Dual Quinone Tagging for MALDI-TOF Mass Spectrometric Quantitation of Cysteine-Containing Peptide

A dual quinone tagging strategy is designed for quantitation of cysteine-containing peptide (CCP) with MALDI-TOF mass spectrometry. The quinone compounds can rapidly and specifically bind to the thiol group of cysteine residues by a Michael addition reaction, which is used to identify both CCP and the number of cysteine residues in CCP through the direct observation of untagged and tagged products. After reduced with DL-dithiothreitol, the intramolecular disulfide bond can also be identified. Using benzoquinone (BQ) and methyl-<i>p</i>-benzoquinone (MBQ) as dual tags and a peptide with an amino acid sequence of SSDQFRPDDCT (C-pep1) as a model target, respectively, the quantitation strategy is performed through the intensity ratio of MBQ-tagged C-pep1 to BQ-tagged C-pep1 as the internal standard. The logarithm value of the intensity ratio is proportional to C-pep1 concentration in a range from 5.0 to 5000 nM. The limit of detection is as low as 2.0 nM. The proposed methodology provides a novel tool for rapid characterization, identification, and quantitation of biomolecules containing thiol reactive sites and has a promising application in the large-scale detection and analysis of cysteine-containing biomolecules

PM_2.5-Bound Organophosphate Flame Retardants in Hong Kong: Occurrence, Origins, and Source-Specific Health Risks

Organophosphate flame retardants (OPFRs) are emerging organic pollutants in PM2.5, which have caused significant public health concerns in recent years, given their potential carcinogenic and neurotoxic effects. However, studies on the sources, occurrence, and health risk assessment of PM2.5-bound OPFRs in Hong Kong are lacking. To address this knowledge gap, we characterized 13 OPFRs in one-year PM2.5 samples using gas chromatography–atmospheric pressure chemical ionization tandem mass spectrometry. Our findings showed that OPFRs were present at a median concentration of 4978 pg m–3 (ranging from 1924 to 8481 pg m–3), with chlorinated OPFRs dominating and accounting for 82.7% of the total OPFRs. Using characteristic source markers and positive matrix factorization, we identified one secondary formation and five primary sources of OPFRs. Over 94.0% of PM2.5-bound OPFRs in Hong Kong were primarily emitted, with plastic processing and waste disposal being the leading source (61.0%), followed by marine vessels (14.1%). The contributions of these two sources to OPFRs were more pronounced on days influenced by local pollution emissions (91.9%) than on days affected by regional pollution (44.2%). Our assessment of health risks associated with human exposure to PM2.5-bound OPFRs indicated a low-risk level. However, further source-specific health risk assessment revealed relatively high noncarcinogenic and carcinogenic risks from chlorinated OPFRs emitted from plastic processing and waste disposal, suggesting a need for more stringent emission control of OPFRs from these sources in Hong Kong

A new liquid chromatography–fluorescence method for determination of perfluorooctanesulphonyl fluoride upon derivatisation with 1-naphthol

<div><p>Perfluorooctanesulphonyl fluoride (PFOSF), as a main precursor of perfluorooctanesulphonate (PFOS) that is ubiquitous in the environment, has been released to the environment with substantial quantity. Determination of PFOSF presents significant analytical challenges for using liquid chromatography with UV (LC–UV) and fluorescence detection (LC–FLD) due to the lack of chromophore in the molecular structure. In this study, a new method was developed by derivatising PFOSF with 1-naphthol to form 1-naphthylperfluorooctanesulphonate (NPFOS), which allowed rapid qualitative and quantitative analysis using LC–UV and LC–FLD. The derivatising product was confirmed from the analyses by proton nuclear magnetic resonance and quadrupole–time of flight mass spectrometry. The LC–FLD method demonstrated good linearity in the NPFOS concentration range from 20 pg µL⁻¹ to 20 ng µL⁻¹ with a correlation coefficient better than 0.999, with the instrument detection limit of 1.5 pg µL⁻¹.</p></div

Three-Dimensional Mass Spectrometry Imaging Reveals Distributions of Lipids and the Drug Metabolite Associated with the Enhanced Growth of Colon Cancer Cell Spheroids Treated with Triclosan

The application of mass spectrometry imaging (MSI) to explore the responses of cancer cell spheroids (CCS) after treatment of exogenous molecules has attracted growing attention. Increasing studies have utilized MSI to image the two-dimensional distributions of exogenous and endogenous molecules in planar CCS sections. However, because CCS are volumetric and heterogenous, maintaining their three-dimensional (3D) information is essential for acquiring a better understanding of the tumor microenvironment and mechanisms of action of exogenous molecules. Here, an established method of 3D MSI was applied to distinguish the distributions of triclosan sulfate and endogenous lipids in three microregions of colon CCS with an enhanced growth induced by the treatment of triclosan, a common antimicrobial agent. The results of 3D MSI showed that triclosan sulfate gradually accumulated from the periphery to the entire structure of CCS and finally localized in the core region. Spatial lipidomics analysis revealed that the upregulated phosphatidylethanolamine (fold change (FD) = 1.26, p = 0.0021), phosphatidylinositol (FD = 1.17, p = 0.0180), and phosphatidylcholine (FD = 1.22, p = 0.0178) species mainly distributed in the outer proliferative region, while the upregulated sphingomyelin (FD = 1.18, p = 0.024) species tended to distribute in the inner necrotic region. Our results suggest that a competitive mechanism between inhibiting and promoting CCS growth might be responsible for the proliferation of CCS treated with triclosan

Three-Dimensional Mass Spectrometry Imaging Reveals Distributions of Lipids and the Drug Metabolite Associated with the Enhanced Growth of Colon Cancer Cell Spheroids Treated with Triclosan

The application of mass spectrometry imaging (MSI) to explore the responses of cancer cell spheroids (CCS) after treatment of exogenous molecules has attracted growing attention. Increasing studies have utilized MSI to image the two-dimensional distributions of exogenous and endogenous molecules in planar CCS sections. However, because CCS are volumetric and heterogenous, maintaining their three-dimensional (3D) information is essential for acquiring a better understanding of the tumor microenvironment and mechanisms of action of exogenous molecules. Here, an established method of 3D MSI was applied to distinguish the distributions of triclosan sulfate and endogenous lipids in three microregions of colon CCS with an enhanced growth induced by the treatment of triclosan, a common antimicrobial agent. The results of 3D MSI showed that triclosan sulfate gradually accumulated from the periphery to the entire structure of CCS and finally localized in the core region. Spatial lipidomics analysis revealed that the upregulated phosphatidylethanolamine (fold change (FD) = 1.26, p = 0.0021), phosphatidylinositol (FD = 1.17, p = 0.0180), and phosphatidylcholine (FD = 1.22, p = 0.0178) species mainly distributed in the outer proliferative region, while the upregulated sphingomyelin (FD = 1.18, p = 0.024) species tended to distribute in the inner necrotic region. Our results suggest that a competitive mechanism between inhibiting and promoting CCS growth might be responsible for the proliferation of CCS treated with triclosan

Three-Dimensional Mass Spectrometry Imaging Reveals Distributions of Lipids and the Drug Metabolite Associated with the Enhanced Growth of Colon Cancer Cell Spheroids Treated with Triclosan

The application of mass spectrometry imaging (MSI) to explore the responses of cancer cell spheroids (CCS) after treatment of exogenous molecules has attracted growing attention. Increasing studies have utilized MSI to image the two-dimensional distributions of exogenous and endogenous molecules in planar CCS sections. However, because CCS are volumetric and heterogenous, maintaining their three-dimensional (3D) information is essential for acquiring a better understanding of the tumor microenvironment and mechanisms of action of exogenous molecules. Here, an established method of 3D MSI was applied to distinguish the distributions of triclosan sulfate and endogenous lipids in three microregions of colon CCS with an enhanced growth induced by the treatment of triclosan, a common antimicrobial agent. The results of 3D MSI showed that triclosan sulfate gradually accumulated from the periphery to the entire structure of CCS and finally localized in the core region. Spatial lipidomics analysis revealed that the upregulated phosphatidylethanolamine (fold change (FD) = 1.26, p = 0.0021), phosphatidylinositol (FD = 1.17, p = 0.0180), and phosphatidylcholine (FD = 1.22, p = 0.0178) species mainly distributed in the outer proliferative region, while the upregulated sphingomyelin (FD = 1.18, p = 0.024) species tended to distribute in the inner necrotic region. Our results suggest that a competitive mechanism between inhibiting and promoting CCS growth might be responsible for the proliferation of CCS treated with triclosan

Three-Dimensional Mass Spectrometry Imaging Reveals Distributions of Lipids and the Drug Metabolite Associated with the Enhanced Growth of Colon Cancer Cell Spheroids Treated with Triclosan

The application of mass spectrometry imaging (MSI) to explore the responses of cancer cell spheroids (CCS) after treatment of exogenous molecules has attracted growing attention. Increasing studies have utilized MSI to image the two-dimensional distributions of exogenous and endogenous molecules in planar CCS sections. However, because CCS are volumetric and heterogenous, maintaining their three-dimensional (3D) information is essential for acquiring a better understanding of the tumor microenvironment and mechanisms of action of exogenous molecules. Here, an established method of 3D MSI was applied to distinguish the distributions of triclosan sulfate and endogenous lipids in three microregions of colon CCS with an enhanced growth induced by the treatment of triclosan, a common antimicrobial agent. The results of 3D MSI showed that triclosan sulfate gradually accumulated from the periphery to the entire structure of CCS and finally localized in the core region. Spatial lipidomics analysis revealed that the upregulated phosphatidylethanolamine (fold change (FD) = 1.26, p = 0.0021), phosphatidylinositol (FD = 1.17, p = 0.0180), and phosphatidylcholine (FD = 1.22, p = 0.0178) species mainly distributed in the outer proliferative region, while the upregulated sphingomyelin (FD = 1.18, p = 0.024) species tended to distribute in the inner necrotic region. Our results suggest that a competitive mechanism between inhibiting and promoting CCS growth might be responsible for the proliferation of CCS treated with triclosan

Occurrence and Partitioning of Bisphenol Analogues in Adults’ Blood from China

Widespread human exposure and associated adverse health effects led to regulations on the usage of bisphenol A (BPA). Several bisphenol analogues (BPs) have been introduced as BPA alternatives in various applications. However, these BPs have been shown to exhibit similar or even stronger endocrine-disrupting activities compared with that of BPA. Currently, information on the human exposure to BPA alternatives remains limited. In this study, nine BPs were quantified in 81 pairs of plasma and red blood cell (RBC) samples from Chinese participants. In human plasma, the predominant BPs was BPA, bisphenol S (BPS), and bisphenol AF (BPAF), with the mean concentrations of 0.40, 0.15, and 0.073 ng/mL, respectively. BPA (accounting for 63% of total BPs) and BPS (18%) were the major BPs in the RBC fraction. Mass fractions in plasma (<i>F</i>_p) were found to be highest for BPS (mean, 0.78), followed by BPAF (0.71) and BPA (0.67), indicating strong partitioning to the plasma fraction. However, bisphenol AP was more frequently detected in the RBC fraction. Estimated total daily intake (EDI) of BPA was in the range of 0.0048–0.75 μg/kg bw/day for the participants, and adults aged >50 years had comparatively lower EDI. To our knowledge, this is the first study to assess the occurrence and partitioning of BPA alternatives in paired human plasma and RBCs from the Chinese general population

Enantiomeric Recognition of Amino Acid Salts by Macrocyclic Crown Ethers Derived from Enantiomerically Pure 1,8,9,16-Tetrahydroxytetraphenylenes

Asymmetric synthesis of (<i>R</i>,<i>R</i>)- and (<i>S</i>,<i>S</i>)-1,8,9,16-tetrahydroxytetraphenylenes was achieved from starting material (2<i>R</i>,3<i>R</i>)-butane-2,3-diol and (2<i>S</i>,3<i>S</i>)-butane-2,3-diol respectively by utilizing a center-to-axis strategy. A series of crown ether compounds <b>20</b>, <b>24</b>, and <b>25</b> and their corresponding enantiomers derived from chiral tetrahydroxytetraphenylene were synthesized in enantiomerically pure forms. Enantiomeric recognition properties of these hosts toward l- and d-amino acid methyl ester hydrochloride were studied by the UV spectroscopy titration. The tetramer hosts (<i>S</i>,<i>S</i>,<i>S</i>,<i>S</i>,<i>­S</i>,<i>S</i>,<i>S</i>,<i>S</i>)-<b>20</b> and (<i>R</i>,<i>R</i>,<i>­R</i>,<i>R</i>,<i>R</i>,<i>R</i>,<i>­R</i>,<i>R</i>)-<b>20</b> exhibited the best enantioselectivities toward l- and d-alanine methyl ester hydrochloride salt with <i>K</i>_L/<i>K</i>_D = 4.1 and <i>K</i>_D/<i>K</i>_L = 3.9, respectively. The new chiral macrocyclic hosts would further enrich the host–guest chemistry

Enantiomeric Recognition of Amino Acid Salts by Macrocyclic Crown Ethers Derived from Enantiomerically Pure 1,8,9,16-Tetrahydroxytetraphenylenes

Asymmetric synthesis of (<i>R</i>,<i>R</i>)- and (<i>S</i>,<i>S</i>)-1,8,9,16-tetrahydroxytetraphenylenes was achieved from starting material (2<i>R</i>,3<i>R</i>)-butane-2,3-diol and (2<i>S</i>,3<i>S</i>)-butane-2,3-diol respectively by utilizing a center-to-axis strategy. A series of crown ether compounds <b>20</b>, <b>24</b>, and <b>25</b> and their corresponding enantiomers derived from chiral tetrahydroxytetraphenylene were synthesized in enantiomerically pure forms. Enantiomeric recognition properties of these hosts toward l- and d-amino acid methyl ester hydrochloride were studied by the UV spectroscopy titration. The tetramer hosts (<i>S</i>,<i>S</i>,<i>S</i>,<i>S</i>,<i>­S</i>,<i>S</i>,<i>S</i>,<i>S</i>)-<b>20</b> and (<i>R</i>,<i>R</i>,<i>­R</i>,<i>R</i>,<i>R</i>,<i>R</i>,<i>­R</i>,<i>R</i>)-<b>20</b> exhibited the best enantioselectivities toward l- and d-alanine methyl ester hydrochloride salt with <i>K</i>_L/<i>K</i>_D = 4.1 and <i>K</i>_D/<i>K</i>_L = 3.9, respectively. The new chiral macrocyclic hosts would further enrich the host–guest chemistry