Polydopamine-Induced Multilevel Engineering of Regenerated Silk Fibroin Fiber for Photothermal Conversion.

Solid photothermal materials with favorable biocompatibility and modifiable mechanical properties demonstrate obvious superiority and growing demand. In this work, polydopamine (PDA) induced functionalization of regenerated silk fibroin (RSF) fibers has satisfactory photothermal conversion ability and flexibility. Based on multilevel engineering, RSF solution containing PDA nanoparticles is wet spun to PDA-incorporating RSF (PDA@RSF) fibers, and then the fibers are coated with PDA via oxidative self-polymerization of dopamine to form PDA@RSF-PDA (PRP) fibers. During the wet spinning process, PDA is to adjust the mechanical properties of RSF by affecting its hierarchical structure. Meanwhile, coated PDA gives the PRP fibers extensive absorption of near-infrared light and sunlight, which is further fabricated into PRP fibrous membranes. The temperature of PRP fibrous membranes can be adjusted and increases to about 50 °C within 360 s under 808 nm laser irradiation with a power density of 0.6 W cm-2 , and PRP fibrous membranes exhibit effective photothermal cytotoxicity both in vitro and in vivo. Under the simulated sunlight, the temperature of PRP fiber increases to more than 200 °C from room temperature and the material can generate 4.5 V voltage when assembled with a differential thermal battery, which means that the material also has the potential for flexible wearable electronic devices.

Control of Head/Tail Isomeric Structure in Polyimide and Isomerism-Derived Difference in Molecular Packing and Properties.

Two sequence isomeric poly(amic acid)s (PAAs) are successfully synthesized from 3,3',4,4'-biphenyltetracarboxylic dianhydride and unsymmetrical 5(6)-amino-2-(4-aminobenzene) benzimidazole (PABZ). The syntheses are based on the site-selective reactivity of head/tail amino groups of PABZ and solubility differences of PABZ in good solvent (dimethyl sulfoxide, DMSO) and poor solvent (N-methyl-2-pyrrolidone, NMP). The proton nuclear magnetic resonance (1 H-NMR) results reveal that the content of head tail-head tail (HTHT) bonding units in PAA-DMSO (PAA synthesized in DMSO) is 37%, while this content increases to 54% in PAA-NMP (PAA synthesized in NMP). The wide-angle X-ray diffraction (WAXD) results indicate polyimide (PI)-NMP film with high HTHT content exhibits a semicrystalline structure, while PI-DMSO film is amorphous. Moreover, PI-NMP also shows higher in-plane orientation than PI-DMSO. The ordered molecular packing and higher in-plane orientation of PI-NMP lead to an increase in mechanical properties and a decrease in in-plane thermal expansion coefficient.

Inactivation of cyclic Di-GMP binding protein TDE0214 affects the motility, biofilm formation, and virulence of Treponema denticola.

As a ubiquitous second messenger, cyclic dimeric GMP (c-di-GMP) has been studied in numerous bacteria. The oral spirochete Treponema denticola, a periodontal pathogen associated with human periodontitis, has a complex c-di-GMP signaling network. However, its function remains unexplored. In this report, a PilZ-like c-di-GMP binding protein (TDE0214) was studied to investigate the role of c-di-GMP in the spirochete. TDE0214 harbors a PilZ domain with two signature motifs: RXXXR and DXSXXG. Biochemical studies showed that TDE0214 binds c-di-GMP in a specific manner, with a dissociation constant (Kd) value of 1.73 µM, which is in the low range compared to those of other reported c-di-GMP binding proteins. To reveal the role of c-di-GMP in T. denticola, a TDE0214 deletion mutant (TdΔ214) was constructed and analyzed in detail. First, swim plate and single-cell tracking analyses showed that TdΔ214 had abnormal swimming behaviors: the mutant was less motile and reversed more frequently than the wild type. Second, we found that biofilm formation of TdΔ214 was substantially repressed (∼6.0-fold reduction). Finally, in vivo studies using a mouse skin abscess model revealed that the invasiveness and ability to induce skin abscesses and host humoral immune responses were significantly attenuated in TdΔ214, indicative of the impact that TDE0214 has on the virulence of T. denticola. Collectively, the results reported here indicate that TDE0214 plays important roles in motility, biofilm formation, and virulence of the spirochete. This report also paves a way to further unveil the roles of the c-di-GMP signaling network in the biology and pathogenicity of T. denticola.

Circularly polarized coherent anti-Stokes Raman scattering microscopy.

We demonstrate circularly polarized coherent anti-Stokes Raman scattering (CP-CARS) microscopy that significantly suppresses the nonresonant background for high-contrast vibrational imaging. Circularly polarized pump and Stokes fields with opposite handedness are used to excite CARS signal. In this case, theoretically the nonresonant CARS signal and resonant CARS signal from isotropic media will completely vanish, while the resonant CARS signal from anisotropic structures can still exist. This allows CARS imaging of anisotropic samples with enhanced resonant contrast. Furthermore, we performed CP-CARS imaging on fibroin fibers from silkworm silk, and the results confirmed its effectiveness in background suppression.

Design and function of lignin/silk fibroin-based multilayer water purification membranes for dye adsorption.

The treatment of dye wastewater poses a significant challenge to the sewage recycling industries. However, the reduction of secondary pollution resulting from the membrane residues, to maintain high performance, remains a considerable obstacle. A novel approach for the fabrication of multilayer nanofiber structures using a layer-by-layer electrostatic spinning technique with biological materials was reported in this study. Incorporating the chemical adsorption advantages of lignin nanofiber and the physical adsorption advantages of silk fibroin (SF) nanofiber enabled the full realization of excellent dye interception performance. A comparative analysis was conducted on the lignin derived from eucalyptus, pine, and straw to determine the most suitable option. Notably, eucalyptus lignin exhibited superior antimicrobial properties. The adsorption of crystal violet by eucalyptus lignin/SF membrane was consistent with the Freundlich isotherm model and the pseudo-second-order kinetic model, revealing a chemisorption mechanism involving Π-Π conjugation, hydrogen bonding, and the binding of anions and cations. The lignin/SF membrane exhibited a retention rate exceeding 99.5 % for crystal violet, methylene blue, and brilliant green dyes. Furthermore, it demonstrated efficacy in retaining heavy metal ions, including cadmium and copper. The original biomass material imparts the property of rapid degradation to a multilayer membrane that can be used as an effective and eco-friendly water purification material.

Stretchable, Biocompatible, and Multifunctional Silk Fibroin-Based Hydrogels toward Wearable Strain/Pressure Sensors and Triboelectric Nanogenerators.

Nowadays, great effort has been devoted to establishing wearable electronics with excellent stretchability, high sensitivity, good mechanical strength, and multifunctional characteristics. Herein, a soft conductive hydrogel is rationally designed by proportionally mixing silk fibroin, polyacrylamide, graphene oxide, and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate). The resultant hydrogel has considerable stretchability and compressibility, which enables it to be assembled into a strain/pressure sensor with a wide sensing range (strain, 2%-600%; pressure, 0.5-119.4 kPa) and reliable stability. Then, the corresponding sensor is capable of monitoring a series of physical signals of the human body (e.g., joint movement, facial gesture, pulse, breathing, etc.). In particular, the hydrogel-based sensor is biocompatible, with no anaphylactic reaction on human skin. More interestingly, this conductive hydrogel exhibits a positive response when it works in a triboelectric nanogenerator; consequently, it lights up 20 commericial green light-emitting diodes. Thus, this silk fibroin-based hydrogel is a kind of multifunctional material toward wearable electronics with versatile applications in health and exercise monitors, soft robots, and power sources.

Nanoengineering of a biocompatible organogel by thermal processing.

The formation of most organogels requires the compatibility of both the gelator and solvent. It is very desirable if the rheological properties of a gel can be manipulated to achieve the desired performance. In this paper, a novel organogel was developed and its rheological properties and fiber network were engineered by controlling the thermal processing conditions. The gel was formed by the gelation of 12-hydroxystearic acid as a gelator in benzyl benzoate. It was observed that the degree of supercooling for gel formation has a significant effect on the rheological properties and fiber network structure. By increasing supercooling, the elasticity of the gel was enhanced, and the correlation length of the fibers was shortened, leading to the formation of denser fiber networks. The good biocompatibility of both the gelator and solvent makes this gel a promising vehicle for a variety of bioapplications such as controlled transdermal drug release and in vivo tissue repair.

Comparison of Clay Ceramsite and Biodegradable Polymers as Carriers in Pack-bed Biofilm Reactor for Nitrate Removal.

In recent years, there is a trend of low C/N ratio in municipal domestic wastewater, which results in serious problems for nitrogen removal from wastewater. The addition of an external soluble carbon source has been the usual procedure to achieve denitrification. However, the disadvantage of this treatment process is the need of a closed, rather sophisticated and costly process control as well as the risk of overdosing. Solid-phase denitrification using biodegradable polymers as biofilm carrier and carbon source was considered as an attractive alternative for biological denitrification. The start-up time of the novel process using PCL (polycaprolactone) as biofilm carrier and carbon source was comparable with that of conventional process using ceramsite as biofilm carrier and acetate as carbon source. Further, the solid-phase denitrification process showed higher nitrogen removal efficiency under shorter hydraulic retention time (HRT) and low carbon to nitrogen (C/N) ratio since the biofilm was firmly attached to the clear pores on the surface of PCL carriers and in this process bacteria that could degrade PCL carriers to obtain electron donor for denitrification was found. In addition, solid-phase denitrification process had a stronger resistance of shock loading than that in conventional process. This study revealed, for the first time, that the physical properties of the biodegradable polymer played a vital role in denitrification, and the different microbial compositions of the two processes was the main reason for the different denitrification performances under low C/N ratio.

Fabrication and biofunctionalization of selenium-polypyrrole core-shell nanoparticles for targeting and imaging of cancer cells.

Selenium-polypyrrole core-shell nanoparticles are fabricated by an in-situ polymerization process and functionalized with transferrin for targeting and imaging of human cervical cancer cells. The shell thickness and chemical composition of the as-synthesized particles can be manipulated by controlling the precursor concentration. The presence of the polymer layer can greatly increase the thermal stability of the selenium nanoparticles. The presence of transferrin molecules on the surface of the core-shell nanoparticles can significantly enhance their cellular uptake. The tranferrin-conjugated core-shell nanoparticles can be potentially used for the targeting and imaging of cancer cells.

Removal of organic micro-pollutants (phenol, aniline and nitrobenzene) via forward osmosis (FO) process: Evaluation of FO as an alternative method to reverse osmosis (RO).

In this study, we have explored and compared the effectiveness of using (1) lab-fabricated forward osmosis (FO) membranes under both FO and reverse osmosis (RO) modes and (2) commercially available RO membranes under the RO mode for the removal of organic micro-pollutants. The lab-fabricated FO membranes are thin film composite (TFC) membranes consisting of a polyamide layer and a porous substrate cast from three different materials; namely, Matrimid, polyethersulfone (PESU) and sulfonated polyphenylene sulfone (sPPSU). The results show that the FO mode is superior to the RO mode in the removal of phenol, aniline and nitrobenzene from wastewater. The rejections of all three TFC membranes to all the three organic micro-pollutants under the FO processes are higher than 72% and can be even higher than 90% for aniline when a 1000 ppm aromatic aqueous solution and 1 M NaCl are employed as feeds. These performances outperform the results obtained from themselves and commercially available RO membranes under the RO mode. In addition, the rejection can be maintained even when treating a more concentrated feed solution (2000 ppm). The removal performance can be further enhanced by using a more concentrated draw solution (2 M). The water flux is almost doubled, and the rejection increment can reach up to 17%. Moreover, it was observed that annealing as a post-treatment would help compact the membrane selective layer and further enhance the separating efficiency. The obtained organic micro-pollutant rejections and water fluxes under various feasible operating conditions indicate that the FO process has potential to be a viable treatment for wastewater containing organic micro-pollutants.

Ultraviolet ZnSe1-xSx gradient-alloyed nanocrystals via a noninjection approach.

Highly emissive ultraviolet ZnSeS nanocrystals (NCs), with a core-shell-like structure, were designed and synthesized via a one-step noninjection approach in 1-octadecene (ODE). These ultraviolet ZnSeS NCs exhibit bright bandgap emission with high color purity and little trap emission. With full width at half-maximum (fwhm) of ∼21 nm only, photoluminescent (PL) quantum yield (QY) of ∼60% was estimated for one ensemble dispersed in toluene exhibiting bandgap absorption peaking at ∼380 nm and bandgap emission at ∼389 nm. These alloyed ZnSeS NCs present a cubic crystal structure consisting of a Se-rich core and a S-rich shell. Such a gradiently alloyed structure was suggested by our investigation on the temporal evolution of optical properties of the growing ZnSeS NCs monitored from 80 to 300 °C, together with structural and compositional characterization performed with XRD, XPS, EDX, and TEM. This newly developed one-step noninjection approach was achieved with zinc oleate (Zn(OA)(2)), diphenylphosphine selenide (SeDPP), and diphenylphosphine sulfide (SDPP) as Zn, Se, and S precursors, respectively. ZnSe monomers mainly participated in nucleation at ∼120 °C, while both ZnSe and ZnS monomers contributed to NC formation in later growth stages (∼160 °C and higher). (31)P NMR study demonstrates that SeDPP is more reactive than SDPP toward Zn(OA)(2), and also supports such a model proposed on the combination of ZnSe and ZnS monomers leading to nucleation/growth of ZnSeS alloyed NCs. The present study offers conceptual methodology to various highly photoluminescent alloyed NCs with high quality, high particle yield, and high synthetic reproducibility.

Ab initio elasticity of poly(lactic acid) crystals.

We investigate the elastic properties of poly(lactic acid) crystals using a first-principles pseudopotential plane wave method within the generalized gradient approximation of the density functional theory. Stiffness and compliance matrices of poly(l-lactic acid) (PLLA) alpha- and beta-forms, and the stereocomplex (sc) between PLLA and poly(D-lactic acid) (PDLA) (50:50) sc-form are calculated using the finite strain technique. The results indicate that crystalline poly(lactic acid) is highly mechanical anisotropic. Contributions from the crystalline phase to the anisotropy of the elastic modulus in an uniaxially oriented poly(lactic acid) fiber are estimated on the basis of a cylindrically symmetric polycrystalline aggregate model. Both symmetry and orientation distribution of the crystals have been taken into account. Voigt and Reuss bounds of Young's moduli and shear moduli and Poisson's ratio are calculated from single crystal elastic properties.

Kinetics and template nucleation of self-assembled hydroxyapatite nanocrystallites by chondroitin sulfate.

Biomineralization is an important process, which is often assisted by biomolecules. In this paper, the effect of chondroitin sulfate on the crystallization of hydroxyapatite was examined quantitatively based on a generic heterogeneous nucleation model. It is found that chondroitin sulfate can suppress the supersaturation-driven interfacial structure mismatch between the hydroxyapatite crystal and the substrate and promote the formation of ordered hydroxyapatite nanocrystallite assemblies. The nucleation mechanism of self-aligned hydroxyapatite nanocrystallites was examined from the viewpoints of kinetics and interfacial structure and properties, which contributes to an understanding of the fundamentals of biomineralization of self-assembled structures. The results obtained from this study will provide a basic principle to design and fabricate highly orderly organic-inorganic hybrid materials.