Nathalie Jarroux - Academia.edu (original) (raw)

Papers by Nathalie Jarroux

Tetrahedron Letters, Dec 1, 2006

The synthesis of per-2,3-di-O-heptyl-b and c-cyclodextrins, a new kind of amphiphilic cyclodextri... more The synthesis of per-2,3-di-O-heptyl-b and c-cyclodextrins, a new kind of amphiphilic cyclodextrins bearing long and stable hydrophobic chains is described. The products are obtained in a three-step synthesis from natural cyclodextrins in good yield. tert-Butyldimethylsilyl protection of the primary hydroxyl group was found to be stable under the basic conditions required for the nucleophilic substitution of the bromine derivatives. The structure of the new amphiphilic molecules was proved by NMR spectroscopy and mass spectrometry (ESI-MS or MALDI-TOF-MS).

Procedia Engineering, 2016

Our society is increasingly exposed to harmful nano and nanobio particles as new viruses, harmful... more Our society is increasingly exposed to harmful nano and nanobio particles as new viruses, harmful proteins (like prions) and metallic nanoparticles that need to be better detected and identified. Solid-state nanopores are rapidly growing candidates for fast and label-free electrical detection and analysis of nanoparticles. Being able to analyze each nanoparticle one at a time, the nanopore technology yields astonishing sensitivity results, a determining asset for early virus or pollutant detection. This proceeding describes our approach to develop an integrated sensor at the nanometer level.

Ces dernieres annees, la fabrication de plastiques a partir de ressources renouvelables s’est ave... more Ces dernieres annees, la fabrication de plastiques a partir de ressources renouvelables s’est averee etre un nouvel enjeu economique. Les biopolymeres, dont le plus connu est la cellulose, sont des polymeres issus d’organismes vivants ou de polymeres synthetises a partir de ressources renouvelables. Ces polymeres connaissent depuis quelques annees un reel essor du fait de leurs origines biologiques et surtout de leur caractere biodegradable. Leurs utilisations en substitution ou meme en melange a d’autres polymeres synthetises a partir d’hydrocarbures offrent donc des applications interessantes.

Macromolecular Chemistry and Physics, Aug 4, 2009

The paper reports on the preparation of a new 2‐rotaxane monomer through an acid coupling reactio... more The paper reports on the preparation of a new 2‐rotaxane monomer through an acid coupling reaction between 1‐pyrenecarboxaldehyde and α‐CD/3,5‐diamino‐1,2,4‐triazole inclusion complex. Pyrenyl groups are large enough to provide a blocking effect toward cyclodextrin de‐threading. The oxidative CC coupling of 2‐rotaxane in the presence of RuCl3 catalyst afforded conjugated azomethine polyrotaxanes. The expected modifications of the solubility, morphology, film forming ability for rotaxane polymer were proved. As shown by fluorescence and UV‐vis spectroscopy, a material with optical properties appropriate for use in photonics was obtained.magnified image

Cellulose, Apr 16, 2019

In order to improve healthcare of injured people, deacetylated acemannan extracted from Aloe vera... more In order to improve healthcare of injured people, deacetylated acemannan extracted from Aloe vera leaves, having high inhibitory properties, was used as an antimicrobial finish on traditional cotton items. Response surface methodology was employed to define quadratic relationships between the polysaccharide grafting degree and the treatment process properties. An optimized modification process, offering the highest funtionalization degree, is obtained. The cellulosic fiber morphology and roughness modifications induced by polymer grafting are revealed using Atomic Force Microscopy and Scanning Electron Microscopy. Infra Red spectroscopy was used to confirm the grafting effectiveness. Thermogravimetric Analysis and Differential Scanning Calorimeter were further employed to confirm chemical modification. Considering the potential use of this new biomaterial, original properties were also studied. Finishing treatment seems to preserve mechanical properties, and hydrophilicity of the cellulosic substrate. MTT assay were done in HepG2 cells to ensure that the obtained dressings are non-toxic. The biomaterial showed high biocompatibility and promoted cell viability. Antimicrobial studies showed that grafting treatment conserved polymer antibacterial activity. Optimized cotton dressings exhibited a significant inhibitory effect against Staphylococcus aureus and Escherichia coli bacteria, killed respectively at 70.2% and 72.4%.Graphical abstract

Journal of Applied Polymer Science, Nov 15, 2008

European Polymer Journal, Jun 1, 2018

Polycondensation of ATMS in the presence of DNA in chloroform is a template reaction. The faster ... more Polycondensation of ATMS in the presence of DNA in chloroform is a template reaction. The faster ATMS hydrolysis reaction rate and highest condensation yields are observed with molecules containing adenosine group (specificity).

Analytical Chemistry, Oct 14, 2011

Polyrotaxanes (PR) are among the most studied interlocked molecules in the field of supramolecula... more Polyrotaxanes (PR) are among the most studied interlocked molecules in the field of supramolecular chemistry. Cyclodextrin based polyrotaxanes (CD based PRs) are wellknown to be difficult to analyze by mass spectrometry (MS). Nanoelectrospray (nanoESI) employed during mass spectrometry (MS) and tandem mass spectrometry (MS/MS) experiments turns out to be particularly useful to analyze these noncovalent assemblies. While ESI/nanoESI based spectra usually contain multicharged species which greatly complicate the interpretation, particularly for such complex mixtures analysis, the hyphenation with a high resolution analyzer such as Orbitrap could overcome this limitation. This Article reports efforts to achieve a detailed structural deciphering by nanoESI-MS and nanoESI-MS/MS of CD based PRs constituted of αCDs, unmodified or surrounded by 1 or 2 sulfation(s), which were threaded along polydisperse poly(ethylene oxide) α,ω-dipyrenyl chains. The described method is more sensitive and less sample consuming than a typical NMR experiment and in good agreement with size-exclusion chromatography (SEC) results. Moreover, as compared to MALDI-TOF MS analysis, all populations were presumably elucidated without discrimination effect. Therefore, this MS development allowed us to estimate the PR sample content with 16 to 35 ethylene oxide units, 1 to 5 αCDs threaded, and 0 to 10 sulfo groups grafted on the overall CDs. Finally, the method afforded the possibility to unambiguously attribute supramolecular architectures from 2276.0278 to 7767.8342 g 3 mol À1 corresponding to poly[2]-to poly[6]rotaxanes.

Biomacromolecules, Jun 3, 2008

The aim of this work is to synthesize new PEO-based polyrotaxanes from modified cyclodextrins. Tw... more The aim of this work is to synthesize new PEO-based polyrotaxanes from modified cyclodextrins. Two strategies are discussed and compared. In the first, a pseudopolyrotaxane was formed between R,ω-PEO dimethacrylate and R-cyclodextrin. A coupling reaction between 1-pyrenebutyric acid N-hydroxysuccinimide ester was carried out to block the cyclic molecules onto the PEO. Cyclodextrins of the supramolecular assemblies were then oxidized using sodium periodate and reacted with spermine to form a potentially highly charged polyrotaxane. In the second strategy, cyclodextrins were first modified, and used to form the polyrotaxane through the pseudopolyrotaxane synthesis followed by the blocking reaction. Acidic titration allowed quantifying the number of amine functions borne by the supramolecular assemblies through two variables: the number of rings per polymer chain and the number of spermine groups per cyclic molecule. The supramolecules obtained by both strategies are discussed.

Macromolecules, Mar 8, 2011

High molecular weight polyrotaxanes are usually characterized by nuclear magnetic resonance and s... more High molecular weight polyrotaxanes are usually characterized by nuclear magnetic resonance and size exclusion chromatography but rarely by mass spectrometry. This article reports effort to detect high molecular weight structures of cyclodextrin based polyrotaxanes (CD based PRs) by matrixassisted laser desorption ionization mass spectrometry (MALDI-TOF MS). A particular attention was paid to verify the composition of the polyrotaxanes by determination of the number of macrocycles borne by the polyrotaxane and the polyrotaxanes synthetic route. Various matrices including crystalline or ionic liquid ones were screened to optimize the detection. Dimethylformamide as solvent widely used in supramolecular chemistry, but unusual in mass spectrometry, was successfully employed during all analyses. To prove the ability of the optimized MALDI-TOF MS conditions, three different polyrotaxane structures varying by polymer nature, i.e., poly(ethylene oxide) or polydimethylsiloxane and cyclodextrins type i.e. R or γ with or without modifications were evaluated. Finally, we have concluded that 1,1,3,3-tetramethylguanidinium salts of both 2-(4-hydroxyphenylazo)benzoic acid and 2 0 ,4 0 ,6 0-trihydroxyacetophenone, are the most reliable and efficient matrices. These ones afforded the possibility to detect masses of 24804 and 26447 g 3 mol-1 , corresponding to poly[17]-and poly[18]rotaxanes, respectively.

Chemical Physics Letters, Nov 1, 2008

The effect of complexation of a poly[2,7-(9,9-dioctylfluorene-alt-2,7-fluorene)] copolymer into t... more The effect of complexation of a poly[2,7-(9,9-dioctylfluorene-alt-2,7-fluorene)] copolymer into the inner cavity of γ-cyclodextrin on the morphology, the optical and the electrical properties was investigated. The fluorescence spectra of the rotaxane copolymer and of a reference, non ...

European Polymer Journal, Apr 1, 2013

The synthesis of polymeric materials based on monomers from renewable feedstocks is a steadily gr... more The synthesis of polymeric materials based on monomers from renewable feedstocks is a steadily growing field. New aliphatic polyesters derived from the 1,18-(Z)-octadec-9-enedioic acid (D18:1), a high oleic sunflower oil fatty acid derivative, and aliphatic diols of different molecular weight (from 1,3-propanediol to 1,12-dodecanediol) have been synthesized and characterized. The polymerization was undertaken by direct bulk polycondensation of a diacid with a diol, with or without a metal catalyst, leading to viscous liquid to solid semi-crystalline polyesters at room temperature, depending on the diol type. The molecular weights of polyesters ranged between 7000 and 20,000 g mol À1. The main attractive aspects of these polyesters are the renewable biomass origin of the diacid and the presence of double bonds on the polymer backbone (oleic acid derivative) allowing subsequent chemical modifications. The epoxidation of these double bonds was undertaken on the macromolecular chains to induce the photochemical cross-linking of the epoxide functions. Transparent and homogeneous cross-linked films were made by photo-polymerization of the epoxy units with less than 5% of extractible products. Enzymatic degradation of these polyesters (cross-linked) was poor over 8 weeks.

Springer eBooks, Nov 26, 2020

The coupling of surface plasmon resonance imaging (SPRi) with mass spectrometry (MS) offers a ver... more The coupling of surface plasmon resonance imaging (SPRi) with mass spectrometry (MS) offers a very promising multidimensional analysis. This system takes advantage of the two well-established techniques: SPR, which allows for the analysis of biomolecular interactions through the determination of kinetic and thermodynamic constants, and MS, which can characterize biological structures from mass measurements and fragmentation experiments. Here, a protocol for the coupling of SPRi with matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is described using a biochip grafted by antibodies in an array format. Interaction between β-lactoglobulin antibodies and the protein antigen is detected and analyzed by SPRi.

HAL (Le Centre pour la Communication Scientifique Directe), Jul 30, 1999

International audienc

ChemInform, Jan 30, 2007

Macromolecules, Apr 20, 2016

The first radical end-coupling synthesis of polydimethylsiloxane (PDMS)−γ-cyclodextrins (γ-CDs) b... more The first radical end-coupling synthesis of polydimethylsiloxane (PDMS)−γ-cyclodextrins (γ-CDs) based polyrotaxane is reported. Conversely to usual chemical way, the radical process leads to fast both controlled size and structure with minimal side reaction while exhibiting very high conversion rate (w/w, 80%). Pure PDMS−γ-CDs molecular necklaces were successfully isolated by preparative size exclusion chromatography and finely characterized both by 1D/2D/STD 1 H and 13 C NMR and MALDI-TOF mass spectrometry. The observations give clear evidence of the supramolecular assembly synthesis where the filling ratio (γ-CD/monomer unit) of PDMS chains is as high as 40% of γ-CDs. Combination of such radical-based coupling supported by detailed analytical characterizations appears at the forefront of a fast, suitable, and easily amenable scaling-up CDs-based polyrotaxane synthesis process.

Journal of Polymers and The Environment, Oct 29, 2015

This work compares the biodegradability of polyesters produced by an esterification reaction betw... more This work compares the biodegradability of polyesters produced by an esterification reaction between glycerol and oleic di-acid (D 18:1) issued from green chemical pathways, via either classical thermo-chemical methods, or an enzymatic method using the immobilized lipase of Candida antartica B (Novozym 435). An elastomeric polymer synthesized by enzymatic catalysis is more biodegradable than an elastomeric thermo-chemical polyester synthesized by

ACS Macro Letters, Apr 10, 2012

An easy and fast approach based on electrospray mass spectrometry (ESI-MS) was developed to provi... more An easy and fast approach based on electrospray mass spectrometry (ESI-MS) was developed to provide a detailed characterization of a mixture containing polydisperse cyclodextrin-based polyrotaxane (CDbased PR). Here, method gave access to usual data such the weight-average molecular weight, the number-average molecular weight and the polydispersity index, but also to more specific features as the average number of CDs threaded and the average threading degree. Moreover, the nature and the average number of groups grafted per CD, such as sulfate or silyl groups, can be accurately determinate. This ESI-MS approach advantageously complements the widely used NMR and SEC methods and, thereby, constituting a milestone in the actual MS bottleneck regarding the analysis of polydisperse supramolecular assemblies.

Faraday Discussions, 2018

Macromolecular Chemistry and Physics, Apr 1, 2001

ABSTRACT Nitroxide- and bromo-terminated polystyrenes resulting from “living” free radical polyme... more ABSTRACT Nitroxide- and bromo-terminated polystyrenes resulting from “living” free radical polymerization processes have been “functionalized” by a combination reaction with tetraphenylethane based derivatives i.e. 1,1,2,2-tetraphenyl-1,2-bis(trimethylsilyloxy)ethane. The substitution of the terminal moiety by diphenylmethyl groups has been characterized by 1H, 13C and 29Si NMR, ESI and MALDI-TOF mass spectrometry.