We gratefully acknowledge the Swedish Research Council Formas for generous financial support.

1. Síntese Gram-escala de metil-6-oxo-l, 3,4,6-triphenylhexanoate <ol><li> Seco 1-etil-3-metil imidazólio de etilo (EMIMAc) em um balão de fundo redondo sobre um evaporador rotativo a 10 mbar, 40 ° C durante 1 h. </li><li> Adicionar 2,1 g de EMIMAc seco e 1,0 g de 1,3-difenil-2-propen-1-ona A uma balão de 100 ml de fundo redondo equipado com um agitador magnético. </li><li> Adicionar 2,019 ml de metanol e 2,3 g de cinamaldeído para o balão. </li><li> À temperatura ambiente (22 ° C) dissolver a mistura em 60 ml de diclorometano por agitao durante 1 min. </li><li> Subsequentemente adiciona 0,37 ml de 1,8-diazabiciclo [5.4.0] undec-7-eno (DBU) à mistura em agitação (passo 1.4) e a tampa do frasco de fundo redondo. </li><li> Agita-se com uma barra de agitação magnética, a uma velocidade de 500 rpm à temperatura ambiente (22 ° C). </li><li> Verificar se completar a reacção com 1 H-RMN. 24 olhar para o desaparecimento da ligação dupla do chalcona na área de 7,8 ppm. </li><li> Quando a reacção atingiu<html> conclusão remover os voláteis num evaporador rotativo a 10 mbar, 20 ° C durante 15 min. </li><li> Adicionar 50 ml de metanol ao resíduo para o dissolver EMIMAc por agitação com uma barra de agitação magnética. </li><li> Remover os sólidos a partir das paredes do balão por agitação violenta com uma barra de agitação magnética, a uma velocidade de 750 rpm durante 30 min. Se necessário, utilizar uma espátula para remover os sólidos restantes das paredes. </li><li> Filtra-se a mistura sobre um filtro poroso (dimensão de poro 3). </li><li> Lava-se com 20 ml adicionais de metanol. Se a reciclagem do EMIMAc é desejado evaporar o filtrado metanólico. (passo 2.1). </li><li> Ainda sobre a frita, dividir suavemente o bolo de filtração (a partir do passo 1.11) em pedaços pequenos com uma espátula e transferir os sólidos através de um funil de pó para um balão de fundo redondo pré-pesados ​​e secar os sólidos sob vácuo. </li><li> Pesa-se o balão e o cálculo do rendimento. </li><li> Analisar o produto por RMN de 1 H (passo 1.7). Compare com espectros relatado 24. </li></ol>title &quot;&gt; 2. Reciclagem de EMIMAc <ol><li> Remover os voláteis a partir da mistura de metanol (a partir do passo 1.12) sob pressão reduzida de 10 mbar, a 40 ° C durante 30 min. </li><li> 24 Analisar o óleo resultante por 1 H RMN e 13 C RMN para verificar se está presente EMIMAc. </li><li> Use a EMIMAc reciclado a partir do passo 1.2. </li></ol> 3. Gelation <ol><li> Preparação de uma solução stock <ol><li> Adicionar 200 mg de metil-6-oxo-l, 3,4,6-triphenylhexanoate (o produto do passo 1.15) e uma barra de agitação magnética a um frasco. Adicionar 2,0 ml de diclorometano para dissolver o cetoéster. Mexa até que tudo se dissolva. </li></ol></li><li> Gelificação <ol><li> Adicionar 50 ml de heptano a um copo de 500 ml. Adicionar 1,5 ml de solução de estoque para o heptano. Agita-se rapidamente para assegurar uma mistura adequada e deixe repousar sem agitação à temperatura ambiente até que a gelificação ocorre. </li></ol></li></ol>

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The authors have nothing to disclose.

Com base na configuração- anti determinado por análise de raios-X de cetoéster 3 e na investigação mecanicista proposto por Bode e colegas de trabalho 30 o seguinte caminho reaccional é sugerido (Figura 5). A desprotonação do IL gera espécies NHC; o NHC reage com o aldeído insaturado, para formar o intermediário I. O Breslow Breslow intermédia e a calcona reagir numa reacção cruzada benzoína para formar dieno II. Intermediário II sofre um rearranjo oxi-Cope via estad...

<img alt="TOC 1" src="/files/ftp_upload/53213/53213TOC.jpg" /> (Acima) síntese Três-componente do 1,6-cetoésteres: uma nova classe de gelators baixo peso molecular. Os líquidos iónicos (ILS) têm uma elevada estabilidade, baixa volatilidade, não inflamabilidade e, portanto, têm prestado atenção como meios de reacção seguras e solventes ideais para reciclagem. 1-3 imidazoliums dialquilo é um certo tipo de líquidos iónicos que, na presença de uma base, , pode ser desprotonado para renderizar um carbeno N-heterocíclicos (NHC) 4. No campo da organocatálise, NHCs, operando sob caminhos de reação distintas, têm encontrado uso generalizado em uma ampla gama de reações genéricas. 5-11 Apesar disso, a ligação entre TIs e ligação CC forming NHC-catálise é relativamente inexplorado. No entanto, NHCs derivado de ILS têm sido relatados para catalisar reacções de formação de ligações CC, tais como a condensação de benzoína e a reacção Stetter 12-22. Por exemplo, Davis et ai. Demonstraram que LIs thiazoliums derivados de N-alquilo servir como no precatalysts 12 formação de benzoína do benzaldeído. Mais recentemente, Chen e colegas de trabalho expandido este conceito utilizando uma base imidazólio IL, 1-etil-3-metil imidazólio de etilo (EMIMAc), para efectuar a condensação de benzoína em 5-hidroximetilfurfural (HMF) para gerar 5,5 &#39;-di (hidroximetil) furoin (DHMF). 23 Dado que as TIs estão disponíveis comercialmente e oferecem uma forma barata de gerar NHCs, estávamos interessados ​​em investigar o que os outros tipos de reações ILs poderia realizar. Para este fim, descobriu-se que de dialquilo imidazoliums poderia ser usado eficientemente como precatalysts no additi formal de conjugadode aldeídos insaturados em a calconas (Figura 1) para dar 1,6-cetoésteres. A IL mais eficiente, EMIMAc, promove uma reacção altamente estereosselectiva entre cinamaldeído e chalcona. A reacção ocorre com elevada preferência pelo anti -diastereero e os 1,6-cetoésteres pode ser isolado com rendimentos de até 92%. 24,25,26 <img alt="figura 1" src="/files/ftp_upload/53213/53213fig1.jpg" /> Figura 1: IL-mediada de três componentes, além estereosselectiva de cinamaldeído a calcona.

<table>
	<tbody>
		<tr>
			<td>1-ethyl-3-methyl imidazolium acetate</td>
			<td>Aldrich</td>
			<td>51053-100G-F</td>
			<td>Produced by BASF &#8805;90%, dried on a rotary evaporated before use (10 mBar, 40 &#176;C, 1h) 
			CAS NUMBER: 143314-17-4</td>
		</tr>
		<tr>
			<td>1,3-diphenyl-2-propen-1-one</td>
			<td>Aldrich</td>
			<td>11970-100G</td>
			<td>98.0% 
			CAS NUMBER: 94-41-7</td>
		</tr>
		<tr>
			<td>trans-cinnamaldehyde&#160;</td>
			<td>Aldrich</td>
			<td>C80687-25G</td>
			<td>99%, stored under nitrogen prior to use 
			CAS NUMBER: 14371-10-9</td>
		</tr>
		<tr>
			<td>1,8-Diazobicyclo[5.4.0]undec-7-ene</td>
			<td>Aldrich</td>
			<td>139009-25G</td>
			<td>98% 
			CAS NUMBER: 6674-22-2</td>
		</tr>
		<tr>
			<td>Methanol</td>
			<td>Sigma-Aldrich</td>
			<td>32213N-2.5L</td>
			<td>puriss. P.a., ACS reagent, reag. ISO, reag. Ph. Eur. &#8805;99.8% (GC) 
			CAS NUMBER: 67-56-1</td>
		</tr>
		<tr>
			<td>Dichloromethane</td>
			<td>Fischer Chemical</td>
			<td>D/1852/17X</td>
			<td>Analytic reagent grade, stabilized with amylene 
			CAS NUMBER:9/2/1975</td>
		</tr>
		<tr>
			<td>n-Heptane</td>
			<td>Fischer Chemical</td>
			<td>H/0160/17X</td>
			<td>Analytic reagent grade 
			CAS NUMBER: 142-82-5</td>
		</tr>
	</tbody>
</table>

highly stereoselective synthesis of 1,6-ketoesters mediated by ionic liquids: a three-component reaction enabling rapid access to a new class of low molecular weight gelators

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form catalytically active N-Heterocyclic Carbenes (NHCs). Here we have used ILs as precatalysts in the addition of &#945;,&#946;-unsaturated aldehydes to chalcones to form 1,6-ketoesters, incorporating an anti-diphenyl moiety in a highly stereoselective fashion. The reaction has a broad substrate scope and several functional groups and heteroaromatics can be integrated into the ketoester backbone in generally good yields with maintained stereoselectivity. The reaction protocol is robust and scalable. The starting materials are inexpensive and the products can be obtained after simple filtration, avoiding solvent-demanding chromatography. Furthermore, the IL can be recycled up to 5 times without any loss of reactivity. Moreover, the 1,6-ketoester end product is a potent gelator in several hydrocarbon based solvents. The method enables rapid access to and evaluation of a new class of low molecular weight gelators (LMWGs) from recyclable and inexpensive starting materials.

Tal como exemplificado antes, EMIMAc servir como um pré-catalisador na adição conjugada de formal de α, β-aldeído insaturado de chalconas. Outros LIs disponíveis comercialmente imidazólio base, tais como cloreto de 1-etil-3-metilimidazólio (EMIMCl) e cloreto de 1-butil-3-metilimidazólio (BMIMCl) também foram investigados, no entanto, estas reacções decorreram de rendimentos mais baixos, indicando que o anião de etilo pode ser importante para a reactividade (Tabela 1, entra...

Watch this Scientific Journal Video about Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular

Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators

Ionic liquids (ILs) mediate fast, simple and cheap access to 1,6-ketoesters in high diastereoselectivities and good yields. The reaction protocol is robust and the 1,6-ketoesters can be obtained in gram scale after a simple filtration protocol. Moreover, the 1,6-ketoesters are potent gelators in hydrocarbon solvents.

Síntese altamente Stereoselective de 1,6-cetoésteres Mediada por líquidos iônicos: A reacção de três componente permitindo o rápido acesso a uma nova classe de baixo peso molecular Gelators Peso

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form ...

highly-stereoselective-synthesis-16-ketoesters-mediated-ionic-liquids

Universidad de Cartagena UDEC

Research

JoVE Journal

Chemistry

8.7K visualizações.  Chalmers University of Technology. Ionic liquids (ILs) mediate fast, simple and cheap access to 1,6-ketoesters in high diastereoselectivities and good yields. The reaction protocol is robust and the 1,6-ketoesters can be obtained in gram scale after a simple filtration protocol. Moreover, the 1,6-ketoesters are potent gelators in hydrocarbon solvents. 

Vídeo: Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators

Preparation and Use of Samarium Diiodide (SmI2) in Organic Synthesis: The Mechanistic Role of HMPA and Ni(II) Salts in the Samarium Barbier Reaction

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of molecular iodine to samarium metal in THF.1,2-3 It is a mild and selective single electron reductant and its versatility is a result of its ability to initiate a wide range of reductions including C-C bond-forming and cascade or sequential reactions. SmI2 can reduce a variety of functional groups including sulfoxides and sulfones, phosphine oxides, epoxides, alkyl and aryl halides, carbonyls, and conjugated double bonds.2-12 One of the fascinating features of SmI-2-mediated reactions is the ability to manipulate the outcome of reactions through the selective use of cosolvents or additives. In most instances, additives are essential in controlling the rate of reduction and the chemo- or stereoselectivity of reactions.13-14 Additives commonly utilized to fine tune the reactivity of SmI2 can be classified into three major groups: (1) Lewis bases (HMPA, other electron-donor ligands, chelating ethers, etc.), (2) proton sources (alcohols, water etc.), and (3) inorganic additives (Ni(acac)2, FeCl3, etc).3
Understanding the mechanism of SmI2 reactions and the role of the additives enables utilization of the full potential of the reagent in organic synthesis. The Sm-Barbier reaction is chosen to illustrate the synthetic importance and mechanistic role of two common additives: HMPA and Ni(II) in this reaction. The Sm-Barbier reaction is similar to the traditional Grignard reaction with the only difference being that the alkyl halide, carbonyl, and Sm reductant are mixed simultaneously in one pot.1,15 Examples of Sm-mediated Barbier reactions with a range of coupling partners have been reported,1,3,7,10,12 and have been utilized in key steps of the synthesis of large natural products.16,17 Previous studies on the effect of additives on SmI2 reactions have shown that HMPA enhances the reduction potential of SmI2 by coordinating to the samarium metal center, producing a more powerful,13-14,18 sterically encumbered reductant19-21 and in some cases playing an integral role in post electron-transfer steps facilitating subsequent bond-forming events.22 In the Sm-Barbier reaction, HMPA has been shown to additionally activate the alkyl halide by forming a complex in a pre-equilibrium step.23
Ni(II) salts are a catalytic additive used frequently in Sm-mediated transformations.24-27 Though critical for success, the mechanistic role of Ni(II) was not known in these reactions. Recently it has been shown that SmI2 reduces Ni(II) to Ni(0), and the reaction is then carried out through organometallic Ni(0) chemistry.28
These mechanistic studies highlight that although the same Barbier product is obtained, the use of different additives in the SmI2 reaction drastically alters the mechanistic pathway of the reaction. The protocol for running these SmI2-initiated reactions is described.

Preparation and Use of Samarium Diiodide SmI2 in Organic Synthesis: The Mechanistic Role of HMPA and NiII Salts in the Samarium Barbier Reaction

A straightforward procedure for the preparation of samarium diiodide (SmI2) in THF is described. The role of two main additives namely hexamethylphosphoramide (HMPA) and Ni(acac)2 in Sm mediated reactions is demonstrated in the Sm-Barbier reaction.

Preparação e Uso de Samário diiodeto (SMI<sub&gt; 2</sub&gt;) Em Organic Synthesis: The Role mecanístico de HMPA e (II) de Ni Sais na Reacção Barbier Samário

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of ...

Química

Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the material with Au(III) ions. The synthesis method was derived from a sol-gel process used to produce micron-sized monosodium titanate (MST), with several key modifications, including altering reagent concentrations, omitting a particle seed step, and introducing a non-ionic surfactant to facilitate control of particle formation and growth. The resultant nMST material exhibits spherical-shaped particle morphology with a monodisperse distribution of particle diameters in the range from 100 to 150&#160;nm. The nMST material was found to have a Brunauer-Emmett-Teller (BET) surface area of 285 m2g-1, which is more than an order of magnitude higher than the micron-sized MST. The isoelectric point of the nMST measured 3.34 pH units, which is a pH unit lower than that measured for the micron-size MST. The nMST material was found to serve as an effective ion exchanger under weakly acidic conditions for the preparation of an Au(III)-exchange nanotitanate. In addition, the formation of the corresponding peroxotitanate was demonstrated by reaction of the nMST with hydrogen peroxide.

The surfactant mediated sol-gel synthesis of nanosized monosodium titanate is described, along with preparation of the corresponding peroxide modified material. An ion-exchange reaction with Au(III) is also presented.

Síntese e Reacção Química de nanosize monossódico Titanate

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the ...

Synthesis and Exfoliation of Discotic Zirconium Phosphates to Obtain Colloidal Liquid Crystals

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and engineers. Growth of such anisotropic nanocrystals through a simple chemical method is a challenging task. In this study, we fabricate discotic nanodisks of zirconium phosphate [Zr(HPO4)2&#183;H2O] as a model material using hydrothermal, reflux and microwave-assisted methods. Growth of crystals is controlled by duration time, temperature, and concentration of reacting species. The novelty of the adopted methods is that discotic crystals of size ranging from hundred nanometers to few micrometers can be obtained while keeping the polydispersity well within control. The layered discotic crystals are converted to monolayers by exfoliation with tetra-(n)-butyl ammonium hydroxide [(C4H9)4NOH, TBAOH]. Exfoliated disks show isotropic and nematic liquid crystal phases. Size and polydispersity of disk suspensions is highly important in deciding their phase behavior.

A two dimensional model material of discotic zirconium phosphate was developed. The inorganic crystal with lamellar structure was synthesized by hydrothermal, reflux, and microwave-assisted methods. On exfoliation with organic molecules, layered crystals can be converted to monolayers, and nematic liquid crystal phase was formed at sufficient concentration of monolayers.

Síntese e esfoliação da discotic Zircônio Fosfatos obter cristais coloidais líquidos

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and ...

Synthesis of Programmable Main-chain Liquid-crystalline Elastomers Using a Two-stage Thiol-acrylate Reaction

This study presents a novel two-stage thiol-acrylate Michael addition-photopolymerization (TAMAP) reaction to prepare main-chain liquid-crystalline elastomers (LCEs) with facile control over network structure and programming of an aligned monodomain. Tailored LCE networks were synthesized using routine mixing of commercially available starting materials and pouring monomer solutions into molds to cure. An initial polydomain LCE network is formed via a self-limiting thiol-acrylate Michael-addition reaction. Strain-to-failure and glass transition behavior were investigated as a function of crosslinking monomer, pentaerythritol tetrakis(3-mercaptopropionate) (PETMP). An example non-stoichiometric system of 15 mol% PETMP thiol groups and an excess of 15 mol% acrylate groups was used to demonstrate the robust nature of the material. The LCE formed an aligned and transparent monodomain when stretched, with a maximum failure strain over 600%. Stretched LCE samples were able to demonstrate both stress-driven thermal actuation when held under a constant bias stress or the shape-memory effect when stretched and unloaded. A permanently programmed monodomain was achieved via a second-stage photopolymerization reaction of the excess acrylate groups when the sample was in the stretched state. LCE samples were photo-cured and programmed at 100%, 200%, 300%, and 400% strain, with all samples demonstrating over 90% shape fixity when unloaded. The magnitude of total stress-free actuation increased from 35% to 115% with increased programming strain. Overall, the two-stage TAMAP methodology is presented as a powerful tool to prepare main-chain LCE systems and explore structure-property-performance relationships in these fascinating stimuli-sensitive materials.

A novel methodology is presented to synthesize and program main-chain liquid-crystalline elastomers using commercially available starting monomers. A wide range of thermomechanical properties was tailored by adjusting the amount of crosslinker, while the actuation performance was dependent on the amount of applied strain during programming.

Síntese de Programmable principal de cadeia Elastômeros líquido-cristalinos Usando um de dois estágios Reação Tiol-acrilato

This study presents a novel two-stage thiol-acrylate Michael addition-photopolymerization (TAMAP) reaction to prepare main-chain liquid-crystalline ...

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.

Síntese de Cd-livre InP / ZnS Quantum Dots Indicado para aplicações biomédicas

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.

Protocolo para a Síntese de Derivados de Anilina Orto-trifluorometoxilados

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

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.

Síntese Facile de micelas Worm-like por luz visível Mediated Dispersão Polimerização Usando Photoredox Catalisador

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

From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

Herein, we demonstrate that a bottom-up approach, based on halogen bonding (XB), can be successfully applied for the design of a new type of ionic liquid crystals (ILCs). Taking advantages of the high specificity of XB for haloperfluorocarbons and the ability of anions to act as XB-acceptors, we obtained supramolecular complexes based on 1-alkyl-3-methylimidazolium iodides and iodoperfluorocarbons, overcoming the well-known immiscibility between hydrocarbons (HCs) and perfluorocarbons (PFCs). The high directionality of the XB combined with the fluorophobic effect, allowed us to obtain enantiotropic liquid crystals where a rigid, non-aromatic, XB supramolecular anion acts as mesogenic core.
X-ray structure analysis of the complex between 1-ethyl-3-methylimidazolium iodide and iodoperfluorooctane showed the presence of a layered structure, which is a manifestation of the well-known tendency to segregation of perfluoroalkyl chains. This is consistent with the observation of smectic mesophases. Moreover, all the reported complexes melt below 100 &#176;C, and most are mesomorphic even at room temperature, despite that the starting materials were non-mesomorphic in nature.
The supramolecular strategy reported here provides new design principles for mesogen design allowing a totally new class of functional materials.

A protocol for the synthesis of a new type of mesogens, based on the halogen-bonded supramolecular anion [CnF2n+1-I&#183;&#183;&#183;I&#183;&#183;&#183;I-CnF2n+1]&#8722;, is reported.

De moléculas a materiais: engenharia de novos cristais líquidos iônicos por meio de ligações de halogênio

Herein, we demonstrate that a bottom-up approach, based on halogen bonding (XB), can be successfully applied for the design of a new type of ionic liquid ...

Rapid Nanoprobe Signal Enhancement by In Situ Gold Nanoparticle Synthesis

The use of nanoprobes such as gold, silver, silica or iron-oxide nanoparticles as detection reagents in bioanalytical assays can enable high sensitivity and convenient colorimetric readout. However, high densities of nanoparticles are typically needed for detection. The available synthesis-based enhancement protocols are either limited to gold and silver nanoparticles or rely on precise enzymatic control and optimization. Here, we present a protocol to enhance the colorimetric readout of gold, silver, silica, and iron oxide nanoprobes. It was observed that the colorimetric signal can be improved by up to a 10000-fold factor. The basis for such signal enhancement strategies is the chemical reduction of Au3+ to Au0. There are several chemical reactions that enable the reduction of Au3+ to Au0. In the protocol, Good&#39;s buffers and H2O2 are used and it is possible to favor the deposition of Au0 onto the surface of existing nanoprobes, in detriment of the formation of new gold nanoparticles. The protocol consists of the incubation of the microarray with a solution consisting of chloroauric acid and H2O2 in 2-(N-morpholino)ethanesulfonic acid pH 6 buffer following the nanoprobe-based detection assay. The enhancement solution can be applied to paper and glass-based sensors. Moreover, it can be used in commercially available immunoassays as demonstrated by the application of the method to a commercial allergen microarray. The signal development requires less than 5 min of incubation with the enhancement solution and the readout can be assessed by naked eye or low-end image acquisition devices such as a table-top scanner or a digital camera.

Rapid Nanoprobe Signal Enhancement by In Situ Gold Nanoparticle Synthesis

In this work, a protocol for signal enhancement of nanoprobe-based biosensing is presented. The protocol is based on the reduction of chloroauric acid onto the surface of existing nanoprobes that consist of gold, silver, silica or iron-oxide nanoparticles.

Sinal de nanossondas rápida realce pela síntese de nanopartículas de ouro em Situ

The use of nanoprobes such as gold, silver, silica or iron-oxide nanoparticles as detection reagents in bioanalytical assays can enable high sensitivity ...

Chemical Synthesis of Porous Barium Titanate Thin Film and Thermal Stabilization of Ferroelectric Phase by Porosity-Induced Strain

Barium titanate (BaTiO3, hereafter BT) is an established ferroelectric material first discovered in the 1940s and still widely used because of its well-balanced ferroelectricity, piezoelectricity, and dielectric constant. In addition, BT does not contain any toxic elements. Therefore, it is considered to be an eco-friendly material, which has attracted considerable interest as a replacement for lead zirconate titanate (PZT). However, bulk BT loses its ferroelectricity at approximately 130 &#176;C, thus, it cannot be used at high temperatures. Because of the growing demand for high-temperature ferroelectric materials, it is important to enhance the thermal stability of ferroelectricity in BT. In previous studies, strain originating from the lattice mismatch at hetero-interfaces has been used. However, the sample preparation in this approach requires complicated and expensive physical processes, which are undesirable for practical applications.
In this study, we propose a chemical synthesis of a porous material as an alternative means of introducing strain. We synthesized a porous BT thin film using a surfactant-assisted sol-gel method, in which self-assembled amphipathic surfactant micelles were used as an organic template. Through a series of studies, we clarified that the introduction of pores had a similar effect on distorting the BT crystal lattice, to that of a hetero-interface, leading to the enhancement and stabilization of ferroelectricity. Owing to its simplicity and cost effectiveness, this fabrication process has considerable advantages over conventional methods.

Here, we present a protocol for the synthesis of porous barium titanate (BaTiO3) thin film by a surfactant-assisted sol-gel method, in which self-assembled amphipathic surfactant micelles are used as an organic template.

Síntese altamente Stereoselective de 1,6-cetoésteres Mediada por líquidos iônicos: A reacção de três componente permitindo o rápido acesso a uma nova classe de baixo peso molecular Gelators Peso

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Preparação e Uso de Samário diiodeto (SMI