Light-emitting molecular machines: pH-induced intramolecular motions in a fluorescent nickel(II) scorpionate complex

A cyclam-like macrocycle has been synthesized with a pendant arm containing a dansylamide group. In the corresponding nickel(II) complex, binding of the pendant arm to the metal is pH controlled. In particular, at pH 4.3, the sulfonamide group deprotonates and coordinates the NiII center, giving rise to a complex of trigonal bipyramidal stereochemistry, as shown by X-ray diffraction studies performed on the crystalline complex salt. At pH 7.5, an OH- ion binds the metal and a six-coordinate species forms. The binding-detachment of the pendant arm to/from the NiII center is signaled by changes in the emission properties of the dansyl subunit in the side chain; the fluorescence of this side chain is high when the pendant arm is not coordinated and low when the sulfonamide group is bound to the metal. The system investigated represents the prototype of a light-emitting molecular machine, driven by a pH change.     

Synthesis and characterization of 4-hydroxy-3-phenylprolines

4-Hydroxy-3-phenylprolines were synthesized via 1-acetyl-2,2-diethoxycarbonyl-2,3-dihydro-3-phenyl-1H-pyrrole. Reversed phase hplc resulted in the isolation of the products which were characterized by ¹H and ¹³C nmr spectroscopy.     

Metal-induced assembling/disassembling of fluorescent naphthalenediimide derivatives signalled by excimer emission

The new quadridentate bischelating ligands 2 and 3 display in solution the typical absorption and emission properties expected for naphthalenediimide derivatives. Spectrophotometric studies show that systems 2 and 3 interact with Zn(II), Cd(II) and Cu(I) in CHCl3 or MeCN according to an apparent 1:1 stoichiometry. Molecular modelling, ESI-MS and 1H NMR experiments indicate that the complex species formed in the presence of stoichiometric amounts of metal ion are nonhelical [2 + 2] adducts. The metal-induced self-assembling process is signalled by an intense excimer-type emission caused by the intramolecular interaction of two naphthalenediimide subunits that face each other in the [2 + 2] adduct, as shown by molecular modelling studies. In the presence of excess metal ion, a disassembling process takes place, leading to a dinuclear complex with a 2:1 metal/ligand stoichiometry, in which the intramolecular excimer is no longer allowed to form because the interaction between the naphthalenediimide subunits has been lost. Thus, the overall metal-induced assembling/disassembling process is signalled by the appearance and disappearance of the excimer band in the emission spectrum.     

Ethylene/hindered phenol substituted norbornene copolymers: Synthesis and NMR structural determination

A new family of ethylene‐based copolymers with controlled amounts of a norbornene comonomer (N_ArOH) bearing a stabilizing antioxidant functionality (2,6‐di‐tert‐butyl phenol) was prepared. Due to unavoidable exo/endo equilibrium operative in N_ArOH comonomer, a complete and detailed NMR assignment of the structure of the prepared ethylene/N_ArOH copolymers was carried out for the determination of the exo/endo ratio inside the polymer. These novel functionalized comonomers can be considered suitable starting material for preparing ethylene‐based copolymers, with tunable comonomer content, as non‐releasing macromolecular antioxidant additives for specific application in safe food and/or drug packaging © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Dynamic processes in the Venice region outlined by environmental isotopes

Research carried out in the last 40 years has shown the scientific importance of groundwater circulation both in the Northern Adriatic sea bed and within the uppermost sedimentary layers of the Venice lagoon and of the Venice plain. Hydrodynamic processes are strictly controlled by a well-cemented sedimentary horizon lying under and around Venice ('caranto'), which plays the role of regional aquitard. This layer was attributed to the subaerial cementation of the Flandrian (8-10 ka Before Present) sedimentary surface. The caranto is generalised as a continuum horizon, being an easy explanation for several environmental, hydrogeological and geotechnical problems, e.g., a base layer for landfills, a confining layer for deep aquifers and the best substratum for locating the oak wooden pile-dwelling needed to support the largest buildings. The preservation of the isotope signal within the deep aquifers and aquiclude system records the changes in surface and groundwater characteristics and suggests the present and past recharge regimes. In this region, the heavily perturbed hydrodynamic conditions do not allow for the use of isotopic signals to derive a correct reconstruction of the present recharge. The perturbations induced by the intensive anthropogenic activity force to follow climate evolution by considering deep groundwater and pore waters. In addition, the presence of carbonatic rocks inside terrigeneous sediments affects the reconstruction of the past. Results indicate that carbonatic rocks are created by seepage, through the sediments, of gaseous carbon compounds from decaying organic layers. The gas interactions with the intra-sedimentary saline and fresh waters produce CO2, inducing the cementation of the sediments.     

Universal teleportation with a twist

We give a transfer theorem for teleportation based on twisting the entanglement measurement. This allows one to say what local unitary operation must be performed to complete the teleportation in any situation, generalizing the scheme to include overcomplete measurements, non-Abelian groups of local unitary operations (e.g., angular momentum teleportation), and the effect of nonmaximally entangled resources.     

Dysregulation of chemo-cytokine production in schizophrenic patients versus healthy controls

Background  

The exact cause of schizophrenia is not known, although several aetiological theories have been proposed for the disease, including developmental or neurodegenerative processes, neurotransmitter abnormalities, viral infection and immune dysfunction or autoimmune mechanisms. Growing evidence suggests that specific cytokines and chemokines play a role in signalling the brain to produce neurochemical, neuroendocrine, neuroimmune and behavioural changes. A relationship between inflammation and schizophrenia was supported by abnormal cytokines production, abnormal concentrations of cytokines and cytokine receptors in the blood and cerebrospinal fluid in schizophrenia. Since the neuropathology of schizophrenia has recently been reported to be closely associated with microglial activation we aimed to determined whether spontaneous or LPS-induced peripheral blood mononuclear cell chemokines and cytokines production is dysregulated in schizophrenic patients compared to healthy subjects. We enrolled 51 untreated first-episode schizophrenics (SC) and 40 healthy subjects (HC) and the levels of MCP-1, MIP-1α, IL-8, IL-18, IFN-γ and RANTES were determined by Elisa method in cell-free supernatants of PBMC cultures.