The Mechanical Role of Metal Ions in Biogenic Protein‐Based Materials

Protein‐metal interactions—traditionally regarded for roles in metabolic processes—are now known to enhance the performance of certain biogenic materials, influencing properties such as hardness, toughness, adhesion, and self‐healing. Design principles elucidated through thorough study of such materials are yielding vital insights for the design of biomimetic metallopolymers with industrial and biomedical applications. Recent advances in the understanding of the biological structure–function relationships are highlighted here with a specific focus on materials such as arthropod biting parts, mussel byssal threads, and sandcastle worm cement.     

Templating nanostructures by mesoporous materials with an emphasis on room temperature and cryogenic TEM studies

Rapid strides realized in the field of ordered mesoporous silica (OMS) with a well-defined pore shape and nanometric sizes, provide new gateways for the preparation of nanostructured materials having controlled shape and size with a very narrow distribution. The focus of the current review is on the synthesis of nanostructures templated by OMS either in bulk or in thin film form. The importance of electron microscopy as an indispensable technique in the structural characterization of OMS templated nanostructures, including cryo-TEM, electron tomography and HR-SEM, is highlighted in this review.     

Synthesis, structure, and reactivity of rhodium and iridium complexes of the chelating bis-sulfoxide tBuSOC2H4SOtBu. Selective O-H activation of 2-hydroxy-isopropyl-pyridine

The chloro-bridged rhodium and iridium complexes [M2(BTSE)2Cl2] (M = Rh 1, Ir 2) bearing the chelating bis-sulfoxide tBuSOC2H4SOtBu (BTSE) were prepared by the reaction of [M2(COE)4Cl2] (M = Rh, Ir; COE = cyclooctene) with an excess of a racemic mixture of the ligand. The cationic compounds [M(BTSE)2][PF6] (M = Rh 3, Ir 4), bearing one S- and one O-bonded sulfoxide, were also obtained in good yields. The chloro-bridges in 2 can be cleaved with 2-methyl-6-pyridinemethanol and 2-aminomethyl pyridine, resulting in the iridium(I) complexes [Ir(BTSE)(Py)(Cl)] (Py = 2-methyl-6-pyridinemethanol 5, 2-aminomethyl-pyridine 6). In case of the bulky 2-hydroxy- isopropyl-pyridine, selective OH oxidative addition took place, forming the Ir(III)-hydride [Ir(BTSE)(2-isopropoxy-pyridine)(H)(Cl)] 7, with no competition from the six properly oriented C-H bonds. The cationic rhodium(I) and iridium(I) compounds [M(BTSE)(2-aminomethyl-pyridine)][X] (M = Rh 8, Ir 10), [Rh(BTSE)(2-hydroxy- isopropyl-pyridine)][X] 9(stabilized by intramolecular hydrogen bonding), [Ir(BTSE)(pyridine)2][PF6] 12, [Ir(BTSE)(alpha-picoline)2][PF6] 13, and [Rh(BTSE)(1,10-phenanthroline)][PF6] 14 were prepared either by chloride abstraction from the dimeric precursors or by replacement of the labile oxygen bonded sulfoxide in 3 or 4. Complex 14 exhibits a dimeric structure in the solid state by pi-pi stacking of the phenanthroline ligands.     

Effect of pore size on adsorption of a polyelectrolyte to porous glass

The adsorption of quaternized poly(vinylpyridine) (QPVP) on controlled pore glass (CPG) size, over the ionic strength range 0.001-0.5 M was found to display nonmonotonic behavior as a function of pore size. Both adsorption kinetics and ionic strength effects deviated dramatically from behavior typical of adsorption on flat surfaces when the ratio of the pore radius Rp to the polymer hydrodynamic radius Rh became smaller than ca. 2. Ionic strength enhancement of adsorption for small pore sizes was observed at much higher salt concentrations than is typical for polycation adsorption on flat surfaces. The amount of polymer adsorbed per unit surface area of glass GammaA, in 0.5 M NaCl, exhibited a shallow maximum at Rp/Rh approximately 5. Since the value of GammaA for small pore size CPG is strongly depressed by the large surface area, an alternative and more interesting observation is that the amount of polymer adsorbed per gram of CPG, Gammaw, displays a strong maximum when Rp is equal to or slightly smaller than Rh. The efficiency with which QPVP binds anionic micelles to (negatively charged) CPG (grams of surfactant/grams of QPVP) increases strongly with diminishing pore size, indicating that the configuration of polycation bound to small pores favors micelle binding. Since the micelles are larger than small pores, the results indicate that when Rp < Rh, adsorbed polycation molecules reside only partially within the pore. The results of this study are supported by simulations of polyelectrolytes within cylindrical cavities.     

Growth of Au/Ag nanowires in thin surfactant solution films: an electron microscopy study

The surfactant templated gold-silver nanowire growth process in a thin solution film was probed by cryo-transmission electron microscopy (cryo-TEM). The increasing surfactant concentration upon film drying appears to induce phase transformations in the film and form a liquid crystalline template for the nanowires growth. High-resolution transmission electron microscopy (HRTEM) and electron holography revealed that the nanowires were polycrystalline with some preferred crystallite orientations and had a roughly cylindrical cross-section. Further improvement of the technique may lead to highly ordered metal nanowire arrays within the surfactant matrix similar to the closely related mesoporous materials.     

Assessment of PHB with varying hydroxyvalerate content for potential packaging applications

Poly-(hydroxybutyrate) (PHB) is biodegradable aliphatic polyester that is produced by a wide range of microorganisms. Basic PHB has relatively high glass transition and melting temperatures. To improve flexibility for potential packaging applications, PHB is synthesized with various co-polymers such as poly-(3-hydroxyvalerate) (HV) leading to a decrease of the glass transitions and melting temperatures. In addition, the HV broadens the processing window since there is improved melt stability at lower processing temperatures. In this study, PHB synthesized with different valerate contents (5%, 12%, and 20%) and varying in molecular weights were characterized. All PHBV materials displayed a glass transition between −10 and 20 °C. The two melting transitions found for Aldrich 5%, 12%, and Tianan 20%, resulted from crystals formed during cooling of the samples. The complex viscosity decreased with increasing temperature due to a decrease in molecular weights of the samples. These results suggest that processing the co-polymer below 160 °C would be beneficial with low screw speed. The mechanical results indicate all PHBV materials had high elastic modulus and flexural strength with low tensile strength and elongation at break. The WVTR results indicated the polymer to be very hydrophilic, resulting in higher water transmission rates.     

Extent and mechanism of metal ion incorporation into precipitated ferrites

The ability of many noniron metals to be incorporated into the structure of ferrites is being utilized in numerous industrial and environmental applications. The incorporation of some of these metals during Fe(II) oxidation-induced precipitation at moderate temperatures (80-100°C) appears to be limited, for reasons not fully understood, and to extents not always agreed (e.g., Ni(2+), Cr(3+)). In this paper, the incorporation maxima of six metals into the structure of precipitated ferrites (in terms of x in Me(x)Fe(3-)(x)O(4), Me represents a noniron metal) were concluded to be 1.0, 1.0, 0.78, 0.49, 0.35, and 0.0 for Zn(2+), Co(2+), Ni(2+), Al(3+), Cd(2+) and Cr(3+), respectively. With the exception of the much larger Cd(2+), these values were associated with kinetic considerations controlled by the H(2)O exchange rate between the hydration shells surrounding the dissolved metal ion.     

Low-pressure hydrogenation of carbon dioxide catalyzed by an iron pincer complex exhibiting noble metal activity

A highly active iron catalyst for the hydrogenation of carbon dioxide and bicarbonates works under remarkably low pressures and achieves activities similar to some of the best noble metal catalysts. A mechanism is proposed involving the direct attack of an iron trans-dihydride on carbon dioxide, followed by ligand exchange and dihydrogen coordination.     

The "funny" current (I(f)) inhibition by ivabradine at membrane potentials encompassing spontaneous depolarization in pacemaker cells

Recent clinical trials have shown that ivabradine (IVA), a drug that inhibits the funny current (I(f)) in isolated sinoatrial nodal cells (SANC), decreases heart rate and reduces morbidity and mortality in patients with cardiovascular diseases. While IVA inhibits I(f), this effect has been reported at essentially unphysiological voltages, i.e., those more negative than the spontaneous diastolic depolarization (DD) between action potentials (APs). We tested the relative potency of IVA to block I(f) over a wide range of membrane potentials, including those that encompass DD governing to the SANC spontaneous firing rate. A clinically relevant IVA concentration of 3 μM to single, isolated rabbit SANC slowed the spontaneous AP firing rate by 15%. During voltage clamp the maximal I(f) was 18 ± 3 pA/pF (at -120 mV) and the maximal I(f) reduction by IVA was 60 ± 8% observed at -92 ± 4 mV. At the maximal diastolic depolarization (~-60 mV) I(f) amplitude was only -2.9 ± 0.4 pA/pF, and was reduced by only 41 ± 6% by IVA. Thus, I(f) amplitude and its inhibition by IVA at physiologically relevant membrane potentials are substantially less than that at unphysiological (hyperpolarized) membrane potentials. This novel finding more accurately describes how IVA affects SANC function and is of direct relevance to numerical modeling of SANC automaticity.