Comparative study of materials-binding peptide interactions with gold and silver surfaces and nanostructures : A thermodynamic basis for biological selectivity of inorganic materials

Controllable 3D assembly of multicomponent inorganic nanomaterials by precisely positioning two or more types of nanoparticles to modulate their interactions and achieve multifunctionality remains a major challenge. The diverse chemical and structural features of biomolecules can generate the compositionally specific organic/inorganic interactions needed to create such assemblies. Toward this aim, we studied the materials-specific binding of peptides selected based upon affinity for Ag (AgBP1 and AgBP2) and Au (AuBP1 and AuBP2) surfaces, combining experimental binding measurements, advanced molecular simulation, and nanomaterial synthesis. This reveals, for the first time, different modes of binding on the chemically similar Au and Ag surfaces. Molecular simulations showed flatter configurations on Au and a greater variety of 3D adsorbed conformations on Ag, reflecting primarily enthalpically driven binding on Au and entropically driven binding on Ag. This may arise from differences in the interfacial solvent structure. On Au, direct interaction of peptide residues with the metal surface is dominant, while on Ag, solvent-mediated interactions are more important. Experimentally, AgBP1 is found to be selective for Ag over Au, while the other sequences have strong and comparable affinities for both surfaces, despite differences in binding modes. Finally, we show for the first time the impact of these differences on peptide mediated synthesis of nanoparticles, leading to significant variation in particle morphology, size, and aggregation state. Because the degree of contact with the metal surface affects the peptide's ability to cap the nanoparticles and thereby control growth and aggregation, the peptides with the least direct contact (AgBP1 and AgBP2 on Ag) produced relatively polydispersed and aggregated nanoparticles. Overall, we show that thermodynamically different binding modes at metallic interfaces can enable selective binding on very similar inorganic surfaces and can provide control over nanoparticle nucleation and growth. This supports the promise of bionanocombinatoric approaches that rely upon materials recognition.

Synchronization by low-amplitude light-dark cycles of 24-hour pineal and plasma melatonin rhythms of hatchling European starlings (Sturnus vulgaris)

In young European starlings, as in other avian species, high-amplitude 24-hr rhythms in plasma and pineal melatonin are already present around the time of hatching. In chickens this rhythmicity results at least partly from the light sensitivity of the melatonin-producing and -secreting system. In contrast to the chicken, the starling is a hole-nesting bird, and it seemed questionable whether the low light intensities in the nest are sufficient to synchronize perinatal melatonin rhythms. We therefore exposed starling eggs to light cycles roughly simulating those measured in nest-boxes, i.e., an 11-hr phase of complete darkness and a 13-hr phase consisting of 15 min of dim light (10 lux) alternating with 30 min of darkness. For one group the photophase lasted from 0600 to 1900 hr; for the other group the photophase lasted from 1800 to 0700 hr. In approximately 10-hr-old hatchlings of both groups, plasma and pineal melatonin concentrations were high during the dark phase and low during the light phase. We conclude that perinatal low-amplitude light intensity changes of the kind experienced by hatching starlings in the field are sufficient for synchronizing the melatonin-producing and -secreting system in the pineal and possibly other organs.

Isotherm, kinetic, and thermodynamic equations for cefalexin removal from liquids using activated carbon synthesized from loofah sponge

Activated carbon (AC) developed from loofah sponge with phosphoric acid activation was applied to absorb cefalexin (CEX) in aqueous solution. AC was characterized by N2 adsorption–desorption isotherms and Fourier transform infrared spectroscopy (FTIR). Factors influencing the adsorption process were investigated. The equilibrium adsorption isotherms and kinetics of CEX were also studied. The results showed that AC prepared from loofah sponge had rough surface and abundant pores. The determination results of specific surface area (810.12 m²/g) and average pore size (5.28 nm) suggested the high adsorption capability. At low concentration, the AC could adsorb about 95% of CEX. The adsorption effect was independent of the temperature and pH. The maximum adsorption amount of CEX was about 55.11 mg/g at 308 K. The equilibrium data agreed well with Freundlich isotherm equation (R² = 0.9957) at 308 K, which indicated multilayer adsorption. FTIR analysis suggested the existence of phosphorus-containing functional groups, C–O bond, and C=C bond on the surface of AC of which the peak intensity of AC after adsorption was slightly lower after adsorption, indicating that the AC surface groups interacted with or were covered by the CEX species.

Loss of periodicity in breeding success of waders links to changes in lemming cycles in Arctic ecosystems

Lemming population cycles in the Arctic have an important impact on the Arctic food web, indirectly also affecting breeding success in Arctic-nesting birds through shared predators. Over the last two decades lemming cycles have changed in amplitude and even disappeared in parts of the Arctic. To examine the large scale effect of these recent changes we re-analysed published data from the East Atlantic Flyway (EAF), where a relationship between lemming cycles and wader breeding success was earlier found, and new data on breeding success of waders in the East Asian-Australasian Flyway (EAAF). We found that 1) any long-term periodicities in wader breeding success existed only until the year 2000 in the EAAF and until the 1980s in the EAF; 2) studying these patterns at a smaller spatial scale, where the Siberian-Alaskan breeding grounds were divided into five geographical units largely based on landscape features, breeding success of waders from the EAAF was not correlated to an index of predation pressure, but positively correlated to Arctic summer temperatures in some species. We argue that fading out of lemming cycles in some parts of the Arctic is responsible for faltering periodicity in wader breeding success along both flyways. These changed conditions have not yet resulted in any marked changing trends in breeding success across years, and declining numbers of waders along the EAAF are therefore more likely a result of changing conditions at stop-over and wintering sites.

Nanoscale variation in energy dissipation in austenitic shape memory alloys in ultimate loading cycles

Wavy behaviours of hysteresis energy variation in nanoscale bulk of thermomechanical austenitic NiTi shape memory alloy are reported in ultimate nanoindentation loading cycles. One sharp and two spherical tips were used while two loading-unloading rates were applied. For comparison, another austenitic copper-based shape memory alloy, CuAlNi shape memory alloy, and a metal with no phase transition, elastoplastic Cu, were investigated. In shape memory alloys, the hysteresis energy variation ultimately undergoes a linear decrease with internal wavy fluctuations and no stabilisation was observed. The internal energy fluctuation in these alloys was found dissimilar depending on the loading-unloading rate and the indentation tip geometry. In contrast, there was an absence of both overall and internal variations in hysteresis energy for Cu after the second loading cycle. The underlying physics of these variations is discussed and found to be attributed to both the created dislocations and ratcheting thermal-mechanical behaviour of the phase-transformed volume in shape memory alloys.

The drowned apostles: the longevity of sea stacks over eustatic cycles

Cliffed rocky coasts are erosional environments, the remnants of which can be preserved as sea stacks as the shoreline retreats. These sea stacks form spectacular landscapes, such as the iconic Twelve Apostles in Victoria, Australia. However, they are ephemeral features formed on a centennial scale, continually eroding and collapsing, meaning that coasts characterised by sea stacks often have fewer features than when first described. The question arises then as to the longevity of such features and whether they can be preserved over eustatic cycles. The modern Twelve Apostles, of which 8 are still standing, are comprised of the Miocene Port Campbell Limestone and reach 45 m above sea level. Recent multibeam sonar data show five features around 6 km offshore, in 40-50 m water depth that appear to be relict sea stacks. Based on the morphology and geology of both the modern and drowned Apostles, it is inferred that the drowned and modern stacks evolved in a similar manner. While the modern sea stacks have an average height of 45 m, the drowned stacks have an average height of 4 m, suggesting a much greater age and also the possibility of multiple exposures to subaerial processes. The drowned stacks lay 655 m seaward of a drowned cliff averaging 14 m high which likely represents a former interstadial shoreline. This is much greater than the 91 m average distance between stack and cliff for the Modern Apostles, which may imply a more prolonged period of erosion along the drowned coastline.