Rare fluctuations of native proteins sampled by equilibrium hydrogen exchange

We present a method for determining the ensembles of native protein structures that result from the large fluctuations of low probability revealed by hydrogen-exchange experiments. The measured protection factors are used to bias Monte Carlo simulations to sample the structures of the exchange competent species. The approach is illustrated by its application to the case of alpha-lactalbumin.     

DNA and RNA noncovalent interaction of platinum(II) polypyridine complexes

A comparative investigation of the noncovalent interaction of the platinum(II) polypyridine complexes [Pt(dipy)(n-Rpy)2]2+ and [Pt(4,4'-Me2dipy)(2-Rpy)2]2+ (dipy = 2,2'-dipyridine; Me = CH3; n = 2-4; R = H or CH3) with double-helical DNA (calf thymus) and RNA [poly(A).poly(U)] has been conducted. With the exception of [Pt(dipy)(2-Mepy)2]2+, all of the complexes interact strongly, by intercalation, with both nucleic acids giving rise to large changes in the electronic spectra and induced circular dichroism signals; in addition, viscosity experiments on rodlike DNA and RNA show that both biopolymers elongate upon interaction with the complexes. The binding constant values, KB, determined at 25 degrees C, indicate that, at 0.101 M ionic strength, the affinity for poly(A).poly(U) is strongly dependent on the complexes nature, while for DNA it is leveled off. [Pt(dipy)(2-Mepy)2]2+ binds to DNA but does not interact appreciably with poly(A).poly(U).     

Rheological behavior and structural interpretation of waxy crude oil gels

A waxy crude oil which gels below a threshold temperature has been investigated under static and dynamic conditions, using a combination of rheological methods, optical microscopy, and DSC. Particular attention is given in this work to the influence of the mechanical history on gel strength and to describing the time-dependent rheological behavior. The gels display a strong dependence of the yield stress and moduli on the shear history, cooling rate, and stress loading rate. Of particular interest is the partial recovery of the gel structure after application of small stress or strain (much smaller than the critical values needed for flow onset) during cooling, which can be used to reduce the ultimate strength of the crude oil gel formed below the pour point. A second focus of this study is to further develop the physical interpretation of the mechanism by which wax crystallization produces gelation. Gelation of the waxy crude oil studied is suggested to be the result of the association between wax crystals, which produces an extended network structure, and it is shown that the system displays features common to attractive colloidal gels, for one of which, fumed silica (Aerosil 200) in paraffin oil, rheological data are reported. The colloidal gel model provides a simple and economical basis for explaining the response of the gelled oil to various mechanical perturbations and constitutes a fruitful basis from which to develop technologies for controlling the gelation phenomenon, as suggested by the rheological results reported.     

Evaluation by chemical parameters of the pollution state of the agricultural-industrial settlement of the Fucino Plain

In the present work are reported the results of a monitoring on a vast scale, carried out through evaluation of opportune chemical parameters, of the pollution state of the agricultural-industrial settlement of the Fucino Plain. The parameters took into consideration have been the presence of wide consumption pesticides and of ionic species as Cl-, NO2-, NO3-, NH4+, the quantification of the dissolved oxygen, of the temperature, of the conductivity, of pH and eH. Collected data are used for chemometric elaboration. The water systems examined, by means of drawing campaigns carried out at regular intervals in winter, spring, summer, and autumnal seasons, are represented by superficial waters constituting a network of irrigation canals fed by stratum and meteoric waters. In this work are reported the results relative to the drawing campaigns.     

Multiplicity studies and effective energy in ALICE at the LHC

In this work we explore the possibility to perform “effective energy” studies in very high energy collisions at the CERN large hadron collider (LHC). In particular, we focus on the possibility to measure in pp collisions the average charged multiplicity as a function of the effective energy with the ALICE experiment, using its capability to measure the energy of the leading baryons with the zero degree calorimeters. Analyses of this kind have been done at lower centre-of-mass energies and have shown that, once the appropriate kinematic variables are chosen, particle production is characterized by universal properties: no matter the nature of the interacting particles, the final states have identical features. Assuming that this universality picture can be extended to ion–ion collisions, as suggested by recent results from RHIC experiments, a novel approach based on the scaling hypothesis for limiting fragmentation has been used to derive the expected charged event multiplicity in AA interactions at LHC. This leads to scenarios where the multiplicity is significantly lower compared to most of the predictions from the models currently used to describe high energy AA collisions. A mean charged multiplicity of about 1000–2000 per rapidity unit (at η∼0) is expected for the most central Pb–Pb collisions at . In memory of A. Smirnitskiy     

Dipyridylketone as a versatile ligand precursor for new cationic heteroleptic cyclometalated iridium complexes

Three new bis-cyclometalated iridium(III) complexes, of general formula [Ir(2-phenylpyridine)(2)(L)](+), are reported. The compounds contain a dipyridine-type ligand (L) derived from di-2-pyridylketone (dipyridin-2-ylmethanol, 2,2'-(hydrazonomethylene)dipyridine and 3-hydroxy-3,3-di(pyridine-2-yl)propanenitrile) and were synthesized through two different reaction pathways. The alternative synthetic pathway herein proposed, namely the direct reactions on the complex [Ir(2-phenylpyridine)(2)(2,2'-dipyridylketone)](+), overcame the inconveniences encountered with the standard reaction between the dimeric precursor [Ir(2-phenylpyridine)(2)(μ-Cl)](2) and the ancillary ligands (L). The photophysical characterization of the iridium complexes reveals that modifications on the ancillary ligand introduce large changes in the photophysical behaviour of the complexes. High emission quantum yield is associated with the presence of a saturated carbon between the two pyridyl moieties: [Ir(2-phenylpyridine)(2)(2,2'-dipyridylketone)](+) and [Ir(2-phenylpyridine)(2)(2,2'-(hydrazonomethylene)dipyridine)](+) are extremely low emissive, while [Ir(2-phenylpyridine)(2)(dipyridin-2-ylmethanol)](+) and [Ir(2-phenylpyridine)(2)(3-hydroxy-3,3-di(pyridine-2-yl)propanenitrile)](+) are good photoemitters. DFT and TD-DFT calculations confirmed the mixed LC/MLCT character of the excited states involved in the absorption and emission processes and highlighted the role of the π-conjugation between the two subunits of the ancillary ligand in determining the nature of the LUMO.     

Accelerating water exchange for GdIII chelates by steric compression around the water binding site

The water exchange process was accelerated for nine-coordinate, monohydrated macrocyclic GdIII complexes by inducing steric compression around the water binding site; the increased steric crowding was achieved by replacing an ethylene bridge of DOTA4- by a propylene bridge; in addition to the optimal water exchange rate, the stability of [Gd(TRITA)(H2O)]- is sufficiently high to ensure safe medical use which makes it a potential synthon for the development of high relaxivity, macromolecular MRI contrast agents.