Self-recognition in the coordination-driven self-assembly of three-dimensional M3L2 polyhedra

[reaction: see text] Self-recognition in the coordination-driven self-assembly of three-dimensional (3-D) polyhedra is described. Multiple discrete 3-D polyhedra were formed in one vessel through the self-recognition of a mixture of subunits. The dynamic self-recognition process is determined by the information stored within the geometry and directionality of multiple rigid building blocks as well as the thermodynamic stability of the discrete products.     

Physicochemical studies on pepsin-CTAB interaction: energetics and structural changes

The interaction between pepsin and CTAB has been elaborately studied with a number of techniques. The enzyme-induced interaction produced complexes, aggregates, and micelles of CTAB with distinct physicochemical features. It was found that at very low surfactant concentration (much below the critical micellar concentration (cmc) of pure CTAB), the surfactant got adsorbed both in monomeric and lower aggregated forms to the high-energy sites of the native biopolymer, leading to enhanced hydrophobicity of the combine, and hence, lowering of the interfacial (air/solution) tension. This was followed by the formation of a faintly turbid solution of the polymer-surfactant coacervate. The CTAB interacted unfolded pepsin along with the surfactant monomer remained adsorbed at the interface to decrease the interfacial tension (gamma) to a low level to produce a break in the gamma vs log [CTAB] plot prior to the normally observed extended cmc (cmce) in presence of polymers. The cac-like aggregation (as observed in tensiometry and viscometry) was not found in conductometry and microcalorimetry, whereas microcalorimetry evidenced the formation of the cmce of CTAB in the presence of the biopolymer. The CTAB influenced structural features of the pepsin were assessed from spectral, viscometric, and circular dichroism measurements.     

Structural,optical and photoelectron spectroscopic studies of nano/micro ZnO:Cd rods synthesized via sol-gel route

Thin films of cadmium doped zinc oxide rod like microstructure have been synthesized by a very simple sol-gel dip coating technique. Sols were prepared from hydrated zinc oxide precursor and 2-methoxyethanol solvent with monoethanolamine as a sol stabilizer. XRD pattern confirmed the hexagonal wurtzite structure of the deposited ZnO films. Surface morphologies of the films have been studied by a scanning electron microscope and an atomic force microscope, which confirmed that the films are composed of densely packed randomly oriented nano/submicron rods with diameter in the range 300–400 nm having various lengths. We proposed a possible growth mechanism for this rodlike structure. X-ray photoelectron spectroscopic study was used to determine the binding energies and the Zn 2p3/2, Cd 3d5 and O 1s peaks in the XPS spectra were located at 1021.08 eV, 404.6 eV and 529.8 eV respectively, which confirmed the Cd doping in ZnO. Cadmium content in the film was estimated both from energy dispersive X-ray analysis and XPS measurement. Band gap energy determined from optical transmittance spectra systematically varied from 3.28 eV to 3.15 eV for 0% to 5.6% of Cd doping. Urbach parameter determined from the band tail of the transmittance spectra showed that it increased with doping percentage and this parameter for a fixed cadmium doping level decreased with increase of temperature.     

Ultrafast proton transfer of pyranine in a supramolecular assembly: PEO-PPO-PEO triblock copolymer and CTAC

Excited-state proton transfer (ESPT) of pyranine (8-hydroxypyrene-1,3,6-trisulfonate, HPTS) is studied in a polymer-surfactant aggregate using femtosecond emission spectroscopy. The polymer-surfactant aggregate is a supramolecular assembly consisting of a triblock copolymer (PEO)(20)-(PPO)(70)-(PEO)(20) (P123) and a cationic surfactant, cetyltrimethylammonium chloride (CTAC). ESPT of the protonated species (HA) in HPTS leads to the formation of A(-). The dynamics of ESPT may be followed from the decay of the HA emission (at approximately 440 nm) and rise of the A(-) emission (at approximately 550 nm). Both steady-state and time-resolved studies suggest that ESPT of HPTS in P123-CTAC aggregate is much slower than that in bulk water, in P123 micelle, or in CTAC micelle. The ratio of the steady-state emission intensities (HA/A(-)) in P123-CTAC aggregate is 2.2. This ratio is approximately 50, 12, and 2 times higher than that respectively in water, in P123 micelle, and in CTAC micelle. Retardation of ESPT causes an increase in the rise time of the A(-) emission of HPTS. In P123-CTAC aggregate, A(-) displays three rise times: 30, 250, and 2400 ps. These rise times are longer than those in CTAC micelle (23, 250, and 1800 ps), in bulk water (0.3, 3, and 90 ps), and in P123 micelle (15 and 750 ps). The rate constants for initial proton transfer, recombination, and dissociation of the ion pair are estimated using a simple kinetic scheme. The slow fluorescence anisotropy decay of HPTS in P123-CTAC aggregate is analyzed in terms of the wobbling-in-cone model.     

Six coordinate Ni(II) complexes of ONN donor aroylhydrazone ligands: synthesis,spectral studies,and crystal structures

A new ligand N′-(pyridin-2-ylmethylene)nicotinohydrazide (HL²) and two Ni(II) complexes of stoichiometry NiL¹·H₂O [L¹-2-benzoylpyridine nicotinoylhydrazone] and NiL²·H₂O have been synthesized and characterized by elemental analyses, IR and UV–Vis spectral studies. Structures of HL² and Ni(II) compounds have been determined by single crystal X-ray diffraction studies which reveal a distorted octahedral geometry around the two Ni(II) centers.

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Graphical abstract A new ligand N￠-(pyridin-2-ylmethylene)nicotinohydrazide (HL2) and two Ni(II) complexes of stoichiometry NiL1·H2O [L1-2-benzoylpyridine nicotinoylhydrazone] and NiL2·H2O have been synthesized and characterized by elemental analyses, IR, UV–Vis spectral studies and single crystal X-ray analysis.

     

Supercritical ethanol--a fascinating dispersion medium for silica nanoparticles

For the first time, the dispersion stability of silica nanoparticles has been investigated in high-temperature and high-pressure ethanol by measuring the hydrodynamic diffusion coefficient of the particles by means of dynamic light scattering. The silica nanoparticles remain stable in ethanol within a wide temperature range of 24-304 degrees C at 12.3 MPa, and they start to aggregate at T >or= 305 degrees C. Numerical analysis reveals that the net interparticle repulsive potential barrier decreases dramatically with increasing temperature due to the changes in the properties of the medium. We observed that particles remain highly stable in the nonpolar supercritical ethanol in the temperature regime 241-304 degrees C, where the DLVO potential barrier is only 5-2 k(B)T. The dispersion stability of silica nanoparticles at this low potential barrier in high-temperature and high-pressure ethanol, especially in the supercritical ethanol, is fascinating. The silica-ethanol system might be a unique and special example in the colloidal dispersions. Results suggest that silica nanoparticles may be used as a model colloid to investigate the colloidal transport phenomena in the supercritical ethanol.     

Werner Complexes with ω‐Dimethylaminoalkyl Substituted Ethylenediamine Ligands: Bifunctional Hydrogen‐Bond‐Donor Catalysts for Highly Enantioselective Michael Additions

The racemic carbonate complex [Co(en)₂O₂CO]⁺ Cl^? (en=1,2‐ethylenediamine) and (S)‐[H₃NCH((CH₂)_nNHMe₂)CH₂NH₃]³⁺ 3 Cl^? (n=1–4) react (water, charcoal, 100 °C) to give [Co(en)₂((S)‐H₂NCH((CH₂)_nNHMe₂)CH₂NH₂)]⁴⁺ 4 Cl^? ( 3 a – d H⁴⁺ 4 Cl^?) as a mixture of Λ/Δ diastereomers that separate on chiral‐phase Sephadex columns. These are treated with NaOH/Na⁺ BAr_f^? (BAr_f=B(3,5‐C₆H₃(CF₃)₂)₄) to give lipophilic Λ‐ and Δ‐ 3 a–d ³⁺ 3 BAr_f^?, which are screened as catalysts (10 mol %) for additions of dialkyl malonates to nitroalkenes. Optimal results are obtained with Λ‐ 3 c ³⁺ 3 BAr_f^? (CH₂Cl₂, ?35 °C; 98–82 % yields and 99–93 % ee for six β‐arylnitroethenes). The monofunctional catalysts Λ‐ and Δ‐[Co(en)₃]³⁺ 3 BAr_f^? give enantioselectivities of <10 % ee with equal loadings of Et₃N. The crystal structure of Δ‐ 3 a H⁴⁺ 4 Cl^? provides a starting point for speculation regarding transition‐state assemblies.     

Novel Motif of Hydrogen Bonds in the Water-assisted Supramolecular Self-assembly of 2-acetylamino-6-methylpyridine-N-oxide and Hetero-assembly of 1:1 Co-crystal of o-Phenylenediamine with Catechol

Abstract

Water assisted supramolecular structures of 2-acetylamino-6-methylpyridine-1-oxide (1) and 1:1 complex of o-phenylenediamine with catechol (2) were determined. The crystal structure of 2-acetylamino-6-methylpyridine-1-oxide. H₂O (1), triclinic, a = 7.1276 (6), b = 7.8860 (6), c = 8.9938 (7) Å, α = 100. 143 (2), β = 91.493 (2), γ = 110.972 (1)°, V =462.47 (6) ų, Z = 2, D _calc = 1.323 mg.m^?3(293°K) reveals a novel centrosymmetric supramolecular assembly that is sustained by water molecules linking the dimers of pyridine-1-oxide through C—H…O, N—H…O, N⁺—O^? … H hydrogen bonds. The pyridine rings of the dimers are stacked at 3.473 Å apart, involving π- stacking interactions. Complex (2), C₆H₈N₂.—C₆ H₆O₂. 1/2H₂O crystallises in the monoclinic space group P2/c: a = 9.0498(2), b = 5.2275(1), c = 25.0771(2) A, β = 97.71°, V= 1175.62(4) ų, Z = 4. Refinement led to a final conventional R value of 0.041 for 2016 reflections. In these crystals (2), the water molecules lie on the twofold axis and they are linked to the pyrocatechol molecules through an O—H…O hydrogen bond.