Enzyme- and Relative Humidity-Responsive Antimicrobial Fibers for Active Food Packaging.

Active food packaging materials that are sustainable, biodegradable, and capable of precise delivery of antimicrobial active ingredients (AIs) are in high demand. Here, we report the development of novel enzyme- and relative humidity (RH)-responsive antimicrobial fibers with an average diameter of 225 ± 50 nm, which can be deposited as a functional layer for packaging materials. Cellulose nanocrystals (CNCs), zein (protein), and starch were electrospun to form multistimuli-responsive fibers that incorporated a cocktail of both free nature-derived antimicrobials such as thyme oil, citric acid, and nisin and cyclodextrin-inclusion complexes (CD-ICs) of thyme oil, sorbic acid, and nisin. The multistimuli-responsive fibers were designed to release the free AIs and CD-ICs of AIs in response to enzyme and RH triggers, respectively. Enzyme-responsive release of free AIs is achieved due to the degradation of selected polymers, forming the backbone of the fibers. For instance, protease enzyme can degrade zein polymer, further accelerating the release of AIs from the fibers. Similarly, RH-responsive release is obtained due to the unique chemical nature of CD-ICs, enabling the release of AIs from the cavity at high RH. The successful synthesis of CD-ICs of AIs and incorporation of antimicrobials in the structure of the multistimuli-responsive fibers were confirmed by X-ray diffraction and Fourier transform infrared spectrometry. Fibers were capable of releasing free AIs when triggered by microorganism-exudated enzymes in a dose-dependent manner and releasing CD-IC form of AIs in response to high relative humidity (95% RH). With 24 h of exposure, stimuli-responsive fibers significantly reduced the populations of foodborne pathogenic bacterial surrogates Escherichia coli (by ∼5 log unit) and Listeria innocua (by ∼5 log unit), as well as fungi Aspergillus fumigatus (by >1 log unit). More importantly, the fibers released more AIs at 95% RH than at 50% RH, which resulted in a higher population reduction of E. coli at 95% RH. Such biodegradable, nontoxic, and multistimuli-responsive antimicrobial fibers have great potential for broad applications as active and smart packaging systems.

High Interlaminar Shear Strength Enhancement of Carbon Fiber/Epoxy Composite through Fiber- and Matrix-Anchored Carbon Nanotube Networks.

To improve the interlaminar shear strength (ILSS) of carbon fiber reinforced epoxy composite, networks of multiwalled carbon nanotubes (MWNTs) were grown on micron-sized carbon fibers and single-walled carbon nanotubes (SWNTs) were dispersed into the epoxy matrix so that these two types of carbon nanotubes entangle at the carbon fiber (CF)/epoxy matrix interface. The MWNTs on the CF fiber (CF-MWNTs) were grown by chemical vapor deposition (CVD), while the single-walled carbon nanotubes (SWNTs) were finely dispersed in the epoxy matrix precursor with the aid of a dispersing agent polyimide-graft-bisphenol A diglyceryl acrylate (PI-BDA) copolymer. Using vacuum assisted resin transfer molding, the SWNT-laden epoxy matrix precursor was forced into intimate contact with the "hairy" surface of the CF-MWNT fiber. The tube density and the average tube length of the MWNT layer on CF was controlled by the CVD growth time. The ILSS of the CF-MWNT/epoxy resin composite was examined using the short beam shear test. With addition of MWNTs onto the CF surface as well as SWNTs into the epoxy matrix, the ILSS of CF/epoxy resin composite was 47.59 ± 2.26 MPa, which represented a ∼103% increase compared with the composite made with pristine CF and pristine epoxy matrix (without any SWNT filler). FESEM established that the enhanced composite did not fail at the CF/epoxy matrix interface.