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Готові списки джерел за темами / Superacid Chemistry

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Добірка наукової літератури з теми "Superacid Chemistry"

Автор: Grafiati

Опубліковано: 10 березня 2023

Оновлено: 11 березня 2023

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Статті в журналах з теми "Superacid Chemistry"

1

Kotun, Stefan P., and Darryl D. DesMarteau. "Superacid-induced ring-opening reactions of fluorinated heterocycles." Canadian Journal of Chemistry 67, no. 11 (November 1, 1989): 1724–28. http://dx.doi.org/10.1139/v89-265.

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HF/AsF5 and HF/SbF5 superacid mixtures react with fluorinated small-ring heterocycles such as 1,2-oxazetidines and oxetanes with consequent addition of HF to give alcohol and amine ring-opened products in high yield. Excess HF serves as solvent and reactant. Ring compounds containing both nitrogen and oxygen as heteroatoms protonate predominantly on nitrogen; a case with competing O-protonation arises in the case of a chloro-substituted oxazetidine. In general, rings containing two heteroatoms retain the heteroatom–heteroatom bond and it is a carbon–heteroatom bond that opens. The resulting OH and NH functional groups are not protonated and lost in the superacid medium due to the instability of the highly fluorinated cations that would be left behind. Most of the heterocycles react at or below room temperature, although the very weakly basic 2,2-bis(trifluoromethyl)-3,3,4,4-tetrafluorooxetane requires the stronger HF/SbF5 superacid system and more severe conditions. Keywords: superacids, hydrogen fluoride, ring opening, fluorinated oxazetidines, fluorinated oxetanes.

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2

Rasul, Golam, G. K. Surya Prakash, and George A. Olah. "Chemistry in Superacids. 15. Gitonic Protodiazonium and Bisdiazonium Dications and Their Potential Role in Superacid Chemistry." Journal of the American Chemical Society 116, no. 20 (October 1994): 8985–90. http://dx.doi.org/10.1021/ja00099a016.

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3

Enami, Shinichi, Logan A. Stewart, Michael R. Hoffmann, and Agustín J. Colussi. "Superacid Chemistry on Mildly Acidic Water." Journal of Physical Chemistry Letters 1, no. 24 (December 3, 2010): 3488–93. http://dx.doi.org/10.1021/jz101402y.

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4

Knoecer, Larecia, Daniel DeSchepper, and Douglas A. Klumpp. "Superacid-Induced Reactions of Nefopam." Organic Chemistry International 2010 (June 13, 2010): 1–5. http://dx.doi.org/10.1155/2010/496818.

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The analgesic drug nefopam reacts in superacidic media to form a dicationic superelectrophiles by ring opening. The dication species is capable of reacting with arenes in Friedel-Crafts-type conversions. This chemistry is used to prepare novel derivatives of nefopam.

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5

Olah, George A., Nikolai Hartz, Golam Rasul, Arwed Burrichter, and G. K. Surya Prakash. "Chemistry in Superacids. Part 18. Ester Cleavage in Superacid Media Involving Diprotonated Gitonic Carboxonium Dications." Journal of the American Chemical Society 117, no. 24 (June 1995): 6421–27. http://dx.doi.org/10.1021/ja00129a001.

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6

Hartz, Nikolai, Golam Rasul, and George A. Olah. "Chemistry in superacids. 10. Role of oxonium, sulfonium, and carboxonium dications in superacid-catalyzed reactions." Journal of the American Chemical Society 115, no. 4 (February 1993): 1277–85. http://dx.doi.org/10.1021/ja00057a009.

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7

Kulsha, Andrey V., and Dmitry I. Sharapa. "Superhalogen and Superacid." Journal of Computational Chemistry 40, no. 26 (June 29, 2019): 2293–300. http://dx.doi.org/10.1002/jcc.26007.

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8

Wang, Siqi, Yaroslav V. Zonov, Victor M. Karpov, Olga A. Luzina, and Tatyana V. Mezhenkova. "Carbonylation of Polyfluorinated 1-Arylalkan-1-ols and Diols in Superacids." Molecules 27, no. 24 (December 10, 2022): 8757. http://dx.doi.org/10.3390/molecules27248757.

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We describe the carbonylation of a series of mono and dihydroxy derivatives of polyfluorinated alkylbenzenes and benzocycloalkenes with OH groups at benzylic positions using carbon monoxide in the presence of a superacid (TfOH, a TfOH–SbF5 mixture, or a FSO3H–SbF5 mixture). It was shown that the superacid-catalyzed addition of CO to various primary and secondary polyfluorinated alcohols and diols gives the corresponding mono- and dicarboxylic acids or lactones. The efficiency of various superacids depending on alcohol structure was evaluated, and FSO3H–SbF5 yielded the best results in most transformations. The addition of CO to secondary 1-arylalkan-1-ols containing vicinal fluorine atoms was found to be accompanied by elimination of HF with the formation of α,β-unsaturated aryl-carboxylic acids. In contrast to primary and secondary alcohols, conversion of tertiary perfluoro-1,1-diarylalkan-1-ols into carbonylation products is not complete, and the resulting carboxylic acids are easily decarboxylated after water treatment of the reaction mixture.

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9

Olah, George A., and Omar Farooq. "Chemistry in superacids. 7. Superacid-catalyzed isomerization of endo- to exo-trimethylenenorbornane (tetrahydrodicyclopentadiene) and to adamantane." Journal of Organic Chemistry 51, no. 26 (December 1986): 5410–13. http://dx.doi.org/10.1021/jo00376a067.

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10

Mazej, Zoran, Primož Benkič, Alain Tressaud, and Boris Žemva. "Palladium Chemistry in Anhydrous HF/AsF5 Superacid Medium." European Journal of Inorganic Chemistry 2004, no. 9 (May 2004): 1827–34. http://dx.doi.org/10.1002/ejic.200300681.

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Більше джерел

Дисертації з теми "Superacid Chemistry"

1

Stiel, Jason A. "Fundamental Chemistry of Chlorophosphazenes and Polysilanes." University of Akron / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=akron1467990664.

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2

Anderson, Bruce Gordon. "Methane-olefin coupling using supported-nickel and solid superacid catalysts." Thesis, University of Ottawa (Canada), 1993. http://hdl.handle.net/10393/7900.

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In this thesis, we have investigated the coupling of methane with olefins, such as ethylene and propylene using silica-supported nickel and sulphate-promoted zirconia-silica catalysts. Control experiments over hydrogen-reduced Ni/SiO$\sb2$ in which propylene was co-fed with helium rather than with methane resulted in increased propylene conversions and in an increase of the yields of propane, C$\sb2$'s and C$\sb4$'s. It was concluded that the production of C$\sb4$'s was due to homologation or metathesis reactions, rather than to methane coupling. Variation of the temperature of the methane preactivation treatment from 350$\sp\circ$C to 600$\sp\circ$C revealed an increased CH$\sb4$ conversion from approximately 1% at 350$\sp\circ$C to 60% at 600$\sp\circ$C. Subsequent reaction of $\rm C\sb3H\sb6/CH\sb4$ mixtures over these catalysts at 350$\sp\circ$C revealed that there was virtually no activity over the former catalyst and very little over the latter. However, catalysts activated between 400$\sp\circ$C and 500$\sp\circ$C showed very similar activities. Experiments in which helium was co-fed with propylene rather than methane over CH$\sb4$-preactivated catalysts suggested that the same processes were responsible for C$\sb4$ production over CH$\sb4$-reduced NiO/SiO$\sb2$ and hydrogen-reduced NiO/SiO$\sb2$ i.e. propylene homologation and/or metathesis. Dissociatively adsorbed methane only served to block metal sites at which reactions could otherwise occur. Zirconia-silica, like many binary oxide mixtures, possesses enhanced surface acidity relative to its parent components. TPD experiments using NH$\sb3$ found that samples of 5, 10, and 20 wt.% ZrO$\sb2$/SiO$\sb2$, previously activated by evacuation at 450$\sp\circ$C, contained a similar amount of surface acid sites, 260 $\mu$mole/g sample. XRD analysis revealed no peaks due to crystalline phases following calcination at 450$\sp\circ$C, suggesting that these materials were amorphous, even with zirconia loadings as high as 20 wt.%. Infrared analysis of 10 wt.% ZrO$\sb2$/SiO$\sb2$ with sulphate loadings ranging from 100 to 1000 $\mu$mole/g revealed that the nature of the surface sulphate species was dependent on the temperature of activation. IR analysis using NH$\sb4$ as a probe revealed that both Lewis and Bronsted acid sites existed after 500$\sp\circ$C activation. The amount of each type of acid site appeared to increase with increased sulphate loading. The acidity of 10 wt.% ZrO$\sb2$/SiO$\sb2$ with various loadings of sulphate was measured by gravimetric ammonia adsorption following evacuation at various temperatures. The amounts of irreversibly adsorbed ammonia were found to increase with increased sulphate loading at 25, 100, and 200$\sp\circ$C. Attempts to measure the amount of irreversible adsorption at temperatures greater than 200$\sp\circ$C were hampered by weight loss due to sulphate. Thus, precise measurement of the number of acid sites at high temperature was not possible. Sulphate-promoted ZrO$\sb2$/SiO$\sb2$, previously activated by evacuation at 500$\sp\circ$C, was tested as a catalyst for the coupling of methane and ethylene (or propylene) in a fixed-bed reactor at atmospheric pressure and at temperatures ranging from 225 to 275$\sp\circ$C. All experiments were hampered by rapid deactivation of the catalyst (within 35 minutes on stream) due to oligomerization. Only minute quantities of propane were detected. Reactions of methane alone showed that it also interacted strongly with the catalyst, leading to deactivation. (Abstract shortened by UMI.)

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3

Tun, Zin-Min. "Fundamental Chlorophosphazene Chemistry." University of Akron / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=akron1321278169.

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4

Musrock, Henry, Patrick Nshizirungu, Esther Alorkpa, and Aleksey Vasiliev. "SUPERACIDIC MATERIALS BASED ON IMMOBILIZED PHOSPHOTUNGSTIC ACID." Digital Commons @ East Tennessee State University, 2018. https://dc.etsu.edu/asrf/2018/schedule/141.

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Phosphotungstic acid H3[PMo12O40](PTA) with the Keggin structure has become well known as a solid superacid with pKa≈-13. Such a strong acidity is caused by delocalization of the negative charge of the anion on many oxygen atoms over the surface of the Keggin structure. High acidity of PTA and its good solubility in water and other polar solvents enables its use as a highly active homogeneous catalyst. However, in spite of relatively higher reaction rate, homogeneous catalysis has various drawbacks that limit its practical application. The main drawback is the difficult and expensive removal of the used catalyst from the reaction mixture and its recycling. PTA also demonstrated good catalytic activity as a heterogeneous catalyst of various organic reactions, e.g. hydrolysis, hydration and polymerization. Wide application of a pure superacid in catalysis is limited by its low surface area and solubility in polar solvents. The objective of this work is the synthesis and study of insoluble superacidic catalysts covalently embedded into the silica matrix. The catalyst PTA/SiO2 was synthesized by the sol-gel method. Tetraethoxysilane was co-condensed with PTA in acidic media in the presence of Pluronic P123 surfactant as a pore-forming agent. The obtained gel was air-dried and calcined at 500 °C producing a mesoporous material with a significant fraction of micropores in its structure. Isotherms of adsorption/desorption of nitrogen indicated cylindrical shape of the pores with necks that is typical for materials obtained with Pluronic P123 as a template. Cs-exchanged material was prepared by mixing PTA/SiO2 with a solution of CsCl. The cation exchange on cesium decreased the total pore volume due to a much higher volume of cesium ions as compared to protons. In addition, partial pore blocking by these ions restricted access to small pores thus reducing accessible surface area. Heteropolyacids are unstable in alkaline media that makes direct solid-state titration impossible. Surface acidity of the samples was determined by reversed titration. Dry samples were dispersed in a solution of pyridine in tetrahydrofuran. After equilibration, the solid phase was filtered, and the filtrate was titrated by HCl. PTA/SiO2 has a very high adsorption capacity on pyridine, which corresponds to 15 molecules of pyridine per [PMo12O40]3- anion. This number exceeded the number of available protons. The catalysts were successfully tested in the alkylation of mesitylene by alkenes. The use of superacidic materials in catalytic reactions can significantly improve the effectiveness of the processes.

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5

Carr, G. "The chemistry of oxygen heterocycles in superacidic media." Thesis, University of Liverpool, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.233754.

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6

Kuvayskaya, Anastasia, Saul Garcia, and Aleksey Vasiliev. "Synthesis of Long-chain Alkylbenzenes on Superacidic Catalysts Containing Embedded Phosphotungstic Acid." Digital Commons @ East Tennessee State University, 2019. https://dc.etsu.edu/asrf/2019/schedule/200.

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Heteropolyacids (HPAs), such as phosphotungstic acid (PTA) and phosphomolybdic acid (PMA), with the Keggin structure are well known as solid superacids with estimated pKa of -13. High acidity of HPAs enabled their use as highly active homogeneous catalysts. However, homogeneous catalysis has many drawbacks, e.g. difficult and expensive separation of the used catalyst from the reaction mixture and its recycling. Application of pure HPAs in heterogeneous catalysis is limited by their low surface area and solubility in polar solvents. For increasing their surface area, HPAs should be immobilized on solid support. The objective of this work is the development of an active and stable HPA-containing catalyst for synthesis of long chain alkylbenzenes, which are essential precursors in the manufacture of surfactants. To prevent leachability of HPA from the support, it was covalently bonded into the silica matrix via Si‑O‑W bridges. The catalysts were obtained by co-condensation of tetraethoxysilane (TEOS) with PTA using sol-gel method in the presence of various surfactants as pore-forming agents. The synthesis was conducted by simultaneous addition of 20% HCl and ethanol solution of a mixture of TEOS and PTA to a solution of a surfactant. The reaction mixture was refluxed for 24 h. The obtained product was filtered, washed, air-dried, and calcined for total removal of a surfactant from pores. Use of Pluronic P123 as a non-ionic pore-forming agent produced the most acidic material. The synthesized mesoporous materials were tested as heterogeneous catalysts in liquid-phase alkylation of mesitylene by long-chain alkenes. They demonstrated higher activity than well-known zeolite HY. The analysis of catalyst recovered after the alkylation indicated no PTA leaching from silica matrix. Obtained superacidic mesoporous materials can potentially replace hazardous liquid Lewis acids currently used for long-chain alkylbenzene synthesis in petrochemical industry.

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7

Berrino, Emanuela, Claudiu Supuran, Alessandro Mugelli, and Fabrizio Carta. "Carbonic Anhydrase Inhibitors: Versatile Agents for the Treatment of Human Diseases." Doctoral thesis, 2020. http://hdl.handle.net/2158/1188882.

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The Carbonic Anhydrases (CAs, EC 4.2.1.1) are ubiquitous metalloenzymes expressed in almost all living organisms. Being one of the main actors in pH regulation and in the maintenance of proper concentrations of CO2, the dysruption of the activity of such enzymes, by means of adequate modulators, is a validated strategy for the treatment of human affecting pathologies and for the eradication of etiological agents (i.e. pathogenic bacteria, fungi and protozoa). In addition, CA-based biotechnological applications (i.e. CO2 capture) may benefit from modulation of the enzymatic activity. CA Inhibitors (CAIs) have been extensively investigated over the time, and have been validated for the management of hypertensive glaucoma, systemic hypertension, epilepsy, obesity related diseases and recently neuropathic pain, inflammation and hypoxic tumors. Although CA activators (CAA) traditionally lacked interests, currently a repurposing of such compounds is underway with promising results as potential agents for the management of memory deficits related to neurodegenerative diseases. In this Thesis work, an introductive overview on CAs as the main biological targets (Chapter 1) and three distinctive projets (Chapters 2-4) are reported ranging from synthetic chemistry to enzyme biology and spctrophotometry. The first one (Chapter 2) concerns the synthesis and evaluation of new CAIs with Carbon Monoxide (CO) releasing properties for the management of RA. The reported compounds have been fully characterized, their CA inhibitory properties along with the CO releasing effect were assessed. In particular, a spectrophotometric assay was properly set with slight modifications of the protocols reported in the literature. This allowed to obtain a precise and quantitative evaluation of CO released over time from our compounds. The pain refief effect of the designed CAI-CORMs was also evaluated in a rat model of RA with very promising results. The second project (Chapter 3) was aimed to synthetize a small series of CAI-AZT hybrids and to evaluate them as Telomerase Inhibitors, thus with possible antitumoral applications. The compounds synthetized have been profiled in vitro on seven CA isoforms (i.e. I, II, Va, VB, VII, IX and XII). The effects of our compounds on Telomerase Activity have been also determined showing a low-medium inhibition potency. Two promising derivatives have been identified with good IC50 and IC90 values. Co-crystallyzation of selected compounds in adduct with hCA II has been performed and their binding modes were determined. The third project (Chapter 4) was entirely carried out during my six-months visiting student experience at the University of Poitiers in France, and it concerns the synthesis in Superacid medium of new mono and di-fluorinated diamines as CAIs. Insertion of one or more C-F bonds is a validated strategy in Medicinal Chemistry. Fluorine insertion can modulate pharmacokinetic and pharmacodynamic properties of the compounds, thus being an attractive tool in the design of bioactive compounds. Another unrelated project included in this Chapter, is the synthesis of enantiopure fluorinated tricyclic scaffolds obtained by means of a diastereoselective approach.

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8

"Novel Anhydrous Superprotonic Ionic Liquids and Membranes for Application in Mid-temperature Fuel Cells." Doctoral diss., 2013. http://hdl.handle.net/2286/R.I.18121.

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abstract: This thesis studies three different types of anhydrous proton conducting electrolytes for use in fuel cells. The proton energy level scheme is used to make the first electrolyte which is a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The protons are introduced into a cross-linked polyphospazene rubber by the superacid HOTf, which is absorbed by partial protonation of the backbone nitrogens. The decoupling of conductivity from segmental relaxation times assessed by comparison with conductivity relaxation times amounts to some 10 orders of magnitude, but it cannot be concluded whether it is purely protonic or due equally to a mobile OTf- or H(OTf)2-; component. The second electrolyte is built on the success of phosphoric acid as a fuel cell electrolyte, by designing a variant of the molecular acid that has increased temperature range without sacrifice of high temperature conductivity or open circuit voltage. The success is achieved by introduction of a hybrid component, based on silicon coordination of phosphate groups, which prevents decomposition or water loss to 250ºC, while enhancing free proton motion. Conductivity studies are reported to 285ºC and full H2/O2 cell polarization curves to 226ºC. The current efficiency reported here (current density per unit of fuel supplied per sec) is the highest on record. A power density of 184 (mW.cm-2) is achieved at 226ºC with hydrogen flow rate of 4.1 ml/minute. The third electrolyte is a novel type of ionic liquids which is made by addition of a super strong Brønsted acid to a super weak Brønsted base. Here it is shown that by allowing the proton of transient HAlCl4, to relocate on a very weak base that is also stable to superacids, we can create an anhydrous ionic liquid, itself a superacid, in which the proton is so loosely bound that at least 50% of the electrical conductivity is due to the motion of free protons. The protic ionic liquids (PILs) described, pentafluoropyridinium tetrachloroaluminate and 5-chloro-2,4,6-trifluoropyrimidinium tetrachloroaluminate, might be the forerunner of a class of materials in which the proton plasma state can be approached.
Dissertation/Thesis
Ph.D. Chemistry 2013

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Книги з теми "Superacid Chemistry"

1

O'Donnell, T. A. Superacids and acidicmelts as inorganic chemical reaction media. New York: VCH Publishers, 1993.

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2

O'Donnell, Thomas A. Superacids and acidic melts as inorganic chemical reaction media. New York, N.Y: VCH Publishers, 1992.

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3

Superacid chemistry. 2nd ed. Hoboken, N.J: Wiley, 2009.

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4

Superacid Chemistry. John Wiley & Sons Inc, 2007.

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5

Superacid Chemistry. Wiley & Sons, Incorporated, John, 2009.

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6

O'Donnell, Thomas A. Superacids and Acidic Melts As Inorganic Chemical Reaction Media. Wiley & Sons, Incorporated, John, 1992.

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Частини книг з теми "Superacid Chemistry"

1

Jacquesy, Jean-Claude. "Organic Synthesis in Superacids." In Carbocation Chemistry, 359–76. Hoboken, NJ, USA: John Wiley & Sons, Inc., 2014. http://dx.doi.org/10.1002/9780471678656.ch14.

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2

"A Life of Magic Chemistry." In The Case of the Poisonous Socks: Tales from Chemistry, 202–4. The Royal Society of Chemistry, 2011. http://dx.doi.org/10.1039/bk9781849733243-00202.

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The brief story of how the Nobel Prize for 1994 was awarded to the Hungarian–American chemist, George Olah, for a “magic acid” (superacid) that helped resolve a long-standing dispute over the mechanism of certain reactions in organic chemistry.

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3

"Solid Superacid Catalysis." In World Scientific Series in 20th Century Chemistry, 583. World Scientific Publishing Company, 2003. http://dx.doi.org/10.1142/9789812791405_others12.

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4

"Magic Acid and Superacid Chemistry." In World Scientific Series in 20th Century Chemistry, 549–50. World Scientific Publishing Company, 2003. http://dx.doi.org/10.1142/9789812791405_others11.

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5

Olah, George A., Khosrow Laali, and Omar Farooq. "Superacid-Catalyzed Formylation of Aromatics with Carbon Monoxide." In World Scientific Series in 20th Century Chemistry, 88–91. World Scientific Publishing Company, 2003. http://dx.doi.org/10.1142/9789812791405_0022.

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6

Strausz, Otto P., Thomas W. Mojelsky, John D. Payzant, George A. Olah, and G. K. Surya Prakash. "Upgrading of Alberta's Heavy Oils by Superacid-Catalyzed Hydrocracking." In World Scientific Series in 20th Century Chemistry, 1190–201. World Scientific Publishing Company, 2003. http://dx.doi.org/10.1142/9789812791405_0234.

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7

Olah, George A. "Methods for Preparing Energetic Nitrocompounds: Nitration with Superacid Systems, Nitronium Salts, and Related Complexes." In Chemistry of Energetic Materials, 139–204. Elsevier, 1991. http://dx.doi.org/10.1016/b978-0-12-525440-3.50012-2.

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8

Olah, George A., Khosrow Laali, and Omar Farooq. "Chemistry in Superacids. 6: Perfluoroalkanesulfonic Acid–Boron Perfluoroalkanesulfonates: New Superacid Systems for Generation of Carbocations and Catalysts for Electrophilic Transformations of Hydrocarbons." In World Scientific Series in 20th Century Chemistry, 578–81. World Scientific Publishing Company, 2003. http://dx.doi.org/10.1142/9789812791405_0109.

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9

Olah, George A., G. K. Surya Prakash, Thomas Mathew, and Eric R. Marinez. "Superacid-Catalyzed Selective Formylation–Rearrangement of Isoalkanes with Carbon Monoxide to Branched Ketones." In World Scientific Series in 20th Century Chemistry, 686–87. World Scientific Publishing Company, 2003. http://dx.doi.org/10.1142/9789812791405_0126.

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10

Olah, George A., Mark R. Bruce, Edward H. Edelson, and Altaf Husain. "Superacid coal chemistry 1: HF:BF3 catalysed depolymerization–ionic hydroliquefaction of coals under mild conditions." In World Scientific Series in 20th Century Chemistry, 1202–9. World Scientific Publishing Company, 2003. http://dx.doi.org/10.1142/9789812791405_0235.

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Тези доповідей конференцій з теми "Superacid Chemistry"

1

YANG, HUA, and RONG LU. "SOLID SUPERACIDS OF SULFATED ZIRCONIA-SILICON NANOCRYSTALS." In Proceedings of the International Symposium on Solid State Chemistry in China. WORLD SCIENTIFIC, 2002. http://dx.doi.org/10.1142/9789812776846_0069.

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Звіти організацій з теми "Superacid Chemistry"

1

Olah, G. A. Superacid catalyzed coal conversion chemistry. Final technical report, September 1, 1983-September 1, 1986. Office of Scientific and Technical Information (OSTI), January 1986. http://dx.doi.org/10.2172/5253008.

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