catalysts. A selectivity of 100 % with a remarkable maximum yield of 88 % were obtained, which opens the route to downstream phosgene-free processes for the synthesis of polycarbonates. Interpretation of the results of various acidity measurements (NH(3) and pyridine desorption, methanol oxidation as a probe reaction) allowed us to identify the catalytic sites as Lewis acid sites. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

QM/MM simulations identify the determinants of catalytic activity differences between type II dehydroquinase enzymes.

PubMed

Lence, Emilio; van der Kamp, Marc W; González-Bello, Concepción; Mulholland, Adrian J

2018-05-16

Type II dehydroquinase enzymes (DHQ2), recognized targets for antibiotic drug discovery, show significantly different activities dependent on the species: DHQ2 from Mycobacterium tuberculosis (MtDHQ2) and Helicobacter pylori (HpDHQ2) show a 50-fold difference in catalytic efficiency. Revealing the determinants of this activity difference is important for our understanding of biological catalysis and further offers the potential to contribute to tailoring specificity in drug design. Molecular dynamics simulations using a quantum mechanics/molecular mechanics potential, with correlated ab initio single point corrections, identify and quantify the subtle determinants of the experimentally observed difference in efficiency. The rate-determining step involves the formation of an enolate intermediate: more efficient stabilization of the enolate and transition state of the key step in MtDHQ2, mainly by the essential residues Tyr24 and Arg19, makes it more efficient than HpDHQ2. Further, a water molecule, which is absent in MtDHQ2 but involved in generation of the catalytic Tyr22 tyrosinate in HpDHQ2, was found to destabilize both the transition state and the enolate intermediate. The quantification of the contribution of key residues and water molecules in the rate-determining step of the mechanism also leads to improved understanding of higher potencies and specificity of known inhibitors, which should aid ongoing inhibitor design.

Ni0 encapsulated in N-doped carbon nanotubes for catalytic reduction of highly toxic hexavalent chromium

NASA Astrophysics Data System (ADS)

Yao, Yunjin; Zhang, Jie; Chen, Hao; Yu, Maojing; Gao, Mengxue; Hu, Yi; Wang, Shaobin

2018-05-01

N-doped carbon nanotubes encapsulating Ni0 nanoparticles (Ni@N-C) were fabricated via thermal reduction of dicyandiamide and NiCl2·6H2O, and used to remove CrVI in polluted water. The resultant products present an excellent catalytic activity for CrVI reduction using formic acid under relatively mild conditions. The CrVI reduction efficiency of Ni@N-C was significantly affected by the preparation conditions including the mass of nickel salt and synthesis temperatures. The impacts of several reaction parameters, such as initial concentrations of CrVI and formic acid, solution pH and temperatures, as well as inorganic anions in solution on CrVI reduction efficiency were also evaluated in view of scalable industrial applications. Owing to the synergistic effects amongst tubes-coated Ni0, doped nitrogen, oxygen containing groups, and the configuration of carbon nanotubes, Ni@N-C catalysts exhibit excellent catalytic activity and recyclable capability for CrVI reduction. Carbon shell can efficiently protect inner Ni0 core and N species from corrosion and subsequent leaching, while Ni0 endows the Ni@N-C catalysts with ferromagnetism, so that the composites can be easily separated via a permanent magnet. This study opens up an avenue for design of N-doped carbon nanotubes encapsulating Ni0 nanoparticles with high CrVI removal efficiency and magnetic recyclability as low-cost catalysts for industrial applications.

Fe3O4@MOF core-shell magnetic microspheres as excellent catalysts for the Claisen-Schmidt condensation reaction

NASA Astrophysics Data System (ADS)

Ke, Fei; Qiu, Ling-Guang; Zhu, Junfa

2014-01-01

Separation and recycling of catalysts after catalytic reactions are critically required to reduce the cost of catalysts as well as to avoid the generation of waste in industrial applications. In this work, we present a facile fabrication and characterization of a novel type of MOF-based porous catalyst, namely, Fe3O4@MIL-100(Fe) core-shell magnetic microspheres. It has been shown that these catalysts not only exhibit high catalytic activities for the Claisen-Schmidt condensation reactions under environmentally friendly conditions, but remarkably, they can be easily separated and recycled without significant loss of catalytic efficiency after being used for many times. Therefore, compared to other reported catalysts used in the Claisen-Schmidt condensation reactions, these catalysts are green, cheap and more suitable for large scale industrial applications.Separation and recycling of catalysts after catalytic reactions are critically required to reduce the cost of catalysts as well as to avoid the generation of waste in industrial applications. In this work, we present a facile fabrication and characterization of a novel type of MOF-based porous catalyst, namely, Fe3O4@MIL-100(Fe) core-shell magnetic microspheres. It has been shown that these catalysts not only exhibit high catalytic activities for the Claisen-Schmidt condensation reactions under environmentally friendly conditions, but remarkably, they can be easily separated and recycled without significant loss of catalytic efficiency after being used for many times. Therefore, compared to other reported catalysts used in the Claisen-Schmidt condensation reactions, these catalysts are green, cheap and more suitable for large scale industrial applications. Electronic supplementary information (ESI) available: SEM and TEM images, and GC-MS spectra for chalcones. See DOI: 10.1039/c3nr05051c

A new V-doped Bi2(O,S)3 oxysulfide catalyst for highly efficient catalytic reduction of 2-nitroaniline and organic dyes.

PubMed

Abay, Angaw Kelemework; Kuo, Dong-Hau; Chen, Xiaoyun; Saragih, Albert Daniel

2017-12-01

A new type of convenient, and environmentally friendly, Vanadium (V)-doped Bi 2 (O,S) 3 oxysulfide catalyst with different V contents was successfully synthesized via a simple and facile method. The obtained V-doped Bi 2 (O,S) 3 solid solution catalysts were fully characterized by conventional methods. The catalytic performance of the samples was tested by using the reduction of 2-nitroaniline (2-NA) in aqueous solution. The reduction/decolorization of methylene blue (MB) and rhodamine B (RhB) was also chosen to evaluate the universality of catalysts. It was observed that the introduction of V can improve the catalytic performance, and 20%V-Bi 2 (O,S) 3 was found to be the optimal V doping concentration for the reduction of 2-NA, MB, and RhB dyes. For comparative purposes, a related V-free Bi 2 (O, S) 3 oxysulfide material was synthesized and tested as the catalyst. The superior activity of V-doped Bi 2 (O,S) 3 over pure Bi 2 (O,S) 3 was ascribed mainly to an increase in active sites of the material and also due to the presence of synergistic effects. The presence of V 5+ as found from XPS analysis may interact with Bi atoms and enhancing the catalytic activity of the sample. In the catalytic reduction of 2-NA, MB and RhB, the obtained V-doped Bi 2 (O,S) 3 oxysulfide catalyst exhibited excellent catalytic activity as compared with other reported catalysts. Furthermore this highly efficient, low-cost and easily reusable V-doped Bi 2 (O,S) 3 catalyst is anticipated to be of great potential in catalysis in the future. Copyright © 2017 Elsevier Ltd. All rights reserved.

Catalytic Activity and Impedance Behavior of Screen-Printed Nickel Oxide as Efficient Water Oxidation Catalysts.

PubMed

Singh, Archana; Fekete, Monika; Gengenbach, Thomas; Simonov, Alexandr N; Hocking, Rosalie K; Chang, Shery L Y; Rothmann, Mathias; Powar, Satvasheel; Fu, Dongchuan; Hu, Zheng; Wu, Qiang; Cheng, Yi-Bing; Bach, Udo; Spiccia, Leone

2015-12-21

We report that films screen printed from nickel oxide (NiO) nanoparticles and microballs are efficient electrocatalysts for water oxidation under near-neutral and alkaline conditions. Investigations of the composition and structure of the screen-printed films by X-ray diffraction, X-ray absorption spectroscopy, and scanning electron microscopy confirmed that the material was present as the cubic NiO phase. Comparison of the catalytic activity of the microball films to that of films fabricated by using NiO nanoparticles, under similar experimental conditions, revealed that the microball films outperform nanoparticle films of similar thickness owing to a more porous structure and higher surface area. A thinner, less-resistive NiO nanoparticle film, however, was found to have higher activity per Ni atom. Anodization in borate buffer significantly improved the activity of all three films. X-ray photoelectron spectroscopy showed that during anodization, a mixed nickel oxyhydroxide phase formed on the surface of all films, which could account for the improved activity. Impedance spectroscopy revealed that surface traps contribute significantly to the resistance of the NiO films. On anodization, the trap state resistance of all films was reduced, which led to significant improvements in activity. In 1.00 m NaOH, both the microball and nanoparticle films exhibit high long-term stability and produce a stable current density of approximately 30 mA cm(-2) at 600 mV overpotential. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrasensitive colorimetric immunoassay for hCG detection based on dual catalysis of Au@Pt core-shell nanoparticle functionalized by horseradish peroxidase

NASA Astrophysics Data System (ADS)

Wang, Weiguo; Zou, Yake; Yan, Jinwu; Liu, Jing; Chen, Huixiong; Li, Shan; Zhang, Lei

2018-03-01

In this paper, an ultrasensitive colorimetric biosensor for human chorionic gonadotrophin (hCG) detection was designed from bottom-up method based on the dual catalysis of the horseradish peroxidase (HRP) and Au@Pt nanoparticles (NPs) relative to H2O2-TEM system. HRP and monoclonal mouse anti-hCG antibody (β-submit, mAb1) were co-immobilized onto the Au@Pt NP surface to improve catalytic efficiency and specificity, which formed a dual functionalized Au@Pt-HRP probe with the mean size of 42.8 nm (D50). The colorimetric immunoassay was developed for the hCG detection, and the Au@Pt-HRP probe featured a higher sensitivity in the concentration range of 0.4-12.8 IU L- 1 with a low limit of detection (LOD) of 0.1 IU L- 1 compared with the LODs of 0.8 IU L- 1 for BA-ELISA and of 2.0 IU L- 1 for Au@Pt, which indicated that the Au@Pt-HRP probe possessed higher catalytic efficiency with 2.8-fold increase over Au@Pt and 33.8-fold increase over HRP. Also, the Au@Pt-HRP probe exhibited good precision and reproducibility, high specificity and acceptable accuracy with CV being less than 15%. The dual functionalized Au@Pt-HRP probe as a type of signal amplified method was firstly applied in the colorimetric immunoassay for the hCG detection.

Design of the hairpin ribozyme for targeting specific RNA sequences.

PubMed

Hampel, A; DeYoung, M B; Galasinski, S; Siwkowski, A

1997-01-01

The following steps should be taken when designing the hairpin ribozyme to cleave a specific target sequence: 1. Select a target sequence containing BN*GUC where B is C, G, or U. 2. Select the target sequence in areas least likely to have extensive interfering structure. 3. Design the conventional hairpin ribozyme as shown in Fig. 1, such that it can form a 4 bp helix 2 and helix 1 lengths up to 10 bp. 4. Synthesize this ribozyme from single-stranded DNA templates with a double-stranded T7 promoter. 5. Prepare a series of short substrates capable of forming a range of helix 1 lengths of 5-10 bp. 6. Identify these by direct RNA sequencing. 7. Assay the extent of cleavage of each substrate to identify the optimal length of helix 1. 8. Prepare the hairpin tetraloop ribozyme to determine if catalytic efficiency can be improved.

Catalytic oxidation of gaseous reduced sulfur compounds using coal fly ash.

PubMed

Kastner, James R; Das, K C; Melear, Nathan D

2002-11-11

Activated carbon has been shown to oxidize reduced sulfur compounds, but in many cases it is too costly for large-scale environmental remediation applications. Alternatively, we theorized that coal fly ash, given its high metal content and the presence of carbon could act as an inexpensive catalytic oxidizer of reduced sulfur compounds for "odor" removal. Initial results indicate that coal fly ash can catalyze the oxidization of H(2)S and ethanethiol, but not dimethyl sulfide (DMS) and dimethyl disulfide (DMDS) at room temperature. In batch reactor systems, initial concentrations of 100-500 ppmv H(2)S or ethanethiol were reduced to 0-2 ppmv within 1-2 and 6-8 min, respectively. This was contrary to control systems without ash in which concentrations remained constant. Diethyl disulfide was formed from ethanethiol substantiating the claim that catalytic oxidation occurred. The presence of water increased the rate of adsorption/reaction of both H(2)S and ethanethiol for the room temperature reactions (23-25 degrees C). Additionally, in a continuous flow packed bed reactor, a gaseous stream containing an inlet H(2)S concentration of 400-500 ppmv was reduced to 200 ppmv at a 4.6s residence time. The removal efficiency remained at 50% for approximately 4.6h or 3500 reactor volumes. These results demonstrate the potential of using coal fly ash in reactors for removal of H(2)S and other reduced sulfur compounds.

Catalytic reduction of 4-nitrophenol using gold nanoparticles biosynthesized by cell-free extracts of Aspergillus sp. WL-Au.

PubMed

Shen, Wenli; Qu, Yuanyuan; Pei, Xiaofang; Li, Shuzhen; You, Shengnan; Wang, Jingwei; Zhang, Zhaojing; Zhou, Jiti

2017-01-05

A facile one-pot eco-friendly process for synthesis of gold nanoparticles (AuNPs) with high catalytic activity was achieved using cell-free extracts of Aspergillus sp. WL-Au as reducing, capping and stabilizing agents. The surface plasmon resonance band of UV-vis spectrum at 532nm confirmed the presence of AuNPs. Transmission electron microscopy images showed that quite uniform spherical AuNPs were synthesized and the average size of nanoparticles increased from 4nm to 29nm with reaction time. X-ray diffraction analysis verified the formation of nano-crystalline gold particles. Fourier transform infrared spectra showed the presence of functional groups on the surface of biosynthesized AuNPs, such as OH, NH, CO, CH, COH and COC groups, which increased the stability of AuNPs. The biogenic AuNPs could serve as a highly efficient catalyst for 4-nitrophenol reduction. The reaction rate constant was linearly correlated with the concentration of AuNPs, which increased from 0.59min -1 to 1.51min -1 with the amount of AuNPs increasing form 1.46×10 -6 to 17.47×10 -6 mmol. Moreover, the as-synthesized AuNPs exhibited a remarkable normalized catalytic activity (4.04×10 5 min -1 mol -1 ), which was much higher than that observed for AuNPs synthesized by other biological and conventional chemical methods. Copyright © 2016 Elsevier B.V. All rights reserved.

Uniformity index measurement technology using thermocouples to improve performance in urea-selective catalytic reduction systems

NASA Astrophysics Data System (ADS)

Park, Sangki; Oh, Jungmo

2018-05-01

The current commonly used nitrogen oxides (NOx) emission reduction techniques employ hydrocarbons (HCs), urea solutions, and exhaust gas emissions as the reductants. Two of the primary denitrification NOx (DeNOx) catalyst systems are the HC-lean NOx trap (HC-LNT) catalyst and urea-selective catalytic reduction (urea-SCR) catalyst. The secondary injection method depends on the type of injector, injection pressure, atomization, and spraying technique. In addition, the catalyst reaction efficiency is directly affected by the distribution of injectors; hence, the uniformity index (UI) of the reductant is very important and is the basis for system optimization. The UI of the reductant is an indicator of the NOx conversion efficiency (NCE), and good UI values can reduce the need for a catalyst. Therefore, improving the UI can reduce the cost of producing a catalytic converter, which are expensive due to the high prices of the precious metals contained therein. Accordingly, measurement of the UI is an important process in the development of catalytic systems. Two of the commonly used methods for measuring the reductant UI are (i) measuring the exhaust emissions at many points located upstream/downstream of the catalytic converter and (ii) acquisition of a reductant distribution image on a section of the exhaust pipe upstream of the catalytic converter. The purpose of this study is to develop a system and measurement algorithms to measure the exothermic response distribution in the exhaust gas as the reductant passes through the catalytic converter of the SCR catalyst system using a set of thermocouples downstream of the SCR catalyst. The system is used to measure the reductant UI, which is applied in real-time to the actual SCR system, and the results are compared for various types of mixtures for various engine operating conditions and mixer types in terms of NCE.

Low density microcellular carbon or catalytically impregnated carbon forms and process for their preparation

DOEpatents

Hopper, Robert W.; Pekala, Richard W.

1989-01-01

Machinable and structurally stable, low density microcellular carbon, and catalytically impregnated carbon, foams, and process for their preparation, are provided. Pulverized sodium chloride is classified to improve particle size uniformity, and the classified particles may be further mixed with a catalyst material. The particles are cold pressed into a compact having internal pores, and then sintered. The sintered compact is immersed and then submerged in a phenolic polymer solution to uniformly fill the pores of the compact with phenolic polymer. The compact is then heated to pyrolyze the phenolic polymer into carbon in the form of a foam. Then the sodium chloride of the compact is leached away with water, and the remaining product is freeze dried to provide the carbon, or catalytically impregnated carbon, foam.

Catalytic production of metal carbonyls from metal oxides

DOEpatents

Sapienza, Richard S.; Slegeir, William A.; Foran, Michael T.

1984-01-01

This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150.degree.-260.degree. C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO.sub.4 and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect.

Catalytic production of metal carbonyls from metal oxides

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; Foran, M.T.

1984-01-06

This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150 to 260/sup 0/C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO/sub 4/ and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect. 3 tables.

Gold nanoparticles stabilized by poly(4-vinylpyridine) grafted cellulose nanocrystals as efficient and recyclable catalysts.

PubMed

Zhang, Zhen; Sèbe, Gilles; Wang, Xiaosong; Tam, Kam C

2018-02-15

pH-responsive poly(4-vinylpyridine) (P4VP) grafted cellulose nanocrystals (P4VP-g-CNC) were prepared by Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) and subsequently used to stabilize gold nanoparticles (Au NPs) as efficient and recyclable nanocatalysts for the reduction of 4-nitrophenol (4NP). The presence of P4VP brushes on the CNC surface controlled the growth of Au NPs yielding smaller averaged diameter compared to Au NPs deposited directly on pristine CNC. The catalytic performances of pristine Au NPs, Au@CNC and Au@P4VP-g-CNC were compared by measuring the turnover frequency (TOF) for the catalytic reduction of 4NP. Compared to pristine Au NPs, the catalytic activity of Au@CNC and Au@P4VP-g-CNC were 10 and 24 times better. Moreover, the Au@P4VP-g-CNC material could be recovered via flocculation at pH>5, and the recycled nanocatalyst remained highly active. Copyright © 2017 Elsevier Ltd. All rights reserved.

On the dynamical nature of the active center in a single-site photocatalyst visualized by 4D ultrafast electron microscopy

PubMed Central

Yoo, Byung-Kuk; Su, Zixue; Thomas, John Meurig; Zewail, Ahmed H.

2016-01-01

Understanding the dynamical nature of the catalytic active site embedded in complex systems at the atomic level is critical to developing efficient photocatalytic materials. Here, we report, using 4D ultrafast electron microscopy, the spatiotemporal behaviors of titanium and oxygen in a titanosilicate catalytic material. The observed changes in Bragg diffraction intensity with time at the specific lattice planes, and with a tilted geometry, provide the relaxation pathway: the Ti4+=O2− double bond transformation to a Ti3+−O1− single bond via the individual atomic displacements of the titanium and the apical oxygen. The dilation of the double bond is up to 0.8 Å and occurs on the femtosecond time scale. These findings suggest the direct catalytic involvement of the Ti3+−O1− local structure, the significance of nonthermal processes at the reactive site, and the efficient photo-induced electron transfer that plays a pivotal role in many photocatalytic reactions. PMID:26729878

Rapid bursts and slow declines: on the possible evolutionary trajectories of enzymes.

PubMed

Newton, Matilda S; Arcus, Vickery L; Patrick, Wayne M

2015-06-06

The evolution of enzymes is often viewed as following a smooth and steady trajectory, from barely functional primordial catalysts to the highly active and specific enzymes that we observe today. In this review, we summarize experimental data that suggest a different reality. Modern examples, such as the emergence of enzymes that hydrolyse human-made pesticides, demonstrate that evolution can be extraordinarily rapid. Experiments to infer and resurrect ancient sequences suggest that some of the first organisms present on the Earth are likely to have possessed highly active enzymes. Reconciling these observations, we argue that rapid bursts of strong selection for increased catalytic efficiency are interspersed with much longer periods in which the catalytic power of an enzyme erodes, through neutral drift and selection for other properties such as cellular energy efficiency or regulation. Thus, many enzymes may have already passed their catalytic peaks. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

A novel liquid organic hydrogen carrier system based on catalytic peptide formation and hydrogenation

PubMed Central

Hu, Peng; Fogler, Eran; Diskin-Posner, Yael; Iron, Mark A.; Milstein, David

2015-01-01

Hydrogen is an efficient green fuel, but its low energy density when stored under high pressure or cryogenically, and safety issues, presents significant disadvantages; hence finding efficient and safe hydrogen carriers is a major challenge. Of special interest are liquid organic hydrogen carriers (LOHCs), which can be readily loaded and unloaded with considerable amounts of hydrogen. However, disadvantages include high hydrogen pressure requirements, high reaction temperatures for both hydrogenation and dehydrogenation steps, which require different catalysts, and high LOHC cost. Here we present a readily reversible LOHC system based on catalytic peptide formation and hydrogenation, using an inexpensive, safe and abundant organic compound with high potential capacity to store and release hydrogen, applying the same catalyst for loading and unloading hydrogen under relatively mild conditions. Mechanistic insight of the catalytic reaction is provided. We believe that these findings may lead to the development of an inexpensive, safe and clean liquid hydrogen carrier system. PMID:25882348

Invoking Direct Exciton-Plasmon Interactions by Catalytic Ag Deposition on Au Nanoparticles: Photoelectrochemical Bioanalysis with High Efficiency.

PubMed

Ma, Zheng-Yuan; Xu, Fei; Qin, Yu; Zhao, Wei-Wei; Xu, Jing-Juan; Chen, Hong-Yuan

2016-04-19

In this work, direct exciton-plasmon interactions (EPI) between CdS quantum dots (QDs) and Ag nanoparticles (NPs) were invoked ingeniously by catalytic Ag deposition on Au NPs for the stimulation of high efficient damping effect toward the excitonic responses in CdS QDs, on the basis of which a novel photoelectrochemical (PEC) bioanalytical format was achieved for sensitive microRNA detection. Specifically, upon the configurational change from the hairpin probe DNA to the "Y"-shaped ternary conjugate consisting of the original probe DNA, assistant DNA, and the target microRNA, the alkaline phosphatase (ALP) catalytic chemistry would then trigger the transition of the interparticle interplay from the CdS QDs-Au NPs to the CdS QDs-Ag NPs systems for the microRNA detection due to the dependence of the photocurrent quenching on the target concentration. This work not only provided a unique method for EPI generation among the PEC nanosystems but also offered a versatile and general protocol for future PEC bioanalysis development.

Hierarchical Nanoporous Gold-Platinum with Heterogeneous Interfaces for Methanol Electrooxidation

PubMed Central

Xiao, Shuang; Xiao, Fei; Hu, Yuan; Yuan, Songliu; Wang, Shuai; Qian, Lihua; Liu, Yunqi

2014-01-01

The electrocatalysts utilized as the prospective electrodes in fuel cells and high efficient energy conversion devices require both the interconnected channels for efficient electrolyte transportation and the superior catalytic activity with long service life. In this work, nanoporous gold with the rigid skeletons in three dimensions is partially decorated by porous platinum shell containing nanoscale interstitials, aiming to create the heterogeneous gold-platinum interfaces and facilitate the electrolyte transportation as well. In comparison with no catalytic activity of bare nanoporous gold, the catalytic activity of hierarchical nanoporous gold-platinum towards electrochemical oxidation of methanol increases with the loading level of platinum shells, resulting in the highest electrochemical area of 70.4 m2·g−1 after the normalization by the mass of platinum. Heterogeneous gold-platinum interfaces affect the tolerance of the absorbed intermediate species because of the oxidization by the oxygenated species absorbed on the gold surface and the enhanced ion transportation within the porous platinum shell. PMID:24621809

Alcohol conversion

DOEpatents

Wachs, Israel E.; Cai, Yeping

2002-01-01

Preparing an aldehyde from an alcohol by contacting the alcohol in the presence of oxygen with a catalyst prepared by contacting an intimate mixture containing metal oxide support particles and particles of a catalytically active metal oxide from Groups VA, VIA, or VIIA, with a gaseous stream containing an alcohol to cause metal oxide from the discrete catalytically active metal oxide particles to migrate to the metal oxide support particles and to form a monolayer of catalytically active metal oxide on said metal oxide support particles.

Catalyst and method for aqueous phase reactions

DOEpatents

Elliott, Douglas C.; Hart, Todd R.

1999-01-01

The present invention is a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional metal deposited onto the support in a second dispersed phase. The additional metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase without substantially affecting the catalytic activity, thereby increasing the life time of the catalyst.

INVESTIGATION OF SELECTIVE CATALYTIC REDUCTION IMPACT ON MERCURY SPECIATION UNDER SIMULATED NOX EMISSION CONTROL CONDITIONS

EPA Science Inventory

Selective catalytic reduction (SCR) technology is being increasingly applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury in the coal com...

Catalytic conversion of lignin pyrolysis model compound- guaiacol and its kinetic model including coke formation.

PubMed

Zhang, Huiyan; Wang, Yun; Shao, Shanshan; Xiao, Rui

2016-11-21

Lignin is the most difficult to be converted and most easy coking component in biomass catalytic pyrolysis to high-value liquid fuels and chemicals. Catalytic conversion of guaiacol as a lignin model compound was conducted in a fixed-bed reactor over ZSM-5 to investigate its conversion and coking behaviors. The effects of temperature, weight hourly space velocity (WHSV) and partial pressure on product distribution were studied. The results show the maximum aromatic carbon yield of 28.55% was obtained at temperature of 650 °C, WHSV of 8 h -1 and partial pressure of 2.38 kPa, while the coke carbon yield was 19.55%. The reaction pathway was speculated to be removing methoxy group to form phenols with further aromatization to form aromatics. The amount of coke increased with increasing reaction time. The surface area and acidity of catalysts declined as coke formed on the acid sites and blocked the pore channels, which led to the decrease of aromatic yields. Finally, a kinetic model of guaiacol catalytic conversion considering coke deposition was built based on the above reaction pathway to properly predict product distribution. The experimental and model predicting data agreed well. The correlation coefficient of all equations were all higher than 0.90.

Catalytic conversion of lignin pyrolysis model compound- guaiacol and its kinetic model including coke formation

PubMed Central

Zhang, Huiyan; Wang, Yun; Shao, Shanshan; Xiao, Rui

2016-01-01

Lignin is the most difficult to be converted and most easy coking component in biomass catalytic pyrolysis to high-value liquid fuels and chemicals. Catalytic conversion of guaiacol as a lignin model compound was conducted in a fixed-bed reactor over ZSM-5 to investigate its conversion and coking behaviors. The effects of temperature, weight hourly space velocity (WHSV) and partial pressure on product distribution were studied. The results show the maximum aromatic carbon yield of 28.55% was obtained at temperature of 650 °C, WHSV of 8 h−1 and partial pressure of 2.38 kPa, while the coke carbon yield was 19.55%. The reaction pathway was speculated to be removing methoxy group to form phenols with further aromatization to form aromatics. The amount of coke increased with increasing reaction time. The surface area and acidity of catalysts declined as coke formed on the acid sites and blocked the pore channels, which led to the decrease of aromatic yields. Finally, a kinetic model of guaiacol catalytic conversion considering coke deposition was built based on the above reaction pathway to properly predict product distribution. The experimental and model predicting data agreed well. The correlation coefficient of all equations were all higher than 0.90. PMID:27869228

Structural and Functional Characterization of an Ancient Bacterial Transglutaminase Sheds Light on the Minimal Requirements for Protein Cross-Linking.

PubMed

Fernandes, Catarina G; Plácido, Diana; Lousa, Diana; Brito, José A; Isidro, Anabela; Soares, Cláudio M; Pohl, Jan; Carrondo, Maria A; Archer, Margarida; Henriques, Adriano O

2015-09-22

Transglutaminases are best known for their ability to catalyze protein cross-linking reactions that impart chemical and physical resilience to cellular structures. Here, we report the crystal structure and characterization of Tgl, a transglutaminase from the bacterium Bacillus subtilis. Tgl is produced during sporulation and cross-links the surface of the highly resilient spore. Tgl-like proteins are found only in spore-forming bacteria of the Bacillus and Clostridia classes, indicating an ancient origin. Tgl is a single-domain protein, produced in active form, and the smallest transglutaminase characterized to date. We show that Tgl is structurally similar to bacterial cell wall endopeptidases and has an NlpC/P60 catalytic core, thought to represent the ancestral unit of the cysteine protease fold. We show that Tgl functions through a unique partially redundant catalytic dyad formed by Cys116 and Glu187 or Glu115. Strikingly, the catalytic Cys is insulated within a hydrophobic tunnel that traverses the molecule from side to side. The lack of similarity of Tgl to other transglutaminases together with its small size suggests that an NlpC/P60 catalytic core and insulation of the active site during catalysis may be essential requirements for protein cross-linking.

The structure of S . lividans acetoacetyl-CoA synthetase shows a novel interaction between the C-terminal extension and the N-terminal domain

DOE PAGES

Mitchell, Carter A.; Tucker, Alex C.; Escalante-Semerena, Jorge C.; ...

2014-12-09

The adenosine monoposphate-forming acyl-CoA synthetase enzymes catalyze a two-step reaction that involves the initial formation of an acyl adenylate that reacts in a second partial reaction to form a thioester between the acyl substrate and CoA. These enzymes utilize a Domain Alternation catalytic mechanism, whereby a ~110 residue C-terminal domain rotates by 140° to form distinct catalytic conformations for the two partial reactions. In this paper, the structure of an acetoacetyl-CoA synthetase (AacS) is presented that illustrates a novel aspect of this C-terminal domain. Specifically, several acetyl- and acetoacetyl-CoA synthetases contain a 30-residue extension on the C-terminus compared to othermore » members of this family. Finally, whereas residues from this extension are disordered in prior structures, the AacS structure shows that residues from this extension may interact with key catalytic residues from the N-terminal domain.« less

Detection of Damaged DNA Bases by DNA Glycosylase Enzymes†

PubMed Central

Friedman, Joshua I.; Stivers, James T.

2010-01-01

A fundamental and shared process in all forms of life is the use of DNA glycosylase enzymes to excise rare damaged bases from genomic DNA. Without such enzymes, the highly-ordered primary sequences of genes would rapidly deteriorate. Recent structural and biophysical studies are beginning to reveal a fascinating multistep mechanism for damaged base detection that begins with short-range sliding of the glycosylase along the DNA chain in a distinct conformation we refer to as the search complex (SC). Sliding is frequently punctuated by the formation of a transient “interrogation” complex (IC) where the enzyme extrahelically inspects both normal and damaged bases in an exosite pocket that is distant from the active site. When normal bases are presented in the exosite, the IC rapidly collapses back to the SC, while a damaged base will efficiently partition forward into the active site to form the catalytically competent excision complex (EC). Here we review the unique problems associated with enzymatic detection of rare damaged DNA bases in the genome, and emphasize how each complex must have specific dynamic properties that are tuned to optimize the rate and efficiency of damage site location. PMID:20469926

The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.

PubMed

Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M

2011-01-07

Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully understanding the activity of gold are considered.

Fe-Impregnated Mineral Colloids for Peroxide Activation: Effects of Mineral Substrate and Fe Precursor.

PubMed

Li, Yue; Machala, Libor; Yan, Weile

2016-02-02

Heterogeneous iron species at the mineral/water interface are important catalysts for the generation of reactive oxygen species at circumneutral pH. One significant pathway leading to the formation of such species arises from deposition of dissolved iron onto mineral colloids due to changes in redox conditions. This study investigates the catalytic properties of Fe impregnated on silica, alumina, and titania nanoparticles (as prototypical mineral colloids). Fe impregnation was carried out by immersing the mineral nanoparticles in dilute Fe(II) or Fe(III) solutions at pH 6 and 3, respectively, in an aerobic environment. The uptake of iron per unit surface area follows the order of nTiO2 > nAl2O3 > nSiO2 for both types of Fe precursors. Impregnation of mineral particles in Fe(II) solutions results in predominantly Fe(III) species due to efficient surface-mediated oxidation. The catalytic activity of the impregnated solids to produce hydroxyl radical (·OH) from H2O2 decomposition was evaluated using benzoic acid as a probe compound under dark conditions. Invariably, the rates of benzoic acid oxidation with different Fe-laden particles increase with the surface density of Fe until a critical density above which the catalytic activity approaches a plateau, suggesting active Fe species are formed predominantly at low surface loadings. The critical surface density of Fe varies with the mineral substrate as well as the aqueous Fe precursor. Fe impregnated on TiO2 exhibits markedly higher activity than its Al2O3 and SiO2 counterparts. The speciation of interfacial Fe is analyzed with diffuse reflectance UV-vis analysis and interpretation of the data in the context of benzoic oxidation rates suggests that the surface activity of the solids for ·OH generation correlates strongly with the isolated (i.e., mononuclear) Fe species. Therefore, iron dispersed on mineral colloids is a significant form of reactive iron surfaces in the aquatic environment.

Enhanced photo-catalytic activity of ordered mesoporous indium oxide nanocrystals in the conversion of CO2 into methanol.

PubMed

Gondal, M A; Dastageer, M A; Oloore, L E; Baig, U; Rashid, S G

2017-07-03

Ordered mesoporous indium oxide nanocrystal (m-In 2 O 3 ) was synthesized by nanocasting technique, in which highly ordered mesoporous silca (SBA-15) was used as structural matrix. X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halanda (BJH) studies were carried out on m-In 2 O 3 and the results revealed that this material has a highly ordered mesoporous surface with reduced grain size, increased surface area and surface volume compared to the non porous indium oxide. The diffuse reluctance spectrum exhibited substantially improved light absorption efficiency in m-In 2 O 3 compared to normal indium oxide, however, no considerable change in the band gap energies of these materials was observed. When m-In 2 O 3 was used as a photo-catalyst in the photo-catalytic process of converting carbon dioxide (CO 2 ) into methanol under the pulsed laser radiation of 266-nm wavelengths, an enhanced photo-catalytic activity with the quantum efficiency of 4.5% and conversion efficiency of 46.3% were observed. It was found that the methanol production yield in this chemical process is as high as 485 µlg -1 h -1 after 150 min of irradiation, which is substantially higher than the yields reported in the literature. It is quite clear from the results that the introduction of mesoporosity in indium oxide, and the consequent enhancement of positive attributes required for a photo-catalyst, transformed photo-catalytically weak indium oxide into an effective photo-catalyst for the conversion of CO 2 into methanol.

Detailed functional analysis of two clinical glucose-6-phosphate dehydrogenase (G6PD) variants, G6PDViangchan and G6PDViangchan+Mahidol: Decreased stability and catalytic efficiency contribute to the clinical phenotype.

PubMed

Boonyuen, Usa; Chamchoy, Kamonwan; Swangsri, Thitiluck; Saralamba, Naowarat; Day, Nicholas P J; Imwong, Mallika

2016-06-01

Deficiency of glucose-6-phosphate dehydrogenase (G6PD) is an X-linked hereditary genetic defect that is the most common polymorphism and enzymopathy in humans. To investigate functional properties of two clinical variants, G6PDViangchan and G6PDViangchan+Mahidol, these two mutants were created by overlap-extension PCR, expressed in Escherichia coli and purified to homogeneity. We describe an overexpression and purification method to obtain substantial amounts of functionally active protein. The KM for G6P of the two variants was comparable to the KM of the native enzyme, whereas the KM for NADP(+) was increased 5-fold for G6PDViangchan and 8-fold for G6PDViangchan+Mahidol when compared with the native enzyme. Additionally, kcat of the mutant enzymes was markedly reduced, resulting in a 10- and 18-fold reduction in catalytic efficiency for NADP(+) catalysis for G6PDViangchan and G6PDViangchan+Mahidol, respectively. Furthermore, the two variants demonstrated significant reduction in thermostability, but similar susceptibility to trypsin digestion, when compared with the wild-type enzyme. The presence of NADP(+) is shown to improve the stability of G6PD enzymes. This is the first report indicating that protein instability and reduced catalytic efficiency are responsible for the reduced catalytic activity of G6PDViangchan and G6PDViangchan+Mahidol and, as a consequence, contribute to the clinical phenotypes of these two clinical variants. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

H2O-Polyaluminium chloride-TBAB as synergistic catalysts for the synthesis of cyclic carbonate

NASA Astrophysics Data System (ADS)

Liu, X. J.; Yan, P.; Han, Y.

2018-01-01

An efficient catalytic system consisting of H2O, Polyaluminium chloride (PAC) and Tetrabutylammonium bromide (TBAB) was applied to the cycloaddition of carbon dioxide (CO2) to epoxides under mild conditions. Their catalytic cycloaddition activities were found to be well correlated with H2O and polyaluminium chloride, which had a synergetic effect with the halide anion of TBAB. The presence of H2O and PAC could remarkably improve the yield of propylene carbonate (PC) by which the reaction yield is about 4-5 times higher than TBAB. alone.The catalytic system also exhibited excellent cycloaddition activities for various epoxide substrates.

Immobilization of a molecular catalyst on carbon nanotubes for highly efficient electro-catalytic water oxidation.

PubMed

Li, Fusheng; Li, Lin; Tong, Lianpeng; Daniel, Quentin; Göthelid, Mats; Sun, Licheng

2014-11-21

Electrochemically driven water oxidation has been performed using a molecular water oxidation catalyst immobilized on hybrid carbon nanotubes and nano-material electrodes. A high turnover frequency (TOF) of 7.6 s(-1) together with a high catalytic current density of 2.2 mA cm(-2) was successfully obtained at an overpotential of 480 mV after 1 h of bulk electrolysis.

Chemiluminescence analyzer of NOx as a high-throughput screening tool in selective catalytic reduction of NO

PubMed Central

Oh, Kwang Seok; Woo, Seong Ihl

2011-01-01

A chemiluminescence-based analyzer of NOx gas species has been applied for high-throughput screening of a library of catalytic materials. The applicability of the commercial NOx analyzer as a rapid screening tool was evaluated using selective catalytic reduction of NO gas. A library of 60 binary alloys composed of Pt and Co, Zr, La, Ce, Fe or W on Al2O3 substrate was tested for the efficiency of NOx removal using a home-built 64-channel parallel and sequential tubular reactor. The NOx concentrations measured by the NOx analyzer agreed well with the results obtained using micro gas chromatography for a reference catalyst consisting of 1 wt% Pt on γ-Al2O3. Most alloys showed high efficiency at 275 °C, which is typical of Pt-based catalysts for selective catalytic reduction of NO. The screening with NOx analyzer allowed to select Pt-Ce(X) (X=1–3) and Pt–Fe(2) as the optimal catalysts for NOx removal: 73% NOx conversion was achieved with the Pt–Fe(2) alloy, which was much better than the results for the reference catalyst and the other library alloys. This study demonstrates a sequential high-throughput method of practical evaluation of catalysts for the selective reduction of NO. PMID:27877438

Catalytic biofilms on structured packing for the production of glycolic acid.

PubMed

Li, Xuan Zhong; Hauer, Bernhard; Rosche, Bettina

2013-02-01

While structured packing modules are known to be efficient for surface wetting and gas-liquid exchange in abiotic surface catalysis, this model study explores structured packing as a growth surface for catalytic biofilms. Microbial biofilms have been proposed as self-immobilized and self-regenerating catalysts for the production of chemicals. A concern is that the complex and dynamic nature of biofilms may cause fluctuations in their catalytic performance over time or may affect process reproducibility. An aerated continuous trickle-bed biofilm reactor system was designed with a 3 L structured packing, liquid recycling and pH control. Pseudomonas diminuta established a biofilm on the stainless steel structured packing with a specific surface area of 500 m2 m-3 and catalyzed the oxidation of ethylene glycol to glycolic acid for over two months of continuous operation. A steady-state productivity of up to 1.6 gl-1h-1 was achieved at a dilution rate of 0.33 h-1. Process reproducibility between three independent runs was excellent, despite process interruptions and activity variations in cultures grown from biofilm effluent cells. The results demonstrate the robustness of a catalytic biofilm on structured packing, despite its dynamic nature. Implementation is recommended for whole-cell processes that require efficient gas-liquid exchange, catalyst retention for continuous operation, or improved catalyst stability.

Heterogeneous Single-Atom Catalyst for Visible-Light-Driven High-Turnover CO2 Reduction: The Role of Electron Transfer.

PubMed

Gao, Chao; Chen, Shuangming; Wang, Ying; Wang, Jiawen; Zheng, Xusheng; Zhu, Junfa; Song, Li; Zhang, Wenkai; Xiong, Yujie

2018-03-01

Visible-light-driven conversion of CO 2 into chemical fuels is an intriguing approach to address the energy and environmental challenges. In principle, light harvesting and catalytic reactions can be both optimized by combining the merits of homogeneous and heterogeneous photocatalysts; however, the efficiency of charge transfer between light absorbers and catalytic sites is often too low to limit the overall photocatalytic performance. In this communication, it is reported that the single-atom Co sites coordinated on the partially oxidized graphene nanosheets can serve as a highly active and durable heterogeneous catalyst for CO 2 conversion, wherein the graphene bridges homogeneous light absorbers with single-atom catalytic sites for the efficient transfer of photoexcited electrons. As a result, the turnover number for CO production reaches a high value of 678 with an unprecedented turnover frequency of 3.77 min -1 , superior to those obtained with the state-of-the-art heterogeneous photocatalysts. This work provides fresh insights into the design of catalytic sites toward photocatalytic CO 2 conversion from the angle of single-atom catalysis and highlights the role of charge kinetics in bridging the gap between heterogeneous and homogeneous photocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of magnetic imprinted graphene oxide composite for catalytic degradation of Congo red under dark ambient conditions.

PubMed

Yang, Xiaochao; You, Xiaoxiao; Zhang, Bin; Guo, Chuigen; Yu, Chaosheng

2017-10-01

Magnetic imprinted N-doped P25/Fe 3 O 4 -graphene oxide (MIGNT) was prepared with methyl orange as the dummy template and pyrrole as functional monomer for catalytic degradation of Congo red (CR). Hummers method and the hydrothermal method were used to synthesize Fe 3 O 4 -GO and N-doped P25, respectively. The results of adsorption and degradation experiments showed that the adsorption capacity and catalytic degradation ability of the imprinted composite for CR were obviously higher than those of a non-imprinted one. Moreover, the effect factors on degradation efficiency of CR, such as the initial concentration of CR, catalysis time, pH of the solution and temperature, were investigated. The MIGNT was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, a physical property measurement system and a thermal gravimetric analyzer. The degradation products of CR were detected with high performance liquid chromatography and a mass spectrometer. The MIGNT was a brand-new imprinted composite and had high degradation efficiency for CR under dark ambient conditions. The MIGNT could be recycled conveniently, due to its magnetic property, and could be used as an effective, environmentally friendly and low-cost catalytic degradation material for the treatment of water contaminated by CR.

Determining the Catalytic Activity of Transition Metal-Doped TiO2 Nanoparticles Using Surface Spectroscopic Analysis

NASA Astrophysics Data System (ADS)

Yang, Sena; Lee, Hangil

2017-11-01

The modified TiO2 nanoparticles (NPs) to enhance their catalytic activities by doping them with the five transition metals (Cr, Mn, Fe, Co, and Ni) have been investigated using various surface analysis techniques such as scanning electron microscopy (SEM), Raman spectroscopy, scanning transmission X-ray microscopy (STXM), and high-resolution photoemission spectroscopy (HRPES). To compare catalytic activities of these transition metal-doped TiO2 nanoparticles (TM-TiO2) with those of TiO2 NPs, we monitored their performances in the catalytic oxidation of 2-aminothiophenol (2-ATP) by using HRPES and on the oxidation of 2-ATP in aqueous solution by taking electrochemistry (EC) measurements. As a result, we clearly investigate that the increased defect structures induced by the doped transition metal are closely correlated with the enhancement of catalytic activities of TiO2 NPs and confirm that Fe- and Co-doped TiO2 NPs can act as efficient catalysts.

Heterogeneous catalytic ozonation of biologically pretreated Lurgi coal gasification wastewater using sewage sludge based activated carbon supported manganese and ferric oxides as catalysts.

PubMed

Zhuang, Haifeng; Han, Hongjun; Hou, Baolin; Jia, Shengyong; Zhao, Qian

2014-08-01

Sewage sludge of biological wastewater treatment plant was converted into sewage sludge based activated carbon (SBAC) with ZnCl₂ as activation agent, which supported manganese and ferric oxides as catalysts (including SBAC) to improve the performance of ozonation of real biologically pretreated Lurgi coal gasification wastewater. The results indicated catalytic ozonation with the prepared catalysts significantly enhanced performance of pollutants removal and the treated wastewater was more biodegradable and less toxic than that in ozonation alone. On the basis of positive effect of higher pH and significant inhibition of radical scavengers in catalytic ozonation, it was deduced that the enhancement of catalytic activity was responsible for generating hydroxyl radicals and the possible reaction pathway was proposed. Moreover, the prepared catalysts showed superior stability and most of toxic and refractory compounds were eliminated at successive catalytic ozonation runs. Thus, the process with economical, efficient and sustainable advantages was beneficial to engineering application. Copyright © 2014 Elsevier Ltd. All rights reserved.

Mutational analysis of polynucleotide phosphorylase from Escherichia coli.

PubMed

Jarrige, Anne; Bréchemier-Baey, Dominique; Mathy, Nathalie; Duché, Ophélie; Portier, Claude

2002-08-16

Polynucleotide phosphorylase (PNPase), a homotrimeric exoribonuclease present in bacteria, is involved in mRNA degradation. In Escherichia coli, expression of this enzyme is autocontrolled at the translational level. We introduced about 30 mutations in the pnp gene by site-directed mutagenesis, most of them in phylogenetically conserved residues, and determined their effects on the three catalytic activities of PNPase, phosphorolysis, polymerisation and phosphate exchange, as well as on the efficiency of translational repression. The data are presented and discussed in the light of the crystallographic structure of PNPase from Streptomyces antibioticus. The results show that both PNPase activity and the presence of the KH and S1 RNA-binding domains are required for autocontrol. Deletions of these RNA-binding domains do not abolish any of the three catalytic activities, indicating that they are contained in a domain independent of the catalytic centre. Moreover, the catalytic centre was located around the tungsten-binding site identified by crystallography. Some mutations affect the three catalytic activities differently, an observation consistent with the presence of different subsites.

Facile fabrication of hollow mesosphere of crystalline SnO2 nanoparticles and synthesis of SnO2@SWCNTs@Reduced Graphene Oxide nanocomposite as efficient Pt-Free counter electrode for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Khan, Muhammad Wasim; Yao, Jixin; Zhang, Kang; Zuo, Xueqin; Yang, Qun; Tang, Huaibao; Ur Rehman, Khalid Mehmood; Li, Guang; Wu, Mingzai; Zhu, Kerong; Zhang, Haijun

2018-06-01

In this research, SnO2@SWCNTs@Reduced Graphene Oxide based nanocomposite was synthesized by a one step hydrothermal method and reported new cost effective platinum-free counter-electrodes (CEs) in dye-sensitized solar cells (DSSCs). The CEs were formed by using the nanocomposites with the help of a pipette using a doctor-blade technique. The efficiency of this nanocomposite revealed significant elctrocatalytic properties upon falling the triiodide, possessing to synergistic effect of SnO2 nano particles and improved conductivity when SWCNTs dispersed on graphene sheet. Therefore, the power conversion efficiency (PCE) of prepared SnO2@SWCNTs@RGO nanocomposite CE attained of (6.1%) in DSSCs which is equivalent to the value (6.2%) which attained to the value (6.2%) with pure Pt CE as a reference. SnO2@SWCNTs@RGO nanocomposite CEs give more stable catalytic activities for triiodide reduction than SnO2 and SWCNTs CEs in the cyclic voltammetry (CV) analysis. Furthermore, to the subsistence of graphene oxide, the nanocomposite acquired both higher stability and efficiency in the nanocomposite.

The study of integrated coal-gasifier molten carbonate fuel cell systems

NASA Technical Reports Server (NTRS)

1983-01-01

A novel integration concept for a coal-fueled coal gasifier-molten carbonate fuel cell power plant was studied. Effort focused on determining the efficiency potential of the concept, design, and development requirements of the processes in order to achieve the efficiency. The concept incorporates a methane producing catalytic gasifier of the type previously under development by Exxon Research and Development Corp., a reforming molten carbonate fuel cell power section of the type currently under development by United Technologies Corp., and a gasifier-fuel cell recycle loop. The concept utilizes the fuel cell waste heat, in the form of hydrogen and carbon monoxide, to generate additional fuel in the coal gasifier, thereby eliminating the use of both an O2 plant and a stream bottoming cycle from the power plant. The concept has the potential for achieving coal-pile-to-busbar efficiencies of 50-59%, depending on the process configuration and degree of process configuration and degree of process development requirements. This is significantly higher than any previously reported gasifier-molten carbonate fuel cell system.

Supported versus colloidal zinc oxide for advanced oxidation processes

NASA Astrophysics Data System (ADS)

Laxman, Karthik; Al Rashdi, Manal; Al Sabahi, Jamal; Al Abri, Mohammed; Dutta, Joydeep

2017-07-01

Photocatalysis is a green technology which typically utilizes either supported or colloidal catalysts for the mineralization of aqueous organic contaminants. Catalyst surface area and surface energy are the primary factors determining its efficiency, but correlation between the two is still unclear. This work explores their relation and hierarchy in a photocatalytic process involving both supported and colloidal catalysts. In order to do this the active surface areas of supported zinc oxide nanorods (ZnO NR's) and colloidal zinc oxide nanoparticles (having different surface energies) were equalized and their phenol oxidation mechanism and capacity was analyzed. It was observed that while surface energy had subtle effects on the oxidation rate of the catalysts, the degradation efficiency was primarily a function of the surface area; which makes it a better parameter for comparison when studying different catalyst forms of the same material. Thus we build a case for the use of supported catalysts, wherein their catalytic efficiency was tested to be unaltered over several days under both natural and artificial light, suggesting their viability for practical applications.

Ultrafine cobalt nanoparticles supported on reduced graphene oxide: Efficient catalyst for fast reduction of hexavalent chromium at room temperature

NASA Astrophysics Data System (ADS)

Xu, Tingting; Xue, Jinjuan; Zhang, Xiaolei; He, Guangyu; Chen, Haiqun

2017-04-01

A novel composite ultrafine cobalt nanoparticles-reduced graphene oxide (Co-RGO) was firstly synthesized through a modified one-step solvothermal method with Co(OH)2 as the precursor. The prepared low-cost Co-RGO composite exhibited excellent catalytic activity for the reduction of highly toxic Cr(VI) to nontoxic Cr(III) at room temperature when formic acid (HCOOH) was employed as the reductant, and its catalytic performance was even comparable with that of noble metal-based catalysts in the same reduction reaction. Moreover, Co-RGO composite could be readily recovered under an external magnetic field and efficiently participated in recycled reaction for Cr(VI) reduction.

Photolytic AND Catalytic Destruction of Organic Waste Water Pollutants

NASA Astrophysics Data System (ADS)

Torosyan, V. F.; Torosyan, E. S.; Kryuchkova, S. O.; Gromov, V. E.

2017-01-01

The system: water supply source - potable and industrial water - wastewater - sewage treatment - water supply source is necessary for water supply and efficient utilization of water resources. Up-to-date technologies of waste water biological treatment require for special microorganisms, which are technologically complex and expensive but unable to solve all the problems. Application of photolytic and catalytically-oxidizing destruction is quite promising. However, the most reagents are strong oxidizers in catalytic oxidation of organic substances and can initiate toxic substance generation. Methodic and scientific approaches to assess bread making industry influence on the environment have been developed in this paper in order to support forecasting and taking technological decisions concerning reduction of this influence. Destructive methods have been tested: ultra violet irradiation and catalytic oxidation for extraction of organic compounds from waste water by natural reagents.

Effect of High-Pressure Treatment on Catalytic and Physicochemical Properties of Pepsin.

PubMed

Wang, Jianan; Bai, Tenghui; Ma, Yaping; Ma, Hanjun

2017-10-11

For a long time, high-pressure treatment has been used to destroy the compact structures of natural proteins in order to promote subsequent enzymatic hydrolysis. However, there are few reports evaluating the feasibility of directly improving the catalytic capability of proteases by using high-pressure treatments. In this study, the effects of high-pressure treatment on the catalytic capacity and structure of pepsin were investigated, and the relationship between its catalytic properties and changes in its physicochemical properties was explored. It was found that high-pressure treatment could lead to changes of the sulfhydryl group/disulfide bond content, hydrophobicity, hydrodynamic radius, intrinsic viscosity, and subunit composition of pepsin, and the conformational change of pepsin resulted in improvement to its enzymatic activity and hydrolysis efficiency, which had an obvious relationship with the high-pressure treatment conditions.

Catalytic ignition model in a monolithic reactor with in-depth reaction

NASA Technical Reports Server (NTRS)

Tien, Ta-Ching; Tien, James S.

1990-01-01

Two transient models have been developed to study the catalytic ignition in a monolithic catalytic reactor. The special feature in these models is the inclusion of thermal and species structures in the porous catalytic layer. There are many time scales involved in the catalytic ignition problem, and these two models are developed with different time scales. In the full transient model, the equations are non-dimensionalized by the shortest time scale (mass diffusion across the catalytic layer). It is therefore accurate but is computationally costly. In the energy-integral model, only the slowest process (solid heat-up) is taken as nonsteady. It is approximate but computationally efficient. In the computations performed, the catalyst is platinum and the reactants are rich mixtures of hydrogen and oxygen. One-step global chemical reaction rates are used for both gas-phase homogeneous reaction and catalytic heterogeneous reaction. The computed results reveal the transient ignition processes in detail, including the structure variation with time in the reactive catalytic layer. An ignition map using reactor length and catalyst loading is constructed. The comparison of computed results between the two transient models verifies the applicability of the energy-integral model when the time is greater than the second largest time scale of the system. It also suggests that a proper combined use of the two models can catch all the transient phenomena while minimizing the computational cost.

Regulation of Catalytic and Non-catalytic Functions of the Drosophila Ste20 Kinase Slik by Activation Segment Phosphorylation.

PubMed

Panneton, Vincent; Nath, Apurba; Sader, Fadi; Delaunay, Nathalie; Pelletier, Ariane; Maier, Dominic; Oh, Karen; Hipfner, David R

2015-08-21

Protein kinases carry out important functions in cells both by phosphorylating substrates and by means of regulated non-catalytic activities. Such non-catalytic functions have been ascribed to many kinases, including some members of the Ste20 family. The Drosophila Ste20 kinase Slik phosphorylates and activates Moesin in developing epithelial tissues to promote epithelial tissue integrity. It also functions non-catalytically to promote epithelial cell proliferation and tissue growth. We carried out a structure-function analysis to determine how these two distinct activities of Slik are controlled. We find that the conserved C-terminal coiled-coil domain of Slik, which is necessary and sufficient for apical localization of the kinase in epithelial cells, is not required for Moesin phosphorylation but is critical for the growth-promoting function of Slik. Slik is auto- and trans-phosphorylated in vivo. Phosphorylation of at least two of three conserved sites in the activation segment is required for both efficient catalytic activity and non-catalytic signaling. Slik function is thus dependent upon proper localization of the kinase via the C-terminal coiled-coil domain and activation via activation segment phosphorylation, which enhances both phosphorylation of substrates like Moesin and engagement of effectors of its non-catalytic growth-promoting activity. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Synthesis and catalytic performance of SiO2@Ni and hollow Ni microspheres

NASA Astrophysics Data System (ADS)

Liu, Xin; Liu, Yanhua; Shi, Xueting; Yu, Zhengyang; Feng, Libang

2016-11-01

Nickel (Ni) catalyst has been widely used in catalytic reducing reactions such as catalytic hydrogenation of organic compounds and catalytic reduction of organic dyes. However, the catalytic efficiency of pure Ni is low. In order to improve the catalytic performance, Ni nanoparticle-loaded microspheres can be developed. In this study, we have prepared Ni nanoparticle-loaded microspheres (SiO2@Ni) and hollow Ni microspheres using two-step method. SiO2@Ni microspheres with raspberry-like morphology and core-shell structure are synthesized successfully using SiO2 microsphere as a template and Ni2+ ions are adsorbed onto SiO2 surfaces via electrostatic interaction and then reduced and deposited on surfaces of SiO2 microspheres. Next, the SiO2 cores are removed by NaOH etching and the hollow Ni microspheres are prepared. The NaOH etching time does no have much influence on the crystal structure, shape, and surface morphology of SiO2@Ni; however, it can change the phase composition evidently. The hollow Ni microspheres are obtained when the NaOH etching time reaches 10 h and above. The as-synthesized SiO2@Ni microspheres exhibit much higher catalytic performance than the hollow Ni microspheres and pure Ni nanoparticles in the catalytic reduction of methylene blue. Meanwhile, the SiO2@Ni catalyst has high stability and hence it can be recycled for reuse.

PCDD/F adsorption and destruction in the flue gas streams of MWI and MSP via Cu and Fe catalysts supported on carbon.

PubMed

Chang, Shu Hao; Yeh, Jhy Wei; Chein, Hung Min; Hsu, Li Yeh; Chi, Kai Hsien; Chang, Moo Been

2008-08-01

Catalytic destruction has been applied to control polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) emissions from different facilities. The cost of carbon-based catalysts is considerably lower than that of the metal oxide or zeolite-based catalysts used in the selective catalytic reduction (SCR) system. In this study, destruction and adsorption efficiencies of PCDD/Fs achieved with Cu/C and Fe/C catalysts from flue gas streams of a metal smelting plant (MSP) and a large-scale municipal waste incinerator (MWI), respectively, are evaluated via the pilot-scale catalytic reactor system (PCRS). The results indicate that Cu and Fe catalysts supported on carbon surface are capable of decomposing and adsorbing PCDD/ Fs from gas streams. In the testing sources of MSP and MWI, the PCDD/F removal efficiencies achieved with Cu/C catalyst at 250 degrees C reach 96%, however, the destruction efficiencies are negative (-1,390% and -112%, respectively) due to significant PCDD/F formation on catalyst promoted by copper. In addition, Fe/C catalyst is of higher removal and destruction efficiencies compared with Cu/C catalyst in both testing sources. The removal efficiencies of PCDD/Fs achieved with Fe/C catalyst are 97 and 94% for MSP and MWI, respectively, whereas the destruction efficiencies are both higher than 70%. Decrease of PCDD/F destruction efficiency and increase of adsorption efficiency with increasing chlorination of dioxin congeners is also observed in the test via three-layer Fe/C catalyst. Furthermore, the mass of 2,3,7,8-PCDD/Fs retained on catalyst decreases on the order of first to third layer of catalyst. Each gram Fe/C catalyst in first layer adsorbs 10.9, 6.91, and 3.04 ng 2,3,7,8-PCDD/Fs in 100 min testing duration as the operating temperature is controlled at 150, 200, and 250 degrees C, respectively.

Evidence from in Situ X-ray Absorption Spectroscopy for the Involvement of Terminal Disulfide in the Reduction of Protons by an Amorphous Molybdenum Sulfide Electrocatalyst

DOE PAGES

Lassalle-Kaiser, Benedikt; Merki, Daniel; Vrubel, Heron; ...

2015-11-26

The reduction of protons into dihydrogen is important because of its potential use in a wide range of energy applications. The preparation of efficient and cheap catalysts for this reaction is one of the issues that need to be tackled to allow the widespread use of hydrogen as an energy carrier. In this paper, we report the study of an amorphous molybdenum sulfide (MoS x) proton reducing electrocatalyst under functional conditions, using in situ X-ray absorption spectroscopy. We probed the local and electronic structures of both the molybdenum and sulfur elements for the as prepared material as well as themore » precatalytic and catalytic states. The as prepared material is very similar to MoS 3 and remains unmodified under functional conditions (pH = 2 aqueous HNO 3) in the precatalytic state (+0.3 V vs RHE). In its catalytic state (-0.3 V vs RHE), the film is reduced to an amorphous form of MoS 2 and shows spectroscopic features that indicate the presence of terminal disulfide units. These units are formed concomitantly with the release of hydrogen, and we suggest that the rate-limiting step of the HER is the reduction and protonation of these disulfide units. In conclusion, these results show the implication of terminal disulfide chemical motifs into HER driven by transition-metal sulfides and provide insight into their reaction mechanism.« less

Gas phase oxidation downstream of a catalytic combustor

NASA Technical Reports Server (NTRS)

Tien, J. S.; Anderson, D. N.

1979-01-01

Effect of the length available for gas-phase reactions downstream of the catalytic reactor on the emission of CO and unburned hydrocarbons was investigated. A premixed, prevaporized propane/air feed to a 12/cm/diameter catalytic/reactor test section was used. The catalytic reactor was made of four 2.5 cm long monolithic catalyst elements. Four water cooled gas sampling probes were located at positions between 0 and 22 cm downstream of the catalytic reactor. Measurements of unburned hydrocarbon, CO, and CO2 were made. Tests were performed with an inlet air temperature of 800 K, a reference velocity of 10 m/s, pressures of 3 and 600,000 Pa, and fuel air equivalence ratios of 0.14 to 0.24. For very lean mixtures, hydrocarbon emissions were high and CO continued to be formed downstream of the catalytic reactor. At the highest equivalence ratios tested, hydrocarbon levels were much lower and CO was oxidized to CO2 in the gas phase downstream. To achieve acceptable emissions, a downstream region several times longer than the catalytic reactor could be required.

Synthesis and Catalytic Evaluation of Dendrimer-Encapsulated Cu Nanoparticles: An Undergraduate Experiment Exploring Catalytic Nanomaterials

ERIC Educational Resources Information Center

Feng, Z. Vivian; Lyon, Jennifer L.; Croley, J. Sawyer; Crooks, Richard M.; Vanden Bout, David A.; Stevenson, Keith J.

2009-01-01

Copper nanoparticles were synthesized using generation 4 hydroxyl-terminated (G4-OH) poly(amidoamine) (PAMAM) dendrimers as templates. The synthesis is conducted by coordinating copper ions with the interior amines of the dendrimer, followed by chemical reduction to form dendrimer-encapsulated copper nanoparticles (Cu-DEN). The catalytic…

Defect Effects on TiO2 Nanosheets: Stabilizing Single Atomic Site Au and Promoting Catalytic Properties.

PubMed

Wan, Jiawei; Chen, Wenxing; Jia, Chuanyi; Zheng, Lirong; Dong, Juncai; Zheng, Xusheng; Wang, Yu; Yan, Wensheng; Chen, Chen; Peng, Qing; Wang, Dingsheng; Li, Yadong

2018-03-01

Isolated single atomic site catalysts have attracted great interest due to their remarkable catalytic properties. Because of their high surface energy, single atoms are highly mobile and tend to form aggregate during synthetic and catalytic processes. Therefore, it is a significant challenge to fabricate isolated single atomic site catalysts with good stability. Herein, a gentle method to stabilize single atomic site metal by constructing defects on the surface of supports is presented. As a proof of concept, single atomic site Au supported on defective TiO 2 nanosheets is prepared and it is discovered that (1) the surface defects on TiO 2 nanosheets can effectively stabilize Au single atomic sites through forming the Ti-Au-Ti structure; and (2) the Ti-Au-Ti structure can also promote the catalytic properties through reducing the energy barrier and relieving the competitive adsorption on isolated Au atomic sites. It is believed that this work paves a way to design stable and active single atomic site catalysts on oxide supports. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lysosome-controlled efficient ROS overproduction against cancer cells with a high pH-responsive catalytic nanosystem

NASA Astrophysics Data System (ADS)

Fu, Jingke; Shao, Yiran; Wang, Liyao; Zhu, Yingchun

2015-04-01

Excess reactive oxygen species (ROS) have been proved to damage cancer cells efficiently. ROS overproduction is thus greatly desirable for cancer therapy. To date, ROS production is generally uncontrollable and outside cells, which always bring severe side-effects in the vasculature. Since most ROS share a very short half-life and primarily react close to their site of formation, it would be more efficient if excess ROS are controllably produced inside cancer cells. Herein, we report an efficient lysosome-controlled ROS overproduction via a pH-responsive catalytic nanosystem (FeOx-MSNs), which catalyze the decomposition of H2O2 to produce considerable ROS selectively inside the acidic lysosomes (pH 5.0) of cancer cells. After a further incorporation of ROS-sensitive TMB into the nanosystem (FeOx-MSNs-TMB), both a distinct cell labeling and an efficient death of breast carcinoma cells are obtained. This lysosome-controlled efficient ROS overproduction suggests promising applications in cancer treatments.Excess reactive oxygen species (ROS) have been proved to damage cancer cells efficiently. ROS overproduction is thus greatly desirable for cancer therapy. To date, ROS production is generally uncontrollable and outside cells, which always bring severe side-effects in the vasculature. Since most ROS share a very short half-life and primarily react close to their site of formation, it would be more efficient if excess ROS are controllably produced inside cancer cells. Herein, we report an efficient lysosome-controlled ROS overproduction via a pH-responsive catalytic nanosystem (FeOx-MSNs), which catalyze the decomposition of H2O2 to produce considerable ROS selectively inside the acidic lysosomes (pH 5.0) of cancer cells. After a further incorporation of ROS-sensitive TMB into the nanosystem (FeOx-MSNs-TMB), both a distinct cell labeling and an efficient death of breast carcinoma cells are obtained. This lysosome-controlled efficient ROS overproduction suggests promising applications in cancer treatments. Electronic supplementary information (ESI) available: Experimental section, supplementary figures and characterization of as-prepared compounds. See DOI: 10.1039/c5nr00706b

Elucidation of peptide sequence effects that control the activity, size, and function of nanoparticles

NASA Astrophysics Data System (ADS)

Coppage, Ryan

Bio-inspired nanoparticle catalysis offers the opportunity to improve on current catalytic standards with respect to turnover efficiency, organic solvent use, and thermal activation. Unfortunately, projected energy demands will soon outweigh our fuel supplies. The task of creating multifunctional catalysts that both lower thermal activation and possess a number of functions in aqueous conditions is daunting. Similar to these needs, nature has evolved to create a wide range of highly specialized catalytic processes, which incorporate inorganic materials, take place in ambient temperatures, and in an aqueous environment. These specialized biological systems provide inspiration, but are not applicable to current needs. Exploitation of these biotic-abiotic systems could allow for green, multifunctional catalysts. In the resulting works, a peptide sequence has been isolated via phage display with affinity for Pd surfaces, that forms stable, peptide-capped nanoparticles. Substitution of residues results in the tuning of both nanocatalyst activity and nanoparticle size, such that a peptide surface-controlling effect can be noted. These characteristics can be exploited to ultimately understand the binding interactions among bio-inorganic interfaces, such that a rational design of biomolecules can be realized for the synthesis of highly active, green, multifunctional nanomaterials.

Pd-NiO decorated multiwalled carbon nanotubes supported on reduced graphene oxide as an efficient electrocatalyst for ethanol oxidation in alkaline medium

NASA Astrophysics Data System (ADS)

Rajesh, Dhanushkotti; Indra Neel, Pulidindi; Pandurangan, Arumugam; Mahendiran, Chinnathambi

2018-06-01

The synthesis of Pd-NiO nanoparticles decorated multiwalled carbon nanotubes (MWCNTs) on reduced graphene oxide (rGO) for ethanol electrooxidation is reported. NiO nanoparticles (NPs) were deposited on functionalized MWCNTs by wet impregnation method. Pd nanoparticles were formed on NiO-MWCNTs by the addition of PdCl2 and its reduction using NaBH4. The Pd-NiO/MWCNTs nanocomposite then deposited on rGO support using ultrasound irradiation which led to the formation of the Pd-NiO/MWCNTs/rGO electrocatalyst. The prepared electrocatalysts were characterized by XRD, SEM, HR-TEM and XPS analysis. Electrochemical measurements demonstrate that as synthesized Pd-NiO/MWCNTs/rGO electrocatalyst exhibit higher catalytic activity (90.89 mA/cm2) than either Pd/MWCNTs/rGO (43.05 mA/cm2) or Pd/C (28.0 mA/cm2) commercial catalyst. Chronoamperometry study of Pd-NiO/MWCNTs/rGO electrocatalyst showed long-term electrochemical stability. The enhanced catalytic activity of Pd-NiO/MWCNTs/rGO electrocatalyst for electrooxidation of ethanol can be attributed to the synergistic effect between Pd & NiO active sites.

Structural intermediates and directionality of the swiveling motion of Pyruvate Phosphate Dikinase

NASA Astrophysics Data System (ADS)

Minges, Alexander; Ciupka, Daniel; Winkler, Christian; Höppner, Astrid; Gohlke, Holger; Groth, Georg

2017-03-01

Pyruvate phosphate dikinase (PPDK) is a vital enzyme in cellular energy metabolism catalyzing the ATP- and Pi-dependent formation of phosphoenolpyruvate from pyruvate in C4 -plants, but the reverse reaction forming ATP in bacteria and protozoa. The multi-domain enzyme is considered an efficient molecular machine that performs one of the largest single domain movements in proteins. However, a comprehensive understanding of the proposed swiveling domain motion has been limited by not knowing structural intermediates or molecular dynamics of the catalytic process. Here, we present crystal structures of PPDKs from Flaveria, a model genus for studying the evolution of C4 -enzymes from phylogenetic ancestors. These structures resolve yet unknown conformational intermediates and provide the first detailed view on the large conformational transitions of the protein in the catalytic cycle. Independently performed unrestrained MD simulations and configurational free energy calculations also identified these intermediates. In all, our experimental and computational data reveal strict coupling of the CD swiveling motion to the conformational state of the NBD. Moreover, structural asymmetries and nucleotide binding states in the PPDK dimer support an alternate binding change mechanism for this intriguing bioenergetic enzyme.

Metallic ions catalysis for improving bioleaching yield of Zn and Mn from spent Zn-Mn batteries at high pulp density of 10.

PubMed

Niu, Zhirui; Huang, Qifei; Wang, Jia; Yang, Yiran; Xin, Baoping; Chen, Shi

2015-11-15

Bioleaching of spent batteries was often conducted at pulp density of 1.0% or lower. In this work, metallic ions catalytic bioleaching was used for release Zn and Mn from spent ZMBs at 10% of pulp density. The results showed only Cu(2+) improved mobilization of Zn and Mn from the spent batteries among tested four metallic ions. When Cu(2+) content increased from 0 to 0.8 g/L, the maximum release efficiency elevated from 47.7% to 62.5% for Zn and from 30.9% to 62.4% for Mn, respectively. The Cu(2+) catalysis boosted bioleaching of resistant hetaerolite through forming a possible intermediate CuMn2O4 which was subject to be attacked by Fe(3+) based on a cycle of Fe(3+)/Fe(2+). However, poor growth of cells, formation of KFe3(SO4)2(OH)6 and its possible blockage between cells and energy matters destroyed the cycle of Fe(3+)/Fe(2+), stopping bioleaching of hetaerolite. The chemical reaction controlled model fitted best for describing Cu(2+) catalytic bioleaching of spent ZMBs. Copyright © 2015 Elsevier B.V. All rights reserved.

Identification of optimal solar fuel electrocatalysts via high throughput in situ optical measurements

DOE PAGES

Shinde, Aniketa; Guevarra, Dan; Haber, Joel A.; ...

2014-10-21

For many solar fuel generator designs involve illumination of a photoabsorber stack coated with a catalyst for the oxygen evolution reaction (OER). In this design, impinging light must pass through the catalyst layer before reaching the photoabsorber(s), and thus optical transmission is an important function of the OER catalyst layer. Many oxide catalysts, such as those containing elements Ni and Co, form oxide or oxyhydroxide phases in alkaline solution at operational potentials that differ from the phases observed in ambient conditions. To characterize the transparency of such catalysts during OER operation, 1031 unique compositions containing the elements Ni, Co, Ce,more » La, and Fe were prepared by a high throughput inkjet printing technique. Moreover, the catalytic current of each composition was recorded at an OER overpotential of 0.33 V with simultaneous measurement of the spectral transmission. By combining the optical and catalytic properties, the combined catalyst efficiency was calculated to identify the optimal catalysts for solar fuel applications within the material library. Our measurements required development of a new high throughput instrument with integrated electrochemistry and spectroscopy measurements, which enables various spectroelectrochemistry experiments.« less

The physicochemical properties and catalytic performance of carbon-covered alumina for oxidative dehydrogenation of ethylbenzene with CO2

NASA Astrophysics Data System (ADS)

Wang, Tehua; Chong, Siying; Wang, Tongtong; Lu, Huiyi; Ji, Min

2018-01-01

In order to correlate the physicochemical properties of carbon-covered alumina (CCA) materials with their catalytic performance for oxidative dehydrogenation of ethylbenzene with CO2 (CO2-ODEB), a series of CCA materials with diverse carbon contents (8.7-31.3 wt%) and pyrolysis temperatures (600-800 °C), which were synthesized via an impregnation method followed by pyrolysis, were applied. These catalytic materials were characterized by TGA, N2 physisorption, XRD, Raman spectroscopy and XPS techniques. It was found that the catalytic performance of these CCA materials highly depended on their physicochemical properties, and the optimum CCA catalyst exhibited much better catalytic stability than conventional hydroxyl carbon nanotubes. Below an optimum value of carbon content, the CCA catalyst preserved the main pore characteristics of the Al2O3 support and its catalytic activity increased with the carbon content. Excessive carbon loading resulted in significant textural alterations and thereby decreased both the ethylbenzene conversion and styrene selectivity. On the other hand, high pyrolysis temperature was detrimental to the ordered graphitic structure of the carbon species within the Al2O3 pore. The decreased ordered graphitic degree was found to be associated with the loss of the surface active carbonyl groups, consequently hampering the catalytic efficiency of the CCA catalyst.

Protein arginine methyltransferase 7 has a novel homodimer-like structure formed by tandem repeats.

PubMed

Hasegawa, Morio; Toma-Fukai, Sachiko; Kim, Jun-Dal; Fukamizu, Akiyoshi; Shimizu, Toshiyuki

2014-05-21

Protein arginine methyltransferase 7 (PRMT7) is a member of a family of enzymes that catalyze the transfer of methyl groups from S-adenosyl-l-methionine to nitrogen atoms on arginine residues. Here, we describe the crystal structure of Caenorhabditis elegans PRMT7 in complex with its reaction product S-adenosyl-L-homocysteine. The structural data indicated that PRMT7 harbors two tandem repeated PRMT core domains that form a novel homodimer-like structure. S-adenosyl-L-homocysteine bound to the N-terminal catalytic site only; the C-terminal catalytic site is occupied by a loop that inhibits cofactor binding. Mutagenesis demonstrated that only the N-terminal catalytic site of PRMT7 is responsible for cofactor binding. Copyright © 2014 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Advanced purification of petroleum refinery wastewater by catalytic vacuum distillation.

PubMed

Yan, Long; Ma, Hongzhu; Wang, Bo; Mao, Wei; Chen, Yashao

2010-06-15

In our work, a new process, catalytic vacuum distillation (CVD) was utilized for purification of petroleum refinery wastewater that was characteristic of high chemical oxygen demand (COD) and salinity. Moreover, various common promoters, like FeCl(3), kaolin, H(2)SO(4) and NaOH were investigated to improve the purification efficiency of CVD. Here, the purification efficiency was estimated by COD testing, electrolytic conductivity, UV-vis spectrum, gas chromatography-mass spectrometry (GC-MS) and pH value. The results showed that NaOH promoted CVD displayed higher efficiency in purification of refinery wastewater than other systems, where the pellucid effluents with low salinity and high COD removal efficiency (99%) were obtained after treatment, and the corresponding pH values of effluents varied from 7 to 9. Furthermore, environment estimation was also tested and the results showed that the effluent had no influence on plant growth. Thus, based on satisfied removal efficiency of COD and salinity achieved simultaneously, NaOH promoted CVD process is an effective approach to purify petroleum refinery wastewater. Copyright 2010 Elsevier B.V. All rights reserved.

Renewable Wood Pulp Paper Reactor with Hierarchical Micro/Nanopores for Continuous-Flow Nanocatalysis.

PubMed

Koga, Hirotaka; Namba, Naoko; Takahashi, Tsukasa; Nogi, Masaya; Nishina, Yuta

2017-06-22

Continuous-flow nanocatalysis based on metal nanoparticle catalyst-anchored flow reactors has recently provided an excellent platform for effective chemical manufacturing. However, there has been limited progress in porous structure design and recycling systems for metal nanoparticle-anchored flow reactors to create more efficient and sustainable catalytic processes. In this study, traditional paper is used for a highly efficient, recyclable, and even renewable flow reactor by tailoring the ultrastructures of wood pulp. The "paper reactor" offers hierarchically interconnected micro- and nanoscale pores, which can act as convective-flow and rapid-diffusion channels, respectively, for efficient access of reactants to metal nanoparticle catalysts. In continuous-flow, aqueous, room-temperature catalytic reduction of 4-nitrophenol to 4-aminophenol, a gold nanoparticle (AuNP)-anchored paper reactor with hierarchical micro/nanopores provided higher reaction efficiency than state-of-the-art AuNP-anchored flow reactors. Inspired by traditional paper materials, successful recycling and renewal of AuNP-anchored paper reactors were also demonstrated while high reaction efficiency was maintained. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Renewable Wood Pulp Paper Reactor with Hierarchical Micro/Nanopores for Continuous‐Flow Nanocatalysis

PubMed Central

Namba, Naoko; Takahashi, Tsukasa; Nogi, Masaya; Nishina, Yuta

2017-01-01

Abstract Continuous‐flow nanocatalysis based on metal nanoparticle catalyst‐anchored flow reactors has recently provided an excellent platform for effective chemical manufacturing. However, there has been limited progress in porous structure design and recycling systems for metal nanoparticle‐anchored flow reactors to create more efficient and sustainable catalytic processes. In this study, traditional paper is used for a highly efficient, recyclable, and even renewable flow reactor by tailoring the ultrastructures of wood pulp. The “paper reactor” offers hierarchically interconnected micro‐ and nanoscale pores, which can act as convective‐flow and rapid‐diffusion channels, respectively, for efficient access of reactants to metal nanoparticle catalysts. In continuous‐flow, aqueous, room‐temperature catalytic reduction of 4‐nitrophenol to 4‐aminophenol, a gold nanoparticle (AuNP)‐anchored paper reactor with hierarchical micro/nanopores provided higher reaction efficiency than state‐of‐the‐art AuNP‐anchored flow reactors. Inspired by traditional paper materials, successful recycling and renewal of AuNP‐anchored paper reactors were also demonstrated while high reaction efficiency was maintained. PMID:28394501

Dissecting the Catalytic Mechanism of Betaine-Homocysteine S-Methyltransferase Using Intrinsic Tryptophan Fluorescence and Site-Directed Mutagenesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Castro, C.; Gratson, A.A.; Evans, J.C.

2010-03-05

Betaine-homocysteine S-methyltransferase (BHMT) is a zinc-dependent enzyme that catalyzes the transfer of a methyl group from glycine betaine (Bet) to homocysteine (Hcy) to form dimethylglycine (DMG) and methionine (Met). Previous studies in other laboratories have indicated that catalysis proceeds through the formation of a ternary complex, with a transition state mimicked by the inhibitor S-({delta}-carboxybutyl)-l-homocysteine (CBHcy). Using changes in intrinsic tryptophan fluorescence to determine the affinity of human BHMT for substrates, products, or CBHcy, we now demonstrate that the enzyme-substrate complex reaches its transition state through an ordered bi-bi mechanism in which Hcy is the first substrate to bind andmore » Met is the last product released. Hcy, Met, and CBHcy bind to the enzyme to form binary complexes with K{sub d} values of 7.9, 6.9, and 0.28 {micro}M, respectively. Binary complexes with Bet and DMG cannot be detected with fluorescence as a probe, but Bet and DMG bind tightly to BHMT-Hcy to form ternary complexes with K{sub d} values of 1.1 and 0.73 {micro}M, respectively. Mutation of each of the seven tryptophan residues in human BHMT provides evidence that the enzyme undergoes two distinct conformational changes that are reflected in the fluorescence of the enzyme. The first is induced when Hcy binds, and the second, when Bet binds. As predicted by the crystal structure of BHMT, the amino acids Trp44 and Tyr160 are involved in binding Bet, and Glu159 in binding Hcy. Replacing these residues by site-directed mutagenesis significantly reduces the catalytic efficiency (V{sub max}/K{sub m}) of the enzyme. Replacing Tyr77 with Phe abolishes enzyme activity.« less

New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Daria L.; Beltrán-Suito, Rodrigo; Thomsen, Julianne M.

2016-02-05

This paper introduces IrI(CO)2(pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*IrIII(pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO4 results in formation of a blue IrIV species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation processmore » requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting IrIV species. The species formed from oxidation of the Ir(CO)2(pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO)2(pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By 1H NMR, activated Ir(CO)2(pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3.« less