Mass Spectrometry Spectroscopy Research Articles

Interaction mechanism and pollutant emission characteristics of sewage sludge and corncob co-combustion

The co-combustion of sewage sludge and biomass has demonstrated significant potential for reducing carbon emissions and realizing the resource utilization of solid waste. In this study, the co-combustion behavior and pollutant emissions of sewage sludge and corncob were systematically investigated using thermogravimetric-Fourier transform infrared spectroscopy-mass spectrometry (TG-FTIR-MS) and a fixed-bed reactor. When the corncob blending ratio reached 30 %, the ignition temperature was 179.01 °C lower than that of sewage sludge, and the comprehensive combustion index increased by 13.92 times. The corncob in the mixed fuel dominated the volatiles' release and combustion process. The interaction strength increased as the corncob blending ratio increased. When the corncob blending ratio reached 70 %, it promoted the thermal weight loss process of sewage sludge. The release rate of CO2 increased as the biomass ratio increased, and a 30 % corncob content could inhibit CO2 emissions. Simultaneously, the interaction between sewage sludge and corncob inhibited the emissions of CO and NO during the co-combustion process, improving the combustion efficiency. This study provides theoretical support for developing the fuel value of sewage sludge, improving the amount of solid waste collaborative disposal, and realizing the leading carbon peak in thermal power industry.

Thermal decomposition kinetics and spectral analysis of mixed ester propellants

Mixed ester propellants are extensively used in artillery weapons due to their superior mechanical properties. This study investigates the decomposition kinetics and mechanism of mixed ester propellants using Differential Scanning Calorimetry (DSC) and Thermogravimetry-Fourier Transform Infrared Spectroscopy-Mass Spectrometry (TG-FTIR-MS). Kinetic parameters were determined via a model-free approach, while laser diagnostic technology captured radicals and molecular fragments during the decomposition-combustion process. Results indicate a single exothermic peak during decomposition, with apparent activation energy (Ea) increasing initially (0.01 ≤ α ≤ 0.4) and stabilizing around 278.43 kJ/mol later. The thermal decomposition behavior of mixed ester propellants follows the Sestak-Berggren equation, consistent with an autocatalytic reaction. NO2 generated during decomposition acts as a catalyst, accelerating the decomposition process. CN* radicals were detected throughout the combustion stages, indicating the resilience of the CN bond against breaking. This study can provide a theoretical basis for predicting fire development and for the selection or design of fire sensors.

Chemical and Biological Characterization of the Ethyl Acetate Fraction from the Red Sea Marine Sponge Hymedesmia sp.

Hymedesmiidae is one of the largest families of marine sponges and stands out as an exceptional source of variable metabolites with diverse biological activities. In this study, the ethyl acetate fraction (HE) of a Hymedesmia sp. marine sponge from the Red Sea, Egypt, was analyzed for the first time using Ultra-performance liquid chromatography electrospray ionization tandem mass spectrometry (UPLC-ESI-MS/MS) analysis. The analysis tentatively identified 29 compounds in this fraction, including the isolation and identification of six compounds (two pyrimidine nucleosides, one purine, and two pyrimidine bases in addition to one cerebroside) for the first time. The structures of the isolated compounds were established by 1D and 2D NMR (nuclear magnetic resonance), MS (mass spectrometry), and IR (infrared) spectroscopy. Furthermore, the cytotoxic, antioxidant, and antimicrobial activities of the ethyl acetate fraction were evaluated in vitro. The fraction exhibited strong DPPH scavenging activity with an IC50 of 78.7 µg/mL, compared to ascorbic acid as a positive control with an IC50 of 10.6 µg/mL. It also demonstrated significant cytotoxic activity with IC50 values of 13.5 µg/mL and 25.3 µg/mL against HCT-116 and HEP-2 cell lines, respectively, compared to vinblastine as a positive control with IC50 values of 2.34 µg/mL and 6.61 µg/mL against HCT-116 and HEP-2, respectively. Additionally, the ethyl acetate fraction displayed promising antibacterial activity against S. aureus with a MIC value of 62.5 µg/mL, compared to ciprofloxacin as a positive control with MIC values of 1.56 µg/mL for Gram-positive bacteria and 3.125 µg/mL for Gram-negative bacteria. It also exhibited activity against E. coli and P. aeruginosa with MIC values of 250 µg/mL and 500 µg/mL, respectively. Briefly, this is the first report on the biological activities and secondary metabolite content of the ethyl acetate fraction of Hymedesmia sp. marine sponge, emphasizing the potential for further research against resistant bacterial and fungal strains, as well as different cancer cell lines. The ethyl acetate fraction of Hymedesmia sp. is a promising source of safe and unique natural drugs with potential therapeutic and pharmaceutical benefits.

Effect of outdoor ageing on pyrolytic characteristics and kinetics of different organic components in waste photovoltaic panels

Pyrolysis is a potential approach for volume reduction and utilization of organic components in waste photovoltaic panels. During a usage period of 20–25 years, the physical and chemical properties of photovoltaic panels might undergo ageing and deterioration, thereby affecting their thermal decomposition characteristics. The characteristics of samples before and after ageing were studied using Fourier transform infrared spectroscopy, scanning electron microscopy, elemental analyzer, and thermogravimetry-Fourier transform infrared spectroscopy-mass spectrometry. There were certain differences in the weight loss temperature, time, residual mass, and activation energy of the samples in the pyrolysis reaction. After ageing, the production of acetic acid and methane in ethylene vinyl acetate pyrolysis products increased, while the production of CO2 decreased. After ageing, Tedlar-Polyethylene Terephalate-Tedlar mainly produced water, carbon dioxide, and fluorocarbon compounds, and the percentage of harmful fluorocarbon compounds in the human body increased. Cyclosiloxane, CO2, and hydrocarbons containing C-H bond were detected in each weight-loss stage of aged silica gel. As the heating rate changed, the amount of pyrolysis products also changed. Controlling the sample's heating rate would help to lessen the quantity of hazardous pollutants that were produced. The influence of ageing on the weight loss of mixed samples was discussed. This study seeks to give a fundamental understanding of the physicochemical properties, pyrolysis behaviour, and volatiles of samples before and after ageing, thus providing helpful insights for the final disposal or recovery of waste photovoltaic panels through pyrolysis.

Abstract PO5-13-03: Early Detection of Breast Cancer using Targeted Plasma Metabolomic Profiling

Abstract Background: Breast cancer (BC) is the second leading cause of cancer death among women. Accordingly, early diagnosis is key to the successful treatment, management, and care of BC. Recent studies confirmed that plasma metabolites could be reliable cancer biomarkers, allowing for the development of a minimally invasive routine blood test that can be used for screening, as well as for monitoring disease evolution in patients. The exact metabolic pathways involved in early BC development remain unclear. Metabolomic profiling of women with BC may help to identify new biomarkers to predict breast cancer long before symptoms appear. The purpose of this study was to validate a plasma metabolomic biomarker panel for an improved risk assessment for early detection BC in 241 patients, and to understand the potential role and the relationship between BC subtypes and hormone receptor status. Methods: Our study included a total of 185 plasma samples from women with biopsy-confirmed BC and 56 plasma samples from healthy controls. A targeted, quantitative mass spectrometry (MS)-based metabolomics approach was used to analyze 138 metabolites in plasma samples using a combination of direct injection (DI) MS and reverse-phase high performance liquid chromatography (HPLC) tandem mass spectrometry (MS/MS). The sample set was split into a discovery set and validation set. Metabolite concentration data, clinical data, and hormones receptor status were used to determine optimal biomarker sets. The same biomarkers and regression models were used and assessed on the validation models. The area under the receiver operator characteristic curves (AUROC), sensitivities and specificities at selected cut off points were calculated for each subgroup. Results: A large proportion of BC patients were at an early stage, with 98 at stage I (53.0 %), 70 at stage II (37.8%), and 17 at stage III (9.2%). The BC patients were of all subtypes: 138 luminal A (76,2%), 23 luminal B (12.7%), 5 hormone receptor-negative/HER2-positive (2.8%), and 15 triples negative (8.3%). A feature selection was performed on the training set using Partial Least-Squares Discriminant Analysis (PLS-DA), and the top performing metabolites were identified as the most important in discriminating BC from healthy subjects. The impact of age was also investigated. Features with >80% missing values were removed. To predict BC, the best signature comprised 9 variables implicated in fatty acid metabolism, amino acid metabolism, polyamine biosynthesis and related signaling pathways We further developed and validated a logistic regression with AUROC > 0.9 using these metabolites and other clinical data for detecting different stages and subtypes of BC. Conclusion: This study identified and validated a simple, high-performing, metabolite-based test for the early detection of BC. After confirmation in other independent cohort studies, our findings could provide the foundations for the development of a blood-based routine test for women at the highest risk for BC that is cost-effective, accurate and reliable. In addition, this approach could be used to complement other modalities especially for BC patients with dense breasts. Citation Format: Jean-Francois Haince, Lun Zhang, Rashid Ahmed Bux, Paramjit S. Tappia, Bram Ramjiawan, David Wishart, Andrew Maksymiuk. Early Detection of Breast Cancer using Targeted Plasma Metabolomic Profiling [abstract]. In: Proceedings of the 2023 San Antonio Breast Cancer Symposium; 2023 Dec 5-9; San Antonio, TX. Philadelphia (PA): AACR; Cancer Res 2024;84(9 Suppl):Abstract nr PO5-13-03.

Stability and Compatibility of an Intramuscular Fetal Anesthetic Cocktail for Fetal Intervention

Introduction: The aim of the study was to evaluate chemical stability and physical compatibility when combining fentanyl, rocuronium, and atropine in a fixed ratio to support intramuscular drug delivery during fetal intervention and surgery. Methods: A highly concentrated combination of fentanyl, rocuronium, and atropine was created based on common prescribing practices at a maternal-fetal care center. Chemical stability testing was completed using liquid chromatograph mass spectrometry-mass spectrometry (LC/MS-MS) to detect and quantitate atropine, rocuronium, and fentanyl, with fentanyl-d5 being an internal standard at 6, 12, 24, and 36 h following sample preparation. Physical compatibility testing was completed using United States Pharmacopeia (USP) <788> recommended analytical technique of light obscuration in addition to novel backgrounded membrane imaging at 6 and 24 h following sample preparation. Physical compatibility was determined using USP <788> particle count limits for both techniques. Results: Based on LC/MS-MS results, the samples retained expected medication concentrations at all time points tested. For physical compatibility testing, the particle counts met criteria to be considered compatible per USP <788> large-volume particle count thresholds at 6 h by both methods but exceeded tolerable thresholds at 24 h. Discussion/Conclusion: The combination of rocuronium, fentanyl, and atropine for intramuscular fetal administration is physically compatible and chemically stable for 6 h.

Towards Responsive Spiroborate‐Based Assemblies of Podand‐Type Ligands Functionalized with Two Terminal/Peripheral Catecholate Moieties in the Presence of Alkali Cations

AbstractThe synthesis of two ligands bearing two terminal catecholate binding sites connected by an oligo(ethyleneglycol) bridge of two distinct lengths and their self‐assembly upon boron coordination and alkali cation binding (M=Li, Na, K, Cs) are reported. Attempts to synthesize positional isomers of the ligands are also described. Binding of the four alkali cations M+ through M−O interactions was studied depending on the length of the oligo(ethyleneglycol) chain in solution by 1H and DOSY NMR, mass spectrometry (MS) and in the solid‐state by X‐ray diffraction (XRD) on single crystals. MS spectrometry as well as 1H NMR revealed the presence of monomeric and oligomeric spiroborate compounds. Two monomeric macrocycles could be characterized by XRD, entrapping either lithium or cesium cations within the spiroborate macrocycle.

Mass spectrometry-guided isolation of thiodiketopiperazines from an EtOAc-extract of Setosphaeria rostrata culture medium and their anti-skin aging effects on TNF-α-induced human dermal fibroblasts.

Using mass spectrometry (MS)-guided isolation methods, a new thiodiketopiperazine derivative (1) and exserohilone (2) were isolated from an EtOAc-extract of Setosphaeria rostrata culture medium. The chemical structure of the new compound was elucidated by MS and NMR spectroscopy, and the absolute configurations were established by the quantum mechanical calculations of electronic circular dichroism. All isolated compounds were examined for their effects on reactive oxygen species (ROS) production, matrix metalloproteinase 1 (MMP-1) secretion, and procollagen type I α1 secretion in tumor necrosis factor (TNF)-α-induced human dermal fibroblasts. Compound 1 and exserohilone (2) exhibited the inhibition of TNF-α-induced ROS generation and MMP-1 secretion. Additionally, compound 1 and exserohilone (2) increased the procollagen type I α1 secretion. Compound 1 docked computationally into the active site of MMP-1 (-6.0 kcal/mol).

Recent Advances in the Detection of Food Toxins Using Mass Spectrometry.

Edibles are the only source of nutrients and energy for humans. However, ingredients of edibles have undergone many physicochemical changes during preparation and storage. Aging, hydrolysis, oxidation, and rancidity are some of the major changes that not only change the native flavor, texture, and taste of food but also destroy the nutritive value and jeopardize public health. The major reasons for the production of harmful metabolites, chemicals, and toxins are poor processing, inappropriate storage, and microbial spoilage, which are lethal to consumers. In addition, the emergence of new pollutants has intensified the need for advanced and rapid food analysis techniques to detect such toxins. The issue with the detection of toxins in food samples is the nonvolatile nature and absence of detectable chromophores; hence, normal conventional techniques need additional derivatization. Mass spectrometry (MS) offers high sensitivity, selectivity, and capability to handle complex mixtures, making it an ideal analytical technique for the identification and quantification of food toxins. Recent technological advancements, such as high-resolution MS and tandem mass spectrometry (MS/MS), have significantly improved sensitivity, enabling the detection of food toxins at ultralow levels. Moreover, the emergence of ambient ionization techniques has facilitated rapid in situ analysis of samples with lower time and resources. Despite numerous advantages, the widespread adoption of MS in routine food safety monitoring faces certain challenges such as instrument cost, complexity, data analysis, and standardization of methods. Nevertheless, the continuous advancements in MS-technology and its integration with complementary techniques hold promising prospects for revolutionizing food safety monitoring. This review discusses the application of MS in detecting various food toxins including mycotoxins, marine biotoxins, and plant-derived toxins. It also explores the implementation of untargeted approaches, such as metabolomics and proteomics, for the discovery of novel and emerging food toxins, enhancing our understanding of potential hazards in the food supply chain.

Effect of ferrocene as a combustion catalyst on the premixed combustion flame characteristics of Jatropha biodiesel

Fuel additives are widely used to optimize the combustion process, reduce the harmful emissions, and improve the performance of engines. Among the metal-based additives, ferrocene is soluble in most fuels, including biodiesel. Furthermore, it is easily available and has high stability, low toxicity, and high lipophilicity. It can evenly disperse in biodiesel without causing any change in the physicochemical properties. Therefore, it can serve as an effective combustion catalyst for biodiesel. In this study, the effect of ferrocene as a combustion catalyst on the pyrolysis and combustion performance of Jatropha biodiesel is investigated. The coupled technique of thermogravimetry-Fourier transform infrared spectroscopy-mass spectrometry (TG-FTIR-MS) is used to analyze the evolution characteristics of multicomponent gaseous products generated during the pyrolysis and high-temperature oxidation of Jatropha biodiesel (JB100) and Jatropha biodiesel + ferrocene (JBF). The laminar premixed combustion flame and pollutant emissions of JB100 and JBF are examined using a variety of techniques, including OH planar laser-induced fluorescence (OH-PLIF), flue gas analysis, spectral analysis, transmission electron microscopy, etc. The results reveal that after adding ferrocene, the activation energy for the pyrolysis reaction of JB100 decreases by 4.66 kJ/mol and the complete weight loss temperature decreases by 10 ℃. Further, the addition of ferrocene reduces the endothermic heat by 0.38 mW/mg during the initial stage of the high-temperature oxidation reaction of JB100, and the amounts of final products CO2 and H2O are increased. Compared with JB100, JBF shows an enhanced OH group intensity in the combustion flame and a lower soot spectral peak. Furthermore, compared with JB100, under JBF combustion, the pollutant PM2.5 emissions decrease by 13.3 %, PM10 emissions decrease by 13.2 %, PM> 10 particulate matter emissions decrease by 19.3 %, CO emissions decrease by 6.8 %, NOx emissions increase by 21.2 %, and the size of soot particles decreases by 20.8 %.

Metabolite Profiling in a Diet-Induced Obesity Mouse Model and Individuals with Diabetes: A Combined Mass Spectrometry and Proton Nuclear Magnetic Resonance Spectroscopy Study.

Mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectroscopy techniques have been used extensively for metabolite profiling. Although combining these two analytical modalities has the potential of enhancing metabolite coverage, such studies are sparse. In this study we test the hypothesis that combining the metabolic information obtained using liquid chromatography (LC) MS and 1H NMR spectroscopy improves the discrimination of metabolic disease development. We induced metabolic syndrome in male mice using a high-fat diet (HFD) exposure and performed LC-MS and NMR spectroscopy on plasma samples collected after 1 and 8 weeks of dietary intervention. In an orthogonal projection to latent structures (OPLS) analysis, we observed that combining MS and NMR was stronger than each analytical method alone at determining effects of both HFD feeding and time-on-diet. We then tested our metabolomics approach on plasma from 56 individuals from the Malmö Diet and Cancer Study (MDCS) cohort. All metabolic pathways impacted by HFD feeding in mice were confirmed to be affected by diabetes in the MDCS cohort, and most prominent HFD-induced metabolite concentration changes in mice were also associated with metabolic syndrome parameters in humans. The main drivers of metabolic disease discrimination emanating from the present study included plasma levels of xanthine, hippurate, 2-hydroxyisovalerate, S-adenosylhomocysteine and dimethylguanidino valeric acid. In conclusion, our combined NMR-MS approach provided a snapshot of metabolic imbalances in humans and a mouse model, which was improved over employment of each analytical method alone.

Valorization of slow pyrolysis vapor from biomass waste: Comparative study on pyrolysis characteristics, evolved gas evaluation, and adsorption effects

Pyrolysis vapor is an important byproduct in the production of biochar from biomass waste, and its emission may pose potential environmental risks. To achieve green production of biochar and efficient utilization of pyrolysis vapors, a novel strategy is proposed in this study to use pristine biochar as an adsorbent to adsorb the pyrolysis vapors. According to thermogravimetry-Fourier infrared spectroscopy-mass spectrometry evaluation, the evolved vapors mainly consisted of oxygenated compounds, hydrocarbons, CO2, CO, and H2O. With pyrolysis temperature increasing, ethers, phenols, hydrocarbons, acids/ketones, and CO2 were changed in the same direction based on two-dimensional correlation spectroscopy analysis. Moreover, butene, propargyl alcohol, and butane were the most abundant ionic fragments. After adsorbing pyrolysis vapors, the heating value of the biochar increased by a maximum of 3.2 MJ kg−1 with changes of physicochemical properties. This strategy provides a theoretical basis for green preparation of biochar while recovering energy from pyrolysis vapors.

Exploring the key components of Au catalyst during CO oxidation using TG-MS and operando DRIFTS-MS

Nano-Au has a good catalytic activity for CO oxidation, but its catalytic mechanism is still not clear. Here, CO oxidation on Au2O3 and its thermal decomposition products were studied using thermogravimetric-mass spectrometry (TG-MS) and operando diffuse reflectance infrared Fourier transform spectroscopy-mass spectrometry (DRIFTS-MS) to explore the key active components of Au catalyst for CO oxidation. The TG-MS results showed that Au2O3 decomposed to AuO at 210 °C and Au at 375 °C and was oxidized to form Au oxide above 375 °C. When Au2O3 decomposed into AuxOy (x>y) above 210 °C, the CO oxidation activity obviously increased. Au atoms in the Au-Au system serve as electron donor and CO adsorption sites. Au atom is oxidized to AuO by the O atom from O2 decomposition following the Epling-Xu decomposition mechanism. A schematic diagram of the key components of Au2O3 catalysts during CO oxidation was proposed based on TG-MS and operando DRIFTS-MS analysis results.

Asymmetric Sites on the ZnZrOx Catalyst for Promoting Formate Formation and Transformation in CO2 Hydrogenation.

The role of formate species for CO2 hydrogenation is still under debate. Although formate has been frequently observed and commonly proposed as the possible intermediate, there is no definite evidence for the reaction of formate species for methanol production. Here, formate formation and conversion over the ZnZrOx solid solution catalyst are investigated by in situ/operando diffuse reflectance infrared Fourier transform spectroscopy-mass spectroscopy (DRIFTS-MS) coupled with density functional theory (DFT) calculations. Spectroscopic results show that bidentate carbonate formed from CO2 adsorption is hydrogenated to formate on Zn-O-Zr sites (asymmetric sites), where the Zn site is responsible for H2 activation and the Zr site is beneficial for the stabilization of reaction intermediates. The asymmetric Zn-O-Zr sites with adjacent and inequivalent features on the ZnZrOx catalyst promote not only formate formation but also its transformation. Both theoretical and experimental results demonstrate that the origin of the excellent performance of the ZnZrOx catalyst for methanol formation is associated with the H2 heterolytic cleavage promoted by the asymmetric Zn and Zr sites.

A Highly Efficient Workflow for Detecting and Identifying Sequence Variants in Therapeutic Proteins with a High Resolution LC-MS/MS Method.

Large molecule protein therapeutics have steadily grown and now represent a significant portion of the overall pharmaceutical market. These complex therapies are commonly manufactured using cell culture technology. Sequence variants (SVs) are undesired minor variants that may arise from the cell culture biomanufacturing process that can potentially affect the safety and efficacy of a protein therapeutic. SVs have unintended amino acid substitutions and can come from genetic mutations or translation errors. These SVs can either be detected using genetic screening methods or by mass spectrometry (MS). Recent advances in Next-generation Sequencing (NGS) technology have made genetic testing cheaper, faster, and more convenient compared to time-consuming low-resolution tandem MS and Mascot Error Tolerant Search (ETS)-based workflows which often require ~6 to 8 weeks data turnaround time. However, NGS still cannot detect non-genetic derived SVs while MS analysis can do both. Here, we report a highly efficient Sequence Variant Analysis (SVA) workflow using high-resolution MS and tandem mass spectrometry combined with improved software to greatly reduce the time and resource cost associated with MS SVA workflows. Method development was performed to optimize the high-resolution tandem MS and software score cutoff for both SV identification and quantitation. We discovered that a feature of the Fusion Lumos caused significant relative under-quantitation of low-level peptides and turned it off. A comparison of common Orbitrap platforms showed that similar quantitation values were obtained on a spiked-in sample. With this new workflow, the amount of false positive SVs was decreased by up to 93%, and SVA turnaround time by LC-MS/MS was shortened to 2 weeks, comparable to NGS analysis speed and making LC-MS/MS the top choice for SVA workflow.

Complementarity determining regions in SARS-CoV-2 hybrid immunity.

Pre-vaccination SARS-CoV-2 infection can boost protection elicited by COVID-19 vaccination and post-vaccination breakthrough SARS-CoV-2 infection can boost existing immunity conferred by COVID-19 vaccination. Such 'hybrid immunity' is effective against SARS-CoV-2 variants. In order to understand 'hybrid immunity' at the molecular level we studied the complementarity determining regions (CDR) of anti-RBD (receptor binding domain) antibodies isolated from individuals with 'hybrid immunity' as well as from 'naive' (not SARS-CoV-2 infected) vaccinated individuals. CDR analysis was done by liquid chromatography/mass spectrometry-mass spectrometry. Principal component analysis and partial least square differential analysis showed that COVID-19 vaccinated people share CDR profiles and that pre-vaccination SARS-CoV-2 infection or breakthrough infection further shape the CDR profile, with a CDR profile in hybrid immunity that clustered away from the CDR profile in vaccinated people without infection. Thus, our results show a CDR profile in hybrid immunity that is distinct from the vaccination-induced CDR profile.

Metabolites Profiling and In Vitro Biological Characterization of Different Fractions of Cliona sp. Marine Sponge from the Red Sea Egypt.

Red Sea marine sponges are an important source of biologically active natural products. Therefore, the present study aimed to investigate, for the first time, the components of n-hexane, dichloromethane, and ethyl acetate fractions of Cliona sp. marine sponge collected from the Red Sea, Egypt using UPLC-ESI-MS/MS (Ultra-performance liquid chromatography electrospray ionization tandem mass spectrometry) analysis. The analysis revealed the tentative identification of 23, 16, and 24 compounds from the n-hexane, dichloromethane, and ethyl acetate fractions of Cliona sp., respectively. In addition, the examination of these fractions resulted in the isolation and identification of three sterols and one amino acid. The identification of the isolated compounds was confirmed by 1D and 2D NMR (Nuclear Magnetic Resonance), and MS (Mass spectrometry), and IR (Infrared) spectroscopy. The in vitro cytotoxic, antioxidant, and antimicrobial activities of the total ethanolic extract and its sub-fractions were also evaluated. Interestingly, the ethyl acetate fraction showed potent cytotoxic activity against colon (HCT-116) and human larynx carcinoma (HEP-2) cell lines with IC50 (Half-maximal Inhibitory Concentration) 6.11 ± 0.2 and 12.6 ± 0.9 µg/mL, respectively. However, the dichloromethane fraction showed strong antioxidant activity, with IC50 75.53 ± 3.41 µg/mL. Notably, the total ethanolic extract showed the strongest antibacterial activity against Staphylococcus aureus and Escherichia coli, with MIC (Minimum Inhibitory Concentration) 62.5 ± 0.82 and 125 ± 0.62 µg/mL, respectively, compared to other fractions. In conclusion, this is the first report on the secondary metabolites content and biological activities of Cliona sp. from the Red Sea, Egypt. It also highlights the need for further research on the most active fractions against various cancer cell lines and resistant bacterial and fungal strains. Cliona sp. extract and its fractions could be a potential source of novel and safe natural drugs with a wide range of medicinal and pharmaceutical applications.

Thermogravimetric and spectroscopic analyses along with the kinetic modeling of the pyrolysis of phosphate tailings.

The present study aimed to understand the pyrolysis characteristics of phosphorus tailings and promote the resource utilization of phosphorus tailings. Thermogravimetry was combined with Fourier transform infrared spectroscopy-Raman spectroscopy-mass spectrometry (TG-FTIR-RS-MS) and kinetic models to investigate the possible reaction mechanisms during the pyrolysis of phosphorus tailings and the changes in the release characteristics of pyrolysis volatiles. The results showed that the pyrolysis process occurred in three different stages. First, small amounts of adsorbed water were removed, and organic matter in the tailings was decomposed. Second, CaMg(CO3)2 underwent thermal decomposition to produce CaCO3, MgO, and CO2. Third, CaCO3 further decomposed into CaO and CO2. Similarly, the pyrolysis kinetics were divided into three intervals based on the differences in their activation energy values. The pyrolysis reaction mechanism functions were two-dimensional diffusion (Valensi model), nucleation and growth (Avrami-Erofeev, n = 1/2), and nucleation and growth (Avrami-Erofeev, n = 1/4). The gases released during the pyrolysis of phosphate tailings were mainly CO2, F2, and HF.

A Review on Hyphenated Techniques in Analytical Chemistry

Background: In chemical and pharmaceutical analysis, hyphenated techniques range from the combinations involving separation-separation, separation-identification and identification-identification techniques and are widely used nowadays, as they hold many advantages like fast accurate analysis, a higher degree of automation, higher sample throughput, better reproducibility, specificity and sensitivity. They also reduce contamination due to closed systems and offer simultaneous separation and quantification, leading to better analysis. Objective: Though many reviews have appeared on hyphenated analytical techniques till date, in the past decade, their use has increased manifold and therefore, we thought it imperative to review the latest progress in this field. In the present article, an attempt has been made to cover the latest information on various hyphenated techniques like LC-MS (Liquid Chromatography-Mass Spectroscopy), GC-MS (Gas Chromatography-Mass Spectroscopy), LC-IR (Liquid Chromatography-Infra-Red Spectroscopy), as well as, LC-MS-MS (Liquid Chromatography-Mass Spectroscopy-Mass Spectroscopy), LC-NMR-MS (Liquid Chromatography-Nuclear Magnetic Resonance-Mass Spectroscopy), etc. Conclusion: This review describes a total of seventeen different hyphenated techniques, comprising mainly of the combinations of chromatographic techniques with spectroscopic techniques. We have tried to cover the latest information on various double hyphenated techniques like LC-MS , LC-NMR, LC-IR, HPTLC-MS, HPTLC-IR, GC-MS, GC-IR, GC-TLC, GC-AES, MS-MS, CE-MS, GC-NMR, as well as, triple hyphenated techniques like LC-MS-MS, LC-NMR-MS, LC-UV-MS, GC-MS-MS, GC-IR-MS. Mainly the principle, instrumentation, applications, and advantages of each of the techniques are discussed in this review. Also, disadvantages of a few techniques have been mentioned.

Pyrolysis of hydrazine hydrate waste salt: Thermal behaviors and transformation characteristics of organics under aerobic/anaerobic conditions

The production of large quantities of industrial waste salts is becoming an issue of increasing concern with the adoption of the “zero liquid discharge” process for wastewater treatment. Recovery of waste salts as a useful resource after purification provides the best means of solving this problem. In this study, pyrolysis was studied as a purification technique to treat waste salt generated during hydrazine hydrate production (N2H4 WS) within the temperature range of 25–600 °C under aerobic and anaerobic conditions. Aerobic pyrolysis achieved 99.3% organic removal at a temperature that was 50 °C lower than was that achieved by anaerobic pyrolysis (600 °C). The formation of strong fluorescent species at 400 °C during anaerobic pyrolysis was detected using fluorescence excitation emission matrix (FEEM). These species were confirmed to be heterocyclic-N compounds, including pyridinic N and pyrrolic N, that were formed through cyclization reactions, as revealed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and thermogravimetric-Fourier transform infrared spectroscopy-mass spectrometry (TG-FTIR-MS). Harmful gases such as HCN and NH3 were released during anaerobic pyrolysis, and this may have been partially associated with the decomposition of heterocyclic-N compounds. Moreover, aerobic pyrolysis effectively reduced CO2 emissions by 8.7% based on energy consumption calculations. Therefore, aerobic pyrolysis is preferable for the purification of N2H4 WS owing to its low decomposition temperature, minimal release of harmful gaseous compounds, and low carbon emissions.