Search

Nafion formed on the surface of a boron-doped diamond electrode allows for a chemosensing system for biotin. The modified electrode is capable of oxidizing biotin and offers a detection limit of 5 nM, the average normal level of biotin in blood plasma. The developed method was successfully applied to determine biotin in human plasma samples and a popular health product as two popular models., Competing Interests: The authors declare no competing financial interest.

A novel hierarchical nanotemplated carbon monolithic rod (NTCM) was prepared using a novel facile nanotemplating approach. The NTCM was obtained using C60-fullerene modified silica gels as hard templates, which were embedded in a phenolic resin containing a metal catalyst for localized graphitization, followed by bulk carbonization, and template and catalyst removal. TEM, SEM, and BET measurements revealed that NTCM possessed an integrated open hierarchical porous structure, with a trimodal pore distribution. This porous material also possessed a high mesopore volume and narrow mesopore size distribution. During the course of carbonization, the C60 conjugated to aminated silica was partly decomposed, leading to the formation of micropores. The Raman signature of NTCM was very similar to that of multiwalled carbon nanotubes as exemplified by three major peaks as commonly observed for other carbon materials, i.e., the sp3 and sp2 carbon phases coexisted in the sample. Surface area measurements were obtained using both nitrogen adsorption/desorption isotherms (BET) and with a methylene blue binding assay, with BET results showing the NTCM material possessed an average specific surface area of 435 m2 g(-1), compared to an area of 372 m2 g(-1) obtained using the methylene blue assay. Electrochemical studies using NTCM modified glassy carbon or boron doped diamond (BDD) electrodes displayed quasi-reversible oxidation/reduction with ferricyanide. In addition, the BDD electrode modified with NTCM was able to detect hydrogen peroxide with a detection limit of below 300 nM, whereas the pristine BDD electrode was not responsive to this target compound.

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).

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.

Field-amplified sample stacking using a fused silica capillary coated with gold nanoparticles (AuNPs) embedded in poly(diallyl dimethylammonium) chloride (PDDA) has been investigated for the electrophoretic separation of indoxyl sulfate, homovanillic acid (HVA), and vanillylmandelic acid (VMA). AuNPs (27 nm) exhibit ionic and hydrophobic interactions, as well as hydrogen bonding with the PDDA network to form a stable layer on the internal wall of the capillary. This approach reverses electro-osmotic flow allowing for fast migration of the analytes while retarding other endogenous compounds including ascorbic acid, uric acid, catecholamines, and indoleamines. Notably, the two closely related biomarkers of clinical significance, HVA and VMA, displayed differential interaction with PDDA-AuNPs which enabled the separation of this pair. The detection limit of the three analytes obtained by using a boron doped diamond electrode was approximately 75 nM, which was significantly below their normal physiological levels in biological fluids. This combined separation and detection scheme was applied to the direct analysis of these analytes and other interfering chemicals including uric and ascorbic acids in urine samples without off-line sample treatment or preconcentration.

N-acetyltyramine was synthesized and electropolymerized together with a negatively charged sulfobutylether-beta-cyclodextrin on a boron-doped diamond (BDD) electrode followed by the electropolymerization of pyrrole to form a stable and permselective film for selective dopamine detection. The selectivity and sensitivity of the formed layer-by-layer film was governed by the sequence of deposition and the applied potential. Raman results showed a decrease in the peak intensity at 1329 cm(-1) (sp(3)), the main feature of BDD, upon each electrodeposition step. Such a decrease was correlated well with the change of the charge-transfer resistance derived from impedance data, i.e., reflecting the formation of the layer-by-layer film. The polycrystalline BDD surface became more even with lower surface roughness as revealed by scanning electron and atomic force microscopy. The modified BDD electrode exhibited rapid response to dopamine within 1.5-2 s and a low detection limit of 4-5 nM with excellent reproducibility. Electroactive interferences caused by 4-dihydroxyphenylalanine, 3,4-dihydroxyphenylacetic acid, ascorbic acid, and uric acid were completely eliminated, whereas the signal response of epinephrine and norepinephrine was significantly suppressed by the permselective film.

The use of gold nanoparticles in conjunction with etched capillary-based open-tubular capillary electrochromatography (OTCEC) to improve the efficiency of separation and the selectivity between selected solutes is described. The fused-silica capillaries (50-microm i.d.) were etched with ammonium hydrogen difluoride, followed by prederivatization of the new surface with (3-mercaptopropyl)trimethoxysilane (MPTMS) for the immobilization of dodecanethiol gold nanoparticles, for OTCEC. The electrochromatography of a "reversed-phase" test mixture and of selected polycylic aromatic hydrocarbons was investigated, and efficient separations and high theoretical plate numbers per meter were obtained. The electroosmotic flow characteristics of the etched gold nanoparticle capillary, unetched gold nanoparticle capillary, bare capillary, and etched bare capillary were studied by varying the percentage of organic modifier in buffer, buffer pH, and separation voltage. Optical microscopy and scanning electron microscopy were used to examine the process of etching and modification and the surface features of the etched gold nanoparticle capillary. The results confirm that dodecanethiol gold nanoparticles bonded on the etched inner wall of the fused-silica capillary can provide sufficient solute-bonded phase interactions to obtain OTCEC separations with reproducible retention, as well as characteristic reversed-phase behavior, even with the inner diameter of the capillary of 50 microm.

Chromatographic silica-bonded stationary phases have been prepared using supercritical CO(2) as the reaction medium. (29)Si solid-state NMR spectra of the generated bonded silica phases show unreacted silica species Q(3) and Q(4), alongside important resonances for surface-bound ligands, T(1), T(2), and T(3). Initially, a fluorinated octyl silica (C(8)) phase was produced, by reacting (1)H,(1)H,(2)H,(2)H-perfluorooctyltriethoxysilane with silica particles (3 microm) in sc-CO(2) at 60 degrees C and 450 atm for 3 h. In-house-packed LC columns of this fluorinated sc-C(8) silica phase yielded typical reversed-phase behavior when a standard test mix of benzamide (k' = 1.03), benzophenone (k' = 8.11), and biphenyl (k' = 14.92) was eluted. When packed into fused-silica capillaries for CEC, this fluorinated sc-C(8) silica phase gave linear plots of log k' versus percentage MeOH for benzophenone and biphenyl and, in contrast to octyl or octadecyl silica phases, displayed selectivity for aromatic thioureas when chromatographed among a series of synthetic organic thiourea test solutes. Similarily, an octadecyl silica phase (sc-C(18) silica) was prepared by reaction of n-octadecyltriethoxysilane in sc-CO(2), packed at 9500 psi and examined by LC. The sc-C(18) silica LC column yielded high column efficiency (up to 141 000 N/m (fluorene)) and excellent asymmetry factors (1.06, fluorene) without resource to end-capping. Following a second silylating or end-capping step using hexamethyldisilazane in sc-CO(2), sc-end-capped sc-C(18) silica phases elute N,N-DMA before toluene and the toluidine isomers as a single peak, indicating lowered silanol activity according to the Engelhardt test. A rapid separation of the important pharmaceutical substances, ketoprofen, naproxen, fentoprofen, and ibuprofen, on an sc-end-capped sc-C(18) silica phase is also shown.

Calixarenes are synthetic macrocyclic compounds, described as "molecular baskets" as they possess high ionophoric selectivity and form inclusion complexes with many important ionic guests. In our initial work, hexameric and tetrameric tert-butylcalixarenes, unfunctionalized at the lower rim, are shown to be separable on a diol column using supercritical fluid chromatography with methanol/chloroform-modified CO(2) as mobile phase. The variation in capacity factors for these calixarenes was studied as a function of modifier composition. However, the solubility of these molecular baskets in unmodified supercritical CO(2) is enhanced by fluorination at the upper rim. For example, when p-allylcalix[4]arene is derivatized by a thiol-ene addition reaction with heptadecafluorodecanethiol, CF(3)(CF(2))(7)(CH(2))(2)SH, a solubility of >0.12 mol L(-)(1) in supercritical CO(2) is measured for the p-heptadecafluorodecylthio-n-propylcalix[4]arene at 60 °C and 200 atm. However, subsequent lower rim functionalization to form the tetrahydroxamate derivative, while reducing the solubility, allows supercritical fluid extraction of Fe(III) by the fluorinated calix[4]arene ligands to be studied as a function of temperature and pressure and monitored using UV/visible and atomic absorption spectrometry. In particular, the visible absorption spectra obtained for the extracted Fe(III)-calix[4]arene tetrahydroxamate complex, collected in dimethyl sulfoxide, are indicative of octahedral Fe(III) complexation in a manner similar to that displayed by water-soluble siderophores. Studies on the efficiency and selectivity of Fe(III) extraction are also reported.

A new (-)-menthyl bonded silica phase has been prepared by hydrosilation of a hydride silica intermediate. The hydride silica intermediate was synthesized by the reaction of a monoalkoxysilane (CH(3))(2)SiH(OEt) with silica gel, yielding a relatively high surface coverage (4.4 μmol/m(2)) of SiH groups. This intermediate was then used successfully in the preparation of a monomeric (-)-menthyl bonded silica phase. The bonded phase produced has been used for the chromatographic separation of enantiomers in a reversed phase mode (chiral separations). Solid state (13)C and (29)Si CP-MAS NMR spectroscopy and DRIFT spectroscopy provides valuable information on the structure of the different surface species formed on silica after modification. The surface coverage of the hydride silica intermediate and of the final bonded silica phase produced are also determined. It is found that this modification procedure can exclusively produce a monomeric coverage of SiH groups on the silica surface and can further produce a final monomeric bonded organic silica phase for the separation of enantiomers.