Controlled-release of drugs from cross-linked polymers containing cubane as a crosslinking agent

Two anti-inflammatory drugs, indomethacin and aspirin together with cubane-1, 4-dicarboxylic acid (CDA) were covalently linked with 2-hydroxyethyl methacrylate (HEMA). The drug-linked HEMA (indomethacin-linked HEMA) is abbreviated as HI, aspirin-linked HEMA as HA and cubane-1, 4-dicarboxylic acid (CDA) linked to two HEMA group is the cross-linking agent (CA). A difunctional spacer group was introduced between the drugs and acrylic moiety of the monomer through a hydrolyzable ester linkage. Free radical cross-linking polymerization of the monomers with drug effect was carried out in dioxane solution at various CA ratios, using AIBN as initiator in the temperature range 60-70°C. The compositions of the cross-linked three-dimensional polymers were determined by FT-IR spectroscopy. The glass transition temperature (Tg) of the network polymers was determined calorimetrically. The hydrolysis of drug-polymer conjugates was carried out in cellophane membrane dialysis bags containing an aqueous buffer solution (pH 8 and pH 1) at 37°C. Detection of the hydrolysis product by UV spectroscopy shows that the drugs were released by hydrolysis of the ester bond located between the drug and spacer group.     

Design and synthesis of benzodiazepine-1,2,3-triazole hybrid derivatives as selective butyrylcholinesterase inhibitors

Molecular Diversity - A new series of compounds based on benzodiazepine-1,2,3-triazole were synthesized and evaluated as cholinesterase inhibitors by Ellman’s method. The compounds proved to...     

A metal–organic framework/polymer derived catalyst containing single-atom nickel species for electrocatalysis

While metal–organic frameworks (MOF) alone offer a wide range of structural tunability, the formation of composites, through the introduction of other non-native species, like polymers, can further broaden their structure/property spectrum. Here we demonstrate that a polymer, placed inside the MOF pores, can support the collapsible MOF and help inhibit the aggregation of nickel during pyrolysis; this leads to the formation of single atom nickel species in the resulting nitrogen doped carbons, and dramatically improves the activity, CO selectivity and stability in electrochemical CO₂ reduction reaction. Considering the vast number of multifarious MOFs and polymers to choose from, we believe this strategy can open up more possibilities in the field of catalyst design, and further contribute to the already expansive set of MOF applications.

A metal–organic framework/polymer derived catalyst containing single-atom nickel species shows good performance for electroreduction of CO₂ to CO.     

Syntheses and Spectroscopic Study of Some New N‐4‐Fluorobenzoyl Phosphoric Triamides; Crystal Structures of 4‐F‐C6H4C(O)N(H)P(O)R2, R = NH‐C(CH3)3, NH‐CH2C6H5, N(CH3)(CH2C6H5)

Some new N‐4‐Fluorobenzoyl phosphoric triamides with formula 4‐F‐C₆H₄C(O)N(H)P(O)X₂, X = NH‐C(CH₃)₃ ( 1 ), NH‐CH₂‐CH=CH₂ ( 2 ), NH‐CH₂C₆H₅ ( 3 ), N(CH₃)(C₆H₅) ( 4 ), NH‐CH(CH₃)(C₆H₅) ( 5 ) were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR and Mass spectroscopy and elemental analysis. The structures of compounds 1 , 3 and 4 were investigated by X‐ray crystallography. The P=O and C=O bonds in these compounds are anti. Compounds 1 and 3 form one dimensional polymeric chain produced by intra‐ and intermolecular ‐P=O···H‐N‐ hydrogen bonds. Compound 4 forms only a centrosymmetric dimer in the crystalline lattice via two equal ‐P=O···H‐N‐ hydrogen bonds. ¹H and ¹³C NMR spectra show two series of signals for the two amine groups in compound 1 . This is also observed for the two α‐methylbenzylamine groups in 5 due to the presence of chiral carbon atom in molecule. ¹³C NMR spectrum of compound 4 shows that ²J(P,C_aliphatic) coupling constant for CH₂ group is greater than for CH₃ in agreement with our previous study. Mass spectra of compounds 1 ‐ 3 (containing 4‐F‐C₆H₄C(O)N(H)P(O) moiety) indicate the fragments of amidophosphoric acid and 4‐F‐C₆H₄CN⁺ that formed in a pseudo McLafferty rearrangement pathway. Also, the fragments of aliphatic amines have high intensity in mass spectra.     

Investigation of Cu Doping,Morphology and Annealing Effects on Structural and Optical Properties of ZnO:Dy Nanostructures

Dysprosium (Dy) doped ZnO nanosheets and nanorods were synthesized by hydrothermal method. Effects of Cu doping, morphology and annealing in Oxygen ambient on structural and optical properties of ZnO nanostructures were investigated using X–ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance spectra (DRS) and photoluminescence (PL) spectroscopy. This study recommends that both of intrinsic and extrinsic defects facilitate energy transfer (ET) from the ZnO host to Dy³⁺ ions and consequently have an effective role on producing intense Dy emissions at indirect excitation. The results also revealed that annealing process improved the crystal structure of ZnO nanorods due to decrease of surface; however decreased ET and Dy emissions because of diminishing in oxygen vacancy. In addition, as a result of increasing of surface area in nanorods compared to nanosheets, the oxygen vacancies and ET were enhanced. Moreover the results exhibited that electrical and optical properties of ZnO:Dy can be tuned by various amount of Dy concentrations and also Cu doping.     

Facile Biosynthesis of Silver Nanoparticles Using <Emphasis Type="Italic">Descurainia sophia</Emphasis> and Evaluation of Their Antibacterial and Antifungal Properties

The objective of the present study was to evaluate efficiency of silver nanoparticles (Ag-NPs) biosynthesis using Descurainia sophia as a novel biological resource. The resulting synthesized Ag-NPs were characterized using UV visible spectroscopy, X-ray diffraction, transmission electron microscopy and dynamic light scattering (DLS). The UV–Vis spectra gave surface plasmon resonance at ~420 nm. TEM images revealed formation spherical shaped Ag-NPs with size ranged from to 1–35 nm. DLS confirmed uniformity of the synthesized Ag-NPs with an average size of ~30 nm. Following, the antibacterial and antifungal activities of the synthesized Ag-NPs were investigated. The concentration 25 µg/ml of the Ag-NPs showed maximum inhibitory effect on mycelium growth of Rhizoctonia solani (More than 86 % inhibition), followed by 15 µg/ml (55 % inhibition) and 10 µg/ml (63 % inhibition). The minimum inhibitory concentration and minimum bactericidal concentration of Ag-NPs against Agrobacterium tumefaciens (strain GV3850) and A, rhizogenes (strain 15843) were 4 and 8 µg/ml, respectively. The Ag-NPs were stable in vitro for 3 months without any precipitation or decrease of antifungal effects. Finally, it could be concluded that D. sophia can be used as an effective method for biosynthesis of nanoparticles, especially Ag-NPs.     

Syntheses and structures of four new mixed‐amide phosphoric triamides

Phosphoric triamides have extensive applications in biochemistry and are also used as O‐donor ligands. Four new mixed‐amide phosphoric triamide structures, namely rac‐N‐tert‐butyl‐N′,N′′‐dicyclohexyl‐N′′‐methylphosphoric triamide, C₁₇H₃₆N₃OP, (I), rac‐N,N′‐dicyclohexyl‐N′‐methyl‐N′′‐(p‐tolyl)phosphoric triamide, C₂₀H₃₄N₃OP, (II), N,N′,N′′‐tricyclohexyl‐N′′‐methylphosphoric triamide, C₁₉H₃₈N₃OP, (III), and 2‐[cyclohexyl(methyl)amino]‐5,5‐dimethyl‐1,3,2λ⁵‐diazaphosphinan‐2‐one, C₁₂H₂₆N₃OP, (IV), have been synthesized and studied by X‐ray diffraction and spectroscopic methods. Structures (I) and (II) are the first diffraction studies of acyclic racemic mixed‐amide phosphoric triamides. The P—N bonds resulting from the different substituent –N(CH₃)(C₆H₁₁), (C₆H₁₁)NH–, 4‐CH₃‐C₆H₄NH–, (tert‐C₄H₉)NH– and –NHCH₂C(CH₃)₂CH₂NH– groups are compared, along with the different molecular volumes and electron‐donor strengths. In all four structures, the molecules form extended chains through N—H…O hydrogen bonds.     

Grafting of temperature sensitive PNIPAAm on hydrophilised polysulfone UF membranes

Poly(N-isopropyl acrylamide) (PNIPAAm) was grafted on a polysulfone UF membrane. The changes of permeability as well as retention of PEG (35 kg/mol) and Dextran (500 kg/mol) between 23 and 60 °C were determined for both grafted and unmodified membranes. The results showed that the viscosity corrected water permeability and solute retention were almost constant for the unmodified membranes within the measured temperature range, the permeability of the grafted membranes increased and the retention of Dextran and PEG decreased with temperature. The variation of changes was most obvious in the temperature range 27–37 °C for the modified membranes due to the lower critical solution temperature (LCST) of PNIPAAm. The location and profile of PNIPAAm inside and on the surface of the membrane were analysed by SEM and FTIR. Depth profile calculation for FTIR spectra showed that PNIPAAm was mostly placed inside the membrane (at a depth of 1.06–1.10 μm from the surface) rather than on the surface. The amount of grafted PNIPAAm was low and did not significantly affect the morphology of the membrane. Therefore, a difference in SEM pictures of modified and unmodified membranes could not be seen. The modified membrane exhibited a clearly different thermal response compared to the unmodified one.     

BTX Removal from Polluted Water Through Bioleaching Processes

In this study, benzene, toluene, and xylenes (BTX) removal from contaminated water by physical, chemical, and biological processes was studied. Results showed that air sparging in polluted water can reduce monoaromatic compounds from 140,000 to about 5 microg/l in only 1 h process with a gassing rate of 0.33 VVM. This method cannot be considered as a green technology as pollutants are only transferred from the liquid phase to the gas phase The ultimate objective of this research was thus to evaluate the efficiency of a strategy involving BTX adsorption by granular-activated charcoal (GAC) and subsequent regeneration of this support by a bioleaching process. Analysis of such processes requires the building of analytical tools able to accurately determine the contents of the contaminants in samples containing biomass to make possible the calculation of reliable material balances. Current investigation showed that BTX are readily trapped by GAC particles with low further release in the liquid medium whereas they remain at least partially available for in situ biodegradation. BTX adsorption onto the GAC was shown to reach maximum solute retention close to 350, 250, and 150 (as mg/g GAC) for xylenes, toluene, and benzene, respectively. This approach, which could afford efficient biological active carbon regeneration, is very promising for the removal of BTX compounds from water without any further environment damage.     

γ‐Fe2O3@Cu3Al‐LDH‐TUD as a new Amphoteric,Highly Efficient and Recyclable Heterogeneous Catalyst for the Solvent‐free Synthesis of Dihydropyrano[3,2‐c]pyrazoles and dihydropyrano[3,2‐c]chromens

Thiourea dioxide was immobilized on γ‐Fe₂O₃@Cu₃Al‐LDH magnetic nanoparticles to prepare the γ‐Fe₂O₃@Cu₃Al‐LDH‐TUD MNPs. The structure and properties of these magnetic nanoparticles were established by FT‐IR, EDX, SEM, XRD, and hystogram of particle size analytical methods. The results obtained from these analytical methods confirmed the successful immobilization of the thiourea dioxide onto the magnetic support. The synthesized magnetic nanoparticles (MNPs) exhibited high catalytic activity in one‐pot three‐component reactions under mild and solvent‐free conditions for the synthesis of diverse ranges of dihydropyrano[3,2‐c]pyrazoles and dihydropyrano[3,2‐c]chromens. All the reactions proceeded smoothly to furnish the respective products in excellent yields. Simple isolation of the products, avoidance of harmful organic solvents, versatility of the catalyst and its easy magnetic separation and reusability with no significant loss of activity are the main advantages of the present method.