Binding of nucleobases with single-walled carbon nanotubes: Theory and experiment

We report the binding energy of various nucleobases (guanine (G), adenine (A), thymine (T) and cytosine (C)) with (5,5) single-walled carbon nanotube (SWNT) calculated using first-principle Hartre–Fock method (HF) together with classical force field. The binding energy without including the solvation effects of water decreases in the order G>A>T>C. The inclusion of solvation energy changes the order of binding preference to be G>T>A>C. Using isothermal titration (micro) calorimetry experiments, we also show the relative binding affinity to be T>A>C, in agreement with our calculations.

DMT of Multi-hop Cooperative Networks-Part I: K-Parallel-Path Networks

We consider single-source, single-sink multi-hop relay networks, with slow-fading Rayleigh fading links and single-antenna relay nodes operating under the half-duplex constraint. While two hop relay networks have been studied in great detail in terms of the diversity-multiplexing tradeoff (DMT), few results are available for more general networks. In this two-part paper, we identify two families of networks that are multi-hop generalizations of the two hop network: K-Parallel-Path (KPP) networks and Layered networks. In the first part, we initially consider KPP networks, which can be viewed as the union of K node-disjoint parallel paths, each of length > 1. The results are then generalized to KPP(I) networks, which permit interference between paths and to KPP(D) networks, which possess a direct link from source to sink. We characterize the optimal DMT of KPP(D) networks with K >= 4, and KPP(I) networks with K >= 3. Along the way, we derive lower bounds for the DMT of triangular channel matrices, which are useful in DMT computation of various protocols. As a special case, the DMT of two-hop relay network without direct link is obtained. Two key implications of the results in the two-part paper are that the half-duplex constraint does not necessarily entail rate loss by a factor of two, as previously believed and that, simple AF protocols are often sufficient to attain the best possible DMT.

Dust Deposition on Single Cylinders

The inertial impaction of Lycopodium spores on single wires lying transverse to the direction of flow has been studied. The equations of particle motion in a potential flow field have been modified for the case when Stokes' law is inapplicable. Solutions to the above equations have been obtained by digital computation. Rec, the Reynolds number based on cylinder diameter, varied from 4 to 240; particle trajectories in a flow field at Rec = 10 have been determined for inertia parameter K = 1, 2, 4, 6, and 10. Ten trajectories were developed for the above cases by the numerical stepwise method. Experiments were performed by depositing Lycopodium spores on adhesive-coated wires of various diameters and at different velocities. The weight of dust deposited was determined with a microbalance. The experimental conditions were:. Wire diameters: 345, 457, 1500 μ. Particle diameter: 35 μ. Air velocities: 20-250 cm/sec. Inertia parameter: 1-60. The particle was considered as a point mass in the theoretical analysis. But in the experiments the ratio of particle size to wire size was not negligible (rp/rc = 0·1) and hence the effect of finite size of particle on collection efficiency due to the direct interception effect has been estimated. The effect of particle size distribution on collection efficiency has also been estimated. The experimental efficiencies obtained compare well with the calculated efficiencies at Rec = 10 when direct interception is taken into account.

Photocytotoxic Lanthanum(III) and Gadolinium(III) Complexes of Phenanthroline Bases Showing Light-Induced DNA Cleavage Activity

Lanthanide complexes of formulation [La(B)(2)(NO3)(3)] (1-3) and [Gd(B)(2)(NO3)(3)] (4-6), where B is a N,N-donor phenanthroline base, namely, 1,10-phenanthroline (phen in 1, 4),dipyrido[3,2-d2',3'-f]quinoxaline (dpq in 2,5) and dipyrido[3,2-a2',3'-c]phenazine (dppz in 3, 6), have been prepared, characterized from physicochemical data, and their photoinduced DNA and protein cleavage activity studied The photocytotoxicity of the dppz complexes 3 and 6 has been studied using HeLa cancer cells. The complexes exhibitligand centered bands in the UV region The dppz complexes show thelowest energy band at 380 nm in N,N-dimethylformamide (DMF) The La(III)complexes are diamagnetic. The Gd(III) complexes (4-6) have magneticmoments that correspond to seven unpaired electrons The complexes are1(.)1 electrolytic in aqueous DMF The dpq and dppz complexes in DMFshow ligand-based reductions. The complexes display moderate binding propensity to calf thymus DNA giving binding constant values in the range of 5.7 x 10(4)-5.8 x 10(5) M-1 with a relative 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 complexes do not show any hydrolytic cleavage of plasmid supercoiled pUC19 DNA. The dpq and dppz complexes efficiently cleave SC DNA to its nicked circular form onexposure to UV-A light of 365 nm at nanomolar complex concentration. Mechanistic studies reveal the involvement of singlet oxygen (O-1(2)) and hydroxyl radical (HO center dot) as the cleavage active species.The complexes show binding propensity to bovine serum albumin (BSA)protein giving K-BSA values of similar to 10(5) M-1. The dppz complexes 3 and 6 show BSA protein cleavage activity in UV-A light of 365 nm The dppz complexes 3 and 6 exhibit significant photocytotoxicity in HeLa cells giving respective IC50 values of 341 nM and 573 nM in UV-A light of 365 nm for an exposure time of 15 min (IC50 > 100 mu M in dark for both the complexes) Control experiments show significant dark and phototoxicity of the dppz base alone (IC50 = 413 nM in light with 4 h incubation in dark and 116 mu M in dark with 24 h incubation). A significant decrease in the dark toxicity of the dppz base is observedon binding to the lanthanide ions while retaining similar phototoxicity.

Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

4,4′-Bipyridyl complexes of iron: Magnetic, Mössbauer and other spectroscopic studies

4,4prime-Bipyridyl (4,4prime-bipy) complexes of ferrous salts of the Fe(4,4prime-bipy)x(anion)y type (where x or y=1 or 2) and of ferric salts of the Fe(4,4prime-bipy)m(anion)n type (where m=1 or 2 and n=3) have been synthesised. Elemental analyses, i.r. and electronic spectra, magnetic and Mössbauer studies have been performed to characterize the complexes. 4,4prime-Bipy and some anions are inferred to act as bridging ligands. The magnetic moments, electronic and Mössbauer spectra suggest that the complexes are of high spin type with distorted octahedral structures. The value of the isomer shift and quadrupole splitting are discussed in terms of bonding of the ligand and anions.

Photocytotoxicity and DNA cleavage activity of L-arg and L-lys Schiff base oxovanadium(IV) complexes having phenanthroline bases

Oxovanadium(IV) complexes [VO(sal-argH)(B)] Cl (1-3) and [VO(sal-lysH)(B)] Cl (4-6), where sal-argH2 and sal-lysH(2) are N-salicylidene-L-arginine and N-salicylidene-L-lysine Schiff bases and B is a phenanthroline base, viz. 1,10-phenanthroline (phen in 1 and 4); dipyrido[3,2-d: 2', 3'-f] quinoxaline (dpq in 2 and 5) and dipyrido[3,2-a: 2', 3'-c] phenazine (dppz in 3 and 6), have been prepared, characterized and their DNA photocleavage activity studied. Complex 1, characterized by X-ray crystallography, shows the presence of a vanadyl group in VIVO3N3 coordination geometry with a tridentate Schiff base having a pendant guanidinium moiety and bidentate phen ligand. The complexes exhibit a d-d band at similar to 715 nm in 20% DMF-Tris-HCl buffer. The complexes are redox active showing cathodic and anodic responses near -1.0 V and 0.85 V (vs. SCE) for the V(IV)-V(III) and V(V)-V(IV) couples, respectively, in DMF-Tris-HCl buffer. The complexes bind to calf thymus DNA giving Kb values in the range of 3.8 x 10(4) to 1.6 x 10(5) M-1. Thermal denaturation and viscosity data suggest DNA groove binding nature of the complexes. The complexes do not show any `chemical nuclease'' activity in dark in the presence of 3-mercaptopropionic acid or H2O2. The dpq and dppz complexes are efficient photocleavers of plasmid DNA in UV-A (365 nm) and red light (676 nm) via singlet oxygen pathway. The dppz complexes exhibit photocytotoxicity in HeLa cancer cells giving IC50 values of 15.4 mu M for 3 and 17.5 mu M for 6 in visible light while being non-toxic in dark giving IC50 values of > 100 mu M.

Electronic structure of square planar CuO46− clusters

The results of spin-polarized MSXagr calculations show that the ground state of the CuO 4 6– cluster is essentially non-magnetic in spite of odd number of electrons in the system for short Cu–O distances (1.90 Å) as found in the highT c superconductors. This arises due to the fact that the unpaired electron resides in a molecular orbital with primarily oxygen 3s character. The stability of this molecular orbital is found to be sensitive to the cluster geometry and thus, increase in Cu–O distance (as well as other changes affecting oxygen-oxygen distance) tend to favour a magnetic state. From these calculations we have also estimated the Coulomb correlation strength within the Cu 3d to be about 5.3 eV.

Temperature and concentration dependence of adsorption properties of methane in NaY: a molecular dynamics study

Molecular dynamics calculations on methane sorbed in NaY (Si/Al = 3.0) employing realistic methane-methane and methane-zeolite intermolecular potential functions at different temperatures (50, 150, 220, and 300 K) and concentrations (2, 4, 6, and 8 molecules/cage) are reported. The thermodynamic results are in agreement with the available experimental data. Guest-guest and guest-host radial distribution functions (rdfs), energy distribution functions, distribution of cage occupancy, center-of-cage-center-of-mass (coc-com) rdfs, velocity autocorrelation functions for com and angular motion and the Fourier transformed power spectra, and diffusion coefficients are presented as a function of temperature and concentration. At 50 K, methane is localized near the adsorption site. Site-site migration and essentially free rotational motion are observed at 150 K. Molecules preferentially occupy the region near the inner surface of the alpha-cage. The vibrational frequencies for the com of methane shift toward higher values with decreasing temperature and increasing adsorbate concentration. The observed frequencies for com motion are 36, 53, and 85 cm-1 and for rotational motion at 50 K, 95 and 150 cm-1 in agreement with neutron scattering data. The diffusion coefficients show a type I behavior as a function of loading in agreement with NMR measurements. Cage-to-cage diffusion is found to be always mediated by the surface.

Detection and characterisation of circulating cysticercal antigens in human cerebrospinal fluid

With biotin labelled and unlabelled immunoglobulin fraction of anticysticercal antibodies raised in rabbits, tandem-enzyme linked immunosorbent assay (T-ELISA), capture-dot immunobinding assay (C-DIA) and reverse passive haemagglutination (RPHA) tests were developed for the detection of cysticercal antigens. The sensitivity levels were respectively, 9 ng ml−1, 2 ng ml−1 and 45 ng ml−1. All three methods were of equal specificity as none of the antigens of Mycobacterium tuberculosis, Japanese encephalitis virus and Echinococcus granulosus reacted with anticysticercal IgG. Cysticercal antigens were detected in the cerebrospinal fluid (CSF) of confirmed neurocysticercosis at sensitivity levels of 91·6% by T-ELISA, 83·33% by C-DIA and 75% by RPHA and specificity levels of >93%. Western analysis of these antigens in CSF showed mainly antigens of 64–68 kDa and 24–28 kDA. By crossed immunoelectrophoresis (CIE) with an intermediate gel technique, five circulating antigens were found to be released from scolex and fluid.

Chiral polyhydroxylated tetrahydrothiophene derivatives: novel synthesis and structural elucidation by X-ray crystallography, NMR spectroscopy and molecular mechanics calculations

The dideoxygenation reaction of 1,3;4,6-di-O-alkylidene-2,5-di-S-methylthiocarbonyl-D-mannitol derivatives under Barton-McCombie reaction conditions gave the hexahydrodipyranothiophenes 4 and 7 instead of the expected 2,5-dideoxy products. Structural and conformational information on these novel derivatives has been obtained by NMR spectroscopy, single-crystal X-ray crystallography and molecular mechanics calculations.

Investigation of the (PEG)xLiCl system using conductivity, DSC and NMR techniques

Electrolytes based on polyethylene glycol (PEG, mol.wt.8000) and LiCl of compositions, (PEG)(x)LiCl, x=4, 6, 8, 10, 12, 40, 60, where x is the O/Li ratio, were prepared by solution casting from methanol solutions. FTIR studies indicate that the ether oxygens of the polymer chain participate in Li+ ion conduction. The presence of a salt-polymer complex that melts around 190 degrees C was evidenced by DSC measurements for the electrolytes with compositions x<12. The highest conductivity was obtained at the composition x=10 which was attributed to the presence of a mostly amorphous compound. NMR measurements indicated two regions of motional narrowing, one attributable to the glass transition and another to translational diffusion.

Double Aromaticity in the 3,5-Dehydrophenyl Cation and in Cyclo[6]carbon

The presence of two (4n+2)-electron conjugated systems in perpendicular planes results in considerable aromatic stabilization. Despite having two fewer hydrogens, the 6 pi e-2 sigma e 3,5-dehydrophenyl cation (C6H3+, 1) is 32.7 (CCSD(T)/6-31G**) and 35.2 kcal/mol (RMP4sdtq/6-3iG*//RMP2(fu)/6-31G*) more stable than the phenyl cation (evaluated by an isodesmic reaction involving benzene and m-dehydrobenzene (4)). Cation 1, the global C6H3+ minimum, is 11.7,24.2, 11.8, and 30.4 kcal/mol lower in energy than the 2,6- (11) and 3,4-dehydrophenyl (12) cations as well as the open-chain isomers 13 and 14 (RMP4sdtq/6-31G*//RMP2(fu)/6-31G* + ZPE(RMP2(fu)/6-31G*)). The stability of 1 is increased hyperconjugatively by 2,4,6-trisilyl substitution. The double aromaticity of 1 is indicated by the computed magnetic susceptibility exaltations (IGLO/II//RMP2(fu)/6-31G*) of -5.2, -6.8, -15, and -23.2 relative to 11, 12, 13, and 14, respectively. Thus, 1 fulfills the geometric, energetic, and magnetic criteria of aromaticity. The double aromaticity of the D-6h cyclo[6]carbon is apparent from the same criteria

Ferromagnetic La0.6Pb0.4MnO3 thin films with giant magnetoresistance at 300 K

Highly textured, as-deposited La0.6Pb0.4MnO3 thin films have been grown on LaAlO3 by pulsed laser deposition. The films are ferromagnetic metals below 300 K. Giant negative magnetoresistance of over 40% is observed at 300 K at 6 T.