Synthesis and reactivity of a nickel(ii) thioperoxide complex: demonstration of sulfide-mediated N2O reduction.

The thiohyponitrite ([SNNO]2-) complex, [K(18-crown-6)][L tBuNiII(κ2-SNNO)] (L tBu = {(2,6-iPr2C6H3)NC( t Bu)}2CH), extrudes N2 under mild heating to yield [K(18-crown-6)][L tBuNiII(η2-SO)] (1), along with minor products [K(18-crown-6)][L tBuNiII(η2-OSSO)] (2) and [K(18-crown-6)][L tBuNiII(η2-S2)] (3). Subsequent reaction of 1 with carbon monoxide (CO) results in the formation of [K(18-crown-6)][L tBuNiII(η2-SCO)] (4), [K(18-crown-6)][L tBuNiII(S,O:κ2-SCO2)] (5), [K(18-crown-6)][L tBuNiII(κ2-CO3)] (6), carbonyl sulfide (COS) (7), and [K(18-crown-6)][L tBuNiII(S2CO)] (8). To rationalize the formation of these products we propose that 1 first reacts with CO to form [K(18-crown-6)][L tBuNiII(S)] (I) and CO2, via O-atom abstraction. Subsequently, complex I reacts with CO or CO2 to form 4 and 5, respectively. Similarly, the formation of complex 6 and COS can be rationalized by the reaction of 1 with CO2 to form a putative Ni(ii) monothiopercarbonate, [K(18-crown-6)][L tBuNiII(κ2-SOCO2)] (11). The Ni(ii) monothiopercarbonate subsequently transfers a S-atom to CO to form COS and [K(18-crown-6)][L tBuNiII(κ2-CO3)] (6). Finally, the formation of 8 can be rationalized by the reaction of COS with I. Critically, the observation of complexes 4 and 5 in the reaction mixture reveals the stepwise conversion of [K(18-crown-6)][L tBuNiII(κ2-SNNO)] to 1 and then I, which represents the formal reduction of N2O by CO

Developing novel intervention materials to aid the development of dressing skills in young children with visual impairment

Independent living skills such as dressing are fundamental in everyday life. Compared to sighted peers, children with visual impairment (VI) are often delayed in developing independence skills, arguably due to the inability to observe others. The present study investigated whether an interactive suite of intervention materials would aid the development of dressing skills in children with VI. The aim of the current study was to develop intervention materials to aid dressing skills. The materials included: an interactive story, an interactive puzzle game (IPG), a commercially available soft toy and a standardised outdoor coat. 9 children with VI and 4 typically developing children (aged between 4 and 11 years) took part in the study. A pre-test, intervention, post-test design was used to assess the impact of the intervention materials over a 10 week period. The current results indicate that the suite of intervention materials could support the development of dressing skills in both sighted children and young children with visual impairment

Lights Out: Examining Sleep in Children with Vision Impairment.

Sleep is crucial for development across cognitive, physical, and social-emotional domains. Sleep quality and quantity impact domains of daytime functioning, attainment, and global development. Previous work has explored sleep profiles in typically developing children and children with developmental disorders such as Down syndrome and Williams Syndrome, yet there is a complete absence of published work regarding the sleep profiles of children with vision impairment aged 4–11 years. This is the first known study that examines the sleep profiles in children with vision impairment (n = 58) in comparison to 58 typically developing children (aged 4–11 years) in the UK. Sleep was measured using the Childhood Sleep Habits Questionnaire (CSHQ; parental report), actigraphy and sleep diaries. Results showed group differences in subjective CSHQ scores but not objective actigraphy measures. Surprisingly, the findings revealed disordered sleep (namely, poor sleep quantity) in both groups. Discordance between CSHQ and actigraphy measures could represent heightened awareness of sleeping problems in parents/caregivers of children with vision impairment. The implications of this study extend beyond group comparison, examining disordered sleep in ‘typically developing’ children, exploring the potential role of light perception and the importance of sleep quality and quantity in both groups

Let's Get It On: Dressing Skill Development in Children With Vision Impairment and Children With Down Syndrome

Dressing is a fundamental independent living skill often haphazardly acquired via visual observation. For children with vision impairment and children with Down Syndrome (where vision impairment is a component), dressing skill acquisition can be delayed due to a reduced/absent visual modality. Independent living skills is an aspect of habilitation practice and training, designed to maximise independence in children and young people with vision impairment and prepare them for adulthood. This paper, presented in two parts, first details a systematic (UK based) survey exploring fastening use across a clothing sample of birth-adult clothing (N = 12,967). Study 1 presents a frequency distribution exploring types of fastenings used on clothing items from birth-adulthood. The data are fundamental in exploring the likelihood of fastening exposure across developmental phases. Further, Study 1 details the process behind developing a novel dressing skill intervention. Informed by Study 1, Study 2 qualitatively explored the effectiveness of an original resource/group-based intervention over a 10-week period. Eighteen children were recruited for the study, namely children with vision impairment (n = 9) and children with Down Syndrome (n = 9) aged 5–11 years. Collective and illustrative case studies are presented based on emergent themes from intervention observations. The findings reveal areas for consideration by Habilitation Specialists and the multidisciplinary team surrounding children with vision impairment and/or Down Syndrome as this may inform Habilitation Plans, and Educational Health Care Plan reports. The implications of this study extend beyond dressing skill development in children with vision impairment and/or Down Syndrome and inform resource development and subsequent practice when working with children with special educational needs and disabilities

Stabilized hot electron bolometer heterodyne receiver at 2.5 THz

We report on a method to stabilize a hot electron bolometer (HEB) mixer at 2.5 THz. The technique utilizes feedback control of the local oscillator (LO) laser power by means of a swing-arm actuator placed in the optical beam path. We demonstrate that this technique yields a factor of 50 improvement in the spectroscopic Allan variance time which is shown to be over 30 s in a 12 MHz noise fluctuation bandwidth. Furthermore, broadband signal direct detection effects may be minimized by this technique. The technique is versatile and can be applied to practically any local oscillator at any frequency

Anisotropic Assembly of Colloidal Nanoparticles: Exploiting Substrate Crystallinity

We show that the crystal structure of a substrate can be exploited to drive the anisotropic assembly of colloidal nanoparticles. Pentanethiol-passivated Au particles of approximately 2 nm diameter deposited from toluene onto hydrogen-passivated Si(111) surfaces form linear assemblies (rods) with a narrow width distribution. The rod orientations mirror the substrate symmetry, with a high degree of alignment along principal crystallographic axes of the Si(111) surface. There is a strong preference for anisotropic growth with rod widths substantially more tightly distributed than lengths. Entropic trapping of nanoparticles provides a plausible explanation for the formation of the anisotropic assemblies we observe

Neogene stratigraphic architecture and tectonic evolution of Wanganui, King Country, and eastern Taranaki Basins, New Zealand

Analysis of the stratigraphic architecture of the fills of Wanganui, King Country, and eastern Taranaki Basins reveals the occurrence of five 2nd order Late Paleocene and Neogene sequences of tectonic origin. The oldest is the late Eocene-Oligocene Te Kuiti Sequence, followed by the early-early Miocene (Otaian) Mahoenui Sequence, followed by the late-early Miocene (Altonian) Mokau Sequence, all three in King Country Basin. The fourth is the middle Miocene to early Pliocene Whangamomona Sequence, and the fifth is the middle Pliocene-Pleistocene Rangitikei Sequence, both represented in the three basins. Higher order sequences (4th, 5th, 6th) with a eustatic origin occur particularly within the Whangamomona and Rangitikei Sequences, particularly those of 6th order with 41 000 yr periodicity

Megasequence architecture of Taranaki, Wanganui, and King Country basins and Neogene progradation of two continental margin wedges across western New Zealand.

Taranaki, Wanganui and King Country basins (formerly North Wanganui Basin) have been regarded as discrete basins, but they contain a very similar Neogene sedimentary succession and much of their geological history is held in common. Analysis of the stratigraphic architecture of the fill of each basin reveals the occurrence of four 2nd order megasequences of tectonic origin. The oldest is the early-early Miocene (Otaian Stage) Mahoenui Group/megasequence, followed by the late-early Miocene (Altonian Stage) Mokau Group/megasequence (King Country Basin), both of which correspond to the lower part of the Manganui Formation in Taranaki Basin. The third is the middle to late Miocene Whangamomona Group/megasequence, and the fourth is the latest Miocene-Pleistocene Rangitikei Supergroup/megasequence, both represented in the three basins. Higher order sequences (4th, 5th, 6th), having a eustatic origin, are evident in the Whangamomona and Rangitikei megasequences, particularly those of 5th order with 41 ka periodicity. The distribution of the megasequences are shown in a series of cross-section panels built-up from well -to-well correlations, complemented by time-stratigraphic cross-sections. The base of each megasequence is marked by marine flooding and represents a discrete phase in basin development. For the first megasequence this corresponded to rapid subsidence of the King Country Basin in a compressional setting and basement overthrusting on the Taranaki Fault, with the rapid introduction of terrigenous sediment during transgression. The Mahoenui megasequence accumulated mostly at bathyal depths; no regressive deposits are evident, having been eroded during subsequent uplift. The second (Mokau) megasequence accumulated during reverse movement on the Ohura Fault, formation of the Tarata Thrust Zone, and onlap of the basement block between the Taranaki Fault and the Patea-Tongaporutu-Herangi High (PTH). The Whangamomona megasequence accumulated during extensive reflooding of King Country Basin, onlap of the PTH High and of basement in the Wanganui Basin. This is an assymetrical sequence with a thin transgressive part (Otunui Formation) and a thick regressive part (Mount Messenger to Matemateaonga Formations). It represents the northward progradation of a continental margin wedge with bottom-set, slope-set and top-set components through Wanganui and King Country basins, with minor progradation over the PTH High and into Taranaki Basin. The Rangitikei megasequence is marked by extensive flooding at its base (Tangahoe Mudstone) and reflects the pull-down of the main Wanganui Basin depocentre. This megasequence comprises a second progradational margin wedge, which migrated on two fronts, one northward through Wanganui Basin and into King Country Basin, and a second west of the PTH High, through the Toru Trough and into the Central and Northern Grabens of Taranaki Basin and on to the Western Platform as the Giant Foresets Formation, thereby building up the modern shelf and slope. Fifth and 6th order sequences are well expressed in the shelf deposits (top-sets) of the upper parts of the Whangamomona and Rangitikei megasequences. They typically have a distinctive sequence architecture comprising shellbed (TST), siltstone (HST) and sandstone (RST) beds. Manutahi-1, which was continuously cored, provides calibration of this sequence architecture to wireline log character, thereby enabling shelf deposits to be mapped widely in the subsurface via the wireline data for hydrocarbon exploration holes. Similar characterization of slope-sets and bottom-sets is work ongoing. The higher order (eustatic) sequences profoundly influenced the local reservoir architecture and seal properties of formations, whereas the megasequence progradation has been responsible for the regional hydrocarbon maturation and migration. Major late tilting, uplift and erosion affected all three basins and created a regional high along the eastern Margin of Taranaki Basin, thereby influencing the migration paths of hydrocarbons sourced deeper in the basin and allowing late charge of structural and possibly stratigraphic traps

Megasequence architecture of Taranaki, Wanganui, and King Country basins and Neogene progradation of two continental margin wedges across western New Zealand.

Taranaki, Wanganui and King Country basins (formerly North Wanganui Basin) have been regarded as discrete basins, but they contain a very similar Neogene sedimentary succession and much of their geological history is held in common. Analysis of the stratigraphic architecture of the fill of each basin reveals the occurrence of four 2nd order megasequences of tectonic origin. The oldest is the early-early Miocene (Otaian Stage) Mahoenui Group/megasequence, followed by the late-early Miocene (Altonian Stage) Mokau Group/megasequence (King Country Basin), both of which correspond to the lower part of the Manganui Formation in Taranaki Basin. The third is the middle to late Miocene Whangamomona Group/megasequence, and the fourth is the latest Miocene-Pleistocene Rangitikei Supergroup/megasequence, both represented in the three basins. Higher order sequences (4th, 5th, 6th), having a eustatic origin, are evident in the Whangamomona and Rangitikei megasequences, particularly those of 5th order with 41 ka periodicity. The distribution of the megasequences are shown in a series of cross-section panels built-up from well -to-well correlations, complemented by time-stratigraphic cross-sections. The base of each megasequence is marked by marine flooding and represents a discrete phase in basin development. For the first megasequence this corresponded to rapid subsidence of the King Country Basin in a compressional setting and basement overthrusting on the Taranaki Fault, with the rapid introduction of terrigenous sediment during transgression. The Mahoenui megasequence accumulated mostly at bathyal depths; no regressive deposits are evident, having been eroded during subsequent uplift. The second (Mokau) megasequence accumulated during reverse movement on the Ohura Fault, formation of the Tarata Thrust Zone, and onlap of the basement block between the Taranaki Fault and the Patea-Tongaporutu-Herangi High (PTH). The Whangamomona megasequence accumulated during extensive reflooding of King Country Basin, onlap of the PTH High and of basement in the Wanganui Basin. This is an assymetrical sequence with a thin transgressive part (Otunui Formation) and a thick regressive part (Mount Messenger to Matemateaonga Formations). It represents the northward progradation of a continental margin wedge with bottom-set, slope-set and top-set components through Wanganui and King Country basins, with minor progradation over the PTH High and into Taranaki Basin. The Rangitikei megasequence is marked by extensive flooding at its base (Tangahoe Mudstone) and reflects the pull-down of the main Wanganui Basin depocentre. This megasequence comprises a second progradational margin wedge, which migrated on two fronts, one northward through Wanganui Basin and into King Country Basin, and a second west of the PTH High, through the Toru Trough and into the Central and Northern Grabens of Taranaki Basin and on to the Western Platform as the Giant Foresets Formation, thereby building up the modern shelf and slope. Fifth and 6th order sequences are well expressed in the shelf deposits (top-sets) of the upper parts of the Whangamomona and Rangitikei megasequences. They typically have a distinctive sequence architecture comprising shellbed (TST), siltstone (HST) and sandstone (RST) beds. Manutahi-1, which was continuously cored, provides calibration of this sequence architecture to wireline log character, thereby enabling shelf deposits to be mapped widely in the subsurface via the wireline data for hydrocarbon exploration holes. Similar characterization of slope-sets and bottom-sets is work ongoing. The higher order (eustatic) sequences profoundly influenced the local reservoir architecture and seal properties of formations, whereas the megasequence progradation has been responsible for the regional hydrocarbon maturation and migration. Major late tilting, uplift and erosion affected all three basins and created a regional high along the eastern Margin of Taranaki Basin, thereby influencing the migration paths of hydrocarbons sourced deeper in the basin and allowing late charge of structural and possibly stratigraphic traps

A reconceptualization of fear of failure in entrepreneurship

Fear of failure both inhibits and motivates entrepreneurial behavior and therefore represents a rich opportunity for better understanding entrepreneurial motivation. Although considerable attention has been given to the study of fear of failure in entrepreneurship, scholars in this field have investigated this construct from distinct disciplinary perspectives. These perspectives use definitions and measures of fear of failure that are potentially in conflict and are characterized by a static approach, thereby limiting the validity of existing findings about the relationship between fear of failure and entrepreneurship. The purpose of this paper is to delineate more precisely the nature of fear of failure within the entrepreneurial setting. Using an exploratory and inductive qualitative research design, we frame this construct in terms of socially situated cognition by adopting an approach that captures a combination of cognition, affect and action as it relates to the challenging, uncertain, and risk-laden experience of entrepreneurship. In so doing, we provide a unified perspective of fear of failure in entrepreneurship in order to facilitate progress in understanding its impact on entrepreneurial action and outcomes