Ultralight, highly flexible in situ thermally crosslinked polyimide aerogels with superior mechanical and thermal protection properties via nanofiber reinforcement.

HYPOTHESIS: Advanced thermal-insulation materials for human use in high-temperature and ultra-low-temperature environments have received extensive attention. However, facile synthesis of aerogels with excellent mechanical and thermal properties via freeze-drying or electrospinning alone is still challenging. We hypothesized that a polyimide aerogel with high mechanical strength and good thermal-insulation performance and suitability for various applications at high and low temperatures could be prepared facilely using a simple and novel preparation strategy that combines electrospinning, freeze-drying, and in situ thermal crosslinking. EXPERIMENTS: Polyamideimide (PAI) nanofibers loaded with bismaleimide (BMI) were electrospun and dispersed into a polyamic acid aqueous solution. PAI/BMI-nanofiber-reinforced polyimide (IBNR-PI) aerogels with an interpenetrating network structure were prepared by freeze-drying and heat treatment. FINDINGS: The IBNR-PI aerogels possessed extremely low volume density (26 mg cm-3) and high porosity (94.92%). Most importantly, they showed high tensile strength and good compressive fatigue resistance with plastic deformation of only 7% after 1000 compression cycles. The aerogels also showed a significantly low thermal conductivity (30.06 mW m-1 K-1) and excellent thermal insulation over a wide temperature range. Thus, the IBNR-PI aerogels are excellent candidates for thermal-insulation materials at high and low temperatures.

Dual-template imprinted polymers for class-selective solid-phase extraction of seventeen triazine herbicides and metabolites in agro-products.

A novel dual-template molecularly imprinted polymer (DMIP) was prepared with atrazine and prometryn as the template and applied as a class-specific adsorbent for simultaneously selective solid-phase extraction of seventeen triazine herbicides and metabolites from complex matrices. For comparison, a non-imprinted polymer (NIP) and two single-template imprinted polymers (SMIPs) were also synthesized using the same procedure of DMIP, but in the absence of the template (NIP) or with one template (SMIP). Various parameters affecting the extraction performance of DMIP-SPE were investigated in detail. Under the optimum conditions, the enrichment efficiency, class-selectivity and reusability of DMIP-SPE were evaluated. Only DMIP-SPE possessed high affinity and good selective recognition ability for all the seventeen targets including chloro-, thiomethyl- and methoxy- triazines. Further, a DMIP-SPE-LC-MS/MS method was developed for simultaneously determining trace triazine herbicides and metabolites in maize, wheat and cottonseed samples. The method showed good linearity (r>0.9941) in the range of 10-200 µg kg-1, high sensitivity with low limits of detection of 0.5-8.8 µg kg-1, and satisfactory recoveries of 61.3-105.9% with relative standard deviations of 2.1-10.7%. These results highlighted the good application prospect of the multi/dual-template imprinting strategy in the high-throughput analysis of various concerned contaminants in agro-products.

The determination of patulin from food samples using dual-dummy molecularly imprinted solid-phase extraction coupled with LC-MS/MS.

A molecularly imprinted polymer (MIP) with specific adsorption for patulin was successfully polymerized by precipitation polymerization using 2-oxindole (2-oxin) and 6-hydroxynicotinic acid (6-HNA) as dummy template molecules, methylacrylic acid (MAA) as a functional monomer, trimethylolpropane trimethacrylate (TRIM) as a crosslinker, 2,2-azobis-(2-methylpropionitrile) (AIBN) as a initiator, and methanol as a porogen solvent. The molecularly imprinted solid phase extraction (MI-SPE) column was prepared using the polymer as a sorbent and applied for the selective extraction of patulin from real samples. The results showed that the MI-SPE method had high selectivity and specific adsorption towards patulin with mean recoveries ranged between 81.3% and 106.3% and a relative standard deviation (RSD) < 4.5%. Additionally, the developed MI-SPE method coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) exhibited good linearity in the range of 1-100 ng mL-1 with correlation coefficients (R2) >0.998. The limits of detection (LODs, S/N = 3) were 0.05-0.2 ng g-1, and the limits of quantification (LOQs, S/N = 10) were 0.2-0.5 ng g-1. The developed method showed a better purification and higher patulin recovery for real samples than the quick, easy, cheap, effective, rugged, safe "QuEChERS" method.

Encapsulation of Poly I:C and the natural phosphodiester CpG ODN enhanced the efficacy of a hyaluronic acid-modified cationic lipid-PLGA hybrid nanoparticle vaccine in TC-1-grafted tumors.

FDA approval of CpG oligodeoxynucleotide (CpG ODN) adjuvants for a human hepatitis B virus vaccine has been delayed until late 2017 because of concerns regarding the severe side effects, which may be attributed to the high dosage and systemic diffusion of this proinflammatory material. Considering that PLGA could provide shelter to resist nucleases in tissue and that cationic lipids could confine anionic oligonucleotides in the nanoparticles via electrostatic attraction to avoid systemic diffusion, we encapsulated a natural phosphodiester or the expensive phosphorothioate CpG ODNs in our previously reported hyaluronic acid-modified cationic lipid-PLGA hybrid nanoparticles and evaluated vaccine efficacy in a TC-1-grafted mouse model. Our results showed that together with Poly I:C, CpG ODN could promote the maturation of bone marrow-derived dendritic cells and the cross-presentation of exogenous antigens in vitro. For the coencapsulation with Poly I:C, in vivo studies showed that adjuvant effects on the vaccine efficacy of tumor depression, immune cell activation, and memory T-cell elevation of phosphodiester CpG ODNs were comparable to those of the phosphorothioate CpG ODNs at a low concentration (5 µg/dose). In conclusion, the combination of oligonucleotide adjuvants and synthetic particulate systems not only potentiated the immunogenicity of these nanoparticles but also made these adjuvants safer and more economical, which may be helpful for their wide application.