Simultaneous toughness and stiffness of 3D printed nano-reinforced polylactide matrix with complete stereo-complexation via hierarchical crystallinity and reactivity.

A novel strategy adaptive to 3D printing of stereo-complexed polylactide matrix for simultaneous toughness and stiffness was designed. Stereo-complexation is a potent way to enhance both aqueous stability and heat resistance of polylactide, but also aggravates brittleness problem of polylactide. Though poly(butyleneadipate-co-terephthalate) elastomer with epoxidized compatibilizer improved stiffness and toughness of common polylactide, their effectiveness on mechanical and crystallization properties of stereo-complexed polylactide remained unknown. More importantly, incorporation of above techniques into 3D printing kept a fundamental challenge. Both stereo-complexation of polylactide and covalent coupling of polylactide and poly(butyleneadipate-co-terephthalate) by epoxidized compatibilizer are easy to occur when preparing the filaments for printing, impeding the following 3D printing procedure. The hypothesis for this research is that controlled hierarchical crystallization and reaction in three thermal processes could ensure simultaneous toughness and stiffness, and complete stereo-complexation in polylactide matrices. Reinforcing effects of a selected epoxidized compatibilizer, POSS(epoxy)8, on crystallinities, thermal properties, mechanical properties and morphologies were systematically studied. Such a strategy not only removed the obstacles in incorporating stereo-complexation and coupling techniques of polylactide into 3D printing, but also revealed the mechanism to produce high-performance 3D printed polylactide matrix via hierarchical crystallization and reaction.

Hierarchical crystallization strategy adaptive to 3-dimentional printing of polylactide matrix for complete stereo-complexation.

A novel strategy adaptive to 3D printing of PLA matrix for complete stereo-complexation was designed. Stereo-complexation has been demonstrated for its effectiveness in simultaneously improving aqueous stability and heat resistance of PLA. However, current techniques could not be directly incorporated into 3D printing of stereo-complexed PLA since stereo-complexed crystallites are easily formed before printing. High printing temperatures are thus required but decompose PLA materials at the same time. The hypothesis for this research is that controllable hierarchical crystallization in three thermal processes, the filament preparation, 3D printing and post annealing, could ensure feasibility of the strategy and a 100% stereo-complexation level in PLA matrices. Effects of extrusion, ambient and annealing temperatures on material structures were analyzed via WAXD, DSC and DMA. Resistance to hydrolysis and heat of the 3D printed PLA matrix was evaluated under practical conditions. It was showed that homo-crystallites anchored molecular chains of PLA during the post-annealing process for a high retention of tensile properties, while stereo-complexed crystallites provided stronger intermolecular interactions for improved hydrolytic and thermal resistance. This novel strategy via incorporating controlled hierarchical crystallization into 3D printing would enrich the fabrication and exploration of high-performance 3D printed PLA materials.

Correction: Potent and regularizable crosslinking of ultrafine fibrous protein scaffolds for tissue engineering using a cytocompatible disaccharide derivative.

Correction for 'Potent and regularizable crosslinking of ultrafine fibrous protein scaffolds for tissue engineering using a cytocompatible disaccharide derivative' by Helan Xu et al., J. Mater. Chem. B, 2015, 3, 3609-3616, DOI: 10.1039/C4TB02100B.

Transferring feather wastes to ductile keratin filaments towards a sustainable poultry industry.

Technology for the transformation of waste feathers to quality regenerated filaments has been developed. Regardless of superior properties of natural keratin materials, previously developed regenerated materials from keratin had tensile properties much lower than their natural counterparts due to backbone hydrolysis and inefficient reconstruction of disulfide crosslinkages. In this work, tough keratin filaments have been regenerated from white duck feathers via efficient restoration of disulfide crosslinkages using a dithiol reducing agent. Dithiol substantially reserves free thiol groups in the extraction and formed lengthy intermolecular crosslinkages in regenerated keratin filaments. Due to the high degree of intermolecular reconstruction of disulfide bonds and formation of lengthy crosslinkages via dithiol chain-extension, the keratin filaments exhibited considerable improvements in mechanical properties, especially for ductility and water stability. The tenacity and elongation at break were 160.7 MPa and 14%, respectively. The filaments retained about 80% of the tenacity of natural feathers at either dry or wet conditions and demonstrated stretchability 150% higher than natural feathers. The fiber regeneration technology makes it possible to substitute primary fiber sources by renewable poultry feathers. Successful filament substitution or addition can bring more than 88-billion-dollar revenue. The technology not only contributes to a sustainable fiber and poultry industry but adds substantial values to poultry feathers.

Chitosan/gallnut tannins composite fiber with improved tensile, antibacterial and fluorescence properties.

Natural extracts gallnut tannins (GTs) were used as functional components to prepare chitosan/gallnut tannins (CS/GTs) composite fiber by blended solution spinning. Chitosan fiber has great potential to be used as absorbent suture and dressing due to its good biocompatibility. However, the weak mechanical properties limited its application. Chitosan and GTs were blended in aqueous solution of acetic acid to spin the composite fiber. The results indicated that CS/GTs fiber can be easily prepared due to the appropriate rheology characteristics for blended solution. Compared with pure chitosan fiber, CS/GTs fiber with 10% GTs showed lower hydrophilicity and higher dry, wet breaking strength by more than 40% due to ionic cross-linking between chitosan and GTs. The bacterial reduction to Staphylococcus aureus increased from 49.0 to 99.7% and about double green and red fluorescent intensity were observed for CS/GTs fiber. GTs have great potentiality in improving the properties of chitosan fiber.

Valorization of keratin from food wastes via crosslinking using non-toxic oligosaccharide derivatives.

Oligosaccharide derivatives were developed to crosslink keratin materials from poultry feathers, swine bristles and ox hairs to valorize these major wastes from meat industry. Global butchery generates more than 8,600,000 tons of keratinous wastes annually. Keratin was considered a promising resource for developing bio-based products as alternatives to petroleum products. Regenerated keratin products, such as films, usually showed insufficient mechanical properties, and required external crosslinking. However, most crosslinkers for proteins are either toxic, expensive, or with low efficiencies under mild conditions. In this research, regenerated keratin films were crosslinked by oxidized sucrose, a safe and potent bio-polyaldehyde. The crosslinker with verified low toxicity improved both tensile strength and elongation of keratin films, surpassing many other safe crosslinkers. Mechanism of the crosslinking reaction was proposed as forming Schiff bases and aminals and verified via 1H NMR and 13C NMR. Relationship between tensile properties and crosslinking degree of keratin films was also quantified.

Poly(l-lactic acid) bio-composites reinforced by oligo(d-lactic acid) grafted chitosan for simultaneously improved ductility, strength and modulus.

PLA bio-composites reinforced by oligo(d-lactic acid) grafted chitosan has been developed for simultaneously improved ductility, strength and modulus. Brittleness problem greatly limits the applications of PLA, a polymer derived from corn. Various methods have been developed to solve the brittleness problem. Unfortunately, these methods have their limitations, such as sacrifice of strength and modulus of PLA, use of toxic chemicals and high costs. Bio-based elastomers such as chitosan also have poor compatibility with PLA, leading to poor mechanical properties. The hypothesis for this research is that CS-g-oligo(D-LA) particles with good ductility could form strong interfacial interactions with PLLA matrix. Reinforcing effect of CS-g-oligo(D-LA) particles on PLLA matrix was systematically studied. Compatibility and intermolecular interactions between CS-g-oligo(D-LA) particles and PLLA matrix were studied by SEM, DSC and 13C NMR analyses. The reinforcing mechanism was summarized. Due to effective transfer of stress from PLLA matrix to the strong but ductile skeletons of CS-g-oligo(D-LA), ductility, strength and modulus of PLLA bio-composites were substantially improved. This novel reinforcing strategy via formation of strong interactions between enantiomeric lactyl units would enrich the fabrication and exploration of high-performance PLA-based bio-composites.

Submicron amino acid particles reinforced 100% keratin biomedical films with enhanced wet properties via interfacial strengthening.

Keratin films with wet stability and strength suitable for biomedical applications were developed via reinforcement with submicron cysteine particles for improved interfaces. Keratin products regenerated from wool or human hair were widely investigated as wound dressing and tissue engineering scaffolds for their satisfactory biomedical properties. However, regenerated keratin scaffolds usually did not have good mechanical properties, and also could not stand humid or wet biological environment due to poor moisture stability. Reinforcements for keratin materials were usually polysaccharides or synthetic polymers, and thus usually had non-ideal interfacial properties due to limited compatibility. In this research, submicron cystine particles were employed to reinforce keratin films for their high compatibility with keratin and bio-safety. Transition of primary and secondary structures of keratin due to matrix-reinforcement interaction was analyzed. The keratin films showed unprecedented pliancy, good tensile properties under humid conditions and biocompatibility, and thus had good potential for biomedical engineering applications.

Quantitation of fast hydrolysis of cellulose catalyzed by its substituents for potential biomass conversion.

This paper investigates the accelerated acidic hydrolysis of cellulose by its substituents for potential biomass conversion. Insufficient pretreatments and slow cellulose hydrolysis are major obstacles that impede efficient hydrolysis of cellulose. Substituted cellulose, such as dyed cotton, has large availability. It is susceptible to acidic hydrolysis and can be used for biomass conversion without any pretreatments. To understand the mechanism of accelerated hydrolysis of cellulose by its substituents is a prerequisite for cellulosic biomass conversion with high efficiency. Substituents with different charge properties were synthesized and their interactions with oxocarbenium ions were studied based on Density Functional Theory. Results indicate that hydrolysis rate is affected by field effect from substituents. Such field effect is dominated by amounts of negative charges on substituents and distance between negatively charged groups and oxocarbenium. Hydrolysis rate of dye-substituted cotton is higher than or comparable to that applied with other catalytic approaches.

Cellulose nanocrystal-reinforced keratin bioadsorbent for effective removal of dyes from aqueous solution.

High-efficiency and recyclable three-dimensional bioadsorbents were prepared by incorporating cellulose nanocrystal (CNC) as reinforcements in keratin sponge matrix to remove dyes from aqueous solution. Adsorption performance of dyes by CNC-reinforced keratin bioadsorbent was improved significantly as a result of adding CNC as filler. Batch adsorption results showed that the adsorption capacities for Reactive Black 5 and Direct Red 80 by the bioadsorbent were 1201 and 1070mgg-1, respectively. The isotherms and kinetics for adsorption of both dyes on bioadsorbent followed the Langmuir isotherm model and pseudo-second order model, respectively. Desorption and regeneration experiments showed that the removal efficiencies of the bioadsorbent for both dyes could remain above 80% at the fifth recycling cycles. Moreover, the bioadsorbent possessed excellent packed-bed column operation performance. Those results suggested that the adsorbent could be considered as a high-performance and promising candidate for dye wastewater treatment.

Green and Sustainable Technology for High-Efficiency and Low-Damage Manipulation of Densely Crosslinked Proteins.

A two-step technology using nontoxic and eco-friendly chemicals is developed for the durable setting of densely/highly crosslinked proteins, such as wool and hair. Currently, most technologies for morphological modification are effective only for materials from non-highly-crosslinked proteins and cellulose. Before their morphological change, only water is needed to interrupt hydrogen bonds and ionic linkages, which stabilize the relative positions of molecules in non-highly-crosslinked proteins and cellulose. However, highly crosslinked proteins contain disulfide crosslinks, which are insusceptible to water. Thus, the controlled cleavage of disulfide bonds is required for creating new morphologies of highly crosslinked protein materials, such as hair and wool. Herein, cysteine and citric acid (CA) were used for the two-step setting of highly crosslinked proteins. This recipe showed better morphological change and less mechanical loss than commercial hair styling products. A reaction between CA and keratin was proposed, and verified via NMR and Raman spectra and titration. This technology could be a prospective alternative to achieve durable hair setting, anticrease finishing of wool textiles, and other durable morphological changes needed for highly crosslinked proteins.

Biodegradable sizing agents from soy protein via controlled hydrolysis and dis-entanglement for remediation of textile effluents.

Fully biodegradable textile sizes with satisfactory performance properties were developed from soy protein with controlled hydrolysis and dis-entanglement to tackle the intractable environmental issues associated with the non-biodegradable polyvinyl alcohol (PVA) in textile effluents. PVA derived from petroleum is the primary sizing agent due to its excellent sizing performance on polyester-containing yarns, especially in increasingly prevailing high-speed weaving. However, due to the poor biodegradability, PVA causes serious environmental pollution, and thus, should be substituted with more environmentally friendly polymers. Soy protein treated with high amount of triethanolamine was found with acceptable sizing properties. However, triethanolamine is also non-biodegradable and originated from petroleum, therefore, is not an ideal additive. In this research, soy sizes were developed from soy protein treated with glycerol, the biodegradable triol that could also be obtained from soy. The soy sizes had good film properties, adhesion to polyester and abrasion resistance close to PVA, rendering them qualified for sizing applications. Regarding desizing, consumption of water and energy for removal of soy size could be remarkably decreased, comparing to removal of PVA. Moreover, with satisfactory degradability, the wastewater containing soy sizes was readily dischargeable after treated in activated sludge for two days. In summary, the fully biodegradable soy sizes had potential to substitute PVA for sustainable textile processing.

Accelerated hydrolysis of substituted cellulose for potential biofuel production: kinetic study and modeling.

In this work, kinetics of substitution accelerated cellulose hydrolysis with multiple reaction stages was investigated to lay foundation for mechanism study and molecular design of substituting compounds. High-efficiency hydrolysis of cellulose is critical for cellulose-based bioethanol production. It is known that, substitution could substantially decrease activation energy and increase reaction rate of acidic hydrolysis of glycosidic bonds in cellulose. However, reaction kinetics and mechanism of the accelerated hydrolysis were not fully revealed. In this research, it was proved that substitution therefore accelerated hydrolysis only occurred in amorphous regions of cellulose fibers, and was a process with multiple reaction stages. With molar ratio of substitution less than 1%, the overall hydrolysis rate could be increased for around 10 times. We also quantified the relationship between the hydrolysis rate of individual reaction stage and its major influences, including molar ratio of substitution, activation energy of acidic hydrolysis, pH and temperature.

Cellulosic fibers with high aspect ratio from cornhusks via controlled swelling and alkaline penetration.

Cellulosic fibers with high aspect ratio have been firstly obtained from cornhusks via controlled swelling in organic solvent and simultaneous tetramethylammonium hydroxide (TMAOH) post treatment within restricted depth. Cornhusks, with around 42% cellulose content, are a copious and inexpensive source for natural fibers. However, cornhusk fibers at 20tex obtained via small-molecule alkaline extraction were too coarse for textile applications. Continuous NaOH treatment would result in fine fibers but with length of about 0.5-1.5mm, too short for textile use. In this research, post treatment using TMAOH and under controlled swelling significantly reduced fineness of cornhusk fibers from 21.3±2.88 to 5.72±0.21tex. Fiber length was reduced from 105.47±10.03 to47.2±27.4mm. The cornhusk fibers had more oriented microstructures and cellulose content increased to 84.47%. Besides, cornhusk fibers had similar tenacity, longer elongation, and lower modulus compared to cotton and linen, which endowed them with durability and flexibility.

Controlled delivery of hollow corn protein nanoparticles via non-toxic crosslinking: in vivo and drug loading study.

In this research, controlled delivery of hollow nanoparticles from zein, the corn storage protein, to different organs of mice was achieved via crosslinking using citric acid, a non-toxic polycarboxylic acid derived from starch. Besides, crosslinking significantly enhanced water stability of nanoparticles while preserving their drug loading efficiency. Protein nanoparticles have been widely investigated as vehicles for delivery of therapeutics. However, protein nanoparticles were not stable in physiological conditions, easily cleared by mononuclear phagocyte system (MPS), and thus mainly accumulated and degraded in spleen and liver, the major MPS organs. Effective delivery to major non-MPS organs, such as kidney, was usually difficult to achieve, as well as long resident time of nanoparticles. In this research, hollow zein nanoparticles were chemically crosslinked with citric acid. Controlled delivery and prolonged accumulation of the nanoparticles in kidney, one major non-MPS organ, were achieved. The nanoparticles showed improved stability in aqueous environment at pH 7.4 without affecting the adsorption of 5-FU, a common anticancer drug. In summary, citric acid crosslinked hollow zein nanoparticles could be potential vehicles for controllable delivery of anticancer therapeutics.

A sustainable slashing industry using biodegradable sizes from modified soy protein to replace petro-based poly(vinyl alcohol).

Biodegradable sizing agents from triethanolamine (TEA) modified soy protein could substitute poly(vinyl alcohol)(PVA) sizes for high-speed weaving of polyester and polyester/cotton yarns to substantially decrease environmental pollution and impel sustainability of textile industry. Nonbiodegradable PVA sizes are widely used and mainly contribute to high chemical oxygen demand (COD) in textile effluents. It has not been possible to effectively degrade, reuse or replace PVA sizes so far. Soy protein with good biodegradability showed potential as warp sizes in our previous studies. However, soy protein sizes lacked film flexibility and adhesion for required high-speed weaving. Additives with multiple hydroxyl groups, nonlinear molecule, and electric charge could physically modify secondary structure of soy protein and lead to about 23.6% and 43.3% improvement in size adhesion and ability of hair coverage comparing to unmodified soy protein. Industrial weaving results showed TEA-soy protein had relative weaving efficiency 3% and 10% higher than PVA and chemically modified starch sizes on polyester/cotton fabrics, and had relative weaving efficiency similar to PVA on polyester fabrics, although with 3- 6% lower add-on. In addition, TEA-soy sizes had a BOD5/COD ratio of 0.44, much higher than 0.03 for PVA, indicating that TEA-soy sizes were easily biodegradable in activated sludge.

Potent and regularizable crosslinking of ultrafine fibrous protein scaffolds for tissue engineering using a cytocompatible disaccharide derivative.

Sucrose, a naturally-occurring disaccharide, could be oxidized to polar polyaldehydes to improve the performance properties of tissue engineering scaffolds composed of three-dimensionally arranged ultrafine protein fibers in a controllable manner. With significantly better water stability, an in vitro study demonstrated that the biocompatibility of the oxidized sucrose crosslinked scaffolds was similar to the citric acid crosslinked ones. Due to their structural similarity to the major component in native extracellular matrices (ECMs), proteins had advantages over other macromolecules for development of tissue engineering scaffolds. We have successfully developed three-dimensional (3D) ultrafine fibrous structures from proteins that could mimic the authentic 3D architectures of native ECMs. However, the enlarged contacting area exposed to water worsened the poor water stability of proteins, and thus necessitated potent and non-toxic crosslinking. Citric acid, a biobased crosslinker, was widely recognized as safe and showed good crosslinking efficiency among non-toxic crosslinkers for proteins, though was still less potent than aldehydes. In this research, sucrose was oxidized to non-volatile polyaldehydes with high polarity and low toxicity. Compared to those crosslinked with citric acid, the 3D ultrafine fibrous zein scaffolds crosslinked with oxidized sucrose showed significantly better water stability and similar cytocompatibility via an in vitro study with preosteoblasts. In summary, oxidized sucrose could be a safe and potent crosslinker to improve water stability of macromolecule-based materials for medical and industrial applications.

Development of wheat glutenin nanoparticles and their biodistribution in mice.

Wheat glutenin nanoparticles intended for targeted drug delivery were biocompatible and were detected in the kidney, liver, and spleen in mice. Protein-based nanoparticles are preferred for therapeutic drug and gene delivery owing to their biocompatibility and ability to load various types of drugs. However, proteins such as a collagen and albumin are unstable in aqueous environments and are not ideal for drug delivery applications. Wheat glutenin has been demonstrated to be biocompatible and have good stability under aqueous conditions. Films and fibers have been made from wheat glutenin for medical applications but there are no reports on developing micro- or nanoparticles. In this research, wheat glutenin nanoparticles (70-140 nm) were prepared and the stability of the nanoparticles under various physiological conditions was investigated. Nanoparticles were fluorescently labeled and later injected into mice and the ability of the nanoparticles to penetrate into the cells in various organs was studied. Strong acidic or alkaline conditions provided glutenin nanoparticles with low diameters and the particles were more stable under the pH 7 rather than pH of 4. Glutenin nanoparticles were predominantly found in the liver in mice. Our in vivo and in vitro studies suggest that glutenin nanoparticles are suitable for drug delivery applications.

Intrinsically water-stable keratin nanoparticles and their in vivo biodistribution for targeted delivery.

Highly water-stable nanoparticles of around 70 nm and capable of distributing with high uptake in certain organs of mice were developed from feather keratin. Nanoparticles could provide novel veterinary diagnostics and therapeutics to boost efficiency in identification and treatment of livestock diseases to improve protein supply and ensure safety and quality of food. Nanoparticles could penetrate easily into cells and small capillaries, surpass detection of the immune system, and reach targeted organs because of their nanoscale sizes. Proteins with positive and negative charges and hydrophobic domains enable loading of various types of drugs and, hence, are advantageous over synthetic polymers and carbohydrates for drug delivery. In this research, the highly cross-linked keratin was processed into nanoparticles with diameters of 70 nm under mild conditions. Keratin nanoparticles were found supportive to cell growth via an in vitro study and highly stable after stored in physiological environments for up to 7 days. At 4 days after injection, up to 18% of the cells in kidneys and 4% of the cells in liver of mice were penetrated by the keratin nanoparticles.