Mononuclear to polynuclear transition induced by ligand coordination: synthesis, X-ray structure, and properties of mono-, di-, and polynuclear copper(II) complexes of pyridyl-containing azo ligands

Reactions of two hydrated cupric salts (CuCl(2).2H(2)O and Cu(ClO(4))(2).6H(2)O) with three azopyridyl ligands, viz. 2-[(arylamino)phenylazo]pyridine [aryl = phenyl (HL(1a)), p-tolyl (HL(1b)), and 2-thiomethyl phenyl (HL(1c))], 2-[2-(pyridylamino)phenylazo]pyridine (HL(2)), and 2-[3-(pyridylamino)phenylazo]pyridine (HL(3)), afford the mononuclear [CuClL(1)] (1), dinuclear [Cu(2)X(2)L(2)(2)](n)()(+) (X = Cl, H(2)O, ClO(4); n = 0, 1; 2, 3), and polynuclear [CuClL(3)](n)() (4) complexes, respectively, in high yields. Representative X-ray structures of these complexes 1-4 are reported. X-ray structure analysis of 4 reveals an infinite 1D zigzag chain that adopts a saw-tooth-like structure. Variable-temperature cryomagnetic measurements (2-300 K) on the complexes 2-4 have revealed weak magnetic interactions between the copper centers with J values -1.04, 9.88, and -1.31 cm(-1), respectively. Positive ion ESI mass spectra of the soluble complexes 1-3 are studied which provide the evidence for the integrity of the complexes also in solution. Visible range spectra of the complexes 1-3 in solution consist of intense and broad transitions in the range 700-600 nm. The solid-state spectrum of the insoluble copper complex 4, on the other hand, shows a structured band near 700 nm. The intensities of the transitions of the dinuclear complexes are much higher than those of the corresponding mononuclear copper complexes. Redox properties of the present copper complexes are reported. Notably, the dinuclear complex, 3, displays two successive redox processes: Cu(II)Cu(II) right harpoon over left harpoon Cu(II)Cu(I) right harpoon over left harpoon Cu(I)Cu(I). It catalyzes aerial oxidation of L-ascorbic acid. The catalytic cycle is most effective up to H(2)A/3 (H(2)A = L-ascorbic acid) molar ratio of 20:1.     

Static and dynamic critical behavior of a symmetrical binary fluid: a computer simulation

A symmetrical binary, A+B Lennard-Jones mixture is studied by a combination of semi-grand-canonical Monte Carlo (SGMC) and molecular dynamics (MD) methods near a liquid-liquid critical temperature T(c). Choosing equal chemical potentials for the two species, the SGMC switches identities (A-->B-->A) to generate well-equilibrated configurations of the system on the coexistence curve for TT(c). A finite-size scaling analysis of the concentration susceptibility above T(c) and of the order parameter below T(c) is performed, varying the number of particles from N=400 to 12 800. The data are fully compatible with the expected critical exponents of the three-dimensional Ising universality class. The equilibrium configurations from the SGMC runs are used as initial states for microcanonical MD runs, from which transport coefficients are extracted. Self-diffusion coefficients are obtained from the Einstein relation, while the interdiffusion coefficient and the shear viscosity are estimated from Green-Kubo expressions. As expected, the self-diffusion constant does not display a detectable critical anomaly. With appropriate finite-size scaling analysis, we show that the simulation data for the shear viscosity and the mutual diffusion constant are quite consistent both with the theoretically predicted behavior, including the critical exponents and amplitudes, and with the most accurate experimental evidence.     

The role of terminal tyrosine residues in the formation of tripeptide nanotubes: a crystallographic insight

Terminally protected acyclic tripeptides containing tyrosine residues at both termini self-assemble into nanotubes in crystals through various non-covalent interactions including intermolecular hydrogen bonds. The nanotube has an average internal diameter of 5 Å (0.5 nm) and the tubular ensemble is developed through the hydrogen-bonded phenolic-OH side chains of tyrosine (Tyr) residues [Org. Lett.2004, 6, 4463]. We have synthesized and studied several tripeptides 3-6 to probe the role of tyrosine residues in nanotube structure formation. These peptides either have only one Tyr residue at N- or C-termini or they have one or two terminally located phenylalanine (Phe) residues. These tripeptides failed to form any kind of nanotubular structure in the solid state. Single crystal X-ray diffraction studies of these peptides 3-6 clearly demonstrate that substitution of any one of the terminal Tyr residues in the Boc-Tyr-X-Tyr-OMe (X=Val or Ile) sequence disrupts the formation of the nanotubular structure indicating that the presence of two terminally located Tyr residues is vital for nanotube formation.     

Nanostaircase formation in the solid state from self-assembling synthetic terephthalamides with a common molecular scaffold

The design and construction of nanostructured materials using proper self-assembling molecular building blocks is a real challenge to scientists. Here, we present the formation of a new nano-architecture, i.e., nanostaircase in the solid state by using molecular building blocks, which are amenable to self-assembly in a directed manner to form the specific nanostructure. The molecular building blocks are terephthalamides 1-4, which are bis-terephthalamides of methyl esters of various α-amino acids including l-leucine 1, d-leucine 2, l-isoleucine 3, and α-aminoisobutyric acid (Aib) 4. All terephthalamides presented here, irrespective of their different side chain residues or stereochemistry, self-assemble to form supramolecular nanostaircase structures in crystals. Each terephthalamide contains two good hydrogen-bond donors and two hydrogen-bond acceptors. Two N-H?O hydrogen bonds and C-H?π interactions are responsible for the formation and stabilization of the nanostaircase structures in crystals. The molecular building blocks are packed orthogonally to each other in crystals and this arrangement can help the formation of nanostaircase structure upon self-assembly.     

A convergent synthesis of the macrolide core of migrastatin

We describe an efficient synthesis of the 14-membered macrolide core 2 of migrastatin via key intermediate 3 employing a diastereoselective aldol condensation, Lewis acid mediated diastereoselective addition and an exclusive (Z)-olefination sequence. Yamaguchi esterification of the key intermediate 3 followed by ring-closing metathesis (RCM) produced macrolide 2 with high selectivity and good yield.     

A cross metathesis approach to the synthesis of the C11-C23 fragment of (−)-16-normethyldictyostatin

The synthesis of the C11-C23 fragment 2 of (−)-16-normethyldictyostatin has been achieved by cross metathesis between two olefinic fragments 4 and 5 followed by a reduction of the double bond at C16-C17. Both the olefinic fragments are easily synthesized in a diastereoselective manner from the common precursor alcohol 7.     

Self-assembly of a luminescent zinc(II) complex: a supramolecular host-guest fluorescence signaling system for selective nitrobenzene inclusion

A luminescent Zn(II) complex, [Zn(bpy)(aba)2] (1) {bpy = 2,2'-bipyridyl and aba = 4-dimethylaminobenzoate} has been synthesized as a white solid. Complex 1 shows unusually high selectivity toward nitrobenzene in the presence of other organic guests in solution, as well as in the vapor phase, resulting in both a dramatic color change and a concomitant quenching of luminescence. When crystallized from nitrobenzene, 1 affords deep red crystals with the composition [Zn(bpy)(aba)2] x C6H5NO2 (2) as a hydrogen-bonded channel structure via unusual intermolecular C-H...C(sp3) and H...H interactions. Inside the channels, nitrobenzene molecules form infinite polar linear tapes through strong C-H...O interactions in a head-to-tail fashion. The desorption and resorption of nitrobenzene can be achieved in a thermally reversible manner that can be monitored by X-ray powder diffraction patterns.     

Simultaneous Determination of Acetylsalicylic Acid and Caffeine in Pharmaceutical Formulation by First Derivative Synchronous Fluorimetric Method

A sensitive, rapid, and specific assay has been developed for the simultaneous determination of acetylsalicylic acid and caffeine in commercial tablets based on their natural fluorescence. The mixture of these drugs was resolved by first derivative synchronous fluorimetric technique using two scans. At Δλ=106 nm, using first derivative synchronous scanning, only acetylsalicylic acid yields a detectable signal at 316 nm (peak to zero method) which is unaffected by caffeine. At Δλ=30 nm, the signal of caffeine at 288 nm (peak to zero method) is not affected by acetylsalicylic acid. The range of application is between 0.021 and 41.62 μg ml⁻¹ (correlation coefficient, R=0.9995) for acetylsalicylic acid and between 0.4486 and 44.86 μg ml⁻¹ (correlation coefficient, R=0.99786) for caffeine. The recovery range of 98.40–102% for acetylsalicylic acid and 90–100.5% for caffeine from their synthetic mixture was reported. Overall recovery of both compounds about 97–99% for acetylsalicylic acid and 97–98% for caffeine was obtained from real sample analysis. The detection limits are 0.0013 μg ml⁻¹ and 0.0306 μg ml⁻¹ for acetylsalicylic acid and caffeine, respectively. The relative standard deviation (n=10) for 20 μg ml⁻¹ of acetylsalicylic acid is 2.75% and for 2.2 μg ml⁻¹of caffeine is 1.7%.     

Field-induced phase transitions and reversible field-induced inversion of chirality in tilted smectic phases of bent-core mesogens

Three homologous achiral five-ring bent-core mesogens are presented where 4-chlororesorcinol is the central core and the aromatic rings are linked by ester groups. These compounds form smectic phases with a tilted arrangement of the molecules (tilt angle ≈ 45^°). On cooling the isotropic liquid this phase adopts a fan-like texture which shows for two homologues at relatively high electric fields ( 25-35V μm^-1) an antiferroelectric electro-optical response based on the collective rotation of the molecules around their long axes. At lower temperature the application of a sufficiently high electric field leads to a continuous transition into a non-birefringent texture which exhibits randomly distributed domains of opposite handedness. These domains can be reversibly switched into a state of opposite chirality by reversal of the field polarity. This switching is bistable and shows a current response typical for a ferroelectric ground state. The possible mechanism of the field-induced phase transition, of the ferroelectric switching and of the field-induced inversion of the chirality is discussed on the base of XRD, ¹³C- and ¹H-NMR investigations, dielectric and electro-optical measurements.     

Hall effect on MHD free convection boundary layer flow past a vertical flat plate

Effects of Hall current on MHD free convection boundary layer flow of a viscous incompressible electrically conducting fluid past a heated vertical flat plate of finite dimension in the presence of a uniform transverse magnetic field have been studied. An exact solution of the governing equations describing the flow has been obtained. The velocity field, induced magnetic field and bulk temperature distributions in the boundary layer flow have been discussed. It is found that the velocity components increase with an increase in Hall parameter. It is noticed that the induced magnetic field components are radically influenced by the Hall parameter. It is also found that the magnitude of bulk temperature in the x-direction decreases with an increase in either Hall parameter or magnetic parameter. On the other hand, the magnitude of the bulk temperature in the z-direction increases with an increase in Hall parameter whereas it decreases with an increase in magnetic parameter.