A Raman spectroscopic study of bukovskýite Fe2(AsO4)(SO4)(OH)•7H2O-a mineral phase with a significant role in arsenic migration

The Raman spectrum of bukovskýite, Fe3+2(OH)(SO4)(AsO4)•7H2O has been studied and compared with the Raman spectrum of an amorphous gel containing specifically Fe, As and S elements and is understood as an intermediate product in the formation of bukovskýite. Observed bands are assigned to the stretching and bending vibrations of (SO4)2- and (AsO4)3- units, stretching and bending vibrations and librational modes of hydrogen bonded water molecules, stretching and bending vibrations of hydrogen bonded (OH)- ions and Fe3+-(O,OH) units. Approximate range of O-H...O hydrogen bond lengths is inferred from the Raman spectra. Raman spectra of crystalline bukovskýite and of the amorphous gel differ in that the bukovskýite spectrum is more complex, observed bands are sharp, the degenerate bands of (SO4)2- and (AsO4)3- are split and more intense. Lower wavenumbers of  H2O bending vibration in the spectrum of the amorphous gel may indicate the presence of weaker hydrogen bonds compared with those in bukovskýite.

A collagen network phase improves cell seeding of open-pore structure scaffolds under perfusion

Scaffolds with open-pore morphologies offer several advantages in cell-based tissue engineering, but their use is limited by a low cell seeding efficiency. We hypothesized that inclusion of a collagen network as filling material within the open-pore architecture of polycaprolactone-tricalcium phosphate (PCL-TCP) scaffolds increases human bone marrow stromal cells (hBMSC) seeding efficiency under perfusion and in vivo osteogenic capacity of the resulting constructs. PCL-TCP scaffolds, rapid prototyped with a honeycomb-like architecture, were filled with a collagen gel and subsequently lyophilized, with or without final crosslinking. Collagen-free scaffolds were used as controls. The seeding efficiency was assessed after overnight perfusion of expanded hBMSC directly through the scaffold pores using a bioreactor system. By seeding and culturing freshly harvested hBMSC under perfusion for 3 weeks, the osteogenic capacity of generated constructs was tested by ectopic implantation in nude mice. The presence of the collagen network, independently of the crosslinking process, significantly increased the cell seeding efficiency (2.5-fold), and reduced the loss of clonogenic cells in the supernatant. Although no implant generated frank bone tissue, possibly due to the mineral distribution within the scaffold polymer phase, the presence of a non crosslinked collagen phase led to in vivo formation of scattered structures of dense osteoids. Our findings verify that the inclusion of a collagen network within open morphology porous scaffolds improves cell retention under perfusion seeding. In the context of cell-based therapies, collagen-filled porous scaffolds are expected to yield superior cell utilization, and could be combined with perfusion-based bioreactor devices to streamline graft manufacture.

Shifting : one-inclusion mistake bounds and sample compression

We present new expected risk bounds for binary and multiclass prediction, and resolve several recent conjectures on sample compressibility due to Kuzmin and Warmuth. By exploiting the combinatorial structure of concept class F, Haussler et al. achieved a VC(F)/n bound for the natural one-inclusion prediction strategy. The key step in their proof is a d = VC(F) bound on the graph density of a subgraph of the hypercube—oneinclusion graph. The first main result of this paper is a density bound of n [n−1 <=d-1]/[n <=d] < d, which positively resolves a conjecture of Kuzmin and Warmuth relating to their unlabeled Peeling compression scheme and also leads to an improved one-inclusion mistake bound. The proof uses a new form of VC-invariant shifting and a group-theoretic symmetrization. Our second main result is an algebraic topological property of maximum classes of VC-dimension d as being d contractible simplicial complexes, extending the well-known characterization that d = 1 maximum classes are trees. We negatively resolve a minimum degree conjecture of Kuzmin and Warmuth—the second part to a conjectured proof of correctness for Peeling—that every class has one-inclusion minimum degree at most its VCdimension. Our final main result is a k-class analogue of the d/n mistake bound, replacing the VC-dimension by the Pollard pseudo-dimension and the one-inclusion strategy by its natural hypergraph generalization. This result improves on known PAC-based expected risk bounds by a factor of O(logn) and is shown to be optimal up to an O(logk) factor. The combinatorial technique of shifting takes a central role in understanding the one-inclusion (hyper)graph and is a running theme throughout.

Corrigendum to “Shifting : one-inclusion mistake bounds and sample compression” [J. Comput. System Sci. 75 (1) (2009) 37–59]

H. Simon and B. Szörényi have found an error in the proof of Theorem 52 of “Shifting: One-inclusion mistake bounds and sample compression”, Rubinstein et al. (2009). In this note we provide a corrected proof of a slightly weakened version of this theorem. Our new bound on the density of one-inclusion hypergraphs is again in terms of the capacity of the multilabel concept class. Simon and Szörényi have recently proved an alternate result in Simon and Szörényi (2009).

Shifting : one-inclusion mistake bounds and sample compression

We present new expected risk bounds for binary and multiclass prediction, and resolve several recent conjectures on sample compressibility due to Kuzmin and Warmuth. By exploiting the combinatorial structure of concept class F, Haussler et al. achieved a VC(F)/n bound for the natural one-inclusion prediction strategy. The key step in their proof is a d=VC(F) bound on the graph density of a subgraph of the hypercube—one-inclusion graph. The first main result of this report is a density bound of n∙choose(n-1,≤d-1)/choose(n,≤d) < d, which positively resolves a conjecture of Kuzmin and Warmuth relating to their unlabeled Peeling compression scheme and also leads to an improved one-inclusion mistake bound. The proof uses a new form of VC-invariant shifting and a group-theoretic symmetrization. Our second main result is an algebraic topological property of maximum classes of VC-dimension d as being d-contractible simplicial complexes, extending the well-known characterization that d=1 maximum classes are trees. We negatively resolve a minimum degree conjecture of Kuzmin and Warmuth—the second part to a conjectured proof of correctness for Peeling—that every class has one-inclusion minimum degree at most its VC-dimension. Our final main result is a k-class analogue of the d/n mistake bound, replacing the VC-dimension by the Pollard pseudo-dimension and the one-inclusion strategy by its natural hypergraph generalization. This result improves on known PAC-based expected risk bounds by a factor of O(log n) and is shown to be optimal up to a O(log k) factor. The combinatorial technique of shifting takes a central role in understanding the one-inclusion (hyper)graph and is a running theme throughout

Politics and school education in Australia : a case of shifting purposes

Purpose – The paper aims to argue that there has been a privileging of the private (social mobility) and economic (social efficiency) purposes of schooling at the expense of the public (democratic equality) purposes of schooling. Design/methodology/approach – The paper employs a literature review, policy and document analysis. Findings – Since the late 1980s, the schooling agenda in Australia has been narrowed to one that gives primacy to purposes of schooling that highlight economic orientations (social efficiency) and private purposes (social mobility). Practical implications – The findings have wider relevance beyond Australia, as similar policy agendas are evident in many other countries raising the question as to how the shift in purposes of education in those countries might mirror those in Australia. Originality/value – While earlier writers have examined schooling policies in Australia and noted the implications of managerialism in relation to these policies, no study has analysed these policies from the perspective of the purposes of schooling. Conceptualising schooling, and its purposes in particular, in this way refocuses attention on how societies use their educational systems to promote (or otherwise) the public good.