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

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

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

Highlight on the Mechanism of Linear Polyamidoamine Degradation in Water

This paper aims at elucidating the degradation mechanism of linear polyamidoamines (PAAs) in water. PAAs are synthesized by the aza-Michael polyaddition of prim-monoamines or bis-sec-amines with bisacrylamides. Many PAAs are water-soluble and warrant potential for biotechnological applications and as flame-retardants. PAAs have long been known to degrade in water at pH 65 7, but their degradation mechanism was never explored in detail. Filling this gap was necessary to assess the suitability of PAAs for the above applications. To this aim, a small library of nine PAAs was expressly synthesized and their degradation mechanism in aqueous solution studied by 1H-NMR in different conditions of pH and temperature. The main degradation mechanism was in all cases the retro-aza-Michael reaction triggered by dilution but, in some cases, hints were detected of concurrent hydrolytic degradation. Most PAAs were stable at pH 4.0; all degraded at pH 7.0 and 9.0. Initially, the degradation rate was faster at pH 9.0 than at pH 7.0, but the percent degradation after 97 days was mostly lower. In most cases, at pH 7.0 the degradation followed first order kinetics. The degradation rates mainly depended on the basicity of the amine monomers. More basic amines acted as better leaving groups

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

Sericin-based resins from silk degumming wastewater for the removal of heavy metal ions from water

Chromium (VI) is a water pollutant categorized as \u2018likely to be a carcinogen to humans\u2019 compound when orally ingested with estimated cancer potency 0.5 mg/kg/day. The European Directive 2001/59/EC poses a 5 \ub5g/L threshold concentration for Cr(VI) in groundwaters. In this work, a chemical process was devised to obtain heavy metal ion absorbing resins by the polyaddition of bisacrylamides and 1,2-diaminoethane with sericin using as reaction solvent raw waste-water from silk degumming processes. Silk sericin (SS) is a natural globural protein deriving from silk worm Bombyx mori with molecular weight ranging from 10000 to 300000. Following the alkaline degumming process, sericin is degraded to peptides with molecular weight 20000. These peptides contain lysine-deriving residues that participate in the polyaddition leaving to a resin. This resin is a hybrid one in which a substantial portion is constituted by sericin peptides. The rationale of this approach is that the guanidinum ion has the ability to strongly bind oxoanions, due to its geometrical Y-shaped, planar orientation, optimizing charge distribution and hydrogen bonds [1]. SS resins were evaluated for the removal of both positively charged (Cu2+, Co2+, Ni2+, Mn2+) and negatively charged heavy metals oxoanions (CrO42-) from water. Different resins were obtained containing different amounts of sericin. These resins were characterized by elemental analysis and their structure confirmed by FT-IR/ATR spectroscopy. The swelling capacity of the new absorbents in different media and their thermal stability by DSC and TGA techniques were evaluated. The removal properties of resins towards Cu2+, Co2+, Ni2+, Mn2+ and CrO42- ions in aqueous single metal dilute and concentrate solutions were performed in batch absorption experiments and evaluated by EDTA titration in the case of Cu2+, Co2+, Ni2+, Mn2+, and by the UV-VIS spectroscopy in the case of CrO42-. The products showed different absorption capacities depending on the SS content in the resin. Treatment with 0.1 M HCl showed excellent regeneration with maintenance of the resins absorption capacity for 20 regeneration cycles. In conclusion, sericin-based resins, besides being biocompatible, were endowed with environmental friendly preparation process; biodegradability; moderate cost; ability to fast and quantitatively absorb from aqueous solutions even at low pollutant concentration; full reversibility of the absorption process making it economically convenient both for regeneration and metal recovery

Tuning Polyamidoamine Design to Increase Uptake and Efficacy of Ruthenium Complexes for Photodynamic Therapy

Nanomedicine holds great promises to change the way drugs are delivered to their target, owing to the use of nano-sized drug carriers capable to enter cells and be trafficked intracellularly via energy dependent pathways [1, 2]. This is very different from the way most drugs arrive to their target, often based simply on their solubility and partition coefficients in lipids and water. Despite some valuable successes, drug delivery remains rather challenging and several factors are still limiting its potential. Among such factors, it has emerged, for instance, that most nano-sized carriers entering cells via endocytosis are later trafficked along the endolysosomal pathway to the lysosomes, where the low pH and abundant proteases can degrade and destroy the internalised cargo. Strategies to escape the endosomes and lysosomes are being investigated. Among the many polymer species employed as drug delivery vectors, linear polyamidoamines (PAAs) are very interesting and promising materials. In this communication it will be presented a new polycationic PAA endowed with a luminescent Ru complex (Ru-PhenAN) and its ability to target the cell nucleus. It shows unique trafficking to the cell nucleus of all the treated cells, also at polymer doses as low as cytotoxicity is very low. Also, it will be shown the efficacy of Ru-PhenAN as photosensitizers for photodynamic therapy (PDT), a treatment of pathological conditions based on the photo-activation of a bioactive compound, which is not harmful in the absence of light irradiation [3]