Single-molecule magnets constructed from cyanometalates: {[Tp*Fe(III)(CN)3M(II)(DMF)4]2[OTf]2} x 2DMF (M(II) = Co, Ni)

Treatment of several divalent transition-metal trifluoromethanesulfonates [M(II)(OTf)2; M(II) = Mn, Co, Ni] with [NEt4][Tp*Fe(III)(CN)3] [Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate] in DMF affords three isostructural rectangular clusters of {[Tp*Fe(III)(CN)3M(II)(DMF)4]2[OTf]2} x 2DMF (M(II) = Mn, 3; Co, 4; Ni, 5) stoichiometry. Magnetic studies of 3-5 indicate that the Tp*Fe(CN)3(-) centers are highly anisotropic and exhibit antiferromagnetic (3 and 4) and ferromagnetic (5) exchange to afford S = 4, 2, and 3 spin ground states, respectively. ac susceptibility measurements suggest that 4 and 5 exhibit incipient single-molecule magnetic behavior below 2 K.     

1,3,6,9,12,14,17,20-octaethynyltetrabenz[a,b,f,j,k,o]-4,5,10,11,15,16,21,22- octadehydro[18]annulene: a carbon-rich hydrocarbon

Dodecaynes 1a-d have been prepared via a convergent strategy that employs Sonogashira couplings as the carbon-carbon bond-forming tool. Due to the steric bulk of the DMTS groups, 1c adopts a nonplanar conformation, the dynamics of which have been probed by VT-NMR. The cobalt-catalyzed isomerization of 1a,b produced the new conjugated phenylenes 2a,b and 3a,b, respectively. [structure: see text]     

α‐Tetraphosphorus Trichalcogenide Diamides and Imides containing both Sulfur and Selenium

Reaction of a mixture of bicyclic phosphorus sulfide selenide iodides α‐P₄S_nSe_3−nI₂ (n = 0–3) with PrⁱNH₂ and Et₃N gave corresponding diamides α‐P₄S_nSe_3−n(NHPrⁱ)₂ (n = 0–3) and imides α‐P₄S_nSe_3−n(μ‐NPrⁱ) (n = 2–3), identified in solution by ³¹P NMR. In one isomer of α‐P₄S₂Se(μ‐NPrⁱ), the C₂ symmetry of imides such as α‐P₄S₃(μ‐NPrⁱ) was broken, allowing relative assignment of ²J NMR couplings to the PNP bridge and the PSP bridge opposite to it. The coupling through the sulfur bridge was found to be reduced to ca. zero, in contrast to previous assumptions for this class of compounds. Ab initio models were calculated at the MPW1PW91/svp level for the sulfide selenide imides and for a selection of bond rotamers of the diamides, and at the MPW1PW91/LanL2DZ(d) level for the sulfide selenide diiodides. Different skeletal isomers were prevalent for the mixed chalcogenide diamides than for the diiodides, showing that exchange of chalcogen between skeletal positions took place in the amination reaction even at room temperature. Similar differences to those observed were predicted by the models, suggesting that equilibrium was attained.     

A classification of subgroups of the Monster isomorphic to S4 and an application

We classify all subgroups of the Monster isomorphic to S₄. We then use this classification to prove that there are no maximal subgroups of the Monster with socles isomorphic to PSU₃(3), PSL₃(3), PSL₂(17), or PSL₂(7).     

Spatially Localized Models of Extended Systems

We investigate the construction of low-dimensional spatiallylocalized models of extended systems. Specifically, theKuramoto–Sivashinsky (KS) equation on large one-dimensional domainsdisplays spatiotemporally complex dynamics that are remarkablywell-localized in both real and Fourier space, as demonstrated by a(spline) wavelet representation. We show how wavelet projectionsmay be used to construct various localized, relativelylow-dimensional models of KS spatiotemporal chaos. There ispersuasive evidence that short, periodized systems, internally forcedat their largest scales, form minimal models for chaotic dynamics inarbitrarily large domains. Such models assist in the understandingof extended systems.     

A fibrous dynamic continuum model of the tympanic membrane

The geometry and anisotropic ultrastructure of the tympanic membrane are used in combination with curvilinear shell equations to formulate a general continuum model describing its dynamic behavior. Primary terms appearing in the model are associated with shell membrane restoring forces, bending-type structural damping, and transverse inertia. Since the model is based extensively on the physical characteristics of the membrane, it is relatively easy to account for differences between species as well as pathological conditions. The fibrous structure and cone-shaped geometry, readily apparent in mammalian eardrums, introduce several small parameters into the model that are exploited in order to construct a closed-form asymptotic solution. The solution includes the coupling to the three-dimensional motion of the ossicular chain and it includes the frequency-dependent pressure distribution in the auditory canal. When applied to the cat eardrum, this asymptotic solution is shown to reproduce a large manifold of experimentally observed frequency and excitation-dependent vibrational shapes. In addition to the shapes, transient amplitude and phase data for the cat are reproduced.     

Synthesis of simplified analogues of eleutherobin via a Claisen rearrangement/RCM strategy

The enantioselective synthesis of a number of simplified analogues of the cytotoxic natural product eleutherobin is reported.     

Microwave bonding of poly(methylmethacrylate) microfluidic devices using a conductive polymer

Component binding within microfluidic devices is a problem that has long been seeking a solution. In this investigation, the use of microwave radiation to seal PMMA components has been investigated using polyaniline as an absorber that is capable of inducting interfacial bonding. Straight microchannels were machined into PMMA using a Datron CAT3DM6 CNC machine with widths and depths across a range of 100-1000 μm. Prototype fluidic devices were prepared with channel patterns utilizing varying feature sizes, bends and flow profiling to demonstrate the application of the technique to real microfluidic devices. Experimental data illustrated the successful bonding of channels in the range stated previously and bonding (tensile) strength was assessed via pull tests on bonded PMMA using an Engstrom Zwick 100 tensile testing system (Engstrom Ltd, US). Coherent, defect free seals were attained with breakage tests requiring an excess of 1 kN force.