Phototoxicity of Some Bromine-Substituted Rhodamine Dyes: Synthesis, Photophysical Properties and Application as Photosensitizers

Abstract— The synthesis of some bromine-substituted rhodamine derivatives viz. , 4,5-dibromorhodamine methyl ester (dye 2) and 4,5-dibromorhodamine n -butyl ester (dye 3) are reported. These dyes were synthesized to promote a more efficient cancer cell photosensitizer for potential use in in vitro bone marrow purging in preparation for autologous bone marrow transplantation. Spectroscopic and photo-physical characterization of these dyes together with rhodamine 123 (dye 1) are reported in water, methanol, eth-anol and also in a microheterogeneous system, sodium dodecyl sulfate. The possible mechanism of photosensi-tization is characterized in terms of singlet oxygen efficiency of these dyes. Singlet oxygen quantum yields for bromine-substituted dyes are in the range of 0.3-0.5 depending on the solvent. For dye 1 no singlet oxygen production is found. The photodynamic actions of these dyes in different cell lines are tested. It was found that dye 2 and dye 3 are efficient photosensitizers and mediate eradication of K562, EM2, myeloid cell lines (CML) and the SMF-AI rhabdomyosarcoma line.     

A sequence of improvements over the James-Stein estimator

In this article, we consider the problem of estimating a p-variate (p ≥ 3) normal mean vector in a decision-theoretic setup. Using a simple property of the noncentral chi-square distribution, we have produced a sequence of smooth estimators dominating the James-Stein estimator and each improved estimator is better than the previous one. It is also shown by using a technique of [5]. J. Multivariate Anal.36 121–126) that our smooth estimators can be dominated by non-smooth estimators.     

Axions from chiral family symmetry

We investigate the possibility that family symmetry, G_F, is spontaneously broken chiral global symmetry. We classify the interesting cases when family symmetry can result in an automatic Peccei-Quinn symmetry U(1)_PQ and thus provide a solution to the strong CP problem. The result disfavors having two or four families. For more than four families, U(1)_PQ is in general automatic. In the case of three families, a unique Higgs sector allows U(1)_PQ in the simplest case of G_F = [SU(3)]³. Cosmological consideration also puts strong constraint on the number of families. For G_F = [SU(N)]³ cosmology singles out the three-family (N = 3) case as a unique solution if there are three light neutrinos. Possible implication of decoupling theorem as applied to family symmetry breaking is also discussed.     

Spectrophotometric study of the interaction of some hydroxyanthraquinones (HAQs) with magnesium(II) in a cationic micelle

Six different hydroxyanthraquinones (HAQs) in aqueous micellar (cationic, anionic and non-ionic) media were tested as effective and selective chelators for the MgII ion in alkaline conditions. Of these 1,4 and 1,8-dihydroxyanthraquinones were found to effectively bind to MgII ions and were useful for the ppm level spectral determination of MgII ion. The MgII ion forms 1 : 1 and 1 : 2 chelates with 1,4-and 1,8-dihydroxyanthraquinones, respectively, which have maximum absorption at 610 and 575 nm, respectively. MgII can be determined in the presence of a large excess of foreign ions including the CaII ion. The statistical analysis of the results, apparent pK(a), expected bathchromic shift of the reagent absorption, molar absorptivity change and electronic spectra in various organized media are discussed.     

A Bis(azo-imine)palladium(II) System with 10 Ligand pi Electrons. Synthesis, Structure, Serial Redox, and Relationship to Bis(azooximates) and Other Species

The first azo-imine chelate system, Pd(N(H)C(R)NNPh)(2) (Pd(RA)(2)), has been isolated in the form of diamagnetic solids by the 6e(-)-6H(+) reduction of bis(phenylazooximato)palladium(II), Pd(N(O)C(R)NNPh)(2) (abbreviated Pd(RB)(2)), with ascorbic acid in a mixed solvent (R = Ph, alpha-naphthyl). Selected spectral features are described. The X-ray structures of Pd(PhA)(2) and Pd(PhB)(2) have revealed trans-planar geometry consistent with metal oxidation state of +2. Bond length trends within the chelate rings are rationalized in terms of steric and electronic factors. In Pd(PhA)(2) a total of 10 ligand pi electrons are present, each formally monoanionic ligand contributing five. Model EHMO studies have revealed that the filled HOMO (a(u)) in Pd(RA)(2) is a bonding combination of two ligand pi orbitals with large azo contributions. The LUMO (b(g)) is roughly the corresponding antibonding combination. The outer pi-electron configuration of Pd(RA)(2) is (a(u))(2)(b(g))(0). Four successive voltammetric responses, two oxidative and two reductive, are observed. The E(1/2) range is -1.3 to +0.8 V vs SCE for Pd(PhA)(2) in a 1:9 MeCN-CH(2)Cl(2) mixture (Pt electrode). EPR and electronic spectra of the electrogenerated one-electron-oxidized complex Pd(PhA)(2)(+) are described. The azo-imine system is compared with imine-imine and azo-azo systems. Crystal data for the complexes are as follows. Pd(PhA)(2): crystal system monoclinic; space group C2/c; a = 18.167(5) ?, b = 7.420(3) ?, c = 16.527(6) ?; beta = 92.70(3) degrees; V = 2225(1) ?(3); Z = 4; R = 2.61%, R(w) = 3.58%. Pd(PhB)(2): crystal system monoclinic; space group P2(1)/n; a = 5.735(5) ?, b = 10.797(6) ?, c = 18.022(11) ?; beta = 97.73(6) ?; V = 1105(1) ?(3); Z = 2; R = 3.37%; R(w) = 3.40%.