A new class of ammonium ylid for [2,3]-sigmatropic rearrangement reactions: ene-endo-spiro ylids

The first examples of sigmatropic rearrangements of ene-endo-spirocyclic, tetrahydropyridine-derived ammonium ylids are reported. Thus, spiro[6.7]-ylids rearrange primarily by a [2,3]-pathway, whereas the analogous [6.6]-ylids rearrange by [1,2]- and [2,3]-mechanisms in roughly equal proportions. This method serves as a rapid entry to the core of a range of alkaloids bearing a pyrrolo[1,2-a]azepine or octahydroindolizidine nucleus.

Spin-canted antiferromagnetic phase transitions in alternating phenoxo- and carboxylato-bridged Mn(III)-salen complexes

Three new MnIII complexes, {[Mn-2(salen)(2)(OCn)](ClO4)}(n) (1), {[Mn-2(salen)(2)(OPh)](ClO4)}(n) (2) and {[Mn-2(salen)(2)(OBz)](ClO4)}(2) (3) (where salen = N,N'-bis(salicylidene)-1,2-diaminoethane dianion, OCn = cinnamate, OPh = phenylacetate and OBz = benzoate), have been synthesized and characterized structurally and magnetically. The crystal structures reveal that all three structures contain syn-anti carboxylatebridged dimeric [Mn-2(salen)(2)(OOCR)](+) cations (OOCR = bridging carboxylate) that are joined together by weak Mn center dot center dot center dot O(phenoxo) interactions to form infinite alternating chain structures in 1 and 2, but the relatively long Mn center dot center dot center dot O(phenoxo) distance [3.621(2)angstrom] in 3 restricts this structure to tetranuclear units. Magnetic studies showed that 1 and 2 exhibited magnetic long-range order at T-N = 4.0 and 4.6 K (T-N = Neel transition temperature), respectively, to give spin-canted antiferromagnetic structures. Antiferromagnetic coupling was also observed in 3 but no peaks were recorded in the field-cooled magnetization (FCM) or zero-field-cooled magnetization (ZFCM) data, indicating that 3 remained paramagnetic down to 2 K. This dominant antiferromagnetic coupling is attributed to the carboxylate bridges. The ferromagnetic coupling expected due to the Mn-O(phenoxo)center dot center dot center dot Mn bridge plays an auxiliary role in the magnetic chain, but is an essential component of the bulk magnetic properties of the material.

Sodomy laws and gender variance in Tahiti and Hawai‘i

In both Hawaiian and Tahitian, the central meaning of mahu denotes gender-variant individuals, particularly male-bodied persons who have a significant investment in femininity. However, in Hawai‘i, unlike Tahiti, the word mahu is now more commonly used as an insult against gay or transgender people. The negative connotation of the term in Hawaiian indexes lower levels of social acceptability for mahu identity on O‘ahu (Hawai‘i’s most populous island) as compared to Tahiti. The article argues that these differences are partly due to a historical legacy of sexually repressive laws. The article traces the history of sodomy laws in these two Polynesian societies and argues that this history supports the hypothesis that sodomy laws (in conjunction with such social processes as urbanisation and Christianisation) are partially to blame for the diminished social status of mahu on O‘ahu. A different social and legal history in Tahiti accounts for the fact that the loss of social status experienced by Tahitian mahu has been lesser than that of their Hawaiian counterparts.

Enhanced biodiversity and pollination in UK agroforestry systems

Monoculture farming systems have had serious environmental impacts such as loss of biodiversity and pollinator decline. The authors explain how temperate agroforestry systems show potential in being able to deliver multiple environmental benefits.

Considering the Feasibility of Semantic Model Design in the Built-Environment

Building Information Modeling (BIM) is the process of structuring, capturing, creating, and managing a digital representation of physical and/or functional characteristics of a built space [1]. Current BIM has limited ability to represent dynamic semantics, social information, often failing to consider building activity, behavior and context; thus limiting integration with intelligent, built-environment management systems. Research, such as the development of Semantic Exchange Modules, and/or the linking of IFC with semantic web structures, demonstrates the need for building models to better support complex semantic functionality. To implement model semantics effectively, however, it is critical that model designers consider semantic information constructs. This paper discusses semantic models with relation to determining the most suitable information structure. We demonstrate how semantic rigidity can lead to significant long-term problems that can contribute to model failure. A sufficiently detailed feasibility study is advised to maximize the value from the semantic model. In addition we propose a set of questions, to be used during a model’s feasibility study, and guidelines to help assess the most suitable method for managing semantics in a built environment.

Ant larval demand reduces aphid colony growth rates in an ant-aphid interaction

Ants often form mutualistic interactions with aphids, soliciting honeydew in return for protective services. Under certain circumstances, however, ants will prey upon aphids. In addition, in the presence of ants aphids may increase the quantity or quality of honeydew produced, which is costly. Through these mechanisms, ant attendance can reduce aphid colony growth rates. However, it is unknown whether demand from within the ant colony can affect the ant-aphid interaction. In a factorial experiment, we tested whether the presence of larvae in Lasius niger ant colonies affected the growth rate of Aphis fabae colonies. Other explanatory variables tested were the origin of ant colonies (two separate colonies were used) and previous diet (sugar only or sugar and protein). We found that the presence of larvae in the ant colony significantly reduced the growth rate of aphid colonies. Previous diet and colony origin did not affect aphid colony growth rates. Our results suggest that ant colonies balance the flow of two separate resources from aphid colonies- renewable sugars or a protein-rich meal, depending on demand from ant larvae within the nest. Aphid payoffs from the ant-aphid interaction may change on a seasonal basis, as the demand from larvae within the ant colony waxes and wanes.

Design and analysis of a haptic device design for large and fast movements

Haptic devices tend to be kept small as it is easier to achieve a large change of stiffness with a low associated apparent mass. If large movements are required there is a usually a reduction in the quality of the haptic sensations which can be displayed. The typical measure of haptic device performance is impedance-width (z-width) but this does not account for actuator saturation, usable workspace or the ability to do rapid movements. This paper presents the analysis and evaluation of a haptic device design, utilizing a variant of redundant kinematics, sometimes referred to as a macro-micro configuration, intended to allow large and fast movements without loss of impedance-width. A brief mathematical analysis of the design constraints is given and a prototype system is described where the effects of different elements of the control scheme can be examined to better understand the potential benefits and trade-offs in the design. Finally, the performance of the system is evaluated using a Fitts’ Law test and found to compare favourably with similar evaluations of smaller workspace devices.