Anatase-rutile transformation in Fe/TiO2, Th/TiO2 and Cu/TiO2 catalysts and its possible role in metal-support interaction

Based onin-situ Mössbauer and X-ray diffraction studies, it is shown that in the Fe/TiO₂ catalyst, the anatase-rutile transformation of the TiO₂ support is facilitated by the Fe²⁺ ions formed during the reduction. The transformation occurs at lower temperatures in Th/TiO₂ and Cu/TiO₂ compared to pure TiO₂. In general, the transformation of anatase to rutile seems to occur at or below the temperature (770 K) at which strong-metal-support-interaction manifests itself.Contribution No. 718 from the Solid State and Structural Chemistry Unit.     

Synthesis,spectral, thermal,and chelation potentials of polymeric hydrazone based on 2,4‐dihydroxy benzophenone

A chelating polymer, poly(2,4‐dihydroxy benzophenone hydrazone–formaldehyde) [poly(DHBPH–F)], was synthesized by the polycondensation of 2,4‐dihydroxy benzophenone hydrazone with formaldehyde in the presence of oxalic acid as a catalyst. Poly(DHBPH–F) was characterized by Fourier transform infrared and ¹H‐NMR spectral data. The molecular weight of the polymer was determined by gel permeation chromatography. Polychelates were obtained when the dimethylformamide solution of the polymer containing a few drops of ammonia was treated with an aqueous solution of metal ions. Elemental analysis of the polychelates indicated that the metal–ligand ratio was 1 : 2. The IR spectra of the polymer–metal complexes suggested that the metals were coordinated through the oxygen of the phenolic? OH group and the nitrogen of the azomethine group. The electron paramagnetic resonance and magnetic moment data indicated a square planar configuration for Cu(II) chelate and an octahedral structure for Ni(II) chelate. The thermogravimetric analysis, differential scanning calorimetry, and X‐ray diffraction data indicated that the incorporation of the metal ions significantly enhanced the degree of crystallinity. The polymerization initiation, electrical conductivity, and catalytic activity of the polychelates are discussed. Heavy‐metal ions [viz., Cu(II) and Ni(II)] were removed with this formaldehyde resin, and the metal‐ion uptake efficiency at different pH's, the nature and concentration of the electrolyte, and the reusability of the resin were also studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Skin permeation of buflomedil form adhesive matrix patches

The main objective of this research work was to fabricate and evaluate adhesive matrix-type transdermal patches of buflomedil hydrochloride, employing different ratios of pressure sensitive adhesives (PSAs) by solvent casting technique. The adhesive matrix-type transdermal patches were evaluated by their in vitro physicochemical properties such as thickness, moisture content, weight variation, drug content uniformity, etc. The effects of PSAs ratio, drug loading, and concentration of permeation enhancer were evaluated thoroughly. Ex vivo skin permeation studies with kinetic modeling of adhesive matrix patches were systematically evaluated. Based on the above observations, the best optimized buflomedil hydrochloride-loaded adhesive matrix-type transdermal patch was further characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction study, and differential scanning calorimetry analyses. Drug containing adhesive matrix patches showed sustained release property without showing any incompatibility in adhesive matrix system. Hence, adhesive matrix-type transdermal patches of buflomedil hydrochloride can be used as a potential carrier for sustained transdermal delivery of hydrophilic drugs like buflomedil hydrochloride.     

Subspace Identification of Transfer Function Models for an Unstable Bioreactor

This work deals with the identification of transfer function model of an unstable bioreactor by a subspace-based identification method. The data set is generated from the simulated closed loop system by giving a random signal at the reference signal. The linear system matrices are estimated through the Multivariable Output Numerical algorithms for Subspace State Space System Identification (MON4SID) algorithm. The delay is estimated directly from the input–output data by the impulse response method. The identified First Order Plus Time Delay (FOPTD) model is compared with the locally linearized transfer function model derived around the unstable operating point. A Proportional Integral Derivative (PID) controller is designed for the identified model using the equating coefficient method. The closed loop servo and regulatory responses show that the model identified by MON4SID is similar to the linearized model and the optimization method.     

Gold Nanoparticle–Protein Agglomerates as Versatile Nanocarriers for Drug Delivery

The fabrication of a versatile nanocarrier based on agglomerated structures of gold nanoparticle (Au NP)–lysozyme (Lyz) in aqueous medium is reported. The carriers exhibit efficient loading capacities for both hydrophilic (doxorubicin) and hydrophobic (pyrene) molecules. The nanocarriers are finally coated with an albumin layer to render them stable and also facilitate their uptake by cancer cells. The interaction between agglomerated structures and the payloads is non‐covalent. Cell viability assay in vitro showed that the nanocarriers by themselves are non‐cytotoxic, whereas the doxorubicin‐loaded ones are cytotoxic, with efficiencies higher than that of the free drug. Transmission electron microscopy and fluorescence microscopy along with flow cytometry analysis confirm the uptake of the drug‐loaded nanocarriers by a human cervical cancer HeLa cell line. Field‐emission scanning electron microscopy reveals the formation of apoptotic bodies leading to cell death, confirming the release of the payloads from the nanocarriers into the cell. Overall, the findings suggest the fabrication of novel Au NP–protein agglomerate‐based nanocarriers with efficient drug‐loading and ‐releasing capabilities, enabling them to act as multimodal drug‐delivery vehicles.     

Conformation Analysis of GalNAc‐Appended Sugar Amino Acid Foldamers as Glycopeptide Mimics

Sugar amino acid (SAA)‐based foldamers with well‐defined secondary structures were appended with N‐acetylgalactosamine (GalNAc) sugars to access sequence‐defined, multidentate glycoconjugates with full control over number, spacing and position. Conformation analysis of these glycopeptides by extensive NMR spectroscopic studies revealed that the appended GalNAc units had a profound influence on the native conformational behaviour of the SAA foldamers. Whereas the 2,5‐cis glycoconjugate showed a helical structure in water, comprising of two consecutive 16‐membered hydrogen bonds, its 2,5‐trans congener displayed an unprecedented 16/10‐mixed turn structure not seen before in any glycopeptide foldamer.     

Facile heterogenisation of molecular Ti(OSiPh3)4 to form a highly active epoxidation catalyst

The simple grafting procedure of Ti(OSiPh₃)₄ onto the internal surface of MCM-41 to produce an epoxidation catalyst of high activity and selectivity is described. The presence of the phenyl groups on each titanium centre increases the longevity of their catalytic activity towards attack from atmospheric moisture. The conversion of the catalytically inactive titanium centre of the precursor compound to an active centre is followed using XANES.     

Efficient Host-Guest Complexation of a Bisporphyrin Host with Electron Deficient Guests: Synthesis,Structure, and Photoinduced Electron Transfer

The encapsulation of 1,8-naphthalic anhydride (NAN), 9-dicyanomethylenefluorene (9-DCF), acenaphthenequinone (ANQ), and 4-chloro-7-nitrobenzofurazan (NBD-Cl) by diethylpyrrole-bridged bisporphyrin (H₄DEP) and its dizinc(II) analogue (Zn₂DEP) are employed to investigate the structural and spectroscopic changes within the bisporphyrin cavity upon substrate binding. Synthesis and X-ray structures of all four encapsulated host-guest complexes (H₄DEP⋅NAN, H₄DEP⋅9-DCF, Zn₂DEP⋅ANQ, and Zn₂DEP⋅NBD-Cl) are reported here. The binding constant calculations show strong 1 : 1 binding between the hosts (H₄DEP and Zn₂DEP) and the guests (NAN/9-DCF/ANQ/NBD-Cl). ¹H-NMR spectra also support the retention of the host-guest assemblies in solution. Negative and positive shifts of the reduction and oxidation potentials, respectively, indicate that it is difficult to reduce/oxidize the encapsulated complexes. The emission intensities of the bisporphyrins (H₄DEP and Zn₂DEP) are substantially quenched in all the complexes, owing to photoinduced electron transfer from the excited state of the bisporphyrins to guest molecules. All the experimental evidence is further substantiated by DFT calculations. Such an efficient electron transfer is only possible when the donor and the acceptor moieties are in close propinquity to each other, which eventually lowers the reorganization energy.     

Application of Strong Arcs in m-Polar Fuzzy Graphs

Neural Processing Letters - Recently, m-polar fuzzy graph (mPF graph) becomes a growing research topic as the generalization of fuzzy graph. In this paper, at first mPF path, mPF cycle in an mPF...     

Dynamic rheological,morphology and mechanical properties of compatibilized LLDPE/EMA blends

Blends of linear low density polyethylene (LLDPE) and ethylene-co-methyl acrylate (EMA) having 60/40 composition was studied with and without compatibilizing agent. The compatibilizing agent used was maleic anhydride grafted linear low density polyethylene (LLDPE-g-MA). The LLDPE backbones of the compatibilizer are compatible with LLDPE blend component, whereas the maleic anhydride is affinated with carbonyl groups of EMA. The effectiveness of the compatibilizing agent was evaluated using different techniques like mechanical, thermal, scanning electron microscopy and rheological studies. Best compatibilization effect was found in the blend at a loading of 3 wt% of compatibilizer since at this level of compatibilizer complex viscosity, tensile strength, modulus, elongation at break, impact strength was found to be higher. The increase in the melt viscosity, storage modulus and thermal stability of the compatibilized blends indicated enhanced interactions between the discrete LLDPE and EMA phases induced by the functional compatibilizer.