Mono- and Dialkyne Insertion Reactions of Cyclopalladated N,N `,N `'-Triarylguanidines kappa(2)(C,N)Pd(mu-Br)](2) and cis-/trans-kappa(2)(C,N)Pd(Lewis Base)Br]. Scaffolds for Enlarged, Rearranged, and Zwitterionic Palladacycles through Ring Contraction cum Amine-Imine Tautomerization

Insertion reactions of six-membered cyclopalladated N,N',N''-triarylguanidines, kappa(2)(C,N)Pd(mu-Br)](2) with various alkynes in CH2Cl2 under ambient conditions afforded diinserted eight-membered palladacycles, (kappa(2)(C,N):eta(2)(C=C)-PdBr] (1-11), in high yield (76-96%), while insertion reactions of six-membered cyclopalladated N,N',N''-triarylguanidines, kappa(2)(C,N)Pd(Lewis base)Br] (VI-XI), with various alkynes under the aforementioned conditions afforded monoinserted six-membered palladacycles, kappa(2)(C,N)-Pd(Lewis base)Br] (12-21), in high yield (81-91%) except for 14 (23%). The insertion reaction of VI with 2 equiv of dimethyl acetylenedicarboxylate (DMAD) and the insertion reaction of 12 with 1 equiv of DMAD in CH2Cl2 under ambient conditions resulted in the formation of a diinserted zwitterionic five-membered palladacycle, kappa(2)(C,C)Pd(2,6-lutidine)Br] (22), in 76% and 70% yields, respectively. Palladacycle 22 upon reaction with AgOTf in wet MeCN afforded the ionic palladacycle kappa(2)(C,C)Pd(2,6-lutidine)(H2O)]OTf] (23) in 78% yield. The ring size of the ``kappa(2)(C,N)Pd]'' unit in the structurally characterized diinserted palladacycles (1 center dot 2CH(2)Cl(2)center dot H2O, 2, 5, and 7), and monoinserted palladacycles (17, 18, and 20 center dot C7H8 H2O) is smaller than that anticipated for mono- and diinserted palladacycles, and this feature is mainly ascribed to the proclivity of III-XI to undergo ring contraction cum amine-imine tautomerization upon alkyne insertion. Palladacycle 22 represents the first diinserted product obtained in alkyne insertion reactions of kappa(2)(C,N)Pd(Lewis base)X] type palladarycles. The molecular structure of 22 center dot H2O determined by X-ray diffraction indicates that the positive charge on the guanidinium moiety is balanced by the negative charge on the palladium atom and thus represents the first structurally characterized zwitterionic palladacycle to be reported in alkyne insertion chemistry. Plausible mechanisms of formation of 12-21 and 22 have been outlined. The presence of more than one species in solution for some of the palladacycles in the series 1-7 and 12-21 was explained by invoking the C-N single-bond rotation of the CN3 unit of the guanidine moiety, while this process in conjunction with Pd-N(lutidine) bond rotation was invoked to explain the presence of four isomers of 15, as studied with the aid of variable-concentration H-1 NMR experiments carried out for 14 and 15.

An inhomogeneous multispecies TASEP on a ring

We reinterpret and generalize conjectures of Lam and Williams as statements about the stationary distribution of a multispecies exclusion process on the ring. The central objects in our study are the multiline queues of Ferrari and Martin. We make some progress on some of the conjectures in different directions. First, we prove Lam and Williams' conjectures in two special cases by generalizing the rates of the Ferrari-Martin transitions. Secondly, we define a new process on multiline queues, which have a certain minimality property. This gives another proof for one of the special cases; namely arbitrary jump rates for three species. (C) 2014 Elsevier Inc. All rights reserved.

Molecular topology of three ring nematogens from C-13-H-1 dipolar couplings

Molecules in their liquid crystalline phase undergo rotational motion about the long axis of the molecule and the shape adopted by the rotating molecule plays an important role in influencing the mesophase morphology. In this context, obtaining the topology and the relative orientation of the different sub-units are important steps. For studying the liquid crystalline phase, C-13 NMR spectroscopy is a convenient method and for certain specifically designed nematogens, 2-dimensional separated local field (2D-SLF) NMR spectroscopy provides a particularly simple and straightforward means of arriving at the molecular topology. We demonstrate this approach on two three ring based nematogens designed with a phenyl or a thiophene ring at one of the termini. From the C-13-H-1 dipolar couplings of the terminal carbon obtained using the 2D-SLF NMR technique, the order parameter of the local symmetry axis of the terminal phenyl ring as well as of the long molecular axis could be easily estimated. For the thiophene nematogen, the lack of symmetry of the thiophene moiety necessitates some additional computational steps. The results indicate that the thiophene unit has its local ordering axis oriented away from the long molecular axis by a small angle, consistent with a bent structure expected in view of the thiophene geometry. The experiment also demonstrates the ability of 2D-SLF NMR to provide high resolution spectra by separation of several overlapped resonances in terms of their C-13-H-1 dipolar couplings. The results are consistent with a rod-like topology of the core of the investigated mesogens. The investigation demonstrates the potential of 2D-SLF NMR C-13 spectroscopy for obtaining atomistic level information and its utility for topological studies of different mesogens.

Formation of annular austenitic ring between outer ferrite layer and solid globule in a semi-solid processed SS 304L

The microstructure of an austenitic SS 304L rapidly quenched from its semi-solid state shows a unique annular austenitic ring in between the core of each globule and its ferritic outer layer. On the basis of experimental results and microstructural analysis, it is proposed that the ring is formed as a result of preferential austenitic phase nucleation in a small quantity of liquid entrapped between adjacent solid globules during rapid quenching, in spite of the fact that ferrite is the thermodynamically stable phase for the alloy. (C) 2014 Elsevier B.V. All rights reserved.

An Unusual Ring-Contraction/Rearrangement Sequence for Making Functionalized Di- and Triquinanes

A novel ring contraction/rearrangement sequence leading to functionalized 2,8-oxymethano-bridged di- and triquinane compounds is observed in the reaction of various substituted 1-methyl-4-isopropenyl-6-oxabicylo3.2.1]octan-8-ones with Lewis acids. The reaction is novel and is unprecedented for the synthesis of di- and triquinane frameworks.

An Unusual Ring-Contraction/Rearrangement Sequence for Making Functionalized Di- and Triquinanes

A novel ring contraction/rearrangement sequence leading to functionalized 2,8-oxymethano-bridged di- and triquinane compounds is observed in the reaction of various substituted 1-methyl-4-isopropenyl-6-oxabicylo3.2.1]octan-8-ones with Lewis acids. The reaction is novel and is unprecedented for the synthesis of di- and triquinane frameworks.

An Unusual Ring-Contraction/Rearrangement Sequence for Making Functionalized Di- and Triquinanes

A novel ring contraction/rearrangement sequence leading to functionalized 2,8-oxymethano-bridged di- and triquinane compounds is observed in the reaction of various substituted 1-methyl-4-isopropenyl-6-oxabicylo3.2.1]octan-8-ones with Lewis acids. The reaction is novel and is unprecedented for the synthesis of di- and triquinane frameworks.

Tetrathiomolybdate-Mediated Ring Opening of Isatoic Anhydrides: An Entry to S-Alkyl or S-Aryl 2-Aminobenzenecarbothioate Derivatives

Decarboxylative thioesterification of isatoic anhydrides mediated by benzyl(triethyl)ammonium tetrathiomolybdate gave the corresponding S-alkyl or S-aryl 2-aminobenzenecarbothioate derivatives at 60 degrees C. At ambient temperature, organic disulfides were reductive cleaved in the presence of tetrathiomolybdate to generate thiolate anions in situ; this was followed by attack on isatoic anhydrides to give the corresponding S-alkyl or S-aryl 2-aminobenzenecarbothioate derivatives. Additionally, it was shown that multistep reactions could be performed with tetrathiomolybdate, starting with an alkyl halide as a precursor of an alkyl disulfide, which, in turn, was used for ring opening of isatoic anhydrides.

One-pot synthesis of functionalized beta-amino sulfides/beta-amino selenides via ring opening of cyclic sulfamidates

A number of functionalized beta-amino and gamma-amino sulfides and selenides have been synthesized involving a one-pot process of ring opening of cyclic sulfamidates with `in situ' generated thiolate and selenoate species from diaryl disulfides and diphenyl diselenide using rongalite. A mild and efficient method has been developed for the synthesis of cysteines from serine.

MEMS Tunable Optical Filter Based on Multi-Ring Resonator

We propose a novel MEMS tunable optical filter with a flat-top pass band based on multi-ring resonator in an electrostatically actuated microcantilever for communication application. The filter is basically structured on a microcantilever beam and built in optical integrated ring resonator which is placed in one end of the beam to gain maximum stress on the resonator. Thus, when a DC voltage is applied, the beam will bend, that induces a stress and strain in the ring, which brings a change in refractive index and perimeter of the rings leading to change in the output spectrum shift, providing the tenability as high as 0.68nm/mu N. and it is capable of tuning up to 1.7nm.

Sphere to ring morphological transformation in drying nanofluid droplets in a contact-free environment

Understanding the transients of buckling in drying colloidal suspensions is pivotal for producing new functional microstructures with tunable morphologies. Here, we report first observations and elucidate the buckling instability induced morphological transition (sphere to ring structure) in an acoustically levitated, heated nanosuspension droplet using dynamic energy balance. Droplet deformation featuring the formation of symmetric cavities is initiated by capillary pressure that is two to three orders of magnitude greater than the acoustic radiation pressure, thus indicating that the standing pressure field has no influence on the buckling front kinetics. With an increase in heat flux, the growth rate of surface cavities and their post-buckled volume increase while the buckling time period reduces, thereby altering the buckling pathway and resulting in distinct precipitate structures. However, irrespective of the heating rate, the volumetric droplet deformation exhibits a linear time dependence and the droplet vaporization is observed to deviate from the classical D-2-law.

A Mild Protocol for the Regioselective Ring Opening of Doubly Activated Cyclopropanes by Using Selenolates Generated in Situ: Synthesis of Functionalized Organoselenium Compounds

A variety of functionalized organoselenium compounds were synthesized from doubly activated cyclopropanes and diselenides in the presence of sodium borohydride. A range of substituents were stable under these reaction conditions. Additionally, we extended the scope of the method by reducing nitro groups in the products to give the corresponding selenium-containing unnatural amino acids.

Interaction of a vortex ring with a single bubble: bubble and vorticity dynamics

The interaction of a single bubble with a single vortex ring in water has been studied experimentally. Measurements of both the bubble dynamics and vorticity dynamics have been done to help understand the two-way coupled problem. The circulation strength of the vortex ring (Gamma) has been systematically varied, while keeping the bubble diameter (D-b) constant, with the bubble volume to vortex core volume ratio (V-R) also kept fixed at about 0.1. The other important parameter in the problem is a Weber number based on the vortex ring strength. (We = 0.87 rho(Gamma/2 pi a)(2)/(sigma/D-b); a = vortex core radius, sigma = surface tension), which is varied over a large range, We = 3-406. The interaction between the bubble and ring for each of the We cases broadly falls into four stages. Stage I is before capture of the bubble by the ring where the bubble is drawn into the low-pressure vortex core, while in stage II the bubble is stretched in the azimuthal direction within the ring and gradually broken up into a number of smaller bubbles. Following this, in stage III the bubble break-up is complete and the resulting smaller bubbles slowly move around the core, and finally in stage IV the bubbles escape. Apart from the effect of the ring on the bubble, the bubble is also shown to significantly affect the vortex ring, especially at low We (We similar to 3). In these low-We cases, the convection speed drops significantly compared to the base case without a bubble, while the core appears to fragment with a resultant large decrease in enstrophy by about 50 %. In the higher-We cases (We > 100), there are some differences in convection speed and enstrophy, but the effects are relatively small. The most dramatic effects of the bubble on the ring are found for thicker core rings at low We (We similar to 3) with the vortex ring almost stopping after interacting with the bubble, and the core fragmenting into two parts. The present idealized experiments exhibit many phenomena also seen in bubbly turbulent flows such as reduction in enstrophy, suppression of structures, enhancement of energy at small scales and reduction in energy at large scales. These similarities suggest that results from the present experiments can be helpful in better understanding interactions of bubbles with eddies in turbulent flows.

Tandem aziridine ring opening-disulfide formation-reduction-Michael addition in one-pot mediated by tetrathiomolybdate

A detailed study of tetrathiomolybdate mediated tandem regio- and stereoselective ring opening of aziridine, disulfide formation, reduction of disulfide bond and Michael reaction in a one-pot operation is reported. This constitutes four reactions that take place in one-pot operation. In the reaction of BnEt3N](4)MoS4 with an aziridine derived from cyclohexene and in the absence of Michael acceptor intermediates sulfonamidodisulfide and sulfonamidothiol were isolated and fully characterized. It has also been shown that it is possible to carry out selective opening of the aziridine ring in the presence of an epoxide. By incorporating a suitable Michael acceptor as part of the substrate, intramolecular 1,4-addition could be performed, to achieve the synthesis of sulfur containing acyclic, cyclic amino acid ester derivatives and thia-bicyclo3.3.1]nonane derivatives in good yields. (C) 2015 Elsevier Ltd. All rights reserved.

Bearing Capacity Factors for Ring Foundations

Bearing capacity factors because of the components of cohesion, surcharge, and unit weight, respectively, have been computed for smooth and rough ring footings for different combinations of r(i)= r(o) and. by using lower and upper bound theorems of the limit analysis in conjunction with finite elements and linear optimization, where r(i) and r(o) refer to the inner and outer radii of the ring, respectively. It is observed that for a smooth footing with a given value of r(o), the magnitude of the collapse load decreases continuously with an increase in r(i). Conversely, for a rough base, for a given value of r(o), hardly any reduction occurs in the magnitude of the collapse load up to r(i)= r(o) approximate to 0.2, whereas for r(i)= r(o) > 0.2, the magnitude of the collapse load, similar to that of a smooth footing, decreases continuously with an increase in r(i)= r(o). The results from the analysis compare reasonably well with available theoretical and experimental data from the literature. (C) 2015 American Society of Civil Engineers.