Qualitative Analysis of Nitrogen and Sulfur Compounds in Vacuum Gas Oils via Matrix-Assisted Laser Desorption Ionization Time of Flight Mass Spectrometry.

Analysis of the heavy fractions in crude oil has been important in petroleum industries. It is well known that heavy fractions such as vacuum gas oils (VGOs) include heteroatoms, of which sulfur and nitrogen are often characterized in many cases. We conducted research regarding the molecular species analysis of VGOs. Further refine processes using VGOs are becoming important when considering carbon recycling. In this work, we attempted to classify compounds within VGOs provided by Kuwait Institute for Scientific Research. Two VGOs were priorly distillated from Kuwait Export crude and Lower Fars crude. Quantitative analysis was performed mainly using matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOFMS). MALDI-TOF-MS has been developed for analyzing high-molecular-weight compounds such as polymer and biopolymers. As matrix selection is one of the most important aspects in MALDI-TOFMS, the careful selection of a matrix was firstly evaluated, followed by analysis using a Kendrick plot with nominal mass series (z*). The objective was to evaluate if this work could provide an effective classification of VGOs compounds. The Kendrick plot is a well-known method for processing mass data. The difference in the Kendrick mass defect (KMD) between CnH2n-14S and CnH2n-20O is only 0.0005 mass units, which makes it difficult in general to distinguish these compounds. However, since the z* value showed effective differences during the classification of these compounds, qualitative analysis could be possible. The analysis using nominal mass series showed the potential to be used as an effective method in analyzing heavy fractions.

Evolution of Phosphorus-Containing Groups on Activated Carbons during Heat Treatment.

Two types of activated carbons have been prepared by H3PO4 activation of lignocellulose and by H3PO4 modification of activated carbon, and then heat-treated at temperatures from 400 to 900 °C in an atmosphere of N2 or H2 to investigate the evolution of phosphorus-containing groups. Elemental analysis, X-ray photoelectron spectroscopy, 31P nuclear magnetic resonance, nitrogen adsorption, and scanning electron microscopy have been used to analyze the physicochemical properties of the activated carbons. The results show that C-O-P linkages of phosphorus-containing groups can progressively evolve into C-P-O, C3-P═O, C3-P, and eventually elemental phosphorus as a result of heat treatment. Phosphate-like groups are much more thermally stable in an N2 than in an H2 atmosphere. In N2, C-O-P linkages significantly evolve into C-P-O and C3-P═O at up to 800 °C, whereas C3-P linkages are not formed even at 900 °C. In H2, the corresponding evolution remarkably occurs at 500 °C, forming C3-P linkages and eventually elemental phosphorus. Moreover, the two activated carbons exhibit different evolution trends, suggesting that the evolution happens more easily for phosphorus-containing groups located on the edges of graphite-like crystallites than those in the lattice. Finally, we propose different evolution pathways of phosphorus-containing groups upon heat treatment in N2 and H2 atmospheres.

Fast Water Relaxation through One-Dimensional Channels by Rapid Energy Transfer.

Water in carbon nanotubes is surrounded by hydrophobic carbon surfaces and shows anomalous structural and fast transport properties. However, the dynamics of water in hydrophobic nanospaces is only phenomenologically understood. In this study, water dynamics in hydrophobic carbon nanotubes is evaluated based on water relaxation using nuclear magnetic resonance spectroscopy and molecular dynamics simulations. Extremely fast relaxation (0.001 s) of water confined in carbon nanotubes of 1 nm in diameter on average is observed; the relaxation times of water confined in carbon nanotubes with an average diameter of 2 nm (0.40 s) is similar to that of bulk water (0.44 s). The extremely fast relaxation time of water confined in carbon nanotubes with an average diameter of 1 nm is a result of frequent energy transfer between water and carbon surfaces. Water relaxation in carbon nanotubes of average diameter 2 nm is slow because of the limited number of collisions between water molecules. The dynamics of interfacial water can therefore be controlled by varying the size of the hydrophobic nanospace.

Formation of single-layered Pt islands on Au(111) using irreversible adsorption of Pt and selective adsorption of CO to Pt.

This communication compares two different multiple deposition routes of Pt on Au(111), using irreversible adsorption of Pt precursor ions and selective adsorption of CO. A scanning tunneling microscopy study revealed that the conventional route, not utilizing CO, produced multiple-layered Pt cluster islands, while the CO route, employing CO, formed single-layered Pt islands exclusively. The role of CO selectively adsorbed on pre-existing Pt islands was to prevent additional irreversible adsorption of Pt precursor ions onto Pt islands. Cyclic voltammetric works disclosed that the CO and hydrogen coverages on single-layered Pt islands were higher than those on multiple-layered ones, and that the Pt islands on Au were more effective in adsorbing CO than hydrogen.

Effective Removal of Acetaldehyde Using Piperazine/Nitric Acid Co-Impregnated Bead-Type Activated Carbon.

Acetaldehyde (CH3CHO) in the atmosphere is associated with adverse health effects. Among the various options for use in removing CH3CHO, adsorption is often employed because of its convenient application and economical processes, particularly when using activated carbon. In previous studies, the surface of activated carbon has been modified with amines to remove CH3CHO from the atmosphere via adsorption. However, these materials are toxic and can have harmful effects on humans when the modified activated carbon is used in air-purifier filters. Therefore, in this study, a customized bead-type activated carbon (BAC) with surface modification options via amination was evaluated for removing CH3CHO. Various amounts of non-toxic piperazine or piperazine/nitric acid were used in amination. Chemical and physical analyses of the surface-modified BAC samples were performed using Brunauer-Emmett-Teller measurements, elemental analyses, and Fourier transform infrared and X-ray photoelectron spectroscopy. The chemical structures on the surfaces of the modified BACs were analyzed in detail using X-ray absorption spectroscopy. The amine and carboxylic acid groups on the surfaces of the modified BACs are critical in CH3CHO adsorption. Notably, piperazine amination decreased the pore size and volume of the modified BAC, but piperazine/nitric acid impregnation maintained the pore size and volume of the modified BAC. In terms of CH3CHO adsorption, piperazine/nitric acid impregnation resulted in a superior performance, with greater chemical adsorption. The linkages between the amine and carboxylic acid groups may function differently in piperazine amination and piperazine/nitric acid treatment.

IVS6+5G>A found in Wiskott-Aldrich syndrome and X-linked thrombocytopenia in a Korean family.

Wiskott-Aldrich syndrome (WAS) and X-linked thrombocytopenia (XLT) are caused by a mutation in the WAS gene on Xp11.22. We report two patients with IVS6+5G>A of WAS in a Korean family. The proband presented with classic WAS, whereas his maternal cousin had symptoms limited to XLT. Their mothers were proved to be carriers. The IVS6+5G>A mutation was reported to result in incomplete splicing of the donor site and typically associated with mild form of disease, XLT. Our observation of the intrafamilial variability of clinical manifestations of WAS further expands the genotype-phenotype correlations and suggests the presence of modifying genetic factors.

Synthesis of silicon monoxide-pyrolytic carbon-carbon nanofiber composites and their hybridization with natural graphite as a means of improving the anodic performance of lithium-ion batteries.

Novel composites of silicon monoxide, pyrolytic carbon and carbon nanofiber (SiO/PyC/CNF) were hybridized with natural graphite (NG) as a means of improving the anodic performance of Li-ion batteries. Samples were made with hybridization levels of 10-30 wt% of NG exhibited excellent cyclability with a discharge capacity of 389-522 mAh g(-1) in a Li-ion battery system. SiO/PyC/CNF composite hybrids showed better cyclability than other carbon composites containing SiO/PyC and SiO/CNF. These hybridization effects were attributed to the lower contact resistance of SiO/PyC/CNF in the electrode. The internal spaces created throughout the SiO/PyC/CNF composite and their effect on material dispersion in the hybridized electrodes may have prevented electrode damage by relieving tensions induced by the expansion of SiO particles in the electrode over the course of repeated charge and discharge processes.

Structure and electrochemical applications of boron-doped graphitized carbon nanofibers.

Boron-doped graphitized carbon nanofibers (CNFs) were prepared by optimizing CNFs preparation, surface treatment, graphitization and boron-added graphitization. The interlayer spacing (d002) of the boron-doped graphitized CNFs reached 3.356 Å, similar to that of single-crystal graphite. Special platelet CNFs (PCNFs), for which d002 is less than 3.400 Å, were selected for further heat treatment. The first heat treatment of PCNFs at 2800 °C yielded a d002 between 3.357 and 3.365 Å. Successive nitric acid treatment and a second heat treatment with boric acid reduced d002 to 3.356 Å. The resulting boron-doped PCNFs exhibited a high discharge capacity of 338 mAh g⁻¹ between 0 and 0.5 V versus Li/Li⁺ and 368 mAh g⁻¹ between 0 and 1.5 V versus Li/Li⁺. The first-cycle Coulombic efficiency was also enhanced to 71-80%. Such capacity is comparable to that of natural graphite under the same charge/discharge conditions. The boron-doped PCNFs also exhibited improved rate performance with twice the capacity of boron-doped natural graphite at a discharge rate of 5 C.

Pt nanoparticle-reduced graphene oxide nanohybrid for proton exchange membrane fuel cells.

A platinum nanoparticle-reduced graphene oxide (Pt-RGO) nanohybrid for proton exchange membrane fuel cell (PEMFC) application was successfully prepared. The Pt nanoparticles (Pt NPs) were deposited onto chemically converted graphene nanosheets via ethylene glycol (EG) reduction. According to the powder X-ray diffraction (XRD) pattern and transmission electron microscopy (TEM) analysis, the face-centered cubic Pt NPs (3-5 nm in diameter) were homogeneously dispersed on the RGO nanosheets. The electrochemically active surface area and PEMFC power density of the Pt-RGO nanohybrid were determined to be 33.26 m2/g and 480 mW/cm2 (maximum values), respectively, at 75 degrees C and at a relative humidity (RH) of 100% in a single-cell test experiment.

High magnetic field solid-state NMR analyses by combining MAS, MQ-MAS, homo-nuclear and hetero-nuclear correlation experiments.

A general strategy of structural analysis of alumina silicate by combining various solid-state NMR measurements such as single pulse, multi-quantum magic angle spinning, double-quantum homo-nuclear correlation under magic angle spinning (DQ-MAS), and cross-polarization hetero-nuclear correlation (CP-HETCOR) was evaluated with the aid of high magnetic field NMR (800 MHz for (1) H Larmor frequency) by using anorthite as a model material. The high magnetic field greatly enhanced resolution of (27) Al in single pulse, DQ-MAS, and even in triple-quantum magic angle spinning NMR spectra. The spatial proximities through dipolar couplings were probed by the DQ-MAS methods for homo-nuclear correlations between both (27) Al-(27) Al and (29) Si-(29) Si and by CP-HETCOR for hetero-nuclear correlations between (27) Al-(29) Si in the anorthite framework. By combining various NMR methodologies, we elucidated detailed spatial correlations among various aluminum and silicon species in anorthite that was hard to be determined using conventional analytical methods at low magnetic field. Moreover, the presented approach is applicable to analyze other alumina-silicate minerals.

Study on the applicability of pressurized physically activated carbon as an adsorbent in adsorption heat pumps.

Activated carbon is a suitable adsorbent for adsorption heat pumps (AHPs) with ethanol refrigerants. Although chemically activated carbon with highly developed pore structures exhibits good ethanol adsorption, the associated high production costs inhibit its practical application as an AHP adsorbent. Moreover, although physical activation can produce inexpensive activated carbon, the limited pore development limits the ethanol uptake. Recently, we developed a pressurized physical activation method that can produce activated carbon with a well-developed pore structure and characteristic pore size distribution. In this study, we investigated the applicability of the pressurized physically activated carbon as an adsorbent in activated carbon-ethanol AHP systems. Because of the large number of pressurization-induced pores of appropriate size, the pressurized physically activated carbon showed effective ethanol uptake comparable with that of chemically activated carbon on a weight basis. Furthermore, on a volume basis, the pressurized physically activated carbon, with a high bulk density, showed much higher effective ethanol uptake than chemically activated carbon. These results confirm the potential of the pressurized physically activated carbon as a relatively inexpensive high-performance adsorbent for AHP systems with ethanol refrigerants.

Electrochemical catalytic activity for oxygen reduction reaction of nitrogen-doped carbon nanofibers.

The electrocatalytic activity of nitrogen-doped carbon nanofibers (N-CNFs), which are synthesized directly from vaporized acetonitrile over nickel-iron based catalysts, for oxygen reduction reaction (ORR), was investigated. The nitrogen content and specific surface area of N-CNFs can be controlled through the synthesis temperature (300-680 degrees C). The graphitization degree of N-CNFs also are significantly affected by the temperature, whereas the chemical compositions of nitrogen species are similar irrespective of the synthesis conditions. From measurement of the electrochemical double layer capacitance, the surface of N-CNFs is found to have stronger interaction with ions than undoped-carbon surfaces. Although N-CNFs show higher over-potential than Pt catalysts do, N-CNFs were observed to have a noticeable ORR activity, as opposed to the carbon samples without nitrogen doping. The activity dependency of N-CNFs on the content of the nitrogen with which they were doped is discussed, based on the experiment results. The single cell of the direct methanol fuel cell (DMFC) was tested to investigate the performance of a membrane-electrode assembly that includes N-CNFs as the cathode catalyst layer.

Preparation of Isotropic Carbon Fibers from Kerosene-Purified Coal Tar Pitch by Co-Carbonization with Pyrolysis Fuel Oil.

An inexpensive and general-purpose carbon fiber was prepared using coal tar pitch. In contrast to the solvent extraction process employing expensive solvents, a low-cost centrifugal separation method facilitated the reduction of loss due to the pitch purification and an overall yield increase. The coal tar pitch purified by centrifugation and subsequently co-carbonized with pyrolysis fuel oil improved in spinnability. Moreover, the resulting spinnable pitch had a softening point of 250 °C. The obtained carbon fibers were heat-treated at 1000 °C for 5 min, resulting in a tensile strength of approximately 1000 MPa and an average diameter of 9 µm. In this study, we present an effective method for obtaining low-cost general-purpose isotropic carbon fibers.

Preparation of nitrogen-doped graphene sheets by a combined chemical and hydrothermal reduction of graphene oxide.

Nitrogen-doped graphene sheets were prepared through a hydrothermal reduction of colloidal dispersions of graphite oxide in the presence of hydrazine and ammonia at pH of 10. The effect of hydrothermal temperature on the structure, morphology, and surface chemistry of as-prepared graphene sheets were investigated though XRD, N(2) adsorption, solid-state (13)C NMR, SEM, TEM, and XPS characterizations. Oxygen reduction and nitrogen doping were achieved simultaneously under the hydrothermal reaction. Up to 5% nitrogen-doped graphene sheets with slightly wrinkled and folded feature were obtained at the relative low hydrothermal temperature. With the increase of hydrothermal temperature, the nitrogen content decreased slightly and more pyridinic N incorporated into the graphene network. Meanwhile, a jellyfish-like graphene structure was formed by self-organization of graphene sheets at the hydrothermal temperature of 160 °C. Further increase of the temperature to 200 °C, graphene sheets could self-aggregate into agglomerate particles but still contained doping level of 4 wt % N. The unique hydrothermal environment should play an important role in the nitrogen doping and the jellyfish-like graphene formation. This simple hydrothermal method could provide the synthesis of nitrogen-doped graphene sheets in large scale for various practical applications.

Highly Chlorinated Polyvinyl Chloride as a Novel Precursor for Fibrous Carbon Material.

Pure, highly chlorinated polyvinyl chloride (CPVC), with a 63 wt % of chlorine, showed a unique-thermal-pyrolytic-phenomenon that meant it could be converted to carbon material through solid-phase carbonisation rather than liquid-phase carbonisation. The CPVC began to decompose at 270 °C, with a rapid loss in mass due to dehydrochlorination and novel aromatisation and polycondensation up to 400 °C. In this study, we attempted to prepare carbon fibre (CF) without oxidative stabilisation, using the aforementioned CPVC as a novel precursor. Through the processes of solution spinning and solid-state carbonisation, the spun CPVC fibre was directly converted to CF, with a carbonisation yield of 26.2 wt %. The CPVC-derived CF exhibited a relatively smooth surface; however, it still demonstrated a low mechanical performance. This was because the spun fibre was not stretched during the heat treatment. Tensile strength, Young's modulus and elongation values of 590 ± 84 MPa, 50 ± 8 GPa, and 1.2 ± 0.2%, respectively, were obtained from the CPVC spun fibre, with an average diameter of 19.4 µm, following carbonisation at 1600 °C for 5 min.

Chemoselective hydrogenation of nitroarenes with carbon nanofiber-supported platinum and palladium nanoparticles.

Platinum and palladium nanoparticles supported on three types of carbon nanofibers (CNFs) are synthesized and used as catalysts in the hydrogenation of nitroarenes. Nanosized platinum particles dispersed on platelet-type CNF efficiently catalyze the reduction of functionalized nitroarenes to the corresponding substituted anilines in high turnover numbers with other functional groups remaining intact.

Methanol-Tolerant Platinum-Palladium Catalyst Supported on Nitrogen-Doped Carbon Nanofiber for High Concentration Direct Methanol Fuel Cells.

Pt-Pd catalyst supported on nitrogen-doped carbon nanofiber (N-CNF) was prepared and evaluated as a cathode electrode of the direct methanol fuel cell (DMFC). The N-CNF, which was directly synthesized by the catalytic chemical vapor deposition from acetonitrile at 640 °C, was verified as having a change of electrochemical surface properties such as oxygen reduction reaction (ORR) activities and the electrochemical double layer compared with common carbon black (CB). To attain the competitive oxygen reduction reaction activity with methanol tolerance, the Pt and Pd metals were supported on the CB or the N-CNF. The physical and electrochemical characteristics of the N-CNF-supported Pt-Pd catalyst were examined and compared with catalyst supported on the CB. In addition, DMFC single cells using these catalysts as the cathode electrode were applied to obtain I-V polarization curves and constant current operating performances with high-concentration methanol as the fuel. Pt-Pd catalysts had obvious ORR activity even in the presence of methanol. The higher power density was obtained at all the methanol concentrations when it applied to the membrane electrode assembly (MEA) of the DMFC. When the N-CNF is used as the catalyst support material, a better performance with high-concentration methanol is expected.

A simple and easy home-based pulmonary rehabilitation programme for patients with chronic lung diseases.

BACKGROUND AND AIM: To develop a simple and easy home-based pulmonary rehabilitation programme and investigate its effectiveness. METHODS: Patients with stable chronic lung disease were divided into a rehabilitation group (n = 25) and a control group (n = 18). Rehabilitation consisted of education and 12 weeks of enforced aerobic and muscle-strengthening exercises. Aerobic exercise training was performed mostly by walking based on the functional capacity of the patients assessed by the maximal incremental exercise test. Patients visited hospital every two weeks for evaluation and a new exercise regimen. RESULTS: Five patients dropped out of the rehabilitation group but three were due to development of unrelated diseases, five controls did not co-operate in the second evaluation. After 12 weeks of rehabilitation, exercise capacity (maximum work load and VO2max), exercise endurance, 6-minute walking distance, and quality of life measured by the St. George Respiratory Questionnaire had significantly improved in the rehabilitation group but not in the controls. At a follow-up evaluation one year after the rehabilitation, some exercise parameters were still significantly higher than baseline in the rehabilitation group. CONCLUSIONS: We developed a simple home-based pulmonary rehabilitation programme, which seems to be clinically feasible and effective.