Dihydrogen complexes of iridium and rhodium

A series of iridium and rhodium pincer complexes have been synthesized and characterized: [(POCOP)Ir(H)(H(2))] [BAr(f)(4)] (1-H(3)), (POCOP)Rh(H(2)) (2-H(2)), [(PONOP)Ir(C(2)H(4))] [BAr(f)(4)] (3-C(2)H(4)), [(PONOP)Ir(H)(2))] [BAr(f)(4)] (3-H(2)), [(PONOP)Rh(C(2)H(4))] [BAr(f)(4)] (4-C(2)H(4)) and [(PONOP)Rh(H(2))] [BAr(f)(4)] (4-H(2)) (POCOP = κ(3)-C(6)H(3)-2,6-[OP(tBu)(2)](2); PONOP = 2,6-(tBu(2)PO)(2)C(5)H(3)N; BAr(f)(4) = tetrakis(3,5-trifluoromethylphenyl)borate). The nature of the dihydrogen-metal interaction was probed using NMR spectroscopic studies. Complexes 1-H(3), 2-H(2), and 4-H(2) retain the H-H bond and are classified as η(2)-dihydrogen adducts. In contrast, complex 3-H(2) is best described as a classical dihydride system. The presence of bound dihydrogen was determined using both T(1) and (1)J(HD) coupling values: T(1) = 14 ms, (1)J(HD) = 33 Hz for the dihydrogen ligand in 1-H(3), T(1)(min) = 23 ms, (1)J(HD) = 32 Hz for 2-H(2), T(1)(min) = 873 ms for 3-H(2), T(1)(min) = 33 ms, (1)J(HD) = 30.1 Hz for 4-H(2).     

Ligand exchange and spin state equilibria of Fe(II)(N4Py) and related complexes in aqueous media

We report the characterization and solution chemistry of a series of Fe(II) complexes based on the pentadentate ligands N4Py (1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine), MeN4Py (1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)ethanamine), and the tetradentate ligand Bn-N3Py (N-benzyl-1,1-di(pyridin-2-yl)-N-(pyridin-2-ylmethyl)methanamine) ligands, i.e., [Fe(N4Py)(CH(3)CN)](ClO(4))(2) (1), [Fe(MeN4Py)(CH(3)CN)](ClO(4))(2) (2), and [Fe(Bn-N3Py)(CH(3)CN)(2)](ClO(4))(2) (3), respectively. Complexes 2 and 3 are characterized by X-ray crystallography, which indicates that they are low-spin Fe(II) complexes in the solid state. The solution properties of 1-3 are investigated using (1)H NMR, UV/vis absorption, and resonance Raman spectroscopies, cyclic voltammetry, and ESI-MS. These data confirm that in acetonitrile the complexes retain their solid-state structure, but in water immediate ligand exchange of the CH(3)CN ligand(s) for hydroxide or aqua ligands occurs with full dissociation of the polypyridyl ligand at low (<3) and high (>9) pH. pH jumping experiments confirm that over at least several minutes the ligand dissociation observed is fully reversible for complexes 1 and 2. In the pH range between 5 and 8, complexes 1 and 2 show an equilibrium between two different species. Furthermore, the aquated complexes show a spin equilibrium between low- and high-spin states with the equilibrium favoring the high-spin state for 1 but favoring the low-spin state for 2. Complex 3 forms only one species over the pH range 4-8, outside of which ligand dissociation occurs. The speciation analysis and the observation of an equilibrium between spin states in aqueous solution is proposed to be the origin of the effectiveness of complex 1 in cleaving DNA in water with (3)O(2) as terminal oxidant.     

Controlled association in suspensions of charged nanoparticles with a weak polyelectrolyte

The properties of high-pH suspensions of mixtures of silica with low-molecular-weight samples of the water-soluble polymer polyethylenimine (PEI) have been studied. At pH > 10 and low ionic strength, silica nanoparticles are stabilized by a negative surface charge, and PEI has only a very low positive charge. The adsorption of PEI induces a localized positive charge on the segments of polymer closest to the silica surface. The parts of the molecule furthest away from the surface have little charge because of the high pH of the medium. The polymer-covered particle remains negatively charged, imparting some electrostatic stabilization. Suspensions of silica and low-molecular-weight PEI are low-viscosity fluids immediately after mixing, but aggregation occurs leading to the eventual gelation (or sedimentation at lower concentrations) of these mixtures, indicating colloidal instability. The gelation time passes through a minimum with increasing surface coverage. The rate of gelation increases exponentially with molecular weight: for molecular weight > or = 10,000 Da PEI, the instability is so severe that uniform suspensions cannot be produced using simple mixing techniques. The gelation rates increase rapidly with temperature, ionic strength, and reduction in pH. The rate of gelation increases with increasing particle concentration at low surface coverage but decreases at high coverage as a consequence of a small increase in pH. Gels are broken by application of high shear into aggregates that re-gel more rapidly than the original discrete coated particles.     

Controlled, simultaneous assembly of polyethylenimine onto nanoparticle silica colloids

A novel precision-assembly methodology is described on the basis of the controlled, simultaneous assembly (CSA) of a core nanoparticle substrate and polyelectrolyte solutions. The method is capable of assembly rates at least as fast as 10(16) core particles s(-1) L(-1) and affords concentrated suspensions of stable colloids with an adsorbed polyelectrolyte. The resulting dispersions are highly homogeneous, have a low viscosity and narrow particle-size distribution, and are stable colloids, even at solid concentrations of at least 33 wt %. The adsorption isotherm and the saturation adsorption for polyethylenimine (PEI) assemblies onto a 15 nm silica colloid have been evaluated with 1H NMR spectroscopy. The saturation adsorption is highly dependent upon the pH at assembly and is given by the equation PEIa (micromol m(-2)) = 1.73pH - 1.89, R2 = 0.986, where micromoles refers to the concentration of the EI monomer. The saturation concentration increases from 6.8 micromol m(-2) at pH 5.0 to 13.7 micromol m(-2) at pH 9.0. The adsorbed polyelectrolyte may be cross-linked and thereby permanently fixed to the colloid surface to prepare nanoparticle-polyelectrolyte colloidal assemblies having enhanced colloid stability, high homogeneity, and a high fraction (>80%) of permanently adsorbed polyelectrolyte. These assemblies are stable at physiological pH and ionic strength and may represent ideal substrates for bioconjugation and, ultimately, the design of nanocarriers for in vivo applications.     

Investigation of the morphology of the mesoporous SBA-16 and SBA-15 materials

Mesoporous SBA-16 and SBA-15 were studied in order to control their possible morphologies. SBA-16 is synthesized using a silicon source (tetraethoxysilane, TEOS) and a ternary system consisting of surfactant F127 (EO106PO70EO106), water, and butanol. The same ternary system, with higher butanol concentration, is used to form SBA-15 material as well. An increase of the TEOS concentration results in a morphology shift of SBA-16 from micron-sized spheres, over randomly shaped aggregated particles, to macrospheres with a size of 15 mm. An identical increase in TEOS concentration also results in the formation of SBA-15 macrospheres, which can be controlled in size. Micron-sized spheres of SBA-15 were formed using a quaternary system of surfactant P123 (EO20PO70EO20), cetyltrimethylammonium bromide (CTAB), ethanol, and water. All mesoporous silica materials were characterized using SEM, XRD, and N2 sorption techniques.     

High-order excitations in state-universal and state-specific multireference coupled cluster theories: model systems

For the first time high-order excitations (n>2) have been studied in three multireference couple cluster (MRCC) theories built on the wave operator formalism: (1) the state-universal (SU) method of Jeziorski and Monkhorst (JM) (2) the state-specific Brillouin-Wigner (BW) coupled cluster method, and (3) the state-specific MRCC approach of Mukherjee (Mk). For the H4, P4, BeH(2), and H8 models, multireference coupled cluster wave functions, with complete excitations ranging from doubles to hextuples, have been computed with a new arbitrary-order string-based code. Comparison is then made to corresponding single-reference coupled cluster and full configuration interaction (FCI) results. For the ground states the BW and Mk methods are found, in general, to provide more accurate results than the SU approach at all levels of truncation of the cluster operator. The inclusion of connected triple excitations reduces the nonparallelism error in singles and doubles MRCC energies by a factor of 2-10. In the BeH(2) and H8 models, the inclusion of all quadruple excitations yields absolute energies within 1 kcal mol(-1) of the FCI limit. While the MRCC methods are very effective in multireference regions of the potential energy surfaces, they are outperformed by single-reference CC when one electronic configuration dominates.     

Biomonitoring of 137Cs fall-out in Kudankulam coastal waters, Gulf of Mannar, India

Concentration of fall-out ¹³⁷Cs activity was monitored for a period of 3 years in coastline surface, near-shore surface and bottom waters of Kudankulam coast where a mega nuclear power station is being set up. Activity of ¹³⁷Cs was estimated by HPGe gamma spectrometry after chemical processing with AMP (ammonium molybdophosphate). The total ¹³⁷Cs concentration ranged from 1.2 to 1.6 mBq/L in coastline surface waters and between 0.75 and 1.4 mBq/L in near-shore surface and bottom waters. The data set followed a log-normal distribution. An insignificant relationship between ¹³⁷Cs and salinity, temperature and pH was noted. No yearly variation and no variation between surface and bottom waters were observed (p > 0.05) in the concentration of ¹³⁷Cs. The ¹³⁷Cs activity between seasons was found to be significantly different (p < 0.05).     

Interaction between parallel polymer fibers insonificated by ultrasound of low/mild intensity: an analytical theory and experiments

The purpose of this article is to develop a simple mathematical model to address some bioeffects which may be caused by a static attractive force between two long neighboring parallel thin fibers (for example, a pair of collagen bundles of connective tissue) when they are insonificated by a continuous (CW) traveling plane ultrasound (US) under the condition that the fiber length (L)?the distance between them (h) and h?the wavelength of US (λ). The theory predicts that there is an attractive force between these fibers when they are exposed to the CW US with an intensity of a magnitude of 100mW/cm(2). The relationship between the relative approaching velocity of the fibers and the acoustic pressure amplitude can be calculated using the theory. An experiment was performed to verify the theoretical predictions. A plastic test chamber (diameter × height=6mm × 3.5mm) with a cap made of a sound-absorbing material and filled full with distilled water was placed on a microscope stage. A polymer fiber pair of 100μm diameter (d) and 4mm length (L) were immersed in water and aligned parallel in a plane which is normal to the US propagation direction. They floated at the central area of the chamber and h ≤10d. A 25mm diameter, 1MHz quartz crystal was used as an ultrasound source as well as the bottom of the test chamber. The quartz crystal was gold-coated on both sides, but a 5mm diameter center was left transparent (electrode free) to enable optical observation via a microscope. The maximum acoustic intensity, I(max), of the CW wave generated by the source was set at 300mW/cm(2); the corresponding acoustic pressure amplitude was 100kPa. The magnitude of the average approaching velocity of the fiber pair due to the attractive force was found in agreement with that predicted by the theory.     

Parallel Computing for Long-Time Simulations of Calcium Waves in a Heart Cell

Calcium waves are modeled by parabolic partial differential equations, whose simulation codes contain Krylov subspace methods as computational kernels. This paper presents GPU-based parallel computations for the conjugate gradient method applied to the finite difference discretization of a Poisson equation as prototype problem for the computational kernel. The CUDA algorithm tests the three memory systems of global memory, texture memory, and shared memory of a CUDA-enabled GPU. Due to the caching mechanism and coalesced read/write operations, the CUDA algorithm using global memory and single precision floating point numbers outperforms algorithms accessing texture memory and the shared memory. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)