Peak Tailing Research Articles

Retention Mechanisms of Basic Compounds in Liquid Chromatography with Sodium Dodecyl Sulfate and 1-Hexyl-3-Methylimidazolium Chloride as Mobile Phase Reagents in Two C18 Columns

Reversed-phase liquid chromatography (RPLC) relies on a non-polar stationary phase and a more polar hydro-organic mobile phase, where compound retention is primarily governed by hydrophobicity, with more hydrophobic compounds being retained longer. The introduction of secondary equilibria in the chromatographic system through additives, such as anionic surfactants and ionic liquids (ILs), was proposed to mitigate ionic interactions between positively charged analytes and the anionic free silanol groups in non-endcapped stationary phases, thereby preventing increased retention and peak tailing. Additionally, the combined hydrophobic and ionic interactions between cationic analytes and the ions in these additives was demonstrated to create mixed retention mechanisms that influence retention and selectivity. In this regard, this study investigates aqueous chromatographic systems incorporating both the anionic surfactant sodium dodecyl sulfate (SDS) and the IL 1-hexyl-3-methylimidazolium chloride as mobile phase reagents. This combination of reagents modulates the retention, eliminating the need for organic solvents and resulting in highly sustainable HPLC procedures. The chromatographic behavior was assessed using two different C18 columns (Zorbax Eclipse and XTerra-MS). The strength of solute interactions was estimated by calculating equilibrium parameters and the contributions of hydrophobic and ionic interactions through simple mathematical models. Focusing on the retention of six basic drugs (β-adrenoceptor antagonists), the study highlighted the significant role of ionic interactions. The results demonstrate the feasibility of using aqueous systems combining SDS and an IL for the efficient separation of moderately polar basic compounds without the use of organic solvents.

Assays of Variant Effect and Automated Patch Clamping Improve KCNH2-LQTS Variant Classification and Cardiac Event Risk Stratification.

Long QT syndrome is a lethal arrhythmia syndrome, frequently caused by rare loss-of-function variants in the potassium channel encoded by KCNH2. Variant classification is difficult, often because of lack of functional data. Moreover, variant-based risk stratification is also complicated by heterogenous clinical data and incomplete penetrance. Here we sought to test whether variant-specific information, primarily from high-throughput functional assays, could improve both classification and cardiac event risk stratification in a large, harmonized cohort of KCNH2 missense variant heterozygotes. We quantified cell-surface trafficking of 18 796 variants in KCNH2 using a multiplexed assay of variant effect (MAVE). We recorded KCNH2 current density for 533 variants by automated patch clamping. We calibrated the strength of evidence of MAVE data according to ClinGen guidelines. We deeply phenotyped 1458 patients with KCNH2 missense variants, including QTc, cardiac event history, and mortality. We correlated variant functional data and Bayesian long QT syndrome penetrance estimates with cohort phenotypes and assessed hazard ratios for cardiac events. Variant MAVE trafficking scores and automated patch clamping peak tail currents were highly correlated (Spearman rank-order ρ=0.69; n=433). The MAVE data were found to provide up to pathogenic very strong evidence for severe loss-of-function variants. In the cohort, both functional assays and Bayesian long QT syndrome penetrance estimates were significantly predictive of cardiac events when independently modeled with patient sex and adjusted QT interval (QTc); however, MAVE data became nonsignificant when peak tail current and penetrance estimates were also available. The area under the receiver operator characteristic curve for 20-year event outcomes based on patient-specific sex and QTc (area under the curve, 0.80 [0.76-0.83]) was improved with prospectively available penetrance scores conditioned on MAVE (area under the curve, 0.86 [0.83-0.89]) or attainable automated patch clamping peak tail current data (area under the curve, 0.84 [0.81-0.88]). High-throughput KCNH2 variant MAVE data meaningfully contribute to variant classification at scale, whereas long QT syndrome penetrance estimates and automated patch clamping peak tail current measurements meaningfully contribute to risk stratification of cardiac events in patients with heterozygous KCNH2 missense variants.

An adhesive hydrogel functionalized silica sphere for polar analytes separation and analysis

In response to the challenges associated with the chromatographic separation of polar compounds, this study aims to devise a solution by introducing a novel stationary phase. Hydrogels, characterized by a three-dimensional network structure, have aroused wide attention owing to its functional designability, multiple interaction sites and good adhesion, etc. In this work, an adhesive hydrogel functionalized silica stationary phase (Sil@PVA/TA) was synthesized using physical coating technique. Due to the co-existence of hydroxyl and benzene ring in the hydrogel structure, the obtained composites materials exhibited excellent separation performance for various of compounds and excellent column efficiency up to 71385.6 plates/m for thymidine. Furthermore, the hydrogel functionalized silica demonstrated superior selectivity to bare silica, diol-column and NH2-column for the separation of various of polar molecules, including, nucleosides/bases, alkaloids, organic acids, antibiotics and amino acids. Notably, for alkaloids, which frequently encounter peak tailing issues, Sil@PVA/TA demonstrated superior peak shape compared with C18 column. In short, this study successfully synthesized a hydrogel functionalized silica stationary phase, offering a novel method for the separation and analysis of polar compounds.

Molybdenum Disulfide Nanosheet-Based Nanocomposite for the Topical Delivery of Umbelliferone: Evaluation of Anti-inflammatory and Analgesic Potentials.

This study aimed to develop a nanocomposite formulation comprising umbelliferone (UMB) and molybdenum disulfide (MoS2) nanosheets as a carrier, termed as the UMB-MoS2 nanocomposite in gel for topical delivery. MoS2 nanosheets were successfully synthesized via a green-hydrothermal reaction of 10 mg of ammonium molybdate and 10 mg of thiourea in 80 mL of deionized water under predetermined conditions. The UMB-MoS2 nanocomposite was prepared by sonicating UMB and MoS2 nanosheets (each of 1 mg/mL) in dimethylformamide. Scanning electron microscopy revealed crumpled nanosheets with an open-ended structure and a nanocomposite as a layered structure. The X-ray diffraction pattern revealed the amorphous nature of UMB in the UMB-MoS2 nanocomposite. Fourier-transform infrared spectra of the UMB-MoS2 nanocomposite had modified bands of the functional group, which confirmed the formation of the nanocomposite. The size and polydispersity-index (435 nm and 0.415, respectively) of the nanocomposite were within the limit for an efficient topical application. Carbopol 934 (2%) was used to prepare the UMB-MoS2 nanocomposite gel (F1) and UMB-Carbopol gel (F2, for comparative evaluation). The pH, spreadability, and viscosity of F1 were found to be 5.56, 5.89 g·cm/s, and 32.5 Pa-sec, respectively, which were optimal for the topical application of gel-based formulations. In vitro release characteristics of both formulations were deemed to be suitable for topical application, where F1 exhibited a biphasic drug release profile and a superior release rate of 94.8% compared to 43.5% for F2 at 24 h. In the carrageenan-induced rat paw edema model, the animal group treated with F1 demonstrated the lowest increase in paw thickness of 26.6%, which was significantly lower as compared to the F2-treated group (52.9%) and the diclofenac sodium-treated group (32.2%). Similarly, in the tail immersion method, F1 exhibited the highest peak tail withdrawal latency of 10.9 s, significantly greater than F2 (8.9 s) and standard treatment (10 s), indicating the superior analgesic activity of F1. This pioneering work introduces a novel UMB-MoS2 nanocomposite with promising anti-inflammatory and analgesic potentials, paving the way for further research into the biomedical applications of MoS2-based nanocarriers.

Determination of Choline-Containing Compounds in Rice Bran Fermented with Aspergillus oryzae Using Liquid Chromatography/Tandem Mass Spectrometry.

Choline-containing compounds are essential nutrients for human activity, as they are involved in many biological processes, including cell membrane organization, methyl group donation, neurotransmission, signal transduction, lipid transport, and metabolism. These compounds are normally obtained from food. Fermented brown rice and rice bran with Aspergillus oryzae (FBRA) is a fermented food product derived from rice and rice ingredients. FBRA exhibits a multitude of functional properties with respect to the health sciences. This study has a particular focus on choline-containing compounds. We first developed a simultaneous liquid chromatography/tandem mass spectrometry (LC/MS/MS) analysis method for seven choline-containing compounds. The method was subsequently applied to FBRA and its ingredients. Hydrophilic interaction chromatography (HILIC) and selected reaction monitoring were employed for the simultaneous analysis of seven choline-containing compounds. MS ion source conditions were optimized in positive ion mode, and the product ions derived from the choline group were obtained through MS/MS optimization. Under optimized HILIC conditions, the peaks exhibited good shape without peak tailing. Calibration curves demonstrated high linearity across a 300- to 10,000-fold concentration range. The application of the method to FBRA and other ingredients revealed significant differences between food with and without fermentation. In particular, betaine and α-glycerophosphocholine were found to be highest in FBRA and brown rice malt, respectively. The results indicated that the fermentation processing of rice ingredients results in alterations to the choline-containing compounds present in foods. The developed HILIC/MS/MS method proved to be a valuable tool for elucidating the composition of choline-containing compounds in foods.

An endogenous evolution mechanism model of asset prices based on time-varying risk aversion coefficient

In the traditional heterogeneous agent model, investors are assumed to be risk averse, and the wealth expected utility function maximization principle is used to form the optimal asset quantity demand. In such models, the risk aversion coefficient of investors is often assumed to be constant. This paper considers that the risk aversion coefficient of investors is time-varying and changes with the change of wealth, and establishes an endogenous evolutionary mechanism model formed by fundamental analysts, technical analysts, and market makers. Compared with the fixed risk aversion coefficient model, this paper analyzes the investor’s behavior, the interaction between investor behaviors, and the influence of different types of investors on the stability of the market. At the same time, we test asset price and asset behavior and conclude that investor behavior affects the stability of the system model. The numerical simulation of the corresponding stochastic model shows that the model can simulate the basic characteristics of financial time series, such as the partial peak and thick tail of asset return series, and the long memory of fluctuations.

Cool Classical EI - A New Standard in EI and Its Many Benefits.

GC-MS with Cold EI improves all of the central GC-MS performance aspects, but it is known mostly for its provision of enhanced molecular ions. This occasionally leads to the misconception that, like chemical ionization, Cold EI is a supplementary ion source to standard EI. However, Cold EI is a highly superior replacement ion source to standard EI. While Cold EI mass spectra are the most informative and fully compatible with mass spectral library (such as NIST) identification, in some cases, the Cold EI mass spectra with their enhanced molecular ions result in a "picture" that is not as one is used to seeing. In this paper, we describe the "Cool Classical EI" mode, which produces classical EI mass spectra like standard EI. The change of Cold EI into the Cool Classical EI mode is software-based, requires no hardware change, and can be achieved even during the analysis. Several mass spectra that were obtained in the Cool Classical EI mode are presented and compared with standard EI and Cold EI mass spectra. In this paper we further demonstrate and discuss several benefits that Cold EI brings that are retained while using Cool Classical EI, including (a) much faster speed of analysis, (b) uniform response, (c) extended range of compounds amenable for analysis, (d) improved sample identification, (e) elimination of ion source related peak tailing, (f) elimination of intraion-source degradation, and (g) better signal-to-noise ratio of the sample compounds.

Deciphering the uranium isotopic signature of coastal water and sediments from Tokyo Bay using a multi-collector inductively coupled plasma mass spectrometer

We have measured 236U/238U and 235U/238U values in JMS-1 (geochemical reference material of Tokyo Bay sediments) and coastal seawater using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) equipped with both the retarding potential quadrupole lens and desolvating nebuliser system. For the accurate measurement of 236U/238U values (e.g., in the range of 10−9), mass spectrometric interferences on 236U isotope from both the peak tailing of 238U and polyatomic ion of 235UH were carefully corrected. With the sequential extraction experiments for JMS-1, whose U isotopic signatures were characteristic of isotopically-depleted U with industrial uses, authigenic U was extracted into a soluble fraction, and lithogenic U and anthropogenic U were gathered in an insoluble fraction. The anthropogenic U is likely to have been provided in insoluble forms and have deposited on the bay floor. Absence in differences of 236U/238U and 235U/238U values for seawater observed between inside and outside Tokyo Bay implies the negligibly small contribution of the anthropogenic U to U in the seawater. The data obtained here demonstrate the effective reduction of the interferences on 236U and the versatility of the isotopic signatures of U as an effective tracer for environmental circulation of U in nature.

Extending the emission peak tail of indole cyanine for deep-near-infrared bioimaging

We propose a novel strategy for tailoring the structure of fluorescent molecules to achieve emission at the tail end of the NIR-II window. The favorable spectroscopic properties and low cytotoxicity of YNs make them powerful tools for bioimaging. Notably, YN-4 exhibits a brightness 2.5 times greater than YN-3, 6 times that of IR-783, and 5 times that of ICG. This enhanced brightness enabled high-resolution imaging of mouse thoracic and abdominal cavities, tumor vasculature, and real-time monitoring of gastrointestinal motility using YN-4. Furthermore, covalent grafting of glucose onto the YN-Glu scaffold significantly improved tumor-targeting capability and facilitated tracking of glucose metabolism. This work aims to extend the application of fluorescent molecule imaging beyond the NIR-IIa window.

The role of the cation and anion in aqueous liquid chromatography with sodium dodecyl sulphate and imidazolium-based ionic liquids as mobile phase reagents

BackgroundIn reversed-phase liquid chromatography, solute retention is primarily influenced by interactions between a nonpolar stationary phase and a moderately polar hydro-organic mobile phase, based on the solute lipophilicity. However, challenges regarding retention and peak tailing can arise due to ionic interactions between positively charged analytes and free silanols present on silica-based stationary phases. To address these challenges, incorporating surfactants and ionic liquids (ILs) into the mobile phase offers an effective solution. These additives synergistically enhance chromatographic performance through electrostatic and lipophilic interactions, which enable fine-tuning of selectivity and improved separation efficiency. ResultsThis study explores the chromatographic behaviour of several basic compounds in aqueous mixtures containing the anionic surfactant sodium dodecyl sulphate (SDS), above its critical micellar concentration, combined with various 1-alkyl-3-methylimidazolium-based ionic liquids (ILs) featuring chloride, tetrafluoroborate, and hexafluorophosphate anions, all without the addition of organic solvents. Specifically, this research investigates the influence of different anion types within the ILs and considers the impact of the IL cations. Analysis of solute peak profiles reveals narrow and symmetrical peaks. By introducing tetrafluoroborate and hexafluorophosphate IL anions into a mobile phase that contains an anionic surfactant, the study sheds light on the interactions occurring within the chromatographic column. This enhanced understanding of the combined effects of surfactants and ILs contributes to refining chromatographic methodologies. SignificanceThis research highlights the importance of carefully selecting the appropriate IL when incorporating it into a micellar mobile phase alongside SDS. This combination results in practical retention times that surpass the performance achieved with either the surfactant or IL alone in the mobile phase. The study particularly emphasises the impact of the IL anion, especially in the absence of SDS and organic solvents. This unveils interactions that are otherwise obscured in micellar and hydro-organic media, providing new insights into chromatographic dynamics.

Multiplexed Assays of Variant Effect and Automated Patch-clamping Improve KCNH2-LQTS Variant Classification and Cardiac Event Risk Stratification.

Long QT syndrome (LQTS) is a lethal arrhythmia syndrome, frequently caused by rare loss-of-function variants in the potassium channel encoded by KCNH2. Variant classification is difficult, often owing to lack of functional data. Moreover, variant-based risk stratification is also complicated by heterogenous clinical data and incomplete penetrance. Here, we sought to test whether variant-specific information, primarily from high-throughput functional assays, could improve both classification and cardiac event risk stratification in a large, harmonized cohort of KCNH2 missense variant heterozygotes. We quantified cell-surface trafficking of 18,796 variants in KCNH2 using a Multiplexed Assay of Variant Effect (MAVE). We recorded KCNH2 current density for 533 variants by automated patch clamping (APC). We calibrated the strength of evidence of MAVE data according to ClinGen guidelines. We deeply phenotyped 1,458 patients with KCNH2 missense variants, including QTc, cardiac event history, and mortality. We correlated variant functional data and Bayesian LQTS penetrance estimates with cohort phenotypes and assessed hazard ratios for cardiac events. Variant MAVE trafficking scores and APC peak tail currents were highly correlated (Spearman Rank-order ρ = 0.69). The MAVE data were found to provide up to pathogenic very strong evidence for severe loss-of-function variants. In the cohort, both functional assays and Bayesian LQTS penetrance estimates were significantly predictive of cardiac events when independently modeled with patient sex and adjusted QT interval (QTc); however, MAVE data became non-significant when peak-tail current and penetrance estimates were also available. The area under the ROC for 20-year event outcomes based on patient-specific sex and QTc (AUC 0.80 [0.76-0.83]) was improved with prospectively available penetrance scores conditioned on MAVE (AUC 0.86 [0.83-0.89]) or attainable APC peak tail current data (AUC 0.84 [0.81-0.88]). High throughput KCNH2 variant MAVE data meaningfully contribute to variant classification at scale while LQTS penetrance estimates and APC peak tail current measurements meaningfully contribute to risk stratification of cardiac events in patients with heterozygous KCNH2 missense variants.

Improving the intestinal lipidome coverage in a gnotobiotic mouse model using UHPLC-MS-based approach through optimization of mobile phase modifiers and column selection

Lipidomics is focusing on the screening of lipid species in complex mixtures using mass spectrometry-based approaches. In this work, we aim to enhance the intestinal lipidome coverage within the Oligo-Mouse-Microbiota (OMM12) colonized mouse model by testing eight mobile phase conditions on five reversed-phase columns. Our selected mobile phase modifiers included two ammonium salts, two concentrations, and the addition of respective acids at 0.1 %. We compared two columns with hybrid surface technology, two with ethylene bridged hybrid technology and one with core–shell particles. Best performance was attained for standards and intestinal lipidome, using either ammonium formate or acetate in ESI(+) or ammonium acetate in ESI(−) for all column technologies. Notably, a concentration of 5 mM ammonium salt showed optimal results for both modes, while the addition of acids had a negligible effect on lipid ionization efficiency. The HST BEH C18 column improved peak width and tailing factor parameters compared to other technologies. We achieved the highest lipid count in colon and ileum content, including ceramides, phosphatidylethanolamines and phosphatidylcholines, when using 5 mM ammonium acetate in ESI(−). Conversely, in ESI(+) 5 mM ammonium formate demonstrated superior coverage for diacylglycerols and triacylglycerols.

Indole-3-pyruvate: Analysis and Control of Tautomerism and Reactivity.

It is well-known in biochemistry that structure confers function, meaning that chemical structural elucidation is critical to truly understanding the function of a given metabolite. Indole-3-pyruvate (IPyA) exists in an equilibrium between the keto and enol tautomeric forms. IPyA is suggested to play a role in immune function; however, determining whether the tautomeric forms function differently can only be studied if an analytical method is capable of distinguishing between the two forms. Herein, we describe the use of UHPLC-HRMS to gain insight into the physical variables that govern IPyA tautomer equilibrium, reactivity, and detection limit. We use hydrogen-deuterium exchange (HDX) to identify enol and keto peaks, and we show that tautomers exhibit a valley of fronting followed by a tailing peak shape (though separation is still attainable) and identical MS/MS spectra. We observed drastically different ratios of keto and enol forms in different solvents, which is an important consideration for in vitro studies. IPyA was found to be highly unstable with accelerated reactivity in peroxides. Through in vitro reactivity studies, IPyA produced a myriad of known and unknown metabolites via nonenzymatic processes, many of which were mapped in vivo via the analysis of human plasma. Finally, we show that vitamin C (ascorbic acid) can slow this reactivity and enable sensitive detection in whole blood.

Optimizing Messenger RNA Analysis Using Ultra-Wide Pore Size Exclusion Chromatography Columns.

Biopharmaceutical products, in particular messenger ribonucleic acid (mRNA), have the potential to dramatically improve the quality of life for patients suffering from respiratory and infectious diseases, rare genetic disorders, and cancer. However, the quality and safety of such products are particularly critical for patients and require close scrutiny. Key product-related impurities, such as fragments and aggregates, among others, can significantly reduce the efficacy of mRNA therapies. In the present work, the possibilities offered by size exclusion chromatography (SEC) for the characterization of mRNA samples were explored using state-of-the-art ultra-wide pore columns with average pore diameters of 1000 and 2500 Å. Our investigation shows that a column with 1000 Å pores proved to be optimal for the analysis of mRNA products, whatever the size between 500 and 5000 nucleotides (nt). We also studied the influence of mobile phase composition and found that the addition of 10 mM magnesium chloride (MgCl2) can be beneficial in improving the resolution and recovery of large size variants for some mRNA samples. We demonstrate that caution should be exercised when increasing column length or decreasing the flow rate. While these adjustments slightly improve resolution, they also lead to an apparent increase in the amount of low-molecular-weight species (LMWS) and monomer peak tailing, which can be attributed to the prolonged residence time inside the column. Finally, our optimal SEC method has been successfully applied to a wide range of mRNA products, ranging from 1000 to 4500 nt in length, as well as mRNA from different suppliers and stressed/unstressed samples.

Measurement of ultra-trace level 237Np in soil and sediment by triple-quadrupole inductively coupled plasma-mass spectrometry with different mass modes combined with chemical separation

Long-lived trans‑uranium nuclides such as 237Np, may reside in the environment for long period and result in ecological impact and human health threat. Accurate measurement of 237Np in the environment is important for the risk assessment and ecological evaluation. However, the spectral peak tailing and polyatomic ions interference greatly limit the measurement of 237Np with triple quadrupole ICP-MS (ICP-MS/MS), which have been successfully used for analysis of ultra-trace level 239,240Pu and 241Am. The novel methods for 237Np measurement with ICP-MS/MS in both on-mass and mass-shift modes were examined in this paper. When helium was used as the collision gas for the ICP-MS/MS measurement with on-mass mode, the interference contribution to the counts for 237Np (at m/z 237) as low as 4 × 10−8 was observed only from Hg, while no measurable interference from Tl and Pb was observed. Moreover, when the mass-shift mode is employed with O2/He and He as the collision/reaction gas, the interference contributions from Hg, Tl and Pb were all negligible. The detection limit of 237Np was reduced to 0.014 fg/g and 0.019 fg/g for on-mass and mass-shift mode, respectively. The novel methods were demonstrated to enable accurate determination of 1.0 fg/g level 237Np in the emulated sample solutions with a 237Np/238U atomic ratio as low as 10−9. Combined with appropriate chemical separation procedure, the developed methods were verified with certified reference materials and soil samples.

Flow and contaminant transport dynamics in clay-amended barriers through flushing experiments and multi-porosity-based modeling

Clay-amended barriers are widely used to prevent hazardous leachate percolation from landfill to subsurface. The performance of these barriers is mostly evaluated through numerical simulations with limited experimental investigation through leachate flushing experiments. To bridge this gap, contaminant loading and its flushing experiments were carried out to assess the performance of clay-amended composite materials as landfill liners. River sand (Sa), loamy soil (Ns), and alternative waste materials like fly ash (Fa) and flushed silt (Si) were used to prepare the composites. Composites fulfilling the hydraulic conductivity (<10−7 cm/s) and compressive strength (200 kPa) criteria were selected for contaminant loading and its flushing experiments to understand the fate of fluoride ions. The experimentally determined hydraulic conductivity (Ks) values for all the composites were in the order of 10−8 cm/s. The experimental breakthrough curves exhibited skewed shape, long tailing, and dual peaks. Dual porosity and dual permeability with immobile water models were employed to simulate these curves, revealing that preferential flow pathways and random chemical sorption sites significantly affect solute transport in clay-amended barriers. Further, scanning electron microscopy and energy-dispersive X-ray spectroscopy were employed to trace the preferred path of fluoride ions through the barrier. The removal efficiency and temporal moments were used to determine the percentage mass retained, mean arrival time, and spreading within the barrier. The highest solute mass was retained by sand-clay barrier (SaB30) (91%), followed by loam-clay barrier (NsB30) (59%), fly ash-clay barrier (FaB30) (38%), and silt-clay barrier (SiB30) (4%) with the least mass. The lowest mean arrival time was calculated for NsB30 (269 h) and the highest for SaB30 (990 h), with FaB30 (384 h) and SiB30 (512 h) having values in between. This study concludes that validating the design hypothesis of clay-amended barriers through contaminant loading and its flushing studies leads to an effective and sustainable design.

Interval evaluation of wind power prediction based on skew-slash t distribution

Wind resources have characteristics of stochastic volatility, resulting in wind power forecast errors greatly. The short and medium-term wind power forecast error distribution of the actual wind farm operating system is analyzed, and a sharp peak and thick tail, with heavy tail and skewness characteristics, are presented. A skew-slash t distribution (SST distribution) is proposed to describe the error distribution of short-term wind power prediction, and the parameter estimation is carried out by probability density curve fitting. The fitting results of the wind power forecast error historical data of the Wind power plant based on SST distribution, t distribution, and t Location-slash distribution (TLS distribution) are obtained, and the fitting goodness and prediction accuracy are compared. The results show that the SST distribution can more effectively estimate the wind power prediction interval.

Comparison of carrier gases for the separation and quantification of mineral oil hydrocarbon (MOH) fractions using online coupled high performance liquid chromatography-gas chromatography-flame ionisation detection

On-line coupled high performance liquid chromatography-gas chromatography-flame ionisation detection (HPLC-GC-FID) was used to compare the effect of hydrogen, helium and nitrogen as carrier gases on the chromatographic characteristics for the quantification of mineral oil hydrocarbon (MOH) traces in food related matrices. After optimisation of chromatographic parameters nitrogen carrier gas exhibited characteristics equivalent to hydrogen and helium regarding requirements set by current guidelines and standardisation such as linear range, quantification limit and carry over. Though nitrogen expectedly led to greater peak widths, all required separations of standard compounds were sufficient and humps of saturated mineral oil hydrocarbons (MOSH) and aromatic mineral oil hydrocarbons (MOAH) were appropriate to enable quantitation similar to situations where hydrogen or helium had been used. Slightly increased peak widths of individual hump components did not affect shapes and widths of the MOSH and MOAH humps were not significantly affected by the use of nitrogen as carrier gas. Notably, nitrogen carrier gas led to less solvent peak tailing and smaller baseline offset. Overall, nitrogen may be regarded as viable alternative to hydrogen or helium and may even extend the range of quantifiable compounds to highly volatile hydrocarbon eluting directly after the solvent peak.

The changes in the annual distribution of mountain runoff during the period of 1965–2018 in Hexi Corridor, Northwest China

The annual distribution characteristics of river runoff in arid regions have significant implications for water resource stability and management. Based on the mountain runoff data from 1965 to 2018, this study examines the annual change characteristics of monthly runoff of the Shiyang River Basin, Heihe River Basin, and Shule River Basin in the Hexi Corridor, Northwest China. Many indexes are used and analyzed, including the coefficient of variance, the complete regulation coefficient, the concentration degree and concentration period, the magnitude of change, the skewness coefficient, and the kurtosis coefficient of the annual distribution curves. The results reveal the following: (1) The inhomogeneity of annual runoff distribution in the Taolai River and the rivers to the west of it, except the Shiyou River, show an increasing trend. Conversely, the inhomogeneity of the rivers to the east of the Taolai River generally show a downward trend, but the coefficient of variance value is still very high. (2) In the Shiyang River Basin, the annual distribution of the concentration period is characterized by a relatively discrete pattern. Conversely, the Heihe River Basin exhibits a relatively concentrated pattern, and the distribution pattern of the Shule River Basin is quite different. Notably, all concentration periods in the three basins have shifted backward after the 2000s. (3) The Shiyang River Basin exhibits disordered annual distribution curves of runoff in different years. In contrast, the Heihe River Basin presents a typical ‘single-peak’ pattern with a prominent right-skewed. The Shule River Basin has regular distribution curves, with a gradually significant ‘double-peak’ pattern from east to west. Overall, there has been a slight change in runoff in the Shiyang River Basin, while the Heihe River Basin and Shule River Basin have experienced significant increases in runoff. The annual distribution curves of runoff in the Liyuan River and the rivers to the east of it exhibit a gentle peak pattern, and the appearance probability of extreme runoff during the year is low. Conversely, the rivers to the west of the Liyuan River, excluding the Danghe River, display a sharp peak and thick tail pattern, indicating that the appearance probability of extreme runoff during the year is high. These findings have practical implications for the planning and management of water resources in the Hexi Corridor. Moreover, they provide a solid foundation for predicting future changes in regional water resources.

Novel HPLC Method Validation for Quantification of Dapagliflozin in Bulk Drug and Formulation

A new, steady, easy-to-use, and straightforward high-performance liquid chromatography (HPCL) technique was also tested to determine dapagliflozin concentration in medicinal and API forms. For the chromatographic extraction study, a Phenomenex Gemini-NX C18 Column was used. This column was filled with a mobile phase that was 70:30 v/v methanol to sodium 1-octanesulphonate. This experiment used a 20-liter syringe amount and a flow rate of 1-mL per minute. A bunch of factors were used to make sure the new method worked. The drug dapagliflozin was released at a wavelength of 203 nm after 6.5 ± 0.5 minutes. A correlation coefficient (r2) of 0.9994 between 15 to 55 μg/mL shows that the planned process is linear. The theoretical plates and peak tailing were found to be 4129 and 1.03, respectively. In terms of healing, the percent accuracy that was reached was within the acceptable range of 98 to 100. New suggestions say that the regular testing of dapagliflozin in large amounts must be done using a proven method that is unique and easy to repeat. Forced breakdown tests with drugs were used to show that the proposed method is stable. The product was tested according to the steps laid out in the ICH Q2R1 Guidelines. The test looked at many chemical processes, such as oxidation, photolysis, heat stress, and acids and alkaline hydrolysis.