Bio-Based Flame-Retardant Coatings Based on the Synergistic Combination of Tannic Acid and Phytic Acid for Nylon-Cotton Blends.

Natural and synthetic polymeric fibers are used extensively in making fabrics for a variety of civilian and military applications. Due to the durability and comfort, nyco, a 50-50% blend of nylon 66 and cotton, is used as the material of choice in many applications including military uniforms. This fabric is flammable due to the presence of cotton and nylon but has good mechanical properties and is comfortable to wear. Here, we report a novel surface functionalization method that utilizes a synergistic combination of bio-based materials, tannic acid (TA) and phytic acid (PA), to impart flame-retardant (FR) properties to the nyco fabric. TA and PA were sequentially attached to nylon and cotton fibers through hydrogen bonding interactions and phosphorylation, respectively. The surface functionalization of the treated fabrics was confirmed using Fourier-transform infrared spectroscopy. Thermogravimetric analysis, microscale combustion calorimetry, cone calorimetry, and vertical flame testing were employed to study the effect of the functionalization on the thermal stability and flammability of the nyco fabric. Though reasonable durable functionalization is observed from elemental analysis, it is not enough to impart wash-durable FR treatment. These results indicate that flame retardancy is enabled through the enhanced char formation provided by the combination of TA and PA. The TA-PA system applied to nyco shows great promise as a bio-based FR system. This study for the first time also provides evidence for the selectivity of TA in imparting FR characteristics for nylon and PA in imparting FR properties for cotton. The combination of TA and PA provides promising FR characteristics to nyco.

Effects of mask-wearing on the inhalability and deposition of airborne SARS-CoV-2 aerosols in human upper airway.

Even though face masks are well accepted as tools useful in reducing COVID-19 transmissions, their effectiveness in reducing viral loads in the respiratory tract is unclear. Wearing a mask will significantly alter the airflow and particle dynamics near the face, which can change the inhalability of ambient particles. The objective of this study is to investigate the effects of wearing a surgical mask on inspiratory airflow and dosimetry of airborne, virus-laden aerosols on the face and in the respiratory tract. A computational model was developed that comprised a pleated surgical mask, a face model, and an image-based upper airway geometry. The viral load in the nose was particularly examined with and without a mask. Results show that when breathing without a mask, air enters the mouth and nose through specific paths. When wearing a mask, however, air enters the mouth and nose through the entire surface of the mask at lower speeds, which favors the inhalation of ambient aerosols into the nose. With a 65% filtration efficiency (FE) typical for a three-layer surgical mask, wearing a mask reduces dosimetry for all micrometer particles except those of size 1 µm-3 µm, for which equivalent dosimetry with and without a mask in the upper airway was predicted. Wearing a mask reduces particle penetration into the lungs, regardless of the FE of the mask. The results also show that mask-wearing protects the upper airway (particularly the nose and larynx) best from particles larger than 10 µm while protecting the lungs best from particles smaller than 10 µm.

Antioxidant Activity of Synthetic Polymers of Phenolic Compounds.

In recent years, developing potent antioxidants has been a very active area of research. In this context, phenolic compounds have been evaluated for their antioxidant activity. However, the use of phenolic compounds has also been limited by poor antioxidant activity in several in vivo studies. Polymeric phenols have received much attention owing to their potent antioxidant properties and increased stability in aqueous systems. To be truly effective in biological applications, it is important that these polymers be synthesized using benign methods. In this context, enzyme catalyzed synthesis of polymeric phenols has been explored as an environmentally friendly and safer approach. This review summarizes work in enzymatic syntheses of polymers of phenols. Several assays have been developed to determine the antioxidant potency of these polymeric phenols. These assays are discussed in detail along with structure-property relationships. A deeper understanding of factors affecting antioxidant activity would provide an opportunity for the design of versatile, high performing polymers with enhanced antioxidant activity.

A reinforced thermal barrier coat of a Na-tannic acid complex from the view of thermal kinetics.

The poor burning resistance of cotton necessitates the control of its pyrolytic reactions, but many approaches have relied on the use of synthetically engineered chemicals. Herein, we show how a natural polyphenol from plants-tannic acid-acts with sodium ions to create a robust thermal barrier coat on cotton, with a focus on thermal kinetics. The kinetic information, combined with thermal and spectral analyses, revealed that the outer layer of galloyl units in tannic acid decomposes via a two-step reaction, producing a multicellular char of crosslinked aromatic rings, followed by the blowing of carbonaceous cells into a further expanded structure. This intumescent function of tannic acid was found to be enhanced upon its complexation with sodium ions, which greatly increased the activation energy for the first step of the reaction of tannic acid, to promote the formation of a stable char. The resulting blown char coated the cotton fiber below the thermal decomposition temperature of cellulose and was sustained throughout the decomposition. The enhanced thermal barrier performance of the Na-tannic acid complex was demonstrated by the reduced heat release capacity of cotton, the value of which was only about one-third that of tannic acid itself, and the inhibition of flame generation on cotton.

Microwave-assisted synthesis and characterization of hydrophilically functionalized polygalacturonic acid.

Microwave-assisted synthesis of a new class of polymeric surfactants based on polygalacturonic acid (PGA) is presented. PGA is water-insoluble and not surface-active under normal conditions. Single-step hydrophilic modification of PGA with taurine (2-aminoethane sulfonic acid) renders it surface-active. The modification can be carried out either using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDCl) as a coupling agent or using microwave irradiation without a catalyst. Microwave irradiation significantly shortens reaction times and eliminates the need for a coupling agent. In all cases, functionalization was confirmed using 1H NMR, FTIR spectroscopy and elemental analysis. PGA-SO3 exhibits surface-active properties comparable to commercial surfactants, Triton X-100 and sodium lauryl sulfate. Detailed cytotoxicity evaluation performed using human dermal fibroblast (HDF) and human leukemic (HL-60) cell lines indicate that PGA-SO3 is not toxic even at 20 fold higher concentrations. These polymeric surfactants synthesized from PGA with no demonstrable cytotoxicity have the potential for serving as 'greener' alternatives to common petrochemical-based surfactants.

Biocatalytic Synthesis of Fluorescent Conjugated Indole Oligomers.

Fluorescent conjugated materials exhibiting reasonable biocompatibility that are capable of interacting with biological molecules are of interest for bio-sensing and imaging applications. Traditional approaches do not allow for the synthesis of conjugated materials in the presence of biologically relevant substrates. Further conjugated polymers synthesized using conventional methods are doped and not fluorescent. Here we explore the possibility of synthesizing fluorescent oligomers of indole using enzymes as catalyst under mild conditions. The peroxidase catalyzed coupling reaction presented here creates a photoluminescent material that allows for direct utilization (without purification and separation of the dopant) in biosensing applications. The polymerization reaction proceeds smoothly in just deionized water and ethanol. Monitoring of the absorption and fluorescence spectra over one hour shows that the concentration of both absorbing and emitting species grows steadily over time. The presence of anionic buffers and templates is shown to effectively retard the development of light emitting species and instead leads to the formation of an electrically doped conjugated polymer. Structural characterization through FTIR and ¹H-NMR analysis suggests that the oligomer is coupled through the 2 and 3 positions on the indole ring.

Micellar nanoreactors for hematin catalyzed synthesis of electrically conducting polypyrrole.

Enzymatic synthesis of doped polypyrrole (PPy) complexes using oxidoreductases (specifically peroxidases) is very well established "green" methods for producing conducting polypyrrole. The importance of this approach is realized by the numerous potential opportunities of using PPy in biological applications. However, due to very high costs and low acid stability of these enzymes, there is need for more robust alternate biomimetic catalysts. Hematin, a hydroxyferriprotoporphyrin, has a similar iron catalytic active center like the peroxidases and has previously shown to catalyze polymerization of phenol monomers at pH 12. The insolubility of hematin due to extensive self-aggregation at low pH conditions has prevented its use in the synthesis of conjugated polymers. In this study, we have demonstrated the use of a micellar environment with sodium dodecylbenzenesulfonate (DBSA) for biomimetic synthesis of PPy. The micellar environment helps solubilize hematin, generating nanometer size reactors for the polymerization of pyrrole. The resulting PPy is characterized using UV-visible, Fourier transform infrared, and X-ray photoelectron spectroscopy and reveals the formation of an ordered PPy/DBSA complex with conductivities approaching 0.1 S/cm.

Biocatalytically oligomerized epicatechin with potent and specific anti-proliferative activity for human breast cancer cells.

Catechins, naturally occurring flavonoids derived from wine and green tea, are known to exhibit multiple health benefits. Epigallocatechin gallate (EGCG) is one of the most widely investigated catechins, but its efficacy in cancer therapy is still inconsistent and limited. The poor stability of EGCG has contributed to the disparity in the reported anti-cancer activity and other beneficial properties. Here we report an innovative enzymatic strategy for the oligomerization of catechins (specifically epicatechin) that yields stable, water-soluble oligomerized epicatechins with enhanced and highly specific anti-proliferative activity for human breast cancer cells. This one-pot oxidative oligomerization is carried out in ambient conditions using Horseradish Peroxidase (HRP) as a catalyst yielding water-soluble oligo(epicatechins). The oligomerized epicatechins obtained exhibit excellent growth inhibitory effects against human breast cancer cells with greater specificity towards growth-inhibiting cancer cells as opposed to normal cells, achieving a high therapeutic differential. Our studies indicate that water-soluble oligomeric epicatechins surpass EGCG in stability, selectivity and efficacy at lower doses.

Biomimetic synthesis of water-soluble conducting copolymers/homopolymers of pyrrole and 3,4-ethylenedioxythiophene.

A novel biomimetic route for the synthesis of electrically conducting homopolymers/copolymers of pyrrole and 3,4-ethylenedioxythiophene (EDOT) in the presence of a polyelectrolyte, such as polystyrene sulfonate (SPS), is presented. A poly(ethylene glycol)-modified hematin (PEG-hematin) was used to catalyze the homopolymerization of pyrrole and EDOT as well as copolymerization of EDOT and pyrrole in the presence of SPS to yield homopolymers of polypyrrole/SPS and PEDOT/SPS as well as a polypyrrole-co-poly(3,4-ethylenedioxythiophene)/SPS complex. Spectroscopic characterization [UV-visible, Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS)], thermal analysis, (TGA), and electrical conductivity studies for these complexes indicated the presence of a stable and electrically conductive form of these polymers. Furthermore, the presence of SPS that serves as a charge-compensating dopant in this complex provides a unique combination of properties such as processability and water solubility.

Photo-cross-linked immobilization of polyelectrolytes for enzymatic construction of conductive nanocomposites.

Horseradish peroxidase has been demonstrated to catalyze the oxidative polymerization of aniline to form conductive polyaniline. This process is facilitated by the presence of a macromolecular template with sulfonic acid groups that provide a unique environment for the formation of the conducting polymer. Here we report the use of a photo-cross-linkable thymine-based polymer with phenylsulfonate groups as a templating substrate. This allows for an aqueous-based environmentally benign photopatterning of a conductive material. A description and results of this process are presented.

Solvent specified conformation in poly(alpha-L-glutamic acid) thin films.

The ability to control conformational properties of polypeptides in their films is of considerable interest for many possible applications of these materials. By rational choice of the solvent system for film fabrication, control over the conformation of the main chain, the intermolecular hydrogen bonding in the side chain is easily achieved in poly(alpha-L-glutamic acid) (PLGA) thin films. The spectral data from circular dichromism (CD), FT-IR, and solid state (13)C NMR spectroscopies suggest that the beta-sheet conformation is dominant in PLGA films cast from trifluoroacetic acid (TFA) solution, whereas the right-handed alpha-helix is dominant in those cast from pyridine or DMF solution. In comparison with films cast from TFA solutions, the films fabricated from pyridine or DMF solutions exhibit strong intermolecular hydrogen bondings between -COOH groups and have a more ordered arrangement of side chains. Moreover, the extent of alpha-helix conformation of the PLGA backbone in films cast from pyridine or DMF solution is several times higher than that observed in the PLGA powder precipitated from aqueous solution at pH 4. All spectroscopic studies indicate clearly that the solvents (used for casting these films) play a crucial role in directing the organization of PLGA in these thin films.

Biomimetic synthesis of a water soluble conducting molecular complex of polyaniline and lignosulfonate.

A new biomimetic route for the synthesis of a conducting molecular complex of polyaniline (Pani) and a natural polyelectrolyte, lignosulfonate (LGS) is presented. A poly(ethylene glycol) modified hematin (PEG-hematin) was used to catalyze the polymerization of aniline in the presence of LGS to form a Pani/LGS complex. UV-vis, FTIR, conductivity and TGA studies for the LGS-polyaniline complex indicate the presence of a thermally stable and electrically conductive form of polyaniline. Also the presence of LGS in this complex, an inexpensive byproduct from pulp processing, provides a unique combination of properties such as electronic conductivity, processability and biodegradability. The use of this conductive complex for corrosion protection is also proposed.