Size evolution of gold nanoparticles in a millifluidic reactor

The size evolution of gold nanoparticles in a millifluidic reactor is investigated using spatially resolved transmission electron microscopy (TEM). The experimental data is supported by numerical simulations, carried out to study the residence-time distribution (RTD) of tracers that have the same properties as Au ions. Size and size distribution of the particles within the channels are influenced by the mixing zones as well as the RTD. However, the Au nanoparticles obtained show a broader size distribution even at the shortest investigated residence time of 3.53 s, indicating that in addition to surface growth reaction kinetics also plays an important role. The comparison of time resolved particle growth within the millifluidic channel with flask-based reactions reveals that the particle size can be controlled better within millifluidic channels. Overall, the results indicate potential opportunities to utilize easy to fabricate millifluidic reactors for the synthesis of nanoparticles, as well as as for carrying out time resolved kinetic studies.     

Triple-stranded helicates of zinc(II) and cadmium(II) involving a new redox-active multiring nitrogenous heterocyclic ligand: synthesis, structure, and electrochemical and photophysical properties

The protonated form [H(2)(L)](CF(3)SO(3))(2) (1) of a new redox-active bis-bidentate nitrogenous heterocyclic ligand, viz., 3,3'-dipyridin-2-yl[1,1']bi[imidazo[1,5-a]pyridinyl] (L), and its zinc(II) and cadmium(II) complexes (2 and 3) have been synthesized and characterized by single-crystal X-ray diffraction analysis. In the solid state, both 2 and 3 have triple-stranded helical structures involving ligands that experience twisting and bending to the extent needed by the stereoelectronic demand of the central metal ion. The metal centers in the zinc(II) complex [Zn(2)(L)(3)](ClO(4))(4) (2) are equivalent, each having a distorted octahedral geometry, flattened along the C(3) axis with a Zn1···Zn1# separation of 4.8655(13) ?. The cadmium complex [Cd(2)(L)(3)(H(2)O)](ClO(4))(4) (3), on the other hand, has a rare type of helical structure, showing coordination asymmetry around the metal centers with a drastically reduced Cd1···Cd2 separation of 4.070 ?. The coordination environment around Cd1 is a distorted pentagonal bipyramid involving a N(6)O donor set with the oxygen atom coming from a coordinated water, leaving the remaining metal center Cd2 with a distorted octahedral geometry. The structures of 2 and 3 also involve anion-π- and CH-π-type noncovalent interactions that play dominant roles in shaping the extended structures of these molecules in the solid state. In solution, these compounds exhibit strong fluxional behavior, making the individual ligand strands indistinguishable from one another, as revealed from their (1)H NMR spectra, which also provide indications about these molecules retaining their helical structures in solution. Electrochemically, these compounds are quite interesting, undergoing ligand-based oxidations in two successive one-electron steps at E(1/2) of ca. 0.65 and 0.90 V versus a Ag/AgCl (3 M NaCl) reference. These molecules are all efficient emitters in the red and blue regions because of ligand-based π*-π fluorescent emissions, tuned appropriately by the attached Lewis acid centers.     

Photoinduced intermolecular electron transfer from dimethyl aniline to 7-amino coumarin dyes in the surface of beta-cyclodextrin

The photoinduced electron-transfer reaction between Coumarin dyes and N,N-dimethylaniline has been investigated using steady-state and Time-resolved fluorescence spectroscopy in the surface of beta-cyclodextrin in dimethyl formamide (DMF) solvent. The electron-transfer rate constant has been correlated with the free-energy change during the process. We have observed a diffusion-controlled ET process in pure DMF by showing a normal Marcus region. However, the picture is different in presence of cyclodextrin. Here the ET is retarded at higher free-energy region. This unusual feature in bimolecular electron-transfer reaction is assumed to be arising from the different binding possibility of the Coumarin molecules to the cyclodextrin moity.     

Cluster based copper(II)-azide polymer: Synthesis,structure and magnetic study

The reaction of ethylene diamine with Cu(NO₃)₂·3H₂O and an excess of NaN₃ (1:2:4 molar ratio) lead to the formation of copper-azido based polymer [Cu₄(N₃)₈(en)₂]_n (1), which has been successfully characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction and variable temperature magnetic study. X-ray crystal structure determination of 1 reveals that the structure consists of 1D chains of a centrosymmetric tetranuclear copper(II)-azido cluster, connected through double azido end-to-end bridges. Variable-temperature magnetic studies (between 2 and 300 K) suggest dominant antiferromagnetic interactions in this complex, although ferromagnetic interactions have been observed in all other copper-azido based polymers produced with ethylene diamine reported so far.     

Undirected power graphs of semigroups

The undirected power graph G(S) of a semigroup S is an undirected graph whose vertex set is S and two vertices a,b∈S are adjacent if and only if a≠b and a ^m =b or b ^m =a for some positive integer m. In this paper we characterize the class of semigroups S for which G(S) is connected or complete. As a consequence we prove that G(G) is connected for any finite group G and G(G) is complete if and only if G is a cyclic group of order 1 or p ^m . Particular attention is given to the multiplicative semigroup ℤ _n and its subgroup U _n , where G(U _n ) is a major component of G(ℤ _n ). It is proved that G(U _n ) is complete if and only if n=1,2,4,p or 2p, where p is a Fermat prime. In general, we compute the number of edges of G(G) for a finite group G and apply this result to determine the values of n for which G(U _n ) is planar. Finally we show that for any cyclic group of order greater than or equal to 3, G(G) is Hamiltonian and list some values of n for which G(U _n ) has no Hamiltonian cycle.     

A Quinoxaline−Naphthaldehyde Conjugate for Colorimetric Determination of Copper Ion

This work facilitates detection of bivalent copper ion by a simple Schiff base probe QNH based on a quinoxaline−naphthaldehyde framework. The detailed study in absorption spectroscopy and theoretical aspects and crystal study of the probe and probe−copper complex has been discussed. The detection limit of the probe in the presence of Cu²⁺ is 0.45 µM in HEPES−buffer/acetonitrile (3/7, v/v) medium for absorption study. The reversibility of the probe−copper complex has been investigated by EDTA. The selective visual detection of copper has been established also in gel form.