Reactivity of bis(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopent-1-yl)tin with CO(2), OCS, and CS(2) and comparison to that of bis[bis(trimethylsilyl)amido]tin

The heterocumulenes carbon dioxide (CO(2)), carbonyl sulfide (OCS), and carbon disulfide (CS(2)) were treated with bis(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopent-1-yl)tin {[(CH(2))Me(2)Si](2)N}(2)Sn, an analogue of the well-studied bis[bis(trimethylsilyl)amido]tin species [(Me(3)Si)(2)N](2)Sn, to yield an unexpectedly diverse product slate. Reaction of {[(CH(2))Me(2)Si](2)N}(2)Sn with CO(2) resulted in the formation of 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane, along with Sn(4)(μ(4)-O){μ(2)-O(2)CN[SiMe(2)(CH(2))(2)]}(4)(μ(2)-N═C═O)(2) as the primary organometallic Sn-containing product. The reaction of {[(CH(2))Me(2)Si](2)N}(2)Sn with CS(2) led to formal reduction of CS(2) to [CS(2)](2-), yielding [{[(CH(2))Me(2)Si](2)N}(2)Sn](2)CS(2){[(CH(2))Me(2)Si](2)N}(2)Sn, in which the [CS(2)](2-) is coordinated through C and S to two tin centers. The product [{[(CH(2))Me(2)Si](2)N}(2)Sn](2)CS(2){[(CH(2))Me(2)Si](2)N}(2)Sn also contains a novel 4-membered Sn-Sn-C-S ring, and exhibits a further bonding interaction through sulfur to a third Sn atom. Reaction of OCS with {[(CH(2))Me(2)Si](2)N}(2)Sn resulted in an insoluble polymeric material. In a comparison reaction, [(Me(3)Si)(2)N](2)Sn was treated with OCS to yield Sn(4)(μ(4)-O)(μ(2)-OSiMe(3))(5)(η(1)-N═C═S). A combination of NMR and IR spectroscopy, mass spectrometry, and single crystal X-ray diffraction were used to characterize the products of each reaction. The oxygen atoms in the final products come from the facile cleavage of either CO(2) or OCS, depending on the reacting carbon dichalogenide.     

Synthesis of azepino[3,4b]indoles via the Plancher rearrangement

The reaction of benzyl 3-formylpiperidine-1-carboxylate and aryl hydrazines under standard Fisher Indole conditions followed by reductive work-up affords azepino[3,4b]indoles in moderate to good yields. The products are proposed to be derived via a Plancher rearrangement [(a) Plancher, G. Gazz. Chim. Ital. 1898, 28, II, 374; (b) Plancher, G. Atti. Accad.Lincei1900, 9, 5, 115; (c) Boyd-Barrett, H. S. J. Chem. Soc.1932, 321].     

Extreme nonlinear optical enhancement in chalcogenide glass fibers with deep-subwavelength metallic nanowires

A nanostructured chalcogenide-metal optical fiber is proposed. This hybrid nanofiber is embedded with a periodic array of triangular-shaped deep-subwavelength metallic nanowires set up in a bowtie configuration. Our simulations show that the proposed nanostructured fiber supports a guided plasmonic mode enabling both subwavelength field confinement and extreme nonlinear light-matter interactions, much larger than a bare chalcogenide nanowire of comparable diameter. This is all achieved with less than 3% by volume of metal content.     

A multi-objective genetic algorithm for robust flight scheduling using simulation

Traditional methods of developing flight schedules generally do not take into consideration disruptions that may arise during actual operations. Potential irregularities in airline operations such as equipment failure are not adequately considered during the planning stage of a flight schedule. As such, flight schedules cannot be met as planned and their performance is compromised, which may eventually lead to huge losses in revenue for airlines. In this paper, we seek to improve the robustness of a flight schedule by re-timing its departure times. The problem is modeled as a multi-objective optimization problem, and a multi-objective genetic algorithm (MOGA) is developed to solve the problem. To evaluate flight schedules, SIMAIR 2.0, a simulation model which simulates airline operations under operational irregularities, has been employed. The simulation results indicate that we are able to develop schedules with better operation costs and on-time performance through the application of MOGA.     

Co-ordinating Two Searchers for an Object Hidden on an Interval

Two unit-speed searchers starting at 0 seek a stationary target hidden according to a known bounded symmetric distribution. The objective is to minimize the expected time for the searchers to return to 0 after one of them has found the target. We find a general optimality condition and use it to solve the problem when the target has a uniform, triangular, or truncated, exponential distribution. The problem has applications to parallel processing and to the optimal choice of drilling depths in the search for an underground mineral.     

Home to School: Numeracy Practices and Mathematical Identities

Drawing on a perspective of mathematics as situated social practice, we focus on 4 children in an urban preschool classroom and follow those children between home and school sites to shed light on urban children's persistent underachievement in mathematics. In this article, we describe the ways in which numeracy practices travel with children between home and school and, within those contexts, shape complex and sometimes limited social identities for children. We found that school imperatives, such as assessments and socialization curricula, often obscure teachers' views of children's mathematical practices. Deficit assumptions about family and community support for children, and limited interaction between caregivers and teachers, further contribute to the tendency of school personnel to overlook the mathematical practices that children bring with them to school. We further suggest that vignettes drawn from ethnographic-type research such as this have potential for professional development for classroom teachers.     

A new ent-clerodane diterpenoid from Crassocephalum bauchiense Huch. (Asteraceae)

A phytochemical investigation of the whole plant of Crassocephalum bauchiense Huch. resulted in the isolation of a new clerodane diterpenoid, ent-2β,18,19-trihydroxycleroda-3,13-dien-16,15-olide (1), together with two known flavonoids 3′,5-dihydroxy-4′,5′,6,7,8-pentamethoxyflavone (2) and 4′,5-dihydroxy-3′,5′,6,7,8-pentamethoxyflavone (3). The compounds were tested against the chloroquine-sensitive 3D7 strain of Plasmodium falciparum. Compound 2 showed weak activity (IC₅₀ = 10.1 g/mL) whilst compounds 1 and 3 were inactive. The structures of the compounds were elucidated by using detailed spectral analyses, especially ¹H and ¹³C NMR, ¹H–¹H COSY, NOESY, HMBC and HR-ESI-MS.     

A REVIEW OF POLAR STRATOSPHERIC CLOUD FORMATION

Liquid and solid particles in polar stratospheric clouds （PSCs） have been known to play a crucial role in the chemical loss of stratospheric ozone over the Antarctic and Arctic regions in late winter and early spring. The stratospheric aerosol and cloud particles provide the sites where fast heterogeneous chemical reactions convert inactive halogen reservoir species into potential ozone destroying radicals. The sedimentation of nitric acid-containing PSC particles irreversibly removes HNO3 gas （denitrification） from the lower stratosphere, which slows the return of chlorine to its inactive forms, resulting in more severe stratospheric ozone destruction. Although these clouds have been investigated extensively during the past decade using in situ field observation, laboratory experiment and modeling studies, the detailed microphysics processes under cold stratospheric conditions are still uncertain. This paper reviews the recent advances in our understanding of PSCs.