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231.
Eckers C Laures AM Giles K Major H Pringle S 《Rapid communications in mass spectrometry : RCM》2007,21(7):1255-1263
Many formulated products contain complex polymeric excipients such as polyethylene glycols (PEGs). Such excipients can be readily ionized by electrospray and may be present at very high concentrations, thus making it very difficult to identify trace level impurities such as degradants in samples, even if hyphenated techniques such as liquid chromatography/mass spectrometry (LC/MS) are used. Ion mobility (IM) spectrometry is a very rapid gas-phase separation technique and offers additional separation capability within the LC timeframe. This work investigates the use of an IM separator in combination with high-pressure liquid chromatography (HPLC) and MS, to improve the separation of drug-related materials from excipients, thus aiding the identification of trace-level impurities in an anti-HIV medication, Combivir. 相似文献
232.
Pandey D Zemlyanov DY Bevan K Reifenberger RG Dirk SM Howell SW Wheeler DR 《Langmuir : the ACS journal of surfaces and colloids》2007,23(9):4700-4708
Molecular layers formed from 4-trifluoromethylbenzenediazonium tetrafluoroborate and 4-Methylbenzenediazonium tetrafluoroborate have been assembled on H-passivated Si(111) and studied by UHV STM and XPS. STM imaging shows well-developed Si(111) step edges and terraces both on Si(111):H and Si(111) substrates covered with a molecular layer. STM I(V) data acquired at different tip-substrate separations reveals a factor of approximately 10 enhancement in current for positive bias voltage when current flows through the 4-trifluoromethyl molecule when compared to the 4-methyl variant. The observed current enhancement in I(V) can be understood by comparing the projected density of states of the two molecule-Si systems calculated using a density functional theory local density approximation after geometry optimization was performed via the conjugate gradient method. XPS data independently confirm that H-passivated Si(111) remains oxygen free for short exposures to ambient conditions and provide evidence that the molecules chemically react with the silicon surface. 相似文献
233.
Motoaki Kimura Steve Tung James Lew Chih-Ming Ho Fukang Jiang Yu-Chong Tai 《Fluid Dynamics Research》1999,24(6):679-342
Measurements of wall shear-stress streaks of a turbulent boundary layer in the channel flow were carried out using a MEMS-based micro-shear-stress imaging chip, which contains about 100 sensors. The chip is designed and fabricated by surface micromachining technology. One arrray of 25 micro-shear-stress sensors in the chip that covers a length of 7.5 mm is used to measure the instantaneous spanwise distribution of the surface shear stress. The statistics of high shear-stress streaks were established. Based on the measurement, the physical quantities associated with the high shear-stress streaks, such as their length, width and peak shear-stress level, were obtained. We found out that a high correlation exists between the peak shear-stress level and front-end shear-stress slope of a high shear-stress streak. This important property is currently being applied to the deisgn of a real-time flow control logic. 相似文献
234.
Rafa Wysokiski Wiktor Zierkiewicz Mariusz Michalczyk Steve Scheiner 《Molecules (Basel, Switzerland)》2021,26(21)
Molecules of the type XYT = Ch (T = C, Si, Ge; Ch = S, Se; X,Y = H, CH3, Cl, Br, I) contain a σ-hole along the T = Ch bond extension. This hole can engage with the N lone pair of NCH and NCCH3 so as to form a chalcogen bond. In the case of T = C, these bonds are rather weak, less than 3 kcal/mol, and are slightly weakened in acetone or water. They owe their stability to attractive electrostatic energy, supplemented by dispersion, and a much smaller polarization term. Immersion in solvent reverses the electrostatic interaction to repulsive, while amplifying the polarization energy. The σ-holes are smaller for T = Si and Ge, even negative in many cases. These Lewis acids can nonetheless engage in a weak chalcogen bond. This bond owes its stability to dispersion in the gas phase, but it is polarization that dominates in solution. 相似文献
235.
The central C atom of the OCCCO skeleton of the malonaldehyde molecule is replaced by N, and the effects upon the intramolecular H-bond and the proton transfer are monitored by ab initio calculations in the ground and excited electronic states. The H-bond is weakened in the singlet and triplet states arising from n→π* excitation in both molecules, which is accompanied by a heightened barrier to proton transfer.3ππ* behaves in the same manner, but the singlet ππ* state has a stronger H-bond and lower barrier. Replacement of the central C atom by N strengthens the intramolecular H-bond. Although the proton transfer barrier in the ground state of formimidol is lower than in malonaldehyde, the barriers in all four excited states are higher in the N-analog. The latter substitution also dampens the effect of the n→π* excitation upon the H-bond and increases the excitation energies of the various states, particularly ππ*. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 129–138, 1998 相似文献
236.
Yoon-Kyoung Cho Ali Dhinojwala Steve Granick 《Journal of Polymer Science.Polymer Physics》1997,35(17):2961-2968
We study the drainage of a near-theta solvent through densely grafted polymer layers and compare to recent notions that these layers display little permeability to solvent flow at surface separations less than a “hydrodynamic thickness.” The solvent is trans-decalin (a near-theta solvent at the experimental temperature of 24°C). The polymer is polystyrene (PS) end-attached to two opposed mica surfaces via the selective adsorption of the polyvinylpyridine (PVP) block of a PS-PVP diblock copolymer. The experimental probe was a surface forces apparatus modified to apply small-amplitude oscillatory displacements in the normal direction. Out-of-phase responses reflected viscous flow of solvent alone—the PS chains did not appear to contribute to dissipation over the oscillation frequencies studied. The value of the hydrodynamic thickness (RH) was less than the coil thickness (Lo) measured independently from the onset of surface–surface interactions in the force-distance profile, implying significant penetration of the velocity field into the polymer layer. As the surface–surface separation was reduced from 3Lo to 0.3Lo, the apparent hydrodynamic thickness (R) decreased monotonically to values R ≪ RH. Physically, this indicates that the “slip plane” moved progressively closer to the solid surfaces with decreasing surface–surface separation. This was accompanied by augmentation of the effective viscosity by a factor of up to approximately 5, indicating somewhat diminished permeability of solvent through the overlapping polymer layers. Similar results hold for the flow through surface-anchored polymers in a good solvent. It is interesting to note the strong stretching of densely end-grafted polymers in a theta solvent. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2961–2968, 1997 相似文献
237.
At the single-molecule level, this laboratory has been making direct measurements of polymer diffusion at and near surfaces. Parameters of special interest have been to understand (a) the role of molecular weight, N; (b) the role of surface coverage, which may range from dilute to saturated, and (c) the role of the surface, which may range from hard (a silicon wafer) to soft (a supported lipid bilayer), and (d) the use of external fields to direct the transport of small molecules through narrow surface channels that are one macromolecule thick. 相似文献
238.
Fridrun Podczeck Steve Brown J. Michael Newton 《Particle & Particle Systems Characterization》1999,16(4):185-190
Tablets of five different compression formulations were investigated for their surface roughness using scanning electron microscopy and non-contact laser profilometry. It was found that the composition of a formulation not only influenced the tabletting properties of the powder mixtures, but also the surface properties of the final product. The addition of larger quantities of very brittle materials such as dibasic calcium phosphate dihydrate increased the surface roughness of tablets. An increase in tabletting pressure reduced the tablet surface roughness. Tablets were found to have smoother edges than faces, presumably due to the comparatively higher shear stress at the die walls and a polishing effect during tablet ejection. The assessment of surface roughness in three dimensions appeared more powerful than a simple line profile measurement. 相似文献
239.
Sameer Bargir Steve Dunn Bruce Jefferson Simon Parsons 《Applied Surface Science》2009,255(9):4873-4879
We have studied a series of solids using contact angle measurements; stainless steel, gold, aluminium, titanium nitride and PTFE that are frequently used in domestic water environments. It was found the influence of electron-donor (γ−) and electron-acceptor (γ+) free energies on material scaling rate was dominated by water wetting angles, providing materials exhibit an average roughness below 100 nm. The γ− component had the greatest influence on theoretical adhesion, while γLW, (Lifshitz-van der Waals) γ+ and γAB (acid-base) had little effect. From the materials analysed, amorphous carbon coatings were least adhesive, while ‘kettle coating’ and highly roughened steel the most adhesive. The size and distribution of asperities also influenced the polar free energies and subsequent adhesion due to fluctuations in the wetting angle. The results obtained indicate works of adhesion can be used as a complementary technique with Lewis acid-base theory to deliver useful information about the propensity of scale to deposit on solids. 相似文献
240.
Stefan Antusch Mar Bastero-Gil Koushik Dutta Steve F. King Philipp M. Kostka 《Physics letters. [Part B]》2009
We propose the introduction of a Heisenberg symmetry of the Kähler potential to solve the problems with chaotic inflation in supergravity, as a viable alternative to the use of shift symmetry. The slope of the inflaton potential emerges from a small Heisenberg symmetry breaking term in the superpotential. The modulus field of the Heisenberg symmetry is stabilized and made heavy with the help of the large vacuum energy density during inflation. The observable predictions are indistinguishable from those of typical chaotic inflation models, however the form of the inflationary superpotential considered here may be interpreted in terms of sneutrino inflation arising from certain classes of string theory. 相似文献