A simpler method affords evaluation of π stabilization by phenylalanine of several biochemical carbocations

2020 ◽  
Vol 18 (38) ◽  
pp. 7597-7607
Author(s):  
Thomas A. Spencer ◽  
Robert Ditchfield
Keyword(s):  
Active Sites ◽  
X Ray ◽  
Simpler Method ◽  
Simple Models

Simple models based on measurements taken from X-ray structures of relevant active sites are used to evaluate π stabilization by phenylalanine of several biochemical carbocations.

Scanning luminescence x-ray microscopy: Progress toward selective staining using microspheres

1994 ◽  
Vol 52 ◽  
pp. 74-75
Author(s):  
C. Jacobsen ◽  
J. Fu ◽  
S. Mayer ◽  
Y. Wang ◽  
S. Williams
Keyword(s):  
Visible Light ◽  
Active Sites ◽  
Light Emission ◽  
Chinese Hamster ◽  
Polystyrene Spheres ◽  
Good Resistance ◽  
X Ray ◽  
Selective Staining ◽  
Visible Light Emission ◽  
Specific Labelling

In scanning luminescence x-ray microscopy (SLXM), a high resolution x-ray probe is used to excite visible light emission (see Figs. 1 and 2). The technique has been developed with a goal of localizing dye-tagged biochemically active sites and structures at 50 nm resolution in thick, hydrated biological specimens. Following our initial efforts, Moronne et al. have begun to develop probes based on biotinylated terbium; we report here our progress towards using microspheres for tagging.Our initial experiments with microspheres were based on commercially-available carboxyl latex spheres which emitted ~ 5 visible light photons per x-ray absorbed, and which showed good resistance to bleaching under x-ray irradiation. Other work (such as that by Guo et al.) has shown that such spheres can be used for a variety of specific labelling applications. Our first efforts have been aimed at labelling ƒ actin in Chinese hamster ovarian (CHO) cells. By using a detergent/fixative protocol to load spheres into cells with permeabilized membranes and preserved morphology, we have succeeded in using commercial dye-loaded, spreptavidin-coated 0.03μm polystyrene spheres linked to biotin phalloidon to label f actin (see Fig. 3).

Structural/Texture Evolution During Facile Substitution of Ni into ZSM-5 Nanostructure vs. its Impregnation Dispersion Used in Selective Transformation of Methanol to Ethylene and Propylene

2020 ◽  
Vol 23 ◽  
Author(s):  
Parisa Sadeghpour ◽  
Mohammad Haghighi ◽  
Mehrdad Esmaeili
Keyword(s):  
High Temperature ◽  
Physicochemical Properties ◽  
Active Sites ◽  
Catalytic Performance ◽  
Fixed Bed Reactor ◽  
Light Olefins ◽  
Isomorphous Substitution ◽  
Impregnation Method ◽  
Hydrothermal Temperature ◽  
X Ray

Aim and Objective: Effect of two different modification methods for introducing Ni into ZSM-5 framework was investigated under high temperature synthesis conditions. The nickel successfully introduced into the MFI structures at different crystallization conditions to enhance the physicochemical properties and catalytic performance. Materials and Methods: A series of impregnated Ni/ZSM-5 and isomorphous substituted NiZSM-5 nanostructure catalysts were prepared hydrothermally at different high temperatures and within short times. X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Energy dispersive X-ray (EDX), Brunner, Emmett and Teller-Barrett, Joyner and Halenda (BET-BJH), Fourier transform infrared (FTIR) and Temperature-programmed desorption of ammonia (TPDNH3) were applied to investigate the physicochemical properties. Results: Although all the catalysts showed pure silica MFI–type nanosheets and coffin-like morphology, using the isomorphous substitution for Ni incorporation into the ZSM-5 framework led to the formation of materials with lower crystallinity, higher pore volume and stronger acidity compared to using impregnation method. Moreover, it was found that raising the hydrothermal temperature increased the crystallinity and enhanced more uniform incorporation of Ni atoms in the crystalline structure of catalysts. TPD-NH3 analysis demonstrated that high crystallization temperature and short crystallization time of NiZSM-5(350-0.5) resulted in fewer weak acid sites and medium acid strength. The MTO catalytic performance was tested in a fixed bed reactor at 460ºC and GHSV=10500 cm3 /gcat.h. A slightly different reaction pathway was proposed for the production of light olefins over impregnated Ni/ZSM-5 catalysts based on the role of NiO species. The enhanced methanol conversion for isomorphous substituted NiZSM-5 catalysts could be related to the most accessible active sites located inside the pores. Conclusion: The impregnated Ni/ZSM-5 catalyst prepared at low hydrothermal temperature showed the best catalytic performance, while the isomorphous substituted NiZSM-5 prepared at high temperature was found to be the active molecular sieve regarding the stability performance.

Role of the Structure and Electronic Properties of Fe2O3-MoO3 Catalyst on the Dehydration of Isopropyl Alcohol

1993 ◽  
Vol 58 (7) ◽  
pp. 1591-1599 ◽  
Author(s):  
Abd El-Aziz A. Said
Keyword(s):  
Active Sites ◽  
Isopropyl Alcohol ◽  
Oxide Catalyst ◽  
Flow System ◽  
Charge Carriers ◽  
X Ray Diffraction ◽  
X Ray ◽  
Catalyst Composition ◽  
Surface Active

Molybdenum oxide catalyst doped or mixed with (1 - 50) mole % Fe3+ ions were prepared. The structure of the original samples and the samples calcined at 400 °C were characterized using DTA, X-ray diffraction and IR spectra. Measurements of the electrical conductivity of calcined samples with and without isopropyl alcohol revealed that the conductance increases on increasing the content of Fe3+ ions up to 50 mole %. The activation energies of charge carriers were determined in presence and absence of the alcohol. The catalytic dehydration of isopropyl alcohol was carried out at 250 °C using a flow system. The results obtained showed that the doped or mixed catalysts are active and selective towards propene formation. However, the catalyst containing 40 mole % Fe3+ ions exhibited the highest activity and selectivity. Correlations were attempted to the catalyst composition with their electronic and catalytic properties. Probable mechanism for the dehydration process is proposed in terms of surface active sites.

Physicochemical and Catalytic Properties of Spinels Formed by Solid-Solid Interaction Between Fe2O3and V2O5

1996 ◽  
Vol 61 (8) ◽  
pp. 1131-1140 ◽  
Author(s):  
Abd El-Aziz Ahmed Said
Keyword(s):  
Vanadium Oxide ◽  
Active Sites ◽  
Catalyst Surface ◽  
Catalytic Properties ◽  
Flow System ◽  
Oxide Catalysts ◽  
X Ray Diffraction ◽  
Selective Catalyst ◽  
X Ray ◽  
Solid Catalysts

Vanadium oxide catalysts doped or mixed with 1-50 mole % Fe3+ ions were prepared. The structure of the original samples and those calcined from 200 up to 500 °C were characterized by TG, DTA, IR and X-ray diffraction. The SBET values and texture of the solid catalysts were investigated. The catalytic dehydration-dehydrogenation of isopropanol was carried out at 200 °C using a flow system. The results obtained showed an observable decrease in the activity of V2O5 on the addition of Fe3+ ions. Moreover, Fe2V4O13 is the more active and selective catalyst than FeVO4 spinels. The results were correlated with the active sites created on the catalyst surface.

scholarly journals Searching novel complex solid solution electrocatalysts in unconventional element combinations

Nano Research ◽  
2021 ◽  
Author(s):  
Olga A. Krysiak ◽  
Simon Schumacher ◽  
Alan Savan ◽  
Wolfgang Schuhmann ◽  
Alfred Ludwig ◽  
...  
Keyword(s):  
High Throughput ◽  
High Throughput Screening ◽  
Active Sites ◽  
Search Space ◽  
Reduction Reaction ◽  
Film Material ◽  
X Ray ◽  
High Entropy ◽  
Catalyst Composition ◽  
Scanning Transmission

AbstractDespite outstanding accomplishments in catalyst discovery, finding new, more efficient, environmentally neutral, and noble metal-free catalysts remains challenging and unsolved. Recently, complex solid solutions consisting of at least five different elements and often named as high-entropy alloys have emerged as a new class of electrocatalysts for a variety of reactions. The multicomponent combinations of elements facilitate tuning of active sites and catalytic properties. Predicting optimal catalyst composition remains difficult, making testing of a very high number of them indispensable. We present the high-throughput screening of the electrochemical activity of thin film material libraries prepared by combinatorial co-sputtering of metals which are commonly used in catalysis (Pd, Cu, Ni) combined with metals which are not commonly used in catalysis (Ti, Hf, Zr). Introducing unusual elements in the search space allows discovery of catalytic activity for hitherto unknown compositions. Material libraries with very similar composition spreads can show different activities vs. composition trends for different reactions. In order to address the inherent challenge of the huge combinatorial material space and the inability to predict active electrocatalyst compositions, we developed a high-throughput process based on co-sputtered material libraries, and performed high-throughput characterization using energy dispersive X-ray spectroscopy (EDS), scanning transmission electron microscopy (SEM), X-ray diffraction (XRD) and conductivity measurements followed by electrochemical screening by means of a scanning droplet cell. The results show surprising material compositions with increased activity for the oxygen reduction reaction and the hydrogen evolution reaction. Such data are important input data for future data-driven materials prediction.

scholarly journals Control of zeolite microenvironment for propene synthesis from methanol

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Longfei Lin ◽  
Mengtian Fan ◽  
Alena M. Sheveleva ◽  
Xue Han ◽  
Zhimou Tang ◽  
...  
Keyword(s):  
Active Sites ◽  
Inelastic Neutron Scattering ◽  
Sustainable Manufacturing ◽  
Methanol Conversion ◽  
Acid Sites ◽  
Light Olefins ◽  
Carbon Bond ◽  
X Ray ◽  
Carbon Carbon Bond ◽  
Catalytic Stability

AbstractOptimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon–carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within the pores of commercial MFI-zeolites by incorporating tantalum(V) and aluminium(III) centres into the framework. The resultant TaAlS-1 zeolite exhibits simultaneously remarkable propene selectivity (51%), propene/ethene ratio (8.3) and catalytic stability (>50 h) at full methanol conversion. In situ synchrotron X-ray powder diffraction, X-ray absorption spectroscopy and inelastic neutron scattering coupled with DFT calculations reveal that the first carbon–carbon bond is formed between an activated methanol molecule and a trimethyloxonium intermediate. The unprecedented cooperativity between tantalum(V) and Brønsted acid sites creates an optimal microenvironment for efficient conversion of methanol and thus greatly promotes the application of zeolites in the sustainable manufacturing of light olefins.

Determination of the GH3.12 protein conformation through HPLC-integrated SAXS measurements combined with X-ray crystallography

2013 ◽  
Vol 69 (10) ◽  
pp. 2072-2080 ◽  
Author(s):  
Adam Round ◽  
Elizabeth Brown ◽  
Romain Marcellin ◽  
Ulrike Kapp ◽  
Corey S. Westfall ◽  
...  
Keyword(s):  
Protein Conformation ◽  
Active Sites ◽  
Solution Structure ◽  
Critical Role ◽  
X Ray ◽  
Hplc Purification ◽  
Closed Conformation ◽  
Terminal Domain ◽  
Redundant Data ◽  
On Line

The combination of protein crystallography and small-angle X-ray scattering (SAXS) provides a powerful method to investigate changes in protein conformation. These complementary structural techniques were used to probe the solution structure of the apo and the ligand-bound forms of theArabidopsis thalianaacyl acid–amido synthetase GH3.12. This enzyme is part of the extensive GH3 family and plays a critical role in the regulation of plant hormones through the formation of amino-acid-conjugated hormone productsviaan ATP-dependent reaction mechanism. The enzyme adopts two distinct C-terminal domain orientations with `open' and `closed' active sites. Previous studies suggested that ATP only binds in the open orientation. Here, the X-ray crystal structure of GH3.12 is presented in the closed conformation in complex with the nonhydrolysable ATP analogue AMPCPP and the substrate salicylate. Using on-line HPLC purification combined with SAXS measurements, the most likely apo and ATP-bound protein conformations in solution were determined. These studies demonstrate that the C-terminal domain is flexible in the apo form and favours the closed conformation upon ATP binding. In addition, these data illustrate the efficacy of on-line HPLC purification integrated into the SAXS sample-handling environment to reliably monitor small changes in protein conformation through the collection of aggregate-free and highly redundant data.

Structural study of the X-ray-induced enzymatic reaction of octahaem cytochromecnitrite reductase

2015 ◽  
Vol 71 (5) ◽  
pp. 1087-1094 ◽  
Author(s):  
A. A. Trofimov ◽  
K. M. Polyakov ◽  
V. A. Lazarenko ◽  
A. N. Popov ◽  
T. V. Tikhonova ◽  
...  
Keyword(s):  
Nitrite Reductase ◽  
Catalytic Reaction ◽  
Active Sites ◽  
Enzymatic Reaction ◽  
Absorbed Dose ◽  
Free Form ◽  
Data Sets ◽  
X Rays ◽  
X Ray ◽  
Site Water

Octahaem cytochromecnitrite reductase from the bacteriumThioalkalivibrio nitratireducenscatalyzes the reduction of nitrite to ammonium and of sulfite to sulfide. The reducing properties of X-ray radiation and the high quality of the enzyme crystals allow study of the catalytic reaction of cytochromecnitrite reductase directly in a crystal of the enzyme, with the reaction being induced by X-rays. Series of diffraction data sets with increasing absorbed dose were collected from crystals of the free form of the enzyme and its complexes with nitrite and sulfite. The corresponding structures revealed gradual changes associated with the reduction of the catalytic haems by X-rays. In the case of the nitrite complex the conversion of the nitrite ions bound in the active sites to NO species was observed, which is the beginning of the catalytic reaction. For the free form, an increase in the distance between the oxygen ligand bound to the catalytic haem and the iron ion of the haem took place. In the case of the sulfite complex no enzymatic reaction was detected, but there were changes in the arrangement of the active-site water molecules that were presumably associated with a change in the protonation state of the sulfite ions.

Surface properties and adsorption characteristics to methylene blue and iodine of adsorbents from sludge

2010 ◽  
Vol 62 (8) ◽  
pp. 1705-1712 ◽  
Author(s):  
L. Y. Deng ◽  
G. R. Xu ◽  
G. B. Li
Keyword(s):  
Methylene Blue ◽  
Electrostatic Interactions ◽  
Active Sites ◽  
Pyrolysis Temperature ◽  
Weight Ratio ◽  
Surface Characteristics ◽  
Wastewater Sludge ◽  
X Ray ◽  
Adsorption Characteristics ◽  
Adsorbent Surface

Adsorbent materials created from wastewater sludge have unique surface characteristics and could be effective in adsorption applications. In this research, the sludge-adsorbents were generated by pyrolyzing mixtures of sewage sludge and H2SO4. Scanning electron microscope (SEM), thermal analysis, X-ray diffraction (XRD) and X-ray photoelectron spectroscope (XPS) were used to analyze the properties of sludge-adsorbent. XPS results show that the adsorbent surface functional groups with high contents of oxygen-containing groups serve as active sites for the adsorption and affect the surface characteristics; the adsorption mechanism of methylene blue (MB) is mainly Brönsted acid-base reaction between the adsorbent surface and MB; and iodine atoms are bonded to the surface of the adsorbent mainly by dispersive interactions rather than by electrostatic interactions. The results also show that H2SO4 level, pyrolysis temperature and sulfuric acid/sludge weight ratio actually affected the adsorption characteristics. Using the conditions (H2SO4 level of 1–18 M, pyrolysis temperature of 650°C, and weight ratio of 0.8), the adsorption capacities for MB and iodine were 74.7–62.3 mg g−1 and 169.5–209.3 mg g−1, respectively.

scholarly journals CO Oxidation over Metal Oxide (La2O3, Fe2O3, PrO2, Sm2O3, and MnO2) Doped CuO-Based Catalysts Supported on Mesoporous Ce0.8Zr0.2O2 with Intensified Low-Temperature Activity

Catalysts ◽  
2019 ◽  
Vol 9 (9) ◽  
pp. 724 ◽  
Author(s):  
Yan Cui ◽  
Leilei Xu ◽  
Mindong Chen ◽  
Chufei Lv ◽  
Xinbo Lian ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Low Temperature ◽  
Metal Oxide ◽  
Metal Oxides ◽  
Co Oxidation ◽  
Active Sites ◽  
Earth Metal ◽  
High Dispersion ◽  
Impregnation Method ◽  
X Ray

CuO-based catalysts are usually used for CO oxidation owing to their low cost and excellent catalytic activities. In this study, a series of metal oxide (La2O3, Fe2O3, PrO2, Sm2O3, and MnO2)-doped CuO-based catalysts with mesoporous Ce0.8Zr0.2O2 support were simply prepared by the incipient impregnation method and used directly as catalysts for CO catalytic oxidation. These mesoporous catalysts were systematically characterized by X-ray powder diffraction (XRD), N2 physisorption, transmission electron microscopy (TEM), energy-dispersed spectroscopy (EDS) mapping, X-ray photoelectron spectroscopy (XPS), and H2 temperature programmed reduction (H2-TPR). It was found that the CuO and the dopants were highly dispersed among the mesoporous framework via the incipient impregnation method, and the strong metal framework interaction had been formed. The effects of the types of the dopants and the loading amounts of the dopants on the low-temperature catalytic performances were carefully studied. It was concluded that doped transition metal oxides could regulate the oxygen mobility and reduction ability of catalysts, further improving the catalytic activity. It was also found that the high dispersion of rare earth metal oxides (PrO2, Sm2O3) was able to prevent the thermal sintering and aggregation of CuO-based catalysts during the process of calcination. In addition, their presence also evidently improved the reducibility and significantly reduced the particle size of the CuO active sites for CO oxidation. The results demonstrated that the 15CuO-3Fe2O3/M-Ce80Zr20 catalyst with 3 wt. % of Fe2O3 showed the best low-temperature catalytic activity toward CO oxidation. Overall, the present Fe2O3-doped CuO-based catalysts with mesoporous nanocrystalline Ce0.8Zr0.2O2 solid solution as support were considered a promising series of catalysts for low-temperature CO oxidation.

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