金属表面纳米粒子/聚合物复合防腐涂层的研究进展

纳米材料(NMs)具有独特的性能,由其构成的纳米粒子/聚合物复合涂层在金属表面防腐蚀方面是非常经济有效的。本文总结了氧化物基和碳基两种不同纳米材料对纳米粒子/聚合物涂层性能的影响,概述了典型纳米粒子/聚合物复合防腐涂层防腐机理,表明碳基纳米材料可以作为提高防腐涂层阻隔性能的较有前途的纳米填料。最后展望了将纳米粒子/聚合物材料有效应用到金属表面防腐涂层中所面临的挑战和未来发展前景。

无机纳米粒子/聚合物复合材料研究进展

综述了无机纳米粒子 /聚合物复合材料的制备方法 ,纳米粒子的表面改性处理 ;着重介绍了纳米粒子在改进聚合物力学、热学、电性能、光学性能等方面的应用。

聚合物热电复合材料的研究进展

本文综述了碳纳米材料/聚合物、半导体合金/聚合物、金属纳米粒子/聚合物以及聚合物/聚合物等热电复合材料的研究进展。简要分析了热电复合材料的性能提升机理及现有材料尚存在的问题,并指出了聚合物热电复合材料今后的发展方向。

Water-dispersed bone morphogenetic protein nanospheres prepared by co-precipitation method

A modified complex coacervation-co-precipitation method was used to prepare bone morphogenetic protein (BMP)-loaded nanospheres. Three natural polymers were used as packing materials to obtain nanoscale delivery device for BMP,in the presence of phosphatidylcholine functioning as stabilizer. Positively charged polysaccharide, N,N-diethylaminoethyl dex-tran (DEAE-dextran) tended to form stable, uniform and smaller size particles carrying BMP. Negatively charged bovine serum albumin (BSA) induced precipitation of the produced BMP particles due to its weak interaction with BMP molecules, although it produced nanosized BMP spheres. While collagen, a weakly positively charged protein shaped larger particles due to the strong interaction among themselves. A mechanism of co-precipitation process was also deduced to depict the formation of stable nanospheres.

A new method for storing Ag nanoparticles

Silver nanoparticles were obtained by reduction method. Various techniques, such as UV-Vis spectroscopy, transmission electron microscopy （TEM） and light-scattering spectroscopy, were used to characterize nanoparticles. Sodium borohydride or sodium citrate was adopted as reduction regent, and polyvinyl alcohol or polyethylene glycol was adopted as stabilizing regent. An experimental condition was studied in detail. After the water was eliminated, the silver nanoparticle was fixed in the solid polymer. The silver nanoparticle in polymer could be re-dissolved in water. It was found that light scattering characteristic of silver nanoparticle storied in polymer was not changed. A new method of storing silver nanoparticles in solid polymer was given in this paper.

Surface Structure, Spectroscopic and Photocatalytic Activity Study of Polyaniline/TiO2 Nanocomposites

PANI （polyaniline） as a promising conducting polymer and photosensitizer has been used to prepare PANI/TiO2 （polyaniline/TiO2） nanocomposite as photocatalyst. TiO2 nanoparticles with size of 5-100 nm were encapsulated by PANI via the ＂in situ＂ polymerization of aniline on the surface of TiO2 nanoparticles. IR, SEM, EPR techniques were used to characterize the mechanism of electron interaction in PANI/TiO2 nanocomposite. The resulting PANI-modified TiO2 composites exhibit significantly higher photocatalytic activity than that of neat PANI on degradation of MB （methylen blue） aqueous solution under UV irradiation.

Improvement of Impact Absorbed Energy of CFRPs on Adding the Nanoparticles into Epoxy Resins

The present study investigates the effect of the addition of nanoparticles into epoxy resins as the matrix on the impact absorbed energy of CFRP （carbon fiber reinforced polymer）. Impact absorbed energy is one of the main properties to evaluate the CFRP＇s performance for transportation and aerospace structures. Two types of nanoparticle, namely nanofibers and nano-silica beads, were added into the epoxy resin to improve the impact absorption capacity of the CFRP. Two modified additives and conventional epoxy resins were quantitatively compared. The impact test results showed that impact absorbed energy for nanofibers was higher than nano-silica beads, and nanofibers as the additive promoted about 11% of impact absorbed energy compared with neat epoxy resin.

Spatial control of palladium nanoparticles in flexible click-based porous organic polymers for hydrogenation of olefins and nitrobenzene

Two flexible click-based porous organic polymers （CPP-F1 and CPP-F2） have been readily synthesized. SEM images show CPP-F1 is a 3D network, while CPP-F2 exhibits a granular morphology. Pd（OAc）2 can be easily incorporated into CPP-F1 and CPP-F2 to form Pd@CPP-F1 and Pd@CPP-F2, respectively. The interactions between the polymers and palladium are confirmed by solid-state 13C NMR, IR and XPS. Palladium nanoparticles （NPs） are formed after hydrogenation of olefins and nitrobenzene. Palladium NPs in CPP-F1 are well dispersed on the external surface of the polymer, while palladium NPs in CPP-F2 are located in the interior pores and on the external surface. In comparison with NPs in CPP-F1, the dual distribution of palladium NPs in CPP-F2 results in higher selectivity in the hydrogenation of 1,3-cyclohexadiene to cyclohexane. The catalytic systems can be recycled several times without obvious loss of catalytic activity or agglomeration of palladium NPs. Hot filtration, mercury drop tests and ICP analyses suggest that the catalytic systems proceed via a heterogeneous pathway.

One-step preparation of branched PEG functionalized AIE-active luminescent polymeric nanoprobes

The synthesis of amphiphilic aggregation-induced emission （ALE） dyes based organic nanoparticles has recently attracted in- creasing attention in the biomedical fields. These AlE dyes based nanoparticles could effectively overcome the aggregation caused quenching effect of conventional organic dyes, making them promising candidates for fabrication of ultrabright organic luminescent nanomaterials. In this work, AIE-active luminescent polymeric nanoparticles （4-NH2-PEG-TPE-E LPNs） were facilely fabricated through Michael addition reaction between tetraphenylethene acrylate （TPE-E） and 4-arm-poly（ethylene glycol）-amine （4-NH2-PEG） in rather mild ambient. The 4-NH2-PEG can not only endow these AlE-active LPNs good water dispersibility, but also provide functional groups for further conjugation reaction. The size, morphology and luminescent prop- erties of 4-NH2-PEG-TPE-E LPNs were characterized by a series of techniques in detail. Results suggested that these AlE-active LPNs showed spherical morphology with diameter about 100-200 nm. The obtained 4-NH2-PEG-TPE-E LPNs display high water dispersibility and strong fluorescence intensity because of their self assembly and AlE properties of TPE-E. Biological evaluation results demonstrated that 4-NH2-PEG-TPE-E LPNs showed negative toxicity toward cancer cells and good fluorescent imaging performance. All of these features make 4-NHz-PEG-TPE-E LPNs promising candidates for biolog- ical imaging and therapeutic applications.

Preparation and self-assembly of amphiphilic polymer with aggregation-induced emission characteristics

An amphiphilic polymer bearing tetraphenylethene (TPE) moiety was synthesized by convenient reactions. The polymer exhibits unique aggregation-induced emission (AIE) characteristics and can self-assemble to size-tunable particles in DMF/water mixtures. The polymer nanoparticles can be used for cell imaging, which provides a potential stable fluorescent tool to monitor the distribution of drugs and bioconjugates in living cells.

Biodegradable polymeric nanoparticles based on amphiphilic principle:construction and application in drug delivery

The use of nanotechnology in drug-delivery systems(DDS) is attractive for advanced diagnosis and treatment of cancer diseases. Biodegradable polymeric nanoparticles, for example, have promising applications as advanced drug carriers in cancer treatment. In this review, we discuss the development of drug-delivery systems based on an amphiphilic principle mainly conducted by our group for anti-cancer drug delivery. We first briefly address the synthetic chemistry for amphiphilic biodegradable polymers. In the second part, we summarize progress in the application of self-assembled polymer micelles using amphiphilic biodegradable copolymers as anti-tumor drug carriers.

Facile synthesis of size-tunable stable nanoparticles via click reaction for cancer drug delivery

The stability and size of polymeric nanoparticles are two of the most important parameters determining their pharmacokinetics and tumor/drug accumulation efficiency in cancer-drug delivery. Herein, we report a facile one-pot synthesis of crosslinked nanoparticles(CNPs) with tunable sizes and polyethylene glycol(PEG) shells via click reactions. Simply by adjusting the contents of the macromonomer(PEG monoacrylate) in its reaction with ethylene diacrylate and a crosslinker containing hexa-thiols groups, the sizes of the resulting PEGylated crosslinked nanoparticles could be easily tuned from 10 to 90 nm. These nanoparticle cores could encapsulate hydrophobic drugs such as doxorubicin(DOX), and the unreacted thiol and acrylate groups could be used for drug conjugation or labeling. Thus, the nanoparticles provide a multifunctional platform for drug delivery. In vivo studies showed that the larger nanoparticles(about 83.7 nm) had a much longer blood-circulation time and better tumor-targeting efficiency. One of our most important findings was that the drug encapsulated in the crosslinked nanoparticles, even though little was released at pH 7.4 under in vitro conditions, had much faster blood clearance than the nanoparticles' carrier, suggesting that drug release in the bloodstream was significant.

Wide range temperature detection with hybrid nanoparticles traced by surface-enhanced Raman scattering

We report on the fabrication of a class of surface-enhanced Raman scattering(SERS)active thermometers,which consists of60 nm gold nanoparticles,encoded with Raman-active dyes,and a layer of thermoresponsive poly(N-isopropylacrylamide)(PNIPAM)brush with different chain lengths.These SERS-active nanoparticles can be optimized to maintain spectrally silent when staying as single particles in dispersion.Increasing temperature in a wide range from 25 to 55°C can reversibly induce the interparticle self-aggregation and turn on the SERS fingerprint signals with up to 58-fold of enhancement by taking advantage of the interparticle plasmonic coupling generated in the process of thermo-induced nanoparticles self-aggregation.Moreover,the most significative point is that these SERS probes could maintain their response to temperature and present all fingerprint signals in the presence of a colored complex.However,the UV-Vis spectra can distinguish the differences faintly and the solution color shows little change in such complex mixture.This proof-of-concept and Raman technique applied here allow for dynamic SERS platform for onsite temperature detection in a wide temperature range and offer unique advantages over other detection schemes.

A simple catalyst for aqueous phase Suzuki reactions based on palladium nanoparticles immobilized on an ionic polymer

Palladium nanoparticles immobilized on a cross-linked imidazolium-containing polymer were evaluated as a catalyst for Suzuki carbon-carbon cross-coupling reactions using water as the solvent. The nanocatalysts show good catalytic activities for aryl iodides and aryl bromides and moderate activity with aryl chloride substrates. Coupling of sterically hindered substrates could also be achieved in reasonable yields. The heterogeneous catalyst is stable, can be stored without precautions to exclude air or moisture, and can be easily recycled and reused.

Selective Gold Deposition on a Nanostructured Block Copolymer Film Crystallized by Epitaxy

An ordered nanostructure formed by epitaxial crystallization of a semicrystalline block copolymer on a substrate has been used as a patterned template for the selective deposition of thermally evaporated gold nanoparticles, resulting in the formation of structure-guiding host nanocomposites in which the ordered distribution of the guest particles is guided by the ordering of the host nanostructured block copolymer matrix. This opens new perspectives in the field of polymeric composites related to the maximum enhancement of effective physical properties and to the numerous possible applications that arise due to the presence of long-range order in the spatial distribution of functional nanoparticles.

Entrapment and Sustained Release of Hydrophobic Drugs with Different Molecular Weights from PHBHHx-PEG Nanoparticles

Biodegradable polymeric nanoparticles are more and more frequently used in drug delivery systems, which represent one of the most rapidly developing areas. In our previous study, a novel natural hybrid polyester, polyethylene glycol 200 （PEG200） end-capped poly （3-hydroxybutyrate-co-3-hydroxyhcxanoate） （PHBHHx-PEG） was directly produced by Aeromonas hydrophila fermentation. In this study, the performance of the novel biodegradable PHBHHx-PEG copolyester as a sustained release carrier for hydrophobic drugs with different molecular weights and the in vitro sustained release profile were investigated. 5-Fluorouracil （5-Fu, Mw=130.1）, TGX221 （Mw=364.4）, and Rapamycin （RAP, Mw=914.2） were used as the model drugs. PHBHHx-PEG nanoparticles entrapped with 5-Fu, TGX221 and RAP were fabricated by a modified emulsification/solvent evaporation method, respectively. The average diameter of 5-Fu, TGX221, and RAP loaded PHBHHx-PEG nanoparticles was between 198.2-217.4 nm, and the entrapment efficiency of the three drugs was 62.5%, 93.4% and 91.9%, respectively. The in vitro release profiles of 5-Fu, TGX221 and RAP from PHBHHx-PEG nanoparticles were different. 5-Fu showed faster release rate and an obvious initial burst release phase. TGX221 and RAP were demonstrated to be released more slowly and steadily. The release percentages of 5-Fu, TGX221 and RAP were 97.7%, 85.1% and 74.7% after releasing for 72 h. PHBHHx-PEG is a kind of promising material as a carrier for the entrapment and delivery of hydrophobic drugs especially for those drugs with high molecular weight.

Curcumin-encapsulated polymeric nanoparticles for metastatic osteosarcoma cells treatment

Osteosarcoma is a high-class malignant bone cancer with a less than 20% five-year survival rate due to its early metastasis potential. There is an urgent need to develop a versatile and innoxious drug to treat metastatic osteosarcoma.Curcumin（Cur） has shown its potential for the treatment of many cancers; however,the clinical implication of native curcumin is severely hindered by its intrinsic property. In this study,a mixed system of monomethoxy（polyethylene glycol）-poly（d,l-lactide-co-glycolide）/poly（ε-caprolactone）（m PEGPLGA/PCL） was used to build a formulation of curcuminencapsulated nanoparticles（Cur-NPs）,which significantly improved the solubility,stability and cellular uptake of curcumin. Moreover,the Cur-NPs were superior to free curcumin in the matter of inhibition on the proliferation,migration and invasion of osteosarcoma 143B cells. It was found that both free curcumin and Cur-NPs could decrease the expressions of c-Myc and MMP7 in the level of mRNA and protein,which explained why free curcumin and Cur-NPs could inhibit the proliferation and invasion of metastatic osteosarcoma 143B cells. The Cur-NPs provided a promising strategy for metastatic osteosarcoma treatment.

Electrogenerated chemiluminescence aptasensor for thrombin incorporating poly(pyrrole-co-pyrrole propylic acid) nanoparticles loaded with aptamer and ruthenium complex

A novel electrogenerated chemiluminescence （ECL） aptasensor for highly sensitive detection of thrombin was developed on the basis of poly（pyrrole-co-pyrrole propylic acid） nanoparticles loaded with aptamer and ruthenium complex. Thrombin binding aptamers served as the molecular recognition elements and ruthenium bis（2,2＇-bipyridine） （2,2＇-bipyridine-4,4＇-dicarboxylic acid）-ethylenediamine （Rul） was used as an ECL signal complex. Novel electroactive polymers poly（pyrrole-co-pyr- role propylic acid） nanoparticles （Ppy-pa NPs） were synthesized by a simple alcohol-assisted microemulsion polymerization. Rul-Ppy-pa NPs were synthesized by covalently coupling Rul with the Ppy-pa NPs. Ppy-pa NPs and Rul-Ppy-pa NPs were characterized using a fourier transform infrared spectrometer, super-conducting fourier digital NMR spectrometer, and trans- mission electron microscope. One ECL chemical sensor fabricated by immobilizing the Rul-Ppy-pa NPs on PIGE was developed for the determination of TprA with a high sensitivity and stability. The ECL aptasensor was fabricated by covalenfly coupling the thrombin binding aptamer-I （TBA-I） onto the surface of the paraffin-impregnated graphite electrode, which had been covalently modified with a monolayer of 4-aminobenzene sulfonic acid via electrochemical oxidations, for capturing thrombin onto the electrode and then the TBA-II labeled with Rul-Ppy-pa NPs was bound with epitope of thrombin. The ECL aptasensot showed an extremely low detection limit of 3.0×10^-16 mol/L for thrombin and a good selectivity. This work demonstrated that using Ppy-pa NPs as a carrier of ruthenium complex and molecular recognition element was a promising approach for the fabrication of ECL biosensor with high sensitivity.