scholarly journals New Approach to Synthesis of Tetralin via Naphthalene Hydrogenation in Supercritical Conditions Using Polymer-Stabilized Pt Nanoparticles

Catalysts ◽  
2020 ◽  
Vol 10 (11) ◽  
pp. 1362
Author(s):  
Alexey V. Bykov ◽  
Daria V. Alekseeva ◽  
Galina N. Demidenko ◽  
Alexandre L. Vasiliev ◽  
Linda Nikoshvili ◽  
...  

Supercritical (SC) fluid technologies are well-established methods in modern green chemical synthesis. Using SC fluids as solvents instead of traditional liquids gives benefits of higher diffusivity and lower viscosity, which allows mass transfer intensification and, thus, an increased production rate of chemical transformations. Therefore, a conjugation of heterogeneous catalysis with SC media is a large step toward a green chemistry. Tetralin (TL) is an important hydrogen donor solvent used for biomass liquefaction. In industry, TL is obtained via catalytic hydrogenation of naphthalene (NL). Herein, for the first time we have demonstrated the NL hydrogenation with close to 100% selectivity to TL at almost full conversion in the SC hexane. The observed transformation rates in SC hexane were much higher allowing process intensification. The downstream processes can be also facilitated since hexane after depressurisation can be easily separated from the reaction products via simple rectification. The TL synthesis was studied in a batch reactor at variation of reaction temperature and overall pressure. For the first time for this process, low Pt-loaded (1 wt.%) nanoparticles stabilized within hyper-cross-linked aromatic polymer (HAP) were applied. The Pt/HAP catalyst was stable under reaction conditions (250 °C, 6 MPa) allowing its recovery and reuse.

2020 ◽  
Vol 86 (9) ◽  
pp. 55-72
Author(s):  
Maryna Stasevich ◽  
Viktor Zvarych ◽  
Volodymyr Novikov ◽  
Mykhailo Vovk

For the first time, the literature sources concerning the chemical transformations of diazonium salts of 1(2)-amino-9,10-anthracenediones are generalized and systematized. The potential of 9,10-dioxoanthracenyldiazonium salts as key substrates in the preparation of various linear-functionalized, acyclic and heterocyclic derivatives has been determined. The main synthetic transformations of diazonium salts of amino-9,10-anthracenediones, which are  realized without preserving the azo function lead to the formation of reaction products of Sandmeyer, Meerwein, and Gomberg–Bachmann–Hay, are analyzed. The use of 9,10-dioxoanthracenyldiazonium salts or products of their transformations for obtaining heteryl-containing condensed and functionalized derivatives is presented.


Author(s):  
Daiya Kobayashi ◽  
Hirokazu Kobayashi ◽  
Kohei Kusada ◽  
Tomokazu Yamamoto ◽  
Takaaki Toriyama ◽  
...  

We report PtW solid-solution alloy nanoparticles (NPs) as a reverse water-gas shift (RWGS) reaction catalyst for the first time. Atomic-level alloying of Pt and W significantly enhanced the RWGS reaction activity of Pt NPs.


2021 ◽  
Vol 19 (1) ◽  
Author(s):  
Tong Chen ◽  
Qiang Chu ◽  
Mengyang Li ◽  
Gaorong Han ◽  
Xiang Li

AbstractElectrodynamic therapy (EDT) has recently emerged as a potential external field responsive approach for tumor treatment. While it presents a number of clear superiorities, EDT inherits the intrinsic challenges of current reactive oxygen species (ROS) based therapeutic treatments owing to the complex tumor microenvironment, including glutathione (GSH) overexpression, acidity and others. Herein for the first time, iron oxide nanoparticles are decorated using platinum nanocrystals (Fe3O4@Pt NPs) to integrate the current EDT with chemodynamic phenomenon and GSH depletion. Fe3O4@Pt NPs can effectively induce ROS generation based on the catalytic reaction on the surface of Pt nanoparticles triggered by electric field (E), and meanwhile it may catalyze intracellular H2O2 into ROS via Fenton reaction. In addition, Fe3+ ions released from Fe3O4@Pt NPs under the acidic condition in tumor cells consume GSH in a rapid fashion, inhibiting ROS clearance to enhance its antitumor efficacy. As a result, considerable in vitro and in vivo tumor inhibition phenomena are observed. This study has demonstrated an alternative concept of combinational therapeutic modality with superior efficacy.


Catalysts ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 415
Author(s):  
Xinsheng Li ◽  
Jifeng Pang ◽  
Jingcai Zhang ◽  
Xianquan Li ◽  
Yu Jiang ◽  
...  

Catalytic conversion of biomass-derived feedstock to high-value chemicals is of remarkable significance for alleviating dependence on fossil energy resources. MgAl spinel-supported Pt catalysts were prepared and used in furfuryl alcohol conversion. The approaches to tune the reaction selectivity toward pentanediols (PeDs) were investigated and the catalytic performance was correlated to the catalysts’ physicochemical properties based on comprehensive characterizations. It was found that 1–8 wt% Pt was highly dispersed on the MgAl2O4 support as nanoparticles with small sizes of 1–3 nm. The reaction selectivity did not show dependence on the size of Pt nanoparticles. Introducing LiOH onto the support effectively steered the reaction products toward the PeDs at the expense of tetrahydrofurfuryl alcohol (THFA) selectivity. Meanwhile, the major product in PeDs was shifted from 1,5-PeD to 1,2-PeD. The reasons for the PeDs selectivity enhancement were attributed to the generation of a large number of medium-strong base sites on the Li-modified Pt catalyst. The reaction temperature is another effective factor to tune the reaction selectivity. At 230 °C, PeDs selectivity was enhanced to 77.4% with a 1,2-PeD to 1,5-PeD ratio of 3.7 over 4Pt/10Li/MgAl2O4. The Pt/Li/MgAl2O4 catalyst was robust to be reused five times without deactivation.


2019 ◽  
Vol 57 (2) ◽  
pp. 90-100
Author(s):  
Alexey V. Larionov ◽  
◽  
Ludmila Y. Udoeva ◽  
Vladimir M. Chumarev ◽  
◽  
...  

In order to study the effect of yttrium additives on the oxidation of molybdenum silicide alloys, thermodynamic modeling of the interaction in Mo-Mo3Si-Sc5Si3 и Mo-Mo3Si-NdSi systems with dry and moist air was performed in the temperature range 25-2000 °C. The calculations were performed using the HSC Chemistry 6.12 software, into the database of which the calculated missing thermochemical characteristics silicates, molybdates of scandium and neodymium were entered. Based on the obtained dependences of the composition of phases on temperature and charge of the oxidant (air or vapor-air mixture), the sequence of phase formation was determined and the compositions of oxidation products were estimated. It is shown that, under equilibrium conditions, the oxidation process with dry and moist air proceeds almost equally, since the interaction of the components of the alloy with oxygen is thermodynamically preferable than with water vapor. According to the obtained thermodynamic models, the oxidation process of the Mo-5Si-3(Sc, Nd) (wt.%) alloys involves a sequence of the following chemical transformations: at the beginning Mo and Sc (Nd) silicides oxidize forming Sc2O3 ( Nd2O3), SiO2 and elemental Mo, then molybdenum is oxidized to MoO2 and Sc2O3 or Nd2O3 interacts with SiO2 with the formation of appropriate silicates Sc2Si2O7 или Nd2Si2O7. As a result of the complete oxidation of the alloy, MoO3 and Sc2(MoO4)3 or Nd2Mo4O15 are added to the condensed product, and molybdenum oxide (MoO3)n vapor appears in the gas phase. In addition, the formation of Nd2Mo2O7 and Nd2 (MoO4)3 is possible. During the oxidation of the Mo-5Si-3Nd alloy at T> 1700 oC, Nd(OH)3 can be formed in the condensed reaction products. According to the results of complete thermodynamic analysis, the formation of silicates and molybdates of scandium and neodymium can promote to the formation of a protective film on the surface of the alloys, which limits the diffusion of oxygen in them, and as a result, the oxidation resistance of alloys should increase.


2020 ◽  
pp. jbc.RA120.015905
Author(s):  
Elena D Nosyreva ◽  
David Thompson ◽  
Ruhma Syeda

Mechanotransduction is the process by which cells convert physical forces into electro-chemical responses. On a molecular scale these forces are detected by mechanically activated ion channels, which constitute the basis for hearing, touch, pain, cold and heat sensation amongst other physiological processes. Exciting high-resolution structural details of these channels are currently emerging that will eventually allow us to delineate the molecular determinants of gating and ion permeation. However, our structural-functional understanding across the family remains limited. Piezo1 is one of the largest and least understood of these channels, with various structurally identified features within its trimeric assembly. This study seeks to determine the modularity and function of Piezo1 channels by constructing deletion proteins guided by cryo EM structural knowledge. Our comprehensive functional study identified, for the first time, the minimal amino acid sequence of the full-length Piezo1 that can fold and function as the channel’s pore domain between E2172 and the last residue E2547. While, the addition of an anchor region has no effect on permeation properties. The Piezo1 pore domain is not pressure sensitive and the appending of Piezo Repeat-A did not restore pressure-dependent gating, hence the sensing module must exist between residues 1-1952. Our efforts delineating the permeation and gating regions within this complex ion channel have implications in identifying small molecules that exclusively regulate the activity of the channel’s pore module to influence mechanotransduction and downstream processes.


Author(s):  
Vivek D. Talnikar ◽  
Onkar A. Deorukhkar ◽  
Amit Katariya ◽  
Yogesh S. Mahajan

Abstract The reaction of acrylic acid and 2-ethyl-1 hexanol was explored in this work with the intent of process intensification. In order to assess the effect of important parameters on the course of reaction, this work initially conducted batch reactor experiments. Reaction conditions in the batch reactor for a specific conversion (~ 30 %) were obtained. A kinetic model was then obtained through regression to arrive at a rate expression that is later used in process development. Experiments were performed in the reactive distillation (RD) environment in batch mode, which showed substantial increase in conversion (~ 80 %) indicating the applicability of RD. Further, this work performed simulation in the RD environment to assess process intensification. Simulations show that it is possible to obtain complete conversion of the acid.


1999 ◽  
Vol 65 (12) ◽  
pp. 5504-5509 ◽  
Author(s):  
M. Quirasco ◽  
A. López-Munguía ◽  
M. Remaud-Simeon ◽  
P. Monsan ◽  
A. Farrés

ABSTRACT Dextransucrase production by Leuconostoc mesenteroidesNRRL B-512F in media containing carbon sources other than sucrose is reported for the first time. Dextransucrases were analyzed by gel electrophoresis and by an in situ activity assay. Their polymers and acceptor reaction products were also compared by 13C nuclear magnetic resonance and high-performance liquid chromatography techniques, respectively. From these analyses, it was found that, independently of the carbon source, L. mesenteroides NRRL B-512F produced dextransucrases of the same size and product specificity. The 5′ ends of dextransucrase mRNAs isolated from cells grown under different culture conditions were identical. Based on this evidence, we conclude that dextransucrases obtained from cells grown on the various carbon sources result from the transcription of the same gene. The control of expression occurs at this level. The low dextransucrase yields from cultures in d-glucose ord-fructose and the enhancement of dextransucrase gene transcription in the presence of sucrose suggest that an activating phenomenon may be involved in the expression mechanism. Dextransucrase mRNA has a size of approximately 4.8 kb, indicating that the gene is located in a monocistronic operon. The transcription start point was localized 34 bp upstream from the ATG start codon. The −10 and −35 sequences found, TATAAT and TTTACA, were highly homologous to the only glycosyltransferase promoter sequence reported for lactic acid bacteria.


Polymers ◽  
2019 ◽  
Vol 11 (1) ◽  
pp. 144 ◽  
Author(s):  
Dawid Kansy ◽  
Kornelia Bosowska ◽  
Krystyna Czaja ◽  
Anna Poliwoda

The purpose of this work was to synthesize and characterize oligoglycerols with the chains of more than four repeating units. Those oligoglycerols may have some interesting applications, among others, as polyoxyalkylation starters. The glycerol oligomerization process was carried out during 12 h, at 230 °C, under the pressure of 0.4 bar, with the use of sodium carbonate as a homogeneous basic catalyst; various concentrations of the catalyst in the reaction medium were used. The reaction products were analyzed with the use of direct infusion electrospray ionization mass spectrometry (ESI-MS), nuclear magnetic resonance (13C NMR) and Fourier transform infrared spectroscopy (FTIR) techniques. Based on the analytical findings, the compositions of the obtained product mixtures and the structures of oligoglycerols present in individual fractions were determined. The effect of catalyst concentration on the composition of the post-reaction mixture was observed. Moreover, in addition to the conventional linear oligomers (α,α-oligoglycerols), two new types of the oligomers were for the first time detected in the post-reaction mixture: one with two hydroxyl groups and the other with a carboxylate group at the α-carbon atom.


Molecules ◽  
2019 ◽  
Vol 24 (7) ◽  
pp. 1386 ◽  
Author(s):  
Eloy Rodríguez-deLeón ◽  
J. Jiménez-Halla ◽  
José Báez ◽  
M. Bah

Carotenoids are natural compounds that have important roles in promoting and maintaining human health. Synthetic astaxanthin is a highly requested product by the aquaculture industry, but natural astaxanthin is not. Various strategies have been developed to synthesize this carotenoid. Nonetheless, these approaches have not only provided limited global yields, but its main commercial source also carries several health risks for humans. In this contribution, the one-pot base-catalyzed reaction of (3R,3’R,6’R)-lutein (1) esters has resulted in a successful isomerization process to easily obtain up to 95% meso-zeaxanthin (2), which in turn is oxidized to (3R,3’S)-astaxanthin (3) with a global yield of 68%. The same oxidation performed with UV irradiation (365 nm) for 5 min provided the highest global yield (76%). These chemical transformations have also been achieved with a significant reduction of the health risks associated with its potential human consumption. Furthermore, this is the first time only one of the configurational isomers has been obtained semisynthetically. The poorly understood formation mechanisms of these two compounds were also investigated using Density-Functional Theory (DFT) calculations. These theoretical studies revealed that the isomerization involves a base-catalyzed deprotonation at C-6’, followed by C-4’ protonation, while the oxidation occurs via free radical mechanisms.


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