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Vinylporphyrins containing one vinyl group at the pyrrole or benzene ring and their complexes with Cu²⁺ and Zn²⁺ have been obtained by the Wittig reaction. The compounds obtained were characterized by physicochemical methods. X-ray diffraction analysis of 5-(4-vinylphenyl)-10,15,20-triphenylporphyrin has been carried out. It is likely that the inclusion of the vinyl group is accompanied by weak electron effects on the macrocycles. The radical-induced copolymerization of meso-tetraphenylporphyrin monomers with the vinyl group in a benzene or pyrrole ring and their copper and zinc complexes with styrene and methacrylate was studied. Porphyrin comonomers decrease the overall polymerization rate and the number-average molecular weight of the products formed compared with the weight of polystyrene obtained under similar conditions. The main reasons for termination of chain growth by vinylporphyrins were revealed and some quantitative parameters of these reactions were obtained. IR and electronic absorption spectra of porphyrin-containing copolymers are discussed. According to the ESR spectra, the copper-containing centres in the copolymers are fairly remote from each other, and the metal-containing polymeric systems are magnetically dilute. The spectral luminescence properties of solutions of zinc 5-(4-vinylphenyl)-10,15,20-triphenylporphyrin–methyl methacrylate copolymers with various contents of porphyrin groups were studied. It was shown that a new long-wave band appears in the absorption spectra of the copolymers, the intensity of which depends on the copolymer composition, and the quantum yield of fluorescence decreases with increasing molar fraction of porphyrin groups.

This article reports the first perbromination of β-pyrrole and meso-phenyl groups of the 5,10,15,20-tetrakis(3',5'-dimethoxyphenyl)porphinato copper(II) to generate highly brominated porphyrin, 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(2',6'-dibromo-3',5'-dimethoxyphenyl)-porphinato copper(II), CuT(3',5'-DMP)PBr₁₆ complex. Its crystal structure exhibited unusual five-coordination geometry with saddle shaped conformation of the porphyrin core. H₂T(3',5'-DMP)PBr₁₆ and its metal complexes exhibited large anodic shift of oxidation potentials with marginal changes in reduction potentials relative to their corresponding octabromotetraphenylporphyrin, MTPPBr₈ derivatives. The enhanced electron deficiency of the ZnT(3',5'-DMP)PBr₁₆ complex was probed by axial ligation of various Lewis bases with differing pK_a values. The ZnT(3',5'-DMP)PBr₁₆ complex exhibited decrease in equilibrium constants for the ligation of bases relative to sterically unhindered ZnTPPBr₈. This has been ascribed to the sterics induced by the bulky ortho-bromo phenyl substituents that prevents the facile binding of Lewis bases to the Zn(II)-center.

“Non-fluorescent” chlorophyll catabolites (NCCs) were named “rusty pigments” originally, as they easily oxidized to yellow chlorophyll catabolites (YCCs) and other colored natural “phyllobilins.” In the present work, binding of Zn(II)-ions by YCC and its methyl ester YCC-Me, and structural investigations of the resulting Zn(II)-complexes are reported. Binding of Zn-ions to the weakly luminescent YCC or YCC-Me in DMSO produces orange-yellow complexes that exhibit strong green emission. The Zn-complex of YCC-Me was isolated and characterized by UV-vis-, fluorescence-, mass- and NMR-spectra. The data revealed a 2:1 complex, Zn(YCC-Me)${}_2$, in which YCC-Me serves as bidentate ligand. The Zn(II)-center in Zn(YCC-Me)${}_2$ is, thereby, deduced to be coordinated in a pseudo tetrahedral fashion. Formation of Zn(YCC-Me)${}_2$ (and of Zn(YCC)${}_2)$ is compatible with an isomerization of the lactam form of ring D to the corresponding lactim tautomer in these neutral Zn(II)-complexes.

A new series of mono-/di-aminated meso-tetraarylporphyrins has been synthesized and characterized by conventional spectroscopic methods. Crystal structure analysis shows that interactions involving halogens are the major contributors, and the relative contributions are 56% and 53% respectively for MB2c and MB3c. All the compounds were electrochemically analyzed under different reaction conditions and showed a positive shift in the reduction and oxidation potentials. The HOMO–LUMO energy gap was altered with respect to the nature of the supporting electrolyte and reference electrodes used. The linear behavior of Randles-Sevcik plots indicate that the redox processes are diffusion controlled; the first reduction/oxidation is a reversible one-electron step whereas the second reduction/oxidation is a quasi-reversible one-electron process. Results also reveal that the mono-aminated porphyrins are more electron deficient than non-aminated and di-aminated porphyrins.

Expanded nonaromatic stable porphyrins(2.1.2.1) were successfully synthesized by 2,3-di(1H-pyrrol-2-yl)naphthalene as buliding blocks and aromatic aldehydes under acid catalyzed condensation conditions in acceptable isolated yields. NMR, X-ray diffraction analysis, absorption, electrochemical, and density functional theory revealed these macrocycles to be non-aromatic due to highly saddle-shaped molecular structures of dinaphthoporphyrin(2.1.2.1). The saddle-shaped dinaphthoporphyrins(2.1.2.1) with embedded naphthalene units as $\pi$-conjugation units show perturbations to molecular structure, optical and electronic properties. The dinaphthoporphyrins(2.1.2.1) are effective macrocyclic ligands giving copper(II) and nickel(II) complexes.

The dynamical properties of interacting colloids spatially restricted to move in one-dimensional channels [J. Chem. Phys. 133, 114902 (2010)] and subjected to external periodic energy landscapes [Phys. Rev. E 86, 081123 (2012)] have been recently reported in terms of the long-time self-diffusion behavior. However, the full description of the mean-square displacement, ranging from short times to long times, is still missing. Thus, by means of Brownian dynamics computer simulations, we revisit the process known as single-file diffusion in driven interacting colloidal systems at all time scales. In particular, we review three different pair potentials, namely, Weeks–Chandler–Andersen, Yukawa and superparamagnetic potentials. We mainly focus on the importance of the correlation between particles via the coupling among hydrodynamic interactions and the external periodic field, resulting in nontrivial particle dynamics along the file in systems composed of repulsively interacting particles.

 Special Issue Comments: This article reviews results on the dynamical properties of interacting colloids in a single file when they are subjected to external periodic energy landscapes presented before in [J. Chem. Phys. 33, 114902 (2010)] and [ Phys. Rev. E 86, 081123 (2012)]. We analyze different interactions that cover from short to long ranges of the interparticle potentials. We mainly focus on the importance of the correlation between particles via the coupling among the hydrodynamic interactions and the external periodic field.

Note from Publisher: In the captions of Figs. 1 through 4, "??" has appeared where the number 9 should appear.

In table 1, in the WCA section, the variable "φ" shows the values: 0.2,0.3,0.3,0.3,0.3,0.3.

The correct values are: 0.2, 0.3, 0.4, 0.5 , 0.6 , 0.7.

Naturally derived biopolymers have been widely used for biomedical applications such as drug carriers, wound dressings, and tissue engineering scaffolds. Chitosan is a typical polysaccharide of great interest due to its biocompatibility and film-formability. Chitosan membranes with controllable porous structures also have significant potential in membrane chromatography. Thus, the processing of membranes with porous nanoscale structures is of great importance, but it is also challenging and this has limited the application of these membranes to date. In this study, with the aid of a carefully selected surfactant, polyethyleneglycol stearate-40, chitosan membranes with a well controlled nanoscale structure were successfully prepared. Additional control over the membrane structure was obtained by exposing the suspension to high intensity, low frequency ultrasound. It was found that the concentration of chitosan/surfactant ratio and the ultrasound exposure conditions affect the structural features of the membranes. The stability of nanopores in the membrane was improved by intensive ultrasonication. Furthermore, the stability of the blended suspensions and the intermolecular interactions between chitosan and the surfactant were investigated using scanning electron microscope and Fourier transform infrared spectroscopy (FTIR) analysis, respectively. Hydrogen bonds and possible reaction sites for molecular interactions in the two polymers were also confirmed by FTIR analysis.

We have investigated the crystal structure, the microstructural and morphological characteristics, as well as the magnetic properties of Co nanoparticles (NPs) synthesized by a hydrothermal method. A series of samples has been elaborated for different concentrations of sodium hydroxide. The analysis of X-ray diffraction patterns, using two different wavelengths, has evidenced the coexistence of both $\alpha$-Co and $\beta$-Co phases in the samples. The lattice parameter for both phases is in good agreement with those values expected for their bulk Co counterparts; the grain sizes of NPs were found to be dependent on the NaOH concentration. The scanning electron microscope micrographs show that Co NPs are agglomerated forming micrometer-sized entities whose shape evolves, indicating that the synthesis process affects the morphology of the powdered samples. Magnetic measurements indicate that the coercivity is slightly larger, $H_C>200$ Oe, for Co NPs with dendritic-like shape, probably due to an increase in the magnetocrystalline anisotropy.

Magnetometry and atomic force microscopy (AFM) were used to study the magnetic and structural properties of the R–Fe–B-type (R = Y, Nd, Gd, Ho) alloys. The alloys were synthesized by means of induction melting. The nanocrystalline state of the R–Fe–B-type alloys was reached, mainly, by melt spinning (MS). A multistage treatment of R–Fe–B-type alloys, which included severe plastic deformation of melt-quenched ribbons and subsequent heat treatment, was also used. The surface morphology of samples was studied in detail to interpret the observed magnetic hysteresis loops of the samples. It was found that the type of rare earth ion and treatment methods had the most important influence on the microstructure and magnetic properties.

The structural, electronic, magnetic, and optical properties of Au, Cu, Cr, Mn, Co, Ni, and Fe atoms doped 13-atom silver clusters were investigated by the density functional theory (DFT) in the theoretical frame of the generalized gradient approximation (GGA) exchange-collection function. The results show that all the ground state structures of Au, Cu, Cr, Mn, Co, Ni, and Fe atoms doped 13-atom silver clusters are icosahedral, respectively. The Au atom doped on the surface of Ag${}_{13}$ cluster is stable, while other atoms doped in the center of Ag${}_{13}$ cluster are stable. The electronic stability order from high to small is Ag${}_{12}$Cr₁, Ag${}_{12}$Cu₁, Ag${}_{12}$Co₁, Ag${}_{12}$Fe₁, Ag${}_{12}$Au₁, Ag${}_{12}$Mn₁, Ag${}_{12}$Ni₁. Their magnetic moments are not only related to the doping atom but also the doping location of the atom. The magnetic moments of the Cu, Au, Mn, Co, Ni, Fe, and Cr atoms doped in the Ag${}_{13}$ cluster are 5.0, 3.0, 1.0, 3.0, 4.0, 2.0, and 0.0${\mu }_B$, respectively. Compared with the optical absorption spectrum of the Ag${}_{13}$ cluster, the Au, Cr, and Mn atoms doped the Ag${}_{13}$ cluster leading to blue shift, and the Cu, Co, Ni, and Fe atoms doped the Ag${}_{13}$ cluster resulting in red shift. These studies provide a theoretical basis on applications for clusters in electronic, magnetic, and optical devices.