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Three "dimeric" C(9)-carbamates of quinine (QN) and quinidine (QD), that is, QN-QN, QD-QD, and QN-QD (chemically prepared mixture of the two cinchona-derived subunits), separated by an ethylene spacer were synthesized and used as chiral selectors for HPLC and capillary electrophoresis (CE) for the resolution of chiral acids. The chiral recognition abilities of these dimers and of several physically prepared mixtures thereof were compared in order to estimate the contribution of every cinchona scaffold to the overall enantioselectivity. The diverse phenomena observed in nonaqueous capillary electrophoresis (NACE), either using the selector added to the background electrolyte (BGE) in the total filling or partial filling mode, led us to rationalize, taking into account the relative mobilities of the chiral selectors in the capillary. The chromatographic and electrophoretic properties were compared with those of the corresponding "monomeric" QN and QD carbamates.

Tritium ( 3 H) is an important hydrological tracer commonly used for over 60 years to evaluate water residence times and water dynamics in shallow/recent groundwaters, streams, lakes and the ocean. We tested the analytical performance of 78 international laboratories engaged in low-level 3 H assays for water age dating and monitoring of environmental waters. METHODS:Seven test waters were distributed by the IAEA to 78 international tritium laboratories. Set 1 included a tritium-free groundwater plus three ultra-low 3 H samples (0.5-7 TU) for meeting groundwater dating specifications. Set 2 contained three higher 3 H-content samples (40-500 TU) suitable for testing of environmental monitoring laboratories. RESULTS:Seventy of the laboratories used liquid scintillation counting with or without electrolytic enrichment, seven utilized 3 He accumulation and mass-spectrometry, and one used gas-proportional counting. Only ~50 % of laboratories demonstrated the ability to generate accurate 3 H data that was precise enough for water age dating purposes.CONCLUSIONS: TRIC2018 helped identify recurrent weaknesses and potential solutions.Strategies for performance improvement of 3 H laboratories include: a) improved quantification of 3 H detection limits and analytical uncertainty, b) stricter quality control practices in routine operations along with care and recalibration of 3 H standards traceable to primary NIST standards, c) annual assessment of enrichment factors and instrumental performance, and d) for water age dating purposes the use of electrolytic enrichment systems having the highest possible 3 H enrichment factors (e.g. > 50x).

SummarySix new quinine (QN) O9-hydrazide derivatives with different substituents have been synthesized and immobilized on porous silica gel for HPLC. The chiral resolving power of these anion-exchange-type chiral stationary phases (CSPs) has been investigated and compared with that of four carbamate QN derivatives with analogous substitution. The unsubstituted QN-hydrazide derivative was usually the best chiral selector of the hydrazide series. Among the substituted hydrazide derivatives the introduction of a tritylcarbonyl or a tertbutylcarbonyl group at the fl position of the hydrazide function improved chiral recognition by the resulting CSPs. Although carbamate functionality seemed to favour the resolution of the enantiomers of many of the racemic compounds tested, the hydrazide series resulted in better separations of the enantiomers of the DNP derivatives of amino acids and of certain acidic drugs of therapeutic interest, such as the profens. The selectivity factors of these types of compounds on these QN-hydrazide derivatives are the best yet obtained on QNderived chiral selectors.