Polyoxomolybdenum(V/VI)-sulfite compounds: synthesis, structural, and physical studies

Reaction of Na(2)Mo(VI)O(4) x 2H(2)O with (NH(4))(2)SO(3) in the mixed-solvent system H(2)O/CH(3)CN (pH = 5) resulted in the formation of the tetranuclear cluster (NH(4))(4)[Mo(4)(VI)SO(16)] x H(2)O (1), while the same reaction in acidic aqueous solution (pH = 5) yielded (NH(4))(4)[Mo(5)(VI)S(2)O(21)] x 3H(2)O (2). Compound {(H(2)bipy)(2)[Mo(5)(VI)S(2)O(21)] x H(2)O}(x) (3) was obtained from the reaction of aqueous acidic solution of Na(2)Mo(VI)O(4) x 2H(2)O with (NH(4))(2)SO(3) (pH = 2.5) and 4,4'-bipyridine (4,4'-bipy). The mixed metal/sulfite species (NH(4))(7)[Co(III)(Mo(2)(V)O(4))(NH(3))(SO(3))(6)] x 4H(2)O (4) was synthesized by reacting Na(2)Mo(VI)O(4) x 2H(2)O with CoCl(2) x 6H(2)O and (NH(4))(2)SO(3) with precise control of pH (5.3) through a redox reaction. The X-ray crystal structures of compounds 1, 2, and 4 were determined. The structure of compound 1 consists of a ring of four alternately face- and edge-sharing Mo(VI)O(6) octahedra capped by the trigonal pyramidal sulfite anion, while at the base of the Mo(4) ring is an oxo group which is asymmetrically shared by all four molybdenum atoms. Compound 3 is based on the Strandberg-type heteropolyion [Mo(5)(VI)S(2)O(21)](4-), and these coordinatively saturated clusters are joined by diprotonated 4,4'-H(2)bipy(2+) through strong hydrogen bonds. Compound 3 crystallizes in the chiral space group C2. The structure of compound 4 consists of a novel trinuclear [Co(III)Mo(2)(V)SO(3)(2-)] cluster. The chiral compound 3 exhibits nonlinear optical (NLO) and photoluminescence properties. The assignment of the sulfite bands in the IR spectrum of 4 has been carried out by density functional calculations. The cobalt in 4 is a d(6) octahedral low-spin metal atom as it was evidenced by magnetic susceptibility measurements, cw EPR, BVS, and DFT calculations. The IR and solid-state UV-vis spectra as well as the thermogravimetric analyses of compounds 1-4 are also reported.     

Block-coordinate and incremental aggregated proximal gradient methods for nonsmooth nonconvex problems

Mathematical Programming - This paper analyzes block-coordinate proximal gradient methods for minimizing the sum of a separable smooth function and a (nonseparable) nonsmooth function, both of...     

Versatile gold-polymer nanointerfaces probed by GISAXS

An increasing trend toward integration of polymers in microelectronics and organic electronics has recently boosted research focusing in metal-polymer interfaces. These two materials differ vastly, with the former forming dense, crystalline, cohesive structures and the latter forming open structures bound together by weak van der Waals forces. As a result, there is dire need to assess their surface features (e.g., roughness) and correlate them with corresponding growth parameters, as metal-polymer interfaces are mainly determined by the preparation process. Here, we report a laboratory-based grazing-incidence small-angle x-ray scattering (GISAXS) study on distinct gold-polymer interfaces fabricated with different growth mechanisms, utilizing in-plane and oblique sputter geometries. GISAXS provided an improved analytic scheme for the buried surface in free-standing 2D gold-polymer nanosheets (with 19% porosity) revealing their fractal structure (Porod slope: ?1.71). Two quantitative approaches (Height-Height Correlation and Power Spectral Density functions) were used to describe rough surfaces characterized by Atomic Force Microscopy (AFM) in consort with GISAXS data; different correlation length dependencies on growth time were revealed for gold rough surfaces grown on bare and polymerized Si. The results are considered pertinent to interfacial nanoscience and engineering, enabling statistical data collection from large surface areas, in a fast and nondestructive manner.     

A singular perturbation analysis with applications to delay differential equations

We prove an approximation result for the solutions of a singularly perturbed, nonautonomous ordinary differential equation which has interesting applications to problems in higher dimensions. Here our result is applied to a singularly perturbed, delay differential equation with state dependent time-lags (i.e., aninfinite dimensional problem). We find a new dynamical system (also in infinite dimensions), which describes, in a certain sense, the dynamics of our delay equations for very small values of the singular parameter.     

Douglas–Rachford splitting and ADMM for nonconvex optimization: accelerated and Newton-type linesearch algorithms

Computational Optimization and Applications - Although the performance of popular optimization algorithms such as the Douglas–Rachford splitting (DRS) and the ADMM is satisfactory in convex...     

Study of poly(N,N-dimethylacrylamide)/CdS nanocomposite organic/inorganic gels

CdS nanoparticles have been synthesized and stabilized in poly(N,N-dimethylacrylamide) hydrogels. The properties of the composite material have been characterized by UV-vis spectroscopy, scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, and steady-state and time-resolved luminescence spectroscopy. This material can be obtained in three different states: swollen, shrunk, and freeze-dried. The swollen and the freeze-dried states correspond to a nanocomposite organic/inorganic (wet or dry) gel containing CdS nanoparticles of approximately 50 nm diameter while the shrunk state is a two-phase system containing CdS crystals, which precipitate forming interesting geometrical shapes.     

Protein adsorption on the mesoporous molecular sieve silicate SBA-15: effects of pH and pore size

A mesoporous molecular sieve silicate, SBA-15, with three pore sizes (38.1 A, 77.3 A, and 240 A) has been synthesized using a non-ionic, tri-block copolymer as a template in a sol-gel method. The effects of synthesis conditions on the pore size and pore-size distribution of this adsorbent have been described. The adsorption of proteins on these crystalline, ordered, materials has been studied. The kinetics of adsorption and equilibrium capacity have been probed with three proteins of different dimensions. The effects of electrostatic interactions and protein size are illustrated. It has been shown that SBA-15 materials can be tailored to show size selectivity for proteins, and very high capacities (450 mg/g) can be obtained. Furthermore, the rates of adsorption are shown to be dependent on the pore size, protein structure and solution pH.     

Heterogeneous oxidation of ethanol over Cu(OH)2/-α-Fe2O3 under visible light

A Cu(OH)₂/α-Fe₂O₃ photocatalyst is shown to be active in the gas phase oxidation of ethanol under visible light. The calculated initial quantum efficiency of the ethanol photooxidation is 0.1-1%. However, ethanol is oxidized only into acetic acid, which deactivates the catalyst. This revised version was published online in August 2006 with corrections to the Cover Date.