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121.
Cai H Kiplinger JP Goetzinger WK Cole RO Laws KA Foster M Schrock A 《Rapid communications in mass spectrometry : RCM》2002,16(6):544-554
Flow splitting to a mass spectrometer is a common way of coupling a highly specific detector to preparative or semi-preparative high-performance liquid chromatography (HPLC) purification of combinatorial libraries, drug metabolites, and characterizable impurities. The sensitive mass spectrometer consumes only a small fraction of the analyte while providing online structure-specific detection, and its output can thus be used to trigger collection of the desired fraction. Coupling mass spectrometry to preparative HPLC is difficult due to the susceptibility of the detector to fouling under conditions of high analyte concentration or solute amount, or to changes in solvent composition. We report here on a device, the mass rate attenuator (MRA), which automatically produces split ratios over a range of 100:1 to 100 000:1 under programmable user control. The MRA is a flow-control device that periodically gates a small aliquot from one liquid stream into another. The design allows the user to set the frequency of the gating without interruption of the HPLC flow stream. The MRA also allows control of the volume of the aliquot that is transferred between the flow streams. This additional control, compared to passive splitting devices, facilitates optimization of the tubing connecting the separation, detection and collection events. We demonstrate that such optimization can reduce the volume of the collected fraction without compromising recovery, thus reducing the time spent in evaporating solvents to reclaim purified products. 相似文献
122.
New acid/base salts as co‐catalysts for the organocatalyzed ring opening polymerization of lactide
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Yong Miao Nicholas Stanley Audrey Favrelle Till Bousquet Marc Bria André Mortreux Philippe Zinck 《Journal of polymer science. Part A, Polymer chemistry》2015,53(5):659-664
(R)‐(+)‐binaphathyl‐diyl hydrogen phosphate (BNPH)/ diazabicyclo[5.4.0]undec‐7‐ene (DBU) and (1R)‐(?)?10‐camphorsulfonic acid (CSA)/4‐dimethylaminopyridine (DMAP) acid–base salts were synthesized and assessed for the ring‐opening polymerization of rac‐lactide. They were found to be inactive toward the polymerization in the presence of a protic initiator. When used in combination with a base such as DBU or DMAP and a protic initiator, these acid/base conjugates led to well‐controlled polymerization in mild conditions (DM < 1.1 in all cases). With DBU, the presence of the salt was found to lead to narrower molecular weight distributions than those obtained using the base alone, and to prevent undesirable transesterification reactions occurring at the end of the reaction. An increase in activity was observed using the salts in combination with DMAP as compared with DMAP alone, together with an improvement of the control over the molecular weight. The results were discussed on the basis of 1H nuclear magnetic resonance analyzes including acid/base equilibria involving the use of two different bases. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 659–664 相似文献
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125.
T. Neuhaus A. Härtel M. Marechal M. Schmiedeberg H. Löwen 《The European physical journal. Special topics》2014,223(3):373-387
This mini-review summarizes recent progress in describing heterogeneous crystallization processes and microstructure formation within microscopic classical density functional theory (DFT). After outlining the basic features of DFT, we discuss several applications ranging from the structure and thermodynamics of fluid-crystal interfaces for hard sphere and Yukawa systems to dynamical phenomena such as crystal growth on structured substrates and induced by externally imposed seeds. 相似文献
126.
Stable Isotope Labeling by Amino acid in Vivo (SILAV): a new method to explore protein metabolism
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127.
We use computer simulations to investigate the crystallization dynamics of sedimenting hard spheres in large systems (hundreds of thousands of particles). We show that slow sedimentation results primarily in face-centered cubic (fcc) stacked crystals, instead of random hexagonal close packed or hexagonal close packed (hcp) crystals. We also find slanted stacking faults, in the fcc regions. However, we attribute the formation of fcc to the free energy difference between fcc and hcp and not to the presence of these slanted stacking faults. Although the free energy difference between hcp and fcc per particle is small (only 10(-3) times the thermal energy), it can become considerable, when multiplied by the number of particles in each domain. The ratio of fcc to hcp obtained from dynamic simulations is in excellent agreement with well-equilibrated Monte Carlo simulations, in which no slanted stacking faults were found. Our results explain a range of experiments on colloids, in which the amount of fcc increases upon lowering the sedimentation rate or decreasing the initial volume fraction. 相似文献
128.
The reactivity ratios relative to cationic polymerization of three chlorostyrenes and styrene were studied. The values of r1 and r2 were determined for various experimental conditions. The influence of the solvent, of the polymerization temperature, of the nature of the initiator and of the molecular weight distribution were examined in particular. The relative activation entropies and enthalpies were determined (against styrene as reference) and an Isokinetic relationship was found for 2- and 3-chlorostyrenes. All the experimental reactivities were correlated with the quantum chemistry parameters. From this correlation it is found that the interaction is possible not only with C8, but also with C7 and CI, depending on the nature of the monomer. 相似文献
129.
A vinyl ester resin was modified into half ester-acids by reaction with phthalic, maleic, and succinic anhydrides, using pyridine as catalyst. GPC analysis indicated that the reaction proceeds without crosslinking or polymerization. 13C-NMR analysis showed that the β-isomer of the vinyl ester resin containing a primary hydroxyl group reacts much more rapidly than the α-isomer with a secondary hydroxyl group. 相似文献
130.
1-Isopropenylnaphthalene has been dimerized by cationic initiation. The structure of the dimer does not depend on the initiator. The cyclization of the dimeric ion takes place on carbon 8 (peri). The structure has been established both by x-ray diffractometry and by NMR. The complete crystallographic structure has been determined. The dimers of various substituted isopropenylnaphthalenes have been obtained in the same way and have the same structure. 相似文献