Scaling exponents and probability distributions of DNA end-to-end distance

The scaling of the average gyration radius of polymers as a function of their length can be experimentally determined from ensemble measurements, such as light scattering, and agrees with analytical estimates. Ensemble techniques, yet, do not give access to the full probability distributions. Single molecule techniques, instead, can deliver information on both average quantities and distribution functions. Here we exploit the high resolution of atomic force microscopy over long DNA molecules adsorbed on a surface to measure the average end-to-end distance as a function of the DNA length, and its full distribution function. We find that all the scaling exponents are close to the predicted 3D values (upsilon=0.589+/-0.006 and delta=2.58+/-0.77). These results suggest that the adsorption process is akin to a geometric projection from 3D to 2D, known to preserve the scaling properties of fractal objects of dimension df<2.     

Water-enhanced catalysis of CO oxidation on free and supported gold nanoclusters

The enhancement by water molecules of the catalytic activity of gas-phase and supported gold nanoclusters toward CO oxidation is investigated with first-principles calculations. Coadsorption of H(2)O and O(2) leads to formation of a complex well bound to the gold cluster, even on a defect-free MgO(100) support. Formation of the complex involves partial proton sharing between the adsorbates, that in certain configurations results in proton transfer leading to the appearance of a hydroperoxyl-like complex. The O-O bond is activated, leading to a weakened peroxo or superoxolike state, and consequently the reaction with CO to form CO2 occurs with a small activation barrier of approximately 0.5 eV. A complete catalytic cycle of the water-enhanced CO oxidation is discussed.     

Does a Reinforced Kinetic Macrocyclic Effect Exist? The Demetallation in Strong Acid of Copper(II) Complexes with Open and Cyclic Tetramines Containing a Piperazine Fragment

The demetallation in acidic solution of the Cu(II) complexes with open-chain and cyclic tetramines containing a piperazine unit (2 and 3) has been investigated in terms of its kinetic aspects and compared with the behaviour of unsubstituted counterparts (tetramines 1 and 4). The presence of the piperazine fragment slows demetallation of the open-chain-ligand complex owing to the activation barrier associated with the conformational change from boat-to-half-boat; however, it does not affect the demetallation of the macrocyclic complex, which involves the spontaneous boat-to-twist conformational change. Thus, lateral reinforcement of a cyclam-like ligand does not add any further contribution to the typical inertness in demetallation of macrocyclic complexes.     

Determination of creatinine in human serum by short-end injection capillary zone electrophoresis

A new ultra-rapid free-solution capillary zone electrophoresis method to measure serum creatinine is presented. Procedural parameters such as injection mode, concentration and pH of phosphate running buffer and acidic deproteinization of serum samples were investigated. Short-end injection permits a decrease of the analysis time by injecting samples at the outlet end of a silica capillary closest to the detection window, so reducing the migration distance. Thus, when a capillary with an effective length of 10.2 cm and a 40 mmol/L sodium phosphate buffer pH 2.35 was used, the obtained migration time of the creatinine peak was the shortest never described before, about 1.1 min. These conditions give a good reproducibility of the migration times (coefficient of variation, CV% < 0.5) and the peak areas (CV% < 2.8). Intra- and interassay CV were 3.06 and 6.26%, respectively, and analytical recovery was 99.4%. We compared our proposed method to Jaffé colorimetric assay, by measuring serum creatinine in 128 normal subjects. The obtained data were analyzed by the Passing and Bablok regression and Bland-Altman test. Creatinine concentration in healthy subjects was also used to investigate on its relationships with plasma thiols levels.     

Quasilinear degenerate evolution equations in Banach spaces

The quasilinear degenerate evolution equation of parabolic type 0< t T considered in a Banach space X is written, putting Mv = u, in the from 0< t T, where A(u)=L(u)M^–1 are multivalued linear operators in X for u K, K being a bounded ball ||u||_Z<R in another Banach space Z continuously embedded in X. Existence and uniqueness of the local solution for the related Cauchy problem are given. The results are applied to quasilinear elliptic-parabolic equations and systems.     

Functional MRI using intravascular contrast agents: detrending of the relative cerebrovascular (rCBV) time course

In pharmacological fMRI experiments in animal models, blood pool contrast agents may be used to map cerebral blood volume change as a surrogate for neural activation. When the background signal drift due to contrast agent washout is non-negligible over the duration of the signal changes of interest, time-course detrending is essential for accurate interpretation of the experiment. Detrending approaches based on estimation of the background signal from a baseline period of the time course prior to pharmacological (or functional) challenge were evaluated with the aim of identifying a robust method of estimating the contrast agent washout contribution to the background signal drift. For fMRI studies in the rat, it was found that a constrained fit of a mono-exponential washout model was more accurate than a constant background approximation and unconstrained fits for experiments investigating the functional response to rapid pharmacological challenges such as cocaine and amphetamine. Moreover, the constrained fitting approach allows shorter baseline periods than unconstrained extrapolation, reducing the required duration of the experiment.     

Synthesis and ab-initio XRPD structure of group 12 imidazolato polymers

Two new 3D homoleptic binary imidazolates, Cd(im)2 and Hg(im)2 (Him = imidazole), as well as [Hg(im)]NO3, containing 1D polycations of [Hg(im)]n(n+) formulation, have been prepared and characterized by ab-initio XRPD methods.