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81.
Sara L. Schaefer Connor L. RobertsErasmus O. Volz Monika R. GrassoGregory W. O’Neil 《Tetrahedron letters》2013
Aromatic allylic benzoates can be selectively transformed to the corresponding benzoate eliminated olefin by the action of samarium diiodide. Depending on the substrate and the elimination conditions, high selectivity for the non-conjugated alkene product can be achieved. 相似文献
82.
83.
Thermodynamic studies were performed on 12 pairs of N-trifluoroacetyl-O-alkyl nipecotic acid ester enantiomers on diluted permethylated beta-cyclodextrin stationary phase (CP Chirasil-Dex CB). The influence of ester alkyl group structure on interaction with permethylated beta-cyclodextrin (Me-CD) and enantioselectivity was studied. The types of alkyl groups studied included n-alkyl (C1-C5) and groups containing branching at differing locations relative to the chiral center of the molecule. The results show that for a given molecular weight, the n-alkyl esters have stronger interactions with Me-CD than esters containing branched alkyl groups. However, although having weaker interactions with Me-CD, esters containing alpha-branched alkyl groups exhibit higher enantioselectivity than the corresponding n-alkyl or beta-branched isobutyl esters. From the retention data, thermodynamic parameters were estimated using the retention increment method and enthalpy-entropy compensation plots (ln R' versus deltaH) were constructed. The results suggest that ester enantiomers with branching at the alpha-carbon of the ester alkyl group have additional and/or different types of enantioselective interactions with Me-CD than the C1-C5 n-alkyl esters or beta-branched isobutyl ester. In order to obtain a qualitative sense of the interaction with Me-CD, structures of the diastereomeric complexes formed between Me-CD and some of the ester enantiomers were modeled using simulated annealing molecular dynamics. 相似文献
84.
Fotouh R. Mansour Christine L. Kirkpatrick Neil D. Danielson 《Chromatographia》2013,76(11-12):603-609
An ion-exclusion chromatography (IELC) comparison between a conventional ion-exchange column and an ultra high-performance liquid chromatography (UHPLC) dynamically surfactant modified C18 column for the separation of an aliphatic carboxylic acid and two aromatic carboxylic acids is presented. Professional software is used to optimize the conventional IELC separation conditions for acetylsalicylic acid and the hydrolysis products: salicylic acid and acetic acid. Four different variables are simultaneously optimized including H2SO4 concentration, pH, flow rate, and sample injection volume. Thirty different runs are suggested by the software. The resolutions and the time of each run are calculated and feed back to the software to predict the optimum conditions. Derringer’s desirability functions are used to evaluate the test conditions and those with the highest desirability value are utilized to separate acetylsalicylic acid, salicylic acid, and acetic acid. These conditions include using a 0.35 mM H2SO4 (pH 3.93) eluent at a flow rate of 1 mL min?1 and an injection volume of 72 μL. To decrease the run time and improve the performance, a UHPLC C18 column is used after dynamic modification with sodium dodecyl sulfate. Using pure water as a mobile phase, a shorter analysis time and better resolution are achieved. In addition, the elution order is different from the IELC method which indicates the contribution of the reversed-phase mode to the separation mechanism. 相似文献
85.
86.
Dr. Annalisa Mancini Dr. M. Carla Aragoni Dr. Neil Bricklebank Dr. Carlo Castellano Prof. Francesco Demartin Prof. Francesco Isaia Prof. Vito Lippolis Dr. Anna Pintus Dr. Massimiliano Arca 《化学:亚洲杂志》2013,8(3):639-647
The reactions of 4,5,6,7‐tetrathiocino‐[1,2‐b:3,4‐b′]‐1,3,8,10‐tetrasubstituted‐diimidazolyl‐2,9‐dithiones (R2,R′2‐todit; 1 : R=R′=Et; 2 : R=R′=Ph; 3 : R=Et, R′=Ph) with Br2 exclusively afforded 1:1 and 1:2 “T‐shaped” adducts, as established by FT‐Raman spectroscopy and single‐crystal X‐ray diffraction in the case of complex 1? 2 Br2. On the other hand, the reactions of compounds 1 – 3 with molecular I2 provided charge‐transfer (CT) “spoke” adducts, among which the solvated species 3? 2 I2 ? (1?x)I2 ? x CH2Cl2 (x=0.94) and ( 3 )2 ? 7 I2 ? x CH2Cl2, (x=0.66) were structurally characterized. The nature of all of the reaction products was elucidated based on elemental analysis and FT‐Raman spectroscopy and supported by theoretical calculations at the DFT level. 相似文献
87.
Katell Bathany Neil W. Owens Gilles Guichard Jean-Marie Schmitter 《Journal of the American Society for Mass Spectrometry》2013,24(3):458-462
This study is focused on sequence analysis of peptidomimetic helical oligoureas by means of tandem mass spectrometry, to build a basis for de novo sequencing for future high-throughput combinatorial library screening of oligourea foldamers. After the evaluation of MS/MS spectra obtained for model compounds with either MALDI or ESI sources, we found that the MALDI-TOF-TOF instrument gave more satisfactory results. MS/MS spectra of oligoureas generated by decay of singly charged precursor ions show major ion series corresponding to fragmentation across both CO-NH and N′H-CO urea bonds. Oligourea backbones fragment to produce a pattern of a, x, b, and y type fragment ions. De novo decoding of spectral information is facilitated by the occurrence of low mass reporter ions, representative of constitutive monomers, in an analogous manner to the use of immonium ions for peptide sequencing. 相似文献
88.
Chao Huang Steven M. Santana He Liu Neil H. Bander Benjamin G. Hawkins Brian J. Kirby 《Electrophoresis》2013,34(20-21):2970-2979
The capture of circulating tumor cells (CTCs) from cancer patient blood enables early clinical assessment as well as genetic and pharmacological evaluation of cancer and metastasis. Although there have been many microfluidic immunocapture and electrokinetic techniques developed for isolating rare cancer cells, these techniques are often limited by a capture performance tradeoff between high efficiency and high purity. We present the characterization of shear‐dependent cancer cell capture in a novel hybrid DEP–immunocapture system consisting of interdigitated electrodes fabricated in a Hele‐Shaw flow cell that was functionalized with a monoclonal antibody, J591, which is highly specific to prostate‐specific membrane antigen expressing prostate cancer cells. We measured the positive and negative DEP response of a prostate cancer cell line, LNCaP, as a function of applied electric field frequency, and showed that DEP can control capture performance by promoting or preventing cell interactions with immunocapture surfaces, depending on the sign and magnitude of the applied DEP force, as well as on the local shear stress experienced by cells flowing in the device. This work demonstrates that DEP and immunocapture techniques can work synergistically to improve cell capture performance, and it will aid in the design of future hybrid DEP–immunocapture systems for high‐efficiency CTC capture with enhanced purity. 相似文献
89.
Dr. Amy C. Topley Valerio Isoni Dr. Thomas A. Logothetis Dr. Duncan Wynn Dr. Harry Wadsworth Dr. Alex M. R. Gibson Imtiaz Khan Dr. Neil J. Wells Prof. Cécile Perrio Prof. Richard C. D. Brown 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(5):1720-1725
A Resin‐linker‐vector (RLV) strategy is described for the radiosynthesis of tracer molecules containing the radionuclide 18F, which releases the labelled vector into solution upon nucleophilic substitution of a polystyrene‐bound arylsulfonate linker with [18F]‐fluoride ion. Three model linker‐vector molecules 7 a – c containing different alkyl spacer groups were assembled in solution from (4‐chlorosulfonylphenyl)alkanoate esters, exploiting a lipase‐catalysed chemoselective carboxylic ester hydrolysis in the presence of the sulfonate ester as a key step. The linker‐vector systems were attached to aminomethyl polystyrene resin through amide bond formation to give RLVs 8 a – c with acetate, butyrate and hexanoate spacers, which were characterised by using magic‐angle spinning (MAS) NMR spectroscopy. On fluoridolysis, the RLVs 8 a , b containing the longer spacers were shown to be more effective in the release of the fluorinated model vector (4‐fluorobutyl)phenylcarbamic acid tert‐butyl ester ( 9 ) in NMR kinetic studies and gave superior radiochemical yields (RCY≈60 %) of the 18F‐labelled vector. The approach was applied to the synthesis of the radiopharmaceutical O‐(2‐[18F]‐fluoroethyl)‐L ‐tyrosine ([18F]‐FET), delivering protected [18F]‐FET in >90 % RCY. Acid deprotection gave [18F]‐FET in an overall RCY of 41 % from the RLV. 相似文献
90.
Ahmed M. Eissa Michael J.P. Smith Artur Kubilis Jackie A. Mosely Neil R. Cameron 《Journal of polymer science. Part A, Polymer chemistry》2013,51(24):5184-5193
Copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) was used to prepare glycosylated polyethylene (PE)–poly(ethylene glycol) (PEG) amphiphilic block copolymers. The synthetic approach involves preparation of alkyne‐terminated PE‐b‐PEG followed by CuAAC reaction with different azide functionalized sugars. The alkyne‐terminated PE‐b‐PEG was prepared by etherification reaction between hydroxyl‐terminated PE‐b‐PEG (Mn ~ 875 g mol?1) and propargyl bromide and azidoethyl glycosides were prepared by glycosylation of 2‐azidoethanol. Atmospheric pressure solids analysis probe‐mass spectrometry was used as a novel solid state characterization tool to determine the outcome of the CuAAC click reaction and end‐capping of PE‐b‐PEG by the azidoethyl glycoside group. The aqueous solution self‐assembly behavior of these amphiphilic glycosylated polymers was explored by TEM and dye solubilization studies. Carbohydrate‐bearing spherical aggregates with the ability to solubilize a hydrophobic dye were observed. The potential of these amphiphilic glycosylated polymers to self‐assemble via electro‐formation into giant carbohydrate‐bearing polymersomes was also investigated using confocal fluorescence microscopy. An initial bioactivity study of the carbohydrate‐bearing aggregates is furthermore presented. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5184–5193 相似文献