Conjugated Gold-Porphyrin Monolayers Assembled on Inorganic Surfaces.

Gold nanoparticles show important properties owing to their electronic structures. A limitation of some gold nanoparticles is that they either show surface plasmons or luminescence. The increase in size of the gold nanoparticles, and the appearance of the surface plasmons may result in the disappearance of luminescence. The aim of our study is the nanoscale assembly of Au nanoparticles on a monolayer of porphyrin molecules anchored to functionalized inorganic surfaces. This functional architecture not only exhibits a strong surface plasmon due to the gold nanoparticles, but also a strong luminescence signal from the porphyrin molecules. Finally we observed a long-range order in the Au nanoparticles conjugated to the porphyrin monolayer.

Communication between Discrete Nanostructures Triggered by Fine Tuning of an External Stimulus.

The design of molecular architectures able to transfer mass to each other is a field of extreme importance. In the present study it is shown that two especially designed covalently assembled nanostructures can interchange Cu(2+) ions upon an external OH(-) trigger. The obtained solid interfaces are of interest for signaling, communication, memory storage and optical devices.

Solid nanoarchitecture--Cu(II) solution: dynamics of the chemical communication.

Molecular monolayers and similar nanoarchitectures represent a promising future of the nanotechnology. Many of these systems behave as stimuli responsive materials since they undergo readable changes upon external stimuli. Therefore, chemical communication between these systems and the surrounding environment is a field extremely important. In the present study we explored by optical read-out the chemical communication between a porphyrin monolayer covalently bound to a quartz substrate (hardware) and copper(II) ions (stimulus). Different physical states can be safely distinguished since the intensity of the Soret band (output) associated with a calculated distribution diagram provided the degree of porphyrin complexation and, therefore, of the state of the optically active system as a result of a solution mediated interfacial communication.

The pivotal role of copper(II) in the enantiorecognition of tryptophan and histidine by gold nanoparticles.

Stereoselective amino acid analysis has increasingly moved into the scope of interest of the scientific community. In this work, we report a study on the chiral recognition of D,L-Trp and D,L-His using L -Cys-capped gold nanoparticles (AuNPs) and copper(II) ion. In the L -Cys-capped AuNPs, the thiol group of the amino acid interacts with AuNPs through the formation of Au­S bond, whereas the α-amino and α-carboxyl groups of the surface-confined cysteine can coordinate the copper(II) ion, which in turn, binds the L- or D-amino acid present in solution forming diastereoisomeric complexes. The resulting systems have been characterized by UV­Vis spectra and dynamic light scattering measurements, obtaining different results for L- and D-Trp, as well as for L- and D-His. The knowledge of the solution equilibria of the investigated systems allowed us to accurately calculate in advance the concentrations of the species presentin solution and to optimize the system performances, highlighting the pivotal role of copper(II) ion in the enantiodiscrimination processes.

Exploiting thermodynamic data to optimize the enantioseparation of underivatized amino acids in ligand exchange capillary electrophoresis.

Stereoselective amino acid analysis has increasingly moved into the scope of interest of the scientific community. In this work, we report a study on the chiral separation of underivatized D,L-His by ligand exchange capillary electrophoresis (LECE), utilizing accurate ex ante calculations. This has been obtained by the addition to the background electrolytes (BGE) of NaClO(4) which renders the separations "all in solution processes", allowing to accurately calculate in advance the concentrations of the species present in solution and to optimize the system performances. To this aim, the formation of ternary complexes of Cu(2+) ion and L-lysine (L-Lys) or L-ornithine (L-Orn) with L- and D-histidine (His), and histamine (Hm) have been studied by potentiometry and calorimetry at 25 °C and with 0.1 mol dm(-3) (KNO(3)) in aqueous solution. The ternary species [Cu(L)(L-His)H](+) and [Cu(L)(D-His)H](+) (where L = L-Lys or L-Orn) show a slight but still detectable stereoselectivity, and the determination of ΔH° and ΔS° values allowed the understanding of the factors which determine this phenomenon. The stereoselectivity showed by the protonated ternary species has been exploited to chirally separate D,L-His in LECE, by using the binary complexes of copper(II) with L-Lys or L-Orn as background electrolytes added with the appropriate amounts of NaClO(4).

Internalization of Pegylated Er:Y2O3 Nanoparticles inside HCT-116 Cancer Cells: Implications for Imaging and Drug Delivery.

Lanthanide-doped nanoparticles, featuring sharp emission peaks with narrow bandwidth, exhibit high downconversion luminescence intensity, making them highly valuable in the fields of bioimaging and drug delivery. High-crystallinity Y2O3 nanoparticles (NPs) doped with Er3+ ions were functionalized by using a pegylation procedure to confer water solubility and biocompatibility. The NPs were thoroughly characterized using transmission electron microscopy (TEM), inductively coupled plasma mass spectrometry (ICP-MS), and photoluminescence measurements. The pegylated nanoparticles were studied both from a toxicological perspective and to demonstrate their internalization within HCT-116 cancer cells. Cell viability tests allowed for the identification of the "optimal" concentration, which yields a detectable fluorescence signal without being toxic to the cells. The internalization process was investigated using a combined approach involving confocal microscopy and ICP-MS. The obtained data clearly indicate the efficient internalization of NPs into the cells with emission intensity showing a strong correlation with the concentrations of nanoparticles delivered to the cells. Overall, this research contributes significantly to the fields of nanotechnology and biomedical research, with noteworthy implications for imaging and drug delivery applications.

Smartphone-Assisted Sensing of Trinitrotoluene by Optical Array.

Here we report the design and fabrication of an array-based sensor, containing functionalized Carbon Dots, Bodipy's and Naphthalimide probes, that shows high fluorescence emissions and sensitivity in the presence of low amounts of TNT explosive. In particular, we have fabricated the first sensor device based on an optical array for the detection of TNT in real samples by using a smartphone as detector. The possibility to use a common smartphone as detector leads to a prototype that can be also used in a real-life field application. The key benefit lies in the possibility of even a nonspecialist operator in the field to simply collect and send data (photos) to the trained artificial intelligence server for rapid diagnosis but also directly to the bomb disposal unit for expert evaluation. This new array sensor contains seven different fluorescent probes that are able to interact via noncovalent interactions with TNT. The interaction of each probe with TNT has been tested in solution by fluorescence titrations. The solid device has been tested in terms of selectivity and linearity toward TNT concentration. Tests performed with other explosives and other nitrogen-based analytes demonstrate the high selectivity for TNT molecules, thus supporting the reliability of this sensor. In addition, TNT can be detected in the range of 98 ng∼985 µg, with a clear different response of each probe to the different amounts of TNT.

Mass spectrometry detection as an innovative and advantageous tool in ligand exchange capillary electrophoresis.

The copper(II) complex of a modified cyclodextrin, namely 6-mono-deoxy-6-[4-(2-aminoethyl)imidazolyl]-ß-CD (CDmh), previously synthesized and characterized in our laboratory and already used as chiral selector for ligand exchange capillary electrophoresis (LECE) with optical detection, is investigated here in LECE using electrospray-mass spectrometry (ESI-MS) as the detection device. The potential of this hyphenated method is compared with the results previously obtained with optical detection by studying the chiral resolution of tryptophan racemate. Chiral separation conditions compatible with LECE-ESI-MS could be achieved based on the figures of merit obtained by LECE-UV. Interestingly, the values of LOD obtained by LECE-ESI-MS were significantly better than those obtained by LECE-UV and thus, ESI-MS detection seems to open new perspectives in chiral separations by LECE.

Intramolecular weak interactions in the thermodynamic stereoselectivity of copper(II) complexes with carnosine-trehalose conjugates.

The interactions of metal ions with chiral molecules are of particular interest for relevant biochemical processes, as many of them are made possible only with a selected chirality of the stereocenters. In this work we report a study of the stereoselectivity of copper(II) complexes with D-trehalose-L-carnosine and D-trehalose-D-carnosine as a prototypical case of natural chirality selection. The interest in L-carnosine dipeptide is compounded by its antioxidant and antitumor properties, which are further enhanced when combined with D-trehalose. Potentiometric, calorimetric, and UV/circular dichroism (CD) spectroscopic measurements show that the copper(II) dimer of D-trehalose-L-carnosine is more stable than the D-trehalose-D-carnosine diastereoisomeric copper(II) dimer (log ß(L)(22-2) - log ß(D)(22-2) = 3.6). Free-energy calculations highlight that the cause of this different behavior lies with different intramolecular weak interactions between the diastereoisomers. The different pattern of hydrogen bonds and the different CH-π interactions between the π-electron-rich imidazole and the α-glucose rings are more favorable by 5 kcal mol(-1) in the L dimer.

A Lewis basicity scale in dichloromethane for amines and common nonprotogenic solvents using a zinc(II) Schiff-base complex as reference Lewis acid.

A consistent, reliable scale of Lewis basicity in dichloromethane for 26 bases, involving amines and nonprotogenic solvents, is presented. A Lewis acidic Zn(II) Schiff-base complex, involving formation of stable 1:1 adducts is used as reference acid. Evaluation of binding constants is achieved from spectrophotometric titrations, by the least-squares nonlinear regression of multiwavelength spectrophotometric data. This Lewis basicity scale represents a unique set of data reflecting the actual Lewis basicity with respect this "real world" Lewis acidic species. The comparison of present Lewis basicity scale with data reported in the literature indicates that while for the involved solvents their relative basicity is scarcely affected by the reference Lewis acid, in contrast for sterically encumbered amines the Lewis basicity seems to be dependent from the reference species. Thus, Lewis basicity is governed by the steric hindrance at the donor atom and involves very different relative basicities than those predicted considering typical reference Lewis acids. This is expected to have a major involvement in the organic synthesis and catalysis, given the sterically encumbered nature of commonly involved Lewis acidic organometallic complexes.

Oculo-pyramidal crossed syndrome heralded by seizure: a case report.

Ischemic oculo-pyramidal crossed syndrome, i.e. amaurosis fugax contralateral to hemiparesis, is caused by an embolus from internal carotid artery occluding the retinal or the ophthalmic artery as well as the middle cerebral artery. We report on a patient with an oculopyramidal crossed syndrome due to internal carotid artery dissection and clinically manifesting with amaurosis fugax and seizure. Ischemic lesions can present with symptomatic seizures and, conversely, seizures may precede ischemic strokes, thus being a warning sign of a cerebrovascular event.

Diaminotrehalose-capped ß-cyclodextrin, a new member of hemispherodextrins: synthesis, thermodynamic and spectroscopic characterization and its exploitation in chiral electrokinetic chromatography.

The diaminotrehalose-capped derivative of ß-CD, a new member of hemispherodextrins, was synthesized and characterized by NMR spectroscopy. Its protonation constants were determined by potentiometry, and the inclusion of both the enantiomers of dansyl-phenylalanine was investigated by NMR spectroscopy. Its stereoselective properties were exploited in electrokinetic chromatography by separating four enantiomeric pairs of dansyl derivatives of amino acids.

Dinuclear zinc(ii) salen-type Schiff-base complexes as molecular tweezers.

In this contribution, the synthesis and the unusual aggregation/deaggregation properties in solution of two dinuclear ZnII Schiff-base complexes of tetradentate Schiff-base units, having non-conjugated spacers between each molecular unit, are reported in comparison to the mononuclear model complex. Through detailed 1H NMR, DOSY NMR, optical absorption, fluorescence emission, and multivariate analysis of optical absorption data, emerge some interesting findings. In solution of non-coordinating solvents, these Lewis acidic species are characterized as monomers stabilized by formation of intramolecular aggregates, having distinct spectroscopic properties in comparison to intermolecular aggregates derived from the mononuclear model analogue. Instead, in coordinating solvents they exhibit a typical behaviour, with formation of stable adducts showing a strong fluorescence. Deaggregation studies using pyridine as reference Lewis base allowed establishing a larger thermodynamic stability of these intramolecular aggregates, in comparison to intermolecular aggregates, even larger than that of aggregates of conjugated multinuclear complexes. The combined analysis of spectroscopic data upon deaggregation with ditopic Lewis bases unambiguously demonstrated the formation of stable 1 : 1 adducts, with higher binding constants in comparison to those related to monotopic species. Therefore, the present Lewis acidic, dinuclear complexes behave as molecular tweezers of ditopic guests having a strong Lewis basicity.

Fast and Efficient Sun Light Photocatalytic Activity of Au_ZnO Core-Shell Nanoparticles Prepared by a One-Pot Synthesis.

Gold nanostructures absorb visible light and show localized surface plasmon resonance bands in the visible region. Semiconducting ZnO nanostructures are excellent for ultraviolet detection, thanks to their wide band gap, large free exciton binding energy, and high electron mobility. Therefore, the coupling of gold and ZnO nanostructures represents the best-suited way to boost photodetection. With the above perspective, we report on the high photocatalytic activity of some Au_ZnO core-shell nanoparticles (NPs) recently prepared by a one-pot synthesis in which a [zinc citrate]- complex acted as the ZnO precursor, a reducing agent for Au3+, and a capping anion for the obtained Au NPs. The overall nanostructures proved to be Au(111) NPs surrounded by a thin layer of [zinc citrate]- that evolved to Au_ZnO core-shell nanostructures. Worthy of note, with this photocatalyst, sun light efficiently decomposes a standard methylene blue solution according to ISO 10678:2010. We rationalized photodetection, reaction rate, and quantum efficiency.

Preclinical evidence of enhanced analgesic activity of duloxetine complexed with succinyl-ß-cyclodextrin: A comparative study with cyclodextrin complexes.

Chronic pain represents one of the most important public health problems, with a great prevalence of comorbidity with depression and cognitive decline. Antidepressants such as duloxetine, a serotonin-norepinephrine reuptake inhibitor, represent an essential part of the therapeutic strategy for chronic pain management in addition to classical analgesics. Duloxetine is endowed with good efficacy and a good profile of safety and tolerability. Yet, duloxetine is metabolized by the cytochrome P450 system 2D6 and 1A2 (CYP2D6 and CYP1A2) and it exhibits moderate inhibitory activity on CYP2D6, resulting in side effects and metabolic interactions that may occur on a long term therapeutic schedule. Cyclodextrins (CyDs) are used in pharmaceutical applications for numerous purposes, including the improvement of drug bioavailability. In order to evaluate their effects on the activity of duloxetine, we first spectrophotometrically studied the host-guest complexes obtained combining duloxetine and different ß-CyD derivatives (ß-CyD, ß-CyDen-c-(Glu-Glu), and succinyl-ß-CyD) and then performed in vivo and in vitro studies. Among duloxetine/CyDs complexes, succinyl-ß-CyD ameliorated the analgesic activity of duloxetine in the tail flick test and in the formalin test in mice and significantly protected the drug from CYP2D6 metabolism.

Unveiling the role of histidine and tyrosine residues on the conformation of the avian prion hexarepeat domain.

The prion protein (PrPC) is a glycoprotein that in mammals, differently from avians, can lead to prion diseases, by misfolding into a beta-sheet-rich pathogenic isoform (PrPSc). Mammal and avian proteins show different N-terminal tandem repeats: PHGGGWGQ and PHNPGY, both containing histidine, whereas tyrosine is included only in the primary sequence of the avian protein. Here, by means of potentiometric, circular dichroism (CD), and molecular dynamics (MD) studies at different pH values, we have investigated the conformation of the avian tetrahexarepeat (PHNPGY)4 (TetraHexaPY) with both N- and C-termini blocked by acetylation and amidation, respectively. We have found, also with the help of a recently proposed protein chirality indicator (Pietropaolo, A.; Muccioli, L.; Berardi, R.; Zannoni, C. Proteins 2008, 70, 667-677), a conformational dependence on the protonation states of histidine and tyrosine residues: the turn formation is pH driven, and at physiological pH a pivotal role is played by the tyrosine OH groups which give rise to a very compact bent structure of backbone upon forming a hydrogen-bond network.

Separation and quantitation of metal ions by 4-(2-pyridylazo)resorcinol complexation in capillary electrophoresis-electrospray ionisation mass spectrometry.

The possibility of using capillary electrophoresis-electrospray ionisation (ESI)/MS to separate and quantify cobalt and iron was explored. It was necessary to tackle and overcome problems from different sources, some of them being rather unpredictable. The results obtained suggest the occurrence of oxidation processes of metal ions during the formation of the electrospray. The quantitative oxidation of cobalt(II) to cobalt(III), a process at our knowledge never described before, appears particularly interesting. The results obtained, though not optimised for sensitivity appear promising, since a limit of detection of the order of tenths of picograms was obtained. Further, from the comparison with the results obtained by optical detection, the use of CE-ESI/MS appears advantageous.

Ag-NPs induce apoptosis, mitochondrial damages and MT3/OSGIN2 expression changes in an in vitro model of human dental-pulp-stem-cells-derived neurons.

Silver nanoparticles (Ag-NPs) are one of the most popular nanotechnologies because of their unique antibacterial and antifungal properties. Given their increasing use in a wide range of commercial, biomedical and food products, exposure to Ag-NPs is now a reality in people's lives. However, there is a serious lack of information regarding their potential toxic effects in the central nervous system. In this study, we investigated the biocompatibility of "homemade" Ag-NPs in an in vitro model of human neurons derived from dental pulp mesenchymal stem cells. Our results showed that acute exposure to Ag-NPs cause cytotoxicity, by triggering cell apoptosis, damaging neuronal connections, affecting the mitochondrial activity and changing the mRNA expression level of MT3 and OSGIN2, two genes involved in heavy metals metabolism and cellular growth during oxidative stress conditions. Further studies are needed to understand the molecular mechanisms and the physiological consequences underlying Ag-NPs exposure.

Tyrosine capped silver nanoparticles: A new fluorescent sensor for the quantitative determination of copper(II) and cobalt(II) ions.

Nanoparticles have been increasingly used as sensors for several organic and inorganic analytes. In this work, we report a study on the synthesis of novel highly fluorescent l-Tyr capped silver nanoparticles (AgNPs) and their use for the determination of metal ions. The AgNPs have been characterized by TEM, UV-Vis and Photoluminescence (PL) spectroscopy and dynamic light scattering (DLS) measurements and used for the quantitative determination of Co(II) and Cu(II) ions. In the l-Tyr capped AgNPs, the α-amino and α-carboxyl groups of the surface-confined amino acid can coordinate the entitled metal ions, giving rise to a decrease of the silver surface plasmon absorption, that is linearly correlated with the metal ions concentrations. The addition of Co(II) and Cu(II) solutions to the l-Tyr AgNPs also induces a paramagnetic quenching of the fluorescence in the PL spectra and the related Stern Volmer plots highlight a linear correlation over the whole concentration range for both metal ions, with a more pronounced effect for the copper(II) ion.

The 6-derivative of beta-cyclodextrin with succinic acid: a new chiral selector for CD-EKC.

6-O-Succinil-beta-cyclodextrin (CDsuc6) was synthesized with very good yield by one pot synthesis and characterized by NMR spectroscopy and ESI-MS. It was used as a chiral selector in capillary electrophoresis to resolve catecholamine racemates, namely norepinephrine, epinephrine, terbutaline and norphenilephrine. The CE experiments at pH 5.6 show very promising selector ability by 6-O-succinil-beta-cyclodextrin for the chiral recognition of all the catecholamines tested, while at pH 9.2, only racemic terbutaline was successfully separated.