Measurement of one-bond 13Calpha-1Halpha residual dipolar coupling constants in proteins by selective manipulation of CalphaHalpha spins

We have developed new 2D and 3D experiments for the measurement of C(alpha)-H(alpha) residual dipolar coupling constants in (13)C and (15)N labelled proteins. Two experiments, 2D (HNCO)-(J-CA)NH and 3D (HN)CO-(J-CA)NH, sample the C(alpha)-H(alpha) splitting by means of C(alpha) magnetization, while 2D (J-HACACO)NH and 3D J-HA(CACO)NH use H(alpha) magnetization to achieve a similar result. In the 2D experiments the coupling evolution is superimposed on the evolution of the (15)N chemical shifts and the IPAP principle is used to obtain (1)H-(15)N HSQC-like spectra from which the splitting is determined. The use of a third dimension in 3D experiments reduces spectral overlap to the point where use of an IPAP scheme may not be necessary. The length of the sampling interval in the J-dimension of these experiments is dictated solely by the relaxation properties of C(alpha) or H(alpha) nuclei. This was made possible by the use of C(alpha) selective pulses in combination with either a DPFGSE or modified BIRD pulses. Inclusion of these pulse sequence elements in the J-evolution periods removes unwanted spin-spin interactions. This allows prolonged sampling periods ( approximately 25 ms) yielding higher precision C(alpha)-H(alpha) splitting determination than is achievable with existing frequency based methods.     

Paleodiet characterisation of an Etrurian population of Pontecagnano (Italy) by Isotope Ratio Mass Spectrometry (IRMS) and Atomic Absorption Spectrometry (AAS)(#)

Human bones recovered from the archaeological site of Pontecagnano (Salerno, Italy) have been studied to reconstruct the diet of an Etrurian population. Two different areas were investigated, named Library and Sant' Antonio, with a total of 44 tombs containing human skeletal remains, ranging in age from the 8th to the 3rd century B.C. This time span was confirmed by 14C dating obtained using Accelerator Mass Spectrometry (AMS) on one bone sample from each site.Atomic Absorption Spectrometry (AAS) was used to extract information about the concentration of Sr, Zn, Ca elements in the bone inorganic fraction, whilst stable isotope ratio measurements (IRMS) were carried out on bone collagen to obtain the delta13C and delta15N. A reliable technique has been used to extract and separate the inorganic and organic fractions of the bone remains.Both IRMS and AAS results suggest a mixed diet including C3 plant food and herbivore animals, consistent with archaeological indications.     

New properties of convex functions in the Heisenberg group

We prove some new properties of the weakly -convex functions recently introduced by Danielli, Garofalo and Nhieu. As an interesting application of our results we prove a theorem of Busemann-Feller-Alexandrov type in the Heisenberg groups , .

     

Exactly quantized dynamics of classical incommensurate sliders

We report peculiar velocity quantization phenomena in the classical motion of an idealized 1D solid lubricant, consisting of a harmonic chain interposed between two periodic sliders. The ratio upsilon(c.m.)/upsilon(ext) of the chain center-of-mass velocity to the externally imposed relative velocity of the sliders stays pinned to exact "plateau" values for wide ranges of parameters, such as slider corrugation amplitudes, external velocity, chain stiffness, and dissipation, and is strictly determined by the commensurability ratios alone. The phenomenon is explained by one slider rigidly dragging the kinks that the chain forms with the other slider. Possible consequences of these results for some real systems are discussed.     

Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach

Transition-metal centers are the active sites for a broad variety of biological and inorganic chemical reactions. Notwithstanding this central importance, density-functional theory calculations based on generalized-gradient approximations often fail to describe energetics, multiplet structures, reaction barriers, and geometries around the active sites. We suggest here an alternative approach, derived from the Hubbard U correction to solid-state problems, that provides an excellent agreement with correlated-electron quantum chemistry calculations in test cases that range from the ground state of Fe2 and Fe2- to the addition elimination of molecular hydrogen on FeO+. The Hubbard U is determined with a novel self-consistent procedure based on a linear-response approach.     

A Synthetic Fluorescent Mitochondria‐Targeted Sensor for Ratiometric Imaging of Calcium in Live Cells

Ca²⁺ handling by mitochondria is crucial for cell life and the direct measure of mitochondrial Ca²⁺ concentration in living cells is of pivotal interest. Genetically‐encoded indicators greatly facilitated this task, however they require demanding delivery procedures. On the other hand, existing mitochondria‐targeted synthetic Ca²⁺ indicators are plagued by several drawbacks, for example, non‐specific localization, leakage, toxicity. Here we report the synthesis and characterization of a new fluorescent Ca²⁺ sensor, named mt‐fura‐2, obtained by coupling two triphenylphosphonium cations to the molecular backbone of the ratiometric Ca²⁺ indicator fura‐2. Mt‐fura‐2 binds Ca²⁺ with a dissociation constant of ≈1.5 μm in vitro. When loaded in different cell types as acetoxymethyl ester, the probe shows proper mitochondrial localization and accurately measures matrix [Ca²⁺] variations, proving its superiority over available dyes. We describe the synthesis, characterization and application of mt‐fura‐2 to cell types where the delivery of genetically‐encoded indicators is troublesome.     

Tight Xenon Confinement in a Crystalline Sandwich‐like Hydrogen‐Bonded Dimeric Capsule of a Cyclic Peptide

A cyclic hexapeptide with three pyridyl moieties connected to its backbone forms a hydrogen‐bonded dimer, which tightly encapsulates a single xenon atom, like a pearl in its shell. The dimer imprints its shape and symmetry to the captured xenon atom, as demonstrated by ¹²⁹Xe NMR spectroscopy, single‐crystal X‐ray diffraction, and computational studies. The dimers self‐assemble hierarchically into tubular structures to form a porous supramolecular architecture, whose cavities are filled by small molecules and gases.     

Cosmological Horizons and Reconstruction of Quantum Field Theories

As a starting point, we state some relevant geometrical properties enjoyed by the cosmological horizon of a certain class of Friedmann-Robertson-Walker backgrounds. Those properties are generalised to a larger class of expanding spacetimes M admitting a geodesically complete cosmological horizon common to all co-moving observers. This structure is later exploited in order to recast, in a cosmological background, some recent results for a linear scalar quantum field theory in spacetimes asymptotically flat at null infinity. Under suitable hypotheses on M, encompassing both the cosmological de Sitter background and a large class of other FRW spacetimes, the algebra of observables for a Klein-Gordon field is mapped into a subalgebra of the algebra of observables constructed on the cosmological horizon. There is exactly one pure quasifree state λ on which fulfills a suitable energy-positivity condition with respect to a generator related with the cosmological time displacements. Furthermore λ induces a preferred physically meaningful quantum state λ _M for the quantum theory in the bulk. If M admits a timelike Killing generator preserving , then the associated self-adjoint generator in the GNS representation of λ _M has positive spectrum (i.e., energy). Moreover λ _M turns out to be invariant under every symmetry of the bulk metric which preserves the cosmological horizon. In the case of an expanding de Sitter spacetime, λ _M coincides with the Euclidean (Bunch-Davies) vacuum state, hence being Hadamard in this case. Remarks on the validity of the Hadamard property for λ _M in more general spacetimes are presented. Dedicated to Professor Klaus Fredenhagen on the occasion of his 60th birthday.     

Lévy processes and Schrödinger equation

We analyze the extension of the well known relation between Brownian motion and the Schrödinger equation to the family of the Lévy processes. We consider a Lévy-Schrödinger equation where the usual kinetic energy operator-the Laplacian-is generalized by means of a selfadjoint, pseudodifferential operator whose symbol is the logarithmic characteristic of an infinitely divisible law. The Lévy-Khintchin formula shows then how to write down this operator in an integro-differential form. When the underlying Lévy process is stable we recover as a particular case the fractional Schrödinger equation. A few examples are finally given and we find that there are physically relevant models-such as a form of the relativistic Schrödinger equation-that are in the domain of the non stable Lévy-Schrödinger equations.