Improved efficiency of reversed-phase carbon/nanodiamond/polymer core-shell particles for HPLC using carbonized poly(divinylbenzene) microspheres as the core materials.

Here, we report efficiencies up to 112,000 plates per meter (a reduced plate height, h, of 2.22) for RP, carbon/nanodiamond/aminopolymer particles using conventional injection conditions in HPLC. This efficiency greatly exceeds our best previously reported value of 71,000 N/m (h = 3.52). The carbon cores used in this study were derived from carbonized poly(divinylbenzene) spheres that were either made in-house by a two-step polymerization procedure or obtained commercially. The resulting particles showed good uniformity and were oxidized in nitric acid to increase their dispersability. X-ray photoelectron spectroscopy confirms particle oxidation and subsequent aminopolymer deposition. Layer-by-layer (LbL) growth of poly(allyamine) and nanodiamond was demonstrated to produce core-shell particles. After LbL growth, the particles were functionalized, sieved, and packed into columns. The column functionalization and packing were reproducible. Van Deemter curves indicated that the commercially obtained poly(divinylbenzene) spheres outperformed those synthesized in our laboratory. The columns appear to be stable at 120°C in a pH 11.3 mobile phase. Longer columns (2.1 × 50 mm) than previously reported were packed. Four essential oils were separated by gradient elution.

Stable, microfabricated thin layer chromatography plates without volume distortion on patterned, carbon and Al2O3-primed carbon nanotube forests.

Some of us recently described the fabrication of thin layer chromatography (TLC) plates from patterned carbon nanotube (CNT) forests via direct infiltration/coating of the CNTs by low pressure chemical vapor deposition (LPCVD) of silicon from SiH4, followed by high temperature oxidation of the CNTs and Si. Herein we present an improved microfabrication process for the preparation of these TLC plates. First, a few nanometers of carbon and/or a thin film of Al2O3 is deposited on the CNTs. This method of priming the CNTs for subsequent depositions appears to be new. X-ray photoelectron spectroscopy confirms the presence of additional oxygen after carbon deposition. After priming, the plates are coated by rapid, conformal deposition of an inorganic material that does not require subsequent oxidation, i.e., by a fast pseudo atomic layer deposition (ψ-ALD) of SiO2 from trimethylaluminum and tris(tert-butoxy)silanol. Unlike devices described previously, faithful reproduction of the features in the masks is still observed after oxidation. A bonded, amino phase on the resulting plates shows fast, highly efficient separations of fluorescent dyes (plate heights in the range of 1.6-7.7 µm). Extensive characterization of the new materials by TEM, SEM, EDAX, DRIFT, and XPS is reported. A substantially lower process temperature for the removal of the CNT scaffold is possible as a result of the already oxidized materials used.

Functionalization/passivation of porous graphitic carbon with di-tert-amylperoxide.

Porous graphitic carbon (PGC) particles were functionalized/passivated in situ in packed beds at elevated temperature with neat di-tert-amylperoxide (DTAP) in a column oven. The performance of these particles for high performance liquid chromatography (HPLC) was assayed before and after this chemistry with the following analytes: benzene, toluene, ethyl benzene, n-propyl benzene, n-butyl benzene, p-xylene, phenol, 4-methylphenol, phenetole, 3,5-xylenol, and anisole. After the first functionalization/passivation, the retention factors, k, of these compounds decreased by about 5% and the number of theoretical plates (N) increased by ca. 15%. These values of k then remained roughly constant after a second functionalization/passivation but a further increase in N was noticed. In addition, after each of the reactions, the peak asymmetries decreased by ca. 15%, for a total of ca. 30%. The columns were then subjected twice to methanol at 100°C for 5h at 1 mL/min. After these stability tests, the values of k remained roughly constant, the number of plates increased, which is favorable, and the asymmetries rose and then declined, where they remained below the initial values for the unfunctionalized columns. Functionalized and unfunctionalized particles were characterized by scanning electron microscopy and BET measurements, which showed no difference between the functionalized and unfunctionalized materials, and X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS), where ToF-SIMS suggested some chemical differences between the functionalized and unfunctionalized materials. In particular ToF-SIMS suggested that the expected five-carbon fragments from DTAP exist at higher concentrations on DTAP-functionalized PGC. First principle calculations on model graphitic surfaces suggest that the first addition of a DTAP radical to the surface proceeds in an approximately isothermal or slightly favorable fashion, but that subsequent DTAP additions are then increasingly thermodynamically favorable. Thus, this analysis suggests that the direct functionalization/passivation of PGC with DTAP is plausible. Chemometric analyses of the chromatographic and ToF-SIMS data are also presented.

Pellicular particles with spherical carbon cores and porous nanodiamond/polymer shells for reversed-phase HPLC.

A new stationary phase for reversed-phase high performance liquid chromatography (RP HPLC) was created by coating spherical 3 µm carbon core particles in a layer-by-layer (LbL) fashion with poly(allylamine) (PAAm) and nanodiamond. Unfunctionalized core carbon particles were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and Raman spectroscopy. After LbL of PAAm and nanodiamond, which yields ca. 4 µm core-shell particles, the particles were simultaneously functionalized and cross-linked using a mixture of 1,2-epoxyoctadecane and 1,2,7,8-diepoxyoctane to obtain a mechanically stable C(18)/C(8) bonded outer layer. Core-shell particles were characterized by SEM, and their surface area, pore diameter, and volume were determined using the Brunauer-Emmett-Teller (BET) method. Short stainless steel columns (30 × 4.6 mm i.d.) were packed and the corresponding van Deemter plots obtained. The Supporting Information contains a MATLAB program used to fit the van Deemter data. The retentions of a suite of analytes were investigated on a conventional HPLC at various organic solvent compositions, pH values of mobile phases, including extreme pH values, and column temperatures. At 60 °C, a chromatogram of 2,6-diisopropylphenol showed 71,500 plates/m (N/m). Chromatograms obtained under acidic conditions (pH 2.7) of a mixture of acetaminophen, diazepam, and 2,6-diisopropylphenol and a mixture of phenol, 4-methylphenol, 2-chlorophenol, 4-chlorophenol, 4-bromophenol, and 1-tert-butyl-4-methylphenol are presented. Retention of amitriptyline, cholesterol, and diazinon at temperatures ranging from 35 to 80 °C and at pH 11.3 is reported. A series of five basic drugs was also separated at this pH. The stationary phase exhibits considerable hydrolytic stability at high pH (11.3) and even pH 13 over extended periods of time. An analysis run on a UHPLC with a "sandwich" injection appeared to reduce extra column band broadening and gave best efficiencies of 110,000-120,000 N/m.

Direct modification of hydrogen/deuterium-terminated diamond particles with polymers to form reversed and strong cation exchange solid phase extraction sorbents.

We describe direct polymer attachment to hydrogen and deuterium-terminated diamond (HTD and DTD) surfaces using a radical initiator (di-tert-amyl peroxide, DTAP), a reactive monomer (styrene) and a crosslinking agent (divinylbenzene, DVB) to create polystyrene encapsulated diamond. Chemisorbed polystyrene is sulfonated with sulfuric acid in acetic acid. Surface changes were followed by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and diffuse reflectance Fourier transform infrared spectroscopy (DRIFT). Finally, both polystyrene-modified DTD and sulfonated styrene-modified DTD were used in solid phase extraction (SPE). Percent recovery and column capacity were investigated for both phenyl (polystyrene) and sulfonic acid treated polystyrene SPE columns. These diamond-based SPE supports are stable under basic conditions, which is not the case for silica-based SPE supports.

Core-shell diamond as a support for solid-phase extraction and high-performance liquid chromatography.

We report the formation of core-shell diamond particles for solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) made by layer-by-layer (LbL) deposition. Their synthesis begins with the amine functionalization of microdiamond by its immersion in an aqueous solution of a primary amine-containing polymer (polyallylamine (PAAm)). The amine-terminated microdiamond is then immersed in an aqueous suspension of nanodiamond, which leads to adsorption of the nanodiamond. Alternating (self-limiting) immersions in the solutions of the amine-containing polymer and the suspension of nanodiamond are continued until the desired number of nanodiamond layers is formed around the microdiamond. Finally, the core-shell particles are cross-linked with 1,2,5,6-diepoxycyclooctane or reacted with 1,2-epoxyoctadecane. Layer-by-layer deposition of PAAm and nanodiamond is also studied on planar Si/SiO(2) surfaces, which were characterized by scanning electron microscopy (SEM), Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA). Core-shell particles are characterized by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), environmental scanning electron microscopy (ESEM), and Brunauer-Emmett-Teller (BET) surface area and pore size measurements. Larger (ca. 50 microm) core-shell diamond particles have much higher surface areas and analyte loading capacities in SPE than nonporous solid diamond particles. Smaller (ca. 3 microm), normal and reversed-phase, core-shell diamond particles have been used for HPLC, with 36,300 plates/m for mesitylene in a separation of benzene and alkyl benzenes and 54,800 plates/m for diazinon in a similar separation of two pesticides on a C(18) adsorbent.

C18, C8, and perfluoro reversed phases on diamond for solid-phase extraction.

In spite of advances in solid-phase extraction (SPE) technology there are certain disadvantages to current SPE silica-based, column packings. The pH range over which extraction can occur is limited and each column is generally only used once. New diamond-based reversed SPE phases (C(18), C(8), and perfluorinated) were developed in our laboratories. Studies were done which show that these phases do not have the same limitations as traditional silica-based stationary phases. The synthesis and properties of these diamond-based phases are presented, and the stability, percent recovery, and column capacity are given for the C(18) phase.

Amino-modified diamond as a durable stationary phase for solid-phase extraction.

We report the formation of a highly stable amino stationary phase on diamond and demonstrate its use in solid-phase extraction (SPE). This process consists of spontaneous and self-limiting adsorption of polyallylamine (PAAm) from aqueous solution onto oxidized diamond. Thermal curing under reduced pressure or chemical cross-linking with a diepoxide was shown to fix the polymer to the particles. The resulting adsorbents are stable under even extreme pH conditions (from at least pH 0-14) and significantly more stable than a commercially available amino SPE adsorbent. Coated diamond particles were characterized by X-ray photoelectron spectroscopy (XPS) and diffuse reflectance Fourier transform-infrared spectroscopy (DRIFT). Model silicon surfaces were characterized by spectroscopic ellipsometry and wetting. Solid-phase extraction was demonstrated using cholesterol, hexadecanedioic acid, and palmitoyloleoylphosphatidylcholine as analytes, and these results were compared to those obtained with commercially available materials. Breakthrough curves indicate that, as expected, porous diamond particles have higher analyte capacity than nonporous solid particles.