Reversible polymerization of novel monomers bearing furan and plant oil moieties: a double click exploitation of renewable resources

Monomers based on plant oil derivatives bearing furan heterocycles appended through thiol-ene click chemistry were prepared and, subsequently, polymerized via a second type of click reaction, i. e. the Diels-Alder (DA) polycondensation between furan and maleimide complementary moieties. Two basic approaches were considered for these DA polymerizations, namely (i) the use of monomers with two terminal furan rings in conjunction with bismaleimides (AA + BB systems) and (ii) the use of a protected AB monomer incorporating both furan and maleimide end groups. This study clearly showed that both strategies were successful, albeit with different outcomes, in terms of the nature of the ensuing products. The application of the retro-DA reaction to these polymers confirmed their thermoreversible character, i. e. the clean-cut return to their respective starting monomers, opening the way to original macromolecular materials with interesting applications, like mendability and recyclability.

Copper Nanoparticles in Click Chemistry

Conspectus: The challenges of the 21st century demand scientific and technological achievements that must be developed under sustainable and environmentally benign practices. In this vein, click chemistry and green chemistry walk hand in hand on a pathway of rigorous principles that help to safeguard the health of our planet against negligent and uncontrolled production. Copper-catalyzed azide–alkyne cycloaddition (CuAAC), the paradigm of a click reaction, is one of the most reliable and widespread synthetic transformations in organic chemistry, with multidisciplinary applications. Nanocatalysis is a green chemistry tool that can increase the inherent effectiveness of CuAAC because of the enhanced catalytic activity of nanostructured metals and their plausible reutilization capability as heterogeneous catalysts. This Account describes our contribution to click chemistry using unsupported and supported copper nanoparticles (CuNPs) as catalysts prepared by chemical reduction. Cu(0)NPs (3.0 ± 1.5 nm) in tetrahydrofuran were found to catalyze the reaction of terminal alkynes and organic azides in the presence of triethylamine at rates comparable to those achieved under microwave heating (10–30 min in most cases). Unfortunately, the CuNPs underwent dissolution under the reaction conditions and consequently could not be recovered. Compelling experimental evidence on the in situ generation of highly reactive copper(I) chloride and the participation of copper(I) acetylides was provided. The supported CuNPs were found to be more robust and efficient catalyst than the unsupported counterpart in the following terms: (a) the multicomponent variant of CuAAC could be applied; (b) the metal loading could be substantially decreased; (c) reactions could be conducted in neat water; and (d) the catalyst could be recovered easily and reutilized. In particular, the catalyst composed of oxidized CuNPs (Cu2O/CuO, 6.0 ± 2.0 nm) supported on carbon (CuNPs/C) was shown to be highly versatile and very effective in the multicomponent and regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles in water from organic halides as azido precursors; magnetically recoverable CuNPs (3.0 ± 0.8 nm) supported on MagSilica could be alternatively used for the same purpose under similar conditions. Incorporation of an aromatic substituent at the 1-position of the triazole could be accomplished using the same CuNPs/C catalytic system starting from aryldiazonium salts or anilines as azido precursors. CuNPs/C in water also catalyzed the regioselective double-click synthesis of β-hydroxy-1,2,3-triazoles from epoxides. Furthermore, alkenes could be also used as azido precursors through a one-pot CuNPs/C-catalyzed azidosulfenylation–CuAAC sequential protocol, providing β-methylsulfanyl-1,2,3-triazoles in a stereo- and regioselective manner. In all types of reaction studied, CuNPs/C exhibited better behavior than some commercial copper catalysts with regard to the metal loading, reaction time, yield, and recyclability. Therefore, the results of this study also highlight the utility of nanosized copper in click chemistry compared with bulk copper sources.

Java Applets for teaching quantum mechanics: Particle in a box

These Java Applets help to illustrate some of the difficult to grasp concepts of quantum mechanics. To run this Applet, use the 'Download as zip files' option. Make sure you extract the files first, then double click on the .html file to run the Applet. These are released as open access resources for the purpose of testing, and are to be deployed at the users own risk. Please report any errors you find.

Java Applets for teaching quantum mechanics: Particle in a 2D box

These Java Applets help to illustrate some of the difficult to grasp concepts of quantum mechanics. To run this Applet, use the 'Download as zip files' option. Make sure you extract the files first, then double click on the .html file to run the Applet. These are released as open access resources for the purpose of testing, and are to be deployed at the users own risk.

Java Applets for teaching quantum mechanics: Particle in a well

These Java Applets help to illustrate some of the difficult to grasp concepts of quantum mechanics. To run this Applet, use the 'Download as zip files' option. Make sure you extract the files first, then double click on the .html file to run the Applet. These are released as open access resources for the purpose of testing, and are to be deployed at the users own risk.

Introductory Physical Chemistry Lecture 1

These lectures are designed to show new students different lecturing styles they will encounter at Southampton University. This lecture is in the style of 'Chalk and Talk'. The lectures also teach students some of the fundamental parts of physics which are relevant to the Physical Chemistry course. This will be particularly useful for students who have forgotten their GCSE physics! To view the videos, download the zip file and 'extract' the contents by right clicking on the folder. Then double click on the file 'Play video.html'. Note that the video has been compressed heavily so it can be downloaded, which means there is a slight loss in quality. If you have a problem with this, please e-mail David Read (d.read@soton.ac.uk). NOTE: YOU MUST EXTRACT THE ZIP FOLDER BEFORE CLICKING ON 'Play video.html' OTHERWISE IT WON'T WORK.

Introductory Physical Chemistry Lecture 2

These lectures are designed to show new students different lecturing styles they will encounter at Southampton University. This lecture is delivered using a Tablet PC. These lectures also teach students some of the fundamental parts of physics which are relevant to the Physical Chemistry course. This will be particularly useful for students who have forgotten their GCSE physics! To view the videos, download the zip file and 'extract' the contents by right clicking on the folder. Then double click on the file 'Play video.html'. Note that the video has been compressed heavily so it can be downloaded, which means there is a slight loss in quality. If you have a problem with this, please e-mail David Read (d.read@soton.ac.uk). NOTE: YOU MUST DOWNLOAD AND EXTRACT THE ZIP FOLDER BEFORE CLICKING ON 'Play video.html' OTHERWISE IT WON'T WORK.

Introductory Physical Chemistry Lecture 3

These lectures are designed to show new students different lecturing styles they will encounter at Southampton University. This lecture is delivered using PowerPoint. These lectures also teach students some of the fundamental parts of physics which are relevant to the Physical Chemistry course. This will be particularly useful for students who have forgotten their GCSE physics! To view the videos, download the zip file and 'extract' the contents by right clicking on the folder. Then double click on the file 'Play video.html'. Note that the video has been compressed heavily so it can be downloaded, which means there is a slight loss in quality. If you have a problem with this, please e-mail David Read (d.read@soton.ac.uk). NOTE: YOU MUST DOWNLOAD AND EXTRACT THE ZIP FOLDER BEFORE CLICKING ON 'Play video.html' OTHERWISE IT WON'T WORK.

¿Sirve un programa de educación en el manejo de niños con asma?

Con el objetivo de conocer la calidad de vida y los conocimientos en asma se plantea el estudio ¿Sirve un programa de educación en el manejo de niños con asma? dirigido por el Dr. Juan Manuel Castillo Neumólogo Pediatra quien lleva el diagnóstico y seguimiento de los pacientes incluidos en el estudio. Con este estudio queremos demostrar que el programa educativo de asma es necesario crearlo e incluirlo dentro del tratamiento de la enfermedad para el mejoramiento de la calidad de vida de los niños asmáticos y su familia, ya que la mayoría de lo médicos no incluyen en su tratamiento ningún tipo de educación de la enfermedad, ni remiten a los pacientes a programas educativos.

Improving computer interaction for older people - studying mouse clicks

Interactions using a standard computer mouse can be particularly difficult for novice and older adult users. Tasks that involve positioning the mouse over a target and double-clicking to initiate some action can be a real challenge for many users. Hence, this paper describes a study that investigates the double-click interactions of older and younger adults and presents data that can help inform the development of methods of assistance. Twelve older adults (mean age = 63.9 years) and 12 younger adults (mean age = 20.8 years) performed click and double-click target selections with a computer mouse. Initial results show that older users make approximately twice as many errors as younger users when attempting double-clicks. For both age groups, the largest proportion of errors was due to difficulties with keeping the cursor steady between button presses. Compared with younger adults, older adults experienced more difficulties with performing two button presses within a required time interval. Understanding these interactions better is a step towards improving accessibility, and may provide some suggestions for future directions of research in this area.

Gráfico interactivo de las relaciones derivativas entre palabras del español

[ES] La aplicación Gráfico interactivo de las relaciones derivativas entre palabras del español se centra en realizar un tratamiento a la información recabada en la tesis Sistema computacional de la gestión morfológica del español, de toda la información que contiene esta tesis este proyecto hace uso recogiendo cualquier palabra introducida por el usuario, buscando su forma canónica y devolviendo en forma gráfica la familia de palabras relacionada con esta, mediante un grafo. Esta aplicación web tiene como objetivo hacer amena la legibilidad y consulta de la información mencionada. Para lograr este objetivo se ha desarrollado una interfaz muy sencilla para el usuario, en la que éste solo tiene que introducir una palabra y relacionarla mediante un click. Una vez realizada la búsqueda, la aplicación permite al usuario interactuar con el grafo, pudiendo moverlo por la pantalla a su antojo, también tiene la función de mostrar los hijos de un nodo hoja al pasar el puntero por encima de éste y al hacer doble click sobre un nodo hoja, sea hijo o nieto de la raíz, devolviendo un nuevo grafo con el nodo seleccionado como raíz del mismo y mostrando sus hijos y nietos si los tuviera.

Sintesi, modifica e caratterizzazione di polimeri da fonti rinnovabili

Gli argomenti trattati all’interno di questa tesi di dottorato riguardano la sintesi e la modifica di polimeri ottenuti a partire da fonti rinnovabili. L’acido polilattico (PLA) è stato modificato per ottenere film estensibili per uso alimentare. La scelta del materiale si è basata sull’analisi del suo ciclo di vita e perché è riconosciuto come sicuro per l’utilizzo nel campo alimentare. Le formulazioni testate, a base di PLA, sono state preparate con l’aggiunta di una serie di additivi utilizzati per migliorare le proprietà meccaniche del materiale. La lavorazione è stata eseguita mediante estrusione, ottenendo dei pellet a composizione omogenea successivamente lavorati nell’estrusore a bolla, modalità industriale di produzione dei film estensibili. È stata poi effettuata la sintesi diretta di nuovi poliesteri insaturi a base di dimetil succinato e 1,6-esandiolo. L’insaturazione della catena è stata ottenuta mediante l’uso, durante la sintesi, di derivati dell’olio di ricino, l’acido ricinoleico e il suo derivato insaturo metil undecenoato. Un’altra molecola insatura utilizzata è stata il citronellolo, scelto tra i terpeni. I polimeri così ottenuti sono stati modificati tramite reazioni radicaliche indotte con radiazioni UV utilizzando sostanze antibatteriche (sale 3-esadecil-1-vinilimidazolo bromuro) al fine di ottenere materiali con attività biocida a lungo termine e senza rilascio. Si è proceduto inoltre alla polimerizzazione reversibile di monomeri furanici con oli vegetali utilizzando una strategia di tipo double click. Si è partiti dalla sintesi di monomeri derivanti da oli vegetali contenenti eterocicli furanici attaccati mediante addizione tiol-enica (prima reazione click chemistry) e si è proseguito con la loro successiva polimerizzazione attraverso una reazione di tipo Diels-Alder con molecole con gruppi maleimmidici (seconda reazione click chemistry). I polimeri così ottenuti sono materiali potenzialmente auto-riparanti, grazie alla possibilità di spostare l’equilibrio verso i prodotti o i reagenti semplicemente variando le condizioni di temperatura.

Facile double-functionalization of designed ankyrin repeat proteins using click and thiol chemistries

Click chemistry is a powerful technology for the functionalization of therapeutic proteins with effector moieties, because of its potential for bio-orthogonal, regio-selective, and high-yielding conjugation under mild conditions. Designed Ankyrin Repeat Proteins (DARPins), a novel class of highly stable binding proteins, are particularly well suited for the introduction of clickable methionine surrogates such as azidohomoalanine (Aha) or homopropargylglycine (Hpg), since the DARPin scaffold can be made methionine-free by an M34L mutation in the N-cap which fully maintains the biophysical properties of the protein. A single N-terminal azidohomoalanine, replacing the initiator Met, is incorporated in high yield, and allows preparation of "clickable" DARPins at about 30 mg per liter E. coli culture, fully retaining stability, specificity, and affinity. For a second modification, we introduced a cysteine at the C-terminus. Such DARPins could be conveniently site-specifically linked to two moieties, polyethylene glycol (PEG) to the N-terminus and the fluorophore Alexa488 to the C-terminus. We present a DARPin selected against the epithelial cell adhesion molecule (EpCAM) with excellent properties for tumor targeting as an example. We used these doubly modified molecules to measure binding kinetics on tumor cells and found that PEGylation has no effect on dissociation rate, but slightly decreases the association rate and the maximal number of cell-bound DARPins, fully consistent with our previous model of PEG action obtained in vitro. Our data demonstrate the benefit of click chemistry for site-specific modification of binding proteins like DARPins to conveniently add several functional moieties simultaneously for various biomedical applications.

Double hydrophilic polyphosphoester containing copolymers as efficient templating agents for calcium carbonate microparticles

International audience