Activity Comparison of MCM-41 and V-MCM-4 Catalysts for Ethanol Selective Oxidation and DRIFTS Analysis

2009 ◽  
Vol 7 (1) ◽  
Author(s):  
Yesim Gucbilmez ◽  
Timur Dogu ◽  
Suna Balci
Keyword(s):  
Hydrogen Atom ◽  
Gas Phase ◽  
Selective Oxidation ◽  
The Other ◽  
Lattice Oxygen ◽  
Molar Ratio ◽  
Surface Species ◽  
Other Hand ◽  
Activity Comparison ◽  
Mcm 41

The activity of a V-MCM-41 catalyst with a V/Si molar ratio of 0.04 was compared with the activity of a pure MCM-41 catalyst and some DRIFTS studies were performed in order to understand the mechanism of selective oxidation of ethanol. V-MCM-41 was found to be much more active than pure MCM-41, favouring the formation of high amounts of ethylene over 300°C. MCM-41, on the other hand, was found to favour the formation of acetaldehyde over ethylene at all studied temperatures. It was shown by reaction findings that over V-MCM-41, ethylene was produced mainly in the presence of gas phase oxygen whereas acetaldehyde was produced using the lattice oxygen even in the absence of gas phase oxygen. DRIFTS studies indicated the formation of acetaldehyde molecules from acetate-like surface species which were formed by the removal of a hydrogen atom from the ?-carbon of chemisorbed ethoxy species by the help of the lattice oxygen. On the other hand, removal of a hydrogen atom from the ?-carbon of the ethoxy species, in the presence of gas phase oxygen, resulted in the formation of vinyl-like surface species which then yielded ethylene molecules.

Degradation of chlorpyriphos in water by advanced oxidation processes

2010 ◽  
Vol 10 (1) ◽  
pp. 1-6 ◽  
Author(s):  
R. Murillo ◽  
J. Sarasa ◽  
M. Lanao ◽  
J. L. Ovelleiro
Keyword(s):  
Reaction Time ◽  
Light Source ◽  
Advanced Oxidation Processes ◽  
Advanced Oxidation ◽  
The Other ◽  
Molar Ratio ◽  
Optimum Conditions ◽  
Oxidation Processes ◽  
Other Hand ◽  
Initial Ph

The degradation of chlorpyriphos by different advanced oxidation processes such as photo-Fenton, TiO2, TiO2/H2O2, O3 and O3/H2O2 was investigated. The photo-Fenton and TiO2 processes were optimized using a solar chamber as light source. The optimum dosages of the photo-Fenton treatment were: [H2O2]=0.01 M; [Fe3 + ]=10 mg l−1; initial pH = 3.5. With these optimum conditions total degradation was observed after 15 minutes of reaction time. The application of sunlight was also efficient as total degradation was achieved after 60 minutes. The optimum dosage using only TiO2 as catalyst was 1,000 mg l−1, obtaining the maximum degradation at 20 minutes of reaction time. On the other hand, the addition of 0.02 M of H2O2 to a lower dosage of TiO2 (10 mg l−1) provides the same degradation. The ozonation treatment achieved complete degradation at 30 minutes of reaction time. On the other hand, it was observed that the degradation was faster by adding H2O2 (H2O2/O3 molar ratio = 0.5). In this case, total degradation was observed after 20 minutes.

Methylene. III. Gas phase reactions with 1-chloropropane

1969 ◽  
Vol 312 (1509) ◽  
pp. 141-161 ◽  
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Hydrogen Abstraction ◽  
The Other ◽  
Gas Phase Reactions ◽  
Other Hand ◽  
Chlorine Substituent ◽  
High Degree ◽  
Singlet Methylene

The work described in this and the following paper is a continuation of that in parts I and II, devoted to elucidation of the mechanism of the reactions of methylene with chloroalkanes, with particular reference to the reactivities of singlet and triplet methylene in abstraction and insertion processes. The products of the reaction between methylene, prepared by the photolysis of ketene, and 1-chloropropane have been identified and estimated and their dependence on reactant pressures, photolysing wavelength and presence of foreign gases (oxygen and carbon mon­oxide) has been investigated. Both insertion and abstraction mechanisms contribute significantly to the over-all reaction, insertion being relatively much more important than with chloroethane. This type of process appears to be confined to singlet methylene. If, as seems likely, there is no insertion into C—Cl bonds under our conditions (see part IV), insertion into C2—H and C3—H bonds occurs in statistical ratio, approximately. On the other hand, the chlorine substituent reduces the probability of insertion into C—H bonds in its vicinity. As in the chloroethane system, both species of methylene show a high degree of selectivity in their abstraction reactions. We find that k S Cl / k S H >7.7, k T Cl / k T H < 0.14, where the k ’s are rate constants for abstraction, and the super- and subscripts indicate the species of methylene and the type of atom abstracted, respectively. Triplet methylene is discriminating in hydrogen abstraction from 1-C 3 H 7 Cl, the overall rates for atoms attached to C1, C2, C3 being in the ratios 2.63:1:0.

scholarly journals Determination of the Ratios of Ligands to Metal Ion of some Metal Complexes of Triazoles by Using Eleetronie Speetra in Organie Solvents

2004 ◽  
Vol 1 (1) ◽  
pp. 110-115
Author(s):  
Baghdad Science Journal
Keyword(s):  
Solid State ◽  
Metal Complexes ◽  
Electronic Spectra ◽  
Metal Ion ◽  
The Other ◽  
Molar Ratio ◽  
Other Hand

We found that 4,5- diphenyl- 3(2- propynyl) thio- 1??-triazole [1? forms a complex with Pd (11) ion of ratio 1:1 which absorbs light in CH2CI2 at 400 nm, and 4,5- diphenyl- 3(2- propenyl) thio- 1,2,4- triazole [II] forms complexes with Pd (II) ion of ratio 1:1 which absorbs light at 390 nm, and of ratio 2:1 which absorbs light at 435 nm. On the other hand, we found that the new derivative 4- phenyl- 5( p- amino phenyl) -3- mercapto- 1,2,4- triazole ?111? forms complexes with Cu (II) ion of the ratio 1:1 which absorbs light at 380 nm, with Ni (II) ion of the ratio 3:1 which absorbs light at 358 nm; and with Co (11) ion of the ratio 3.2:1 which absorbs light at 588 nm. The ratio of the complexes were determined by measuring the electronic spectra of the complexes in CH2G2 and (CH^NCHO at different concentrations ofthe ligands and f?xed ' •' of the metal ion in every case, then applying the molar ratio plots on the data. Our results were confirmed by precipitating most ofthe above complexes in solid state, and then each complex was analyzed elementally.

scholarly journals Effect of additional side groups on the vibrational frequencies of benzoquinone molecules

BIBECHANA ◽  
2016 ◽  
Vol 14 ◽  
pp. 66-76
Author(s):  
Nabin Kumar Raut ◽  
Hari Prasad Lamichhane
Keyword(s):  
Ir Spectra ◽  
Gas Phase ◽  
Vibrational Frequencies ◽  
The Other ◽  
Methyl Groups ◽  
Computational Investigation ◽  
Strongly Coupled ◽  
Solvent Phase ◽  
Other Hand

The present work enumerates detailed computational investigation into the IR spectra in gas phase and in solvent of 1, 4- Benzoquinone family (benzoquinone (BQ), duroquinone (DQ), plastoquinone (PQ), ubiquinone (UQ), and dimethoxy dimethyl benzoquinone (MQo)). In  the spectra of BQ, PQ, and DQ, we observed separate intense carbonyl (C=O) and C=C bands respectively around 1730 cm-1 (intense), 1645 cm-1 (weak). On the other hand, for UQ and MQo, three prominent bands around 1652, 1703, and 1733 cm-1 were observed, where two C=O modes were uncoupled but one of the carbonyl is strongly coupled with C=C vibrations. The additional methyl groups downshift the intense carbonyl bands and upshift C=C mode frequencies. The carbonyl modes further downshifted in the solvent phase calculation.BIBECHANA 14 (2017) 66-76

INFLUENCE OF ION IMPLANTATION ON OXIDATION BEHAVIOR OF TiAl

2006 ◽  
Vol 20 (25n27) ◽  
pp. 4667-4672 ◽  
Author(s):  
MICHIKO YOSHIHARA ◽  
SHIGEJI TANIGUCHI
Keyword(s):  
Ion Implantation ◽  
Selective Oxidation ◽  
Oxidation Behavior ◽  
Complex Oxide ◽  
The Other ◽  
Alloying Elements ◽  
Implantation Technique ◽  
Other Hand ◽  
Initial Stage ◽  
Cu And Zn

The influence of alloying elements on oxidation behavior of TiAl has been investigated using an ion-implantation technique and the mechanisms were discussed. The influence can be classified into several groups according to their effects. The implantation of β-forming elements, halogens, Cu and Zn results in a significant improvement of the oxidation behavior through formation of Al 2 O 3 layer in the initial stage of oxidation. The improvement by Zn is attributed to the formation of complex oxide of Zn and selective oxidation of Al beneath the layer. The implantation of Al , Si or P is also effective. On the other hand, implantation of Ag , Se and other several elements enhance the oxidation. The deterioration by Ag or Se is explained in terms of Al depletion in the implanted layer.

Borierungsreaktionen an den N-Oxiden und -Iminen ungesättigter Stickstoffbasen / Boration Reactions with the N-Oxides and m-Imines of Unsaturated Nitrogen Bases

1980 ◽  
Vol 35 (5) ◽  
pp. 568-577 ◽  
Author(s):  
Peter Paetzold ◽  
Günther Schimmel
Keyword(s):  
Nitrous Oxide ◽  
Liquid Phase ◽  
Gas Phase ◽  
The Other ◽  
Double Bonds ◽  
Similar Reduction ◽  
Nitrogen Bases ◽  
Other Hand

1,3-Dipolar reagents with an unsaturated CNO- or CNN-skeleton undergo 1,3-organoboration by triorganoboranes. On the other hand, the unsaturated NNO-skeletons in azoxybenzene or nitrous-oxide are reduced to the corresponding NN-fragment by trialkylboranes. The 1,3-addition of aminoborane Cl2BNMe2 to the aldimineoxide PhHC = NMe-0 represents one of the rare examples of analogous reactivity of BN- and CC-double bonds. O-Borylhydroxylamines PhHCR-NMe-OBR2 are reduced by BR′3 to PhHCR-NMe-BR′2 and R′0-BR2. Similar reduction products are isolated from liquid-phase thermolysis of PhHCEt-NMe-OBEt2 (16), whereas gas-phase thermolysis of 16 gives PhCH = NMe, (EtBO)3, and C4H10.

A study of the properties of hydrogen films on tungsten by the method of contact potentials

1937 ◽  
Vol 33 (3) ◽  
pp. 394-402 ◽  
Author(s):  
R. C. L. Bosworth
Keyword(s):  
Dipole Moment ◽  
Hydrogen Atom ◽  
Gas Phase ◽  
Atomic Hydrogen ◽  
The Other ◽  
Condensation Coefficient ◽  
Effective Dipole Moment ◽  
Tungsten Atom ◽  
Contact Potential ◽  
Hydrogen Molecules

In a study of the properties of hydrogen on tungsten by the method of contact potentials the following points have been established:(1) The contact potential of a 92% covered surface of hydrogen on tungsten against bare tungsten is 1·04 V., and the Richardson constants for such a surface are, approximately,A = 30, b = 5·60 V.(2) A film of deuterium is 20 m V. positive relative to a similar hydrogen film.(3) Over the range of temperatures and pressures used by Bryce in a study of the production of atomic hydrogen the films are nearly saturated, so that the production of atomic hydrogen is primarily due to a molecule striking a bare tungsten atom, one atom being adsorbed and the other going into the gas phase.(4)The condensation coefficient for hydrogen molecules on cold tungsten is 0·01.(5) The effective dipole moment of each hydrogen atom on the surface is −0·42 Debye unit and is independent of the fraction of the surface covered.

Effect of different oxygen concentrations in the gas phase on biochemical activities of goat mammary tissue in organ culture

1989 ◽  
Vol 56 (1) ◽  
pp. 1-5 ◽  
Author(s):  
Josef Škarda ◽  
Eva Urbanová
Keyword(s):  
Protein Synthesis ◽  
Organ Culture ◽  
Gas Phase ◽  
The Other ◽  
Mammary Tissue ◽  
Relative Response ◽  
Other Hand ◽  
Rna And Protein Synthesis ◽  
Casein Synthesis ◽  
Oxygen Concentrations

SummaryNon-secretory mammary expiants from virgin goats showed higher RNA and protein synthesis in a low O2 gas phase (air) than in high O2 (95% O2). Lipid and casein synthesis was not affected significantly by the concentration of O2 in the atmosphere during culture. on the other hand, the more developed mammary tissue from primigravid goats showed higher lipid, casein and protein synthesis in 95% O2. The relative response of mammary tissue to hormones was not substantially different when cultured in the presence of a low or high O2 gas phase. As Hepes-buffered medium was found not to need a supply of CO2 to maintain the correct pH and as Hepes did not interfere with biochemical activities of cells, it is recommended to use it for cultures in a low O2 gas phase.

scholarly journals Structural and Functional Changes of Reconstituted High-Density Lipoprotein (HDL) by Incorporation of α-synuclein: A Potent Antioxidant and Anti-Glycation Activity of α-synuclein and apoA-I in HDL at High Molar Ratio of α-synuclein

Molecules ◽  
2021 ◽  
Vol 26 (24) ◽  
pp. 7485
Author(s):  
Kyung-Hyun Cho
Keyword(s):  
Amino Acids ◽  
Secondary Structure ◽  
Expression System ◽  
Lipoprotein Metabolism ◽  
The Other ◽  
Ldl Oxidation ◽  
Molar Ratio ◽  
Binding Ability ◽  
Functional Changes ◽  
Other Hand

α-synuclein (α-syn) is a major culprit of Parkinson’s disease (PD), although lipoprotein metabolism is very important in the pathogenesis of PD. α-syn was expressed and purified using the pET30a expression vector from an E. coli expression system to elucidate the physiological effects of α-syn on lipoprotein metabolism. The human α-syn protein (140 amino acids) with His-tag (8 amino acids) was expressed and purified to at least 95% purity. Isoelectric focusing gel electrophoresis showed that the isoelectric point (pI) of α-syn and apoA-I were pI = 4.5 and pI = 6.4, respectively. The lipid-free α-syn showed almost no phospholipid-binding ability, while apoA-I showed rapid binding ability with a half-time (T1/2) = 8 ± 0.7 min. The α-syn and apoA-I could be incorporated into the reconstituted HDL (rHDL, molar ratio 95:5:1:1, palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC):cholesterol:apoA-I:α-syn with the production of larger particles (92 Å) than apoA-I-rHDL (86 and 78 Å) and α-syn-rHDL (65 Å). An rHDL containing both apoA-I and α-syn showed lower α-helicity around 45% with a red shift of the Trp wavelength maximum fluorescence (WMF) from 339 nm, while apoA-I-HDL showed 76% α-helicity and 337 nm of WMF. The denaturation by urea addition showed that the incorporation of α-syn in rHDL caused a larger increase in the WMF than apoA-I-rHDL, suggesting that the destabilization of the secondary structure of apoA-I by the addition of α-syn. On the other hand, the addition of α-syn induced two-times higher resistance to rHDL glycation at apoA-I:α-syn molar ratios of 1:1 and 1:2. Interestingly, low α-syn in rHDL concentrations, molar ratio of 1:0.5 (apoA-I:α-syn), did not prevent glycation with more multimerization of apoA-I. In the lipid-free and lipid-bound state, α-syn showed more potent antioxidant activity than apoA-I against cupric ion-mediated LDL oxidation. On the other hand, microinjection of α-syn (final 2 μM) resulted in 10% less survival of zebrafish embryos than apoA-I. A subcutaneous injection of α-syn (final 34 μM) resulted in less tail fin regeneration than apoA-I. Interestingly, incorporation of α-syn at a low molar ratio (apoA-I:α-syn, 1:0.5) in rHDL resulted destabilization of the secondary structure and impairment of apoA-I functionality via more oxidation and glycation. However, at a higher molar ratio of α-syn in rHDL (apoA-I:α-syn = 1:1 or 1:2) exhibited potent antioxidant and anti-glycation activity without aggregation. In conclusion, there might be a critical concentration of α-syn and apoA-I in HDL-like complex to prevent the aggregation of apoA-I via structural and functional enhancement.

The Effect of Lithium Alkoxides on Deprotonizations by Superbases Made from Butyllithium and Potassium tert-Pentoxide

1993 ◽  
Vol 58 (6) ◽  
pp. 1445-1451 ◽  
Author(s):  
Lubomír Lochmann ◽  
Hana Jakubův ◽  
Lambert Brandsma
Keyword(s):  
High Reactivity ◽  
The Other ◽  
Molar Ratio ◽  
Side Chain ◽  
Other Hand

The presence or absence of lithium tert-pentoxide (t-PeOLi) in Superbases, prepared from butyllithium (BuLi) and potasium tert-pentoxide (t-PeOK), affects the metallation rate of toluene only slightly, the rate factors being between 1.0 and 0.3. Thus, lithium alkoxide is not essential for the high reactivity of Superbases. However, the ring-to-side chain metallation ratio is increased in the presence of t-PeOLi. On the other hand, an excess of t-PeOK (molar ratio t-PeOK/BuLi ≥ 3)considerably increases in the rate and yield of the side chain methallation of toluene and suppresses its ring mrtallation. In this way, alkoxides enable some control on regioselectivity in Superbase reactions.

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