GAM-7: an organic-inorganic hybrid layered aluminophosphate crystal formed by zeolite transformation.

The interzeolite conversion (IZC) of metallo- and aluminophosphate zeolites was demonstrated using a non-cyclic secondary amine, diisopropylamine, as the organic structure-directing agent (OSDA). The IZC of AlPO4-5 with AFI topology could successfully produce an unknown highly crystalline phase, named GAM-7. In metallo-aluminophosphates (metal-AlPOs), SAPO-5 with a small amount of SiO2 was also interconverted to a single crystal GAM-7, designated as [Si]GAM-7. However, in other metal-AlPOs, the corresponding GAM-7 crystals were formed as either an intermediate or a mixture of plural crystals. Additionally, it was found that GAM-7 could also be obtained by hydrothermal synthesis (HTS), but not synthesized from a silico-aluminophosphate hydrogel, indicating that [Si]GAM-7 can be prepared by only the IZC technique. The obtained GAM-7 crystal was well-characterized to elucidate the framework structure, and this revealed that GAM-7 was a new organic-inorganic hybrid layered aluminophosphate having a terminal POH group in the corrugated layered sheets, and the OSDA molecule between the layers was robustly interacting with an acidic POH site by a hydrogen bond. Furthermore, we have performed the tracking of pH values during the transformation from AlPO4-5 into GAM-7 and have argued a reasonable consideration for the IZC process.

Discovery of long-chain polyamines embedded in the biosilica on the Bacillus cereus spore coat.

Biosilicification is the process by which organisms incorporate soluble, monomeric silicic acid, Si(OH)4, in the form of polymerized insoluble silica, SiO2. Although the mechanisms underlying eukaryotic biosilicification have been intensively investigated, prokaryotic biosilicification has only recently begun to be studied. We previously reported that biosilicification occurs in the gram-positive, spore-forming bacterium Bacillus cereus, and that silica is intracellularly deposited on the spore coat as a protective coating against acids, although the underlying mechanism is not yet fully understood. In eukaryotic biosilicifying organisms, such as diatoms and siliceous sponges, several relevant biomolecules are embedded in biogenic silica (biosilica). These biomolecules include peptides, proteins, and long-chain polyamines. In this study, we isolated organic compounds embedded in B. cereus biosilica to investigate the biomolecules involved in the prokaryotic biosilicification process and identified long-chain polyamines with a chemical structure of H2N-(CH2)4-[NH-(CH2)3]n-NH2 (n: up to 55). Our results demonstrate the common presence of long-chain polyamines in different evolutionary lineages of biosilicifying organisms, i.e., diatoms, siliceous sponges, and B. cereus, suggesting a common mechanism underlying eukaryotic and prokaryotic biosilicification.

Two-dimensional microporous GAM-6 formed by the interzeolite conversion of CoAPO-5.

The interzeolite conversion of CoAPO-5 with piperidine assistance yielded a new microporous zeotype, GAM-6. Characterization and structural elucidation revealed that GAM-6 has a 3-ring local structure and two-dimensional 10-ring pore channels, and shows reasonable microporosity and solid acidity.

Correlated Rattling of Sodium-Chains Suppressing Thermal Conduction in Thermoelectric Stannides.

Tin-based intermetallics with tunnel frameworks containing zigzag Na chains that excite correlated rattling impinging on the framework phonons are attractive as thermoelectric materials owing to their low lattice thermal conductivity. The correlated rattling of Na atoms in the zigzag chains and the origin of the low thermal conductivity is uncovered via experimental and computational analyses. The Na atoms behave as oscillators along the tunnel, resulting in substantial interactions between Na atoms in the chain and between the chain and framework. In these intermetallic compounds, a shorter inter-rattler distance results in lower thermal conductivity, suggesting that phonon scattering by the correlated rattling Na-chains is enhanced. These results provide new insights into the behavior of thermoelectric materials with low thermal conductivity and suggest strategies for the development of such materials that utilize the correlated rattling.

Highly Precise and Sensitive Polymerase Chain Reaction Using Mesoporous Silica-Immobilized Enzymes.

A highly precise and sensitive technology that enables DNA amplification/detection from minimal amounts of nucleic acid is expected to find applicability in genetic testing involving small amounts of samples. The use of a free enzyme in conventional DNA amplification techniques, such as the polymerase chain reaction (PCR), frequently causes side reactions (i.e., nonspecific DNA amplification) when ≤103 substrate DNA molecules are present, thereby preventing selective amplification of the target DNA. To address this issue, we have developed a novel DNA amplification system, mesoporous silica-enhanced PCR (MSE-PCR), which involves the immobilization of a thermostable DNA polymerase from Thermococcus kodakaraensis (KOD DNA polymerase) into highly ordered nanopores of the mesoporous silica to control the reaction environment around the enzyme. In the MSE-PCR system using immobilized KOD DNA polymerase, such nonspecific DNA amplification was remarkably inhibited under the same conditions. Furthermore, the optimization of mesoporous silica pore sizes enabled selective and efficient DNA amplification from DNA substrates at the single-molecule level, i.e., one ten-thousandth of the amount of substrate DNA required for a DNA amplification reaction using a free enzyme. The results obtained in this study have shown that the nanopores of mesoporous silica can inhibit nonspecific reactions in DNA amplification, thereby considerably improving the specificity and sensitivity of the DNA polymerase reaction.

Oxidation Catalysis over Solid-State Keggin-Type Phosphomolybdic Acid with Oxygen Defects.

Keggin-type phosphomolybdic acid (PMo12O40), treated with pyridine (Py), forms a crystalline material (PyPMo-HT) following heat treatment under an inert gas flow at ∼420 °C. Although this material is known to have attractive catalytic properties for gas-phase oxidation, the origin of this catalytic activity requires clarification. In this study, we investigated the crystal structure of PyPMo-HT. PyPMo-HT comprises a one-dimensional array of Keggin units and pyridinium cations (HPy), with an HPy/Keggin unit ratio of ∼1.0. Two oxygen atoms were removed from the Keggin unit during crystal structure transformation, which resulted in an electron being localized on the Mo atom in close contact with the adjacent Keggin unit. Upon the introduction of molecular oxygen, electron transfer from this Mo atom resulted in the formation of an electrophilic oxygen species that bridged two Keggin units. The electrophilic oxygen species acted as a catalytically active oxygen species, as confirmed by the selective oxidation of propylene. PyPMo-HT showed excellent catalytic activity for the selective oxidation of methacrolein, with the methacrylic acid yield being superior to that obtained with PMo12O40 and comparable to that obtained with an industrial Keggin-type polyoxometalate (POM) catalyst. The oxidation catalysis observed over PyPMo-HT provides a deeper understanding of POM-based industrial catalytic processes.

Na3MgB37Si9: an icosa-hedral B12 cluster framework containing {Si8} units.

Single crystals of a novel sodium-magnesium boride silicide, Na3MgB37Si9 [a = 10.1630 (3) Å, c = 16.5742 (6) Å, space group R m (No. 166)], were synthesized by heating a mixture of Na, Si and crystalline B with B2O3 flux in Mg vapor at 1373 K. The Mg atoms in the title compound are located at an inter-stitial site of the Dy2.1B37Si9-type structure with an occupancy of 0.5. The (001) layers of B12 icosa-hedra stack along the c-axis direction with shifting in the [-a/3, b/3, c/3] direction. A three-dimensional framework structure of the layers is formed via B-Si bonds and {Si8} units of [Si]3-Si-Si-[Si]3.

Ba33Zn22Al8O67 with a Framework of ([O(Zn/Al)4]/Ba)(Zn/AlO4)4 Motifs.

Single crystals of a new oxide, Ba33Zn22Al8O67 (melting point = 1452 K), were grown in a melt-solidified sample prepared by heating a compact of a BaCO3, ZnO, and Al2O3 mixed powder in a dry airflow. Ba33Zn22Al8O67 can be handled in dry air, but it decomposes into carbonates, hydroxides, and hydrates in humid air. Single-crystal X-ray structure analysis clarified that Ba33Zn22Al8O67 crystallizes in a cubic cell (a = 16.3328 (3) Å, space group F23) having a three-dimensional Zn/AlO4 framework in which {([OZn4]/Ba)(Zn/AlO4)4} motifs are connected to each other by bridging Zn/AlO4 tetrahedra. A Ba atom or a [OZn4] cluster is statistically situated at the center of the motif with a probability of 0.5. Motifs of another type, {([O(Zn/Al)4])(Zn/AlO4)4}, are isolated from the Zn/AlO4 framework. These motifs, {([OZn4]/Ba)(Zn/AlO4)4} and {([O(Zn/Al)4])(Zn/AlO4)4}, are alternatingly arranged along the a axis like a checkered cube, and Ba atoms are situated between the motifs. A linear thermal expansion coefficient of 10.4 × 10-6 K-1 was measured in an Ar gas flow at 301-873 K for a sintered Ba33Zn22Al8O67 polycrystalline sample with a relative density of 73%. A relative permittivity of 31 and a temperature coefficient of 15 ppm K-1 at 301 K were obtained for another sintered sample (relative density = 70%) in a dry airflow. The electrical conductivity at 1073 K and the activation energy for conduction at 923-1073 K measured for the sintered samples in dry and wet airflows were 6.2 × 10-7 S cm-1 and 0.65 eV and 2.9 × 10-6 S cm-1 and 0.59 eV, respectively.

Efficient production of γ-aminobutyric acid by glutamate decarboxylase immobilized on an amphiphilic organic-inorganic hybrid porous material.

A novel organic-inorganic hybrid porous material (KCS-2), containing both lipophilic and hydrophilic nanospaces to mimic a lipid bilayer, was utilized as an immobilization support and reaction accelerator for glutamate decarboxylase (GADß). Upon evaluation of the adsorption of GADß on KCS-2, the amount of immobilization was found to be approximately four times higher than that on non-porous silica, and a comparable adsorbability to mesoporous silica was observed. Following γ-aminobutyric acid (GABA) production by the decarboxylation of l-glutamic acid using these immobilized enzymes, the enzymatic activity of the GADß-KCS-2 composite was found to be significantly higher than that of the free enzyme. In contrast, the activity of the more common GADß-mesoporous silica composite decreased. Furthermore, the enzymatic activity of the GADß-KCS-2 composite was superior to those of the un-immobilized free enzyme and the amorphous material itself over a wide temperature range. Thereby, these findings suggest that the amphiphilic nanospace of KCS-2 is suitable as a stable enzyme immobilization field and reaction acceleration field under such conditions. In addition, the durability of the immobilized enzyme was examined in terms of GABA production, with approximately 20% activity retention being observed after 10 cycles using KCS-2. Such durability was not observed for the non-porous silica material due to enzyme desorption.

GAM-3: a zeolite formed from AlPO4-5 via multistep structural changes.

The interzeolite conversion of AlPO4-5 gave a new zeolitic material GAM-2 and the calcination caused further structural changes, forming a new zeolite GAM-3 with a 3-dimensional 12-8-6 ring pore system. This is the first synthetic example of a zeolite formed through multistep structural changes in the metastable phase.

A new microporous 12-ring zincosilicate THK-2 with many terminal silanols characterized by automated electron diffraction tomography.

A newly synthesized microporous zincosilicate THK-2 (estimated structural composition: |(H2O)6.7(C6H13N)0.9|[Li0.5Zn3.1Si32O62.7(OH)9.3]) was characterized by single-crystal electron diffraction using the automated electron diffraction tomography (ADT) approach in combination with powder X-ray diffraction. The lattice constants and space group of as-synthesized THK-2 were a = 2.50377(7) nm, b = 1.43866(4) nm, c = 0.505369(8) nm, and Pccn (no. 56) with orthorhombic symmetry. Because the crystal lattice was almost identical to a hexagonal lattice (), the first several peaks in its powder X-ray diffraction data severely overlapped, which suppressed the structural information to decide the framework topology. In order to overcome this intrinsic difficulty, the structure model of THK-2 was initially obtained by the direct method based on ADT data and refined by the Rietveld method. Its 3-dimensional framework structure was elucidated and it consisted of 4-, 5-, 6-rings of tetrahedral Si and Zn atoms and a one-dimensional straight channel with a 12-ring pore opening. Zn atoms were incorporated into the framework as four-coordinated [ZnO4], although their distribution was confirmed to be disorderly. In the as-synthesized THK-2, the site occupancy of Zn was as low as 0.39; that is, more than 60% of the Zn sites were vacant. Hexamethyleneimine and water molecules were accommodated in the straight channel in a disordered manner. The material was stable upon calcination, and the BET specific surface area and micropore volume of calcined THK-2 were 240.6 m2 g-1 and 0.12 ml g-1, respectively.

Crystalline Naphthylene Macrocycles Capturing Gaseous Small Molecules in Chiral Nanopores.

A series of chiral naphthylene macrocycles, [n]cyclo-epi-naphthylenes ([n]CeNAPs), possessing epi-linkages were synthesized by one-pot macrocyclization. With chiral (R)- or (S)-1,1'-linkages embedded in binaphthyl precursors, the macrocycles were assembled in polygonal structures possessing chiral hinges as corners. Among four chiral [n]CeNAP variants, [8]CeNAP with eight naphthylene panels formed robust columnar assemblies in crystals. The nanoporous crystals maintained a columnar assembly structure even after the removal of encapsulated solvent molecules, and their gas adsorption behavior was thoroughly investigated. Gas adsorption, including state-of-the-art in situ crystallographic analyses, revealed accurate atomic-level structures of the nanopores trapping gaseous N2 molecules in chiral C2 arrangements. With macrocycles as basic frameworks, functional nanopores may be exploited for chiral small-molecule alignments.

Draft Genome Sequences of Three Flavobacterium psychrophilum Strains Isolated from Diseased Ayu (Plecoglossus altivelis altivelis) Caught at Three Sites in the Kagami River in Kochi, Japan.

Flavobacterium psychrophilum is a Gram-negative, psychrophilic bacterium within the family Flavobacteriaceae Here, we report the draft genome sequences of three F. psychrophilum strains isolated from skin ulcers of diseased ayu caught by tomozuri angling at three sites in the Kagami River in Japan.

Draft Genome Sequence of Vibrio harveyi Strain GAN1807, Isolated from Diseased Greater Amberjack (Seriola dumerili) Farmed in Nomi Bay, Japan, in 2018.

Vibrio harveyi is a Gram-negative, bioluminescent bacterium within the family Vibrionaceae Here, we report the draft genome sequence of V. harveyi strain GAN1807, which was isolated from a diseased greater amberjack (Seriola dumerili) with symptoms of V. harveyi-associated vibriosis in Nomi Bay in Japan.

Draft Genome Sequences of Six Flavobacterium psychrophilum Strains Isolated from Dead Juvenile Ayu (Plecoglossus altivelis altivelis) near the Mouth of the Nahari River, Kochi, Japan.

Flavobacterium psychrophilum causes bacterial cold-water disease in ayu inhabiting clear rivers in Japan. In this study, we report the draft genome sequences of six F. psychrophilum strains isolated from the gills and skin of dead juvenile ayu near the mouth of the Nahari River.

Novel crystalline organic-inorganic hybrid silicate material composed of the alternate stacking of semi-layered zeolite and microporous organic layers.

A novel type of crystalline organic-inorganic hybrid microporous silicate material, KCS-5, was synthesized supposedly from a lamellar precursor composed of amphiphilic organosilicic acids. This well-ordered material has a crystalline structure, is thermally stable up to 500 °C and has lipophilic 1-dimensional micropores.

A Microporous Aluminosilicate with 12-, 12-, and 8-Ring Pores and Isolated 8-Ring Channels.

Synthesis of new zeolites with controlled pore architectures is important in the field of catalysis and separation related to chemical transformation, environmental protection, and energy-saving. Zeolites containing channels of different sizes in the same framework have been desirable. We report here the synthesis and structure of a novel aluminosilicate zeolite (designated as YNU-5), the first zeolite containing interconnected 12-, 12-, and 8-ring pores, as well as independent straight 8-ring channels. The synthesis procedure is quite simple and consists of conventional hydrothermal conditions as well as readily available starting materials. The framework structure is stable enough and Si/Al ratio is controllable between 9 and 350. Determination of the crystal structure is performed by utilizing X-ray diffraction-based techniques, revealing 9 independent tetrahedrally coordinated atoms. This robust structure is expected to be industrially valuable and several unusual combinations of composite building units are of considerable interest in an academic sense. The new zeolite YNU-5 is promising catalyst for the production of useful light olefins such as propylene and butylenes in the dimethyl ether-to-olefin reaction, when the Si/Al ratio is properly tuned by dealumination through simple acid treatments.

Synthesis, crystal structure and characterization of novel open framework CHA-type aluminophosphate involving a chiral diamine.

A highly crystalline new precursor of CHA-type zeolite AlPO4-34 was obtained by using an aluminophosphate gel with a chiral diamine [(S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine; C9H18N2] as an organic structure directing agent under hydrothermal synthesis conditions. This precursor (called GAM-1) was changed into the zeolite AlPO4-34 which had a high porosity (the Brunauer-Emmett-Teller (BET) surface area is approximately 700 m3 g-1) using calcination. The GAM-1 obtained was characterized by various measurements, e.g., powder X-ray diffraction, scanning electron microscopy, and solid-state nuclear magnetic resonance spectroscopy, and so on. Structure determination from powder diffraction data revealed that the new precursor GAM-1 has triclinic symmetry [space group P1[combining macron], a = 9.16535(11) Å, b = 9.23042(11) Å, c = 9.29228(11) Å, α = 79.8243(7)°, ß = 87.4593(7)°, γ = 86.5365(7)°] and the chemical formula was estimated to be: |Al6P6O24H2F2|(C9H18N2)·2.5(H2O). It also revealed that a two edge sharing AlO4F2 octahedron with an [triple bond, length as m-dash]Al-F-Al[triple bond, length as m-dash] bridge was included in the framework. GAM-1 was transformed into AlPO4-34 with rhombohedral symmetry (R3[combining macron]) by elevating temperature to over 400 °C. At high temperatures, AlO4F2 octahedron connectivity was changed into an AlO4 tetrahedron. The crystal structure of the dehydrated AlPO4-34 changed back to a triclinic symmetry (P1) model again after rehydration in the atmosphere.

Carbon-Rich Active Materials with Macrocyclic Nanochannels for High-Capacity Negative Electrodes in All-Solid-State Lithium Rechargeable Batteries.

A high-capacity electrode active material with macrocyclic nanochannels is developed for a negative electrode of lithium batteries. With appropriate design of the molecular and crystal structures, a ubiquitous chemical commonly available in reagent stocks of any chemistry laboratories, naphthalene, was transformed into a high-performance electrode material for all-solid-state lithium batteries.