Calix[4]arene-based metal-organic frameworks: towards hierarchically porous materials

An upper rim-functionalised calix[4]arene dicarboxylic acid (H(2)caldc) has been used to prepare four metal-organic frameworks, three of which have been structurally characterised and shown to form two- or three-dimensional network structures. Simulations suggest that such networks are likely to display interesting selectivity to guest molecules.     

Determination of complex modes in photonic crystal waveguides using the phase variation in characteristic coefficients

An efficient frequency-domain method, the phase variation monitoring (PVM) method, is proposed to determine the electromagnetic eigenmodes in two-dimensional photonic crystal waveguides. The proposed method is based on monitoring the reflection and transmission coefficients of incident plane waves. It is successfully applied to an illustrative line-defect photonic crystal waveguide and proved to be capable of calculating the in-plane leakage through the finite-size photonic crystal surrounding the line-defect. Calculation of the leakage loss is not only important for proper understanding of wave propagation within the defect but also for its significant role in applications of photonic structures.     

Anticancer and DNA Binding Activities of Platinum (IV) Complexes; Importance of Leaving Group Departure Rate

The two six-coordinate Pt(IV) complexes, containing bidentate nitrogen donor/methyl ligands with general formula [Pt(X)₂Me₂(^tbu₂bpy)], where ^tbu₂bpy = 4,4′-ditert-butyl-2,2′-bipyridine and X = Cl (C₁) or Br (C₂), serving as the leaving groups were synthesized for evaluation of their anticancer activities and DNA binding properties. To examine anticancer activities of the synthetic complexes, 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay and ethidium bromide/acridine orange (EB/AO) staining method were performed. The binding properties of these complexes to DNA and purine nucleotides were examined, using different spectroscopic techniques. These complexes demonstrated significant anticancer activities against three cancer cell lines Jurkat, K562, and MCF-7. On the basis of the results of EB/AO staining, C₁ and C₂ were also capable to induce apoptosis in cancer cells. These complexes comprise halide leaving groups, displaying different departure rates; accordingly, they demonstrated slightly dissimilar anticancer activity and significantly different DNA/purine nucleotide binding properties. The results of DNA interaction studies of these complexes suggest a mixed-binding mode, comprising partial intercalation and groove binding. Overall, the results presented herein indicate that the newly synthesized Pt(IV) complexes are promising class of the potential anticancer agents which can be considered as molecular templates in designing novel platinum anticancer drugs. This study also highlights the importance of leaving group in anticancer activity and DNA binding properties of Pt(IV) complexes.     

One‐Pot Synthesis of (1,2,3‐Triazolyl)methyl 3,4‐Dihydro‐2‐oxo‐1H‐pyrimidine‐5‐carboxylates as Potentially Active Antimicrobial Agents

A simple and efficient one‐pot four‐component procedure has been developed for the synthesis of a wide range of compounds containing the (triazolyl)methyl oxo‐pyrimidine‐carboxylate system from propargyl β‐keto esters, various azides, aldehydes, and urea in the presence of catalytic amounts of (AcO)₂Cu/sodium ascorbate in AcOH. The method worked well with different aryl and heteroaryl aldehydes, and for a variety of substituents in the triazolyl part of the molecule. The antimicrobial activities of the products were evaluated against two Gram‐positive and Gram‐negative bacteria, and one fungus. Compound 5j was active against Staphylococcus aureus and Candida albicans.     

Enantioselective Addition of Diethylzinc to Aromatic Aldehydes Catalyzed by Pyrolidine and Piperidine β-Amino Alcohols

The enantioselective alkylation of aryl aldehydes by diethylzinc in the presence of catalytic amounts of several chiral pyrolidine- and piperidine-based amino alcohol ligands, synthesized from the reaction of (R)-2-amino-1-butanol and (S)-2-amino-3-phenylpropan-1-ol with appropriate dibromoalkanes, was studied. The influence of temperature and ligand structure has been investigated. Addition of diethylzinc to aromatic aldehydes under the optimized condition gave the corresponding products in excellent yields with ee values of up to 77%.     

Silica Sulfuric Acid: An Efficient and Versatile Acidic Catalyst for the Rapid and Ecofriendly Synthesis of 1,3,4‐Oxadiazoles at Ambient Temperature

A rapid and green synthesis of 2,5‐disubstituted 1,3,4‐oxadiazoles is reported. The title compounds were prepared by the reaction of different acyl hydrazides and orthoesters in the presence of silica sulfuric acid under solvent‐free conditions. In this new process, reactions were run at ambient temperature and completed in a short period of time with high yields.     

Novel,Efficient, and Green Procedure for the Knoevenagel Condensation Catalyzed by Diammonium Hydrogen Phosphate in Water

Knoevenagel condensation of various aromatic and heteroaromatic aldehydes with active methylene compounds like methyl and ethyl cyanoacetate, malononitrile, and cyanoacetamide proceeds smoothly with stirring in water in the presence of 4 mol% of diammonium hydrogen phosphate. The reactions were carried out at room temperature in short periods with very simple workup procedure and good to high yields.     

Enhanced Nucleation and Crystallization in PLA/CNT Composites via Disperse Orange 3 with Corresponding Improvement in Nanomechanical Properties

The potential for the material property improvement through the addition of carbon nanotubes (CNTs) in composite materials is often limited due to CNT agglomeration. In this work, Disperse Orange 3 (DO3) was investigated to determine its effectiveness in dispersing CNTs in a poly (lactic acid) (PLA) matrix. First, adsorption studies of DO3 onto CNTs were performed to determine the appropriate amount of DO3 to add so that the CNT surface will be nearly saturated with DO3 while limiting the excess DO3 dissolved in the polymer. The resultant improvements in the mechanical properties were determined via nanoindentation. Highly stable dispersion of CNTs in tetrahydrofuran with DO3 was observed 72 hours after sonication. Scanning electron microscopy confirmed that DO3‐functionalized CNTs were able to separate and disperse well inside of the PLA matrix. Addition of DO3 to the nanocomposite resulted in an increase in the glass transition temperature and crystallinity of the composite due to the more effective dispersion of the nanofiller which serves as a nucleation agent. The CNTs treated with DO3 also increased the elastic modulus and hardness of the composite compared to neat PLA and untreated PLA‐CNT composites. From this study, DO3 was demonstrated to be an effective dispersing agent in the solvent and the PLA matrix which allowed for enhanced crystallization and improved nanomechanical properties in the resultant composite.     

Discrete ordinates method for propagation of light in highly scattering vascular tissues

This work considers the propagation of light in a semitransparent layer of vascular tissue, submitted to radiative boundary conditions. The solution procedure must provide accurate light distribution in the layer, so a discrete ordinates method based on the exact transport theory is carried out. An advantage of this method is its ability to account easily for various boundary conditions as well as optical heterogeneity. The influences of anisotropic scattering, optical discontinuity, optical parameters of tissue and refractive index on radiant fluence rate are investigated carefully. It is shown that reflections tend to produce more uniform profiles within the tissue.