Conductive electrospun composite fibers based on solid-state polymerized Poly(3,4-ethylenedioxythiophene) for simultaneous electrochemical detection of metal ions.

Conductive composite fibers containing poly (3,4-ethylenedioxythiophene) (PEDOT) and silver nanoparticles (AgNPs) were fabricated by emulsion electrospinning of 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) in toluene together with aqueous solution of poly (vinyl alcohol) (PVA) and silver nanoparticles (AgNPs) in the presence of sodium dodecylsulfate followed by heat treatment at 70 °C to convert DBEDOT to conductive PEDOT via solid state polymerization (SSP). The composite fibers were characterized by scanning electron microscopy, transmission electron microscopy, x-ray photoelectron spectroscopy and thermogravimetric analysis. The PEDOT/PVA/AgNPs composite fibers deposited on a screen-printed carbon electrode (SPCE) surface exhibited good electrochemical response and was applied for simultaneous detection of heavy metal ions in a mixture, namely Zn(II), Cd(II), and Pb(II) via square wave anodic stripping voltammetry (SWASV). With added Bi+3 into the detection system, the bismuth film formed on the electrode allows effective alloy formation with the deposited heavy metals obtained upon reduction of the heavy metal ions, the detection of heavy metal ions after stripping was successfully accomplished with a linear range of 10-80 ppb and limits of detections (LOD) of 6, 3 and 8 ppb for Zn(II), Cd(II), and Pb(II), respectively.

Synthesis and Acidity of 5-(m-Terphenyl-2'-yl)-1H-tetrazoles: Evidence for an Enhanced Polar-π Effect Compared to Carboxylic Acids.

The polar-π effect on tetrazoles, medicinal chemistry isosteres of carboxylate, is tested by a Hammett pKa (microtitration) analysis over a series of 5-(m-terphenyl-2'-yl)-1H-tetrazoles. A comparison with m-terphenyl-2'-yl-carboxylic acids supports the isostere analogy also in response to environmental changes. Computational (B97D/def2TZVPPD) extension of the series plus a scan of solvents (vacuum to water) demonstrates the trend with the dielectric constant. The effect is energetically small but may make statistically significant contributions to the tetrazole pharmacological profile.

Doxorubicin-conjugated dexamethasone induced MCF-7 apoptosis without entering the nucleus and able to overcome MDR-1-induced resistance.

BACKGROUND: Doxorubicin (DOX) is the most widely used chemotherapeutic agent that has multimodal cytotoxicity. The main cytotoxic actions of DOX occur in the nucleus. The emergence of drug-resistant cancer cells that have the ability to actively efflux DOX out of the nucleus, and the cytoplasm has led to the search for a more effective derivative of this drug. MATERIALS AND METHODS: We created a new derivative of DOX that was derived via simple conjugation of the 3' amino group of DOX to the dexamethasone molecule. RESULTS: Despite having a lower cytotoxic activity in MCF-7 cells, the conjugated product, DexDOX, exerted its actions in a manner that was different to that of DOX. DexDOX rapidly induced MCF-7 cell apoptosis without entering the nucleus. Further analysis showed that Dex-DOX increased cytosolic oxidative stress and did not interfere with the cell cycle. In addition, the conjugated product retained its cytotoxicity in multidrug resistance-1-overexpressing MCF-7 cells that had an approximately 16-fold higher resistance to DOX. CONCLUSION: We have synthesized a new derivative of DOX, which has the ability to overcome multidrug resistance-1-induced resistance. This molecule may have potential as a future chemotherapeutic agent.

Substituent effects on chiral resolutions of derivatized 1-phenylalkylamines by heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-ß-cyclodextrin GC stationary phase.

Chiral resolutions of trifluoroacetyl-derivatized 1-phenylalkylamines with different type and position of substituent were investigated by capillary gas chromatography by using heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-ß-cyclodextrin diluted in OV-1701 as a chiral stationary phase. The influence of column temperature on retention and enantioselectivity was examined. All enantiomers of meta-substituted analytes as well as fluoro-substituted analytes could be resolved. Temperature had a favorable influence on enantioselectivity for small amines with substituents at the ortho-position. The type of substituent at the stereogenic center of amines also had a crucial effect as the ethyl group led to poor enantioseparation. Among all analytes studied, trifluoroacetyl-derivatized 1-(2'-fluorophenyl)ethylamine exhibited baseline resolution with the shortest analysis time.

Use of a hexasubstituted benzene scaffold in the development of multivalent HIV-1 integrase inhibitors.

The highly directional hexasubstituted benzene moiety was used as the central scaffold to create new human immunodeficiency virus (HIV)-1 integrase inhibitors through the attachment of multiple active groups. A series of potential inhibitors having substituted polyhydroxylated mono, bis and tris-cinnamoyl derivatives connected on the scaffold were prepared through Claisen-Schmidt condensations with substituted benzaldehydes, followed by partial demethylation to uncover the active phenolic groups required for the interactions with the integrase enzyme active sites. Using a multiplate integration assay method, four compounds carrying at least two sets of interacting moieties were found to be relatively potent integrase inhibitors with IC50 values in the low micromolar range. The results confirmed that multiple polyhydroxylated groups were required on the platform in order to effectively interact with the enzyme. The results from molecular docking studies consistently complemented the experimental results and revealed the nature of the potential key binding interactions responsible for the apparent activity of the active compounds.

Through-space interactions between parallel-offset arenes at the van der Waals distance: 1,8-diarylbiphenylene syntheses, structure and QM computations.

A model for studying polar-pi interactions between arenes spaced at van der Waals distances is developed on the basis of peri-diarylbiphenylenes. A set of 1,8-diarylbiphenylenes is synthesized comprising two Hammett series, one with reference to mesityl ring interactions and the other with reference to pentafluorophenyl ring interactions. X-Ray crystal structures of several derivatives are determined. Barriers to rotation of the probe aryl ring are derived from dynamic NMR data and show a trend for the mesityl reference series (DeltaG(not equal) vs. sigma(0)). The model is also used as a test for comparison of modern density functional methods, including B3LYP, M06-2X and BMK functionals; dispersive effects are seen to be an important factor in the proper theoretical treatment of arene interactions.

UV absorption and photoisomerization of p-methoxycinnamate grafted silicone.

p-Methoxycinnamate moieties, UV-B-absorptive chromophores of the widely used UV-B filter, 2-ethylhexyl p-methoxycinnamate (OMC), were grafted onto the 7 mol% amino functionalized silicone polymer through amide linkages. Comparing with OMC, the resulting poly [3-(p-methoxycinnamido)(propyl)(methyl)-dimethyl] siloxane copolymer (CAS) showed less E to Z isomerization when exposed to UV-B light. The absorption profiles of the product showed the maximum absorption wavelength to be similar to that of OMC but with less sensitivity to the type of solvent. Poly (methylhydrosiloxane) grafted with 10 mol% p-methoxycinnamoyl moieties was prepared through hydrosilylations of 2-propenyl-p-methoxycinnamate, in which the resulting copolymer showed similar results to those of CAS.