Photocytotoxicity and DNA photocleavage activity of La(III) and Gd(III) complexes of phenanthroline bases

Lanthanide(II) complexes La(B)(acac)(3)] (1-3) and Gd(B)(acac)(3)] (4-6), where B is a N,N-donor phenanthroline base, viz., 1,10-phenanthroline (phen in 1, 4), dipyrido3,2-d:2',3'-f]quinoxaline (dpq in 2, 5) and dipyrido3,2-a:2',3'-c]phenazine (dppz in 3, 6), have been prepared and characterized. The Gd(111) complexes 4 6 are structurally characterized by single crystal X-ray crystallography. The complexes display GdO6N2 coordination with the ligands showing bidentate chelating mode of bonding. The complexes are non-electrolytic in aqueous DMF and exhibit ligand-centered absorption bands in the UV region. The dppz complexes show a band at 380 nm in DMF. The La(111) complexes are diamagnetic. The Gd(III) complexes are paramagnetic with magnetic moment that corresponds to seven unpaired electrons. The Complexes are avid binders to calf thymus DNA giving K-b values in the range of 4.7 x 10(4) 6.1 x 10(5) M-1 with a relative binding order: 3, 6 (dppz) > 2, 5 (dpq) > 1, 4 (phen). The binding data suggest DNA surface and/or groove binding nature of the complexes. The dpq and dppz complexes efficiently cleave SC DNA to its nicked circular form in UV-A light of 365 nm via formation of both singlet oxygen (O-1(2)) and hydroxyl radical (HO center dot) species. The dppz complexes 3 and 6 exhibit significant PDT effect in He La cervical cancer cells giving respective IC50 value of 460(+/- 50) and 530(+/- 30) nM in UV-A light of 365 rim, and are essentially non-toxic in dark with an IC50 value of >100 mu M. The dppz ligand alone is cytotoxic in dark and UV-A light. A significant decrease in the dark toxicity of the dppz base is observed on binding to the Ln(III) ion while retaining its photocytotoxicity.

Study of corrugations in motor bearings

Corrugation formation is investigated in bearing components in squirrelcage induction motors. The study, conducted on site, measured shaft voltage and analysed motor bearing vibrations from 48 motors on nine sites. The on-site frequency data was compared with the measured natural frequency of the motors. Detailed profilometric, optical and SEM studies were carried out on the surface of failed bearings to aid discussion on the formation of corrugations in bearings used in squirrelcage induction motors.

Synthesis, properties and crystal structures of diastereomeric areneruthenium(II) chiral Schiff-base complexes

Diastereomers (SRu,Sc)-1a and (RRu,Sc)-1b, in a ratio of 85: 15 and formulated as [Ru(η-MeC6H4Pri-p)Cl(L*)], have been prepared by treating [{Ru(η-MeC6H4Pri-p)Cl2}2] with the sodium salt of (S)-α-methylbenzylsalicylaldimine (HL*) in tetrahydrofuran at –70 °C. The reaction of 1(1a+1b) with AgClO4 in acetone followed by an addition of PPh3 or 4-methylpyridine (4Me-py) leads to the formation of adducts [Ru(η-MeC6H4Pri-p)(PPh3)(L*)]ClO42[(SRu,Sc)2a, (FRu,Sc)2b] and [Ru(η-MeC6H4Pri-p)(4Me-py)(L*)]ClO43[(SRu,Sc)3a, (RRu,Sc)3b] in the diastereomeric ratios (SRu,Sc) : (RRu,Sc) of 2 : 98 and 76 : 24, respectively. Complex 1 crystallises with equal numbers of 1a and 1b molecules in an asymmetric unit of monoclinic space group P21 with a= 10.854(1), b= 17.090(1), c= 12.808(4)Å, β= 110.51(1)°, and Z= 4. The structure was refined to R= 0.0552 and R′= 0.0530 with 2893 reflections having I[gt-or-equal] 1.5σ(I). The absolute configurations of the chiral centres in the optically pure single crystal of the PPh3 adduct have been obtained from an X-ray study. Crystals of formulation [Ru(η-MeC6H4Pri-p)-(PPh3)(L*)]2[ClO4][PF6]·1.5 CHCl3, obtained in presence of both ClO4 and PF6 anions, belong to the non-centric triclinic space group P1 with a= 10.852(2), b= 14.028(1), c= 15.950(2)Å, α= 91.51(1), β= 105.97(1), γ= 106.11(1)°, and Z= 2. The final residuals were R= 0.0713, R′= 0.0752 with 7283 reflections having I[gt-or-equal] 2.5σ(I). The crystal structures of 1a,1b, and the PPh3 adduct (2b,2b′) consist of a ruthenium(II) centre bonded to a η-p-cymene, a bidentate chelating Schiff base, and a unidentate ligand (Cl or PPh3). The chirooptical properties of the complexes have been studied using 1H NMR and CD spectral data. The presence of a low-energy barrier for the intermediate involved in these reactions, showing both retention as well as inversion of the metal configuration, is discussed.

Secretion is a stimulus for the synthesis of human chorionic gonadotrophin by first trimester human placenta

Time course of release of immunoreactive hCG to a placental incubation in the medium revealed a steady increase over a period of 4 hours. However, levels in the tissue, showed an increase at 10' and 60' after an initial decrease. Studies using A23187 which stimulated hCG secretion also revealed a net increase in the quantity of hCG in the tissue. These results sugest that the secretion of hCG acts as a stimulus for fresh synthesis of hCG.

Moving boundaries due to distributed sources in a slab

Analytical and numerical solutions have been obtained for some moving boundary problems associated with Joule heating and distributed absorption of oxygen in tissues. Several questions have been examined which are concerned with the solutions of classical formulation of sharp melting front model and the classical enthalpy formulation in which solid, liquid and mushy regions are present. Thermal properties and heat sources in the solid and liquid regions have been taken as unequal. The short-time analytical solutions presented here provide useful information. An effective numerical scheme has been proposed which is accurate and simple.

Controlled synthesis of CuO nanostructures on Cu foil, rod and grid

CuO nanowires are synthesized by heating Cu foil, rod and grid in ambient without employing a catalyst or gas flow at temperatures ranging from 400 to 800 degrees C for a duration of 1-12 h. Scanning electron microscopy (SEM) investigation reveals the formation of nanowires. The structure, morphology and phase of the as-synthesized nanowires are analyzed by various techniques such as X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). It is found that these nanowires are composed of CuO phase and the underlying film is of Cu2O. A systematic study is carried out to find the possibilities for the transformation of one phase to another completely. A possible growth mechanism for the nanowires is also discussed. (C) 2011 Elsevier B.V. All rights reserved.

Thermal sensitivity analysis of spacecraft battery

Transient thermal sensitivity is studied for systems that are subjected to conductive heat transfer within themselves and radiative heat transfer with the surrounding environment, including solar heat radiation, The battery in the Indian national communication satellite is one such system for which the studies are conducted with respect to panel conduction, conductance of insulating blanket, power dissipation within the battery, and absorptance and emittance of various elements, Comparison of sensitivities revealed that battery temperature is sensitive to its power dissipation during the beginning of life of the spacecraft, whereas toward the end of life of the spacecraft mission, the effect of absorptance of optical solar reflector is dominating, The influence of optical property values of the multilayer insulation blanket is almost negligible. Among the parameters studied in this analysis, the battery temperature is found to be mast sensitive to emittance of the optical solar reflector.

Resent radar observations of asteroid 1566 Icarus

We report Doppler-only radar observations of Icarus at Goldstone at a transmitter frequency of 8510 MHz (3.5 cm wavelength) during 8-10 June 1996, the first radar detection of the object since 1968. Optimally filtered and folded spectra achieve a maximum opposite-circular (OC) polarization signal-to-noise ratio of about 10 and help to constrain Icarus' physical properties. We obtain an OC radar cross section of 0.05 km(2) (with a 35% uncertainty), which is less than values estimated by Goldstein (1969) and by Pettengill et al. (1969), and a circular polarization (SC/OC) ratio of 0.5+/-0.2. We analyze the echo power spectrum with a model incorporating the echo bandwidth B and a spectral shape parameter it, yielding a coupled constraint between B and n. We adopt 25 Hz as the lower bound on B, which gives a lower bound on the maximum pole-on breadth of about 0.6 km and upper bounds on the radar and optical albedos that are consistent with Icarus' tentative QS classification. The observed circular polarization ratio indicates a very rough near-surface at spatial scales of the order of the radar wavelength. (C) 1999 Elsevier Science Ltd. All rights reserved.

Biological water: Femtosecond dynamics of macromolecular hydration

The unique features of a macromolecule and water as a solvent make the issue of solvation unconventional, with questions about the static versus dynamic nature of hydration and the, physics of orientational and translational diffusion at the boundary. For proteins, the hydration shell that covers the surface is critical to the stability of its structure and function. Dynamically speaking, the residence time of water at the surface is a signature of its mobility and binding. With femtosecond time resolution it is possible to unravel the shortest residence times which are key for the description of the hydration layer, static or dynamic. In this article we review these issues guided by experimental studies, from this laboratory, of polar hydration dynamics at the surfaces of two proteins (Subtilisin Carlsberg (SC) and Monellin). The natural probe tryptophan amino acid was used for the interrogation of the dynamics, and for direct comparison we also studied the behavior in bulk water - a complete hydration in 1 ps. We develop a theoretical description of solvation and relate the theory to the experimental observations. In this - theoretical approach, we consider the dynamical equilibrium in the hydration shell, defining the rate processes for breaking and making the transient hydrogen bonds, and the effective friction in the layer which is defined by the translational and orientational motions of water molecules. The relationship between the residence time of water molecules and the observed slow component in solvation dynamics is a direct one. For the two proteins studied, we observed a "bimodal decay" for the hydration correlation function, with two primary relaxation times: ultrafast, typically 1 ps or less, and longer, typically 15-40 ps, and both are related to the residence time at the protein surface, depending on the binding energies. We end by making extensions to studies of the denatured state of the protein, random coils, and the biomimetic micelles, and conclude with our thoughts on the relevance of the dynamics of native structures to their functions.

Control of transient thermal response during sequential open-die forging: A trajectory optimization approach

A trajectory optimization approach is applied to the design of a sequence of open-die forging operations in order to control the transient thermal response of a large titanium alloy billet. The amount of time tire billet is soaked in furnace prior to each successive forging operation is optimized to minimize the total process time while simultaneously satisfying constraints on the maximum and minimum values of the billet's temperature distribution to avoid microstructural defects during forging. The results indicate that a "differential" heating profile is the most effective at meeting these design goals.

Minimizing buffer requirements under rate-optimal schedule in regular dataflow networks

Large-grain synchronous dataflow graphs or multi-rate graphs have the distinct feature that the nodes of the dataflow graph fire at different rates. Such multi-rate large-grain dataflow graphs have been widely regarded as a powerful programming model for DSP applications. In this paper we propose a method to minimize buffer storage requirement in constructing rate-optimal compile-time (MBRO) schedules for multi-rate dataflow graphs. We demonstrate that the constraints to minimize buffer storage while executing at the optimal computation rate (i.e. the maximum possible computation rate without storage constraints) can be formulated as a unified linear programming problem in our framework. A novel feature of our method is that in constructing the rate-optimal schedule, it directly minimizes the memory requirement by choosing the schedule time of nodes appropriately. Lastly, a new circular-arc interval graph coloring algorithm has been proposed to further reduce the memory requirement by allowing buffer sharing among the arcs of the multi-rate dataflow graph. We have constructed an experimental testbed which implements our MBRO scheduling algorithm as well as (i) the widely used periodic admissible parallel schedules (also known as block schedules) proposed by Lee and Messerschmitt (IEEE Transactions on Computers, vol. 36, no. 1, 1987, pp. 24-35), (ii) the optimal scheduling buffer allocation (OSBA) algorithm of Ning and Gao (Conference Record of the Twentieth Annual ACM SIGPLAN-SIGACT Symposium on Principles of Programming Languages, Charleston, SC, Jan. 10-13, 1993, pp. 29-42), and (iii) the multi-rate software pipelining (MRSP) algorithm (Govindarajan and Gao, in Proceedings of the 1993 International Conference on Application Specific Array Processors, Venice, Italy, Oct. 25-27, 1993, pp. 77-88). Schedules generated for a number of random dataflow graphs and for a set of DSP application programs using the different scheduling methods are compared. The experimental results have demonstrated a significant improvement (10-20%) in buffer requirements for the MBRO schedules compared to the schedules generated by the other three methods, without sacrificing the computation rate. The MBRO method also gives a 20% average improvement in computation rate compared to Lee's Block scheduling method.

System Dy-Fe-O: thermodynamic properties of ternary oxides using Calvet calorimetry and solid-state electrochemical cell

The enthalpy increments and the standard molar Gibbs energies of formation-of DyFeO3(s) and Dy3Fe5O12(s) have been measured using a Calvet micro-calorimeter and a solid oxide galvanic cell, respectively. A co-operative phase transition, related to anti-ferromagnetic to paramagnetic transformation, is apparent. from the heat capacity data for DyFeO3 at similar to 648 K. A similar type of phase transition has been observed for Dy3Fe5O12 at similar to 560 K which is related to ferrimagnetic to paramagnetic transformation. Enthalpy increment data for DyFeO3(s) and Dy3Fe5O12(s), except in the vicinity of the second-order transition, can be represented by the following polynomial expressions:{H(0)m(T) - H(0)m(298.15 K)) (Jmol(-1)) (+/-1.1%) = -52754 + 142.9 x (T (K)) + 2.48 x 10(-3) x (T (K))(2) + 2.951 x 10(6) x (T (K))(-1); (298.15 less than or equal to T (K) less than or equal to 1000) for DyFeO3(s), and {H(0)m(T) - H(0)m(298.15 K)} (Jmol(-1)) (+/-1.2%) = -191048 + 545.0 x (T - (K)) + 2.0 x 10(-5) x (T (K))(2) + 8.513 x 10(6) x (T (K))(-1); (208.15 less than or equal to T (K) less than or equal to 1000)for Dy3Fe5O12(s). The reversible emfs of the solid-state electrochemical cells: (-)Pt/{DyFeO3(s) + Dy2O3(s) + Fe(s)}/YDT/CSZ//{Fe(s) + Fe0.95O(s)}/Pt(+) and (-)Pt/{Fe(s) + Fe0.95O(s)}//CSZ//{DyFeO3(s) + Dy3Fe5O12(s) + Fe3O4(s)}/Pt(+), were measured in the temperature range from 1021 to 1250 K and 1035 to 1250 K, respectively. The standard Gibbs energies of formation of solid DyFeO3 and Dy3Fe5O12 calculated by the least squares regression analysis of the data obtained in the present study, and data for Fe0.95O and Dy2O3 from the literature, are given by Delta(f)G(0)m(DyFeO3,s)(kJmol(-1))(+/-3.2)= -1339.9 + 0.2473 x (T(K)); (1021 less than or equal to T (K) less than or equal to 1548)and D(f)G(0)m(Dy3Fe5O12,s) (kJmol(-1)) (+/-3.5) = -4850.4 + 0.9846 x (T (K)); (1035 less than or equal to T (K) less than or equal to 1250) The uncertainty estimates for Delta(f)G(0)m include the standard deviation in the emf and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagram and chemical potential diagrams for the system Dy-Fe-O were developed at 1250 K. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Thermodynamic studies on NdFeO3(s)

The enthalpy increments and the standard molar Gibbs energy of formation of NdFeO3(s) have been measured using a hightemperature Calvet microcalorimeter and a solid oxide galvanic cell, respectively. A lambda-type transition, related to magnetic order-disorder transformation (antiferromagnetic to paramagnetic), is apparent from the heat capacity data at similar to 687 K. Enthalpy increments, except in the vicinity of transition, can be represented by a polynomial expression: {Hdegrees(m)(T)-Hdegrees(m) (298.15 K)} /J(.)mol(-1) (+/- 0.7%)=-53625.6+146.0(T/K) +1.150 X 10(-4)(T/K)(2) +3.007 x 10(6)(T/K)(-1); (298.15 less than or equal to T/K less than or equal to 1000). The heat capacity, the first differential of {Hdegrees(m)(T)-Hdegrees(m)(298.15 K)}with respect to temperature, is given by Cdegrees(pm)/J(.)K(-1.)mol(-1)=146.0+ 2.30x10(-4) (T/K) - 3.007 X 10(6)(T/K)(-2). The reversible emf's of the cell, (-) Pt/{NdFeO3(s) +Nd2O3(s)+Fe(s)}//YDT/CSZ// Fe(s)+'FeO'(s)}/Pt(+), were measured in the temperature range from 1004 to 1208 K. It can be represented within experimental error by a linear equation: E/V=(0.1418 +/- 0.0003)-(3.890 +/- 0.023) x 10(-5)(T/K). The Gibbs energy of formation of solid NdFeO, calculated by the least-squares regression analysis of the data obtained in the present study, and data for Fe0.95O and Nd2O3 from the literature, is given by Delta(f)Gdegrees(m)(NdFeO3 s)/kJ (.) mol(-1)( +/- 2.0)=1345.9+0.2542(T/K); (1000 less than or equal to T/K less than or equal to 1650). The error in Delta(f)Gdegrees(m)(NdFeO3, s, T) includes the standard deviation in emf and the uncertainty in the data taken from the literature. Values of Delta(f)Hdegrees(m)(NdFeO3, s, 298.15 K) and Sdegrees(m) (NdFeO3 s, 298.15 K) calculated by the second law method are - 1362.5 (+/-6) kJ (.) mol(-1) and 123.9 (+/-2.5) J (.) K-1 (.) mol(-1), respectively. Based on the thermodynamic information, an oxygen potential diagram for the system Nd-Fe-O was developed at 1350 K. (C) 2002 Elsevier Science (USA).