Questo lavoro è stato supportato dalla nazionale natura Science Foundation of China (21301104), i fondi di ricerca fondamentali per le Università centrale (FRF-TP-16-019A3) e lo stato chiave laboratorio di ingegneria chimica (SKL--14A04).

1. sintesi di Mono-(2,3-dimethylbutyl) Acido fosfinico 18 , 19 <ol><li>reazione <ol><li>pesare 31,80 g idrato ipofosfito di sodio, ore 16.00 g di acido acetico, 8,42 g 2,3-dimetil-1-butene, 0,73 g di - tert-butylnperoxide (DTBP) e g 25,00 tetraidrofurano (THF) in autoclave a 100 mL in acciaio inox rivestito in Teflon, mettere un agitatore magnetico in autoclave e sigillare it.</li>
		<li>Mettere l'autoclave in un forno tubolare verticale che sotto il quale è un stirringapparatus magnetico. Avviare il mescolatore magnetico e impostare la velocità a 800 giri/min.</li>
		<li>Impostare il programma di riscaldamento del termoregolatore collegato all'autoclave: riscaldare da temperatura ambiente a 120 ° C durante 90 min, mantenere a 120 ° C per 8 h, poi raffreddare a temperatura ambiente, naturalmente. Avviare il programma di riscaldamento.</li>
	</ol></li> <li>Post-trattamento <ol><li>trasferire i prodotti in un pallone a sfondo sferico uno-collo 250 mL, lavare il rivestimento in Teflon con 50 mL di THF e aggiungerlo nel pallone stesso per garantire che tutti i prodotti vengono trasferiti.</li>
		<li>Rimuovere il THF e olefine non reagite utilizzando un evaporatore rotante.</li>
		<li>Trasferire il residuo in un imbuto separatore da 250 mL, lavare il matraccio con etere etilico 80 mL e 30 mL di acqua deionizzata rispettivamente e aggiungerli nell'imbuto stesso per garantire che tutti i prodotti vengono trasferiti.</li>
		<li>Aggiungere 50 mL della soluzione di NaOH 4% nell'imbuto sopra, agitare vigorosamente e separare la fase acquosa. Estrarre la fase organica con soluzioni di NaOH 4% 20 mL per tre volte (20 mL × 3) per assicurare che la fase acquosa superiore a pH 10.</li>
		<li>Combinare le soluzioni acquose nel passaggio precedente e trasferirli in un imbuto separatore da 500 mL.</li>
		<li>Aggiungere 90 mL di 10% H 2 così 4 soluzione e 50 mL di etere etilico, agitare vigorosamente e separare la fase organica; quindi estrarre la fase acquosa con 30 mL di etere etilico per tre volte (30 mL × 3).</li>
		<li>Combinare le soluzioni di etere etilico nel passaggio 1.2.6 e trasferirli in un altro imbuto separatore da 500 mL.</li>
		<li>Lavarlo con 100 mL di soluzioni sature di NaCl quattro volte (100 mL × 4).</li>
		<li>Aggiungere 4G di anidro MgSO 4 per rimuovere l'eventuale acqua solubile. Filtrare per rimuovere il solido e raccogliere il liquido in un pallone a sfondo sferico uno-collo pulito 250ml.</li>
		<li>Eliminare l'etere etilico con l'evaporatore rotante per ottenere 17,92 g del prodotto grezzo.</li>
	</ol></li></ol> 2. Purificazione di Mono-(2,3-dimethylbutyl) Acido fosfinico <ol><li>preparazione della soluzione di amantadina <ol><li>sciogliere 22,28 g di cloridrato di amantadina in 100 mL di acqua deionizzata in un becher da mL 500.</li>
		<li>Aggiungere 100 mL di soluzione di NaOH, saturi e mescolare per 5 min</li>
		<li>Aggiungere 150 mL di etere etilico e mescolare fino a quando scomparirà il precipitato bianco generato nel passaggio 2.1.2.</li>
		<li>Trasferire le soluzioni in un imbuto separatore da 500 mL, lavare il becher con etere etilico per tre volte (50 mL × 3) e combinarli nell'imbuto stesso.</li>
		<li>Separare la fase acquosa e lavare la fase organica con soluzioni sature di NaCl cinque volte (100 mL × 5).</li>
		<li>Aggiungere 4G di anidro MgSO 4 per rimuovere l'eventuale acqua solubile. Filtro per ottenere la soluzione di etere etilico amantadina.</li>
	</ol></li> <li>Preparazione di amantadina &#8729; mono-(2,3-dimethylbutyl) sale acido fosfinico <ol><li>drop-wise aggiungere il prodotto acido fosfinico grezzo mono-(2,3-dimethylbutyl) alla soluzione di amantadina. Durante la caduta, aggiungere 150 mL di etere etilico per garantire che può mescolare correttamente.</li>
		<li>Lavare il pallone a sfondo sferico uno-collo contenente il mono-(2,3-dimethylbutyl) prodotto acido fosfinico con 50 mL di etere etilico per garantire che tutto il prodotto viene trasferito alla soluzione di amantadina. Sotto agitazione per 30 minuti e lasciate riposare una notte.</li>
		<li>Filtro sotto pressione ridotta e lavare il panello con 200 mL di etere etilico.</li>
	</ol></li> <li>Rilasciare l'acido fosfinico mono-(2,3-dimethylbutyl) <ol><li>trasferire la torta filtrata in un becher da 500 mL, aggiungere 80 mL di 1 M HCl e mescolare per 5 min.</li>
		<li>Aggiungere 70 mL di acetato di etile e mescolare per un altro 5 min</li>
		<li>Trasferire le soluzioni in un imbuto separatore da 250 mL e separare la fase acquosa.</li>
		<li>Estrarre nuovamente la fase acquosa con 40 mL di acetato di etile e combinare le soluzioni di acetato di etile.</li>
		<li>Lavare la soluzione di acetato di etile con 30 mL di 1 M HCl due volte (30 mL × 2) e satura di NaCl tre volte (80 mL × 3), in modo sequenziale.</li>
		<li>Aggiungere 4G anidro MgSO 4 per rimuovere l'eventuale acqua solubile. Filtrare e raccogliere il liquido in un pallone a sfondo sferico uno-collo 250ml.</li>
		<li>Rimuovere l'acetato di etile utilizzando l'evaporatore rotante e ottenere 12,45 g dell'acido fosfinico puro mono-(2,3-dimethylbutyl) (resa: 82,9%).</li>
	</ol></li></ol> 3. Sintesi di (2,3-dimethylbutyl) (2.4.4 &#39;-trimethylpentyl) Acido fosfinico <ol><li>reazione <ol><li>trasferimento tutti del pura mono-(2,3-dimethylbutyl) prodotto acido fosfinico in un 100 mL in acciaio inox rivestito in Teflon autoclave, aggiungere 4,95 g di acido acetico, 25,39 g di diisobutylene, 0,30 g di DTBP, mettere un agitatore magnetico in autoclave e seal it.</li>
		<li>Mettere l'autoclave in un forno tubolare verticale sotto il quale è un mescolatore magnetico e avviare il mescolatore magnetico.</li>
		<li>Impostare il programma di riscaldamento del termoregolatore: riscaldare da temperatura ambiente fino a 135 ° C durante 90 min, mantenere a 135 ° C per 8 h, poi raffreddare a temperatura ambiente, naturalmente. Avviare il programma di riscaldamento.</li>
		<li>Quando il sistema di reazione si raffredda a temperatura ambiente, aggiungere un altro 0,30 g di DTBP e riavviare il programma di riscaldamento.</li>
		<li>Ripetere una volta il punto 3.1.4.</li>
	</ol></li> <li>Post-trattamento <ol><li>diluire il prodotto con 100 mL di etere etilico e poi il trasferimento a un imbuto separatore da 250 mL.</li>
		<li>Lavare con 30 mL di 4% NaOH tre volte (30 mL × 3) per verificare che la fase acquosa superiore a pH 10.</li>
		<li>Aggiungere 70 mL di 10% H 2 così 4 soluzione di acidificare il prodotto.</li>
		<li>Lavare con soluzione satura di NaCl parecchie volte (80 mL ciascuno) fino a quando il pH della fase acquosa è uguale a pH 6-7.</li>
		<li>Aggiungere 4G di anidro MgSO 4 per rimuovere l'eventuale acqua solubile. Filtrare per rimuovere il solido e raccogliere il liquido in un pallone a sfondo sferico uno-collo pulito 250ml.</li>
		<li>Rimuovere l'etere etilico e olefine non reagite con l'evaporatore rotante per ottenere 15,10 g di prodotto grezzo.</li>
	</ol></li></ol> 4. Purificazione di (2,3-dimethylbutyl) (2.4.4 &#39;-trimethylpentyl) Acido fosfinico <ol><li>ottenere co-(2,3-dimethylbutyl) puro (2.4.4 &#39;-trimethylpentyl) complesso acido fosfinico <ol><li>2.30 sciogliere g di NaOH in 40 mL acqua deionizzata. Aggiungere la soluzione di NaOH il matraccio contenente il greggio (2,3-dimethylbutyl) (2.4.4 &#39;-trimethylpentyl) prodotto acido fosfinico e scuoterlo energicamente per 5 min.</li>
		<li>Aggiungi 0,5 M CoCl 2 soluzione goccia a goccia mentre si stringono fino a quando non più precipitato blu viene generato e la soluzione in un matraccio è rosa. < / li> <li>Filtro e lavare il precipitato blu con acqua deionizzata fino a quando la torta del filtro è incolore.</li>
		<li>Trasferire la torta del filtro in un becher da 250 mL, aggiungere 100 mL di acetone, sigillare con pellicola conservante e poi in frigorifero a 4 ° C per una notte.</li>
		<li>Pulverize il precipitato blu di rilasciare eventuali impurità intrappolato nel bulk.</li>
		<li>Filtro e lavarlo con 100 mL di acetone fresco. Asciugare la torta del filtro a temperatura ambiente e poi trasferirlo in un imbuto separatore da 250 mL.</li>
	</ol></li> <li>Rigenerare il (2,3-dimethylbutyl) (2.4.4 &#39;-trimethylpentyl) Acido fosfinico <ol><li>aggiungere 120 mL etere etilico e 80 mL 10% H 2 così 4 e agitare vigorosamente fino a quando il precipitato blu scompare.</li>
		<li>Separare la fase acquosa, lavare l'organico fase in sequenza con 30 mL di 10% H 2 SO 4 una volta e satura NaCl soluzioni diverse volte (80 mL ciascuno) fino a quando il pH della fase acquosa è uguale a pH 6-7.</li>
		<li>Aggiungere 4G di anidro MgSO 4 per rimuovere l'eventuale acqua solubile. Filtro per rimuovere il solido e raccogliere il liquido in un pallone a sfondo sferico uno-collo pulito 250ml.</li>
		<li>Eliminare l'etere etilico utilizzando l'evaporatore rotante e ottenere 11,46 g del prodotto puro (resa: 52,8%).</li>
	</ol>
	</li>
</ol>

<ol>
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Il punto più critico all'interno del protocollo è la sintesi mono-alkylphosphinic acido (Figura 1a). In questa reazione, un rendimento più elevato e meno sottoprodotto di acido dialkylphosphinic è meglio. Aumentando il rapporto molare di NaH2PO2/olefin A migliorerà il rendimento e inibire la generazione di sottoprodotto acido dialkylphosphinic. Tuttavia, un dosaggio elevato di NaH2PO2 sarà anche aumentare il costo e causare u...

Acidi solventi organofosforici sono ampiamente usati nel campo tradizionale Idrometallurgia per estrazione e separazione delle terre rare ioni1,2, metalli non ferrosi (come Co/Ni3,4), metalli rari ( ad esempio Hf/Zr5, V6,7), attinidi8, ecc. Negli ultimi anni, hanno anche attirato più attenzione nei campi della risorsa secondaria riciclaggio e smaltimento dei rifiuti liquidi ad alto livello9. Di-(2-etilesile) (D2EHPA o P204), 2-ethylhexylphosphoric acid mono-2-etilesil estere dell'acido fosforico (EHEHPA, PC 88A o P507) e Di-(2,4, 4'-trimethylpentyl)-Acido fosfinico (Cyanex272), che sono rappresentanti di acidi dialkylphosphoric, alchilfosforici acido mono-alchil esteri e acidi dialkylphosphinic rispettivamente, sono i solventi più comunemente usati. Loro acidità diminuisce nella seguente sequenza: P204 &#62; P507 &#62; Cyanex 272. La corrispondente capacità di estrazione, capacità di estrazione e stripping acidità sono tutti in ordine P204 &#62; P507 &#62; Cyanex 272 e le prestazioni di separazione è nell'ordine opposto. Questi tre solventi sono efficaci nella maggior parte dei casi. Tuttavia, ci sono ancora alcune condizioni dove non sono così efficienti: nella separazione di terre rare pesanti, di cui i principali problemi esistenti sono la scarsa selettività ed elevata acidità stripping per P204 e P507, bassa capacità di estrazione e tendenza di emulsione durante l'estrazione per Cyanex 272. Così, lo sviluppo di nuovi solventi ha attirato maggiore attenzione negli ultimi anni.
La classe di solventi acidi dialkylphosphinic è considerata uno degli aspetti più importanti di ricerca per sviluppare nuovi solventi. Recenti ricerche hanno dimostrato che la capacità di estrazione di acidi dialkylphosphinic dipende in gran parte dalla struttura del alchile sostituenti10,11. Può essere una vasta gamma da significativamente superiore a quello di P507 inferiore a quella di Cyanex 27212. Tuttavia, l'esplorazione di solventi acidi dialkylphosphinic romanzo è limitato per le olefine commerciale struttura10,12,13,14,15, 16. Anche se dialkylphosphinic acidi solventi possono anche essere sintetizzato dal metodo reazione di Grignard, le condizioni di reazione sono rigorosi12,17.
NSDAPA, di cui i due alchili sono diversi, si apre una porta all'esplorazione di nuovi solventi. Rende le strutture di dialkylphosphinic acido più diversificata e sua estrazione e separazione delle prestazioni possono essere ottimizzata modificando sia delle sue strutture di alchile. Il tradizionale metodo sintetico di NSDAPA usato PH3 come una fonte di fosforo, che ha molti svantaggi come alta tossicità, condizioni di reazione rigorosa e difficile purificazione. Recentemente abbiamo segnalato un nuovo metodo per sintetizzare usando ipofosfito di sodio come un fosforo origine (vedere Figura 1) e sintetizzato con successo tre NSDAPAs18NSDAPA. Questo protocollo dettagliato può aiutare nuovi praticanti ripetere gli esperimenti e padroneggiare il metodo sintetico di solventi NSDAPA. Prendiamo (2,3-dimethylbutyl) (2,4, 4'-trimethylpentyl) Acido fosfinico come un esempio. I nomi e le strutture di olefine A, l'acido mono-alkylphosphinic intermedio, olefine B e la corrispondente NSDAPA sono riportati nella tabella 1.

<table><tbody><tr><td>2,3-dimethyl-1-butene</td><td>Adamas Reagent Co., Ltd.</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;12&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity &amp;ge;99%&lt;/span&gt;</td></tr><tr><td>diisobutylene</td><td>Shanghai&amp;nbsp;Aladdin&amp;nbsp;Bio-Chem&amp;nbsp;Technology&amp;nbsp;Co.,&amp;nbsp;LTD</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;8&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;16&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity 97%&lt;/span&gt;</td></tr><tr><td>acetic acid</td><td>Sinopharm Chemical Reagent Co., Ltd.</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;O&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity &amp;ge;99.5%&lt;/span&gt;</td></tr><tr><td>di-&lt;span class=&quot;font9&quot;&gt;tert&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;-butylnperoxide&lt;/span&gt;</td><td>Sinopharm Chemical Reagent Co., Ltd.</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;8&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;18&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;O&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity &amp;ge;97.0%&lt;/span&gt;</td></tr><tr><td>tetrahydrofuran</td><td>Beijing Chemical Works</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;8&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;O, purity A.R.&lt;/span&gt;</td></tr><tr><td>ethyl ether</td><td>Sinopharm Chemical Reagent Co., Ltd.</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;10&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;O, purity &amp;ge;99.7%&lt;/span&gt;</td></tr><tr><td>ethyl acetate</td><td>Xilong Chemical Co., Ltd.</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;8&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;O&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity &amp;ge;99.5%&lt;/span&gt;</td></tr><tr><td>acetone</td><td>Beijing Chemical Works</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;O, purity &amp;ge;99.5%&lt;/span&gt;</td></tr><tr><td>sodium hydroxide</td><td>Xilong Chemical Co., Ltd.</td><td></td><td>Molecular formula: NaOH, purity &amp;ge;96.0%</td></tr><tr><td>concentrated sulfuric acid</td><td>Sinopharm Chemical Reagent Co., Ltd.</td><td></td><td>Molecular formula: H&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;SO&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity 95-98%&lt;/span&gt;</td></tr><tr><td>hydrochloric acid</td><td>Beijing Chemical Works</td><td></td><td>Molecular formula: HCl, purity 36-38%</td></tr><tr><td>sodium chloride</td><td>Sinopharm Chemical Reagent Co., Ltd.</td><td></td><td>Molecular formula: NaCl, purity &amp;ge;99.5%</td></tr><tr><td>anhydrous magnesium sulfate</td><td>Tianjin Jinke Institute of Fine Chemical Industry</td><td></td><td>Molecular formula: MgSO&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity &amp;ge;99.0%&lt;/span&gt;</td></tr></tbody></table>

synthesis of high purity nonsymmetric dialkylphosphinic acid extractants

Vi presentiamo la sintesi di (2,3-dimethylbutyl) (2,4, 4'-trimethylpentyl) Acido fosfinico come esempio per illustrare un metodo per la sintesi di elevata purezza il dialkylphosphinic acido solventi. Ipofosfito di sodio basso tossico è stato scelto come la fonte di fosforo a reagire con olefine un (2,3-dimetil-1-butene) per generare un acido monoalkylphosphinic intermedio. L'amantadina è stata adottata per rimuovere il sottoprodotto di acido dialkylphosphinic, come solo l'acido monoalkylphosphinic può reagire con amantadina per formare un sale acido di amantadine∙mono-alkylphosphinic, mentre l'acido dialkylphosphinic non può reagire con amantadina a causa sua grande impedimento sterico. L'acido purificato monoalkylphosphinic quindi è stato reagito con olefine B (diisobutylene) per produrre il dialkylphosphinic acido (NSDAPA). L'acido non reagito monoalkylphosphinic possa essere facilmente rimossi con un semplice post-trattamento base-acido e altre impurità organiche possono essere separati attraverso la precipitazione del sale di cobalto. La struttura della (2,3-dimethylbutyl) (2,4, 4'-trimethylpentyl) Acido fosfinico è stata confermata dalla RMN 31P, 1H NMR, ESI-MS e FT-IR. La purezza è stata determinata con un metodo di titolazione potenziometrica, ed i risultati indicano che la purezza può superare i 96%.

31 Gli spettri RMN P sono stati raccolti per l'acido fosfinico mono-(2,3-dimethylbutyl) prima e dopo la purificazione dal metodo amantadina (Figura 1a-b). 31 Gli spettri RMN P, spettri di 1H NMR, MS spettri e spettri FT-IR sono stati raccolti per (2,3-dimethylbutyl) (2,4, 4'-trimethylpentyl) Acido fosfinico (vedere Figura 3, Figura 4, <strong class="x...

Watch this Scientific Journal Video about Synthesis of High Purity Nonsymmetric Dialkylphosphinic Acid Extractants at JoVE.com

Synthesis of High Purity Nonsymmetric Dialkylphosphinic Acid Extractants

Sintesi di elevata purezza il Dialkylphosphinic acido solventi

Un protocollo per la sintesi di elevata purezza il dialkylphosphinic acido solventi è presentato, prendendo (2,3-dimethylbutyl) (2,4, 4'-trimethylpentyl) Acido fosfinico come un esempio.

We present the synthesis of (2,3-dimethylbutyl)(2,4,4&#39;-trimethylpentyl)phosphinic acid as an example to demonstrate a method for the synthesis of high ...

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Acid-base and Solubility Equilibria

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7.4K Views.  University of Science and Technology Beijing. Un protocollo per la sintesi di elevata purezza il dialkylphosphinic acido solventi è presentato, prendendo (2,3-dimethylbutyl) (2,4, 4'-trimethylpentyl) Acido fosfinico come un esempio.

Video: Synthesis of High Purity Nonsymmetric Dialkylphosphinic Acid Extractants

Compact Quantum Dots for Single-molecule Imaging

Single-molecule imaging is an important tool for understanding the mechanisms of biomolecular function and for visualizing the spatial and temporal heterogeneity of molecular behaviors that underlie cellular biology 1-4. To image an individual molecule of interest, it is typically conjugated to a fluorescent tag (dye, protein, bead, or quantum dot) and observed with epifluorescence or total internal reflection fluorescence (TIRF) microscopy. While dyes and fluorescent proteins have been the mainstay of fluorescence imaging for decades, their fluorescence is unstable under high photon fluxes necessary to observe individual molecules, yielding only a few seconds of observation before complete loss of signal. Latex beads and dye-labeled beads provide improved signal stability but at the expense of drastically larger hydrodynamic size, which can deleteriously alter the diffusion and behavior of the molecule under study.
Quantum dots (QDs) offer a balance between these two problematic regimes. These nanoparticles are composed of semiconductor materials and can be engineered with a hydrodynamically compact size with exceptional resistance to photodegradation 5. Thus in recent years QDs have been instrumental in enabling long-term observation of complex macromolecular behavior on the single molecule level. However these particles have still been found to exhibit impaired diffusion in crowded molecular environments such as the cellular cytoplasm and the neuronal synaptic cleft, where their sizes are still too large 4,6,7.
Recently we have engineered the cores and surface coatings of QDs for minimized hydrodynamic size, while balancing offsets to colloidal stability, photostability, brightness, and nonspecific binding that have hindered the utility of compact QDs in the past 8,9. The goal of this article is to demonstrate the synthesis, modification, and characterization of these optimized nanocrystals, composed of an alloyed HgxCd1-xSe core coated with an insulating CdyZn1-yS shell, further coated with a multidentate polymer ligand modified with short polyethylene glycol (PEG) chains (Figure 1). Compared with conventional CdSe nanocrystals, HgxCd1-xSe alloys offer greater quantum yields of fluorescence, fluorescence at red and near-infrared wavelengths for enhanced signal-to-noise in cells, and excitation at non-cytotoxic visible wavelengths. Multidentate polymer coatings bind to the nanocrystal surface in a closed and flat conformation to minimize hydrodynamic size, and PEG neutralizes the surface charge to minimize nonspecific binding to cells and biomolecules. The end result is a brightly fluorescent nanocrystal with emission between 550-800 nm and a total hydrodynamic size near 12 nm. This is in the same size range as many soluble globular proteins in cells, and substantially smaller than conventional PEGylated QDs (25-35 nm).

We describe the preparation of colloidal quantum dots with minimized hydrodynamic size for single-molecule fluorescence imaging. Compared to conventional quantum dots, these nanoparticles are similar in size to globular proteins and are optimized for single-molecule brightness, stability against photodegradation, and resistance to nonspecific binding to proteins and cells.

Compact Quantum Dots per singola molecola Imaging

Single-molecule imaging is an important tool for  understanding the mechanisms of biomolecular function and for visualizing the  spatial and temporal ...

Ricerca

Ingegneria

Synthesis and Purification of Iodoaziridines Involving Quantitative Selection of the Optimal Stationary Phase for Chromatography

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. Diiodomethyllithium is prepared by the deprotonation of diiodomethane with LiHMDS, in a THF/diethyl ether mixture, at -78 &#176;C in the dark. These conditions are essential for the stability of the LiCHI2 reagent generated. The subsequent dropwise addition of N-Ts aldimines to the preformed diiodomethyllithium solution affords an amino-diiodide intermediate, which is not isolated. Rapid warming of the reaction mixture to 0 &#176;C promotes cyclization to afford iodoaziridines with exclusive cis-diastereoselectivity. The addition and cyclization stages of the reaction are mediated in one reaction flask by careful temperature control.
Due to the sensitivity of the iodoaziridines to purification, assessment of suitable methods of purification is required. A protocol to assess the stability of sensitive compounds to stationary phases for column chromatography is described. This method is suitable to apply to new iodoaziridines, or other potentially sensitive novel compounds. Consequently this method may find application in range of synthetic projects. The procedure involves firstly the assessment of the reaction yield, prior to purification, by 1H NMR spectroscopy with comparison to an internal standard. Portions of impure product mixture are then exposed to slurries of various stationary phases appropriate for chromatography, in a solvent system suitable as the eluent in flash chromatography. After stirring for 30 min to mimic chromatography, followed by filtering, the samples are analyzed by 1H NMR spectroscopy. Calculated yields for each stationary phase are then compared to that initially obtained from the crude reaction mixture. The results obtained provide a quantitative assessment of the stability of the compound to the different stationary phases; hence the optimal can be selected. The choice of basic alumina, modified to activity IV, as a suitable stationary phase has allowed isolation of certain iodoaziridines in excellent yield and purity.

A protocol for the diastereoselective one-pot preparation of cis-N-Ts-iodoaziridines is described. The generation of diiodomethyllithium, addition to N-Ts aldimines and cyclization of the amino gem-diiodide intermediate to iodoaziridines is demonstrated. Also included is a protocol to rapidly and quantitatively assess the most appropriate stationary phase for purification by chromatography.

Sintesi e purificazione di Iodoaziridines Coinvolgere quantitativa Selezione del Ottimale fase stazionaria per cromatografia

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. ...

Chimica

Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous polymer monoliths. The developed approach is based on the preparation of a macroporous polymer containing carboxylic acid functional groups and the subsequent step-by-step solution-based controlled growth of a layer of a porous coordination polymer on the surface of the pores of the polymer monolith. The prepared metal-organic polymer hybrid has a high specific micropore surface area. The amount of iron(III) sites is enhanced through metal-organic coordination on the surface of the pores of the functional polymer support. The increase of metal sites is related to the number of iterations of the coating process.
The developed preparation scheme is easily adapted to a capillary column format. The functional porous polymer is prepared as a self-contained single-block porous monolith within the capillary, yielding a flow-through separation device with excellent flow permeability and modest back-pressure. The metal-organic polymer hybrid column showed excellent performance for the enrichment of phosphopeptides from digested proteins and their subsequent detection using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The presented experimental protocol is highly versatile, and can be easily implemented to different organic polymer supports and coatings with a plethora of porous coordination polymers and metal-organic frameworks for multiple purification and/or separation applications.

A procedure for the preparation of porous hybrid separation media composed of a macroporous polymer monolith internally coated by a high surface area microporous coordination polymer is presented.

Preparazione di altamente poroso Coordinamento rivestimenti polimerici su macroporosi Polymer Monoliti di avanzata Arricchimento fosfopeptidi

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous ...

Extraction and Characterization of Surfactants from Atmospheric Aerosols

Surface-active compounds, or surfactants, present in atmospheric aerosols are expected to play important roles in the formation of liquid water clouds in the Earth&#39;s atmosphere, a central process in meteorology, hydrology, and for the climate system. But because specific extraction and characterization of these compounds have been lacking for decades, very little is known on their identity, properties, mode of action and origins, thus preventing the full understanding of cloud formation and its potential links with the Earth&#39;s ecosystems.
In this paper we present recently developed methods for 1) the targeted extraction of all the surfactants from atmospheric aerosol samples and for the determination of 2) their absolute concentrations in the aerosol phase and 3) their static surface tension curves in water, including their Critical Micelle Concentration (CMC). These methods have been validated with 9 references surfactants, including anionic, cationic and non-ionic ones. Examples of results are presented for surfactants found in fine aerosol particles (diameter &#60;1 &#956;m) collected at a coastal site in Croatia and suggestions for future improvements and other characterizations than those presented are discussed.

Methods are presented for the targeted extraction of surfactants present in atmospheric aerosols and the determination of their absolute concentrations and surface tension curves in water, including their Critical Micelle Concentration (CMC).

Estrazione e caratterizzazione di tensioattivi da Atmospheric Aerosol

Surface-active compounds, or surfactants, present in atmospheric aerosols are expected to play important roles in the formation of liquid water clouds in ...

Ambiente

Facile Protocol for the Synthesis of Self-assembling Polyamine-based Peptide Amphiphiles (PPAs) and Related Biomaterials

Polyamine-based Peptide Amphiphiles (PPAs) are a new class of self-assembling amphiphilic biomaterials-related to the peptide amphiphiles (PAs). Traditional PAs possess charged amino acids as solubilizing groups (lysine, arginine), which are directly connected to a lipid segment or can contain a linker region made of neutral amino acids. Tuning the peptide sequence of PAs can yield diverse morphologies. Similarly, PPAs possess a hydrophobic segment and neutral amino acids, but also contain polyamine molecules as water solubilizing (hydrophilic) groups. As is the case with PAs, PPAs can also self-assemble into diverse morphologies, including small rods, twisted nano-ribbons, and fused nano-sheets, when dissolved in water. However, the presence of both primary and secondary amines on a single polyamine molecule poses a significant challenge when synthesizing PPAs. In this paper, we show a simple protocol, based on literature precedents, to achieve a facile synthesis of PPAs using solid phase peptide synthesis (SPPS). This protocol can be extended to the synthesis of PAs and other similar systems. We also illustrate the steps that are needed for cleavage from the resin, identification, and purification.

Facile Protocol for the Synthesis of Self-assembling Polyamine-based Peptide Amphiphiles PPAs and Related Biomaterials

The synthesis of polyamine-based peptide amphiphiles (PPAs) is a significant challenge due to the presence of multiple amine nitrogens, which requires judicious use of protecting groups to mask these reactive functionalities. In this paper, we describe a facile method for the preparation of these new class of self-assembling molecules.

Facile protocollo per la sintesi di auto-assemblaggio basato su poliammina Peptide anfifili (PPA) e biomateriali correlate

Polyamine-based Peptide Amphiphiles (PPAs) are a new class of self-assembling amphiphilic biomaterials-related to the peptide amphiphiles (PAs). ...

Synthesis of Esters Via a Greener Steglich Esterification in Acetonitrile

The Steglich esterification is a widely-used reaction for the synthesis of esters from carboxylic acids and alcohols. While efficient and mild, the reaction is commonly performed using chlorinated or amide solvent systems, which are hazardous to human health and the environment. Our methodology utilizes acetonitrile as a greener and less hazardous solvent system. This protocol exhibits rates and yields that are comparable to traditional solvent systems and employs an extraction and wash sequence that eliminates the need for the purification of the ester product via column chromatography. This general method can be used to couple a variety of carboxylic acids with 1&#176; and 2&#176; aliphatic alcohols, benzylic and allylic alcohols, and phenols to obtain pure esters in high yields. The goal of the protocol detailed here is to provide a greener alternative to a common esterification reaction, which could serve useful for ester synthesis in both academic and industrial applications.

A modified Steglich esterification reaction was used to synthesize a small library of ester derivatives with primary and secondary alcohols. The methodology uses a non-halogenated and greener solvent, acetonitrile, and enables product isolation in high yields without the need for chromatographic purification.

Sintesi degli esteri tramite un'esterificazione Steglich più verde in Acetonitrile

The Steglich esterification is a widely-used reaction for the synthesis of esters from carboxylic acids and alcohols. While efficient and mild, the ...

Preparation of Poly(pentafluorophenyl acrylate) Functionalized SiO2 Beads for Protein Purification

We demonstrate a simple method to prepare poly(pentafluorophenyl acrylate) (poly(PFPA)) grafted silica beads for antibody immobilization and subsequent immunoprecipitation (IP) application. The poly(PFPA) grafted surface is prepared via a simple two-step process. In the first step, 3-aminopropyltrimethoxysilane (APTMS) is deposited as a linker molecule onto the silica surface. In the second step, poly(PFPA) homopolymer, synthesized via the reversible addition and fragmentation chain transfer (RAFT) polymerization, is grafted to the linker molecule through the exchange reaction between the pentafluorophenyl (PFP) units on the polymer and the amine groups on APTMS. The deposition of APTMS and poly(PFPA) on the silica particles are confirmed by X-ray photoelectron spectroscopy (XPS), as well as monitored by the particle size change measured via dynamic light scattering (DLS). To improve the surface hydrophilicity of the beads, partial substitution of poly(PFPA) with amine-functionalized poly(ethylene glycol) (amino-PEG) is also performed. The PEG-substituted poly(PFPA) grafted silica beads are then immobilized with antibodies for IP application. For demonstration, an antibody against protein kinase RNA-activated (PKR) is employed, and IP efficiency is determined by Western blotting. The analysis results show that the antibody immobilized beads can indeed be used to enrich PKR while non-specific protein interactions are minimal.

Preparation of Polypentafluorophenyl acrylate Functionalized SiO2 Beads for Protein Purification

A protocol for the preparation of poly(pentafluorophenyl acrylate) (poly(PFPA)) grafted silica beads is presented. The poly(PFPA) functionalized surface is then immobilized with antibodies and used successfully for the protein separation through immunoprecipitation.

Preparazione di Poly(pentafluorophenyl acrylate) funzionalizzati SiO2 perline per la purificazione della proteina

We demonstrate a simple method to prepare poly(pentafluorophenyl acrylate) (poly(PFPA)) grafted silica beads for antibody immobilization and subsequent ...

Enzymatic Synthesis of Epoxidized Metabolites of Docosahexaenoic, Eicosapentaenoic, and Arachidonic Acids

The epoxidized metabolites of various polyunsaturated fatty acids (PUFAs), termed epoxy fatty acids, have a wide range of roles in human physiology. These metabolites are produced endogenously by the cytochrome P450 class of enzymes. Because of their diverse and potent biological effects, there is considerable interest in studying these metabolites. Determining the unique roles of these metabolites in the body is a difficult task, as the epoxy fatty acids must first be obtained in significant amounts and with high purity. Obtaining compounds from natural sources is often labor intensive, and soluble epoxide hydrolases (sEH) rapidly hydrolyze the metabolites. On the other hand, obtaining these metabolites via chemical reactions is very inefficient, due to the difficulty of obtaining pure regioisomers and enantiomers, low yields, and extensive (and expensive) purification. Here, we present an efficient enzymatic synthesis of 19(S),20(R)- and 16(S),17(R)-epoxydocosapentaenoic acids (EDPs) from DHA via epoxidation with BM3, a bacterial CYP450 enzyme isolated originally from Bacillus megaterium (that is readily expressed in Escherichia coli). Characterization and determination of purity is performed with nuclear magnetic resonance spectroscopy (NMR), high-performance liquid chromatography (HPLC), and mass spectrometry (MS). This procedure illustrates the benefits of enzymatic synthesis of PUFA epoxy metabolites, and is applicable to the epoxidation of other fatty acids, including arachidonic acid (AA) and eicosapentaenoic acid (EPA) to produce the analogous epoxyeicosatrienoic acids (EETs) and epoxyeicosatetraenoic acids (EEQs), respectively.

We present a method useful for large-scale enzymatic synthesis and purification of specific enantiomers and regioisomers of epoxides of arachidonic acid (AA), docosahexaenoic acid (DHA), and eicosapentaenoic acid (EPA) with the use of a bacterial cytochrome P450 enzyme (BM3).

Sintesi ezimatica dei metaboliti epossidici degli acidi docosahexaenoici, eicosapentaenoici e aracidonici

The epoxidized metabolites of various polyunsaturated fatty acids (PUFAs), termed epoxy fatty acids, have a wide range of roles in human physiology. These ...

Preparation of Contiguous Bisaziridines for Regioselective Ring-Opening Reactions

Aziridines, a class of reactive organic molecules containing a three-membered ring, are important synthons for the synthesis of a large variety of functionalized nitrogen-containing target compounds through the regiocontrolled ring-opening of C-substituted aziridines. Despite the tremendous progress in aziridine synthesis over the past decade, accessing contiguous bisaziridines efficiently remains difficult. Therefore, we were interested in synthesizing contiguous bisaziridines bearing an electronically diverse set of N-substituents beyond the single aziridine backbone for regioselective ring-opening reactions with diverse nucleophiles. In this study, chiral contiguous bisaziridines were prepared by organocatalytic asymmetric aziridination of chiral (E)-3-((S)-1-((R)-1-phenylethyl)aziridin-2-yl)acrylaldehyde with N-Ts-O-tosyl or N-Boc-O-tosyl hydroxylamine as the nitrogen source in the presence of (2S)-[diphenyl(trimethylsilyloxy)methyl]pyrrolidine as a chiral organocatalyst. Also demonstrated here are representative examples of regioselective ring-opening reactions of contiguous bisaziridines with a variety of nucleophiles such as sulfur, nitrogen, carbon, and oxygen, and the application of contiguous bisaziridines to the synthesis of multi-substituted chiral pyrrolidines by Pd-catalyzed hydrogenation.

Contiguous bisaziridines containing non-activated and activated aziridines were synthesized by asymmetric organocatalytic aziridinations and then subjected to chemoselective ring-opening reactions under acidic or basic conditions. The non-activated aziridine ring opens with less reactive nucleophiles under acidic conditions, whereas the activated aziridine ring opens with more reactive nucleophiles under basic conditions.

Preparazione di bisaziridine contigue per reazioni regioselettive di apertura dell'anello

Aziridines, a class of reactive organic molecules containing a three-membered ring, are important synthons for the synthesis of a large variety of ...

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers

The growing consumption of synthetic polymers and the accumulation of polymer waste have led to a pressing need for new routes to sustainable materials. Achieving a closed-loop polymer economy via chemical recycling to monomer (CRM) is one such promising route. Our group recently reported a new CRM system based on polymers prepared by ring-opening metathesis polymerization (ROMP) of trans-cyclobutane fused cyclooctene (tCBCO) monomers. This system offers several key advantages, including the ease of polymerization at ambient temperatures, quantitative depolymerization to monomers under mild conditions, and a broad range of functionalities and thermomechanical properties. Here, we outline detailed protocols for the preparation of tCBCO-based monomers and their corresponding polymers, including the preparation of elastic polymer networks and compression molding of linear thermoplastic polymers. We also outline the preparation of high ring strain E-alkene tCBCO monomers and their living polymerization. Finally, the procedures for the depolymerization of linear polymers and polymer networks are also demonstrated.

Here, we describe protocols for the preparation of trans-cyclobutane fused cyclooctenes (tCBCO),&#160;their polymerization to prepare depolymerizable olefinic polymers, and the depolymerization of these polymers under mild conditions. Additionally, protocols for the preparation of depolymerizable networks and compression molding of rigid linear plastics based on this system are described.

Polimeri olefinici depolimerizzabili a base di monomeri cicloottini ad anello fuso

The growing consumption of synthetic polymers and the accumulation of polymer waste have led to a pressing need for new routes to sustainable materials. ...