Sintering Metal–Organic Framework Gels for Application as Structural Adhesives

Metal–organic frameworks (MOFs)/coordination polymers are promising materials for gas separation, fuel storage, catalysis, and biopharmaceuticals. However, most applied research on MOFs is limited to these functional materials thus far. This study focuses on the potential of MOFs as structural adhesives. A sintering technique is applied to a zeolitic imidazolate framework-67 (ZIF-67) gel that enables the joining of Cu substrates, resulting in a shear strength of over 30 MPa, which is comparable to that of conventional structural adhesives. Additionally, systematic experiments are performed to evaluate the effects of temperature and pressure on adhesion, indicating that the removal of excess 2-methylimidazole and the by-product (acetic acid) from the sintered material by vaporization results in a microstructure composed of large spherical ZIF-67 crystals that are densely aggregated, which is essential for achieving a high shear strength.     

A small three-way valve using particle excitation with piezoelectric transducers for hydraulic actuators

Abstract

Robots composed of hydraulic actuators have been utilized in various fields and at disaster sites. However, the hydraulic control system for multiple-degree-of-freedom mechanisms is large because such systems require many control components. The purpose of this research was to develop a small hydraulic flow control valve. This paper describes the fabrication and evaluation of a small three-way valve by particle excitation using a piezoelectric transducer. This valve consists of two transducers and can switch the inlet and outlet ports by applying an AC voltage of different driving frequencies to each transducer because each transducer has different resonant frequencies. The flow rate was controlled by applying a voltage to the piezoelectric transducer. We evaluated the vibration characteristics of the fabricated three-way valve. The vibration velocity exhibited peaks at 120 and 155 kHz for the inlet and outlet port, respectively, and that of each transducer increased with the applied voltage. Therefore, this three-way valve can switch the opening port by changing the driving frequencies and continuously controlling the flow rate. As a result, we have succeeded in driving the novel small three-way valve.     

Postnatal changes in activation of polyunsaturated fatty acid,acylation of lysophosphoglyceride,and phosphorylation of diacylglycerol in cortical gray matter of rat cerebrum

Activation of polyunsaturated fatty acid, acylation of lysophosphoglyceride, and phosphorylation of diacylglycerol in postnatal developing rat cerebrum were studiedin vitro, using cortical gray matter homogenates. The rate of n-3 and n-6 fatty acid activation was maximal at ten days after birth and minimal at adulthood. Acylation of lysophosphoglyceride was most active at the neonatal stage and gradually decreased with age. In addition, the amount of phosphatidic acid formed from 1, 2-dioleoyl-glycerol was also maximum at the neonatal stage, and then gradually decreased. These results suggest that the specific activity of glycerolipid synthesis in cortical gray matter declines during postnatal development.     

Hydrogen-bond-assisted isotactic-specific radical polymerization of N-isopropylacrylamide with pyridine N-oxide

Radical polymerization of N-isopropylacrylamide (NIPAAm) in CHCl₃ at low temperatures in the presence of pyridine N-oxide (PNO) was investigated. An isotactic poly(NIPAAm) with meso diad content of 61% was successfully prepared at −60 °C in the presence of a two-fold amount of PNO. Thermodynamic analysis suggested that the isotactic-specificity was entropically induced, probably due to conformational fixation near the propagating chain-end through coordination by PNO.     

Identification of the Biosynthetic Gene Cluster for Himeic Acid A: A Ubiquitin‐Activating Enzyme (E1) Inhibitor in Aspergillus japonicus MF275

Himeic acid A, which is produced by the marine fungus Aspergillus japonicus MF275, is a specific inhibitor of the ubiquitin‐activating enzyme E1 in the ubiquitin–proteasome system. To elucidate the mechanism of himeic acid biosynthesis, feeding experiments with labeled precursors have been performed. The long fatty acyl side chain attached to the pyrone ring is of polyketide origin, whereas the amide substituent is derived from leucine. These results suggest that a polyketide synthase–nonribosomal peptide synthase (PKS‐NRPS) is involved in himeic acid biosynthesis. A candidate gene cluster was selected from the results of genome sequencing analysis. Disruption of the PKS‐NRPS gene by Agrobacterium‐mediated transformation confirms that HimA PKS‐NRPS is involved in himeic acid biosynthesis. Thus, the him biosynthetic gene cluster for himeic acid in A. japonicus MF275 has been identified.     

Electron spin resonance of transparent alumina ceramics fabricated by spark plasma sintering

Transparent α‐alumina ceramics are fabricated using spark plasma sintering. Paramagnetic defects related to the optical properties of the ceramics have been investigated using electron spin resonance (ESR) analyses. An isotropic ESR signal at g = 2.003 (S = 1/2) with a linewidth of 0.5 mT is formed during sintering. The g = 2.003 signal intensity has a weak correlation with the absorbance in the visible region but does not correlate with the real in‐line transmission (RIT) at 650 nm. An ESR signal with a fine structure attributed to Fe³⁺ was detected in both the α‐Al₂O₃ starting powder and the sintered ceramic samples. The degree of c‐axis orientation of the grains has been determined using the Fe³⁺ signal intensity, which depends on the angle between the directions of the c‐axis and the applied magnetic field. The ESR analysis indicated that the c‐axis tends to be oriented in the direction of the sintering pressure. The degree of c‐axis orientation was found to correlate with the RIT in highly densified ceramics.     

Selective labeling of proteins by using protein farnesyltransferase

The challenging task of identifying and studying protein function has been greatly aided by labeling proteins with reporter groups. Here, we present a strategy that utilizes an enzyme that labels a four-residue sequence appended onto the C terminus of a protein, with an alkyne-containing substrate. By using a bio-orthogonal cycloaddition reaction, a fluorophore that carried an azide moiety was then covalently coupled to the alkyne appended on the protein. FRET was used to calculate a F?rster (R) distance of 40 A between the eGFP chromophore and the newly appended Texas Red fluorophore. This experimental value is in good agreement with the predicted R value determined by using molecular modeling. The small recognition tag, the high specificity of the enzyme, and the orthogonal nature of the derivatization reaction will make this approach highly useful in protein chemistry.     

Coexpression of platelet-derived growth factor receptor alpha and fetal liver kinase 1 enhances cardiogenic potential in embryonic stem cell differentiation in vitro

Nascent mesodermal cells derived from EB5 embryonic stem (ES) cells were sorted in terms of cardiogenic potential on the basis of their expression levels of platelet-derived growth factor receptor alpha (PDGFRalpha) and fetal liver kinase 1 (Flk-1). The sorted cells were cocultured with OP9 stromal cells to induce terminal differentiation into contractile cardiac colonies. A significant number of cardiac colonies were found in the Flk-1+/PDGFRalpha+ fraction. The enrichment double-positive fraction produced approximately fivefold more cardiac colonies than the Flk-1+/PDGFRalpha- fraction and 10-fold more than the Flk-1-/PDGFRalpha+ fraction. To investigate the involvement of these markers in embryonic cardiogenesis, the cells that disseminated from the E7.5-7.75 embryos were fractionated and seeded on OP9 cells. The cardiogenic potential was markedly enhanced in the Flk-1+/PDGFRalpha+ fraction. These results suggest that some of the precursor cells coexpressing these markers are selectively involved in cardiogenic events, and that the identification of ES-cell-derived precursors with these markers will contribute to the effective production of cardiomyocytes for cell therapies.     

The three-dimensional structure of human RNase 4, unliganded and complexed with d(Up), reveals the basis for its uridine selectivity

The RNase 4 family is unique among RNase enzymes, displaying the highest level of sequence similarity and encompassing the shortest polypeptide chain. It is the only one showing high specificity. The human representative is an intracellular and plasma enzyme, first isolated from colon adenocarcinoma cell line HT-29. The crystal structures of human recombinant RNase 4, unliganded and in complex with d(Up), have been determined, revealing in the unique active site an explanation for the uridine specificity. Arg101, at a position not involved in catalysis in the other RNase enzymes, penetrates the enzyme moiety shaping the recognition pocket, a flip that is mediated by the interaction with the (shorter chain) C-terminal carboxylate group, providing an anchoring point for the O4 atom of the substrate uridine. The bulky Phe42 side-chain forces Asp80 to be in the chi1=-72.49 degrees rotamer, accepting a hydrogen bond from Thr44, further converting the latter into a hydrogen bond acceptor. This favours an interaction with the -NH-donor group of uridine at position 3 over that with the =N-acceptor of cytidine. The two chemical groups that distinguish uracyl from cytosine are used by the enzyme to discriminate between these two bases.     

Solid-state characterization of polyethylene reactor powders and their structural changes upon annealing

Polyethylene reactor powders prepared under different conditions were characterized using transmission electron microscopy, ¹H nuclear magnetic resonance and X-ray diffraction techniques. The molecular weight of the polyethylene reactor powders was around 1 × 10⁵. A unique domain morphology, quite different from the usual melt- or solution-crystallized lamellar structure, was observed, independent of polymerization temperature (T_poly). Annealing of reactor powders caused the aggregation of these crystalline domains, due to the significant molecular motion of the amorphous chains, before melting. The critical temperature was 20 °C higher than each T_poly, and corresponded to the temperature at the active catalyst site producing the chain growth. The morphologies of powders prepared at the lower T_poly contained smaller crystals that exhibited a constrained monoclinic form. In contrast, only usual orthorhombic crystals of larger size were found within the powder prepared at the higher T_poly. These results suggest that the competitive processes of chain propagation and crystal growth upon polymerization may lead to unique variations of the crystalline and amorphous phases, but with similar intermediate components in the phase that connects them.