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21.
22.
Holly D. Bendorf Kyle E. Ruhl Andrew J. Shurer Jennie B. Shaffer Tess O. Duffin Theresa L. LaBarte Michelle L. Maddock Oscar W. Wheeler 《Tetrahedron letters》2012,53(10):1275-1277
Medium-ring heterocycles are prepared via an amine-directed, rhodium(I)-catalyzed intramolecular hydroacylation. The presence of an allyl substituent on the amine accelerates the reaction and increases product yields. 相似文献
23.
G B Richter-Addo R A Wheeler C A Hixson L Chen M A Khan M K Ellison C E Schulz W R Scheidt 《Journal of the American Chemical Society》2001,123(26):6314-6326
The six-coordinate nitrosyl sigma-bonded aryl(iron) and -(ruthenium) porphyrin complexes (OEP)Fe(NO)(p-C(6)H(4)F) and (OEP)Ru(NO)(p-C(6)H(4)F) (OEP = octaethylporphyrinato dianion) have been synthesized and characterized. Single-crystal X-ray structure determinations reveal an unprecedented bending and tilting of the MNO group for both [MNO](6) species as well as significant lengthening of trans axial bond distances. In (OEP)Fe(NO)(p-C(6)H(4)F) the Fe-N-O angle is 157.4(2) degrees, the nitrosyl nitrogen atom is tilted off of the normal to the heme plane by 9.2 degrees, Fe-N(NO) = 1.728(2) A, and Fe-C(aryl) = 2.040(3) A. In (OEP)Ru(NO)(p-C(6)H(4)F) the Ru-N-O angle is 154.9(3) degrees, the nitrosyl nitrogen atom is tilted off of the heme normal by 10.8 degrees, Ru-N(NO) = 1.807(3) A, and Ru-C(aryl) = 2.111(3) A. We show that these structural features are intrinsic to the molecules and are imposed by the strongly sigma-donating aryl ligand trans to the nitrosyl. Density functional-based calculations reproduce the structural distortions observed in the parent (OEP)Fe(NO)(p-C(6)H(4)F) and, combined with the results of extended Hückel calculations, show that the observed bending and tilting of the FeNO group indeed represent a low-energy conformation. We have identified specific orbital interactions that favor the unexpected bending and tilting of the FeNO group. The aryl ligand also affects the Fe-NO pi-bonding as measured by infrared and (57)Fe M?ssbauer spectroscopies. The solid-state nitrosyl stretching frequencies for the iron complex (1791 cm(-)(1)) and the ruthenium complex (1773 cm(-)(1)) are significantly reduced compared to their respective [MNO](6) counterparts. The M?ssbauer data for (OEP)Fe(NO)(p-C(6)H(4)F) yield the quadrupole splitting parameter +0.57 mm/s and the isomer shift 0.14 mm/s at 4.2 K. The results of our study show, for the first time, that bent Fe-N-O linkages are possible in formally ferric nitrosyl porphyrins. 相似文献
24.
J E Harris N Desai K E Seaver R T Watson N A Kane-Maguire J F Wheeler 《Journal of chromatography. A》2001,919(2):427-436
Several buffer additives that may facilitate chiral separation for optically active transition metal (TM) systems are investigated using capillary zone electrophoresis. The TM complexes evaluated exhibit considerable heterogeneity with respect to total complex charge (0 to 4+), ligand type, and identity of the central metal including Ru2+, Ni2+, Cr3+, and Co3+, threo-D[+]-Isocitrate, potassium antimonyl-d-tartrate and dibenzoyl-L-tartrate are identified as the most efficient chiral selectors. Interestingly, TM complexes exhibiting a (3+) total complex charge exhibit a reversal of enantiomer elution order versus all other complexes when separated using the tartrate additives. Operating parameters including pH, temperature, and capillary length are discussed, and chiral separations of complex mixtures are demonstrated. 相似文献
25.
Digital microfluidics for cell-based assays 总被引:1,自引:0,他引:1
We introduce a new method for implementing cell-based assays. The method is based on digital microfluidics (DMF) which is used to actuate nanolitre droplets of reagents and cells on a planar array of electrodes. We demonstrate that this method is advantageous for cell-based assays because of automated manipulation of multiple reagents in addition to reduced reagent use and analysis time. No adverse effects of actuation by DMF were observed in assays for cell viability, proliferation, and biochemistry. A cytotoxicity assay using Jurkat T-cells was performed using the new method, which had approximately 20 times higher sensitivity than a conventional well plate assay. These results suggest that DMF has great potential as a simple yet versatile analytical tool for implementing cell-based assays on the microscale. 相似文献
26.
Proteomic analysis of the endoplasmic reticulum from developing and germinating seed of castor (Ricinus communis) 总被引:10,自引:0,他引:10
Endoplasmic reticulum (ER) has been prepared and analysed from germinating and developing castor bean endosperm. A combination of one- and two-dimensional (1-D and 2-D) gel electrophoresis was used to study the complexity of sample and protein differences between the two stages. The ER of the developing oilseed is central to the synthesis, sorting and storage of protein and lipid reserves while the germinating seed is concerned with their degradation. Sample complexity has been reduced by separation of ER proteins into lumenal, peripheral membrane and integral membrane subfractions. Membrane proteins pose specific problems in aggregation and binding to passive surfaces. We have overcome this by collection of membranes at density gradient interfaces and by silanization of plastic ware. Several major components have been identified from 1-D gels by N-terminal sequencing and matrix-assisted laser desorption/ionization (MALDI) peptide mass fingerprints. These include protein disulphide isomerase (PDI), calreticulin and developing-ER-specific oleate-12-hydroxylase involved in the biosynthesis of ricinoleic acid. In excess of 300 spots are detectable in each developmental fraction by high sensitivity 2-D gels. This is the first 2-D electrophoretic analysis of plant ER. These gels reveal significant differences between germinating and developing ER. Preparative loading 2-D gels of germinating ER have been run and 14 selected spots characterized by quadrupole time of flight tandem mass spectrometry (Q-TOF MS/MS). Ten of these proteins were assigned function on the basis of identity with existing castor database entries, or by homology with other species. Two proteins, aspartate proteinase precursor and N-carbamyl-L-aminohydrolase-like protein, appear to be absent from developing profiles. Most of the proteins identified are concerned with roles in protein processing and storage, and lipid metabolism which occur in the ER. Data from three of the assigned spots included unidentified peptides indicating the presence of more than one protein in these spots following 2-D electrophoresis. More extensive analysis will have to await developments in genomics but the basic separation technologies to simplify sample identity for a plant ER preparation have been established. 相似文献
27.
Pingli Lv Rongxiu Zhu Tongxiang Lu Steven E. Wheeler Dongju Zhang Ruoxi Wang Chengbu Liu 《Tetrahedron: Asymmetry》2013,24(24):1598-1604
Computational studies to determine the origin of enantioselectivity in the (1R,2R)-1,2-diphenylethane-1,2-diamine (DEPN)–Brønsted acid catalyzed epoxidation of 2-cyclohexen-1-one have been performed using density functional theory. Transition states for conjugate addition and ring closure steps of the epoxidations catalyzed by three different catalyst systems were characterized. Our calculations show that the Csp2H?O H-bond interaction between the benzene ring of the catalyst and H2O is mainly responsible for the chiral discrimination observed. The Brønsted acid counterion plays a very important role in ensuring high enantioselectivity by improving the rigidity of the transition state structures to allow the efficient formation of the Csp2H?O H-bond. Moreover, we explain why these two diamine catalysts (1S,2S)-DACH and (1R,2R)-DPEN display consistent enantioselectivities in the catalytic epoxidation of 2-cyclohexen-1-one when combining with three different cocatalysts; achiral TFA, and chiral (R)- and (S)-TRIP. 相似文献
28.
Four species of linear DNA and the first four members of a linking series, generated by treatment of plasmid DNA (PUC19, 2.7 kb) with mitochondrial topoisomerase I, were differentiated by transverse agarose pore gradient gel electrophoresis. The experimental curves of migration distance vs. agarose concentration (Ferguson curves) of supercoiled DNA exhibit a steeper trajectory than those of linear DNA of the same size range. As a consequence, the four supercoiled species exhibit an increase in apparent size (relative to linear DNA standards) with increasing agarose concentration. Both the crossing of the Ferguson curves with those of linear standards as well as the apparent size increase with agarose concentration can serve to detect supercoiled plasmid-sized DNA in mixtures with linear DNA. 相似文献
29.
This communication is an announcement of the availability on the Internet of a computer output of discontinuous buffer systems operative at pH 2.5-11.0, 0 degrees C and 25 degrees C, generated by the theory and program of T. M. Jovin. The output and instructions for its use can be accessed under http://www.buffers.nichd.nih.gov. 相似文献
30.
Molecular Control of Bioactivity in Sol-Gel Glasses 总被引:2,自引:0,他引:2
Hench Larry L. Wheeler Donna L. Greenspan David C. 《Journal of Sol-Gel Science and Technology》1998,13(1-3):245-250
Bioactive materials can be divided into: Class A bioactive glasses which exhibit rapid bonding to bone and soft connective tissue and are osteoproductive, and osteoconductive; and Class B bioactive ceramics, which bond slowly only to bone and are only osteoconductive. Bioactive sol-gel glasses composed of SiO2-CaO-P2O5 have Class A behavior in vitro and in vivo and also resorb as they enhance the proliferation of new trabecular bone. 相似文献