Name: sulfate separation by selective crystallization with a bis-iminoguanidinium ligand
Uploaded: 2016-09-08T13:00:00
Description: Watch this Scientific Journal Video about Sulfate Separation by Selective Crystallization with a Bis-iminoguanidinium Ligand at JoVE.com

This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. We thank the University of North Carolina Wilmington for providing the seawater.

1. Syntese af 1,4-Benzen-bis (iminoguanidinium) chlorid (BBIG-CI) <ol><li> In Situ Syntese af 1,4-Benzen-bis (iminoguanidinium) Chloride ligand (BBIG-CI) og dens Krystallisation med sulfat <ol><li> Tilføj 0,067 g terephthalaldehyde og 2,2 ml af en 0,5 M vandig opløsning af aminoguanidinium chlorid til 10 ml deioniseret vand i en 25 ml rundbundet kolbe udstyret med en magnetisk omrører. </li><li> Omrør opløsningen magnetisk i fire timer ved 20 ° C. Dette vil give en svagt gul opløsning af BBIG-CI. </li>...

<ol>
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J., Miller, K. A., Balakrishna, R., Nguyen, T. B., Kimbrell, M. R., Georg, G. I., David, S. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Novel+Endotoxin-Sequestering+Compounds+with+Terephthaldehyde-bis-guanylhydrazone+Scaffolds.">Novel Endotoxin-Sequestering Compounds with Terephthaldehyde-bis-guanylhydrazone Scaffolds.</a> Bioorg. Med. Chem. Lett. 16, 1305-1308 (2006).</li><li>Pecharsky, V. K., Zavalij, P. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Fundamentals of Powder Diffraction and Structural Characterization of Materials. , (2005).</li><li>Goldenberg, D. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Principles of NMR Spectroscopy: An Illustrated Guide. , (2016).</li></ol>

Denne teknik er temmelig tolerant over for mange afvigelser fra den skriftlige forhandling, hvilket gør det ganske robust. Der er dog to vigtige skridt, der skal følges. For det første har BBIG-CI ligand skal være så ren som muligt. Urenheder vil ikke kun påvirke krystallisering og opløselighed af det resulterende sulfat salt, men vil også gøre det vanskeligt at beregne det beløb der kræves for kvantitativ sulfat fjernelse fra opløsningen. For det andet, alle trin i β væskescintillationstælling sektion sk...

Selektiv adskillelse af hydrofile oxoanioner (f.eks sulfat, chromat, fosfat) fra konkurrencedygtige vandige opløsninger er en grundlæggende udfordring med relevans for udbedring af miljøskader, energiproduktion, og menneskers sundhed. 1,2 Sulfate især er vanskeligt at udvinde fra vand på grund af sin iboende modvilje mod at kaste sin hydrering sfære og migrere ind mindre polære miljøer. 3 Gør vandig sulfat udvinding mere effektiv kræver typisk komplekse receptorer, der er vanskelige og trættende at syntetisere og rense, ofte involverer toksiske reagenser og opløsningsmidler. 4,5 Selektiv krystallisation tilbyder en enkel men effektiv alternativ til sulfat adskillelse fra vand. 6-9 Selvom nogle metalkationer såsom Ba2 +, Pb2 +, eller Ra 2+ danner meget uopløselige sulfatsalte, deres anvendelse i sulfat adskillelse er ikke altid praktisk grund af deres høje toxiby og undertiden-lav selektivitet. Anvender organiske ligander som sulfat fældningsmidler drager fordel af strukturel diversitet og modtagelighed for designe karakteristisk for organiske molekyler. En ideel organisk ligand for vandig sulfat krystallisation bør være opløselig i vand, hvorimod det et uopløseligt sulfatsalt eller kompleks i en relativt kort tid og i nærvær af høje koncentrationer af konkurrerende ioner. Derudover bør det være let at syntetisere og genanvende. Et sådant En ligand, 1,4-benzen-bis (iminoguanidinium) (BBIG), selv-samlet in situ ud fra to kommercielt tilgængelige prækursorer, terephthalaldehyde og aminoguanidinium chlorid, blev for nylig vist sig at være yderst effektive i vandig sulfat adskillelse. 10 Liganden er vandopløselig i chloridform, og selektivt krystalliserer med sulfat i en ekstremt uopløseligt salt, der let kan fjernes fra opløsning ved simpel filtrering. Den BBIG ligand kan derefter genvindes ved deprotonering med enqueous NaOH og krystallisation af det neutrale bis-iminoguanidine, som kan omdannes tilbage til chloridform med vandig HCI, og genbruges i en anden adskillelse cyklus. Effekten af ​​denne ligand til fjernelse sulfat fra vandet er så stor, at overvåge de resterende koncentration sulfat i opløsning er ikke længere en triviel opgave, der kræver en mere avanceret teknik, der tillader nøjagtig måling af spormængder af anionen. Til dette formål blev radioaktivt mærket 35S-sulfat tracer sammen med β væskescintillationstælling anvendes, en teknik der almindeligvis anvendes i væske-væske ekstraktive separationer, og for nylig vist at være effektiv i overvågningen sulfat krystallisation. 8 Denne protokol viser one-pot in situ syntese af BBIG liganden og dens krystallisation som sulfatsaltet fra vandige opløsninger. Ex situ syntese af liganden 11 er også præsenteret som en convenient metode til produktion af større mængder af BBIG-Cl, der kan gemmes i den krystallinske form indtil den er klar til brug. Sulfat fjernelse fra havvand fra den tidligere fremstillede BBIG-CI ligand derefter påvises. Endelig er anvendelsen af 35S-mærket sulfat og β væskescintillationstælling til måling koncentrationen sulfat i havvand påvist. Denne protokol er beregnet til at give en tutorial for dem bredt interesseret i at udforske brugen af ​​selektive krystallisering for vandig anion separation.

<table border="0" cellpadding="0" cellspacing="0" width="740">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Terephthalaldehyde</td>
			<td style="width:92px;">Sigma</td>
			<td style="width:119px;">T2207</td>
			<td style="width:313px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Aminoguanidinium Chloride</td>
			<td style="width:92px;">Sigma</td>
			<td style="width:119px;">#396494</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Sodium Sulfate</td>
			<td style="width:92px;">Sigma</td>
			<td style="width:119px;">#239313</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Barium Chloride</td>
			<td style="width:92px;">Sigma</td>
			<td style="width:119px;">#342920</td>
			<td>Highly Toxic</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Ethanol</td>
			<td style="width:92px;">Any</td>
			<td style="width:119px;"></td>
			<td>Reagent Grade (190 proof)</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Sodium Hydroxide</td>
			<td style="width:92px;">EMD</td>
			<td style="width:119px;">SX0590-1</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Hydrochloric Acid</td>
			<td style="width:92px;">Sigma</td>
			<td style="width:119px;">#258148</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Filter Paper</td>
			<td style="width:92px;">Any</td>
			<td style="width:119px;">-</td>
			<td>Any qualitative or analytical filter paper will work</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Syringe Filter (0.22 um)</td>
			<td style="width:92px;">Any</td>
			<td style="width:119px;">-</td>
			<td>Nylon filter</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">35S Labeled Sulfate</td>
			<td style="width:92px;">Perkin Elmer</td>
			<td style="width:119px;">NEX041005MC</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Ultima Gold Scintillation Cocktail</td>
			<td style="width:92px;">Perkin Elmer</td>
			<td style="width:119px;">#6013329</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Polypropylene Vials&#160;</td>
			<td style="width:92px;">Any</td>
			<td style="width:119px;">-</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Disposable Syringe (2-3 mL)</td>
			<td style="width:92px;">Any</td>
			<td style="width:119px;">-</td>
			<td>Any disposable plastic syringe works</td>
		</tr>
	</tbody>
</table>

sulfate separation by selective crystallization with a bis-iminoguanidinium ligand

A simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, 1,4-benzene-bis(iminoguanidinium) (BBIG), is demonstrated. The ligand is synthesized as the chloride salt (BBIG-Cl) by in situ imine condensation of terephthalaldehyde with aminoguanidinium chloride in water, followed by crystallization as the sulfate salt (BBIG-SO4). Alternatively, BBIG-Cl is synthesized ex situ in larger scale from ethanol. The sulfate separation ability of the BBIG ligand is demonstrated by selective and quantitative crystallization of sulfate from seawater. The ligand can be recycled by neutralization of BBIG-SO4 with aqueous NaOH and crystallization of the neutral bis-iminoguanidine, which can be converted back into BBIG-Cl with aqueous HCl and reused in another separation cycle. Finally, 35S-labeled sulfate and &#946; liquid scintillation counting are employed for monitoring the sulfate concentration in solution. Overall, this protocol will instruct the user in the necessary skills to synthesize a ligand, employ it in the selective crystallization of sulfate from aqueous solutions, and quantify the separation efficiency.

Pulver-røntgendiffraktionsmønster af BBIG-SO 4 (figur 1) giver mulighed for utvetydig bekræftelse af identiteten af det krystalliserede faststof. I sammenligning af det opnåede mønster versus referencen én, topintensitet matters mindre end peak positionering. Alle stærke toppe er vist i referencen bør være til stede i den opnåede prøve. Udseendet af stærke toppe i prøven, som er fraværende i henvisningen mønster indikerer tilstedeværelsen af ?...

Watch this Scientific Journal Video about Sulfate Separation by Selective Crystallization with a Bis-iminoguanidinium Ligand at JoVE.com

Sulfate Separation by Selective Crystallization with a Bis-iminoguanidinium Ligand

En protokol til in situ vandig syntese af en bis (iminoguanidinium) ligand og dens anvendelse i selektiv adskillelse af sulfat præsenteres.

Sulfat Separation ved selektiv krystallisation med en Bis-iminoguanidinium ligand

A simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, ...

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