Porous Column Research Articles

Temporal reverse osmotic salt filtration mechanism of multi-layered porous graphene

Reverse osmosis (RO) technology is currently the most progressive, energy-saving and efficient membrane separation technology . Meanwhile, graphene becomes a promising candidate for fabricating the RO membranes in water desalination due to its high salt rejection and water flux. The concept of “temporal selectivity” is first proposed in our previous work in terms of the time difference between the penetration time of an ion passing through the pore and the tangential slipping time for the ion sliding across the pore. Nevertheless, the temporal selectivity mechanism of multilayered graphene membrane remains ambiguous. In this paper, the RO process of saltwater through porous graphene column RO membrane is studied by using molecular dynamics (MD) simulations method, and the effects of rotating angular velocity and the thickness of RO membrane on desalination performance of seawater are considered first. The MD results show that the salt rejection increases with the rotation speed of porous membrane increasing while the water flux initially increases and then decreases . Meanwhile, the interfacial slip velocity increases linearly with angular velocity increasing. On the other hand, the increasing thickness of porous graphene membrane can enhance the selectivity and reduce the permeability of water molecules. As expected, the tri-layered porous graphene RO membrane can achieve high salt rejection at low interfacial slip velocity. In order to ensure high selectivity and energy conservation and efficient, the pore structure of the porous graphene RO membrane is optimized. The results show that the optimized nanopores can increase the water flux significantly, whereas the salt rejection is not changed appreciably. It is found that the pore size of the innermost layer membrane near the feed region has the most significant effect on the water flux. The water flux increases sharply with the increase of pore diameter and the salt rejection remains totally higher than 80%. Moreover, the RO membrane with a special Type 3 structure exhibits excellent performance in seawater desalination, specifically, the ultrahigh water flux reaches 20029 L·cm<sup>–2</sup>·d<sup>–1</sup> and the super salt rejection arrives at 94%. The research results further clarify and verify the mechanism of the temporal selectivity in RO process, and improve the water flux under the condition of the same membrane thickness by designing gradient hole. The findings can conduce to the in-depth theoretical understanding of porous graphene-based membranes and designing and developing the large-scale seawater desalination devices and water filtration equipment.

Sample displacement chromatography of monoclonal antibody charge variants and aggregates.

The rise of biosimilar monoclonal antibodies has renewed the interest in monoclonal antibody (mAb) charge variants composition and separation. The sample displacement chromatography (SDC) has the potential to overcome the low separation efficiency and productivity associated with bind-elute separation of mAb charge variants. SDC in combination with weak cation exchanging macroporous monolithic chromatographic column was successfully implemented for a separation of charge variants and aggregates of monoclonal IgG under overloading conditions. The charge variants composition was at-line monitored by a newly developed, simple and fast analytical method, based on weak cation exchange chromatography. It was proven that basic charge variants acted as displacers of IgG molecules with lower pI, when the loading was performed 1 to 1.5pH unit below the pI of acidic charge variants. The efficiency of the SDC process is flow rate independent due to a convection-based mass transfer on the macroporous monolith. The productivity of the process at optimal conditions is 35mg of purified IgG fraction per milliliters of monolithic support with 75-80% recovery. As such, an SDC approach surpasses the standard bind-elute separation in the productivity for a factor of 3, when performed on the same column. The applicability of the SDC approach was confirmed for porous particle-based column as well, but with 1.5 lower productivity compared to the monoliths.

Capillary hysteresis and gravity segregation in two phase flow through porous media

We study the gravity driven flow of two fluid phases in a one dimensional homogeneous porous column when history dependence of the pressure difference between the phases (capillary pressure) is taken into account. In the hyperbolic limit, solutions of such systems satisfy the Buckley-Leverett equation with a non-monotone flux function. However, solutions for the hysteretic case do not converge to the classical solutions in the hyperbolic limit in a wide range of situations. In particular, with Riemann data as initial condition, stationary shocks become possible in addition to classical components such as shocks, rarefaction waves and constant states. We derive an admissibility criterion for the stationary shocks and outline all admissible shocks. Depending on the capillary pressure functions, flux function and the Riemann data, two cases are identified a priori for which the solution consists of a stationary shock. In the first case, the shock remains at the point where the initial condition is discontinuous. In the second case, the solution is frozen in time in at least one semi-infinite half. The predictions are verified using numerical results.

Preparation and properties of GC capillary column with hypercrosslinked stationary phase.

For the first time, highly porous hypercrosslinked polystyrene layer was synthesized within a gas chromatography capillary column and successfully deposited onto the capillary walls generating porous layer open-tubular capillary column. Elaborated three steps synthetic procedure provides tightly bonded porous polymeric layer and ensues complete elimination of particle shedding and the needs for particle traps. Due to highly developed surface area, porous layer open-tubular column provides strong solute retention that is useful for the separation of various volatile solvents and light gas compounds including ethane, ethylene, ethyne. Aqueous injections will not harm the column.

Determination of Hydrocarbons in n-Butane on Porous Layer Capillary Columns with Nonpolar Stationary Phase

Determination of Hydrocarbons in n-Butane on Porous Layer Capillary Columns with Nonpolar Stationary Phase

Porous layer open-tubular column with styrene and itaconic acid-copolymerized polymer as stationary phase for capillary electrochromatography-mass spectrometry.

Enhancing the specific surface area of stationary phase is important in chromatographic science, especially in open-tubular column in which the coating only exists on the inner surface. In this work, a porous layer open-tubular (PLOT) column with stationary phase of styrene and itaconic acid-copolymerized polymer was developed. Thermal-initiated polymerization method with strategies like controlling the ratio of reaction reagents to solvents and reaction time, confinement by the narrow inner diameter of capillary were used for preparing the stationary phase with uniform structure and relatively thick layer. Due to the high separation efficiency and capacity, the PLOT column was used for capillary electrochromatography (CEC) separation of multiple groups of analytes like alkylbenzenes, phenyl amines, phenols, vanillins, and sulfonamides with theoretical plates (N) up to 1,54,845 N/m. In addition, due to high permeability of the CEC column and large electroosmotic flow mobility generated by abundant carboxyl groups in the coating material, the PLOT-CEC column was successfully coupled with mass spectrometry (MS) through a sheath flow interface. The developed PLOT-CEC-MS method was used for the analysis of antiseptics like parabens and herbicides like pyridines.

Investigation of stationary phases performance for eicosanoids profiling in RP-HPLC.

Eicosanoids - oxidative derivatives from arachidonic acid - represent biologically active lipid mediators in inflammatory processes. Different analytical methods treat eicosanoid analysis. Among which, reverse phase liquid chromatography figures as the appropriate method for eicosanoid profiling. RP-HPLC for eicosanoid analysis is often conducted on C18 columns. Some studies focused on profiling one family of eicosanoids; others considered all eicosanoid families. In both cases, co-elution remained a major issue and detection in mass spectrometry partially resolves this problem. In fact, the mass transitions used to monitor eicosanoid species are not specific enough and many isobars can be listed. For this, optimizing the RP-HPLC separation remains important. Based on the parameter Fs - deriving from the hydrophobic-subtraction model - and radar plots, we chose columns with different selectivities. The hydrophobic-subtraction model guided our interpretation of molecular interactions between eicosanoids and stationary phases. We founded our approach for selectivity optimization on peak capacity per minute and time needed values. Herein, we screened seven stationary phases and evaluated their chromatographic performances in RP-HPLC. Stationary phases presented different chemistry, type of silica, length, and particle size. Superficially porous particle columns registered better chromatographic profiles than classical stationary phases; and columns with embedded polar group did not serve our purpose. The stationary phase Accucore C30 - even being the least retentive - revealed the best selectivity and efficiency, and recorded the shorter duration for eicosanoid analysis.

Efficient Sub-1 Minute Analysis of Selected Biomarker Catecholamines by Core-Shell Hydrophilic Interaction Liquid Chromatography (HILIC) with Nanomolar Detection at a Boron-Doped Diamond (BDD) Electrode

A rapid, sensitive method for the separation of catecholamine biomarkers (CAs), of importance in traumatic brain injury (TBI) and in Parkinson’s disease (PD), has been successfully developed using hydrophilic interaction liquid chromatography (HILIC). Dopamine (DA), epinephrine (EPI), and norepinephrine (NE) are known to be three to fivefold elevated above normal in traumatic brain injury (TBI) patients. HILIC facilitates the rapid and efficient separation of these polar biomarkers, which can be poorly retained by reversed-phase liquid chromatography (RPLC), while electrochemical detection (ECD) at the boron-doped diamond (BDD) electrode provides enhanced nanomolar detection. Three HILIC columns were compared, namely the superficially porous (core-shell) Z-HILIC column and the Z-cHILIC and Z-HILIC fully porous columns. The core-shell Z-HILIC showed the highest efficiency with a rapid separation within 60 s. The HILIC method utilizing the core-shell Z-HILIC column was initially optimized for the simultaneous analysis of DA, EPI, and NE using UV detection. The advantages of using the BDD electrode over UV detection were explored, and the improved limits of detection (LODs, S/N = 3) measured were 40, 50, and 50 nM for DA, EPI, and NE, respectively. Method validation is reported in terms of the linearity, repeatability, reproducibility, and LODs. Furthermore, the proposed method was successfully applied to the real sample analysis of urinary CAs following phenylboronic acid (PBA) solid phase extraction (SPE) pretreatment.

Front Cover: A thermodynamic study of capillary electrochromatographic retention of aromatic hydrocarbons on a lauryl acrylate porous polymer monolithic column with measured phase ratio

Front Cover: A thermodynamic study of capillary electrochromatographic retention of aromatic hydrocarbons on a lauryl acrylate porous polymer monolithic column with measured phase ratio

Utilizing RAFT Polymerization for the Preparation of Well-Defined Bicontinuous Porous Polymeric Supports: Application to Liquid Chromatography Separation of Biomolecules

Polymer-based monolithic high-performance liquid chromatography (HPLC) columns are normally obtained by conventional free-radical polymerization. Despite being straightforward, this approach has serious limitations with respect to controlling the structural homogeneity of the monolith. Herein, we explore a reversible addition-fragmentation chain transfer (RAFT) polymerization method for the fabrication of porous polymers with well-defined porous morphology and surface chemistry in a confined 200 μm internal diameter (ID) capillary format. This is achieved via the controlled polymerization-induced phase separation (controlled PIPS) synthesis of poly(styrene-co-divinylbenzene) in the presence of a RAFT agent dissolved in an organic solvent. The effects of the radical initiator/RAFT molar ratio as well as the nature and amount of the organic solvent were studied to target cross-linked porous polymers that were chemically bonded to the inner wall of a modified silica-fused capillary. The morphological and surface properties of the obtained polymers were thoroughly characterized by in situ nuclear magnetic resonance (NMR) experiments, nitrogen adsorption-desorption experiments, elemental analyses, field-emission scanning electron microscopy (FESEM), scanning electron microscopy-energy-dispersive X-ray (SEM-EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS) as well as time-of-flight secondary ion mass spectrometry (ToF-SIMS) revealing the physicochemical properties of these styrene-based materials. When compared with conventional synthetic methods, the controlled-PIPS approach affects the kinetics of polymerization by delaying the onset of phase separation, enabling the construction of materials with a smaller pore size. The results demonstrated the potential of the controlled-PIPS approach for the design of porous monolithic columns suitable for liquid separation of biomolecules such as peptides and proteins.

A thermodynamic study of capillary electrochromatographic retention of aromatic hydrocarbons on a lauryl acrylate porous polymer monolithic column with measured phase ratio.

The phase ratio of a chromatographic system is an important measurement that has long been estimated or calculated, but rarely directly measured. This study utilized a nanoflow liquid chromatography instrument to more accurately measure the phase ratio for a lauryl acrylate porous polymer monolith. Direct measurement of the phase ratio, and its dependence on temperature, allows for a better understanding of the thermodynamics of retention of small analytes. This study investigates the retention of an alkyl benzene series, toluene to octylbenzene, via capillary electrochromatography. The phase ratio was determined to be 0.202 at 303 K and 0.213 at 333K. Using the directly measured phase ratio, entropic contributions to retention can also be obtained. Therefore, the Gibbs free energy calculations from these measurements and methods can give insight to modes of retention. The free energy of retention for toluene is -3.97kJ/mol at 303 K and -3.78kJ/mol at 333K. The trends for enthalpy, entropy, and Gibbs free energy of transfer show that retention is enthalpically driven in this capillary electrochromatography (CEC) porous polymer monolith system.

Effect of Water Hardness on Catechin and Caffeine Content in Green Tea Infusions.

The health benefits of green tea are associated with its high catechin content. In scientific studies, green tea is often prepared with deionized water. However, casual consumers will simply use their local tap water, which differs in alkalinity and mineral content depending on the region. To assess the effect of water hardness on catechin and caffeine content, green tea infusions were prepared with synthetic freshwater in five different hardness levels, a sodium bicarbonate solution, a mineral salt solution, and deionized water. HPLC analysis was performed with a superficially porous pentafluorophenyl column. As water hardness increased, total catechin yield decreased. This was mostly due to the autoxidation of epigallocatechin (EGC) and epigallocatechin gallate (EGCG). Epicatechin (EC), epicatechin gallate (ECG), and caffeine showed greater chemical stability. Autoxidation was promoted by alkaline conditions and resulted in the browning of the green tea infusions. High levels of alkaline sodium bicarbonate found in hard water can render some tap waters unsuitable for green tea preparation.

AN ANALYTICAL SOLUTION OF THE SATURATED AND INCOMPRESSIBLE POROELASTIC MODEL FOR TRANSIENT WAVE PROPAGATION

A transient wave propagation model is provided as a consequence of a new theory of porous media and wave propagation in saturated poroelastic media. This theory, in the linear case, becomes to be equivalent to the theory proposed by de Boer, R., Ehlers, W. & Liu, Z. in 1993. It leads to a model for the 1-D porous saturated column problem, which after the appropriate establishment of boundary and initial conditions, can be solved analytically with the aid of the Laplace transform concerning time. Numerical experiments are performed to illustrate the behavior of constituents displacement fields. The theory results in having an inertial effect on the motion of solid constituents as commonly expected. However, in contrast to Biot’s theory, is not introduced by the present theory the relative acceleration as an interactive force between solid and fluid constituents to account for the apparent inertial effect.

One-step synthesis of mercapto modified hierarchical porous polymer capillary monolithic column for chip based array microextraction of mercury species in cells

Exploitation of efficient adsorbent for analyzing mercury species in complex biological samples is still a big challenge. Herein, a MIL-101 covalently bonded and mercapto functionalized capillary monolithic column was prepared by one-step strategy involving simultaneous initiation of thiol-ene click reaction and radical polymerization. It showed improved specific surface area, hierarchical porous structure, rich sulfhydryl groups and high adsorption capacity for mercury species. It was embedded in the microchannel of microfluidic chip for chip-based array monolithic capillary microextraction (CMCME) of mercury species in cells. Methylmercury (MeHg+) and inorganic Hg (Hg2+) could be simultaneously retained on the prepared column and sequentially eluted; both species could also be simultaneously eluted with 4% thiourea in 0.5 mol L-1 HNO3 solution. Based on it, CMCME was combined with two online detection modes separately, direct inductively coupled plasma mass spectrometry (ICP-MS) detection and high-performance liquid chromatography (HPLC)-ICP-MS detection. The CMCME-ICP-MS system is applicable for the analysis of MeHg+ and Hg2+ with the ratio of lower than 5/1, with the limits of detection (LODs) of 2.6 (MeHg+) and 5.8 (Hg2+) ng L-1 and throughput of 8 h-1. Comparatively, the CMCME-HPLC-ICP-MS system is universal for Hg speciation in cells, providing LODs of 9.7 and 18.9 ng L-1 for MeHg+ and Hg2+ with a throughput of 10 h-1. Both systems exhibited good endurance to complex cell matrix and automated operation. The species analysis of Hg in cells incubated by Hg2+ or MeHg+ was achieved and the demethylation of MeHg+ in HepG2 cells was observed.

Selective Preparation of Mo2N and MoN with High Surface Area for Flexible SERS Sensing.

γ-Mo2N and δ-MoN are the two most important molybdenum nitrides, but controllable preparation of them with high surface area has not been achieved. Herein, we achieved selective preparation of γ-Mo2N and δ-MoN. The key factor for the selective preparation of γ-Mo2N and δ-MoN is to control the crystal phase of the precursor MoO3. In H2O and NH3 mixed gas, the α-MoO3 nanoribbons are nitridated to obtain γ-Mo2N single-crystal porous nanobelts, while the h-MoO3 prisms are nitrided to obtain δ-MoN hierarchical porous columns. The corrosion effect of H2O plays a key role in the formation of single-crystal porous structure. The γ-Mo2N flexible membrane composed of the single-crystal porous nanobelts exhibits strong localized surface plasmon resonance and surface enhanced Raman scattering effect, which show highly sensitive response to polychlorinated phenol.

Evaporation-induced salt crystallization and feedback on hydrological functions in porous media with different grain morphologies

Evaporation from porous media in the presence of dissolved salts is an important topic in relation to several environmental issues. In this study, we investigated the interaction of evaporation, salt crystallization and the internal structure of the porous material. Porous columns with different internal structures were generated through random packing of angular quartz sand and round glass beads. Evaporation-induced salt efflorescence on the surface of porous media was recorded by a camera with micro lens. The internal pore structure before and after salt crystallization was visualized using the x-ray computed tomography and quantified by the extracted pore networks. Hydraulic properties in the absence/presence of salt crystals were simulated numerically using the pore-network approach and partially measured experimentally. The evaporative water loss ratio in the angular quartz sand was greater than that in the glass beads with the same sieving size. The evaporation of saline water in angular quartz sand and round glass beads can be separated into three stages similar to water evaporation. Salt efflorescence was generated a crust dome architecture on the surface of the angular sand, but was in tight patchy contact with the round glass beads. The presence of salt crust interrupted the exchange of vapor between the porous media and atmosphere, hindering evaporation. Salt subflorescence clogged some of the pores, and the pore size distribution shifted to smaller sizes part. The porosity decreased and the geometric tortuosity of the porous materials increased owing to salt subflorescence. The presence of subflorescence salt crystals decreased the intrinsic permeability and relative diffusion coefficient of different porous media. The relationship between the vapor diffusion coefficients and porosity is linear in the presence/absence of salt crystallization, considering the geometric tortuosity. The findings indicate that the feedback of salt precipitation on hydraulic properties and vapor diffusion must be considered to accurately quantify hydrological processes, particularly in arid and semi-arid areas where intensive evaporation is accompanied by soil salinization and water shortage.

Performance of nanoflow liquid chromatography using core-shell particles: A comparison study

Due to its unique structure, core-shell material has presented significantly improved chromatographic performance in comparison with conventional totally porous material. This has been well demonstrated in the analytical column format, e.g. 4.6 mm i.d. columns. In the proteomics field, there is always a demand for high resolution microseparation tools. In order to explore core-shell material's potential in proteomics-oriented microseparations, we investigated chromatographic performance of core-shell material in a nanoLC format, as well as its resolving power for protein digests. The results show core-shell nanoLC columns have similar van Deemter curves to the totally porous particle-packed nanoLC columns. For 100 µm i.d. capillary columns, the core-shell material does not have significantly better dynamics. However, both core-shell and totally porous particle-packed nanoLC columns have shown high efficiencies: plate heights of ~11 µm, equivalent to 90000 plates per meter, have been achieved with 5 µm particles. Using a 60 cm long core-shell nanoLC column, 72000 plates were realized in an isocratic separation of neutral compounds. For a 15 cm long nanoLC column, a maximum peak capacity of 220 has been achieved in a 5 hour gradient separation of protein digests, indicating the high resolving power of core-shell nanoLC columns. With a standard HeLa cell lysate as the sample, 2546 proteins were identified by using the core-shell nanoLC column, while 2916 proteins were identified by using the totally porous particle-packed nanoLC column. Comparing the two sets of proteomics data, it was found that 1830 proteins were identified by both columns, while 1086 and 716 proteins were uniquely identified by using totally porous and core-shell particle-packed nanoLC columns, respectively, suggesting their complementarity in nanoLC-MS based proteomics.

Development of a Novel, Fast, Simple HPLC Method for Determination of Atorvastatin and its Impurities in Tablets

Our main target and concept was to develop a method for the determination of the most prescribed antilipemic drug, atorvastatin, together with its related substances, with a single sample preparation and during a single chromatographic run, in the shortest possible period of time, with the lowest possible mobile phase consumption. A new rapid, simple chromatographic method for the determination of atorvastatin and its main specified impurities was developed, using different chromatographic columns. With this new concept of a mobile phase and a powerful core–shell, or a superficially porous silica-based column, satisfactory results for targeted parameters, such as critical peak resolution, run time length, and column backpressure, were achieved. The analysis is performed within a run duration of less than 15 min, which is about six times shorter than the official European Pharmacopoeia method. The chromatogram performances suggests that the method limit of quantification (LOQ) can be about 7 times lower, and the limit of detection (LOD) about 20 times lower, using an injection volume of only 2 µl. This was confirmed by the performed method validation in accordance with the International Conference on Harmonization (ICH) guideline for the validation of analytical procedures Q2(R1), where the selectivity, linearity, accuracy, precision, limit of quantification, and limit of detection were tested and confirmed.

3D microstructure controls on mineral carbonation

Magnesium-based mineral carbonation experiments in model porous columns are presented. The temporal evolution and interplay of 3D microstructure and mineralogy was quantified using a novel combination of X-ray computerized tomography (CT), and mineralogical analyses, conducted at five timepoints over 108 days. We constrain bulk reaction progress (X-ray diffraction, XRD), surface 2D reaction rates (non-destructive diffuse reflectance Fourier transform infrared spectroscopy, DRIFTS) as well as 3D reaction progress (X-ray CT). A new method of normalizing X-ray CT attenuation intensity values was used to provide a proxy measurement for the evolving density of the cement phase to quantify reaction progress on a 3D, microscopic level. The results demonstrate how 3D structural characteristics impact reaction progress; e.g., regions within samples with reduced access to connected void volume exhibit slower reaction, while enhanced access to connected void promotes carbonate formation. Our study shows that 3D characterization is essential for understanding the fundamental processes in mineral carbonation, whereas non-destructive 2D characterization defines reaction rates at the surface−CO2 interface.

Porous Co3O4 column as a high-performance Lithium anode material

Porous Co3O4 column as a high-performance Lithium anode material