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High-performance liquid chromatography coupled with ion spray mass spectrometry in the tandem mode with both negative and positive ionization was used for investigating a variety of polyphenolic compounds in four genotypes of Fragaria vesca berries. About 60 phenolic compounds belonging to the compound classes of phenolic acids, ellagitannins, ellagic acid derivatives, flavonols, monomeric and oligomeric flavanols, dihydrochalcones and anthocyanins were reported, providing for the first time a quite complete picture of polyphenolic composition of F. vesca berries. Some of the polyphenols herein investigated, such as a tris-galloyl-hexahydroxydiphenoyl-hexose, two castalagin/vescalagin-like isomers and peonidin-malonylglucoside, were described for the first time. Principal component analysis applied on original HPLC-MS/MS data, acquired in multiple reaction monitoring mode, successfully discriminated the four investigated cultivars on the basis of their polyphenolic composition, highlighting the fundamental role of mass spectrometry for food characterization.

The synthesis of hydrophilic graphene-based yolk-shell magnetic nanoparticles functionalized with copolymer pluronic F-127 (GYSMNP@PF127) is herein reported to achieve an efficient multifunctional biomedical system for mild hyperthermia and stimuli-responsive drug delivery. In vitro tests revealed the extraordinary ability of GYSMNP@PF127 to act as smart stimuli-responsive multifunctional nanomedicine platform for cancer therapy, exhibiting (i) an outstanding loading capacity of 91% (w/w, representing 910 μg mg −1) of the chemotherapeutic drug doxorubicin, (ii) a high heating efficiency under an alternating (AC) magnetic field (intrinsic power loss ranging from 2.1-2.7 nHm 2 kg −1), and (iii) a dual pH and thermal stimuli-responsive drug controlled release (46% at acidic tumour pH vs 7% at physiological pH) under AC magnetic field, in just 30 min. Additionally, GYSMNP@PF127 presents optimal hydrodynamic diameter (D H = 180 nm) with negative surface charge, high haemocompatibility for blood stream applications and tumour cellular uptake of drug nanocarriers. Due to its physicochemical, magnetic and biocompatibility properties, the developed graphene-based magnetic nanocarrier shows high promise as dual exogenous (AC field)/endogenous (pH) stimuli-responsive actuators for targeted thermo-chemotherapy, combining magnetic hyperthermia and controlled drug release triggered by the abnormal tumour environment. The presented strategy and findings can represent a new way to design and develop highly stable added-value graphene-based nanostructures for the combined treatment of cancer.

a b s t r a c tThe distribution of Cd, Cu, Pb and Zn between a contaminated soil and the tree species Paulownia tomentosa was investigated in a pilot-scale assisted phytoremediation study. The influence of the addition of EDTA, tartrate and glutamate at 1, 5 and 10 mM concentrations on metal accumulation by the plant and on metal mobilization in soil was evaluated. Root/shoot metal concentration ratios were in the range of 3-5 for Zn, 7-17 for Cu, 9-18 for Cd and 11-39 for Pb, depending on the type and concentration of complexing agent. A significant enhancement of metal uptake in response to complexing agent application was mainly obtained in roots for Pb (i.e. 359 mg kg À1 for EDTA 10 mM and 128 mg kg À1 for the control), Cu (i.e. 594 mg kg À1 for glutamate 10 mM and 146 mg kg À1 for the control) and, with the exception of glutamate, also for Zn (i.e. 670 mg kg À1 for tartrate 10 mM and 237 mg kg À1 for the control). Despite its higher metal mobilization capacity, EDTA produced a metal accumulation in plants quite similar to those obtained with tartrate and glutamate. Consequently the concentration gradient between soil pore water and plant tissues does not seem to be the predominant mechanism for metal accumulation in Paulownia tomentosa and a role of the plant should be invoked in the selection of the chemical species taken up. Metal bioavailability in soil at the end of the experiment was higher in the trials treated with EDTA than in those treated with tartrate and glutamate, the latter not being significantly different from the control. These findings indicated the persistence of a leaching risk associated to the use of this chelator, while an increase of the environmental impact is not expected when glutamate and tartrate are applied.

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a b s t r a c tRecently our findings have shown that the integration of the gene coding for the rat gluco-corticoid receptor (GR receptor) in Nicotiana langsdorffii plants induced morphophysiological effects in transgenic plants through the modification of their hormonal pattern. Phytohormones play a key role in plant responses to many different biotic and abiotic stresses since a modified hormonal profile up-regulates the activation of secondary metabolites involved in the response to stress. In this work transgenic GR plants and isogenic wild type genotypes were exposed to metal stress by treating them with 30 ppm cadmium(II) or 50 ppm chromium(VI). Hormonal patterns along with changes in key response related metabolites were then monitored and compared. Heavy metal up-take was found to be lower in the GR plants. The transgenic plants exhibited higher values of S-abscisic acid (S-ABA) and 3-indole acetic acid (IAA), salicylic acid and total polyphenols, chlorogenic acid and antiradical activity, compared to the untransformed wild type plants. Both Cd and Cr treatments led to an increase in hormone concentrations and secondary metabolites only in wild type plants. Analysis of the results suggests that the stress responses due to changes in the plant's hormonal system may derive from the interaction between the GR receptor and phytosteroids, which are known to play a key role in plant physiology and development.

Nanotechnology is addressing major urgent needs for cancer treatment. We conducted a study to compare the frequency of 3-(2-deoxy-β-d-erythro-pentafuranosyl)pyrimido[1,2-α]purin-10(3H)-one deoxyguanosine (M1dG) and 8-oxo-7,8-dihydro-2′-deoxyguanosine (8-oxodG) adducts, biomarkers of oxidative stress and/or lipid peroxidation, on human hepatocarcinoma HepG2 cells exposed to increasing levels of Fe3O4-nanoparticles (NPs) versus untreated cells at different lengths of incubations, and in the presence of increasing exposures to an alternating magnetic field (AMF) of 186 kHz using 32P-postlabeling. The levels of oxidative damage tended to increase significantly after ≥24 h of incubations compared to controls. The oxidative DNA damage tended to reach a steady-state after treatment with 60 μg/mL of Fe3O4-NPs. Significant dose–response relationships were observed. A greater adduct production was observed after magnetic hyperthermia, with the highest amounts of oxidative lesions after 40 min exposure to AMF. The effects of magnetic hyperthermia were significantly increased with exposure and incubation times. Most important, the levels of oxidative lesions in AMF exposed NP treated cells were up to 20-fold greater relative to those observed in nonexposed NP treated cells. Generation of oxidative lesions may be a mechanism by which magnetic hyperthermia induces cancer cell death.