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PubMed2003

Novel bioactive materials with different mechanical properties.

Some ceramics, such as Bioglass, sintered hydroxyapatite, and glass-ceramic A-W, spontaneously bond to living bone. They are called bioactive materials and are already clinically used as important bone substitutes. However, compared with human cortical bone, they have lower fracture toughness and higher elastic moduli. Therefore, it is desirable to develop bioactive materials with improved mechanical properties. All the bioactive materials mentioned above form a bone-like apatite layer on their surfaces in the living body, and bond to bone through this apatite layer. The formation of bone-like apatite on artificial material is induced by functional groups, such as Si-OH, Ti-OH, Zr-OH, Nb-OH, Ta-OH, -COOH, and PO(4)H(2). These groups have specific structures revealing negatively charge, and induce apatite formation via formations of an amorphous calcium compound, e.g., calcium silicate, calcium titanate, and amorphous calcium phosphate. These fundamental findings provide methods for preparing new bioactive materials with different mechanical properties. Tough bioactive materials can be prepared by the chemical treatment of metals and ceramics that have high fracture toughness, e.g., by the NaOH and heat treatments of titanium metal, titanium alloys, and tantalum metal, and by H(3)PO(4) treatment of tetragonal zirconia. Soft bioactive materials can be synthesized by the sol-gel process, in which the bioactive silica or titania is polymerized with a flexible polymer, such as polydimethylsiloxane or polytetramethyloxide, at the molecular level to form an inorganic-organic nano-hybrid. The biomimetic process has been used to deposit nano-sized bone-like apatite on fine polymer fibers, which were textured into a three-dimensional knit framework. This strategy is expected to ultimately lead to bioactive composites that have a bone-like structure and, hence, bone-like mechanical properties.

Animals↗

PubMed2003

Interfacial molecular recognition between polysaccharides and calcium carbonate during crystallization.

Based on the basic principles of biomineralization, using beta-cyclodextrin, hepatin and soluble starch as organic matrices, employing the biomimetic method, the crystallization of CaCO(3) was studied by Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction analysis (XRD), scanning electronic microscopy (SEM), thermal gravity-differential thermal analysis and conductivity analysis. The results show that polysaccharides have an effect on the crystallization of CaCO(3). CaCO(3) crystals also have an effect on polysaccharides. The possible mechanism of this interaction is discussed.

Biomimetics↗

PubMed2003

Voltammetric sensor for vanillylmandelic acid based on molecularly imprinted polymer-modified electrodes.

Despite the increasing number of applications of molecularly imprinted polymers (MIPs) in analytical chemistry, the construction of a biomimetic voltammetric sensor remains still challenging. This work investigates the development of a voltammetric sensor for vanillylmandelic acid (VMA) based on acrylic MIP-modified electrodes. Thin layers of MIPs for VMA have been prepared by spin coating the surface of a glassy carbon electrode with the monomers mixture (template, methacrylic acid, a cross-linking agent and solvent), followed by in situ photopolymerisation. After extraction of the template molecule, the peak current recorded with the imprinted sensor after rebinding was linear with VMA concentration in the range 19-350 microg ml(-1), whereas the response of the control electrode is independent of incubation concentration, and was about one-tenth of the value recorded with the imprinted sensor at the maximum concentration tested. Under the conditions used, the sensor is able to differentiate between VMA and other closely structural-related compounds, such as 3-methoxy-4-hydroxyphenylethylene glycol (not detected), or 3,4- and 2,5-dihydroxyphenilacetic acids, which are adsorbed on the bare electrode surface but not at the polymer layer. Homovanillic acid was detected with the imprinted sensors after incubation, indicating that the presence of both methoxy and carboxylic groups in the same position as in VMA is necessary for effective binding in the imprinted sites. Nevertheless, both species can be differentiated by the oxidation potential. It can be concluded that MIP-based voltammetric electrodes are very promising analytical tool for the development of highly selective analytical sensors.

Biomimetic Materials↗

PubMed2006

Modeling polychlorinated biphenyl mass transfer after amendment of contaminated sediment with activated carbon.

The sorption kinetics and concentration of polychlorinated biphenyls (PCBs) in historically polluted sediment is modeled to assess a remediation strategy based on in situ PCB sequestration by mixing with activated carbon (AC). We extend our evaluation of a model based on intraparticle diffusion by including a biomimetic semipermeable membrane device (SPMD) and a first-order degradation rate for the aqueous phase. The model predictions are compared with the previously reported experimental PCB concentrations in the bulk water phase and in SPMDs. The simulated scenarios comprise a marine and a freshwater sediment, four PCB congeners, two AC grain sizes, four doses of AC, and comparison with laboratory experiments for up to 540 days of AC amendment slowly mixed with sediment. The model qualitatively reproduces the observed shifts in the PCB distribution during repartitioning after AC amendment but systematically overestimates the overall effect of the treatment in reducing aqueous and SPMD concentrations of PCBs by a factor of 2-6. For our AC application in sediment, competitive sorption of the various solutes apparently requires a reduction by a factor of 16 of the literature values for the AC-water partitioning coefficient measured in pure aqueous systems. With this correction, model results and measurements agree within a factor of 3. We also discuss the impact of the nonlinearity of the AC sorption isotherm and first-order degradation in the aqueous phase. Regular mixing of the sediment accelerates the benefit of the proposed amendment substantially. But according to our scenario, after AC amendment is homogeneously mixed into the sediment and then left undisturbed, aqueous PCB concentrations tend toward the same reduction after approximately 5 or more years.

Absorption↗

PubMed2003

Formation of porphyrins in the presence of acid-labile metalloporphyrins: a new route to mixed-metal multiporphyrin arrays.

The ability to incorporate distinct metalloporphyrins at designated sites in multiporphyrin arrays is essential for diverse applications in materials and biomimetic chemistry. The synthesis of such mixed-metal arrays via acid catalyzed reactions has largely been restricted to metalloporphyrins of stability class II (e.g., Cu, Co, Ni) or I. We describe routes for the rational synthesis of mixed-metal arrays via acid-catalyzed condensations that are compatible with metalloporphyrins of stability class III (e.g., Zn) and IV (e.g., Mg). The routes are demonstrated for p-phenylene-linked arrays. The key finding is that several mild Lewis acids [InCl(3), Sc(OTf)(3), Yb(OTf)(3), and Dy(OTf)(3)], which are known to catalyze the dipyrromethane + dipyrromethane-dicarbinol condensation in CH(2)Cl(2) at room temperature without acidolysis, do not demetalate zinc or magnesium porphyrins under the same conditions. Rational routes to porphyrin dyads and triads employ reaction of a (porphyrin)-dipyrromethane and a (porphyrin)-dipyrromethane-dicarbinol. The porphyrin-forming reactions (six examples) proceed in yields of 18-28%. The metalation states of the arrays prepared in this manner include Zn-free base (ZnFb), MgFb, ZnFbMg, ZnFbZn, and ZnFbFb. Studies of the catalysis process indicate that the dipyrromethane + dipyrromethane-dicarbinol condensation is catalyzed by both the Lewis acid and a Brønsted acid derived in situ from the Lewis acid. Taken together, the ability to employ otherwise "acid-labile" metalloporphyrins as precursors in condensation procedures should broaden the scope of accessible mixed-metal multiporphyrin arrays and motivate further studies of the application of mild Lewis acid catalysts in porphyrin chemistry.

Biomimetic Materials↗

PubMed2005

Aromatic interactions in unusual backbone nitrogen-coordinated zinc peptide complexes: a crystallographic and spectroscopic study.

A series of zinc complexes with dipeptide ligands of the type Dpg-Xaa was synthesized, where Dpg is dipicolylglycine and Xaa is phenylalanine (Phe), tyrosine (Tyr), tryptophan (Trp), 2-naphthylalanine (Nal), or glycine (Gly). It was shown that aromatic interactions promote the unusual coordination of an anionic peptide backbone nitrogen atom to zinc. This binding mode was, for the first time, characterized by X-ray structure analyses of the electrically neutral complexes [(Dpg-Phe)(-H)Zn], [(Dpg-Tyr)(-H)Zn], [(Dpg-Trp)(-H)Zn], and [(Dpg-Nal)(-H)Zn]. The pKa values for amide nitrogen deprotonation were determined by 1H NMR titrations {[(Dpg-Phe)Zn], 7.17; [(Dpg-Tyr)Zn], 6.85; [(Dpg-Trp)Zn], 6.85; [(Dpg-Nal)Zn], 6.64; [(Dpg-Gly)Zn], 8.54}. It was calculated that aromatic interactions contribute ca. -8 to -11 kJ/mol of stabilizing free enthalpy changes in the derivatives with aromatic amino acid side chains. These are the first quantitative data obtained for crystallographically characterized metal complexes. A comparison with the literature shows that it is difficult to distinguish between pi-cation attraction and pi-pi stacking. However, it is evident that modification of small peptides with synthetic pyridine ligands enhances their ability to stabilize secondary structures by noncovalent interactions. This is an important consideration for the design of biomimetic metallopeptides.

Amino Acids, Aromatic↗

PubMed2002

Mimicking biological electron transport in sol-gel glass: photoinduced electron transfer from zinc cytochrome C to plastocyanin or cytochrome C mediated by mobile inorganic complexes.

Biomimetic studies of electron-transport chains are important for establishing the molecular mechanisms of long-range communications between proteins. We mimic these biological assemblies by encapsulating metalloproteins in sol-gel silica glass and letting mobile inorganic complexes shuttle electrons between the immobilized proteins. We present two examples of such rudimentary electron-transport chains. In both of them the immobilized electron donor is the zinc-substituted cytochrome c, Zncyt; the immobilized electron acceptor is either cupriplastocyanin, pc(II), or ferricytochrome c, cyt(III); and the mobile charge carrier Q/Q(-) is the redox couple FeEDTA(-)(/2)(-) or Ru(NH(3))(6)(3+/2+). The redox processes are photoinduced: Zncyt is excited by the laser pulse and converted to the triplet state, (3)Zncyt, which is a strong reducing agent. Visible absorption, circular dichroism, and electron paramagnetic resonance spectra of the metalloproteins show that encapsulation in sol-gel glass does not affect their intrinsic redox properties. The rigid silica glass spatially separates the proteins from each other. In this matrix, the electron-transfer reactions between (3)Zncyt and pc(II) and between (3)Zncyt and cyt(III), which occur fast in solution, are completely suppressed in the absence of a charge carrier Q/Q(-). The reactivity of FeEDTA(-) and Ru(NH(3))(6)(3+) (as quenchers Q of (3)Zncyt) is minimally affected by the interior of the sol-gel glass. In the glass, the second-order rate constants for the excited-state electron transfer, from (3)Zncyt to Q, are (8.9 +/- 0.6) x 10(6) and (8.0 +/- 2.4) x 10(6) M(-)(1) s(-)(1) for FeEDTA(-) and Ru(NH(3))(6)(3+), respectively. This reaction is followed by the ground-state back electron transfer, from Q(-) to Zncyt(+). In the "monoprotein" glasses Zncyt/Q, the respective second-order rate constants for this back electron-transfer reaction are (4.9 +/- 0.2) x 10(7) and (7.8 +/- 2.7) x 10(7) M(-)(1) s(-)(1). In the "diprotein" glasses Zncyt/Q/pc(II) and Zncyt/Q/cyt(III), containing also the acceptor protein pc(II) or cyt(III), Zncyt(+) decays on two time scales. The faster and major component of this decay is analogous to the only mode of the decay in the Zncyt/Q glasses and is a second-order process. Between 25 and 40% of the initially formed Zncyt(+), however, lives longer (k(slow) =1.1 +/- 0.2 s(-)(1)) and decays by a first-order process. We attribute the lengthening of the Zncyt(+) lifetime to a partial escape of the photogenerated Q(-) into the glass pores, where it reacts with the immobilized pc(II) or cyt(III). Indeed, the visible absorption spectra show the photoinduced reduction of pc(II) and cyt(III). Evidently, the small inorganic complexes, FeEDTA(-)(/2)(-) and Ru(NH(3))(6)(3+/2+), move through the glass pores, react with the encapsulated metalloproteins, and establish the interprotein electron transfer. Each interprotein reaction now occurs in two steps: a mobile charge carrier Q receives an electron from (3)Zncyt, and Q(-) then delivers an electron to pc(II) or cyt(III). Ultimately, the energy of visible light is converted to reducing equivalents for plastocyanin and cytochrome c. The sequential electron transfer described here resembles the events in a rudimentary electron-transport chain. Our findings demonstrate the promise of integrating proteins, with their optimally adjusted redox sites, in photocatalytic materials.

Biomimetic Materials↗

PubMed2003

Mussel adhesive protein mimetic polymers for the preparation of nonfouling surfaces.

A new biomimetic strategy for modification of biomaterial surfaces with poly(ethylene glycol) (PEG) was developed. The strategy exploits the adhesive characteristics of 3,4-dihydroxyphenylalanine (DOPA), an important component of mussel adhesive proteins, to anchor PEG onto surfaces, rendering the surfaces resistant to cell attachment. Linear monomethoxy-terminated PEGs were conjugated either to a single DOPA residue (mPEG-DOPA) or to the N-terminus of Ala-Lys-Pro-Ser-Tyr-Hyp-Hyp-Thr-DOPA-Lys (mPEG-MAPD), a decapeptide analogue of a protein found in Mytilus edulis adhesive plaques. Gold and titanium surfaces were modified by adsorption of mPEG-DOPA and mPEG-MAPD from solution, after which surface analysis by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy confirmed the presence of immobilized PEG on the surface. The ability of modified surfaces to resist cell attachment was examined by culturing 3T3 fibroblasts on the surfaces for up to 14 days. Quantitative image analysis revealed that cell adhesion to mPEG-DOPA and mPEG-MAPD modified surfaces decreased by as much as 98% compared to control surfaces. Modified Ti surfaces exhibited low cell adhesion for up to 2 weeks in culture, indicating that the nonfouling properties of mPEG-DOPA and mPEG-MAPD treated surfaces persist for extended periods of time. This strategy paradoxically exploits the strong fouling characteristics of MAP analogues for antifouling purposes and may be broadly applied to medical implants and diagnostics, as well as numerous nonmedical applications in which the minimization of surface fouling is desired.

3T3 Cells↗

PubMed2004

Biofunctionalized, ultrathin coatings of cross-linked star-shaped poly(ethylene oxide) allow reversible folding of immobilized proteins.

Dense, ultrathin networks of isocyanate terminated star-shaped poly(ethylene oxide) (PEO) molecules, cross-linked at their chain ends via urea groups, were shown to be extremely resistant to unspecific adsorption of proteins while at the same time suitable for easy biocompatible modification. Application by spin coating offers a simple procedure for the preparation of minimally interacting surfaces that are functionalized by suitable linker groups to immobilize proteins in their native conformations. These coatings form a versatile basis for biofunctional and biomimetic surfaces. We have demonstrated their advantageous properties by using single-molecule fluorescence microscopy to study immobilized proteins under destabilizing conditions. Biotinylated ribonuclease H (RNase H) was labeled with a fluorescence resonance energy transfer (FRET) pair of fluorescent dyes and attached to the surface by a biotin-streptavidin linkage. FRET analysis demonstrated completely reversible denaturation/renaturation behavior upon exposure of the surface-immobilized proteins to 6 M guanidinium chloride (GdmCl) followed by washing in buffer. A comparison with bovine serum albumin (BSA) coated surfaces and linear PEO brush surfaces yielded superior performance in terms of chemical stability, inertness and noninteracting nature of the star-polymer derived films.

Biomimetic Materials↗

PubMed2005

Ferrioxamine B analogues: targeting the FoxA uptake system in the pathogenic Yersinia enterocolitica.

A series of ferrioxamine B analogues that target the bacterium Yersinia enterocolitica were prepared. These iron carriers are composed of three hydroxamate-containing monomeric units. Two identical monomers consist of N-hydroxy-3-aminopropionic acid coupled with beta-alanine, and a third unit at the amino terminal is composed of N-hydroxy-3-aminopropionic acid and one of the following amino acids: beta-alanine (1a), phenylalanine (1b), cyclohexylalanine (1c), or glycine (1d). Thermodynamic results for representatives of the analogues have shown a strong destabilization (3-4 orders of magnitude) of the ferric complexes with respect to ferrioxamine B, probably due to shorter spacers and a more strained structure around the metal center. No significant effect of the variations at the N-terminal has been observed on the stability of the ferric complexes. By contrast, using in vivo radioactive uptake experiments, we have found that these modifications have a substantial effect on the mechanism of iron(III) uptake in the pathogenic bacteria Yersinia enterocolitica. Analogues 1a and 1d were utilized by the ferrioxamine B uptake system (FoxA), while 1b and 1c either used different uptake systems or were transported to the microbial cell nonspecifically by diffusion via the cell membrane. Transport via the FoxA system was also confirmed by uptake experiments with the FoxA deficient strain of Yersinia enterocolitica. A fluorescent marker, attached to 1a in a way that did not interfere with its biological activity, provided additional means to monitor the uptake mechanism by fluorescence techniques. Of particular interest is the observation that 1a was utilized by the uptake system of ferrioxamine B in Yersinia enterocolitica (FoxA) but failed to use the ferrioxamine uptake route in Pseudomonas putida. Here, we present a case in which biomimetic siderophore analogues deliberately designed for a particular bacterium can distinguish between related uptake systems of different microorganisms.

Bacterial Outer Membrane Proteins↗

PubMed2003

Incorporation of unprotected heterocyclic side chains into peptoid oligomers via solid-phase submonomer synthesis.

Peptoids (N-substituted glycines) are an important class of biomimetic oligomers that have made a significant impact in the areas of combinatorial drug discovery, gene therapy, drug delivery, and biopolymer folding in recent years. Sequence-specific peptoid oligomers are easily assembled from primary amines by the solid-phase submonomer method. However, most amines that contain heterocyclic nitrogens in the side chain do not incorporate efficiently. We present here a straightforward revision of the submonomer method that allows efficient incorporation of unprotected imidazoles, pyridines, pyrazines, indoles, and quinolines into oligomers as long as 15 monomers in length. This improved method uses chloroacetic acid instead of bromoacetic acid in the acylation step of the monomer addition cycle, and allows for the incorporation of new side chains that should enable the synthesis of peptoids with entirely new properties.

Acylation↗

PubMed2004

Fine control of the release and encapsulation of Fe ions in dendrimers through ferritin-like redox switching.

Numerous dendrimers incorporating metal ions or clusters have received much attention as catalytic and drug delivery materials. We expanded the variety of metal ions that complex with DPA through a radial stepwise complexation to create novel organic-inorganic hybrid materials. As one of the most common and significant iron ions, Fe3+ was used. It was confirmed that iron ions, FeCl3, are coordinated to the imine groups of a spherical phenylazomethine dendrimer (DPA) in a stepwise radial fashion, which should make it possible to control the number and location of the Fe3+ ions incorporated into the dendrimers. Iron possesses very interesting properties such as magnetism, redox chemistry, and catalysis and is also one of the essential elements of our body. Here, we show the first successful attempt to control the biomimetic switching of iron ions' release/encapsulation in the dendrimer driven by their redox response of the Fe2+/Fe3+ couple, which might find uses as a drug delivery system.

Azo Compounds↗

PubMed2005

Understanding the template preorganization step of an artificial arginine receptor.

A biomimetic complex which mimics the arginine-phosphonate diester interaction of the arginine fork is investigated with respect to structure and energetics of stable configurations. Within this work, we provide knowledge on local minima of the isolated system obtained from first-principles calculations. Non-negligible solvation effects are studied in a microsolvation approach. The interactions which govern the structural patterns of molecular recognition in this tweezer-guest complex can be significantly modulated by the action of hydrogen bond accepting and donating solvent molecules, such as dimethyl sulfoxide or water, which were present in experimental investigations on this system. Different tweezer-guest structures are evaluated with respect to their temperature-dependent thermodynamical properties as products of the first association reaction step of the bisphosphonate tweezer template and the guanidinium moiety.

Arginine↗

PubMed2005

Enzymatic lithography of phospholipid bilayer films by stereoselective hydrolysis.

The stereoselective phospholipase A2-catalyzed hydrolysis of patterned phospholipid bilayers consisting of the l- and d-isomers of alpha-dilauroylphosphatidylcholine (DLPC) and alpha-dipalmitoylphosphatidylcholine (DPPC) is reported. The stereochemically directed enzyme lithography demonstrated herein allows the parallel modification of large surface areas and constitutes a potentially useful method to structure biomimetic films, given the stereospecific action of many enzymes.

1,2-Dipalmitoylphosphatidylcholine↗

PubMed2006

Computational design of heterochiral peptides against a helical target.

Polypeptides incorporating D-amino acids occasionally occur in nature and are an important class of pharmaceutical molecules. With the use of heterochiral Monte Carlo (HCMC), a method inspired by the de novo design of proteins, we develop peptide scaffolds for interacting with a molecular target, a left-handed alpha-helix. The HCMC approach concurrently seeks to optimize a peptide sequence, its internal conformation, and its docked conformation with a target surface. Several major classes of interactions are observed: (1) homochiral interactions between two alphaL helices, (2) heterochiral interactions between an alphaL and an alphaR helix, and (3) heterochiral interactions between the alphaL target and novel nonhelical structures. We explore the application of HCMC to simulating the preferential enantioselectivity of heterochiral complexes. Implications for biomimetic design in molecular recognition are discussed.

Alanine↗

PubMed2005

The cucurbit[n]uril family: prime components for self-sorting systems.

We determined the values of Ka for a wide range of host-guest complexes of cucurbit[n]uril (CB[n]), where n = 6-8, using 1H NMR competition experiments referenced to absolute binding constants measured by UV/vis titration. We find that the larger homologues--CB[7] and CB[8]--individually maintain the size, shape, and functional group selectivity that typifies the recognition behavior of CB[6]. The cavity of CB[7] is found to effectively host trimethylsilyl groups. Remarkably, the values of Ka for the interaction of CB[7] with adamantane derivatives 22-24 exceeds 10(12) M(-1)! The high levels of selectivity observed for each CB[n] individually is also observed for the CB[n] family collectively. That is, the selectivities of CB[6], CB[7], and CB[8] toward a common guest can be remarkably large. For example, guests 1, 3, and 11 prefer CB[8] relative to CB[7] by factors greater than 10(7), 10(6), and 3000, respectively. Conversely, guests 23 and 24 prefer CB[7] relative to CB[8] by factors greater than 5100 and 990, respectively. The high levels of selectivity observed individually and collectively for the CB[n] family renders them prime components for the preparation of functional biomimetic self-sorting systems.

Biomimetic Materials↗

PubMed2006

Monoliths of aligned silica-polypeptide hexagonal platelets.

Water soluble alpha-helical polypeptides were used to prepare silica coated hexagonal single crystal platelets in concentrated solutions. To our knowledge, there is no other instance where polymer single crystals, typically formed under high dilution, can be grown in a bulk material. This unprecedented self-assembly process relies on complex cooperative interactions where silica condensation mediates the growth of polypeptide crystals, which in turn template silica overgrowth. The helices were also used to align samples giving monoliths composed of highly oriented layers of platelets. Overall, this procedure allows preparation of composites with good structural order and complexity via a simple biomimetic process.

Biomimetic Materials↗

PubMed2006

Interfacing carbon nanotubes with living cells.

We developed a polymer coating for carbon nanotubes (CNTs) that mimics the mucin glycoprotein coating of mammalian cells. CNTs coated with these mucin mimic polymers have two novel properties: they can bind to carbohydrate receptors, providing a means for biomimetic interactions with cell surfaces, and, importantly, they are rendered nontoxic to cells.

Animals↗