Graphene oxide-octadecylsilane incorporated monolithic nano-columns with 50 μm id and 100 μm id for small molecule and protein separation by nano-liquid chromatography

In this study, graphene oxide-octadecylsilane incorporated monolithic nano-columns were developed for protein analysis by nano liquid chromatography (nano LC). The monolithic column with 100 μm id was first prepared by an in situ polymerization using ethylene dimethacrylate (EDMA), 3-chloro-2-hydroxypropylmethacrylate (HPMA-Cl), and methacryloyl graphene oxide nanoparticles (MGONPs). MGONPs were synthesized by the treatment of 3-(trimethoxysilyl)propylmethacrylate (TMSPM) and GO. Tetrahydrofuran (THF) and dodecanol were used as the porogenic solvent. The resulting column was functionalized by dimethyloctadecylch lorosilane (DODCS) for the enhancement of hydrophobicity. The functionalization greatly improved the baseline separation of hydrophobic compounds such as polyaromatic hydrocarbons (PAHs). The optimized monolith with respect to total polymerization mixture was characterized by using Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) X-ray diffraction (XRD) and chromatographic analyses. The blank monoliths without functionalization exhibited poor separation while a good separation performance of MGONPs functionalized monoliths was achieved. The monolith with 100 μm id was evaluated in protein separation in nano LC using RNase A, Cytochrome C, Lysozyme, Trypsin, and Ca isozyme II as the test proteins. It was shown that protein separation mechanism was based on large π-system of GO and hydrophobicity of the monolithic structure. Theoretical plates number up to 57 600 plates were achieved. The nano-column with 50 μm id was also prepared using the same polymerization mixture under the same chemical conditions. These nano-columns were employed for protein separation by nano LC, and the dependence of both nano-column performance on the internal diameter was also discussed.     

Further remarks on simple flows of fluids with pressure-dependent viscosities

Recently Suslov and Tran (2008) [1] claimed to have found an error in one of the solutions given in the paper by Hron (2001) et al. [2] concerning the flows of fluids with pressure-dependent viscosities. We show that their arguments are related to the question of the continuity of the pressure, and we show that the original solution, although it is not a classical one, can be interpreted as a solution in a generalized sense. Mathematical and physical implications of such generalizations are briefly discussed. The discussion in the paper highlights the importance of recognizing what is meant by a “solution” to a partial differential equation, whether by a solution we mean a classical solution, a weak solution, or a solution in some other sense.     

A beaker without walls: formation of deeply supercooled binary liquid solutions of alcohols from nanoscale amorphous solid films

Layered nanoscale amorphous solid films of methanol and ethanol undergo complete intermixing prior to the onset of measurable desorption at 120 K. This intermixing precedes and inhibits crystallization. Subsequent desorption of the film is described quantitatively by a kinetic model describing evaporation from a continuously mixed ideal binary liquid solution. This occurs at temperatures below the melting point of the binary mixture, indicating ideal behavior for the supercooled liquid solution. This approach provides a new method for preparing and examining deeply supercooled solutions.     

The evaluation of overlap and Coulomb integrals in complexes with rare-earth or transition-metal central ions

Tables are given to enable effective algorithms to be formed for computer calculation of the overlap and Coulomb integrals with Slater-type orbitals in complexes with rare-earth or transition-metal central ions.     

Modeling deoxyribose radicals by neutralization-reionization mass spectrometry. Part 2. Preparation,dissociations, and energetics of 3-hydroxyoxolan-3-yl radical and cation

The title radical (1) is generated in the gas-phase by collisional neutralization of carbonyl-protonated oxolan-3-one. A 1.5% fraction of 1 does not dissociate and is detected following reionization as survivor ions. The major dissociation of 1 (approximately 56%) occurs as loss of the hydroxyl H atom forming oxolan-3-one (2). The competing ring cleavages by O[bond]C-2 and C-4[bond]C-5 bond dissociations combined account for approximately 42% of dissociation and result in the formation of formaldehyde and 2-hydroxyallyl radical. Additional ring-cleavage dissociations of 1 resulting in the formation of C(2)H(3)O and C(2)H(4)O cannot be explained as occurring competitively on the doublet ground (X) electronic state of 1, but are energetically accessible from the A and higher electronic states accessed by vertical electron transfer. Exothermic protonation of 2 also produces 3-oxo-(1H)-oxolanium cation (3(+)) which upon collisional neutralization gives hypervalent 3-oxo-(1H)-oxolanium radical (3). The latter dissociates spontaneously by ring opening and expulsion of hydroxy radical. Experiment and calculations suggest that carbohydrate radicals incorporating the 3-hydroxyoxolan-3-yl motif will prefer ring-cleavage dissociations at low internal energies or upon photoexcitation by absorbing light at approximately 590 and approximately 400 nm.     

Development and Validation of an LC–ESI-MS Ion-Trap Method for Analysis of Impurities in Transkarbam 12, a Novel Transdermal Accelerant

A new, sensitive LC–MS method for evaluation of the purity of Transkarbam 12 (T12), a novel and highly effective accelerant of transdermal penetration, has been developed and validated. T12 and its impurities (6-aminohexanoic acid, AH, ε-caprolactam, CA, and dodecyl 6-(6-aminohexanamido)hexanoate, DAH) were characterized by MS and MS–MS analysis. Separation was achieved on a 150 mm × 3 mm, 5-μm particle, phenyl–hexyl column. The mobile phase was a gradient prepared from water, formic acid, and acetonitrile. The method was validated within the concentration range 50–250 ng mL^?1; correlation coefficients were >0.998. The accuracy of the method was from 98.6–105.0% for AH, 102.6–104.8% for CA, and 97.9–100.9% for DAH. Precision was in the range 3.19–4.42% for AH, 3.22–5.81% for CA, and 4.8–8.78% for DAH. The selectivity of the method and sample stability were also confirmed. The practical applicability of the method was proven by analysis of T12 bulk substance.