Increased Photosensitivity in HL60 Cells Expressing Wild-Type p53

Loss of p53 function has been correlated with decreased sensitivity to chemotherapy and radiation therapy in a variety of human tumors. Comparable analysis of p53 status with sensitivity to oxidative stress induced by pho-todynamic therapy has not been reported. In the current study we examined photosensitivity in human promye-locytic leukemia HL60 cells exhibiting either wild-type p53, mutated p53 or deleted p53 expression. Experiments were performed using a purpurin, tin ethyl etiopurpurin (SnET2)-, or a porphyrin, Photofrin (PH)-based photo-sensitizer. Total SnET2 accumulation was comparable in all three cell lines. Uptake of PH was highest in cells expressing wild-type p53 but incubation conditions could be adjusted to achieve equivalent cellular PH levels during experiments that analyzed photosensitivity. Survival measurements demonstrated that HL60 cells expressing wild-type p53 were more sensitive to PH- and SnET2-mediated photosensitization, as well as to UVC irradiation, when compared to HL60 cells exhibiting deleted or mutated p53 phenotypes. A rapid apoptotic response was observed following purpurin- and porphyrin-induced photosensitization in all cell lines. Results of this study indicate that photosensitivity is increased in HL60 cells expressing wild-type p53 and that photosensitizer-medi-ated oxidative stress can induce apoptosis through a p53-independent mechanism in HL60 cells .     

Dynamics of solvation and rotational relaxation of Coumarin 153 in ionic liquid confined nanometer-sized microemulsions

The effects of confinement of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate on solvation dynamics and rotational relaxation of Coumarin 153 (C-153) in Triton X-100/cyclohexane microemulsions have been explored using steady-state and picosecond time-resolved emission spectroscopy. The steady-state and rotational relaxation data indicate that C-153 molecules are incorporated in the core of the microemulsions. The average rotational relaxation time increases with increase in w ([bmim][BF(4)]/[TX-100]) values. The solvent relaxation in the core of the microemulsion occurs on two different time scales and is almost insensitive to the increase in w values. The solvent relaxation is retarded in the pool of the microemulsions compared to the neat solvent. Though, the retardation is very small compared to several-fold retardation of the solvation time of the conventional solvent inside the pool of the microemulsions.     

Impact of extended pi conjugation on methyl rotor-induced IVR in aromatic molecules

Laser-induced fluorescence excitation and resolved fluorescence spectra following excitations of the single vibronic levels (SVL) of p-vinyltoluene (p-VT) and p-vinylfluorobenzene (p-VFB) have been measured in a seeded supersonic free-jet expansion. A complete vibronic assignment of the fluorescence spectrum measured following excitation of the 0(0)0-band of p-VT has been presented. Normal vibrational modes in the S0 and S1 states of the molecule have been calculated by CASSCF method, and the correlation between the two set of modes is made by expressing the excited-state normal modes in terms of those of the ground state. The calculations predict that in the excited state methyl and vinyl torsional motions of p-VT are extensively mixed with many of the out-of-plane modes of the aromatic ring. Our resolved fluorescence spectral data measured following SVL excitations essentially agree with such predictions. In the excited state, the molecule exhibits a dramatically low threshold for the rotor-induced IVR in a supersonic jet expansion. Several mechanisms have been discussed to explain the phenomenon.     

Heavy-metal remediation by a fungus as a means of production of lead and cadmium carbonate crystals

We show here that reaction of the fungus, Fusarium oxysporum, with the aqueous heavy-metal ions Pb2+ and Cd2+ results in the one-step formation of the corresponding metal carbonates. The metal carbonates are formed by reaction of the heavy-metal ions with CO2 produced by the fungus during metabolism and thus provide a completely biological method for production of crystals of metal carbonates. The PbCO3 and CdCO3 crystals thus produced have interesting morphologies that are shown to arise because of interaction of the growing crystals with specific proteins secreted by the fungus during reaction. An additional advantage of this approach is that the reaction leads to detoxification of the aqueous solution and could have immense potential for bioremediation of heavy metals. Under conditions of this study, the metal ions are not toxic to the fungus, which readily grows after exposure to the metal ions.     

Synthesis of tricyclo[6.2.2.0]dpdecane and tricyclo[6.3.1.0]dodecane ring systems involving intramolecular cyclisation of diazomethyl ketones

2,8-Dimethyltricyclo[6.2.2.0^1,6]dodeca-2,5-diene-4,9-dione ( ), 2,9-dimethyltricyclo [6.3.1.0^1,6]dodeca-2,5-diene-4,10-dione ( ) and 2-methyltricyclo[6.3.1.0^1,6]dodeca-2,5-diene-4,10-dione ( ) have been synthesised for entry into the ring systems of a few tetracyclic diterpenes.     

Kinetics and mechanism of oxidation of 8-hydroxyquinoline and its derivatives by cerium(IV) through precursor complex formation

Summary In acid (HClO₄) medium Ce^IV is reduced to Ce^III by 8-hydroxyquinoline (1) and its derivatives, the 5-sulphonate (2) and 7-iodo-5-sulphonate (3), through precursor complex formation. The rates of precursor complex formation have been studied by stopped-flow spectrophotometry for both (1) and (2). Formation of the precursor complex occurs in two concurrent paths involving Ce _aq ⁴⁺ and [Ce(OH)] _aq ³⁺ reacting by I_a and I_d processes respectively. The reaction with (3) is, however, too fast for the stopped-flow method. The rates for subsequent intramolecular electron transfer processes in the precursor complexes are sufficiently slow for all the three species(1)–(3) for evaluation by conventional spectrophotometry. For the electron transfer process the rate varies in the sequence:(2)>(1)(3) due to electron-withdrawing character of the substituent SO ₃ ^– and electron-releasing character of I.     

Kinetics and mechanism of formation of square-planar copper(II) and nickel(II) complexes of ethylenebisbiguanide in aqueous acetate buffer media

Summary The kinetics of formation of square-planar Cu^II and Ni^II complexes of the quadridentate ligand, ethylenebisbiguanide, have been studied spectrophotometrically in aqueous HOAc–NaOAc buffer, at ionic strength 0.2 mol dm^–3, in the 25–35°C temperature range. The observed rate constants for the formation reactions are independent of pH (and of OAc^– concentration) in the pH range used (3.6–4.8 for Cu^II and 5.0–5.8 for Ni^II) where the product complexes form stoichiometrically, but show first-order dependence on the ligand concentration;i.e. k_obs=k_f[L]_total. At 25°C k_f values (dm³ mol^–1s^–1) are 35.2±0.4 for Cu^II and (8.4±0.1)×10^–3 for Ni^II. The mechanism of the reactions is discussed.     

Studies on the kinetics and mechanism of dissociation of copper(II) and nickel(II) complexes of the macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene in perchloric acid media

Summary Acid catalysed dissociation of the copper(II) and nickel(II) complexes (ML²⁺ of the quadridentate macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene (L) has been studied spectrophotometrically. Both complexes dissociate quite slowly with the observed pseudo-first order rate constants (k_obs) showing acid dependence; for the nickel(II) complex (k_obs)=k_O+k_H[H⁺], the k_o path is however absent with the copper(II) complex. At 60°C (I=0.1M) the k_H values areca 10^–4 M^–1 s^–1 for both complexes; k _H ^Cu /k _H ^Ni =ca. 3.9, comparable to some other square-planar complexes of these metal ions. The rate difference is primarily due to H values [copper(II) complex, 29.4±0.5 kJ mol^–1; nickel(II) complex, 35.6±1.5 kJ mol^–1] with highly negative S values [for copper(II), –215.5 ±6.1 JK^–1 mol^–1 and for nickel(II), –208.1 ±5.6 JK^–1 mol^–1] which are much higher than the entropy of solvation of Ni²⁺ (ca. –160 JK^–1 mol^–1) and Cu²⁺ (ca. –99 JK^–1 mol^–1) ions; significant solvation of the released metal ions and the ligand is indicated.     

Kinetics and mechanism of reactions of bis(biguanide)copper(II) ion with 2,2′-bipyridyl and 1,10-phenanthroline in aqueous solution

Summary In aqueous solution [Cu(bigH)₂]²⁺ (bigH=biguanide) reacts with 2,2-bipyridyl (bipy) and 1,10-phenanthroline (phen) through intermediate formation of ternary complexes [Cu(bigH)(L)]²⁺ and [Cu(bipy)(phen)]²⁺ and binary complexes [CuL₂]²⁺ (L=bipy, phen). The rates of the different steps have been followed in borax buffer (pH 8.0±0.1) by stopped-flow spectrophotometry. For each step k_obs=k₀+k_L[L] and the k_L path appears to be associative. H and S values for the k_L path conform to an isokinetic trend.