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At least 451 records · Page 25Linked to original sources
PubMed2005

A density functional study on a biomimetic non-heme iron catalyst: insights into alkane hydroxylation by a formally HO-FeV=O oxidant.

The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane.

Algorithms↗
PubMed2003

Biomimetic peptides that engage specific integrin-dependent signaling pathways and bind to calcium phosphate surfaces.

Many important matrix proteins involved in bone remodeling contain separate domains that orient the protein on hydroxyapatite and interact with target cell receptors, respectively. We have designed two synthetic peptides that mimic the dual activities of these large, complex proteins by binding to calcium phosphate minerals and by engaging integrin-dependent signaling pathways in osteoblasts. The addition of either PGRGDS from osteopontin or PDGEA from collagen type I to the HAP-binding domain of statherin (N15 domain) did not alter its alpha-helical structure or diminish its affinity for hydroxyapatite. Immobilized N15-PGRGDS bound MC3T3-E1 osteoblasts predominantly via the alpha v beta 3 integrin and induced focal adhesion kinase (FAK) phosphorylation at comparable levels to immobilized osteopontin. Immobilized N15-PDGEA bound MC3T3-E1 osteoblasts predominantly through the alpha 2 beta 1 integrin and induced similar levels of FAK phosphorylation. Although both peptides induced FAK phosphorylation with similar time courses, only the N15-PDGEA peptide induced ERK1/2 phosphorylation, showing that these peptides are also capable of engaging integrin-specific signaling pathways. This peptide system can be used to study adhesion-dependent control of signaling in the context of the relevant biomineral surface and may also be useful in biomaterial and tissue engineering applications.

Adsorption↗
PubMed2007

Three-dimensional growth behavior of osteoblasts on biomimetic hydroxylapatite scaffolds.

The authors used rapid prototyping to produce three-dimensional hydroxylapatite scaffolds with controlled, fully interconnected porosity. The purpose of this study was to illuminate the effect of hormones on the osteogenic differentiation and to investigate how osteoblasts colonize the three-dimensional scaffold focusing on the formation of the cellular network. Preosteoblasts were seeded onto scaffolds, were optionally treated with the osteogenic hormones triiodo-L-thyronine (T3) and 1,25-dihydroxyvitamin-D3 (D3), and the expression of osteoblastic marker genes was investigated. Confocal laser scanning microscopy was used to investigate the three-dimensional growth behavior. Culturing cells on scaffolds strongly increased the expression of osteocalcin, osteoprotegerin, Runx2, and receptor activator of NFkB-ligand (RANKL). Treatment with T3 increased the expression of osteocalcin but did not change that of osteoprotegerin and Runx2. Treatment with D3 inhibited the expression of osteocalcin, Runx2, and osteoprotegerin. Both hormones had similar effects in the three-dimensional system as found in two-dimensional cultures although more accentuated, indicating that preosteoblasts behave more naturally on three-dimensional structures. The osteoblasts colonized the three-dimensional squared pores of scaffolds by forming a cellular network with a round central channel keeping it into the depth and depositing collagen fibrils. These results provide insight how osteoblasts colonize a three-dimensional system and underline the importance of this environment in osteoblastic differentiation studies.

Animals↗
PubMed2007

Regulation of implant surface cell adhesion: characterization and quantification of S-phase primary osteoblast adhesions on biomimetic nanoscale substrates.

Integration of an orthopedic prosthesis for bone repair must be associated with osseointegration and implant fixation, an ideal that can be approached via topographical modification of the implant/bone interface. It is thought that osteoblasts use cellular extensions to gather spatial information of the topographical surroundings prior to adhesion formation and cellular flattening. Focal adhesions (FAs) are dynamic structures associated with the actin cytoskeleton that form adhesion plaques of clustered integrin receptors that function in coupling the cell cytoskeleton to the extracellular matrix (ECM). FAs contain structural and signalling molecules crucial to cell adhesion and survival. To investigate the effects of ordered nanotopographies on osteoblast adhesion formation, primary human osteoblasts (HOBs) were cultured on experimental substrates possessing a defined array of nanoscale pits. Nickel shims of controlled nanopit dimension and configuration were fabricated by electron beam lithography and transferred to polycarbonate (PC) discs via injection molding. Nanopits measuring 120 nm diameter and 100 nm in depth with 300 nm center-center spacing were fabricated in three unique geometric conformations: square, hexagonal, and near-square (300 nm spaced pits in square pattern, but with +/-50 nm disorder). Immunofluorescent labeling of vinculin allowed HOB adhesion complexes to be visualized and quantified by image software. Perhipheral adhesions as well as those within the perinuclear region were observed, and adhesion length and number were seen to vary on nanopit substrates relative to smooth PC. S-phase cells on experimental substrates were identified with bromodeoxyuridine (BrdU) immunofluorescent detection, allowing adhesion quantification to be conducted on a uniform flattened population of cells within the S-phase of the cell cycle. Findings of this study demonstrate the disruptive effects of ordered nanopits on adhesion formation and the role the conformation of nanofeatures plays in modulating these effects. Highly ordered arrays of nanopits resulted in decreased adhesion formation and a reduction in adhesion length, while introducing a degree of controlled disorder present in near-square arrays, was shown to increase focal adhesion formation and size. HOBs were also shown to be affected morphologicaly by the presence and conformation of nanopits. Ordered arrays affected cellular spreading, and induced an elongated cellular phenotype, indicative of increased motility, while near-square nanopit symmetries induced HOB spreading. It is postulated that nanopits affect osteoblast-substrate adhesion by directly or indirectly affecting adhesion complex formation, a phenomenon dependent on nanopit dimension and conformation.

Biomimetic Materials↗
PubMed2004

Biomimetic piezoelectric quartz sensor for caffeine based on a molecularly imprinted polymer.

A piezoelectric quartz sensor coated with molecularly imprinted polymer (MIP) for caffeine was developed. The MIP was prepared by co-polymerizing methacrylic acid (MAA) and ethylene glycol dimethacrylate (EDMA) in the presence of azobis(isobutyronitrile) as initiator, caffeine as template molecule, and chloroform as solvent. The MIP suspension in polyvinyl chloride/tetrahydrofuran (6:2:1 w/w/v) solution was spin coated onto the surface of the electrode of a 10 MHz AT-cut quartz crystal. The sensor exhibited a linear relationship between the frequency shift and caffeine concentration in the range of 1 x 10(-7) mg mL(-1 )up to 1 x 10(-3) mg mL(-1) [correlation coefficient ( r)=0.9935] in a stopped flow measurement mode. It has a sensitivity of about 24 Hz/ln(concentration, mg mL(-1)). A steady-state response was achieved in less than 10 min. The performance characteristic of the sensor shows a promising and inexpensive alternative method of detecting caffeine. Surface studies were carried out for the reagent phase of the sensor using SEM, AFM, and XPS analysis in order to elucidate the imprinting of the caffeine molecule. The SEM micrograph, AFM image, and XPS spectra confirmed the removal of caffeine by Soxhlet extraction in the imprinting process and the rebinding of caffeine to the MIP sensing layer during measurement.

Biomimetics↗
PubMed2005

Biomimetic measurement of allelochemical dynamics in the rhizosphere.

Polydimethylsiloxane (PDMS) materials were used to quantify levels of the photosynthesis inhibitor sorgoleone in the undisturbed rhizosphere of sorghum plants. The materials used included stir bars coated with PDMS (stir bar sorptive extraction), technical grade optical fiber coated with a thin film of PDMS (matrix-solid phase microextraction), and PDMS tubing. PDMS tubing retained the most sorgoleone. As analyzed by high performance liquid chromatography, amounts of sorgoleone retained on the PDMS materials increased with time. Other materials tested (polyurethane foam plugs, C18 and Tenax disks, and resin capsules) proved less suitable, as they were subject to sometimes extensive penetration by fine root hairs. These results demonstrate the potential for PDMS-based materials to monitor the release of allelochemicals in the undisturbed rhizosphere of allelopathic plants. Unlike extraction procedures that recover all available compounds present in the soil, PDMS functions in a manner more analogous to plant roots in sorbing compounds from soil solution or root exudates. Information on chemical dynamics in the rhizosphere is crucial for evaluating specific hypotheses of allelopathic effects, understanding allelopathic mechanisms, and assessing the importance of allelopathic processes in plant communities.

Benzoquinones↗
PubMed2005

Adhesion enhancement in a biomimetic fibrillar interface.

Two important putative functions of the fibrillar contact interfaces commonly found in lizards and insects are to provide contact compliance and enhanced adhesion. To explore the question of whether a fibrillar architecture inherently enhances adhesion, we constructed model structures consisting of thin sheets of poly(vinyl butyral) (PVB) bonded on one of their thin sides to glass plates. The PVB samples had two flat, unstructured regions interrupted by a central fibrillar region along the bonded interface. The effect of the fibrillar geometry on the performance of the adhesive bond was tested using a tensile pull-off test, in which failure occurred by interfacial crack propagation, starting at an end where a crack initiator was introduced. We observed that fibrils in all samples fail consistently at the same critical stress, which is consistent with a previous theoretical result we have determined for flaw insensitivity during fibrillar pull-off. In addition, we measured the energy release rate required to fail the interface in the fibrillar region to be about an order of magnitude greater than that in the non-fibrillar region. We present experimental evidence demonstrating that this increase results partly from dissipation of strain energy stored in the fibrils.

Adhesiveness↗
PubMed2026

Biomimetic mesoporous silica nanosphere ameliorate experimental autoimmune uveitis by delivering sCD83.

Autoimmune uveitis (AU) is an autoimmune disease that may lead to blindness, but there are currently no precise targeted therapies for its prevention and treatment. Dendritic cell (DC) is key cell involved in the pathogenesis of AU, and specific regulation of their state can help improve AU. In this work, mesoporous silica nanospheres were loaded with the immunomodulator soluble CD83 (sCD83) and subsequently camouflaged with dendritic cell (DC) membranes to fabricate the nanocarrier DCM@MSN/sCD83 for treating experimental autoimmune uveitis (EAU). Research results show that DCM@MSN/sCD83 effectively alleviated the symptoms of uveitis in EAU, reduced the proportion of CD4+CD25-T cell/CD4+CD25+T cell and the percentage of DC in the eyes and cervical lymph nodes. It also decreased the expression of STING in Müller cell. Furthermore, the efficacy of DCM@MSN/sCD83 was found to be primarily targeting DC, and promoted the expression of IL-10 and TGF-β1 in DC by activating the phosphorylated HIF/STAT3 pathway, to induce the production of CD4+CD25+ T. This effect is superior to nanomedicine loaded with dexamethasone. Moreover，DCM enabled the nanocarriers to efficiently cross the blood-eye barrier and reach cervical lymph nodes, thereby regulating peripheral immunity. This research indicate that cell membrane-modified nanoparticles targeting homologous cells can effectively improve treatment efficiency and duration, which is potential therapy strategy for uveitis.

Animals↗
PubMed2005

Spectroscopic and electrochemical characterization of interfacial biomimetic assemblies on electrochemically generated gold oxide surfaces.

We report on the formation of a gold oxide layer and the reaction of this oxide with an acid chloride to form a stable, relatively complete monolayer bound through an ester-like bond to the gold oxide surface. We have used cyclic voltammetry, FTIR and optical ellipsometry to characterize this novel monolayer structure. The exposed functional groups of this monolayer can participate in subsequent surface reactions, opening the door to the use of oxide-based surface attachment chemistry on metallic substrates. This chemistry will allow for the formation of films tailored to contain both hydrophobic and hydrophilic regions, stacked at predetermined distances from the substrate that may serve as biomembrane mimetic assemblies.

Adipates↗
PubMed2006

The effect of the ionophore valinomycin on biomimetic solid supported lipid DPPTE/EPC membranes.

Self assembled monolayers and bilayers are produced on a flat glass surface, bound by a thiolipid onto bare gold. 1,2-Dipalmitoyl-sn-Glycero-3-Phosphothioethanol (DPPTE) is used as the molecule binding to the electrode surface. The lipid lambda-alpha-Phosphatidyl-Choline-beta-Oleoyl-g-Palmitoyl (POPC) and the lipid mixture eggphosphatadiylcholine (EPC) are used as spacer lipids with the aim of achieving solid-supported artificial lipid membranes. With the aim of creating and investigating more natural systems, ion carrier proteins such as valinomycin are introduced into the DPPTE/EPC system. The direct influence on the membranes as well as the effects of different ionic solutions on the proteins is shown.

Biomimetic Materials↗
PubMed2006

Biomimetic implant coatings.

Biomaterials and tissue engineering technologies are becoming increasingly important in biomedical practice, particularly as the population ages. Cellular responses depend on topographical properties of the biomaterial at the nanometer scale. Structures on biomaterial surfaces are used as powerful tools to influence or even control interactions between implants and the biological system [; ]. The influence of nanometer sized surface structures on osteoblastlike cell interactions was tested with niobium oxide coatings on polished titanium slices (cp-Ti grade 2). The aim of the study was to investigate the influence of nanoscopic surface structures on osteoblast interactions in order to support collagen I production and cell adhesion. The coatings were done by means of the sol-gel process. The surface structure was adjusted by annealing of the metaloxide ceramic coatings due to temperature depended crystal growth. The applied annealing temperatures were 450, 550 and 700 degrees C for 1 h, corresponding to Ra-numbers of 7, 15 and 40 nm. The surfaces were characterized by means of AFM, DTA/TG, diffractometry and white light interferometry. The cell reactions were investigated concerning adhesion kinetics, migration, spreading, cell adhesion, and collagen I synthesis. The smooth surface (Ra=7 nm) resulted in the fastest cell anchorage and cell migration. The closest cell adhesion was reached with the surface structure of Ra=15 nm. The roughest surface (Ra=40 nm) impedes the cell migration as well as a proper spreading of the cells. The best results concerning cell adhesion and spreading was reached with an intermediate surface roughness of Ra=15 nm of the niobium oxide coating on cp-titanium slices.

3T3 Cells↗
PubMedDate not supplied

Biomimetic apatite formation on chemically treated titanium.

Titanium treated in NaOH can form hydroxycarbonated apatite (HCA) after exposition in simulated body fluid (SBF). Generally, titanium is covered with a passive oxide layer. In NaOH this passive film dissolves and an amorphous layer containing alkali ions is formed on the surface. When exposed to SBF, the alkali ions are released from the amorphous layer and hydronium ions enter into the surface layer, resulting in the formation of Ti-OH groups in the surface. The released Na(+) ions increase the degree of supersaturation of the soaking solution with respect to apatite by increasing pH, and Ti-OH groups induce apatite nucleation on the titanium surface. The acid etching of titanium in HCl under inert atmosphere was examined as a pretreatment to obtain a uniform initial titanium surface before alkali treatment. Acid etching in HCl leads to the formation of a micro-roughened surface, which remains after alkali treatment in NaOH. It was shown by SEM, gravimetric and solution analysis that the apatite nucleation was uniform and the thickness of precipitated HCA layer increased continuously with time. The treatment of titanium by acid etching in HCl and subsequently in NaOH is a suitable method for providing the metal implant with bone-bonding ability.

Apatites↗
PubMed2004

Electrospun P(LLA-CL) nanofiber: a biomimetic extracellular matrix for smooth muscle cell and endothelial cell proliferation.

Poly(L-lactide-co-epsilon-caprolactone) [P(LLA-CL)] with L-lactide to epsilon-caprolactone ratio of 75 to 25 has been electrospun into nanofibers. The relationship between electrospinning parameters and fiber diameter has been investigated. The fiber diameter decreased with decreasing polymer concentration and with increasing electrospinning voltage. The X-ray diffractometer and differential scanning colorimeter results suggested that the electrospun nanofibers developed highly oriented structure in CL-unit sequences during the electrospinning process. The biocompatibility of the nanofiber scaffold has been investigated by culturing cells on the nanofiber scaffold. Both smooth muscle cell and endothelial cell adhered and proliferated well on the P(LLA-CL) nanofiber scaffolds.

Biocompatible Materials↗