Direct in situ observation of increasing structural dimensionality during the hydrothermal formation of open-framework zinc phosphates

The first time-resolved in situ X-ray diffraction studies of the hydrothermal crystallisation of open-framework zinc phosphates reveal a pathway of sequential crystallisation involving formation of a metastable low dimensional chain phase before the growth of three-dimensional zeolitic architectures.     

Structural models of quasicrystals: Significance of positron annihilation studies

We discuss implications of our results of positron annihilation studies of various icosahedral quasicrystalline alloys on the structural models of this new phase. We have studied Al-Mn, Al-Mn-Si, Al-Cu-Li and Al-Cu-Fe and a two component positron annihilation lifetime spectrum seems characteristics of all these icosahedral quasicrystalline alloy phases. Analysis of the lifetime spectra yields vacancy sizes varying from monovacancies to hexavacancies with concentration of 1 to 8 ppm in various quasicrystalline alloys. These vacancy concentrations are about three orders of magnitude less than that observed in metallic glasses. We also notice that in the case of metastable quasicrystalline alloys such as Al-Mn and Al-Mn-Si, these vacancy clusters disappear during the crystallization process resulting in single lifetime spectra. On the other hand, for stable quasicrystalline alloys, two component life time spectra, which indicate the presence of vacancy clusters, continue to exist even after prolonged heat treatment. Our results seem incompatible with the space filling Penrose tiling or random tiling models and favour cluster-based models.     

A novel mixed valence iodide bridged Te(II)-Te(IV) complex featuring diisopropyldithiocarbamate(L) and iodide: ILTeII(I)TeIVL2I

The title compound is a novel mixed ligand and mixed valence complex of tellurium, the crystal structure of which is reported here. The compound crystallizes in the orthorhombic space group, Pca2₁ with four molecules per unit cell, the dimensions of which area=15.209(1),b=20.159(2),c=12.453(1) Å. The structure was solved by the heavy-atom method and refined by fullmatrix least-squares method to a finalR=0.046 andR _w=0.046 for 3011 unique reflections. The structure could be considered as 11 adduct of Te^IVL₂I₂ and Te^IILI (L=diisopropyldithiocarbamate). The two tellurium atoms, Te^II[Te(1)] and Te^IV[Te(2)] display entirely different coordinations and are bridged through iodine I(1) in a symmetrical manner. There is a short Te(1)Te(2) contact distance of 3.542(1) Å.     

Visible‐Light‐Activated C−C Bond Cleavage and Aerobic Oxidation of Benzyl Alcohols Employing BiMXO5 (M=Mg,Cd, Ni,Co, Pb,Ca and X=V,P)

The synthesis, structure, optical and photocatalytic studies of a family of compounds with the general formula, BiMXO₅; M=Mg, Cd, Ni, Co, Pb, Ca and X=V, P is presented. The compounds were prepared by regular solid‐state reaction of constituents in the temperature range of 720–810 °C for 24 h. The compounds were characterized by powder X‐ray diffraction (PXRD) methods. The Rietveld refinement of the PXRD patterns have been carried out to establish the structure. The optical absorption spectra along with the colors in daylight have been explained employing the allowed d‐d transition. In addition, the observed colors of some of the V⁵⁺ containing compounds were explained using metal‐to‐metal charge transfer (MMCT) from the partially filled transition‐metal 3d orbitals to the empty 3d orbitals of V⁵⁺ ions. The near IR (NIR) reflectivity studies indicate that many compounds exhibit good NIR reflectivity, suggesting that these compounds can be employed as ‘cool pigments’. The experimentally determined band gaps of the prepared compounds were found to be suitable to exploit them for visible light activated photocatalysis. Photocatalytic C?C bond cleavage of alkenes and aerobic oxidation of alcohols were investigated employing visible light, which gave good yields and selectivity. The present study clearly demonstrated the versatility of the Paganoite family of compounds (BiMXO₅) towards new colored inorganic materials, visible‐light photocatalysts and ‘cool pigments’.     

A Series of Collaborations between Various Pharmaceutical Companies and Regulatory Authorities Concerning the Analysis of Biomolecules Using Capillary Electrophoresis: Additional Instruments/Buffer

An international project team (including members from US, Canada and UK) was formed from a number of interested biopharmaceutical companies and regulatory authorities to conduct a cross-organisation collaboration exercise. The results of the first comparison with eight different organisations that used instruments of the same equipment model, the same reagents, and the same methodology has been reported previously [1]. This report represents the addition of other instruments using a different run buffer. The relative migration times were different, as expected, prohibiting a direct comparison between companies. The within-organisation variability was low for both relative migration time (<0.34% RSD% for all companies save one) and the peak area (<5% RSD% for all companies save one) when measuring the purity of a representative IgG sample. The apparent molecular weight of bovine serum albumin was measured with good precision (less than 10% RSD% across all companies) to the theoretical value when all data is utilized (67.5 kDa compared to 66.4 kDa). For a representative IgG sample, the three main components, IgG Light Chain, IgG Non-glycosylated Heavy Chain, and IgG Heavy Chain, could not be separated, specifically the IgG Non-glycosylated Heavy Chain and IgG Heavy Chain. When the IgG Non-glycosylated Heavy Chain and IgG Heavy Chain were combined for all organisations, the fractional peak area for the IgG Light Chain and IgG Non-glycosylated Heavy Chain + IgG Heavy Chain peak also showed excellent agreement, with less than 7.5 and 3.5% RSD%, respectively. The value of this exercise is in demonstrating the reliability of CE for the determination of apparent size of biopharmaceutical proteins. This underpins the appropriate use of such CE data in support of regulatory submissions.

     

Amine-templated open-framework zinc arsenates of varying dimensionalities: synthesis, structure, polymorphism, and transformation reactions

Eight new open-framework zinc arsenates, encompassing the entire hierarchy of open-framework structures, have been prepared hydrothermally. The structures include zero-dimensional, one-dimensional chains, two-dimensional layers, and three-dimensional structures formed through the transformation of the molecular zinc arsenates. The structure of [C6N4H21][Zn(HAsO4)2(H2AsO4)], I, is composed of ZnO4 and H2AsO4 units connected through the vertices forming four-membered rings with HAsO4 units hanging from the Zn center. The four-membered rings are connected through the corners forming the one-dimensional chain structures in [C4N2H12][Zn(HAsO4)2] x H2O, II, and [C5N2H14][Zn(HAsO4)2] x H2O, III. ZnO4 and AsO4 units form a fully four-connected two-dimensional structure in [C4N2H12][Zn(AsO4)]2, IV. One-dimensional zigzag ladders are connected through HAsO4 units forming two-dimensional layers in [C4N2H12]1.5[Zn2(AsO4)(HAsO4)2] x H2O, V, while the similar building units form a layer with hanging HAsO4 units in the layered arsenate [C6N4H21]6[Zn12(HAsO4)21], VI. Hanging HAsO4 units are also observed in the polymorphic structures of [C6N3H20][Zn2(AsO4)(HAsO4)2] x 2H2O, VII and VIII. Formation of zero-dimensional monomer, I, a fully four-connected layer, IV, and the polymorphic structures, VII and VIII, are important and noteworthy. The transformation reactions of I indicate that the monomer is reactive and gives rise to structures of higher dimensionalities, indicating a possible Aufbau-type building-up process in these structures.     

CoMn2O4 spinel from a MOF: synthesis, structure and magnetic studies

A hydrothermal reaction of Mn(OAc)(2)·4H(2)O, Co(OAc)(2)·4H(2)O and 1,2,4 benzenetricarboxylic acid at 220 °C for 24 h gives rise to a mixed metal MOF compound, [CoMn(2){C(6)H(3)(COO)(3)}(2)], I. The structure is formed by the connectivity between octahedral CoO(6) and trigonal prism MnO(6) units connected through their vertices forming a Kagome layer, which are pillared by the trimellitate. Magnetic susceptibility studies on the MOF compound indicate a canted anti-ferromagnetic behavior, due to the large antisymmetric DM interaction between the M(2+) ions (M = Mn, Co). Thermal decomposition studies indicate that the MOF compound forms a tetragonal mixed-metal spinel phase, CoMn(2)O(4), with particle sizes in the nano regime at 400 °C. The particle size of the CoMn(2)O(4) can be controlled by varying the decomposition temperature of the parent MOF compound. Magnetic studies of the CoMn(2)O(4) compound suggests that the coercivity and the ferrimagnetic ordering temperatures are dependent on the particle size.     

Mononuclear iron(III) complexes of 3N ligands in organized assemblies: spectral and redox properties and attainment of regioselective extradiol dioxygenase activity

Four octahedral iron(III) complexes of the type [Fe(L)Cl(3)], where L is a tridentate 3N ligand like N,N-bis(pyrid-2-ylmethyl)amine (bpa, L1), N,N-bis(benzimidazol-2-ylmethyl)amine (bba, L2), 1,4,7-triazacyclononane (tacn, L3) and 2,2';6',2'-terpyridine (terpy, L4), have been isolated and their catechol dioxygenase activity investigated in dichloromethane, water and different aqueous micellar media. The positions of both the catecholato-to-iron(III) LMCT bands observed for the DBC(2-) (H(2)DBC = 3,5-di-tert-butylcatechol) adducts reveal that the adducts are present as cationic [Fe(L)(DBC)(H(2)O)](+) species, which interact strongly with anionic SDS micelles and dock themselves on the anionic micellar surface, and that they exist in the aqueous phase in CTAB and TX 100 micelles. The Fe(III)/Fe(II) redox potentials of the complexes throw light on the Lewis acidity of the iron(III) center as modified by the ligand donor atoms and hence the interaction of the complexes with different micelles. The DBSQ/DBC(2-) redox potentials in SDS micellar media are more positive than those in aqueous solution confirming the presence of the aqua species [Fe(L)(DBC)(H(2)O)](+). The DBC(2-) adducts of the iron(III) complexes of bpa, bba and tacn ligands, all with facial coordination, elicit extradiol (E) cleavage to different extents while the adduct of the terpy complex with meridional coordination of the ligand shows always intradiol (I) cleavage. It is remarkable that the bpa complex shows the highest yield of extradiol product and high product selectivity in aqueous SDS solution (E, 84.0%; E/I, 61.0?:?1) and in SDS?:?n-hexane reverse micellar medium (E, 93.7%) illustrating that a vacant or solvent coordinated site is essential for observing extradiol cleavage. Interestingly, the rates of dioxygenase reactions in aqueous and aqueous micellar solutions are significantly higher than those in non-aqueous solvents. Also, they diminish in the order, SDS > TX-100 > CTAB, illustrating the facile substitution of coordinated water molecule by molecular oxygen in [Fe(L)(DBC)(H(2)O)](+) bound to anionic SDS micelles.     

Enhanced direct sunlight photocatalytic oxidation of methanol using nanocrystalline TiO2 calcined at different temperature

The pharmacokinetics (PK) of carrier-mediated agents (CMA) is dependent upon the carrier system. As a result, CMA PK differs greatly from the PK of small molecule (SM) drugs. Advantages of CMAs over SMs include prolonged circulation time in plasma, increased delivery to tumors, increased antitumor response, and decreased toxicity. In theory, CMAs provide greater tumor drug delivery than SMs due to their prolonged plasma circulation time. We sought to create a novel PK metric to evaluate the efficiency of tumor and tissue delivery of CMAs and SMs. We conducted a study evaluating the plasma, tumor, liver, and spleen PK of CMAs and SMs in mice bearing subcutaneous flank tumors using standard PK parameters and a novel PK metric entitled relative distribution over time (RDI-OT), which measures efficiency of delivery. RDI-OT is defined as the ratio of tissue drug concentration to plasma drug concentration at each time point. The standard concentration versus time area under the curve values (AUC) of CMAs were higher in all tissues and plasma compared with SMs. However, 8 of 17 SMs had greater tumor RDI-OT AUC_0–last values than their CMA comparators and all SMs had greater tumor RDI-OT AUC_0–6 h values than their CMA comparators. Our results indicate that in mice bearing flank tumor xenografts, SMs distribute into tumor more efficiently than CMAs. Further research in additional tumor models that may more closely resemble tumors seen in patients is needed to determine if our results are consistent in different model systems.