Protein-textile/paper-composites and articles containing the same

Abstract

Disclosed herein is a multilayered biopolymeric composite comprising a first crosslinked proteinaceous biopolymer layer disposed on a substrate; where the substrate comprises a fabric, paper, or a combination thereof; and wherein the first crosslinked proteinaceous biopolymer layer and/or the substrate comprises at least one of a nanoclay, a dye, a colorant, a radio-opaque additive, an electrically conductive filler, or a combination thereof.

What is claimed is: 
     
         1 . A multilayered biopolymeric composite comprising:
 a first crosslinked proteinaceous biopolymer layer disposed on a substrate; where the substrate comprises a fabric, paper, or a combination thereof; and wherein the first crosslinked proteinaceous biopolymer layer and/or the substrate comprises at least one of a nanoclay, a dye, a colorant, a radio-opaque additive, an electrically conductive filler, or a combination thereof.   
     
     
         2 . The multilayered biopolymeric composite of  claim 1 , where the dye is a fluorescent dye that is selected from the group consisting of fluorescein, rhodamine B, rhodamine 6G, sulforhodamine 101, cyanine dyes, BODIPY dyes, Texas Red, Nile Red, coumarin derivatives, eosin Y, erythrosin B, pyrene derivatives, lanthanide-based complexes such as europium and terbium chelates, or a combination thereof. 
     
     
         3 . The multilayered biopolymeric composite of  claim 1 , where the dye is a polyazaindacene, a coumarin, a lanthanide complex, a hydrocarbon and substituted hydrocarbon dye, a polycyclic aromatic hydrocarbon, a scintillation dye, an aryl- and heteroaryl-substituted polyolefin, a carbocyanine dye, a phthalocyanine dye, an oxazine dye, a carbostyryl dye, a porphyrin dye, an acridine dye, an anthraquinone dye, an anthrapyridone dye, a naphtalimide dye, a benzimidazole derivative, an arylmethane dye, an azo dye, a diazonium dye, a nitro dye, a quinone imine dye, a tetrazolium dye, a thiazole dye, a perylene dye, a perinone dye, a bis-benzoxazolylthiophene, a xanthene dye, an indigoid dye, a chromone dyes, a flavones dye, or a combination thereof. 
     
     
         4 . The multilayered biopolymeric composite of  claim 1 , where the dye is a quantum dot; where the quantum dot is a cadmium selenide (CdSe), a cadmium telluride (CdTe), a cadmium sulfide (CdS), a zinc sulfide (ZnS), an indium phosphide (InP), a lead sulfide (PbS) nanocrystal. 
     
     
         5 . The multilayered biopolymeric composite of  claim 1 , where the quantum dot comprises a core-shell structure, and where the core-shell comprises a CdSe core in contact with a ZnS shell or an InP core in contact with a ZnS shell. 
     
     
         6 . The multilayered biopolymeric composite of  claim 1 , wherein the dye and/or the colorant is a fluorescing dye or a fluorescing colorant that fluoresces between 350 to 900 nanometers. 
     
     
         7 . The multilayered biopolymeric composite of  claim 1 , wherein the crosslinked proteinaceous biopolymer layer is electrically conducting with an electrical resistivity less than about 1×10 11  ohm-cm, an IZOD notched impact strength greater than about 200 Joules per meter (J/m) when measured as per ASTM D 256, while at the same time exhibiting fluorescence at wavelengths between 540 and 600 nanometers. 
     
     
         8 . The multilayered biopolymeric composite of  claim 1 , wherein the crosslinked proteinaceous biopolymer layer is radio-opaque to xrays, has an IZOD notched impact strength greater than about 200 Joules per meter (J/m) when measured as per ASTM D 256, while at the same time exhibiting fluorescence at wavelengths between 540 and 600 nanometers. 
     
     
         9 . The multilayered biopolymeric composite of  claim 1 , wherein the multilayered biopolymeric composite has a mass attenuation coefficient of 1.9 to 2.2 cm 2 /g at 70 keV, while at the same time exhibiting fluorescence at wavelengths between 540 and 600 nanometers. 
     
     
         10 . The multilayered biopolymeric composite of  claim 1 , wherein the first crosslinked proteinaceous biopolymer layer comprises at least one of a nanoclay, a dye, a colorant, a radio-opaque additive, an electrically conductive filler, fire retardant or a combination thereof. 
     
     
         11 . The multilayered biopolymeric composite of  claim 1 , wherein the nanoclay is a smectite-type clay or layered phosphate or MXenes. 
     
     
         12 . The multilayered biopolymeric composite of  claim 1 , wherein the nanoclay is intercalated with a proteinaceous biopolymer used in the first crosslinked proteinaceous biopolymer layer. 
     
     
         13 . The multilayered biopolymeric composite of  claim 1 , wherein the first crosslinked proteinaceous biopolymer layer comprises albumin. 
     
     
         14 . The multilayered biopolymeric composite of  claim 1 , wherein the crosslinked proteinaceous biopolymer is crosslinked via an unsaturated carboxylic acid, an amine, a carboxylic acid functionalized with an amine, or a combination thereof. 
     
     
         15 . The multilayered biopolymeric composite of  claim 6 , wherein the amine is a naturally occurring amine or a synthetic amine. 
     
     
         16 . The multilayered biopolymeric composite of  claim 1 , wherein the electrically conducting filler forms a percolating network in at least the first crosslinked proteinaceous biopolymer layer. 
     
     
         17 . The multilayered biopolymeric composite of  claim 1 , wherein the radio-opaque additive is barium sulfate, bismuth sub-carbonate, bismuth oxychloride, bismuth trioxide, tungsten powder, tantalum powder, zirconium oxide, iodine-containing organic compounds, strontium sulfate, strontium carbonate, or a combination thereof. 
     
     
         18 . The multilayered biopolymeric composite of  claim 13 , further comprising a plurality of crosslinked proteinaceous biopolymer layers and a plurality of substrates, where each substrate of the plurality of substrates has a crosslinked proteinaceous biopolymer layer on opposing surfaces. 
     
     
         19 . The multilayered biopolymeric composite of  claim 1 , further comprising a second crosslinked proteinaceous biopolymer layer that is disposed on a surface of the substrate that is opposite of the surface that contacts the first crosslinked proteinaceous biopolymer layer. 
     
     
         20 . An article comprising the multilayered biopolymeric composite of  claim 1 , wherein the article is a space suit, radiation protection clothing, a radiation protection shelter, a bullet proof vest or flame retardant clothing. 
     
     
         21 . A method of manufacturing the multilayered biopolymeric composite of  claim 1 , the method comprising:
 mixing an uncrosslinked proteinaceous biopolymer and a crosslinking agent to form a solution;   disposing the solution on at least one surface of the substrate; and   crosslinking the uncrosslinked proteinaceous biopolymer to form the first crosslinked proteinaceous biopolymer layer on the substrate with the chemical crosslinking agent or physical crosslinking by heating the article to 60 to 80° C. for 5 to 20 minutes.