Trifluoroethylene Sultone: Structure and Chemistry

The gas phase structure of trifluoroethylene sultone, ( 1 ) (3,4,4-trifluoro-1,2-oxathietane-2,2-dioxide) was determined by gas electron diffraction, and the four-membered ring was found to be planar. The following ring parameters (r_a distances and ∠_α angles with 3σ uncertainties) were derived in the electron diffraction analysis: C? O = 1.41 Å (ass.), C? C = 1.541(18) Å, S? O = 1.652(5) Å, S? C = 1.822(8) Å, S? C? C = 86.2(15)°, C? C? O = 97.1(28)°, C? O? S = 97.5(21)°, and O? S? C = 79.1(8)°. New spectral data (IR, NMR) of 1 , its acyclic isomer FSO₂CFHC(O)F ( 2 ), and the related anhydride, FSO₂OSO₂CFHC(O)F ( 3 ), are reported. New esters containing the fluorosulfonyl function, FSO₂CFHC(O)OCH₂CF₃ ( 4 ), FSO₂CFHC(O)OCH₂CH = CH₂ ( 5 ), and (FSO₂CFHC(O)OCH₂CH? CH₂? )_n ( 6 ) have been prepared and characterized.     

Chip-based nLC-TOF-MS is a highly stable technology for large-scale high-throughput analyses

Many studies focused on the discovery of novel biomarkers for the diagnosis and treatment of disease states are facilitated by mass spectrometry-based technology. HPLC coupled to mass spectrometry is widely used; miniaturization of this technique using nano-liquid chromatography (LC)-mass spectrometry (MS) usually results in better sensitivity, but is associated with limited repeatability. The recent introduction of chip-based technology has significantly improved the stability of nano-LC-MS, but no substantial studies to verify this have been performed. To evaluate the temporal repeatability of chip-based nano-LC-MS analyses, N-glycans released from a serum sample were repeatedly analyzed using nLC-PGC-chip-TOF-MS on three non-consecutive days. With an average inter-day coefficient of variation of 4 %, determined on log₁₀-transformed integrals, the repeatability of the system is very high. Overall, chip-based nano-LC-MS appears to be a highly stable technology, which is suitable for the profiling of large numbers of clinical samples for biomarker discovery.     

Radial sample load distribution under overload conditions: Analytical scale columns

The homogeneity of the sample load across the radial cross section of analytical scale columns was determined when operating under overload conditions. The study was performed using active flow technology columns operating in parallel segmentation mode. The outlet segmentation ratio was varied to enable different volume fractions of mobile phase, and thus sample, to elute from the peripheral and central flow regions of the column. The amount of solute exiting the peripheral and radial central exit ports was determined as a function of the flow segmentation ratio. The experimental data using an analytical scale column with dimensions, 100?×?4.6?mm, indicated that the sample load distribution was essentially uniform as a function of the column radial cross section.     

p-Alkoxy- and p-alkylbenzoates of α, a'-bi-p-hydroxytoluene. New series of liquid-crystalline compounds

Abstract

Six p-alkoxy and eight p-alkylbenzoates of 1,2-(p-hydroxyphenyl)ethane were synthesized for potential use as stationary phases in gas-liquid chromatography. All the p-alkoxy derivatives were nematic. The first five members of the alkyl series were nematic and the rest exhibited both smectic and nematic character. Most possess the desired combination of a wide liquid-crystalline temperature range and a high mesomorphic-isotropic transition temperature. The nematic-isotropic transition temperatures and entropies show the usual alternations characteristic of a high-melting series.     

Bis‐clickable Mesoporous Silica Nanoparticles: Straightforward Preparation of Light‐Actuated Nanomachines for Controlled Drug Delivery with Active Targeting

Bis(clickable) mesoporous silica nanospheres (ca. 100 nm) were obtained by the co‐condensation of TEOS with variable amounts (2–5 % each) of two clickable organosilanes in the presence of CTAB. Such nanoparticles could be easily functionalized with two independent functions using the copper‐catalyzed alkyne‐azide cycloaddition (CuAAC) reaction to transform them into nanomachines bearing cancer cell targeting ligands with the ability to deliver drugs on‐demand. The active targeting was made possible after anchoring folic acid by CuAAC click reaction, whereas the controlled delivery was performed by clicked azobenzene fragments. Indeed, the azobenzene groups are able to obstruct the pores of the nanoparticles in the dark whereas upon irradiation in the UV or in the blue range, their trans‐to‐cis photoisomerization provokes disorder in the pores, enabling the delivery of the cargo molecules. The on‐command delivery was proven in solution by dye release experiments, and in vitro by doxorubicin delivery. The added value of the folic acid ligand was clearly evidenced by the difference of cell killing induced by doxorubicin‐loaded nanoparticles under blue irradiation, depending on whether the particles featured the clicked folic acid ligand or not.     

Fluorescence and absorbance spectroscopy of the uranyl ion in nitric acid for process monitoring applications

Near real time process monitoring of the uranium content in an aqueous fuel recycling plant is a desired component of an advanced safeguards suite; Ultraviolet–Visible spectroscopy and Time Resolved Laser induced Fluorescence Spectroscopy can contribute to this technology gap. This work presents the observation of the spectroscopic parameters (molar absorptivities, fluorescent response) of the uranyl ion across the range of conditions expected in reprocessing chemistry. From this data, a monitor using the ratio of the absorbance of the uranyl ion at 403 and 426 nm has been developed. This technique can determine the nitrate solution concentration and can be coupled with a condition appropriate molar absorptivity to determine the uranyl concentration. This method provides a reliable technique for online, real time process monitoring of the uranyl and nitrate concentration under a wide range of solution compositions.