Development of a coffee bean certified reference material (KRISS CRM 108-10-023) for elemental analysis.

The development of a novel coffee bean matrix certified reference material (CRM) for elemental analysis is described. The CRM was prepared by processing green coffee beans into a dry homogeneous powder. Mass fractions of elements in the CRM were measured using double isotope dilution inductively coupled plasma mass spectrometry (double ID-ICP-MS), and measurement results for eight elements (Mg, Ca, Fe, Cu, Zn, Cd, Hg, and Pb) of sufficient quality were certified. The mass fraction range was from 0.09476 mg/kg (Cd) to 1908 mg/kg (Mg), with relative expanded uncertainty range of 0.66% (Cd) to 12% (Pb). Measurement results of two elements (Cr and Ni) with insufficient quality were provided for information only. During characterization, an effective approach for the measurement of isotopic abundances and molar masses of elements with high natural isotopic variations for double ID-ICP-MS was developed and applied. The CRM developed in the present study is expected to be a useful measurement standard for assuring the quality of measurement procedures for coffee beans or related materials.

Isotopic Analysis of Lead at Ultratrace Levels Using Thermal Ionization Mass Spectrometry (TIMS) Coupled with the Continuous Heating Method: Optimization of the Data Integration Range and Method.

This study systematically and experimentally evaluates data integration methods for the isotopic analysis of Pb at ultratrace levels using thermal ionization mass spectrometry (TIMS) with a continuous heating method. The evaluation utilized a certified reference material of Pb (SRM 981). The experimental evaluations encompass different data calculation methods (methods I, II, and III) and integration ranges (full, over 1%, 25%, and 75%). Method I, in which isotope ratios were calculated based on summed ion signal intensities compensating for mass fractionation, was consistent with the certified values for 10 and 1 ng standard samples across all integration ranges. For 100 pg samples, full range calculations failed for specific isotope ratios, but reduced ranges (over 1%, 25%, and 75%) yielded values overlapping with certified ones. Method II, in which isotope ratios were calculated by averaging the precalculated isotope ratios, exhibited inferior performance compared to method I. Method III, using weighted averaging to reduce anomalous values, showed results consistent with those of method I but was recommended only for single measurements. An integration range of over 1% or 25% is preferred to exclude anomalies while compensating for mass fractionation. The optimized method was validated by comparing two different instruments used for the isotopic analysis of the reference material. The enhanced accuracy and precision provide valuable insights for researchers working in ultratrace-level Pb isotopic analysis using TIMS.

Observations of Nematicity, Dopants, and Zero-Bias Conductance Peaks for the Ca0.9La0.1FeAs2 Superconductor.

Ca1-xLaxFeAs2 (CLFA112) belongs to a new family of Fe-based superconductors (FeSCs) and has a unique crystal structure featuring an arsenic zigzag chain layer, which has been proposed to be a possible two-dimensional topological insulator. This suggests that CLFA112 is a potential topological superconductor-a platform to realize Majorana fermions. Up to now, even a clear superconducting (SC) gap in CLFA112 has never been observed, and the SC properties of CLFA112 remain largely elusive. In this letter, we report the results of an atomic-scale investigation of the electronic structure of CLFA112 crystals using low-temperature scanning tunneling microscopy (STM). We revealed four different types of surfaces exhibiting distinct electronic properties, with all surfaces displaying dominating 2 × 1 surface reconstructions. On a Ca/La layer on top of an FeAs layer, a clear SC gap of ~12 mV was observed only at the crevices (vacancies) where the FeAs layer can be directly accessed. Remarkably, the FeAs termination layer displayed a dispersing nematic modulation both in real and q space. We also present peculiar zero-bias conductance peaks for the very As chain layer that is believed to exhibit a topological edge state as well as the influence of La dopants on the As chain layer.

Development of a Certified Reference Material (NMIJ CRM 7203-a) for Elemental Analysis of Tap Water.

A certified reference material (CRM), NMIJ CRM 7203-a, was developed for the elemental analysis of tap water. At least two independent analytical methods were applied to characterize the certified value of each element. The elements certified in the present CRM were as follows: Al, As, B, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, Rb, Sb, Se, Sr, and Zn. The certified value for each element was given as the (property value ± expanded uncertainty), with a coverage factor of 2 for the expanded uncertainty. The expanded uncertainties were estimated while considering the contribution of the analytical methods, the method-to-method variance, the sample homogeneity, the long-term stability, and the concentrations of the standard solutions for calibration. The concentration of Hg (0.39 µg kg-1) was given as the information value, since loss of Hg was observed when the sample was stored at room temperature and exposed to light. The certified values of selected elements were confirmed by a co-analysis carried out independently by the NMIJ (Japan) and the KRISS (Korea).

Generation of ultra-high-molecular-weight polyethylene from metallocenes immobilized onto N-doped graphene nanoplatelets.

Catalytic natures of organometallic catalysts are modulated by coordinating organic ligands with proper steric and electronic properties to metal centers. Carbon-based nanomaterials such as graphene nanoplatelets are used with and without N-doping and multiwalled carbon nanotube as a ligand for ethylene polymerizations. Zirconocenes or titanocenes are immobilized on such nanomaterials. Polyethylenes (PEs) produced by such hybrids show a great increase in molecular weight relative to those produced by free catalysts. Specially, ultra-high-molecular-weight PEs are produced from the polymerizations at low temperature using the hybrid with N-doped graphene nanoplatelets. This result shows that such nanomaterials act a crucial role to tune the catalytic natures of metallocenes.

Generation of B-doped graphene nanoplatelets using a solution process and their supercapacitor applications.

Chemically modified graphene (CMG) nanoplatelets have shown great promise in various applications due to their electrical properties and high surface area. Chemical doping is one of the most effective methods to tune the electronic properties of graphene materials. In this work, novel B-doped nanoplatelets (borane-reduced graphene oxide, B-rG-O) were produced on a large scale via the reduction of graphene oxide by a borane-tetrahydrofuran adduct under reflux, and their use for supercapacitor electrodes was studied. This is the first report on the production of B-doped graphene nanoplatelets from a solution process and on the use of B-doped graphene materials in supercapacitors. The B-rG-O had a high specific surface area of 466 m(2)/g and showed excellent supercapacitor performance including a high specific capacitance of 200 F/g in aqueous electrolyte as well as superior surface area-normalized capacitance to typical carbon-based supercapacitor materials and good stability after 4500 cycles. Two- and three-electrode cell measurements showed that energy storage in the B-rG-O supercapacitors was contributed by ion adsorption on the surface of the nanoplatelets in addition to electrochemical redox reactions.

Direct observation of the primary and secondary C-Br bond cleavages from the 1,2-dibromopropane photodissociation at 234 and 265 nm using the velocity map ion imaging technique.

Photodissociation dynamics of 1,2-dibromopropane has been investigated at 234 and 265 nm by using the velocity map ion imaging method. At both pump energies, a single Gaussian-shaped speed distribution is observed for the Br*((2)P(1/2)) fragment, whereas at least three velocity components are found to be existent for the Br((2)P(3/2)) product. The secondary C-Br bond cleavage of the bromopropyl radical which is energized from the ultrafast primary C-Br bond rupture should be responsible for the multicomponent translational energy distribution at the low kinetic energy region of Br((2)P(3/2)). The recoil anisotropy parameter (beta) of the fragment from the primary C-Br bond dissociation is measured to be 0.53 (0.49) and 1.26 (1.73) for Br((2)P(3/2)) and Br*((2)P(1/2)), respectively, at 234 (265) nm. The beta value of Br((2)P(3/2)) from the secondary C-Br bond dissociation event at 265 nm is found to be 0.87, reflecting the fact that the corresponding Br((2)P(3/2)) fragment carried the initial vector component of the bromopropyl radical produced from the primary bond dissociation event. Density functional theory has been used to calculate energetics involved both in the primary and in the secondary C-Br bond dissociation dynamics.

State-selective predissociation dynamics of methylamines: the vibronic and HD effects on the conical intersection dynamics.

The photodissociation dynamics of methylamines (CH(3)NH(2) and CD(3)ND(2)) on the first electronically excited state has been investigated using the velocity map ion imaging technique probing the H or D fragment. Two distinct velocity components are found in the H(D) translational energy distribution, implying the existence of two different reaction pathways for the bond dissociation. The high H(D) velocity component with the small internal energy of the radical fragment is ascribed to the N-H(D) fragmentation via the coupling of S(1) to the upper-lying S(2) repulsive potential energy surface along the N-H(D) bond elongation axis. Dissociation on the ground S(0) state prepared via the nonadiabatic dynamics at the conical intersection should be responsible for the slow H(D) fragment. Several S(1) vibronic states of methylamines including the zero-point level and nnu(9) states (n=1, 2, or 3) are exclusively chosen in order to explore the effect of the initial quantum content on the chemical reaction dynamics. The branching ratio of the fast and slow components is found to be sensitive to the initial vibronic state for the N-H bond dissociation of CH(3)NH(2), whereas it is little affected in the N-D dissociation event of CD(3)ND(2). The fast component is found to be more dominant in the translational distribution of D from CD(3)ND(2) than it is in that of H from CH(3)NH(2). The experimental result is discussed with a plausible mechanism of the conical intersection dynamics.

Graphene oxide papers modified by divalent ions-enhancing mechanical properties via chemical cross-linking.

Significant enhancement in mechanical stiffness (10-200%) and fracture strength (approximately 50%) of graphene oxide paper, a novel paperlike material made from individual graphene oxide sheets, can be achieved upon modification with a small amount (less than 1 wt %) of Mg(2+) and Ca(2+). These results can be readily rationalized in terms of the chemical interactions between the functional groups of the graphene oxide sheets and the divalent metals ions. While oxygen functional groups on the basal planes of the sheets and the carboxylate groups on the edges can both bond to Mg(2+) and Ca(2+), the main contribution to mechanical enhancement of the paper comes from the latter.

Nonadiabatic dynamics in the photodissociation of ICH2CN at 266 and 304 nm studied by the velocity map imaging.

Photodissociation dynamics of iodoacetonitrile (ICH2CN) have been investigated at pump wavelengths of 266 and 304 nm using a photofragment ion image velocity mapping technique. At both wavelengths, the prompt C-I bond rupture takes place on the repulsive excited states to give I(2P3/2) and I*(2P1/2), and their speed and spatial distributions are simultaneously measured. The recoil anisotropy parameter (beta) at 266 nm is determined to be 1.10 and 1.60 for I and I*, respectively, while it is found to be much higher at 304 nm to give beta=1.70 and 1.90 for I and I*, respectively. The branching ratios for I*I channels are measured to be 0.724 and 0.136 at 266 and 304 nm, respectively, giving insights on nonadiabatic transition phenomena and relative oscillator strengths of optically accessible transitions of ICH2CN. Accordingly, relative oscillator strengths of parallel/perpendicular transitions and nonadiabatic transitions among the excited states are quantitatively characterized. A large portion of the available energy (41%-48%) goes into the internal energy of the CH2CN fragment. A modified impulsive model in which the CH2CN fragment is assumed to be rigid predicts the energy disposal quite well. Delocalization of an unpaired electron of the CH2CN radical during the C-I bond cleavage, leading to a large structural change of the CH2CN moiety, may be responsible for internally hot fragments.

The dynamics of Br(2Pj) formation in the photodissociation of vinyl and perfluorovinyl bromides.

The photodissociation dynamics of vinyl bromide and perfluorovinyl bromide have been investigated at 234 nm using a photofragment ion imaging technique coupled with a state-selective [2+1] resonance-enhanced multiphoton ionization scheme. The nascent Br atoms stem from the primary C-Br bond dissociation leading to the formation of C2H3(X) and Br(2Pj;j=1/2,3/2). The obtained translational energy distributions have been well fitted by a single Boltzmann and three Gaussian functions. Boltzmann component has not been observed in the perfluorovinyl bromide. The repulsive 3A'(n,sigma *) state has been considered as the origin of the highest Gaussian components. Middle translational energy components with Gaussian shapes are produced from the 1A"(pi,sigma*) and/or 3A"(pi,sigma*) which are very close in energy. Low-energy Gaussian components are produced via predissociation from the 3A'(pi,pi*) state. The assignments have also been supported by the recoil anisotropy corresponding to the individual components. It is suggested that intersystem crossing from the triplet states to the ground state has been attributed to the Boltzmann component and the fluorination reduces the probability of this electronic relaxation process.