A new N-hydroxyethyliminodiacetic acid modified core-shell silica phase for chelation ion chromatography of alkaline earth, transition and rare earth elements.

Bare core-shell silica (1.7µm) has been modified with iminodiacetic acid functional groups via standard silane chemistry, forming a new N-hydroxyethyliminodiacetic acid (HEIDA) functionalised core-shell stationary phase. The column was applied in high-performance chelation ion chromatography and evaluated for the retention of alkaline earth, transition and heavy metal cations. The influence of nitric acid eluent concentration, addition of complexing agent dipicolinic acid, eluent pH and column temperature on the column performance was investigated. The efficiencies obtained for transition and heavy metal cations (and resultant separations) were comparable or better than those previously obtained for alternative fully porous silica based chelation stationary phases, and a similarly modified monolithic silica column, ranging from ∼15 to 56µm HETP. Increasing the ionic strength of the eluent with the addition of KNO3 (0.75M) and increasing the column temperature (70°C) facilitated the isocratic separation of a mixture of 14 lanthanides and yttrium in under 12min, with HETP averaging 18µm (7µm for Ce(III)).

Porous graphitized carbon monolith as an electrode material for probing direct bioelectrochemistry and selective detection of hydrogen peroxide.

For the first time, graphitized carbon particles with a high surface area have been prepared and evaluated as a new material for probing direct electrochemistry of hemoglobin (Hb). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) imaging revealed that the carbon monolithic skeleton was constructed by a series of mesopores with irregular shapes and an average pore diameter of ~5.6 nm. With a surface area of 239.6 m(2)/g, carbon particles exhibited three major Raman peaks as commonly observed for carbon nanotubes and other carbon materials, i.e., the sp(3) and sp(2) carbon phases coexisted in the sample. A glassy carbon electrode modified with carbon monoliths and didodecyldimethylammonium bromide exhibited direct electron transfer between Hb molecules and the underlying electrode with a transfer rate constant of 6.87 s(-1). The enzyme electrode displayed a pair of quasi-reversible reduction-oxidation peaks at -0.128 and -0.180 V, reflecting the well-known feature of the heme [Fe(3+)/Fe(2+)] redox couple: a surface-controlled electrochemical process with one electron transfer. This reagentless biosensing approach was capable of detecting H(2)O(2), a simple molecule but plays an important role in analytical and biological chemistry, as low as 0.1 µM with linearity of 0.1-60 µM and a response time of <0.8 s, comparing favorably with other carbon based electrodes (5 s).

Comparison between the efficiencies of sub-2 µm C18 particles packed in narrow bore columns.

The chromatographic performance of two types of core-shell particles and two fully porous particles packed in 2.1 ID × 50 mm columns was investigated. Comparisons of the performances of the EiS-150-C(18) to that of the Kinetex-1.7 µm-C(18), Acquity-BEH-1.7 µm-C(18), and Zorbax-XDB-1.8 µm-C(18) are made and discussed. The physical factors that govern the performance of these columns, such as particle size distribution and column external, total, and particle porosity of the C(18) packing materials were among the prime foci of investigation. The differences in the mass transfer behavior measured using naphtho[2,3-a]pyrene between these columns provides an indication of improved performance of the new EiS-150-C(18) column. The minimum reduced height equivalent to a theoretical plate (HETP) value for the EiS-150-C(18), h(min) = 1.95, was achieved and was comparable to that obtained from the C(18) phases of the Kinetex (h(min) = 2.53), the Acquity (h(min) = 2.26), and the Zorbax (h(min) = 2.57) columns. This study reveals the importance of the dimension of the shell thickness in controlling the performance of columns packed with shell particles in narrow bore columns.

Structural variation of solid core and thickness of porous shell of 1.7 µm core-shell silica particles on chromatographic performance: narrow bore columns.

Chromatographic and mass transfer kinetic properties of three narrow bore columns (2.1×50 mm) packed with new core-shell 1.7 µm EIROSHELL™-C(18) (EiS-C(18)) particles have been studied. The particles in each column varied in the solid-core to shell particle size ratio (ρ), of 0.59, 0.71 and 0.82, with a porous silica shell thickness of 350, 250 and 150 nm respectively. Scanning and transmission electron microscopy (SEM and TEM), Coulter counter analysis, gas pycnometry, nitrogen sorption analysis and inverse size exclusion chromatography (ISEC) elucidated the physical properties of these materials. The porosity measurement of the packed HILIC and C(18) modified phases provided the means to estimate the phase ratios of the three different shell columns (EiS-150-C(18), EiS-250-C(18) and EiS-350-C(18)). The dependence of the chromatographic performance to the volume fraction of the porous shell was observed for all three columns. The naphtho[2,3-a]pyrene retention factor of k'∼10 on the three EiS-C(18s) employed to obtain the height equivalents to theoretical plates (HETPs) data were achieved by varying the mobile phase compositions and applying the Wilke and Chang relationship to obtain a parallel reduced linear velocity. The Knox fit model gave the coefficient of the reduce HETPs for the three EiS-C(18s). The reduced plate height minimum h(min)=1.9 was achieved for the EiS-150-C(18) column, and generated an efficiency of over 350,000 N/m and h(min)=2.5 equivalent to an efficiency of 200,000 N/m for the EiS-350-C(18) column. The efficiency loss of the EiS-C18 column emanating from the system extra-column volume was discussed with respect to the porous shell thickness.

Retention and selectivity properties of carbamate pesticides on novel polar-embedded stationary phases.

This study describes the use of stationary phases with polar functionality suitable for the chemical analysis of carbamates pesticides and comparing with conventional alkyl C8 and C18 phases. The emphasis of this study was to compare the selectivity and retention of the pesticides on different stationary phases, bonded onto 1.7 microm partially porous silica particles under isocratic separation condition. Four stationary phases including: phenylaminopropyl (PAP) phase, bidentate propylurea-C18 (BPUC(18)), C8 and C18, were successfully bonded on the partially porous silica spheres as evidenced by (29)Si and (13)C solid-state NMR analysis. The phenylaminopropyl phase exhibited smaller retentivity and enhanced selectivity compared to the alkyl C8 phase; the analysis time to run separation of the six carbamate pesticides (i.e., methomyl, propoxur, carbofuran, carbaryl, isoprocarb, and promecarb) on the PAP phase was threefold faster than alkyl C8 phase. In a similar manner, the BPUC(18) phase shows similar selectivity to that of the PAP phase, but with longer retentivity; although the BPUC(18) phase is characterized with a lesser degree of retentivity for the carbamate pesticides than the conventional alkyl C18 phase. We propose that pi-pi and weak polar interactions between the carbamate pesticides and the PAP phase dominates the separation mechanism and providing a superior selectivity; faster separation time was also achieved as a result of smaller retentivity. Whereas the C8 and C18 bonded phases exhibits only hydrophobic interactions with the pesticides, leading to larger retentivity. The BPUC(18) phase is shown to interact via polar-polar interactions in addition to hydrophobic interactions with the pesticides, providing similar selectivity with the PAP phase but with larger retentivity.

Cyclodextrin-modified capillary electrophoresis for achiral and chiral separation of ergostane and lanostane compounds extracted from the fruiting body of Antrodia camphorata.

A CD-modified capillary electrophoretic method has been developed for achiral and chiral analysis of seven bioactive compounds isolated from the fruiting body of Antrodia camphorata. Such important target analytes exhibit similar chemical structures and are known for their diverse properties including antioxidant and anticancer effects. The analytes were separated in 25 min using a pH 9.3, 20 mM sodium borate buffer containing 20 mM methyl-beta-CD and 30 mM sulfobutylether-beta-CD. With the exception of the optical isomer pairs (antcin B or zhankuic acid A, zhankuic acid C, and antcin A), the remaining bioactive compounds including the chiral pair antcin C were baseline-separated. Analysis time was noticeably longer to baseline separate all of the above chiral pairs (approximately 38 min) by adding 5% DMF to the running buffer. The migration order was reversed compared with the HPLC elution. More hydrophobic compounds complexed favorably with methyl-beta-CD and emerged earlier in the electropherogram than their more hydrophilic counterparts which were strongly associated with sulfobutylether-beta-CD. The simple capillary electrophoretic method developed was applicable for rapid separation and characterization of several important bioactive compounds isolated from the fruiting body of A. camphorata.