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In-situ powder X-ray diffraction study of AlMepO-α under varied nitrogen equilibrium pressures identifies two phases np and lp with the same space group and slightly different lattice constants and...

Topotactic pillaring of lamellar aluminophosphate (ALPO) layers with zinc cations is used to prepare microporous zincoaluminophosphate (ZnAPO) with an AFY-type framework for the first time. This approach should be promising for the preparation of metalloaluminophosphates (MeAPOs) with predicted structures containing no organic structure-directing agents (OSDAs).

Single-walled carbon nanotubes were fluorinated between 298 and 473 K using elemental F2, and their adsorption properties were investigated through N2 and CO2 adsorption measurements. Inter...

We propose a novel technique to prepare carbon fibers from cotton fibers while retaining the unique hollow structure of these natural fibers. We were able to introduce micropores and mesopores into the hollow structure by using zinc nitrate as an activating agent. We revealed that the porosity of the obtained carbon fibers and the pore size increase as the concentration of the activating agents is increased. Moreover, the obtained carbon fibers were applied in electric double-layer capacitors and found to exhibit excellent performance due to the rapid ion transport through the hollow cores and nanopores.

Porous solids have gathered much attention because of their impact on efficient separation/purification technologies. However, it is still a great challenge to separate molecules with similar physical and chemical properties using adsorbents. Flexible metal–organic frameworks (MOFs) have the potential to make a breakthrough in this technology because they can construct ordered framework structures and change their structures depending on the guest species. Here, we show the successful incorporation of “molecular gates” into one dimensional (1D) pores of a novel copper-based MOF. The MOF was formed by the stacking of bumpy 2D sheets composed of Cu(I) ions and 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) ligands. The 2D MOF had 1D channels along the stacking direction, and BF4 anions partitioned the 1D channels to form restricted nano-space. By in situ XAFS and XRD analyses, it was revealed that the molecular gates open/close the pore windows depending on the species of adsorbates retaining the framework structure through the adsorption, resulting in selective adsorption. The MOF adsorbed 1.2 mmol g−1 (273 K) and 0.9 mmol g−1 (303 K) of CO2 at 100 kPa and showed almost no N2 and H2 uptake at 300 K and 100 kPa. Furthermore, the MOF showed gas/liquid phase selective adsorption properties (e.g. methanol adsorption from a methanol/1-propanol/1-butanol ternary liquid mixture with selectivity SMeOH/1-PrOH ∼61), which were evaluated by theoretical calculations and GC experiments.

The oxygen deficiency of SnO 2 was investigated by thermogravimetric analysis (TGA). The powder samples were reduced in 0.5% H 2 /N 2 at 200–500 °C and, their weight changes were evaluated by TGA under flowing O 2 . The results showed that the response of SnO 2 against H 2 /N 2 differed from that against H 2 /air, which is the gas mixture typically used to evaluate SnO 2 -based gas sensors. The subsequently obtained TGA traces of the powders reduced under H 2 /N 2 showed two stepwise weight gains. The first weight gain began near room temperature and ended at approximately 200 °C. The second weight gain was observed between 400 and 600 °C, which became prominent when the sample was reduced at 400 °C or above. The existence of two types of oxygen sites was deduced from the temperature dependence of the weight changes in the TGA traces and they were related to the positions of oxygen sites in the surface and bulk regions. SnO 2 was tolerant to the oxygen deficiency, and the extent of deficiency was dependent on the crystallinity and the grain size. For example, the composition of SnO 2 precipitated in SnF 2 aqueous solution through a hydrolysis reaction was estimated to be SnO 1.94 after the reduction at 400 °C in 0.5% H 2 /N 2 . Small grains with lower crystallinity tended to accept greater oxygen deficiency under a certain condition.

A scaffold-hopping strategy towards a new pyrazolo[1,5- a ]pyridine based core using molecular hybridization of two structurally distinct EP 1 antagonists, followed by structure-activity relationship-guided optimization, resulted in the identification of potent EP 1 antagonists exemplified by 4c , 4f , and 4j , which were shown to reduce pathological intravesical pressure in rats when administered at 1 mg/kg iv.

Novel pyrazolo[1,5- a ]pyridine derivatives were designed, synthesized and evaluated as orally active EP 1 antagonists for the treatment of overactive bladder. Matched molecular pair analysis (MMPA) allowed the design of a new series of pyrazolo[1,5- a ]pyridine derivatives 4 – 6 . Structure-activity relationships (SAR) studies of 4 – 6 were performed, leading to identification of the nanomolar-level EP 1 antagonist 4c , which exhibited good pharmacological effect through intraduodenal (id) administration in a 17-phenyltrinor prostaglandin E2-induced bladder contraction model in rats.

Porous carbon nanosheets (PCNS) with high surface areas were prepared by thermal decomposition of polyvinyl alcohol (PVA) films impregnated with Zn 2+ and NO 3 − . Through this simple preparation method that required no additional activation processes, curved carbon nanosheets ( 2+ and NO 3 − indicated that the sheet-like structures originated from exothermic pyrolysis of NO 3 − associated with the thermal decomposition of PVA. According to the nitrogen adsorption isotherm analyses at 77 K, the PCNS had a high specific surface area (>1600 m 2 g -1 ) and bimodal pore structure consisting of micropores and mesopores. Because of their unique structural properties, the PCNS are attractive for use as electrode materials. The electrode performance of the PCNS was investigated in 1-M tetraethylammonium tetrafluoroborate ((C 2 H 5 ) 4 NBF 4 ) in propylene carbonate. The PCNS electrodes displayed high specific capacitance (86 F g -1 for cations and 115 F g -1 for anions). They also showed exceptionally high rate performance with ∼90% capacitance retention at current densities up to 2 A g -1 because their nanosheet structure allowed the rapid diffusion of ions inside the electrode.

A new 3D metal-organic framework (MOF), in which 2D layers are interlaced to form a 3D architecture, was synthesized by a reaction of Cu(BF4)2 and 1,3-bis(4-pyridyl)propane (bpp) in a water/1-hexanol solvent system, and the crystal structure of the MOF was successfully solved. The MOF is reversibly transformed to a 1D chain MOF, which shows gate adsorption properties. The dynamic transformation gives crystal size reduction resulting in a slight change in CO2 adsorption isotherms. The 1D MOF shows selective adsorption/separation properties on benzene and its analogues with similar sizes and shapes (benzene, toluene, and cyclohexane).

Si is one of the most attractive negative electrode materials for balanced design of high energy density Li-ion, Li-O2 and Li-S batteries because of the high theoretical capacity of 3580 mAh g-1 delivered by Li3.75Si. Li pre-doping should be an essential technology to reduce the irreversible capacity of Si negative electrodes in the first cycle or to load Li source to positive electrode materials free of Li such as for Li-O2 or Li-S batteries.Various methods of Li pre-doping have been reported: direct contact with Li metal foil or a solution of organo-lithium radical salt like n-butyl lithium, electrochemical Li pre-doping, and mixing Li metal, etc. [1]. So far, we have reported that Si electrode pre-doped by direct contact with Li metal in an electrolyte solution containing fluoroethylene carbonate showed an excellent cycle life and high Coulombic efficiency [2]. Although this method is suitable to shallow impregnation for thin Si electrodes, it is not applicable to thick and dense electrodes of practical use [3]. Therefore, we focused on method of solution of organo-lithium, Li-naphthalene, to pre-dope Li into Si. As for the method, the choice of solvent is critical to control the reactivity such as reaction velocity and penetration depth of Li. Five kinds of ether solvents were adopted in this study: three of cyclic ethers i.e. tetrahydrofuran (THF), 2-methyltetrahydrofuran (MeTHF) and tetrahydropyran (THP), and two of linear chain ethers i.e. dimethoxy ethane (G1) and trietylene glycol dimethyl ether (G3). Figure 1 shows discharge capacities of Li pre-doped Si electrodes as a function of pre-dope time at 30 °C. It is explicit that the discharge capacities of cyclic ethers such as MeTHF, THP and THF are higher than those of chain ethers such as G1 and G3. Moreover, MeTHF, THP, and G3 exhibited monotonous increasing capacities as pre-doping time increases, while THF and G1 showed decreasing tendencies. The XRD diffraction results exhibited the formation of Li3.75Si in the Si electrodes doped in the cyclic ether solutions for 24 hours. Figure 2 shows that the equilibrium potential of each Li-NTL solution decreased with increasing temperature in the order of G3 > G1 > THF > THP, MeTHF. The equilibrium potential is a good index of formation of Li-NTL radical salt. Therefore, the order of the potential is consistent with the order of discharge capacities shown in Figure 1, although the order of G1 and G3 is inconsistent between them. Figure 2 also suggests clear dependency of pre-doping rate on temperature: The higher the temperature, the higher the pre-doping rate. The dissociation degree of Li-NTL solutions were estimated from the Walden plots of the solutions by using the data of the fluidity and ionic conductivity. The result demonstrated that the dissociation degree of Li and naphthalene radical was in the order of MeTHF << THP ≤ THF. Considering the above results, this should indicate that Li-NTL(solvent)n contact ion pairs are relatively stable in MeTHF or THP solution without the reductive decomposition compared with those in THF solutions. The present results reveal that Si electrode can be effectively pre-doped with Li by using Li-NTL solution, and that the choice of solvent for Li-NTL solution is one of the critical factors to obtain high Li pre-doping level. Li3.75Si phase was formed by pre-doping for 24 hours in the Li-NTL solution using MeTHF or THP, achieving high Li pre-doping levels over 3000 mAh g-1. The solution pre-doping adopting Li-NTL is one of the promising methods for deep Li-doping, revealing that the lower equilibrium potentials resulting from deep Li doping is due to stable Li-NTL(solvent)n contact ion pairs. This work was partially supported by NEDO RISING2 project (JPNP16001). References [1] T. Placke et al., Batteries, 4, 4 (2018). [2] M. Saito et al., J. Electrochem. Soc., 166 (3), A5174 (2019). [3] M. Saito et al., Abstracts of ACEPS-10, T2-P-083 (2019). Figure 1

Structural analyses of a flexible 1D MOF [Cu(BF4)2(bpp)2] (bpp =1,3-bis(4-pyridyl)propane) with/without guest molecules were performed by synchrotron powder X-ray diffraction analysis and single crystal structural analysis. The guest-free MOF is composed of 1D chains composed of Cu(II) ions and bpp ligands which are accumulated to form quasi-2D layers, resulting in a quasi-layered compound. The guest-free MOF has no open pore windows; it, however, has latent quasi-hexagonal cavities surrounded by six BF4 anions. This MOF shows molecular selective sorption, which stems from guest-dependent dynamic structural transformation including pore-opening/closing processes. It shows selective alcohol sorption based on the molecular recognition properties; it sorbs C1–C3 alcohols, but not a C4 alcohol (1-butanol). Sorption properties can be enhanced by accumulation of several functionalities. In the case of the flexible MOF, the sorption properties should be synergetically enhanced by several key properties; it has m...

We have developed a laser-induced chemical vapor deposition (LCVD) method for preparing nanocarbons with the aid of SF 6 . This method would offer advantages for the production of aggregates of nanoscale foams (nanofoams) at high rates. Pyrolysis of the as-grown nanofoams induced the high surface area (1120 m 2 g −1 ) and significantly enhanced the adsorption of supercritical H 2 (16.6 mg g −1 at 77 K and 0.1 MPa). We also showed that the pyrolized nanofoams have highly ultramicroporous structures. The pyrolized nanofoams would be superior to highly microporous nanocarbons for the adsorption of supercritical gases.

Novel ordered lamellar mesostructure pZrPS-2 was hydrothermally prepared by using zirconium propoxide and 4-(EtO)2OPC6H4Si(OEt)3 (pPPS-E), which was hydrolyzed to organic building units substituted with both siliconate and phosphonate groups, in the presence of Cn TAB and TMAOH. The pZrPS-2 materials were obtained at a Zr/PPS ratio of 2 or higher and the basal spacing was increased by using a longer-chain surfactant (n = 12-18). Removal of the occluded surfactants at 300 °C resulted in retention of the lamellar structure with negligible shrinkage of the interlayer distance. Nitrogen adsorption studies revealed the ordered mesoporous nature of pZrPS-2 with a pore diameter of approximately 2 to 3 nm. The lamellar structure is assumed to be composed of layers that include zirconia-based crystalline nanodomains and interlayer pillars mainly based on PPS units. Although lamellar structures with the same crystalline phase also formed when no surfactant was added or when the meta isomer of PPS was used, no mesoporous materials were obtained except pZrPS-2. A possible schematic model to elucidate these results is also proposed.

The adsorption states of NH3 molecules and NH4+ ions on various sites, such as hydroxyl, H+ and Na+, of ZSM-5 zeolites with different SiO2/Al2O3 ratios were investigated by near and middle infrared spectroscopy. For Na+-type and siliceous ZSM-5 zeolites, only hydrogen-bonded NH3 clusters were observed at 5021 and 4519 cm−1, due to the lack of Bronsted acid sites. The NH3 molecules interacting with the hydroxyl groups easily desorbed at room temperature (r.t.), while the molecules interacting with the Na+ sites desorbed at 473 K. For the H+-type ZSM-5, when NH3 adsorption amount was small, the NH4+ formed on the H+ sites as well as the NH3 adsorbed on the H+ (or possibly Al3+) sites were independently observed at 4846 and 5044 cm−1, respectively. As the amount of NH3 adsorption increased, the NH4+ stabilized by the 2nd layer of NH3 molecules as well as the hydrogen-bonded NH3 clusters were observed at 4782 and 5017 cm−1, respectively. The hydrogen-bonded NH3 molecules desorbed at lower than 423 K but the NH4+ ions decomposed at 573–623 K to form Bronsted acid sites.

Metal-organic frameworks (MOFs) provide access to structures with nanoscale pores, the size and connectivity of which can be controlled by combining the appropriate metals and linkers. To date, there have been no reports of using MOFs as templates to make porous, crystalline metal oxides. Microporous titania replicas were made from the MOF template HKUST-1 by dehydration, infiltration with titanium isopropoxide, and subsequent hydrothermal treatment at 200 °C. Etching of the MOF with 1 M aqueous HCl followed by 5% H2O2 yielded a titania replica that retained the morphology of the parent HKUST-1 crystals and contained partially ordered micropores as well as disordered mesopores. Interestingly, the synthesis of porous titania from the HKUST-1 template stabilized the formation of brookite, a rare titania polymorph.

Polystyrene (PS) was selected as a costless polymer matrix for graded index polymer optical fibers (GI POFs) with low attenuation at a wavelength of 670 nm. However, fabricated PS-based GI POFs showed attenuation of more than 300 dB/km. This high attenuation PS-based GI POF had a quite broad molecular weight distribution. In contrast, a PS-based GI POF with a narrow molecular weight distribution showed low attenuation of around 160 dB/km. This is because the refractive index of PS, different from general polymers, is greatly affected by the molecular weight. The PS-based GI POF showed the high thermal stability of this low loss performance at a temperature of 70°C , despite the low glass transition temperature caused by plasticization. The measured refractive index profile was near optimum (g=2.5), and a high bandwidth of 5.8 GHz for a 50 m length was obtained.

The gate adsorption mechanism and kinetics of an elastic layer-structured metal–organic framework (ELM), [Cu(bpy)2(BF4)2]n (ELM-11), that shows typical single-step CO2 gate adsorption/desorption isotherms accompanied with dynamic structural transformation in a wide temperature range were investigated. Adsorption of quite a small amount of CO2 on the external surface of ELM-11 crystals was observed at the pressure just below a gate adsorption pressure and induced a slight structural change in ELM-11. The structural change should start occurring at the outer parts of ELM-11 and transmit to more inner parts with rising pressure. The adsorption provides the stabilization of the framework through the interaction between fluid–solid and fluid–fluid and enables the framework to expand largely along the stacking direction. The CO2 adsorption rate of ELM-11 is almost comparable to that of Zeolite 5A at around ambient temperatures and shows temperature dependence with an anti-Arrhenius trend: higher adsorption rate...

Organosilyl aluminophosphates (AlPOs) were prepared by using organosilyl agents such as methyltriethoxysilane and ethyltriethoxysilane, and characterized by XRD, TG, ICP, CHN elemental analysis, NMR, SEM, and TEM, and gas adsorption properties of them were investigated. The organosilyl agents formed amorphous phases on the AlPO crystal surfaces. The amorphous phases play two roles; changing the size of pore and forming the new pore spaces. The change of pore size induces molecular sieving phenomenon for small molecules. The pore in the amorphous phase is more effective for i-butane than toluene molecules, although they have the similar molecular sizes each other.

Selective synthetic routes to coordination polymers [Cu(bpy)(2)(OTf)(2)](n) (bpy = 4,4'-bipyridine, OTf = trifluoromethanesulfonate) with 2- and 3-dimensionalities of the frameworks were established by properly choosing each different solvent-solution system. They show a quite similar local coordination environment around the Cu(II) centers, but these assemble in a different way leading to the 2D and 3D building-up structures. Although the two kinds of porous coordination polymers (PCPs) both have flexible frameworks, the 2D shows more marked flexibility than the 3D, giving rise to different flexibility-associated gas adsorption behaviors. All adsorption isotherms for N(2), CO(2), and Ar on the 3D PCP are of type I, whereas the 2D PCP has stepwise gas adsorption isotherms, also for CH(4) and water, in addition to these gases. The 3D structure, having hydrophilic and hydrophobic pores, shows the size-selective and quadrupole-surface electrical field interaction dependent adsorption. Remarkably, the 2D structure can accommodate greater amounts of gas molecules than that corresponding to the inherent crystallographic void volume through framework structural changes. In alcohol adsorption isotherms, however, the 2D PCP changes its framework structure through the guest accommodation, leading to no stepwise adsorption isotherms. The structural diversity of the 2D PCP stems from the breathing phenomenon and expansion/shrinkage modulation.

A new three-dimensional copper-based interpenetrated porous coordination polymer (PCP) was synthesized using 1,2-di(4-pyridyl)ethylene (bpe), which is an N-donor neutral organic linker. The PCP has...

Inorganic–organic hybrid materials composed of [O3P–C6H4–SiO3] units and zirconium hydrothermally prepared in the presence of cationic surfactant showed nanoporosity and considerably high specific ...

A two-dimensional flexible porous coordination polymer (2D-PCP) that shows expansion/shrinkage structural transformation accompanied by molecular accommodation was synthesized by control of dimensionality in zero-dimensional and one-dimensional PCPs: The dynamic structural transformation cooperatively proceeds in the solid state with a drastic molecular rearrangement. Kinetics of the structural transformation was investigated.

Elastic layer-structured metal organic frameworks (ELMs) having flexible two-dimensional structure show a gate phenomenon in sorption/desorption of simple gas molecules. The gate phenomenon is accompanied by expansion/shrinkage of the layers. The gas sorption/desorption is not based on a physical adsorption, but on a chemical reaction, which includes high cooperativity. The cooperative reaction could be analyzed thermodynamically. The gate phenomenon showed advantages in separation of CO2 from mixed gases and in storage of CH4 owing to easy release of absorbed molecules.

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.

The formation of a solid electrolyte interface (SEI) at the surface of a SWNT electrode was investigated by SEM, TEM, XRD, and Raman spectroscopy. These analyses were carried out at different charge-discharge cycles, showing the cycle dependent character of the SEI formation. The changes in chemical species of SEI with increased number of cycles have been examined. This study shows by XRD, that inorganic species of SEI are LiF and Li2CO3, and that the SEI formation depends on the number of discharge-charge cycles.

Calcium signaling systems are widely employed in eukaryotes and are implicated in the regula- tion of diverse biological processes. Calcineurin is an important signaling component, which mediates ion homeostasis and virulence in several fungi. Based on intensive studies conducted on budding yeast, transcription factor Crz1p is thought to be a target of calcineurin. To provide insight into calcium signaling, a Crz1p homolog (CrzA) in a filamentous fungus Aspergillus nidulans was identified and its function with special reference to calcium response was characterized. A crzA gene disruption mutant exhibited sensitivity to high concentrations of Mn 2? and Ca 2? , and mediated the expression of P-type calcium- ATPase homologous genes. Comprehensive transcriptional analysis with DNA microarrays indicated that CrzA regu- lates the expression of a vacuolar Ca 2? /H ? exchanger gene in response to external calcium stimuli. It is suggested that the calcineurin-CrzA pathway is the mediator of Ca 2? homeostasis in A. nidulans. Moreover, a crzA/hogA double mutant showed hypersensitivity to osmotic stress, indicat- ing the importance of calcium homeostasis for adaptation to osmotic stress, a universal stress in filamentous fungi.

The crystal structure of [Cu(4,4'-bipyridine) 2(CF 3SO 3) 2] n metal-organic framework (CuBOTf) of one-dimensional pore networks after pre-evacuation at 383 K was determined with synchrotron X-ray powder diffraction measurement. Effective nanoporosity of the pre-evacuated CuBOTf was determined with N 2 adsorption at 77 K. The experimental H 2 and D 2 adsorption isotherms of CuBOTf at 40 and 77 K were measured and then compared with GCMC-simulated isotherms using the effective nanoporosity. The quantum-simulated H 2 and D 2 isotherms at 77 K using the Feynman-Hibbs effective potential coincided with the experimental ones, giving a direct evidence on the quantum molecular sieving effect for adsorption of H 2 and D 2 on CuBOTf. However, the selectivity for the 1:1 mixed gas of H 2 and D 2 was 1.2. On the contrary, experimental H 2 and D 2 isotherms at 40 K had an explicit adsorption hysteresis, originating from the marked pore blocking effect on measuring the adsorption branch. The blocking effect for quantum H 2 is more prominent than that for quantum D 2; the selectivity for D 2 over H 2 at 40 K was in the range of 2.6 to 5.8. The possibility of the quantum molecular sieving effect for H 2 and D 2 adsorption on [Cu 3(benzene-1,3,5-tricarboxylate) 2(H 2O) 3] n of three-dimensional pore networks was also shown at 77 K.

Today, the number of services, which includes large information contents like high-definition movies, is rapidly increasing. The graded-index plastic optical fiber (GI-POF) has been proposed as a solution. The conventional fabrication method of GI-POF, however, is unsuitable for mass production. Therefore, we propose the dopant diffusion coextrusion process for fabricating high-bandwidth GI-POF. It has been generally thought that formation mechanism of refractive-index distribution in optical polymer materials by this process would be a Fick's diffusion with constant diffusion coefficient and, therefore, has a tailing part at the core-cladding boundary. Contrary to predictions, we succeed in fabricating GI-POF with an almost optimum-index distribution. It is made evident by experiments and simulation that the formation mechanism of GI-POF by this process is a Fick's diffusion with diffusion coefficient dependent on dopant concentration. These results indicate high possibility of fabrication of high-bandwidth fibers of a polymethyl methacrylate-diphenyl sulfide system by the dopant diffusion coextrusion process.

We showed water adsorption isotherms at 303 K on water-resistant three-dimensional (3-D) pillared-layer metal organic frameworks (MOFs) with 1-D semi-rectangular pores, of which size depends on the length of ligand. The shapes of all three adsorption isotherms are type I by IUPAC classification showing strong water-MOFs interaction. The adsorbed amount of water molecules on the hydrophilic site of carboxylic group in 2-D sheets coincided with the crystal water amount. The adsorption on the hydrophilic sites occurs at similar relative pressure even if the used ligand is different.

The synthesis, crystal structures, and adsorption properties of a series of pillared layered copper phosphonates are reported herein. A hydrothermal reaction of copper oxide, 1,3,5-benzenetriphosphonic acid (BTP = H6bpt), and N-donor ligands with different lengths gives three new and one previously reported copper organophosphonates. X-ray crystal structural analyses revealed that compound 1, [Cu2(H4btp)2(pyr)] (pyr = pyrazine), forms a dense 3D network structure without open pores, and on the other hand, compounds 2–4, [Cu2(H2btp)(H2O)2(L)] (L = bipyridine for 2, 1,2-bis(4-pyridyl)ethylene for 3, and 1,3-bis(4-pyridyl)propane for 4), show topologically identical pillared layered frameworks with micropores. The framework structures are composed of copper phosphonate layers and N-donor ligands expanding the interlayer distances. Guest water molecules occupy the pores and are removable by drying treatment. Compounds 2–4 adsorb and desorb water vapor reversibly with structural transformation. Interestingly, compounds 2–4 adsorb ethanol vapor in spite of no adsorption of N2 molecules, indicating selective adsorption properties based not on the molecular size but on the molecular affinities to the surfaces.

Microporous amorphous hydrophobic silica materials with well-defined pores were synthesized by replication of the metal-organic framework (MOF) [Cu3 (1,3,5-benzenetricarboxylate)2 ] (HKUST-1). The silica replicas were obtained by using tetramethoxysilane or tetraethoxysilane as silica precursors and have a micro-meso binary pore system. The BET surface area, the micropore volume, and the mesopore volume of the silica replica, obtained by means of hydrothermal treatment at 423 K with tetraethoxysilane, are 620 m(2) g(-1) , 0.18 mL g(-1) , and 0.55 mL g(-1) , respectively. Interestingly, the silica has micropores with a pore size of 0.55 nm that corresponds to the pore-wall thickness of the template MOF. The silica replica is hydrophobic, as confirmed by adsorption analyses, although the replica has a certain amount of silanol groups. This hydrophobicity is due to the unique condensation environment of the silica precursors in the template MOF.

The supercritical N2, O2, and CH4 adsorption isotherms on a Cu-based metal−organic framework, [Cu(4,4‘-bipyridine)2(BF4)2]n, over the temperature range of 196−303 K were measured by a gravimetric method. The N2 and O2 adsorption isotherms at 196 K showed a vertical adsorption accompanied by a rectangular hysteresis loop. A method of evaluating the absolute adsorption amount of these gases was developed taking into account the intermolecular interactions for the buoyancy-mediated method. The isotherms of the absolute adsorption amount were obviously different from the isotherms of the surface-excess mass adsorption at 196 K. We also obtained isotherms of the absolute adsorption amount of CH4 at different temperatures. The isosteric heat of adsorption from the isotherms of the absolute adsorption amount of CH4 is larger than the liquefaction heat of CH4 at its boiling point by more than 3 kJ mol-1.

Magnesium carbenoids were generated from aryl 1-chloroalkyl sulfoxides with i-PrMgCl in THF at low temperature in quantitative yields. The magnesium carbenoids were found to be reactive with N-lithio alkylamines to afford an olefin, which was derived from dimerization of the magnesium carbenoid, in moderate yield. On the other hand, reaction of the magnesium carbenoids with N-substituted N-lithio arylamines gave non-stabilized α-amino-substituted carbanions in good yields. Reactivity of the α-amino-substituted carbanions with some electrophiles was investigated and it was found that ethyl chloroformate reacted to give α-amino acid derivatives in good yields. As a whole, a new method for one-pot, three-component combined synthesis of α-amino acid derivatives from aryl 1-chloroalkyl sulfoxides was realized.

Novel isomorphous pillared-layer-type crystalline lanthanide 1,3,5-benzenetriphosphonates were prepared with bpy and dbo as organic pillars (LnBP-bpy and LnBP-dbo; Ln: Ce, Pr, and Nd). Ab initio crystal structure solution using synchrotron X-ray powder diffraction data revealed that the organic pillars do not exist as neutral coordinating ligands but as cationic molecules. Especially the LnBP-dbo phases have ordered interlayer space filled with water molecules between the dbo pillars, and the interlayer water is successfully removed by heating under vacuum with slightly distorted but basically retained pillared layer structures. Microporosity of the materials is confirmed by adsorption of nitrogen, carbon dioxide, and hydrogen gases. Such microporous layered metal phosphonates pillared with cationic molecules should be unprecedented and should offer new strategies to design ordered microporous materials.

Lanthanum 1,3,5-benzenetriphosphonate (LBP-II) with layered structure was obtained by a hydrothermal synthesis. LBP-II was successfully exfoliated to give nanosheets as confirmed by AFM observation. Europium or terbium-doped LBP-II as well as their dispersion solutions show photoluminescence.

Treatment of 1-chloroalkyl phenyl sulfoxides with a Grignard reagent at low temperature gave magnesium carbenoids in quantitative yields. The generated magnesium carbenoids were found to be stable at lower than −60 °C for long periods of time and are reactive with Grignard reagents to give alkylated products. The reaction of the generated magnesium carbenoids with various kinds of lithium α-sulfonyl carbanions gave olefins with carbon–carbon bond-formation in good to high yields. This method offers a good way for the preparation of olefins. The scope and limitations of the above-mentioned reactions are described.

In a previous report, the age softening phenomenon of the copper electrodepostits obtained from a copper sulfide plating solution containing a hardener was studied using hardness and SIM measurements. Here results on the continuation of the study of this phenomenon are presented. It was found that for Cu/Ni base plate, the phenomenon called “age softening” at room temperature could be inhibited by adding a polymer containing nitrogen in a concentration of 30 mg/L or above to the plating solution. At 60°C, a concentration of 60 mg/L or above was necessary to inhibit the age softening. It was found that the orientation 100 of the electrodeposits is strengthened in preference to the age softening. On the other hand, adding a concentration of 120 mg/L or above of SPS to a plating solution promotes the age softening at 60°C.

An inhibitory effect on the increase in the postprandial blood glucose level was evaluated with a test soft drink containing indigestible dextrin (ID). After 27 healthy volunteers consisting of 14 males and 13 females were given the test soft drink supplemented with ID (6g as dietary fiber) together with a 537 kcal starchy diet, blood glucose levels were determined at 30, 60, and 120 minutes after meal. Additionally, after the same subjects were given a control soft drink without ID together with the same starchy diet, blood glucose levels were determined to compare inhibitory effect on the increase in postprandial blood levels in a cross over experimental design. Subjects were first divided into two groups with a peak blood glucose level at 30 minutes and 60 minutes after meal and they were further divided into two groups the higher and lower blood glucose levels. The effects were comparatively evaluated with the respective subjects between the test and control soft drink ingesting periods.As a result, a clear significant inhibitory effect of the soft drink supplemented with ID on the postprandial blood glucose level in 23 subjects who showed a peak blood glucose level at 30 minutes after diet and 12 subjects who were apt to elevate their blood sugar levels (the former at p

It was clarified for the first time that the slight attenuation increment observed in the previous poly methyl methacrylate (PMMA)-dopant system graded-index polymer optical fiber (GI POF) we reported originated in the excess scattering loss induced by the aggregation of absorbed water into the POF. Although the PMMA material generally absorbs two weight% of water at maximum, the low attenuation of the conventional step-index (SI) POF whose core material is PMMA can be maintained at 70/spl deg/C, 80% relative humidity (RH) atmosphere because the absorbed water might be homogeneously dispersed without any aggregation in the core of POF. On the other hand, addition of dopant material having higher refractive index than that of PMMA is required to form the refractive index distribution in the GI POF, which decreases the amount of water absorption into polymer, because the dopant material is more hydrophobic than PMMA. Therefore, in spite of the small amount of absorbed water such as 0.5 wt.%, the absorbed water molecules can not be uniformly dispersed but must be aggregated to form heterogeneities in the refractive index of the polymer matrix. It was clarified that a dopant material that is as hydrophilic as PMMA was required to maintain the attenuation of the PMMA-dopant system GI POF under high temperature and high humidity atmosphere, and such a suitable dopant system GI POF was proposed.

In 0.53 Ga 0.47 As/GaAs 0.5 Sb 0.5 /In 0.52 Al 0.48 As asymmetric type II multiple quantum well (MQW) structures lattice-matched to InP substrates were successfully grown by molecular beam epitaxy . In this structure, a large excitonic absorption change by applying an electric field is expected because of its asymmetric structure. Structural dependence of photoluminescence spectrum and optical absorption spectrum was studied. It was found that the emission wavelength changes from 1.4 to 2.5 μm with increasing the GaAsSb layer thickness from 0 to 70 A, and the thickness dependence of the emission energy agrees fairly well with the calculation. A clear excitonic absorption was observed at 1.5 μm at 300 K in the asymmetric type II MQW structures.

For realizing selective adsorption of targeted molecules, a flexible metal–organic framework (MOF) was modified with monodentate secondary ligands. Although the modified MOF retains CO2 adsorptivities with a vertical adsorption uptake, the material also shows gate adsorptivities of a specific gas molecule that the pristine MOF does not adsorb.

Nanosheets and nanorolls of a metal–organic framework (MOF) with N-donor type neutral bridging ligands were obtained from a layered copper-based MOF by exfoliation treatment in wet process, and were characterized by TEM, SEM, and AFM. The thinnest nanosheet indicates monolayer thickness of the mother MOF.

An ab initio powder X-ray crystal structure analysis revealed that layered zinc 1,3,5-benzenetriphosphonates containing interlayer tetramethylammonium (ZBP-TMA) or 4,4'-bipyridinium cations (ZBP-bpy) are transformed to novel isomorphous 3D open-framework compounds ZBP-M (M: K, Rb, and Cs) by treatment in aqueous alkali metal chloride solutions. ZBP-Ms have a pillared layer-type of anionic framework containing 2D zigzag channels connected with cage-like spaces. The potassium atoms in ZBP-K are located near 8MR windows in the 2D zigzag channels, and the potassium cations are successfully exchanged with ammonium cations retaining the open-framework structure. The ammonium form (ZBP-NH4) showed remarkable cation exchange selectivity for Rb(+) and Cs(+) in a mixture of alkali metal cations. It is assumed that zinc ions partially dissolved from the starting layered ZBP precursors are intercalated in ZBP layers to form pillared layered 3D open-frameworks. These results clearly show that topotactic pillared layer approaches are applicable not only to zeolite-related materials but also to novel open-framework metal organophosphonates.

A flexible one-dimensional copper-based coordination polymer (CP) crystal was synthesized and the crystal structure was solved. This CP crystal shows a single step gate adsorption uptake of CO(2) under moderate conditions (268 K ≤ T ≤ 303 K, P1 atm) irrespective of no N(2) uptake at 77 K.

Human γδ T cells can recognize and respond to a wide variety of stress-induced antigens, thereby developing innate broad anti-tumor and anti-infective activity. The majority of γδ T cells in peripheral blood have the Vγ9Vδ2 T cell receptor. These cells recognize antigen in a major histocompatibility complex-independent manner and develop strong cytolytic and Th1-like effector functions. Therefore, γδ T cells are attractive candidate effector cells for cancer immunotherapy. Vγ9Vδ2 T cells respond to phosphoantigens such as (E)-4-hydroxy-3-methyl-but-2-enyl pyrophosphate (HMBPP), which is synthesized in bacteria via isoprenoid biosynthesis; and isopentenyl pyrophosphate (IPP), which is produced in eukaryotic cells through the mevalonate pathway. In physiological condition, the generation of IPP in nontransformed cell is not sufficient for the activation of γδ T cells. Dysregulation of mevalonate pathway in tumor cells leads to accumulation of IPP and γδ T cells activation. Because aminobisphosphonates (such as pamidronate or zoledronate) inhibit farnesyl pyrophosphate synthase (FPPS), the enzyme acting downstream of IPP in the mevalonate pathway, intracellular levels of IPP and sensitibity to γδ T cells recognition can be therapeutically increased by aminobisphosphonates. IPP accumulation is less efficient in nontransformed cells than tumor cells with a pharmacologically relevant concentration of aminobisphosphonates, that allow us immunotherapy for cancer by activating γδ T cells with aminobisphosphonates. Interestingly, IPP accumulates in monocytes when PBMC are treated with aminobisphosphonates, because of efficient drug uptake by these cells. Monocytes that accumulate IPP become antigen-presenting cells and stimulate Vγ9Vδ2 T cells in the peripheral blood. Based on these mechanisms, we developed a technique for large-scale expansion of γδ T cell cultures using zoledronate and interleukin-2 (IL-2). Other methods for expansion of γδ T cells utilize the synthetic phosphoantigens bromohydrin pyrophosphate (BrHPP) or 2-methyl-3-butenyl-1-pyrophosphate (2M3B1PP). All of these methods allow ex vivo expansion, resulting in large numbers of γδ T cells for use in adoptive immunotherapy. However, only zoledronate is an FDA-approved commercially available reagent. Zoledronate-expanded γδ T cells display CD27(-)CD45RA(-) effector memory phenotype and thier function can be evaluated by IFN-γ production assay.

It is important to tune the sorption behavior of metal-organic framework (MOF) materials. Ethanol treatment on the hydrated form of [Cu(bpy)(2)(BF(4))(2)], which is a representative flexible MOF showing the fascinating gate phenomenon on CO(2) sorption, induces an easier dehydration and a significant decrease in the CO(2) gate pressure. The results of IR, X-ray diffraction (XRD), and X-ray absorption fine structure (XAFS) measurements indicated that water molecules in the lattice of the hydrated form can be removed even at room temperature after the ethanol treatment and the basic 2D layered structure remains with a slight interlayer expansion. The results of thermogravimetric (TG) and gas chromatograph/mass spectrometry (GC/MS) analyses and of CO(2) sorptions indicated that the change of the gate phenomenon was caused by a trace of residual ethanol molecules included in the structure. Similar phenomena were observed on alcohols with different polarity and molecular size.