Introducing Enantioselective Ultrahigh-Pressure Liquid Chromatography (eUHPLC): Theoretical Inspections and Ultrafast Separations on a New Sub-2-μm Whelk-O1 Stationary Phase

A new chiral stationary phase for ultrahigh-pressure liquid chromatography (UHPLC) applications was prepared by covalent attachment of the Whelk-O1 selector to spherical, high-surface-area 1.7-μm porous silica particles. Columns of varying dimensions (lengths of 50, 75, 100, and 150 mm and internal diameters of 3.0 or 4.6 mm) were packed and characterized in terms of permeability, efficiency, retention, and enantioselectivity, using both organic and water-rich mobile phases. A conventional HPLC Whelk-O1 column based on 5.0-μm porous silica particles and packed in a 250 mm × 4.6 mm column was used as a reference. Van Deemter curves, generated with low-molecular-weight solutes on a 100 mm × 4.6 mm column packed with the 1.7-μm particles, showed H(min) (μm) and μ(opt) (mm/s) values of 4.10 and 5.22 under normal-phase and 3.74 and 4.34 under reversed-phase elution conditions. The flat C term of the van Deemter curves observed with the 1.7-μm particles allowed the use of higher-than-optimal flow rates without significant efficiency loss. Kinetic plots constructed from van Deemter data confirmed the ability of the column packed with the 1.7-μm particles to afford subminute separations with good efficiency and its superior performances in the high-speed regime, compared to the column packed with 5.0-μm particles. Resolutions in the time scale of seconds were obtained using a 50-mm-long column in the normal phase or polar organic mode. The intrinsic kinetic performances of 1.7-μm silica particles are retained in the Whelk-O1 chiral stationary phase, clearly demonstrating the potentials of enantioselective UHPLC in terms of high speed, throughput, and resolution.     

Layer-by-layer self-assembly of multilayer zirconia nanoparticles on silica spheres for HPLC packings

A novel zirconia-based HPLC packing material, ZrO2/SiO2, which consists of micrometer-sized silica spheres as core and nanometer-sized zirconia particles as surface coating, was prepared by a layer-by-layer self-assembly technique. The material exhibits favorable characteristics for HPLC applications, including high surface area and pore volume, good pore structure, narrow particle size, and pore size distribution. Not only the support ZrO2/SiO2 but also the stationary-phase C18 bonded ZrO2/SiO2 exhibits excellent chemical stability. In addition, good permeability was observed for both of them. High specific area surface and good permeability of ZrO2/SiO2 permit a high loading amount of chiral polymer on it and greatly improved the enantioselectivity and resolution for some chiral separations.     

Conformal nanocoating of zirconia nanoparticles by atomic layer deposition in a fluidized bed reactor

Primary zirconia nanoparticles were conformally coated with alumina ultrathin films using atomic layer deposition (ALD) in a fluidized bed reactor. Alternating doses of trimethylaluminium and water vapour were performed to deposit Al(2)O(3) nanolayers on the surface of 26?nm zirconia nanoparticles. Transmission Fourier transform infrared spectroscopy was performed ex situ. Bulk Al(2)O(3) vibrational modes were observed for coated particles after 50 and 70?cycles. Coated nanoparticles were also examined with transmission electron microscopy, high-resolution field emission scanning electron microscopy and energy dispersive spectroscopy. Analysis revealed highly conformal and uniform alumina nanofilms throughout the surface of zirconia nanoparticles. The particle size distribution and surface area of the nanoparticles are not affected by the coating process. Primary nanoparticles are coated individually despite their high aggregation tendency during fluidization. The dynamic aggregation behaviour of zirconia nanoparticles in the fluidized bed plays a key role in the individual coating of nanoparticles.     

核壳结构的氧化锆包裹氧化铝纳米复合粉体的制备研究

采用简单的一步醇盐水解包裹工艺在市售纳米氧化铝颗粒表面均匀地包裹了一层厚度为4～5nm的纳米晶氧化锆, 形成核壳结构的氧化物纳米复合粉体. 通过简单的锆源及酸浓度的控制, 可以实现包裹的氧化锆层厚度的可控调节. 借助XRD、TEM、FE-SEM及 EDS等测试手段对合成的材料进行了形貌与结构表征, 结果表明这种纳米氧化锆包裹氧化铝的核壳复合结构材料, 可以有效地抑制氧化铝在高温煅烧下的晶粒过分长大, 实现在较低煅烧温度下即具有均匀致密的表面形貌.     

Influence of zirconia on biomimetic apatite formation in pure titanium coated via plasma electrolytic oxidation

This work demonstrated the effect of zirconia incorporation on the formation of biomimetic apatite in pure titanium coated by plasma electrolytic oxidation (PEO) method. To incorporate zirconia particles into the oxide layer, electrochemical coating was carried out under AC condition in an electrolyte containing zirconia powder. After PEO coatings, zirconia particles were distributed uniformly throughout the titanium oxide layer while the size and distribution of micro-pores remained unchanged when compared to titanium coated by PEO in an electrolyte without zirconia. It was found that a number of fine zirconia particles played an important role in triggering the occurrence of biomimetic apatite on top of the PEO-coated titanium in a simulated body fluid solution. This was mainly attributed to increased surface roughness of the oxide layer as well as inherent activation of zirconia particles to form biomimetic apatite.     

堇青石-氧化锆红外辐射复合粉体的制备

为获得具有高红外辐射性能的粉体,以堇青石颗粒为基体,采用液相共沉淀法,用氧化锆前驱体包覆堇青石基体,煅烧后得到堇青石-氧化锆红外辐射复合粉体;对制备的复合粉体进行热分析、物相分析及形貌分析,并测试其红外辐射性能。结果表明,利用非均匀形核可将氧化锆前驱体包覆于堇青石颗粒表面,氧化锆结晶温度在800～900℃之间,900℃煅烧后得到的氧化锆晶粒尺寸约为8 nm;当在一定初始溶液浓度范围内改变反应物的用量时,可以控制氧化锆的包覆量并且避免其自发团聚;通过氧化锆纳米颗粒包覆的工艺可以提高堇青石粉体在3～5μm波段的红外辐射性能,当氧化锆包覆质量分数为21.11%时,复合粉体具有最佳的红外辐射性能。     

Open tubular anion exchange chromatography. Controlled layered architecture of stationary phase by successive condensation polymerization

The preparation and performance of a multilayered stationary phase for open tubular anion exchange chromatography in relatively large bore (75 microm diameter) columns are described. The inner surface of a fused-silica capillary tube is coated with up to 25 successive porous polymeric layers formed by condensation polymerization of a primary amine with a diepoxide. Each layer of the anion exchange stationary phase consists of copolymer of methylamine (MA) and 1,4-butanedioldiglycidyl ether (BDDE). The polymer layers are sufficiently porous or permeable; each successive layer of the stationary phase incrementally increases the observed column capacity and chromatographic performance in the open tubular mode. Even though the column inner diameter is far from optimum for open tubular liquid chromatography, we demonstrate the baseline separation of a suite of inorganic anions (F-, Cl-, NO2-, Br-, NO3-) in a 5 m x 75 microm column coated with 25 layers of the anion exchange polymer using 1 mM KOH eluent and suppressed contactless conductometric detection at a flow rate of 1 microL/min (operating pressure of approximately 1 bar) with a plate count of >30,000. Strategies for construction of microsuppressor devices used in open tubular ion chromatography are discussed.     

Nonaqueous capillary electrochromatographic separation of synthetic neutral polymers by size exclusion chromatography using polymeric stationary phases

In this paper, we report the separations of large, neutral, synthetic polymers using primarily a nonaqueous mobile phase without the use of a supporting electrolyte. The size- exclusion-based mechanism for separation was achieved on sulfonated polystyrene/divinylbenzene stationary phases. The effect of water, voltage, stationary phase exchange capacity, and pore size were investigated. The stationary phase and solvent interactions were studied by attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR) and a possible mechanism for the generation of EOF in the THF/water system is provided. Linear calibration curves were obtained for polystyrenes ranging in MW from 5K to 2M, for columns made using a combination of high capacity ion exchanger and a neutral polystyrene/divinylbenzene material of varied pore sizes. Analysis of polyurethane, polystyrene, and other polymer samples using CEC correlated well with results obtained by conventional HPLC. The size exclusion CEC separations provide an alternative mode for determining the relative molecular weights of polymers, with reduced solvent consumption.     

Characterization and bioactive properties of zirconia based polymeric hybrid for orthopedic applications

Zirconia is a transition metal oxide with current applications to orthopedic implants. It has been shown to up-regulate specific genes involved in bio-integration and injury repair. This study examines the effects of zirconia and polydimethylsiloxane (PDMS) hybrids on the proliferation and viability of human primary osteoblast and fibroblast cells. In this study, zirconia–PDMS hybrid coatings were synthesized using a modified sol gel process. The hybrid material was characterized using optical microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and contact angle analysis. This study demonstrates that Zr–PMDS surface materials display hydrophobic surface properties coupled with a preferential deposition of polymer near the surface. Primary osteoblast and fibroblast proliferation and viability on hybrid coated surfaces were evaluated via a rapid screening methodology using WST-1 and calcein AM assays. The cells were seed at 5,000 cells per well in 96-well plates coated with various composition of Zr–PDMS hybrids. The results showed increasing cell proliferation with increasing zirconia concentration, which peaked at 90 % v/v zirconia. Proliferation of osteoblasts and fibroblasts displayed similar trends on the hybrid material, although osteoblasts displayed a bi-phasic dose response by the calcein AM assay. The results of this current study show that Zr–PDMS may be used to influence tissue–implant integration, supporting the use of the hybrid as a promising coating for orthopedic trauma implants.     

Magnetically immobilized beds for capillary electrochromatography

Fritless packed beds comprised of magnetically responsive octadecylsilane bonded silica particles have been constructed for reversed-phase electrochromatography. The magnetic particles were immobilized in the capillary by applying an external magnetic field transverse to the direction of electroosmotic flow. Being subjected to the interplay of fluid dragging and magnetic forces, the initial loosely packed particle assembly was compacted into a uniform packing structure. The magnetically immobilized beds obtained were used as stationary phases for separation of neutral compounds, with retention behavior and column efficiency similar to those of slurry-packed columns. The results suggest that the magnetic attraction approach to fritless column packing may be used for construction of advanced chip-based chromatography, especially in complex architectures comprising curved and intersecting channels.     

Tentacle-type zwitterionic stationary phase prepared by surface-initiated graft polymerization of 3-[N,N-dimethyl-N-(methacryloyloxyethyl)-ammonium] propanesulfonate through peroxide groups tethered on porous silica

A novel stationary phase with tentacle-type zwitterionic interaction layer was synthesized by free radical graft polymerization of 3-[N,N-dimethyl-N-(methacryloyloxyethyl)ammonium]propanesulfonate (SPE) from the surface of Kromasil porous silica particles. The polymerization was initiated by thermal cleavage of tert-butylperoxy groups covalently attached to the particle surface, and the material therefore carries a tentacle-type polymeric interaction layer with 3-sulfopropylbetaine functional moieties. The composition of the surface graft was determined by elemental analysis, and the surface charge was measured using photon correlation spectroscopy. The measured zeta-potentials were close to 0 and nearly independent of pH, and the tentacle character of the interactive layers were evident from the lack of colloidal stability in the absence of salt (antipolyelectrolytic behavior) and a marked increase in column back-pressure when the concentration of perchloric acid or perchlorate salt was increased. The chromatographic properties were evaluated on columns packed with the functionalized material, and it was shown that this zwitterionic stationary phase could simultaneously and independently separate inorganic anions and cations using aqueous solutions of perchloric acid or perchlorate salts as eluents. The material was also capable of separating two acidic and three basic proteins in a single run, using gradient salt elution at constant pH.     

Formulation and development of oral dry suspension using taste masked Ornidazole particles prepared using Kollicoat® Smartseal 30 D

The purpose of this work was to taste mask highly bitter active, Ornidazole by means of particle coating. The aim of the work was further extended into formulating these coated particles into an acceptable oral dosage form such as dry suspension. Ornidazole drug particles were coated using Kollicoat^® Smartseal 30 D as a taste masking polymer. Kollicoat^® Smartseal 30 D is a methyl methacrylate – diethylaminoethyl methacrylate copolymer (6:4). Successful taste masking was achieved for Ornidazole with both top spray and bottom spray techniques using fluid bed processor. Effective taste masking was achieved at a weight gain of 50% w/w and 40% w/w for bottom and top spray techniques respectively without having a significant effect on the release pattern. A taste masked dry suspension was prepared with around 80% w/w coated Ornidazole particles and pH was maintained around 7–8. The suspension prepared with these coated Ornidazole particles, which were maintained in the alkaline pH was found to be stable for 7 days without affecting the taste. The bitter taste intensity was evaluated using volunteers by comparison of test samples with standard solutions containing Ornidazole at various concentrations. Thus, Kollicoat^® Smartseal 30 D was found to be an effective polymer for taste masking of a bitter active like Ornidazole. The formulation development of taste masked dry suspensions was only possible due to unique properties possessed by Kollicoat^® Smartseal 30 D.     

An integrated fritless column for on-chip capillary electrochromatography with conventional stationary phases

A new polymer device for use with conventional particulate stationary phases for on-chip, fritless, capillary electrochromatography (CEC) has been realized. The structure includes an injector and a tapered column in which the particles of the stationary phase are retained and stabilized. The chips were easily fabricated in poly(dimethylsiloxane) using deep-reactive-ion-etched silicon masters, and tested using a capillary electrophoretic separation of FITC-labeled amino acids. To perform CEC, the separation channel was packed using a vacuum with 3-microm, octadecylsilanized silica microspheres. The packing was stabilized in the column by a thermal treatment, and its stability and quality were evaluated using in-column indirect fluorescence detection. The effects of voltage on electro-osmotic flow and on efficiency were investigated, and the separation of two neutral compounds was achieved in less than 15 s.     

Nanocoating of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> additive on ZrO<Subscript>2</Subscript> powder and its effect on the sintering behaviour in ZrO<Subscript>2</Subscript> ceramic

ZrO₂ powder was coated with Al₂O₃ precursor generated by a polymeric precursor method in aqueous solution. The system of nanocoated particles formed a core shell-like structure in which the particle is the core and the nanocoating (additive) is the shell. A new approach is reported in order to control the superficial mass transport and the exaggerated grain growth during the sintering of zirconia powder. Transmission electron microscopy (TEM) observations clearly showed the formation of an alumina layer on the surface of the zirconia particles. This layer modifies the sintering process and retards the maximum shrinkage temperature of the pure zirconia.     

Capillary ion chromatography at high pressure and temperature

The application of high pressure and temperature in ion chromatography (IC) can significantly improve the efficiency and reduce the analysis time. In this work, the kinetic-performance limits of capillary IC columns with inner diameters of 400 μm packed with 4 and 7 μm macroporous anion-exchange particles were investigated employing a capillary ion-exchange instrument allowing column pressures up to 34 MPa and column temperatures up to 80 °C. Plate heights below 10 μm could be realized using capillary columns packed with 4 μm particles. Compared to conventional IC using 7 μm particles and pressures up to 21 MPa, a 40% improvement in plate number could be achieved when working at the kinetic performance limits at 34 MPa and using columns packed with 4 μm particles. Using coupled columns with a total length of 400 mm, a mixture of seven anions was separated within 7.5 min while yielding 20?000 plates. Increasing the temperature improved the performance limits when operating in the C-term region (for fast IC separation using columns <75 cm). Temperature also affected the retention properties and hence the selectivity. At higher temperature, retention for monovalent ions was mainly governed by ion diameter. An increase in retention with temperature was observed for small ions, and there was a decrease for ions having a larger diameter. The retention factor for divalent and trivalent anions increased with temperature.     

Chromatographic determination of metallic impurities in reversed-phase HPLC columns

A new test procedure is proposed for the characterization of packed RP columns with respect to their metal content. It is based on the peak asymmetry of 2,2'-bipyridyl, which can be directly correlated to the metal content of the stationary phase. Since an unbuffered eluent (methanol/water, 49:51 w/w) is used, the influence of the simultaneously present silanol groups on peak asymmetry is assessed via 4,4'-bipyridyl, which exhibits no chelating activity. A metal factor, MF, is introduced, which is the ratio of the peak asymmetries of 2,2'-bipyridyl and 4,4'-bipyridyl multiplied by 100. The superiority of this test compared to others is demonstrated via various commercially available columns. It is also demonstrated that columns continuously collect metal ions from the column components and the instrument hardware. Stainless steel nets and frits are the principal source of the metallic contamination. But even in totally metal-free LC systems, the stationary phase collects metal ions from the HPLC grade eluent components.     

Single-walled carbon nanotubes used as stationary phase in GC

Single-walled carbon nanotubes (SWNTs) have high surface area, high adsorption ability, and nanoscale interactions. In this study, capillary columns including SWNTs, ionic liquid (IL), and IL + SWNTs for GC were prepared. The separation results showed that SWNTs possessed a wide selectivity toward alkanes, alcohols, aromatic compounds, and ketones, and a SWNT capillary column was a very useful GC column for the separation of gas samples. Coating the IL stationary phase on the SWNT capillary column, the SWNTs were able to improve chromatographic characteristic of ionic liquid. Comparing the IL coated on three graphite carbon black capillary columns, which were prepared by dynamic coating, static coating, and chemical bonding the Carbopack C with on SWNTs capillary column, the capacity factors were much higher on the SWNT column. The SEM showed that SWNTs could be bonded to the inner surface of capillary tubing, and most of them were linked end-to-end to form a layer of network structure of skeletons resulting in a high surface area, which increased the interactions between stationary phase and analytes. This is the first single-wall carbon nanotubes bonded to the fused-silica capillary tubing. In the first approach, SWNTs assist ionic liquid with enhanced chromatographic characteristic in GC. This work indicates that SWNTs make it possible to extend the application range on the newly prepared chromatographic stationary phases for GC.     

溶解乳化法制备SBS包覆FeSiAl片状吸收剂的微波电磁性能

片状FeSiAl吸收剂低频磁性能优异,但复介电常数大、阻抗失配严重,导致难以兼顾高频吸波性能。通过将有机高分子溶解、混合、乳化及吸附析出的多步骤过程,直接将线性苯乙烯-丁二烯-苯乙烯嵌段共聚物（SBS）包覆到微米级片状FeSiAl合金粒子表面,并研究其电磁性质。结果表明,SBS在片状FeSiAl合金粒子表面形成了均匀致密的包覆层,显著提高了合金粒子的电阻率,其与石蜡2：1混合样品复介电常数的实部由72降低到30左右。包覆后片状FeSiAl合金粒子的低频磁性能没有受到负面影响,而其高频性能由于阻抗匹配性的提升得到了明显的改善,因而片状FeSiAl@SBS复合粒子具有兼顾低频与宽带的吸波特性。     

Stochastic theory of size exclusion chromatography: peak shape analysis on single columns

The stochastic theory of size exclusion chromatography (SEC) was applied to analyze the peak shape of chromatograms obtained with a wide range of polystyrene standards on various columns. The columns were packed with stationary phases of different pore sizes. The stochastic-dispersive model of SEC results in a peak shape model that fits well the symmetrical and asymmetrical peaks observed in SEC. From the peak shape parameters obtained after nonlinear parameter estimation, information can be gained regarding the fundamental characteristics of the size exclusion process. When a series of polymer standards are analyzed on one column-in a manner similar to other methods of inverse chromatography-the stationary phase can be characterized. The dependence of the ingress and the egress processes on the relative size of the macromolecule to the pore size was determined. We found that for small molecules the selectivity in SEC arises from the ingress process, while when the size of the macromolecule is comparable to that of the pore-i.e., close to the exclusion limit-the egress process will also strongly affect the selectivity.     

Simple and comprehensive two-dimensional reversed-phase HPLC using monolithic silica columns

Simple and comprehensive two-dimensional (2D)-HPLC was studied in a reversed-phase mode using monolithic silica columns for second-dimension (2nd-D) separation. Every fraction from the first column, 15 cm long (4.6-mm i.d.), packed with fluoroalkylsilyl-bonded (FR) silica particles, was subjected to the separation in the 2nd-D using one or two octadecylsilylated (C(18)) monolithic silica columns (4.6-mm i.d., 3 cm). Monolithic silica columns in the 2nd-D were eluted at a flow rate of up to 10 mL/min with separation time of 30 s that meets the fractionation every 15-30 s at the first dimension (1st-D) operated at a flow rate of 0.4-0.8 mL/min. Three cases were studied. (1) In the simplest scheme of 2D-HPLC, effluent of the 1st-D was directly loaded into an injector loop of 2nd-D HPLC for 28 s, and 2 s was allowed for injection. (2) Two six-port valves each having a sample loop were used to hold the effluent of the 1st-D alternately for 30 s for one 2nd-D column to effect comprehensive 2D-HPLC without the loss of 1st-D effluent. (3) Two monolithic silica columns were used for 2nd-D by using a switching valve and two sets of 2nd-D chromatographs separating each fraction of the 1st-D effluent with the two 2nd-D columns alternately. In this case, two columns of the same stationary phase (C(18)) or different phases, C(18) and (pentabromobenzyloxy)propylsilyl-bonded (PBB), could be employed at the 2nd-D, although the latter needed two complementary runs. The systems produced peak capacity of approximately 1000 in approximately 60 min in cases 1 and 2 and in approximately 30 min in case 3. The three stationary phases, FR, C(18), and PBB, showed widely different selectivity from each other, making 2D separations possible. The simple and comprehensive 2D-HPLC utilizes the stability and high efficiency at high linear velocities of monolithic silica columns.