Heterogeneity of polyelectrolyte diffusion in polyelectrolyte-protein coacervates: a 1H pulsed field gradient NMR study

Proton pulsed field gradient (PFG) NMR was used to study the diffusion of poly(diallyldimethylammonium chloride) (PDADMAC) in coacervates formed from this polycation and the protein bovine serum albumin (BSA). Application of high (up to 30 T/m) magnetic field gradients in PFG NMR measurements allowed probing the diffusion of PDADMAC on a length scale of displacements as small as 100 nm in coacervates formed at different pH's and ionic strengths, i.e., conditions of varying protein-polycation interaction energy. Studies were carried out for a broad range of diffusion times and corresponding values of the mean square displacements. Several ensembles of PDADMAC polycations with different diffusivities were observed in the measured range of diffusion times. The existence of these ensembles and the pattern of their changes with increasing diffusion time support the hypothesis about the microscopic heterogeneity of PDADMAC-BSA coacervates and also provide evidence for the dynamic disintegration and reformation of dense domains.     

Synthesis and structural characterisation of new Re(III) complexes using aldimines of α-amino acids as coligands

Complexes of the general formula [Re^III(L)Cl(PPh₃)₂] have been synthesised by reacting H₂L and [ReOCl₃(PPh₃)₂] in ethanol. Here H₂L represents imines of α-amino acids (glycine, l-alanine, l-valine, l-phenylalanine) derived from salicylaldehyde and naphthaldehyde. The crystal structure of one complex has been determined. The complexes are mononuclear, paramagnetic and display paramagnetic ¹H NMR in CDCl₃ solution. Their spectral and redox properties are scrutinised.     

Three new pseudohalide bridged dinuclear Zn(II) Schiff base complexes: Synthesis,crystal structures and fluorescence studies

Three new dinuclear Zn(II) complexes [Zn(L)(μ_1,1-N₃)Zn(L)(N₃)] · 1.5H₂O (1), [Zn(L)(μ_1,1-NCO)Zn(L)(NCO)] · 1.5H₂O (2) and [Zn(L)(μ_1,1-NCS)Zn(L)(NCS)(OH₂)] (3) have been synthesized from a potentially tetradentate N₂O₂-donor Schiff base ligand LH, [LH = (OCH₃)(OH)C₆H₃CHN(CH₂)₂N(CH₃)₂], which is the condensation product of o-vanillin and 2-dimethylaminoethylamine. All the three complexes 1, 2 and 3 have been characterized by elemental analysis, IR and ¹H NMR spectroscopy, TGA and fluorescence studies. Finally, their structures have been established by the single crystal X-ray diffraction method. Structural studies reveal that in complexes 1, 2 and 3 the two Zn(II) centers are held together by a μ₂-phenolato oxygen atom and also by an end-on pseudohalide nitrogen (azide for 1; cyanate for 2; thiocyanate for 3) atom. Among the two deprotonated Schiff base ligands present in each complex, one acts as a tetradentate ligand (N₂O₂ donor set) while the other acts as a tridentate ligand (N₂O donor set), having a non-coordinated methoxy group. All the synthesized complexes display intraligand ¹(π–π^∗) fluorescence and can potentially serve as photoactive materials.     

Spray reagents for the detection of amino-acids on thin-layer plates

Three spray reagents for the detection of amino-acids on silica-gel thin-layer chromatography plates are reported. The reagents produce various colours, which may be used to identify some of the amino-acids directly, and assist in their detection.     

First example of the C-alkylation of indoles with Baylis-Hillman acetates

Baylis-Hillman acetates undergo S_N2′ allylic substitution with indoles in the presence of 20 mol % of indium tribromide under mild conditions to afford a new class of substituted indoles in high yields with (E)-stereoselectivity. The stereochemistry of the products was assigned by various NMR experiments.     

Ultrafast energy-electron transfer cascade in a multichromophoric light-harvesting molecular square

A molecular square with dimensions of about 4 nm, incorporating sixteen pyrene chromophores attached to four ditopic bay-functionalized perylene bisimide chromophores, has been synthesized by coordination to four Pt(II) phosphine corner units and fully characterized via NMR spectroscopy and ESI-FTICR mass spectrometry. Steady-state and time-resolved emission as well as femtosecond transient absorption studies reveal the presence of a highly efficient (>90%) and fast photoinduced energy transfer (k(en) approximately equal to 5.0 x 10(9) s(-1)) from the pyrene to the perylene bisimide chromophores and a very fast and efficient electron transfer (>94%, k(et) approximately equal to 5 x 10(11) up to 43 x 10(11) s(-1)). Spectrotemporal parametrization indicates upper excited-state electron-transfer processes, various energy and electron-transfer pathways, and chromophoric heterogeneity. Temperature-dependent time-resolved emission spectroscopy has shown that the acceptor emission lifetime increases with decreasing temperature from which an electron-transfer barrier is obtained. The extremely fast electron-transfer processes (substantially faster and more efficient than in the free ligand) that are normally only observed in solid materials, together with the closely packed structure of 20 chromophoric units, indicate that we can consider the molecular square as a monodisperse nanoaggregate: a molecularly defined ensemble of chromophores that partly behaves like a solid material.