Molecular Weight Cut-off Research Articles

V-shape Tröger's base-based organic solvent nanofiltration membranes for fast and precise molecular separation

Organic solvent nanofiltration (OSN) membranes with precise molecular-sieving performance have become increasingly important in chemical and pharmaceutical industries, desiring superior membranes with both high permeability and selectivity. Herein, the V-shape Tröger's base (TB) structure is incorporated in the polyamide network to engineer microporosity as well as the molecular-sieving performance of the thin-film composite (TFC) polyamide membrane for organic solvent nanofiltration (OSN). The TFC membrane containing the TB structure features a rigid and contorted chain structure, which affords high and stable methanol permeability in OSN applications. Furthermore, the H-bond interaction between the H of amide groups and N in TB reinforces the interchain interaction, endowing the membrane with a precise selectivity to organic solutes. The as-prepared TFC membrane demonstrated high methanol permeance of 16.6 L m−2 h−1 bar−1 and sieving performance to organic molecules with molecular weight cut-off (MWCO) down to 349 Da. Furthermore, the membrane demonstrates shape selectivity for organic solutes, exploiting the fine microporous structure. This study may provide insights into the molecular design of TFC membranes by finely tuning the molecular features for precise solute separations.

IgG-BSA separation and purification by internally staged ultrafiltration

Purification of IgG from residual host cell proteins (HCPs) in post-Protein A chromatography is important since some HCPs bind with Protein A and elute with the monoclonal antibody (mAb); removal of HCPs from CHO cell lines is essential. To that end, an advanced separation and purification technique in biopharmaceutical manufacturing, namely, internally staged ultrafiltration (ISUF), is investigated here. Choosing BSA as a model for HCPs in post-protein A eluate, separation of a binary mixture of IgG and BSA containing 1.0 mg/ml IgG and 0.1 mg/ml BSA is successfully demonstrated here using a modified ISUF technique: two Omega 100 kDa membranes on top followed by one Omega 70 kDa membrane at the bottom. This modified configuration demonstrated exceptional performance with almost complete rejection, 99 % purity, and 99.5 % retention of IgG, along with 96.5 % recovery of BSA over 10 diavolumes. This modified membrane stacking resulted from strategic considerations of membrane stacking and careful selection of molecular weight cutoffs and materials, and performance analysis of different membranes and stacking configurations using rejection behaviors, purity levels, and recovery rates under varying diavolume and pressure differential. The approach adopted here enhances flexibility in membrane choices in ISUF and provides valuable insights for optimizing membrane-based biopharmaceutical separation techniques.

Dual-phase microporous polymer nanofilms by interfacial polymerization for ultrafast molecular separation.

Fine-tuning microporosity in polymers with a scalable method has great potential for energy-efficient molecular separations. Here, we report a dual-phase molecular engineering approach to prepare microporous polymer nanofilms through interfacial polymerization. By integrating two micropore-generating units such as a water-soluble Tröger's base diamine (TBD) and a contorted spirobifluorene (SBF) motif, the resultant TBD-SBF polyamide shows an unprecedentedly high surface area. An ultrathin TBD-SBF membrane (~20 nm) exhibits up to 220 times improved solvent permeance with a moderate molecular weight cutoff (~640 g mol-1) compared to the control membrane prepared by conventional chemistry, which outperforms currently reported polymeric membranes. We also highlight the great potential of the SBF-based microporous polyamides for hydrocarbon separations by exploring the isomeric effects of aqueous phase monomers to manipulate microporosity.

Microporous polyarylate membranes based on 3D phenolphthalein for molecular sieving.

Thin-film composite (TFC) membranes have gradually replaced some traditional technologies in the extraction, separation, and concentration of high value-added pharmaceutical ingredients due to their controllable microstructure. Nevertheless, devising solvent-stable, scalable TFC membranes with high permeance and efficient molecule selectivity is urgently needed to improve the separation efficiency in the separation process. Here, we propose phenolphthalein, a commercial acid-base indicator, as an economical monomer for optimizing the micropore structure of selective layers with thickness down to 30 nanometers formed by in situ interfacial reactions. Molecular dynamics simulations indicate that the polyarylate membranes prepared using three-dimensional phenolphthalein monomers exhibit tunable microporosity and higher pore interconnectivity. Moreover, the TFC membranes show a high methanol permeance (9.9 ± 0.1 liters per square meter per hour per bar) and small molecular weight cutoff (≈289 daltons) for organic micropollutants in organic solvent systems. The polyarylate membranes exhibit higher mechanical strength (2.4 versus 0.8 gigapascals) compared to the traditional polyamide membrane.

Polyfunctional Arylamine Based Nanofiltration Membranes with Enhanced Aggressive Organic Solvents Resistance.

Organic solvent nanofiltration (OSN) membranes with high separation performance and excellent stability in aggressive organic solvents are urgently desired for chemical separation. Herein, we utilized a polyfunctional arylamine tetra-(4-aminophenyl) ethylene (TAPE) to prepare a highly cross-linked polyamide membrane with a low molecular weight cut-off (MWCO) of 312 Da. Owing to its propeller-like conformation, TAPE formed micropores within the polyamide membrane and provided fast solvent transport channels. Importantly, the rigid conjugated skeleton and high connectivity between micropores effectively prevented the expansion of the polyamide matrix in aggressive organic solvents. The membrane maintained high separation performance even immersed in N,N-dimethylformamide for 90 days. Based on the aggregation-induced emission (AIE) effect of TAPE, the formation of polyamide membrane can be visually monitored by fluorescence imaging technology, which achieved visual guidance for membrane fabrication. This work provides a vital foundation for utilizing polyfunctional monomers in the interfacial polymerization reaction to prepare high-performance OSN membranes.

What Is the Molecular Weight of "High" Molecular Weight Dissolved Organic Matter?

The use of ultrafiltration to isolate high molecular weight dissolved organic matter (HMWDOM) from seawater is a fundamental tool in the environmental organic chemist's toolbox. Yet, important characteristics of HMWDOM relevant to its origin and cycling, such as its molecular weight distribution, remain poorly defined. We used diffusion-ordered NMR spectroscopy coupled with mixed-mode chromatography to separate and characterize two major components of marine HMWDOM: acylpolysaccharides (APS) and high molecular weight humic substances (HS). The molecular weights (MWs) of APS and HS both fell within distinct, narrow envelopes; 2.0-16 kDa for APS and 0.9-6.5 kDa for HS. In water samples from the North Pacific Ocean the average MW of both components decreased with depth through the mesopelagic. However, the minimum MW of APS was >2 kDa, well above the molecular weight cutoff of the ultrafilter, suggesting APS removal processes below 2 kDa are highly efficient. The MW distribution of APS shows only small variations with depth, while the MW distribution of HS narrowed due to removal of HMW components. Despite the narrowing of the MW distribution, the concentration of HS did not decrease with depth between 15 and 915 m. This suggests that HMW HS produced in surface waters was either degraded into lower MW compounds without significant remineralization, or that HMW HS was remineralized but replaced by an additional source of HS in the mesopelagic ocean. Based on these results, we propose potential pathways for the production and removal of these major components of HMWDOM.

Measuring Erosion of Biodegradable Polymers in Brimonidine Drug Delivery Implants by Quantitative Proton NMR Spectroscopy (q-HNMR)

Erosion of biodegradable polymeric excipients, such as polylactic acid (PLA) and polylactic-co-glycolic acid (PLGA), is generally characterized by microbalance for the remaining mass of PLA and/or PLGA and Gel Permeation Chromatography (GPC) for molecular weight (MW) decrease. For polymer erosion studies of intravitreal sustained release brimonidine implants, however, both microbalance and GPC present several challenges. Mass loss measurement by microbalance does not have specificity for excipient polymers and drug substances. Accuracy of the remaining mass by weighing could also be low due to sample mass loss through retrieval-drying steps, especially at later drug release (DR) time points. When measuring the decrease of polymer MW by GPC, trace amounts of polymeric degradants (oligomers and/or monomers) trapped inside the implants during DR tests may not be measurable due to sensitivity limitations of the GPC detector and column MW range. Previous efforts to measure remained PLGA weight of dexamethasone micro-implants using qNMR with external calibration have been performed, however, these measurements do not account for chemical structure changes (i.e. LA to GA ratio changes from time zero) of PLGA implants during drug release tests. Here, a qNMR method with an internal standard was developed to monitor the following changes in micro-implants during drug release tests: 1. The remaining overall PLA/PLGA mass. 2. The remaining lactic acid (LA), glycolic acid (GA) unit and PLGA's lauryl ester end group percentages. 3. The trace content of PLA/PLGA oligomers as degradants retained in the implants. Unlike microbalance analysis, qNMR has both specificity for drug substance, excipient polymer, and accuracy due to minimal implant loss during sample preparation. Compared to the overall PLA/PLGA remaining mass generally monitored in erosion studies, the percentage of remaining LA, GA, and the ester end group provide more information about the microstructure change (such as hydrophobicity) of PLA/PLGA. Additionally, the qNMR method can complement GPC methods by measuring the change of remaining PLA and PLGA oligomer concentrations in brimonidine implants, with tenfold less sample and no MW cutoff. The qNMR method can be used as a sensitive tool for both polymer excipient characterization and kinetics studies of brimonidine implant erosion.

Scalable isolation of surface-engineered extracellular vesicles and separation of free proteins via tangential flow filtration and size exclusion chromatography (TFF-SEC)

BackgroundExtracellular vesicles (EVs) represent small lipid bilayer structures pivotal in mediating intercellular communication via biomolecular transfer. Their inherent characteristics, including packaging, non-immunogenicity, and biofluid stability, position EVs as promising drug delivery vectors. However, developing clinical quality EVs requires multifaceted technological advancement.MethodsIn this study, a method is introduced for engineering extracellular vesicles (eEVs) from cultured cells and their subsequent isolation using lab-scale tangential flow filtration (TFF). This is the first study to evaluate DNA loading efficacy into EVs isolated by TFF, marking a significant milestone in the field of targeted drug delivery. Initially, cells are transfected with EV-display constructs to facilitate the secretion of eEVs bearing the desired coding molecules. Following brief centrifugation, the cell culture media undergoes filtration using hollow fiber filters. TFF, by applying a constant flow, effectively segregates molecules based on designated molecular weight cut-off (MWCO), enriching particles between 50 and 650 nm.ResultsCompared to conventional methods like ultracentrifugation, TFF demonstrates higher efficiency in removing undesired molecules/aggregates while exerting less stress on EVs. Characterization of eEVs through various assays confirms TFF’s superiority in isolating pure EV populations. Additionally, the necessity of size-exclusion chromatography (SEC) after tangential flow filtration (TFF) becomes evident for effectively removing unbound protein contaminants.ConclusionIn conclusion, TFF-SEC emerges as a scalable and superior approach for eEV isolation, promising significant advancements in clinical applications.

Ultrafiltration of Rapeseed Protein Concentrate: Effect of Pectinase Treatment on Membrane Fouling.

Membrane filtration technologies have shown great potential as a gentle and effective method for concentrating and fractionating proteins for food applications. However, the application of this technology to plant-derived protein streams is in its infancy. In this study, an aqueous rapeseed protein concentrate was obtained with wet milling, and its performance during ultrafiltration with two distinct molecular weight cut-offs (10 and 100 kDa) was tested. All rapeseed proteins were retained during filtration. The addition of pectinase during extraction prior to filtration caused important structural modifications to the extract, resulting in increased permeate fluxes, increased carbohydrate permeation and a reduction in irreversible fouling. Lager pore sizes led to more pronounced fouling. FTIR analysis of the spent membranes showed that proteins and lipids are causing irreversible fouling.

3D-/2D-covalent organic framework (COF) bilayered membranes for efficient pharmaceutical purification

Covalent organic frameworks (COFs), with their regularly organized structures and solvent resistance, offer distinct advantages for constructing liquid-phase separation membranes. In nearly a decade of development, research has mainly focused on two-dimensional (2D) COFs, which yet give insufficient molecular selectivity due to inherent large pores. Here, we present a mixed-dimensional strategy of growing three-dimensional (3D) COFs on 2D COFs to build bilayered membranes for efficient organic solvent nanofiltration (OSN). The pores of 3D COFs interlace with those of 2D counterparts, resulting in a subnanoporous composite. We develop this 3D-/2D-COFs composite as robust membranes with a nanoscale thickness. The optimal bilayered membrane yields ethanol permeance of 12.2 L m−2 h−1 bar−1 with a molecular weight cutoff as low as ∼400 g mol−1, surpassing conventional COF-based OSN membranes. Importantly, the designed 3D-/2D-COFs membrane exhibits stable separation performance and excellent sieving ability to discriminate molecular mixtures. This exceptional molecular selectivity ultimately allows the separation of bioactive pharmaceuticals from impurities through our membrane. Overall, this work provides a design strategy for producing mixed-dimensional COF membranes to advance molecular separation in liquids.

Exploring Canine Picornavirus Diversity in the USA Using Wastewater Surveillance: From High-Throughput Genomic Sequencing to Immuno-Informatics and Capsid Structure Modeling.

The SARS-CoV-2 pandemic resulted in a scale-up of viral genomic surveillance globally. However, the wet lab constraints (economic, infrastructural, and personnel) of translating novel virus variant sequence information to meaningful immunological and structural insights that are valuable for the development of broadly acting countermeasures (especially for emerging and re-emerging viruses) remain a challenge in many resource-limited settings. Here, we describe a workflow that couples wastewater surveillance, high-throughput sequencing, phylogenetics, immuno-informatics, and virus capsid structure modeling for the genotype-to-serotype characterization of uncultivated picornavirus sequences identified in wastewater. Specifically, we analyzed canine picornaviruses (CanPVs), which are uncultivated and yet-to-be-assigned members of the family Picornaviridae that cause systemic infections in canines. We analyzed 118 archived (stored at -20 °C) wastewater (WW) samples representing a population of ~700,000 persons in southwest USA between October 2019 to March 2020 and October 2020 to March 2021. Samples were pooled into 12 two-liter volumes by month, partitioned (into filter-trapped solids [FTSs] and filtrates) using 450 nm membrane filters, and subsequently concentrated to 2 mL (1000×) using 10,000 Da MW cutoff centrifugal filters. The 24 concentrates were subjected to RNA extraction, CanPV complete capsid single-contig RT-PCR, Illumina sequencing, phylogenetics, immuno-informatics, and structure prediction. We detected CanPVs in 58.3% (14/24) of the samples generated 13,824,046 trimmed Illumina reads and 27 CanPV contigs. Phylogenetic and pairwise identity analyses showed eight CanPV genotypes (intragenotype divergence <14%) belonging to four clusters, with intracluster divergence of <20%. Similarity analysis, immuno-informatics, and virus protomer and capsid structure prediction suggested that the four clusters were likely distinct serological types, with predicted cluster-distinguishing B-cell epitopes clustered in the northern and southern rims of the canyon surrounding the 5-fold axis of symmetry. Our approach allows forgenotype-to-serotype characterization of uncultivated picornavirus sequences by coupling phylogenetics, immuno-informatics, and virus capsid structure prediction. This consequently bypasses a major wet lab-associated bottleneck, thereby allowing resource-limited settings to leapfrog from wastewater-sourced genomic data to valuable immunological insights necessary for the development of prophylaxis and other mitigation measures.

Purification of Eucalyptus globulus steam explosion hydrolysates via nanofiltration to recover xylooligosaccharides

Nanofiltration was applied to purify steam explosion hydrolysates obtained from Eucalyptus globulus woodchips. The complex hydrolysate comprised xylooligosaccharides, monosaccharides, glucuronic acid (GluA), and degradation products, including acetic acid, furfural, and 5-hydroxymethylfurfural (HMF). Membranes with 750 and 200 Da molecular weight cut-offs were assessed for their ability to retain oligosaccharides while allowing degradation products to permeate. Using the 750 Da membrane, the average compound retention order was: acetic acid (9.8 %) < furfural (10.8 %) < HMF (31.4 %) ≪ arabinose (52.5 %) < xylose (63.8 %) < glucose (76.0 %) < GluA (90.6 %). The separation mechanism for neutral saccharides and furans was primarily molecular sieving, while Donnan exclusion was the primary retention mechanism responsible for GluA. Separation factors obtained for acetic acid and furfural over xylotriose and xylobiose exceeded 10 and 3, respectively, for both membranes, showing that desired compounds were predominantly retained. Permeability loss during nanofiltration was fully restored after implementing cleaning-in-place for both membranes.

Cleaning of Ultrafiltration Membranes: Long-Term Treatment of Car Wash Wastewater as a Case Study.

Car wash wastewaters (CWWs) contain various pollutants with different contents. Hence, selecting an appropriate process for their treatment is a great challenge. Undoubtedly, the ultrafiltration (UF) process is one of the most interesting and reliable choices. Therefore, the main aim of the current study was to investigate the performance of the UF membranes used for the long-term treatment of real CWWs. For this purpose, two polyethersulfone (PES) membranes with molecular weight cut-off (MWCO) values equal to 10 and 100 kDa were applied. As expected, a significant decrease in the permeate flux during the UF run was observed. However, it was immediately demonstrated that the systematic cleaning of membranes (every day) with Insect agent (pH = 11.5) prevented a further decline in the process's performance. In addition, this study focused on the relative flux during the process run with breaks lasting a few days when the UF installation was filled with distilled water. The results of this research indicated that aqueous media favor microorganism adherence to the surface which leads to the formation of biofilms inside processing installations. As a consequence, many attempts have been made to restore the initial membrane performance. It has been found that the application of several chemical agents is required. More precisely, the use of an Insect solution, P3 Ultrasil 11 agent, and phosphoric acid increases the relative flux to a value of 0.8. Finally, it has been indicated that the membranes used in this work are resistant to the long-term exposure to bacteria and chemical agents. However, during the separation of CWWs for the membrane with an MWCO of 10 kDa, a lesser fouling influence and higher effectiveness of cleaning were obtained. Finally, the present study demonstrates a novel analysis and innovative implications towards applying the UF process for the CWW treatment.

Characterization of Low-Molecular-Weight Dissolved Organic Matter Using Optional Dialysis and Orbitrap Mass Spectrometry.

Low-molecular-weight (LMW, <1000 Da) dissolved organic matter (DOM) plays a significant role in metal/organic pollutant complexation, as well as photochemical/microbiological processes in freshwater ecosystems. The micro size and high reactivity of LMW-DOM hinder its precise characterization. In this study, Suwannee River fulvic acid (SRFA), a commonly used reference material for aquatic DOM, was applied to examine the optical features and molecular composition of LMW-DOM by combining membrane separation, ultraviolet-visible absorption and Orbitrap mass spectrometry (MS) characterization. The 100-500 Da molecular weight cut-off (MWCO) membrane had a better performance in regard to separating the tested LMW-DOM relative to the 500-1000 Da MWCO membrane. The ultraviolet-visible absorbance decreased dramatically for the retentates, whereas it increased for the dialysates. Specifically, carbohydrates, lipids and peptides exhibited high selectivity to the 100-500 Da MWCO membrane in early dialysis. Lignins, tannins and condensed aromatic molecules displayed high permeability to the 500-1000 Da MWCO membrane in late dialysis. Overall, the retentates were dominated by aromatic rings and phenolic hydroxyls with high O/Cwa (weighted average of O/C) and low H/Cwa. Conversely, such dialysates had numerous aliphatic chains with high H/Cwa and low O/Cwa compared to SRFA. In particular, LMW-DOM below 200 Da was identified by Orbitrap MS. This work provides an operational program for identifying LMW-DOM based on the SRFA standard and MS analysis.

Catalytic Ozonation of Pharmaceuticals Using CeO2-CeTiOx-Doped Crossflow Ultrafiltration Ceramic Membranes.

The removal of persistent organic micropollutants (OMPs) from secondary effluent in wastewater treatment plants is critical for meeting water reuse standards. Traditional treatment methods often fail to adequately degrade these contaminants. This study explored the efficacy of a hybrid ozonation membrane filtration (HOMF) process using CeO2 and CeTiOx-doped ceramic crossflow ultrafiltration ceramic membranes for the degradation of OMPs. Hollow ceramic membranes (CM) with a 300 kDa molecular weight cut-off (MWCO) were modified to serve as substrates for catalytic nanosized metal oxides in a crossflow and inside-out operational configuration. Three types of depositions were tested: a single layer of CeO2, a single layer of CeTiOx, and a combined layer of CeO2 + CeTiOx. These catalytic nanoparticles were distributed uniformly using a solution-based method supported by vacuum infiltration to ensure high-throughput deposition. The results demonstrated successful infiltration of the metal oxides, although the yield permeability and transmembrane flow varied, following this order: pristine > CeTiOx > CeO2 > CeO2 + CeTiOx. Four OMPs were examined: two easily degraded by ozone (carbamazepine and diclofenac) and two recalcitrant (ibuprofen and pCBA). The highest OMP degradation was observed in demineralized water, particularly with the CeO2 + CeTiOx modification, suggesting O3 decomposition to hydroxyl radicals. The increased resistance in the modified membranes contributed to the adsorption phenomena. The degradation efficiency decreased in secondary effluent due to competition with the organic and inorganic load, highlighting the challenges in complex water matrices.

Application of Recycled Ultrafiltration Membranes in an Aerobic Membrane Bioreactor (aMBR): A Validation Study.

A validation study using recycled ultrafiltration membranes (r-UF) on an aerobic membrane bioreactor (aMBR) was conducted for the first time. Four different polyethersulfone (PES) membranes were tested using synthetic urban wastewater (COD 0.4-0.5 g/L) during two experimental periods: (i) recycled ultrafiltration membrane (r-UF) and commercial UF membrane (molecular weight cut-off (MWCO) 150 kDa) (c-150 kDa); (ii) r-UF membrane modified by dip-coating using catechol (CA) and polyethyleneimine (PEI) (mr-UF) and c-20 kDa membrane. Permeability, fouling behavior, and permeate quality were evaluated. Extensive membrane characterization was conducted using scanning electron microscopy (SEM), atomic force microscopy (AFM), energy-dispersive X-ray (EDX), and confocal laser scanning microscopy (CLSM). Permeate quality for r-UF and mr-UF membranes was excellent and comparable to that obtained using commercial membranes under similar conditions. Additionally, r-UF and mr-UF membranes presented a steadier performance time. Additionally, r-UF membrane demonstrated less tendency to be fouled (Rf, m-1) r-UF 7.92 ± 0.57 × 1012; mr-UF 9.90 ± 0.14 × 1012, c-150 kDa 1.56 ± 0.07 × 1013 and c-20 kDa 1.25 ± 0.50 × 1013. The r-UF membrane showed an excellent antibiofouling character. Therefore, r-UF membranes can be successfully implemented for wastewater treatment in aMBR, being a sustainable and cost-effective alternative to commercial membranes that can contribute to overcome membrane fouling and membrane replacement issues.

Vapor/Vapor‐Solid Interfacial Growth of Covalent Organic Framework Membranes on Alumina Hollow Fiber for Advanced Molecular Separation

AbstractCovalent organic frameworks (COFs), known for their chemical stability and porous crystalline structure, hold promises as advanced separation membranes. However, fabricating high‐quality COF membranes, particularly on industrial‐preferred hollow fiber substrates, remains challenging. This study introduces a novel vapor/vapor‐solid (V/V−S) method for growing ultrathin crystalline TpPa‐1 COF membranes on the inner lumen surface of alumina hollow fibers (TpPa‐1/Alumina). Through vapor‐phase monomer introduction onto polydopamine‐modified alumina at 170 °C and 1 atm, efficient polymerization and crystallization occur at the confined V−S interface. This enables one‐step growth within 8 h, producing 100 nm thick COF membranes with strong substrate adhesion. TpPa‐1/Alumina exhibits exceptional stability and performance over 80 h in continuous cross‐flow organic solvent nanofiltration (OSN), with methanol permeance of about 200 L m−2 h−1 bar−1 and dye rejection with molecular weight cutoff (MWCO) of approximately 700 Da. Moreover, the versatile V/V−S method synthesizes two additional COF membranes (TpPa2Cl/Alumina and TpHz/Alumina) with different pore sizes and chemical environments. Adjusting the COF membrane thickness between 100–500 nm is achievable easily by varying the growth cycle numbers. Notably, TpPa2Cl/Alumina demonstrates excellent OSN performance in separating the model active pharmaceutical ingredient glycyrrhizic acid (GA) from dimethyl sulfoxide (DMSO), highlighting the method's potential for large‐scale industrial applications.

Vapor/Vapor-Solid Interfacial Growth of Covalent Organic Framework Membranes on Alumina Hollow Fiber for Advanced Molecular Separation.

Covalent organic frameworks (COFs), known for their chemical stability and porous crystalline structure, hold promises as advanced separation membranes. However, fabricating high-quality COF membranes, particularly on industrial-preferred hollow fiber substrates, remains challenging. This study introduces a novel vapor/vapor-solid (V/V-S) method for growing ultrathin crystalline TpPa-1 COF membranes on the inner lumen surface of alumina hollow fibers (TpPa-1/Alumina). Through vapor-phase monomer introduction onto polydopamine-modified alumina at 170 °C and 1 atm, efficient polymerization and crystallization occur at the confined V-S interface. This enables one-step growth within 8 h, producing 100 nm thick COF membranes with strong substrate adhesion. TpPa-1/Alumina exhibits exceptional stability and performance over 80 h in continuous cross-flow organic solvent nanofiltration (OSN), with methanol permeance of about 200 L m-2 h-1 bar-1 and dye rejection with molecular weight cutoff (MWCO) of approximately 700 Da. Moreover, the versatile V/V-S method synthesizes two additional COF membranes (TpPa2Cl/Alumina and TpHz/Alumina) with different pore sizes and chemical environments. Adjusting the COF membrane thickness between 100-500 nm is achievable easily by varying the growth cycle numbers. Notably, TpPa2Cl/Alumina demonstrates excellent OSN performance in separating the model active pharmaceutical ingredient glycyrrhizic acid (GA) from dimethyl sulfoxide (DMSO), highlighting the method's potential for large-scale industrial applications.

Determination of unbound platinum concentrations in human plasma using ultrafiltration and precipitation methods

Quantification of the unbound portion of platinum (Pt) in human plasma is important for assessing the pharmacokinetics of the chemotherapeutic drug cisplatin. In this study, we sought to compare the recovery of unbound Pt using Nanosep® filters to 1) traditional filters (Centrifree®, Centrisart®, Amicon®) or trichloroacetic acid (TCA) protein precipitation, and 2) unbound, bound, and total Pt concentrations in clinical specimens. For the tested filters, the impact of 1) molecular weight cut-offs, 2) centrifugation force, and 3) total Pt concentration on Pt binding in human plasma was evaluated. Pt was quantified using inductively coupled-plasma mass spectrometry. In human plasma spiked with 0.9 μg/mL Pt, the percent of unbound Pt increased at higher centrifugation speeds. By comparison, the percent of unbound Pt was highest (42.1%) following TCA protein precipitation. When total Pt was ≤0.9 μg/mL, unbound Pt (∼20–30%) was consistent across filters. Conversely, when plasma was spiked with Pt exceeding 0.9 μg/mL, the percent of unbound Pt increased from 36.5 to 48% using ultrafiltration, compared to 63.4% to 79% with TCA precipitation. In patients receiving cisplatin-containing chemotherapy, the fraction of unbound Pt at concentrations exceeding 0.9 μg/mL ranged between 35 and 90%. Moreover, the unbound fraction of Pt in plasma correlated with the concentration of unbound (R2 = 0.738) and total Pt (R2 = 0.335). In summary, this study demonstrates that 1) the percent of unbound Pt is influenced by total and unbound Pt levels in vitro and in clinical specimens, and 2) ultrafiltration with Nanosep® filters is a feasible method for quantifying unbound Pt concentrations in human plasma.

Low MWCO non-polyamide nanofiltration membranes synthesized in aqueous by coupling with catechol-amine chemistry and the oxidation-induced self-polymerization of m-phenylenediamine

Catechol-amine coatings offer versatile routes for surface modifications and nanofiltration (NF) membrane preparations. However, the formation of the selective layer is time-consuming and often deficient, rendering it unsuitable for large-scale applications. In this work, oxidation-induced self-polymerization and catechol-amine chemistry were combined to rapidly construct nanofiltration membranes in an aqueous medium. M-phenylenediamine (MPD) underwent oxidation and self-polymerized on a polysulfone (PSF) support. The addition of sodium periodate facilitated the subsequent tannic acid (TA) coating. The catechol-amine reaction between oxidized TA and poly-MPD forms crosslinked poly TA-MPD complexes, offering the resulting membrane a high selectivity. The role of NaIO4 in the selective layer formation and the influences of the synthesis parameters on the membrane performance were discussed. Utilizing the facile method enabled the achievement of a low molecular weight cut-off (MWCO) NF membrane (180 Da). The membrane exhibited a high water permeance (10.9 Lm−2h−1bar−1) and good salt rejections (93 % for Na2SO4). The filtration of the bovine serum acid (BSA) solution demonstrated the membrane has good antifouling performance with a flux recovery ratio (FRR) of 95.1 %. The proposed method offers a straightforward and rapid approach to fabricating low MWCO NF membranes in an aqueous medium, which has potential in large-scale applications.