Interpreting nucleation as a network formation process

In this paper we interpret nucleation as a network formation process. Inspired by this interpretation we propose a social network model which produces networks with communities.     

Site-selective C–H nitration of N-aryl-7-azaindoles under palladium(II) catalysis

The site-selective C–H nitration reaction of 7-azaindoles with t-butyl nitrite under palladium catalysis is described. This protocol provides an efficient method for the construction of ortho-nitrated N-aryl-7-azaindoles with excellent site-selectivity and functional group compatibility. The formed 7-azaindole derivatives can be readily transformed into 7-azaindoles containing an aniline functional group under palladium-catalyzed hydrogenation conditions.     

Structure and bonding in Hartwig stretched eta(3)-hydridoborate sigma-complex of niobium(III)

Ab initio calculations at the SCF, MP2, CASSCF, and CASPT2 levels of theory with basis sets using atomic pseudopotentials have been carried out for the stretched eta(3)-hydridoborate sigma-complex of niobium, [Cl2Nb(H2B(OH)2)], in order to investigate the nature and energetics of the interaction between the transition metal and the eta(3)-hydridoborate ligand. The geometry of the complex [Cl2Nb(H2B(OH)2] and its fragments [Cl2Nb](+) and [H2B(OH)2](-) were optimized at SCF and CASSCF levels. These results are consistent with [Cl2Nb(eta(3)-H2B(OH)2)] being a Nb(III) complex in which both hydrogen and boron of the [eta(3)-H2B(OH)2](-) ligand have a bonding interaction with the niobium preserving stretching B-H bond character. The calculated values of DEF (energy required to restore the fragment from the equilibrium structure to the structure it takes in the complex) for [Cl2Nb](+) are 5.35 kcal/mol at SCF, 3.27 kcal/mol at MP2, 4.80 kcal/mol at CASSCF, and 2.82 kcal/mol at CASPT2 and for [H2B(OH)2](-) 21.13 kcal/mol at SCF, 23.85 kcal/mol at MP2, 20.69 kcal/mol at CASSCF, and 23.48 kcal/mol at CASPT2. Values of INT (stabilization energy resulting from the coordination of distorted ligand to the metal fragment) for the complex [Cl2Nb(H2B(OH)2)] are -239.35 kcal/mol at SCF, -260.00 kcal/mol at MP2, -230.76 kcal/mol at CASSCF, and -252.60 kcal/mol at CASPT2. For the complex [(eta(5)-C5H5)2Nb(H2B(OH)2)], calculations at the SCF and MP2 levels were carried out. Values of INT for [(eta(5)-C5H5)2Nb(H2B(OH)2)] are -169.93 kcal/mol at SCF and -210.62 kcal/mol at MP2. The results indicate that the bonding of the [eta(3)-H2B(OH)2](-) ligand with niobium is substantially stable. The electronic structures of [Cl2Nb(H2B(OH)2)], [(eta(5)-C5H5)2Nb(H2B(OH)2)], and its fragments are analyzed in detail as measured by Mulliken charge distributions and orbital populations.     

Photochemical and electrochemical properties of zinc chlorin-C60 dyad as compared to corresponding free-base chlorin-C60, free-base porphyrin-C60, and zinc porphyrin-C60 dyads.

The photochemical and electrochemical properties of four chlorin-C60 or porphyrin-C60 dyads having the same short spacer between the macrocycle and the fullerene are examined. In contrast with all the previous results on porphyrin-fullerene dyads, the photoexcitation of a zinc chlorin-C60 dyad results in an unusually long-lived radical ion pair which decays via first-order kinetics with a decay rate constant of 9.1 x 10(3) x s(-1). This value is 2-6 orders of magnitude smaller than values reported for all other porphyrin or chlorin donor-acceptor of the molecule dyad systems. The formation of radical cations of the donor part and the radical anion of the acceptor part was also confirmed by ESR measurements under photoirradiation at low temperature. The photoexcitation of other dyads (free-base chlorin-C60, zinc porphyrin-C60, and free-base porphyrin-C60 dyads) results in formation of the ion pairs which decay quickly to the triplet excited states of the chlorin or porphyrin moiety via the higher lying radical ion pair states as is expected from the redox potentials.     

A novel photoadditive for polyolefin photostabilization: hindered amine light stabilizer

Hindered‐amine light stabilizers were surface anchored to polyethylene and polypropylene thin films by: i) direct photo‐grafting of 1,2,2,6,6‐pentamethyl piperidinyl‐4‐acrylate onto the surface and ii) by reacting of 1,2,2,6,6‐pentamethyl‐4‐piperidinol with succinic anhydride functionalized polyolefin surface. The samples were exposed to UV irradiation in air and the oxidative‐degradation of the polymers was studied with FT‐IR spectroscopy. The photo‐stability of surface anchored Hindered‐amine stabilizers (HAS) was compared with films stabilized with commercial HAS by melt blending. The results of the study evince superiority of surface anchored HAS over that of melt blended polyolefins.     

Controlled growth of flower-like,rod-like,and snowflake-like ZnO nanostructures using agarose as biotemplate and its photoluminescence property

Different nanostructures such as flower-like, rod-like, and snowflake-like of ZnO have been synthesized by varying the amount of agarose using sonochemical method. It is found that morphology is governed by amount of agarose as well as ultrasonic treatment. Three amounts of agarose 0.01, 0.1, and 1.00 g are used to investigate its effect on ZnO. X-ray diffraction (XRD) confirmed the formation of single phase with hexagonal structure. Scanning electron microscopy (SEM) showed flower-like, rod-like, and snowflake-like morphology for 1.00, 0.1, and 0.01 g agarose, respectively. UV/Visible absorption study showed blue shift at band-edge absorption in comparison to bulk ZnO. Photoluminescence spectra showed band-edge emission at 399 nm for lowest amount of agarose which quenched on increasing the agarose amount. These findings show a better and more environment friendly procedure for production of ZnO of readily adjustable morphology.     

Manifestation of strong magneto-electric dipolar coupling in ferromagnetic nanoparticles−FLC composite: evaluation of time-dependent memory effect

Rod-shaped 5 wt.% copper-doped ZnO (ZnO:Cu²⁺) ferromagnetic nanoparticles (NPs), prepared by hydrothermal method, were dispersed in ferroelectric liquid crystal (FLC) named Felix 17/100. The effect of ferromagnetic NPs on the physical properties of FLC material (Felix 17/100) has been investigated by dielectric, electro-optical and polarising optical microscopic methods. A noteworthy time-dependent memory has been observed in the NPs-dispersed FLC composite attributed to the coupling of magnetic field associated to NPs with the director orientation of FLC. Improvement in spontaneous polarisation and dielectric susceptibility of FLC material has been ensued with the addition of ferromagnetic NPs. Faster electro-optic response, at lower applied voltage, has also been observed in NPs-dispersed FLC composite. These changes are accredited to the magneto-electric dipolar coupling existing due to the interactions between magnetic-dipole and electric-dipole moments of magnetic NPs and FLC material, respectively. The formation of periodic domains capable to show memory effect has been observed in composite. The observed time-dependent memory was confirmed by dielectric and electro-optical methods. FLC material enriched with the properties of ferromagnetic NPs can be utilised in advanced multifunctional optical devices, time-dependent memory-based security devices and computational purposes.     

Fluorescent zinc(II) complex exhibiting "on-off-on" switching toward Cu2+ and Ag+ ions

Binuclear zinc(II) and copper(II) complexes based on a new Schiff base ligand N,N'-bis(2-hydroxybenzilidene)-2,4,6-trimethylbenzene-1,3-diamine (H(2)L) have been synthesized. The ligand H(2)L and complexes under investigation have been characterized by elemental analyses, spectral (FT-IR, (1)H, (13)C NMR, ESI-MS, electronic absorption, emission), and electrochemical studies. The structures of H(2)L and complexes [{Zn(C(23)H(18)N(2)O(2))}(2)] (1) and [{Cu(C(23)H(18)N(2)O(2))}(2)]·H(2)O (2) have been determined crystallographically. Selective "On-Off-On" switching behavior of the fluorescent complex 1 has been studied. The fluorescence intensity of 1 quenches (turns-off) upon addition of Cu(2+), while enhances (turns-on) in the presence of Ag(+) ions. The mechanisms of "On-Off-On" signaling have been supported by (1)H NMR, ESI-MS, electronic absorption, and emission spectral studies. Job's plot analysis supported 1:1 and 1:2 stoichiometries for Cu(2+) and Ag(+) ions, respectively. Association and quenching constants have been estimated by the Benesi-Hildebrand method and Stern-Volmer plot. Moreover, 1 mimics a molecular keypad lock that follows correct chemical input order to give maximum output signal.     

Unique role of hydrophilic ionic liquid in modifying properties of aqueous Triton X-100

Modification of important physicochemical properties of aqueous surfactant solutions can be achieved by addition of environmentally benign room temperature ionic liquids (ILs). While low aqueous solubility of "hydrophobic" ILs limits the amount of IL that may be added to achieve desired changes in the physicochemical properties, hydrophilic ILs do not have such restrictions associated to them. Alterations in the key physicochemical properties of aqueous solutions of a common nonionic surfactant Triton X-100 (TX100) on addition of up to 30 wt % hydrophilic IL 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) are reported. The presence of micellar aggregates in as high as 30 wt % [bmim][BF4]-added aqueous TX100 solutions is established by dynamic light scattering and fluorescence probe behavior. Increasing the concentration of [bmim][BF4] results in decrease in average micellar size and aggregation number and increase in critical micelle concentration, indicating an overall unfavorable aggregation process. Increase in the dipolarity and the microfluidity of the probe cybotactic region within the palisade layer of the micellar phase upon [bmim][BF4] addition implies increased water penetration and the possibility of TX100-[bmim][BF4] interactions. While the changes in some of the physicochemical properties indicate the role of [bmim][BF4] to be similar to a cosurfactant, the IL acts like a cosolvent as far as changes in other properties are concerned. Effectiveness of IL [bmim][BF4] in modifying physicochemical properties of aqueous TX100 is demonstrated.