Name: synthesis of a water-soluble metal&#8211;organic complex array
Uploaded: 2016-10-08T14:00:00
Description: Watch this Scientific Journal Video about Synthesis of a Water-soluble MetalÃ¢â‚¬â€œOrganic Complex Array at JoVE.com

This work was supported by the World Premier International Research Center (WPI) Initiative on Materials Nanoarchitectonics and a Grant-in-Aid for Challenging Exploratory Research (No. 26620139), both of which were provided from MEXT, Japan.

1. Fremstilling af metal Komplekse monomerer (2 CAS RN 1381776-70-0, 3 CAS RN 1261168-42-6, 4 CAS RN 1261168-43-7, figur 1) <ol><li> Fremstilling af Ru monomer 2 <ol><li> Kombiner den organiske forløber (5 9 CAS RN 1381776-63-1, figur 1) (380 mg, 0,48 mmol) og [Ru (p-cymen) Cl 2] dimer (224 mg, 0,37 mmol) med en omrører i en 100 ml enkelt-halset rundbundet kolbe. </li><li> Tilsæt methanol (MeOH) (25 ml) til blandingen, forbinde en kon...

<ol>
	<li>Takanashi, K., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Heterometal+Assembly+in+Dendritic+Polyphenylazomethines.">Heterometal Assembly in Dendritic Polyphenylazomethines.</a> Bull. Chem. Soc. Jpn. 80, 1563-1572 (2007).</li><li>Packheiser, R., Ecorchard, P., R&#252;ffer, T., Lang, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Heteromultimetallic+Transition+Metal+Complexes+Based+on+Unsymmetrical+Platinum(II)+Bis-Acetylides.">Heteromultimetallic Transition Metal Complexes Based on Unsymmetrical Platinum(II) Bis-Acetylides.</a> Organometallics. 27, 3534-3536 (2008).</li><li>Sculfort, S., Braunstein, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Intramolecular+d10-d10+Interactions+in+Heterometallic+Clusters+of+the+Transition+Metals.">Intramolecular d10-d10 Interactions in Heterometallic Clusters of the Transition Metals.</a> Chem. Soc. Rev. 40, 2741-2760 (2011).</li><li>Vairaprakash, P., Ueki, H., Tashiro, K., Yaghi, O. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+Metal-Organic+Complex+Arrays.">Synthesis of Metal-Organic Complex Arrays.</a> J. Am. Chem. Soc. 133, 759-761 (2011).</li><li>Jacoby, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis:+Method+Couples+Various+Metals+in+Predetermined+Sequences.">Synthesis: Method Couples Various Metals in Predetermined Sequences.</a> C&amp;EN. 89, (2011).</li><li>White, P., Eds D&#246;rner, B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthetic+Notes.">Synthetic Notes.</a> Peptide Synthesis 2008/2009. , (2009).</li><li>Sajna, K. V., Fracaroli, A. M., Yaghi, O. M., Tashiro, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Modular+Synthesis+of+Metal-Organic+Complex+Arrays+Containing+Precisely+Designed+Metal+Sequences.">Modular Synthesis of Metal-Organic Complex Arrays Containing Precisely Designed Metal Sequences.</a> Inorg. Chem. 54, 1197-1199 (2015).</li><li>Sukul, P. K., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Water-Soluble+Metal-Organic+Complex+Array+as+a+Multinuclear+Heterometallic+Peptide+Amphiphile+That+Shows+Unconventional+Anion+Dependency+in+Its+Self-Assembly.">A Water-Soluble Metal-Organic Complex Array as a Multinuclear Heterometallic Peptide Amphiphile That Shows Unconventional Anion Dependency in Its Self-Assembly.</a> Chem. Commun. 52, 1579-1581 (2016).</li><li>Fracaroli, A. M., Tashiro, K., Yaghi, O. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Isomers+of+Metal-Organic+Complex+Arrays.">Isomers of Metal-Organic Complex Arrays.</a> Inorg. Chem. 51, 6437-6439 (2012).</li><li>Gude, M., Ryf, J., White, P. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+Accurate+Method+for+the+Quantitation+of+Fmoc-Derivatized+Solid+Phase+Supports.">An Accurate Method for the Quantitation of Fmoc-Derivatized Solid Phase Supports.</a> Letters in Peptide Science. 9, 203-206 (2002).</li><li>Merrifield, R. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solid+Phase+Peptide+Synthesis.+I.+The+Synthesis+of+a+Tetrapeptide.">Solid Phase Peptide Synthesis. I. The Synthesis of a Tetrapeptide.</a> J. Am. Chem. Soc. 85, 2149-2154 (1963).</li></ol>

Perfekt fjernelse af de uønskede kemikalier fra harpiksen ikke altid er muligt blot ved vask med opløsningsmidler, der let kan opløse disse kemikalier. Et centralt teknik til effektivt at vaske harpiksen er at få det til at svulme op og krympe repetitivt så de kemikalier forblive inde vil blive tvunget ud. Dette er grunden til harpiksen i vores procedure behandles med CH2C 2 og MeOH skift som den vaskes (fx protokol 2.1.4). Som følge af successive flere i...

Kontrolleret syntese af komplicerede molekylære strukturer har altid været et stort problem i syntetisk kemi. Ud fra dette synspunkt, at syntetisere multinukleære heterometallic komplekser i en designable mode er stadig en værdig emne at blive udfordret på området for uorganisk kemi på grund af antallet af mulige strukturelle resultater fra ligand-metalleringen tilgang, der almindeligvis anvendes til fremstilling af monomere metalkomplekser. Selv om flere eksempler på multinucleare heterometallic komplekser er blevet rapporteret hidtil 1,2,3, trial-and-error eller besværlige karakter af deres syntese kræver udviklingen af en simpel metode, der er gældende for en lang række strukturer. Som en ny tilgang til at løse dette problem, vi i 2011 rapporterede en syntetisk metode 4,5 hvor forskellige mononukleære metalkomplekser har en Fmoc-beskyttet aminosyre-delen er sekventielt koblet til at give multimetallisk peptidiske arrays ved hjælp af de protokoller fast-fase polypeptid syntese 6. På grund af den fortløbende karakter polypeptidsyntese, en specifik sekvens af flere metalcentre er rationelt designable ved at styre antallet og rækkefølgen af ​​koblingsreaktioner af disse metalkompleksfarvestoffer monomerer. Senere denne fremgangsmåde blev yderligere modulopbygget at foretage forskellige større og / eller forgrenede array-strukturer ved at kombinere med kovalente binding mellem to kortere arrays 7. Her vil vi vise, hvordan syntesen af sådanne multimetalliske peptidiske arrays typisk drives ved at vælge den nylig rapporteret WSMOCA (1 8 CAS RN 1827663-18-2, figur 1) som et repræsentativt eksempel. Selv syntesen af en bestemt array er beskrevet i denne protokol, de samme procedurer gælder for syntesen af en bred vifte af forskellige sekvenser, herunder isomerer 9. Vi forventer, at denne protocol vil inspirere flere forskere til at deltage i videnskaben om sekvens-kontrollerede forbindelser, hvor molekylerne undersøgt hidtil har typisk været biopolymerer men sjældent omfatter eksempler på metal-kompleks-baserede arter.

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>Dichloro(p&#8208;cymene)ruthenium(II), dimer</td>
			<td>Kanto Chemical</td>
			<td>11443-65</td>
			<td></td>
		</tr>
		<tr>
			<td>Dichloro(1,5-cyclooctadiene)platinum(II)</td>
			<td>TCI</td>
			<td>D3592</td>
			<td></td>
		</tr>
		<tr>
			<td>Rhodium(III) chloride trihydrate</td>
			<td>Kanto Chemical</td>
			<td>36018-62</td>
			<td></td>
		</tr>
		<tr>
			<td>Phosphate buffered saline, tablet</td>
			<td>Sigma Aldrich</td>
			<td>P4417-50TAB&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>NovaSyn TG Sieber resin</td>
			<td>Novabiochem</td>
			<td>8.55013.0005</td>
			<td></td>
		</tr>
		<tr>
			<td>HBTU</td>
			<td>TCI</td>
			<td>B1657</td>
			<td></td>
		</tr>
		<tr>
			<td>Benzoic anhydride</td>
			<td>Kanto Chemical</td>
			<td>04116-30</td>
			<td></td>
		</tr>
		<tr>
			<td>Fmoc-Glu(OtBu)-OH&#12539;H2O</td>
			<td>Watanabe Chemical Industries</td>
			<td>K00428</td>
			<td></td>
		</tr>
		<tr>
			<td>Trifluoroacetic acid</td>
			<td>Kanto Chemical</td>
			<td>40578-30</td>
			<td></td>
		</tr>
		<tr>
			<td>Triethylsilane</td>
			<td>TCI</td>
			<td>T0662</td>
			<td></td>
		</tr>
		<tr>
			<td>2-[2-(2-Methoxyethoxy)ethoxy]acetic acid</td>
			<td>Sigma Aldrich</td>
			<td>407003</td>
			<td>Dried over 3&#197; sieves</td>
		</tr>
		<tr>
			<td>Dithranol</td>
			<td>Wako Pure Chemical Industries</td>
			<td>191502</td>
			<td></td>
		</tr>
		<tr>
			<td>N-methylimidazole</td>
			<td>TCI</td>
			<td>M0508</td>
			<td></td>
		</tr>
		<tr>
			<td>N&#8208;ethyldiisopropylamine</td>
			<td>Kanto Chemical</td>
			<td>14338-32</td>
			<td></td>
		</tr>
		<tr>
			<td>Piperidine</td>
			<td>Kanto Chemical</td>
			<td>32249-30</td>
			<td></td>
		</tr>
		<tr>
			<td>4&#39;-(4-methylphenyl)-2,2&#39;:6&#39;,2&#34;-terpyridine</td>
			<td>Sigma Aldrich</td>
			<td>496375</td>
			<td></td>
		</tr>
		<tr>
			<td>Dehydrated grade dimethylsulfoxide</td>
			<td>Kanto Chemical</td>
			<td>10380-05&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>Dehydrated grade methanol</td>
			<td>Kanto Chemical</td>
			<td>25506-05&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>Dehydrated grade N,N&#8208;Dimethylformamide</td>
			<td>Kanto Chemical</td>
			<td>11339-84</td>
			<td>Amine Free</td>
		</tr>
		<tr>
			<td>Dehydrated grade dichloromethane</td>
			<td>Kanto Chemical</td>
			<td>11338-84</td>
			<td></td>
		</tr>
		<tr>
			<td>MeOH</td>
			<td>Kanto Chemical</td>
			<td>25183-81&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>Dimethylsulfoxide</td>
			<td>Kanto Chemical</td>
			<td>10378-70</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethyl acetate</td>
			<td>Kanto Chemical</td>
			<td>14029-81</td>
			<td></td>
		</tr>
		<tr>
			<td>Acetonitrile</td>
			<td>Kanto Chemical</td>
			<td>01031-70&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>1,2-dichloroethane</td>
			<td>Kanto Chemical</td>
			<td>10149-00</td>
			<td></td>
		</tr>
		<tr>
			<td>Diethyl ether</td>
			<td>Kanto Chemical</td>
			<td>14134-00&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>Dichloromethane</td>
			<td>Kanto Chemical</td>
			<td>10158-81</td>
			<td></td>
		</tr>
	</tbody>
</table>

synthesis of a water-soluble metal&#8211;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 Ru(II), Pt(II), and Rh(III). The compound, named as a water-soluble metal-organic complex array (WSMOCA), is obtained through 1) the conventional solution-chemistry-based preparation of the corresponding metal complex monomers having a 9-fluorenylmethyloxycarbonyl (Fmoc)-protected amino acid moiety and 2) their sequential coupling together with other water-soluble organic building units on the surface-functionalized polymeric resin by following the procedures originally developed for the solid-phase synthesis of polypeptides, with proper modifications. Traces of reactions determined by mass spectrometric analysis at the representative coupling steps in stage 2 confirm the selective construction of a predetermined sequence of metal centers along with the peptide backbone. The WSMOCA cleaved from the resin at the end of stage 2 has a certain level of solubility in aqueous media dependent on the pH value and/or salt content, which is useful for the purification of the compound.

Figur 1 viser de molekylære strukturer af de endelige målforbindelse, prækursorer, og mellemprodukter. Figur 2 viser billeder af harpiksen og Figur 3 viser MALDI-TOF massespektre af prøver på udvalgte fremgangsmådetrin. Billeder fra figur 2a til 2h vise ændringerne i farve og udseende af harpiks, det gennemgår under reaktionen trin i § 2 i protokollen. MALDI-TOF massespektrometri anvendes til at...

Watch this Scientific Journal Video about Synthesis of a Water-soluble MetalÃ¢â‚¬â€œOrganic Complex Array at JoVE.com

Synthesis of a Water-soluble MetalÃƒÆ’Ã‚Â¢ÃƒÂ¢Ã¢â‚¬Å¡Ã‚Â¬ÃƒÂ¢Ã¢â€šÂ¬Ã…â€œOrganic Complex Array

A potential general method for the synthesis of water-soluble multimetallic peptidic arrays containing a predetermined sequence of metal centers is presented.

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 ...

Research

JoVE Journal

Chemistry

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

Synthesis, Cellular Delivery and In vivo Application of Dendrimer-based pH Sensors

Synthesis, Cellular Delivery and In vivo Application of Dendrimer-based pH Sensors

Synthesis, Cellular Levering og<em&gt; In vivo</em&gt; Anvendelse af Dendrimer-baserede pH-sensorer

The development of  fluorescent indicators represented a revolution for life sciences. Genetically  encoded and synthetic fluorophores with sensing ...

Atomically Defined Templates for Epitaxial Growth of Complex Oxide Thin Films

Atomically skabeloner til epitaksial vækst af komplekse Oxide Thin Films

Atomically defined substrate surfaces are prerequisite for the epitaxial growth of complex oxide thin films. In this protocol, two approaches to obtain ...

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

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. ...

Synthesis and Exfoliation of Discotic Zirconium Phosphates to Obtain Colloidal Liquid Crystals

Syntese og Eksfoliering af Discotic Zirconium Fosfater fås Kolloid Flydende Krystaller

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and ...

A Direct, Early Stage Guanidinylation Protocol for the Synthesis of Complex Aminoguanidine-containing Natural Products

En Direct, Early Stage Guanidinylation Protokol til syntese af komplekse aminoguanidin-holdige Naturprodukter

The guanidine functional group, displayed most prominently in the amino acid arginine, one of the fundamental building blocks of life, is an important ...

Synthesis and Characterization of Supramolecular Colloids

Syntese og karakterisering af supramolekylære Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

Chemo-enzymatic Synthesis of N-glycans for Array Development and HIV Antibody Profiling

Chemo-enzymatic Synthesis of N-glycans for Array Development and HIV Antibody Profiling

Kemo-enzymatisk syntese af N- glycans for arrayet udvikling og HIV antistof profilering

We present a highly efficient way for the rapid preparation of a wide range of N-linked oligosaccharides (estimated to exceed 20,000 structures) that are ...

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

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 ...

Negative Additive Manufacturing of Complex Shaped Boron Carbides

Negative tilsætningsstof fremstilling af komplekse formet Boron metalcarbider

Boron carbide (B4C) is one of the hardest materials in existence. However, this attractive property also limits its machineability into complex shapes for ...

Molten-Salt Synthesis of Complex Metal Oxide Nanoparticles

Smeltet Salt syntese af komplekse metaloxid nanopartikler

The development of feasible synthesis methods is critical for the successful exploration of novel properties and potential applications of nanomaterials. ...