Direct evidence for the reactive species, and their reaction orders, in the addition reaction of methylmagnesium bromide Grignard to 2-methylbenzophenone

1971 ◽  
Vol 93 (18) ◽  
pp. 4601-4602 ◽  
Author(s):  
E. C. Ashby ◽  
J. Laemmle ◽  
H. M. Neumann
Keyword(s):  
Direct Evidence ◽  
Addition Reaction ◽  
Reactive Species ◽  
Reaction Orders

Direct Evidence of a Radical Mechanism in the Addition Reaction of Iododifluoroesters to Olefins by Spin Trapping

2000 ◽  
Vol 65 (17) ◽  
pp. 5098-5103 ◽  
Author(s):  
Luis Julià ◽  
M. Pilar Bosch ◽  
Sergio Rodriguez ◽  
Angel Guerrero
Keyword(s):  
Direct Evidence ◽  
Addition Reaction ◽  
Spin Trapping ◽  
Radical Mechanism

Autoxidation of cysteine generates hydrogen peroxide: cytotoxicity and attenuation by pyruvate

1993 ◽  
Vol 264 (2) ◽  
pp. F306-F314 ◽  
Author(s):  
K. A. Nath ◽  
A. K. Salahudeen
Keyword(s):  
Hydrogen Peroxide ◽  
Transition Metals ◽  
Direct Evidence ◽  
Reactive Species ◽  
Cysteine Oxidation ◽  
Diethyl Dithiocarbamate ◽  
Active Metal ◽  
Catalytically Active ◽  
Metal Catalyzed ◽  
Cytotoxicity Cysteine

The reactivity of cysteine presents a paradox: although regarded as an antioxidant, cysteine interacts with oxygen in a metal-catalyzed reaction to produce reactive species. Because ischemia provokes the appearance of millimolar amounts of cysteine and increased amounts of transition metals, we studied whether cysteine, in the presence of transition metals, consumes oxygen, generates hydrogen peroxide, and is toxic. Using fluorescence cytometry, we provide direct evidence that hydrogen peroxide is copiously generated during cysteine autoxidation. Pyruvate attenuates such generation of hydrogen peroxide and cytotoxicity. Cysteine oxidation is stimulated by an EDTA-chelatable diethyl-dithiocarbamate-chelatable constituent of kidney extract; this suggests that copper is the catalytically active metal. The toxicity resulting from cysteine oxidation is less than that induced by amounts of reagent hydrogen peroxide that produce comparable fluorescence. Cysteine also prevents hydrogen peroxide-induced toxicity. Thus, although cysteine generates hydrogen peroxide, it can guard against hydrogen peroxide toxicity, possibly by binding metals on which the toxicity of hydrogen peroxide is dependent. Thus the behavior of cysteine can be salutary or pernicious; the net effect of cysteine, within this wide ambit of actions, is decisively influenced by the conditions to which cysteine is exposed.

Photoaddition of α-diketones to olefins. Stereospecificity of the addition reaction

1970 ◽  
Vol 48 (19) ◽  
pp. 3045-3052 ◽  
Author(s):  
Y. L. Chow ◽  
T. C. Joseph ◽  
H. H. Quon ◽  
J. N. S. Tam
Keyword(s):  
Charge Transfer ◽  
Addition Reaction ◽  
Reactive Species ◽  
Large Excess ◽  
Transfer Structure ◽  
A Charge ◽  
Cis And Trans

Phenanthraquinone (PQ) photolytically adds to cis- and trans-alkenes to give a mixture of cis- and trans-1,4-dioxenes and two reduction products. The ratios of cis- to trans- 1,4-dioxenes remain the same irrespective of the photoaddition to cis- or trans-alkenes and are 1:1 for 2-butenes, 6:4 for 3-hexenes, and 8:2 for cyclohexene. A triplet excited phenanthraquinone is proposed as the reactive species which initiates the addition leading to the intermediate diradical 10. Depending on the nature of addenda the diradical 10 may be stabilized by a charge transfer structure in different conformations leading to the observed stereochemistry of the adducts. The PQ fails to add to fumaronitrile photolytically or thermally and thermally adds to 2-butenes only inefficiently. Biacetyl undergoes photoreduction readily in the presence of a large excess of cyclohexene.

The Immuno-Electron Microscopic Localization of the Mo-Fe Protein Component of Nitrogenase in Cells of Azotobacter Vinelandii

1973 ◽  
Vol 31 ◽  
pp. 574-575
Author(s):  
J. T. Stasny ◽  
R. C. Burns ◽  
R. W. F. Hardy
Keyword(s):  
Cellular Localization ◽  
Direct Evidence ◽  
Azotobacter Vinelandii ◽  
Intracellular Localization ◽  
Protein Component ◽  
Electron Microscopic ◽  
Thin Sections ◽  
Fe Protein ◽  
Intracytoplasmic Membranes

Structure-functlon studies of biological N2-fixation have correlated the presence of the enzyme nitrogenase with increased numbers of intracytoplasmic membranes in Azotobacter. However no direct evidence has been provided for the internal cellular localization of any nitrogenase. Recent advances concerned with the crystallizatiorTand the electron microscopic characterization of the Mo-Fe protein component of Azotobacter nitrogenase, prompted the use of this purified protein to obtain antibodies (Ab) to be conjugated to electron dense markers for the intracellular localization of the protein by electron microscopy. The present study describes the use of ferritin conjugated to goat antitMo-Fe protein immunoglobulin (IgG) and the observations following its topical application to thin sections of N2-grown Azotobacter.

Structural similarity of ribosomes from E. coli and A. salina

1978 ◽  
Vol 36 (2) ◽  
pp. 242-243
Author(s):  
M. Boublik ◽  
R.M. Wydro ◽  
W. Hellmann ◽  
F. Jenkins
Keyword(s):  
Ribosomal Proteins ◽  
Direct Evidence ◽  
Structural Similarity ◽  
Carbon Support ◽  
Artemia Salina ◽  
Uranyl Acetate ◽  
Biological Assays ◽  
E Coli ◽  
And Function ◽  
Fine Carbon

Ribosomes are ribonucleoprotein particles necessary for processing the genetic information of mRNA into proteins. Analogy in composition and function of ribosomes from diverse species, established by biochemical and biological assays, implies their structural similarity. Direct evidence obtained by electron microscopy seems to be of increasing relevance in understanding the structure of ribosomes and the mechanism of their role in protein synthesis.The extent of the structural homology between prokaryotic and eukaryotic ribosomes has been studied on ribosomes of Escherichia coli (E.c.) and Artemia salina (A.s.). Despite the established differences in size and in the amount and proportion of ribosomal proteins and RNAs both types of ribosomes show an overall similarity. The monosomes (stained with 0.5% aqueous uranyl acetate and deposited on a fine carbon support) appear in the electron micrographs as round particles with a diameter of approximately 225Å for the 70S E.c. (Fig. 1) and 260Å for the 80S A.s. monosome (Fig. 2).

Stress Relaxation and the Formation of Silicides in the Process of the Crystallization of NI-NB Films on SI

1991 ◽  
Vol 49 ◽  
pp. 898-899
Author(s):  
N. Rozhanski ◽  
V. Lifshitz
Keyword(s):  
Thin Films ◽  
Stress Relaxation ◽  
Integrated Circuits ◽  
Direct Evidence ◽  
Alloy Film ◽  
Diffusion Barriers ◽  
Effective Barrier

Thin films of amorphous Ni-Nb alloys are of interest since they can be used as diffusion barriers for integrated circuits on Si. A native SiO2 layer is an effective barrier for Ni diffusion but it deformation during the crystallization of the alloy film lead to the appearence of diffusion fluxes through it and the following formation of silicides. This study concerns the direct evidence of the action of stresses in the process of the crystallization of Ni-Nb films on Si and the structure of forming NiSi2 islands.

Point and planar defects in the iron sulfide compounds Fe1-xS

1984 ◽  
Vol 42 ◽  
pp. 434-435
Author(s):  
Thao A. Nguyen
Keyword(s):  
Low Temperatures ◽  
Direct Evidence ◽  
Iron Sulfide ◽  
Planar Defects ◽  
Selective Area ◽  
Vacancy Ordering ◽  
Different Types ◽  
Lattice Images ◽  
The Subject ◽  
Beam Lattice

It is well known that the large deviations from stoichiometry in iron sulfide compounds, Fe1-xS (0≤x≤0.125), are accommodated by iron vacancies which order and form superstructures at low temperatures. Although the ordering of the iron vacancies has been well established, the modes of vacancy ordering, hence superstructures, as a function of composition and temperature are still the subject of much controversy. This investigation gives direct evidence from many-beam lattice images of Fe1-xS that the 4C superstructure transforms into the 3C superstructure (Fig. 1) rather than the MC phase as previously suggested. Also observed are an intrinsic stacking fault in the sulfur sublattice and two different types of vacancy-ordering antiphase boundaries. Evidence from selective area optical diffractograms suggests that these planar defects complicate the diffraction pattern greatly.

Evidence for ordered Fe3Ni

1987 ◽  
Vol 45 ◽  
pp. 216-217
Author(s):  
K.B. Reuter ◽  
D.B. Williams ◽  
J.I. Goldstein
Keyword(s):  
Experimental Data ◽  
Martensitic Transformation ◽  
Electron Diffraction ◽  
Room Temperature ◽  
Direct Evidence ◽  
Transformation Product ◽  
Iron Meteorites ◽  
X Ray ◽  
Ni Content ◽  
Temperature Transformation

In the Fe-Ni system, although ordered FeNi and ordered Ni3Fe are experimentally well established, direct evidence for ordered Fe3Ni is unconvincing. Little experimental data for Fe3Ni exists because diffusion is sluggish at temperatures below 400°C and because alloys containing less than 29 wt% Ni undergo a martensitic transformation at room temperature. Fe-Ni phases in iron meteorites were examined in this study because iron meteorites have cooled at slow rates of about 10°C/106 years, allowing phase transformations below 400°C to occur. One low temperature transformation product, called clear taenite 2 (CT2), was of particular interest because it contains less than 30 wtZ Ni and is not martensitic. Because CT2 is only a few microns in size, the structure and Ni content were determined through electron diffraction and x-ray microanalysis. A Philips EM400T operated at 120 kV, equipped with a Tracor Northern 2000 multichannel analyzer, was used.

Incommensurate modulated phases of the NbxTa1-xTe4 charge density wave system

1992 ◽  
Vol 50 (1) ◽  
pp. 58-59
Author(s):  
S. Ritchie ◽  
J. C. Bennett ◽  
A. Prodan ◽  
F.W. Boswell ◽  
J.M. Corbett
Keyword(s):  
Charge Density ◽  
Charge Density Wave ◽  
Direct Evidence ◽  
Density Wave ◽  
Wave System ◽  
Modulated Phases ◽  
Metal Atoms ◽  
Incommensurate Modulation ◽  
End Members ◽  
Modulation Wave Vector

A continuous sequence of compounds having composition NbxTa1-xTe4; 0 ≤ x ≤ 1 have been studied by electron diffraction and microscopy. Previous studies have shown that the end members of the series, TaTε4 and NbTε4 possess a quasi-one-dimensional character and exhibit charge density wave (CDW) distortions. In these compounds, the subcell structure is tetragonal with axes (a × a × c) and consists of the metal atoms (Nb or Ta) centered within an extended antiprismatic cage of Te atoms. At room temperature, TaTε4 has a commensurate modulation structure with a 2a × 2a × 3c unit cell. In NbTε4, an incommensurate modulation with × ∼ 16c axes is observed. Preliminary studies of the mixed compounds NbxTα1-xTε4 showed a discontinuous jump of the modulation wave vector commensurate to incommensurate when the Nb dopant concentration x, exceeded x ≃ 0.3, In this paper, the nature of the compositional dependence of is studied in greater detail and evidence is presented for a stepwise variation of . This constitutes the first direct evidence for a Devil's staircase in CDW materials.

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