Novel photocatalysts for the decomposition of organic dyes based on metal-organic framework compounds

Three novel metal-organic frameworks (MOFs) [Co(2)(C(10)H(8)N(2))][C(12)H(8)O(COO)(2)](2), 1, [Ni(2)(C(10)H(8)N(2))(2)][C(12)H(8)O(COO)(2)](2).H(2)O, 2, and [Zn(2)(C(10)H(8)N(2))][C(12)H(8)O(COO)(2)](2), 3, with three-dimensional structures have been synthesized and characterized. The structures of the three compounds appear somewhat related, formed by the connectivity involving the metal polyhedra (Co(4)N trigonal bipyramids in 1, NiO(4)N(2) octahedra in 2, and ZnO(4) tetrahedra and ZnO(3)N(2) trigonal bipyramids in 3), 4,4'-oxybis(benzoate), and 4,4'-bipyridine. The photocatalytic studies on 1-3 indicate that they are active catalysts for the degradation of orange G, rhodamine B, Remazol Brilliant Blue R and methylene blue. The compounds have also been characterized by powder X-ray diffraction, IR, thermogravitmetric analysis, UV-vis, photoluminescence, and magnetic studies.     

Nucleation of Tiny Silver Nanoparticles by Using a Tetrafacial Organic Molecular Barrel: Potential Use in Visible-Light-Triggered Photocatalysis

Coordination-driven self-assembly of discrete molecular architectures of diverse shapes and sizes has been well studied in the last three decades. Use of dynamic imine bonds for designing analogous metal-free architectures has become a growing challenge recently. This article reports an organic molecular barrel ( OB4^R ) as a potential template for nucleation and stabilization of very tiny (<1.5 nm) Ag nanoparticles (AgNPs). Imine bond condensation of a rigid tetra-aldehyde with a flexible diamine followed by imine-bond reduction yielded the discrete tetragonal organic barrel ( OB4^R ). The presence of a molecular pocket ornamented with eight diamine moieties gives the potential for encapsulation of silver(I). The organic barrel was finally used as a molecular vessel for the controlled nucleation of silver nanoparticles (AgNPs) with fine size tuning through binding of Ag^I ions in the confined space of the barrel followed by reduction. Transmission electron microscopy (TEM) analysis of the Ag⁰@OB4^R composite revealed that the mean particle size is 1.44±0.16 nm. The composite material has approximately 52 wt % silver loading. The barrel-supported ultrafine AgNPs [ Ag⁰@OB4^R ] are found to be an efficient photocatalyst for facile Ullmann-type aryl-amination coupling of haloarenes at ambient temperature without using any additives. The catalyst was stable for several cycles of reuse without any agglomeration. The new composite Ag⁰@OB4^R represents the first example of discrete organic barrel-supported AgNPs employed as a photocatalyst in Ullmann-type coupling reactions at room temperature.     

Central limit theorem for first-passage percolation time across thin cylinders

We prove that first-passage percolation times across thin cylinders of the form [0, n] × [?h _n , h _n ] ^d-1 obey Gaussian central limit theorems as long as h _n grows slower than n ^1/(d+1). It is an open question as to what is the fastest that h _n can grow so that a Gaussian CLT still holds. Under the natural but unproven assumption about existence of fluctuation and transversal exponents, and strict convexity of the limiting shape in the direction of (1, 0, . . . , 0), we prove that in dimensions 2 and 3 the CLT holds all the way up to the height of the unrestricted geodesic. We also provide some numerical evidence in support of the conjecture in dimension 2.     

Synthesis of a 1,8-naphthyridin-5-one derivative via an intramolecular 1,3-dipolar cycloaddition reaction

Synthesis of a 1,8-naphthyridin-5-one derivative [(5,6,7,8-tetrahydro-(3-chloro-6-hydroxymethyl-8-methyl)-1,8-naphthyridin-5-one (9) ] is described starting from 2-chloronicotinic acid using an intramolecular 1,3-dipolar cycloaddition reaction as the key step.     

On the incompatibility of standard quantum mechanics and conventional de Broglie-Bohm theory

It is shown that conventional de Broglie-Bohm quantum theory is incompatible with the standard quantum theory of a system unless the former is ergodic.     

A new approach of binary addition and subtraction by non-linear material based switching technique

Here, we refer a new proposal of binary addition as well as subtraction in all-optical domain by exploitation of proper non-linear material-based switching technique. In this communication, the authors extend this technique for both adder and subtractor accommodating the spatial input encoding system.     

A bifurcated pathway of oxygen atom transfer reactions from a monooxo molybdenum(VI) complex under electrospray ionisation mass spectrometric conditions

A stable molybdenum(V) complex, LMoOCl2(where L is hydrotris(3,5-dimethylpyrazolyl)borate), has been oxidized under mass spectrometric conditions. The oxidized species reacts with tertiary phosphines and the products have been detected by mass spectrometry. The product distribution has been followed by isotope labeling experiments, and energy dependent electrospray mass spectrometry. These experiments reveal not only oxygen atom transfer but also loss of a chlorine atom from the resulting species.     

Oxomolybdenum tetrathiolates with sterically encumbering ligands: modeling the effect of a protein matrix on electronic structure and reduction potentials

The effect of sterically encumbering ligands on the electronic structure of oxomolybdenum tetrathiolate complexes was determined using a combination of electronic absorption and magnetic circular dichroism spectroscopies, complimented by DFT bonding calculations, to understand geometric and electronic structure contributions to reduction potentials. These complexes are rudimentary models for a redox-active metalloenzyme active site in a protein matrix and allow for detailed spectroscopic probing of specific oxomolybdenum-thiolate interactions that are directly relevant to Mo-S(cysteine) bonding in pyranopterin molybdenum enzymes. Data are presented for three para-substituted oxomolybdenum tetrathiolate complexes ([PPh4][MoO(p-SPhCONHCH3)4], [PPh4][MoO(p-SPhCONHC(CH2O(CH2)2CN)3)4], and [PPh4][MoO(p-SPhCONHC(CH2O(CH2)2COOCH2CH3)3)4]). The Mo(V/IV) reduction potentials of the complexes in DMF are -1213, -1251, and -1247 mV, respectively. The remarkably similar electronic absorption and magnetic circular dichroism spectra of these complexes establish that the observed reduction potential differences are not a result of significant changes in the electronic structure of the [MoOS4]- cores as a function of the larger ligand size. We provide evidence that these reduction potential differences result from the driving force for a substantial reorganization of the O-Mo-S-C dihedral angle upon reduction, which decreases electron donation from the thiolate sulfurs to the reduced molybdenum center. The energy barrier to favorable O-Mo-S-C geometries results in a reorganizational energy increase, relative to [MoO(SPh)4](-/2-), that correlates with ligand size. The inherent flexible nature of oxomolybdenum-thiolate bonds indicate that thiolate ligand geometry, which controls Mo-S covalency, could affect the redox processes of monooxomolybdenum centers in pyranopterin molybdenum enzymes.