Mössbauer, X-ray, electrical and magnetic properties of lithium borosilicate glasses containing iron and manganese Part I. Mössbauer measurements

The effect of the replacement of MnO₂ by Fe₂O₃ on the oxidation states of iron in some lithium borosilicate glasses were studied using Mössbauer spectroscopy. DTA and infrared measurements showed the presence of two glassy phases, one of them containing iron and the other manganese. The Mössbauer spectra were measured at room temperature for all the glass samples. The spectra revealed the presence of Fe ions only in ferric state in both tetrahedral and octahedral coordination. Also, it was observed that the ratio between the number of iron ions in both coordination states has not changed with the increase of MnO₂ content.     

A Complete Classification of Curvature Collineations of Cylindrically Symmetric Static Metrics

Curvature collineations are symmetry directions for the Riemann tensor, as isometries are for the metric tensor and Ricci collineations are for the Ricci tensor. Complete listings of many metrics possessing some minimal symmetry have been given for a number of symmetry groups for the latter two symmetries. It is shown that a claimed complete listing of cylindrically symmetric static metrics by their curvature collineations [1] was actually incomplete and is completed here. It turns out that in this complete list, unlike the previous claim, there are curvature collineations that are distinct from the set of isometries and of Ricci collineations. The physical interpretation of some of the metrics obtained is given.     

Association between the photodynamic loss of Bcl-2 and the sensitivity to apoptosis caused by phthalocyanine photodynamic therapy

We have reported that photodynamic therapy (PDT) using the photosensitizer phthalocyanine (Pc) 4 and red light damages the antiapoptotic protein Bcl-2. Recently, using transient transfection of Bcl-2 deletion mutants, we identified the membrane anchorage domains of Bcl-2 as necessary to form the photosensitive target. However, it is not clear how Bcl-2 photodamage sensitizes cells to Pc 4-PDT-induced apoptosis, whether overall cell killing is also sensitized or how up-regulation of Bcl-2 in tumors might make them more or less responsive to Pc 4-PDT. In this study we report on MCF-7c3 cells (human breast cancer cells expressing stably transfected procaspase-3) overexpressing wild-type Bcl-2 or certain deletion mutants in either a transient or a stable mode. By flow cytometric analysis of transiently transfected cells, we found that wild-type Bcl-2, Bcl-2delta33-54 and Bcl-2delta37-63 (each of which can be photodamaged) protected cells from apoptosis caused by Pc 4-PDT. In contrast, Bcl-2delta210-239, which lacks the C-terminal transmembrane domain and cannot be photodamaged, afforded no protection. We then evaluated the PDT sensitivity of transfected cell lines stably overexpressing high levels of wild-type Bcl-2 or one of the Bcl-2 mutants. Overexpression of wild-type Bcl-2, Bcl-2delta33-54 or Bcl-2delta37-63 resulted in relative resistance of cells to Pc 4-PDT, as assessed by morphological apoptosis or loss of clonogenicity. Furthermore, overexpression of Bcl-2 also inhibited the activation-associated conformational change of the proapoptotic protein Bax, and higher doses of Pc 4 and light were required to activate Bax in cells expressing high levels of Bcl-2. Many advanced cancer cells have elevated amounts of Bcl-2. Our results show that increasing the dose of Pc 4-PDT can overcome the resistance afforded by either Bcl-2 or the two mutants. PDT regimens that photodamage Bcl-2 lead to activation of Bax, induction of apoptosis and elimination of the otherwise resistant tumor cells.     

Dichotenone-a and -b: two new enones from the marine brown alga Dictyota dichotoma (Hudson) Lamour

Marine brown alga Dictyota dichotoma (Dictyotaceae) collected from Karachi coast of Arabian Sea yielded two new (1 and 2) enones (dolastane-diterpenoids) named: dichotenone-A and -B along with an olide (loliolide, 3) as a new source. Their structures have been characterized with the aid of 2D-NMR spectroscopic techniques.     

The peripheral benzodiazepine receptor in photodynamic therapy with the phthalocyanine photosensitizer Pc 4

The peripheral benzodiazepine receptor (PBR) is an 18 kDa protein of the outer mitochondrial membrane that interacts with the voltage-dependent anion channel and may participate in formation of the permeability transition pore. The physiological role of PBR is reflected in the high-affinity binding of endogenous ligands that are metabolites of both cholesterol and heme. Certain porphyrin precursors of heme can be photosensitizers for photodynamic therapy (PDT), which depends on visible light activation of porphyrin-related macrocycles. Because the apparent binding affinity of a series of porphyrin analogs for PBR paralleled their ability to photoinactivate cells, PBR has been proposed as the molecular target for porphyrin-derived photocytotoxicity. The phthalocyanine (Pc) photosensitizer Pc 4 accumulates in mitochondria and structurally resembles porphyrins. Therefore, we tested the relevance of PBR binding on Pc 4-PDT. Binding affinity was measured by competition with 3H-PK11195, a high-affinity ligand of PBR, for binding to rat kidney mitochondria (RKM) or intact Chinese hamster ovary (CHO) cells. To assess the binding of the Pc directly, we synthesized 14C-labeled Pc 4 and found that whereas Pc 4 was a competitive inhibitor of 3H-PK11195 binding to the PBR, PK11195 did not inhibit the binding of 14C-Pc 4 to RKM. Further, 14C-Pc 4 binding to RKM showed no evidence of saturation up to 10 microM. Finally, when Pc 4-loaded CHO cells were exposed to activating red light, apoptosis was induced; Pc 4-PDT was less effective in causing apoptosis in a companion cell line overexpressing the antiapoptotic protein Bcl-2. For both cell lines, PK11195 inhibited PDT-induced apoptosis; however, the inhibition was transient and did not extend to overall cell death, as determined by clonogenic assay. The results demonstrate (1) the presence of low-affinity binding sites for Pc 4 on PBR; (2) the presence of multiple binding sites for Pc 4 in RKM and CHO cells other than those that influence PK11195 binding; and (3) the ability of high supersaturating levels of PK11195 to transiently inhibit apoptosis initiated by Pc 4-PDT, with less influence on overall cell killing. We conclude that the binding of Pc 4 to PBR is less relevant to the photocytotoxicity of Pc 4-PDT than are other mitochondrial events, such as photodamage to Bcl-2 and that the observed inhibition of Pc 4-PDT-induced apoptosis by PK11195 likely occurs through a mechanism independent of PBR.     

QUANTITATION OF PYRIMIDINE DIMERS BY IMMUNOSLOT BLOT FOLLOWING SUBLETHAL UV-IRRADIATION OF HUMAN CELLS

An immunoslot blot assay was developed to detect pyrimidine dimers induced in DNA by sublethal doses of UV (254 nm) radiation. Using this assay, one dimer could be detected in 10 megabase DNA using 200 ng or 0.5 megabase DNA using 20 ng irradiated DNA. The level of detection, as measured by dimer specific antibody binding, was proportional to the dose of UV and amount of irradiated DNA used. The repair of pyrimidine dimers was measured in human skin fibroblastic cells in culture following exposure to 0.5 to 5 J m^-2 of 254 nm UV radiation. The half-life of repair was approximately 24, 7 and 6 h in cells exposed to 0.5, 2 and 5 J m^-2 UV radiation, respectively. This immunological approach utilizing irradiated DNA immobilized to nitrocellulose should allow the direct quantitation of dimers following very low levels of irradiation in small biological samples and isolated gene fragments.     

Preparative isolation and characterization of some minor impurities of astaxanthin by high-performance liquid chromatography

A simple and rapid preparative high-performance liquid chromatography (HPLC) method has been developed to isolate and characterize some minor impurities of astaxanthin using a normal-phase Lichrosorb silica column with n-hexane-acetone-tetrahydrofuran (90:2:8, v/v/v) as mobile-phase and detection at 475 nm. The isolated impurities were characterized as astacene, dehydro astacene and apoastaxanthinal by UV-vis, ESI-MS, 1H and 13C NMR spectroscopy and the molecular structures were assigned. The impurities collected using the developed conditions were over 98% pure.     

Sol–gel derived ZnO nanoparticulate films for ultraviolet photodetector (UV) applications

Zinc oxide nanoparticles based UV detector was fabricated on thermally oxidized silicon substrate. ZnO nanoparticle films were deposited using sol–gel route. The seed solution was prepared using two different solvents (methanol and isopropyl alcohol (IPA)). The surface morphology of the prepared films was characterized by FESEM. Structural characterization along with optical measurements was carried out using XRD and UV–vis spectroscopy. For the UV photo-detector, ZnO thin film prepared in IPA is selected based on their structural and optical analysis. The changes in photo-response of ZnO thin film with respect to time was studied under the dark and variable UV intensities. It was observed that the photocurrent increased with a factor of 4.82 under 1.16 mW of UV intensity. It is believe that the synthesized ZnO thin films have potential to use in the ultraviolet photo-detector applications.     

New heteroleptic palladium(II) dithiocarbamates: synthesis,characterization, packing and anticancer activity against five different cancer cell lines

Two new heteroleptic palladium(II) complexes have been synthesized by reacting equimolar quantities of palladium(II) chloride, sodium 4‐(2‐methoxyphenyl)piperazine‐1‐carbodithioate and diphenyl‐p‐tolylphosphine ( 1 ) or tri‐p‐tolylphosphine ( 2 ). Complexes 1 and 2 have been characterized using elemental analysis, Fourier transform infrared spectroscopy, multinuclear NMR (¹H, ¹³C and ³¹P) spectroscopy and single‐crystal X‐ray analysis. The latter technique confirms a pseudo square‐planar geometry in which two adjacent positions are occupied by bidentate dithiocarbamate while chloro and substituted triphenylphosphine are present at the remaining two positions. The anticancer activity of both complexes against five different cancer cell lines (LU – human lung carcinoma, established at UIC, Department of Surgical Oncology; MCF7 – human breast adenocarcinoma, ATCC number HTB‐22?; MDA‐MB‐231 – human breast adenocarcinoma, ATCC number HTB‐26?; Hepa‐1c1c7 – mouse liver hepatoma, ATCC number CRL‐2026?; PC‐3 – human prostate adenocarcinoma, ATCC number CRL‐1435?) was determined by MTT assay, revealing 2 has higher activity than 1 . A drug–calf thymus DNA binding study with UV–visible spectroscopy reveals a higher DNA binding affinity of 2 (3.511 × 10⁴ M^?1) than 1 (4.213 × 10³ M^?1). Density functional theory studies confirm the relatively more stable nature of 2 than 1 . Copyright © 2016 John Wiley & Sons, Ltd.     

A study of heat and mass transfer of Non-Newtonian fluid with surface chemical reaction

Considering the significance of non-Newtonian fluid usage in manufacturing such as molten plastics, polymeric materials, pulps, and so on, significant efforts have been made to investigate the phenomenon of non-Newtonian fluids. In this article the influences of heat and mass transfer on non-Newtonian Walter's B fluid flow over uppermost catalytic surface of a paraboloid is encountered. An elasticity of the fluid layer is considered in the freestream together with heat source/sink and has the tendency to cause heat flow in the fluid saturated domain. The flow problem of two-dimensional Walter's B fluid is represented using Law of conservation of mass, momentum, heat, and concentration along with thermal and solutal chemical reactive boundary conditions. The governing equations are non-linear partial differential equation and are non-dimensionalized by employing stream function and similarity transformation. The final dimensionless equations yielded are coupled non-linear ordinary differential equations. Furthermore, shooting technique along with RK-4th order method is used to get the numerical results. Graphs and tables are modeled by using MATLAB software to check the effects of Walter's B parameter, Chemical reaction parameter and Thickness parameter on temperature, velocity, and concentration profiles. Tabular analysis shows the results of some physical parameters like skin friction coefficient, Nusselt number and Sherwood number due to the variation of Walter's B parameter, thickness parameter and chemical reactive parameter.