Rebuildable Silver Nanoparticles Employed as Seeds for Synthesis of Pure Silver Nanopillars with Hexagonal Cross-Sections under Room Temperature.

Silver nanopillars with strong plasmonic effects are used for localized electromagnetic field enhancement and regulation and have wide potential applications in sensing, bioimaging, and surface-enhanced spectroscopy. Normally, the controlled synthesis of silver nanopillars is mainly achieved using heterometallic nanoparticles, including Au nanobipyramids and Pd decahedra, as seeds for inducing nanostructure growth. However, the seed materials are usually doped in silver nanopillar products. Herein, the synthesis of pure silver nanopillars with hexagonal cross-sections is achieved by employing rebuildable silver nanoparticles as seeds. An environmentally friendly, stable, and reproducible synthetic route for obtaining silver nanopillars is proposed using sodium dodecyl sulfate as the surface stabilizer. Furthermore, the seed particles induce the formation of regular structures at different temperatures, and, specifically, room temperature is beneficial for the growth of nanopillars. The availability of silver nanoparticle seeds using sodium alginate as a carrier at different temperatures was verified. A reproducible method was developed to synthesize pure silver nanopillars from silver nanoparticles at room temperature, which can provide a strategy for designing plasmonic nanostructures for chemical and biological applications.

Clinical and hemodynamic features of acute pulmonary embolism patients diagnosed in cold weather predicts adverse clinical outcome.

Background: Acute pulmonary embolism (APE) is associated with peak incidence and mortality rate in winter. The present study sought to characterize the clinical and hemodynamic features of cold weather on APE patients. Methods: All enrolled 224 APE patients underwent clinical and hemodynamic evaluation and baseline parameters were collected. Recruited patients were grouped by weather pattern on admission into cold and warm weather group. The correlation and prognostic values among cold weather and other variables were analyzed. Results: Compared to warm weather group, patients in cold weather group present with more severe cardiac function, with adverse WHO-functional class (P = 0.032) and higher NT-proBNP concentration [1,853.0 (398.0, 5,237.0) pg/ml vs. 847.5 (56.8, 3,090.5) pg/ml, P = 0.001]. The cold weather group also displayed much critical hemodynamic status and heavier thrombosis load, with higher mPAP (29.1 ± 11.2mmHg vs. 25.6 ± 14.2mmHg, P = 0.045), higher PVR [3.3 (1.7, 6.0) wood units vs. 1.8 (0.9, 3.8) wood units, P < 0.001], higher Miller index (21.4 ± 5.9 vs. 19.1 ± 8.0, P = 0.024), and higher D-dimer levels [2,172.0 (854.5, 3,072.5) mg/L vs. 1,094.5 (210.5, 2,914.5) mg/L, P = 0.008]. Besides, cold weather showed well correlation with the above variables. Survival analysis showed APE patients in cold weather had significantly higher clinical worsening event rate (P = 0.010) and could be an independent predictor of adverse clinical outcome in the multivariate analysis (HR 2.629; 95% CI 1.127, 6.135; P = 0.025). Conclusion: APE patients in cold weather were associated with thrombus overload, cardiac dysfunction, hemodynamic collapse and higher clinical worsening event rate. Cold weather proves to be an independent predictor of adverse clinical outcome.

Extracellular matrix-mimicking nanofibrous chitosan microspheres as cell micro-ark for tissue engineering.

In the present study, extracellular matrix (ECM)-mimicking nanofibrous chitosan microspheres (NCM) were developed via thermal induction of chitosan molecular chain from alkaline/urea aqueous solution. The regeneration of NCM from chitosan was proved to be physical process. The morphology of NCM could be precisely controlled by adjusting the initial solution concentration and the reaction temperature. The NCM possessed desirable in vitro/vivo biocompatibility and biodegradability. The excellent cell adhesion capability of NCM facilitated the formation of large-sized 3D geometric constructs in vitro. The NCM promoted in vitro osteogenic differentiation of rat bone marrow stem cells (rMSCs). Finally, pre-differentiated rMSCs-NCM constructs obviously enhanced in vivo bone healing of rat calvarial defects. This work opened up a new avenue for the construction of chitosan microspheres with ECM-like nanofibrous structure, indicated the great potential of the NCM as micro-Noah's Ark for stem cells to anchor, proliferate, and pre-differentiate for tissue engineering.

Controllable Wrinkling Patterns on Chitosan Microspheres Generated from Self-Assembling Metal Nanoparticles.

Materials with surface wrinkles at a micro/nanoscale possess extraordinary fascinating properties, and various techniques have been employed to create controllable wrinkles. Herein, natural polysaccharide was used to construct the surface wrinkled microsphere with controllable wrinkling patterns. A robust microsphere with an average size of about 55 µm fabricated from chitosan in alkali/urea aqueous solution was swelled and then coated orderly by introducing rigid silver nanoparticles (Ag NPs) with an average size of about 5 nm as the shell onto the surface through electrostatic layer-by-layer (LBL) self-assembly followed by deswelling, resulting in a surface wrinkled microsphere. The significant difference in the swelling behaviors between the stiff Ag shell and swelled chitosan microsphere could generate enough driving forces to form 3D micro- and nanoscale wrinkling surface topography. The surface wrinkled microspheres exhibited the hierarchically porous structure and hydrophobicity, and the topographical patterns could be adjusted by controlling the thickness of the Ag NP layer to achieve the sizes of wrinkling ranging from 60 to 300 nm. It was demonstrated that the wrinkled microspheres were superior as 3D surface-enhanced Raman spectroscopy (SERS) substrates, in which the wrinkled structure with spatial periodicity was proved to be effective for enhancing the SERS signal. The microsphere with controllable wrinkled surface topography could be applied to be a miniature 3D device, which promises potential technological applications in various areas.

Rubbery Chitosan/Carrageenan Hydrogels Constructed through an Electroneutrality System and Their Potential Application as Cartilage Scaffolds.

In the present work, the bulk and homogeneous composite hydrogels were successfully constructed from positively charged chitosan (CS) and negatively charged carrageenan (CG) in alkali/urea aqueous solution via a simple one-step approach for the first time. An electroneutral CS solution was achieved in alkali/urea, leading to a homogeneous solution blended by CS and CG, which could not be realized in acidic medium because of the agglomeration caused by polycation and polyanion. Subsequently, the CS/CG composite hydrogels with multiple cross-linked networks were prepared from blend solution by using epichlorohydrin (ECH) as the cross-linking agent. The composite hydrogels exhibited hierarchically porous architecture, excellent mechanical properties as well as pH- and salt-responsiveness. Importantly, the composite hydrogels were successfully applied for spreading ATDC5 cells, showing high attachment and proliferation of cells. The results of fluorescent micrographs and scanning electronic microscope images revealed that the CS/CG composite hydrogels enhanced the adhesion and viability of ATDC5 cells. The alcian blue staining, glycosaminoglycan quantification, and real-time PCR analysis proved that the CS/CG composite hydrogels could induce chondrogenic differentiation of ATDC5 cells in vitro, exhibiting great potential for application in cartilage repair. This work provides a facile and fast fabrication pathway for the construction of ampholytic hydrogel from polycation and polyanion in an electroneutrality system.

High Strength and Hydrophilic Chitosan Microspheres for the Selective Enrichment of N-Glycopeptides.

Protein glycosylation is an important post-translational modification that plays a crucial role in many biological processes. Because of the low abundance of glycoproteins and high complexity of clinical samples, the development of methods to selectively capture glycoproteins/glycopeptides is crucial to glycoproteomics study. In this work, a kind of highly cross-linked chitosan microspheres (CSMs) was prepared using epichlorhydrine as a cross-linker from chitosan solution in an alkaline/urea aqueous system. The results showed that CSMs had high amino groups content, large surface area, mesoporous structure, good acidic resistance, and high strength by various tests. On the basis of hydrophilic interaction between the polar groups (amino groups and hydroxyl groups) on CSMs and glycan moieties on glycopeptides, the prepared CSMs were applied to specific capture of N-glycopeptides from standard protein digests and complex biological samples (body fluids and tissues). The CSMs exhibited high selectivity (HRP/BSA = 1:100), good sensitivity (4.5 × 10-10 M of HRP), good recovery yield (74.9-106.4%), and high binding capacity (100 mg g-1) in glycopeptides enrichment. Because of the excellent performance in glycopeptides enrichment, CSMs were applied to selectively enrich N-glycopeptides from tryptic digests of human serum and rat brain followed by nanoLC-MS/MS analysis. We identified 194 and 947 unique N-glycosylation sites from 2 µL of human serum and 0.1 mg of rat brain, respectively. Additionally, the extraction time of our method was much shorter than the previously reported methods. Therefore, the fabricated CSMs with desirable properties will find broad application in large-scale and in-depth N-glycoproteome analysis.

Bilayer hydrogel actuators with tight interfacial adhesion fully constructed from natural polysaccharides.

Smart hydrogel actuators with excellent biocompatibility and biodegradation are extremely desired for biomedical applications. Herein, we have constructed bio-hydrogel actuators inspired by the bilayer structures of plant organs from chitosan and cellulose/carboxymethylcellulose (CMC) solution in an alkali/urea aqueous system containing epichlorohydrin (ECH) as a crosslinker, and demonstrated tight adhesion between two layers through strong electrostatic attraction and chemical crosslinking. The bilayer hydrogels with excellent mechanical properties could carry out rapid, reversible, and repeated self-rolling deformation actuated by pH-triggered swelling/deswelling, and transformed into rings, tubules, and flower-, helix-, bamboo-, and wave-like shapes by effectively designing the geometric shape and size. The significant difference in the swelling behavior between the positively charged chitosan and the negatively charged cellulose/CMC layers generated enough force to actuate the performance of the hydrogels as soft grippers, smart encapsulators, and bioinspired lenses, showing potential applications in a wide range of fields including biomedicine, biomimetic machines, etc.

Ultra-Stretchable and Force-Sensitive Hydrogels Reinforced with Chitosan Microspheres Embedded in Polymer Networks.

An ultra-stretchable and force-sensitive hydrogel with surface self-wrinkling microstructure is demonstrated by in situ synthesizing polyacrylamide (PAAm) and polyaniline (PANI) in closely packed swollen chitosan microspheres, exhibiting ultra-stretchability (>600%), high sensitivity (0.35 kPa-1 ) for subtle pressures (<1 kPa), and can detect force in a broad range (102 Pa-101 MPa) with excellent electrical stability and rapid response speed, potentially finding applications for E-skin.

Effects of Chitin Whiskers on Physical Properties and Osteoblast Culture of Alginate Based Nanocomposite Hydrogels.

Novel nanocomposite hydrogels composed of polyelectrolytes alginate and chitin whiskers with biocompatibility were successfully fabricated based on the pH-induced charge shifting behavior of chitin whiskers. The chitin whiskers with mean length and width of 300 and 20 nm were uniformly dispersed in negatively charged sodium alginate aqueous solution, leading to the formation of the homogeneous nanocomposite hydrogels. The experimental results indicated that their mechanical properties were significantly improved compared to alginate hydrogel and the swelling trends were inhibited as a result of the strong electrostatic interactions between the chitin whiskers and alginate. The nanocomposite hydrogels exhibited certain crystallinity and hierarchical structure with nanoscale chitin whiskers, similar to the structure of the native extracellular matrix. Moreover, the nanocomposite hydrogels were successfully applied as bone scaffolds for MC3T3-E1 osteoblast cells, showing their excellent biocompatibility and low cytotoxicity. The results of fluorescent micrographs and scanning electronic microscope (SEM) images revealed that the addition of chitin whiskers into the nanocomposite hydrogels markedly promoted the cell adhesion and proliferation of the osteoblast cells. The biocompatible nanocomposite hydrogels have potential application in bone tissue engineering.