Flame Retardancy of Short Flax Fibers Modified by Radiation-Induced Grafting of Phosphonated Monomers: Comparison between Pre- and Simultaneous Irradiation Grafting.

Short flax fibers have been modified by radiation-induced grafting using methacrylate monomers containing phosphorus to give them a flame-retardant character. Two methodologies, namely pre-irradiation and simultaneous irradiation grafting, were examined. Certain parameters, notably the dose and the irradiation source (e-Beam and γ rays), were evaluated. The grafting efficiency, in terms of phosphorus content (mass percentage), was measured by X-ray fluorescence spectrometry (XRF). Using simultaneous irradiation, 2.39 wt% phosphorus could be obtained from 10 kGy, compared to 100 kGy in pre-irradiation. Furthermore, for similar phosphorus levels, the location of the grafted polymer chains was different for the two methodologies. The effect of phosphorus content on thermal properties and fire behavior was evaluated on a microscopic scale using a pyrolytic flow combustion calorimeter (PCFC) and on a laboratory scale using a cone calorimeter. It was then pointed out that flammability was linked to the phosphorus content and likely its location, which is associated with the radiation-induced grafting methodology, showing that the grafting conditions influence the final fire properties. Simultaneous irradiation, thus, proved to be more interesting in terms of efficiency and final properties.

Conception and Evaluation of a Library of Cleavable Mass Tags for Digital Polymers Sequencing.

A library of phosphoramidite monomers containing a main-chain cleavable alkoxyamine and a side-chain substituent of variable molar mass (i.e. mass tag) was prepared in this work. These monomers can be used in automated solid-phase phosphoramidite chemistry and therefore incorporated periodically as spacers inside digitally-encoded poly(phosphodiester) chains. Consequently, the formed polymers contain tagged cleavable sites that guide their fragmentation in mass spectrometry sequencing and enhance their digital readability. The spacers were all prepared via a seven steps synthetic procedure. They were afterwards tested for the synthesis and sequencing of model digital polymers. Uniform digitally-encoded polymers were obtained as major species in all cases, even though some minor defects were sometimes detected. Furthermore, the polymers were decoded in pseudo-MS3 conditions, thus confirming the reliability and versatility of the spacers library.

Thionolactone as a Resin Additive to Prepare (Bio)degradable 3D Objects via VAT Photopolymerization.

Three-dimensional (3D) printing and especially VAT photopolymerization leads to cross-linked materials with high thermal, chemical, and mechanical stability. Nevertheless, these properties are incompatible with requirements of degradability and re/upcyclability. We show here that thionolactone and in particular dibenzo[c,e]-oxepane-5-thione (DOT) can be used as an additive (2 wt %) to acrylate-based resins to introduce weak bonds into the network via a radical ring-opening polymerization process. The low amount of additive makes it possible to modify the printability of the resin only slightly, keep its resolution intact, and maintain the mechanical properties of the 3D object. The resin with additive was used in UV microfabrication and two-photon stereolithography setups and commercial 3D printers. The fabricated objects were shown to degrade in basic solvent as well in a homemade compost. The rate of degradation is nonetheless dependent on the size of the object. This feature was used to prepare 3D objects with support structures that could be easily solubilized.

Precise Alkoxyamine Design to Enable Automated Tandem Mass Spectrometry Sequencing of Digital Poly(phosphodiester)s.

A major step towards reliable reading of information coded in the sequence of long poly(phosphodiester)s was previously achieved by introducing an alkoxyamine spacer between information sub-segments. However, MS/MS decoding had to be performed manually to safely identify useful fragments of low abundance compared to side-products from the amide-based alkoxyamine used. Here, alternative alkoxyamines were designed to prevent side-reactions and enable automated MS/MS sequencing. Different styryl-TEMPO spacers were prepared to increase radical delocalization and stiffness of the structure. Their dissociation behavior was investigated by EPR and best results were obtained with spacers containing in-chain benzyl ring, with no side-reaction during synthesis or sequencing. Automated decoding of these polymers was performed using the MS-DECODER software, which interprets fragmentation data recorded for each sub-segment and re-align them in their original order based on location tags.

Selective Bond Cleavage in Informational Poly(Alkoxyamine Phosphodiester)s.

The collision-induced dissociation (CID) of sequence-defined poly(alkoxyamine phosphodiester)s is studied by electrospray ionization mass spectrometry. These informational polymers are synthesized using three different nitroxide building blocks, namely proxyl-, SG1-, and TEMPO-derivatives. For a polymer containing TEMPO- and SG1-based main chain alkoxyamines, it is found that both types of alkoxyamines break in CID tandem mass spectrometry (MS/MS). However, SG1-sites are preferentially cleaved and this predominance can be increased by reducing collision energy, even though selective bond fragmentation is not observed. On the other hand, for a polymer containing proxyl- and SG1-alkoxyamines, selective bond cleavage is observed at all studied collision energies. The SG1-alkoxyamines can be first cleaved in MS/MS conditions and secondly the proxyl-alkoxyamines in pseudo-MS3 conditions. These results open up interesting new avenues for the design of readable, erasable or programmable informational polymers.

Light-Sensitive Alkoxyamines as Versatile Spatially- and Temporally- Controlled Precursors of Alkyl Radicals and Nitroxides.

The use of UV/visible light irradiation as a means to initiate organic syntheses is increasingly attractive due to the high spatial and temporal control conferred by photochemical processes. The aim of this work is thus to demonstrate that alkoxyamines bearing a chromophore on the alkyl moiety can provide a photoprotecting group for the sensitive nitroxide functionality, that is known to degrade through redox processes. The dissociation of various photosensitive alkoxyamines was studied from 223 to 298 K under UV/visible irradiation, depending on the nature of the chromophore. In each case a rapid (typically in less than 1 h) and near-quantitative dissociation was observed. As an illustration of the interest of this approach, a pyrene-based alkoxyamine was employed for the spatially controlled coupling of polymer chains onto Si wafers to produce micropatterned surfaces.

New Amino-Acid-Based ß-Phosphorylated Nitroxides for Probing Acidic pH in Biological Systems by EPR Spectroscopy.

There is increasing interest in measuring pH in biological samples by using nitroxides with pH-dependent electron paramagnetic resonance (EPR) spectra. Aiming to improve the spectral sensitivity (ΔaX ) of these probes (i.e., the difference between the EPR hyperfine splitting (hfs) in their protonated and unprotonated forms), we characterized a series of novel linear α-carboxy, α'-diethoxyphosphoryl nitroxides constructed on an amino acid core and featuring an (α or α')-C-H bond. In buffer, the three main hfs (aN , aH , and aP ) of their EPR spectra vary reversibly with pH and, from aP or aH titration curves, a two- to fourfold increase in sensitivity was achieved compared to reference imidazoline or imidazolidine nitroxides. The crystallized carboxylate 10 b (pKa ≈3.6), which demonstrated low cytotoxicity and good resistance to bioreduction, was applied to probe stomach acidity in rats. The results pave the way to a novel generation of highly sensitive EPR pH markers.

Polymerization Initiated by Organic Electron Donors.

Polymerization reactions with organic electron donors (OED) as initiators are presented herein. The metal-free polymerization of various activated alkene and cyclic ester monomers was performed in short reaction times, under mild conditions, with small amounts of organic reducing agents, and without the need for co-initiators or activation by photochemical, electrochemical, or other methods. Hence, OED initiators enabled the development of an efficient, rapid, room-temperature process that meets the technical standards expected for industrial processes, such as energy savings, cost-effectiveness and safety. Mechanistic investigations support an electron-transfer initiation pathway that leads to the reduction of the monomer.

UV-Induced Micropatterning of Complex Functional Surfaces by Photopolymerization Controlled by Alkoxyamines.

We report on the use of an alkoxyamine (AA) for fabrication of functional micropatterns with complex structures by UV mask lithography. The living character of the polymer surface and the vertical spatial control of the repolymerization reaction from few tens of nanometers to few micrometers were demonstrated. The impact of the main parameters governing the controlled polymerization and the reinitiation process activated by light or heat was investigated. Micropatterning is shown to be a powerful method to investigate the physicochemical molecular phenomena. It is possible to control the polymer microstructure thickness from few tens of nanometers to few micrometers. In the last section, some applications are provided showing the potential of the AA for generating covalently bonded hydrophilic/hydrophobic micropatterns or luminescent surfaces. This demonstrates the high versatility and interest of this route.

On the synthesis, characterization and reactivity of N-heteroaryl-boryl radicals, a new radical class based on five-membered ring ligands.

The synthesis and physical characterization of a new class of N-heterocycle-boryl radicals is presented, based on five membered ring ligands with a N(sp(2) ) complexation site. These pyrazole-boranes and pyrazaboles exhibit a low bond dissociation energy (BDE; BH) and accordingly excellent hydrogen transfer properties. Most importantly, a high modulation of the BDE(BH) by the fine tuning of the N-heterocyclic ligand was obtained in this series and could be correlated with the spin density on the boron atom of the corresponding radical. The reactivity of the latter for small molecule chemistry has been studied through the determination of several reaction rate constants corresponding to addition to alkenes and alkynes, addition to O2 , oxidation by iodonium salts and halogen abstraction from alkyl halides. Two selected applications of N-heterocycle-boryl radicals are also proposed herein, for radical polymerization and for radical dehalogenation reactions.

Online headspace monitoring of volatile organic compounds using proton transfer reaction-mass spectrometry: Application to the multiphase atmospheric fate of 2,4-hexadienedial.

Chemical processes in clouds have been suggested to contribute significantly to the mass of organic aerosol particles in the atmosphere. Experimental and theoretical evidence suggest that organic mass production in clouds can be substantial and depends on the concentration of organic precursor compounds available in the gas phase. The present study aims at studying the aqueous phase reactivity of one of these overlooked precursors, i.e. 2,4-hexadienedial, an important and toxic intermediate in the atmospheric oxidation of aromatic species. Cautious synthesis and purification of 2,4-hexadienedial was performed. Its effective Henry's law constant was measured using a new simple and fast method based on online flow-injection analysis. The reactivity of 2,4-hexadienedial in the aqueous phase relevant to atmospheric conditions was studied, including hydrate formation, photolysis, ∙OH- and SO4∙--oxidation as well as reaction with NH3. The results revealed a low hydration constant compared to other dicarbonyls (Khyd1 = 7 × 10-2) and no dihydrate formation, indicating in an intermediate solubility (KH = 1.0 × 104 M atm-1) and high absorption cross sections (σ278nm > 10-16 cm2 molecule-1). Compared to its gas phase photolysis, its aqueous phase photolysis showed low quantum yields (Φ290-380nm = 0.9 %), and a significant red shift of the absorbance maximum, leading to a fast aqueous photolysis kinetics (Jaq,atm = 8.7 × 10-5 s-1) under atmospheric solar radiation, but no triplet state formation was detected. Radical oxidation experiments revealed extremely rapid oxidation kinetics (k∙OH = 1.10 × 1010 M-1 s-1 and kSO4∙- = 1.4 × 109 M-1 s-1) driven by fast addition of the radicals to the unsaturated bonds. In contrast, the reaction with aqueous NH3 (kNH3 = 2.6 × 10-3 M-1 s-1) was found slower than glyoxal and 2-butenedial, likely due to the hyperconjugation of 2,4-hexadienedial. Using these new data complemented with assumed aqueous phase kinetics (for NO3, 3C* and 1O2 reactions) and previous gas-phase kinetic ones, the multiphase atmospheric fate of 2,4-hexadienedial was established under atmospheric conditions reported from previous field measurements and models. The results revealed a short day lifetime (∼1 h) and a long night lifetime (>12 h). It was shown that daytime atmospheric chemistry of 2,4-hexadienedial can be influenced by aqueous-phase reactivity during cloud events, up to ∼50 % under thick cloud conditions (Liquid Water Content >2000 g/m3), indicating that even a compound of intermediate solubility can be strongly affected by condensed-phase reactivity. Besides its fast aqueous phase reactivity towards ∙OH and photolysis, its daytime condensed-phase reactivity may be driven by reactions with dissolved triplet states (3C*), up to 35 %, highlighting the need to study further the kinetics, the nature and concentrations of dissolved 3C* under various atmospheric conditions. In addition, the molecular properties and atmospheric behavior of 2,4-hexadienedial were found different from those of glyoxal and 2-butenedial, highlighting the need for detailed atmospheric reactivity studies of polyfunctional compounds, in particular unsaturated compounds.

A fast and efficient method for the analysis of α-dicarbonyl compounds in aqueous solutions: Development and application.

Among the highly oxygenated species formed in situ in the atmosphere, α-dicarbonyl compounds are the most reactive species, thus contributing to the formation of secondary organic aerosols that affect both air quality and climate. They are ubiquitous in the atmosphere and are easily transferred to the atmospheric aqueous phase due to their high solubility. In addition, α-dicarbonyl compounds are toxic compounds found in food in biochemistry studies as they can be produced endogenously through various pathways and exogenously through the Maillard reaction. In this work, we take advantage of the high reactivity of α-dicarbonyl compounds in alkaline solutions (intramolecular Cannizzaro reaction) to develop an analytical method based on high performance ion chromatography. This fast and efficient method is suitable for glyoxal, methylglyoxal and phenylglyoxal which are detected as glycolate, lactate and mandelate anions respectively, with 100% conversion at pH > 12 and room temperature for exposure times to hydroxide ranging from 5 min to 4 h. Diacetyl is detected as 2,4-dihydroxy-2,4-dimethyl-5-oxohexanoate due to a base-catalysed aldol reaction that occurs before the Cannizzaro reaction. The analytical method is successfully applied to monitor glyoxal consumption during aqueous phase HO∙-oxidation, an atmospherically relevant reaction using concentrations that can be observed in fog and cloud water. The method also reveals potential analytical artifacts that can occur in the use of ion chromatography for α-hydroxy carboxylates measurements in complex matrices due to α-dicarbonyl conversion during the analysis time. An estimation of the artifact is given for each of the studied α-hydroxy carboxylates. Other polyfunctional and pH-sensitive compounds that are potentially present in environmental samples (such as nitrooxycarbonyls) can also be converted into α-hydroxy carboxylates and/or nitrite ions within the HPIC run. This shows the need for complementary analytical measurements when complex matrices are studied.

Spin-trapping evidence for the formation of alkyl, alkoxyl, and alkylperoxyl radicals in the reactions of dialkylzincs with oxygen.

The reactions of dialkylzincs (Me(2)Zn, Et(2)Zn, and nBu(2)Zn) with oxygen have been investigated by EPR spectroscopy using spin-trapping techniques. The use of 5-diethoxyphosphoryl-5-methyl-1-pyrrroline N-oxide (DEPMPO) as a spin-trap has allowed the involvement of alkyl, alkylperoxyl, and alkoxyl radicals in this process to be probed for the first time. The relative ratio of the corresponding spin-adducts depends strongly on the nature of the R group, which controls the C-Zn bond dissociation enthalpy, and on the experimental conditions (excess of spin-trap compared with R(2)Zn and vice versa). The results have demonstrated that Et(2)Zn and, to a lesser extent, nBu(2)Zn are much better traps for oxygen-centered species than Me(2)Zn. When the dialkylzincs were used in excess with respect to the spin-trap, the concentration of the oxygen-centered radical adducts of DEPMPO was much lower for Et(2)Zn and nBu(2)Zn than for Me(2)Zn. A detailed reaction mechanism is discussed and C-Zn, O-Zn, and O-O bond dissociation enthalpies for the proposed reaction intermediates were calculated at the UB3LYP/6-311++G(3df,3pd)//UB3LYP/6-31G(d,p) level of theory to support the rationale.

CyDEPMPOs: a class of stable cyclic DEPMPO derivatives with improved properties as mechanistic markers of stereoselective hydroxyl radical adduct formation in biological systems.

The cis/trans diastereoisomeric composition of hydroxyl radical adducts to chiral cyclic nitrones can be used to approach mechanisms of free radical formation in biological systems. Such determination is greatly simplified when both diastereoisomers have ESR spectra with at least two non-overlapping lines. To achieve this prerequisite, a series of DEPMPO-derived spin traps bearing one unsubstituted or alkyl-substituted 2-oxo-1,3,2-dioxaphosphorinane ring were synthesized and their structures were confirmed by X-ray diffraction, (1)H, (13)C and (31)P NMR. These CyDEPMPOs nitrones showed variable lipophilicities and LD(50) values on murine fibroblasts compatible with a safe use in biological spin trapping. All CyDEPMPOs formed persistent spin adducts with a series of free radicals, including superoxide and hydroxyl (i.e., CyDEPMPOs-OH) and the in vitro half-life times of these two latter were at least as extended as those of parent DEPMPO. Using four methods of CyDEPMPOs-OH formation, the cis-CyDEPMPOs-OH percentage was found significantly varied with substitution on the P-containing ring and, more interestingly, with the generating system.

Laser Direct Writing of Arbitrary Complex Polymer Microstructures by Nitroxide-Mediated Photopolymerization.

In this paper, we demonstrate the possibility of generating arbitrary polymer microstructures covalently linked to a first polymer layer by laser direct writing. At the molecular scale, the process relies on nitroxide-mediated photopolymerization triggered by a light-sensitive alkoxyamine. In addition to the proof of concept and examples of achievable structures, including multichemistry patterns and 3D structures, this paper aims at investigating the physicochemical phenomena involved under such conditions. In particular, the parameters influencing the repolymerization process are considered, and special attention is paid to the study of the impact of oxygen on the spatial control of the polymerization. Such a work opens many possibilities toward the fabrication of on-demand high-resolution (multi)functional polymer micro and nanostructures.

Reaction of endogenous Coenzyme Q10 with nitrogen monoxide and its metabolite nitrogen dioxide.

Objectives: Coenzyme Q10, incorporated in DOPC lyposomes or naturally present in liver bovine mitochondria or in human blood plasma, was reacted with nitrogen dioxide •NO2 or with a •NO/•NO2 mixture. Methods and Results: The reaction course was monitored by Electron Paramagnetic Resonance (EPR) spectroscopy and in all cases the formation of a di-tert-alkyl nitroxide was observed, deriving from the addition of •NO2 to one of the double bonds, most likely the terminal one, of the isoprenic chain. The rate constant for nitroxide formation was also determined by EPR spectroscopy and an initial rate of ca. 7 × 10-8 M s-1 was obtained.

Investigation of subcellular acidic compartments using alpha-aminophosphonate 31P nuclear magnetic resonance probes.

The 31P nuclear magnetic resonance (NMR) characteristics, toxicity, and cellular penetration of five linear or cyclic alpha-aminophosphonate highly sensitive pH probes were investigated in Dictyostelium discoideum cells and isolated rat hearts and were compared with three phosphonic acid derivatives. The line width broadening at pH approximately pK(a), which was satisfactorily modelized for all compounds, was significantly limited in biological milieu for the new markers, affording a four- to sixfold better accuracy in pH determination. Cellular uptake or washout of nontoxic concentrations (< 15 mM) of alpha-aminophosphonates occurred by rapid passive permeation, whereas standard probes required a much slower fluid-phase pinocytosis and transport processes that could ultimately lead to trapping. Using mild concentrations (< 4 mM) three alpha-aminophosphonates having 6 < pK(a) < 7 allowed an easy and simultaneous 31P NMR determination of cytosolic, acidic, and extracellular compartments in anoxic-reoxygenated or starving D. discoideum.

Catalyst-Free Synthesis of Alkylpolyglycosides Induced by High-Frequency Ultrasound.

The irradiation of concentrated feeds of carbohydrates in alcoholic solution by high-frequency ultrasound (550 kHz) induces the formation of alkylpolyglycosides (APGs). This work is distinct from previous reports in that it does not involve any (bio)catalyst or activating agent, it takes place at only 40 °C, thus avoiding degradation of carbohydrates, and it selectively yields APGs with a degree of polymerization in a window of 2-7, an important limitation of the popular Fischer glycosylation. This ultrasound-based technology proved successful with a range of different valuable carbohydrates and alkyl alcohols. The elucidation of the structure of all the produced glycosides strongly suggests that 1,6-anhydrosugars formed in situ are key intermediate species.

The line asymmetry of electron spin resonance spectra as a tool to determine the cis:trans ratio for spin-trapping adducts of chiral pyrrolines N-oxides: the mechanism of formation of hydroxyl radical adducts of EMPO, DEPMPO, and DIPPMPO in the ischemic-reperfused rat liver.

Nonstereospecific addition of free radicals to chiral nitrones yields cis/trans diastereoisomeric nitroxides often displaying different electron spin resonance (ESR) characteristics. Glutathione peroxidase-glutathione (GPx-GSH) reaction was applied to reduce the superoxide adducts (nitrone/*OOH) to the corresponding hydroxyl radical (HO*) adducts (nitrone/*OH) of two nitrones increasingly used in biological spin trapping, namely 5-diethoxyphosphoryl-5-methyl-1-pyrroline N-oxide (DEPMPO) and 5-ethoxycarbonyl-5-methyl-1-pyrroline N-oxide, and of 5-diisopropoxyphosphoryl-5-methyl-1-pyrroline N-oxide (DIPPMPO), a sterically hindered DEPMPO analogue. The method offered improved conditions to record highly resolved ESR spectra and by accurate simulation of line asymmetry we obtained clear evidence for the existence of previously unrecognized isomer pairs of cis- and trans-[DEPMPO/*OH] and [DIPPMPO/*OH]. Additional nitrone/*OH generation methods were used, i.e. photolysis of hydrogen peroxide and the Fenton reaction. We developed a kinetic model involving first- and second-order decay and a secondary conversion of trans to cis isomer to fully account for the strongly configuration-dependent behavior of nitrone/*OH. In the reductive system and, to a lower extent, in the Fenton or photolytic systems cis-nitrone/*OH was the more stable diastereoisomer. In various biologically relevant milieu, we found that the cis:trans-nitrone/*OH ratio determined right after the spin adduct formation significantly differed upon the GPx-GSH vs (Fenton or photolytic) systems of formation. This new mechanistic ESR index consistently showed for all nitrones that nitrone/*OH signals detected in the postischemic effluents of ischemic isolated rat livers are the reduction products of primary nitrone/*OOH. Thus, ESR deconvolution of cis/trans diastereoisomers is of great interest in the study of HO* formation in biological systems.

Early specific free radical-related cytotoxicity of gas phase cigarette smoke and its paradoxical temporary inhibition by tar: An electron paramagnetic resonance study with the spin trap DEPMPO.

Electron paramagnetic resonance (EPR) spin trapping studies demonstrated aqueous tar particulate matter (TPM) and gas phase cigarette smoke (GPCS) to behave as different sources of free radicals in cigarette smoke (CS) but their cytotoxic implications have been only assessed in CS due to its relevance to the natural smoking process. Using a sensitive spin trapping detection with 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide (DEPMPO), this study compared the respective roles of CS- and GPCS-derived free radicals on smoke-induced cytotoxicity and lipid peroxidation of filtered and unfiltered, machine-smoked experimental and reference cigarettes yielding a wide range of TPM yields. In buffer bubbled with CS the DEPMPO/superoxide spin adduct was the major detected nitroxide. Use of appropriate control experiments with nitric oxide radical (NO*) or carbonyl sulfide, and a computer analysis of spin adduct diastereoisomery showed that the hydroxyl radical (HO*) adduct of DEPMPO seen in GPCS-bubbled was rather related to metal-catalyzed nucleophilic synthesis than to direct HO* trapping. Unexpectedly a protective effect of TPM on murine 3T3 fibroblasts was observed in early (<3h) free radical-, GPCS-induced cell death, and carbon filtering decreased free radical formation, toxicity and lipid peroxidation in three cell lines (including human epithelial lung cells) challenged with GPCS. These results highlight an acute, free radical-dependent, harmful mechanism specific to the GPCS phase, possibly involving NO* chemistry, whose physical or chemical control may be of great interest with the aim of reducing the toxicity of smoke.