Development of a peptide probe for the occurrence of hydrogen (1H/2H) scrambling upon gas-phase fragmentation

Hydrogen (1H/2H) exchange combined with mass spectrometry (HX-MS) has become a valuable method for the analysis of protein structural dynamics. Currently, localization of the incorporated deuterons is made by enzymatic cleavage of the labeled proteins, and single-residue resolution is typically only achieved for a few residues. Determination of site-specific deuterium levels by gas-phase fragmentation would greatly increase the applicability of the HX-MS method. It is, however, mandatory for this gas-phase approach that hydrogen (1H/2H) scrambling in the gaseous peptide is negligible. Thus, it is important to have a simple reference system where the onset of scrambling processes is readily detected. Here we describe a simple well-characterized set of peptides with a unique regioselective labeling that ensures an inherent high sensitivity for the detection of scrambling. This selective labeling is achieved by utilizing differences in the intrinsic exchange rates between various amino acid residues. We demonstrate that our peptides can be infused directly into an electrospray ion source by means of a cooled glass syringe, while maintaining their selective labeling in solution. We further show that the selective labeling is completely erased upon low-energy collisional activation in a tandem mass spectrometry experiment as a result of extensive hydrogen (1H/2H) scrambling.     

Lattice dynamics of the Zn-Mg-Sc icosahedral quasicrystal and its Zn-Sc periodic 1/1 approximant

Quasicrystals are long-range-ordered materials that lack translational invariance, so the study of their physical properties remains a challenging problem. Here, we have carried out inelastic-X-ray- and neutron-scattering experiments on single-grain samples of the Zn-Mg-Sc icosahedral quasicrystal and of the Zn-Sc periodic cubic 1/1 approximant, with the aim of studying the respective influence of the local order and of the long-range order (periodic or quasiperiodic) on lattice dynamics. Besides the overall similarities and the existence of a pseudo-gap in the transverse dispersion relation, marked differences are observed, the pseudo-gap being larger and better defined in the approximant than in the quasicrystal. This can be qualitatively explained using the concept of a pseudo-Brillouin-zone in the quasicrystal. These results are compared with simulations on atomic models and using oscillating pair potentials, and the simulations reproduce in detail the experimental results. This paves the way for a detailed understanding of the physics of quasicrystals.     

Electromagnetic interference shielding characteristics of carbon nanofiber-polymer composites

Electromagnetic interference (EMI) shielding characteristics of carbon nanofiber-polystyrene composites were investigated in the frequency range of 12.4-18 GHz (Ku-band). It was observed that the shielding effectiveness of such composites was frequency independent, and increased with increasing carbon nanofiber loading within Ku-band. The experimental data exhibited that the shielding effectiveness of the polymer composite containing 20 wt% carbon nanofibers could reach more than 36 dB in the measured frequency region, indicating such composites can be applied to the potential EMI shielding materials. In addition, the results showed that the contribution of reflection to the EMI shielding effectiveness was much larger than that of absorption, implying the primary EMI shielding mechanism of such composites was reflection of electromagnetic radiation within Ku-band.     

Correlation effects in wave function mapping of molecular beam epitaxy grown quantum dots

We investigate correlation effects in the regime of a few electrons in uncapped InAs quantum dots by tunneling spectroscopy and wave function (WF) mapping at high tunneling currents where electron-electron interactions become relevant. Four clearly resolved states are found, whose approximate symmetries are roughly s and p, in order of increasing energy. Because the major axes of the p-like states coincide, the WF sequence is inconsistent with the imaging of independent-electron orbitals. The results are explained in terms of many-body tunneling theory, by comparing measured maps with those calculated by taking correlation effects into account.     

Oxygenation monitoring of tissue vasculature by resonance Raman spectroscopy

Resonance Raman spectroscopy offers a mechanism for the noninvasive measurement of in vivo and in situ hemoglobin oxygen saturation (HbO(2)Sat) in living tissue. Clinically informative signals can be provided by resonance enhancement with deep violet excitation. It is notable that fluorescence does not significantly degrade the quality of the signals. During the controlled hemorrhage and resuscitation of rats, signal intensity ratios of oxy- vs. deoxyhemoglobin from sublingual mucosa correlated with co-oximetry values of blood withdrawn from a central venous catheter. The spectroscopic application described here has potential as a noninvasive method for the diagnosis of clinical shock and guidance of its therapy.     

Impedance spectroscopy: Over 35 years of electrochemical sensor optimization

There is considerable interest in the development of electroanalytical sensors (i.e., potentiometric, amperometric, electrochemical biosensors) for the detection of a wide range of analytes. The success of many of these sensors is governed by the condition and stability of the membrane/electrode surface. In fact, the response mechanism is dictated primarily by the surface structure and a considerable amount of work has been undertaken to characterize the interfacial region. Consequently, electrochemical impedance spectroscopy (EIS) has played a pivotal role in the characterization of many types of sensors. EIS has been used to provide information on various fundamental processes (i.e., adsorption/film formation, rate of charge transfer, ion exchange, diffusion, etc.) that occur at the electrode–electrolyte interface. Understanding and manipulating these interfacial processes has assisted in the development of membranes/electrodes with new and improved response characteristics. This paper reviews some of the work that has been undertaken using EIS over the past 35 years. More importantly, it evaluates the power of EIS in characterizing a wide range of electrochemical sensor systems.     

The effect of the contact between platinum and soot particles on the catalytic oxidation of soot deposits on a diesel particle filter

Experiments were performed with two model soot aerosols brought into different forms of contact with Pt aerosol particles, to investigate the effectiveness of this contact in lowering the catalytic soot oxidation temperature. The contact was either generated between individual particles in the aerosol state (Pt-doped soot to simulate a fuel borne catalyst), or by sequential or simultaneous deposition of separately generated soot and Pt aerosols onto a sintered metal filter. (Formation of a soot cake on previously deposited Pt aerosol would simulate a catalyst coated diesel particle filter.) The catalytic activity was determined in all cases from temperature ramped oxidation in air of the filtered particles, and defined as the 50% conversion temperature.

It was found that Pt-doped soot and simultaneously filtered aerosols were both equally effective in reducing the oxidation temperature by up to 140–250 °C for the spark discharge soot (with 3–47 wt% Pt concentration in the soot cake), and by up to 140 °C for the pyrolysis soot (3 wt% Pt). Conversely, the deposition of a thin soot layer of 5–10 μm thickness onto Pt, or vice versa, produced only a slight temperature reduction on the order of about 13–42 °C. These results suggest that the distance between soot and Pt particles plays a key role in promoting an effective oxidation on the filter, which is consistent with the role of Pt particles as local generators of activated oxygen.