A Raman spectroscopic study of M2+M3+ sulfate minerals, römerite Fe2+Fe23+ (SO4)4· 14H2O and botryogen Mg2+Fe3+ (SO4)2(OH)·7H2O

The mixed valency (M2+M3+) sulphate minerals, römerite Fe2+Fe23+(SO4)4•14H2O and botryogen Mg2+Fe3+(SO4)2(OH).7H2O have been studied by Raman spectroscopy. The Raman spectra of the two types of crystals proved very similar but not identical. The observation of two symmetric stretching modes confirmed the presence of the two non-equivalent sulphate units in the römerite structure. The observation of multiple bands in the antisymmetric stretching region and in the bending regions proves the symmetry of the sulphate anion is significantly reduced in the römerite structure. The number of Raman bands related to the (SO4)2- symmetric and antisymmetric vibrations support the X-ray single crystal structure conclusion that two symmetrically distinct S6+ are present in the structure of botryogen. Römerite is a mineral of environmental significance as it is commonly found in tailings and dumps.

Nascent entrepreneurship and the developing individual : early entrepreneurial competence in adolescence and venture creation success during the career

What predicts a person's venture creation success over the course of the career, such as making progress in the venture creation process and multiple successful venture creations? Applying a life span approach of human development, this study examined the effect of early entrepreneurial competence in adolescence, which was gathered retrospectively by means of the Life History Calendar method. Human and social capitals during the founding process were investigated as mediators between adolescent competence and performance. Findings were derived from regression analyses on the basis of prospective and retrospective data from two independent samples (N = 88 nascent founders; N = 148 founders). We found that early entrepreneurial competence in adolescence had a positive effect on making progress in the venture creation process. Nascent founders' current human and social capital also had a direct effect, but it did not mediate the effect of early competences. Finally, the data revealed that early entrepreneurial competence in adolescence positively predicted habitual entrepreneurship (multiple successful venture creations) exhibited over a longer period of the individual career (specifically, 18 years). In line with the results from prospective longitudinal studies on early precursors of entrepreneurship, our findings underscore the long neglected importance of adolescent development in the explanation of entrepreneurial performance during the subsequent working life.

Immunohistochemical analysis of structural changes in collagen for the assessment of osteoarthritis

Collagen fibrillation within articular cartilage (AC) plays a key role in joint osteoarthritis (OA) progression and, therefore, studying collagen synthesis changes could be an indicator for use in the assessment of OA. Various staining techniques have been developed and used to determine the collagen network transformation under microscopy. However, because collagen and proteoglycan coexist and have the same index of refraction, conventional methods for specific visualization of collagen tissue is difficult. This study aimed to develop an advanced staining technique to distinguish collagen from proteoglycan and to determine its evolution in relation to OA progression using optical and laser scanning confocal microscopy (LSCM). A number of AC samples were obtained from sheep joints, including both healthy and abnormal joints with OA grades 1 to 3. The samples were stained using two different trichrome methods and immunohistochemistry (IHC) to stain both colourimetrically and with fluorescence. Using optical microscopy and LSCM, the present authors demonstrated that the IHC technique stains collagens only, allowing the collagen network to be separated and directly investigated. Fluorescently-stained IHC samples were also subjected to LSCM to obtain three-dimensional images of the collagen fibres. Changes in the collagen fibres were then correlated with the grade of OA in tissue. This study is the first to successfully utilize the IHC staining technique in conjunction with laser scanning confocal microscopy. This is a valuable tool for assessing changes to articular cartilage in OA.

Structural reliability prediction of a steel bridge element using Dynamic Object Oriented Bayesian Network (DOOBN)

Different from conventional methods for structural reliability evaluation, such as, first/second-order reliability methods (FORM/SORM) or Monte Carlo simulation based on corresponding limit state functions, a novel approach based on dynamic objective oriented Bayesian network (DOOBN) for prediction of structural reliability of a steel bridge element has been proposed in this paper. The DOOBN approach can effectively model the deterioration processes of a steel bridge element and predict their structural reliability over time. This approach is also able to achieve Bayesian updating with observed information from measurements, monitoring and visual inspection. Moreover, the computational capacity embedded in the approach can be used to facilitate integrated management and maintenance optimization in a bridge system. A steel bridge girder is used to validate the proposed approach. The predicted results are compared with those evaluated by FORM method.

Raman spectroscopy of gallium- and zinc-based hydrotalcites

Insight into the unique structure of hydrotalcites (HTs) has been obtained using Raman spectroscopy. Gallium-contg. HTs of formula Zn4 Ga2(CO3)(OH)12 · xH2O (2:1 ZnGa-HT), Zn6 Ga2(CO3)(OH)16 · xH2O (3:1 ZnGa-HT) and Zn8 Ga2(CO3)(OH)18 · xH2O (4:1 ZnGa-HT) have been successfully synthesized and characterised by X-ray diffraction (XRD) and Raman spectroscopy. The d(003) spacing varies from 7.62 Å for the 2:1 ZnGa-HT to 7.64 Å for the 3:1 ZnGa-HT. The 4:1 ZnGa-HT showed a decrease in the d(003) spacing, compared to the 2:1 and 3:1 compds. Raman spectroscopy complemented with selected IR data has been used to characterize the synthesized gallium-contg. HTs. Raman bands obsd. at around 1050, 1060 and 1067 cm-1 are attributed to the sym. stretching modes of the (CO32-) units. Multiple ν3 (CO32-) antisym. stretching modes are found between 1350 and 1520 cm-1, confirming multiple carbonate species in the HT structure. The splitting of this mode indicates that the carbonate anion is in a perturbed state. Raman bands obsd. at 710 and 717 cm-1 and assigned to the ν4 (CO32-) modes support the concept of multiple carbonate species in the interlayer.

A Raman spectroscopic study of copiapites Fe2+Fe3+(SO4)6(OH)2 · 20H2O: environmental implications

Raman spectroscopy has been used to study selected mineral samples of the copiapite group. Copiapite (Fe2+Fe3+(SO4)6(OH)2 · 20H2O) is a secondary mineral formed through the oxidn. of pyrite. Minerals of the copiapite group have the general formula AFe4(SO4)6(OH)2 · 20H2O, where A has a + 2 charge and can be either magnesium, iron, copper, calcium and/or zinc. The formula can also be B2/3Fe4(SO4)6(OH)2 · 20H2O, where B has a + 3 charge and may be either aluminum or iron. For each mineral, two Raman bands are obsd. at around 992 and 1029 cm-1, assigned to the (SO4)2-ν1 sym. stretching mode. The observation of two bands provides evidence for the existence of two non-equiv. sulfate anions in the mineral structure. Three Raman bands at 1112, 1142 and 1161 cm-1 are obsd. in the Raman spectrum of copiapites, indicating a redn. of symmetry of the sulfate anion in the copiapite structure. This redn. in symmetry is supported by multiple bands in the ν2 and ν4(SO4)2- spectral regions.

Structural inquiry, human agency and the contribution of Harre and Bhaskar : a case study of Wright’s “Classes”

This paper examines the contribution of aspects of critical and referential realism to the “logic” of structural explanation through an analysis of Erik Olin Wright’s Classes and the debate surrounding this work. Wright’s Classes has been selected as a case study because it offers an opportunity to examine issues pertaining to “objective” and “subjective” determinations of class and related questions of agency and structure at the level of actual methodological strategies. A close examination of the structure of Wright’s inquiry reveals a number of places where Harre’s and Bhaskar’s approaches may contribute to the prescription of methodological strategies which could overcome some of the antinomies on which the debate on Classes is based. As a case study, the paper underlines the important “underlabourer” role of critical and referential realism and their contribution to questions of agency and structure in the context of actual stages involved in structural explanation

Analysis of micro-structural changes and measurement of their parameters of a food material

Food microstructure represents the way their elements arrangement and their interaction. Researchers in this field benefit from identifying new methods of examination of the microstructure and analysing the images. Experiments were undertaken to study micro-structural changes of food material during drying. Micro-structural images were obtained for potato samples of cubical shape at different moisture contents during drying using scanning electron microscopy. Physical parameters such as cell wall perimeter, and area were calculated using an image identification algorithm, based on edge detection and morphological operators. The algorithm was developed using Matlab.

Investigation of hybridized polyurethane, glass fibre reinforced cement and steel laminate in structural floor plate systems

Sandwich components have emerged as light weight, efficient, economical, recyclable and reusable building systems which provide an alternative to both stiffened steel and reinforced concrete. These components are made of composite materials in which two metal face plates or Glassfibre Reinforced Cement (GRC) layers are bonded and form a sandwich with light weight compact polyurethane (PU) elastomer core. Existing examples of product applications are light weight sandwich panels for walls and roofs, Sandwich Plate System (SPS) for stadia, arena terraces, naval construction and bridges and Domeshell structures for dome type structures. Limited research has been conducted to investigate performance characteristics and applicability of sandwich or hybrid materials as structural flooring systems. Performance characteristics of Hybrid Floor Plate Systems comprising GRC, PU and Steel have not been adequately investigated and quantified. Therefore there is very little knowledge and design guidance for their application in commercial and residential buildings. This research investigates performance characteristics steel, PU and GRC in Hybrid Floor Plate Systems (HFPS) and develops a new floor system with appropriate design guide lines.

A vibrational spectroscopic study of the mixed anion mineral sanjuanite Al2(PO4)(SO4)(OH)•9H2O

The mineral sanjuanite Al2(PO4)(SO4)(OH)•9H2O has been characterised by Raman spectroscopy complimented by infrared spectroscopy. The mineral is characterised by an intense Raman band at 984 cm-1, assigned to the (PO4)3- ν1 symmetric stretching mode. A shoulder band at 1037 cm-1 is attributed to the (SO4)2- ν1 symmetric stretching mode. Two Raman bands observed at 1102 and 1148 cm-1 are assigned to (PO4)3- and (SO4)2- ν3 antisymmetric stretching modes. Multiple bands provide evidence for the reduction in symmetry of both anions. This concept is supported by the multiple sulphate and phosphate bending modes. Raman spectroscopy shows that there are more than one non-equivalent water molecules in the sanjuanite structure. There is evidence that structural disorder exists, shown by the complex set of overlapping bands in the Raman and infrared spectra. At least two types of water are identified with different hydrogen bond strengths. The involvement of water in the sanjuanite structure is essential for the mineral stability.

Raman spectroscopic study of the minerals diadochite and destinezite Fe3+2(PO4,SO4)2(OH)•6H2O – implications for soil science

The two minerals diadochite and destinezite of formula Fe2(PO4,SO4)2(OH)•6H2O have been characterised by Raman spectroscopy and complimented with infrared spectroscopy. These two minerals are both found in soils and are identical except for their morphology. Diadochite is amorphous whereas destinezite is highly crystalline. The spectra of diadochite are broad and ill-defined, whereas the spectra of destinezite are intense and well defined. Bands are assigned to phosphate and sulphate stretching and bending modes. Two symmetric stretching modes for both the phosphate and sulphate symmetric stretching modes support the concept of non-equivalent phosphate and sulphate units in the mineral structure. Multiple water bending and stretching modes imply that non-equivalent water molecules in the structure exist with different hydrogen bond strengths.

High-pressure Raman spectroscopic and other structural studies of hydrotalcites containing intercalated dicarboxylic acid anions

The results of pressure-tuning Raman spectroscopic, X-ray powder diffraction and solid-state 13C-NMR studies of selected dicarboxylate anions intercalated in a Mg-Al layered double hydroxide (talcite) lattice are reported. The pressure dependences of the vibrational modes are linear for pressures up to 4.6 GPa indicating that no phase transitions occur. The interlayer spacings show that the oxalate, malonate and succinate dianions are oriented perpendicular to the layers, but the glutarate and adipate are tilted. The solid-state 13C-NMR spectra of these materials show full chemical shift anisotropy and, therefore, the anions are not mobile at room temperature.

Sustainable assessment for large science classes : non-multiple choice, randomised assignments through a Learning Management System

This paper reports on the development of a tool that generates randomised, non-multiple choice assessment within the BlackBoard Learning Management System interface. An accepted weakness of multiple-choice assessment is that it cannot elicit learning outcomes from upper levels of Biggs’ SOLO taxonomy. However, written assessment items require extensive resources for marking, and are susceptible to copying as well as marking inconsistencies for large classes. This project developed an assessment tool which is valid, reliable and sustainable and that addresses the issues identified above. The tool provides each student with an assignment assessing the same learning outcomes, but containing different questions, with responses in the form of words or numbers. Practice questions are available, enabling students to obtain feedback on their approach before submitting their assignment. Thus, the tool incorporates automatic marking (essential for large classes), randomised tasks to each student (reducing copying), the capacity to give credit for working (feedback on the application of theory), and the capacity to target higher order learning outcomes by requiring students to derive their answers rather than choosing them. Results and feedback from students are presented, along with technical implementation details.

Multiple evolutionary rate classes in animal genome evolution

The proportion of functional sequence in the human genome is currently a subject of debate. The most widely accepted figure is that approximately 5% is under purifying selection. In Drosophila, estimates are an order of magnitude higher, though this corresponds to a similar quantity of sequence. These estimates depend on the difference between the distribution of genomewide evolutionary rates and that observed in a subset of sequences presumed to be neutrally evolving. Motivated by the widening gap between these estimates and experimental evidence of genome function, especially in mammals, we developed a sensitive technique for evaluating such distributions and found that they are much more complex than previously apparent. We found strong evidence for at least nine well-resolved evolutionary rate classes in an alignment of four Drosophila species and at least seven classes in an alignment of four mammals, including human. We also identified at least three rate classes in human ancestral repeats. By positing that the largest of these ancestral repeat classes is neutrally evolving, we estimate that the proportion of nonneutrally evolving sequence is 30% of human ancestral repeats and 45% of the aligned portion of the genome. However, we also question whether any of the classes represent neutrally evolving sequences and argue that a plausible alternative is that they reflect variable structure-function constraints operating throughout the genomes of complex organisms.