Development and Validation of the RAFFLE: A Measure of Reasons and Facilitators for Loot Box Engagement.

Qualitative studies have identified a diverse array of motivations for purchasing items within video games through chance-based mechanisms (i.e., "loot boxes"). Given that some individuals-particularly those at risk of disordered gaming and/or gambling-are prone to over-involvement with loot box purchasing, it is important to have a reliable, valid means of measuring the role of different motivations in driving purchasing behaviour. Building on prior qualitative research, this paper reports the development and validation of the "RAFFLE" scale, to measure the Reasons and Facilitators for Loot box Engagement. A 23-item, seven-factor scale was developed through cognitive interviews (n = 25) followed by two surveys of UK-based gamers who purchase loot boxes; analysed via exploratory (n = 503) and confirmatory (n = 1495) factor analysis, respectively. Subscales encompassed "enhancement'; "progression'; "social pressure'; "distraction/compulsion'; "altruism'; "fear of missing out'; and "resale". The scale showed good criterion and construct validity (correlating well with measures of loot box engagement; the risky loot box index (r = 0.63) and monthly self-reported spend (r = 0.38)), and good internal validity (Cronbach's alpha = 0.84). Parallels with, and divergence from, motivations for related activities of gaming and gambling, and alignment with broader theoretical models of motivation, are discussed.

Role of Collagen Fiber Morphology on Ovarian Cancer Cell Migration Using Image-Based Models of the Extracellular Matrix.

Remodeling of the extracellular matrix (ECM) is an important part in the development and progression of many epithelial cancers. However, the biological significance of collagen alterations in ovarian cancer has not been well established. Here we investigated the role of collagen fiber morphology on cancer cell migration using tissue engineered scaffolds based on high-resolution Second-Harmonic Generation (SHG) images of ovarian tumors. The collagen-based scaffolds are fabricated by multiphoton excited (MPE) polymerization, which is a freeform 3D method affording submicron resolution feature sizes (~0.5 µm). This capability allows the replication of the collagen fiber architecture, where we constructed models representing normal stroma, high-risk tissue, benign tumors, and high-grade tumors. These were seeded with normal and ovarian cancer cell lines to investigate the separate roles of the cell type and matrix morphology on migration dynamics. The primary finding is that key cell-matrix interactions such as motility, cell spreading, f-actin alignment, focal adhesion, and cadherin expression are mainly determined by the collagen fiber morphology to a larger extent than the initial cell type. Moreover, we found these aspects were all enhanced for cells on the highly aligned, high-grade tumor model. Conversely, the weakest corresponding responses were observed on the more random mesh-like normal stromal matrix, with the partially aligned benign tumor and high-risk models demonstrating intermediate behavior. These results are all consistent with a contact guidance mechanism. These models cannot be synthesized by other conventional fabrication methods, and we suggest this approach will enable a variety of studies in cancer biology.

Migration dynamics of ovarian epithelial cells on micro-fabricated image-based models of normal and malignant stroma.

A profound remodeling of the collagen in the extracellular matrix (ECM) occurs in human ovarian cancer but it is unknown how this affects migration dynamics and ultimately tumor growth. Here, we investigate the influence of collagen morphology on ovarian cell migration through the use of second harmonic generation (SHG) image-based models of ovarian tumors. The scaffolds are fabricated by multiphoton excited (MPE) polymerization, where the process is akin to 3D printing except it achieves much greater resolution (∼0.5 µm) and utilizes collagen and collagen analogs. We used this technique to create scaffolds with complex 3D submicron features representing the collagen fiber morphology in normal stroma, high risk stroma, benign tumors, and high grade ovarian tumors. We found the highly aligned malignant stromal structure promoted enhanced motility and also increased cell and f-Actin alignment relative to the other tissues. However, using models based on fiber crimping characteristics, we found cells seeded on linear fibers based on normal stromal models yielded the highest degree of alignment but least motility. These results show that both the fiber properties themselves and as well as their overall alignment govern the resulting migration dynamics. These models cannot be synthesized by other conventional fabrication methods and we suggest the MPE image-based fabrication method will enable a variety of studies in cancer biology. STATEMENT OF SIGNIFICANCE: The extracellular matrix collagen in ovarian cancer is highly remodeled but the consequences on cell function remain unknown. It is important to understand the operative cell matrix interactions, as this could lead to better prognostics and better prediction of therapeutic efficacy. We probe migration dynamics using high resolution (∼0.5 µm) multiphoton excited fabrication to synthesize scaffolds whose designs are derived directly from Second Harmonic Generation microscope images of the collagen in normal ovarian tissues as well as benign and malignant tumors. Collectively our results show the importance of the matrix morphology (fiber shape and alignment) on driving cell motility, cell shape and f-Actin alignment. These collagen-based models have complex fiber morphology and cannot be created by conventional fabrication technologies.

Mapping Forbidden Emission to Structure in Self-Assembled Organic Nanoparticles.

The interplay between micromorphology and electronic properties is an important theme in organic electronic materials. Here, we show that a spirofluorene-functionalized boron-dipyrromethene (BODIPY) with an alkyl norbornyl tail self-assembles into nanoparticles with qualitatively different properties as compared to the polymerized species. Further, the nanoparticles exhibit a host of unique emissive properties, including photobrightening, a blue satellite peak, and spectral diffusion. Extensive photophysical characterization, including single-particle imaging and spectroscopy, and time-resolved fluorescence, coupled with electronic structure calculations based on an experimentally determined crystal structure, allow a mechanism to be developed. Specifically, BODIPY chromophores are observed to form quasi-two-dimensional layers, where stacking of unit cells adds either J-aggregate character or H-aggregate character depending on the direction of the stacking. Particularly strongly H-coupled domains show the rare process of emission from an upper exciton state, in violation of Kasha's rule, and result in the blue satellite peak. The spatial heterogeneity of structure thus maps onto a gradient of photophysical behavior as seen in single-particle imaging, and the temporal evolution of structure maps onto fluctuating emissive behavior, as seen in single-particle spectroscopy. Taken together, this system provides a striking example of how physical structure and electronic properties are intertwined, and a rare opportunity to use one to chart the other.

A large-scale examination of the effectiveness of anonymous marking in reducing group performance differences in higher education assessment.

The present research aims to more fully explore the issues of performance differences in higher education assessment, particularly in the context of a common measure taken to address them. The rationale for the study is that, while performance differences in written examinations are relatively well researched, few studies have examined the efficacy of anonymous marking in reducing these performance differences, particularly in modern student populations. By examining a large archive (N = 30674) of assessment data spanning a twelve-year period, the relationship between assessment marks and factors such as ethnic group, gender and socio-environmental background was investigated. In particular, analysis focused on the impact that the implementation of anonymous marking for assessment of written examinations and coursework has had on the magnitude of mean score differences between demographic groups of students. While group differences were found to be pervasive in higher education assessment, these differences were observed to be relatively small in practical terms. Further, it appears that the introduction of anonymous marking has had a negligible effect in reducing them. The implications of these results are discussed, focusing on two issues, firstly a defence of examinations as a fair and legitimate form of assessment in Higher Education, and, secondly, a call for the re-examination of the efficacy of anonymous marking in reducing group performance differences.

Tracking Lithium Ions via Widefield Fluorescence Microscopy for Battery Diagnostics.

Direct tracking of lithium ions with time and spatial resolution can provide an important diagnostic tool for understanding mechanisms in lithium ion batteries. A fluorescent indicator of lithium ions, 2-(2-hydroxyphenyl)naphthoxazole, was synthesized and used for real-time tracking of lithium ions via widefield fluorescence microscopy. The fluorophore can be excited with visible light and was shown to enable quantitative determination of the lithium ion diffusion constant in a microfluidic model system for a plasticized polymer electrolyte lithium battery. The use of widefield fluorescence microscopy for in situ tracking of lithium ions in batteries is discussed.

Probing Heterogeneity and Bonding at Silica Surfaces through Single-Molecule Investigation of Base-Mediated Linkage Failure.

The nature of silica surfaces is relevant to many chemical systems, including heterogeneous catalysis and chromatographies utilizing functionalized-silica stationary phases. Surface linkages must be robust to achieve wide and reliable applicability. However, silyl ether-silica support linkages are known to be susceptible to detachment when exposed to basic conditions. We use single-molecule spectroscopy to examine the rate of surface linkage failure upon exposure to base at a variety of deposition conditions. Kinetic analysis elucidates the role of thermal annealing and addition of blocking layers in increasing stability. Critically, it was found that successful surface modification strategies alter the rate at which base molecules approach the silica surface as opposed to reducing surface linkage reactivity. Our results also demonstrate that the innate structural diversity of the silica surface is likely the cause of observed heterogeneity in surface-linkage disruption kinetics.

Single-Molecule Investigation of Initiation Dynamics of an Organometallic Catalyst.

The action of molecular catalysts comprises multiple microscopic kinetic steps whose nature is of central importance in determining catalyst activity and selectivity. Single-molecule microscopy enables the direct examination of these steps, including elucidation of molecule-to-molecule variability. Such molecular diversity is particularly important for the behavior of molecular catalysts supported at surfaces. We present the first combined investigation of the initiation dynamics of an operational palladium cross-coupling catalyst at the bulk and single-molecule levels, including under turnover conditions. Base-initiated kinetics reveal highly heterogeneous behavior indicative of diverse catalyst population. Unexpectedly, this distribution becomes more heterogeneous at increasing base concentration. We model this behavior with a two-step saturation mechanism and identify specific microscopic steps where chemical variability must exist in order to yield observed behavior. Critically, we reveal how structural diversity at a surface translates into heterogeneity in catalyst behavior, while demonstrating how single-molecule experiments can contribute to understanding of molecular catalysts.