Theoretical calculations and experimental studies on the electronic structures of hydrazones and hydrazone radical cations: formaldehyde hydrazone and benzaldehyde diphenylhydrazones

1990 ◽  
Vol 94 (1) ◽  
pp. 90-98 ◽  
Author(s):  
J. Pacansky ◽  
A. D. McLean ◽  
M. D. Miller
Keyword(s):  
Electronic Structures ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Radical Cations

Theoretical and experimental studies of palladium-catalyzed site-selective C(sp3)−H bond functionalization enabled by transient ligands

2017 ◽  
Author(s):  
Haibo Ge ◽  
Lei Pan ◽  
Piaoping Tang ◽  
Ke Yang ◽  
Mian Wang ◽  
...  
Keyword(s):  
Bond Activation ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Bond Functionalization ◽  
Aliphatic Ketones ◽  
Site Selectivity ◽  
Mechanistic Investigation ◽  
Palladium Catalyzed ◽  
Metal Catalyzed ◽  
Site Selective

Transition metal-catalyzed selective C–H bond functionalization enabled by transient ligands has become an extremely attractive topic due to its economical and greener characteristics. However, catalytic pathways of this reaction process on unactivated sp<sup>3</sup> carbons of reactants have not been well studied yet. Herein, detailed mechanistic investigation on Pd-catalyzed C(sp<sup>3</sup>)–H bond activation with amino acids as transient ligands has been systematically conducted. The theoretical calculations showed that higher angle distortion of C(sp2)-H bond over C(sp3)-H bond and stronger nucleophilicity of benzylic anion over its aromatic counterpart, leading to higher reactivity of corresponding C(sp<sup>3</sup>)–H bonds; the angle strain of the directing rings of key intermediates determines the site-selectivity of aliphatic ketone substrates; replacement of glycine with β-alanine as the transient ligand can decrease the angle tension of the directing rings. Synthetic experiments have confirmed that β-alanine is indeed a more efficient transient ligand for arylation of β-secondary carbons of linear aliphatic ketones than its glycine counterpart.<br><br>

scholarly journals Substituent Effects on EI-MS Fragmentation Patterns of 5-Allyloxy-1-aryl-tetrazoles and 4-Allyl-1-aryl-tetrazole-5-ones; Correlation with UV-Induced Fragmentation Channels

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3282
Author(s):  
Alina Secrieru ◽  
Rabah Oumeddour ◽  
Maria L. S. Cristiano
Keyword(s):  
Theoretical Calculations ◽  
Substituent Effects ◽  
Radical Cations ◽  
Electronic Effects ◽  
Diverse Range ◽  
The Matrix ◽  
Electron Impact Mass ◽  
Fragmentation Patterns ◽  
Tetrazole Derivatives ◽  
Impact Mass

1,4- and 1,5-disubstituted tetrazoles possess enriched structures and versatile chemistry, representing a challenge for chemists. In the present work, we unravel the fragmentation patterns of a chemically diverse range of 5-allyloxy-1-aryl-tetrazoles and 4-allyl-1-aryl-tetrazolole-5-ones when subjected to electron impact mass spectrometry (EI-MS) and investigate the correlation with the UV-induced fragmentation channels of the matrix-isolated tetrazole derivatives. Our results indicate that the fragmentation pathways of the selected tetrazoles in EI-MS are highly influenced by the electronic effects induced by substitution. Multiple pathways can be envisaged to explain the mechanisms of fragmentation, frequently awarding common final species, namely arylisocyanate, arylazide, arylnitrene, isocyanic acid and hydrogen azide radical cations, as well as allyl/aryl cations. The identified fragments are consistent with those found in previous investigations concerning the photochemical stability of the same class of molecules. This parallelism showcases a similarity in the behaviour of tetrazoles under EI-MS and UV-irradiation in the inert environment of cryogenic matrices of noble gases, providing efficient tools for reactivity predictions, whether for analytical ends or more in-depth studies. Theoretical calculations provide complementary information to articulate predictions of resulting products.

Research of stamping of unequal channel bars. Part 5. Methods for calculating the extrusion of channels. 2. Extrusion of non-strengthening material

2021 ◽  
pp. 46-52
Author(s):  
A.L. Vorontsov
Keyword(s):  
Plane Strain ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
High Accuracy ◽  
Experimental Results ◽  
Die Forging

The results of experimental studies on the extrusion of channels from non-strengthening material are presented. Comparison of theoretical calculations with experimental results showed the high accuracy of the derived formulas. Keywords: die forging, extrusion, punch, matrix, misalignment, plane strain. [email protected]

scholarly journals Platinum–copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Xi Zhang ◽  
Guoqing Cui ◽  
Haisong Feng ◽  
Lifang Chen ◽  
Hui Wang ◽  
...  
Keyword(s):  
Active Sites ◽  
High Performance ◽  
Reaction Pathway ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Value Added ◽  
Catalytic Performance ◽  
Single Atom ◽  
Glycerol Hydrogenolysis ◽  
Single Atom Alloy

AbstractSelective hydrogenolysis of biomass-derived glycerol to propanediol is an important reaction to produce high value-added chemicals but remains a big challenge. Herein we report a PtCu single atom alloy (SAA) catalyst with single Pt atom dispersed on Cu nanoclusters, which exhibits dramatically boosted catalytic performance (yield: 98.8%) towards glycerol hydrogenolysis to 1,2-propanediol. Remarkably, the turnover frequency reaches up to 2.6 × 103 molglycerol·molPtCu–SAA−1·h−1, which is to our knowledge the largest value among reported heterogeneous metal catalysts. Both in situ experimental studies and theoretical calculations verify interface sites of PtCu–SAA serve as intrinsic active sites, in which the single Pt atom facilitates the breakage of central C–H bond whilst the terminal C–O bond undergoes dissociation adsorption on adjacent Cu atom. This interfacial synergistic catalysis based on PtCu–SAA changes the reaction pathway with a decreased activation energy, which can be extended to other noble metal alloy systems.

scholarly journals Numerical simulation of the stress-strain state of complex-reinforced elements

2019 ◽  
Vol 13 (2) ◽  
pp. 110-115
Author(s):  
Olena Krantovska ◽  
Mykola Petrov ◽  
Liubov Ksonshkevych ◽  
Matija Orešković ◽  
Sergii Synii ◽  
...  
Keyword(s):  
Numerical Simulation ◽  
Strain State ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Theoretical Studies ◽  
Stress Strain ◽  
Narrow Strip ◽  
Stress Strain State ◽  
Graphical Environment ◽  
Experimental And Theoretical Studies

The article describes a developed technique of a numerical simulation of the stress-strain state of complex-reinforced elements, which allows you to create models of double-span continuous. The performed experimental and theoretical studies allowed us to carry out the testing of the developed design model and to justify the reliability of the proposed numerical simulation methodology. The results of the experimental studies were compared with those of the theoretical studies. The theoretical calculus algorithm was developed by using the finite element method. Theoretical calculations were performed by using the mathematical-graphical environment software system LIRA-SOFT and the mathematical and computer program MATLAB. On the basis of the experimental research, the iso-fields of displacements and stresses in the materials of an eccentrically compressed beam with a small bend of the slab were constructed, which collapse behind the inclined narrow strip of concrete and displacements and stresses in the materials of the eccentrically stretched beam, which is destroyed due to the yield of the upper mounting armature.

Graph-Analytical Estimation Method of Natural Ventilation Efficiency during Natural Gas Combustion

2018 ◽  
Vol 931 ◽  
pp. 901-904 ◽  
Author(s):  
Victor I. Chebotarev ◽  
Anastasia P. Pirozhnikova ◽  
Alla V. Koroleva
Keyword(s):  
Natural Gas ◽  
Natural Ventilation ◽  
Theoretical Calculations ◽  
Residential Buildings ◽  
Experimental Studies ◽  
Estimation Method ◽  
Combustion Products ◽  
Gas Combustion ◽  
Analytical Estimation ◽  
Ventilation Duct

Open burning of natural gas when using gas equipment in the premises of residential buildings is considered, taking into account the formation of combustion products, depending on the coefficients of excess air. Theoretical and experimental studies of combustion processes are presented. To determine the aerodynamic process in the ventilation duct, theoretical calculations of the dependence of the discharge at the entrance to the ventilation duct from the outside temperature of the atmospheric air were made. Graph-analytic method of evaluating the effectiveness of natural ventilation is carried out.

scholarly journals Multilayered stable 2D nano-sheets of Ti2NTx MXene: synthesis, characterization, and anticancer activity

2019 ◽  
Vol 17 (1) ◽  
Author(s):  
A. Szuplewska ◽  
A. Rozmysłowska-Wojciechowska ◽  
S. Poźniak ◽  
T. Wojciechowski ◽  
M. Birowska ◽  
...  
Keyword(s):  
Biological Activity ◽  
Mammary Epithelial Cells ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Reactive Oxygen ◽  
Decisive Role ◽  
Max Phase ◽  
Mechanisms Of Toxicity ◽  
Biological Studies

Abstract Background The biological activity of MXenes has been studied for several years because of their potential biomedical applications; however, investigations have so far been limited to 2D titanium carbides. Although monolayered Ti2NTx MXene has been expected to have biological activity, experimental studies revealed significant difficulties due to obstacles to its synthesis, its low stability and its susceptibility to oxidation and decomposition. Results In this paper, we report our theoretical calculations showing the higher likelihood of forming multilayered Ti2NTx structures during the preparation process in comparison to single-layered structures. As a result of our experimental work, we successfully synthesized multilayered Ti2NTx MXene that was suitable for biological studies by the etching of the Ti2AlN MAX phase and further delamination. The biocompatibility of Ti2NTx MXene was evaluated in vitro towards human skin malignant melanoma cells, human immortalized keratinocytes, human breast cancer cells, and normal human mammary epithelial cells. Additionally, the potential mode of action of 2D Ti2NTx was investigated using reactive oxygen tests as well as SEM observations. Our results indicated that multilayered 2D sheets of Ti2NTx showed higher toxicity towards cancerous cell lines in comparison to normal ones. The decrease in cell viabilities was dose-dependent. The generation of reactive oxygen species as well as the internalization of the 2D sheets play a decisive role in the mechanisms of toxicity. Conclusions We have shown that 2D Ti2NTx in the form of multilayered nanoflakes exhibits fair stability and can be used for in vitro studies. These results show promise for its future applications in biotechnology and nanomedicine.

scholarly journals Modeling the mechanical wear of the contact elements of pantograph during high-speed movement

2020 ◽  
Vol 157 ◽  
pp. 01022
Author(s):  
Victor Philippov ◽  
Alexandr Smerdin
Keyword(s):  
Service Life ◽  
High Speed ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Maximum Error ◽  
Life Assessment ◽  
Rolling Stock ◽  
Mechanical Wear ◽  
Wear Process ◽  
Mechanical Component

The use of contact elements with an extended service life is one of the most economical and least costly ways to ensure reliable, economical and environmentally friendly transmission of electricity to rolling stock. To evaluate the service life in OSTU, a methodology for conducting experimental studies of contact pairs of pantograph has been developed and successfully tested, involving bench tests for each pair of contact materials “contact insert - contact wire” in order to determine their optimal combination to reduce wear and increase service life. Assessment of the amount of wear and prediction of the life of the contact elements are made, including using mathematical modeling. The purpose of this article is to improve the mechanical component of the wear model of the contact elements of pantograph in high-speed conditions. The results of experimental studies and theoretical calculations of the mechanical wear of contact elements are presented. The analysis of the graphs allows us to conclude that it is possible to use an improved mathematical model for modeling the mechanical component of the wear process of the elements of contact pairs with a maximum error value of not more than 5%.

Aryl Sulfoxide Radical Cations. Generation, Spectral Properties, and Theoretical Calculations

2006 ◽  
Vol 110 (32) ◽  
pp. 9940-9948 ◽  
Author(s):  
Enrico Baciocchi ◽  
Tiziana Del Giacco ◽  
Maria Francesca Gerini ◽  
Osvaldo Lanzalunga
Keyword(s):  
Spectral Properties ◽  
Theoretical Calculations ◽  
Radical Cations
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