Name: heterogeneous removal of water-soluble ruthenium olefin metathesis catalyst from aqueous media via host-guest interaction
Uploaded: 2018-08-23T14:00:00
Description: Watch this Scientific Journal Video about Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction Video at JoVE.com

Dette arbejde blev støttet af Florida State University energi og materialer leje initiativ og FSU afdeling af kemiske og Biomedicinsk teknik.

Bemærk: Vi præsenteret syntesen af 4-(97-(adamantan-1-yloxy)-2,5,8,11,14,17,20,23,26,29,32,35,38,41,44,47,50,53,56,59,62,65,68,71,74,77,80,83,86,89,92,95-dotriacontaoxaheptanonacontyl)-1,3-dimesityl-4,5-dihydro-1H-imidazol-3-ium tetrafluoroborate (imidazolium salt A) og vært komplekse, β-CD podet silica, i vores tidligere papir38. I protokollen beskrive vi en syntese af vores vandopløselige Ru olefin metathesis katalysator og metathesis reaktioner (RCM og BOLTRE).
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Vi beskrev syntesen af flytbare ensartet Ru olefin metathesis katalysator og dens fjernelse fra både vandige og den organiske løsninger. Homogen katalyse giver mange fordele i forhold til heterogene katalysatorer, såsom høj reaktivitet og hurtige reaktionshastigheden; fjernelse af brugt katalysator fra produktet er imidlertid vanskeligere end heterogene katalysator3. Hovedaksen i syntetiserede katalysator er NHC ligand, som bærer adamantyl tøjret vand opløselige oligo(ethylene glycol). Den ...

Fjernelse af den homogene metalorganiske katalyse fra produktet er et vigtigt spørgsmål i moderne kemi1,2. Resterende katalysator forårsager ikke kun en toksicitet problem fra sin heavy metal element, men også en uønsket transformation af produktet fra sine potentielle reaktivitet. Homogen katalysator giver mange fordele, såsom høj aktivitet, hurtig reaktion sats og kemoselektivitet3, men dens fjernelse fra produktet er meget vanskeligere end heterogene katalysator, som er blot fjernes ved filtrering eller dekantering. Kombinationen af fordelene ved homogene og heterogene katalysator, dvs, homogen reaktion og heterogene fjernelse, repræsenterer vigtigt begreb for meget reaktive og let aftageligt metalorganiske katalysator. Figur 1 illustreret Funktionsprincip for homogene reaktion og heterogene fjernelse af katalysator via vært-gæst interaktion.
Vært-gæst kemi er noncovalent limning molekylære anerkendelse mellem vært molekyler og gæst molekyler i Supramolekylær kemi4,5,6,7,8. Cyclodextrins (CDs), cyklisk oligosaccharider, er repræsentative vært molekyler9,10,11,12, og de har været anvendt i store områder af videnskab som polymer videnskab 13 , 14, katalyse15,16, biomedicinske anvendelser6,10og analytisk kemi17. En gæst molekyle, adamatane, binder stærkt til at de hydrofobe hulrum af β-CD (vært, 7-leddede cyklisk saccharid) med høj association konstant, Ka (log Ken = 5,04)18. Denne Supramolekylær bindende affinitet er stærk nok til at fjerne resterende katalysator komplekse fra vandige reaktion løsning med solid understøttede β-CD.
Blandt mange katalysatorer, der er berettiget til vært-gæst fjernelse, blev Ru olefin metathesis katalysator undersøgt på grund af høje praktiske værktøjer og høj stabilitet mod luft og fugt. Olefin metathesis reaktion er et vigtigt redskab i syntetisk kemi til at danne en kulstof-kulstof-dobbeltbinding i overværelse af en overgang metal katalysator19,20,21,22. Udviklingen af stabil Ru olefin metathesis katalysator trigget metathesis som et stort felt i syntetisk kemi (fx, RCM og cross metathesis (CM)) samt polymer videnskab (fx, BOLTRE og acycliske Dien metathesis (ADMET)). Især syntetiserer RCM'EN macrocycles og mellemstore ringe, der har været svært at konstruere23.
På trods af syntetiske utilities af Ru katalyseret olefin metathesis er fuldstændig fjernelse af brugte Ru katalysator fra den ønskede vare en stor udfordring for mange praktiske anvendelser24. For eksempel, blev 1912 ppm af Ru rester observeret i ring-lukning metathesis produkt efter silicagel kolonne kromatografi25. Resterende Ru kan forårsage problemer som olefin isomerisation, nedbrydning, farvelægningsmetode og toksicitet af farmaceutiske produkter26. Internationale konference om harmonisering (ICH) offentliggjort en retningslinje af resterende metal reagenser i pharmaceuticals. Maksimalt tilladte Ru niveau i farmaceutiske produkt er 10 ppm27. Af disse grunde var forskellige tilgange forsøgte at fjerne Ru rester fra produkt løsning28,29,30,31,32,33. Også, udviklingen af flytbare Ru katalysatorer er blevet undersøgt for rensning uden nogen særlig behandling efter reaktionen. Blandt forskellige rensning metoder, blev katalysator ligand ændringer forsøgt at forbedre effektiviteten af silicagel filtrering og flydende udvinding. For eksempel, kan højeffektive silicagel filtrering opnås af indførte ion tag på bensylidencamphor34 eller rygraden i NHC ligand35,36. Katalysatoren forsynet med poly(ethylene glycol)37 eller ion tag35 på en NHC ligand kan forbedre effektiviteten af vandige udtræk til Ru katalysator fjernelse.
For nylig, vi rapporterede en meget vandopløselige Ru olefin metathesis katalysator, som vist ikke kun høj reaktivitet, men også høj katalysator fjernelse sats. Desuden opstod metathesis og katalysator fjernelse i både vand og methylenchlorid34,35,36,37. Hovedaksen i nye katalysator er, at den nye NHC bærer adamantyl bundet oligo(ethylene glycol). Oligo(ethylene glycol) giver høj vandopløselighed af hele katalysatoren komplekse. Derudover besidder oligo(ethylene glycol) adamantyl ende gruppe, der kan bruges i host-gæst samspil med eksterne β-CD.
Vi beskrevet protokoller for katalysator syntese, metathesis reaktioner og katalysator fjernelse i både vand og dichlormethan.

<table border="0" cellpadding="0" cellspacing="0" style="width:767px;" width="767">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Hoveyda-Grubbs Catalyst 1st Generation</td>
			<td style="width:160px;">Sigma-Aldrich</td>
			<td style="width:157px;">577944</td>
			<td style="width:167px;">Air sensitivie. Light sensitivie.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Diethyl diallylmalonate</td>
			<td style="width:160px;">Sigma-Aldrich</td>
			<td style="width:157px;">283479</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Ethyl vinyl ether</td>
			<td style="width:160px;">Sigma-Aldrich</td>
			<td style="width:157px;">422177</td>
			<td>Air sensitive.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Aluminum oxide</td>
			<td style="width:160px;">Sigma-Aldrich</td>
			<td style="width:157px;">06300</td>
			<td>Activated, neutral, Brockmann Activity I</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:283px;">Potassium bis(trimethylsilyl)amide solution (0.5 M in toluene)</td>
			<td style="width:160px;">Sigma-Aldrich</td>
			<td style="width:157px;">277304</td>
			<td>Moisture sensitive.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Etyhl acetate</td>
			<td style="width:160px;">VWR</td>
			<td style="width:157px;">BDH1123</td>
			<td>Flammable liquid.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Methanol</td>
			<td style="width:160px;">VWR</td>
			<td style="width:157px;">BDH1135</td>
			<td>Flammable liquid. Toxic.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Deuterium Oxide 99.8%D</td>
			<td style="width:160px;">TCI</td>
			<td style="width:157px;">W0002</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:283px;">Methylene Chloride-D2 (D, 99.8%)</td>
			<td style="width:160px;">Cambridge Isotope Laboratories, Inc.</td>
			<td style="width:157px;">DLM-23</td>
			<td>Flammable liquid. Toxic.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Activated carbon</td>
			<td style="width:160px;">Sigma-Aldrich</td>
			<td style="width:157px;">242276</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Magnesium sulfate</td>
			<td style="width:160px;">EMD Millipore</td>
			<td style="width:157px;">MX0075</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:283px;">Ethyl ether</td>
			<td style="width:160px;">EMD Millipore</td>
			<td style="width:157px;">EX0190</td>
			<td>Flammable liquid.</td>
		</tr>
	</tbody>
</table>

heterogeneous removal of water-soluble ruthenium olefin metathesis catalyst from aqueous media via host-guest interaction

En yderst effektiv overgang metal katalysator fjernelse metode er udviklet. De vandopløselige katalysator indeholder en nyligt designet NHC ligand for katalysator fjernelse via vært-gæst interaktioner. Den nye NHC ligand besidder en adamantyl (gæst) tøjret lineær ethylenglycol enheder for hydrofobe medtagelse i hulrummet af en β-cyclodextrin (β-CD) vært sammensatte. Den nye NHC ligand blev anvendt til Ru-baserede olefin metathesis katalysator. Ru katalysator udvist fremragende aktivitet i repræsentative ring-lukning metathesis (RCM) og ring-åbning metathesis polymerisation (BOLTRE) reaktioner i vandige medier såvel som organisk opløsningsmiddel, CH2Cl2. Efter reaktionen var komplet, dvælende Ru rester blev fjernet fra den vandige opløsning med effektiviteten af mere end 99% (53 ppm af Ru rest) ved simpel filtrering udnytter en vært-gæst interaktion mellem uopløselige silica-podet β-CD (vært) og den adamantyl gruppe (gæst) på katalysatoren. Den nye Ru katalysator også demonstreret høj fjernelse effektivitet via udvinding når reaktionen køres i organisk opløsningsmiddel ved partitionering rå reaktionsmiljøet mellem lag af diethylether og vand. På denne måde bliver katalysatoren i vandige lag kun. I organiske lag var det resterende beløb, Ru kun 0,14 ppm i RCM reaktioner af diallyl-forbindelser.

Figur 2 beskriver ligand exchange reaktion for vores katalysator 1. 1H NMR spektret er vist i figur 3.
Figur 4 viser RCM'EN i vandig opløsning og efterfølgende fjernelse af brugt katalysator fra reaktionsmiljøet via vært-gæst interaktion, og tabel 1 opsummerer RCM i vandige medier. Kvaternæ...

Watch this Scientific Journal Video about Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction Video at JoVE.com

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction Video (Video) | JoVE

En aftagelig vandopløselige N-Heterocycliske carbene (NHC) ligand i vandige medier via vært-gæst interaktion er blevet udviklet. Vi viste repræsentative olefin metathesis reaktioner i vand samt dichlormethan. Via enten vært-gæst interaktion eller udvinding var resterende ruthenium (Ru) katalysatoren så lavt som 0,14 ppm efter reaktionen.

Heterogene fjernelse af vandopløselige Ruthenium Olefin Metathesis katalysator fra vandige medier Via vært-gæst interaktion

A highly efficient transition metal catalyst removal method is developed. The water-soluble catalyst contains a newly-designed NHC ligand for the catalyst ...

Research

JoVE Journal

Chemistry

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia Video (Video) | JoVE

Udarbejdelse af Hydrofobe Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition af perfluoralkaner til fjernelse af ammoniak

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high ...

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes Video (Video) | JoVE

Den sammenfattende, karakterisering og reaktivitet af en række Ruthenium<em&gt; N</em&gt; -triphos<sup&gt; Ph</sup&gt; Komplekser

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the ...

Water in Oil Emulsions: A New System for Assembling Water-soluble Chlorophyll-binding Proteins with Hydrophobic Pigments

Water in Oil Emulsions: A New System for Assembling Water-soluble Chlorophyll-binding Proteins with Hydrophobic Pigments Video (Video) | JoVE

Vand i olie Emulsioner: Et nyt system til samling Vandopløselige klorofyl-bindende proteiner med Hydrofobe Pigmenter

Chlorophylls (Chls) and bacteriochlorophylls (BChls) are the primary cofactors that carry out photosynthetic light harvesting and electron transport. ...

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin Video (Video) | JoVE

HKUST-1 som en heterogen katalysator til syntese af vanillin

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately ...

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

Synthesis of a Water-soluble Metalâ€“Organic Complex Array Video (Video) | JoVE

Syntese af en Vandopløseligt Metal-Organic Complex Array

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

Synthesis and Evaluation of a Ruthenium-based Mitochondrial Calcium Uptake Inhibitor

Synthesis and Evaluation of a Ruthenium-based Mitochondrial Calcium Uptake Inhibitor Video (Video) | JoVE

Sammenfatning og evaluering af en Ruthenium-baserede mitokondrie Calcium Uptake hæmmer

We detail the synthesis and purification of a mitochondrial calcium uptake inhibitor, [(OH2)(NH3)4Ru(&#181;-O)Ru(NH3)4(OH2)]5+. The optimized synthesis of ...

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction Video (Video) | JoVE

Syntese og ydeevne beskrivelser af overgangen Metal enkelt Atom katalysator for elektrokemisk CO2 reduktion

This protocol presents both the synthesis method of the Ni single atom catalyst, and the electrochemical testing of its catalytic activity and selectivity ...

Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts

Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts Video (Video) | JoVE

Forberedelse af Polyoxometalate-baseret foto-responderende membraner til foto-aktivering af mangan oxid katalysatorer

This paper presents a method to prepare charge-transfer chromophores using polyoxotungstate (PW12O403-), transition metal ions (Ce3+ or Co2+), and organic ...

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization Video (Video) | JoVE

Photogeneration af N-Heterocycliske Carbenes: ansøgning i lysinducerede Ring-åbning Metathesis polymerisering

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes ...

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics Video (Video) | JoVE

Multiscale prøveudtagning af en heterogene vand/Metal katalysator Interface ved hjælp af tæthed funktionelle teori og kraftfelt Molekylær dynamik

A significant number of heterogeneously-catalyzed chemical processes occur under liquid conditions, but simulating catalyst function under such conditions ...