Self-Assembled Pd(II) Metallocycles Using an Ambidentate Donor and the Study of Square-Triangle Equilibria

The self-assembly reaction of a cis-blocked 90° square planar metal acceptor with a symmetrical linear flexible linker is expected to yield a [4 + 4] self-assembled square, a [3 + 3] assembled triangle, or a mixture of these.However, if the ligand is a nonsymmetrical ambidentate, it is expected to form a complex mixture comprising several linkage isomeric squares and triangles as a result of different connectivities of the ambidentate linker. We report instead that the reaction of a 90° acceptor cis-(dppf)Pd(OTf)2 [where dppf ) 1,1′-bis(diphenylphosphino)- ferrocene] with an equimolar amount of the ambidentate unsymmetrical ligand Na-isonicotinate unexpectedly yields a mixture of symmetrical triangles and squares in the solution. An analogous reaction using cis-(tmen)Pd(NO3)2 instead of cis-(dppf)Pd(OTf)2 also produced a mixture of symmetrical triangles and squares in the solution. In both cases the square was isolated as the sole product in the solid state, which was characterized by a single crystal structure analysis. The equilibrium between the triangle and the square in the solution is governed by the enthalpic and entropic contributions. The former parameter favors the formation of the square due to less strain in the structure whereas the latter one favors the formation of triangles due to the formation of more triangles from the same number of starting linkers. The effects of temperature and concentration on the equilibria have been studied by NMR techniques. This represents the first report on the study of square-triangle equilibria obtained using a nonsymmetric ambidentate linker. Detail NMR spectroscopy along with the ESI-mass spectrometry unambiguously identified the components in the mixture while the X-ray structure analysis determined the solid-state structure.

Unsteady Natural Convection Flow in a Square Cavity Filled with a Porous Medium Due to Impulsive Change in Wall Temperature

Unsteady natural convection flow in a two- dimensional square cavity filled with a porous material has been studied. The flow is initially steady where the left- hand vertical wall has temperature T-h and the right- hand vertical wall is maintained at temperature T-c ( T-h > T-c) and the horizontal walls are insulated. At time t > 0, the left- hand vertical wall temperature is suddenly raised to (T-h) over bar ((T-h) over bar > T-h) which introduces unsteadiness in the flow field. The partial differential equations governing the unsteady natural convection flow have been solved numerically using a finite control volume method. The computation has been carried out until the final steady state is reached. It is found that the average Nusselt number attains a minimum during the transient period and that the time required to reach the final steady state is longer for low Rayleigh number and shorter for high Rayleigh number.

Low PAPR Square STBCs from Complex Partial-Orthogonal Designs (CPODs)

Space-time codes from complex orthogonal designs (CODs) with no zero entries offer low Peak to Average Power Ratio (PAPR) and avoid the problem of switching off antennas. But square CODs for 2(a) antennas with a + 1. complex variables, with no zero entries were discovered only for a <= 3 and if a + 1 = 2(k), for k >= 4. In this paper, a method of obtaining no zero entry (NZE) square designs, called Complex Partial-Orthogonal Designs (CPODs), for 2(a+1) antennas whenever a certain type of NZE code exists for 2(a) antennas is presented. Then, starting from a so constructed NZE CPOD for n = 2(a+1) antennas, a construction procedure is given to obtain NZE CPODs for 2n antennas, successively. Compared to the CODs, CPODs have slightly more ML decoding complexity for rectangular QAM constellations and the same ML decoding complexity for other complex constellations. Using the recently constructed NZE CODs for 8 antennas our method leads to NZE CPODs for 16 antennas. The class of CPODs do not offer full-diversity for all complex constellations. For the NZE CPODs presented in the paper, conditions on the signal sets which will guarantee full-diversity are identified. Simulation results show that bit error performance of our codes is same as that of the CODs under average power constraint and superior to CODs under peak power constraint.

Lower-bound collapse load Of square footing

Based on a radial moment field and the square yield criterion, a lower-bound collapse load is developed for a square footing subjected to a generalized contact pressure distribution. The current lower-bound collapse load compares well with the available upper-bound solutions.

Bearing capacity of square footings on geosynthetic reinforced sand

The results from laboratory model tests and numerical simulations on square footings resting on sand are presented. Bearing capacity of footings on geosynthetic reinforced sand is evaluated and the effect of various reinforcement parameters like the type and tensile strength of geosynthetic material, amount of reinforcement, layout and configuration of geosynthetic layers below the footing on the bearing capacity improvement of the footings is studied through systemati model studies. A steel tank of size 900 x 900 x 600 mm is used for conducting model tests. Four types of grids, namely strong biaxial geogrid, weak biaxial geogrid, uniaxial geogrid and a geonet, each with different tensile strength, are used in the tests. Geosynthetic reinforcement is provided in the form of planar layers, varying the depth of reinforced zone below the footing, number of geosynthetic layers within the reinforced zone and the width of geosynthetic layers in different tests. Influence of all these parameters on the bearing capacity improvement of square footing and its settlement is studied by comparing with the test on unreinforced sand. Results show that the effective depth of reinforcement is twice the width of the footing and optimum spacing of geosynthetic layers is half the width of the footing. It is observed that the layout and configuration of reinforcement play a vital role in bearing capacity improvement rather than the tensile strength of the geosynthetic material. Experimental observations are supported by the findings from numerical analyses.

Self-assembly of three new coordination complexes: Formation of 2-D square grid, 1-D chain and tape structures

Three distinct coordination complexes, viz., [Co(imi)(2)(tmb)(2)] (1) [where imi = imidazole], {[Ni(tmb)(2)(H2O)(3)]center dot 2H(2)O}(n) (2) and [Cu-2(mu-tmb)(4)(CH3OH)(2)] (3), have been synthesized hydrothermally by the reactions of metal acetates,2,4,6-trimethylbenzoic acid (Htmb) and with or without appropriate amine. The Ni analogue of 1 and the Co analogue of 2 have also been synthesized. X-ray single-crystal diffraction suggests that complex 1 represents discrete mononuclear species and complex 2 represents a 1D chain coordination polymer in which the Ni(H) ions are connected by the bridging water molecules. Complex 3 represents a neutral dinuclear complex. In 1, the central metal ions are associated by the carboxylate moiety and imidazole ligands, whereas the central metal atom is coordinated to the carboxylate moiety and the respective solvent molecules in 2 and 3. In 3, the four 2,4,6-trimethylbenzoate moieties act as a bridge connecting two copper (11) ions and the 0 atoms of methanol coord geometry, with the methanol molecule at the apical position. In all the three structures the central metal atom sits on a crystallographic inversion centre. In all the cases, the coordination entities are further organized via hydrogen bonding interactions to generate multifarious supramolecular networks. Complexes 1, 2 and 3 have also been characterized by spectroscopic (UV/Vis and IR) and thermal analysis (TGA). In addition, the complexes were found to exhibit antimicrobial activity. The magnetic susceptibility measurements, measured from 8 to 300 K, revealed antiferromagnetic interactions between the Co(II) ions in compound 1 and the Ni(II) ions in la, respectively.

Analysis of two degrees of freedom systems through weighted mean square linearization approach

In this paper a study of the free, forced and self-excited vibrations of non-linear, two degrees of freedom systems is reported. The responses are obtained by linearizing the nonlinear equations using the weighted mean square linearization approach. The scope of this approach, in terms of the type of non-linearities the method can tackle, is also discussed.

Analysis of two degrees of freedom systems through weighted mean square linearization approach

In this paper a study of the free, forced and self-excited vibrations of non-linear, two degrees of freedom systems is reported. The responses are obtained by linearizing the nonlinear equations using the weighted mean square linearization approach. The scope of this approach, in terms of the type of non-linearities the method can tackle, is also discussed.

Analysis of vibration of clamped square plates by the Rayleigh-Ritz method with asymptotic solutions from a modified Bolotin method

Estimates of flexural frequencies of clamped square plates are initially obtained by the modified Bolotin's method. The mode shapes in “each direction” are then determined and the product functions of these mode shapes are used as admissible functions in the Rayleigh-Ritz method. The data for the first twenty eigenvalues in each of the three (four) symmetric groups obtained by the (i) Bolotin, (ii) Rayleigh and (iii) Rayleigh-Ritz methods are reported here. The Rayleigh estimates are found to be much closer to the true eigenvalues than the Bolotin estimates. The present product functions are found to be much superior to the conventional beam eigenmodes as admissible functions in the Rayleigh-Ritz method of analysis.

Flexural Strength of Modified Square Footings

The ultimate flexural strength behavior of isolated square tapered and beam-slab reinforced footings are presented. Yield line solutions are developed for generalized contact pressure distributions and the influence of taper, beam size, fillet size, negative moment capacity, and contact pressure distribution on the collapse load is brought out. In beam-slab footings the optimum relative beam capacity required to make the beam rigid is indicated. Results of experimental investigations on footings resting on sand reveal that tapered (with isotropic as well as with alternative reinforcement patterns) and beam-slab footings exhibit superior structural behavior in terms of normalized first crack load, collapse load, relative rigidity, relative efficiency, and failure mechanism.

Effect of metal coating and residual stress on the resonant frequency of MEMS resonators

MEMS resonators are designed for a fixed resonant frequency. Therefore, any shift in the resonant frequency of the final fabricated structure can be a denting factor for its suitability towards a desired application. There are numerous factors which alter the designed resonant frequency of the fabricated resonator such as the metal layer deposited on top of the beam and the residual stresses present in the fabricated structure. While the metal coating, which acts as electrode, increases the stiffness and the effective mass of the composite structure, the residual stress increases or decreases the net stiffness if it is a tensile or compressive type respectively. In this paper, we investigate both these cases by taking two different structures, namely, the micro cantilever beam with gold layer deposited on its top surface and the MEMS gyroscope with residual stresses. First, we carry out experiments to characterize both these structures to find their resonant frequencies. Later, we analytically model those effects and compare them with the experimentally obtained values. Finally, it is found that the analytical models give an error of less than 10% with respect to the experimental results in both the cases.

Microstrip square ring antenna for dual-band operation

This paper presents a generalized approach to design an electromagnetically coupled microstrip ring antenna for dual-band operation. By widening two opposite sides of a square ring antenna, its fractional bandwidth at the primary resonance mode can be increased significantly so that it may be used for practical applications. By attaching a stub to the inner edge of the side opposite to the feed arm, some of the losses in electrical length caused by widening can be regained. More importantly, this addition also alters the current distribution on the antenna and directs radiations at the second resonant frequency towards boresight. It has also been observed that for the dual frequency configurations studied, the ratio of the resonant frequencies (center dot r(2)center dot center dot r(1)) can range between 1.55 and 2.01. This shows flexibility in designing dual frequency antennas with a desired pair of resonant frequencies.

Self-Assembly of a Pd-6-Molecular Double-Square and a Cu-3-Trigonalbipyramidal Cage via a New Tripodal Flexible Ligand

A new tripodal flexible ligand (L) containing pyrazolyl functionality has been prepared and successfully used to obtain a pd(6) (1) molecular double-square and a cu(3) trigonalbipyramidal cage (2), where complex 1 represents the first example of a double-square obtained using a flexible tripodal ligand.

Effect of reinforcement form on the bearing capacity of square footings on sand

This paper presents the results of laboratory model loading tests and numerical studies carried out on square footings supported on geosynthetic reinforced sand beds. The relative performance of different forms of geosynthetic reinforcement (i.e. geocell, planar layers and randomly distributed mesh elements) in foundation beds is compared; using same quantity of reinforcement in each test. A biaxial geogrid and a geonet are used for reinforcing the sand beds. Geonet is used in two forms of reinforcement, viz. Planar layers and geocell, while the biaxial geogrid was used in three forms of reinforcement, viz. planar layers, geocell and randomly distributed mesh elements. Laboratory load tests on unreinforced and reinforced footings are simulated in a numerical model and the results are analyzed to understand the distribution of displacements and stresses below the footing better. Both the experimental and numerical studies demonstrated that the geocell is the most advantageous form of soil reinforcement technique of those investigated, provided there is no rupture of the material during loading. Geogrid used in the form of randomly distributed mesh elements is found to be inferior to the other two forms. Some significant observations on the difference in reinforcement mechanism for different forms of reinforcement are presented in this paper.

Dual-frequency characteristics of Minkowski-square ring antennas

Fractal Minkowski curves to design a compact dual-frequency microstrip ring antenna are proposed. Sides of a square ring have been selectively replaced with first and second iterations of the generalised fractal geometry to design a smaller antenna with dual-frequency operation. This behaviour has been explained based on current distributions on the antenna structure. Measured results compare well with electromagnetic simulations.