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Jonathan J Wilker

Publications and source records attributed to Jonathan J Wilker.

14 recordsLinked to original sources
PubMed2006

EPR investigation and spectral simulations of iron-catecholate complexes and iron-peptide models of marine adhesive cross-links.

Electron paramagnetic resonance (EPR) spectra are presented for iron complexes of catecholate, tironate, and a 3,4-dihydroxyphenylalanine (DOPA)-containing peptide of sequence Ac-Ala-DOPA-Thr-Pro-CONH2 ("AdopaTP"). This peptide was prepared to model potential metal-protein cross-links in the adhesive used by marine mussels, Mytilus edulis, for affixing themselves to surfaces. Spectra are shown for iron bound to each ligand in mono, bis, and tris coordination environments. For example, the catecholate complexes {Fe(cat)}, {Fe(cat)2}, and [Fe(cat)3]3- are provided. Detailed simulations are presented to describe the origin of spectra for the iron-catecholate and iron-peptide species, which show that the spectral features can be accounted for only with the inclusion of D- and E-strain. The spectroscopy of each compound is shown under both anaerobic and aerobic conditions. When exposed to air, the high-spin Fe3+ signal of [Fe(AdopaTP)3]3- decreases and an organic radical is formed. No other sample exhibited an appreciable radical signal. These data are discussed in light of the biomaterial synthesis carried out by marine mussels.

Adhesiveness↗
PubMed2006

Structural effects of crosslinking a biopolymer hydrogel derived from marine mussel adhesive protein.

In an effort to explore new biocompatible substrates for biomedical technologies, we present a structural study on a crosslinked gelatinous protein extracted from marine mussels. Prior studies have shown the importance of iron in protein crosslinking and mussel adhesive formation. Here, the structure and properties of an extracted material were examined both before and after crosslinking with iron. The structures of these protein hydrogels were studied by SEM, SANS, and SAXS. Viscoelasticity was tested by rheological means. The starting gel was found to have a heterogeneous porous structure on a micrometer scale and, surprisingly, a regular structure on the micron to nanometer scale. However disorder, or "no periodic structure", was deduced from scattering on nanometer length scales at very high q. Crosslinking with iron condensed the structure on a micrometer level. On nanometer length scales at high q, small angle neutron scattering showed no significant differences between the samples, possibly due to strong heterogeneity. X-ray scattering also confirmed the absence of any defined periodic structure. Partial crosslinking transformed the viscoelastic starting gel into one with more rigid and elastic properties.

Animals↗
PubMed2006

Alkylation of inorganic oxo compounds and insights on preventing DNA damage.

Metabolism of food- and tobacco-borne procarcinogens results in the exposure of DNA to toxic alkylating agents. These assaults can bring about DNA alkylation damage, mutations, and cancer. Dietary inorganic compounds such as selenium and vanadium are known to prevent cancer, possibly by reacting directly with alkylating agents, thereby preventing DNA damage. To understand potential interactions between oxo species and alkylating toxins, we reacted a series of alkylating agents with varied classes of oxo compounds (i.e., vanadates, selenate, phosphate, sulfate, acetate, nitrate, and nitrite). A new organic-soluble selenate, [(C6H5)4P]3(O3SeOCH2OSeO3)(HSeO4), was synthesized and characterized for these studies. Vanadates were found to convert ethylating agents into ethanol, whereas other anions formed esters upon alkylation. General trends show that oxo anions of the greatest charge density were the most reactive. These studies suggest that the design of new compounds for cancer prevention should incorporate reactive oxo groups with high anionic charge density.

Acetates↗
PubMed2005

Absorption spectroscopy and binding constants for first-row transition metal complexes of a DOPA-containing peptide.

A diverse array of biological systems incorporate 3,4-dihydroxyphenlyalanine (DOPA) into proteins and small molecules for cross-linking and material generation. Marine worm eggshells, sea squirt wound plugs, and marine mussel adhesives may all be formed by combining DOPA-containing molecules with high levels of metals. In order to provide model systems for characterizing these biomaterials, we carried out a study on metal binding to a DOPA-containing peptide. Ultraviolet-visible absorption spectra are presented for the AdopaTP peptide binding to Fe3+, V3+, VO2+, Mn3+, Ti4+, Cu2+, Co2+, and Ni2+ in mono, bis, and where applicable, tris coordination modes. Association constants were determined for selected metal ions binding to the peptide. In general, the spectroscopic and binding properties of this DOPA-containing peptide were found to be similar to those of catechol.

Animals↗
PubMed2004

Inhibition of DNA alkylation damage with inorganic salts.

Human exposure to alkylating agents metabolized from tobacco- and food-borne carcinogens occurs regularly. Dietary inorganic compounds such as selenium and vanadium have been shown previously to provide chemoprotective benefits in rat and human trials. Here, we present biochemical data on the ability of inorganic compounds to protect DNA from alkylation damage. An enzyme cleavage assay is used to observe alkylated DNA. Simple salts (e.g., NaCl or NiCl(2)) did not prevent DNA alkylation, whereas anionic oxo species (e.g., Na(2)SeO(4) or Na(3)VO(4)) did inhibit alkylation. We propose that these oxo species behave as nucleophilic targets for the electrophilic alkylating agents, thereby preventing DNA damage.

Alkylation↗
PubMed2004

Rapid chromatography for evaluating adsorption characteristics of cellulase binding domain mimetics.

The cost of cellulolytic enzymes is one barrier to the economic production of fermentable sugars from lignocellulosic biomass for the production of fuels and chemicals. One functional characteristic of cellulolytic enzymes that improves reaction kinetics over mineral acids is a cellulose binding domain that concentrates the catalytic domain to the substrate surface. We have identified maleic acid as an attractive catalytic domain with pK(a) and dicarboxylic acid structure properties that hydrolyze cellulose while producing minimal degradation of the glucose formed. In this study we report results of a rapid chromatographic method to assess the binding characteristics of potential cellulose binding domains for the construction of a synthetic cellulase over a wide range of temperatures (20 degrees to 120 degrees C). Aromatic, planar chemical structures appear to be key indicators of cellulose adsorption. Indole, the side-chain of the amino acid tryptophan, has been shown to reversibly adsorb to cellulose at temperatures between 30 degrees and 120 degrees C. Trypan blue, a polyaromatic, planar molecule, was shown to be irreversibly adsorbed to cotton cellulose at temperatures of <120 degrees C on the time scale of the experiments. These results confirm the importance of hydrophobic cellulose and the cellulose-binding component of cellulolytic enzymes and cellulolytic enzyme mimetics.

Biomimetics↗
PubMed2004

Cross-linking the protein precursor of marine mussel adhesives: bulk measurements and reagents for curing.

Marine mussels affix themselves to surfaces by use of a highly cross-linked, protein-based adhesive. Metal levels (e.g., Fe, Zn, Cu, Mn) of the cured glue are significantly concentrated relative to surrounding waters. Specific details on the reagents used by mussels to induce protein cross-linking are not known at this time. To provide insight on the cross-linking agents and reactions taking place while curing mussel glues, we performed a study in which various compounds were tested for the ability to bring about protein curing. A precursor to adhesion, with proteins containing the unusual amino acid 3,4-dihydroxyphenylalanine, was extracted from mussel feet. Potential cross-linking agents were mixed with this gelatinous pellet. The compressibility and shear properties of the resulting material were investigated by use of a penetration test. The reagents examined included simple metal ions (e.g., Na+, Zn2+), oxidizing transition metals (e.g., Fe3+, Cr2O7(2-)), nonmetallic oxidants (e.g., H2O2,IO4-), and oxidizing enzymes (e.g., tyrosinase). We found that protein curing was brought about by simple oxidants and transition metal ions. The results show that optimal curing occurs when the reagent is an oxidizing metal ion (e.g., MnO4-, Fe3+). We conclude that marine mussels are likely to employ Mn3+ and Fe3+ for protein cross-linking and adhesive synthesis.

Adhesiveness↗
PubMed2004

Visible absorption spectra of metal-catecholate and metal-tironate complexes.

Interactions between metals and catechol (1,2-dihydroxybenzene) or other ortho-dihydroxy moieties are being found in an increasing number of biological systems with functions ranging from metal ion internalization to biomaterial synthesis. Although metal-catecholate interactions have been studied in the past, we present the first systematic study of an array of these compounds, all prepared under identical conditions. We report the ultraviolet-visible absorption (UV-vis) spectra for catecholate and tironate complexes of the first row transition elements. Generation and identification of these species were accomplished by preparing aqueous solutions with varied ligand:metal ratios and subsequently titrating with base (NaOH). Controlled ligand deprotonation and metal binding resulted in sequential formation of complexes with one, two, and sometimes three catecholate or tironate ligands bound to a metal ion. We prepared the mono-, bis- and tris-catecholates and -tironates of Fe(3+), V(3+), V(4+)and Mn(3+), the mono- and bis-catecholates and -tironates of Cu(2+), Co(2+), Ni(2+), Zn(2+), Cr(2+) and Mn(2+), and several Ti(4+) and Cr(3+) species. The UV-vis spectra of each complex are described, some of which have not been reported previously. These data can now be applied to characterization of biological metal-catecholate systems.

Catechols↗
PubMed2003

Adhesive strength of marine mussel extracts on porcine skin.

The adhesive characteristics of marine mussel adhesive extracts were examined. Adhesive protein extracted from mussels (Mytilus edulis) was used to bond porcine skin in an end-to-end joint cured in controlled environments, without the use of chemical cross-linking reagents. The two curing conditions were similar to common surgical environments-"dry" (25 degrees C and 40% relative humidity) and "humid" (37 degrees C and 80% relative humidity). The first condition is similar to that of an external incision while the second is similar to conditions for internal incisions that are not exposed to significant flow of body fluids. Results were compared with performance of the commercial adhesive fibrin. Cyanoacrylate was also examined to validate the testing procedure. The tissue joint strength was approximately 1MPa for mussel extract joints cured for 24h under "humid" conditions. Under both conditions, joints bonded with mussel extract showed adhesive strengths similar to those bonded with fibrin, for cure times between 12 and 24h. For shorter cure times (<12h) the mussel adhesive bond was weaker than the fibrin bond under both conditions. The presence of moisture seemed to have a significant effect on the performance of both adhesives, especially mussel extracts. These results indicate that tissue joints formed using mussel extract adhesives have comparable strengths to those formed using fibrin (P=0.38), albeit with a slower curing rate. Further investigation of curing agents for the mussel adhesive extract is warranted.

Adhesives↗
PubMed2002

The elusive vanadate (V(3)O(9))(3-): isolation, crystal structure, and nonaqueous solution behavior.

The isolation, crystal structure, and nonaqueous solution characteristics of the first trinuclear vanadate are presented. The crystal structure reveals a six-membered cyclic arrangement of alternating vanadium and oxygen atoms for the anion of [(C(4)H(9))(4)N](3)(V(3)O(9)). The (51)V NMR spectrum of this compound in CD(3)CN exhibits multiple peaks. The relative intensities of each resonance can be altered by concentration and temperature changes, the later of which are reversible. Addition of [(C(4)H(9))(4)N]Br and NaClO(4) also perturbs the equilibria between species observed. Conductivity data for [(C(4)H(9))(4)N](3)(V(3)O(9)) in CH(3)CN as a function of concentration display pronounced curvature and indicate formation of a neutral species in solution at the highest concentrations studied. Stoichiometric mixtures of [(C(4)H(9))(4)N](3)(V(3)O(9)) with the known vanadates [(C(4)H(9))(4)N](3)(HV(4)O(12)), [(C(4)H(9))(4)N](3)(V(5)O(14)), and [(C(4)H(9))(4)N](3)(H(3)V(10)O(28)) are prepared and examined by (51)V NMR. Equilibration between the various vanadates is observed and characterized. Resonances for these known vanadates, however, cannot be used to identify the peaks found for [(C(4)H(9))(4)N](3)(V(3)O(9)), alone, in solution. The existence of ion pairs in acetonitrile is the only interpretation for the solution behavior of [(C(4)H(9))(4)N](3)(V(3)O(9)) consistent with all data. As such, we can directly observe each possible ion pairing state by (51)V NMR: (V(3)O(9))(3-) at -555 ppm, [[(C(4)H(9))(4)N](V(3)O(9))] (2-) at -569 ppm, [[(C(4)H(9))(4)N](2)(V(3)O(9))](-) at -576 ppm, and [(C(4)H(9))(4)N](3)(V(3)O(9)) at -628 ppm. To the best of our knowledge, [(C(4)H(9))(4)N](3)(V(3)O(9)) presents the first case in which every possible ion paired state can be observed directly from a parent polyion. Isolation and characterization of this simple metal oxo moiety may now facilitate efforts to design functional polyoxometalates.

Journal Article↗