Name: synthesis of high purity nonsymmetric dialkylphosphinic acid extractants
Uploaded: 2017-10-19T12:30:00.000+00:00
Duration: 12 min 6 s
Description: Watch this Scientific Journal Video about Synthesis of High Purity Nonsymmetric Dialkylphosphinic Acid Extractants at JoVE.com

이 작품은 자연 과학 재단의 중국 국가 (21301104), 중앙 대학 (FRF-TP-16-019A3), 그리고는 주 키 연구소의 화학 공학 (SKL-체-14A04)에 대 한 근본적인 연구 자금에 의해 지원 되었다.

1. 합성의 모노-(2, 3-dimethylbutyl)에 phosphinic 산 18 , 19 <ol><li>반응 <ol><li>무게 31.80 g 나트륨 hypophosphite 수화물, 16.00 g 초 산, 8.42 g 2, 3-디 메 틸-1-butene, 0.73 g 디-tert-butylnperoxide (DTBP), 그리고 25.00 g tetrahydrofuran (THF) 100ml 테 플 론-줄지어 스테인리스 압력솥에는 압력솥에는 자력을 넣어 그것을 봉인</li>
		<li>수직 튜브로 자기 stirringapparatus는에 있는 오토 클레이 브를 넣어. 자석 교 반 장치를 시작 하 고 800 rpm 속도 설정.</li>
		<li>오토 클레이 브에 연결 된 온도 조절기의 난방 프로그램 설정: 90 분 동안 120 ° C로 실 온에서 열, 8 h, 120 ° C에서 유지 후 자연스럽 게 실내 온도에 아래로 냉각. 난방 프로그램 시작.</li>
	</ol></li> <li>Post-treatment <ol><li>250 mL 1 목 둥근 바닥 플라스 크에 제품을 전송, 50 mL, THF와 테 프 론 라이닝 세척 및 모든 제품 전송 됩니다 있도록 같은 플라스 크에 추가.</li>
		<li>THF와 회전 증발 기를 사용 하 여 unreacted 올레 핀 제거.</li>
		<li>분리 깔때기 250 mL에 잔류물을 전송, 각각, 30 mL 이온된 물 80 mL 에틸 에테르와 플라스 크를 씻고 그리고 모든 제품 전송 됩니다 있도록 같은 분리 깔때기에 그들을 추가.</li>
		<li>추가 50 mL 4 %NaOH 솔루션 위의 분리 깔때기로 그것을 적극적으로, 악수 하 고 수성 단계를 분리. 3 회 대 한 20 mL 4 %NaOH 솔루션 유기 단계를 추출 (20 m l × 3) 수성 단계의 pH 10 초과 되도록.</li>
		<li>위의 단계에서 수성 솔루션을 결합 하 고 분리 깔때기 500 mL에 그들을 전송.</li>
		<li>10% H 2의 추가 90 mL 4 솔루션 및 에틸 에테르 50 mL, 적극적으로 악수 하 고 유기 단계; 분리는 다음 추출 한다 3 번에 대 한 에틸 에테르 30 mL로 수성 단계 (30 mL × 3).</li>
		<li>단계 1.2.6에서 에틸 에테르 솔루션을 결합 하 고 그들을 퍼 널을 분리 하는 또 다른 500 mL에 전송.</li>
		<li>4 포화 NaCl 솔루션의 100 mL (100 mL × 4) 시간 그것 씻어.</li>
		<li>무수 MgSO 4 녹는 물 제거의 4g를 추가 합니다. 필터는 고체를 제거 하 고 깨끗 한 250ml 한 목 둥근 바닥 플라스 크에 액체를 수집.</li>
		<li>원유 제품의 17.92 g를 회전 증발 기를 사용 하 여 에틸 에테르 제거.</li>
	</ol></li></ol> 2. 모노-(2, 3-dimethylbutyl) phosphinic 산의 정화 <ol><li>소나 솔루션의 준비 <ol><li>22.28 g 100 ml 500 mL 비 커에 이온된 수의 소나 염 산 염의 분해.</li>
		<li>포화 NaOH 솔루션, 그리고 5 분에 대 한 혼란의 추가 100 mL</li>
		<li>에틸 에테르의 150 mL을 추가 하 고 흰색 침전 단계 2.1.2에서에서 생성 사라질 때까지 저 어.</li>
		<li>솔루션 500ml 분리 깔때기로 전송, 에틸 에테르와 비 커 세 번 세척 (50 m l × 3), 같은 분리 깔때기로 그들을 결합 하는 고.</li>
		<li>수성 단계를 분리 하 고 (100 m l × 5) 시간 5 포화 NaCl 솔루션과 유기 단계를 씻어.</li>
		<li>무수 MgSO 4 녹는 물 제거의 4g를 추가 합니다. 소나 에틸 에테르 해결책을 얻기 위해 필터.</li>
	</ol></li> <li>소나의 준비 &#8729; 모노-(2, 3-dimethylbutyl) phosphinic 산 성 소금 <ol><li>소나 솔루션 drop-wise 원유 모노-(2, 3-dimethylbutyl) phosphinic의 산 성 제품을 추가. 떨어지는 중 추가 제대로 저 수 있도록 에틸 에테르의 150 mL.</li>
		<li>모노-(2, 3-dimethylbutyl) phosphinic 산 제품의 모든 제품 소나 솔루션에 전송 되도록 에틸 에테르 50 mL를 포함 한 목 라운드 바닥 플라스 크를 씻으십시오. 30 분 동안 저 어 하 고 밤새 앉아 보자.</li>
		<li>필터 아래 압력을 감소 하 고 200 mL 에틸 에테르와 필터 케이크 세척.</li>
	</ol></li> <li>릴리스 모노-(2, 3-dimethylbutyl) phosphinic 산 <ol><li>500 mL 비 커에 필터링 된 케이크를 전송, 80 mL의 1 M HCl 추가 하 고 5 분 동안 저 어</li>
		<li>추가 70 mL 에틸 아세테이트, 그리고 또 다른 5 분에 대 한 혼란</li>
		<li>분리 깔때기 250 mL에 솔루션을 전송 하 고 수성 단계 구분.</li>
		<li>40 mL 에틸 아세테이트와 수성 단계를 다시 추출 하 고 에틸 아세테이트 솔루션 결합.</li>
		<li>30 mL의 1 M HCl에 두 번 (30 mL × 2)와 에틸 아세테이트 솔루션을 세척 하 고 순차적으로 (80 m l × 3), 시간 3 NaCl 포화.</li>
		<li>추가 4 g 무수 MgSO 4 녹는 물 제거. 필터링 및 250 mL 1 목 둥근 바닥 플라스 크에 액체를 수집.</li>
		<li>회전 증발 기를 사용 하 여 에틸 아세테이트 제거 고 순수한 모노-(2, 3-dimethylbutyl) phosphinic 산의 12.45 g (수율: 82.9%).</li>
	</ol></li></ol> 3. 합성 (2, 3-dimethylbutyl) (2,4,4 &#39;-trimethylpentyl) phosphinic 산 <ol><li>반응 <ol><li>전송 모든 순수한 모노-(2, 3-dimethylbutyl) phosphinic 산 제품의 100 mL에 테 플 론-줄지어 스테인리스 압력솥, 초 산, diisobutylene, DTBP의 0.30 g의 25.39 g의 4.95 g 추가, 자기 활동가 압력솥에 넣고 그것을 봉인</li>
		<li>오토 클레이 브는 자석 교 반 장치는 수직 튜브 용광로에 넣고 자석 교 반 장치를 시작.</li>
		<li>설정 온도 조절기의 난방 프로그램: 135 ° C에 90 분 동안 실 온에서 열, 8h, 135 ° C에서 유지 후 자연스럽 게 실내 온도에 아래로 냉각. 난방 프로그램 시작.</li>
		<li>때 반응 시스템은 실내 온도에 냉각, DTBP의 다른 0.30 g을 추가 하 고 난방 프로그램을 다시 시작.</li>
		<li>반복 단계 3.1.4 한 번.</li>
	</ol></li> <li>Post-treatment <ol><li>100 mL 에틸 에테르와 함께 제품을 희석 하 고 250 ml 깔때기를 분리 전송.</li>
		<li>4%의 30 mL로 씻어 NaOH 3 번 (30 mL × 3) 수성 단계 pH 10 초과 되도록.</li>
		<li>그래서 10% H 2의 70 mL을 추가 4 솔루션 제품을 시 어 지 다.</li>
		<li>씻어 포화 NaCl 솔루션으로 여러 번 (각 80 mL)까지 수성 단계의 pH가 pH 6-7.</li>
		<li>무수 MgSO 4 녹는 물 제거의 4g를 추가 합니다. 필터는 고체를 제거 하 고 깨끗 한 250ml 한 목 둥근 바닥 플라스 크에 액체를 수집.</li>
		<li>에틸 에테르와 원유 제품의 15.10 g를 회전 증발 기를 사용 하 여 unreacted 올레 핀 제거.</li>
	</ol></li></ol> 4. 정화 (2, 3-dimethylbutyl) (2,4,4 &#39;-trimethylpentyl) phosphinic 산 <ol><li>순수한 co-(2,3-dimethylbutyl)를 얻을 (2,4,4 &#39;-trimethylpentyl) 복잡 한 phosphinic 산 <ol><li>분해 2.30 g NaOH의 40 mL에 이온을 제거 된 물입니다. 원유를 포함 하는 플라스 크에 NaOH 솔루션을 추가 (2, 3-dimethylbutyl) (2,4,4 &#39;-trimethylpentyl), phosphinic 산 성 제품을 적극적으로 5 분 위해 그것을 흔들어</li>
		<li>추가 0.5 M CoCl 2 솔루션 때까지 더 이상 푸른 침전이 생성 되 고 플라스 크에서 솔루션은 핑크. 흔들어 동안 dropwise < /li> <li>필터 세척 필터 케이크까지 이온을 제거 된 물으로 블루 침전은 무색.</li>
		<li>250ml 비 커에 필터 케이크를 옮기고 아세톤의 100 mL를 추가, 방부 제 필름, 그것을 봉인 하 고 1 박 4 ° C에서 냉장.</li>
		<li>Pulverize는 대량에 갇혀 있는 모든 불순물을 출시 블루 침전.</li>
		<li>필터 신선한 아세톤의 100 mL와 함께 그것을 씻어. 실내 온도에, 필터 케이크를 건조 하 고 다음 250 mL 분리 깔때기로 전송.</li>
	</ol></li> <li>재생성은 (2, 3-dimethylbutyl) (2,4,4 &#39;-trimethylpentyl) phosphinic 산 <ol><li>120 mL 에틸 에테르와 80 mL 10% H 2 추가 4, 그리고 푸른 침전까지 적극적으로 쉐이크 사라집니다.</li>
		<li>수성 단계를 구분, 유기 세척 10% H 2의 30 mL와 순차적으로 한 번 등 4 단계 고 수성 단계의 pH는 pH 6-7를 같아질 때까지 여러 번 (각 80 mL) NaCl 솔루션을 포화.</li>
		<li>무수 MgSO 4 녹는 물 제거의 4g를 추가 합니다. 필터를 고체를 제거 하 고 깨끗 한 250ml 한 목 둥근 바닥 플라스 크에 액체를 수집.</li>
		<li>회전 증발 기를 사용 하 여 에틸 에테르를 제거 고 순수한 제품의 11.46 g (수율: 52.8%).</li>
	</ol>
	</li>
</ol>

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L., 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=Solvent+extraction+of+rare+earth+ions+from+nitrate+media+with+new+extractant+di-(2,3-dimethylbutyl)-phosphinic+acid.">Solvent extraction of rare earth ions from nitrate media with new extractant di-(2,3-dimethylbutyl)-phosphinic acid.</a> J Rare Earths. 34 (7), 724-730 (2016).</li><li>Hu, W. X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+properties+of+di-tertiary+alkylphosphinic+acids.">Synthesis and properties of di-tertiary alkylphosphinic acids.</a> Chem J Chin Univ-Chin. 15 (6), 849-853 (1994).</li><li>Wang, J. L., Chen, G., Xu, S. M., Li, L. Y. <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+novel+nonsymmetric+dialkylphosphinic+acid+extractants+and+studies+on+their+extraction-separation+performance+for+heavy+rare+earths.">Synthesis of novel nonsymmetric dialkylphosphinic acid extractants and studies on their extraction-separation performance for heavy rare earths.</a> Hydrometallurgy. 154, 129-136 (2015).</li><li>Wang, J. L., Xie, M. Y., Wang, H. J., Xu, S. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solvent+extraction+and+separation+of+heavy+rare+earths+from+chloride+media+using+nonsymmetric+(2,3-dimethylbutyl)(2,4,4'-trimethylpentyl)phosphinic+acid.">Solvent extraction and separation of heavy rare earths from chloride media using nonsymmetric (2,3-dimethylbutyl)(2,4,4'-trimethylpentyl)phosphinic acid.</a> Hydrometallurgy. 167, 39-47 (2017).</li><li>Menoyo, B., Elizalde, M. P., Almela, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Determination+of+the+degradation+compounds+formed+by+the+oxidation+of+thiophosphinic+acids+and+phosphine+sulfides+with+nitric+acid.">Determination of the degradation compounds formed by the oxidation of thiophosphinic acids and phosphine sulfides with nitric acid.</a> Anal Sci. 18 (7), 799-804 (2002).</li><li>Darvishi, D., 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=Synergistic+effect+of+Cyanex+272+and+Cyanex+302+on+separation+of+cobalt+and+nickel+by+D2EHPA.">Synergistic effect of Cyanex 272 and Cyanex 302 on separation of cobalt and nickel by D2EHPA.</a> Hydrometallurgy. 77, 227-238 (2005).</li></ol>

저자는 공개 없다.

프로토콜 내에서 가장 중요 한 단계는 모노-alkylphosphinic 산 합성입니다 (그림 1a). 이 반응에서 높은 수율 및 적은 dialkylphosphinic 산 성 부산물이 좋습니다. NaH2포2/olefin A의 어 금 니 비율 증가 수율 향상 되며 dialkylphosphinic 산 성 부산물의 생성을 억제. 그러나, 큰 NaH2포2 복용량 또한 비용을 증가 하 고 교 반 문제가 발생할. NaH2포2/olefin A의 기본 어 금 니 비율은 3:1입니다. 용 매로 THF n보다 낫다-옥 탄, 1, 4-dioxane 및 cyclohexane이이 반응에서. 창시자로 DTBP 2, 2-azobisisobutyronitrile (AIBN)18보다 낫다. 모노-alkylphosphinic 분리 하 디 alkylphosphinic 산 성 부산물에서 산 소나 메서드 수 있다 채택 될. 모노-alkylphosphinic 산 디 alkylphosphinic 산의 큰 공간 제한으로 인해 수 없습니다 하는 동안 유기 솔루션에 여전히 남아 백색 강 수를 생성 하는 소나로 반응 수 있습니다. 흰색 강 수 여과, 여 고 추가 무기 강한 산 (HCl 또는 H2를 너무 좋아4) 모노-alkylphosphinic 산 및 디-alkylphosphinic 산의 분리를 완료 하는 모노-alkylphosphinic 산을 다시 생성 하려면 부산물은 실현 될 수 있다.
NSDAPA 합성 (그림 1b)에 어 금 니 올레 B/모노-alkylphosphinic 산의 비율은 1:1 보다 더 많은 (2:1-4: 1은 기본) 초과 올레 B 솔벤트의 역할. 비록 올레 B 초과에서, 모노-alkylphosphinic 산 완전히 반응 수 없습니다. Unreacted 모노-alkylphosphinic 산 (NaOH, KOH) 같은 기지와 반응 때 유기 단계에서 수성 단계에 들어갈 것 이다 그래서 기본 산 후 치료 하면 쉽게 제거할 수 있습니다. 기본 산 후 치료 중에서 NSDAPA 항상 유기 단계에 남아 하 고 따라서 원유 제품 항상 unreacted 올레 B, 자유 래 디 칼 조각, 올리고, 등유기 불순물을 포함. 이러한 유기 불순물은 Co NSDAPA 복합물의 용 해도 매우 작은 얼음 아세톤, 아세톤에 용 해. 이 차이가 더 NSDAPA를 정화 하는 방법을 제공: Co NSDAPA 복합물을 형성, 복잡 한 유기 불순물 제거를 얼음 아세톤으로 세척 다음 강한 산을 추가 하는 Co2 + NSDAPA 반응 (같은 H2이렇게4 또는 HCl)에 NSDAPA를 다시 생성 하려면 복잡입니다.
이 프로토콜 NSDAPA 합성 및 정화에 대 한 보편적인 방법을 설명합니다. PH3 인 원본으로 전통적인 NSDAPA 합성 방법에 비해, 우리의 메서드는 낮은 독성, 온화한 반응 조건, 쉬운 정화, 그리고 대규모 생산을 위한 잠재력의 장점이 있습니다. 이 메서드는 dialkylphosphinic 산의 성능을 세밀 하 게 조정 하는 방법을 제공 합니다. P204, P507, Cyanex 272 등 다른 organophosphorus 산 extractants, 처럼 NSDAPA hydrometallurgy 추출 및 희토류 이온, 비-철 금속, 희귀 금속, actinides, 등등의 분리에 대 한 소송에 사용할 수 있습니다. NSDAPA의 합성 방법 우리의 탐험이 클래스 extractants의 잠재적인 분리 시스템의 수를 가능 하 게.

산 성 organophosphorus extractants 추출 및 분리 희토류 이온1,2, (공동/Ni3,4) 같은 비-철 금속, 희귀 금속 (전통적인 hydrometallurgy 필드에서 널리 이용 된다 Hf/Zr5, V6,7), 같은 actinides8, 등. 최근 몇 년 동안, 그들은 또한 높은 수준의 액체 폐기물 처리9보조 자원 재활용 분야에 더 많은 관심을 받고 있다. 디-(2-ethylhexyl) 인산 D2EHPA (P204), 2-ethylhexylphosphoric 산 성 모노-2-ethylhexyl 에스테 르 (EHEHPA, 88A, PC 또는 P507) 그리고 디-(2, 4, 4'-trimethylpentyl)-phosphinic 산 (Cyanex272), dialkylphosphoric 산의 대표는 alkylphosphoric 산 성 모노 알 킬 에스테 르 및 dialkylphosphinic은 각각, 가장 일반적으로 사용 되는 extractants 있습니다. 그들의 산 성도 다음 순서로 감소: P204 &#62; P507 &#62; Cyanex 272. 해당 추출 능력, 추출 용량 및 스트립 산 성도 모두 P204 순서는 &#62; P507 &#62; Cyanex 272, 반대 순서로 분리 성능입니다. 이 3 개의 extractants는 대부분의 경우에 효과적입니다. 그러나, 여전히 몇 가지 조건이 있다 어디 있는지 너무 효율적: 무거운 희토류 분리는 기존 하는 주요 문제는 가난한 선택도 및 P204 및 P507, 높은 스트립 산 낮은 추출 용량 및 유제 경향 동안에 Cyanex 272에 대 한 추출. 따라서, 소설 extractants의 개발은 최근 몇 년 동안에서 큰 관심을 받고 있다.
Dialkylphosphinic 산 extractants의 클래스는 새로운 extractants를 개발 하는 가장 중요 한 연구 측면 중 하나 간주 됩니다. 최근 연구에 dialkylphosphinic 산의 추출 능력 알 킬 치환 기10,11의 구조에 크게 의존 했다. 그것은 Cyanex 27212의 그것 보다 낮은 P507의 그것 보다 훨씬 더 높은에서 광범위 한 수 있습니다. 그러나, 소설 dialkylphosphinic 산 extractants의 탐험은 상업 올레 구조10,12,13,,1415, 제한 16. Dialkylphosphinic 산 extractants 또한 그리 반응 방법으로 종합 될 수, 있지만 반응 조건은 엄격한12,17입니다.
NSDAPA, 2 개의 alkyls는 다른, 새로운 extractants의 탐험에 문을 엽니다. Dialkylphosphinic 산의 구조 더 다양 한와 그것의 추출 및 분리 성능을 모두 알 킬 구조를 수정 하 여 미세 조정 수 있습니다. NSDAPA의 전통적인 합성 방법 높은 독성, 엄격한 반응 조건, 그리고 어려운 정화 같은 많은 단점이 인 원본으로 PH3 사용. 최근 우리 NSDAPA 한 인 ( 그림 1참조) 소스와 성공적으로 합성 3 NSDAPAs18나트륨 hypophosphite를 사용 하 여 합성 하는 새로운 방법을 보고. 이 상세한 프로토콜 새로운 실무자 실험을 반복 하 고 NSDAPA extractants의 합성 방법 마스터 수 있습니다. 우리 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) 예를 들어 phosphinic 산. 이름 및 올레 A, 중간 모노-alkylphosphinic 산, 올레 B, 및 해당 NSDAPA의 구조는 표 1에 표시 됩니다.

<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

우리 선물의 합성 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) 고 순도 nonsymmetric dialkylphosphinic 산 extractants의 합성에 대 한 메서드를 보여 주기 위해 예제로 phosphinic 산. 낮은 독성 나트륨 hypophosphite 올레와 반응 인 소스는 (2, 3-디 메 틸-1-butene) 중간 monoalkylphosphinic 산을 생성 하기 위해 선정 되었다. 소나만 monoalkylphosphinic 산 dialkylphosphinic 산 수 없습니다 때문에 소나로 반작용 하는 동안 amantadine∙mono alkylphosphinic 산 성 소금 형성 소나 반응 수로 dialkylphosphinic 산 성 부산물을 제거 하 채택 되었다 그것의 큰 입체 지 장입니다. 순화 monoalkylphosphinic 산 다음 올레 B (diisobutylene) nonsymmetric dialkylphosphinic 산 (NSDAPA)를 가진 반응 했다. Unreacted monoalkylphosphinic 산 간단한 기본 산 후 처리에 의해 쉽게 제거 될 수 있다 고 다른 유기 불순물 코발트 소금의 강 수를 통해 밖으로 분리 될 수 있다. 구조는 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) phosphinic 산 31P NMR, 1H NMR, ESI-MS, 및 FT-적외선에 의해 확인 되었다 순도 potentiometric 적정 방법으로 결정 했다 고는 나타냅니다 순도 96%를 초과할 수 있습니다.

31 P NMR 스펙트럼 수집 했다 모노-(2, 3-dimethylbutyl) phosphinic 산에 대 한 정화 전후 소나 메서드 (그림 1-b). 31 P NMR 스펙트럼, 1H NMR 스펙트럼, MS 스펙트럼 및 FT-적외선 스펙트럼에 대 한 수집 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) phosphinic 산 (참조 그림 3, 그림 4, 그림 5, 그림 6, 각각) 후 코발트 소금 강 수 방법으로 정화입니다. Potentiometric 적정 곡선의 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) phosphinic 산 했다 기록된 (그림 7)19.
모노-alkylphosphinic 산 합성을 하는 동안 그것은 해당 dialkylphosphinic 산 성 부산물의 생성을 피하기 위해 어려운 (참조 그림 1는)는 기본 산 후 처리에 의해 제거할 수 없습니다. 그림 2는에 디-(2, 3-dimethylbutyl) phosphinic 산의 흡수 피크 (62.507 ppm)에 대 한 이유입니다. 올레 A 1 octene 또는 cyclohexene 일 때, 비슷한 현상 발생18. 2, 4-디 메 틸-1-heptene, 9 개의 탄소 원자를 포함 하는 테스트도 하지만 같은 현상 또한 발생 했습니다. 그림 2 b 31P NMR 스펙트럼의 순수한 모노-(2, 3-dimethylbutyl) phosphinic 산을 보여줍니다.
구조적 특성은 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) phosphinic 산. 
31 P (243 m h z, CDCl3) NMR δ (그림 3): 61.40 (s). 1 H NMR (600mhz, CDCl3) δ (그림 4): 0.82-0.88 (m, 6 H 2CH3), 0.92 (s, 9h, 3CH3), 1.01-1.04 (m, 3h, CH3), 1.12 1.15 (m, 3h, CH3), 1.15-1.21 (m, 1 시간), 1.32 1.38 (m, 1 시간), 1.41-1.49 (m, 1 시간) 1.51-1.60 (m, 1 시간), 1.61-1.78 (m, 3 H), 1.87-1.95 (m, 1 시간), 2.04-.14 (m, 1 시간), 11.862 (s, 1 H, 오하이오).
ESI-MS (+) m/z (그림 5는): 263 [M + H]+, 304 [M + C3H6]+, 525 [2 M + H]+, 547 [2 M + 나]+, 567 [2 M + C3H7]+. ESI-MS (-) m/z (그림 5b): 261 [M-H]-, 523 [2 M-H]-, 566 [2 M + C3H7-H]-. FT-적외선 wavenumbers (cm-1) (그림 6): 2876.55 2902.84 C-H 스트레칭, 2619.51 O-H 스트레칭 이합체 형성, 1667.29 O-H 벤딩, 1467.91 C H 절곡, 1366.13 C H 락, tert-부 틸 그룹의 1237.41 C C 스트레칭으로 인 한 1165.57 P = O 스트레칭, 962.69 P-O(H) 스트레칭, 821.97 P C 스트레칭. 관련 진동 특성 밴드 phosphonic 산, 인산 산 및 다른 phosphinic 산20,21와 유사 하다.
31P, 1H NMR 스펙트럼, ESI MS 스펙트럼 및 FT-적외선 스펙트럼의 구조 확인 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) phosphinic 산. Potentiometric 적정 결과 (그림 719) 최종 제품의 순도 96%를 초과할 수 있습니다 나타냅니다.
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56156/56156fig1.jpg"> 
그림 1. NSDAPA 산의 합성 경로입니다. <a href="//ecsource.jove.com/files/ftp_upload/56156/56156fig1large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭 하십시오.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56156/56156fig2.jpg"> 
그림 2. 31 모노-(2, 3-dimethylbutyl) phosphinic (한) 전에 산과의 (b) P NMR 스펙트럼 (243 m h z, CDCl3) 소나 메서드에서 정화 후. <a href="//ecsource.jove.com/files/ftp_upload/56156/56156fig2large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭 하십시오.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/56156/56156fig3.jpg"> 
그림 3. 31 P NMR 스펙트럼 (243 m h z, CDCl3)의 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl)는 코발트 정화 후 phosphinic 산 소금 강 수 방법. <a href="//ecsource.jove.com/files/ftp_upload/56156/56156fig3large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭 하십시오.</a>
<img alt="Figure 4" class="xfigimg" src="/files/ftp_upload/56156/56156fig4.jpg"> 
그림 4. 1 H NMR 스펙트럼 (600mhz, CDCl3)의 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl)는 코발트 정화 후 phosphinic 산 소금 강 수 방법. <a href="//ecsource.jove.com/files/ftp_upload/56156/56156fig4large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭 하십시오.</a>
<img alt="Figure 5" class="xfigimg" src="/files/ftp_upload/56156/56156fig5.jpg"> 
그림 5. ESI MS 스펙트럼의 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) 코발트 정화 후 phosphinic 산 소금 강 수 방법, (한) 긍정적이 고 (b) 부정. <a href="//ecsource.jove.com/files/ftp_upload/56156/56156fig5large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭 하십시오.</a>
<img alt="Figure 6" class="xfigimg" src="/files/ftp_upload/56156/56156fig6.jpg"> 
그림 6. FT-적외선 스펙트럼의 순수 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl)는 코발트 정화 후 phosphinic 산 소금 강 수 방법. <a href="//ecsource.jove.com/files/ftp_upload/56156/56156fig6large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭 하십시오.</a>
<img alt="Figure 7" class="xfigimg" src="/files/ftp_upload/56156/56156fig7.jpg"> 
그림 7. Potentiometric 적정 곡선의 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) phosphinic 산 (m = 0.1270 g) 0.1127 mol/L NaOH와 75% 알코올 (v/v)에서.<a href="//ecsource.jove.com/files/ftp_u href=""></a href="//ecsource.jove.com/files/ftp_u>pload/56156/56156fig7large.jpg"스타일 =" 글꼴-크기: 14px; "target ="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭 하십시오.

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

고 순도 Nonsymmetric Dialkylphosphinic 산 Extractants의 합성

고 순도 nonsymmetric dialkylphosphinic 산 extractants의 합성에 대 한 프로토콜 제시, 복용 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) 예를 들어 phosphinic 산.

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 ...

synthesis-high-purity-nonsymmetric-dialkylphosphinic-acid

Nanyang Technological University

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Acid-base and Solubility Equilibria

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7.4K 조회수.  University of Science and Technology Beijing. 고 순도 nonsymmetric dialkylphosphinic 산 extractants의 합성에 대 한 프로토콜 제시, 복용 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) 예를 들어 phosphinic 산.

비디오: 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.

단일 분자 이미징을위한 소형 양자 점

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

연구

공학

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.

합성 및 크로마토 그래피에 대한 최적의 고정상의 양이 선택의 참여 Iodoaziridines의 정화

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

화학

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.

포스 포의 향상된 농축을위한 거대 다공성 고분자 모노리스에 다공성 조정 폴리머 코팅의 제조

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).

대기 에어로졸의 추출 및 계면 활성제의 특성

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

환경과학

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.

Polyamine 기반 펩타이드 Amphiphiles (PPAs) 및 관련된 생체 자기 조립의 합성에 대 한 손쉬운 프로토콜

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.

이기에 친 환 경적 Steglich 에스테 르 화를 통해 에스테 르의 합성

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.

단백질 정화에 대 한 Poly(pentafluorophenyl acrylate) 기능성 SiO2 구슬의 준비

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).

도코사헥사에노믹, 에이코사펜타에노믹, 아라키돈산의 에폭시화된 대사산물의 효소 합성

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.

위치 선택적 개환 반응을위한 연속 비사 지리딘의 제조

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.

융합 고리 사이클로옥텐 단량체를 기반으로 하는 해중합 가능한 올레핀 폴리머

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