Financial support from the DFG (Heisenberg scholarship to M.K., KL 2221/4-1; KL 2221/3-1) and the Max-Planck-Institut fuer Kohlenforschung is gratefully acknowledged.

Tetrahydrocarbazole 과산화물의 1. 합성 <ol><li> tetrahydrocarbazole 매우 착색되면 로퍼 옥사이드의 형성이 느려진다. 이 경우, 무색의 출발 물질을 얻기 위하여, 톨루엔 / 펜​​ 테인을 사용하여 재결정 화 또는 컬럼 크로마토 그래피로 정제. 칼럼 크로마토 그래피에 의한 정제를 위해, 실리카 겔의 하층과 알루미나의 상층과 열을 포장한다. 칼럼의 상단에 tetrahydrocarbazole을 넣고 톨루엔으로 용출. 모든 원치 않는 노란색과 검은 색의 부산물은 열 무색 t​​etrahydrocarbazole이 용출됩니다에 흡착된다. 즉시 용매를 증발 어둠 속에서 아르곤 분위기에서 정제 된 흰색 제품을 저장합니다. </li><li> 250 ㎖의 플라스크에 (보고 방법 16에 따라 합성 1) tetrahydrocarbazole의 또는 치환 tetrahydrocarbazole의 1g을 달다. 이 플라스크에 100 ㎖의 톨루엔을 추가합니다. </li><li> 로즈 벵갈 (2 달다MG) 및 상기 반응 혼합물에 추가합니다. </li><li> 교반 막대를 추가하고 격막과 플라스크를 커버. </li><li> 격막을 통해 산소 풍선을 추가; 이 반응에서, 산소 분위기의 양압을 유지한다. </li><li> 23w 램프로 반응 혼합물을 조사. </li><li> (70:30 비율로 헥산 / 에틸 아세테이트의 혼합물을 사용하여, TLC, 본원에 기재된 하이드 로퍼 옥사이드의 R의 F 값은 0.2과 0.3 사이) 박층 크로마토 그래피로 반응 진행을 확인 또는 1 H NMR에 의해 샘플 (회전 증발기상에서 용매를 증발 DMSO-D6에서 잔사를 용해) 찍은. 1.1 부분에서 언급 한 바와 같이, 반응 시간은, 광원 및 출발 물질의 순도에 의존 될 수있다. 일반적으로, tetrahydrocarbazoles 1의 전체 변환은 3 시간이 걸립니다. </li><li> 출발 물질의 완전한 변환 후 석출 된 고체를 필터. 고체의 세탁의 대부분을 제거하기 위해 펜탄으로 행해질 수있다톨루엔,하지만 정제 할 필요가 없습니다. </li><li> 감압 고립 된 고체를 건조. </li></ol> 주의 : 우리가 작업을하거나 작업에 설명 된 화합물을 취급 한 모든 문제를 경험 한 적이 있지만 과산화물 작업을 할 때,주의를 기울여야한다. 특히, 가열 또는 금속 또는 금속염과이를 섞어 깔끔한 과산화물을 노출 극력 피해야한다. 폭발 방패 뒤에 수행 등의 반응을 권장합니다. .이 커플 링 반응 - 메탄올 중 10 몰 % 트리 플루오로 아세트산을 사용하는 방법 <ol><li> 12 ㎖의 유리 병 또는 적당한 둥근 바닥 플라스크에 하이드 로퍼 옥사이드 (0.49 밀리몰, 1.0 당량. 1 단계) 원하는 아닐린 친핵체 (0.49 밀리몰, 1.0 당량.) 달다. </li><li> 트리 플루오로 아세트산 10 ㎖의 메탄올을 추가하고 이후에 3.74 μL (TFA를 0.049 밀리몰, 0.1 당량.) 유리 병 또는 둥근 바닥 플라스크에. </li><li> 캡 용기를 닫고4 시간 동안 실온에서 반응 혼합물을 교반 하였다. (반응의 과정을 통해 침전 제품) 정밀 검사의 변형 A1 : </li><li> 원하는 제품을 얻을 수있는 침전 된 고체를 필터링합니다. 메탄올 (3 × 0.5 ml)으로 제품을 세척 할 것. </li><li> 상품의 두번째 분획을 얻기 위해 여과 액으로부터 메탄올을 증발. 40 ° C에서의 에틸 아세테이트 5 ㎖에 실온 후 시원한 조 생성물을 용해하고 순수한 제품은 침전 펜탄 3-5 ML을 추가합니다. </li><li> 제품의 다른 분수를 결합하고 높은 진공 상태에서 건조 시키십시오. (침전하지 않는 제품에 대한) 검사 결과 변종 A2 : </li><li> 직접 회전 증발기를 사용하여, 반응 후 용매를 증발시키고 목적 생성물을 얻기 위해 (실리카겔, 헥산 / 에틸 아세테이트 / 트라이 에틸 아민)을 지정된 컬럼 크로마토 그래피에 의해 잔류 물을 정제. </li></ol> 의 커플 링 반응 -. 방법 B아세트산을 사용하여 <ol><li> 12 ㎖의 유리 병 또는 적당한 둥근 바닥 플라스크에 하이드 로퍼 옥사이드 (0.49 밀리몰, 1.0 당량. 1 단계) 원하는 아닐린 친핵체 (0.49 밀리몰, 1.0 당량.) 달다. </li><li> 유리 병 또는 둥근 바닥 플라스크에 10 ㎖의 초산 (아세트산)를 추가합니다. </li><li> 캡과 용기를 닫고 4 시간 동안 실온에서 반응 혼합물을 교반 하였다. (반응의 과정을 통해 침전 제품) 정밀 검사의 변형 B1 : </li><li> 원하는 제품을 얻을 수있는 침전 된 고체를 필터링합니다. 아세트산 (3 × 0.5 ml)으로 제품을 세척 할 것. </li><li> 상품의 두번째 분획을 얻기 위해 여과 물로부터 아세트산을 증발. 40 ° C에서의 에틸 아세테이트 5 ㎖에 실온 후 시원한 조 생성물을 용해하고 순수한 제품은 침전 펜탄 3-5 ML을 추가합니다. </li><li> 제품의 다른 분수를 결합하고 높은 진공 상태에서 건조 시키십시오. 정밀 검사의 변형 B2 </str사연&gt; (침전하지 않는 제품의 경우) : </li><li> 직접 회전 증발기를 사용하여, 반응 후 용매를 증발시키고 목적 생성물을 얻기 위해 (실리카겔, 헥산 / 에틸 아세테이트 / 트라이 에틸 아민)을 지정된 컬럼 크로마토 그래피에 의해 잔류 물을 정제. </li></ol>

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저자가 공개하는 게 없다.

요약하면, 우리는 tetrahydrocarbazoles의 CH 결합 편리 두 단계 절차에서 CN-커플 링 제품을 생성하도록 작용 될 수 있음을 입증 있었다. 첫 번째 단계는 퍼옥이주는 tetrahydrocarbazole (1) 또는 산소 원자 (17, 19)와 그 유도체의 공지 photocatalyzed 산화이다. 톨루엔에서 수행하는 경우, 하이드 로퍼 옥사이드 제품이 침전 및 여과에 의해 편리하게 단리 할 수...

CH 결합의 직접적인 작용은 유기 화학 1에서 중요하고 오랜 목표입니다. 이러한 변환은 그룹을 활성화 또는 지시의 도입 및 제거를 요구하는 기존의 방법에 비해 단계, 시간과 물질을 저장하여 합성을 간소화하기 위해 매우 강력한 될 수 있습니다. 따라서, CH 결합의 작용은 또한 녹색 화학 2의 매력입니다. 산화 조건, 두 개의 CH 결합 또는 하나 CH 하나의 헤테로 원자-H 결합에서 각각 CC와 C-헤테로 원자 결합, (그림 1) 3-9로 변환 할 수 있습니다. 종종 이러한 산화 커플 링 반응은 합성 산화 방지제, 고가의 촉매 또는 높은 온도를 필요로한다. 따라서, 많은 시도는 터미널 산화제 10으로 저렴한 촉매, 양성 조건과 산소 또는 공기를 사용하는 방법을 개발하기 위해 만들어집니다. <img alt="그림 1" fo:content-width = &quot;5 인치&quot;SRC = &quot;/ files/ftp_upload/51504/51504fig1highres.jpg&quot;폭 = &quot;500&quot;/&gt; 그림 1. 산화 커플 링 반응. <a href="https://www.jove.com/files/ftp_upload/51504/51504fig1highres.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭하십시오.</a> 많은 유기 화합물은 효과적으로 로퍼 옥사이드 부분 (11, 12)를 형성하는 O 2를 삽입하여 CH 결합을 기능화 수 자동 산화 반응에서 공기로부터 산소와 느리게 반응한다. 자동 산화 공정은 탄화수소 공급 원료에서 생성되는 산소 화합물 산업 규모에 사용하지만, 자동 산화는 가치있는 화합물 또는 물질의 분해에 이르게하는 경우도 원치 않는 과정이다됩니다. 어떤 경우에는, 예를 들어 디 에틸 에테르에 대해, 공기 형성 로퍼 또한 폭발성 일 수있다. 최근에, 우리는 산화 - 환원 활성 촉매 (13, 14)의 필요없이 CH 결합에서 새로운 CC 결합을 형성 할 수있는 자동 산화를 활용하는 반응을 발견 </SUP&gt;. 단순히 산 촉매의 존재하에 산소의 기판을 교반하는 새로운 제품의 형성에 이르게한다. 반응의 핵심은 산 촉매 (15)에 의해 제 2 기판으로 대체하는 중간 하이드 로퍼 옥사이드의 손쉬운 형성이다. 반응은, 그러나, 크 산텐하도록 제한하고 쉽게 산소 및 제품의 분위기 하에서 산화 몇 관련 화합물은 지금까지 발견되지 어플리케이션을 가지고있다. 그럼에도 불구하고이 발견에 의해 영감을, 우리는 약학 적 활성 인돌 유도체 (16)를 합성하는 중간 과산화물 (칩)을 통해 CH의 작용의 원리를 활용하여 관련 산화 커플 링 방법을 개발했다. 인돌, 특히 1 tetrahydrocarbazoles 쉽게 증감 제 및 가시광 (20)를 사용하여 생성 될 수있는 일 중항 산소 17-19의 존재하에 하이드 로퍼 옥사이드를이 산화 될 수있다. 유압operoxide 부분 할 수있는 산 촉매에 의해 활성화 및 친핵체 (21, 22)의 도입을 허용하는 경우 이탈 기로서 원칙적으로 행동합니다. 과산화수소는 쿠멘, 호크 과정 (23)로부터 페놀의 산업 합성에 이용으로 산 재 배열 반응을 촉매 받아야하는 것으로 알려져있다. 주의 최적화 연구에 의해, 우리는 재 배열 (16)에 의해 원치 않는 분해 경로를 통해 아닐린 3와 같은 N-친핵체를 사용하여 원하는 치환 반응을 선호하는 조건을 찾아 낼 수 있었다. 여기에서, 우리는 가시 광선, 과민성, 산소와 산을 사용, 구체적으로이 두 단계 CHIPS 절차를 설명합니다. 선택한 제품은 높은 항 바이러스 활성을 나타내거나 종양 치료 24-26에 중요 할 수있다 혈관 내피 성장 인자 (VGF)을 억제하는 인돌 유도체 4입니다 사이.

<table border="0" cellpadding="0" cellspacing="0" width="797">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">1,2,3,4-Tetrahydrocarbazole</td>
			<td style="width:139px;">Sigma Aldrich</td>
			<td style="width:151px;">T12408</td>
			<td style="width:291px;">If coloured, purification may be necessary. See Protocol 1.1</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Methanol</td>
			<td style="width:139px;">Sigma Aldrich</td>
			<td>322415</td>
			<td>99.8% purity</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">4-Nitroaniline</td>
			<td style="width:139px;">Acros Organics</td>
			<td>128371000</td>
			<td>99% purity</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Trifluoroacetic acid</td>
			<td style="width:139px;">Sigma Aldrich</td>
			<td>T6508</td>
			<td>99% purity</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Acetic acid</td>
			<td style="width:139px;">J. T. Baker</td>
			<td style="width:151px;">JTB RS 426960101</td>
			<td>99-100% purity</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Aniline</td>
			<td style="width:139px;">Merck</td>
			<td>8222560100</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">4-Aminobenzonitrile</td>
			<td style="width:139px;">Sigma Aldrich</td>
			<td>147753</td>
			<td>98% purity</td>
		</tr>
	</tbody>
</table>

synthesis of antiviral tetrahydrocarbazole derivatives by photochemical and acid-catalyzed c-h functionalization via intermediate peroxides (chips)

The direct functionalization of C-H bonds is an important and long standing goal in organic chemistry. Such transformations can be very powerful in order to streamline synthesis by saving steps, time and material compared to conventional methods that require the introduction and removal of activating or directing groups. Therefore, the functionalization of C-H bonds is also attractive for green chemistry. Under oxidative conditions, two C-H bonds or one C-H and one heteroatom-H bond can be transformed to C-C and C-heteroatom bonds, respectively. Often these oxidative coupling reactions require synthetic oxidants, expensive catalysts or high temperatures. Here, we describe a two-step procedure to functionalize indole derivatives, more specifically tetrahydrocarbazoles, by C-H amination using only elemental oxygen as oxidant. The reaction uses the principle of C-H functionalization via Intermediate PeroxideS (CHIPS). In the first step, a hydroperoxide is generated oxidatively using visible light, a photosensitizer and elemental oxygen. In the second step, the N-nucleophile, an aniline, is introduced by Br&#248;nsted-acid catalyzed activation of the hydroperoxide leaving group. The products of the first and second step often precipitate and can be conveniently filtered off. The synthesis of a biologically active compound is shown.

1 - (5 - nitroindolin -1 - 일) -2,3,4,9 - 테트라 하이드로-1H-카바 졸 (4A) 방법 A, R의 F = 0.63 (헥산 / 에틸 아세테이트 70:30)에 따라 합성. 정제 : 방법 A, 워크 업 변이체 A1을 사용하여 생성물을 정제는 (2.4, 2.5, 2.6 단계). 오렌지색 고체, 수율 : 95 %. 1 H NMR (500 MHz 이상, DMSO-D6) : <em...

Watch this Scientific Journal Video about Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS at JoVE.com

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

A two-step procedure for the synthesis of pharmaceutically active indole-derivatives by C-H functionalization with anilines is described, using photo- and Br&#248;nsted acid catalysis.

중간 과산화물을 통해 광화학 및 산 - 촉매 CH 기능화에 의한 항 바이러스 Tetrahydrocarbazole 유도체의 합성 (CHIPS)

The direct functionalization of C-H bonds is an important and long standing goal in organic chemistry. Such transformations can be very powerful in order ...

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Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)

Unit 1

Acids and Bases

SCIENTISTS IN ACTION

13.7K 조회수.  Max-Planck-Institut fuer Kohlenforschung. A two-step procedure for the synthesis of pharmaceutically active indole-derivatives by C-H functionalization with anilines is described, using photo- and Brønsted acid catalysis.

비디오: Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

Anticancer Metal Complexes: Synthesis and Cytotoxicity Evaluation by the MTT Assay

Titanium (IV) and vanadium (V) complexes are highly potent anticancer agents. A challenge in their synthesis refers to their hydrolytic instability; therefore their preparation should be conducted under an inert atmosphere. Evaluation of the anticancer activity of these complexes can be achieved by the MTT assay.
The MTT assay is a colorimetric viability assay based on enzymatic reduction of the MTT molecule to formazan when it is exposed to viable cells. The outcome of the reduction is a color change of the MTT molecule. Absorbance measurements relative to a control determine the percentage of remaining viable cancer cells following their treatment with varying concentrations of a tested compound, which is translated to the compound anticancer activity and its IC50 values. The MTT assay is widely common in cytotoxicity studies due to its accuracy, rapidity, and relative simplicity.
Herein we present a detailed protocol for the synthesis of air sensitive metal based drugs and cell viability measurements, including preparation of the cell plates, incubation of the compounds with the cells, viability measurements using the MTT assay, and determination of IC50 values.

A method for synthesis of air-sensitive titanium and vanadium anticancer agents is described, along with the evaluation of their cytotoxic activity towards human cancer cell line by the MTT Assay.

MTT의 분석에 의해 합성 및 세포 독성 평가 : 항암 금속 합성물

Titanium (IV) and vanadium (V) complexes are highly potent anticancer agents. A challenge in their synthesis refers to their hydrolytic instability; ...

연구

화학

Synthesis, Characterization, and Functionalization of Hybrid Au/CdS and Au/ZnS Core/Shell Nanoparticles

Plasmonic nanoparticles are an attractive material for light harvesting applications due to their easily modified surface, high surface area and large extinction coefficients which can be tuned across the visible spectrum. Research into the plasmonic enhancement of optical transitions has become popular, due to the possibility of altering and in some cases improving photo-absorption or emission properties of nearby chromophores such as molecular dyes or quantum dots. The electric field of the plasmon can couple with the excitation dipole of a chromophore, perturbing the electronic states involved in the transition and leading to increased absorption and emission rates. These enhancements can also be negated at close distances by energy transfer mechanism, making the spatial arrangement of the two species critical. Ultimately, enhancement of light harvesting efficiency in plasmonic solar cells could lead to thinner and, therefore, lower cost devices. The development of hybrid core/shell particles could offer a solution to this issue. The addition of a dielectric spacer between a gold nanoparticles and a chromophore is the proposed method to control the exciton plasmon coupling strength and thereby balance losses with the plasmonic gains. A detailed procedure for the coating of gold nanoparticles with CdS and ZnS semiconductor shells is presented. The nanoparticles show high uniformity with size control in both the core gold particles and shell species allowing for a more accurate investigation into the plasmonic enhancement of external chromophores.

The synthesis of uniform gold nanoparticles coated with semiconductor shells of CdS or ZnS is performed. The semiconductor coating is conducted by first depositing a silver sulfide shell and exchanging the silver cations for zinc or cadmium cations.

합성, 특성 및 하이브리드 금 / CD 및 금 /은 ZnS 코어 / 쉘 나노 입자의 작용 화

Plasmonic nanoparticles are an attractive material for light harvesting applications due to their easily modified surface, high surface area and large ...

Facile Preparation of 4-Substituted Quinazoline Derivatives

Reported in this paper is a very simple method for direct preparation of 4-substituted quinazoline derivatives from a reaction between substituted 2-aminobenzophenones and thiourea in the presence of dimethyl sulfoxide (DMSO). This is a unique complementary reaction system in which thiourea undergoes thermal decomposition to form carbodiimide and hydrogen sulfide, where the former reacts with 2-aminobenzophenone to form 4-phenylquinazolin-2(1H)-imine intermediate, whilst hydrogen sulfide reacts with DMSO to give methanethiol or other sulfur-containing molecule which then functions as a complementary reducing agent to reduce 4-phenylquinazolin-2(1H)-imine intermediate into 4-phenyl-1,2-dihydroquinazolin-2-amine. Subsequently, the elimination of ammonia from 4-phenyl-1,2-dihydroquinazolin-2-amine affords substituted quinazoline derivative. This reaction usually gives quinazoline derivative as a single product arising from 2-aminobenzophenone as monitored by GC/MS analysis, along with small amount of sulfur-containing molecules such as dimethyl disulfide, dimethyl trisulfide, etc. The reaction usually completes in 4-6 hr at 160 &#186;C in small scale but may last over 24 hr when carried out in large scale. The reaction product can be easily purified by means of washing off DMSO with water followed by column chromatography or thin layer chromatography.

A protocol for facile preparation of 4-substituted quinazoline derivatives from 2-aminobenzophenones, thiourea and dimethyl sulfoxide is presented.

4 치환 된 퀴나 졸린 파생 상품의 손쉬운 준비

Reported in this paper is a very simple method for direct preparation of 4-substituted quinazoline derivatives from a reaction between substituted ...

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 ...

Functionalization of Single-walled Carbon Nanotubes with Thermo-reversible Block Copolymers and Characterization by Small-angle Neutron Scattering

We demonstrate a protocol for single-walled carbon nanotube functionalization using thermo-sensitive PEO-PPO-PEO triblock copolymers in an aqueous solution. In a carbon nanotube/PEO105-PPO70-PEO105 (poloxamer 407) aqueous solution, the amphiphilic poloxamer 407 adsorbs onto the carbon nanotube surfaces and self-assembles into continuous layers, driven by intermolecular interactions between constituent molecules. The addition of 5-methylsalicylic acid changes the self-assembled structure from spherical-micellar to a cylindrical morphology. The fabricated poloxamer 407/carbon nanotube hybrid particles exhibit thermo-responsive structural features so that the density and thickness of poloxamer 407 layers are also reversibly controllable by varying temperature. The detailed structural properties of the poloxamer 407/carbon nanotube particles in suspension can be characterized by small-angle neutron scattering experiments and model fit analyses. The distinct curve shapes of the scattering intensities depending on temperature control or addition of aromatic additives are well described by a modified core-shell cylinder model consisting of a carbon nanotube core cylinder, a hydrophobic shell, and a hydrated polymer layer. This method can provide a simple but efficient way for the fabrication and in-situ characterization of carbon nanotube-based nano particles with a structure-tunable encapsulation.

A method for the functionalization of carbon nanotubes with structure-tunable polymeric encapsulation layers and structural characterization using small-angle neutron scattering is presented.

작은 각도 중성자 산란에 의한 열 가역적 블록 공중 합체 및 특성 단일 벽 탄소 나노 튜브의 기능화

We demonstrate a protocol for single-walled carbon nanotube functionalization using thermo-sensitive PEO-PPO-PEO triblock copolymers in an aqueous ...

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 ...

Synthesis of Substrate-Bound Au Nanowires Via an Active Surface Growth Mechanism

Advancing synthetic capabilities is important for the development of nanoscience and nanotechnology. The synthesis of nanowires has always been a challenge, as it requires asymmetric growth of symmetric crystals. Here, we report a distinctive synthesis of substrate-bound Au nanowires. This template-free synthesis employs thiolated ligands and substrate adsorption to achieve the continuous asymmetric deposition of Au in solution at ambient conditions. The thiolated ligand prevented the Au deposition on the exposed surface of the seeds, so the Au deposition only occurs at the interface between the Au seeds and the substrate. The side of the newly deposited Au nanowires is immediately covered with the thiolated ligand, while the bottom facing the substrate remains ligand-free and active for the next round of Au deposition. We further demonstrate that this Au nanowire growth can be induced on various substrates, and different thiolated ligands can be used to regulate the surface chemistry of the nanowires. The diameter of the nanowires can also be controlled with mixed ligands, in which another &#34;bad&#34; ligand could turn on the lateral growth. With the understanding of the mechanism, Au nanowire-based nanostructures can be designed and synthesized.

We report a solution-based method to synthesize substrate-bound Au nanowires. By tuning the molecular ligands used during the synthesis, the Au nanowires can be grown from various substrates with different surface properties. Au nanowire-based nanostructures can also be synthesized by adjusting the reaction parameters.

활성 표면 성장 메커니즘을 통해 기판 바인딩된 Au 나노 와이어의 합성

Advancing synthetic capabilities is important for the development of nanoscience and nanotechnology. The synthesis of nanowires has always been a ...

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species

&#945;-Functionalization of ketones via umpolung of enolates by hypervalent iodine reagents is an important concept in synthetic organic chemistry. Recently, we have developed a two-step strategy for ketone enolate umpolung that has enabled the development of methods for chlorination, azidation, and amination using azoles. In addition, we have developed C-C bond&#8211;forming arylation and allylation reactions. At the heart of these methods is the preparation of the intermediate and highly reactive enolonium species prior to addition of a reactive nucleophile. This strategy is thus reminiscent of the preparation and use of metal enolates in classical synthetic chemistry. This strategy allows the use of nucleophiles that would otherwise be incompatible with the strongly oxidizing hypervalent iodine reagents. In this paper we present a detailed protocol for chlorination, azidation, N-heteroarylation, arylation, and allylation. The products include motifs prevalent in medicinally active products. This article will greatly assist others in using these methods.

A two step one-pot protocol for the umpolung of ketone enolates to enolonium species and addition of a nucleophile to the &#945;-position is described. Nucleophiles include chloride, azide, azoles, allyl-silanes, and aromatic compounds.

Enolonium 종 통해 Ketones의 Umpolung 기능화에 대 한 2 단계 프로토콜

&#945;-Functionalization of ketones via umpolung of enolates by hypervalent iodine reagents is an important concept in synthetic organic chemistry. ...

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. However, the main issue limiting their applicability is their poor stability in humid conditions. The common methods to overcome this problem involve the formation of strong metal-linker bonds by using highly charged metals, which is limited to a number of structures, the introduction of alkylic groups to the framework by post-synthetic modification (PSM) or chemical vapour deposition (CVD) to enhance overall hydrophobicity of the framework. These last two usually provoke a drastic reduction of the porosity of the material. These strategies do not permit to exploit the properties of the MOF already available and it is imperative to find new methods to enhance the stability of MOFs in water while keeping their properties intact. Herein, we report a novel method to enhance the water stability of MOF crystals featuring Cu2(O2C)4&#160;paddle-wheel units, such as HKUST (where HKUST stands for Hong Kong University of Science &#38; Technology), with the catechols functionalized with alkyl and fluoro-alkyl chains. By taking advantage of the unsaturated metal sites and the catalytic catecholase-like activity of CuII ions, we are able to create robust hydrophobic coatings through the oxidation and subsequent polymerization of the catechol units on the surface of the crystals under anaerobic and water-free conditions without disrupting the underlying structure of the framework. This approach not only affords the material with improved water stability but also provides control over the function of the protective coating, which enables the development of functional coatings for the adsorption and separations of volatile organic compounds. We are confident that this approach could also be extended to other unstable MOFs featuring open metal sites.

Robust functional catechol coatings were produced in one step by direct reaction of the material known as HKUST with synthetic catechols under anaerobic conditions. The formation of homogeneous coatings surrounding the entire crystal is ascribed to the biomimetic catalytic activity of Cu(II) dimers on the external surface of the crystals.

향상 된 수 분 저항 금속-유기 프레임 워크의 표면 기능화

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. ...

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 ...