pI-based phosphopeptide enrichment combined with nanoESI-MS

IEF is introduced as a new principle for enrichment and separation of phosphopeptides as obtained after digestion of phosphoproteins by trypsin. Tryptic peptides and phosphopeptides exhibit pI values, which overlap in the range of about 4-6. However, after methyl esterification of all carboxyl functions, the pI values of tryptic peptides and phosphopeptides regroup in discrete clusters. In addition, mono- and diphosphorylated peptides show different but very homogeneous pI values, with variations when internal Arg, Lys, or His residues are present. Experimentally, this new concept was applied for separation of model peptides on IPG strips pH 3-10 as used in the first dimension of 2-DE. After IEF of methyl-esterified peptides, the IPG strip was cut into pieces followed by peptide extraction, desalting and MS analysis by nanoESI-MS. Phosphopeptides were found to focus in good agreement with their calculated pI values. This analytical strategy showed a resolution of about 0.2 pI units, and thus turned out to be capable of detecting minor differences in pI values, such as those occurring between pSer, pThr and pTyr residues. Using IPG strips with a pI range of 3-10, methyl esterified nonphosphorylated tryptic peptides are concentrated in the basic part of the IPG strip or even leave the strip. Thus, efficient enrichment of phosphopeptides and their subfractionation according to pI is obtained in one step. Minor hydrolytic side reactions including deamidation of Asn and partial hydrolysis of methyl esters are observed. The results show that IEF opens attractive avenues for the further advancement of analytical phosphoproteomics.     

Extractability of HgS (cinnabar and metacinnabar) by hydrochloric acid

In this work we investigated the behaviour of pure HgS during extraction with dilute HCl to establish its extractability in 1 and 6 M HCl at the concentration level close to those occurring in natural sediments and soils. We found that neither cinnabar nor metacinnabar were soluble in 1 M HCl, whereas both were partially extracted by 6 M HCl. Metacinnabar precipitated in the laboratory was most prone to dissolution in 6 M HCl (up to 90%), followed by crystalline (commercial) metacinnabar (up to 70%) and cinnabar (up to 15%). Solubility of HgS in 6 M HCl was found to be dependent on its concentration, and an exponential relationship between quantity of HgS added to 20 mL of 6 M HCl (the range of 0.1-10 mg was used) and the solubility in 6 M HCl was established. For higher concentrations of HgS (10 mg in 20 mL of acid), a similarly low solubility of cinnabar was obtained as found in the literature. A study of dissolution kinetics of HgS in 6 M HCl indicated that it was a fairly slow process. Unexpected oxidation of HgS in water or 1 M HCl was found for extractions performed in Teflon vials previously used for the digestion of residual undissolved HgS by aqua regia. We presumed that the Teflon material could preserve some oxidising gases (presumably Cl(2)) developed during digestion with aqua regia which can then oxidise HgS during extraction with water or 1 M HCl. Regarding the extraction of Hg from natural sediments, we concluded that 6 M HCl could not be used to extract reactive Hg and predict bioavailability of mercury in sediments containing HgS and that experiments with model compounds should not be done at a concentration level several orders of magnitude higher than in natural samples.     

Measurements of long atomic lifetimes at an ion storage ring

Millisecond lifetimes of excited levels in multicharged ions may be measured at ion storage rings. At the Heidelberg ion storage ring TSR, particle detection after collisions between the circulating ions and electrons of the cooler has been used to obtain dielectronic recombination spectra as well as time curves of ionization and recombination for four-electron ions, with the aim of measuring transition probabilities for magnetic dipole and for electric dipole intercombination decays. The measurements on the 2s2p³P ₁ ^o level in the Be-like ions of N and O indicate lifetime values of =(1.6±0.2) ms for N³⁺ and of =(0.5±0.1) ms for O⁴⁺. Problems of these experiments are discussed as well as the prospects for improved measurements on other such ions of astrophysical interest, planning for state-specific optical detection.     

Femtosecond electron and spin dynamics in Gd(0001) studied by time-resolved photoemission and magneto-optics

Femtosecond electron and spin dynamics of the Gd(0001) surface are investigated by time-resolved photoemission and second harmonic generation. Upon optical excitation the spin polarization of the surface state is reduced by half while its exchange splitting remains nearly unchanged. Electron-magnon interaction is proposed to facilitate electron-spin-flip scattering among spin-mixed surface and bulk states, which provides a mechanism for ultrafast demagnetization.     

Quantum benchmark for storage and transmission of coherent states

We consider the storage and transmission of a Gaussian distributed set of coherent states of continuous variable systems. We prove a limit on the average fidelity achievable when the states are transmitted or stored by a classical channel, i.e., a measure and repreparation scheme which sends or stores classical information only. The obtained bound is tight and serves as a benchmark which has to be surpassed by quantum channels in order to outperform any classical strategy. The success in experimental demonstrations of quantum memories as well as quantum teleportation has to be judged on this footing.     

Engineered inorganic core/shell nanoparticles

It has been for a long time recognized that nanoparticles are of great scientific interest as they are effectively a bridge between bulk materials and atomic structures. At first, size effects occurring in single elements have been studied. More recently, progress in chemical and physical synthesis routes permitted the preparation of more complex structures. Such structures take advantages of new adjustable parameters including stoichiometry, chemical ordering, shape and segregation opening new fields with tailored materials for biology, mechanics, optics magnetism, chemistry catalysis, solar cells and microelectronics. Among them, core/shell structures are a particular class of nanoparticles made with an inorganic core and one or several inorganic shell layer(s). In earlier work, the shell was merely used as a protective coating for the core. More recently, it has been shown that it is possible to tune the physical properties in a larger range than that of each material taken separately. The goal of the present review is to discuss the basic properties of the different types of core/shell nanoparticles including a large variety of heterostructures. We restrict ourselves on all inorganic (on inorganic/inorganic) core/shell structures. In the light of recent developments, the applications of inorganic core/shell particles are found in many fields including biology, chemistry, physics and engineering. In addition to a representative overview of the properties, general concepts based on solid state physics are considered for material selection and for identifying criteria linking the core/shell structure and its resulting properties. Chemical and physical routes for the synthesis and specific methods for the study of core/shell nanoparticle are briefly discussed.     

Some upper and lower bounds on PSD-rank

Positive semidefinite rank (PSD-rank) is a relatively new complexity measure on matrices, with applications to combinatorial optimization and communication complexity. We first study several basic properties of PSD-rank, and then develop new techniques for showing lower bounds on the PSD-rank. All of these bounds are based on viewing a positive semidefinite factorization of a matrix M as a quantum communication protocol. These lower bounds depend on the entries of the matrix and not only on its support (the zero/nonzero pattern), overcoming a limitation of some previous techniques. We compare these new lower bounds with known bounds, and give examples where the new ones are better. As an application we determine the PSD-rank of (approximations of) some common matrices.     

Dynamical entropy production in spiking neuron networks in the balanced state

We demonstrate deterministic extensive chaos in the dynamics of large sparse networks of theta neurons in the balanced state. The analysis is based on numerically exact calculations of the full spectrum of Lyapunov exponents, the entropy production rate, and the attractor dimension. Extensive chaos is found in inhibitory networks and becomes more intense when an excitatory population is included. We find a strikingly high rate of entropy production that would limit information representation in cortical spike patterns to the immediate stimulus response.     

Effect of chain length and electrical charge on properties of ammonium-bearing bisphosphonate-coated superparamagnetic iron oxide nanoparticles: formulation and physicochemical studies

Bisphosphonates BP molecules have shown to be efficient for coating superparamagnetic iron oxide particles. In order to clarify the respective roles of electrical charge and the length of the molecules, bisphosphonates with one or two ammonium moieties with an intermediate aliphatic group of 3, 5 or 7 carbons were synthesized and iron oxide nanoparticles coated. The evaluation on their iron core properties was made by transmission electron microscopy (TEM), nuclear magnetic relaxation dispersion (NMRD) profiles and Mössbauer spectra. The core size is close to 5 nm, with a global superparamagnetic behaviour modified by a paramagnetic Fe-based layer, probably due to surface crystal alteration. The hydrodynamic sizes increase slightly with aliphatic chain length (from 9.8 to 18.6 nm). The presence of one or two ammonium group(s) lowers the negative electrophoretic mobility up to bear zero values but reduces their colloidal stability. These BP-coated iron oxide nanoparticles are promising Magnetic Resonance Imaging (MRI) contrast agents.     

Sonochemical and sonocatalytic degradation of monolinuron in water

The degradation of the phenylurea monolinuron (MLN) by ultrasound irradiation alone and in the presence of TiO(2) was investigated in aqueous solution. The experiments were carried out at low and high frequency (20 and 800 kHz) in complete darkness. The degradation of MLN by ultrasounds occurred mainly by a radical pathway, as shown the inhibitory effect of adding tert-butanol and bicarbonate ions to scavenge hydroxyl radicals. However, CO(3)(-) radicals were formed with bicarbonate and reacted in turn with MLN. In this study, the degradation rate of MLN and the rate constant of H(2)O(2) formation were used to evaluate the oxidative sonochemical efficiency. It was shown that ultrasound efficiency was improved in the presence of nanoparticles of TiO(2) and SiO(2) only at 20 kHz. These particles provide nucleation sites for cavitation bubbles at their surface, leading to an increase in the number of bubbles when the liquid is irradiated by ultrasound, thereby enhancing sonochemical reaction yield. In the case of TiO(2), sonochemical efficiency was found to be greater than with SiO(2) for the same mass introduced. In addition to the increase in the number of cavitation bubbles, activated species may be formed at the TiO(2) surface that promote the formation of H(2)O(2) and the decomposition of MLN.