Preparation of UV-curable functionalized graphene/polyurethane acrylate nanocomposite with enhanced thermal and mechanical behaviors

Functionalized graphene nanosheets (f-GNSs) were synthesized by a simple covalent functionalization of graphene with 3-methacryloxypropyl trimethoxysilane (MPTES). The results from FTIR, XPS and XRD showed that MPTES was successfully attached onto the surface of graphene. Functionalized graphene/polyurethane acrylate (f-GNS/PUA) nanocomposites were prepared by UV radiation of PUA with f-GNS. The onset thermal degradation temperature of f-GNS/PUA nanocomposite was increased by 16 °C, at an f-GNS content of 1 wt%. Meanwhile, the storage modulus and glass transition temperature of the nanocomposites were enhanced by incorporating f-GNS into the PUA. This is believed to be attributed to that the covalent functionalization of graphene can improve both the dispersion of f-GNSs in the polymer matrix and the interfacial interactions between f-GNSs and PUA.     

Preparation of functionalized graphene sheets by a low-temperature thermal exfoliation approach and their electrochemical supercapacitive behaviors

Two kinds of functionalized graphene sheets were produced by thermal exfoliation of graphite oxide. The first kind of functionalized graphene sheets was obtained by thermal exfoliation of graphite oxide at low temperature in air. The second kind was prepared by carbonization of the first kind of functionalized graphene sheets at higher temperature in N₂. Scanning electron microscopy images show that both two kinds of samples possess nanoporous structures. The results of N₂ adsorption-desorption analysis indicate that both of two kinds of samples have high BET surface areas. Moreover, the second kind of functionalized graphene sheets has a relatively higher BET surface area. The results of electrochemical tests is as follows: the specific capacitance values of the first kind of functionalized graphene sheets in aqueous KOH electrolyte are about 230 F g⁻¹; the specific capacitance values of the second kind of functionalized graphene sheets with higher BET surface areas are only about 100 F g⁻¹; however, compared with the first kind of functionalized graphene sheets, the second kind has a higher capacitance retention at large current density because of its good conductive behaviors; furthermore, in non-aqueous EC/DEC electrolyte, the specific capacitance values of the first kind sample and the second kind sample are about 73 F g⁻¹ and 36 F g⁻¹, respectively.     

Electronic structures,field effect transistor and bipolar field-effect spin filtering behaviors of functionalized hexagonal graphene nanoflakes

We report first-principles calculations on the electronic properties, spin magnetism, and potential applications of the functionalized hexagonal armchair graphene nanoflakes (GNFs). It is found that the gap of the GNF changes in an obvious oscillating manner with the size of its hexagonal defect (antidot), and when the antidot is large enough, it will lead to a prominent splitting of the α-spin and β-spin orbitals and the intriguing property of bipolar magnetic semiconductors for the GNF. And also shown is that the electronic structures of the GNF can be tuned from semiconducting to metallic properties by different edge modifications. More importantly, based on the suitable hexagonal defective GNFs, we design a field effect transistor (FET) and a bipolar field-effect spin-filtering (BFESF) device, and find that they all exhibit extremely high performances. For this FET, its ON/OFF ratio reaches ∼10⁵, subthreshold swing ∼90 meV per decade, and the transconductance ∼10³ S/m, and for this BFESF device, the spin polarization nearly reaches 100% with different spin directions only by altering signs of gate voltages.     

Diclofenac-hydrotalcite: In vitro and in vivo release experiments

Solutions of the anti-inflammatory drug diclofenac in ethanol and ethanol–water were prepared and mixed with hydrotalcite and hydrotalcite heated at 500 °C. Hydrotalcite pretreated at 500 °C showed a higher adsorption of diclofenac. Diclofenac-hydrotalcites were used for in vitro release experiments to evaluate the percutaneous absorption of diclofenac, using sets of eight Franz cells with membranes of stratum corneum epidermis obtained from human skin; a 2% diclofenac hydroalcoholic gel was used for comparison. Hydrotalcite pretreated at 500 °C is less suitable for release procedures, despite its higher adsorption capacity, whereas diclofenac adsorbed from ethanolic solution by untreated hydrotalcite presents the most efficient sample and shows the best permeation profiles. This sample was selected for the in vivo experiments. Ten healthy volunteers participated on the in vivo experiments: the diclofenac-hydrotalcite appeared to be useful for an efficient application on human skin as inhibitor of the UV-induced erythemas, also better than the usual gel samples.     

功能化石墨烯在防腐涂料中的应用

介绍了石墨烯的基本特性和作为新型纳米填料在防腐涂料领域发挥的重要作用,论述了采用共价键法和非共价键法修饰石墨烯的方法以及研究进展,并且通过对两种修饰方法对比,可根据不同的实验需求采取相应的修饰方法。同时结合近年来功能化石墨烯在防腐涂料中的研究及应用状况,针对功能化石墨烯在防腐涂料的应用过程中受到限制的原因进行了分析,对功能化石墨烯在防腐涂料中的前景进行了展望。     

Flexible and general synthesis of functionalized phosphoisoprenoids for the study of prenylation in vivo and in vitro

Protein modification with isoprenoid lipids affects hundreds of signaling proteins in eukaryotic cells. Modification of isoprenoids with reporter groups is the main approach for the creation of probes for the analysis of protein prenylation in vitro and in vivo. Here, we describe a new strategy for the synthesis of functionalized phosphoisoprenoids that uses an aminederivatized isoprenoid scaffold as a starting point for the synthesis of functionalized phosphoisoprenoid libraries. This overcomes a long-standing problem in the field, where multistep synthesis had to be carried out for each individual isoprenoid analogue. The described approach enabled us to synthesize a range of new compounds, including two novel fluorescent isoprenoids that previously could not be generated by conventional means. The fluorescent probes that were developed using the described approach possess significant spectroscopic advantages to all previously generated fluorescent isoprenoid analogue. Using these analogues for flow cytometry and cell imaging, we analyzed the uptake of isoprenoids by mammalian cells and zebrafish embryos. Furthermore, we demonstrate that derivatization of the scaffold can be coupled in a one-pot reaction to enzymatic incorporation of the resulting isoprenoid group into proteins. This enables rapid evaluation of functional groups for compatibility with individual prenyltransferases and identification of the prenyltransferase specific substrates.     

In vitro release kinetics of bovine serum albumin from highly swellable dextran hydrogels

Hydrogels synthesized from a polysaccharide‐based polymer, dextran, in the presence of two crosslinking agents, N,N′‐methylenebisacrylamide and epichlorohydrin, were evaluated for the oral colon‐specific delivery of polypeptide drugs. These novel dextran hydrogels had significantly greater swelling ratios than recently developed dextran hydrogels. A model protein, bovine serum albumin, was loaded into 50% (by weight) crosslinker‐containing dextran hydrogels in two ways: during the crosslinking reaction and by a soaking method. The loading capacity was varied between 22 and 25 mg/g of dry gel, depending on the loading procedure. In vitro release experiments were performed with a simulated gastrointestinal system in the presence and absence of dextranase. The diffusion exponents were calculated by means of a semiempirical power‐law equation for the release of protein from swellable hydrogel discs. Bovine serum albumin was mainly released by Fickian diffusion, and this indicated that its hydrodynamic diameter (7.7 nm) was smaller than the hydrogel mesh size (～19 nm). The release of bovine serum albumin from both hydrogel types was substantially higher than expected, especially in the presence of dextranase, and this was attributed to the high swellability of the hydrogels. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

In situ Synthesis and mechanical,thermal properties of polyimide nanocomposite film by addition of functionalized graphene oxide

Polyimide (PI) and chemical modified graphene oxide nanocomposite films are prepared by in situ polymerization from solutions of pyromellitic dianhydride and 4,4′‐oxydianiline with various amount (0.5–2 wt%) of 3‐aminopropyltriethoxysilane (APTS) functionalized graphene oxide (GO) sheets in dimethylacetamide. The APTS functionalized GO (GO‐APTS) is a versatile platform for polymer grafting, improving excellent dispersion of GO in the PI matrix, and forming strong interaction with the PI matrix. The GO‐APTS/PI nanocomposites exhibited improvement in mechanical and thermal properties by addition of a small amount of GO‐APTS. With the addition of a small amount of GO‐APTS (1.5 wt%) to PI matrix, mechanical properties with the tensile strength and Young's modulus improved by 45% and 15%, respectively. The thermal analysis showed that the thermal stability of PI was slightly enhanced by the incorporation of GO‐APTS (1.5 wt%). This approach provides a strategy for developing high performance functionalized GO‐polymer composite materials. POLYM. COMPOS., 37:907–914, 2016. © 2014 Society of Plastics Engineers     

In vivo and in vitro lipid accumulation inBorago officinalis L.

Seeds of 13 accessions of borage (Borago officinalis) varied in total fatty acid content from 28.6 to 35.1% seed weight, with linoleic, γ-linolenic, oleic and palmitic as the predominant fatty acids, averaging 38.1%, 22.8%, 16.3% and 11.3% of total fatty acids, respectively. There was an inverse relation between γ-linolenic acid (25.0 to 17.6%) and oleic acid (14.5 to 21.3%). Fatty acid content of leaf tissues was 9.1% dry weight, with α-linolenic acid 55.2% and γ-linolenic acid 4.4% of total fatty acids. Cotyledons were the major source of fatty acids in seeds. Seed fatty acid content increased from <1 mg at six days postanthesis to about seven mg at maturity (22 to 24 days). Individual fatty acid content of seed was relatively constant after day 8. When immature embryos from 6 to 16 days postanthesis were cultured in a liquid or semisolid basal medium, fatty acid composition was similar to that of in vivo-grown seeds. Growth of cultured embryos decreased as sucrose concentration was increased from 3 to 20% in the basal medium, and most embryos did not survive 30% sucrose; fatty acid as a percentage of dry weight was maximal at 6% sucrose.     

In vitro enhancement of dendritic cell-mediated anti-glioma immune response by graphene oxide

Malignant glioma has extremely poor prognosis despite combination treatments with surgery, radiation, and chemotherapy. Dendritic cell (DC)-based immunotherapy may potentially serve as an adjuvant treatment of glioma, but its efficacy generally needs further improvement. Here we explored whether graphene oxide (GO) nanosheets could modulate the DC-mediated anti-glioma immune response in vitro, using the T98G human glioma cell line as the study model. Pulsing DCs with a glioma peptide antigen (Ag) generated a limited anti-glioma response compared to un-pulsed DCs. Pulsing DCs with GO alone failed to produce obvious immune modulation effects. However, stimulating DCs with a mixture of GO and Ag (GO-Ag) significantly enhanced the anti-glioma immune reaction (p < 0.05). The secretion of interferon gamma (IFN-γ) by the lymphocytes was also markedly boosted by GO-Ag. Additionally, the anti-glioma immune response induced by GO-Ag appeared to be target-specific. Furthermore, at the concentration used in this study, GO exhibited a negligible effect on the viability of the DCs. These results suggested that GO might have potential utility for boosting a DC-mediated anti-glioma immune response.     

功能化石墨烯改性双马来酰亚胺复合材料的微观表征及性能

采用改进Hummers法制备氧化石墨烯（GO）,分别采用水合肼、壳聚糖、KOH还原得到了还原氧化石墨烯（rGO）并对三种还原方法做了对比,选择最佳方案;再通过离子液体（NH₂IL）对rGO功能化得到改性还原氧化石墨烯（NH₂IL-rGO）。以二烯丙基双酚A （BBA）和双酚A双烯丙基醚（BBE）为活性稀释剂,4,4'-二氨基二苯甲烷型双马来酰亚胺（MBMI）为反应单体,制备了MBMI-BBA-BBE （MBAE）树脂基体;同时以NH₂IL-rGO为增强体采用原位聚合法制备NH₂IL-rGO/MBAE复合材料。表征了石墨烯和复合材料的微观形貌并分析了石墨烯对复合材料性能的影响。结果表明：NH₂IL-rGO在树脂基体中以两相形式存在,结构完整,并赋予复合材料优异的性能。当NH₂IL-rGO含量为2%（质量）时,复合材料冲击强度和弯曲强度最大,分别为15.33 kJ/m²和142 MPa,热分解温度为435.73℃、当测试频率为100 Hz～10 kHz时介电常数发生突变达到84。     

聚合物功能化石墨烯的合成及应用研究进展(二)

着重评述了采用共价连接和非共价连接技术制备聚合物功能化石墨烯的方法,介绍了聚合物功能化石墨烯的应用概况。     

Synthesis,characterization and electrochemical properties of functionalized graphene oxide

Graphene oxide (GO) was functionalized by a simple reaction of its carboxylic acid groups with a silanized-metalloid polymer, which gave the resulting hybrid GO the property of efficient dispersion in a variety of solvents. Spectroscopic investigations show that the covalent attachment is effectively accomplished through an amidation process. The combination of a metalloid polymer and GO is unique and the composite material exhibits interesting features not seen in the individual structures. The electrochemical properties of this metalloid–polymer-GO were demonstrated by immobilizing the sample on a conventional gold-printed circuit board (Au-PCB) electrode. Functionalized GO showed a perfect scaling of steady-state currents with correlation coefficients of 0.9600 (I_pc) and 0.9552 (I_pa), indicating the promise of this new GO hybrid as a transducer material for many sensing applications.     

A review on synthesis and properties of polymer functionalized graphene

This review highlights the functionalization chemistry of graphene with polymers by both covalent and non-covalent approaches. Due to the strong cohesive interactions graphene platelets agglomerate, causing difficulty to attain its optimum properties. The covalent functionalization is illuminated both from ‘grafting to’ and ‘grafting from’ techniques discussing the merits and demerits of the processes. The controlled free radical polymerization techniques used for this purpose e.g. ATRP, SET–LRP and RAFT etc. are discussed along with the conventional free radical polymerization. We have also noted the various approaches used in non-covalent functionalization e.g. π–π, H-bonding and hydrophobic interactions. These functionalized graphenes show good and stable dispersion facilitating composite formation with commodity plastics enhancing it's mechanical, thermal and conductivity properties. The optoelectronic properties of these functionalized graphene are interesting to fabricate sensors, photovoltaics, supercapacitors etc. A short account of the properties of these modified graphenes is also embodied with an emphasis on different area where future developments are expected.     

聚合物功能化石墨烯的合成及应用研究进展(一)

着重评述了采用共价连接和非共价连接技术制备聚合物功能化石墨烯的方法,介绍了聚合物功能化石墨烯的应用概况。     

In vitro and in vivo Digestibility of Blended and Corresponding Interesterified Fats in Rats

The process of interesterification of fat blends namely vanaspati-ground-nut oil (40:60) (vanaspati-GNO), sal fat and groundnut oil (30:70) (sal-GNO), sheep tallow and groundnut oil (30:70) (ST-GNO), and cottonseed oil (CSO) was found to bring about limited but consistent increase in in vitro digestibility (compared to starting stocks) during first four hours studied. Apparent digestibility of blends of sal-GNO and vanaspati-GNO in rats was not effected by the process of interesterification while interesterified products had significantly higher in vivo true digestibility compared to starting stocks.     

In vitro and in vivo properties of graphene-incorporated scaffolds for bone defect repair

The employment of graphene and its derivatives, graphene oxide and reduced graphene oxide, is extending from bioimaging and fabrications of biosensors to drug delivery and tissue engineering in the biomedical area. Graphene family-incorporated scaffolds, used in bone tissue engineering and bone regenerative medicine, profit superior properties of these materials, such as enhanced mechanical properties, large surface area, and the existence of functional groups. At the same time, problems related to cytotoxicity and adverse immune response of graphene family are solved when they are applied to produce 3-dimensional scaffolds. The objective of this review is to focus on in vitro properties of scaffolds consisting of graphene or its derivatives, especially osteogenic and antibacterial properties, as well as the influence of graphene and its derivatives on in vivo performances of implanted bone scaffolds. The positive effect of graphene and its two derivatives on attachment, and cell proliferation, as well as in vitro osteogenic differentiation of different cells was undeniable. Besides, the synergetic outcome of using graphene family on the antibacterial feature of scaffolds, especially incorporation with the silver element, was effective. Moreover, successful treatment of critical-sized bone defects was reported during in vivo preclinical tests when graphene or its derivatives-incorporated scaffolds were used. However, the limited number of in vivo studies should be considered as one of the main shortcomings to use graphene as a promising candidate for treating bone defects. It is anticipated that the increased number of well-designed preclinical studies could improve the applications of graphene incorporated scaffolds in bone tissue engineering/regeneration, and find out explanations and appropriate solutions to possible long-term toxicity and nonbiodegradability of these materials.     

Electrospinning of polymer nanofibers loaded with noncovalently functionalized graphene

Pristine graphene/polyvinyl alcohol (PVA) nanofibers were prepared by electrospinning an aqueous solution of polyvinylpyrrolidone‐stabilized graphene and PVA. This is the first report of electrospun nanofibers reinforced with dispersed pristine graphene. We examine the relationship between graphene loading and critical electrospinning parameters. Microscopy indicates uniform fiber formation and excellent graphene dispersion within the fiber. Rheological data indicates that the excellent level of graphene dispersion enhances the modulus of the polymer by 205%. We also find that the graphene significantly increases the fibers' thermal stability (increase of 15°C) and crystallinity (59% increase) above the baseline. In fact, the graphene may act as nucleating points for increased crystallinity. These graphene/polymer nanofibers have the potential to serve in a variety of applications, including electrodes, conductive wires, and biomedical materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Characterization and performance of dodecyl amine functionalized graphene oxide and dodecyl amine functionalized graphene/high‐density polyethylene nanocomposites: A comparative study

Dodecyl amine (DA) functionalized graphene oxide(DA‐GO) and dodecyl amine functionalized reduced graphene oxide (DA‐RGO) were produced by using amidation reaction and chemical reduction, then two kinds of well dispersed DA‐GO/high‐density polyethylene (HDPE) and DA‐RGO/HDPE nanocomposites were prepared by solution mixing method and hot‐pressing process. Thermogravimetric, X‐ray photoelectron spectroscopy, Fourier transforms infrared spectroscopy, X‐ray diffractions, and Raman spectroscopy analyses showed that DA was successfully grafted onto the graphene oxide surface by uncleophilic substitution and the amidation reaction, which increased the intragallery spacing of graphite oxide, resulting in the uniform dispersion of DA‐GO and DA‐RGO in the nonpolar xylene solvent. Morphological analysis of nanocomposites showed that both DA‐GO and DA‐RGO were homogeneously dispersed in HDPE matrix and formed strong interfacial interaction. Although the crystallinity, dynamic mechanical, gas barrier, and thermal stability properties of HDPE were significantly improved by addition of small amount of DA‐GO or DA‐RGO, the performance comparison of DA‐GO/HDPE and DA‐RGO/HDPE nanocomposites indicated that the reduction of DA‐GO was not necessary because the interfacial adhesion and aspect ratio of graphene sheets had hardly changed after reduction, which resulting in almost the same properties between DA‐GO/HDPE and DA‐RGO/HDPE nanocomposites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39803.     

Photochemistry of covalently functionalized graphene oxide with phenothiazinyl units

Phenothiazinyl units have been covalently attached to graphene oxide (GO) by nitrene insertion onto CC bonds. Laser flash photolysis of this material indicates that tethering of phenothiazinyl units to GO enhances significantly the interaction with respect to mixtures of both components, leading to the observation of photoinduced electron transfer.