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.

Tetrahidrokarbazole hidroperoksitlerin 1. Sentezi <ol><li> Tetrahidrokarbazol çok renkli ise hidroperoksit oluşumu yavaşlatılır. Bu durumda, renksiz bir başlangıç ​​malzemesini elde etmek için toluen / pentan kullanılarak yeniden kristalizasyon veya sütun kromatografi ile kendisini saflaştırmak. Kolon kromatografisi ile saflaştırma için, bir silika jel bir alt tabaka ve alüminyum bir üst tabakası ile bir sütun paketi. Kolonun üstüne tetrahidrokarbazol koyun ve toluen ile elüte. Tüm istenmeyen sarı ve siyah renkli yan sütun ve renksiz tetrahidrokarbazo yıkanarak olduğu üzerinde adsorbe edilir. Hemen çözücüyü buharlaştırmak ve karanlıkta argon atmosferi altında, saflaştırılmış ürün, beyaz saklayın. </li><li> 250 ml&#39;lik bir şişeye (16 bildirilen yöntemlere göre sentezlendi 1) tetrahidrokarbazol veya bir ikame edilmiş tetrahidrokarbazol 1 g tartılır. Bu şişeye, 100 ml toluen ekleyin. </li><li> Rose Bengal (2 tarttınmg) ve yukarıdaki reaksiyon karışımına ekleyin. </li><li> Bir karıştırma çubuğu ekleyin ve septumlarla şişesi kapağı. </li><li> Septum üzerinden bir oksijen balonu ekleme; Bu reaksiyon üzerinde oksijen atmosferi içinde, bir pozitif basınç tutar. </li><li> 23 watt lamba ile reaksiyon karışımının ışın tedavisi. </li><li> (70:30 oranında heksan / etil asetat karışımı kullanılarak, TLC, burada tarif edilen hidroperoksitlerin Rf değeri 0.2 ile 0.3 arasındadır), ince-tabaka kromatografisi ile reaksiyonun ilerlemesini kontrol, bir ya da 1 &#39;H NMR ile örneği (bir döner buharlaştırıcı üzerinde buharlaştırılır ve DMSO-d6 içinde çözülür tortu) değerlendirilir. Kısmen 1.1 &#39;de belirtildiği gibi, reaksiyon süreleri, ışık kaynağı ve başlangıç ​​malzemesi saflığına bağlı olarak değişebilir. Genellikle, tetrahidrokarbazolleri 1 tam dönüşüm 3 saat sürer. </li><li> Başlangıç ​​malzemesinin tam dönüşümü sonra çöken katı madde filtre. Katı yıkama çoğunu ortadan kaldırmak için pentan ile yapılabilirtoluen, ancak saflaştırma için gerekli değildir. </li><li> Indirgenmiş basınç altında izole edilmiş katı madde kurutulur. </li></ol> DİKKAT: biz çalışan veya bu çalışmada tarif bileşiklerin işleme herhangi bir sorun yaşamamış olsa peroksit ile çalışırken, önlemler alınmalıdır. Özellikle, ısı ya da metal ya da metal tuzları ile karıştırmak için temiz peroksitleri ortaya çıkarmak için mümkün olduğunca kaçınılmalıdır. Bir sıcaktan koruma kalkanının ardında gerçekleştirme bu tür reaksiyonlar önerilir. . 2 Kuplaj reaksiyonu - metanol içinde% 10 mol trifloroasetik asit kullanılarak Metot A <ol><li> 12 ml bir şişe ya da müsait bir yuvarlak tabanlı bir şişe içine hidroperoksit (0.49 mmol, 1.0 eşdeğ. Aşama 1 &#39;den) ve istenen anilin nükleofil (0.49 mmol, 1.0 eşdeğer.) Tartılır. </li><li> Trifluoroasetik asit 10 ml MeOH eklenir ve daha sonra 3.74 ul (TFA, 0.049 mmol, 0.1 eşdeğ.) Bir şişe veya yuvarlak dipli bir şişeye. </li><li> Bir kapak ile kapatın ve kabı4 saat için oda sıcaklığında reaksiyon karışımı karıştırılmıştır. (Bu reaksiyonun seyri boyunca çökelmeye ürünler için), işlenip varyant A1: </li><li> Arzu edilen ürünü elde etmek için çökelen katı madde filtre. Metanol (3 x 0.5 mi) ile ürün yıkayın. </li><li> Ürünün ikinci bir fraksiyonunun elde edilmesi için, süzüntüden metanol buharlaştırılır. , 40 ° C&#39;de etil asetat içinde 5 ml oda sıcaklığına kadar daha sonra soğuk ham ürün çözülür ve Saf ürün çökelmekte pentan içinde 3-5 ml ekleyin. </li><li> Ürünün farklı kısımları birleştiriniz ve yüksek vakum altında kurutun. (Çökmez ürünler için), işlenip varyant A2: </li><li> Doğrudan bir dönen buharlaştıncı kullanarak reaksiyondan sonra çözücü buharlaştırılmakta ve istenen ürünü elde etmek üzere (silis jel, heksan / etil asetat / trietilamin) belirtilen kolon kromatografisiyle artığı arıtın. </li></ol> 3 Kavrama Reaksiyon -. Yöntem BVe asetik asit kullanılarak <ol><li> 12 ml bir şişe ya da müsait bir yuvarlak tabanlı bir şişe içine hidroperoksit (0.49 mmol, 1.0 eşdeğ. Aşama 1 &#39;den) ve istenen anilin nükleofil (0.49 mmol, 1.0 eşdeğer.) Tartılır. </li><li> Bir şişe ya da yuvarlak tabanlı bir şişeye, 10 ml asetik asit (AcOH) ilave edin. </li><li> Bir kapak ile kabı kapatmak ve 4 saat için oda sıcaklığında reaksiyon karışımı karıştırılmıştır. (Bu reaksiyonun seyri boyunca çökelmeye ürünler için), işlenip varyant B1: </li><li> Arzu edilen ürünü elde etmek için çökelen katı madde filtre. AcOH (3 x 0.5 mi) ile ürün yıkayın. </li><li> Ürünün ikinci bir fraksiyonunun elde edilmesi için, filtre ürününden asetik asit buharlaşır. , 40 ° C&#39;de etil asetat içinde 5 ml oda sıcaklığına kadar daha sonra soğuk ham ürün çözülür ve Saf ürün çökelmekte pentan içinde 3-5 ml ekleyin. </li><li> Ürünün farklı kısımları birleştiriniz ve yüksek vakum altında kurutun. Çalıştırma varyant B2 </strong&gt; (çökmez ürünler için): </li><li> Doğrudan bir dönen buharlaştıncı kullanarak reaksiyondan sonra çözücü buharlaştırılmakta ve istenen ürünü elde etmek üzere (silis jel, heksan / etil asetat / trietilamin) belirtilen kolon kromatografisiyle artığı arıtın. </li></ol>

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Yazarlar ifşa hiçbir şey yok.

Özet olarak, tetrahidrokarbazolleri bir CH bağ uygun bir şekilde iki aşamalı bir prosedürle CN-bağlanma ürünleri üretmek için fonksiyonalize edilebileceğini göstermek olabilir. İlk adım, hidroperoksit 2 vererek tetrahidrokarbazol (1) ya da elemental oksijen 17,19 ile türevlerinin iyi bilinen bir photocatalyzed oksidasyonudur. Toluen içinde gerçekleştirildiği takdirde, hidroperoksit ürün çöker ve uygun süzme ile izole edile...

CH bağlarının doğrudan işlevselleştirme organik kimya 1. önemli ve uzun soluklu bir hedeftir. Bu tür dönüşümler gruplarını aktive veya yönetmenlik giriş ve uzaklaştırılmasını gerektiren geleneksel yöntemlere kıyasla adımlar, zaman ve malzeme tasarrufu ile sentezini kolaylaştırmak için çok güçlü olabilir. Bu nedenle, CH bağlarının fonksiyonlandırmalar da yeşil kimya 2 için cazip olduğunu. Oksidatif koşullar, iki CH bağlar ya da bir CH ve bir hetero-H bağı altında sırasıyla CC ve C-heteroatom tahviller, (Şekil 1) 3-9 dönüştürülebilir. Genellikle bu oksidatif birleştirme reaksiyonları sentetik oksidanlar, pahalı katalizörler veya yüksek sıcaklıklar gerektirir. Bu nedenle, birçok girişimlerde terminali oksidan 10 gibi ucuz katalizörler, benign durumları ve oksijen veya hava kullanan yöntemleri geliştirmek için yapılır. <img alt="Şekil 1" fo:content-width = &quot;5in&quot; src = &quot;/ files/ftp_upload/51504/51504fig1highres.jpg&quot; width = &quot;500&quot; /&gt; Şekil 1.. Oksidatif birleştirme tepkimeleri. <a href="https://www.jove.com/files/ftp_upload/51504/51504fig1highres.jpg" target="_blank">, bu rakamın daha büyük bir versiyonunu görmek için buraya tıklayınız.</a> Birçok organik bileşikler, etkili bir şekilde bir hidroperoksit grubu 11,12 oluşturan, O 2 sokulmasıyla CH bağları işlevselleştirilmesi için oto-oksidasyon reaksiyonlarında havadaki oksijen ile yavaş yavaş reaksiyona girer. Oto-oksidasyon süreçleri hidrokarbon besleme malzemelerinden üretilen oksijenli bileşikler endüstriyel ölçekte kullanılır, ancak bu oto-oksidasyon değerli bileşikler ya da malzeme ayrışmasına neden varsa da istenmeyen bir süreç vardır. Bazı durumlarda, örneğin dietil eter, havada oluşan hidroperoksitler da patlayıcı olabilir. Son zamanlarda, bir redoks-aktif katalizör 13,14 gerek kalmadan CH bağa ​​yeni CC bağ oluşturmak üzere bir oto-oksidasyon reaksiyonu kullanan bir keşfettik </sup&gt;. Bunun için bir asit katalizör mevcudiyetinde oksijen altında alt tabakaların karıştırıldıktan yeni ürünlerin oluşumuna yol açar. Reaksiyona anahtar asit katalizi 15 ile ikinci alt-tabaka ile ikame edilmiş olan ara hidroperoksitler, en kolay oluşumudur. Bu reaksiyon, bununla birlikte, ksanten sınırlıdır ve kolay bir oksijen ve ürün atmosferi altında oksitlenir birkaç ilişkili bileşikler, şimdiye kadar bulunmayan uygulamalar edilir. Ancak bu keşif esinlenerek, biz farmasötik açıdan aktif indol türevleri 16 sentezlemek için Intermediate peroksitler (CİPS) üzerinden CH fonksiyonlandırmalar ilkesini kullanan bir ilişkili oksidatif birleştirme yöntemi geliştirdi. İndoller, özellikle 1 tetrahidrokarbazoller, hassaslaştırıcı ve kolay bir şekilde görünür ışık 20 kullanılarak üretilebilir singlet oksijenin 17-19 mevcudiyetinde 2 hidroperoksitler için oksitlenebilir. Bir hydroperoxide parçası olabilir asit katalizi ile aktive edilen ve bir nükleofil 21,22 tanıtımı için izin verirse bir ayrılan grup olarak prensip eyleminde. Hidroperoksitler, aynı zamanda kümen, Hock işlemi 23 fenol endüstriyel sentezinde kullanılan gibi asit bir yeniden düzenleme tepkimeleri katalize geçmesi bilinmektedir. Dikkatli optimizasyon çalışmaları, biz yeniden düzenlenmesi 16 ile istenmeyen ayrışma yolları üzerinde anilinlerin 3 gibi N-nükleofıllerle istenen ikame reaksiyonu lehine koşullar bulabiliriz. Burada ise, görünür ışık, hassaslaştırıcı, oksijen ve asit kullanılarak, ayrıntılı olarak bu iki aşamalı PATATES prosedürü açıklar. Seçilen ürünler, yüksek anti-viral aktivite gösteren ve tümör terapisi 24-26 için önemli olabilir, vasküler endotelyal büyüme faktörü (VGF) inhibe eden indol türevleri, 4, arasında bulunmaktadır.

<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 l - (5-nitroindolin-1-il) -2,3,4,9-tetrahidro-1 H-karbazol (4a): Yöntem A, Rf = 0.63 (heksan / etil asetat 70:30) &#39;ye göre sentezlenmiş. Saflaştırma: Yöntem A, A1 muamele varyant kullanılarak ürünü saflaştırmak (2.4, 2.5, 2.6 adım). Turuncu katı, Verim: 95%. 1H NMR (500 MHz, DMSO-d6): δ 10.90 (s, 1H), 7.97 (dd, J...

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.

Intermediate Peroksitlerin yoluyla fotokimyasal ve Asit-katalize CH fonksiyonlandırmalar tarafından Antiviral tetrahidrokarbazole Türevlerinin Sentezi (CİPS)

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 Görüntüleme.  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.

Video: 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.

MTT deneyi ile sentez ve Sitotoksisite Değerlendirilmesi: Anticancer Metal Kompleksleri

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

Kimya

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.

Sentezi, Karakterizasyonu ve Hibrid Au / CdS ve Au / ZnS Çekirdek / Shell Nanopartiküller işlevselleştirilmesi

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

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.

Sentezi İçin Protokol<em&gt; Ortho</em&gt; -trifluoromethoxylated Anilin türevleri

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.

Küçük açılı Nötron Saçılma tarafından Thermo-geri dönüşümlü Blok Kopolimer ve Karakterizasyonu Tek duvarlı Karbon Nanotüpler işlevselleştirilmesi

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.

Protein Bioconjugatlar sentezi<em&gt; yoluyla</em&gt; Sistein-maleimid Kimya

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.

Substrat bağlı Au Nanowires bir aktif yüzey büyüme mekanizması yoluyla sentezi

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

Regioselective O-Glycosylation of Nucleosides via the Temporary 2',3'-Diol Protection by a Boronic Ester for the Synthesis of Disaccharide Nucleosides

Disaccharide nucleosides, which consist of disaccharide and nucleobase moieties, have been known as a valuable group of natural products having multifarious bioactivities. Although chemical O-glycosylation is a commonly beneficial strategy to synthesize disaccharide nucleosides, the preparation of substrates such as glycosyl donors and acceptors requires&#160;tedious protecting&#160;group manipulations and a purification at each synthetic step. Meanwhile, several research groups have reported that boronic and borinic esters serve as a protecting or activating group of carbohydrate derivatives to achieve the regio- and/or stereoselective acylation, alkylation, silylation, and glycosylation. In this article, we demonstrate the procedure for the regioselective O-glycosylation of unprotected ribonucleosides utilizing boronic acid. The esterification of 2&#39;,3&#39;-diol of ribonucleosides with boronic acid makes the temporary protection of diol, and, following O-glycosylation with a glycosyl donor in the presence of p-toluenesulfenyl chloride and silver triflate, permits the regioselective reaction of the 5&#39;-hydroxyl group to afford the disaccharide nucleosides. This method could be applied to various nucleosides, such as guanosine, adenosine, cytidine, uridine, 5-metyluridine, and 5-fluorouridine. This article and the accompanying video represent&#160;useful (visual) information for the O-glycosylation of unprotected nucleosides and their analogs for the synthesis of not only disaccharide nucleosides, but also a variety of biologically relevant derivatives.

Regioselective O-Glycosylation of Nucleosides via the Temporary 2&#039;,3&#039;-Diol Protection by a Boronic Ester for the Synthesis of Disaccharide Nucleosides

Here, we present protocols for the synthesis of disaccharide nucleosides by the regioselective O-glycosylation of ribonucleosides via a temporary protection of their 2&#39;,3&#39;-diol moieties utilizing a cyclic boronic ester. This method applies to several unprotected nucleosides such as adenosine, guanosine, cytidine, uridine, 5-methyluridine, and 5-fluorouridine to give corresponding disaccharide nucleosides.

Regioselective O- glikozilasyon nükleozitler üzerinden geçici 2', 3'-Diol koruması tarafından Boronic Ester Disaccharide nükleozitler sentezi için

Disaccharide nucleosides, which consist of disaccharide and nucleobase moieties, have been known as a valuable group of natural products having ...

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.

Ketonlar ile Enolonium türler Umpolung Functionalization için bir iki adım iletişim kuralı

&#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.

Geliştirilmiş nem direnci için Metal organik çerçeveler yüzey Functionalization

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.

Esterleri bir yeşil Steglich esterleşme Asetonitril içinde yolu ile sentezi

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