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151.
Maruthi Kumar Narayanam Yong Liang K. N. Houk Jennifer M. Murphy 《Chemical science》2016,7(2):1257-1261
Density functional theory (DFT) calculations and experiments in tandem led to discoveries of new reactivities and selectivities involving bioorthogonal sydnone cycloadditions. Dibenzocyclooctyne derivatives (DIBAC and BARAC) were identified to be especially reactive dipolarophiles, which undergo the (3 + 2) cycloadditions with N-phenyl sydnone with the rate constant of up to 1.46 M–1 s–1. Most significantly, the sydnone-dibenzocyclooctyne and norbornene-tetrazine cycloadditions were predicted to be mutually orthogonal. This was validated experimentally and used for highly selective fluorescence labeling of two proteins simultaneously. 相似文献
152.
153.
Ying Han Katalin Ebinger Jennifer W. Maloney Harold N. Weller 《Tetrahedron letters》2010,51(4):629-4502
A new, divergent, efficient, and selective synthesis of furo- and thieno[2,3-d]pyrimidin-4-amine derivatives by microwave irradiation has been developed starting from readily available amines and substituted 2-aminofuran-3-carbonitrile or 2-aminothiophene-3-carbonitrile, which are converted into corresponding formamidines in DMF using benzenesulfonyl chloride. 相似文献
154.
155.
Jennifer E. Mihalick William P. Griffiths III James E. Muten Travis A. Olson John B. Hein 《Journal of solution chemistry》1999,28(8):1019-1030
Solution calorimetry was used to determine enthalpies and stability constants for binding of lead(II) or cadmium(II) by galacturonic acid and several monosaccharides in aqueous solution. New values for enthalpies of solution in water are reported for galacturonic acid and maltose monohydrate. The interaction of water solvent with the reactants is the largest factor in the binding process. 相似文献
156.
The ability to discriminate between sounds with different spectral shapes was evaluated for normal-hearing and hearing-impaired listeners. Listeners detected a 920-Hz tone added in phase to a single component of a standard consisting of the sum of five tones spaced equally on a logarithmic frequency scale ranging from 200 to 4200 Hz. An overall level randomization of 10 dB was either present or absent. In one subset of conditions, the no-perturbation conditions, the standard stimulus was the sum of equal-amplitude tones. In the perturbation conditions, the amplitudes of the components within a stimulus were randomly altered on every presentation. For both perturbation and no-perturbation conditions, thresholds for the detection of the 920-Hz tone were measured to compare sensitivity to changes in spectral shape between normal-hearing and hearing-impaired listeners. To assess whether hearing-impaired listeners relied on different regions of the spectrum to discriminate between sounds, spectral weights were estimated from the perturbed standards by correlating the listener's responses with the level differences per component across two intervals of a two-alternative forced-choice task. Results showed that hearing-impaired and normal-hearing listeners had similar sensitivity to changes in spectral shape. On average, across-frequency correlation functions also were similar for both groups of listeners, suggesting that as long as all components are audible and well separated in frequency, hearing-impaired listeners can use information across frequency as well as normal-hearing listeners. Analysis of the individual data revealed, however, that normal-hearing listeners may be better able to adopt optimal weighting schemes. This conclusion is only tentative, as differences in internal noise may need to be considered to interpret the results obtained from weighting studies between normal-hearing and hearing-impaired listeners. 相似文献
157.
Rigid macroporous copolymers of styrene and divinylbenzene have been designed for large-scale preparative and process-scale purification of synthetic peptides and recombinant proteins. The polymeric particles are mechanically stable and hence able to operate at the required high linear velocities. The pore size and pore morphology has been optimised to enable unhindered solute diffusion whilst providing maximum available surface area to enhance loading capacity. A 100 A pore size has been developed for synthetic peptides and a 300 A pore size for recombinant proteins. Precise control of particle size, within the range 10 to 20 microm, is possible which together with the very narrow particle size distribution enables maximum resolution/loading to be obtained within the pressure limits of the instrumentation being used. The chemical stability of the polymer enables cleaning in place with 1 M sodium hydroxide without particle dissolution or a deterioration in selectivity. These materials can be packed into compression hardware and are manufactured as single lots up to 100 kg (300 l) batch size. 相似文献
158.
Capillary zone electrophoresis (CE) under conditions of reversed polarity is used in conjunction with electrochemical detection (EC) at carbon fiber microcylinder electrodes for the selective and sensitive determination of uric acid in human blood serum. Comigration of anions with the electroosmotic flow is accomplished with reversed polarity and the buffer additive cetyltrimethylammonium bromide (CTAB) in a 2-(N-morpholino)ethanesulfonic acid (MES) buffer system, giving rise to rapid and sensitive analyses. Optimal buffer conditions (pH 7.0), detection potential (0.80 V vs. Ag/AgCl), and electrokinetic injection are employed to allow for maximal resolution and signal intensity. Amperometric end-column detection with a carbon fiber microcylinder electrode results in lower limits of detection for uric acid of about 25 nM (ca. 140 amol injected) without the need for decoupling. Linear calibration plots using uric acid standards in water and serum are obtained over a linear range from 5.00 x 10(-4) M to 2.50 x 10(-7) M. Uric acid concentrations obtained for human sera using the CE-EC approach described here are shown to compare favorably to the accepted laboratory values. 相似文献
159.
Spore photoproduct (SP) lyase, which catalyzes the direct reversal of SP (5-thyminyl-5,6-dihydrothymine) to thymine monomers, is the only identified nonphotoactivatable pyrimidine dimer lyase. Unlike DNA photolyase, SP lyase does not contain a flavin cofactor and does not require light for activation. Instead, preliminary studies point to the presence of an iron-sulfur cluster in SP lyase and the requirement for S-adenosylmethionine (AdoMet) for catalytic activity, suggesting that SP lyase belongs to the growing group of iron-sulfur cluster and AdoMet-dependent radical enzymes. Here we provide evidence for the role of AdoMet as a reversible deoxyadenosyl radical generator, which initiates repair by hydrogen atom abstraction from C-6 of SP. Reaction of 6-(3)H-SP, but not methyl-(3)H-SP, with SP lyase and AdoMet results in transfer of (3)H to AdoMet, while no tritiated 5'-deoxyadenosine is observed. When 5'-tritiated AdoMet is used in the reaction with unlabeled SP, transfer of (3)H into the repaired thymine monomers is observed. These results point to the reversible generation of a 5'-deoxyadenosyl radical intermediate, which reacts directly with the DNA lesion to initiate a radical-mediated beta-scission. We also demonstrate that AdoMet is a catalytic cofactor that is not consumed during turnover. Together, these results support a novel radical-based mechanism for the repair of UV-induced DNA damage. 相似文献
160.
Thalladi VR Schwartz A Phend JN Hutchinson JW Whitesides GM 《Journal of the American Chemical Society》2002,124(33):9912-9917
A new physical model based on mesoscale self-assembly is developed to simulate indentation fracture in crystalline materials. Millimeter-scale hexagonal objects exhibiting atom-like potential functions were designed and allowed to self-assemble into two-dimensional (2D) aggregates at the interface between water and perfluorodecalin. Indentation experiments were performed on these aggregates, and the stresses and strains involved in these processes were evaluated. The stress field in the aggregates was analyzed theoretically using the 2D elastic Hertz solution. Comparison of the experimental results with theoretical analysis revealed that fracture develops in regions subjected to high shear stress and some, albeit low, tensile stress. The potential for the broader application of the model is illustrated using indentation of assemblies with point defects and adatoms introduced at predetermined locations, and using a two-phase aggregate simulating a compliant film on a stiff substrate. 相似文献