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.

Acyclic Edge Coloring of Triangle-Free Planar Graphs

An acyclic edge coloring of a graph is a proper edge coloring such that there are no bichromatic cycles. The acyclic chromatic index of a graph is the minimum number k such that there is an acyclic edge coloring using k colors and is denoted by a'(G). It was conjectured by Alon, Sudakov and Zaks (and much earlier by Fiamcik) that a'(G) ? ? + 2, where ? = ?(G) denotes the maximum degree of the graph. If every induced subgraph H of G satisfies the condition |E(H)| ? 2|V(H)|-1, we say that the graph G satisfies Property A. In this article, we prove that if G satisfies Property A, then a'(G) ? ? + 3. Triangle-free planar graphs satisfy Property A. We infer that a'(G) ? ? + 3, if G is a triangle-free planar graph. Another class of graph which satisfies Property A is 2-fold graphs (union of two forests). (C) 2011 Wiley Periodicals, Inc. J Graph Theory

Nodal domains of the equilateral triangle billiard

We characterize the eigenfunctions of an equilateral triangle billiard in terms of its nodal domains. The number of nodal domains has a quadratic form in terms of the quantum numbers, with a non-trivial number-theoretic factor. The patterns of the eigenfunctions follow a group-theoretic connection in a way that makes them predictable as one goes from one state to another. Extensive numerical investigations bring out the distribution functions of the mode number and signed areas. The statistics of the boundary intersections is also treated analytically. Finally, the distribution functions of the nodal loop count and the nodal counting function are shown to contain information about the classical periodic orbits using the semiclassical trace formula. We believe that the results belong generically to non-separable systems, thus extending the previous works which are concentrated on separable and chaotic systems.

Lower bounds for testing triangle-freeness in Boolean functions

Given a Boolean function , we say a triple (x, y, x + y) is a triangle in f if . A triangle-free function contains no triangle. If f differs from every triangle-free function on at least points, then f is said to be -far from triangle-free. In this work, we analyze the query complexity of testers that, with constant probability, distinguish triangle-free functions from those -far from triangle-free. Let the canonical tester for triangle-freeness denotes the algorithm that repeatedly picks x and y uniformly and independently at random from , queries f(x), f(y) and f(x + y), and checks whether f(x) = f(y) = f(x + y) = 1. Green showed that the canonical tester rejects functions -far from triangle-free with constant probability if its query complexity is a tower of 2's whose height is polynomial in . Fox later improved the height of the tower in Green's upper bound to . A trivial lower bound of on the query complexity is immediate. In this paper, we give the first non-trivial lower bound for the number of queries needed. We show that, for every small enough , there exists an integer such that for all there exists a function depending on all n variables which is -far from being triangle-free and requires queries for the canonical tester. We also show that the query complexity of any general (possibly adaptive) one-sided tester for triangle-freeness is at least square root of the query complexity of the corresponding canonical tester. Consequently, this means that any one-sided tester for triangle-freeness must make at least queries.

Heterochromatic paths in edge colored graphs without small cycles and heterochromatic-triangle-free graphs

Conditions for the existence of heterochromatic Hamiltonian paths and cycles in edge colored graphs are well investigated in literature. A related problem in this domain is to obtain good lower bounds for the length of a maximum heterochromatic path in an edge colored graph G. This problem is also well explored by now and the lower bounds are often specified as functions of the minimum color degree of G - the minimum number of distinct colors occurring at edges incident to any vertex of G - denoted by v(G). Initially, it was conjectured that the lower bound for the length of a maximum heterochromatic path for an edge colored graph G would be 2v(G)/3]. Chen and Li (2005) showed that the length of a maximum heterochromatic path in an edge colored graph G is at least v(G) - 1, if 1 <= v(G) <= 7, and at least 3v(G)/5] + 1 if v(G) >= 8. They conjectured that the tight lower bound would be v(G) - 1 and demonstrated some examples which achieve this bound. An unpublished manuscript from the same authors (Chen, Li) reported to show that if v(G) >= 8, then G contains a heterochromatic path of length at least 120 + 1. In this paper, we give lower bounds for the length of a maximum heterochromatic path in edge colored graphs without small cycles. We show that if G has no four cycles, then it contains a heterochromatic path of length at least v(G) - o(v(G)) and if the girth of G is at least 4 log(2)(v(G)) + 2, then it contains a heterochromatic path of length at least v(G) - 2, which is only one less than the bound conjectured by Chen and Li (2005). Other special cases considered include lower bounds for the length of a maximum heterochromatic path in edge colored bipartite graphs and triangle-free graphs: for triangle-free graphs we obtain a lower bound of 5v(G)/6] and for bipartite graphs we obtain a lower bound of 6v(G)-3/7]. In this paper, it is also shown that if the coloring is such that G has no heterochromatic triangles, then G contains a heterochromatic path of length at least 13v(G)/17)]. This improves the previously known 3v(G)/4] bound obtained by Chen and Li (2011). We also give a relatively shorter and simpler proof showing that any edge colored graph G contains a heterochromatic path of length at least (C) 2015 Elsevier Ltd. All rights reserved.

Orientational relaxation in a random dipolar lattice: Wave-number and frequency dependence

In order to understand the role of translational modes in the orientational relaxation in dense dipolar liquids, we have carried out a computer ''experiment'' where a random dipolar lattice was generated by quenching only the translational motion of the molecules of an equilibrated dipolar liquid. The lattice so generated was orientationally disordered and positionally random. The detailed study of orientational relaxation in this random dipolar lattice revealed interesting differences from those of the corresponding dipolar liquid. In particular, we found that the relaxation of the collective orientational correlation functions at the intermediate wave numbers was markedly slower at the long times for the random lattice than that of the liquid. This verified the important role of the translational modes in this regime, as predicted recently by the molecular theories. The single-particle orientational correlation functions of the random lattice also decayed significantly slowly at long times, compared to those of the dipolar liquid.

Practical Algorithms For Mean Velocity Estimation In Pulse Doppler Weather Radars Using A Small Number Of Samples

Doppler weather radars with fast scanning rates must estimate spectral moments based on a small number of echo samples. This paper concerns the estimation of mean Doppler velocity in a coherent radar using a short complex time series. Specific results are presented based on 16 samples. A wide range of signal-to-noise ratios are considered, and attention is given to ease of implementation. It is shown that FFT estimators fare poorly in low SNR and/or high spectrum-width situations. Several variants of a vector pulse-pair processor are postulated and an algorithm is developed for the resolution of phase angle ambiguity. This processor is found to be better than conventional processors at very low SNR values. A feasible approximation to the maximum entropy estimator is derived as well as a technique utilizing the maximization of the periodogram. It is found that a vector pulse-pair processor operating with four lags for clear air observation and a single lag (pulse-pair mode) for storm observation may be a good way to estimate Doppler velocities over the entire gamut of weather phenomena.

On the number of two-line and three-line latin rectangles - an alternative approach

The number of two-line and three-line Latin rectangles is obtained by recursive methods in a setting slightly more general than usually considered. We show how this leads to a generalisation which is proved elsewhere.

Number and proportion of selenocucleosides in the transfer RNA of escherichia-coli

tRNA isolated from escherichia-coli grown in a medium containing [75Se] sodium selenosulfate was converted to nucleosides and analysed for selenonucleosides on a phosphocellulose column. Upon chromatography of the nucleosides on phosphocellulose column, the radioactivity resolved into three peaks. The first peak consisted of free selenium and traces of undigested nucleotides. The second peak was identified as 4-selenouridine by co-chromatographing with an authentic sample of 4-selenouridine. The identity of the third peak was not established. The second and third peaks represented 93% and 7% of the selenium present in nucleosides respectively.

Crystal Physics, Diffraction, Theoretical and General Crystallography

A formula has been derived for the mean-square error in the phases of crystal reflections determined through the multiwavelength anomalous scattering method. The error is written in terms of a simple function of the positions in the complex plane of the 'centres' corresponding to the different wavelengths. For the case of three centres, the mean-square error is inversely proportional to the area of the triangle formed by them. The theoretical values are in good agreement with those obtained by earlier workers from computer simulations. The present method makes it easier to optimize the number and the actual wavelengths to be employed in the multiwavelength method. The maximum benefits of this method are expected in experiments employing synchrotron radiation or neutrons.

Number and proportion of selenocucleosides in the transfer RNA of Image Image

tRNA isolated from . grown in a medium containing [75Se] sodium selenosulfate was converted to nucleosides and analysed for selenonucleosides on a phosphocellulose column. Upon chromatography of the nucleosides on phosphocellulose column, the radioactivity resolved into three peaks. The first peak consisted of free selenium and traces of undigested nucleotides. The second peak was identified as 4-selenouridine by co-chromatographing with an authentic sample of 4-selenouridine. The identity of the third peak was not established. The second and third peaks represented 93% and 7% of the selenium present in nucleosides respectively.

Experimental investigation of cowl shape and location on inlet characteristics at hypersonic Mach number

An experimental study is presented to show the effect of the cowl location and shape on the shock interaction phenomena in the inlet region for a 2D, planar scramjet inlet model. Investigations include schlieren visualization around the cowl region and heat transfer rate measurement inside the inlet chamber.Both regular and Mach reflections are observed when the forebody ramp shock reflects from the cowl plate. Mach stem heights of 3.3 mm and 4.1 mm are measured in 18.5 mm and 22.7 mm high inlet chambers respecively. Increased heat transfer rate is measured at the same location of chamber for cowls of longer lenghs is indicating additional mass flow recovery by the inlet.

Nature of dependence of spin-orbit splittings on atomic number

It has been shown that Dirac equation employing a constant value of the screening constant Z0 does not explain the variation of spin-orbit splittings of 2p and 3p levels with atomic number Z. A model which takes into account the variation of Z0 withZ is shown to satisfactorily predict the dependence of spinorbit splittings onZ.