scholarly journals Microwave-Assisted Ionic Liquid-Catalyzed Selective Monoesterification of Alkylphosphonic Acids—An Experimental and a Theoretical Study

Molecules ◽  
2021 ◽  
Vol 26 (17) ◽  
pp. 5303
Author(s):  
Nikoletta Harsági ◽  
Réka Henyecz ◽  
Péter Ábrányi-Balogh ◽  
László Drahos ◽  
György Keglevich
Keyword(s):  
Ionic Liquid ◽  
Alternative Mechanism ◽  
Green Method ◽  
Phosphonic Acids ◽  
Specific Chemical ◽  
Mw Irradiation ◽  
Acid Esterification ◽  
Alkylphosphonic Acids ◽  
Step Mechanism

It is well-known that the P-acids including phosphonic acids resist undergoing direct esterification. However, it was found that a series of alkylphoshonic acids could be involved in monoesterification with C2–C4 alcohols under microwave (MW) irradiation in the presence of [bmim][BF4] as an additive. The selectivity amounted to 80–98%, while the isolated yields fell in the range of 61–79%. The method developed is a green method for P-acid esterification. DFT calculations at the M062X/6–311+G (d,p) level of theory (performed considering the solvent effect of the corresponding alcohol) explored the three-step mechanism, and justified a higher enthalpy of activation (160.6–194.1 kJ·mol−1) that may be overcome only by MW irradiation. The major role of the [bmim][BF4] additive is to increase the absorption of MW energy. The specific chemical role of the [BF4] anion of the ionic liquid in an alternative mechanism was also raised by the computations.

scholarly journals Overview on the Different Patterns of Tumor Vascularization

Cells ◽  
2021 ◽  
Vol 10 (3) ◽  
pp. 639
Author(s):  
Domenico Ribatti ◽  
Francesco Pezzella
Keyword(s):  
Vasculogenic Mimicry ◽  
Endothelial Cell Proliferation ◽  
Published Data ◽  
Alternative Mechanism ◽  
Tumor Vascularization ◽  
Angiogenic Therapy ◽  
Physiological Processes ◽  
Inhibition Of Angiogenesis ◽  
Therapeutic Development

Angiogenesis is a crucial event in the physiological processes of embryogenesis and wound healing. During malignant transformation, dysregulation of angiogenesis leads to the formation of a vascular network of tumor-associated capillaries promoting survival and proliferation of the tumor cells. Starting with the hypothesis formulated by Judah Folkman that tumor growth is angiogenesis-dependent, this area of research has a solid scientific foundation and inhibition of angiogenesis is a major area of therapeutic development for the treatment of cancer. Over this period numerous authors published data of vascularization of tumors, which attributed the cause of neo-vascularization to various factors including inflammation, release of angiogenic cytokines, vasodilatation, and increased tumor metabolism. More recently, it has been demonstrated that tumor vasculature is not necessarily derived by endothelial cell proliferation and sprouting of new capillaries, but alternative vascularization mechanisms have been described, namely vascular co-option and vasculogenic mimicry. In this article, we have analyzed the mechanisms involved in tumor vascularization in association with classical angiogenesis, including post-natal vasculogenesis, intussusceptive microvascular growth, vascular co-option, and vasculogenic mimicry. We have also discussed the role of these alternative mechanism in resistance to anti-angiogenic therapy and potential therapeutic approaches to overcome resistance.

scholarly journals Microwaves as “Co-Catalysts” or as Substitute for Catalysts in Organophosphorus Chemistry

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1196
Author(s):  
György Keglevich
Keyword(s):  
Coupling Reaction ◽  
Diels Alder ◽  
Typical Case ◽  
Conventional Heating ◽  
Phosphine Oxides ◽  
Phosphonic Acids ◽  
Co Catalysts ◽  
Mw Irradiation ◽  
Organophosphorus Chemistry ◽  
Hydrolysis Of

The purpose of this review is to summarize the importance of microwave (MW) irradiation as a kind of catalyst in organophosphorus chemistry. Slow or reluctant reactions, such as the Diels-Alder cycloaddition or an inverse-Wittig type reaction, may be performed efficiently under MW irradiation. The direct esterification of phosphinic and phosphonic acids, which is practically impossible on conventional heating, may be realized under MW conditions. Ionic liquid additives may promote further esterifications. The opposite reaction, the hydrolysis of P-esters, has also relevance among the MW-assisted transformations. A typical case is when the catalysts are substituted by MWs, which is exemplified by the reduction of phosphine oxides, and by the Kabachnik–Fields condensation affording α-aminophosphonic derivatives. Finally, the Hirao P–C coupling reaction may serve as an example, when the catalyst may be simplified under MW conditions. All of the examples discussed fulfill the expectations of green chemistry.

Efficient and Reusable Silica Gel Supported Metal Ionic Liquid Catalysts for Palmitic Acid Esterification to Biodiesel

2021 ◽  
Vol 43 (1) ◽  
pp. 1-1
Author(s):  
Guo Yingwei Guo Yingwei ◽  
Chen Xuedan Chen Xuedan ◽  
Yan Shiting Yan Shiting ◽  
Zhang Zhengliang Zhang Zhengliang ◽  
Chen Yuqin Chen Yuqin ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Palmitic Acid ◽  
Silica Gel ◽  
High Surface ◽  
High Surface Area ◽  
Kinetic Studies ◽  
Catalytic Performance ◽  
Reaction Conditions ◽  
Acid Esterification ◽  
Supported Metal

A series of silica gel (SG) supported metal ionic liquid catalysts (x[Bmim]Cl-CrCl3/SG) were synthesized and exploited for the esterification of palmitic acid (PA) with methanol (ML) to produce biodiesel efficiently. The 10%[Bmim]Cl-CrCl3/SG catalyst with high surface area and desirable acidity exhibited the best catalytic performance and reusability after six consecutive running cycles. Based on the response surface analysis, the optimal reaction conditions were obtained as follows: methanol/acid mole ratio = 11:1 mol/mol, catalyst amount = 5.3 wt%, reaction time = 65 min, as well as reaction temperature = 373 K, reaching to a biodiesel yield of 96.1%. Further kinetic studies demonstrated that the esterification of PA with ML obeyed 1.41 order kinetics for acid concentration with the activation energy of 16.88 kJ/mol

Probing the microscopic structural organization of neat ionic liquids (ILs) and ionic liquid-based gels through resonance energy transfer (RET) studies

2017 ◽  
Vol 19 (34) ◽  
pp. 23194-23203 ◽  
Author(s):  
Debashis Majhi ◽  
Moloy Sarkar
Keyword(s):  
Ionic Liquid ◽  
Energy Transfer ◽  
Ionic Liquids ◽  
Structural Organization ◽  
Rhodamine 6G ◽  
Resonance Energy Transfer ◽  
Resonance Energy

With the aim to understand the role of the ionic constituents of ionic liquids (ILs) in their structural organization, resonance energy transfer (RET) studies between ionic liquids (donor) and rhodamine 6G (acceptor) have been investigated.

scholarly journals The Role of Glutathione S-Transferases in Urinary Tract Tumors

2008 ◽  
Vol 27 (3) ◽  
pp. 360-366 ◽  
Author(s):  
Tatjana Simić ◽  
Ana Savić-Radojević ◽  
Marija Plješa-Ercegovac ◽  
Marija Matić ◽  
Tatjana Sašić ◽  
...  
Keyword(s):  
Urinary Tract ◽  
Urinary Bladder ◽  
Cell Carcinoma ◽  
Allelic Variation ◽  
Transitional Cell ◽  
Chemotherapy Resistance ◽  
High Recurrence Rate ◽  
Specific Chemical ◽  
Glutathione S Transferases

The Role of Glutathione S-Transferases in Urinary Tract Tumors Exposure to potential carcinogens is among the etiological factors for renal cell carcinoma (RCC) and transitional cell carcinoma (TCC) of the urinary bladder. RCC is very resistant, while TCC exhibits a high recurrence rate and multifocality. Cytosolic glutathione S-transferases (GST) are a superfamily of enzymes which protect normal cells by catalyzing conjugation reactions between electrophylic compounds, including carcinogens, and glutathione. Some GST enzymes posses hydroperoxidase activity. The most well characterized classes have been named Alpha (GSTA), Mu (GSTM), Pi (GSTP) and Theta (GSTT) and each of these classes contains several different isoenzymes. Several types of allelic variation have been identified within classes, among which GSTM1-null and GSTT1-null confer impaired catalytic activity. Individuals with the GSTM1-null genotype carry a substantially higher risk for bladder carcinogenesis. The effects of glutathione S-transferase T1 polymorphism on the increased susceptibility to RCC and TCC of urinary bladder depend on the presence of specific chemical exposures to compounds metabolized via the GSTT1-1 pathway. In the process of kidney cancerisation expression of GST alpha isoenzymes tends to decrease, consequently favoring a prooxidant environment necessary for the growth of RCC. GST pi enzyme activities are generally retained in RCC and might contribute to the chemotherapy resistance of RCC. In the malignant phenotype of TCC of the urinary bladder up regulation of various GST classes occurs. Up regulation of GSTT1-1 and GSTP1-1 might have important consequences on the tumor growth, by providing a reduced environment and inhibition of apoptotic pathways.

Efficient and Reusable Silica Gel Supported Metal Ionic Liquid Catalysts for Palmitic Acid Esterification to Biodiesel

2021 ◽  
Vol 43 (1) ◽  
pp. 1-1
Author(s):  
Guo Yingwei Guo Yingwei ◽  
Chen Xuedan Chen Xuedan ◽  
Yan Shiting Yan Shiting ◽  
Zhang Zhengliang Zhang Zhengliang ◽  
Chen Yuqin Chen Yuqin ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Palmitic Acid ◽  
Silica Gel ◽  
High Surface ◽  
High Surface Area ◽  
Kinetic Studies ◽  
Catalytic Performance ◽  
Reaction Conditions ◽  
Acid Esterification ◽  
Supported Metal

A series of silica gel (SG) supported metal ionic liquid catalysts (x[Bmim]Cl-CrCl3/SG) were synthesized and exploited for the esterification of palmitic acid (PA) with methanol (ML) to produce biodiesel efficiently. The 10%[Bmim]Cl-CrCl3/SG catalyst with high surface area and desirable acidity exhibited the best catalytic performance and reusability after six consecutive running cycles. Based on the response surface analysis, the optimal reaction conditions were obtained as follows: methanol/acid mole ratio = 11:1 mol/mol, catalyst amount = 5.3 wt%, reaction time = 65 min, as well as reaction temperature = 373 K, reaching to a biodiesel yield of 96.1%. Further kinetic studies demonstrated that the esterification of PA with ML obeyed 1.41 order kinetics for acid concentration with the activation energy of 16.88 kJ/mol

scholarly journals Tuning the Biginelli reaction mechanism by the ionic liquid effect: the combined role of supported heteropolyacid derivatives and acidic strength

RSC Advances ◽  
2019 ◽  
Vol 9 (46) ◽  
pp. 27125-27135 ◽  
Author(s):  
Elon F. Freitas ◽  
Roberto Y. Souza ◽  
Saulo T. A. Passos ◽  
José A. Dias ◽  
Silvia C. L. Dias ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Reaction Mechanism ◽  
Biginelli Reaction

Heteropolyacids and ionic liquid effect allowed tuning of the Biginelli reaction mechanism and synthesis of 3,4-dihydropyrimidin-2(1H)-one/thione derivatives in an efficient, recyclable fashion. The role of acidic strength and supported heteropolyacid is disclosed.

CO2 Capture by Supported Ionic Liquid Phase: Highlighting the Role of the Particle Size

2019 ◽  
Vol 7 (15) ◽  
pp. 13089-13097 ◽  
Author(s):  
Ruben Santiago ◽  
Jesus Lemus ◽  
Daniel Hospital-Benito ◽  
Cristian Moya ◽  
Jorge Bedia ◽  
...  
Keyword(s):  
Particle Size ◽  
Ionic Liquid ◽  
Liquid Phase ◽  
Co2 Capture ◽  
Supported Ionic Liquid
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