Calibration method for ESR signal intensity of calcitic shells

A practical method of calibrating intensities of ESR signals with a single crystal of copper pentahydrate (CuSO₄ · 5H₂O) has been developed for calcitic shells containing a large amount of manganese (Mn²⁺). A sample holder is designed to insert the crystal from the bottom of the cavity for use as a standard sample. The signal of Cu²⁺ in the standard does not interfere with the Mn²⁺ signals. The Cu²⁺ signal and dating signal of the shell are recorded simultaneously; the ratio of their intensities is the basis for calibration. It is shown that this calibration method reduces the errors attributed to both coupling and unloadedQ factors of the cavity resonator to within 2%.     

Evaluation of the internal temperatures of an 8.6 kDa protein cation exposed to a hot dispenser cathode employed in electron capture dissociation mass spectrometry

The 'effective' internal temperature of an 8.6 kDa ubiquitin cation was estimated under electron capture dissociation (ECD) conditions, in which a dispenser cathode electron source was mounted just outside an ion cyclotron resonance (ICR) cell, i.e., axially displaced at a distance less than 1 cm from the rear trap plate of the ICR cell. In this ECD configuration, thermal activation of the molecular ions stored in the ICR cell was anticipated since the heated dispenser cathode (T(cathode surface) > 1000 degrees C) emitted a large amount of (both visible and infrared) radiation as well as electrons. An evaluation of the internal temperature of ubiquitin 6+ and 7+ cations was made by comparing our ECD fragmentation patterns with those obtained by McLafferty et al. (J. Am. Chem. Soc. 2002; 124: 6407) as a function of the ion temperature. In McLafferty's configuration, the heating (or thermal activation) effect of their filament source was minimal since the filament was displaced by a distance as far as 70 cm from their ICR cell. A careful comparison reveals that the fragmentation patterns obtained in this work are very similar to those previously measured at T approximately 125 degrees C. In terms of sequence coverage, our ECD configuration provides better results, and in particular without the aid of any other simultaneous activation method, such as thermal heating, infrared multiphoton irradiation, or collisional activation, except for the visible and infrared radiation from the heated cathode.     

Increasing protein stability through control of the nanoscale environment

We have discovered a novel property of single-walled carbon nanotubes (SWNTs)-their ability to stabilize proteins at elevated temperatures and in organic solvents to a greater extent than conventional flat supports. Experimental results and theoretical analysis reveal that the stabilization results from the curvature of SWNTs, which suppresses unfavorable protein-protein lateral interactions. Our results also indicate that the phenomenon is not unique to SWNTs but could be extended to other nanomaterials. The protein-nanotube conjugates represent a new generation of active and stable catalytic materials with potential use in biosensors, diagnostics, and bioactive films and other hybrid materials that integrate biotic and abiotic components.     

Investigation of crystal/electronic structure effects on the photoluminescence properties in the BaO–SiO2:Eu2+ systems

BaO–SiO₂:Eu²⁺ phosphors with different Ba/Si mole ratio were prepared using a solid-state reaction method, and their crystal structure dependent-photoluminescence properties were investigated. The prepared phosphor powders were characterized using X-ray diffraction (XRD), field-emission electron microscopy (FE-SEM) and fluorescence spectroscopy. The emission band of the Eu²⁺ activator varied from orange to blue with varying crystal structure of the host materials, which was related to the crystal field splitting of the Eu 5d orbitals. These emission color changes were examined by calculating the electronic band structure properties such as the density of the state. Moreover, the host material with Ba/Si=1 (BaSiO₃) for Eu²⁺, which exhibited a yellow emission when excited with near UV light, was further characterized for enhancing its emission intensity.     

Direct Determination of Gold in Rock Samples Using Collision Cell Quadrupole ICP-MS

This study investigated the determination of Au in rock samples using collision cell quadrupole inductively coupled plasma mass spectrometry (ICP-MS). It is essential to remove various interferents using a collision cell because polyatomic ions such as ¹⁸¹Ta¹⁶O⁺ and ¹⁸⁰Hf¹⁶O¹H⁺ can interfere with the direct determination of monoisotopic ¹⁹⁷Au when using ICP-MS. The addition of oxygen as a reaction gas removed isobaric interferents by transforming TaO⁺ and HfOH⁺ to TaO₂⁺, TaO₃⁺, and HfO₂H⁺, HfO₃H⁺, respectively, in the cell without significant Au⁺ loss. The ion kinetic energy effect (IKEE) due to the potential difference between the plasma and the hexapole affected the reactions in the cell. Au and interfering ions were very sensitive to cell bias voltage (Vc) at constant plasma potential (Vp) and quadrupole bias voltage (Vq). Under the condition of hot plasma, the transmission of ions was promoted, and the maximum Au signal intensity was 50% greater than under normal conditions. At Vc > 7 V, TaO⁺ ions were removed to background level. Optimized conditions for real sample analysis were obtained by introducing He as an additional collision gas in hot plasma. TaO⁺ ions were removed to background level at He flow rates above 0.6 mL min⁻¹, and the Au signal remained high. The detection limit (three times the standard deviation of the blank) of this method was 3.06 pg g⁻¹. The results for reference materials (STM-1 and DGPM-1) and spiked samples showed good agreement between specified and measured concentrations.     

Comparative Metabolomic Analysis of Moromi Fermented Using Different Aspergillus oryzae Strains

Aspergillus oryzae (A. oryzae) is an important starter in the fermentation of koji and moromi. However, the effect of different A. oryzae strains on the quality of moromi has rarely been studied. For this reason, this study analyzed the physicochemical properties, enzyme activity, sensory quality, and metabolite profiles of moromi samples fermented using two strains (A. oryzae KCCM12012P (moromi-1) and KCCM12804P (moromi-2)), which were newly isolated from fermented soy foods, and compared them to those of a commercialized A. oryzae strain (control). Amino-type nitrogen contents of moromi-1 and moromi-2 samples were higher than that of control moromi, and their amylase and protease activities were also higher. Moreover, metabolite profiles of moromi were significantly altered according to strains. In particular, the levels of many amino acids, peptides, nucleotides, and acidic compounds were altered, which resulted in changes in the sensory quality of moromi. Although volatile compounds were not investigated, the results suggested that the quality of moromi was significantly different for newly isolated strains, especially A. oryzae KCCM12804P, and they were superior to the commercial strain in terms of taste-related substances. Therefore, these strains could be used as good starters to produce moromi and soy sauce with good sensory quality.     

Reconstructive extremity dosimetry with 3D scanned hand model in MCNPX

We present a simulation method that can create accurate virtual models of hand with arbitrarily curved surfaces and perform distortion-free MCNPX simulations. Generally, MCNPX simulations of objects with arbitrarily curved surfaces are performed through voxelization. In this study, a polygon model is tetrahedralized by TetGen for the construction of the MCNPX geometry to be distortion-free. Then, dose estimation was successfully performed after converting the virtual model into an MCNPX input. A voxelized model was constructed for comparison purposes. The dose estimation functions of the two models were found to be similar, showing a similar amount of computing time by using the mesh tally option with 2e7 histories.     

Adsorption of myoglobin to Cu(II)-IDA and Ni(II)-IDA functionalized langmuir monolayers: study of the protein layer structure during the adsorption process by neutron and X-ray reflectivity

The structure and orientation of adsorbed myoglobin as directed by metal-histidine complexation at the liquid-film interface was studied as a function of time using neutron and X-ray reflectivity (NR and XR, respectively). In this system, adsorption is due to the interaction between iminodiacetate (IDA)-chelated divalent metal ions Ni(II) and Cu(II) and histidine moieties at the outer surface of the protein. Adsorption was examined under conditions of constant area per lipid molecule at an initial pressure of 40 mN/m. Adsorption occurred over a time period of about 15 h, allowing detailed characterization of the layer structure throughout the process. The layer thickness and the in-plane averaged segment volume fraction were obtained at roughly 40 min intervals by NR. The binding constant of histidine with Cu(II)-IDA is known to be about four times greater than that of histidine with Ni(II)-IDA. The difference in interaction energy led to significant differences in the structure of the adsorbed layer. For Cu(II)-IDA, the thickness of the adsorbed layer at low protein coverage was < or = 20 A and the thickness increased almost linearly with increasing coverage to 42 A. For Ni(II)-IDA, the thickness at low coverage was approximately 38 A and increased gradually with coverage to 47 A. The in-plane averaged segment volume fraction of the adsorbed layer independently confirmed a thinner layer at low coverage for Cu(II)-IDA. These structural differences at the early stages are discussed in terms of either different preferred orientations for isolated chains in the two cases or more extensive conformational changes upon adsorption in the case of Cu(II)-IDA. Subphase dilution experiments provided additional insight, indicating that the adsorbed layer was not in equilibrium with the bulk solution even at low coverages for both IDA-chelated metal ions. We conclude that the weight of the evidence favors the interpretation based on more extensive conformational changes upon adsorption to Cu(II)-IDA.