Autoxidative annulation cascade of the α-cyano β-TMS-capped alkynyl cycloalkanone system

The autoxidative annulation cascade promoted by an α-cyano β-TMS-capped alkynyl cycloalkanone system under catalysis with pyridine in one oxygen atmosphere has proven to be highly viable. On the basis of this newly developed protocol, a variety of highly functionalized bicyclic frameworks can be effectively constructed.     

Quantitative determination of isoniazid in biological samples by cation-selective exhaustive injection-sweeping-micellar electrokinetic chromatography

Tuberculosis (TB), an infectious disease caused by Mycobacterium tuberculosis, infects approximately one third of the current world population. Isoniazid is one of the most frequently used first-line anti-TB drugs. In this study, we developed a sensitive cation-selective exhaustive injection–sweeping–micellar electrokinetic chromatography method (CSEI-Sweep-MEKC) for analyzing isoniazid in human plasma. Parameters including acetonitrile (ACN) percentage in the separation buffer; the injection time, and concentration of the high-conductivity buffer; sodium dodecyl sulfate (SDS) concentration; phosphate concentration in the sample matrix; and the sample injection time were all optimized to obtain the best analytical performance. The optimal background electrolyte comprised 50 mM phosphate buffer, 100 mM SDS, and 15% ACN. Non-micelle background electrolyte, containing 75 mM phosphate buffer and 15% ACN, was first injected into the capillary, followed by a short plug of 200 mM phosphate (high-conductivity buffer). Run-to-run repeatability (n = 3) and intermediate precision (n = 3) of peak area ratios were found to be lower than 8.7% and 11.4% RSD, respectively. The accuracy of the method was within 98.1–106.9%. The limit of detection of isoniazod in human plasma was 9 ng mL⁻¹. Compared with conventional MEKC, the enhancement factor of the CSEI-Sweep-MEKC method was 85 in plasma samples. The developed method was successfully used to determine isoniazid concentration in patient plasma. The results demonstrated that CSEI-Sweep-MEKC has the potential to analyze isoniazid in human plasma for therapeutic drug monitoring and clinical research.     

DNA-mediated assembly of cytochrome P450 BM3 subdomains

Cytochrome P450 BM3 is a versatile enzyme, which holds great promise for applications in biocatalysis and biomedicine. We here report on the generation of a hybrid DNA-protein device based on the two subdomains of BM3, the reductase domain BMR and the porphyrin domain BMP. Both subdomains were fused genetically to the HaloTag protein, a self-labeling enzyme, allowing for the bioconjugation with chloroalkane-modified oligonucleotides. The subdomain-DNA-chimeras could be reassembled by complementary oligonucleotides, thus leading to reconstitution of the monooxygenase activity of BM3 holoenzyme, as demonstrated by conversion of the reporter substrate 12-pNCA. Arrangement of the two chimeras on a switchable DNA scaffold allowed one to control the distance between both subdomains, as indicated by the DNA-dependent activity of the holoenzyme. Furthermore, a switchable chimeric device was constructed, in which monooxygenase activity could be turned off by DNA strand displacement. This study demonstrates that P450 BM3 engineering and strategies of DNA nanotechnology can be merged to open up novel ways for the development of novel screening systems or responsive catalysts with potential applications in drug delivery.     

Seaweed Chlorophyll on the Light‐electron Efficiency of DSSC

Four different seaweed extracts were employed as the dyes of dye sensitized solar cells (DSSCs) to investigate the light‐electron efficiency. The sensitizers, extracted from Nannochloropsis spp., Tetraselmis spp., Gracilaria spp., and Ulvales spp., showed their light‐electronic transfer ability in different light intensities. Among them, Ulvales output a higher light‐voltage, about 0.4 V. The output voltage increased when light intensity increased. Gracilaria extract produced a higher output voltage at 35 Lux, but its output voltage decreased over 500 Lux. The sensitizers extracted from these seaweeds had monochromatic incident photon‐to‐electron conversion efficiencies (IPCE) between 23‐61% in 220‐260 nm wavelengths. Among them, Ulvales output higher IPCE than Tetraselmis and Nannochloropsis. SEM analysis of DSSC surfaces revealed that the efficiency of seaweed DSSCs was governed by chlorophyll size. The chlorophyll particle size of Ulvales spp. was the largest. The chlorophyll particle size of Gracilaria spp. was the smallest and yielded the lowest IPCE.     

Lagrangian tracking of bubbles interacting with pin-fins in a microchannel

This paper presents new image analysis algorithms to measure the trajectories of breaking and coalescing bubbles in microscale bubbly flows. Image analysis of high-speed movies provides information on bubble dynamics and bubble interaction including bubble coalescence and breakage events. Individual bubbles that overlap in the image are recognized with a presented breakline method. The breakline method discriminates the overlapping bubbles with lines based on the bubble perimeter curvature analysis. Coalescence and breakage events are automatically recognized, and the path lines of bubbles travelling through the field of view are analyzed. The functionality of the algorithms was examined in bubbly flow in a microchannel encompassing two pin-fins in tandem.     

Thermal stabilization of tissues and the preservation of protein phosphorylation states for two‐dimensional gel electrophoresis

2‐DE is typically capable of discriminating proteins differing by a single phosphorylation or dephosphorylation event. However, a reliable representation of protein phosphorylation states as they occur in vivo requires that both phosphatases and kinases are rapidly and completely inactivated. Thermal stabilization of mouse cerebral cortex homogenates effectively inactivated these enzymes, as evidenced by comparison with unstabilized tissues where abscissal pI shifts were a common feature in 2‐D gels. Of the 588 matched proteins separated on 2‐D gels comparing stabilized and unstabilized tissues, 53 proteins exhibited greater than twofold differences in spot volume (ANOVA, p<0.05). Phosphoprotein‐specific staining was corroborated by the identification of 16 phosphoproteins by nano‐LC MS/MS and phosphotyrosine kinase activity assay.     

1,2-Dibromoethane on Cu(100): bonding structure and transformation to C2H4

Temperature-programmed reaction/desorption, mass spectrometry, reflection-absorption infrared spectroscopy, x-ray photoelectron spectroscopy, and density functional theory calculations have been employed to explore the reaction and bonding structure of 1,2-C(2)H(4)Br(2) on Cu(100). Both the trans and gauche conformers are found to dissociate by breaking the C-Br bonds on clean Cu(100) at 115 K, forming C(2)H(4) and Br atoms. Theoretical investigations for the possible paths of 1,2-C(2)H(4)Br(2) → C(2)H(4) + 2Br on Cu(100) suggest that the barriers of the trans and gauche molecules are in the ranges of 0-4.2 and 0-6.5 kcal/mol, respectively. The C-Br scission temperature of C(2)H(4)Br(2) is much lower than that (~170 K) of C(2)H(5)Br on Cu(100). Adsorbed Br atoms can decrease the dissociation rate of the 1,2-C(2)H(4)Br(2) molecules impinging the surface. The 1,2-C(2)H(4)Br(2) molecules adsorbed in the first monolayer are structurally distorted. Both the trans and gauche molecules exist in the second monolayer, but with no preferential adsorption orientation. However, the trans molecule is the predominant species in the third or higher layer formed at 115 K. The layer structure is not thermally stable. Upon heating the surface to 150 K, the orientation of the trans 1,2-C(2)H(4)Br(2) molecules in the layer changes, leading to the rotation of the BrCCBr skeletal plane toward the surface normal on average and the considerable growth of the CH(2) scissoring peak. On oxygen-precovered Cu(100), decomposition of 1,2-C(2)H(4)Br(2) to form C(2)H(4) is hampered and no oxygenated hydrocarbons are formed. The presence of the oxygen atoms also increases the adsorption energy of the second-layer molecules.     

Re-examining the properties of the aqueous vapor-liquid interface using dispersion corrected density functional theory

First-principles molecular dynamics simulations, in which the forces are computed from electronic structure calculations, have great potential to provide unique insight into structure, dynamics, electronic properties, and chemistry of interfacial systems that is not available from empirical force fields. The majority of current first-principles simulations are driven by forces derived from density functional theory with generalized gradient approximations to the exchange-correlation energy, which do not capture dispersion interactions. We have carried out first-principles molecular dynamics simulations of air-water interfaces employing a particular generalized gradient approximation to the exchange-correlation functional (BLYP), with and without empirical dispersion corrections. We assess the utility of the dispersion corrections by comparison of a variety of structural, dynamic, and thermodynamic properties of bulk and interfacial water with experimental data, as well as other first-principles and force field-based simulations.     

Synthesis of isoxazoline N-oxides via [hydroxy(tosyloxy)iodo]benzene (HTIB)-mediated oxidative N-O coupling

An HTIB mediated oxidative N-O coupling strategy for the synthesis of some isoxazoline N-oxide derivatives from β-hydroxyketoximes is described, along with a comparative study of the efficiency of N-O coupling in two different solvents. A plausible mechanism for the conversion is proposed.     

Phase diagram of SrO-InO1.5-CoOx and a new compound Sr3In0.9Co1.1O6

Sr₃In_0.9Co_1.1O₆, isostructural to Ca₃Co₂O₆, is revealed by the study of the phase relations in the system SrO-InO_1.5-CoO_x (1000 °C). The structure of Sr₃In_0.9Co_1.1O₆ is refined by the combination of powder X-ray and neutron diffraction. Sr₃In_0.9Co_1.1O₆ crystallizes in a trigonal lattice with the cell parameters a=b=9.59438(3) Å, c=11.02172(4) Å with the space group R-3c. Its structure possesses 1D (In/Co)O₃ chains running along the c-axis constructed by alternating face-sharing CoO₆ octahedra and (In_0.9Co_0.1)O₆ trigonal prisms. The co-occupation of In³⁺ and Co³⁺ at the trigonal prismatic site is evidenced by elementary analysis and determined by the structure refinement. Sr₃In_0.9Co_1.1O₆ is paramagnetic, and the susceptibility is consistent with the occupation of Co³⁺ at 10% of the trigonal prismatic positions in a high spin state (HS, S=2). The HS Co³⁺ is well separated by diamagnetic CoO₆ octahedra and InO₆ trigonal prisms and shows a g factor of 2.0 in the magnetic measurements.