Tannic acid (TA)-based multilayer assemblies have attracted increasing interest for biomedical applications. Here we explore properties of TA-poly(N-vinylpyrrolidone) (TA-PVPON) hydrogen-bonded multilayers for drug encapsulation and long-term storage. We demonstrate that the small molecular weight anticancer drug, doxorubicin (DOX), can be successfully loaded into (TA-PVPON) capsules with high encapsulation efficiency. We have also found that the encapsulated DOX can be efficiently stored inside the capsules for the pH range from pH = 7.4 to pH = 5. We show that the chemical and functional stability of TA at neutral and basic pH values is achieved through complexation with PVPON. The UV-vis spectrophotometry and in situ ellipsometry analyses of the hydrogen bonding interactions between TA and PVPON at different pH values reveal pH-dependent behavior of TA-PVPON capsules for the pH range from pH = 7.4 to pH = 5. Increasing deposition pH value from pH = 5 to pH = 7.4 leads to a 2-fold decrease in capsule thickness. However, this trend is reversed when salt concentration of the deposition solutions is increased from 0.01 M to 0.1 M NaCl. We have also demonstrated that the permeability of (TA-PVPON) capsules prepared using low salt deposition conditions and pH = 7.4 can be increased 2-fold by exposure of the capsules to 0.1 M NaCl salt solutions at the same pH. Our work opens new perspectives for design of novel polymer carriers for controlled drug delivery in cancer therapy.

Antarctic calcified macroorganisms are particularly vulnerable to ocean acidification because many are weakly calcified, the dissolution rates of calcium carbonate are inversely related to temperature, and high latitude seas are predicted to become undersaturated in aragonite by the year 2100. We examined the post-mortem dissolution rates of aragonitic and calcitic shells from four species of Antarctic benthic marine invertebrates (two bivalves, one limpet, one brachiopod) and the thallus of a limpet shell-encrusting coralline alga exposed to acidified pH (7.4) or non-acidified pH (8.2) seawater at a constant temperature of 48C. Within a period of only 14-35 days, shells of all four species held in pH 7.4 seawater had suffered significant dissolution. Despite calcite being 35% less soluble in seawater than aragonite, there was surprisingly, no consistent pattern of calcitic shells having slower dissolution rates than aragonitic shells. Outer surfaces of shells held in pH 7.4 seawater exhibited deterioration by day 35, and by day 56 there was exposure of aragonitic or calcitic prisms within the shell architecture of three of the macroinvertebrate species. Dissolution of coralline algae was confirmed by differences in weight loss in limpet shells with and without coralline algae. By day 56, thalli of the coralline alga held in pH 7.4 displayed a loss of definition of the conceptacle pores and cracking was evident at the zone of interface with limpet shells. Experimental studies are needed to evaluate whether there are adequate compensatory mechanisms in these and other calcified Antarctic benthic macroorganisms to cope with anticipated ocean acidification. In their absence, these organisms, and the communities they comprise, are likely to be among the first to experience the cascading impacts of ocean acidification.

Electrospun tubular scaffolds (4 mm inner diameter) based on bio-artificial blends of polyglyconate (Maxon) and proteins such as gelatin and elastin having a spatially designed multilayer structure were prepared for use as vascular tissue scaffolds. Scanning electron microscopy analysis of scaffolds showed a random nanofibrous morphology with fiber diameter in the range of 200-400 nm for protein-blended Maxon, which mimics the nanoscale dimensions of collagen (50-500 nm). The scaffolds have a well interconnected pore structure and porosity up to 82%, with protein blending and multi-layering in contrast to electrospun Maxon scaffolds (67%). Fourier-transform infrared spectroscopy, x-ray diffraction and differential scanning calorimetry results confirmed the blended composition and crystallinity of fibers. Uniaxial tensile testing revealed a strength of 14.46 +/- 0.42 MPa and a modulus of 15.44 +/- 2.53 MPa with a failure strain of 322.5 +/- 10% for a pure Maxon scaffold. The blending of polyglyconate with biopolymers decreased the tensile properties in general, with an exception of the tensile modulus (48.38 +/- 2 MPa) of gelatin/Maxon mesh, which was higher than that of the pure Maxon scaffold. Trilayered tubular scaffolds of gelatin/elastin, gelatin/elastin/Maxon and gelatin/Maxon (GE-GEM-GM) that mimic the complex trilayer matrix structure of natural artery have been prepared by sequential electrospinning. Tensile testing under dry conditions revealed a tensile strength of 2.71 +/- 0.2 MPa and a modulus of 20.4 +/- 3 MPa with a failure strain of 140 +/- 10%. However, GE-GEM-GM scaffolds tested under wet conditions after soaking in a phosphate buffered saline medium at 37 degrees C for 24 h exhibited mechanical properties (2.5 MPa tensile strength and 9 MPa tensile modulus) comparable to those of native femoral artery.

We compare electrical and mechanical properties of C70 fullerene with high purity graphite to 48 GPa at room temperature using designer diamond anvils with embedded electrical microprobes. The electrical resistance of C70 shows a minimum at 20 GPa with transformation to an amorphous insulating phase complete above 35 GPa, while graphite remains conducting. Nanoindentation shows hardness values 220 times larger for the pressure quenched amorphous phase than for similarly treated graphite. Our studies establish that the amorphous carbon phase produced from C70 has unique properties not attainable from graphite.

Diamond anvils with diamond encapsulated thin-film microcircuits have been fabricated for ultrahigh pressure electrical conductivity experiments. The diamond films were homoepitaxially deposited onto the diamond anvil substrates with microwave plasma chemical vapor deposition using a 2% methane in hydrogen gas mixture and a diamond substrate temperature of 1300 °C. The diamond embedded thin-film microprobes remain functional to megabar pressures. We have applied this technology to the study of the pressure-induced metallization of KI under pressures up to 1.8 Mbar. This technology has the potential of greatly advancing the pressure range of a number of existing high-pressure diagnostic techniques, and for expanding the capabilities of diamond anvil cells into new directions.

Recent progress in the synthesis, characterization, and biological compatibility of nanostructured ceramics for biomedical implants is reviewed. A major goal is to develop ceramic coating technology that can reduce the friction and wear in mating total joint replacement components, thus contributing to their significantly improved function and longer life span. Particular attention is focused on the enhancement of mechanical properties such as hardness, toughness, and friction coefficient and on the bioactivity as they pertain to the nanostructure of the material. The development of three nanostructured implant coatings is discussed: diamond, hydroxyapatite, and functionally graded metalloceramics based on the Cr-Ti-N ternary system. Nanostructured diamond produced by chemical vapor deposition (CVD) techniques and composed of nano-size diamond grains have particular promise because of the combination of ultrahigh hardness, improved toughness over conventional microcrystalline diamond, low friction, and good adhesion to titanium alloys. Nanostructured processing applied to hydroxyapatite coatings is used to achieve the desired mechanical characteristics and enhanced surface reactivity and has been found to increase osteoblast adhesion, proliferation, and mineralization. Finally, nanostructured metalloceramic coatings provide continuous variation from a nanocrystalline metallic bond at the interface to the hard ceramic bond on the surface and have the ability to overcome adhesion problems associated with ceramic hard coatings on metallic substrates.

A nanofibrous triphasic scaffold was electrospun from a mixture of polycaprolactone (PCL), type-I collagen and hydroxyapatite nanoparticles (nano-HA) with a mixture dry weight ratio of 50/30/20, respectively. Scaffolds were characterized by evaluating fiber morphology and chemical composition, dispersion of HA particles and nanoindentation. Scanning electron microscopy revealed fibers with an average diameter of 180 +/- 50 nm, which coincides well with the collagen fiber bundle diameter characteristic of the native extracellular matrix of bone. The triphasic fibers, stained with calcein and imaged with confocal microscopy, show a uniform dispersion of apatite particles throughout their length with minor agglomeration. Scaffold fibers of triphasic (50/30/20), collagen/nano-HA (80/20), PCL/nano-HA (80/20), pure PCL and pure collagen were each pressure consolidated into non-porous pellets for evaluation by transmission electron microscopy and nanoindentation. While the majority of apatite particles are uniformly dispersed having an average size of 30 nm, agglomerated particles as large as a few microns are sparsely distributed. Nanoindentation of the pressure-consolidated scaffolds showed a range of Young's modulus (0.50-3.9 GPa), with increasing average modulus in the order of (PCL < PCL/nano-HA < collagen < triphasic < collagen/nano-HA). The modulus data emphasize the importance of collagen and its interaction with other components in affecting mechanical properties of osteoconductive scaffolds.

Nanostructured diamond coatings improve the smoothness and wear characteristics of the metallic component of total hip replacements and increase the longevity of these implants, but the effect of nanodiamond wear debris on macrophages needs to be determined to estimate the long-term inflammatory effects of wear debris. The objective was to investigate the effect of the size of synthetic nanodiamond particles on macrophage proliferation (BrdU incorporation), apoptosis (Annexin-V flow cytometry), metabolic activity (WST-1 assay) and inflammatory cytokine production (qPCR). RAW 264.7 macrophages were exposed to varying sizes (6, 60, 100, 250 and 500 nm) and concentrations (0, 10, 50, 100 and 200 μg ml−1) of synthetic nanodiamonds. We observed that cell proliferation but not metabolic activity was decreased with nanoparticle sizes of 6–100 nm at lower concentrations (50 μg ml−1), and both cell proliferation and metabolic activity were significantly reduced with nanodiamond concentrations of 200 μg ml−1. Flow cytometry indicated a significant reduction in cell viability due to necrosis irrespective of particle size. Nanodiamond exposure significantly reduced gene expression of tumor necrosis factor-α, interleukin-1β, chemokine Ccl2 and platelet-derived growth factor compared to serum-only controls or titanium oxide (anatase 8 nm) nanoparticles, with variable effects on chemokine Cxcl2 and vascular endothelial growth factor. In general, our study demonstrates a size and concentration dependence of macrophage responses in vitro to nanodiamond particles as possible wear debris from diamond-coated orthopedic joint implants.