Enhanced host–guest electrochemical recognition of herbicide MCPA using a b-cyclodextrin carbon nanotube sensor

An electrochemical sensor for the determination of the chlorophenoxy herbicide MCPA has been developed, based on a combination of multi-walled carbon nanotubes with incorporated b-cyclodextrin and a polyaniline film modified glassy carbon electrode. The proposed molecular host–guest recogni-tion based sensor has a high electrochemical sensitivity for the determination of MCPA. The electrochemical behaviour of MCPA at the chemically modified electrode was investigated in detail by cyclic voltammetry. The results indicate that the b-CD/MWCNT modified glassy carbon electrode exhibits efficient electrocatalytic oxidation of MCPA with high sensitivity, stability and lifetime. The analytical characteristics of this film were used for the quantitative determination of MCPA in natural waters. Cyclic voltammetry in phosphate buffer solution at pH 6.0, allowed the development of a method to determine MCPA, without any previous steps of extraction, clean-up, or derivatization, in the range of 10–100 mmol L-1, with a detection limit of 0.99 mmol L-1 in water. The results were statistically compared with those obtained through an established high-performance liquid chromato-graphy technique, no significant differences having been found between the two methods.info:eu-repo/semantics/publishedVersio

Host-guest complexes of phenoxy alkyl acid herbicides and cyclodextrins. MCPA and β-cyclodextrin

The chlorophenoxy herbicideMCPA(4-chloro-2-methylphenoxyacetic acid), widely used for the control of broad-leafweeds primarily in cereal and grass seed crops, still remains one of the most often used herbicides in Portugal. As the formation of inclusion complexes with cyclodextrins can improve its solubility properties, the interaction between the herbicide MCPA and β-cyclodextrin was investigated. The stability constants describing the extent of formation of the complexes have been determined by phase-solubility studies. Different analytical techniques [ultraviolet-visible spectroscopy (UV-Vis), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR)] were employed for a thorough investigation of the structural characteristics of the obtained complexes, which exhibited distinct features and properties from both “guest” and “host” molecules. FTIR and 1H NMR data obtained for the MCPA/β-CD complexes gave information about the interaction between MCPA and the nonpolar cyclodextrin cavity. The dramatic change observed in band frequency and proton displacements of OCH2 group and H6 aromatic proton confirmed the inclusion of MCPA in β-CD. The formation of an inclusion complex between MCPA and β-CD increased the aqueous solubility of this herbicide which could be a particularly advantageous property for some specific applications, namely to improve commercial formulation and for environmental protection.info:eu-repo/semantics/publishedVersio

Oxidative behaviour of apomorphine and its metabolites

The metabolism of apomorphine is quite complex due to interactions with proteins and other tissue components that affect its pharmacokinetic profile. The electrochemical oxidation mechanism of apomorphine and of some synthesised apomorphine derivatives was studied. It was found to be related to the reaction of o-diphenol and tertiary amine groups and strongly dependent on pH.http://www.sciencedirect.com/science/article/B6W72-44GDWT0-2/1/3b3b44dfb6b0c11a8d094971768f0a5

Lipophilic Caffeic and Ferulic Acid Derivatives Presenting Cytotoxicity against Human Breast Cancer Cells

In the present work, lipophilic caffeic and ferulic acid derivatives were synthesized, and their cytotoxicity on cultured breast cancer cells was compared. A total of six compounds were initially evaluated: caffeic acid (CA), hexyl caffeate (HC), caffeoylhexylamide (HCA), ferulic acid (FA), hexyl ferulate (HF), and feruloylhexylamide (HFA). Cell proliferation, cell cycle progression, and apoptotic signaling were investigated in three human breast cancer cell lines, including estrogen-sensitive (MCF-7) and insensitive (MDA-MB-231 and HS578T). Furthermore, direct mitochondrial effects of parent and modified compounds were investigated by using isolated liver mitochondria. The results indicated that although the parent compounds presented no cytotoxicity, the new compounds inhibited cell proliferation and induced cell cycle alterations and cell death, with a predominant effect on MCF-7 cells. Interestingly, cell cyle data indicates that effects on nontumor BJ fibroblasts were predominantly cytostatic and not cytotoxic. The parent compounds and derivatives also promoted direct alterations on hepatic mitochondrial bioenergetics, although the most unexpected and never before reported one was that FA induces the mitochondrial permeability transition. The results show that the new caffeic and ferulic acid lipophilic derivatives show increased cytotoxicity toward human breast cancer cell lines, although the magnitude and type of effects appear to be dependent on the cell type. Mitochondrial data had no direct correspondence with effects on intact cells suggesting that this organelle may not be a critical component of the cellular effects observed. The data provide a rational approach to the design of effective cytotoxic lipophilic hydroxycinnamic derivatives that in the future could be profitably applied for chemopreventive and/or chemotherapeutic purposes.info:eu-repo/semantics/publishedVersio