This work demonstrates a general strategy for introducing remarkable changes in matrix organization and, consequently, functional properties of bacterial cellulose (BC). BC-producing cells were induced, using a well-defined atomized droplet nutrient delivery (ADND) system, to form pellicles with a regular layered morphology that persists throughout the mat depth. In contrast, the morphology of mats formed by conventional static medium nutrient delivery (SMND) is irregular with no distinguishable pattern. ADND also resulted in larger meso-scale average pore sizes but did not alter the fibril diameter (∼70 nm) and crystallinity index (92−95%). The specific modulus and specific tensile strength of ADND mats are higher than those of SMND mats. This is due to the regularity of dense layers that are present in ADND mats that are able to sustain tensile loads, when applied parallel to these layers. The density of BC films prepared by ADND is 1.63-fold lower than that of the SMND BC film. Consequently, the water contents (g/g) of ADND-and SMND-prepared BC mats are 263 ± 8.85 and 99.6 ± 2.04, respectively. A model that rationalizes differences in mat morphology resulting from these nutrient delivery methods based on nutrient and oxygen concentration gradients is proposed. This work raises questions as to the extent that ADND can be used to fine-tune the matrix morphology and how the resulting lower density mats will alter the diffusion of actives from the films to wound sites and increase the ability of cells to infiltrate the matrix during tissue engineering.

Self-assembling peptide materials are promising next-generation materials with applications that include tissue engineering scaffolds, drug delivery, bionanomedicine, and enviro-responsive materials. Despite these advances, synthetic methods to form peptides and peptide−polymer conjugates still largely rely on solid-phase peptide synthesis (SPPS) and N-carboxyanhydride ring-opening polymerization (NCA-ROP), while green methods remain largely undeveloped. This work demonstrates a protease-catalyzed peptide synthesis (PCPS) capable of directly grafting leucine ethyl ester (Leu-OEt) from the C-terminus of a methoxy poly(ethylene glycol)-phenylalanine ethyl ester macroinitiator in a one-pot, aqueous reaction. By using the natural tendency of the growing hydrophobic peptide segment to self-assemble, a large narrowing of the (Leu) x distributions for both mPEG 45 -b-Phe(Leu) x and oligo(Leu) x coproducts, relative to oligo(Leu) x synthesized in the absence of a macroinitiator (mPEG 45 -Phe-OEt), was achieved. A mechanism is described where in situ β-sheet coassembly of mPEG 45 -b-Phe(Leu) x and oligo(Leu) x coproducts during polymerization prevents peptide hydrolysis, providing a means to control the degree of polymerization (DP) and dispersity of diblock (Leu) x segments (matrix-assisted laser desorption time-of-flight (MALDI-TOF) x = 5.1, dispersity ≤ 1.02). The use of self-assembly to control the uniformity of peptides synthesized by PCPS paves the way for precise peptide block copolymer architectures with various polymer backbones and amino acid compositions synthesized by a green process.

Manipulation of bacterial cellulose (BC) morphology is important to tune BC properties to meet specific application requirements. In this study, gelatin was added to cultivation media at 0.1–7.5 wt %. After cultivations, gelatin was removed from the BC matrix, and its effects on BC matrix characteristics and fermentation production efficiency were determined. Higher contents of gelatin in cultivation media (up to 5%) resulted in BC that, from scanning electron microscopy observations, had larger pore sizes and formation of a lamina morphology that was highly unidirectional. Crystallinity remained unchanged between 0.1 and 5 wt % gelatin concentrations (92–95%); however, it decreased to 86% at a gelatin concentration of 7.5 wt %. Mechanical properties showed a positive trend as both the specific modulus and specific strength values increased as the gelatin concentration increased to 5 wt %. A breakdown in the ordered structure of the BC matrix occurs at 7.5 wt % gelatin, with corresponding decreases in the specific modulus and specific strength of the BC. The productivity increased by almost 4-fold relative to the control, reaching 1.64 g·L–1h–1 at the 2.5 wt % gelatin content. Also, the water holding capacity increased by 3-fold relative to the control, reaching 306.6 g of water per g BC at the 5.0 wt % gelatin content. The changes observed in these BC metrics can be explained based on literature findings associated with the formation of gelatin aggregates in the cultivation media and an increase in gel stiffness seen at higher media gelatin concentrations. Overall, this work provides a roadmap for manipulating BC properties while creating highly organized lamina morphologies.

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