Linear Polyamidoamines as Novel Biocompatible Intumescent Flame Retardants for Cotton

Since the middle of the last century, many industrial and academic researchers have devoted a lot of effort to the development of safe and effective flame- retardants (FR). As regards cotton, phosphorylated compounds were the predominant FR for several decades [1] despite many of them had been shown to be bioaccumulative.[1] Recently, biomolecules including proteins have been proposed as FR.[2] Many linear polyamidoamines (PAAs), a family of synthetic polymers with exceptional structural versatility,[3] have high thermal stability coupled with chain structure and side substituents reminding those of proteins.[4] These features suggested that PAAs could act as FR. This presentation reports on the results obtained with a library of eight PAAs applied as coatings on cotton fabrics from aqueous solutions. All tested PAAs warrant remarkable potential as surface-confined intumescent FR. In ignitability tests, six of them exposed to direct flame for 10 s do not burn, but produce carbonaceous crusts sheltering the underneath sample. Thermogravimetric analyses show that at T 65 400 \ub0C all PAAs leave in air substantial char residues that oxidize at T > 500 \ub0C. At 450 \ub0C they form porous carbonaceous structures indicating the tendency to intumesce. In horizontal flame spread tests, cotton stripes impregnated with most PAAs extinguish flame at add-ons ranging from 4 to 20%, whereas untreated cotton vigorously burns without leaving residues. Upon 35 kW/m2 heat flux, all PAA-treated samples significantly reduce the main combustion parameters. References [1] R. A. Horrocks, Polym. Degrad. Stab. 2011, 96, 377. [2] L. Costes, F. Laoutid, S. Brohez, P. Dubois, Mater. Sci. Eng. Report, R. 2017, 117, 1. [3] P. Ferruti, J. Polym. Sci, Part A: Polym. Chem. 2013, 51, 2319. [4] F. Danusso, P. Ferruti, Polymer 1970, 11, 88

Sulfur-based copolymeric polyamidoamines as efficient flame-retardants for cotton

The polyamidoamine derived from N,N'-methylenebisacrylamide (M) and glycine (G), M-G, has been shown to be an effective flame-retardant (FR) for cotton in horizontal flame spread tests (HFST), extinguishing the flame at 5% add-on. Its activity was attributed to its intrinsic intumescence. In vertical flame spread tests (VFST), M-G failed to extinguish the flame even at 30% add-on. Conversely, in VFST, the polyamidoamine derived from M and cystine (C), M-C, inhibited cotton combustion at 16% add-on, but in HFST failed to extinguish the flame below 12% add-on. Its activity was ascribed to the release of sulfur-containing volatiles acting as radical scavengers. In this work, the FR effectiveness of M-Gm-Cn copolymers with different G/C ratio was compared with that of the M-G and M-C homopolymers and of M-G/M-C blends of the same compositions. In HFST, both copolymers and blends extinguished the flame. In particular, M-G50-C50 and (M-G/M-C)50/50 extinguished the flame, even at 7% add-on. In VFST, the copolymers with 6550% M-C units, similar to M-C, inhibited cotton combustion at 16% add-on. At the same add-on, the M-G/M-C blends failed to extinguish the flame. It may be concluded that, in contrast to blends, copolymers combined the merits of both homopolymers in all tests

Polyamidoamines derived from natural α-amino acids as effective flame retardants for cotton

In this paper, bioinspired polyamidoamines (PAAs) were synthesized from N,N′-methylene bisacrylamide and nine natural α-amino acids: L-alanine, L-valine, L-leucine (M-LEU), L-histidine, L-serine, L-asparagine, L-glutamine (M-GLN), L-aspartic acid and L-glutamic acid (M-GLU) and their performance as flame retardants (FRs) for cotton were determined. The aim was to ascertain if the ability to protect cotton from fire by the process of intumescing, previously found for the glycine-derived M-GLY, was a general feature of α-amino acid-derived PAAs. None of the PAAs ignited by flame impingement, apart from M-LEU, which burned for a few seconds leaving 93% of residue. All of them formed carbon-and oxygen-rich, porous chars with a graphitic structure in the air at 350◦C, as revealed by X-ray photoelectron spectroscopy. All samples were tested as FRs for cotton by horizontal flame spread tests. At a 5% add-on, M-GLU and M-GLN extinguished the flame. The same results were obtained with all the other PAAs at a 7% add-on. The α-amino acid residues influenced the FR performance. The most effective were those that, by heating, were most suitable for producing thermally stable cyclic aromatic structures. All PAA-treated cotton samples, even when burning, left significant residues, which, according to scanning electron microscopy analysis, maintained the original cotton texture

Probing chiral interactions between L- and D-arginine-based polymers and sodium deoxycholate solutions

Nowadays the spontaneous self-organization of a polymer into an ordered structure is a soughtafter property of many smart materials, whose applications might range from catalysis [1] to drugdelivery [2]. However, literature regarding the role played by these specific conformations in chiral recognition remains scarce. In this context, polyamidoamino acids (PAACs) are an emerging class of stimuli-responsive bioinspired synthetic polymers able to self-assemble into pH depend conformations [3,4]. PAACs are an off-spring of polyamidoamines (PAAs), a family of polymers obtained by the Michael-type polyaddition of prim-monoamines or sec-diamines with bisacrylamides. The reaction occurs in aqueous solution at pH = 8\u20139 and at room temperature. By using \u3b1-amino acids as monomers, PAACs are obtained. The first example of PAAC was named ARGO7, obtained by the stepwise polyaddition in water of L- or D-arginine to N,N\u2019-methylenebisacrylamide. Results indicated Mn 8500, PDI 1.4 and Rh of 1.2 nm [3]. Molecular dynamics (MD) and circular dichroism (CD) showed ARGO7 folded into a rigid structure, reminiscent of the hairpin conformation, solely driven by the polymer main chain. Due to its ability to self-assemble in solution forming chiral structures, L- and D-ARGO7 may selectively interact with biological components. To assess chiral recognition, sodium deoxycholate (NaDC), one of the components of bile salts, was chosen as a chiral model surface. In aqueous solution, NaDC showed three different pH dependent behaviour: homogeneous solution (pH>8), gel phase (pH 7-8) and aggregation/flocculation (pH<6.5). Notwithstanding the ability of NaDC to self-assemble into different conformations at each pH interval, signs of chiral recognition were found in NaDC gel phase only. Conformational modifications were probed by circular dichroism spectroscopy: both D- and L-ARGO7 changed shape and magnitude of the CD pattern, whereas D,L-ARGO7 did not modify the CD spectra of NaDC. After 8 days, NaDC compact structure loosened, ended up being fluid and the CD pattern were completely modified due to NaDC and D- or L-ARGO7 interactions. Incoming diffusion NMR and SANS studies will probably highlight the mechanisms and dynamics of the chiral interactions in these polyelectrolyte-micelle systems. [1] Luo, R.; Zhu, M.; Shen, X.; Li, S. J. Catal. 2015, 331, 49. [2] Qui\uf1ones, J. P.; Peniche, H.; Peniche, C. Polymers. 2018, 10, 3, 235. [3] Manfredi, A.; Mauro, N.; Terenzi, A.; Alongi, J.; Lazzari, F.; Ganazzoli, F.; Raffaini, G.; Ranucci, E.; Ferruti, P. ACS Macro Lett. 2017, 6, 987. [4] Lazzari, F.; Manfredi, A.; Alongi, J.; Mendichi, R.; Ganazzoli, F.; Raffaini, G.; Ferruti, P.; Ranucci, E. Polymers 2018, 10, 1261

Chiral recognition in D-, L-arginine derived polyamidoamino acids and sodium deoxycholate solutions

Nowadays the spontaneous self-organization of a polymer into an ordered structure is a sought-after property of many smart materials, whose applications might range from catalysis1 to drug-delivery2. However, literature regarding the role played by these specific conformations in chiral recognition remains scarce. In this context, polyamidoamino acids (PAACs) are an emerging class of stimuli-responsive bioinspired synthetic polymers able to self-assemble into pH depend conformations.3,4 Arginine based PAACs, named ARGO7, were obtained in water at pH 8-9 from the stepwise polyaddition of L- or D-arginine to N,N\u2019methylenebisacrylamide. Results indicated Mn 8500, PDI 1.4 and Rh of 1.2 nm.3 Molecular dynamics (MD) and circular dichroism (CD) showed ARGO7 folded into a rigid structure, reminiscent of the hairpin conformation, solely driven by the polymer main chain. Due to its ability to self-assemble in solution forming chiral structures, L- and D-ARGO7 may selectively interact with biological components. To assess chiral recognition, sodium deoxycholate (NaDC), one of the components of bile salts, was chosen as a chiral model surface. In aqueous solution, NaDC showed three different pH dependent behaviour: homogeneous solution (pH>8), gel phase (pH 7-8) and aggregation/flocculation (pH<6.5). Notwithstanding the ability of NaDC to self-assemble into different conformations at each pH interval, signs of chiral recognition were found in NaDC gel phase only. Conformational modifications were probed by circular dichroism spectroscopy: both D- and L-ARGO7 changed shape and magnitude of the CD pattern, whereas D,LARGO7 did not modify the CD spectra of NaDC. After 8 days, NaDC compact structure loosened, ended up being fluid and the CD pattern were completely modified due to NaDC and D- or L-ARGO7 interactions. Incoming SANS studies will probably highlight the mechanisms and dynamics of the chiral interactions in these polyelectrolyte-micelle systems. (1) Luo, R.; Zhu, M.; Shen, X.; Li, S. J. Catal. 2015, 331, 49. (2) Qui\uf1ones, J. P.; Peniche, H.; Peniche, C. Polymers. 2018, 10, 3, 235. (3) Manfredi, A.; Mauro, N.; Terenzi, A.; Alongi, J.; Lazzari, F.; Ganazzoli, F.; Raffaini, G.; Ranucci, E.; Ferruti, P. ACS Macro Lett. 2017, 6, 987. (4) Lazzari, F.; Manfredi, A.; Alongi, J.; Mendichi, R.; Ganazzoli, F.; Raffaini, G.; Ferruti, P.; Ranucci, E. Polymers 2018, 10, 1261

Superior flame retardancy of cotton by synergetic effect of cellulose-derived nano-graphene oxide carbon dots and disulphide-containing polyamidoamines

Linear polyamidoamines containing disulphide groups (SS-PAAs) were prepared by polyaddition of L-cystine with 2,2-bisacrylamidoacetic acid (B-CYSS), N,N\u2032-methylenebisacrylamide (M-CYSS) and 1,4-bisacryloylpiperazine (BP-CYSS). They were evaluated as flame retardants for cotton, alone or with cellulose-derived nano-graphene oxide (nGO) carbon dots, to assess whether, due to their potential as radical scavengers, the latter would improve the already good performance of SS-PAAs. In vertical flame spread tests (VFST), cotton treated with 1% nGO burned as quickly as cotton, whereas B-CYSS, M-CYSS and BP-CYSS extinguished the flame at add-ons 65 12, 16 and 20%, respectively. Probably, the gaseous products of SS-PAA thermal degradation quenched the radicals involved in oxidation. Cotton treated with 8, 12 and 15%, respectively, of B-CYSS, M-CYSS and BP-CYSS burned completely, but further addition of 1% nGO either inhibited ignition or shortly extinguished the flame, demonstrating synergism between the two components. Synergism was confirmed by assessing the synergism effectiveness parameter for the residual mass fraction (RMF) and by comparing the calculated and experimental TG curves in air for the cotton/SS-PAA-nGO systems. In cone calorimetry tests, the presence of nGO did not improve the already good performances of SS-PAAs, supporting the hypothesis that the action of both takes place in the gas phase

The thermo-oxidative behavior of cotton coated with an intumescent flame retardant glycine-derived polyamidoamine: A multi-technique study

Linear polyamidoamines (PAAs) derived from the polyaddition of natural α-amino acids and N,N′-methylene bis(acrylamide) are intumescent flame retardants for cotton. Among them, the glycine-derived M-GLY extinguished the flame in horizontal flame spread tests at 4% by weight add-on. This paper reports on an extensive study aimed at understanding the molecular-level transformations of M-GLY-treated cotton upon heating in air at 300◦C, 350◦C and 420◦C. Thermogravimetric analysis (TGA) identified different thermal-oxidative decomposition stages and, coupled to Fourier transform infrared spectroscopy, allowed the volatile species released upon heating to be determined, revealing differences in the decomposition pattern of treated and untreated cotton. XPS analysis of the char residues of M-GLY-treated cotton revealed the formation of aromatic nanographitic char at lower temperature with respect to untreated cotton. Raman spectroscopy of the char residues provided indications on the degree of graphitization of treated and untreated cotton at the three reference temperatures. Solid state13C nuclear magnetic resonance spectroscopy (NMR) provided information on the char structure as a function of the treatment temperature, clearly indicating that M-GLY favors the carbonization of cotton with the formation of more highly condensed aromatic structures

Amphoteric polyamidoamines in the treatment of malaria

The present invention relates to the use of amphoteric polyamidoamines with MW of 10-100 kDa as antimalarial agents or carriers of antimalarial drugs and to formulations thereof

Linear polyamidoamines as novel biocompatible phosphorus-free surface-confined intumescent flame retardants for cotton fabrics

Eight linear polyamidoamines (PAAs) prepared by polyaddition of amines to bisacrylamides are investigated as intumescent surface-confined flame retardants for cotton textiles. The structure of the amine-derived subunits governs their performances. In ignitability tests, aminoacid-deriving PAAs exposed to direct flame for 10 s do not burn, but produce carbonaceous crusts sheltering the underneath sample apparently intact. PAAs carrying guanidine pendants partially volatilize without burning. 2-Methylpiperazine-derived PAAs burn completely. Thermogravimetric analyses show that in air at \ue2\u89\ua5400 \uc2\ub0C all PAAs leave substantial char residues that oxidize at >500 \uc2\ub0C. Horizontal flame spread tests on PAA-impregnated cotton stripes show flame extinction for add-ons ranging from 4 to 20%, apart from 2-methylpiperazine-deriving PAAs that never extinguish flame but slow down flame propagation leaving a substantial residue. In vertical flame spread tests, no PAA induces flame extinguishment at add-ons up to 20%, but all PAA-treated fabrics leave significant residues. In cone calorimetry tests, all PAAs increase the time to ignition and decrease the peak of heat release rate and the effective heat of combustion. Most PAAs remarkably reduce the release of CO and CO2. After the above tests the combustion residues of PAA-treated cotton fabrics present intumescent bubbles. All results indicate that PAAs warrant potential as effective surface-confined intumescent flame retardants

Insight into the self-assembly behavior of nanostructured amino acid-deriving polymers

Polyamidoaminoacids (PAACs) are a new class of stimuli-responsive bioinspired chiral polymers. Recently, amphoteric PAACs isomers named ARGO7 were obtained by the polyaddition of L-, D- and D,L-arginine to an aqueous solution of N,N\u2032-methylenebisacrylamide.[1] Molecular modeling studies in water showed that L- and D-ARGO7 folded into rigid and compact conformations driven by the polymer main chain flexibility. In order to demonstrate that the observed behavior was a general one, a library of amphoteric PAACs were synthesized from different L-, D- and D,L \u3b1-aminoacids by stepwise polyaddition to N,N'-methylenebisacrylamide. The reaction occurred in water at pH > 10 and 50 \ub0C for 6 days with 92% yield, Mn from 4000 \u2013 6000 and PD 1.40. Hydrodynamic radius (Rh) was determined by Dynamic Light Scattering (DLS), revealing only one family of nanoparticles with 1.5 nm average radius. CD spectra, recorded in the 3-12 pH interval, were consistent with the presence of pH-dependent ordered secondary structures, whose changes with pH were rapid and fully reversible. The dependence on temperature, ionic strength and presence of denaturating agents was assessed for the hydrophobic \u3b1-aminoacids deriving PAACs. CD spectral pattern were insensitive to all these parameters, suggesting highly stable and rigid structures. Future studies on cell internalization will assess the potential of PAACs for establishing chirality-dependent selective interactions with cell components