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We present the performance of a feedforward noise canceller (FNC) for the PR1 [(1+D)] channel combined with an 8/10 DC free code. It appears the PR1 channel can he superior to PR4 [(1-D)(1+D)] and EPR4 [(1-D)[(1+D).sup.2]] for high density magnetic recording due to a characteristic of high frequency suppression. Simulation results show that PR1 with FNC is better than EPR4 for K[greater than or equal to] 2.5 [K=[PW.sub.50/T]. We adapted PR1 with FNC into an actual DDS3 (Digital Data Storage 3) system and we got an improved result. Applying FNC to DDS3 system can improve the error rate by around [10.sup.2].

Graphene oxide (GO)-the oxidized form of graphene-is actively studied in various fields, such as energy, electronic devices, separation of water, materials engineering, and medical technologies, owing to its fascinating physicochemical properties. One major drawback of GO is its instability, which leads to the difficulties in product management. A physicochemical understanding of the ever-changing nature of GO can remove the barrier for its growing applications. Here, we evidencde the presence of intrinsic, metastable and transient GO states upon ripening. The three GO states are identified using a [Formula: see text] transition peak of ultraviolet-visible absorption spectra and exhibit inherent magnetic and electrical properties. The presence of three states of GO is supported by the compositional changes of oxygen functional groups detected via X-ray photoelectron spectroscopy and structural information from X-ray diffraction analysis and transmission electron microscopy. Although intrinsic GO having a [Formula: see text] transition at 230.5 ± 0.5 nm is stable only for 5 days at 298 K, the intrinsic state can be stabilized by either storing GO dispersions below 255 K or by adding ammonium peroxydisulfate., (© 2024. The Author(s).)

We present herein that carbon nanospaces are the key reaction space to improve the reversibility of the reaction of SnO 2 with Li-ions for lithium-ion batteries, demonstrated by both ex situ and in situ observations using high-resolution scanning transmission electron microscopy with electron energy loss spectroscopy. Conversion-type electrode materials, such as SnO 2 , undergo large volume changes and phase separation during the charge-discharge process, which lead to degradation in the battery performance. By confining the SnO 2 -Li reaction within carbon nanopores, the battery performance is improved. However, the exact phase changes of SnO 2 in the nanospaces are unclear. By directly observing the electrodes during the charge-discharge process, the carbon walls are capable of preventing the expansion of SnO 2 particles and minimizing the conversion-induced phase separation of Sn and Li 2 O on the sub-nanometer scale. Thus, nanoconfinement structures can effectively improve the reversibility performance of conversion-type electrode materials.

Standard clinical care of neonates and the ventilation status of human patients affected with coronavirus disease involves continuous CO 2 monitoring. However, existing noninvasive methods are inadequate owing to the rigidity of hard-wired devices, insubstantial gas permeability and high operating temperature. Here, we report a cost-effective transcutaneous CO 2 sensing device comprising elastomeric sponges impregnated with oxidized single-walled carbon nanotubes (oxSWCNTs)-based composites. The proposed device features a highly selective CO 2 sensing response (detection limit 155 ± 15 ppb), excellent permeability and reliability under a large deformation. A follow-up prospective study not only offers measurement equivalency to existing clinical standards of CO 2 monitoring but also provides important additional features. This new modality allowed for skin-to-skin care in neonates and room-temperature CO 2 monitoring as compared with clinical standard monitoring system operating at high temperature to substantially enhance the quality for futuristic applications., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 Elsevier B.V. All rights reserved.)

Plants and fungi classified as herbs are utilized for the maintenance of health in humans. In this study, to evaluate the beneficial effects of herbs, we investigated the phenolic content and antioxidative activity of 20 samples. Some herbs, including Cistanche herb, had high phenol levels and exhibited high activities for radical-scavenging and suppression of lipid peroxidation. Phenolic contents and antioxidative activities showed a high positive correlation. In contrast, some herbal medicines with low phenolic content exhibited high suppressive effects on lipid peroxidation, and it was thought that carotenoids contributed to their suppression. The results of this study are expected to support the clarification of the mechanism of herbal medicines in promoting wellness.

Perilla oil is a valuable food source of α-linolenic acids. However, its high reactivity with oxygen shortens its shelf-life after opening. This study investigated the antioxidative profiles of 15 plant materials, including herbs, and examined methods to suppress the oxidation of perilla oil using these plant materials. These plant materials had wide ranges of phenolic, carotenoid, and chlorophyll contents. They exhibit radical scavenging activities and suppress lipid peroxidation, which show highly positive correlations with the phenolic contents. Dipping most of the plant materials examined in perilla oil suppressed its oxidation, and the peroxide values of the oil mixtures indicated a negative correlation with the carotenoid and chlorophyll contents of the plant materials. The leaves of Angelica, Astragalus, and Thyme herbs exhibited the same effect as that of ascorbyl palmitate, which was used as a positive control after 8 wk of incubation in the dark. The suppression of lipid peroxidation was found to be related to the herbal contents of carotenoids and chlorophylls, rather than phenols. Hence, herbal leaves can suppress the oxidation of perilla oil in the dark. The oxidation of n-3 polyunsaturated fatty acids could be suppressed effectively by utilizing plant materials with abundant carotenoids and chlorophylls.

Large scale development of the 2D transition metal di-chalcogenides (TMDC) relies on landmark improvement in performance, which could emerge from nanostructuration. Using p-WS 2 nanoflakes with different degrees of exfoliation and fracturing, perspectives were provided to develop high-surface-area 2D p-WS 2 films for the photocatalytic hydrogen generation. The critical role of inter-nanoflakes contacts within high-surface-area 2D films was demonstrated, highlighting the benefit of plane/plane versus edge/plane contacts. Evidence of the high density of surface states displayed by these 2D films was provided through electrochemical measurements. In addition to operating as recombination centers, the surface states were shown to give rise to deleterious Fermi-level pinning (FLP), which dramatically decreased the efficiency of charge carrier separation. Lastly, promising strategies yielding FLP suppression via surface states modification were proposed. In particular, use of a multifunctional ultrathin film displaying healing, catalytic, and n-type semiconduction properties was shown to greatly enhance charge carrier separation and transport to the photo-electrode/electrolyte interface. When the 2D photoelectrodes were fabricated with the above prerequisites (i. e., a high proportion of plane/plane contacts and a successful surface states chemical modification), a photocurrent up to 4.5 mA cm -2 was achieved for the first time on 2D p-WS 2 photocathodes for hydrogen generation., (© 2022 Wiley-VCH GmbH.)

Robot-assisted gait training using a voluntary-driven wearable cyborg, Hybrid Assistive Limb (HAL), has been shown to improve the mobility of patients with neurological disorders; however, its effect on the quality of life (QOL) of patients is not clear. The aim of this study was to assess the effects of HAL-assisted gait training on QOL and mobility in patients with neuromuscular diseases (NMDs). Ten patients with NMDs (seven men and three women, mean age: 57 ± 11 years), with impairment in mobility but could walk alone with aids underwent two courses of gait training with HAL over 6 months, and the single course consisted of nine sessions of training for 4 weeks. We compared the findings of the 2 min walk test, 10 m walk test, the Short Form-36 (SF-36) questionnaire, and the Hospital Anxiety and Depression Scale at baseline, after the 1st training, before the 2nd training, and after the 2nd training using the Friedman test. A significant improvement was observed in the 2 min walking distance from baseline (93 ± 50 m) to after the 2nd training (115 ± 48 m, P = 0.034), as well as in the domains of vitality (P = 0.019) and mental component summary score (P = 0.019) of SF-36. The improvement in 10 m walking speed was significantly correlated with that in the physical functioning (R = 0.831, P = 0.003) and role physical (R = 0.697, P = 0.025) domains in the SF-36. Our findings suggest that HAL-assisted gait training is effective in improving QOL associated with mental health as well as gait ability in selected patients with NMDs., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

In this study, porous boron nitride (p-BN) with hexagonal phase boron nitride (h-BN) pore walls was synthesized using high-temperature calcination. Negligible variation in pore-wall structure can be observed in powder X-ray diffraction (XRD) profiles and infrared (IR) spectra. However, a highly stable p-BN with a stable pore structure even at 973 K under the oxidative conditions is obtained when synthesized at higher than 1573 K under nitrogen gas flow. For p-BN, this stability is obtained by generating h-BN microcrystals. Nitrogen adsorption-desorption isotherms at 77 K provide type-IV features and typical adsorption-desorption hysteresis, which suggests micropore and mesopore formation. Moreover, adsorption-desorption isotherms of Ar at 87 K are measured and compared with those of nitrogen. The relative adsorbed amount of nitrogen ( i.e. , the amount of nitrogen normalized by that of Ar at each relative pressure or adsorption potential value) on p-BN is considerably larger than that on microporous carbon at low-pressure regions, which suggests the existence of strong adsorption sites on the p-BN surface. In fact, the relative number of adsorbed nitrogen molecules to that of Ar on p-BN is, at most, 150%-200% larger than that on microporous carbon for the same adsorption potential state. Furthermore, additional adsorption enhancement to nitrogen between P / P 0 = 10 -5 can be observed for p-BN treated at 1673 K, which suggests the uniformly adsorbed layer formation of nitrogen molecules in the vicinity of a basal planar surface. Thus, unlike typical nanoporous sp -3 can be observed for p-BN treated at 1673 K, which suggests the uniformly adsorbed layer formation of nitrogen molecules in the vicinity of a basal planar surface. Thus, unlike typical nanoporous sp 2 carbons, p-BN materials have the potential to enhance adsorption for certain gas species because of their unique surface state., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The conventional approach for fabricating all-solid-state batteries has required a highly dense layer of electrode and electrolyte. Their close contact interface is not suitable for alloy- or conversion-based active materials because their large volume change in lithiation/delithiation reactions causes a collapse of the contact interface or reaction limitations under mechanical constriction. In this study, we propose that a SnO 2 -embedded porous carbon electrode shows high cyclability and high capacity even at high constraint pressure owing to the nanopores, which work as a buffer space for the large volume change accompanied with SnO 2 -Sn conversion reaction and Sn-Li alloying-dealloying reaction. A detailed investigation between structural parameters of the electrode material and charge-discharge properties revealed Li ion conduction in carbon nanopores from a solid electrolyte located outside as well as the optimal conditions to yield high performance. SnO 2 -loading (75 wt %) in carbon nanopores, which provides the buffer space corresponding to the inevitable volume expansion by full lithiation, brought out an excellent performance at room temperature superior to that in an organic liquid electrolyte system: a high capacity of 1023 mAh/g-SnO 2 at 50 mA/g, high capacity retention of 97% at 300th cycle at 300 mA/g, and high rate capability with over 75% capacity retention at 1000 against 50 mA/g, whose values are also superior to the system using the organic liquid electrolyte.

Isosteric heat of adsorption is exquisitely sensitive to structural changes in carbon surfaces based on the energetic behavior of the interactions between adsorbates and carbon materials. We discuss the relationships between porous structures, oxygen functional groups, and heat of adsorption based on the behavior of the heat of adsorption of polar and non-polar fluids on porous carbon materials with oxygen functional groups. The porosity and functional groups of porous carbon materials were estimated from N 2 adsorption isotherms at 77 K and temperature-programmed desorption. High-resolution adsorption isotherms of water, acetonitrile (polar fluid), and n-hexane (non-polar fluid) were measured on porous carbon materials with different pore size distributions and amounts of oxygen functional groups at various temperatures. The heats of adsorption were determined by applying the Clausius-Clapeyron equation to the adsorption isotherms. The heat of adsorption curves directly reflect the effects of interactions of fluid-oxygen functional groups, fluid-basal planes of pore walls, and fluid-fluid interfaces. In particular, the heat of adsorption curve of water is very sensitive to surface oxygen functional groups. This finding indicates the possibility of estimating the relative amounts of oxygen functional groups on porous carbon materials based on the amounts of water adsorbed at specific relative pressures., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Extensive research efforts are devoted to development of high performance all-solid-state lithium ion batteries owing to their potential in not only improving safety but also achieving high stability and high capacity. However, conventional approaches based on a fabrication of highly dense electrode and solid electrolyte layers and their close contact interface is not always applicable to high capacity alloy- and/or conversion-based active materials such as SnO 2 accompanied with large volume change in charging-discharging. The present work demonstrates that SnO 2 -embedded nanoporous carbons without solid electrolyte inside the nanopores are a promising candidate for high capacity and stable anode material of all-solid-state battery, in which the volume change reactions are restricted in the nanopores to keep the constant electrode volume. A prototype all-solid-state full cell consisting of the SnO 2 -based anode and a LiNi 1/3 Co 1 / 3 Mn 1/3 O 2 -based cathode shows a good performance of 2040 Wh/kg at 268.6 W/kg based on the anode material weight.

Fabrication of nanographene shows a promising route for production of designed porous carbons, which is indispensable for highly efficient molecular separation and energy storage applications. This process requires a better understanding of the mechanical properties of nanographene in their aggregated structure. We studied the structural and mechanical properties of nanographene monoliths compressed at 43 MPa over different times from 3 to 25 h. While in monoliths compressed over shorter time adsorption isotherms of Ar at 87 K or N 2 at 77 K exhibited a prominent hysteresis due to presence of predominant mesopores, compression for long time induces a low pressure hysteresis. On the other hand, compression for 25 h increases the microporosity evaluated by Ar adsorption, not by N 2 adsorption, indicating that 25 h compression rearranges the nanographene stacking structure to produce ultramicropores that can be accessible only for Ar. TEM, X-ray diffraction, and Raman spectroscopic studies indicated that the compression for 25 h unfolds double-bent-like structures, relaxing the unstable nanographene stacked structure formed on the initial compression without nanographene sheets collapse. This behavior stems from the highly elastic nature of the nanographenes.

The detonation nanodiamonds form the aggregate having interparticle voids, giving a marked hygroscopic property. As the relationship between pore structure and water adsorption of aggregated nanodiamonds is not well understood yet, adsorption isotherms of N 2 at 77 K and of water vapor at 298 K of the well-characterized aggregated nanodiamonds were measured. HR-TEM and X-ray diffraction showed that the nanodiamonds were highly crystalline and their average crystallite size was 4.5 nm. The presence of the graphitic layers on the nanodiamond particle surface was confirmed by the EELS examination. The pore size distribution analysis showed that nanodiamonds had a few ultramicropores with predominant mesopores of 4.5 nm in average size. The water vapor adsorption isotherm of IUPAC Type V indicates the hydrophobicity of the nanodiamond aggregates, with the presence of hydrophilic sites. Then the hygroscopic nature of nanodiamonds should be associated with the surface functionalities of the graphitic shell and the ultramicropores on the mesopore walls.

Thus far, nobody has successfully obtained the accurate information on the properties of the adsorbed phases of gases or vapors formed inside a cylindrical micropore of single-walled carbon nanotube (SWCNT) itself based on the experimental procedure. In this work, we succeeded in analyzing experimentally the properties of adsorbed nitrogen and water confined in the inner pore of SWCNT itself by opening the pore composed of close-ended SWCNT without any changes in the surface state and also by applying the unique method for characterization; both the amounts, as well as properties, of surface functional groups and the bundle structure are the same even after the treatments for introducing an open-ended structure to a close-ended one. As a result, the average pore sizes, as well as characteristic adsorption behavior, on the two types of sample were available from the analysis of respective difference adsorption isotherms of nitrogen measured at 77 K between the adsorbed amounts on the open-ended SWCNT and that on the close-ended one. The evaluated pore sizes well coincide with the results estimated by Raman data. These results strongly support that we could analyze the adsorbed phases formed only in the inner pore of SWCNTs by applying the present method. Furthermore, we could analyze the adsorbed phase of water formed inside the cylindrical micropore of SWCNTs, showing the difference in the densities of adsorbed water depending on the pore sizes from the value of bulk water; the densities of the adsorbed water were evaluated to be 0.62 and 0.71 g mL(-1) for SWCNTs having average pore sizes of 1.3 and 1.7 nm, respectively, which were in harmony with those obtained by the theoretical calculations reported by other researchers. The proposed analysis method makes it possible to recognize the focused states of the adsorbed water formed inside the cylindrical micropore of SWCNT more precisely and correctly. The method proposed will shed light on the discussion related to the detailed nature of various adsorbed gases into SWCNT, to the detailed role of adsorbed species formed inside pore in various phenomena, and to the designing the useful materials based on the gained knowledge.

Almost perfect embedding of SnO2 nanocrystallites in carbon nanopores was achieved by in situ synthesis using vaporized SnCl2 and silica opal-derived nanoporous carbons. The reversibility of SnO2-Sn conversion and Sn-Li alloying/de-alloying reactions was greatly enhanced by the confinement in regulated carbon nanospace.

Nanoparticles of copper(I) oxide (cuprous oxide; Cu2O) were able to be synthesized from nano-restricted copper acetate (Cu(OAc)2) in micropores of single-wall carbon nanotubes (SWNTs) by visible-light photoreduction. The specific structure of confined Cu(OAc)2 in the micropore is indispensable for the reduction process to Cu2O by the irradiation, because, in general, aqueous solution of Cu(OAc)2 can be reduced under UV-light irradiated conditions. The present results strongly suggest that the micropore of SWNTs whose pore width is in the micropore-size range can play as nanoreactor space for the synthesis of Cu2O through the nano-restricted precursor whose reactivity is different from that in the bulk phase., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Carbon electrodes with specific microporous structures are strongly desired to improve the performance of electric double-layer capacitors (EDLCs). We report solvated states of Li ions in confined carbon micropores affecting specific capacitance. The average Li(+) solvation number of 1 M LiClO4/propylene carbonate (PC) electrolyte introduced into porous carbon electrodes was determined using Raman spectroscopy and (7)Li NMR. Micropores with slightly larger pore size against the solvated molecules and the narrow two-dimensional spaces decreased the solvation number, enhancing specific capacitance. Hence, specific carbon morphology may be related to high EDL capacitance, and micropore structure is important in obtaining highly capacitive EDLC materials.

Homogeneous nanocomposites of nanocrystalline Li2MnSiO4 and carbon as well as a carbon nanotubes-embedded nanocomposite are synthesized directly by a novel method using organic-inorganic hybrid polymers which consist of covalently bonded phenolic oligomer and siloxane parts. The nanocomposites show superior charge-discharge performance at room temperature in spite of low carbon contents.

We shed light on the specific hydration structure around a zinc ion of nanosolution restricted in a cylindrical micropore of single-wall carbon nanotube (SWNT) by comparison with the structure restricted in a cylindrical mesopore of multi-wall carbon nanotube (MWNT) and that of bulk aqueous solution. The average micropore width of open-pore SWNT was 0.87 nm which is equivalent to the size of a hydrated zinc ion having 6-hydrated water molecules. We could impregnate the zinc ions into the micropore of SWNT with negligible amounts of ion-exchanged species on surface functional groups by the appropriate oxidation followed by heat treatment under an inert condition. The results of X-ray absorption fine structure (XAFS) spectra confirmed that the proportion of dissolved species in nanospaces against the total adsorbed amounts of zinc ions on the open-pore SWNT and MWNT were 44 and 61%, respectively, indicating the formation of a dehydrated structure in narrower nanospaces. The structure parameters obtained by the analysis of XAFS spectra also indicate that the dehydrated and highly compressed hydration structure can be stably formed inside the cylindrical micropore of SWNT where the structure is different from that inside the slit-shaped micropore whose pore width is less than 1 nm. Such a unique structure needs not only a narrow micropore geometry which is equivalent to the size of a hydrated ion but also the cylindrical nature of the pore.

Despite extensive research for more than 200 years, the experimental isolation of monatomic sulphur chains, which are believed to exhibit a conducting character, has eluded scientists. Here we report the synthesis of a previously unobserved composite material of elemental sulphur, consisting of monatomic chains stabilized in the constraining volume of a carbon nanotube. This one-dimensional phase is confirmed by high-resolution transmission electron microscopy and synchrotron X-ray diffraction. Interestingly, these one-dimensional sulphur chains exhibit long domain sizes of up to 160 nm and high thermal stability (~800 K). Synchrotron X-ray diffraction shows a sharp structural transition of the one-dimensional sulphur occurring at ~450-650 K. Our observations, and corresponding electronic structure and quantum transport calculations, indicate the conducting character of the one-dimensional sulphur chains under ambient pressure. This is in stark contrast to bulk sulphur that needs ultrahigh pressures exceeding ~90 GPa to become metallic.

For the practical use of activated carbon (AC) as an adsorbent of CH(4) , tightly packed monoliths with high microporosity are supposed to be one of the best morphologies in terms of storage capacity per apparent volume of the adsorbent material. However, monolith-type ACs may cause diffusion obstacles in adsorption processes owing to their necked pore structures among the densely packed particles, which result in a lower adsorption performance than that of the corresponding powder ACs. To clarify the relationship between the pore structure and CH₄ adsorptivity, microscopic observations, structural studies on the nanoscale, and conductivity measurements (thermal and electrical) were performed on recently developed binder-free, self-sinterable ACs in both powder and monolithic forms. The monolith samples exhibited higher surface areas and electrical conductivities than the corresponding powder samples. Supercritical CH₄ adsorption isotherms were measured for each powder and monolith sample at up to 7 MPa at 263, 273, and 303 K to elucidate their isosteric heats of adsorption and adsorption rate constants, which revealed that the morphologies of the monolith samples did not cause serious drawbacks for the adsorption and desorption processes. This will further facilitate the availability of diffusion-barrier-free microporous carbon monoliths as practical CH₄ storage adsorbents., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We introduce a way to selectively probe local vibration modes at nanostructured asperities such as tips of carbon nanohorns. Our observations benefit from signal amplification in surface-enhanced Raman scattering (SERS) at sites near a silver surface. We observe nanohorn tip vibration modes in the range 200-500 cm(-1), which are obscured in regular Raman spectra. Ab initio density functional calculations assign modes in this frequency range to local vibrations at the nanohorn cap resembling the radial breathing mode of fullerenes. Careful interpretation of our SERS spectra indicates presence of caps with 5 or 6 pentagons, which are chemically the most active sites. Changes in the peak intensities and frequencies with time indicate that exposure to laser irradiation may cause structural rearrangements at the cap., (© 2012 American Institute of Physics)

An outstanding compression function for materials preparation exhibited by nanospaces of single-walled carbon nanohorns (SWCNHs) was studied using the B1-to-B2 solid phase transition of KI crystals at 1.9 GPa. High-resolution transmission electron microscopy and synchrotron X-ray diffraction examinations provided evidence that KI nanocrystals doped in the nanotube spaces of SWCNHs at pressures below 0.1 MPa had the super-high-pressure B2 phase structure, which is induced at pressures above 1.9 GPa in bulk KI crystals. This finding of the supercompression function of the carbon nanotubular spaces can lead to the development of a new compression-free route to precious materials whose syntheses require the application of high pressure.

Incubation of a cell-sized lipid membrane vesicle (giant vesicle, GV) in a diluted aqueous solution of neutral phosphate buffer salts or glucose transformed the GV to an oligovesicular vesicle (OVV) that encapsulates one or more smaller GVs. During the incubation, the membrane of flaccid vesicle invaginated and closed to form the inner vesicle of an OVV engulfing a part of the bulk aqueous phase. Using the GV-to-OVV transformation, an OVV that has different aqueous contents in each membranous microcompartment was constructed.

Vibrational-rotational properties of CH(4) adsorbed on the nanopores of single-wall carbon nanohorns (SWCNHs) at 105-140 K were investigated using IR spectroscopy. The difference vibrational-rotational bands of the ν(3) and ν(4) modes below 130 K show suppression of the P and R branches, while the Q branches remain. The widths of the Q branches are much narrower than in the bulk gas phase due to suppression of the Doppler effect. These results indicate that the rotation of CH(4) confined in the nanospaces of SWCNHs is highly restricted, resulting in a rigid assembly structure, which is an anomaly in contrast to that in the bulk liquid phase.

The quantum sieving effect of D(2) over H(2) is examined at 40 and 77 K by means of experiments and GCMC simulations, for two types of single-wall carbon nanotubes that are distinguishable by their unique entangled structures; (1) a well-bundled SWCNT and (2) loosely-assembled SWCNT produced by the super growth method (SG-SWCNT). Oxidized SWCNT samples of which the so-called internal sites are accessible for H(2) and D(2), are also studied. Experimental H(2) and D(2) adsorption properties on the well-bundled SWCNTs are compared with the simulated ones, revealing that pore-blocking and restricted diffusion of the molecules suppress the high selectivity of D(2) over H(2). The non-oxidized SG-SWCNT assembly shows the highest selectivity among the SWCNT samples, both at 40 and 77 K. The high selectivity of the SG-SWCNT assembly, which is pronounced even at 77 K, is ascribed to their unique assembly structure.

Surface-enhanced Raman scattering (SERS) was applied to detecting pentagon-heptagon pairs, the so-called Stone-Wales defect, in single-wall carbon nanotubes (SWCNTs). When a probing laser light was scanned over a SWCNT-dispersed silver surface, two distinct SERS spectra were obtained: (1) temporally stable spectra similar to that of resonance Raman spectra of bulk SWCNTs and (2) temporally fluctuating spectra with additional peaks which were not observed in the non-SERS spectra. The fluctuations in the SERS spectra are discussed in association with dynamic reconstruction of defective structures of SWCNTs (nonhexagonal arrangements of carbon atoms) in the vicinity of SERS-active sites under irradiation of the laser light.

The effect of addition of tetraethylammonium tetrafluoroborate (Et(4)NBF(4)) on the structure of propylene carbonate (PC) confined in slit-shaped carbon nanopores of activated carbon fiber (pore width = 1.0 nm) was studied by synchrotron X-ray diffraction and reverse Monte Carlo simulation. PC molecules are randomly packed in the slit carbon nanopores of 1 nm in the absence of Et(4)NBF(4). Addition of Et(4)N(+) and BF(4)(-) ions promotes formation of considerably ordered double layers of PC molecules even in the highly restricted slit pore space. PC molecules can accept these ions efficiently. This structural modulation function of PC molecular assemblies should contribute to the evolution of supercapacitance in carbon nanopores.

Single-wall carbon nanotube (SWCNT) bundles were pillared by fullerene (C60) by the cosonication of C60 and SWCNT in toluene to utilize the interstitial pores for hydrogen storage. C60-pillared SWCNTs were confirmed by the shift in the X-ray diffraction peak and the expanded hexagonal and distorted tetragonal bundles revealed by high-resolution transmission electron microscopy. The H2 adsorptivity of the C60-pillared SWCNT bundles was twice that of the original SWCNT bundles, indicating a design route for SWCNT hydrogen storage.

It is important to study the interaction between water molecules and a host structure for understanding the adsorption mechanism of metal-organic framework (MOF) materials. The evolution of the structure of a flexible Cu-MOF, {[Cu(bpy)(H2O)2(BF4)2](bpy)} (bpy=4,4'-bipyridine), upon dehydration and rehydration was studied by thermogravimetric analysis (TGA), infrared (IR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and water adsorption. A nearly reversible structural change was observed upon rehydration. More importantly, a unique CO2 "gate adsorption" phenomenon was observed despite the exposure of the Cu-MOF to water. This shows that the Cu-MOF has relatively good stability after exposure to water.

I2 was adsorbed on single-walled carbon nanotube from ethanol solution at 303 K. The I2 adsorption isotherm was Langmuirian, giving 35 (+/-10) mg g(-1) of the saturated adsorption amount (coverage 0.06-0.09). The I2-adsorption treatment of SWCNT bundles reduced the N2 adsorption amount at 77 K by only 3%; the adsorption amount of supercritical H2 at 77 K was decreased by 30% because of the I2-adsorption treatment, indicating the blocking of interstitial pores by adsorbed I2. These adsorption results indicated the adsorption of I2 molecules in the narrow interstitial pores. The I2-adsorption treatment increases the Raman intensity coming from metallic SWCNTs, and the dc electrical conductivity increased by 15% because of the I2-adsorption treatment, strongly suggesting the presence of charge-transfer interaction between I2 and SWCNTs irrespective of small coverage by I2.

The nanoporosities and catalytic activities of Pd nanoparticles dispersed on single wall carbon nanohorns (Pd-SWCNHs) and oxidized single wall carbon nanohorns (Pd-ox-SWCNHs) were examined. A transmission electron microscopy (TEM) observation indicated that Pd nanoparticles of 2-3 nm size were highly dispersed on both the SWCNHs. X-ray photoelectron spectra and N2 adsorption isotherms at 77 K illustrated the differences in the deposition process mechanisms of the Pd-SWCNHs and Pd-ox-SWCNHs; the deposition process depended on the surface functional groups. The supercritical H2 adsorption isotherms at 77 K suggested the relationships between the interaction of Pd-SWCNHs and Pd-ox-SWCNHs with H2 and the catalytic activities for a water formation reaction in a gas phase at 273 or 298 K. The catalytic activity measurement and TEM observation of the catalysts after the reactions demonstrated that the Pd-SWCNHs and Pd-ox-SWCNHs are promising catalysts.

Metal-atom migration outside from a defective fullerene cage of a metallofullerene Gd@C(82) (Ca@C(82)), where the Gd(3+) (Ca(2+)) ion is incorporated inside the C(2)(v)()-C(82) cage, is discussed in detail at the B3LYP DFT level of theory. The metal-atom migrations are initiated by the formation of vacancy-type defects involving two coordinatively unsaturated C atoms. This step, which is assumed to proceed due to energy-particle irradiation, leads to the formation of antibonding orbitals between the two C atoms. Since the antibonding orbitals can interact with vacant d-orbitals of the Gd(3)(+)() ion in an in-phase fashion, the attractive interactions allow the Gd ion to insert into the two C atoms in the defect. As a result, the metal ion passes through the defect under energy-particle irradiation. In contrast, the Ca(2+) ion with the vacant s-orbitals does not have such orbital interactions, and thus, a C-C bond is reformed between the two C atoms, which prohibits the Ca ion from penetrating the defected C(82) cage. DFT calculations nicely demonstrate that the orbital interactions control metal-atom migration around the defect site using their orbital symmetries, and therefore, the vacancy-type defect acts as a "gate" that permits a specific atom to go out from a defected fullerene cage.