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Silver linden (Tilia tomentosa Moench, TtM) flowers possess several health-promoting properties, especially at the neurological level, such as intestinal relaxation activity associated with specific flavonols, particularly quercetin and kaempferol derivatives. However, such molecules are susceptible to degradation upon different triggers like heat, light and extreme pH values. To overcome the scarce stability of TtM flowers bioactive molecules and make them suitable for developing functional food and supplements, we applied microencapsulation. Spray-drying microencapsulation of TtM flowers extract was performed using three starch-derived wall materials: maltodextrin 12 DE (MD12) and 19 DE (MD19), and OSA-modified starch (OSA-S). The stability of total phenols, flavanols, and antioxidant capacity was monitored for 70 days under accelerated stress conditions (40 °C/70% RH) by HPLC and spectrophotometric methods, and the intestinal contractile activity was tested in a murine model. In comparison to MD12 and MD19, OSA-S stood out for the higher encapsulation efficiency of quercetin and kaempferol glycosides (+ 36–47% compared to MD12 and + 18–24% compared to MD19) and stability thereof (half-life on average + 30% compared to MD12 and + 51% compared to MD19). The intestinal contractile activity of OAS-S powders resulted comparable to the original extract, indicating that flavonols were biologically active and accessible. Our results underly the potential advantages of OSA-S encapsulated formulation as a functional ingredient for the development of nutraceutical products.

[Ln2L4]2− helicates easily undergo transmetalation. The lanthanide ionic radius difference (ΔEIR) strongly affects the kinetics of the dynamic process while the thermodynamics is independent and mainly entropy driven.

NiO-based films and nanostructured materials have received an increasing attention for a variety of technological applications. Among the possible strategies for their fabrication, atomic layer deposition (ALD) and chemical vapor...

Co3O4 thin films and nanosystems are implemented in a broad range of functional systems, including gas sensors, (photo)catalysts, and electrochemical devices for energy applications. In this regard, chemical vapor deposition (CVD) is a promising route for the fabrication of high-quality films in which the precursor choice plays a key role in the process development. In this work, a heteroleptic cobalt complex bearing fluorinated diketonate ligands along with a diamine moiety [Co(tfa)2·TMEDA; tfa = 1,1,1-trifluoro-2,4-pentanedionate and TMEDA = N,N,N′,N′-tetramethylethylenediamine] is investigated as a potential Co molecular precursor for the CVD of Co3O4 systems. For the first time, the compound is characterized by crystal structure determination and comprehensive analytical studies, focusing also on its thermal properties and fragmentation patterns, important figures of merit for a CVD precursor. The outcomes of this investigation, accompanied by detailed theoretical studies, highlight its very favorable properties for CVD applications. In fact, growth experiments under oxygen atmospheres containing water vapor revealed the suitability of Co(tfa)2·TMEDA for the fabrication of high-quality, phase-pure Co3O4 thin films. The versatility of the proposed strategy in tailoring Co3O4 structural/morphological features highlights its potential to obtain multi-functional films with controllable properties for a variety of eventual technological end-uses.

Seven different [Ln2L4]2− (Ln = La, Nd, Eu, Tb, Er, Tm and Lu) lanthanide-based quadruple-stranded helicates are here reported and transmetalation among pre-assembled cages was studied. Combining two homonuclear helicates [LnA2L4]2− and [LnB2L4]2− leads to the formation of a mixture of homo- and heteronuclear systems due to ion exchange. This dynamic behaviour was studied by electrospray ionization mass spectrometry (ESI-MS) both qualitatively and quantitatively allowing to gain information on the thermodynamics as well as on the kinetics of the process. The rate of the Ln ion exchange is strongly dependent on the difference in lanthanide effective ionic radius (ΔEIR). Upon increasing ΔEIR, the kinetic constants grow exponentially: from the minimum to the maximum value of ΔEIR, the kinetic constants of the forward and backward reactions increase by three orders of magnitude. On the contrary, the equilibrium constant is the same for all the [LnA2L4]2−/[LnB2L4]2− couples, showing that the transmetalation is mainly entropy-driven towards a statistical mixture and not affected by ΔEIR.

Co3O4 thin films and nanosystems are implemented in a broad range of functional systems, including gas sensors, (photo)catalysts, and electrochemical devices for energy applications. In this regard, chemical vapor deposition (CVD) is a promising route for the fabrication of high-quality films in which the precursor choice plays a key role in the process development. In this work, a heteroleptic cobalt complex bearing fluorinated diketonate ligands along with a diamine moiety [Co(tfa)2·TMEDA; tfa = 1,1,1-trifluoro-2,4-pentanedionate and TMEDA = N,N,N',N'-tetramethylethylenediamine] is investigated as a potential Co molecular precursor for the CVD of Co3O4 systems. For the first time, the compound is characterized by crystal structure determination and comprehensive analytical studies, focusing also on its thermal properties and fragmentation patterns, important figures of merit for a CVD precursor. The outcomes of this investigation, accompanied by detailed theoretical studies, highlight its very favorable properties for CVD applications. In fact, growth experiments under oxygen atmospheres containing water vapor revealed the suitability of Co(tfa)2·TMEDA for the fabrication of high-quality, phase-pure Co3O4 thin films. The versatility of the proposed strategy in tailoring Co3O4 structural/morphological features highlights its potential to obtain multi-functional films with controllable properties for a variety of eventual technological end-uses.

Intracellular AGEs accumulation increases RAGE and GLP1R and reduces glucose uptake in adipocytes.

Aerosol particle components can mix and interact with oxidants and organic compounds present in the atmosphere. How these chemical components interact and how the interactions affect the Earth’s climate, particle toxicity and human health is largely unknown. In the case of trace metals, the main focus so far has been the determination of the total amount while much less attention has been directed towards the metal speciation. Aqueous phase processing of aerosol can lead to substantial modifications of aerosol chemical and physical properties [1] by promoting the formation of metal-organic ligand complexes in atmospheric aqueous phases, like fog/cloud droplets and deliquescent aerosol. Such process can increase the solubility of metals, therefore their bioavailability [2], and affect their capability to generate reactive oxygen species.We investigated the formation of metal-organic ligand complexes, especially those involving small dicarboxylic acids, in urban aerosol collected in the city centre of Padua (Italy), in the Po Valley. We assessed the effects of metal-ligand complexes formation on the solubility and solubilisation kinetic of metals from the particles to aqueous solutions simulating fog/cloud water. We found that solubilisation kinetics of many metals depended on the chemical form in which they were present in the aerosol and they were influenced by the environmental conditions during the campaign. Changes in oxidative potential (OP) and cytotoxicity of particles due to the formation of metal-ligand complexes were investigated by performing acellular and cellular in vitro tests, respectively. Preliminary results showed that metals and their complexed forms are both characterized by different OP and cellular toxicity. References[1] Decesari, S., Sowlat, M. H., Hasheminassab, S., Sandrini, S., Gilardoni, S., Facchini, M. C., Fuzzi, S., and Sioutas, C. Atmos. Chem. Phys., 17, 7721‑7731 (2017).[2] Okochi, H., and Brimblecombe, P. Sci. World J., 2, 767–786(2002).

A new model with the aim to predict the temperature dependence of europium emission in coordination systems is presented. The model has been developed from a library of Eu(3+)complexes of general formulaEuL(3)A(2), whereLis a beta-diketone, andAis an ancillary ligand. Three possible deactivation channels have been considered: two competitive metal-related terms describing the primary deactivation channels,i. e. back energy transfer and multiphonon quenching, and a third ligand-related term to describe non-radiative deactivation of the antenna triplet. As many parameters as possible are taken from measurable chemical-physical properties, such as ligand triplet and multiphonon quenching energies. The other parameters have been deduced from selectedEuL(3)A(2)compounds and used asone-size-fits-allvalues. The model proved to be very effective in describing the interplay between back energy transfer and multiphonon deactivation channels. Finally, the model has been implemented in a freeware standalone MATLAB application. Users need to input only the energy of the sensitizer triplet level and choose the coordinated quencher, if present. It simulates the range of applicability of the molecular thermometers and the shape of the thermometric sensitivity curveS(r)employing as thermometric parameter either emission intensity or lifetime.

Molecular engineering of manganese(II) diamine diketonate precursors is a key issue for their use in the vapor deposition of manganese oxide materials. Herein, two closely related b-diketonate diamine Mn(II) adducts with different fluorine contents in the diketonate ligands are examined. The target compounds were synthesized by a simple procedure and, for the first time, thoroughly characterized by a joint experimental-theoretical approach, to understand the influence of the ligand on their structures, electronic properties, thermal behavior, and reactivity. The target compounds are monomeric and exhibit a pseudo-octahedral coordination of the Mn(II) centers, with differences in their structure and fragmentation processes related to the ligand nature. Both complexes can be readily vaporized without premature side decompositions, a favorable feature for their use as precursors for chemical vapor deposition (CVD) or atomic layer deposition applications. Preliminary CVD experiments at moderate growth temperatures enabled the fabrication of high-purity, single-phase Mn3O4 nanosystems with tailored morphology, which hold great promise for various technological applications.

Graphical abstract, Highlights • Phthalates and heavy metals are used as technological adjuvants for food packaging. • Phthalates were widely released from any of the assessed pre-packed coffee products. • Also heavy metals were massively released, even exceeding tolerable daily intake. • Concerns about the wide exposure of humans to these pollutants from consumer products., Phthalate plasticizers and heavy metals are widely recognized to be pollutants that interfere with key developmental processes such as masculinization. We investigated the release of phthalates and heavy metals in coffee brewed from coffee packed in single-serve coffee containers made from different types of materials: metal, biodegradable and plastics. We detected with GC–MS small amounts phthalates, below the tolerated daily risks levels, in all the coffees prepared from the different types of capsules. Specifically, Di (2-ethyl-hexyl)-phthalate and DiBP: Diisobuthyl-pthalate were ubiquitously present despite the high variability among the samples (respective range 0.16–1.87 μg/mL and 0.01–0.36 μg/mL). Whereas, diethyl-phthalate (range 0.20–0.26 μg/mL) and di-n-buthyl-phthalate (range 0.02–0.14 μg/mL) were detected respectively in one and three out of the four types of capsule tested. In contrast, we detected by atomic mass spectrometry on mineralized samples heavy metals lead (Pb) and nickel (Ni), in all coffee tested. PB levels (respective range 0.32–211.57 μg/dose) accounted for 42–79%, whereas Ni levels (respective range 166.25–1950.26 μg/dose) accounted for >100% of the tolerable daily intake. These results add to the already present concerns related to the multiple pathways of human exposure and the ubiquitous presence of these pollutants in consumer products and their long-term effect on human health.

Aims: Type 2 diabetes (DM2) is associated to oxidative modifications of high-density lipoproteins (HDL), which can interfere with their function. Pioglitazone has proved effective in raising HDL cholesterol (HDL-C) and lowering small dense low-density lipoprotein (LDL), but no clinical studies have examined its effect on lipoprotein oxidation in patients with DM2. Methods: We assessed the effect of pioglitazone vs glimepiride after 1 year on HDL oxidation, expressed as relative abundance of peptides containing Met 112 O in ApoA-I (oxApoA-I) estimated by mass spectrometry (MALDI/TOF/TOF), in 95 patients with DM2. The oxLDL and AGE were quantified by ELISA. Results: Patients receiving pioglitazone showed a significant increase in the concentration of ApoA-I (Δ = 7.2 ± 14.8 mg/dL, p < 0.02) and a reduction in oxApoA-I (Δ = − 1.0 ± 2.6%, p < 0.02); this reduction was not significantly different from glimepiride. oxLDL showed a slight, but not significant increase in both treatment groups. Regression analysis showed a correlation between ΔoxApoA-I and ΔAGE (r = 0.30; p = 0.007) in all patients, while both of these parameters were unrelated to changes in HbA1c, HDL-C, duration of illness, or use of statins. Conclusions: Long-term treatment with pioglitazone was effective in reducing the oxidation of HDL, but not LDL in patients with DM2, while glimepiride didn’t. This finding seems to be associated to the change of glyco-oxidation status, not to any improvement in glycemic control or lipid profile. Trial registration: NCT00700856, ClinicalTrials.gov Registered June 18, 2008.

fac-[Re(CO)The release of CO has been investigated by means of product ion spectrometry of electrospray ionization (ESI)-generated [M + H]Tandem mass spectrometry applied to the protonated species [Re(CO)The nature of the co-ligand X drives the primary loss in the MS

A viable route to manganese-based materials of high technological interest is plasma-assisted chemical vapor deposition (PA-CVD), offering various degrees of freedom for the growth of high-purity nanostructures from suitable precursors. In this regard, fluorinated ?-diketonate diamine Mn(II) complexes of general formula Mn(dik)2·TMEDA [TMEDA = N,N,N?,N?-tetramethylethylenediamine; Hdik = 1,1,1,5,5,5-hexafluoro-2,4- pentanedione (Hhfa), or 1,1,1-trifluoro-2,4-pentanedione (Htfa)] represent a valuable option in the quest of candidate molecular sources for PA-CVD environments. In this work, we investigate and highlight the chemico-physical properties of these compounds of importance for their use in PA-CVD processes, through the use of a comprehensive experimental-theoretical investigation. Preliminary PA-CVD validation shows the possibility of varying the Mn oxidation state, as well as the system chemical composition from MnF2 to MnO2, by simple modulations of the reaction atmosphere, paving the way to a successful utilization of the target compounds in the growth of manganese-containing nanomaterials for different technological applications.

RATIONALE fac-[Re(CO)3 (PO)(X)]-type complexes (PO = chelated bidentate tertiary phosphine (1-), X = various neutral, mono-dentate ligands) represent a class of compounds that meets the synthetic criteria for the preparation of potential carbon monoxide (CO) release molecules (CORMs) for medicinal application. The aim of our investigation was to achieve qualitative information whether the nature of the ancillary X ligand might influence the release of CO. METHODS The release of CO has been investigated by means of product ion spectrometry of electrospray ionization (ESI)-generated [M + H]+ species, produced by multiple collisional experiments, using an ion trap mass spectrometer. RESULTS Tandem mass spectrometry applied to the protonated species [Re(CO)3 (PO)(X) + H]+ of seven complexes (those including X = OH2 (1), isonitrile (2, 3), imidazole (4), pyridine (5) and phosphine (6, 7)) shows initial loss of coordinated water (1) or pyridine (5), whereas the majority of investigated entries display initial, sequential release of CO groups. The energetics of CO release have been investigated by breakdown curves for selected collisionally activated decomposition processes involving CO, and compared with those involving X groups. CONCLUSIONS The nature of the co-ligand X drives the primary loss in the MSn processes of [Re(CO)3 (PO)(X) + H]+ compounds. When X = solvent, the energetics of these decompositions follow the trend H2 O

Molecular engineering of manganese(II) diamine diketonate precursors is a key issue for their use in the vapor deposition of manganese oxide materials. Herein, two closely related β-diketonate diamine Mn

The synthesis and characterization of a new series of neutral, six-coordinated compounds [Re

The synthesis and characterization of a new series of neutral, six-coordinated compounds [(ReX3)-X-III(PNPR)], where X is Cl or Br and PNPR is a diphosphinoamine having the general formula (Ph2PCH2CH2)(2)NR (R = H, CH3, CH2CH3, CH2CH2CH3, CH2CH2CH2CH3 and CH2CH2OCH3) are reported. Stable [(ReX3)-X-III(PNPR)] complexes were synthesized, in variable yields, starting from precursors where the metal was in different oxidation states (III and V), by ligand-exchange and/or redox-substitution reactions. The compounds were characterized by elemental analysis, proton NMR spectroscopy, cyclic voltammetry, UV/vis spectroscopy, positive-ion electrospray ionization mass spectrometry (ESI(+)-MS) and X-ray diffraction analysis. Although the formulation of the complexes allows either meridional or facial isomers, the latter arrangement was prevalent both in the solid and solution states. Only [ReCl3(PNPH)] showed a meridional configuration both in solution and in the crystalline state. [ReBr3(PNPme)] prefers the meridional configuration in the crystalline state and the facial one in solution. While ESI(+)-MS and voltammetric data seem to indicate some dependency from the nature of the alkyl substituent at the nitrogen, the available structural data of the complexes show only slight differences both for angles and bond lengths upon change of the alkyl chain tethered to the nitrogen.

Two pairs of enantiomerically pure chiral bidentate nitrogen-donor ligands (N*-N) featuring one sp(3) and one sp(2) nitrogen atom have been applied to the CO/vinyl arene copolymerization reaction catalyzed by the corresponding monocationic palladium(11) complexes [Pd(CH3)(CH3CN)-(N*-N)][PF6]. The ligand frame containing the sp(2) nitrogen atom is a 2-pyridinyl or an 8-quinolinyl building block, while the chiral framework of the ligand derives from (S)-(+)-2.2'-(2-azapropane-1,3-diyl)-1,1'-binaphthalene or from trans-2.5-dimethylpyrrolidinyl. Ligands with the binaphthyl moiety generate catalysts showing a moderate activity, while ligands having the pyrrolidinyl fragment results in very low activity species. The stereochemistry of the synthesized polyketones depends of the sp(2) nitrogen-containing fragment: ligands with the 2-pyridinyl group lead to atactic copolymers, whereas those with the quinolinyl moiety give an isotactic polyketone. The effect of the nature of the quinone, added to the reaction mixture as oxidant, has been investigated MALDI-TOF analysis reveals the formation of several polymeric chains, differing in the presence of various end-groups.

Positive matrix-assisted laser desorption ionization (MALDI) spectra of grape seed raw extracts show the signals of putative proanthocyanidin (PA) oligomers, including those of several sodium and potassium adducts with the same nominal molecular weight. As a result, the MALDI time-of-flight profiles are characterized by several isobaric signals from different PAs. The presence of isobaric PA adducts was studied by sodium and potassium exchange experiments on the seed extracts of six grape varieties. This approach was effective in differentiating PAs with isobaric signals, and 15 different PAs were identified in the MALDI spectra of all samples. Copyright © 2014 John Wiley & Sons, Ltd.

Triacylglycerols are responsible for chocolate's peculiar melting behavior: the type and position of fatty acids on the glycerol molecule strongly affect the melting range of cocoa butter. For this reason, the characterization of triglyceride composition in cocoa products is particularly important. In this work, triacylglycerols extracted from cocoa liquor samples were analyzed by matrix-assisted laser desorption/ionization time-of-flight (TOF) and electrospray ionization tandem mass spectrometry (MS/MS) coupled to liquid chromatography. Extracted samples were initially analyzed by direct injection in MS to obtain information on triglyceride molecular weights; relevant MS parameters were optimized, and the possible formation of the adducts [M + Na]+ and [M + NH4]+ was studied. Tandem mass experiments (both with triple quadrupole and TOF/TOF) were performed to study the fragmentation pathways (in particular, the loss of palmitic, stearic and oleic acid) and identify the triacylglycerols in cocoa liquors. Some signals of the spectra obtained with both MS techniques could indicate the presence of diacylglycerols in the cocoa extract, but different experimental evidences demonstrated that they were generated by the in-source fragmentation of triglycerides. A nonaqueous reversed-phase chromatographic separation was also developed and used to support the identification of the analytes; nine triacylglycerols were recognized in the cocoa liquor extracts. The three different batches of Ecuador cocoa liquor did not show significant differences in the triacylglycerol profile. Copyright © 2014 John Wiley & Sons, Ltd.

RATIONALE To try to find a correlation between the antiproliferative activity of a series of [MI(P)4]+ complexes (M = Cu, Ag and Au; P = tertiary phosphine) and their stability at micromolar concentration under mass spectrometric conditions. METHODS [MI(P)4]+ complexes were investigated by positive ion electrospray ionization mass spectrometry with multiple collisional experiments using an ion trap mass spectrometer. RESULTS The displacement of P from native [MI(P)4]+, previously described for the copper derivative, is common for the triad complexes leading to the formation of [M(P)3]+ and [M(P)2]+ adducts. Further dissociation of [M(P)2]+ depends on the nature of the metal (Cu ~ Ag > Au). More labile [Cu(P)2]+ and [Ag(P)2]+ are more cytotoxic against HCT-15 human colon carcinoma cells compared to less labile [Au(P)2]+ species. CONCLUSIONS The dissociation of P ligand(s) from the [MI(P)4]+ complexes is the driving force for the triggering of the antiproliferative activity. The more favored is the displacement of P from the [M(P)2]+ active form, the more favored is in turn the possibility for the metal to interact with biological substrates related to cancer proliferation. Copyright © 2013 John Wiley & Sons, Ltd.

Increased oxidation of low density lipoprotein (LDL) is characteristic of atherosclerosis. In this frame, high density lipoproteins (HDL) play an important role, being able to remove lipid peroxides (LPOs) and cholesterol from oxidized LDL, so exhibiting a protective role against atherosclerosis. A wide range of reactive compounds lead to the oxidation of methionine (Met) residues with the formation of methionine sulphoxide (MetO) in apolipoprotein A-I (ApoA-I). Consequently, the determination of MetO level can give both an evaluation of oxidative stress and the reduced capability of ApoA-I in LPOs and cholesterol transport. For these reasons, the development of analytical methods able to determine the MetO level is surely of interest, and we report here the results obtained by MALDI mass spectrometry.

Gestational diabetes (GDM) is the most common complication of pregnancy and it is associated with maternal and fetal short- and long-term consequences. GDM modifies placental structure and function, but many of the underlying mechanisms are still unclear. The aim of this study is to develop and compare two different methods, based respectively on gel-based and gel-free proteomics, in order to investigate the placental proteome in the absence or in the presence of GDM and to identify, through a comparative approach, possible changes in protein expression due to the GDM condition. Placenta homogenates obtained by pooling six control samples and six samples from GDM pregnant women were analyzed by two-dimensional (2D) electrophoresis coupled with mass spectrometry [nano-liquid chromatography (nano-LC) tandem mass spectrometry (MS/MS) and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS)] and by a label-free mass spectrometry method based on LC-MSE. The gel-based approach highlights 13 over-expressed proteins and 16 under-expressed proteins, while the label-free method shows the over-expression of 10 proteins and the under-expression of nine proteins. As regards 2D gel electrophoresis, a comparison between two different protein identification methods, based respectively on nLC-electrospray ionization-MS/MS and MALDI-MS/MS, was performed taking into consideration the sequence coverage, the MASCOT score and the exponentially modified protein abundance index. The analysis of the complex proteome through an integrated strategy revealed that the quantitative gel-free and label-free MS approach might be suitable to identify candidate markers of GDM.

International audience; New 3D electrodes are prepared and tested in reductive herbicide dechlorination as the first step of an environmental remediation process. Commercial nickel foams are modified through the spontaneous deposition of silver nanoparticles. Some of the solutions of Ag+ ions employed in the galvanic displacement reactions contain complexing agents, such as thiosulfate or thiocyanate, and a capping agent, polyvinylpyrrolidone (PVP), which influences the morphology and growth kinetics of the silver deposits. Modified foams are used as cathodes for the reductive dechlorination of Alachlor(TM), a common chloroacetanilide herbicide, in a series of tests that confirm the catalytic activity of silver. Electrodes prepared in a thiosulfate solution containing PVP allow extensive reduction of Alachlor(TM) to give deschloroalachlor as the only dechlorinated product.

In this study, we present the aqueous solution behavior of two luminescent lanthanide antenna complexes (Eu3+ ⊂1, Dy3+ ⊂9) with different ligand topologies in the presence of dipicolinic acid (DPA, pyridine-2,6-dicarboxylic acid). Macrocyclic (1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid, DO3A, 9) and acyclic (1,4,7-triazaheptane-1,1,7,7-tetraacetic acid, DTTA, 1) ligands have been selected to form a ratiometric pair in which Dy3+ ⊂9 acts as a reference and Eu3+ ⊂1 acts as a probe for the recognition of DPA. The pair of luminescent complexes in water reveals the capability to work as a DPA luminescent sensor. The change of emission intensity of Eu3+ indicates the occurrence of a new sensitization path for the lanthanide cation through excitation of DPA. NMR evidence implies the presence of free 1 and mass spectrometry shows the formation of emitting [EuDPA2 ]- as a result of a ligand exchange reaction.

Triglyceride profile of seed oil samples from 32 hybrid grape varieties not studied before was investigated. A new method for the analysis of triacylglycerols (TAGs) has been developed based on the direct infusion in the electrospray ionization (ESI) source and employing tetrahydrofuran/methanol/water (85:10:5 v|v|v) as solvent; the formation of [M + Na]+ ions in high yield has been observed. TAGs were identified by ESI-tandem mass spectrometry analysis, and the matrix-assisted-laser-desorption-ionization and time-of-flight profile of samples was determined. Six were the principal TAGs identified in seed oil: trilinolein (LLL) was the most abundant (43%), followed by dilinoleoyl-oleoylglycerol (LOL, 23%), and dilinoleoyl-palmitoylglycerol (LPL, 15%). Compounds present in lower concentration were LSL and LOO (11%), LOP (6%), and LSP (2%). Compared with seed oils produced from V. Vinifera grapes, some significant differences in the relative abundances of TAGs were found, in particular hybrid grape seed oils showed higher LOL and lower LPL content, respectively. Among the samples studied, a particularly high content of LLL (rich in unsaturated fatty acids) was found in seed oils from two red varieties. Copyright © 2012 John Wiley & Sons, Ltd.

Introduction The neutral complex [ 99m Tc(N)(NOEt) 2 ], often referred to as TcN-NOET [NOEt= N -ethoxy, N -ethyldithiocarbamate(1−)], was proposed several years ago as a myocardial imaging agent. Despite some favorable clinical properties evidenced during phase I and phase II studies, the overall results of the European and American phase III clinical studies have been judged insufficient for a successful approval process by the regulatory agencies. Methods Non-carrier-added and carrier-added experiments using short-lived 99m Tc and long-lived 99g Tc have been utilized to prepare a series of bis-substituted [Tc(N)(DTC) 2 ] complexes [DTC=dithiocarbamate(1−)]. They have been purified by means of chromatographic techniques (high-performance liquid chromatography and thin-layer chromatography) and identified via double detection (UV-vis and radiometry) by comparison with authenticated samples of 99g Tc compounds prepared by conventional coordination chemistry procedures. Results The molecular structure of the lipophilic, neutral complex cis -[Tc(N)(NOEt) 2 ] has been assigned by comparison with similar nitrido-Tc(V) complexes already reported in the literature. Novel bis-substituted nitrido-Tc complexes containing hydrolyzed portions of coordinated NOEt, namely, N -ethyldithiocarbamate [NHEt(1−)] and N -hydroxy, N -ethyldithiocarbamate [NOHEt(1−)], have been prepared and characterized by means of multinuclear nuclear magnetic resonance spectroscopy and mass spectrometry. Conclusions Despite the identification of these "hydrolyzed" species, it is still unclear whether the failure to reach the clinical goal of the perfusion tracer [ 99m Tc(N)(NOEt) 2 ] is related to the degradation processes evidenced in this study or is the result of the mediocre imaging properties of the tracer.

This review reports the results of some studies carried out by us on the role of pneumatic aspects in electrospray and desorption electrospray surface ionization, with the aim of proposing some relevant aspects of the mechanisms involved in these ionization methods. Electrospray ion sources, with the exception of the nano-electrospray source, operate with the concurrent action of a strong electric field and a supplementary coaxial gas flow. The electric field is responsible for electrospraying of the analyte solution but the use of a coaxial gas flow leads to a significant increase in the analyte signal and allows the use of higher solution flows. However, by employing capillary voltages much lower than those necessary to activate the electrospray phenomenon, analyte ions are still observed and this indicates that different mechanisms must be operative for ion production. Under these conditions, ion generation could take place from the neutral pneumatically sprayed droplet by field-induced droplet ionization. Also, in the case of desorption electrospray ionization, and without any voltage on the spraying capillary as well as on the surface of interest, ions of analytes present on the surface become detectable and this shows that desorption/ionization of analytes occurs by neutral droplets impinging the surface. Consequently, the pneumatic effect of the impinging droplets plays a relevant role and, for these reasons, the method has been called pneumatic-assisted desorption. Some analogies existing between pneumatic-assisted desorption and surface-activated chemical ionization, based on the insertion of a metallic surface inside an atmospheric pressure chemical ionization source operating without corona discharge, are discussed.

RATIONALE Anthocyanins confer the color to red wines. During wine aging, new anthocyanin derivatives with peculiar chromatic characteristics are formed. A fast and selective method for screening the anthocyanin composition of wine has been developed. METHODS Direct-infusion electrospray ionization tandem mass spectrometry (ESI-MS/MS) analysis of wine extracts has been performed by operating in positive ion mode with a low spray capillary voltage (0.5 kV) to detect only the species already present in ionic form. The method has been called direct-infusion pneumatic spray (DIPS) mass spectrometry. The anthocyanin profiles of thirteen red wines at different aging stages were studied. Using malvidin-3,5-diglucoside as internal standard, the indices of wine color and of wine color evolution were estimated. RESULTS By decreasing the spray capillary voltage a dramatic increase in selectivity toward anthocyanins has been observed and the related peaks are the most abundant in the spectra. Several anthocyanins and anthocyanin derivatives (pyranoanthocyanins and derivatives formed by reaction with flavan-3-ols) have been identified in the wines. The younger wines showed higher total anthocyanin index. The aged wines showed color evolution index higher than 20% while it was lower in the younger samples. CONCLUSIONS The anthocyanin fingerprint is effective for estimating the aging state of wine. The color evolution index can be correlated to barrel conditions during wine aging and used to distinguish between aged and younger wines. The study of pyranoanthocyanins and anthocyanin-flavanol derivatives can be useful to predict wine color stability. Copyright © 2012 John Wiley & Sons, Ltd.

PurposeGermline nonsense and frameshift mutations in the adenomatous polyposis coli (APC) gene are found in approximately 90% of individuals affected by familial adenomatous polyposis (FAP) and a genotype-phenotype relationship has been observed. Missense mutations have also been found in a few cases, even if their role in FAP is still unknown. An association between a missense mutation, APC I1307K, and the risk of sporadic colorectal cancer (CRC) has been reported. In order to improve the knowledge about the genetic effect of APC I1307K on the phenotype, we tried a new approach using matrix-assisted laser desorption/ionization mass spectrometry (MALDI/MS).Experimental designAn APC mutation (I1307K) was found in an index case of a non-Jewish woman and her son with attenuated familial adenomatous polyposis (A-FAP) and no family history of cancer. In order to evaluate whether the presence and abundance of the ionic species are related to the presence of cancer or the presence of mutation, comparative analyses of 11 healthy clean-colon subjects, 59 patients with CRC (stage II n=19, stage III n=23, stage IV n=17) without polyps, and 9 FAP patients, carriers of a nonsense mutation in the APC gene, were evaluated.ResultsComparative analysis of serum protein profiles of the index patient and her healthy son, FAP and sporadic CRC patients, and subjects with preneoplastic lesions showed a characteristic abundance of ionic species at m/z 905, which was not present in healthy controls. Two peptides were identified from MALDI/MS/MS spectra of m/z 905 belonging to the kininogen-1 precursor and the human forkhead box protein 01A (FOXO1A). FOXO1A was present in only two subjects carrying I1307K, but not in other patients.ConclusionsOur findings seem to suggest a relationship between m/z 905, FOXO1A and the development and growth of colorectal cancer. FOXO1A fragment determination in serum with MALDI/MS might be a promising approach for early detection of colon carcinoma or for the development of targeted therapies.

The preparation of the second generation iron(II) complex Fe(hfa)2·TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, TMEDA = N,N,N′,N′-tetramethylethylenediamine) is performed by reacting iron(II) chloride with Hhfa and TMEDA in two subsequent steps. Density functional theory data show that the compound possesses a distorted octahedral geometry, with the two β-diketonate ligands in a cis configuration. The complex mass transport properties and fragmentation pattern are investigated by thermal analyses and electron impact mass spectrometry, respectively. In addition, its experimental and simulated IR spectra are presented. For the first time, Fe(hfa)2·TMEDA was successfully applied in the chemical vapor deposition (CVD) of iron oxide on Si(1 0 0). Structural, compositional and morphological analyses evidence the possibility of obtaining pure, single-phase and homogeneous β-Fe2O3 films.

Five perfluorocompounds [perfluoropentane, 4-(perfluoroethoxy)-perfluorobutane, 5-(perfluoroethyl)-perfluorotetrahydrofuran, 2-(trifluoromethyl)-perfluorotetrahydropyran, and 4-(trifluoromethyl)-perfluorotetrahydropyran] were analyzed by electron ionization (EI) and chemical ionization (CI), using methane and isobutane as reagent gases. Under CI conditions, isobutane does not lead to significative results whereas methane leads to high ionic yields [with respect to both CI (isobutane) and EI]. Under EI conditions, practically only fragment ions are observed, with the complete loss of molecular weight. In contrast under CI(CH4) conditions, [M–F]+ ions are produced. Under these conditions, the behavior of oxygen-containing molecules is strongly different from that of perfluoropentane. This is because oxygen can greatly stabilize the formation of the [M–F]+ carbocation by a π-electron donor effect, especially in the case of cyclic structures. Moreover, π-stabilization can be considered a useful tool to rationalize the position of tertiary carbon atom in trifluoromethyl-perfluoro-pyrane isomeric ions. The experimental data formed the starting point for the theoretical calculation, which allowed us to explore the mechanisms of the reactions of CH5+ ions with selected perfluorocompounds. The computational methods used show that a direct protonation of the perfluoroethers (PFEs) by CH5+ as well as iBu+ is very unlikely. In the theoretical calculations, the PFE molecule served rather as the F− donor, and the elimination of HF molecule occurred when the PFE molecule was placed close to H+ or CH5+ ions. The fact that the latter is very unstable and decomposes to a proton and methane molecule explains why the use of methane in CI is so successful in the generation of [M–F]+ ion. In contrast, the isobutonium cation rearranges to an isopropyl cation/methane complex rather than that it abstracts F− from the PFE molecule. Similar results can be expected for other PFEs and perfluoroalkanes (PFAs) because both CH5+ and H+ were able to abstract the HF molecule also by attacking along the perfluoroalkyl chain of the PFE. Copyright © 2011 John Wiley & Sons, Ltd.

The water-soluble protein profile of the seeds of green, red, and yellow Theobroma cacao L. fruits has been determined by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF-MS). The seeds were powdered under liquid nitrogen and defatted. The residues were dialyzed and lyophilized. The obtained samples were suspended in the matrix solution of sinapinic acid. The obtained MALDI mass spectra showed the presence of a wide number of proteins with molecular weight ranging from 8000 to 13,000 Da and a cluster of peaks centered at 21,000 Da that were attributed to albumin. The abundance of this peak was found to depend on the different portion of the seed (husk, apical and cortical parts); however, the MALDI mass spectra obtained from the different varieties of cocoa were practically superimposable. Changes in the protein profiles were also observed after the cocoa seeds were treated by fermentation and roasting, which are processes usually employed for the commercial production of cocoa.