Design,synthesis, and cytotoxic activity evaluation of new linear pyranoxanthone aminoderivatives

With the aim of enlightening some structure‐activity correlation within the pyranoxanthenone series, we have designed and synthesized a number of new 5‐aminosubstituted pyrano[3,2‐b]xanthen‐6‐ones bearing various 12‐substituents. In vitro cytotoxic potencies of the new derivatives toward the murine leukemia L1210 cell line, human colorectal adenocarcinoma (HT‐29), and human uterine sarcoma (MES‐SA and its 100‐fold resistant to doxorubicin variant MES‐SA/Dx5) cell lines, are described and compared with that of reference drugs. Among the studied compounds, those possessing a second aminosubstituted side‐chain exhibit interesting cytotoxic activity against the solid tumor cell lines, and they retain activity against the multidrug resistant MES‐SA/Dx5 subline. Their selective effect on a phase of the cell cycle was evaluated using HT‐29 cells providing evidence that the compounds induce a G0/G1 arrest. J. Heterocyclic Chem., (2011).     

On the solution‐space geometry of random constraint satisfaction problems

For various random constraint satisfaction problems there is a significant gap between the largest constraint density for which solutions exist and the largest density for which any polynomial time algorithm is known to find solutions. Examples of this phenomenon include random k‐SAT, random graph coloring, and a number of other random constraint satisfaction problems. To understand this gap, we study the structure of the solution space of random k‐SAT (i.e., the set of all satisfying assignments viewed as a subgraph of the Hamming cube). We prove that for densities well below the satisfiability threshold, the solution space decomposes into an exponential number of connected components and give quantitative bounds for the diameter, volume, and number.© 2010 Wiley Periodicals, Inc. Random Struct. Alg., 38, 251–268, 2011     

Characterizing and modeling the free recovery and constrained recovery behavior of a polyurethane shape memory polymer

In this work, tensile tests and one-dimensional constitutive modeling are performed on a high recovery force polyurethane shape memory polymer that is being considered for biomedical applications. The tensile tests investigate the free recovery (zero load) response as well as the constrained displacement recovery (stress recovery) response at extension values up to 25%, and two consecutive cycles are performed during each test. The material is observed to recover 100% of the applied deformation when heated at zero load in the second thermomechanical cycle, and a stress recovery of 1.5 MPa to 4.2 MPa is observed for the constrained displacement recovery experiments.After performing the experiments, the Chen and Lagoudas model is used to simulate and predict the experimental results. The material properties used in the constitutive model - namely the coefficients of thermal expansion, shear moduli, and frozen volume fraction - are calibrated from a single 10% extension free recovery experiment. The model is then used to predict the material response for the remaining free recovery and constrained displacement recovery experiments. The model predictions match well with the experimental data.     

Luttinger liquid of photons and spin-charge separation in hollow-core fibers

In this work we show that light-matter excitations (polaritons) generated inside a hollow-core one-dimensional fiber filled with two types of atoms, can exhibit Luttinger liquid behavior. We first explain how to prepare and drive this quantum-optical system to a strongly interacting regime, described by a bosonic two-component Lieb-Liniger model. Utilizing the connection between strongly interacting bosonic and fermionic systems, we then show how spin-charge separation could be observed by probing the correlations in the polaritons. This is performed by first mapping the polaritons to propagating photon pulses and then measuring the effective photonic spin and charge densities and velocities by analyzing the correlations in the emitted photon spectrum. The necessary regime of interactions is achievable with current quantum-optical technology.     

Effect of heat treatment on morphology, crystalline structure and photocatalysis properties of TiO2 nanotubes on Ti substrate and freestanding membrane

Highly ordered titanium oxide (TiO₂) nanotubes were prepared by electrolytic anodization of titanium electrodes. Morphological evolution and phase transformations of TiO₂ nanotubes on a Ti substrate and that of freestanding TiO₂ membranes during the calcinations process were studied by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction microscopy. The detailed results and mechanisms on the morphology and crystalline structure were presented. Our results show that a compact layer exists between the tubular layer and Ti substrate at 600 °C, and the length of the nanotubes shortens dramatically at 750 °C. The freestanding membranes have many particles on their tubes during calcinations from 450 to 900 °C. The TiO₂ nanotubes on the Ti substrate transform to rutile crystals at 600 °C, while the freestanding TiO₂ membranes retain an anatase crystal with increasing temperature to 800 °C. The photocatalytic activity of TiO₂ nanotubes on a Ti substrate annealed at different temperatures was investigated by the degradation of methyl orange in aqueous solution under UV light irradiation. Due to the anatase crystals in the tubular layer and rutile crystals in the compact layer, TiO₂ nanotubes annealed at 450 °C with pure anatase crystals have a better photocatalytic activity than those annealed at 600 °C or 750 °C.     

Novel glass-forming liquid crystals V. Nematic and chiral-nematic systems with an elevated glass transition temperature

The formerly implemented molecular design concept behind glass-forming liquid crystals (gLCs) was generalized by increasing the volume of the non-mesogenic central core, with an attendant increase in the number of nematic pendants, using 5-hydroxyisophthalic acid as the bridging unit. New nematic gLCs were synthesized and characterized, showing an elevation in T_g by 30 to 40°C with no definite trend in T_c over the benzene, cis, cis-cyclohexane, and exo, endo-bicyclo[2.2.2]oct-7-ene base cores. The exo, exo-configured gLC showed a higher T_g and a higher T _c than the exo, endo-counterpart. Morphological characterization with X-ray diffractometry revealed the non-crystalline nature of pristine samples and the morphological stability of thermally processed gLC films against recrystallization for six months. Nematic gLC films were prepared for characterization by FTIR linear dichroism, resulting in an orientational order parameter in the range 0.52 to 0.63. A chiral-nematic gLC derived from exo, exo-bicyclo[2.2.2.]oct-7-ene also showed an elevation in T_g by 10 to 20°C over the cyclohexane-based systems reported previously. With (S)-(-)-1-phenylethylamine as the chiral moiety, the left-handed, chiral-nematic gLC film yielded a selective reflection band centred around 375 nm. Tunability of selective reflection from the UV to visible region was demonstrated by mixing the chiral-nematic and nematic gLCs at varying ratios.     

Structural study of the inclusion compounds of thymol, carvacrol and eugenol in β-cyclodextrin by X-ray crystallography

The crystal structures of the inclusion compounds of thymol, carvacrol and eugenol, (components of essential oils of vegetable origin) in β-cyclodextrin have been determined. Thymol/β-CD crystallizes in the space group P1 containing two host molecules in its asymmetric unit whereas both carvacrol/β-CD and eugenol/β-CD complexes crystallize in the space group C2. In all three complexes two host molecules form head-to-head dimers their guest/host stoichiometry being: 1/2 (carvacrol/β-CD), 2/2 (thymol/β-CD) and 3/2 (eugenol/β-CD). In the cases of the thymol/β-CD and the carvacrol/β-CD complexes the β-CD dimers are arranged according to the channel packing mode. The accommodation of the geometrical isomer guests is performed solely by their hydrophobic groups revealing the leading role of the hydrophobic driving forces in the complexation process whereas the position of their hydroxyl group affects the stoichiometry of the formed dimeric complexes. In the case of the eugenol/β-CD dimeric complex one guest molecule is found lying between the β-CD groups in a sandwich fashion whereas the other two symmetry related guests protrude outwards the narrower rim of the hosts with only their hydrophobic allyl-chain located inside the hosts’ cavities. This arrangement prohibits the formation of a channel and the observed crystal packing is that of a Tetrad mode.     

Highly efficient circulating tumor cell isolation from whole blood and label-free enumeration using polymer-based microfluidics with an integrated conductivity sensor

A novel microfluidic device that can selectively and specifically isolate exceedingly small numbers of circulating tumor cells (CTCs) through a monoclonal antibody (mAB) mediated process by sampling large input volumes (>/=1 mL) of whole blood directly in short time periods (<37 min) was demonstrated. The CTCs were concentrated into small volumes (190 nL), and the number of cells captured was read without labeling using an integrated conductivity sensor following release from the capture surface. The microfluidic device contained a series (51) of high-aspect ratio microchannels (35 mum width x 150 mum depth) that were replicated in poly(methyl methacrylate), PMMA, from a metal mold master. The microchannel walls were covalently decorated with mABs directed against breast cancer cells overexpressing the epithelial cell adhesion molecule (EpCAM). This microfluidic device could accept inputs of whole blood, and its CTC capture efficiency was made highly quantitative (>97%) by designing capture channels with the appropriate widths and heights. The isolated CTCs were readily released from the mAB capturing surface using trypsin. The released CTCs were then enumerated on-device using a novel, label-free solution conductivity route capable of detecting single tumor cells traveling through the detection electrodes. The conductivity readout provided near 100% detection efficiency and exquisite specificity for CTCs due to scaling factors and the nonoptimal electrical properties of potential interferences (erythrocytes or leukocytes). The simplicity in manufacturing the device and its ease of operation make it attractive for clinical applications requiring one-time use operation.     

Interactive transport, subcellular relocation and enhanced phototoxicity of hypericin encapsulated in guanidinylated liposomes via molecular recognition

Abstract Hypericin (HYP), a photocytotoxic phenanthroperylenquinone was encapsulated in liposomes outfitted with guanidinium-bearing lipids to ensure efficient cell binding through molecular recognition with anionic groups resident on the plasma membrane. The uptake of HYP encapsulated in these liposomes by DU145 human prostate cancer cells, was studied employing fluorescence, versus nonguadinylated liposomes and free HYP. The subcellular localization was in all cases studied by confocal microscopy employing specific subcellular organelle probes. The photocytotoxicity of HYP was assessed, 24 h following irradiation with 15 mWcm(-2) light through a GG 495 Schott filter, by a standard tetrazolium to formazan assay (XTT). HYP uptake by DU145 cells was found to be profoundly enhanced by using guanidinylated liposomes. Also the distance of the guanidinium group from the liposomal surface was found to significantly affect HYP loading, subcellular localization and phototoxicity. The two different modes of liposome cell internalization observed, i.e. plasma membrane fusion and endocytosis, were found to greatly affect the phototoxicity of HYP. Molecular recognition was overall appraised as a promising, novel route for photodynamic therapy, profoundly enhancing its efficacy. HYP encapsulated in liposomes-bearing guanidinium groups was more efficiently taken up by cells, leading to enhanced phototoxicity, in contrast to HYP encapsulated in their nonguanidinylated counterparts.     

Dimensionally stable Nafion–polyethylene composite membranes for direct methanol fuel cell applications

Nafion^® impregnated Solupor^®, microporous UHMWPE film, (N-PE), Nafion^®117 (N117) and a membrane prepared using a DE2020 Nafion^® dispersion (DE2020) were characterized with respect to their swelling degree (SD), methanol cross-over, proton conductivity and DMFC performance at various methanol concentrations in order to understand the effect of impregnation of an ion-conductive polymer membrane to the fuel cell performance.