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International audience; The need of more powerful systems with higher energy density raises a lot of interest in lithium metal batteries (LMBs). As LMBs suffer from safety concerns due to the dendrite growth, several strategies have been studied to limit this growth. Using a highly concentrated electrolyte allows a homogeneous lithium plating that delays the formation of dendrites. Herein, different techniques are used in order to better understand the beneficial role of the salt concentration in the lithium plating/stripping. Operando Fourier transform infrared spectroscopy highlights the better reversibility of the Li+ solvation in the 5 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 1,2-dioxolane/1,3-dimethoxyethane electrolyte in comparison with the 1 M electrolyte. This obviously leads to different electrolyte decompositions during the lithium plating/stripping and changes the nature of the electrode solid electrolyte interphase (SEI) depending on the salt concentration. Gas chromatography coupled with mass spectrometry as well as X-ray photoelectron spectroscopy confirms that with the 5 M LiTFSI electrolyte the salt is preferentially reduced during the plating/stripping, leading to a more inorganic SEI on the lithium metal electrode.

International audience; The hydrogen peroxide initiated radical polymerization of vinylidene fluoride (VDF) at 130 °C in dimethyl carbonate is presented. Various reaction parameters such as the nature of the solvent, the nature and the amount of the additive, and the reaction temperature were optimized. Hydrogen peroxide was activated by azobisisobutyronitrile (AIBN), which is not able to initiate the radical polymerization of VDF, but afforded hydroxyl radicals via selective homolytic cleavage of the O-O bond of H 2 O 2. The reactivity of hydroxyl radicals with the different components of the medium was evaluated. Two pathways were highlighted: the first one is the radical polymerization of VDF initiated by OH • radical, while the second one is the hydrogen abstraction from the solvent that afforded carbon centered carbonate radicals. These latters were also able to initiate the radical polymerization of VDF. The microstructure of the resulting PVDFs was determined by NMR spectroscopy and MALDI-TOF spectrometry. Seven different chain-ends were identified and could be well revealed from synthesized models: 60% were functional, e.g., carbonates, alcohols, carboxylic acids and fluorinated olefins, whereas 40% were CF 2 H and CF 2 CH 3 fluoroalkyls as the products of hydrogen transfer termination reactions. Finally, based on the collected experimental data, a mechanistic pathway of the polymerization was proposed in order to explain the formation of such different functional and non-functional end-groups. In addition, the selectivity of the different radical additions onto VDF was studied and discussed.

2-Trifluoromethacrylic acid (MAF) is a peculiar fluorinated functional monomer. Though it is known to polymerise via CC bond cleavage under anionic initiation, its oxa-Michael addition polymerisation afforded polyesters bearing trifluoromethyl side groups. This oxa-Michael addition was attempted in the presence of radical (peroxides), basic (amines and phosphines) and acidic (AlCl3, triflic acid, and p-toluenesulfonic acid) reactants and catalysts which led to the formation of oligomers with various yields (up to 57%) and molar masses (up to 2200 g mol−1). The obtained polyesters were characterised by GC/MS, IR, 19F NMR, 1H NMR and 13C NMR spectroscopy techniques and MALDI-TOF, and their thermal properties were determined by thermogravimetric analysis and differential scanning calorimetry. Triphenylphosphine and piperidine led to the highest degree of polymerization DPn (up to the 16th adduct) with a degradation temperature of about 200 °C. The glass transition temperatures (Tg) were −59 and −46 °C for the MAF bisadduct (diMAF) and oligoMAF, respectively. Such oligomers were hydrophobic, evidenced by a water contact angle measurement of 107°, showing that the contribution of the trifluoromethyl group was higher than that of the ester function.

Anionic ring-opening polymerization (AROP) of 2-ethyl-2-oxo-1,3,2-dioxaphospholane (EP) has been utilized to create alternative hydrophilic moieties for utilization in surfactants. The current “go-to” hydrophilic unit is poly(ethylene glycol) (PEG), but this is non-biodegradable and there is some evidence that its use can lead to accumulation of toxic by-products. We have created new approaches leading to water-dispersible, fully degradable amphiphilic block copolymers. Our approach utilized poly(ε-caprolactone)-based macroinitiators in a solvent free process with organocatalyst DBU. We have prepared a comprehensive set of novel amphiphilic PCL-b-PEP block copolymers including linear diblock, triblock and star diblock copolymers characterized by SEC, 1H and 31P NMR and MALDI-TOF analyses. Supercritical carbon dioxide (scCO2) was exploited to efficiently extract the residual EP monomer leading to significantly increased gravimetric yields of purified product compared to conventional techniques such as dialysis. The self-assembly of the amphiphilic copolymers in water was investigated by DLS and cryo-TEM and their surface-activity as a function of concentration was investigated by tensiometry showing behavior that matches or exceeds commercially available surfactants.

We report herein a study on the alcohol-free, ring-opening polymerization of trimethylene carbonate (TMC) in THF, catalyzed by 1,5,7-triazabicyclo [4.4.0] ec-5-ene (TBD) with ratios nTBD/nTMC ranging between 1/20 and 1/400. In all cases, the reaction proceeds very rapidly, even faster than in the presence of alcohol initiators, and provides PTMC with molecular weights up to Mn = 34,000 g mol−1. Characterization of the obtained PTMC samples by MALDI-TOF mass spectrometry, triple detection size exclusion chromatography and 1H NMR spectroscopy reveals the presence of both linear and cyclic polymer chains.

International audience; This article is the first report of the RAFT polymerisation of trifluoroethylene (TrFE). Trifluoroethylene is a rare but very important fluoromonomer, as it allows the preparation of materials endowed with unique electroactivity via copolymerisation with vinylidene fluoride (VDF) and other fluoromonomers. RAFT polymerisations carried out using O-ethyl-S-(1-methoxycarbonyl) ethyldithiocarbonate as a chain transfer agent and a thermal initiator were carefully examined. The polymerisation, its kinetics and the chain-end evolution were investigated by GPC, 1H{19F} and 19F{1H} NMR spectroscopy as well as MALDI-TOF mass spectrometry. Similar to the RAFT polymerisation of VDF, irreversible transfer reactions and reverse additions significantly affect the control of the polymerisation as well as the chain-end functionality. However, in contrast to VDF, unusual reverse propagation of TrFE, although limited to a few monomer units, was evidenced thanks to a combined NMR spectroscopy and DFT calculation approach. RAFT polymerisation afforded relatively well-defined PTrFE with a crystalline structure consistent with previous reports.

International audience; The aqueous radical homopolymerization of vinylidene fluoride (VDF), as well as its co-polymerizations with hexafluoropropylene (HFP) or perfluoromethyl vinyl ether (PMVE), and its ter-polymerization with HFP and PMVE, initiated by trifluoromethyl radicals (•CF 3), generated from ammonium persulfate (APS) and potassium trifluoromethyl sulfinate (CF 3 SO 2 K) redox system are presented. The optimization of the experimental conditions in terms of initial reactant molar ratios, temperature and reaction time was achieved. The best results were obtained at 60 o C, in water, without any surfactant, using 0.9 eq of APS as the oxidant with respect to CF 3 SO 2 K. PVDF, poly(VDF-co-HFP), poly(VDF-co-PMVE), or poly(VDFter-PMVE-ter-HFP) co-polymers were obtained in high yields (varying between 89 and 100%), and with molar masses up to 113,000 g/mol. The 1 H and 19 F NMR spectroscopy revealed that, under optimized conditions, the formed chain-ends were exclusively CF 3 or CF 2 H. The influence of the nature of the chain-end on the thermal stability showed that PVDFs terminated by CF 3 were more stable than their analogues bearing sulfate end-groups by 120 o C. In addition, the prepared CF 3-PVDFs had 53% of crystallinity (compared to 47% for PVDF initiated from APS alone), which offers excellent resistance to conventional organic solvents including dimethyl sulfoxide, acetone and dimethyl formamide.

Copper and nickel mixed catalysts obtained by calcination of iron and aluminium hydrotalcites (layered double hydroxides, LDH) have been tested in the conversion of a lignin model dimer in subcritical methanol. Phase distribution and textural properties of the catalysts were characterized by X-ray diffraction Rietveld analysis and N2 physisorption. The presence of copper was critical for effective hydrogenation, both by direct hydrogen transfer from methanol to aldehyde groups and by reactivity of products from methanol reforming. TPR experiments showed that the hydrogenation activity was promoted by an enhanced reducibility of the Cu-catalysts, related to the presence of other oxide components. Characterisation of the catalysts after reaction indicated that metallic copper was formed by the reduction of CuO by methanol and that modifications of the oxide catalysts in the reaction medium played a major role in the formation of active sites.

International audience; The radical polymerization of styrene (St) initiated by a trifluoromethyl radical generated from a perfluorinated highly branched persistent radical (PPFR) is presented with an isolated yield above 70 %. The release of .CF3 radical occurred from a temperature above 85 °C. Deeper 1H and 19F NMR spectroscopies of the resulting fluorinated polystyrenes (CF3‐PSts) evidenced the presence of both CF3 end‐group of the PSt chain and the trifluoromethylation of the phenyl ring (in meta‐position mainly). [PPFR]0/[St]0 initial molar ratios of 3:1, 3:10 and 3:100 led to various molar masses ranging from 1750 to 5400 g mol−1 in 70–86 % yields. MALDI‐TOF spectrometry of such CF3‐PSts highlighted polymeric distributions which evidenced differences between m/z fragments of 104 and 172 corresponding to styrene and trifluoromethyl styrene units, respectively. Such CF3‐PSt polymers were also compared to conventional PSts produced from the radical polymerization of St initiated by a peroxydicarbonate initiator. A mechanism of the polymerization is presented showing the formation of a trifluoromethyl styrene first, followed by its radical (co)polymerization with styrene. The thermal properties (thermal stability and glass transition temperature, Tg) of these polymers were also compared and revealed a much better thermal stability of the CF3‐PSt (10 % weight loss at 356–376 °C) and a Tg of around 70 °C.

Bio-based building blocks and sustainable synthesis pathways were used to synthesise star-shaped polymers composed of a D-sorbitol core and polycaprolactone arms by ring opening polymerisation (ROP). The use of volatile organic solvents was avoided and less energy intense reaction conditions were achieved by performing the ROP in the bulk or in a green solvent, supercritical CO2 (scCO2). Two catalysts were tested: conventional tin(II) 2-ethylhexanoate (Sn(Oct)2) which is a Food and Drug Administration (FDA) approved metal catalyst and an enzyme, Novozym 435 (Lipase B from Candida Antarctica immobilised on a solid support). The influence of the reaction medium and of the nature of the catalyst on the molecular weight, the dispersity and the architecture of the PCL stars was investigated. The star polymers were characterised by 1H and 31P nuclear magnetic resonance (1H and 31P NMR) spectroscopy, size exclusion chromatography – multi-angle light scattering (SEC-MALS) and matrix-assisted laser desorption and ionisation-time of flight (MALDI-TOF) mass spectrometry. The use of scCO2 enabled the reduction of the reaction temperature of Sn(Oct)2 catalysed star D-sorbitol-polycaprolactone polymerisations from 140 to 95 °C. In addition, star polymers were successfully synthesised by enzyme catalysis in the bulk or in scCO2 at 60 °C; lower temperatures that could provide significant energy savings on a commercial scale. The catalyst was shown to have a pronounced influence on the architecture of the PCL stars. Regular star polymers were obtained in the presence of Sn(Oct)2 whereas Novozym 435 gave access to miktoarm-type star PCL. Finally, the influence of the number and length of the arms on the thermal properties of the star polymers was investigated by differential scanning calorimetry (DSC).

LaAlO3 perovskites, as such and with 25% molar Al substitution by Cu, Co, or Ga, have been prepared by sol-gel methods and tested as heterogeneous catalysts in the gas-phase conversion of ethanol. LaAlO3 presented a significant acidic character, with high formation of ethylene by ethanol dehydration. B-site substitutions increased the basicity of the catalysts, favoring the dehydrogenation of ethanol to acetaldehyde. The most reducible Cu- and Co-substituted materials, characterized by easier formation of surface oxygen vacancies, promoted the self-condensation of acetaldehyde by the Tishchenko mechanism, with formation of acetone and odd-carbon number products. Aldol coupling of acetaldehyde, favored on pure and Ga-substituted LaAlO3, led to the formation of butadiene and hexadiene. The role of Ga insertion, favoring both dehydrogenation of ethylene and dehydration of higher alcohols, corresponds to an amphoteric character. The formation of olefins and diolefins on all catalysts suggests that LaAl-based materials present the most acidic character among La-perovskites.

International audience; The radical telomerisation of trifluoroethylene (TrFE) with dimethyl phosphite (DMP) was investigated tosynthesizefluorinated monoadducts bearing a phosphonate end-group such as HTrFEP(O)(OCH3)2.Among various radical initiators, di-tert-butyl peroxide (DTBP) was the most efficient one at 80–140 C.This telomerisation protocol successfully yielded mainly the monoadduct of TrFE and DMP. A structuralstudy of the TrFE-DMP monoadduct was carried out using 1H, 13C, 19F and 31P NMR spectroscopies andshowed that a mixture of dimethyl-1,2,2-trifluoroethylphosphonate and dimethyl-1,1,2-trifluoroethyl-phosphonate was obtained. The best experimental conditions to reach high yields of monoadduct wereachieved at T = 140 C, using initial molar ratios R0 = [DMP]0/[TrFE]0 and C0 = [DTBP]0/[TrFE]0 of 3 and 0.05,respectively, and a reaction time of 15 h. Higher telomeric adducts were also detected by MALDI-TOFmass spectrometry.

Photoinitiated ring-opening polymerization of l-lactide (L-LA) using a photobase generator (PBG) able to release 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) is reported. Polymerization using the PBG with ketoprofenate counteranion (TBDH+.keto–) was studied in dichloromethane either in the presence or in the absence of 1-butanol as initiator. In both cases, full monomer conversion was reached at room temperature after 10 min of irradiation at 254 nm. In the presence of 1-butanol, linear poly(L-LA) chains (PLA) were obtained, as confirmed by 1H NMR and MALDI-TOF analyses. The polymerization was well controlled as attested by the production of polymers with low dispersity (Đ < 1.26) and by the linear evolution of molecular weights with the quantity of initiator. Without 1-butanol, although MALDI-TOF analyses revealed cyclic PLA chains (actually formed in situ during MALDI-TOF analysis), linear PLA chains were formed as proven by 1H NMR, viscosity measurement, and phosphitylation titration. This fast and “on de...

Controlled radical polymerization protocols for vinylidene fluoride (VDF) are still very elusive. MADIX polymerization of VDF has very rarely been reported. The synthesis of PVDF using MADIX solution polymerization was thus investigated in detail. More efficient protocols for solution polymerization were developed and afforded relatively well-defined PVDF. Careful polymer chain-end monitoring using MALDI-TOF as well as 1H, 19F, and HETCOR 1H–19F NMR revealed that VDF reverse additions and transfer to solvent reactions severely affect the control of the polymerization. Indeed, these unwanted reactions are responsible for a non-negligible loss of CTA and for the accumulation of nonreactive polymer chains in the reaction medium. MADIX polymerization lead to the synthesis of PVDF with high chain-end functionality. However, these PVDF chains cannot reinitiate the polymerization of VDF. This work is the first comprehensive study of the MADIX solution polymerization of VDF.

International audience; Unprecedented synthesis of multiblock poly(vinylidene fluoride) (PVDF, up to 16 300 g mol-1) with narrow-dispersity blocks (Ð=1.26) mediated by a fluorinated cyclic xanthate via reversible addition–fragmentation chain transfer (RAFT) polymerization is reported. Theas-synthesized multiblock PVDF was employed as a macroRAFT agent to prepare valuable multiblock copolymers with potentialapplications in emerging areas

Pyrolitic lignin was modified through two methods. First, it was grafted with polylactide chains via a solvent-free process by ring-opening polymerization of l -lactide using calcium hydride as a catalyst. The efficiency of grafting was determined by infra-red, nuclear magnetic resonance and time-of-flight secondary ion mass spectrometry analyses. Then, lignin particles were oxygen plasma-treated and immersed in l -lactide solution. Infra-red and X-ray photoelectron spectroscopy revealed that chains bearing ester groups similar to that of lactide were covalently grafted onto the lignin. Composite cast films based on poly( l -lactide) matrix containing ungrafted lignin (lignin/PLLA), chemically-grafted lignin copolymer (PLA- g -lignin/PLLA) and plasma-treated lignin (plasma-treated lignin/PLLA) were investigated. Differential scanning calorimetry and dynamical mechanical analyses revealed that plasma-treated lignin preserved the crystalline structure of PLLA matrix and had a significant reinforcing effect compared with lignin and PLA- g -lignin. Results were compared with literature data.

In this study, various organic compounds, with different activation modes, have been tested as catalysts for the ring-opening polymerization (ROP) of cyclic butylene terephthalate oligomers (CBT) in bulk at 210 °C, using tert-butylbenzyl alcohol (tBnOH) as initiator. Among them, 1,3,5-triazabicyclo[4.4.0]dec-5-ene (TBD) appeared to be the most efficient, achieving high monomer conversions in short reaction times (within minutes). Analysis by size-exclusion chromatography (SEC) of the poly(butylene terephthalate) (PBT) synthesized using this catalyst also showed that the polymerization follows the expected theoretical Mn trend for molecular weights up to 50 kg·mol−1. Chain-end fidelity relatively to the alcohol initiator has been confirmed by MALDI-TOF mass spectroscopy, which showed that all polymer chains possess the tert-butylbenzyl moiety as chain-end. Finally, to demonstrate the potential of this system for the synthesis of PBT-based block copolymers, a monomethyl ether poly(ethylene glycol) (PEG) of 5000 g·mol−1 has been employed as initiator for the ROP of CBT. A PEO-b-PBT block copolymer of 15,000 g·mol−1 could thus been obtained, as confirmed by the shift of the SEC traces towards higher molecular weights and the same diffusion coefficient determined for 1H NMR signals of the PEO block and the PBT block. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1611–1619

Ethanol organosolv alfa grass lignins were extracted in the presence of sulfuric acid or Lewis acids (Sc(OTf)3, FeCl3) as catalysts and subjected to a comprehensive structural characterization by solid state 13C NMR, GPC, MALDI-TOF, and ASAP-MS/MS. The impact of the severity of the treatment and of the nature of the acid catalyst on the recovered lignin structure was investigated. The lignins isolated at high severity were highly recondensed and partly composed of regular structures composed of furan-like rings. The alfa (Stipa tenacissima L.) organosolv lignins were used for the preparation of formaldehyde-free adhesives which were characterized by TMA and used for the preparation of particleboard without any addition of synthetic resin. It has been demonstrated for the first time that: (1) the addition of 10% to 30% of organosolv alfa lignin in a tannin-based adhesive improved the adhesive performance; and (2) the conditions of the lignin extraction strongly impact the lignin-based adhesive performances. The highly recondensed lignin extracted with sulfuric acid as a catalyst allowed the production of resins with improved performances. Formulations composed of 50% glyoxalated alfa lignin and 50% of Aleppo Pine tannins yielded good internal bond strength results for the panels (IB = 0.45 MPa) and satisfied relevant international standard specifications for interior-grade panels.

This paper reports an original and easy route toward thermosensitive micelles based on a lipidic core and with adjustable cloud point temperatures (TCP) through a simple blending approach between two copolymers of different TCP. The cationic ring-opening polymerization (CROP) of various 2-alkyl-2-oxazoline monomers was first investigated from both mesylated and tosylated lipoinitiators and different lipid-b-poly(2-methyl-2-oxazoline), lipid-b-poly(2-ethyl-2-oxazoline), lipid-b-poly(2-isopropyl-2-oxazoline) and lipid-b-poly((2-ethyl-2-oxazoline)-co-(2-isopropyl-2-oxazoline)) copolymers were synthesized. Blending of lipid-b-p(EtOx) and lipid-b-p(iPrOx) copolymers in various proportions were then prepared and their TCP investigated through UV–visible spectroscopy. Very interesting results were obtained as the blends exhibit a single TCP ranging from 35 to 45 °C. Furthermore, the blends TCP correspond to those of the statistical lipid-b-p((EtOx)-co-(iPrOx)) for the same p(EtOx)/p(iPrOx) content up to 52 wt % ...

International audience; The synthesis and characterization of a new oligo(hexafluoropropylene oxide)-b-oligo(ethylene oxide), oligo(HFPO)-b-oligo(PEG), diblock co-oligomer are presented. First, the model reactions dealing with the radical addition of 1-iodoperfluorohexane (C 6 F 13 I) onto allyl alcohol and allyl-O-PEG-OCH 3 were optimized in terms of the choice of the initiator (azobisisobutyronitrile [AIBN], tert-butylperoxypivalate [TBBPi], and benzoyl peroxide [BPO]) and of the solvent, temperature, and time. Allyl-O-PEG-OCH 3 was obtained from the etherification of ω-hydroxy-PEG with allyl bromide. End-capping of oligo(HFPO) with PEG was successfully achieved by the radical addition of 1-iodoperfluoropropyl-2-oligo(hexafluoropropylene oxide) [oligo(HFPO)-CF(CF 3 )CF 2 I] onto allyl-O-PEG-OCH 3 using the best conditions of the model reactions. Although TBPPi failed and led to oligo(HFPO)-isobutyl iodide, AIBN and BPO yielded oligo (HFPO)-CH 2 CHICH 2 -oligo(PEG). The selective reduction of the latter compound led to oligo(HFPO)-b-oligo(PEG) in 77% yield, the surface tension properties of which were compared to those of commercially available ammonium perfluorooctanoate (APFO) and perfluorooctanoic acid (PFOA). Its critical micelle concentration was 0.04 g mol −1 . All models, intermediates, and diblock co-oligomers were characterized Introduction Polyfluorinated compounds (PFCs) are useful chemicals involved in a wide range of products. Among them, molecules that bear both fluorinated hydrophobic moieties and hydrophilic parts, called "surfactants", 1-4 are valuable compounds. Surfactants are being used in more than 200 applications 5-10 ranging from the protection of surfaces (textile, paper, carpets, masonry, metal, and leather), as stimulating fluids for oil recovery, fire-fighting foam, skin protection from chemical agents, soil and stain-repellents, plane hydraulic fluids, 1,11 paints, lubricants, electroplating, photographic emulsifiers, pressure sensitive additives, pharmaceuticals, and insecticides, or are involved in cosmetic formulations. Perfluorooctanoic by 1 H, 19 F, and 13 C NMR spectroscopy as well as matrix assisted laser desorption ionization (MALDI) and atmospheric pressure solids analysis probe (ASAP) time-of-flight mass spectrometry (TOF-MS).

Two new styryllactones, macrocalactone (1) and 3-deoxycardiobutanolide (2), were isolated from the fruits of Goniothalamus macrocalyx Ban (Annonaceae), together with seven known compounds including four acetogenins, annonacin (3), solamin (4), isoannonacin (5), trans-murisolinone (6), and three other compounds, 7-acetylaltholactone (7), beta-caryophyllene-8R,9R-oxide (8) and 2-(2'-hydroxytetracosanoylamino)-octadecane-1,3,4-triol (9). Their structures were determined by spectroscopic and MS analysis. The absolute configuration of 1 was determined by X-ray crystallographic analysis. The structures of the acetogenins were confirmed by liquid chromatography coupled to a hybrid quadrupole-time of flight mass spectrometer, using post-column lithium infusion. The results were compared with the fragmentation obtained with a hybrid linear trap-orbitrap mass spectrometer. Compound 7 had cytotoxicity against KB, HepG2, Lu, and MCF7 cell lines with IC50 values of 13.1, 23.7, 26.3 and 60.2 microM, respectively, whereas annonacin (3) was selectively active against KB cells (IC50 value of 6.5 microM). The discovery of 3-deoxycardiobutanolide (2) from the fruits of this plant revealed that G. macrocalyx could be a valuable natural resource to obtain this compound as it has been previously reported to have a significant cytotoxicity against different cancer cell lines, especially HL-60 cells.

Two new styryllactones, macrocalactone (1) and 3-deoxycardiobutanolide (2), were isolated from the fruits of Goniothalamus macrocalyx Ban (Annonaceae), together with seven known compounds including four acetogenins, annonacin (3), solamin (4), isoannonacin (5), trans-murisolinone (6), and three other compounds, 7-acetylaltholactone (7), β-caryophyllene-8R,9R-oxide (8) and 2-(2′-hydroxytetracosanoylamino)-octadecane-l,3,4-triol (9). Their structures were determined by spectroscopic and MS analysis. The absolute configuration of I was determined by X-ray crystallographic analysis. The structures of the acetogenins were confirmed by liquid chromatography coupled to a hybrid quadrupole-time of flight mass spectrometer, using post-column lithium infusion. The results were compared with the fragmentation obtained with a hybrid linear trap-orbitrap mass spectrometer. Compound 7 had cytotoxicity against KB, HepG2, Lu, and MCF7 cell lines with IC50 values of 13.1, 23.7, 26.3 and 60.2 μM, respectively, whereas annonacin (3) was selectively active against KB cells (IC50 value of 6.5 μM). The discovery of 3-deoxycardiobutanolide (2) from the fruits of this plant revealed that G. macrocalyx could be a valuable natural resource to obtain this compound as it has been previously reported to have a significant cytotoxicity against different cancer cell lines, especially HL-60 cells.