A novel nano drug delivery system based on tigecycline-loaded calciumphosphate coated with poly-dl-lactide-co-glycolide

The purpose of the study presented in this paper has been to examine the possibility of the synthesis of a new nanoparticulate system for controlled and systemic drug delivery with double effect. In the first step, a drug is released from bioresorbable polymer; in the second stage, after resorption of the polymer, non-bioresorbable calcium phosphate remains the chief part of the particle and takes the role of a filler, filling a bone defect. The obtained tigecycline-loaded calcium-phosphate(CP)/poly(dl-lactide-co-glycolide)(PLGA) nanoparticles contain calcium phosphate coated with bioresorbable polymer. The composite was analyzed by FT-IR, XRD and AFM methods. The average particle size of the nanocomposite ranges between 65 and 95 nm. Release profiles of tigecycline were obtained by UV–VIS spectroscopy in physiological solution at 37°C. Experimental results were analyzed using Peppas and Weibull mathematical models. Based on kinetic parameters, tigecycline release was defined as non-Fickian transport. The cytotoxicity of the nanocomposite was examined on standard cell lines of MC3T3-E1, in vitro. The obtained low values of lactate dehydrogenase (LDH) activity (under 37%) indicate low cytotoxicity level. The behaviour of the composite under real-life conditions was analyzed through implantation of the nanocomposite into living organisms, in vivo. The system with the lowest tigecycline content proved to be an adequate system for local and controlled release. Having in mind the registered antibiotics concentration in other tissues, delivery systems with a higher tigecycline content show both local and systemic effects.     

聚苯乙烯/氧化石墨纳米复合材料的制备与性能

利用十六烷基三甲基溴化铵对氧化石墨进行插层改性。以原住插层聚合的方式合成了聚苯乙烯／氧化石墨（PS／GO）纳米复合材料。用XRD和TEM进行的形态研究表明,氧化石墨被剥离成10nm-30nm厚的层片而分散在聚合物基体中。热重分析证明PS／GO复合材料比PS材料和普通石墨粉填充的PS材料表现出更好的热稳定性。     

聚丙烯酰胺/氧化石墨纳米复合材料的研究

氧化石墨具有良好的层状结构，其层间具有丰富的官能团，能与有机聚合物形成插层纳米复合材料进而改善材料的性能．采用层离吸收-原位聚合法制备了聚丙烯酰胺／氧化石墨纳米复合材料，并采用XRD、HREM及DSC等对其结构和性能进行了表征。结果表明，聚丙烯酰胺与氧化石墨两者之间存在着较强的相互作用，材料的玻璃化转变温度得到提高，层离吸收-原位聚合法是获得聚丙烯酰胺／氧化石墨层纳米复合材料的有效途径，聚丙烯酰胺在氧化石墨中存在着多种排列方式，不同层间距(1．6nm和2．8nm)的聚丙烯酰胺／氧化石墨纳米复合结构同时存在。     

Effect of graphene oxide nanosheets on the physico-mechanical properties of chitosan/bacterial cellulose nanofibrous composites

In this work, novel chitosan/bacterial cellulose (CS/BC) nanofibrous composites reinforced with graphene oxide (GO) nanosheets are introduced. As cell attachment and permeability of nanofibrous membranes highly depend on their fiber diameter, the working window for successful electrospinning to attain sound nanofibrous composites with a minimum fiber diameter was determined by using the response surface methodology. It is shown that the addition of GO nanosheets to CS/BC significantly reduces the average size of the polymeric fibers. Their mechanical properties are also influenced and can be tailored by the concentration of GO. Fourier transform infrared spectroscopy reveals hydrogen bonding between the GO nanosheets and the polymer matrix. A decrease in the hydrophilicity of the electrospun nanofibers and their water vapor permeability with the addition of GO are also reported. The prepared nanofibrous composites are potentially suitable candidates for biomedical applications such as skin tissue engineering and wound dressing.     

Influence of Surface-functionalized Graphene Oxide on the Cell Morphology of Poly(methyl methacrylate) Composite

The surface chemistry of filler is closely related to the structure and morphology of nanocomposite foams.Changing the property of filler is widely used to control the cell structures and functionalize the composite foams.Surface-functionalized graphene oxide(GO-ODA) was prepared by grafting octadecylamine(ODA) on the surface of graphene oxide(GO) to make the filler disperse better in the nanocomposites and have a strong interfacial interaction with polymer matrix.Poly(methyl methacrylate)(PMMA)/GO-ODA nanocomposite foams were obtained by solution blending and foamed using supercritical carbon dioxide(scCO_2).Compared to neat PMMA and PMMA/GO samples,the PMMA/GO-ODA nanocomposite foams showed improved cell structures with smaller size,higher cell density and more homogeneous distribution,which should be attributed to the heterogeneous nucleation caused by well-dispersed GO-ODA nanosheets.This work not only improved the compatibility and interfacial interaction of GO with polymer matrix but also indicated that the modified GO sheets can act as ideal filler to control the cell density,size and size distribution efficiently.     

Viscosities of l-Histidine/l-Glutamic Acid/l-Tryptophan/Glycylglycine?+?2 M Aqueous KCl/KNO3 Solutions at T?=?(298.15 to 323.15)?K

Viscosity values of l-histidine/l-glutamic acid/l-tryptophan/glycylglycine + 2 M aqueous KCl/KNO₃ solutions have been determined experimentally as a function of molal concentration of amino acid/peptide at different temperatures: (298.15, 303.15, 308.15, 313.15, 318.15, and 323.15) K. Using the viscosity values of the solvent and solution, the relative viscosity, specific viscosity, and viscosity B-coefficient values have been computed. The trends of the variation of experimental and computed parameters with the solute concentration and temperature have been interpreted in terms of zwitterions–ions, zwitterions–water dipoles, ions–water dipoles, and ions–ions interactions operative in the systems.     

Fabrication and characterization of nano composite scaffold of poly(l-lactic acid)/hydroxyapatite

To mimic the nano-fibrous structure of the natural extracellular matrix, a nano composite scaffold of poly(l-lactic acid)/hydroxyapatite(PLLA/HAP) was fabricated by a thermally induced phase separation method. The characterization of the composite scaffold showed that the scaffold had a nano-fibrous PLLA network (fiber size 100–750 nm), an interconnective microporous structure (1–10 μm) and high porosity (>90%). HAP was homogeneously distributed in the scaffold, as a result, the compressive modulus of PLLA/HAP (80:20, w/w) increased to 3.15-fold compared with that of a pure PLLA scaffold. Incorporating HAP into PLLA network also buffered the pH decline in vitro degradation and enhanced the protein adsorption of the composite scaffold significantly. The new nano composite scaffold is potentially a very promising scaffold for tissue engineering.     

In situ thermal preparation of polyimide nanocomposite films containing functionalized graphene sheets

Graphene oxides (GO) were exfoliated in N,N-dimethylformamide by simple sonication treatment of the as-prepared high quality graphite oxides. By high-speed mixing of the pristine poly(amic acid) (PAA) solution with graphene oxide suspension, PAA solutions containing uniformly dispersed GO can be obtained. Polyimide (PI) nanocomposite films with different loadings of functionalized graphene sheets (FGS) can be prepared by in situ partial reduction and imidization of the as-prepared GO/PAA composites. Transmission electron microscopy observations showed that the FGS were well exfoliated and uniformly dispersed in the PI matrix. It is interesting to find that the FGS were highly aligned along the surface direction for the nanocomposite film with 2 wt % FGS. Tensile tests indicated that the mechanical properties of polyimide were significantly enhanced by the incorporation of FGS, due to the fine dispersion of high specific surface area of functionalized graphene nanosheets and the good adhesion and interlocking between the FGS and the matrix.     

Transparent polyimide/graphene oxide nanocomposite with improved moisture barrier property

Colorless and organo-soluble polyimide (PI) films have been synthesized from an alicyclic dianhydride BCDA and aromatic diamine 3,4′-ODA in the cosolvent of DMAc and GBL via one-step process. The graphene oxide (GO) was mixed with the above PI in DMAc solution to fabricate the PI/GO nanocomposite films. With the addition of only 0.001 wt% of GO in PI matrix, the resultant nanocomposite (PI/GO-0.001) exhibits not only the enhanced resistance to moisture but also retains superior visible light transmission, enhanced mechanical strength, and excellent dimensional stability, simultaneously. The water-vapor-transmission-rate (WVTR) significantly reduced to 30 g mil m⁻² day⁻¹ for this nanocomposite compared to 181 g mil m⁻² day⁻¹ for pure PI. Notably, the PI/GO-0.001 nanocomposite also exhibits low coefficient of thermal expansion (CTE) of 41 ppm °C⁻¹, which is benefited from the homogeneous distribution of ultrathin GO nanosheets in PI matrix.     

Reinforcing graphene oxide/cement composite with NH<Subscript>2</Subscript> functionalizing group

In this study, pure and NH₂-functionalized graphene oxide (GO) nanosheets have been added to the cement mortar with different weight percents (0.05, 0.10, 0.15, 0.20 and 0.25 wt%). In addition, the effects of functionalizing GO on the microstructure and mechanical properties (flexural/compressive strengths) of cement composite have been investigated for the first time. Scanning electron microscopy (SEM) images showed that GO filled the pores and well dispersed in concrete matrix, whereas exceeding GO additive from 0.10 wt% caused the formation of agglomerates and microcracks. In addition, mercury intrusion porosimetry confirmed the significant effects of GO and functionalizing groups on filling the pores. NH₂-functionalizing helped to improve the cohesion between GO nanosheets and cement composite. Compressive strengths increased from 39 MPa for the sample without GO to 54.23 MPa for the cement composites containing 0.10 wt% of NH₂-functionalized GO. Moreover, the flexural strength increased to 23.4 and 38.4% by compositing the cement paste with 0.10 wt% of pure and NH₂-functionalized GO, compared to the sample without GO, respectively. It was shown that functionalizing considerably enhanced the mechanical properties of GO/cement composite due to the interfacial strength between calcium silicate hydrates (C-S-H) gel and functionalized GO nanosheets as observed in SEM images. The morphological results were in good agreement with the trend obtained in mechanical properties of GO/cement composites.     

Interfacial stress transfer and property mismatch in discontinuous nanofiber/nanotube composite materials

Novel nanotubes/nanofibers with high strength and stiffness did not lead to high failure strengths/strains of nanocomposite materials. Therefore, the interfacial stress transfer and possible stress singularities, arising at the interfacial ends of discontinuous nanofibers embedded in a matrix, subjected to tensile and shear loading, were investigated by finite element analysis. The effects of Young's moduli and volume fractions on interfacial stress distributions were studied. Round-ended nanofibers were proposed to remove the interfacial singular stresses, which were caused by high stiffness mismatch of the nanoscale reinforcement and the matrix. However, the normal stress induced in the nanofiber through interfacial stress transfer was still less than 2 times that in the matrix. This stress value is far below the high strength of the nanofiber. Therefore, the load transfer efficiency of discontinuous nanofibers or nanotube composites is very low. Hence, nanofibers or nanotubes in continuous forms, which also preclude the formation of singular interfacial stress zones, are recommended over discontinuous nanofibers to achieve high strengths in nanocomposite materials.     

In situ thermal reduction of graphene oxide for high electrical conductivity and low percolation threshold in polyamide 6 nanocomposites

Electrically conductive and thermally stable polyamide 6 (PA 6) nanocomposites were prepared through one-step in situ polymerization of ε-caprolactam monomer in the presence of electrically insulating and thermally unstable graphene oxide (GO) nanosheets. These nanocomposites show a low percolation threshold of ∼0.41 vol.% and high electrical conductivity of ∼0.028 S/m with only ∼1.64 vol.% of GO. Thermogravimetric analysis and X-ray photoelectron spectroscopy results of GO before and after thermal treatment at the polymerization temperature indicate that GO was reduced in situ during the polymerization process. X-ray diffraction patterns and scanning electron microscopy observation confirm the exfoliation of the reduced graphene oxide (RGO) in the PA 6 matrix. The low percolation threshold and high electrical conductivity are attributed to the large aspect ratio, high specific surface area and uniform dispersion of the RGO nanosheets in the matrix. In addition, although GO has a poor thermal stability, its PA 6 nanocomposite is thermally stable with a satisfactory thermal stability similar to those of neat PA 6 and PA 6/graphene nanocomposite. Such a one-step in situ polymerization and thermal reduction method shows significant potential for the mass production of electrically conductive polymer/RGO nanocomposites.     

Graphene oxide reinforced polyimide nanocomposites via in situ polymerization

Graphene oxide (GO) reinforced polyimide nanocomposites were synthesized by in situ polymerization of monomers in the presence of GO sheets dispersed in N,N-Dimethylacetamide (DMAc). The functional groups (e.g., hydroxyl, epoxide, and carboxyl groups) associated with the GO make GO excellent dispersion in the organic solvent, which benefits the subsequent in situ polymerization. This process enabled uniform dispersion of GO sheets in the polymer matrix. The resultant GO-polyimide nanocomposite films were studied by tensile test, TGA and SEM. The results showed that the GO sheets incorporated in the polymer matrix exhibited a layer-aligned structure without destruction of the thermal stability of the polymer matrix, and a loading of GO (10 wt%) resulted in a significant enhancement in elastic modulus (86.4%).     

Morphology, mechanical and thermal properties of graphene-reinforced poly(butylene succinate) nanocomposites

Graphene nanosheets (GNSs) reinforced poly(butylene succinate) (PBS) nanocomposites are facilely obtained by a solution-based processing method. Graphene nanosheets, which are derived from chemically reduced graphite oxide (GO), are characterized by AFM, TEM, XRD and Raman spectra. The state of dispersion of the GNSs in the PBS matrix is examined by SEM observations that reveals homogeneous distribution of GNSs in PBS matrix. A 21% increase in tensile strength and a 24% improvement of storage modulus are achieved by addition of 2.0 wt% of GNS. The electrical conductivity and thermal stability of the graphene-based nanocomposite are also improved. DSC measurement indicates that the presence of graphene sheets does not have a remarkable impact on the crystallinity of the nanocomposites. Therefore, the high performances of the nanocomposites are mainly attributed to the uniform dispersion of GNSs in the polymer matrix and strong interfacial interactions between both components.     

Improved dispersion of attapulgite nanorods in polymer with graphene oxide nanosheets

To improve the dispersion stability of rod-like attapulgite (ATT) in polymers, a small amount of graphene oxide (GO) nanosheets were employed as a supporter to fix ATT before introducing into polymer. The ATT nanorods were found attached tightly and dispersed uniformly on the GO nanosheets from TEM images of GO-ATT hybrids. The dispersion stability of ATT in water was also improved after being attached on GO nanosheets due to the abundant hydrophilic groups of GO, which was paramount for introducing them into polymers through water blending method. Poly(vinyl alcohol) (PVA) was then chosen to be reinforced by these GO-supported ATT via water blending method. Compared to the heavy aggregation of neat ATT in PVA, a homogeneous distribution of ATT nanorods in the matrix was achieved by introducing them in the form of GO-ATT, indicating a favorable assisted dispersion effect of GO nanosheets for ATT. Furthermore, PVA/GO-ATT nanocomposites containing only 2 wt% GO-ATT exhibited a significantly increase of 41.4 and 83.6 % in tensile strength and storage modulus, respectively.     

PLGA/Ag nanocomposites: in vitro degradation study and silver ion release

New nanocomposite films based on a biodegradable poly (DL-Lactide-co-Glycolide) copolymer (PLGA) and different concentration of silver nanoparticles (Ag) were developed by solvent casting. In vitro degradation studies of PLGA/Ag nanocomposites were conducted under physiological conditions, over a 5 week period, and compared to the behaviour of the neat polymer. Furthermore the silver ions (Ag⁺) release upon degradation was monitored to obtain information on the properties of the nanocomposites during the incubation. The obtained results suggest that the PLGA film morphology can be modified introducing a small percentage of silver nanoparticles that do not affect the degradation mechanism of PLGA polymer in the nanocomposite. However results clearly evinced the stabilizing effect of the Ag nanoparticles in the PLGA polymer and the mineralization process induced by the combined effect of silver and nanocomposite surface topography. The Ag⁺ release can be controlled by the polymer degradation processes, evidencing a prolonged antibacterial effect.     

Solution casting versus melt compounding: effect of fabrication route on the structure and thermal behavior of poly(l-lactic acid) clay nanocomposites

Poly(l-lactic acid) (PLLA) nanocomposites containing various loadings of organo-modified montmorillonite were prepared via twin screw extrusion and solution casting in order to investigate the effect of processing route on the structure and the thermal properties of the fabricated nanohybrid materials. X-ray diffraction (XRD) testing indicated that a better dispersion of the modified inorganic filler can be achieved by solution intercalation. The interlayer distance of the mineral, and thus the type and structure of the nanohybrid formed, was found to be affected by the polymer content only in the case of the nanocomposites produced by the solution casting method. Thermogravimetric analysis (TGA) revealed that the hybrids prepared by melt compounding displayed increased thermal stability. Differential scanning calorimetry (DSC) showed that the fabrication route influences the crystallization process of the polymer.     

Simple photoreduction of graphene oxide nanosheet under mild conditions

Graphene oxide (GO) nanosheets were reduced by UV irradiation in H2 or N2 under mild conditions (at room temperature) without a photocatalyst. Photoreduction proceeded even in an aqueous suspension of nanosheets. The GO nanosheets reduced by this method were analyzed by X-ray photoelectron spectroscopy and Raman spectroscopy. It was found that epoxy groups attached to the interiors of aromatic domains of the GO nanosheet were destroyed during UV irradiation to form relatively large sp2 islands resulting in a high conductivity. I-V curves were measured by conductive atomic force microscopy (AFM; perpendicular to a single nanosheet) and a two-electrode system (parallel to the nanosheet). They revealed that photoreduced GO nanosheets have high conductivities, whereas nonreduced GO nanosheets are nearly insulating. Ag+ adsorbed on GO nanosheets promoted the photoreduction. This photoreduction method was very useful for photopatterning a conducting section of micrometer size on insulating GO. The developed photoreduction process based on a photoreaction will extend the applications of GO to many fields because it can be performed in mild conditions without a photocatalyst.     

Nylon-6/Graphene composites modified through polymeric modification of graphene

The covalent functionalization of graphene oxide (GO) with poly(vinyl alcohol) (PVA) via ester linkages (GO-es-PVA) as well as the characterization of modified graphene based Nylon-6 (PA6) composite prepared by solution mixing techniques was examined. The anchoring of PVA chains on GO sheets was confirmed by XPS and FTIR measurements. The resulting functionalized sample became soluble in formic acid, allowing solution-phase processing for preparation of PA6/GO composites. Answering to the efficient polymer-chain grafting, a homogeneously dispersion of GO sheets in PA6 matrix and a dramatic improvement of interface adhesion between nanosheets and matrix were observed in PA6/GO-es-PVA composites by SEM and TEM. The depressed crystallization of PA6 chains in PA6/GO-es-PVA composites was investigated by their DSC and XRD results.     

Fabrication of mineralized electrospun PLGA and PLGA/gelatin nanofibers and their potential in bone tissue engineering

Surface mineralization is an effective method to produce calcium phosphate apatite coating on the surface of bone tissue scaffold which could create an osteophilic environment similar to the natural extracellular matrix for bone cells. In this study, we prepared mineralized poly(d,l-lactide-co-glycolide) (PLGA) and PLGA/gelatin electrospun nanofibers via depositing calcium phosphate apatite coating on the surface of these nanofibers to fabricate bone tissue engineering scaffolds by concentrated simulated body fluid method, supersaturated calcification solution method and alternate soaking method. The apatite products were characterized by the scanning electron microscopy (SEM), Fourier transform-infrared spectroscopy (FT-IR), and X-ray diffractometry (XRD) methods. A large amount of calcium phosphate apatite composed of dicalcium phosphate dihydrate (DCPD), hydroxyapatite (HA) and octacalcium phosphate (OCP) was deposited on the surface of resulting nanofibers in short times via three mineralizing methods. A larger amount of calcium phosphate was deposited on the surface of PLGA/gelatin nanofibers rather than PLGA nanofibers because gelatin acted as nucleation center for the formation of calcium phosphate. The cell culture experiments revealed that the difference of morphology and components of calcium phosphate apatite did not show much influence on the cell adhesion, proliferation and activity.