The authors thank Dr. A. Tejeda-Cruz (X-ray; IIM-UNAM). R.Y. thanks CINVESTAV, Mexico for technical support. M.S.S acknowledges the financial support by Spanish Government, MINECO (MAT2012-31127). I.A.I thanks CONACyT (212318) and PAPIIT UNAM (IN100415), Mexico for financial support. E.G-Z. thanks CONACyT (156801 and 236879), Mexico for financial support. Thanks to U. Winnberg (ITAM and ITESM) for scientific discussions.

주의 :이 촉매 적 절차에서 사용되는 화학 물질의 독성 및 비 - 발암 성이 비교적 낮다. 이러한 안전 안경, 장갑, 실험실 코트, 전체 길이 바지와 폐쇄 발가락 신발로이 실험 절차를 수행 할 때 모든 적절한 안전 예방 조치를 사용하십시오. 다음 절차 중 한 부분은 표준 공기가없는 처리 기술을 포함한다. 카탈리스트 1. 활성화 (HKUST-1) <ol><li> 카탈리스트의 결정의 특성 참고 HKUST-1 시판되는 다공성 배위 고분자 (촉매)이다. 촉매의 결정 성을 확증하기 위해, HKUST-1의 시료는 분말 X 선 회절 (PXRD)을 특징으로 할 필요가있다. <ol><li> 브래그-Brentano 기하학에서의 Cu-Kα 1 방사선 (λ = 1.5406 Å)에 대한 (160 W (40 kV의, 40mA)에서 작동하는 회절에) HKUST-1의 0.1 g 샘플의 PXRD 패턴을 수집합니다. 0.02 # 60 ° (2θ) 5 °에서 PXRD 패턴을 녹음(176); 단계 시간 44 카운트 1 초. </li></ol></li><li> HKUST-1의 탈 용매 <ol><li> 촉매 (HKUST-1) 0.05 g을 달아. </li><li> 스탠드에 250 ml의 두 구 둥근 바닥 플라스크를 고정하고 둥근 바닥 플라스크에 자기 교반 막대를 삽입합니다. </li><li> 둥근 바닥 플라스크에 콘덴서를 연결합니다. </li><li> 완벽한 밀봉을 생성하기 위해 플라스크 및 콘덴서의 관절 사이에 진공 그리스 또는 테프론 테이프를 사용합니다. </li><li> (호스에 꼭지를 통해) 진공 펌프로, 상단에서, 콘덴서를 연결합니다. </li><li> 펌프에 의해 생성 된 진공은 약 10-2 바 있는지 확인합니다. 참고의 편의를 위해,이 실험은 활성화 시스템으로 지칭 될 것이다 (진공 펌프에 접속되는 응축기에 연결된 두 구 둥근 바닥 플라스크)를 설정한다. </li><li> 250 ml의 두 구 둥근 바닥 플라스크 내부의 촉매 (0.05 g)을 놓습니다. </li><li> 의 두 번째 목에 고무 격막을 삽입둥근 바닥 플라스크는 (맞는)를 적절하게 밀봉해야합니다. </li><li> 조심스럽게, 모래 목욕으로 기동 시스템을 배치합니다. </li><li> 진공 펌프를 시작하고 완전히 열릴 때까지 조심스럽게 꼭지를 켭니다. 핫 플레이트로, 1 시간 동안 100 ° C에 정품 인증 시스템을 가열한다. </li><li> 환저 플라스크의 바닥에 균일하게 촉매를 분배하기 위해 핫 플레이트의 낮은 속도로 교반한다. </li><li> 난방 1 시간 후 열 (핫 플레이트)를 끄고 (진공)가 상온이되도록 기동 시스템을 할 수 있습니다. </li><li> 기동 시스템을 실온으로 냉각되면, 콕을 해제 (즉, 활성화 시스템은 수동 진공 하에서 것) 및 펌프를 끄지. </li><li> 두 구 둥근 바닥 플라스크에, 격벽을 통하여 질소로 채워진 벌룬 (N 2)를 연결하고 평형 압력에 도달 잠시 기다린다. 주 : 촉매의 활성화 후, 그것을 U두고파인더 불활성 분위기 (N 2) 조정되지 않은 금속 사이트 (또는 열린 금속 자리)에 접근하기 때문에 활성 촉매를 얻을 수있는 열쇠입니다. </li><li> 평형 압력이 달성 된 N 2, 가득 풍선을 제거합니다. 참고 : 청록색에서 컬러 변화를 (그대로 받아 HKUST-1) (정품 인증시) 짙은 파란색으로 관찰된다. </li></ol></li></ol> 이기종 촉매를 통해 바닐린 2. 합성 <ol><li> 유기 용매의 탈기 <ol><li> 5 분 동안 N이 버블 링에 의해 탈기 에탄올 약 70 ㎖에. </li></ol></li><li> 촉매 반응의 제조 <ol><li> 두 구 둥근 바닥 플라스크에 탈기 된 에탄올 10 ㎖를 첨가하고 부드럽게 핫 플레이트에서 현탁액을 교반 하였다. </li><li> 정지에 (H 2 O 30 %) H 5 ml의 2 O 2를 추가합니다. </li><li> 현탁액에 아세토 니트릴 0.25 ML을 추가합니다. </li><li> 페룰 산 0.50 g을 달아에 용해비커에 탈기 에탄올 20 ㎖. </li><li> 현탁액에 용해 된 페룰 산을 추가합니다. </li><li> 탈기 에탄올 20 mL로 비커를 씻고 정지에 추가합니다. </li></ol></li><li> 바닐린에 트랜스 페룰 산의 산화 <ol><li> 진공 펌프에 콘덴서를 연결하는 호스를 분리합니다. </li><li> 응축기를 통과 수돗물을 켭니다. 바람직하게는, 물 펌프를 사용한다. </li><li> 1 시간 동안 100 ° C (환류)에 서스펜션까지 가열한다. </li><li> 열 교반을 끕니다. 조심스럽게 (응축기에 부착 된) 두 구 둥근 바닥 플라스크를 들어 올려 실내 온도가 식지. </li></ol></li><li> 반응 작업 업 <ol><li> 반응 혼합물을 촉매 (HKUST-1), 복구 (흐너 깔때기 및 플라스크를 사용) 및 에틸 아세테이트 200 ㎖로 씻어 여과 해. 참고 : 빨리 복구합니다 (흐너 플라스크에 연결된)의 진공을 사용하여, 여과 과정을 단축하고, C를 세척하기 위해서는atalyst. </li><li> 제 1과 PXRD에 의해 촉매의 프레임 워크 결정의 유지를 확증. </li><li> (로타리 증발기로 감압 하), 합쳐진 유기 상을 농축시키고, 100ml의 에틸 아세테이트로 다시 그것을 녹인다. </li><li> NH 4 CL (30 ㎖)의 포화 용액으로 유기상을 (a 분리 깔때기를 사용하여) 세척 하였다. </li><li> 유기 상을 복구하고, 무수 나 2 SO 4 (30g)로 섞는다. 현탁액을 15 분 동안 서 보자. </li><li> 현탁액을 여과하고 여액을 복구 할 수 있습니다. </li><li> 회전 증발기로 감압 하에서 (약 20 ㎖까지), 여과 액을 농축시켰다. </li></ol></li><li> 잔류 물 (바닐린)의 정제 <ol><li> 플래시 칼럼 크로마토 그래피 (44)에 의해 잔류 물을 정제. 정지상은 실리카겔하고 이동상을 에틸 아세테이트 - 헥산 (5:95)의 용매 혼합물이다. </li><li> 실리카 겔 크로마토 그래피의 유리 컬럼 (1cm X 30cm)를 포장(1cm X 6cm). 아세테이트 - 헥산 (5:95) 혼합 용매에 열을 포화. </li><li> 조심스럽게 유리 컬럼의 상단에 집중-여과 액을 붓는다. </li><li> 천천히 유리 컬럼에 용매 혼합물을 추가하고 1,200 ml의가 수집 될 때까지 분수를 모두 수집합니다. </li><li> 건조 될 때까지 로타리 증발기로 유기 분획 (1200 ml)에 집중한다. </li><li> 정제 된 바닐린입니다 최종 고체 분말을 복구 할 수 있습니다. </li></ol></li></ol>

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The authors have nothing to disclose.

바닐린 트랜스 -ferulic 산의 촉매 변환을위한 기본적인 공정은 촉매 (HKUST-1)의 활성화이었다. 촉매 (진공하에 100 ℃에서) 반응계에서 활성화되지 않은 경우, 바닐린 트랜스 -ferulic 산의 일부만 변환 (44)이 관찰되었다. 즉, 금속 부위를 열 접근성 촉매 사이클 44 중요하고,이 다공질 코디 폴리머 내의 구리 (II)의 금속 사이트로 조정 된 물을 제거함으로써 달성 될 수...

불균일 촉매 1-4 다공성 배위 고분자 (의 PCP)를 사용하는 비교적 새로운 연구 분야이다. 의 PCP가 보여 매우 흥미로운 특성, 예를 들면, 다공성 규칙, 높은 표면적과 금속 접속으로 인해, 그들은 이종 촉매 5-6에 대한 새로운 대안을 제공 할 수 있습니다. 촉매 활성의 PCP의 생성은 여러 연구 그룹 7-10의 주요 초점이되어왔다. 다공성 배위 중합체 따라서 금속 이온 및 유기 결합제에 의해 구성되며, 이들 재료의 촉매 활성이 부품에 의해 제공된다. 일부의 PCP는 화학 반응 (11)을 촉매 할 수 불포화 (활성) 금속이 포함되어 있습니다. 그러나, 배위 중합체 내에 불포화 금속 자리 (개방 금속 자리)의 발생이 사소한 작업이 아니며은 요약 될 수있는 합성 도전 나타내고 : (I)의 불안정한 리간드 7-11 제거하여 빈 배위 생성하는 단계;(II) 유기 리간드 (이전 합성) 8,12-13를 통합하여 바이메탈의 PCP의 발생; (III) 금속 이온의 PCP의 세공 내에 9,14-15 또는 유기 리간드 (10), 16-17의 합성 후 변형. 방법론 (i)는 이와 같이 단순한이기 때문에 자주 사용이다. 일반적으로, 개방 된 금속 부위의 발생을 H 2 18-19 향해의 PCP의 친 화성을 ​​향상시킬뿐만 아니라, 활성 이종 촉매 20-27 설계에 사용되었다. 양호한 촉매 특성을 달성하기 위해, 추가의 PCP가 열려 금속 사이트, 반응 조건, 촉매의 실험 후에 결정 성의 유지, 상대적으로 높은 열적 안정성 및 화학적 안정성의 접근성에 표시 할 필요가있다. HKUST-1 (구리 3 (BTC) 2 (H 2 O) 3, BTC = 1,3,5- 벤젠 트리 카르 복실 레이트) (7)이카르 복실 리간드와 배위 물 구리 (II) 양이온으로 구성된 잘 조사 다공성 배위 중합체. 흥미롭게도,이 물 분자 (가열)을 제거하고,이 하드 루이스 산의 특성 (11)을 나타내는 구리 이온 주변의 정사각형 평면 조정을 제공 할 수있다. 보르디가와 협력자 (28)이 H 2 O 분자의 제거가 결정 성 (규칙 성 유지율) 및 금속 이온의 산화 상태 (구리 (II))의 영향을받지 한 영향을 미치지 않았 음을 보여 주었다. 촉매로서 HKUST-1의 사용은 광범위하고 특히 29-33 (본 연구에 매우 중요한) 방향족 분자 (34)의 과산화수소 산화 반응을 조사 하였다. 바닐라는 화장품, 의약품 및 식품 산업에서 가장 널리 사용되는 향미 제의 하나이다. 이것은 런 바닐라 planifolia, Vani의 경화 콩으로부터 추출LLA의 tahitiensis와 바닐라 퐁퐁. 이 초콜릿 맛 35-37을 개선하기 때문에 마야와 아즈텍 문명 (콜럼버스 명) 먼저 향미 제로서 바닐라의 엄청난 잠재력을 실현. 바닐라 제 1858 38 단리하며 바닐린의 화학 구조가 마침내 결정되었다 1874 39까지 없었다. (난초 바닐라 planifolia, 바닐라 tahitiensis와 바닐라 퐁퐁에서) 바닐린의 자연 추출은 전 세계 생산량의 1 %를 나타내며,이 과정이 비싸고 (40) 매우 긴이기 때문에, 바닐린의 나머지 (40)를 합성된다. 많은 생물 공학적 접근 그러나, 이러한 방법은 이들 방법은 강한 산화제 독성 용매 41-43를 사용하기 때문에 환경을 해치지 단점이 등 리그닌 페놀 스틸 벤, 이소 유게 놀, 유게 놀, guaicol에서 바닐린의 합성에 사용될 수있다. 여기서, 우리는 r에촉매 HKUST-1을 사용하여 트랜스 -ferulic 산의 산화에 의해 바닐린의 제조 합성 전략 eport.

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>HKUST-1</td>
			<td>Sigma-Aldrich</td>
			<td>MFCD10567003</td>
			<td></td>
		</tr>
		<tr>
			<td>Ferulic Acid (trans-4-Hydroxy-3-methoxycinnamic acid)</td>
			<td>Sigma-Aldrich</td>
			<td>537-98-4</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethanol</td>
			<td>Sigma-Aldrich</td>
			<td>64-17-5</td>
			<td></td>
		</tr>
		<tr>
			<td>Hydrogen peroxide solution</td>
			<td>Sigma-Aldrich</td>
			<td>&#160;7722-84-1</td>
			<td></td>
		</tr>
		<tr>
			<td>Acetonitrile</td>
			<td>Sigma-Aldrich</td>
			<td>75-05-8</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethyl acetate</td>
			<td>Sigma-Aldrich</td>
			<td>141-78-6</td>
			<td></td>
		</tr>
		<tr>
			<td>Ammonium chloride</td>
			<td>Sigma-Aldrich</td>
			<td>12125-02-9</td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium sulfate anhydrous</td>
			<td>Sigma-Aldrich</td>
			<td>7757-82-6</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethyl acetate</td>
			<td>Sigma-Aldrich</td>
			<td>141-78-6</td>
			<td></td>
		</tr>
		<tr>
			<td>n-Hexane</td>
			<td>Sigma-Aldrich</td>
			<td>110-54-3</td>
			<td></td>
		</tr>
		<tr>
			<td>Silica Gel</td>
			<td>Sigma-Aldrich</td>
			<td>112926-00-8</td>
			<td>&#160;Size 70/230</td>
		</tr>
		<tr>
			<td>250 mL two-neck round-bottom flask</td>
			<td>Sigma-Aldrich</td>
			<td>Z516872-1EA</td>
			<td>250 mL capacity</td>
		</tr>
		<tr>
			<td>Magnetic stirring bar</td>
			<td>Bel-Art products</td>
			<td>371100002</td>
			<td>Teflon, octagon</td>
		</tr>
		<tr>
			<td>Condenser</td>
			<td>Cole-Parmer</td>
			<td>JZ-34706-00</td>
			<td>200 mm Jacket length</td>
		</tr>
		<tr>
			<td>Vacuum pump (Approx. 10X-2 bar)</td>
			<td>Cole-Parmer</td>
			<td>JZ-78162-00</td>
			<td>Vacuum/Pressure Diaphragm Pump</td>
		</tr>
		<tr>
			<td>Stopcock</td>
			<td>Cole-Parmer</td>
			<td>EW-30600-00</td>
			<td>with a male luer slip</td>
		</tr>
		<tr>
			<td>Hose</td>
			<td>Cole-Parmer</td>
			<td>JZ-06602-04</td>
			<td>16.0 mm ID and 23.2 mm ED</td>
		</tr>
		<tr>
			<td>Rubber septums</td>
			<td>Cole-Parmer</td>
			<td>JZ-08918-34</td>
			<td>Silicone with PTFE coating</td>
		</tr>
		<tr>
			<td>Hot plate</td>
			<td>Cole-Parmer</td>
			<td>JZ-04660-15</td>
			<td>10.2 cm x 10.2 cm, 5 to 540 &#176;C</td>
		</tr>
		<tr>
			<td>Sand bath&#160;</td>
			<td>Cole-Parmer</td>
			<td>GH-01184-00</td>
			<td>Fluidized Sand Bath SBS-4, 50 to 600 &#176;C</td>
		</tr>
		<tr>
			<td>N2 gas</td>
			<td>INFRA</td>
			<td>Cod. 103</td>
			<td>Cylinder 9m &#179;</td>
		</tr>
		<tr>
			<td>Ballons (filled with N2 gas)</td>
			<td>Sigma-Aldrich</td>
			<td>Z154989-100EA</td>
			<td>Thick-wall, natural latex rubber</td>
		</tr>
		<tr>
			<td>Syringes with removable needles</td>
			<td>Sigma-Aldrich</td>
			<td>Z116912-100EA</td>
			<td>10 mL capacity</td>
		</tr>
		<tr>
			<td>Filter paper</td>
			<td>Cole-Parmer</td>
			<td>JZ-81050-24</td>
			<td>Grade No. 235 qualitative filter paper (90 mm diameter disc)</td>
		</tr>
		<tr>
			<td>Buchner funnel</td>
			<td>Cole-Parmer</td>
			<td>JZ-17815-04</td>
			<td>320 mL capacity which accept standard paper filter sizes&#160;</td>
		</tr>
		<tr>
			<td>Buchner flask</td>
			<td>Cole-Parmer</td>
			<td>JZ-34557-02</td>
			<td>250 mL capacity</td>
		</tr>
		<tr>
			<td>Rotary Evaporator</td>
			<td>Cole-Parmer</td>
			<td>JZ-28710-02</td>
			<td></td>
		</tr>
		<tr>
			<td>Beakers</td>
			<td>Cole-Parmer</td>
			<td>JZ-34502-(02,04,05)</td>
			<td>Pyrex Brand 1000 Griffin; 20, 50 and 100 mL</td>
		</tr>
		<tr>
			<td>Separation funnel&#160;</td>
			<td>Cole-Parmer</td>
			<td>JZ-34505-44</td>
			<td>Capacity for 125 mL with steam lenght of 60 mm</td>
		</tr>
		<tr>
			<td>Glass column for chromatography</td>
			<td>Cole-Parmer</td>
			<td>JZ-34695-42</td>
			<td>Column with fritted disk, 10.5 mm ID x 250 mm L</td>
		</tr>
		<tr>
			<td>PXRD diffractometer</td>
			<td>Bruker</td>
			<td></td>
			<td>AXS D8 Advance XRD</td>
		</tr>
		<tr>
			<td>FTIR spectrophotometer</td>
			<td>Thermo scientific</td>
			<td>FT-IR (JZ-83008-02); ATR (JZ-83008-26)</td>
			<td>Nicolet iS5 FT-IR Spectrometer, with KBr Windows and iD5 Diamond ATR</td>
		</tr>
	</tbody>
</table>

hkust-1 as a heterogeneous catalyst for the synthesis of vanillin

바닐린 (4- 하이드 록시 -3- 메 톡시)는 바닐라 콩 추출물의 주요 성분이다. 천연 바닐라 향기 바닐린 이외에 약 200 취제 다른 화합물의 혼합물이다. (난초 바닐라 planifolia, 바닐라 tahitiensis와 바닐라 퐁퐁에서) 바닐린의 자연 추출은 전 세계 생산량의 1 %를 나타내며,이 과정은 비용이 매우 긴이기 때문에, 바닐린 생산의 나머지 부분은 합성된다. 많은 생물 공학적 방법이 프로세스가 강한 산화제 독성 용매를 사용하기 때문에 환경을 해치지 단점과, 리그닌 등의 페놀 스틸 벤, 이소 유게 놀, 유게 놀, guaicol에서 바닐린의 합성에 사용될 수있다. 따라서, 바닐린 생산에 환경 친화적 인 대안은 현재 조사에서 매우 바람직하므로 있습니다. 다공성 배위 고분자 (의 PCP)는 그 녹화 높은 결정 성 물질의 새로운 클래스입니다고한다면 촉매에 사용되어왔다. HKUST-1 (구리 3 (BTC) 2 (H 2 O) 3, BTC = 1,3,5- 벤젠 트리 카르 복실 레이트)을 광범위 불균일 촉매로서 검토되고있다 매우 잘 알려진 PCP이다. 여기서는 촉매 HKUST-1을 사용하여 트랜스 -ferulic 산의 산화에 의해 바닐린의 제조 합성 전략을보고한다.

오븐에서 1 시간 동안 100 ℃에서 활성화 된 비 - 활성화는 (공기에 노출), 1 100 ℃에서 진공 (10-2 바)하에 활성화 : HKUST-1 세 대표적인 샘플을 적외선 분광법으로 분석 하였다 시간. 따라서, 푸리에 변환 적외선 (FTIR) 스펙트럼은 하나의 반사 다이아몬드 ATR 액세서리 (그림 1)와 분광계를 사용하여 기록 하였다 변환. 모든 스펙트럼의 경우, 4000 ~ 400 cm -1</...

Watch this Scientific Journal Video about HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin at JoVE.com

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

The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained.

HKUST 바닐린-1의 합성에 대해 불균일 촉매로서

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

hkust-1-as-a-heterogeneous-catalyst-for-the-synthesis-of-vanillin

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JoVE Journal

Chemistry

10.1K 조회수.  Autonomous Metropolitan University-Azcapotzalco. The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained. 

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

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. ...

연구

화학

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. Isonicotinic acid, or its derivatives, are coupled to variable length diaminoalkane chains under an inert atmosphere in anhydrous DMF or DMSO with the use of a weak base, triethylamine, and a coupling agent, 1-propylphosphonic anhydride. The products precipitate from solution upon formation or can be precipitated by the addition of water. If desired, the ligands can be further purified by recrystallization from hot water. Dinuclear platinum complex synthesis using the bispyridine ligands is done in hot water using transplatin. The most informative of the chemical characterization techniques to determine the structure and gross purity of both the bispyridine ligands and the final platinum complexes is 1H NMR with particular analysis of the aromatic region of the spectra (7-9 ppm). The platinum complexes have potential application as anticancer agents and the synthesis method can be modified to produce trinuclear and other multinuclear complexes with different hydrogen bonding functionality in the bridging ligand.

This protocol describes the use of amide coupling reactions of isonicotinic acid and diaminoalkanes to form bridging ligands suitable for use in the synthesis of multinuclear platinum complexes, which combine aspects of the anticancer drugs BBR3464 and picoplatin.

이핵 항암제로 플래티넘 비스 피리딘 계 리간드와 이들 착물의 합성 아미드 커플 링 반응

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. ...

Synthesis of Cd-free InP/ZnS Quantum Dots Suitable for Biomedical Applications

Fluorescent nanocrystals, specifically quantum dots, have been a useful tool for many biomedical applications. For successful use in biological systems, quantum dots should be highly fluorescent and small/monodisperse in size. While commonly used cadmium-based quantum dots possess these qualities, they are potentially toxic due to the possible release of Cd2+ ions through nanoparticle degradation. Indium-based quantum dots, specifically InP/ZnS, have recently been explored as a viable alternative to cadmium-based quantum dots due to their relatively similar fluorescence characteristics and size. The synthesis presented here uses standard hot-injection techniques for effective nanoparticle growth; however, nanoparticle properties such as size, emission wavelength, and emission intensity can drastically change due to small changes in the reaction conditions. Therefore, reaction conditions such temperature, reaction duration, and precursor concentration should be maintained precisely to yield reproducible products. Because quantum dots are not inherently soluble in aqueous solutions, they must also undergo surface modification to impart solubility in water. In this protocol, an amphiphilic polymer is used to interact with both hydrophobic ligands on the quantum dot surface and bulk solvent water molecules. Here, a detailed protocol is provided for the synthesis of highly fluorescent InP/ZnS quantum dots that are suitable for use in biomedical applications.

In this protocol, the synthesis of Cd-free InP/ZnS quantum dots (QDs) is detailed. InP-based QDs are gaining popularity due to the toxicity of Cd2+ ions that may be released through nanoparticle degradation. After synthesis, QDs are solubilized in water using an amphiphilic polymer for use in biomedical applications.

바이오 메디컬 응용 프로그램에 적합 InP를 /의 ZnS 양자점 CD-자유의 합성

Fluorescent nanocrystals, specifically quantum dots, have been a useful tool for many biomedical applications. For successful use in biological systems, ...

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of trifluoromethoxylated aromatic compounds remains a formidable challenge in organic synthesis. Conventional approaches often suffer from poor substrate scope, or require use of highly toxic, difficult-to-handle, and/or thermally labile reagents. Herein, we report a user-friendly protocol for the synthesis of methyl 4-acetamido-3-(trifluoromethoxy)benzoate using 1-trifluoromethyl-1,2-benziodoxol-3(1H)-one (Togni reagent II). Treating methyl 4-(N-hydroxyacetamido)benzoate (1a) with Togni reagent II in the presence of a catalytic amount of cesium carbonate (Cs2CO3) in chloroform at RT afforded methyl 4-(N-(trifluoromethoxy)acetamido)benzoate (2a). This intermediate was then converted to the final product methyl 4-acetamido-3-(trifluoromethoxy)benzoate (3a) in nitromethane at 120 &#176;C. This procedure is general and can be applied to the synthesis of a broad spectrum of ortho-trifluoromethoxylated aniline derivatives, which could serve as useful synthetic building blocks for the discovery and development of new pharmaceuticals, agrochemicals, and functional materials.

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

An operationally simple procedure for the synthesis of ortho-trifluoromethoxylated aniline derivatives via a two-step sequence of O-trifluoromethylation of N-aryl-N-hydroxyacetamide followed by thermally induced intramolecular OCF3-migration is reported.

의 합성을위한 프로토콜<em&gt; 직교</em&gt; -trifluoromethoxylated 아닐린 파생 상품

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of ...

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the development of antibody drug conjugates (ADCs) and nanomedicine, fluorescent microscopy and systems chemistry. For many of these applications, specificity of the bioconjugation method used is of prime concern. The Michael addition of maleimides with cysteine(s) on the target proteins is highly selective and proceeds rapidly under mild conditions, making it one of the most popular methods for protein bioconjugation.
We demonstrate here the modification of the only surface-accessible cysteine residue on yeast cytochrome c with a ruthenium(II) bisterpyridine maleimide. The protein bioconjugation is verified by gel electrophoresis and purified by aqueous-based fast protein liquid chromatography in 27% yield of isolated protein material. Structural characterization with MALDI-TOF MS and UV-Vis is then used to verify that the bioconjugation is successful. The protocol shown here is easily applicable to other cysteine - maleimide coupling of proteins to other proteins, dyes, drugs or polymers.

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

This protocol details the important steps required for the bioconjugation of a cysteine containing protein to a maleimide, including reagent purification, reaction conditions, bioconjugate purification and bioconjugate characterization.

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the ...

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (&#955; = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

Photoredox 촉매를 사용하여 가시 광선 중재 분산 중합에 의해 웜 형상 미셀 손쉬운 합성

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

NMR Spectroscopy as a Robust Tool for the Rapid Evaluation of the Lipid Profile of Fish Oil Supplements

The western diet is poor in n-3 fatty acids, therefore the consumption of fish oil supplements is recommended to increase the intake of these essential nutrients. The objective of this work is to demonstrate the qualitative and quantitative analysis of encapsulated fish oil supplements using high-resolution 1H and 13C NMR spectroscopy utilizing two different NMR instruments; a 500 MHz and an 850 MHz instrument. Both proton (1H) and carbon (13C) NMR spectra can be used for the quantitative determination of the major constituents of fish oil supplements. Quantification of the lipids in fish oil supplements is achieved through integration of the appropriate NMR signals in the relevant 1D spectra. Results obtained by 1H and 13C NMR are in good agreement with each other, despite the difference in resolution and sensitivity between the two nuclei and the two instruments. 1H NMR offers a more rapid analysis compared to 13C NMR, as the spectrum can be recorded in less than 1 min, in contrast to 13C NMR analysis, which lasts from 10 min to one hour. The 13C NMR spectrum, however, is much more informative. It can provide quantitative data for a greater number of individual fatty acids and can be used for determining the positional distribution of fatty acids on the glycerol backbone. Both nuclei can provide quantitative information in just one experiment without the need of purification or separation steps. The strength of the magnetic field mostly affects the 1H NMR spectra due to its lower resolution with respect to 13C NMR, however, even lower cost NMR instruments can be efficiently applied as a standard method by the food industry and quality control laboratories.

Here, high-resolution 1H and 13C Nuclear Magnetic Resonance (NMR) spectroscopy was used as a rapid and reliable tool for quantitative and qualitative analysis of encapsulated fish oil supplements.

생선 기름 보충제의 지질 프로필의 신속한 평가를위한 강력한 도구로 NMR 분광학

The western diet is poor in n-3 fatty acids, therefore the consumption of fish oil supplements is recommended to increase the intake of these essential ...

Electrochemical Impedance Spectroscopy as a Tool for Electrochemical Rate Constant Estimation

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). In the case of fast reversible electrochemical processes, current is predominantly affected by the rate of diffusion, which is the slowest and limiting stage. EIS is a powerful technique that allows separate analysis of stages of charge transfer that have different AC frequency response. The capability of the method was used to extract the value of charge transfer resistance, which characterizes the rate of charge exchange on the electrode-solution interface. The application of this technique is broad, from biochemistry up to organic electronics. In this work, we are presenting the method of analysis of organic compounds for optoelectronic applications.

Electrochemical impedance spectroscopy (EIS) of species that undergo reversible oxidation or reduction in solution was used for determination of rate constants of oxidation or reduction.

전기 화학 임피던스 분 광 전기 화학 속도 상수 추정을 위한 도구로

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). ...

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

This protocol presents both the synthesis method of the Ni single atom catalyst, and the electrochemical testing of its catalytic activity and selectivity in aqueous CO2 reduction. Different from traditional metal nanocrystals, the synthesis of metal single atoms involves a matrix material that can confine those single atoms and prevent them from aggregation. We report an electrospinning and thermal annealing method to prepare Ni single atoms dispersed and coordinated in a graphene shell, as active centers for CO2 reduction to CO. During the synthesis, N dopants play a critical role in generating graphene vacancies to trap Ni atoms. Aberration-corrected scanning transmission electron microscopy and three-dimensional atom probe tomography were employed to identify the single Ni atomic sites in graphene vacancies. Detailed setup of electrochemical CO2 reduction apparatus coupled with an on-line gas chromatography is also demonstrated. Compared to metallic Ni, Ni single atom catalyst exhibit dramatically improved CO2 reduction and suppressed H2 evolution side reaction.

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

Here, we present a protocol for the synthesis and electrochemical testing of transition metal single atoms coordinated in graphene vacancies as active centers for selective carbon dioxide reduction to carbon monoxide in aqueous solutions.

합성 및 전기 화학적 CO2 감소를 위한 전이 금속 단일 원자 촉매의 성능 Characterizations

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

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state. Unlike the highly reactive free-standing thiols, which tend to decompose and complicate the crystallization of metal-thiolate open frameworks, the thioester reacts in situ to provide the thiol species, serving to mitigate the reaction between the mercaptan units and the metal centers, and to improve crystallization consequently. Specifically, the thioester was synthesized in a one-pot procedure: an aromatic bromide (hexabromotriphenylene) reacted with excess sodium thiomethoxide under vigorous conditions to first form the thioether intermediate product. The thioether was then demethylated by the excess thiomethoxide to provide the thiolate anion that was acylated to form the thioester product. The thioester was conveniently purified by standard column chromatography, and then used directly in the framework synthesis, wherein NaOH and ethylenediamine serve to revert in situ the thioester to the thiol linker for assembling the single-crystalline Pb(II)-dithiolene network. Compared with other methods for thiol synthesis (e.g., by cleaving alkyl thioether using sodium metal and liquid ammonia), the thioester synthesis here uses simple conditions and economical reagents. Moreover, the thioester product is stable and can be conveniently handled and stored. More importantly, in contrast to the generic difficulty in accessing crystalline metal-thiolate open frameworks, we demonstrate that using the thioester for in situ formation of the thiol linker greatly improves the crystallinity of the solid-state product. We intend to encourage broader research efforts on the technologically important metal-sulfur frameworks by disclosing the synthetic protocol for the thioester as well as the crystalline framework solid.

Here, we present a one-pot, transition-metal-free synthesis of thiols and thioesters from aromatic halides and sodium thiomethoxide, followed by the preparation of single crystals of a metal-dithiolene network using thiol species generated in situ from the more stable and tractable thioester.

반도체 Gyroidal 금속-황 프레임 워크의 결정 화에 대 한 Thiol 빌딩 블록의 합성

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...

HKUST 바닐린-1의 합성에 대해 불균일 촉매로서

요약

더 많은 비디오 탐색

이 비디오의 챕터

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

이핵 항암제로 플래티넘 비스 피리딘 계 리간드와 이들 착물의 합성 아미드 커플 링 반응

바이오 메디컬 응용 프로그램에 적합 InP를 /의 ZnS 양자점 CD-자유의 합성

의 합성을위한 프로토콜

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

Photoredox 촉매를 사용하여 가시 광선 중재 분산 중합에 의해 웜 형상 미셀 손쉬운 합성

생선 기름 보충제의 지질 프로필의 신속한 평가를위한 강력한 도구로 NMR 분광학

전기 화학 임피던스 분 광 전기 화학 속도 상수 추정을 위한 도구로

합성 및 전기 화학적 CO₂ 감소를 위한 전이 금속 단일 원자 촉매의 성능 Characterizations

반도체 Gyroidal 금속-황 프레임 워크의 결정 화에 대 한 Thiol 빌딩 블록의 합성