Phosphonate-Functionalized Polycarbonates Synthesis through Ring-Opening Polymerization and Alternative Approaches.

Well-defined phosphonate-functionalized polycarbonate with low dispersity (Ð = 1.22) was synthesized using organocatalyzed ring-opening polymerization (ROP) of novel phosphonate-based cyclic monomers. Copolymerization was also performed to access different structures of phosphonate-containing polycarbonates (PC). Furthermore, phosphonate-functionalized PC was successfully synthesized using a combination of ROP and post-modification reaction.

New Crosslinked Single-Ion Silica-PEO Hybrid Electrolytes.

New single-ion hybrid electrolytes have been synthetized via an original and simple synthetic approach combining Michael addition, epoxidation, and sol-gel polycondensation. We designed an organic PEO network as a matrix for the lithium transport, mechanically reinforced thanks to crosslinking inorganic (SiO1.5) sites, while highly delocalized anions based on lithium vinyl sulfonyl(trifluoromethane sulfonyl)imide (VSTFSILi) were grafted onto the inorganic sites to produce single-ion hybrid electrolytes (HySI). The influence of the electrolyte composition in terms of the inorganic/organic ratio and the grafted VSTFSILi content on the local structural organization, the thermal, mechanical, and ionic transport properties (ionic conductivity, transference number) are studied by a variety of techniques including SAXS, DSC, rheometry, and electrochemical impedance spectroscopy. SAXS measurements at 25 °C and 60 °C reveal that HySI electrolyte films display locally a spatial phase separation with domains composed of PEO rich phase and silica/VSTFSILi clusters. The size of these clusters increases with the silica and VSTFSILi content. A maximum ionic conductivity of 2.1 × 10-5 S·cm-1 at 80 °C has been obtained with HySI having an EO/Li ratio of 20. The Li+ ion transfer number of HySI electrolytes is high, as expected for a single-ion electrolyte, and comprises between 0.80 and 0.92.

Photolabile Well-Defined Polystyrene Grafted on Silica Nanoparticle via Nitroxide-Mediated Polymerization (NMP).

Herein, the synthesis of a novel nitroxide-mediated polymerization (NMP) initiator bearing a photolabile ortho-nitrobenzyl (oNB) group allowing surface-initiated NMP preparation of well-defined photoresponsive polystyrene grafted on silica nanoparticles is described. The photocleavable and photoresponsive properties of the prepared materials are demonstrated using small angle X-ray scattering (SAXS) characterization.

Poly(ethylene oxide) grafted silica nanoparticles: efficient routes of synthesis with associated colloidal stability.

In this study, poly(ethylene oxide) monomethyl ether (MPEO) of molecular weight of 5000, 10 000, and 20 000 g mol-1 were grafted onto colloidal silica nanoparticles (NPs) of a 27.6 nm diameter using two distinct "grafting to" processes. The first method was based on the coupling reaction of epoxide-end capped MPEO with amine-functionalized silica NPs, while the second method was based on the condensation of triethoxysilane-terminated MPEO onto the unmodified silica NPs. The influence of PEO molecular weight, grafting process and grafting conditions (temperature, reactant concentration, reaction time) on the PEO grafting density was fully investigated. Thermogravimetric analysis (TGA) was used to determine the grafting density which ranged from 0.12 chains per nm2 using the first approach to 1.02 chains per nm2 when using the second approach. 29Si CP/MAS NMR characterization indirectly revealed that above a grafting density value of 0.3 PEO chains per nm2, a dendri-graft PEO network was built around the silica surface which was composed of PEO chains directly anchored to the silica surface and those grafted to silica NPs by intermediate of >CH-O-Si- bonds. The colloidal stability of the particles during different steps of the grafting process was characterized by small-angle X-ray scattering (SAXS). We have found that the colloidal systems are stable whatever the achieved grafting density due to the strong repulsions between the NPs, with the strength of repulsion increasing with the molecular weight of the grafted MPEO chains.

Adduction of ammonium to polylactides to modify their dissociation behavior in collision-induced dissociation.

RATIONALE: The goal of this work was to modify the dissociation pathways of polylactide (PLA) holding benzyl and hydroxyl terminations, in order to circumvent coincidence of product ions generated during collisional activation of sodiated chains, which prevented their reliable characterization. METHODS: Benzyl-, hydroxyl-terminated PLAs were ionized as ammonium adducts in positive ion mode electrospray and subjected to collision-induced dissociation (CID). Tandem mass spectrometry (MS/MS) experiments were conducted in a quadrupole time-of-flight (QTOF) instrument for safe assignment of product ions based on their elemental composition derived from accurate mass measurements. RESULTS: Adduction of ammonium to PLAs was found to induce chain fragmentation via charge-assisted processes, in great contrast to the charge-remote mechanisms experienced by sodiated molecules. The main reaction produced ions containing the ω termination only, hence allowing straightforward end-group determination. Other minor pathways were studied in detail to establish dissociation rules for ammoniated PLAs. Some reactions were found to be end-group specific, highlighting the higher reactivity of ammonium than alkali ion adducts. CONCLUSIONS: Changing the usually employed sodium-cationizing agent to ammonium was shown to induce dramatic changes in the CID behavior of PLAs. This was a simple and efficient approach to address issues encountered for end-group analysis of the particular PLA studied here.

Translocation across a self-healing block copolymer membrane.

Herein, a membrane prepared from the self-assembly of poly(styrene-co-acrylonitrile)-b-poly(ethylene oxide)-b-poly(styrene-co-acrylonitrile) micelles is found to exhibit translocation of nano-objects dispersed in aqueous solution. With the water flow as a driving force, temporary pores are created in between the micelles to facilitate the passage of nano-objects. These temporary pores close afterwards through a self-healing mechanism. As main results, polystyrene and silica nanoparticles exhibited a selective translocation directly influenced by their size and applied pressure.

Separation of parent homopolymers from polystyrene and poly(ethylene oxide) based block copolymers by liquid chromatography under limiting conditions of desorption-3. Study of barrier efficiency according to block copolymers' chemical composition.

Liquid Chromatography under Limiting Conditions of Desorption (LC LCD) is a powerful separation tool for multicomponent polymer systems. This technique is based on a barrier effect of an appropriate solvent, which is injected in front of the sample, and which decelerates the elution of selected macromolecules. In this study, the barrier effects have been evaluated for triblock copolymers polystyrene-b-poly(ethylene oxide)-b-polystyrene (PS-b-PEO-b-PS) according to the content of polystyrene (wt% PS) and PEO-block molar mass. PS-b-PEO-b-PS samples were prepared by Atom Transfer Radical Polymerization (ATRP). The presence of respective parent homopolymers was investigated by applying optimized LC LCD conditions. It was found that the barrier composition largely affects the efficiency of separation and it ought to be adjusted for particular composition range of block copolymers.

Stacking and Colloidal Stability of CdSe Nanoplatelets.

Colloidal CdSe nanoplatelets with monolayer control over their thickness can now be synthesized in solution and display interesting optical properties. From a fundamental point of view, the self-assembly of CdSe nanoplatelets can impact their optical properties through short-range interactions, and achieving control over their dispersion state in solution is of major relevance. The related issue of colloidal stability is important from an applicative standpoint in the perspective of the processing of these materials. Using UV-vis spectroscopy, we assess the colloidal stability of dispersions of CdSe nanoplatelets at different nanoparticle and ligand (oleic acid) concentrations. We unravel an optimum in oleic acid concentration for colloidal stability and show that even moderately concentrated dispersions flocculate on a time scale ranging from minutes to hours. Small-angle X-ray scattering shows that the precipitation proceeds through a face-to-face stacking of the nanoplatelets due to long-ranged van der Waals attraction. To address this issue, we coated the platelets with a carboxylic acid-terminated polystyrene, thus achieving colloidal stability while retaining the optical properties of the platelets.

Up to 100% Improvement in Dynamic Nuclear Polarization Solid-State NMR Sensitivity Enhancement of Polymers by Removing Oxygen.

High-field dynamic nuclear polarization (DNP) has emerged as a powerful technique for improving the sensitivity of solid-state NMR (SSNMR), yielding significant sensitivity enhancements for a variety of samples, including polymers. Overall, depending upon the type of polymer, the molecular weight, and the DNP sample preparation method, sensitivity enhancements between 5 and 40 have been reported. These promising enhancements remain, however, far from the theoretical maximum (>1000). Crucial to the success of DNP SSNMR is the DNP signal enhancement (εDNP ), which is the ratio of the NMR signal intensities with and without DNP. It is shown here that, for polymers exhibiting high affinity toward molecular oxygen (e.g., polystyrene), removing part of the absorbed (paramagnetic) oxygen from the solid-state samples available as powders (instead of dissolved or dispersed in a solvent) increases proton nuclear relaxation times and εDNP, hereby providing up to a two-fold sensitivity increase (i.e., a four-fold reduction in experimental time).

Separation of parent homopolymers from poly(ethylene oxide) and polystyrene-based block copolymers by liquid chromatography under limiting conditions of desorption--1. Determination of the suitable molar mass range and optimization of chromatographic conditions.

We studied molar mass limits for the LC LCD separation of parent polystyrene (PS) and poly(ethylene oxide) (PEO) homopolymers from PEO/PS based block copolymers and we identified optimized chromatographic conditions. Time delays between barriers and sample injections were 0-2-3'10. Eluent was composed of dimethylformamide (DMF) 40 wt.% and 1-chlorobutane (CLB) 60 wt.%; Barrier 1 (B1), which retained block copolymer, was composed of 100 wt.% CLB and Barrier 2 (B2), which retained PEO, was a mixture of DMF and CLB, which proportions were adjusted to studied block copolymers. With B2 composed of DMF 23 wt.% and CLB 77 wt.%, we obtained successful separation of PS23K-b-PEO35K-b-PS23K (56.5 wt.% of PS, the subscripts indicate the molar mass in kg mol(-1) of each polymer part in the block copolymer) from its parent homopolymers. With B2 adjusted to DMF 30 wt.% and CLB 70 wt.%, PS2.3K-b-PEO3.1K (42.6 wt.% of PS) was also efficiently separated from its parent homopolymers.

Enhancing Properties of Anionic Poly(ionic liquid)s with 1,2,3-Triazolium Counter Cations.

A series of anionic poly(ionic liquid)s with 1,2,3-triazolium counter cations are prepared by cation exchange between tailormade 1,3,4-trialkylated-1,2,3-triazolium iodides and a polystyrene derivative having pendant potassium bis(trifluoromethylsulfonyl)imide groups. The physical and ion-conducting properties of the resulting materials are compared to the parent potassium-containing polyelectrolyte based on 1H NMR, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and broadband dielectric spectroscopy (BDS) measurements. Substitution of the potassium counter cation by 1,2,3-triazolium charge carriers affords polyelectrolytes with improved processability (broader solubility and removal of the crystalline behavior) as well as a substantial increase in anhydrous ionic conductivity.

Observing Apparent Nonuniform Sensitivity Enhancements in Dynamic Nuclear Polarization Solid-State NMR Spectra of Polymers.

High-field dynamic nuclear polarization (DNP) may enhance the sensitivity of solid-state NMR experiments on a wide range of systems, including synthetic polymers, owing to the transfer of electron spin polarization from radicals to nuclei upon microwave irradiation (usually at cryogenic temperatures). Provided that the radicals are homogeneously dispersed in the sample, a uniform DNP enhancement is expected for all the signals in the 13C cross-polarization magic angle spinning (CPMAS) spectrum. Here, we show that, in the case of methyl group containing polymers, a change in the cross-polarization (CP) dynamics induced by the moderate increase in sample temperature due to microwave irradiation may lead to the observation of apparent nonuniform enhancements in the DNP-enhanced 13C CPMAS spectra. This peculiar behavior should be accounted for when measuring 13C CP DNP enhancements on polymer materials, especially for heterogeneous polymer samples (for which truly nonuniform DNP enhancements could potentially be detected), or when quantitative results are sought.

End-group cleavage in MALDI of ATRP-made polystyrene: a silver-catalyzed reaction during sample preparation.

Cleavage of the labile halide termination upon matrix-assisted laser desorption/ionization (MALDI) has always been reported as a major concern in mass analysis of polystyrene prepared by atom transfer radical polymerization (ATRP). By studying this issue using nuclear magnetic resonance (NMR) and electrospray ionization-mass spectrometry, we evidence here that the ionization step is not involved in this deleterious process. Instead, removal of the halogen was shown to readily occur upon interaction of the silver salt (AgTFA) used as the cationizing agent in mass spectrometry, either in solution or in the solid-state when performing solvent-free sample preparation. In solution, this silver-induced reaction mostly consists of a nucleophilic substitution, leading to polystyrene molecules holding different terminations, depending on relative nucleophilicity of species present in the liquid-phase solution composition. In chloroform supplemented with AgTFA, trifluoroacetate-terminated PS were evidenced in ESI-MS spectra but experienced end-group cleavage in MALDI. In contrast, the major methoxy-terminated PS macromolecules formed when the silver-catalyzed nucleophilic substitution was performed in methanol were generated as intact gas-phase ions using both ionization techniques. This controlled and fast modification could hence be advantageously used as a rapid sample pretreatment for safe MALDI mass analysis of ATRP-made polystyrene.

Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries.

Electrochemical energy storage is one of the main societal challenges of this century. The performances of classical lithium-ion technology based on liquid electrolytes have made great advances in the past two decades, but the intrinsic instability of liquid electrolytes results in safety issues. Solid polymer electrolytes would be a perfect solution to those safety issues, miniaturization and enhancement of energy density. However, as in liquids, the fraction of charge carried by lithium ions is small (<20%), limiting the power performances. Solid polymer electrolytes operate at 80 °C, resulting in poor mechanical properties and a limited electrochemical stability window. Here we describe a multifunctional single-ion polymer electrolyte based on polyanionic block copolymers comprising polystyrene segments. It overcomes most of the above limitations, with a lithium-ion transport number close to unity, excellent mechanical properties and an electrochemical stability window spanning 5 V versus Li(+)/Li. A prototype battery using this polyelectrolyte outperforms a conventional battery based on a polymer electrolyte.

Immobilization of styrene-substituted 1,3,4-oxadiazoles into thermoreversible luminescent organogels and their unexpected photocatalyzed rearrangement.

A series of styrene-substituted 1,3,4-oxadiazoles has been designed and investigated as new low-molecular-weight organogelators. The photophysical properties of the resulting thermoreversible organogels have been characterized by UV/Vis absorption and luminescence spectroscopies. Surprisingly, the gelation ability of the oxadiazoles depended on the presence of the styrene moiety as gelation of the investigated oxadiazoles did not take place in its absence. Gel formation was accompanied by a modification of the fluorescence of the organogelators in the supramolecular state. UV irradiation of the gels caused a rearrangement of the immobilized 1,3,4-oxadiazoles bearing a styrene moiety by a tandem [4+2] and [3+2] cascade reaction. Structure modification and color change of the gels were also evident upon irradiation.

Dynamic interactive membranes with pressure-driven tunable porosity and self-healing ability.

When pressure is applied to dynamic interactive membranes consisting of micelles composed of a triblock copolymer, their morphologies can be fine-tuned. Membranes with a range of porosities are accessible which can regulate and thereby control filtration performance and also display effective autonomous healing.

Successful MALDI-MS analysis of synthetic polymers with labile end-groups: the case of nitroxide-mediated polymerization using the MAMA-SG1 alkoxyamine.

A sample pretreatment was evaluated to enable the production of intact cationic species of synthetic polymers holding a labile end-group using matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. More specifically, polymers obtained by nitroxide-mediated polymerization involving the MAMA-SG1 alkoxyamine were stirred for a few hours in trifluoroacetic acid (TFA) to induce the substitution of a tert-butyl group on the nitrogen of nitroxide end-group by a hydrogen atom. Nuclear magnetic resonance, electrospray ionization tandem mass spectrometry, and theoretical calculations were combined to scrutinize this sample pretreatment from both mechanistic and energetic points of view. The substitution reaction was found to increase the dissociation energy of the fragile C-ON bond to a sufficient extent to prevent this bond to be spontaneously cleaved during MALDI analysis. This TFA treatment is shown to be very efficient regardless of the nature of the polymer, as evidenced by reliable MALDI mass spectrometric data obtained for poly(ethylene oxide), polystyrene and poly(butylacrylate).

Tandem mass spectrometry of electrosprayed polyhedral oligomeric silsesquioxane compounds with different substituents.

RATIONALE: Polyhedral oligomeric silsesquioxanes (POSSs), defined as [RSiO(3/2) ](n) with R designating an organic substituent, were considered here as models of highly cross-linked polysiloxanes, to be further used as references in tandem mass spectrometric characterization of plasma polymers of hexamethyldisiloxane, expected to be composed of organic polydimethylsiloxane (PDMS) and inorganic (SiO(x) ) silica-based parts. The collision-induced dissociation (CID) behavior of [RSiO(3/2) ](8) compounds was then studied as a function of the R substituent. METHODS: POSS compounds were produced in the gas phase as ammonium adducts and the product ions generated upon CID, amongst which was the protonated precursor, were accurately mass measured in an orthogonal acceleration time-of-flight mass analyzer. RESULTS: The presence of eight propylamine substituents was shown to induce sequential dehydration of the protonated precursor, ultimately leading to a complete unfolding of the POSS cage. Similar opening of the octahedron structure in the protonated molecule substituted with OSi(CH(3) )(3) , OSiH(CH(3) )(2) or OH (formed upon methanolysis of dimethylsiloxy substituents) was proposed to account for the product ions generated during their CID. Sequential charge-remote transfers of a methyl group (and of H in the case of dimethylsiloxy substituents) from one substituent group to a neighboring one was shown to lead to a linear co-oligomeric chain composed of randomly distributed siloxy-based monomers. CONCLUSIONS: All the peaks observed in CID could be accounted for by applying dissociation reactions typically occurring in protonated polysiloxane-like oligomers. The large number of product ions observed in MS/MS was found to result from the variety of possible structural rearrangements, producing numerous linear isomeric forms of the dissociating species.

Improved compositional analysis of block copolymers using diffusion ordered NMR spectroscopy.

Block copolymers constitute a fascinating class of polymeric materials that are used in a broad range of applications. The performance of these materials is highly coupled to the physical and chemical properties of the constituting block copolymers. Traditionally, the composition of block copolymers is obtained by 1H NMR spectroscopy on purified copolymer fractions. Specifically, the integrals of a properly selected set of 1H resonances are compared and used to infer the number average molecular weight (M(n)) of one of the block from the (typically known) M(n) value of the other. As a corollary, compositional determinations achieved on imperfectly purified samples lead to serious errors, especially when isolation of the block copolymer from the initial macro initiator is tedious. This investigation shows that Diffusion Ordered NMR Spectroscopy (DOSY) can be used to provide a way to assess the advancement degree of the copolymerization purification/reaction, in order to optimize it and hence contribute to an improved compositional analysis of the resulting copolymer. To this purpose, a series of amphiphilic polystyrene-b-poly(ethylene oxide) block copolymers, obtained by controlled free-radical nitroxide mediated polymerization, were analyzed and it is shown that, under proper experimental conditions, DOSY allows for an improved compositional analysis of these block copolymers.

Molecular weight determination of block copolymers by pulsed gradient spin echo NMR.

Matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS) is the technique of choice to achieve molecular weight data for synthetic polymers. Because the success of a MALDI-MS analysis critically depends on a proper matrix and cation selection, which in turn relates closely to the polymer chemical nature and size, prior estimation of the polymer size range strongly helps in rationalizing MALDI sample preparation. We recently showed how pulsed gradient spin echo (PGSE) nuclear magnetic resonance could be used as an advantageous alternative to size exclusion chromatography, to rationalize MALDI sample preparation and confidently interpret MALDI mass spectra for homopolymers. Our aim here is to extend this methodology to the demanding case of amphiphilic block copolymers, for which obtaining prior estimates on the Mw values appears as an even more stringent prerequisite. Specifically, by studying poly(ethylene oxide) polystyrene block copolymers of distinct molecular weights and relative block weight fractions, we show how PGSE data can be used to derive the block Mw values. In contrast to homopolymers, such determination requires not only properly recorded calibration curves for each of the polymers constituting the block copolymers but also an appropriate hydrodynamic model to correctly interpret the diffusion data.