J Chromatogr A [JOURNAL]
Sun
200 papers
Analytical strategies for identifying PDE5 inhibitors in damiana (Turnera diffusa) products.
Jiménez-Amezcua I, Rivas-Piña M, Sanz ML … +2 more , Ruiz-Matute AI, Mena-García A
J Chromatogr A · 2026 Jun · PMID 42361690 · Publisher ↗
The growing use of herbal supplements marketed for sexual enhancement has raised concerns regarding their adulteration with pharmaceutical compounds, particularly phosphodiesterase type 5 inhibitors (PDE5i). Damiana (Tur...
The growing use of herbal supplements marketed for sexual enhancement has raised concerns regarding their adulteration with pharmaceutical compounds, particularly phosphodiesterase type 5 inhibitors (PDE5i). Damiana (Turnera diffusa) is commonly included in such supplements due to its traditional aphrodisiac properties. This study presents the development and validation of three analytical methods (LC-DAD, LC-Q MS, and FIA-ToF MS) for the sensitive detection and accurate quantitation of four PDE5i (avanafil, vardenafil, sildenafil, and tadalafil) in damiana-based food supplements. Method performance was assessed and compared using validation parameters such as sensitivity, specificity, accuracy, and precision. Although all three methodologies demonstrated very good analytical performance, the FIA-ToF MS approach offered a clear advantage by reducing the analysis time to just 1 min per sample, compared with 26 min required for the chromatographic methods. This work presents the first validated FIA-ToF MS screening workflow specifically developed for the detection and quantitation of PDE5 inhibitors in damiana-based products. The method combined high-throughput analysis with satisfactory sensitivity, precision and accuracy, and was successfully applied to samples intentionally adulterated at LOQ-level concentrations. None of the four PDE5i were detected in the 20 damiana supplements analyzed. Nevertheless, this methodology offers a rapid and reliable screening tool for the routine analysis of these commercial products in quality control and regulatory laboratories, contributing to adulteration detection, consumer safety and regulatory enforcement.
AI‑assisted screening and chemical derivatization to comprehensive analysis of chemical composition of Shuxuening injection.
Li Y, Guo Y, Han R … +3 more , Xu H, Gao Y, Li Z
J Chromatogr A · 2026 Aug · PMID 42349187 · Publisher ↗
This study established a strategy integrating biosynthesis-guided theoretical library construction and targeted chemical derivatization to characterize various classes of chemical constituents in the Shuxuening injection...
This study established a strategy integrating biosynthesis-guided theoretical library construction and targeted chemical derivatization to characterize various classes of chemical constituents in the Shuxuening injection (SXNI), including flavonoids, ginkgolides, amines, and carboxylic acids. A total of 284 compounds were putatively identified, of which 88 were reported for the first time in SXNI or in Ginkgo biloba. For flavonoids, the expanded theoretical library enabled the putative identification of 88 compounds, including 30 newly discovered structures. These novel flavonoids encompass novel aglycones, glycosyl moieties, and ten new acyl-glycosyl combinations, as well as three types of fatty acyl modification patterns were reported for the first time. Additionally, 68 potential flavonoid analogues were putatively characterized based on fragmentation patterns. For ginkgolides, we first identified 12 known ginkgolides, and then putatively characterized 21 potential ginkgolide analogues based on their fragmentation patterns. For primary metabolites that are difficult to identify by conventional methods, a derivatization strategy employing 5-(dimethylamino)-naphthalene-1-sulfonyl chloride (DNS-Cl) and 5-(dimethylamino) naphthalene-1-sulfonyl piperazine (DNS-PP) probes was utilized, and 35 compounds were putatively identified, including amino acids, organic amines, and carboxylic acids, with 25 of them being reported for the first time. This research comprehensively elucidates the overall chemical profile of SXNI. It provides a systematic methodological reference for in-depth material basis research of complex traditional Chinese medicine preparations and lays a solid chemical foundation for subsequent quality control and pharmacological activity studies.
Characterization of low-level water addition for preparative chiral SFC.
Wang X, Bradow J, Smith J … +1 more , Li C
J Chromatogr A · 2026 Aug · PMID 42349186 · Publisher ↗
Supercritical fluid chromatography (SFC) is widely employed for high-efficiency chiral separations in pharmaceutical applications; however, the influence of water as a co-solvent additive in preparative-scale SFC remains...
Supercritical fluid chromatography (SFC) is widely employed for high-efficiency chiral separations in pharmaceutical applications; however, the influence of water as a co-solvent additive in preparative-scale SFC remains underexplored. In this study, our objective was to assess the effect of incorporating 0-7.5% (v/v) water into the co-solvent on the performance of ten preparative chiral columns. We evaluated commonly used stationary phase chemistries (seven polysaccharide-based columns, one Pirkle-type column, and two macrocyclic glycopeptide-based columns) using CO₂ with 10%, 25%, or 40% MeOH containing 0%, 2.5%, 5%, or 7.5% water. Retention times and baseline peak widths of the second-eluting enantiomer were measured for representative chiral analytes on each column. Except for S,S-Whelk-O1, introducing minor quantity of water into the SFC co-solvent for the remaining nine columns led to decreased run times and narrower collection windows (baseline peak widths reduced by approximately 20-40%). To further interpret the results, we investigated the retention mechanisms of the chiral columns under hydrophilic interaction liquid chromatography (HILIC) conditions to rationalize the observed changes in retention time and collection window with increasing water content in SFC across different stationary phases.
β-cyclodextrin-anchored C18 brush stationary phases with enhanced shape selectivity for reversed-phase HPLC.
Cai C, Shi J, Zhang B … +1 more , Ke Y
J Chromatogr A · 2026 Aug · PMID 42349185 · Publisher ↗
Two β-cyclodextrin-anchored reversed-phase stationary phases (β-CD-COOC18 and β-CD-NHCOOC18) were developed using a "rigid anchor-flexible chain" strategy to simultaneously enhance molecular shape selectivity and high-aq...
Two β-cyclodextrin-anchored reversed-phase stationary phases (β-CD-COOC18 and β-CD-NHCOOC18) were developed using a "rigid anchor-flexible chain" strategy to simultaneously enhance molecular shape selectivity and high-aqueous stability. Octadecyl chains were covalently attached to a rigid β-cyclodextrin scaffold via ester or carbamate linkers and subsequently immobilized onto silica via thiol-ene click chemistry. Tanaka tests revealed that the resulting brush-type architectures possessed markedly improved shape selectivity (α = 2.37 for triphenylene/o-terphenyl) compared to a commercial C18 column (α = 1.41). This exceptional performance is attributed to a synergistic multiple-interaction mechanism, wherein the ordered C18 brush layer forms a flexible "soft cavity" for steric recognition, while the extended CD port (comprising the polar linkers and residual hydroxyls) contributes secondary interactions. Preliminary chiral evaluation using seven diverse probes confirmed that the native CD cavity is chromatographically inaccessible, further supporting this extended-port model. Consequently, the prepared phases enabled improved separation of challenging isomeric systems, including terphenyls, tocopherols, and photo-induced β-carotene geometric isomers. Furthermore, the embedded polar linkers and accessible hydroxyls contributed to outstanding resistance to hydrophobic collapse. In a 1440-min 100% aqueous stop-flow test, both β-CD-C18 phases maintained stable retention and efficiency, in stark contrast to the immediate performance drop of the commercial C18, enabling the effective separation of eleven highly polar nucleosides and bases under extreme aqueous conditions (98-99% HO). Overall, utilizing a rigid macrocyclic scaffold to spatially constrain flexible alkyl chains, combined with extended-port functionality, represents an effective approach to integrate specific shape recognition with broad reversed-phase applicability.
Small-footprint non-suppressed capillary ion chromatography mass spectrometry method for the determination of oxyhalides in water samples.
Schipplick L, Mikhail IE, Lam SC … +3 more , Gooley A, Seubert A, Paull B
J Chromatogr A · 2026 Aug · PMID 42349184 · Publisher ↗
A portable capillary liquid chromatography system (capLC) coupled with a small footprint single quadrupole electrospray mass spectrometer (ESI-MS) was applied to the non-suppressed ion chromatographic separation and dete...
A portable capillary liquid chromatography system (capLC) coupled with a small footprint single quadrupole electrospray mass spectrometer (ESI-MS) was applied to the non-suppressed ion chromatographic separation and determination of oxyhalides as inorganic disinfection by-products in various water samples. The capLC was equipped with a Dionex IonPac AS19 capillary column (0.4 mm x 250 mm) and the separation was performed using an ammonium carbonate gradient in a mobile phase consisting of 50 % acetonitrile. Bromate (BrO), chlorate (ClO), perchlorate (ClO) and iodate (IO) were separated in under 20 min, using just 200 µL of eluent for one run, and were variously quantified in drinking water and swimming pool water samples using standard addition. The method limit of detection (LOD) of bromate was below the regulatory limit of 10 µg/L in drinking water, however the concentrations of oxyhalides in local drinking water were below the method LODs for all analytes. A high concentration of chlorate (116.3 mg/L) was determined in local municipal swimming pool water, together with measurable levels of bromate (235.4 µg/L) and iodate (67.2 µg/L). Results demonstrate the applicability of small-footprint non-suppressed capillary ion chromatography-mass spectrometry (IC‑MS) for the sensitive determination of oxyhalide disinfection by-products in various water samples, and support its potential use for on‑site monitoring in water treatment plants and recreational water facilities.
Pillararene and micelle-assisted matrix solid phase dispersion microextraction of Ginkgo biloba leaves combined with the assessment of greenness and practicality.
Zhang YX, Niu SQ, Fan KY … +1 more , Cao J
J Chromatogr A · 2026 Aug · PMID 42349183 · Publisher ↗
A simple and efficient pillararene and micelle-assisted matrix solid-phase dispersion microextraction (MSPDM) was established for the extraction of phenolic acids and flavonoids from Ginkgo biloba leaves, with Diethoxypi...
A simple and efficient pillararene and micelle-assisted matrix solid-phase dispersion microextraction (MSPDM) was established for the extraction of phenolic acids and flavonoids from Ginkgo biloba leaves, with Diethoxypillar[6]arene as the adsorbent and Triton X-114 as the eluent. Key experimental parameters affecting the extraction efficiency of the target compounds, including adsorbent dosage, grinding time, and Triton X-114 concentration, were optimized by single-factor experiments combined with response surface methodology. The optimal final extraction conditions were as follows: adsorbent dosage of 26.3 mg, grinding time of 78.6 s, and Triton X-114 concentration of 1.51%. The established method exhibited satisfactory linearity with a coefficient of determination greater than 0.999, limits of detection of 14-33 ng/mL, and recoveries of 96.42%-108.67%, 96.68%-108.73% and 91.19%-106.09% at spiked concentration levels of 0.2 μg/mL,5 μg/mL and 50 μg/mL, respectively. Overall, the developed MSPDM method demonstrates excellent potential for the green and efficient extraction of bioactive compounds from complex plant matrices.
The silica-based sorbents for the mixed-mode extraction of risdiplam and its metabolite from serum samples.
Balińska N, Lemska A, Mazurkiewicz-Bełdzińska M … +1 more , Studzińska S
J Chromatogr A · 2026 Aug · PMID 42349182 · Publisher ↗
Analysis of risdiplam and its main metabolite is critical for pharmacokinetic studies and therapeutic drug monitoring in spinal muscular atrophy. However, current analytical methods face challenges due to low analyte sta...
Analysis of risdiplam and its main metabolite is critical for pharmacokinetic studies and therapeutic drug monitoring in spinal muscular atrophy. However, current analytical methods face challenges due to low analyte stability, limited selectivity, and pronounced matrix effects, with only four studies published to date. In this work, a comprehensive analytical strategy was developed for the first time, combining optimized chromatographic separation with a novel sample preparation approach. The effects of methanol content, salt concentration, and pH on retention, peak symmetry, and resolution were systematically investigated. Chromatographic conditions were optimized using a central composite design, enabling rapid selection of mobile phase and achieving efficient separation of both compounds within 3.5 min. General trends in mobile phase composition were identified, indicating optimal performance at either low salt concentration and high pH or high salt concentration and low pH. For sample preparation, dispersive solid-phase extraction was introduced using newly synthesized hydrophobic and mixed-mode sorbents designed to provide hydrophobic, π-π, electrostatic, and hydrogen-bonding interactions. The extraction procedure was extensively optimized with respect to sorbent type and elution conditions (solvent composition and the addition of salt, formic acid, or ammonia). Compared with conventional non-polar sorbents, mixed-mode materials containing alkylamide, benzoic acid, cholesterol, and residual aminopropyl groups demonstrated superior recoveries and reproducibility. Finally, an alkylamide sorbent with acidified methanol-water elution was selected. The method enabled direct extraction from serum without protein precipitation, yielding recoveries of 86% and 53% for risdiplam and its metabolite, respectively. The proposed strategy provides a robust, selective, and efficient approach for risdiplam bioanalysis.
Covalent organic frameworks-bridged bis(β-cyclodextrin) chiral stationary phases for enhanced liquid chromatographic enantioseparation.
Cheng D, Xu W, Chen S … +5 more , Ni H, Xu L, Sun W, Peng Y, Tong S
J Chromatogr A · 2026 Aug · PMID 42341511 · Publisher ↗
Cyclodextrin-based covalent organic frameworks (CD-COFs) have emerged as promising chiral stationary phases (CSPs) for chromatographic enantioseparation. In conventional chiral liquid chromatography, bridged bis(β-cyclod...
Cyclodextrin-based covalent organic frameworks (CD-COFs) have emerged as promising chiral stationary phases (CSPs) for chromatographic enantioseparation. In conventional chiral liquid chromatography, bridged bis(β-cyclodextrin) structures are known for enhancing enantioselectivity by their cooperative interactions. Inspired by this concept, a COF-bridged bis(β-cyclodextrin) architecture was rationally constructed via a thiol-yne click strategy and immobilized onto silica microspheres to obtain a novel chiral stationary phase (2D COF-CSP-1). The resulting material demonstrated significantly incrased enantioseparation performance toward dansylated proteinogenic amino acids (DNS-AAs) under hydrophilic interaction liquid chromatography (HILIC) elution mode. A total of 16 DNS-AAs were successfully resolved, in which 12 achieved baseline separation within 30 min. Notably, high resolution values were obtained for valine (5.02), isoleucine (4.35), and leucine (3.79), indicating excellent enantiorecognition for structurally similar DNS-AAs. Comparative studies with a single-cyclodextrin-functionalized COF confirmed that the present bridged bis(β-cyclodextrin) played an important role in enhancing enantiorecognition. Density functional theory (DFT) calculations revealed that chiral recognition was dominated by cooperative multipoint interactions within the confined COF channels rather than classical inclusion complexation, and high differentiated host-guest interactions were observed with the bridged structure. In summary, this work demonstrated that engineering spatially confined and cooperative chiral microenvironments within COF frameworks represented an efficient strategy for constructing high-performance chiral stationary phases.
A study of volatile compounds in hop by headspace sampling and comprehensive two-dimensional gas chromatography.
Hillebrand J, Resende GAP, Amaral MSS … +1 more , Marriott P
J Chromatogr A · 2026 Aug · PMID 42341510 · Publisher ↗
As a main ingredient in beer production, hop (Humulus lupulus L.) and its essential oils, resins and polyphenols, significantly influence the aroma and bitter taste of beer. This study investigates the volatile organic c...
As a main ingredient in beer production, hop (Humulus lupulus L.) and its essential oils, resins and polyphenols, significantly influence the aroma and bitter taste of beer. This study investigates the volatile organic compound (VOC) profile of ten previously uncharacterised hop cultivars (Super Pride, Centennial, Pacific Jade™, Superdelic™, Nectaron™, Rakau™, Pacifica™, Motueka™, Nelson Sauvin™ and Simcoe®) using headspace solid-phase microextraction (HS-SPME), combined with comprehensive two-dimensional gas chromatography (GC×GC) and mass spectrometry (MS). After SPME conditions were carefully selected the developed method enabled the tentative identification of 136 VOCs across ten hop cultivars, providing insights into their complex chemical composition. Major aspects of this work include the development of a recommended HS-SPME sampling method, and an investigation of the precision of the GC×GC-MS methodology. A detailed analysis of the identified VOCs and compound classes is performed. Consequently, key compounds, classes and markers are determined. This contributes to our understanding of hop VOC profile and offers opportunities for the development of methods for hop characterisation and quality control.
Bayesian optimization for the direct optimization of temperature-programmed separations in ultra-fast gas chromatography electronic nose.
Wang J, Zhao Z, Liu F
J Chromatogr A · 2026 Aug · PMID 42341509 · Publisher ↗
Ultra-Fast gas chromatography electronic nose (UFGC-E-nose) systems are essential for the rapid volatile fingerprinting of complex food and beverage matrices. Despite their efficiency, optimizing separation in these inst...
Ultra-Fast gas chromatography electronic nose (UFGC-E-nose) systems are essential for the rapid volatile fingerprinting of complex food and beverage matrices. Despite their efficiency, optimizing separation in these instruments is technically challenging. The minimal thermal mass of micro-columns, coupled with extreme ramp rates reaching 5°Cs, induces significant thermal hysteresis that often invalidates traditional physical retention models. This study introduces an automated optimization framework based on Bayesian optimization (BO) to systematically improve the separation and discrimination efficiency of UFGC-E-nose systems. By employing a multi-objective chromatographic response function, the framework balances separation quality against analysis duration through a dynamic weighting strategy that shifts the optimization priority from resolution toward throughput. Within only 35 experimental trials, the BO framework identified optimal gradient parameters that increased the number of detected peaks by 28.3% and improved average resolution by 62.5% relative to default settings. Most target volatiles reached baseline separation (R≥1.5), with substantial improvements in the reproducibility of retention times and peak areas, as evidenced by relative standard deviation (RSD) reductions of 75% and 60%, respectively. The practical utility of the optimized method was validated through the discriminant analysis of Baijiu samples with varying mixing ratios. The resulting model captured 82.4% of the total variance and exhibited a clear linear trajectory along the first discriminant factor (DF1) that accurately reflected compositional gradients. This data-efficient strategy bypasses the limitations of physicochemical modeling under thermal non-equilibrium conditions, providing a robust solution for automated method development in high-speed GC systems.
Development and validation of a high-performance thin-layer chromatographic method for the quantitative analysis of polymethoxyflavones in citrus by-products.
Sharma A, Rani A, Nile SH
J Chromatogr A · 2026 Aug · PMID 42341508 · Publisher ↗
Citrus peel and pomace, major byproducts of citrus processing, are rich in polymethoxyflavones (PMFs), such as nobiletin, tangeretin, and sinensetin. In this study, a cost-effective and reliable high-performance thin-lay...
Citrus peel and pomace, major byproducts of citrus processing, are rich in polymethoxyflavones (PMFs), such as nobiletin, tangeretin, and sinensetin. In this study, a cost-effective and reliable high-performance thin-layer chromatography (HPTLC) method was developed and validated for the simultaneous quantification of these PMFs in eleven citrus waste varieties. Separation was achieved on silica gel 60 F₂₅₄ plates using an optimized mobile phase of hexane:1-butanol: formic acid (80:20:1, v/v/v), with densitometric detection at 254 nm. The method exhibited excellent linearity over 0.078-2.50 µg band⁻¹ (R² = 0.9912-0.9986), high precision (intra- and interday %RSD < 2%), satisfactory recoveries (98.14%-100.97%), and robustness against deliberate chromatographic variations, in accordance with International Council for Harmonization (ICH) guidelines. The application of the method to eleven citrus waste varieties revealed pronounced interspecies variability in PMF content. Overall, the validated method provides a rapid, reproducible, and low-solvent analytical platform suitable for routine analysis and high-throughput analytical screening of citrus processing byproducts.
Two-dimensional liquid chromatography (2D-LC) isolation and purification of immunoglobulin G (IgG) and extracellular vesicles (EVs) from cell-culture supernatant using capillary-channeled polymer (C-CP) fiber columns.
Topper CD, Marcus RK
J Chromatogr A · 2026 Aug · PMID 42341507 · Publisher ↗
There is a diversity of therapeutic agents which are manufactured through cellular processes. Prominent among these are the monoclonal antibodies (mAbs) with immunoglobulin G (IgG) being the most common variant. Newer en...
There is a diversity of therapeutic agents which are manufactured through cellular processes. Prominent among these are the monoclonal antibodies (mAbs) with immunoglobulin G (IgG) being the most common variant. Newer entries to the biotherapeutic palette are the extracellular vesicles (EVs), nanosized membrane-bound particles that are released by cells into the extracellular environment, emerging as viable drug delivery vectors possessing low immunogenicity. IgG is commonly manufactured in bioreactors using Chinese hamster ovary (CHO) cells cultured in suspension, with its primary purification involving the passage of cell-culture supernatant through a Protein A (ProA) affinity chromatography column to isolate the antibodies. The waste stream from this process, however, contains valuable EVs that are presently discarded; thus, an opportunity exists for by-product valorization. We describe a two-dimensional liquid chromatography (2D-LC) platform that employs columns packed with capillary-channeled polymer (C-CP) fibers to isolate both IgG and EVs from CHO cell-culture supernatant. The first dimension utilizes ProA to isolate and quantify IgG, while hydrophobic interaction chromatography (HIC) is used in the second dimension to isolate EVs from the first-dimension effluent. Solvent incompatibility between the two dimensions was mediated using a loop-based modulation strategy and an in-line microfluidic mixer to recondition the first-dimension effluent prior to passage to D HIC. Quantitative recoveries of IgG were realized across a range of injected masses, with response linearity and performance comparable to a commercial ProA monolith column. EV recovery was verified by immunofluorescence using nano-flow cytometry while TEM confirmed preservation of vesicular morphology. Isolated EVs demonstrated a purity of 5.86 × 10 particles µg protein, exceeding the target values for high-purity isolates. Thus, we demonstrate a convenient framework for characterizing CHO cell cultures in terms of both IgG and EV production traits which points towards applications in process monitoring and perhaps new product recoveries.
Dual-function deep eutectic solvent for the sustained determination of chromium in water and food samples.
Hassan NN, Eltabey RM, Mortada WI … +1 more , Abdelwahed FT
J Chromatogr A · 2026 Aug · PMID 42335486 · Publisher ↗
A sensitive, selective, and environmentally friendly method for the preconcentration and speciation of trace levels of hexavalent chromium in aqueous solutions is described. The method depends on using a dual-functional...
A sensitive, selective, and environmentally friendly method for the preconcentration and speciation of trace levels of hexavalent chromium in aqueous solutions is described. The method depends on using a dual-functional DES, consisting of 1,5-diphenylcarbazide as a H-bond donor, and oleic acid as a H-bond acceptor. The prepared DES that combines the coordination property (through the ligand) with the ability to separate Cr(VI) from aqueous media (due to the nonpolar nature of oleic acid), allowing for efficient extraction without the need for conventional organic solvents or a complexation step. The novelty of this work lies in the integration of the extraction and complexation functions into a single solvent component, simplifying the process and increasing its efficiency. Furthermore, the solvent can be recycled multiple times without significant loss of performance, enhancing its environmental and economic value in analytical applications. The calibration graphs were linear across the concentration ranges under ideal conditions, from 10 to 300 µg L for Cr(VI). The limit of detection and limit of quantification of the developed method were 3.1 and 10.9 µg L, respectively. The relative standard deviations for 6 replicate determinations were less than 4.0%. Chromium species were successfully determined and speciated in water and tea samples using the proposed approach. Several tools were used to assess the greenness, and applicability of the proposed strategy.
Enabling direct access to proprietary GC-MS data through black-box reconstruction of the Chromatec binary format.
Samokhin A, Sholokhova A, Borisov R
J Chromatogr A · 2026 Aug · PMID 42335485 · Publisher ↗
Proprietary data formats used by vendors of analytical instruments limit data portability, reproducibility, and reuse of raw data. When official application programming interfaces are unavailable, access to such data oft...
Proprietary data formats used by vendors of analytical instruments limit data portability, reproducibility, and reuse of raw data. When official application programming interfaces are unavailable, access to such data often relies on black-box reverse engineering, but the underlying strategies are rarely described in a systematic and transparent manner. In this work, we reconstructed the proprietary Chromatec .msdx binary format for gas chromatography - mass spectrometry (GC-MS) data, explicitly documented the reconstruction workflow, and implemented an open-source parser as the msdxr package for R. The parser was validated using test files corresponding to different acquisition modes, and the extracted data showed quantitative agreement with data exported from the vendor software. The utility of the package for GC-MS data handling was demonstrated using an environmental monitoring dataset comprising soil and water samples. A retrospective screening workflow based on automated prioritization of candidate files revealed signals tentatively assigned to polychlorinated biphenyls in previously acquired GC-MS data, without sample reanalysis or manual data conversion. The results show that reconstructing proprietary analytical data formats can support reproducible data handling, facilitate integration with advanced data-processing workflows, and increase the long-term value of datasets stored in vendor-specific formats.
Adsorption dynamics of dipeptides in a column with chiral zwitterionic quinine-based stationary phase.
Iuzhaninova YA, Asnin LD
J Chromatogr A · 2026 Aug · PMID 42330875 · Publisher ↗
Adsorption-desorption kinetics in chromatographic columns is difficult to study by the moment method because of interference with other mass transfer processes. The Eberly-Spencer method provides another way to determine...
Adsorption-desorption kinetics in chromatographic columns is difficult to study by the moment method because of interference with other mass transfer processes. The Eberly-Spencer method provides another way to determine the desorption rate constant. A combination of these techniques was applied to study the adsorption dynamics of almost unretained (Gly-Gly) and retained (L(D)-Leu-L(D)-Leu and L(D)-Leu-L(D)-Phe) dipeptides in a column packed with chiral stationary phase bearing quinine-l-Ala-l-Leu (AK 57) as a chiral selector. It was shown that eddy diffusion and slow adsorption-desorption kinetics are main contributors to the peak broadening. The lack of enantioselectivity in chromatographic efficiency (i.g. in HETP) despite marked enantioselectivity in retention was observed and explained by the non-selective rate-limiting desorption step, while the adsorption step was enantioselective and faster, except for Gly-Gly, in which case adsorption was slower than desorption. It was also shown that eddy diffusion was characterized by unusually high values of the correponding HETP contribution. This phenomenon was explained by interference between eddy diffusion and slow adsorption-desorption kinetics.
An automated preparative liquid chromatography platform for repetitive purification of coumarins from Cortex Fraxini with virtually unlimited injection capability.
Sun J, Yang W, Xu S … +4 more , Wang B, Ge Z, Schmitz OJ, Li D
J Chromatogr A · 2026 Aug · PMID 42323938 · Publisher ↗
Purification in the industry often requires repeated purification of large volume sample using a fixed chromatographic process. Therefore, this study aimed to design an automated chromatographic system which is able to p...
Purification in the industry often requires repeated purification of large volume sample using a fixed chromatographic process. Therefore, this study aimed to design an automated chromatographic system which is able to process virtually unlimited sample volume using the minimalism principle. An automated repetitive purification liquid chromatography (ARP-LC) system was developed using active-pump-based sampling and cyclic operational control. The system demonstrated exceptional precision, with injection reproducibility yielding RSD ≤ 1.32% in peak area and retention time stability of ≤ 0.69% RSD. When applied to the purification of coumarins from Cortex Fraxini extract, the system efficiently processed 4 L of the sample, yielding 11 distinct fractions in only seven consecutive runs. Subsequent activity-guided purification identified several high-purity coumarin compounds exhibiting significant antioxidant (EC₅₀ values as low as 5 μg/mL) and antibacterial activities. The ARP-LC system showcases high robustness, scalability, and compatibility with medium- to high-pressure chromatographic modes, providing an efficient and reproducible platform for the large-scale purification of complex natural products with clear implications for pharmaceutical development and industrial applications.
Extraction of natural aroma compounds from basidiomycete submerged fermentation of acid whey.
Stýblová S, Kokorina M, Berensmeier S
J Chromatogr A · 2026 Aug · PMID 42322778 · Publisher ↗
Natural aroma compounds are of increasing interest and here, 4-anisaldehyde, benzaldehyde and veratraldehyde were produced during a basidiomycete submerged fermentation of acid whey. An adsorption-based process was devel...
Natural aroma compounds are of increasing interest and here, 4-anisaldehyde, benzaldehyde and veratraldehyde were produced during a basidiomycete submerged fermentation of acid whey. An adsorption-based process was developed to concentrate these bioaromas using polymeric sorbents, Oasis HLB and PoraPak Rxn and food-grade aqueous ethanol. Dynamic binding capacities (DBC) determined using standard solutions ranged from 21.15 to 37.40 mg mL on both adsorbents. When fermented acid whey was used as the feed, effective binding capacities were reduced due to competitive matrix interactions, highlighting the importance of process-relevant evaluation. Purification and concentration were performed using semi-preparative chromatography. Oasis HLB provided sharper elution and higher concentration than PoraPak Rxn, whereas PoraPak Rxn showed broader elution profiles and lower desorption efficiency but higher overall recoveries. In the purification of a 2 L sample using Oasis HLB, all key aroma compounds were recovered with 95-, 89-, and 93-fold concentrations for 4-anisaldehyde, benzaldehyde, and veratraldehyde, respectively. Sample volume was reduced by 99%, providing a concentrated feed for further downstream purification (e.g., distillation).
Advanced spent media analytics and multivariate data analysis for AAV production media optimization.
Lehmkuhl M, Eriksson A, Teschner K … +6 more , Buve A, Krämer N, Brinkert P, Jonsson P, Surowiec I, Steffens T
J Chromatogr A · 2026 Aug · PMID 42320233 · Publisher ↗
Gene therapy with adeno-associated virus (AAV) vectors is rapidly advancing, but manufacturing productivity still limits dose availability and cost. Culture medium composition strongly shapes cellular metabolism and prod...
Gene therapy with adeno-associated virus (AAV) vectors is rapidly advancing, but manufacturing productivity still limits dose availability and cost. Culture medium composition strongly shapes cellular metabolism and production yield; however, the chemical complexity of defined formulations makes relevant components difficult to pinpoint using targeted assays alone. Here, we present an AAV media-development workflow integrating untargeted metabolomics, trace element analysis, and multivariate modeling of spent media containing cell lysate. We applied this workflow to two human embryonic kidney 293 (HEK293) producer lines, cultivated in four chemically defined media. With capsid titer as the response, the models revealed medium- and cell line-dependent chemical signatures linked to AAV2 productivity. We identified 37 compounds significantly positively correlated with this response, providing prospective candidates for media optimization. As a proof-of-concept, nicotinic acid supplementation increased genomic AAV2 titer in VPC2.0 cultures. To our knowledge, this is the first AAV-focused study integrating spent-media chemical profiling with multivariate modeling for media optimization.
Integrated micro-solid-phase extraction with miniature mass spectrometry for on-site detection of illicit drugs in human hair.
Zhang Y, Zhang J, Wu J … +10 more , Liu C, Liu Y, Zou B, Dong L, Wu X, Du Q, Shen Q, Zhang M, Ouyang Z, Wang H
J Chromatogr A · 2026 Aug · PMID 42320232 · Publisher ↗
This study presents a novel, integrated micro-solid-phase extraction/miniature mass spectrometry (micro-SPE/mini-MS) platform designed for the rapid, on-site quantification of conventional illicit drugs and emerging new...
This study presents a novel, integrated micro-solid-phase extraction/miniature mass spectrometry (micro-SPE/mini-MS) platform designed for the rapid, on-site quantification of conventional illicit drugs and emerging new psychoactive substances (NPS) in human hair. The system addresses the critical need for laboratory-grade accuracy in field settings by coupling a streamlined, mixed-mode cation exchange (MCX) pipette-tip micro-SPE protocol with a miniaturized mass spectrometer utilizing paper-capillary spray (PCS) ionization. The method targets three conventional illicit drugs, methamphetamine (MA), 3,4-methylenedioxymethamphetamine (MDMA), and ketamine (KET), and three new NPS, etomidate (ETM), isopropoxate (IPX), and 2-oxo-PCE. By systematically optimizing the micro-SPE enrichment and mini-MS parameters, we achieved significant mitigation of matrix effects, yielding impressive limits of detection (LOD, 1-3 ng/mL in hair extract) and robust linearity (R² ≥ 0.9917). The entire analytical workflow, from sample preparation to result, is completed within 5 min, offering a drastic reduction in turnaround time compared to traditional chromatography-based methods. Validation using authentic hair samples previously confirmed by laboratory LC-MS/MS demonstrated superior quantitative consistency, with relative errors maintained within 15%. By bridging the gap between rigorous laboratory confirmation and point-of-need screening, this field-deployable platform represents a significant advancement in forensic toxicology, workplace drug testing, and clinical diagnostics.
Fragmentation property identity card-assisted reliable structural annotation of calycosin metabolites in vivo: A strategy for isomer discrimination using mass spectrometry.
Wang R, Liu Y, Song W … +10 more , Yu C, Lei J, Weng J, Lin L, Zhang Y, Ma Y, Zhou W, Shen X, Chang Y, Gao Y
J Chromatogr A · 2026 Aug · PMID 42314505 · Publisher ↗
Drug metabolites play a pivotal role in the assessment of pharmacological efficacy and safety. The reliable structural annotation of drug metabolites is challenging due to their inherent complexity. Calycosin (Cal) is a...
Drug metabolites play a pivotal role in the assessment of pharmacological efficacy and safety. The reliable structural annotation of drug metabolites is challenging due to their inherent complexity. Calycosin (Cal) is a bioactive compound derived from Astragali Radix, exhibiting diverse pharmacological activities, including anti-inflammatory, antioxidant and cardioprotective properties; however, its metabolic profile has not yet been comprehensively elucidated. Ultra-high pressure liquid chromatography quadrupole time of flight tandem mass spectrometry (UHPLC-Q-TOF-MS) and ultra-high pressure liquid chromatography triple quadrupole mass spectrometry (UHPLC-QqQ-MS) were integratively employed for the identification of Cal metabolites. A total of 22 metabolites of Cal were detected in biological matrices, including plasma, urine, and feces. Based on the empirical mass fragmentation rules, the chemical structures of certain metabolites were elucidated. For the metabolites exhibiting isomeric forms with highly similar MS/MS spectra, the fragmentation property identity card (FPIC), a descriptor of compound mass spectrometric fragmentation patterns, was developed and its rapid visualization was implemented using Python. The compound FPIC was constructed by fitting, normalization, and transposition of ion transition response intensities under gradient collision energies, enabling the identification of fragment ions with isomer discriminative characteristics. Subsequently, the integration of FPIC with quantum chemical calculations enabled reliable structural elucidation of the isomers. Glucuronidation, sulfation, methylation, and dehydroxylation constituted the predominant in vivo metabolic pathways of Cal. Collectively, the present study comprehensively delineated the in vivo metabolic profile of Cal and proposed a reliable and broadly applicable strategy for the structural characterization of compounds metabolites.
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