The synthesis of new 60 degrees organometallic subunits and self-assembly of three-dimensional M3L2 trigonal-bipyramidal cages

By employing the coupling reaction of trans-PtI2(Et3)2 with C-H bonds in alkynes as the key step, two new 60 degrees organometallic subunits with different size from 3,6-dibromophenanthrene were prepared in reasonable yields. The X-ray structures of both di-Pt(II) diiodide complexes showed that they were indeed suitable candidates for 60 degrees building units. By utilizing these novel linkers as ditopic acceptor subunits, three M3L2 trigonal-bipyramidal (TBP) cages were formed. All three TBP cages were characterized with multinuclear NMR and electrospray ionization mass spectrometry (ESI-MS) along with element analysis.     

Glyoxalase I-type hemithioacetal isomerization reactivity of a mononuclear Ni(II) deprotonated amide complex

The synthesis, characterization, and hemithioacetal isomerization reactivity of a mononuclear Ni(II) deprotonated amide complex, [(bppppa-)Ni]ClO4.CH3OH (1, bppppa- = monoanion of N,N-bis-[(6-phenyl-2-pyridyl)methyl]-N-[(6-pivaloylamido-2-pyridyl)methyl]amine), are reported. Complex 1 was characterized by X-ray crystallography, 1H NMR, UV-vis, FTIR, and elemental analysis. Treatment of 1 with an equimolar amount of the hemithioacetal PhC(O)CH(OH)SCD3 in dry acetonitrile results in the production of the thioester PhCH(OH)C(O)SCD3 in approximately 60% yield. This reaction is conveniently monitored via 2H NMR spectroscopy. A protonated analogue of 1, [(bppppa)Ni](ClO4)2 (2), is unreactive with the hemithioacetal, thus indicating the requirement of the anionic chelate ligand in 1 for hemithioacetal isomerization reactivity. Complex 1 is unreactive with the thioester product, PhCH(OH)C(O)SCD3, which indicates that the pKa value for the PhCH(OH)C(O)SCD3 proton of the thioester must be significantly higher than the pKa value of the C-H proton of the hemithioacetal (PhC(O)CH(OH)SCD3). Complex 1 is the first well-characterized Ni(II) coordination complex to exhibit reactivity relevant to Ni(II)-containing E. coli glyoxalase I. Treatment of NiBr2.2H2O with PhC(O)CH(OH)SCD3 in the presence of 1-methylpyrrolidine also yields thioester product, albeit the reaction is slower and involves the formation of multiple -SCD3 labeled species, as detected by 2H NMR spectroscopy. The results of this study provide the first insight into hemithioacetal isomerization promoted by a synthetic Ni(II) coordination complex versus a simple Ni(II) ion.     

Hyperinols A and B, chymotrypsin inhibiting triterpenes from Hypericum oblongifolium

Hyperinols A (1) and B (2) are new taraxastane type triterpenes which have been isolated from the chloroform soluble fraction of Hypericum oblongifolium and their structures elucidated on the basis of spectroscopic data. Both showed significant inhibitory activity against chymotrypsin enzyme.     

Chain morphologies in semicrystalline polyfluorene: evidence from Raman scattering

The beta phase in di-octyl substituted polyfluorene (PF8) exhibits a surprising level of conformational order at nanometer length scales compared to other phases. We present Raman scattering studies of PF8 as a function of thermal cycling, which establishes a connection between the conformational isomers and the side and main chain morphology. Density-functional calculations of the vibrational spectra of single chain oligomers in conjunction with the experimental results demonstrate the incompatibility of the beta phase with the overall alpha crystalline phase in PF8.     

Two-dimensional fin with convective base condition

When solving a two-dimensional model of an isolated fin, researchers have mainly concentrated on either a constant or a periodic fin base temperature. It is possible to obtain a numerical solution by a convective boundary condition on the fin base. However, in an analytical solution, one cannot calculate an arbitrary constant because of the convective boundary condition of the separation of variables. Therefore a heat balance is applied here to resolve this difficulty. In addition, a modified solution is presented which does not involve any additional mathematics with respect to the classical approach of solving a one-dimensional model. For different values of the Biot number $B_{22}$, a comparison of one- and two-dimensional solutions is given. Relative errors of the heat flow rates predicted by the classical and modified one-dimensional solutions, and the respective exact two-dimensional solution with respect to an, are computed. It is found that, for large values of $B_{22}$ (say 50.0) modified solution, by using a convective condition at the fin base gives significant accuracy improvements in comparison to the classical one-dimensional technique.     

Synthesis of dihydrobenzisoxazoles by the [3 + 2] cycloaddition of arynes and oxaziridines

Dihydrobenzisoxazoles are readily prepared in good yields by the [3 + 2] cycloaddition of oxaziridines and arynes. The reaction involves an unusual cleavage of the C-O bond of the oxaziridine and tolerates a variety of substituents on the oxaziridine and the o-(trimethylsilyl)aryl triflate to form aryl-, heteroaryl-, alkyl-, and naphthyl-substituted dihydrobenzisoxazoles. The resulting halogen-substituted dihydrobenzisoxazoles are readily elaborated to more complex products using palladium-catalyzed crossing-coupling processes.     

Thioester hydrolysis reactivity of zinc hydroxide complexes: investigating reactivity relevant to glyoxalase II enzymes

A recently reported binuclear zinc hydroxide complex [(L(1)Zn(2))(mu-OH)](ClO(4))(2) (, L(1) = 2,6-bis[(bis(2-pyridylmethyl)amino)methyl]-4-methylphenolate monoanion) containing a single bridging hydroxide was examined for thioester hydrolysis reactivity. Treatment of it with hydroxyphenylthioacetic acid S-methyl ester in dry CD(3)CN results in no reaction after approximately 65 h at 45(1) degrees C. Binuclear zinc hydroxide complexes of the N-methyl-N-((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine (L(2)) and N-methyl-N-((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)ethyl)amine (L(3)) chelate ligands were prepared by treatment of each ligand with molar equivalent amounts of Zn(ClO(4))(2).6H(2)O and KOH in methanol. These complexes, [(L(2)Zn)(2)(mu-OH)(2)](ClO(4))(2) and [(L(3)Zn)(2)(mu-OH)(2)](ClO(4))(2) (), which have been structurally characterized by X-ray crystallography, behave as 1 : 1 electrolytes in acetonitrile, indicating that the binuclear cations dissociate into monomeric zinc hydroxide species in solution. Treatment of them with one equivalent of hydroxyphenylthioacetic acid S-methyl ester per zinc center in acetonitrile results in the formation of a zinc alpha-hydroxycarboxylate complex, [(L(2))Zn(O(2)CCH(OH)Ph)]ClO(4).1.5H(2)O or [(L(3))Zn(O(2)CCH(OH)Ph)]ClO(4).1.5H(2)O, and CH(3)SH. These reactions, to our knowledge, are the first reported examples of thioester hydrolysis mediated by zinc hydroxide complexes. The results of this study suggest that a terminal Zn-OH moiety may be required for hydrolysis reactivity with a thioester substrate.     

Laser welding of low carbon steel and thermal stress analysis

Laser welding of mild steel sheets is carried out under nitrogen assisting gas ambient. Temperature and stress fields are computed in the welding region through the finite element method. The residual stress developed in the welding region is measured using the XRD technique and the results are compared with the predictions. Optical microscopy and the SEM are used for the metallurgical examination of the welding sites. It is found that von Mises stress attains high values in the cooling cycle after the solidification of the molten regions. The residual stress predicted agreed well with the XRD results.