Fabrication of eco-friendly and efficient flame retardant modified cellulose with antibacterial property.

Flame retardant and antibacterial investigation of cellulose has attracted more and more attention. In order to improve the modification efficiency, inspired by multiple hydrogen bonding in spider silk, flame retardant and antibacterial dual function modified cellulose was achieved by multi structure hydrogen bonding in this research. A novel nano SiO2 based Schiff base flame retardant (SiAPH) and dodecyl quaternary ammonium salt (HDAC) were synthesized. Tannin (TA) was introduced as medium to provide synergistic flame retardant and antibacterial with SiAPH and HDAC. The flame retardancy assessment demonstrated that the limiting oxygen index (LOI) of modified cotton fabrics increased from 18% to 26.1%, and the peak of heat release rate (pHRR) decreased by 41.0%, UL-94 vertical combustion proved the modified cotton fabrics had capability of self-extinguishing. The antibacterial of modified fabrics were confirmed against Staphylococcus aureus and Escherichia coli, and the inhibition rate reached to 99.1%. In addition, it worth noting that the biocompatibility and antibacterial activity of modified fabrics were evaluated via MTS assay and establishment of animal wound model. Low toxicity of the fabrics was verified by the L929 fibroblast cells. The anti-infection experiment model showed that the modified fabrics had a positive effect on prevention of infection, and the wound healing rate reached to 86.8% after 14 days' treatment. The flame retardancy, antibacterial and biocompatibility of the functional cotton fabrics indicated that they were ideal candidate for applications of vehicle interior, soft decoration in public and medical scene.

Self-assembly of amino acid-based random copolymers for antibacterial application and infection treatment as nanocarriers.

Bacterial infection is one of the most significant complications worldwide and has been one of the main factors of morbidity and mortality for the chronic wounds. Considering the negative charged feature of bacterial pathogens, a positive charged poly(ester amide) (PEA) micellar system based on lysine, arginine and phenylalanine is developed. In this study, a serials of PEA random copolymers can be obtained by altering the sorts of amino acids and feed ratio, and the self-assembled PEA micelles with an average diameter ranging from 150 to 200 nm exhibit the integrated properties of excellent biocompatibility and enzymatic biodegradation. More interesting, the degraded random block micelles can reassemble into smaller sized micelles with the diameter less than 20 nm which have promising applications in drug delivery. The PEA micellar nanocarriers display an intrinsic antibacterial property due to the pendant groups of lysine and arginine based moieties and this killing capacity can be enhanced by grafting levofloxacin without losing the original performance. The in vitro antibacterial evaluation proves all of the micelles display a concentration dependent efficiency of killing bacteria (up to 99.99%). The in vivo Staphylococcus aureus induced infection model demonstrates that the micelles are effective in killing the bacteria and infection treatment. The successful synthesis of the biocompatible and biodegradable amino acid based micellar nanocarriers may provide new insights into the development of biomedical materials for antibacterial applications and drug delivery.

Hydrophilic and degradable polyesters based on l-aspartic acid with antibacterial properties for potential application in hernia repair.

A polyester hernia patch has received extensive attention in mesh hernia repair. However, it is still a challenge to develop polyester-based implants with inherent antibacterial properties due to the lack of active functional groups. In this study, poly(butylene succinate-co-butylene aspartate) (PBSA) was constructed by introducing aspartic acid on a polybutylene succinate (PBS) polyester chain (PBSA). Antimicrobial treatment was conducted by grafting levofloxacin (Lv) on the surface of a PBSA polymer (PBSA-g-Lv). In vitro antibacterial test results showed that PBSA-g-Lv had sufficient local antimicrobiotic effects against Staphylococcus aureus and Escherichia coli and no side effect on L929 cells was observed. Furthermore, almost no change was observed in the thermodynamic properties of PBS and PBSA; in vivo tests demonstrated that this contact-active antibacterial PBSA-g-Lv nanofiber is a promising material to fulfill the dual functions of promoting tissue regeneration and preventing bacterial infection. The presented data confirmed that an antibiotic surface modification of PBSA polyesters was expected to be used as hernia repair materials.

Hyaluronic Acid and Polyethylene Glycol Hybrid Hydrogel Encapsulating Nanogel with Hemostasis and Sustainable Antibacterial Property for Wound Healing.

Immediate hemorrhage control and anti-infection play important roles in the wound management. Besides, a moist environment is also beneficial for wound healing. Hydrogels are promising materials in urgent hemostasis and drug release. However, hydrogels have the disadvantage of rapid release profiles, leading to the exposure to high drug concentrations. In this study, we constructed hybrid hydrogels with rapid hemostasis and sustainable antibacterial property combining aminoethyl methacrylate hyaluronic acid (HA-AEMA) and methacrylated methoxy polyethylene glycol (mPEG-MA) hybrid hydrogels and chlorhexidine diacetate (CHX)-loaded nanogels. The CHX-loaded nanogels (CLNs) were prepared by the enzyme degradation of CHX-loaded lysine-based hydrogels. The HA-AEMA and mPEG-MA hybrid hydrogel loaded with CLNs (labeled as Gel@CLN) displayed a three-dimensional microporous structure and exhibited excellent swelling, mechanical property, and low cytotoxicity. The Gel@CLN hydrogel showed a prolonged release period of CHX over 240 h and the antibacterial property over 10 days. The hemostasis and wound-healing properties were evaluated in vivo using a mouse model. The results showed that hydrogel had the rapid hemostasis capacity and accelerated wound healing. In summary, CLN-loaded hydrogels may be excellent candidates as hemostasis and anti-infection materials for the wound dressing application.

Influence of substitution on the rheological properties and gelation of hydroxyethyl cellulose solution in NaOH-water solvent.

The rheological properties of hydroxyethyl cellulose (HEC) with a low molar substitution (MS) dissolved in 8wt% NaOH-water were studied as a function of solution temperature, polymer concentration and molar substitution. Special attention was paid to gelation kinetics. Similar to cellulose dissolved in alkali or ionic liquids, the intrinsic viscosity of HEC decreased with temperature increase, indicating a decrease of solvent thermodynamic quality. The gelation time of HEC solutions decreased exponentially with temperature but the kinetics is much slower than the gelation of microcrystalline cellulose solutions in the same solvent. Higher molar substitution leads to slower gelation. The small amount of introduced hydroxyethyl groups prevented cellulose aggregation thus increasing solution stability.

Ready-to-use strip for L-ascorbic acid visual detection based on polyaniline/polyamide 66 nano-fibers/nets membranes.

A ready-to-use L-ascorbic acid (L-AA) colorimetric strip based on polyaniline (PANI)/polyamide 66 (PA 66) nanofiber/net (NFN) membrane with spider-web-like structure was fabricated through a facile bend electrospinning/netting process. Introduction of PANI component into the membrane turns the strip undergoes a brilliant brown-to-green color transition within 30 min upon incubation with L-AA. Moreover, ascribing to the three-dimensional microscopic structural, continuous pore channels, and distinctive nano-nets structure, the color change that is caused by 50 ppb L-AA can be easily perceived by naked eyes. Furthermore, RGB (red-green-blue) digital parameters that obtained from photographs of the strips were automatically read out via an iPhone. Subsequently, the parameters were converted into a color-difference map and processed statistically through principal component analysis, then used to elaborate standard curve. Combining the map and curve, we realized a method for assaying and quantifying L-AA concentration in real food samples, which avoids the time-consuming sample preparation, expensive laboratory techniques, and specialized personnel needed to carry out conventional analytical methods.

Structure and properties of novel regenerated cellulose fibers prepared in NaOH complex solution.

Novel spinning solution, prepared by dissolving hydroxyethyl cellulose (HEC) owning a low molar substitution (MS) into NaOH/urea/thiouea aqueous solution with a specific weight ratio of 8:8:6.5, was employed to fabricate a new type of regenerated fibers by wet-spun method. The structure and properties of the resultant HEC fibers were characterized by (13)C NMR, FTIR, synchrotron WAXS, SEM, and tensile tester. The results showed that HEC fibers exhibited structure identical with HEC because of the physical dissolution and coagulation processes, but quite different from native cellulose due to partial breakage of hydrogen bonds and crystal transformation from cellulose I to cellulose II during cellulose modification. The resultant HEC fibers with relatively dense and homogenous structure displayed good moisture related properties and stayed stable in alkali solution with low concentration. Moreover, the novel fibers owned good dry mechanical properties in spit of their slightly poor wet mechanical properties comparable to viscose rayon, showing great potential in substituting the traditional viscose fibers.

Amphiphilic poly(L-lactide)-b-dendritic poly(L-lysine)s synthesized with a metal-free catalyst and new dendron initiators: chemical preparation and characterization.

This study presents investigations on new approaches to novel biodegradable amphiphilic poly(L-lactide)-b-dendritic poly(L-lysine)s bearing well-defined structures. First, two new Boc-protected poly(L-lysine) dendron initiators G(2)OH 4 (generation = 2) and G(3)OH 6 (generation = 3) with hydroxyl end functional groups were efficiently derived from corresponding precursors 3 and 5 via methyl ester substitution with ethanolamine. Subsequently, two series of new diblock copolymers of poly(L-lactide)-b-dendritic Boc-protected poly(L-lysine)s (S1-S2, S3-S4) were prepared in chloroform through ring-opening copolymerization of poly(L-lactide)s with a metal-free catalyst of organic 4-(dimethylamino) pyridine (DMAP) in the presence of a corresponding new poly(L-lysine) dendron initiator. Further, molecular structures of the prepared new dendron initiators as well as those of poly(L-lactide)-b-dendritic Boc-protected poly(L-lysine)s bearing different dendron blocks and PLLA lengths were examined by means of nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), mass spectrometry (ESI-MS, MALDI-FTMS), and thermal gravimetric analysis (TGA). The results demonstrated successful formation of the synthetic precursors, functional dendron initiators, and new diblock copolymers. In addition, the very narrow molecular weight distributions (PDI = 1.10-1.14) of these poly(L-lactide)-b-dendritic Boc-protected poly(L-lysine)s further indicated their well-defined molecular structures. After the efficient Boc-deprotection for the dendron amino groups with TFA/CH(2)Cl(2), new diblock poly(L-lactide)-b-dendritic poly(L-lysine)s bearing lipophilic PLLA and hydrophilic dendritic PLL were finally prepared. It was noteworthy that the MALDI-FTMS result showed that no appreciable intermolecular chain transesterification happened during the ROP of L-lactide catalyzed by the DMAP. Moreover, self-assembly of these new biodegradable amphiphilic copolymers in diverse solvents were also preliminarily studied.

New asymmetric AB(n)-shaped amphiphilic poly(ethylene glycol)-b-[poly(l-lactide)](n) (n = 2, 4, 8) bridged with dendritic ester linkages: I. Syntheses and their characterization.

This study presents new investigations on chemical syntheses and characterization of new asymmetric AB(n)-shaped amphiphilic diblock methoxy poly(ethylene glycol)-b-[poly(l-lactide)](n), MPEG-b-(PLLA)(n) (n = 2, 4, and 8), bridged with dendritic ester linkages. First, a new series of A(OH)(n)-shaped hydroxy end-capped MPEG-(OH)(2), MPEG-(OH)(4), and MPEG-(OH)(8) bearing corresponding one- to three-generation dendritic ester moieties were efficiently derived from the starting MPEG (M(n) = 2 KDa) and 2,2'-bis(hydroxymethyl)propionic acid (Bis-HMPA) via ester coupling and a facile hydroxy protection-deprotection cycle, and then, chemical structures of these functional MPEG-(OH)(n) were characterized by nuclear magnetic resonance spectrometry (NMR) and MALDI-FTMS. Subsequently, by employing these MPEG-(OH)(n) as functional macroinitiators, new asymmetric AB(n)()-shaped amphiphilic MPEG-b-(PLLA)(2) S1, MPEG-b-(PLLA)(4) S2, and MPEG-b-(PLLA)(8) S3 bridged with dendritic Bis-HMPA ester linkages of L1-L3 as well as linear structural MPEG-b-PLLA references (R1-R3) were synthesized through the SnOct(2)-catalyzed ring-opening polymerization (ROP) of l-lactide at 130 degrees C in m-xylene solution, and their structures were further examined by NMR and gel permeation chromatography (GPC). It was demonstrated that the functional MPEG-(OH)(n) efficiently initiated the ROP of LLA, finally leading to successful formation of the AB(n)-shaped amphiphilic MPEG-b-(PLLA)(n) (n = 2, 4, and 8) with each PLLA arm weight close to 2 KDa and very narrow molecular weight distribution. Moreover, thermal history, crystallization, and spherulite morphologies were studied by means of differential scanning calorimeter (DSC), thermal gravimetric analyzer (TGA), and polarized microscope (POM) for these new structural amphiphilic S1-S3 as well as the linear R1-R3, intriguingly indicating a strong molecular architecture dependence of segmental crystallizability, spherulite morphology, and apparent crystal growth rate. Due to the favorable biodegradability and biocompatibility of the PLLA and MPEG, these results may therefore create new possibilities for these novel structural AB(n)-shaped amphiphilic MPEG-b-(PLLA)(n) as potential biomaterials.

Preparation and crystallization kinetics of new structurally well-defined star-shaped biodegradable poly(L-lactide)s initiated with diverse natural sugar alcohols.

This study presents syntheses, structural characterization, and crystallization kinetic investigation of new structurally well-defined star-shaped poly(l-lactide)s (PLLAs). First, a series of new 3- to 6-arm star-shaped PLLAs were synthesized through SnOct(2) catalyzed ring-opening polymerization of (l)-lactide with natural sugar alcohols of glycerol, erythritol, xylitol, and sorbitol as the favorable initiators. Subsequently, their chemical structures were characterized by means of GPC, NMR, and viscometer with respect to the star-shaped structures, demonstrating the well-defined arm structures as evidenced on the g(1/2)/g' values, where g and g' denote the ratios of mean-square radius of gyration and intrinsic viscosity of a star-shaped polymer to those of a linear structural reference with similar absolute molecular weight. Furthermore, spherulite morphologies and growth rates were studied by a polarized microscopy (POM) for the synthesized star-shaped PLLAs with different molecular weights, and it was found that the more arms of a star-shaped PLLA finally resulted in a lower spherulite growth rate. With regard to the crystallization kinetics of these star-shaped PLLAs, isothermal and nonisothermal crystallization were examined by differential scanning calorimeter (DSC). It was found that Avrami exponent n values of isothermal crystallization were almost independent of the isothermal crystallization temperature T(c) for different series of star-shaped PLLAs. In contrast, the values of Avrami exponent n were observed to strongly depend on the star-shaped structures with different arms, implying their distinct nucleation mechanisms, and the more arms of a star-shaped PLLA led to a slower isothermal crystallization rate. On the basis of a modified Avrami equation, new light was shed on the nonisothermal crystallization kinetics for the star-shaped PLLAs, and the activation energies were found to vary from 146.86 kJ/mol for the linear PLLA EG-3 to 221.23 kJ/mol of the star-shaped S-3, demonstrating much decreased crystallizabilities of star-shaped PLLAs with more arms.