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".

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.

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.

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.

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.

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.

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.

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.

Quantifying Na(I)-insulin and K(I)-insulin non-covalent complexes by ESI-MS method and calculation of their equilibrium constants.

In this study, the dissociation and formation equilibrium constants of Na(I)-insulin and K(I)-insulin complexes have been calculated after the quantifying them on ESI mass spectrometer. The ESI-MS spectra of the complexes were measured by using the solvents as 50% MeOH in water and 100% water. The effect of pH on the Na(I)-insulin and K(I)-insulin complex formation were examined. Serial binding of Na(I) and K(I) ions to the insulin molecule were observed in the ESI-MS measurements. The first formation equilibrium constants were calculated as Kf1: 5.48×103 1/M for Na(I)-insulin complex and Kf1: 4.87×103 1/M for K(I)-insulin in water. The binding capability of Na(I) ions to insulin molecule is higher than the capability of K(I) ions. In case of a comparison together with Ca(II)-insulin and Mg(II)-insulin, the formation equilibrium constants (Kf1) are in order of Ca(II)-insulin>Mg(II)-insulin>Na(I)-insulin>K(I)-insulin in water. The results showed that Na(I) and K(I) ions are involved in the formation of the non-covalent complexes with insulin molecule, since high extracellular and intracellular concentrations of them in the body.

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.

Analysis of Saccharides by the Addition of Amino Acids.

In this work, we present the detection sensitivity improvement of electrospray ionization (ESI) mass spectrometry of neutral saccharides in a positive ion mode by the addition of various amino acids. Saccharides of a broad molecular weight range were chosen as the model compounds in the present study. Saccharides provide strong noncovalent interactions with amino acids, and the complex formation enhances the signal intensity and simplifies the mass spectra of saccharides. Polysaccharides provide a polymer-like ESI spectrum with a basic subunit difference between multiply charged chains. The protonated spectra of saccharides are not well identified because of different charge state distributions produced by the same molecules. Depending on the solvent used and other ions or molecules present in the solution, noncovalent interactions with saccharides may occur. These interactions are affected by the addition of amino acids. Amino acids with polar side groups show a strong tendency to interact with saccharides. In particular, serine shows a high tendency to interact with saccharides and significantly improves the detection sensitivity of saccharide compounds. Graphical Abstract ᅟ.

Selenium levels in breads from Sakarya, Turkey.

Selenium (Se) is an important trace element for human and animal health. It accumulates in wheat and corn, which is consumed mostly as bread. The Turkish population consumes mainly white wheat, whole wheat (brown bread) and corn breads. In this study, samples of these breads were collected from six different bakeries in the city of Sakarya, and their selenium levels were determined by ICP-OES after a chemical digestion. It was found that average selenium levels in white wheat, whole wheat and corn breads were 1149, 1204 and 2023 µg/kg, respectively. The results are compared with daily recommended intake and upper tolerable levels for selenium.

Synthesis of a novel dithiooxamide-formaldehyde resin and its application to the adsorption and separation of silver ions.

In this study, a new chelating resin of dithiooxamide (rubeanic acid)-formaldehyde (DTOF) has been synthesized by the reaction of dithiooxamide and formaldehyde. Also a well-known chelating resin of thiourea (thiooxamide)-formaldehyde (TUF) has been prepared by the reaction of thiourea and formaldehyde. DTOF and TUF chelating resins were used in the adsorption, separation and concentration of silver ions by batch and column techniques. These resins were characterized using FTIR and elemental analysis. It was found that DTOF resin has silver adsorption capacity of 3333.3 mg g(-1) or 30.86 mmolg g(-1) and TUF resin has the capacity of 1428.6 mg g(-1) or 13.22 mmol g(-1). DTOF resin showed more affinity to silver ions according to Cu(II), Zn(II), Ni(II) and Co(II) base metal ions than TUF resin. It was also demonstrated that DTOF resin can be used in the separation and concentration of silver ions.