Mass Analysis Research Articles

Performance Evaluation of an EI&CI Dual Ionization TOFMS Hyphenated with a Flow Modulated GC×GC System.

The use and compatibility of a dual-ionization TOFMS operating an EI source and a CI source in parallel using a single TOF mass analyzer with flow modulated two-dimensional GC (GC×GC) is described. Important figures of merit of the mass spectrometer that are required for two-dimensional GC hyphenation such as acquisition speed, ion source response, EI/CI switching, the GC transfer, and data alignment are carefully investigated and addressed. Improved fast switching ion optics allow switching in a 100 Hz frequency between EI and CI spectra sampled from the same GC×GC effluent. The spectra quality also influenced by the preseparation, especially of the EI source, is compared to a standard setup operating a single quadrupole MS coupled to the same GC system. Further, two setups including and excluding an additional flame ionization detector are presented. High increments in CI sensitivities are achieved by utilizing the high pumping efficiencies of the CI stage of the used mass spectrometer. By leading high flow ratios of the GC×GC modulation flows toward the CI source, the intensity can be increased by factors of up to 37 while maintaining the pressure balance of the less robust EI source. Finally, thermal desorption GC×GC-EI&CI-TOFMS analyses of traffic emission samples from a federal highway in Germany are executed with the presented setup.

The Carrier Proteome Should Be Reassessed for Each Mass Analyzer Architecture.

A clever utilization of classic proteomics reagents now allows the effective amplification of the peptide sequencing potential in shotgun proteomics. The application of this method has helped usher in the exciting new field of single cell proteomics. While it was easy to first think that this approach was finally the answer for the polymerase chain reaction in protein chemistry, limitations were carefully described by the authors and others. A study by Cheung et al. systematically identified the consequences of higher concentration carrier proteomes and defined the "carrier proteome limit" [Cheung et al. Nat. Methods 2021, 18, 76]. While this work has been replicated by others, every analysis published to date has used a variation of the same mass analyzer. When the same analysis is performed on alternative instruments, these limits appear to be very different and can be attributed to defined characteristics of each mass analyzer. Specifically, in mass analyzers with a higher relative intrascan linear dynamic range, increased carrier channels appear less detrimental to quantitative accuracy. As such, we may be limiting the power of isobaric peptide signal "amplification" by restricting ourselves to traditional mass analyzer options for shotgun proteomics.

Polyprenylated acylphloroglucinols from Hypericum sampsonii with cytotoxicity against pancreatic carcinomas

Chemical investigation on the 80% EtOH extract of the air dried aerial parts of Hypericum sampsonii resulted in the isolation of two new polycyclic polyprenylated derivatives, hypersampines A and B (1 and 2). The structures of the new compounds were elucidated by spectroscopic data (NMR, IR, and UV) and high resolution mass analysis. The two isolated polyprenylated acylphloroglucinols were tested in vitro for cytotoxic activities against 6 pancreatic cell lines. As a result, compounds 1 and 2 possessed modest cytotoxic activities against all the tested tumor cell lines with IC50 values less than 40 μM.

Square Parametric Excitation: A Digital Resonant Method for the Quadrupole Ion Trap.

Digital ion trap technology is an alternate method for driving quadrupole ion traps and mass filters using variable frequency, fixed amplitude RF square waves in place of variable amplitude, fixed frequency RF sine waves. This technique offers some advantages such as an increase in the high mass analysis range by varying frequency and lower overall voltage requirements. Here, we present a complex square waveform developed for resonant parametric excitation in a quadrupole linear ion trap. Unlike traditional resonance methods, the driving RF square wave and auxiliary square wave are coupled using the same digital circuitry without the need for transformer coupling. In this work, we use this complex waveform to selectively excite the first order parametric resonances of ion motion. The square parametric excitation method presented here employs a simple and repetitive circuit design consisting of a low-voltage waveform generator followed by a series of high-voltage MOSFET switches. This design allows for resonance methods to be easily implemented in the all-digital quadrupole. The complex square waveform can perform the same useful functions as sine wave auxiliary signals, such as selective mass elimination and mass isolation. We also demonstrate that the mass resolution performance and S/N of our digital mass spectrometer is improved by applying the complex square waveform during ion ejection.

Physiological profile of professional handball players regarding playing position

In the handball game players occupied specific position which requires unique physiological and physical attributes relating to technical and tactical requirements of each position in order to maximize sport performance on the court. The aim of this study was to quantify anthropometrical and physiological characteristics in elite Macedonian handball players and compare them regarding four different playing positions. In this study were included 55 handball players, different nationality, from RNM, participated in ergometry testing with Bruce protocol and body mass analysis with bioelectrical impedance analyzer, InBody 720. The players were divided in four groups according to playing position: wings (W), backs (B), pivots (P) and goalkeepers (G). Anthropometric parameters for all players were following: mean height was 186.3  7.1 cm, weight = 85.37 ± 13.7 kg, skeletal muscle mass (SMM) = 42.04 ± 6.2 kg; BMI = 24.54 ± 2.8; BF%=13.4 ± 4.75 and WHR = 0.85 ± 0.06. Regarding the position, B/W/P/G for height were: 187.14cm /180.0cm/191.77cm/186.8cm; weight: 85.72/kg72.67kg/ 99.67kg/85.33kg; body fat percent: 12.26% /11.92% / 16.3% / 14.7%. The mean values for maximal oxygen consumption for B/W/P/G were 48.86 / 44.31 / 44.09 / 47.78 ml/kg/min. The BIA parameters of body composition in handball players regarding the playing position, showed statistically significant differences for all lean body mass parameters and obesity diagnose parameters, except for the body fat percent. According the cardio-physiological parameters derived from Bruce protocol handball players at different playing position had similar aerobic capacity.

Analysis of preoperative assessment of glandular mass in gynecomastia

To investigate the effectiveness of axillary single-site laparoscopic subcutaneous mastectomy in treatment of gynecomastia (GYN) and the assessment method of glandular mass before operation. A clinical data of 65 GYN patients admitted between August 2023 and February 2024 and matched the selection criteria was retrospectively analyzed. The patients were (30.8±7.9) years old, with a body mass index (BMI) of 27.3 (24.9, 29.8) kg/m 2. According to Simon's grading criteria, the GYN was classified as gade Ⅰ in 8 cases, grade Ⅱa in 32 cases, grade Ⅱb in 21 cases, and grade Ⅲ in 4 cases. All patients underwent bilateral axillary single-site laparoscopic subcutaneous mastectomy. The operation time, intraoperative blood loss, postoperative bilateral extubation time, total length of hospital stay, and the occurrence of related complications were recorded. The cosmetic outcome score was assessed by questionnaire at 2 months after operation. Preoperative BMI, lying/standing sternal notch to nipple (SN-N), and lying/standing nipple to nipple (N-N) were measured. The differences in SN-N between standing and lying positions (ΔSN-N) and in N-N between lying and standing positions (ΔN-N) were calculated. The intraoperative resected glandular mass was recorded. The glandular mass-related indicators (BMI, ΔSN-N, ΔN-N) were compared between Simon grades. Spearman's correlation analysis and multiple linear regression analysis of glandular mass with BMI and ΔSN-N, ΔN-N and Simon grading (grades Ⅰ, Ⅱa, Ⅱb, and Ⅲ were assigned values of 1, 2, 3, and 4, respectively) of the corresponding side. All operations were successfully completed with the operation time of 75.0 (60.0, 90.0) minutes, the intraoperative blood loss of 12.0 (11.0, 13.0) mL, and the bilateral extubation time of 1.5 (1.5, 1.5) days after operation. The total length of hospital stay was 3.0 (3.0, 3.0) days. Three cases of subcutaneous hematoma in the chest wall and 1 case of nipple areola numbness and discomfort occurred after operation, while the rest of the patients had no complication, such as postoperative haemorrhage, effusion, infection, and nipple areola necrosis. The subjective cosmetic scores were all 15 at 2 months after operation, which was very satisfactory. The differences in ΔSN-N of right side between Simon grade Ⅰ and grades Ⅱa, Ⅱb, Ⅲ and in ΔSN-N of left side between Simon grade Ⅰ and grades Ⅱb, Ⅲ were significant ( P<0.05), while the differences between the remaining grades were not significant ( P>0.05). The differences in ΔN-N between Simon grade Ⅱa and gradeⅡb and in BMI between Simon grade Ⅱb and grade Ⅲ were not significant ( P>0.05), while the differences between the remaining grades were significant ( P<0.05). The glandular masses of left and right breasts in 65 patients were 69.0 (52.1, 104.0) g and 73.0 (56.0, 94.0) g, respectively; and the difference between left and right breasts was not significant ( Z=-0.622, P=0.534). The data of the right breast was selected for correlation analysis. Correlation analysis showed that the right glandular mass was positive correlated with BMI and Simon grading, ΔSN-N, and ΔN-N ( P<0.05). Multiple linear regression analysis showed that Simon grading had a positive predictive effect on glandular mass, and the regression equation was as follows: right glandular mass=5.541+32.115×Simon grading ( R 2 =0.354, P<0.001). Axillary single-site laparoscopic subcutaneous mastectomy is an ideal surgical procedure for the treatment of GYN. BMI and Simon grading are closely related to GYN glandular mass, and have certain reference value for preoperative glandular mass assessment.

Mass Prediction and Analysis of an Object’s Mass from Its Image Using Deep Learning

Mass Prediction and Analysis of an Object’s Mass from Its Image Using Deep Learning

Experimental Investigation of a Digital Quadrupole Inductively Coupled Plasma Mass Spectrometer for Elemental Analysis.

We describe the development and initial characterization of a digital waveform scanning quadrupole mass filter (digital QMF) used for inductively coupled plasma mass spectrometry (ICP-MS). Unlike a conventional voltage scanning QMF, in the digital QMF, the frequency of the digital waveform is scanned to filter ions with different m/z through the quadrupole, and m/z is proportional to 1/f2. In digital QMF, the duty cycle of the digital waveform driving the quadrupole is modified such that stability regions of interest are accessible for mass analysis with no DC voltage applied. Here, we evaluate the performance of our digital ICP-QMS instrument at several duty cycles and corresponding stability zones: from zone 1 to zone 3,2. We demonstrate that, regardless of the stability zone used, frequency vs m/z calibration matches theory. For lower-order stability zones, the mass range of the analyzer is limited by the high-frequency waveform required; however, at zone 3,2, we demonstrate a mass range from at least 40 to 232 Th, which covers most of the elemental mass range. Similar to the conventional QMF, higher stability regions of the digital QMF can yield a higher resolution. We obtained the best resolution for our current instrument at zone 3,2 with a 62.50/37.50 duty cycle. The resolution at full-width at 10% peak height (R10%) was 1200 and 1100 for 115In+ and 232Th+, respectively. Lower pole bias yielded a R10% of 1400 for 40Ar+. Resolution and sensitivity comparisons indicate that higher q values and higher duty cycles lead to enhanced resolution, but lower sensitivity. Our results validate the operation of digital quadrupole ICP-MS and suggest that, with continuous improvement of electronics and instrumentation, a high resolution digital waveform scanning ICP-QMS for elemental analysis is possible.

Filling the gaps in peptide maps with a platform assay for top-down characterization of purified protein samples.

Liquid chromatography-mass spectrometry (LC-MS) intact mass analysis and LC-MS/MS peptide mapping are decisional assays for developing biological drugs and other commercial protein products. Certain PTM types, such as truncation and oxidation, increase the difficulty of precise proteoform characterization owing to inherent limitations in peptide and intact protein analyses. Top-down MS (TDMS) can resolve this ambiguity via fragmentation of specific proteoforms. We leveraged the strengths of flow-programmed (fp) denaturing online buffer exchange (dOBE) chromatography, including robust automation, relatively high ESI sensitivity, and long MS/MS window time, to support a TDMS platform for industrial protein characterization. We tested data-dependent (DDA) and targeted strategies using 14 different MS/MS scan types featuring combinations of collisional- and electron-based fragmentation as well as proton transfer charge reduction. This large, focused dataset was processed using a new software platform, named TDAcquireX, that improves proteoform characterization through TDMS data aggregation. A DDA-based workflow provided objective identification of αLac truncation proteoforms with a two-termini clipping search. A targeted TDMS workflow facilitated the characterization of αLac oxidation positional isomers. This strategy relied on using sliding window-based fragment ion deconvolution to generate composite proteoform spectral match (cPrSM) results amenable to fragment noise filtering, which is a fundamental enhancement relevant to TDMS applications generally.

Identification of coke species on Fe/USY catalysts used for recycling polyethylene into fuels.

The Fe/USY catalyst used for converting plastic waste into fuels faces coking problems. A comprehensive understanding of coke distribution and structure is crucial for catalyst design, enabling resistance to coke deposition and facilitating regeneration. In this study, we analyze the coke deposition on Fe/USY catalysts after catalytic pyrolysis of polyethylene for fuel oil, and present insights into the coke distribution over the metal and acid sites, as well as its specific molecular structure. The coke distributes over both the metal and acid sites, exhibiting distinct TPO peaks corresponding to metal-site coke (370 °C) and acid-site coke (520 °C). The total coke yields range from 2.0% to 2.4%, with distribution on metal and acid sites dependent on Fe loading and acidity. Structurally, the coke is highly-condensed, containing more than four aromatic rings with limited alkyl groups. The acid-site coke is more condensed than the metal-site coke, showing lower H/C ratios (0.5-0.75) relative to the acid-site coke (0.75-0.9). Identified by MALDI-TOF mass analysis, the predominant molecular structures of the coke located on metal and acid sites are illustrated. The metal-site cokes typically exhibit 4-7 aromatic rings, while the acid-site cokes display even greater condensation with 5-12 aromatic rings.

Assessment of water mass distribution and intrusions of circumpolar deep water in the Amundsen Sea based on the ocean reanalysis product FOAM-GLOSEA5v13

The Amundsen Sea of West Antarctica is one of the regions of particularly interest to the oceanography community due to accelerated basal melting of its ice shelves. Quantitative estimates of the composition of water masses and their sources are essential for understanding the heat and salt budgets and the stability of ice shelves in this region. In this study, the water mass distributions on the Amundsen Sea continental shelf are estimated based on FOAM-GLOSEA5v13, a global oceanographic reanalysis product, using a modified statistical based optimal water mass analysis method. The reanalysis product effectively captures the signal of primary water masses, including the Winter Water (WW) and the Circumpolar Deep Water (CDW) below the Antarctic Summer Surface Water (SSW). The horizontal and vertical distributions and temporal evolution of three water mass endmembers (WW, CDW and DSW) and their mixing ratios are calculated, based on which an intrusion location detection method was established. Using the reanalysis product and intrusion detection method, all potential CDW intrusion sites along the shelf break are identified. Based on the reanalysis product, an intrusion site over the shelf break, away from major deep troughs was captured and confirmed by numerical particle tracking experiments.

Assessment of water mass distribution and intrusions of circumpolar deep water in the Amundsen Sea based on the ocean reanalysis product FOAM-GLOSEA5v13

The Amundsen Sea of West Antarctica is one of the regions of particularly interest to the oceanography community due to accelerated basal melting of its ice shelves. Quantitative estimates of the composition of water masses and their sources are essential for understanding the heat and salt budgets and the stability of ice shelves in this region. In this study, the water mass distributions on the Amundsen Sea continental shelf are estimated based on FOAM-GLOSEA5v13, a global oceanographic reanalysis product, using a modified statistical based optimal water mass analysis method. The reanalysis product effectively captures the signal of primary water masses, including the Winter Water (WW) and the Circumpolar Deep Water (CDW) below the Antarctic Summer Surface Water (SSW). The horizontal and vertical distributions and temporal evolution of three water mass endmembers (WW, CDW and DSW) and their mixing ratios are calculated, based on which an intrusion location detection method was established. Using the reanalysis product and intrusion detection method, all potential CDW intrusion sites along the shelf break are identified. Based on the reanalysis product, an intrusion site over the shelf break, away from major deep troughs was captured and confirmed by numerical particle tracking experiments.

Synthesis and Structure of Novel Phenothiazine Derivatives, and Compound Prioritization via In Silico Target Search and Screening for Cytotoxic and Cholinesterase Modulatory Activities in Liver Cancer Cells and In Vivo in Zebrafish.

Phenothiazines (PTZ) are antipsychotics known to modulate a variety of neurotransmitter activities that include dopaminergic and cholinergic signaling and have been identified as potential anticancer agents in vitro. However, it is important to also test whether a highly cytotoxic, repurposed, or novel PTZ has low toxicity and neuromodulatory activity in vivo using vertebrate model organisms, such as zebrafish. In this study, we synthesized novel phenothiazines and screened them in vitro in liver cancer and in vivo in zebrafish embryos/larvae. The syntheses of several intermediate PTZ 10-yl acyl chlorides were followed by elemental analysis and determination of 1H NMR and 13C NMR mass (ESI+) spectra of a large number of novel PTZ 10-carboxamides. Cytotoxicities of 28 PTZ derivatives (1-28) screened against Hep3B and SkHep1 liver cancer cell lines revealed five intermediate and five novel leads along with trifluoperazine (TFP), prochlorperazine (PCP), and perphenazine, which are relatively more cytotoxic than the basic PTZ core. Overall, the derivatives were more cytotoxic to Hep3B than SkHep1 cells. Moreover, in silico target screening identified cholinesterases as some of the commonest targets of the screened phenothiazines. Interestingly, molecular docking studies with acetylcholinesterase (AChE) and butyrylcholinesterase proteins showed that the most cytotoxic compounds 1, 3, PCP, and TFP behaved similar to Huprin W in their amino acid interactions with the AChE protein. The highly cytotoxic intermediate PTZ derivative 1 exhibited a relatively lower toxicity profile than those of 2 and 3 during the zebrafish development. It also modulated in vivo the cholinesterase activity in a dose-dependent manner while significantly increasing the total cholinesterase activity and/or ACHE mRNA levels, independent of the liver cancer cell type. Our screen also identified novel phenothiazines, i.e., 8 and 10, with significant cytotoxic and cholinesterase modulatory effects in liver cancer cells; yet both compounds had low levels of toxicity in zebrafish. Moreover, they modulated the cholinesterase activity or expression of ACHE in a cancer cell line-specific manner, and compound 10 significantly inhibited the cholinesterase activity in zebrafish. Accordingly, using a successful combination of in silico, in vitro, and in vivo approaches, we identified several lead anticancer and cholinesterase modulatory PTZ derivatives for future research.

Synthesis, Characterization, and Potential Usefulness in Liver Function Assessment of Novel Bile Acid Derivatives with Near-Infrared Fluorescence (NIRBAD).

Conventional serum markers often fail to accurately detect cholestasis accompanying many liver diseases. Although elevation in serum bile acid (BA) levels sensitively reflects impaired hepatobiliary function, other factors altering BA pool size and enterohepatic circulation can affect these levels. To develop fluorescent probes for extracorporeal noninvasive hepatobiliary function assessment by real-time monitoring methods, 1,3-dipolar cycloaddition reactions were used to conjugate near-infrared (NIR) fluorochromes with azide-functionalized BA derivatives (BAD). The resulting compounds (NIRBADs) were chromatographically (FC and PTLC) purified (>95%) and characterized by fluorimetry, 1H NMR, and HRMS using ESI ionization coupled to quadrupole TOF mass analysis. Transport studies using CHO cells stably expressing the BA carrier NTCP were performed by flow cytometry. Extracorporeal fluorescence was detected in anesthetized rats by high-resolution imaging analysis. Three NIRBADs were synthesized by conjugating alkynocyanine 718 with cholic acid (CA) at the COOH group via an ester (NIRBAD-1) or amide (NIRBAD-3) spacer, or at the 3α-position by a triazole link (NIRBAD-2). NIRBADs were efficiently taken up by cells expressing NTCP, which was inhibited by taurocholic acid (TCA). Following i.v. administration of NIRBAD-3 to rats, liver uptake and consequent release of NIR fluorescence could be extracorporeally monitored. This transient organ-specific handling contrasted with the absence of release to the intestine of alkynocyanine 718 and the lack of hepatotropism observed with other probes, such as indocyanine green. NIRBAD-3 administration did not alter serum biomarkers of hepatic and renal toxicity. NIRBADs can serve as probes to evaluate hepatobiliary function by noninvasive extracorporeal methods.

Unraveling the ability of electronically diverse 9H-carbazoles as potential fluorophores in cellular imaging applications with BSA binding affinities

In the present study, fluorophores based on 9H-carbazole have been synthesized from readily synthesizable 2-nitrochalcones in a single-step reductive cyclization reaction with methyl acetoacetate. The molecular geometry was confirmed based on IR, NMR and mass analysis. The ground state geometry for all the synthesized compounds was optimized using DFT-based methods to explore the localization of frontier molecular orbitals in electronically diverse carbazoles. The photophysical studies revealed a higher Stokes shift for PPM 17 due to the presence of the naphthyl group at C-1 of carbazole. The high stability of PPM14, as evidenced by high chemical hardness, prompted us to explore its BSA binding affinity using fluorescence titration, synchronous,3-D fluorescence and energy transfer analysis. The probe (PPM 14) displayed a “turn-off” response in the presence of Fe3+ ions. The less cytotoxic behavior of PPM 14, its “turn-off” fluorescence response with Fe3+, and its utility in cell imaging application establish it as a potential small organic framework-based bio-sensor.

The value of PET/CT radiomic texture analysis of primary mass and mediastinal lymph node on survival in patients with non-small cell lung cancer

ObjectiveThis study was designed to determine the potential prognostic value of radiomic texture analysis and metabolic-volumetric parameters obtained from positron emission tomography (PET) in primary mass and metastatic hilar/mediastinal lymph nodes in stage 2–3 non-small cell lung cancer (NSCLC). MethodsImages of patients diagnosed with stage 2–3 NSCLC who underwent 18F-FDG PET/CT imaging for staging up to 4 weeks before the start of treatment were evaluated using LIFEx software. Volume of interest (VOI) was generated from the primary tumor and metastatic lymph node separately, and volumetric and textural features were obtained from these VOIs. The relationship between the parameters obtained from PET of primary mass and the metastatic hilar/mediastinal lymph nodes with overall survival (OS) and progression-free survival (PFS) was analyzed. ResultsWhen radiomic features, gender and stage obtained from lymph nodes were evaluated by Cox regression analysis; GLCM_correlation (p: 0.033, HR: 4,559, 1.660–12.521, 95% CI), gender and stage were determined as prognostic factors predicting OS. In predicting PFS; stage, smoking and lymph node MTV (p: 0.033, HR: 1.008, 1.001–1.016, 95% CI) were determined as prognostic factors. However, the radiomic feature of the primary tumor could not show a significant relationship with either OS or PFS. ConclusionsIn a retrospective cohort of NSCLC patients with Stage 2 and 3 disease, volumetric and radiomic texture characteristics obtained from metastatic lymph nodes were associated with PFS and OS. Tumor heterogeneity, defined by radiomic texture features of 18 F-FDG PET/CT images, may provide complementary prognostic value in NSCLC.

Enhancing Micro-Raman Spectroscopy: A Variable Spectral Resolution Instrument Using Zoom Lens Technology.

Raman spectroscopy is a powerful analytical technique based on the inelastic scattering of photons. Conventional macro-Raman spectrometers are suitable for mass analysis but often lack the spatial resolution required to accurately examine microscopic regions of interest. For this reason, the development of micro-Raman spectrometers has been driven forward. However, even with micro-Raman spectrometers, high resolution is required to gain better insight into materials that provide low-intensity Raman signals. Here, we show the development of a micro-Raman spectrometer with implemented zoom lens technology. We found that by replacing a second collimating mirror in the monochromator with a zoom lens, the spectral resolution could be continuously adjusted at different zoom factors, i.e., high resolution was achieved at a higher zoom factor and lower spectral resolution was achieved at a lower zoom factor. A quantitative analysis of a micro-Raman spectrometer was performed and the spectral resolution was analysed by FWHM using the Gaussian fit. Validation was also performed by comparing the results obtained with those of a high-grade laboratory Raman spectrometer. A quantitative analysis was also performed using the ANOVA method and by assessing the signal-to-noise ratio between the two systems.

Precision detection of cyanide, fluoride, and hydroxide ions using a new tetraseleno-BODIPY fluorescent sensor

A new chemosensor based on Seleno-BODIPY (4) was designed and synthesized for the rapid and sensitive detection of CN–, F−, and OH– ions in THF, exhibiting ultra-low detection limits of 26.26 nM, 43.05 nM, and 8.64 nM, respectively, through a turn-on fluorescent process. The seleno-funcionalization step was based on a novel methodology developed by our group, allowing direct functionalization of the BODIPY core. This procedure involves a quick reaction utilizing Ph2Se2 as a selenium source, BPO (benzoyl peroxide), and p-TSA (p-toluenesulfonic acid) in acetonitrile, enabling the production of the corresponding chalcogenated BODIPYs containing one to four selenium groups, demonstrating its versatility. The structure of BODIPY 4 was confirmed by HRMS, 1H, 13C, 77Se NMR, and IR spectra, and its photophysical properties were also evaluated. BODIPY 4 was applied to detect CN–, F−, and OH– ions in dual-mode detection (UV–Vis and fluorescence spectra), displaying a ratiometric response. The new probe exhibited a fast response time, visual color change from blue to fluorescent yellow, and high sensitivity and selectivity for these analytes over other selected anions. Mechanistic investigation through mass analysis revealed that the detection of these anions by BODIPY 4 occurs via an Aromatic Nucleophilic Substitution reaction with phenylselenide as the leaving group.

Evaluation and comparison of liquid chromatography/high-resolution mass spectrometry platforms for the separation and characterization of ginsenosides from the leaves of Panax ginseng.

The measurement of data repeatability in small-molecule metabolites acquired within and among different liquid chromatography-mass spectrometry (LC-MS) platforms is crucial for data sharing or data transfer in natural products research. This work was designed to investigate and evaluate the separation and detection performance of three commercial high-resolution LC-MS platforms (e.g., Agilent 6550 QTOF, Waters Vion IM-QTOF, and Thermo Scientific Orbitrap Exploris 120) using 68 ginsenoside references and the extract of Panax ginseng leaf. The retention time (tR), measured on these three platforms (under the same chromatography condition), showed good stability in different concentration tests, and within/among different instruments for both intra-day and inter-day precision examinations. Correlation in tR of ginsenosides was also highly determined on these three platforms. In spite of the different mass analyzers involved, these three platforms gave the accurate mass determination ability, especially enhanced resolution gained because of the ion mobility (IM) separation facilitated by IM-quadrupole time-of-flight. The current study has systematically evaluated the separation and MS detection performance enabled by three high-resolution LC-MS platforms taking ginsenosides as the template, and the reported findings can benefit the researchers for the selection of analytical platforms and the purpose of data sharing or data transfer.

Precision detection of cyanide, fluoride, and hydroxide ions using a new tetraseleno-BODIPY fluorescent sensor

A new chemosensor based on Seleno-BODIPY (4) was designed and synthesized for the rapid and sensitive detection of CN–, F−, and OH– ions in THF, exhibiting ultra-low detection limits of 26.26 nM, 43.05 nM, and 8.64 nM, respectively, through a turn-on fluorescent process. The seleno-funcionalization step was based on a novel methodology developed by our group, allowing direct functionalization of the BODIPY core. This procedure involves a quick reaction utilizing Ph2Se2 as a selenium source, BPO (benzoyl peroxide), and p-TSA (p-toluenesulfonic acid) in acetonitrile, enabling the production of the corresponding chalcogenated BODIPYs containing one to four selenium groups, demonstrating its versatility. The structure of BODIPY 4 was confirmed by HRMS, 1H, 13C, 77Se NMR, and IR spectra, and its photophysical properties were also evaluated. BODIPY 4 was applied to detect CN–, F−, and OH– ions in dual-mode detection (UV–Vis and fluorescence spectra), displaying a ratiometric response. The new probe exhibited a fast response time, visual color change from blue to fluorescent yellow, and high sensitivity and selectivity for these analytes over other selected anions. Mechanistic investigation through mass analysis revealed that the detection of these anions by BODIPY 4 occurs via an Aromatic Nucleophilic Substitution reaction with phenylselenide as the leaving group