Synchrotron X‐ray CT characterization of titanium parts fabricated by additive manufacturing. Part I. Morphology

Synchrotron X‐ray tomography has been applied to the study of titanium parts fabricated by additive manufacturing (AM). The AM method employed here was the Arcam EBM^® (electron beam melting) process which uses powdered titanium alloy, Ti64 (Ti alloy with approximately 6%Al and 4%V), as the feed and an electron beam for the sintering/welding. The experiment was conducted on the Imaging and Medical Beamline of the Australian Synchrotron. Samples were chosen to examine the effect of build direction and complexity of design on the surface morphology and final dimensions of the piece.     

Efficient and highly selective cyclization induced by Lewis acid to generate 2-hydroxyl-α-cyclogeraniol

A cyclization reaction of the hydroxyl-protected geraniol epoxide induced by the different Lewis acids to generate 2-hydroxyl-α-cyclogeraniol has been explored. Compared with the previous methods, this method enhances the production and selectivity of this reaction without the consumption of a large amount of solvent. Also, the coordination of the metal with two oxygen atoms of hydroxyl groups might be crucial for the reaction is first addressed.     

Aminopropyl-modified silica as cross-linkers of polysiloxane containing γ-chloropropyl groups for preparing heat-curable silicone rubber

A series of aminopropyl-modified silica (APS) with different amine contents was prepared and, subsequently, used as cross-linkers of polysiloxane containing γ-chloropropyl groups (CPPS) to prepare heat-curable silicone rubber (MCSR). The dispersion of APS in polysiloxane matrix was studied by scanning electron microscopy. The curing characteristics, mechanical and thermal properties of the MCSR were analyzed by a rheometer, mechanical testing and thermal gravimetric analysis (TGA), respectively. The effects of the silica (TS530) content and the molar ratio of APS/CPPS on the curing characteristics were studied. The influence of the amounts of TS530 and APS, and the kind of APS, on the comprehensive mechanical properties of MCSR is discussed. The optimized conditions to prepare MCSR were obtained as follows: the amount of TS530, 55 parts per hundreds of polysiloxane in weight; the molar ratio of [NH]/[γ-chloropropyl], 1.5: 1; and the amount of amino groups on the surface of APS, 0.65 mmol/g. Additionally, TGA results show that MCSR has high thermal stability.     

Elucidating the Stereochemistry of Enzymatic Benzylsuccinate Synthesis with Chirally Labeled Toluene

Benzylsuccinate synthase is a glycyl radical enzyme that initiates anaerobic toluene metabolism by adding fumarate to the methyl group of toluene to yield (R)‐benzylsuccinate. To investigate whether the reaction occurs with retention or inversion of configuration at the methyl group of toluene, we synthesized both enantiomers of chiral toluene with all three H isotopes in their methyl groups. The chiral toluenes were converted into benzylsuccinates preferentially containing ²H and ³H at their benzylic C atoms, owing to a kinetic isotope effect favoring hydrogen abstraction from the methyl groups. The configuration of the products was analyzed by enzymatic CoA‐thioester synthesis and stereospecific oxidation using enzymes involved in benzylsuccinate degradation. Assessment of the configurations of the benzylsuccinate isomers based on loss or retention of tritium showed that inversion of configuration at the methyl group occurs when the chiral toluenes react with fumarate.     

On a nonoverlapping additive Schwarz method for h‐p discontinuous Galerkin discretization of elliptic problems

The condition number of a discontinuous Galerkin finite element discretization preconditioned with a nonoverlapping additive Schwarz method is analyzed. We improve the result of Antonietti and Houston (J Sci Comput 46 (2011), 124–149), where a bound has been proved for a two‐level nonoverlapping additive Schwarz method with coarse problem using polynomials of degree on a coarse mesh size . In a more general framework, where the concurrency of the algorithm is increased by applying solvers on subdomains smaller than the coarse grid cells, we prove that the condition number of the preconditioned system is where is the coarse space element degree polynomial and is the size of subdomain where local problems are solved in parallel. Our result also extends to the case of discontinuous coefficient, piecewise constant on the coarse grid, for a composite continuous–discontinuous Galerkin discretization. © 2016Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 32: 1572–1590, 2016     

Synthesis of N-functionalized oleamide derivatives

Oleamide is an interesting compound, which shows various pharmacological activities including the inhibitory effect of gap junction formation. Recently, the studies of the gap junction have been some of the hot topics in biology and its inhibitors have become more useful tools [Cravatt, B. F.; Garcia, O. P.; Siuzdak, G.; Gilula, N. B.; Henriksen, S. J.; Boger, D. L.; Lerner, R. A. Science1995, 268, 1506-1509; Cravatt, B. F.; Lerner, R. A.; Boger, D. L. J. Am. Chem. Soc.1996, 118, 580-590; Guan, X; Cravatt, B. F.; Ehring, G. R.; Hall, J. E.; Boger, D. L.; Lerner, R. A.; Gilula, N. B. J. Cell Biol.1997, 139, 1785-1792; Boger, D. L.; Patterson, J. E.; Guan, X.; Cravatt, B. F.; Lerner, R. A.; Gilula, N. B. Proc. Natl. Acad. Sci. U.S.A.1998, 95, 4810-4815; Ito, A.; Morita, N.; Miura, D.; Koma, Y.; Kataoka, T. R.; Yamasaki, H.; Kitamura, Y.; Kita, Y.; Nojima, H. Carcinogenesis2004, 25, 2015-2022]. However, many reports suggest that the functionalizations of oleamide to retain its biological activity were difficult [Boger, D. L.; Patterson, J. E.; Guan, X.; Cravatt, B. F.; Lerner, R. A.; Gilula, N. B. Proc. Natl. Acad. Sci. U.S.A.1998, 95, 4810-4815; Ito, A.; Morita, N.; Miura, D.; Koma, Y.; Kataoka, T. R.; Yamasaki, H.; Kitamura, Y.; Kita, Y.; Nojima, H. Carcinogenesis2004, 25, 2015-2022]. The synthesis of the functionalized oleamide derivatives, whose biological activity is not blocked, has become attractive in both the biological and chemical fields.Herein, by linking the fluorophore to the oleamide by alkyl chains, we synthesized the fluorescently tagged oleamide whose biological feature is similar to that of oleamide. Moreover, we also synthesized other bioactive derivatives tagged by other groups such as the sugars and biotin via alkyl chain linkers.     

The role of aromatic groups in the Tobey-Simon additivity rule for vinylic protons

The Tobey-Simon (additivity) rule for aromatic groups which was devised about 40 years ago has been found to need revision. The rule shows an aromatic group attached to a C==C double bond as causing a downfield chemical shift of a cis-related vinylic proton and a small upfield shift of a trans-related proton. A search of data in the recent literature has shown that this rule should apply mainly to monosubstituted phenyl groups and some polynuclear aromatics. In contrast with them, 2,6-disubstituted phenyl, 2,4,6-trisubstituted phenyl and 9-anthracenyl groups cause cis-related vinylic protons to resonate upfield of comparable trans-related protons. Further, the current rule for o-substituted phenyl groups has been found to be inaccurate. In writing a rule for aromatic groups, therefore, greater attention needs to be given to the diversity of effects that these groups have on chemical shifts of vinylic protons.     

Engel graph associated with a group

Let G be a non-Engel group and let L(G) be the set of all left Engel elements of G. Associate with G a graph as follows: Take G L(G) as vertices of and join two distinct vertices x and y whenever [x,_ky]≠1 and [y,_kx]≠1 for all positive integers k. We call , the Engel graph of G. In this paper we study the graph theoretical properties of .