Livestock grazing to maintain habitat of a critically endangered grassland bird: Is grazer species important?

Livestock grazing is an important management tool for biodiversity conservation in many native grasslands across the globe. Understanding how different grazing species interact with their environment is integral to achieving conservation goals. In the semiarid grasslands of Australia, grazing by sheep or cattle is used to manipulate vegetation structure to suit the habitat needs of a globally unique, critically endangered grassland bird, the plains-wanderer Pedionomus torquatus. However, there has been no investigation of whether sheep and cattle differ in their effects on plains-wanderer habitat and, therefore, it is unknown if these grazers are substitutable as a management tool. Using a grazing experiment in native grasslands over 3 years, we determined the effects of grazer type (sheep, cattle) on occurrence and vocal activity of plains-wanderer, vegetation structure and composition, and food availability. We also examined grazer effects on encounter rates of other grassland birds. Plains-wanderer breeding activity was inferred from vocalization rates captured by bioacoustic recorders. Spotlighting was used to measure encounter rates of other grassland birds. We found that different grazers altered the structure of the habitat. Grasslands grazed by cattle were typically more open, less variable, and lacked patches of dense vegetation relative to those grazed by sheep. Grazer type did not influence the likelihood of plains-wanderer occurrence, but it did interact with year of survey to affect breeding activity. The number of days with one or more calls significantly increased at sheep grazed sites in year-3, which coincided with enduring drought conditions. Similarly, grazer effects on encounter rate of all birds, bird species richness, and Australasian pipit Anthus novaeseelandiae were different between years. Dense vegetation specialists (such as stubble quail Coturnix pectoralis) were positively associated with grasslands grazed by sheep. As a habitat management tool, sheep or cattle grazing are useful when the goal is to support an open grassland structure for the plains-wanderer. However, their substitutability is likely to be dependent upon climate. We caution that a loss of dense vegetation in grasslands grazed by cattle during drought could limit the availability of optimal habitat for the plains-wanderer and habitat for other grassland birds.

POMzites: A Family of Zeolitic Polyoxometalate Frameworks from a Minimal Building Block Library.

We describe why the cyclic heteropolyanion [P8W48O184]40- (abbreviated as {P8W48}) is an ideal building block for the construction of intrinsically porous framework materials by classifying and analyzing >30 coordination polymers incorporating this polyoxometalate (POM) ligand. This analysis shows that the exocyclic coordination of first-row transition metals (TMs) to {P8W48} typically yields frameworks which extend through {W-O-TM-O-W} bridges in one, two, or three dimensions. However, despite the rich structural diversity of such compounds, the coordination of TMs to the {P8W48} ring is poorly understood, and therefore largely unpredictable, and had not until now been present with any structural classification that could allow rational design. Herein, not only do we present a new approach to understand and classify this new class of materials, we also present three {P8W48}-based frameworks which complement those frameworks which have previously been described. These new compounds help us postulate a new taxonomy of these materials. This is possible because the TM coordination sites of the {P8W48} ring are found, once fully mapped, to lead to well-defined classes of connectivity. Together, analysis provides insight into the nature of the building block connectivity within each framework, to facilitate comparisons between related structures, and to fundamentally unite this family of compounds. Hence we have tentatively named these compounds as "POMzites" to reflect the POM-based composition and zeolitic nature of each family member, although crucially, POMzites differ from zeolites in the modular manner of their preparation. As the synthesis of further POMzites is anticipated, the classification system and terminology introduced here will allow new compounds to be categorized and understood in the context of the established materials. A better understanding of TM coordination to the {P8W48} ring may allow the targeted synthesis of new frameworks rather than the reliance on serendipity apparent in current methods.

Osmotically driven crystal morphogenesis: a general approach to the fabrication of micrometer-scale tubular architectures based on polyoxometalates.

The process of osmotically driven crystal morphogenesis of polyoxometalate (POM)-based crystals is investigated, whereby the transformation results in the growth of micrometer-scale tubes 10-100 µm in diameter and many thousands of micrometers long. This process initiates when the crystals are immersed in aqueous solutions containing large cations and is governed by the solubility of the parent POM crystal. Evidence is presented that indicates the process is general to all types of POMs, with solubility of the parent crystal being the deciding parameter. A modular approach is adopted since different POM precursor crystals can form tubular architectures with a range of large cationic species, producing an ion-exchanged material that combines the large added cations and the large POM-based anions. It is also shown that the process of morphogenesis is electrostatically driven by the aggregation of anionic metal oxides with the dissolved cations. This leads to the formation of a semi-permeable membrane around the crystal. The osmotically driven ingress of water leads to an increase in pressure, and ultimately rupture of the membrane occurs, allowing a saturated solution of the POM to escape and leading to the formation of a "self-growing" microtube in the presence of the cation. It is demonstrated that the growth process is sustained by the osmotic pressure within the membrane surrounding the parent crystal, as tube growth ceases whenever this pressure is relieved. Not only is the potential of the modular approach revealed by the fact that the microtubes retain the properties of their component parts, but it is also possible to control the direction of growth and tube diameter. In addition, the solubility limits of tube growth are explored and translated into a predictive methodology for the fabrication of tubular architectures with predefined physical properties, opening the way for real applications.

A metamorphic inorganic framework that can be switched between eight single-crystalline states.

The design of highly flexible framework materials requires organic linkers, whereas inorganic materials are more robust but inflexible. Here, by using linkable inorganic rings made up of tungsten oxide (P8W48O184) building blocks, we synthesized an inorganic single crystal material that can undergo at least eight different crystal-to-crystal transformations, with gigantic crystal volume contraction and expansion changes ranging from -2,170 to +1,720 Å3 with no reduction in crystallinity. Not only does this material undergo the largest single crystal-to-single crystal volume transformation thus far reported (to the best of our knowledge), the system also shows conformational flexibility while maintaining robustness over several cycles in the reversible uptake and release of guest molecules switching the crystal between different metamorphic states. This material combines the robustness of inorganic materials with the flexibility of organic frameworks, thereby challenging the notion that flexible materials with robustness are mutually exclusive.

Organic-soluble lacunary {M2(P2W15)2} polyoxometalate sandwiches showing a previously unseen αßßα isomerism.

New polyoxometalate 'sandwiches' have been formed where two [P(2)W(15)O(56)](12-) lacunary Dawson clusters encapsulate two transition metal ions to give clusters with the general formula [M(II)(2)(P(2)W(15)O(56))(2)](20-) (where M = Mn, Co, and Ni respectively), [Fe(III)(2)(P(2)W(15)O(56))(2)](18-), and [Cu(II)(4)(P(2)W(15)O(56))(2)](16-). The Mn, Co, and Ni clusters exhibit a hitherto unseen αßßα isomeric geometry and all five compounds are associated with tetrabutylammonium cations which allow for their dissolution in non-aqueous solvent.