Electrochemical, spectral, and computational studies of metalloporphyrin dimers formed by cation complexation of crown ether cavities

The effect on the electrochemical oxidation and reduction potentials of 5,10,15,20-tetrakis(benzo-15-crown-5)porphyrin (TCP) and its metal derivatives (MTCP; M = Mg(II), VO(IV), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Ag(II)) upon potassium ion induced dimerization of the porphyrins was systematically performed in benzonitrile containing 0.1 M (TBA)ClO(4) by differential pulse voltammetry technique. The HOMO--LUMO energy level diagram constructed from the electrochemical data revealed destabilization of the HOMO level and stabilization of the LUMO level upon dimer formation while such a perturbation was larger for the HOMO level than the LUMO level. The geometry and electronic structure of a representative ZnTCP and its dimer, K(4)(ZnTCP)(2), were evaluated by the ab initio B3LYP method utilizing a mixed basis set of 3-21G(*) for Zn, K, O, and N and STO-3G for C and H. The inter-porphyrin ring distance of the dimer calculated from the optimized geometry agreed with the spectroscopically determined one, and the calculated HOMO and LUMO frontier orbitals revealed delocalization on both of the porphyrins rings. The metal-metal distances calculated from the triplet ESR spectra of the K(+) induced porphyrin dimers bearing paramagnetic metal ions in the cavity followed the trend Cu--Cu < VO--VO < Ag--Ag. However, the spectral shifts resulting from the exciton coupling of the interacting porphyrin pi-systems revealed no specific trend with respect to the metal ion in the porphyrin cavity. Additionally, linear trends in the electrochemically measured HOMO--LUMO gap and the energy corresponding to the most intense visible band of both MTCP and K(4)(MTCP)(2) were observed. A reduced HOMO--LUMO gap predicted for the dimer by B3LYP/(3-21G(), STO-3G) calculations was confirmed by the results of optical absorption and electrochemical studies.     

Parity of the band head at 3710 keV in 99Rh using clover detector as compton polarimeter

Clover detector has been used as a Compton polarimeter to measure the linear polarization of γ-rays produced in heavy ion fusion reaction. The polarization sensitivity of the clover detector has been measured over γ-ray energies ranging from 386 to 1368 ke V. The E1 multipolarity of the 1117 keV transition in ⁹⁹Rh has been established using this polarimeter. This has resulted in the assignment of negative parity to the band head at 3710 keV in ⁹⁹Rh.     

An alternative approach to determine the spot-size of a multi-mode laser beam and its application to diode laser beams

An alternative approach is suggested to determine the spot-size of a multi-mode laser beam. It has been shown by simulations that the suggested approach can give the beam quality factor and characteristic radius with less than 5% error. Unlike the power content method, the proposed method is applicable to the beams even with diameter one tenth of the CCD size. The new approach has been applied to a multi-mode diode laser output and it is shown that the ABCD matrix analysis can be used for beam propagation, with the measured parameters of the laser.     

Synthesis and properties of iron(II) and manganese(II) complexes derived from a topologically constrained pentadentate ligand

The novel bicyclic pentadentate ligand 5-methyl-1,5,9,24,25-pentaazapentacyclo[7.7.7.5.5]pentacosane11,13,15,18(25),20,22-hexene (L1) has been synthesized. Because of its cross-bridged topology it exhibits a relatively rigid preorganized conformation especially appropriate to complex formation, as shown by the crystal structure of the monoprotonated ligand salt, HL1ClH2O [orthorhombic, P212121, a = 9.4405(5) A, b = 13.3617(5) A, c = 16.710(1) A]. The complexes of L1 with both iron(II) and manganese(II) have been characterized, including the crystal structures of [FeL1CH3CN][FeCL4] and [MnL1Cl][PF6] [monoclinic, P21/n, a = 10.0460(5) A, b = 19.237(9) A, c = 15.6254(8) A, beta = 95.97(2)degrees and a = 7.745(2) A, b = 22.786(4) A, c = 14.639(4) A, beta = 105.074(10)degrees respectively]. The manganese complex is high spin with mueff = 5.96 and theta = 2.5 +/- 0.8 cm(-1), indicating weak ferromagnetic interactions. The reactions of the complexes with tert-butyl hydroperoxide and hydrogen peroxide have been shown by ESR spectroscopy to produce the tert-butyl peroxyl and hydroperoxyl radicals, as evidenced by their spin adducts with the spin traps N,N-dimethyl-1-pyrroline-N-oxide and N-tert-butyl-phenyl-nitrone.     

Thermal characterization of a nanofluid comprising nanocrystalline ZrO2 dispersed in water and ethylene glycol

Nanofluids, comprising Y₂O₃-stabilized (partially; 3?mol%) ZrO₂ nanoparticles (up to 2?vol%) dispersed in water and ethylene glycol, were developed. A suitable surfactant and stirring routine ensured uniformity and stability of dispersion. Thermal conductivity ratio of the nanofluids, measured using an indigenously developed thermal comparator device, showed a significant increase of up to 100% with only 1.5?vol% nanoparticles. Furthermore, it was analytically shown that shape factor and aspect ratio significantly influence the effective thermal conductivity ratio of nanofluids with comparable vol% nanoparticles. The study demonstrated that a nanofluid of nano-ZrO₂ dispersed in water and ethylene glycol could be usefully applied in closed-loop single-phase heat transfer conditions, such as in refrigerators or microchannels.