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.

Impressive Gelation in Organic Solvents by Synthetic, Low Molecular Mass, Self-Organizing Urethane Amides of L-Phenylalanine

Synthetic routes leading to 12 L-phenylalanine based mono- and bipolar derivatives (1-12) and an in-depth study of their structure-property relationship with respect to gelation have been presented. These include monopolar systems such as N-[(benzyloxy)carbonyl]-L-phenylalanine-N-alkylamides and the corresponding bipolar derivatives with flexible and rigid spacers such as with 1,12-diaminododecane and 4,4'-diaminodiphenylmethane, respectively. The two ends of the latter have been functionalized with N-[(benzyloxy)carbonyl]-L-phenylalanine units via amide connection. Another bipolar molecule was synthesized in which the middle portion of the hydrocarbon segment contained polymerizable diacetylene unit. To ascertain the role of the presence of urethane linkages in the gelator molecule protected L-phenylalanine derivatives were also synthesized in which the (benzyloxy)carbonyl group has been replaced with (tert-butyloxy)carbonyl, acetyl, and benzoyl groups, respectively. Upon completion of the synthesis and adequate characterization of the newly described molecules, we examined the aggregation and gelation properties of each of them in a number of solvents and their mixtures. Optical microscopy and electron microscopy further characterized the systems that formed gels. Few representative systems, which showed excellent gelation behavior was, further examined by FT-IR, calorimetric, and powder X-ray diffraction studies. To explain the possible reasons for gelation, the results of molecular modeling and energy-minimization studies were also included. Taken together these results demonstrate the importance of the presence of (benzyloxy)carbonyl unit, urethane and secondary amide linkages, chiral purities of the headgroup and the length of the alkyl chain of the hydrophobic segment as critical determinants toward effective gelation.

2.5-dimensional solution of the advective accretion disk:a self-similar approach

We provide a 2.5-dimensional solution to a complete set of viscous hydrodynamical equations describing accretion- induced outflows and plausible jets around black holes/compact objects. We prescribe a self-consistent advective disk-outflow coupling model, which explicitly includes the information of vertical flux. Inter-connecting dynamics of an inflow-outflow system essentially upholds the conservation laws. We provide a set of analytical family of solutions through a self-similar approach. The flow parameters of the disk-outflow system depend strongly on the viscosity parameter α and the cooling factor.

Synthesis and characterisation of heterometallic molecular triangles using ambidentate linker: self-selection of a single linkage isomer

The coordination driven self-assembly of discrete molecular triangles from a non-symmetric ambidentate linker 5-pyrimidinecarboxylate (5-pmc) and Pd(II)/Pt(II) based 90◦ acceptors is presented. Despite the possibility of formation of a mixture of isomeric macrocycles (linkage isomers) due to different connectivity of the ambidentate linker, formation of a single and symmetrical linkage somer in both the cases is an interesting observation. Moreover, the reported macrocycles represent the first example of discrete metallamacrocycles of bridging 5-pmc. While solution composition in both the cases was characterised by multinuclear NMR study and electrospray ionization mass spectrometry (ESI-MS), the identity of the assemblies in the solid state was established by X-ray single crystals structure analysis. Variable temperature NMR study clearly ruled out the formation of any other macrocycles by [4 + 4] or [2 + 2] self-assembly of the reacting components.

A comparative study of side-band Fresnel holograms recorded with self-imaging and general objects

This paper deals with new results obtained in regard to the reconstruction properties of side-band Fresnel holograms (SBFH) of self-imaging type objects (for example, gratings) as compared with those of general objects. The major finding is that a distribution I2, which appears on the real-image plane along with the conventional real-image I1, remains a 2Z distribution (where 2Z is the axial distance between the object and its self-imaging plane) under a variety of situations, while its nature and focusing properties differ from one situation to another. It is demonstrated that the two distributions I1 and I2 can be used in the development of a novel technique for image subtraction.

Instabilities of a compressible stratified fluid in horizontal sheared motion

The stability characteristics of a Helmholtz velocity profile in a stably stratified, compressible atmosphere in the presence of a lower boundary are studied. A jump in the Brunt–Väisälä frequency is introduced and the level at which this jump occurs is assumed to be different from the shear zone, to simulate sharp temperature discontinuities in the atmosphere. The results are compared with those of Pellacani, Tebaldi, and Tosi and Lindzen and Rosenthal. In the present configuration, new unstable modes with larger growth rates are found. The wavelengths of the most unstable gravity waves for the parameters pertaining to observed cases of clear air turbulence agree quite closely with the experimental values. Physics of Fluids is copyrighted by The American Institute of Physics

Classification and rating of strong-motion earthquake records

Ninety-two strong-motion earthquake records from the California region, U.S.A., have been statistically studied using principal component analysis in terms of twelve important standardized strong-motion characteristics. The first two principal components account for about 57 per cent of the total variance. Based on these two components the earthquake records are classified into nine groups in a two-dimensional principal component plane. Also a unidimensional engineering rating scale is proposed. The procedure can be used as an objective approach for classifying and rating future earthquakes.

The influence of the motion of a rotor grid on a stator grid

In this paper we have used the method of characteristics developed for two dimensional unsteady flow problems to study a simplified axial turbine problem. The system consists of two sets of blades —the guiding vanes which are fixed and the rotor blades which move perpendicular to these vanes. The initial undisturbed constant flow in the system is perturbed by introducing a small velocity normal to the rotor blades to simulate a slight constant inclination. The resulting perturbed flow is periodic after the first three cycles. We have studied the perturbed density distribution throughout the system during a period.

Novel Self-Supported Natural and Synthetic Polymer Membranes for Air Humidification

Novel self-supported natural and synthetic polymer membranes of chitosan-hydroxy ethyl Cellulose-montmorillonite (CS-HEC-MMT) and polyvinyl alcohol (PVA)-polystyrene sulfonic acid (PSSA) are prepared by solution casting method followed by crosslinking. These membranes are employed for air humidification at varying temperatures between 30 degrees C and 70 degrees C and their performances are compared with commercial Nafion membranes. High hater fluxes with desired humidified-air output have been achieved for CS-HEC-MMT and PVA-PSSA hybrid membranes at air-flow rates of 1-10 slpm. Variation in the air/water mixing ratio, dew point, and relative humidity that ultimately results in desired water flux With respect to air-flow rates are also quantified for all the membranes. Water flux values for CS-HEC-MMT are less than those for Nafion (R) and PVA-PSSA membranes, but the operational Stability of CS-HEC-MMT membrane is higher than PVA-PSSA and comparable with Nafion (R) both of which can operate up to 70 degrees C at repetitive cycles of humidification.

Self-similar solution of unsteady compressible three-dimensional stagnation-point boundary layers

The self-similar solution of the unsteady laminar compressible boundary-layer flow with variable properties at a three-dimensional stagnation point with mass transfer has been obtained when the free-stream velocity varies inversely as a linear function of time. The resulting ordinary differential equations have been solved numerically using an implicit finite-difference scheme. The results are found to be strongly dependent on the parameter characterizing the unsteadiness in the free-stream velocity. The velocity profiles show some features not encountered in steady flows.

Self-Assembly of Bile Steroid Analogues: Molecules, Fibers, and Networks

Structural and rheological features of a series of molecular hydrogels formed by synthetic bile salt analogues have been scrutinized. Among seven gelators, two are neutral compounds, while the others are cationic systems among which one is a tripodal steroid derivative. Despite the fact that the chemical structures are closely related, the variety of physical characteristics is extremely large in the structures of the connected fibers (either plain cylinders or ribbons), in the dynamical modes for stress relaxation of the associated SAFINs, in the scaling laws of the shear elasticity (typical of either cellular solids or fractal floc-like assemblies), in the micron-scale texture and the distribution of ordered domains (spherulites, crystallites) embedded in a random mesh, in the type of nodal zones (either crystalline-like, fiber entanglements, or bundles), in the evolution of the distribution and morphology of fibers and nodes, and in the sensitivity to added salt. SANS appears to be a suitable technique to infer all geometrical parameters defining the fibers, their interaction modes, and the volume fraction of nodes in a SAFIN. The tripodal system is particularly singular in the series and exhibits viscosity overshoots at the startup of shear flows, an “umbrella-like” molecular packing mode involving three molecules per cross section of fiber, and scattering correlation peaks revealing the ordering and overlap of 1d self-assembled polyelectrolyte species.

Self-Organization of n-Alkane Chains in Water: Length Dependent Crossover from Helix and Toroid to Molten Globule

We demonstrate a chain length dependent crossover in the structural properties of linear hydrocarbon (n-alkane) chains using detailed atomistic simulations in explicit water. We identify a number of exotic structures of the polymer chain through energy minimization of representative snapshots collected from molecular dynamics trajectory. While the collapsed state is ring-like (circular) for small chains (CnH2n+2; n <= 20) and spherical for very long ones (n = 100), we find the emergence of ordered helical structures at intermediate lengths (n similar to 40). We find different types of disordered helices and toroid-like structures at n = 60. We also report a sharp transition in the stability of the collapsed state as a function of the chain length through relevant free energy calculations. While the collapsed state is only marginally metastable for C20H42, a clear bistable free energy surface emerges only when the chain is about 30 monomers long. For n = 30, the polymer exhibits an intermittent oscillation between the collapsed and the coil structures, characteristic of two stable states separated by a small barrier.

Stream power criterion and design of sand bed channels at incipient motion

The critical stream power criterion may be used to describe the incipient motion of cohesionless particles of plane sediment beds. The governing equation relating ``critical stream power'' to ``shear Reynolds number'' is developed by using the present experimental data as well as the data from several other sources. Simultaneously, a resistance equation, relating the ``particle Reynolds number'' to the``shear Reynolds number'' is developed for plane sediment beds in wide channels with little or no transport. By making use of these relations, a procedure is developed to design plane sediment beds such that any two of the four design variables, including particle size, energy/friction slope, flow depth, and discharge per unit width in the channel should be known to predict the remaining two variables. Finally, a straightforward design procedure using design tables/design curves and analytical methods is presented to solve six possible design problems.

Motion of a viscous fluid with suspended particles in a curved tube

In this paper we have discussed the motion of a viscous fluid with suspended particles through a curved tube of small curvature ratio. The system is treated as two separate interacting continua. Solutions for axial and secondary velocities are obtained in the form of asymptotic expansions in powers of Dean Number. The streamline pattern for the particulate phase reveals many interesting features. The influence of the particulate continium on the fluid is described by the parameter τ which depends on the density ratio of the two continua. The concentration distribution of the particles in a given cross section is determined. It is noticed that the particles move closer to the wall for certain values of the concentration and the density ratio.

Mass transfer effects on the generalised vortex flow over a stationary surface with or without magnetic field

The effect of injection and suction on the generalised vortex flow of a steady laminar incompressible fluid over a stationary infinite disc with or without magnetic field under boundary-layer approximations has been studied. The coupled nonlinear ordinary differential equations governing the self-similar flow have been numerically solved using the finite-difference scheme. The results indicate that the injection produces a deeper inflow layer and de-stabilises the motion while suction or magnetic field suppresses the inflow layer and produces stability. The effect of decreasingn, the parameter characterising the nature of vortex flow, is similar to that of increasing the injection rate.