Portable particle mass spectrometer.

Particle pollutants in air have been confirmed to damage human health. The PM10 concentration is an important parameter for air quality determination. In this study, a portable quadrupole ion trap mass spectrometer (QIT-MS) was developed and used to quantitate microparticles and particulate standards. The instrument can be used to perform online analysis of various microsized particles. The instrument can be used to analyze various sizes of disperse particles with accurate mass by a histogram profile. The overall detection efficiencies of particles in the sample for polystyrene were obtained. PM10-like reference materials were used for calibration to analyze the size and mass distribution of an environmental sample. The instrument shows the potential for quantitation of different particles of an unknown sample.

A quadrupole ion trap mass spectrometer for dry microparticle analysis.

In this work, we report a new design of a charge detection quadrupole ion trap mass spectrometer (QIT-MS) for the analysis of micro-sized dry inorganic and bioparticles including red blood cells (RBCs) and different sizes of MCF-7 breast cancer cells. The developed method is one of the fastest methods to measure the mass of micro-sized particles. This system allows the online analysis of various micro-sized particles up to 1 × 1017 Da. The calibration of the mass spectrometer has been done by using different sizes of polystyrene (PS) particles (2-15 µm). The measured masses of RBCs were around 1.8 × 1013 Da and MCF-7 cancer cells were between 1 × 1014 and 4 × 1014 Da. The calculated mass distribution profiles of the particles and cells were given as histogram profiles. The statistical data were summarized after Gaussian type fitting to the experimental histogram profiles. The new method gives very promising results for the analysis of particles and has very broad application.

ESI MS for Microsized Bioparticles.

An ESI ion trap mass spectrometer was designed for high-throughput and rapid mass analysis of large bioparticles. Mass calibration of the instrument was performed using commercially available polystyrene (PS) microparticles with a size comparable to cancer cells. Different sizes of MCF-7 breast cancer cells (8 to 15 µm) were used in this study. The masses of different cancer cells were measured. This system allows for the analysis of all types of particles.

Investigation of non-covalent complexations of Ca(II) and Mg(II) ions with insulin by using electrospray ionization mass spectrometry.

RATIONALE: Insulin is a peptide hormone secreted by pancreatic ß-cells. Ca(II) and Mg(II) ions play an important role in the secretion of insulin. There is no study about a direct complexation of Ca(II) or Mg(II) with insulin and their equilibrium constants. Electrospray ionization mass spectrometry (ESI-MS) is a practical method for the monitoring of non-covalent complexes such as Ca(II)-insulin and Mg(II)-insulin. Here, the equilibrium constants of Ca(II)-insulin and Mg(II)-insulin non-covalent complexes have been calculated after ESI-MS measurements in aqueous solutions. METHODS: The effects of pH, competitive binding, ion exchange, and Na(I) and K(I) ions on Ca(II)-insulin and Mg(II)-insulin complexation have been examined by measuring by ESI-MS. The dissociation equilibrium constants (K1 and K2 ) of Ca(II)-insulin and Mg(II)-insulin complexes were calculated from the binomial graph derived from the ESI-MS normalized peak intensities. The MS/MS spectra of the complexes have been examined. RESULTS: The dissociation equilibrium constants were found to K1 : 1.29 × 10(-4)  M and K2 : 9.69 × 10(-4)  M for the Ca(II)-insulin complexes, and K1 : 1.37 × 10(-4)  M and K2 : 9.12 × 10(-4)  M for Mg(II)-insulin complexes. Ca(II) ions have higher complexation capability with insulin than Mg(II) ions. CONCLUSIONS: The binding equilibrium constants of Ca(II)- and Mg(II)-insulin non-covalent complexes have been determined successfully by ESI-MS. Ca(II) and Mg(II) ions are involved in the insulin secretion by forming non-covalent complexes. Copyright © 2016 John Wiley & Sons, Ltd.

Determination of iron content and dispersity of intact ferritin by superconducting tunnel junction cryodetection mass spectrometry.

Ferritin is a common iron storage protein complex found in both eukaryotic and prokaryotic organisms. Although horse spleen holoferritin (HS-HoloFt) has been widely studied, this is the first report of mass spectrometry (MS) analysis of the intact form, likely because of its high molecular weight ∼850 kDa and broad iron-core mass distribution. The 24-subunit ferritin heteropolymer protein shell consists of light (L) and heavy (H) subunits and a ferrihydrite-like iron core. The H/L heterogeneity ratio of the horse spleen apoferritin (HS-ApoFt) shell was found to be ∼1:10 by liquid chromatography-electrospray ionization mass spectrometry. Superconducting tunneling junction (STJ) cryodetection matrix-assisted laser desorption ionization time-of-flight MS was utilized to determine the masses of intact HS-ApoFt, HS-HoloFt, and the HS-HoloFt dimer to be ∼505 kDa, ∼835 kDa, and ∼1.63 MDa, respectively. The structural integrity of HS-HoloFt and the proposed mineral adducts found for both purified L and H subunits suggest a robust biomacromolecular complex that is internally stabilized by the iron-based core. However, cross-linking experiments of HS-HoloFt with glutaraldehyde, unexpectedly, showed the complete release of the iron-based core in a one-step process revealing a cross-linked HS-ApoFt with a narrow fwhm peak width of 31.4 kTh compared to 295 kTh for HS-HoloFt. The MS analysis of HS-HoloFt revealed a semiquantitative description of the iron content and core dispersity of 3400 ± 1600 (2σ) iron atoms. Commercially prepared HS-ApoFt was estimated to still contain an average of 240 iron atoms. These iron abundance and dispersity results suggest the use of STJ cryodetection MS for the clinical analysis of iron deficient/overload diseases.

Synthesis, spectroscopy, band gap energy and electrical conductivity of poly(dopamine-co-aniline) copolymer.

Copolymerization is used to improve the solubility and processability of polymers and copolymers includes the individual properties of homopolymer. In this study, the poly(dopamine-co-aniline) (poly(DA-co-ANI) copolymer was synthesized and the UV-vis. absorption, optical band gap energy, fluorescence, FT-IR, SEM-EDS, MALDI-TOF-MS, XRD and electrical conductivity have been investigated. The obtained results for the poly(DA-co-ANI) copolymer were compared with the PDA and PANI homopolymers. It was observed that the poly(DA-co-ANI copolymer is soluble easily in NMP and DMF solvents. The optical band gap energy of the poly(DA-co-ANI) copolymer film were calculated. as 1.00 eV with favorable indirect transition. The poly(DA-co-ANI) copolymer showed the FL emission maximum bands at 390 and 533 nm wavelengths. It was observed from the SEM images that the poly(DA-co-ANI) has 0-1500 nm crystalline rectangular particles prepared in acidic media and 0-600 nm amorphous particles prepared in basic media. The electrical conductivity of the poly(DA-co-ANI) was 1.35 × 10-6 S/cm. In the MALDI-TOF-MS measurements, the number-average molecular weight of the copolymer was found as 2628 Da with a distribution up to 5500 Da. The poly(DA-co-ANI) copolymer, soluble in NMP and DMF solvents and with a low optical band gap energy can be utilized as optical, fluorescent, and semi-conductive material in biomedical applications.

Multicomponent system for development of antimicrobial PLA-based films with enhanced physical characteristics.

This study aims to develop polylactic acid (PLA)-based packaging films with imparted antimicrobial properties and enhanced physical characteristics by evaluating the likely interaction among multiple film components. For this purpose; epoxidized soybean oil (ES) (20 %) serves as a plasticizer, spruce resin (SR) (15 %) functions as both a plasticizer and antimicrobial agent, ZnO (0.1 %) acts as a nanofiller and antimicrobial, and finally thyme and clove essential oil mixture (5 % and 10 %) serves as an antimicrobial agent were incorporated to PLA film formulation. Composite materials were prepared by the solvent casting method using methylene chloride as the solvent. The developed films were characterized in terms of physical, mechanical, thermal, and antimicrobial properties. Tensile strength (59 MPa) and elastic modulus (2625 MPa) of the neat PLA film gradually decreased to 8.99 MPa and 725.4 MPa, respectively, with the sequential addition of all components, indicating enhanced flexibility. SR, ZnO, and EOs significantly imparted antimicrobial property to the PLA film as demonstrated by the inhibition zone of 13.83 mm and 15.67 mm observed for E. coli and S. aureus, respectively. The barrier properties of the films were enhanced by the addition of SR and ZnO; however, EOs increased the water vapor permeability from 0.080 to 0.090 g.mm/m2.day.kPa compared to the neat PLA film. Principal component and hierarchical cluster analysis enabled the successful discrimination of the films, demonstrating how the film properties are affected by the film components. Therefore, this study suggests that selection of a proper combination is essential to highly benefit from the multicomponent film systems for designing alternative food packaging materials with desired properties.

Advancing mass spectrometry-based chemical imaging: A noncontact continuous flow surface probe in mass spectrometry for enhanced signal detection and spatial resolution.

A new method has been developed for mass spectrometric imaging of small molecules and proteins on tissue or in thinly sliced materials. A laser desorption Venturi electrospray ionization-mass spectrometer was developed for molecular imaging. This method combines laser desorption (LD) and electrospray ionization (ESI) systems before a mass spectrometer (MS). To carry out laser desorption, samples are excited with a laser from the back side of a glass substrate. The desorbed molecules or particles are then captured by a solvent flow. In the ESI system, these desorbed particles and molecules are ionized. The spray part of the solvent system consists of two capillaries: one delivers solvent to the sample plate sides to capture desorbed molecules and particles, and the other carries the solution to the mass spectrometry side using the Venturi effect. A 2D stage facilitates sampling. The system is designed to minimize the sample size after desorption using a 355 nm diode laser, and it is optimized for molecules of various sizes, including organic molecules, amino acids, and proteins. Despite challenging atmospheric conditions for protein desorption, this specialized design enables the collection of protein spectra. The amino acids and other small molecules showed high sensitivity in the MSI measurements. This innovative MS imaging system can be directly applied to real tissue systems and other plant samples to visualize the molecular level distributions.

Corrigendum to "Advancing mass spectrometry-based chemical imaging: A noncontact continuous flow surface probe in mass spectrometry for enhanced signal detection and spatial resolution" [Talanta 273 (2024) 125858].

In the statement "This innovative MS imaging system can be directly applied to real tissue systems and other plant samples to visualize the molecular level distributions." "innovative" should be read as "important".

Kelvin spray ionization.

A novel self-powered dual spray ionization source has been developed for applications in mass spectrometry. This new source does not use any power supply and produces both positive and negative ions simultaneously. The idea behind this ionization source comes from the Kelvin water dropper. The source employs one or two syringes, two pneumatic sprays operated over a range of flow rates (0.15-15 µL min(-1)) and gas pressures (0-150 psi), and two double layered metal screens for ion formation. A variable electrostatic potential from 0 to 4 kV can be produced depending on solvent and gas flow rates that allow gentle ionization of compounds. There are several parameters that affect the performance during ionization of molecules including the flow rate of solvent, gas pressure, solvent acidity, position of spray and metal screens with respect to each other and distance between metal screens and the counter electrode. This ionization method has been successfully applied to solutions of peptides, proteins and non-covalent complexes. In comparison with ESI, the charge number of the most populated state is lower than that from ESI. It indicates that this is a softer ionization technique and it produces more protein ions with folded structures. The unique features of Kelvin spray ionization (KeSI) are that the method is self-powered and ionization occurs at very low potentials by providing very low internal energy to the ions. This advantage can be used for the ionization of very fragile molecules and investigation of non-covalent interactions.

Modification of poly(L-lactic acid)-based films and evaluation of physical and antibacterial properties by using multivariate data analysis.

The aim of this study is to prepare new packaging materials with improved physical and antimicrobial properties that prevent the growth of microorganisms. Poly(L-lactic acid) (PLA) based packaging films were prepared by the solvent-casting method using spruce resin (SR), epoxidized soybean oil, an essential oil mixture (calendula and clove oil), and silver nanoparticles (AgNPs). The AgNPs were synthesized by the polyphenol reduction method, using spruce resin dissolved in methylene chloride. The prepared films were tested for antibacterial activity and physical properties, such as tensile strength (TS), elongation at break (EB), elastic modulus (EM), water vapor permeability (WVP), and UV-C blocking effect. The addition of SR decreased the water vapor permeation (WVP) of the films, whereas the addition of essential oils (EOs) increased this property due to their higher polarity. The morphological, thermal, and structural properties were characterized using SEM, UV-Visible spectroscopy, FTIR, and DSC. The agar disc well method showed that SR, AgNPs, and EOs imparted antibacterial activity to the PLA-based films against Staphylococcus aureus and Escherichia coli. Multivariate data analysis tools, such as principal component and hierarchical cluster analysis, were used to discriminate PLA-based films by simultaneously evaluating their physical and antibacterial properties.

Simultaneous detection of positively and negatively charged microparticles by ion trap mass spectrometry.

This study describes the simultaneous detection of positively and negatively charged microparticles by ion trap mass spectrometry (IT-MS) as a novel analytical measurement technique. The instrument was configured with a feeding capillary for particle introduction, an ion trap, and a charge detector that responds to both ions simultaneously. Positively and negatively charged particles are generated by the triboelectric effect inside the capillary entrance of the instrument. The particles were fed in dry form with a cotton tip to provide the best dispersion. No potential was applied to the lenses on the path of particles and end caps on the ion trap. Particle size calibration has been done using well-defined polystyrene spheres in different sizes. For this study, 2 µm standard polystyrene (PS) spheres were used and checked by different particle sizes. A charge detector detected the ejected positive and negative ions, and the results were evaluated by a program that works under the Labview. The positive and negative ions reached the detector sequentially with respect to their m/z amount. The masses of particles were determined depending on their arrival time at the detector. The IT-MS system and charge detector simultaneously allow positively and negatively charged particles to be detected. This is the first study in the literature that simultaneously shows the trapping and detection of oppositely charged particles.

Simultaneous decolorization of binary mixture of reactive yellow and acid violet from wastewaters by electrocoagulation.

Dyes are common pollutants in a large variety of industrial wastewaters, and the treatment of these wastes has been extensively studied by coagulation. For the removal of pollutants from the wastewaters, different techniques have been used and electrocougulation is one of the widely used methods. This process is very effective in removing organic pollutants including dyestuff wastewater. The purposes of this study were to investigate the effects of the operating parameters, such as current density, electrolyte concentration, dyestuff concentration, and pH of solution on decolorization and chemical oxygen demand (COD) removal of wastewater containing two different dyes in same solution by direct current electrocoagulation. The amount of dye removed was found by application of first derivative spectrophotometric method to the synthetic dye mixtures. In this work synthetic dye mixture which include C.I. Reactive Yellow 145 (RY145) and C.I. Acid Violet 90 (AV 90) were used for electrocougulation (EC) process with iron electrodes. In the presence of both dye molecules, the optimum pH was found to be 4, optimum NaCI concentration was 3000 mg/L and optimum current density was 5.56 mA/cm2. Under these conditions in the case of 100 mg/L-1 each dye concentration at 20 degrees C and 3 cm interelectro distance the color removal efficiency was reached 97.7% for AV 90 and 97.1% for RY145 in 10 minutes time duration. Dye concentration dependent highest COD removal efficiency was measured as 82% around at 100 mg/L dye concentration.

Monitoring Silver(I)-Insulin Complexes with Electrospray Ionization Quadrupole Ion Trap Mass Spectrometry.

Ag(I)-insulin complex formation was investigated using electrospray quadrupole ion trap mass spectrometry (ESI-QIT-MS), and Ag(I) ion binding to an insulin molecule was evaluated. The Ag(I) binding ratios were measured in the range of pH 3-8. The highest binding ratio of the Ag(I) ions was obtained at pH 7. Spectrometric titration was carried out at varied molar ratios of Ag(I) ions to insulin from 20/1 to 250/1. It was observed that four Ag(I) ions were bound effectively to an insulin molecule to form Ag(I)1-4-insulin complexes. The formation equilibrium constants of Ag(I)1-4-insulin complexes were calculated from the ESI-QIT-MS peak intensities. The equilibrium constants were found as Kf1 = (2.92 ± 0.18) × 104 M-1, Kf2 = (1.03 ± 0.07) × 104 M-1, Kf3 = (6.67 ± 0.46) × 103 M-1, and Kf4 = (2.00 ± 0.16) × 103 M-1. The tandem MS/MS spectroscopies were studied to evaluate the stability of the Ag(I) complexes. The different flow rates with nano-ESI were performed to determine the binding of Ag(I) ions in solution or gas phase. In conclusion, it was observed that the Ag(I) ion forms stable Ag(I)1-4-complexes with high formation equilibrium constants.

Investigation of solvent microparticle formation in spray ionization-quadrupole ion trap-mass spectrometry.

In the present study, a new method has been developed for the real-time analysis of insource created solvent particles based on spray ionization-quadrupole ion trap-mass spectrometry (SI-QIT-MS). This is the first work in the literature reporting the formation of different solvent particles during solvent spray in mass spectrometry. The solvent particles formed from the solvent droplets are detected by a charge detector. Our ion trap system allows the measurement of a wide range particle masses. Various solvents and solvent mixtures such as water, methanol, acetone, toluene, n-butanol, water-methanol, and water-ethanol were sprayed through a cone system, and the mass of the particles was monitored by different trap frequencies and voltages. While polar molecules produce larger and more diverse particles due to their strong intermolecular forces, apolar solvents generally do not produce a significant number of particles. We obtained results using a homemade ion trap mass spectrometer capable of determining the mass of micro-sized solvent and solvent mixture particles weighing up to 1015 (Da). The instrument uses a charge detector connected to the exit of the ion trap. Simultaneous acquisition of particle mass spectra and measurement of the amount of charge in each particle allow mass assignment of each particle. Sprayed solvent particles were examined at various trap frequencies and voltages to find the best instrumental parameters for the highest trapping efficiency. The custom SI-QIT-MS instrument allows the measurement of the mass distribution of charged particles from the solvent spray.

Effective removal of 137Cs ions from radioactive wastewater by Melamine-Styrene based Polymer (MSP).

Cesium (Cs) is a major product of uranium fission, which is one of the most existed radionuclides in radioactive wastes. Removal of Cs-137 has a critical role in the decontamination of liquid radioactive waste due to its half-life of 30.17 years. Concordantly, melamine styrene based conjugated polymer (MSP) was designed, synthesized, and characterized with FTIR, TGA, SEM and BET measurements. The novelty of the study is that the MSP adsorbent is designed as a highly conjugated structure to have better interaction with Cs over the Cs-π bond of the benzene groups of the adsorbent. In this work, the adsorption behavior and rate of MSP were investigated as parameters of adsorbent amount, pH, contact time, particle size, initial Cs+ concentration, and temperature. Besides, the adsorption efficiency of Cs-137 was examined by Gamma Spectroscopy. Adsorption results were fitted to three different isotherms which were Freundlich, Langmuir and Dubinin-Radushkevich (D-R). The maximum adsorption capacity of polymer for Cs+ ion was found from Langmuir isotherm as 78 mg g-1. As a part of kinetic parameters, pseudo first and second orders were investigated and in terms of the correlation coefficient pseudo second order was much more appropriate for adsorption of Cs-137 onto MSP.

Highly sensitive determination of Co(II) ions in solutions by using modified silver nanoparticles.

In this manuscript, we report the development of a rapid and facile optic sensor for highly sensitive and selective detection of cobalt ions (Co(II)). The detection strategy was based on the specific silver nanoparticle-glutathione interaction and later on secondary interaction of this structure with cysteine and Co(II) ion. The interaction of these structures creates a new absorption band in the UV region. The intensity change of this band can be correlated by Co(II) ion concentration. The addition of cysteine decreases the Surface Plasmon Resonance (SPR) of silver nanoparticles but does not provide quantitative information. The proposed method offers the advantage of improved sensitivity for detection of Co(II) ions in a very short time period. Co(II) ions create a unique absorption peak during the complex formation and this peak provides sensitive determination of this metal ion in existence of other metal ions. The peak is visible only after taking the first derivative of absorption spectra. Under the optimized conditions, the detection limit of the method is around 0.68 µM. In addition, the synthesized silver nanoparticles (AgNPs) were characterized by atomic force microscopy (AFM). The proposed metal ion sensor provides a very facile and convenient way to determine the concentration of Co(II) ions in aqueous system.

A radioactively durable melamine-styrene based polymer: Highly efficient removal of 90Sr.

Removal of strontium has a vital importance for radioactive waste management due to its long half-life. In this context, melamine-styrene based polymer (MSBP) was synthesized and characterized by different spectrophotometric methods. Sr2+ ions were removed from the solution using MSBP sorbent. In this respect, adsorption of Sr2+ onto melamine-based polymer was studied as a part of pH, amount of adsorbent, initial Sr2+ concentration, contact time, temperature and particle size. Also, adsorption rate of radioactive strontium was investigated by using LSC (Liquid Scintillation Counter). The adsorption data were fitted to Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. MSBP sorbent reached maximum adsorption capacity for Sr2+ as 142.9 mg.g-1. Thermodynamic parameters such as free energy (ΔG0), entropy (ΔS0) and enthalpy (ΔH0) of Sr2+ adsorption on MSBP were examined at five different temperatures of 293 K, 303 K, 313 K, 323 K and 333 K. 0 < ΔH0 values indicated that sorption mechanism presented endothermic feature. 0 > ΔG0 and 0 < ΔS0 revealed that Sr2+ adsorption on MSBP occurred spontaneously and irreversible, respectively. Pseudo first and second orders were investigated as a part of kinetic parameters and seen that pseudo second order was much more convenient for adsorption of Sr2+ onto MSBP.

Investigation of manganese(II)-insulin complexes using electrospray ionization mass spectrometry.

Manganese is a trace element in human nutrition. It is involved in many enzymes, proteins and biological activities. Mn(II) ion has the capable of binding to protein or peptides. Insulin is a blood glucose-lowering peptide hormone and it is secreted by the pancreatic ß-cells. In this study, the binding capability of Mn(II) ions to insulin was studied using ESI-MS, nano-ESI-MS and MS/MS methods. The binding of Mn(II) ions to insulin molecule was studied by examining the effect of pH, the molar ratio of Mn(II) ions to insulin, the flow rate with nano-ESI system and MS/MS spectrometry. The ESI-MS measurements showed that the Mn(II)-insulin complexation mostly produces ML and M2L type complexes. The highest binding ratio was found at pH 7. The complex formation equilibrium constants of Mn(II)-insulin were calculated as Kf1: 1.03 ±â€¯0.12 × 104 and Kf2: 1.93 ±â€¯0.17 × 103. The nano-ESI-MS and MS/MS measurements exhibited strong and specific binding of Mn(II) ions to insulin molecule. It was concluded from all the ESI-MS measurements that Mn(II) ion has a high affinity to insulin molecule to form stable complexes.

ESI-MS measurements for the equilibrium constants of copper(II)-insulin complexes.

Trace elements regulate many biological reactions in the body. Copper(II) is known as one of trace elements and capable of binding to proteins. Insulin is a blood glucose-lowering peptide hormone and it is secreted by the pancreatic ß-cells. In this study, Cu(II)-insulin complexes were investigated by using ESI-MS method. Insulin molecule gives ESI-MS peaks at +4, +5, +6 and +7 charged states. Cu(II)-insulin complexes can be monitored and quantified on the ESI-MS spectra as the shifted peaks according to insulin peaks. The solutions of Cu(II)-insulin complexes at different pHs and mole ratios of Cu(II) ions to insulin molecule were measured on the ESI-MS. The highest complex formation ratio for Cu(II)-insulin were found at pH 7. The multiple bindings of Cu(II) ions to insulin molecule was observed. The formation equilibrium constants of Cu(II)-insulin complexes were calculated as Kf1: 3.34 × 104, Kf2: 2.99 × 104, Kf3: 7.00 × 103 and Kf4:2.86 × 103. The specific binding property of Cu(II) ions was controlled by using different spray ion sources including electrospray and nano-electrospray. The binding property of Cu(II) also investigated by MS/MS fragmentation. It was concluded from the ESI-MS measurements that Cu(II) ion has a high affinity to insulin molecules to form stable complexes.