Hydrophobic Modification on Surface of Chitin Sponges for Highly Effective Separation of Oil

A highly hydrophobic and oleophilic chitin sponge was synthesized, for the first time, via a freeze-dried method and then by using a thermal chemical vapor deposition of methyltrichlorosilane (MTCS) at different relative humidity. Fourier-transform infrared, energy-dispersive X-ray spectra, and scanning electron microscopy confirmed that the silanization occurred on the pore wall surface of the chitin sponge. The MTCS-coated chitin sponge had interconnected open-cell structures with the average pore size from 20 to 50 μm, and the MTCS nanofilaments immobilized on the chitin matrix, leading to the high hydrophobicity, as a result of the existence of a solid/air composite rough surface. Cyclic compression test indicated that the hydrophobic chitin sponges exhibited excellent elasticity and high mechanical durability. The sponges could efficiently collect organics both on the surface and bottom from the water with the highest 58 times of their own weight absorption capacities through the combination of the particular wettability and great porosity. Furthermore, the biodegradation kinetics of the chitin sponge forecasted that the chitin could be completely biodegraded within 32 days by the microorganisms in the soil. This work provided a new pathway to prepare the chitin-based materials for highly effective removal of oil from water, showing potential application in the pollutant remediation field

Chitinous Bioplastic Enabled by Noncovalent Assembly

Natural polymeric-based bioplastics usually lack good mechanical or processing performance. It is still challenging to achieve simultaneous improvement for these two usual trade-off features. Here, we demonstrate a full noncovalent mediated self-assembly design for simultaneously improving the chitinous bioplastic processing and mechanical properties via plane hot-pressing. Tannic acid (TA) is chosen as the noncovalent mediator to (i) increase the noncovalent cross-link intensity for obtaining the tough noncovalent network and (ii) afford the dynamic noncovalent cross-links to enable the mobility of chitin molecular chains for benefiting chitinous bioplastic nanostructure rearrangement during the shaping procedure. The multiple noncovalent mediated network (chitin–TA and chitin–chitin cross-links) and the pressure-induced orientation nanofibers structure endow the chitinous bioplastics with robust mechanical properties. The relatively weak chitin–TA noncovalent interactions serve as water mediation switches to enhance the molecular mobility for endowing the chitin/TA bioplastic with hydroplastic processing properties, rendering them readily programmable into versatile 2D/3D shapes. Moreover, the fully natural resourced chitinous bioplastic exhibits superior weld, solvent resistance, and biodegradability, enabling the potential for diverse applications. The full physical cross-linking mechanism highlights an effective design concept for balancing the trade-off of the mechanical properties and processability for the polymeric materials

Biodegradable Theranostic Plasmonic Vesicles of Amphiphilic Gold Nanorods

We have developed surface-initiated organocatalytic ring-opening polymerization on functional nanocrystals and synthesized amphiphilic gold nanorods carrying well-defined mixed polymer brushes of poly(ethylene glycol) and polylactide. Self-assembly of the amphiphilic gold nanorods affords biodegradable plasmonic vesicles that can be destructed by both enzymatic degradation and near-infrared photothermal heating. When tagged with Raman probes, strongly coupled gold nanorods in the self-assembled vesicles give rise to highly active SERS signals. The biodegradable plasmonic vesicles exhibit a unique combination of optical and structural properties that are of particular interest for theranostic applications. We have demonstrated that bioconjugated SERS-active plasmonic vesicles can specifically target EpCAM-positive cancer cells, leading to ultrasensitive spectroscopic detection of cancer cells. Furthermore, integration of photothermal effect of gold nanorods and large loading capacity of the vesicles provides opportunities for localized synergistic photothermal ablation and photoactivated chemotherapy, which have shown higher efficiency in killing targeted cancer cells than either single therapeutic modality. The versatile chemistry of organocatalytic ring-opening polymerization, in conjugation with recent development in synthesizing functional nanocrystals with tailored optical, electronic, and magnetic properties opens the possibilities for constructing multifunctional biodegradable platforms for clinical translation

Hair-Inspired Crystal Growth of HOA in Cavities of Cellulose Matrix via Hydrophobic–Hydrophilic Interface Interaction

As one of the most ordinary phenomena in nature, numerous pores on animal skins induce the growth of abundant hairs. In this study, cavities of a cellulose matrix were used as hard templates to lead the hair-inspired crystal growth of 12-hydroxyoctadecanoic acid (HOA) through hydrophobic–hydrophilic interface interaction, and short hair-like HOA crystals with a smooth surface were formed on cellulose films. In our findings, by using solvent evaporation induced crystallization, hydrophobic HOA grew along the hydrophilic cellulose pore wall to form regular vertical worm-like and pillar-like crystals with an average diameter of about 200 nm, depending on the experimental conditions and HOA concentration. The formation mechanism of the short hair-like HOA crystals as well as the structure and properties of the cellulose/HOA submicrometer composite films were studied. The pores of the cellulose matrix supplied not only cavities for the HOA crystals fixation but also hydrophilic shells to favor the vertical growth of the relatively hydrophobic HOA crystals. The cellulose/HOA submicrometer composite films exhibited high hydrophobicity, as a result of the formation of the solid/air composite surface. Furthermore, 4-(1,2,2-triphenylethenyl) benzoic acid, an aggregation-induced emission luminogen, was used to aggregate on the cellulose surface with HOA to emit and monitor the HOA crystal growth, showing bifunctional photoluminscence and self-cleaning properties. This work opens up a novel one-step pathway to design bio-inspired submicrometer materials by utilizing natural products, showing potential applications in self-cleaning optical devices

Intermolecular Interaction and the Extended Wormlike Chain Conformation of Chitin in NaOH/Urea Aqueous Solution

The intra- and intermolecular interactions of chitin in NaOH/urea aqueous system were studied by a combination of NMR measurements (including ¹³C NMR, ²³Na NMR, and ¹⁵N NMR) and differential scanning calorimetry. The results revealed that the NaOH and chitin formed a hydrogen-bonded complex that was surrounded by the urea hydrates to form a sheath-like structure, leading to the good dissolution. The optimal concentration range, in which chitin was molecularly dispersed in NaOH/urea aqueous, was found to investigate the chain conformation in the dilute solution with a combination of static and dynamic light scattering. The weight-average molecular weight (<i>M</i>_w), radii of gyration (⟨<i>R</i>_g⟩_<i>z</i>), and hydrodynamic radii (⟨<i>R</i>_h⟩_<i>z</i>) values of chitin were determined, and the structure-sensitive parameter (ρ) and persistent length (<i>L</i>_p) were calculated to be >2.0 and ∼30 nm, respectively, suggesting an extended wormlike chain conformation. The visualized images from TEM, cryo-TEM, and AFM indicated that, chitin nanofibers were fabricated from the parallel aggregation of chitin chains in NaOH/urea system. This work would provide a theoretical guidance for constructing novel chitin-based nanomaterials via “bottom-up” method at the molecular level

Hair-Inspired Crystal Growth of HOA in Cavities of Cellulose Matrix via Hydrophobic–Hydrophilic Interface Interaction

As one of the most ordinary phenomena in nature, numerous pores on animal skins induce the growth of abundant hairs. In this study, cavities of a cellulose matrix were used as hard templates to lead the hair-inspired crystal growth of 12-hydroxyoctadecanoic acid (HOA) through hydrophobic–hydrophilic interface interaction, and short hair-like HOA crystals with a smooth surface were formed on cellulose films. In our findings, by using solvent evaporation induced crystallization, hydrophobic HOA grew along the hydrophilic cellulose pore wall to form regular vertical worm-like and pillar-like crystals with an average diameter of about 200 nm, depending on the experimental conditions and HOA concentration. The formation mechanism of the short hair-like HOA crystals as well as the structure and properties of the cellulose/HOA submicrometer composite films were studied. The pores of the cellulose matrix supplied not only cavities for the HOA crystals fixation but also hydrophilic shells to favor the vertical growth of the relatively hydrophobic HOA crystals. The cellulose/HOA submicrometer composite films exhibited high hydrophobicity, as a result of the formation of the solid/air composite surface. Furthermore, 4-(1,2,2-triphenylethenyl) benzoic acid, an aggregation-induced emission luminogen, was used to aggregate on the cellulose surface with HOA to emit and monitor the HOA crystal growth, showing bifunctional photoluminscence and self-cleaning properties. This work opens up a novel one-step pathway to design bio-inspired submicrometer materials by utilizing natural products, showing potential applications in self-cleaning optical devices

SERS-Encoded Nanogapped Plasmonic Nanoparticles: Growth of Metallic Nanoshell by Templating Redox-Active Polymer Brushes

We report a new strategy to synthesize core–shell metal nanoparticles with an interior, Raman tag-encoded nanogap by taking advantage of nanoparticle-templated self-assembly of amphiphilic block copolymers and localized metal precursor reduction by redox-active polymer brushes. Of particular interest for surface-enhanced Raman scattering (SERS) is that the nanogap size can be tailored flexibly, with the sub-2 nm nanogap leading to the highest SERS enhancement. Our results have further demonstrated that surface functionalization of the nanogapped Au nanoparticles with aptamer targeting ligands allows for specific recognition and ultrasensitive detection of cancer cells. The general applicability of this new synthetic strategy, coupled with recent advances in controlled wet-chemical synthesis of functional nanocrystals, opens new avenues to multifunctional core–shell nanoparticles with integrated optical, electronic, and magnetic properties

Construction of Chitin/PVA Composite Hydrogels with Jellyfish Gel-Like Structure and Their Biocompatibility

High strength chitin/poly­(vinyl alcohol) (PVA) composite hydrogels (RCP) were constructed by adding PVA into chitin dissolved in a NaOH/urea aqueous solution, and then by cross-linking with epichlorohydrin (ECH) and freezing–thawing process. The RCP hydrogels were characterized by field emission scanning electron microscopy, FTIR, differential scanning calorimetry, solid-state ¹³C NMR, wide-angle X-ray diffraction, and compressive test. The results revealed that the repeated freezing/thawing cycles induced the bicrosslinked networks consisted of chitin and PVA crystals in the composite gels. Interestingly, a jellyfish gel-like structure occurred in the RCP75 gel with 25 wt % PVA content in which the amorphous and crystalline PVA were immobilized tightly in the chitin matrix through hydrogen bonding interaction. The freezing/thawing cycles played an important role in the formation of the layered porous PVA networks and the tight combining of PVA with the pore wall of chitin. The mechanical properties of RCP75 were much higher than the other RCP gels, and the compressive strength was 20× higher than that of pure chitin gels, as a result of broadly dispersing stress caused by the orderly multilayered networks. Furthermore, the cell culture tests indicated that the chitin/PVA composite hydrogels exhibited excellent biocompatibility and safety, showing potential applications in the field of tissue engineering

Hierarchical Microspheres Constructed from Chitin Nanofibers Penetrated Hydroxyapatite Crystals for Bone Regeneration

Chitin exists abundantly in crab and shrimp shells as the template of the minerals, which inspired us to mineralize it for fabricating bone grafting materials. In the present work, chitin nanofibrous microspheres were used as the matrix for in situ synthesis of hydroxyapatite (HA) crystals including microflakes, submicron-needles, and submicron-spheres, which were penetrated by long chitin nanofibers, leading to the hierarchical structure. The shape and size of the HA crystals could be controlled by changing the HA synthesis process. The tight interface adhesion between chitin and HA through the noncovanlent bonds occurred in the composite microspheres, and HAs were homogeneously dispersed and bounded to the chitin nanofibers. In our findings, the inherent biocompatibilities of the both chitin and HA contributed the bone cell adhesion and osteoconduction. Moreover, the chitin microsphere with submicron-needle and submicron-sphere HA crystals remarkably promoted in vitro cell adhesion and in vivo bone healing. It was demonstrated that rabbits with 1.5 cm radius defect were almost cured completely within three months in a growth factor- and cell-free state, as a result of the unique surface microstructure and biocompatibilities of the composite microspheres. The microsphere scaffold displayed excellent biofunctions and an appropriate biodegradability. This work opened up a new avenue to construct natural polymer-based organic–inorganic hybrid microspheres for bone regeneration

Micro- and Macromechanical Properties of Thermoelectric Lead Chalcogenides

Both n- and p-type lead telluride (PbTe)-based thermoelectric (TE) materials display high TE efficiency, but the low fracture strength may limit their commercial applications. To find ways to improve these macroscopic mechanical properties, we report here the ideal strength and deformation mechanism of PbTe using density functional theory calculations. This provides structure–property relationships at the atomic scale that can be applied to estimate macroscopic mechanical properties such as fracture toughness. Among all the shear and tensile paths that are examined here, we find that the lowest ideal strength of PbTe is 3.46 GPa along the (001)/⟨100⟩ slip system. This leads to an estimated fracture toughness of 0.28 MPa m^1/2 based on its ideal stress–strain relation, which is in good agreement with our experimental measurement of 0.59 MPa m^1/2. We find that softening and breaking of the ionic Pb–Te bond leads to the structural collapse. To improve the mechanical strength of PbTe, we suggest strengthening the structural stiffness of the ionic Pb–Te framework through an alloying strategy, such as alloying PbTe with isotypic PbSe or PbS. This point defect strategy has a great potential to develop high-performance PbTe-based materials with robust mechanical properties, which may also be applied to other materials and applications