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1.
Luminescence ; 39(9): e4895, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39239921

ABSTRACT

Easy, economical, and swift detecting tools are very demanded for assaying various chemical species. The introduction of label-free paper-based read-out devices has significantly reached the demand of analytical science for target analytes assays. Herein, a facile, and disposable inexpensive paper-based sensing tool was fabricated for sensing As3+ ion using graphene quantum dots (GQDs) as a fluorescent reader. The CA-GQDs were synthesized using citric acid (CA) as a precursor via the pyrolysis method, further physisorbed on the cellulose substrate for sensing of As3+ via aggregation-based fluorescence "turn-off" mechanism. The linear range for quantitating As3+ ion is in the range of 0.05-50 µM with a detection limit of 10 nM. The practical application of the CA-GQDs-based analytical platform was verified by assaying As3+ ion in water samples. The CA-GQDs-embedded paper strip can be easily extended for assaying of As3+ ion, which meets the demand for monitoring of As3+ ion in real samples.


Subject(s)
Cellulose , Graphite , Paper , Quantum Dots , Graphite/chemistry , Quantum Dots/chemistry , Cellulose/chemistry , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Spectrometry, Fluorescence , Ions/analysis , Ions/chemistry , Limit of Detection , Fluorescence
2.
Anal Chim Acta ; 1325: 343135, 2024 Oct 09.
Article in English | MEDLINE | ID: mdl-39244297

ABSTRACT

BACKGROUND: Mass spectrometry (MS)-based proteomics is a powerful tool for identifying and quantifying proteins. However, chimeric spectra caused by the fragmentation of multiple precursors within the same isolation window impair the accuracy of peptide identification and isobaric mass tag-based quantification. While there have been advances in computational deconvolution of chimeric spectra and methods to further separate the peptides by ion mobility or through MSn, the use of narrower isolation windows to decrease the fraction of chimeric species remains to be fully explored. RESULTS: We present results obtained on a SCIEX TripleTOF instrument where the quadrupole was optimized and tuned for precursor isolation at 0.1 Da (FWHH). Using a three-proteome model (trypsin digest of protein lysates from yeast, human and E. coli) and 8-plex iTRAQ labeling to document the interference effect, we investigated the impact of co-fragmentation on spectral purity, identification accuracy and quantification accuracy. The narrow quadrupole isolation window significantly improved the spectral purity and reduced the interference of non-target precursors on quantification accuracy. The high-resolution isolation strategy also reduced the number of false identifications caused by chimeric spectra. While these improvements came at the cost of sensitivity loss, combining high-resolution isolation with other advanced techniques, including ion mobility, may result in improved accuracy in identification and quantification. SIGNIFICANCE: Compared to standard-resolution quadrupole isolation (0.7 Da), high-resolution quadrupole isolation (0.1 Da) significantly improved the spectral purity and quantification accuracy while reducing the number of potential false identifications caused by chimeric spectra, thus showing excellent potential for further development to analyze clinical proteomics samples, for which high accuracy is essential.


Subject(s)
Proteomics , Proteomics/methods , Humans , Ions/chemistry , Escherichia coli/chemistry , Saccharomyces cerevisiae/chemistry , Peptides/chemistry , Peptides/analysis , Mass Spectrometry/methods
3.
Luminescence ; 39(9): e4874, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39252570

ABSTRACT

The capped CdS-ZnS quantum dots (QDs) were synthesized with various thiol capping agents of glycolic acid (TGA), mercaptosuccinic acid (MSA), and L-cysteine (LCY) and used as fluorescence probe for determination of Cu (II) ions. The method of two-level three-factor full-factorial experiment design was used to achieve the best optical fluorescence emission. Results revealed that Cu (II) ions can effectively quench the emission of QDs, and the fluorescence intensity is linearly decreased with increasing Cu (II) ion concentration. The limit of detection for CdS-ZnS@ QDs capped with TGA, MSA, and LCY was obtained at 1.15 × 10-7, 1.32 × 10-7, and 2.19 × 10-7 mol L-1, respectively, with linear dynamic range of 3.13 × 10-6 to 1.41 × 10-4 mol L-1. Luminescence quantum yields of CdS-ZnS@LCY, CdS-ZnS@MSA, and CdS-ZnS@TGA were obtained at 4.17, 1.92, and 2.47, respectively. Results indicated that no significant quenching occurred in the presence of the other metal ions. The binding constant (Kb) of capped CdS-ZnS@ QDs with Cu2+ and the other metal ions was also investigated and discussed. The Kb value for Cu2+ was obtained considerably more than that the other ions. This work presents a new and sensitive method for determination of Cu2+ ion.


Subject(s)
Cadmium Compounds , Copper , Fluorescent Dyes , Quantum Dots , Sulfhydryl Compounds , Sulfides , Surface Properties , Zinc Compounds , Quantum Dots/chemistry , Copper/chemistry , Copper/analysis , Sulfides/chemistry , Zinc Compounds/chemistry , Cadmium Compounds/chemistry , Sulfhydryl Compounds/chemistry , Sulfhydryl Compounds/analysis , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Spectrometry, Fluorescence , Fluorescence , Ions/chemistry , Ions/analysis
4.
Sci Rep ; 14(1): 20383, 2024 09 02.
Article in English | MEDLINE | ID: mdl-39223199

ABSTRACT

Metal ion-DNA interactions play a crucial role in modulating the structure and function of genetic material in the natural environment. In this study, we report on the favorable electrochemical activity of holmium(III) (Ho3+) on a glassy carbon electrode (GCE) and its interaction with double-stranded DNA. The interaction between DNA and Ho3+ was investigated for the first time using cyclic voltammetry and differential pulse voltammetry. The electrochemical behavior of Ho3+ ions on a GCE exhibited a reversible electron transfer process, indicative of its redox activity. A linear correlation between the peak current and the square root of the scan rate was observed, suggesting a diffusion-controlled kinetic regime for the electrochemical process. Additionally, fluorescence and absorption spectroscopy were employed to confirm the binding of Ho3+ to DNA. Our findings demonstrate that, at pH 7.2, specific DNA bases and phosphate groups can interact with Ho3+ ions. Moreover, electrochemical measurements suggest that Ho3+ ions bind to DNA via a groove binding mode, with a calculated binding ratio of 1:1 between Ho3+ and DNA. Notably, under optimal conditions, an increase in the amount of DNA leads to a significant reduction in the current intensity of Ho3+ ions.


Subject(s)
DNA , Electrochemical Techniques , Electrodes , Holmium , Holmium/chemistry , DNA/chemistry , Ions/chemistry , Oxidation-Reduction , Carbon/chemistry , Spectrometry, Fluorescence
5.
Photochem Photobiol Sci ; 23(9): 1757-1769, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39242437

ABSTRACT

Porphyrazines (Pzs) are porphyrin derivatives that show potential application as photosensitizers for photodynamic therapy (PDT), but are still far less explored in the literature. In this work, we evaluate how the photophysics and phototoxicity of the octakis(trifluoromethylphenyl)porphyrazine (H2Pz) against tumor cells can be modulated by coordination with Mg(II), Zn(II), Cu(II) and Co(II) ions. Fluorescence and singlet oxygen quantum yields for the Pzs were measured in organic solvents and in soy phosphatidylcholine (PC) liposomes suspended in water. While H2Pz and the respective complexes with Cu(II) and Co(II) showed very low efficiency to fluoresce and to produce 1O2, the Mg(II) and Zn(II) complexes showed significantly higher quantum yields in organic solvents. The fluorescence of these two Pzs in the liposomes was sensitive to the fluidity of the membrane, showing potential use as viscosity markers. The cytotoxicity of the compounds was tested in HaCaT (normal) and A431 (tumor) cells using soy PC liposomes as drug carriers. Despite the low 1O2 quantum yields in water, the Mg(II) and Zn(II) complexes showed IC50 values against A431 cells in the nanomolar range when activated with low doses of red LED light. Their phototoxicity was ca. three times higher for the tumor cells compared to the normal ones, showing promising application as photosensitizers for PDT protocols. Considering that H2Pz and the respective Co(II) and Cu(II) complexes were practically non-phototoxic to the cells, we demonstrate the importance of the central metal ion in the modulation of the photodynamic activity of porphyrazines.


Subject(s)
Liposomes , Photosensitizing Agents , Porphyrins , Humans , Photosensitizing Agents/pharmacology , Photosensitizing Agents/chemistry , Porphyrins/chemistry , Porphyrins/pharmacology , Liposomes/chemistry , Photochemotherapy , Singlet Oxygen/metabolism , Singlet Oxygen/chemistry , Coordination Complexes/pharmacology , Coordination Complexes/chemistry , Coordination Complexes/chemical synthesis , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Antineoplastic Agents/chemical synthesis , Zinc/chemistry , Zinc/pharmacology , Cell Line, Tumor , Cell Survival/drug effects , Drug Screening Assays, Antitumor , Ions/chemistry
6.
Int J Mol Sci ; 25(17)2024 Aug 23.
Article in English | MEDLINE | ID: mdl-39273086

ABSTRACT

The mode of coordination of copper(II) ions with dopamine (DA, L) in the binary, as well as ternary systems with Ado, AMP, ADP, and ATP (L') as second ligands, was studied with the use of experimental-potentiometric and spectroscopic (VIS, EPR, NMR, IR)-methods and computational-molecular modeling and DFT-studies. In the Cu(II)/DA system, depending on the pH value, the active centers of the ligand involved in the coordination with copper(II) ions changed from nitrogen and oxygen atoms (CuH(DA)3+, Cu(DA)2+), via nitrogen atoms (CuH2(DA)24+), to oxygen atoms at strongly alkaline pH (Cu(DA)22+). The introduction of L' into this system changed the mode of interaction of dopamine from oxygen atoms to the nitrogen atom in the hydroxocomplexes formed at high pH values. In the ternary systems, the ML'-L (non-covalent interaction) and ML'HxL, ML'L, and ML'L(OH)x species were found. In the Cu(II)/DA/AMP or ATP systems, mixed forms were formed up to a pH of around 9.0; above this pH, only Cu(II)/DA complexes occurred. In contrast to systems with AMP and ATP, ternary species with Ado and ADP occurred in the whole pH range at a high concentration, and moreover, binary complexes of Cu(II) ions with dopamine did not form in the detectable concentration.


Subject(s)
Copper , Dopamine , Copper/chemistry , Dopamine/chemistry , Nucleotides/chemistry , Nucleotides/metabolism , Nucleosides/chemistry , Hydrogen-Ion Concentration , Coordination Complexes/chemistry , Ions/chemistry , Ligands , Models, Molecular
7.
Molecules ; 29(17)2024 Sep 03.
Article in English | MEDLINE | ID: mdl-39275029

ABSTRACT

Although titanium and its alloys are widely used as dental implants, they cannot induce the formation of new bone around the implant, which is a basis for the functional integrity and long-term stability of implants. This study focused on the functionalization of the titanium/titanium oxide surface as the gold standard for dental implants, with electrospun composite fibers consisting of polyvinylpyrrolidone and Ca2+ ions. Polymer fibers as carriers of Ca2+ ions should gradually dissolve, releasing Ca2+ ions into the environment of the implant when it is immersed in a model electrolyte of artificial saliva. Scanning electron microscopy, energy dispersive X-ray spectroscopy and attenuated total reflectance Fourier transform infrared spectroscopy confirmed the successful formation of a porous network of composite fibers on the titanium/titanium oxide surface. The mechanism of the formation of the composite fibers was investigated in detail by quantum chemical calculations at the density functional theory level based on the simulation of possible molecular interactions between Ca2+ ions, polymer fibers and titanium substrate. During the 7-day immersion of the functionalized titanium in artificial saliva, the processes on the titanium/titanium oxide/composite fibers/artificial saliva interface were monitored by electrochemical impedance spectroscopy. It can be concluded from all the results that the composite fibers formed on titanium have application potential for the development of osteoinductive and thus more biocompatible dental implants.


Subject(s)
Calcium , Dental Implants , Titanium , Titanium/chemistry , Calcium/chemistry , Calcium/metabolism , Povidone/chemistry , Humans , Ions/chemistry , Spectroscopy, Fourier Transform Infrared , Saliva, Artificial/chemistry , Biocompatible Materials/chemistry , Spectrometry, X-Ray Emission , Osteogenesis/drug effects
8.
Molecules ; 29(17)2024 Sep 07.
Article in English | MEDLINE | ID: mdl-39275094

ABSTRACT

MiR-155 is a multifunctional microRNA involved in many biological processes. Since miR-155 is overexpressed in several pathologies, its detection deserves high interest in clinical diagnostics. Biosensing approaches often exploit the hybridization of miR-155 with its complementary strand. Molecular Dynamics (MD) simulations were applied to investigate the complex formed by miR-155 and its complementary strand in aqueous solution with Na+ and Cl- ions at ionic strengths in the 100-400 mM range, conditions commonly used in biosensing experiments. We found that the main structural properties of the duplex are preserved at all the investigated ionic strengths. The radial distribution functions of both Na+ and Cl- ions around the duplex show deviation from those of bulk with peaks whose relative intensity depends on the ionic strength. The number of ions monitored as a function of the distance from the duplex reveals a behavior reminiscent of the counterion condensation near the duplex surface. The occurrence of such a phenomenon could affect the Debye length with possible effects on the sensitivity in biosensing experiments.


Subject(s)
MicroRNAs , Molecular Dynamics Simulation , Sodium , MicroRNAs/chemistry , MicroRNAs/genetics , Osmolar Concentration , Sodium/chemistry , Chlorides/chemistry , Ions/chemistry , Nucleic Acid Conformation
9.
J Phys Chem B ; 128(37): 8966-8973, 2024 Sep 19.
Article in English | MEDLINE | ID: mdl-39254719

ABSTRACT

Magnesium (Mg2+) is the most abundant divalent cation in the cell and is essential to nearly every biochemical reaction involving adenosine triphosphate (ATP) and its lower energy counterpart, adenosine diphosphate (ADP). In this work, we examine the solution dynamics of ADP at different concentrations and record the changes thereof due to the presence of Mg2+ ions. Relaxation and diffusion experiments were performed on a range of ADP solutions with increasing magnesium concentration. The most significant changes of both relaxation and diffusion behaviors are observed when adding Mg2+ up to 0.5 ADP equivalent (eq), with most of the changes complete at 1 eq. Molecular dynamics simulations also show a significant structure introduced by Mg2+ with very stable pyramidal coordination with the phosphate oxygens. A more extended structure found in the presence of Mg2+ is consistent with the experimental slowing of diffusion and an increase in the spin-lattice relaxation rate. We do not observe direct evidence of aggregation in solution, although translational diffusion is slowed down significantly at higher concentrations (while solvent diffusion remains constant).


Subject(s)
Adenosine Diphosphate , Magnesium , Molecular Dynamics Simulation , Magnesium/chemistry , Adenosine Diphosphate/chemistry , Adenosine Diphosphate/metabolism , Magnetic Resonance Spectroscopy , Diffusion , Ions/chemistry
10.
ACS Appl Mater Interfaces ; 16(33): 43244-43256, 2024 Aug 21.
Article in English | MEDLINE | ID: mdl-39136271

ABSTRACT

The development of efficient hemostatic materials is crucial for achieving rapid hemorrhage control and effective wound healing. Inorganic polyphosphate (polyP) is recognized as an effective modulator of the blood coagulation process. However, the specific effect of polyP chain length on coagulation is not yet fully understood. Furthermore, calcium ions (Ca2+) are essential for the coagulation process, promoting multiple enzyme-catalyzed reactions within the coagulation cascade. Hence, calcium ion-coupled polyphosphate powders with three different degrees of polymerization (CaPP-n, n = 20, 50, and 1500) are synthesized by an ion-exchange reaction. CaPP exhibits a crystalline phase at a low polymerization degree and transitions to an amorphous phase as the polymerization degree increases. Notably, the addition of Ca2+ enhances the wettability of polyP, and CaPP promotes hemostasis, with varying degrees of effectiveness related to chain length. CaPP-50 exhibits the most promising hemostatic performance, with the lowest blood clotting index (BCI, 12.1 ± 0.7%) and the shortest clotting time (302.0 ± 10.5 s). By combining Ca2+ with polyP of medium-chain length, CaPP-50 demonstrates an enhanced ability to accelerate the adhesion and activation of blood cells, initiate the intrinsic coagulation cascade, and form a stable blood clot, outperforming both CaPP-20 and CaPP-1500. The hemostatic efficacy of CaPP-50 is further validated using rat liver bleeding and femoral artery puncture models. CaPP-50 is proven to possess hemostatic properties comparable to those of commercial calcium-based zeolite hemostatic powder and superior to kaolin. In addition, CaPP-50 exhibits excellent biocompatibility and long-term storage stability. These results suggest that CaPP-50 has significant clinical and commercial potential as an active inorganic hemostatic agent for rapid control of bleeding.


Subject(s)
Calcium , Hemorrhage , Polymerization , Polyphosphates , Animals , Polyphosphates/chemistry , Polyphosphates/pharmacology , Calcium/chemistry , Rats , Hemorrhage/prevention & control , Hemorrhage/drug therapy , Hemostatics/chemistry , Hemostatics/pharmacology , Blood Coagulation/drug effects , Rats, Sprague-Dawley , Male , Hemostasis/drug effects , Ions/chemistry
11.
J Mater Chem B ; 12(34): 8376-8382, 2024 Aug 28.
Article in English | MEDLINE | ID: mdl-39109420

ABSTRACT

The accumulation of mercury pollution in plants can induce severe injury to human beings. It is a great challenge to monitor ultra-low concentrations of mercury in complicated matrixes. In this study, we successfully developed a strategy via Hg2+-triggered naphthalene-based fluorescent probe 1, which formed excimer that subsequently emitted fluorescence for the successful detection of ultra-low concentrations of Hg2+. The coordination of N and S atoms with Hg2+ facilitated the formation of excimer from the naphthalene-conjugated planes that were in sufficiently close proximity. Suppression of CN bond rotation also induced the chelation-enhanced fluorescence (CHEF) effect, and the cumulative result of these effects was obvious fluorescent enhancement. Compared with probe 2, the other key factor for detection of Hg2+ is that the electrons of the hydroxyl group can easily transfer to a naphthalene moiety, resulting in an augmented π-electron density that enhanced the π-π stacking of the naphthalene-conjugated excimer. After detailed spectral studies and mechanism discussions, it was realized that probe 1 was able to detect ultra-low concentrations of Hg2+ in PBS buffer solution. The detection limit was calculated to be 1.98 nM. On account of the excellent performances, the probe was successfully applied in monitoring Hg2+ in water and pea sprouts with the potential for application as an advanced warning of contamination.


Subject(s)
Fluorescent Dyes , Mercury , Mercury/analysis , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Naphthalenes/chemistry , Spectrometry, Fluorescence , Limit of Detection , Ions/analysis , Ions/chemistry , Molecular Structure
12.
Anal Chim Acta ; 1321: 343038, 2024 Sep 08.
Article in English | MEDLINE | ID: mdl-39155103

ABSTRACT

BACKGROUND: The heavy metal ion Cd2+ is acutely toxic, and excessive concentrations can have adverse effects on human production and life, and even lead to significant public health risks and environmental impacts. There are several mature non-electrochemical methods for heavy metal detection, but these methods are characterized by high cost, which makes it difficult to be applied to the field for timely detection. Therefore, it is necessary to prepare a new electrochemical sensor that is environmentally friendly and capable of detecting Cd2+ in the environment quickly, easily and sensitively. RESULTS: In this study, hydrogen-bonded organic frameworks (HOFs) were synthesized by a simple hydrothermal reaction. The prepared materials consisted of only C, N and O and had a thin lamellar structure. The HOFs were integrated into a novel electrochemical sensor to achieve accurate detection of Cd2+ ions in real aqueous environments by square wave anodic dissolution voltammetry. The sensor has a wide linear range and a detection limit as low as 0.13 µg/L. Several real water samples, such as tap water, lake water, and e-cigarette digest, were analyzed to simulate the working environment of the sensor, and the results showed that the recoveries of Cd2+ ranged from 95.75 % to 101.2 %. SIGNIFICANCE: We pioneered the detection of heavy metal ions Cd2+ in e-cigarette digestate samples with the innovative use of HOFs as the sensor material, which demonstrated the potential application in electrochemical sensing with extremely low background current value and high sensitivity, providing new ideas for environmental monitoring and public health control.


Subject(s)
Cadmium , Electrochemical Techniques , Hydrogen Bonding , Cadmium/analysis , Cadmium/chemistry , Metal-Organic Frameworks/chemistry , Water Pollutants, Chemical/analysis , Limit of Detection , Ions/analysis , Ions/chemistry
13.
Int J Biol Macromol ; 277(Pt 2): 134341, 2024 Oct.
Article in English | MEDLINE | ID: mdl-39089554

ABSTRACT

The Mg-ion battery faces significant limitations due to its liquid electrolyte, which suffers from inherent issues such as leakage and the growth of Mg dendrites. In contrast, gel polymer electrolytes (GPEs) offer heightened safety, a wide voltage window, and excellent flexibility, making them a promising alternative with outstanding electrochemical performance. In this study, a cyano-modified cellulose (CEC) GPE was engineered to aim at enhancing ion transportation and promoting uniform ion-flux through interactions between N and Mg2+ ions. The resulting CEC-based GPE demonstrated a high ionic conductivity of 1.73 mS cm-1 at room temperature. Furthermore, it exhibited remarkable Mg plating/stripping performance (coulombic efficiency ∼96.7 %) and compatibility with electrodes. Importantly, when employed in a Mo6S8//Mg battery configuration, the CEC GPE displayed exceptional cycle stability, with virtually no degradation observed even after 650 cycles at 1C, thereby significantly advancing Mg-ion battery technology due to its excellent electrochemical properties. This study provides valuable insights into the molecular engineering of cellulose-based GPEs.


Subject(s)
Cellulose , Electric Power Supplies , Electrolytes , Gels , Magnesium , Static Electricity , Cellulose/chemistry , Electrolytes/chemistry , Gels/chemistry , Magnesium/chemistry , Electric Conductivity , Ions/chemistry , Electrodes
14.
ACS Appl Bio Mater ; 7(8): 5359-5368, 2024 Aug 19.
Article in English | MEDLINE | ID: mdl-39102354

ABSTRACT

We have studied the endocytic mechanisms that determine subcellular localization for three carrier-free chemotherapeutic-photothermal (chemo-PTT) combination ionic nanomedicines (INMs) composed of doxorubicin (DOX) and an near-infrared (NIR) dye (ICG, IR820, or IR783). This study aims to understand the cellular basis for previously published enhanced toxicity results of these combination nanomedicines toward MCF-7 breast cancer cells. The active transport mechanism of INMs, unlike free DOX, which is known to employ passive transport, was validated by conducting temperature-dependent cellular uptake of the drug in MCF-7 cells using confocal microscopy. The internalization pathway of these INMs was further probed in the presence and absence of different endocytosis inhibitors. Detailed examination of the mode of entry of the carrier-free INMs in MCF-7 cells revealed that they are primarily internalized through clathrin-mediated endocytosis. In addition, time-dependent subcellular localization studies were also investigated. Examination of time-dependent confocal images indicated that the INMs targeted multiple organelles, in contrast to free DOX that primarily targets the nucleus. Collectively, the high cellular endocytic uptake in cancerous cells (EPR effect) and the multimode targeting ability demonstrated the main reason for the low half-maxima inhibitory concentration (IC50) value (the high cytotoxicity) of these carrier-free INMs as compared to their respective parent chemo and PTT drugs.


Subject(s)
Doxorubicin , Endocytosis , Nanomedicine , Doxorubicin/pharmacology , Doxorubicin/chemistry , Humans , Endocytosis/drug effects , MCF-7 Cells , Particle Size , Organelles/metabolism , Organelles/drug effects , Biocompatible Materials/chemistry , Biocompatible Materials/pharmacology , Materials Testing , Drug Screening Assays, Antitumor , Cell Survival/drug effects , Antibiotics, Antineoplastic/pharmacology , Antibiotics, Antineoplastic/chemistry , Ions/chemistry
15.
J Am Soc Mass Spectrom ; 35(9): 2237-2247, 2024 Sep 04.
Article in English | MEDLINE | ID: mdl-39158841

ABSTRACT

Multiply charged ions produced by electrospray ionization (ESI) of heterogeneous mixtures of macromolecular analytes under native conditions are typically confined to relatively narrow ranges of mass-to-charge (m/z) ratio, often with extensive overlap. This scenario makes charge and mass assignments extremely challenging, particularly when individual charge states are unresolved. An ion/ion reaction strategy involving multiply charged ion attachment (MIA) to the mixture components in a narrow range of m/z can facilitate charge and mass assignment. In MIA operation, multiply charged reagent ions are attached to the analyte ions of opposite polarity to provide large m/z displacements resulting from both large changes in mass and charge. However, charge reduction of the high m/z ions initially generated under native ESI conditions requires the ability to isolate high m/z ions and to analyze even higher m/z product ions. Digital ion trap (DIT) operation offers means for both high m/z ion isolation and high m/z mass analysis, in addition to providing conditions for the reaction of oppositely charged ions. The feasibility of conducting MIA experiments in a DIT that takes advantage of high m/z ion operation is demonstrated here using a tandem 2D-3D DIT instrument. Proof-of-concept MIA experiments with cations derived from ß-galactosidase using the 20- charge state of human serum immunoglobulin G (IgG, ∼149 kDa) as the reagent anion are described. MIA experiments involving mixtures of ions derived from the E. coli. ribosome are also described. For example, three components in a mixture of 70S particles (>2.2 MDa) were resolved and assigned with masses and charges following an MIA experiment involving the 20- charge state of human serum IgG.


Subject(s)
Ions , Spectrometry, Mass, Electrospray Ionization , Spectrometry, Mass, Electrospray Ionization/methods , Ions/chemistry , Macromolecular Substances/chemistry , Macromolecular Substances/analysis , beta-Galactosidase/chemistry , beta-Galactosidase/analysis , Humans , Cations/chemistry
16.
Adv Colloid Interface Sci ; 332: 103264, 2024 Oct.
Article in English | MEDLINE | ID: mdl-39116585

ABSTRACT

MXenes belong to one of the recently developed advanced materials with tremendous potential for diverse sensing applications. To date, various types of MXene-based materials have been developed to generate direct/indirect ultrasensitive sensing signals against various forms of analytes via fluorescence quenching or enhancement. In this work, the fluorescence sensing/biosensing capabilities of the MXene-based materials have been explored and evaluated against a list of ionic/emerging pollutants in environment and food matrices. The suitability of an MXene-based sensing approach is also validated through the assessment of the performance based on the basic quality assurance parameters, e.g., limit of detection (LOD), sensing range, and response time. Accordingly, the best performing MXene-based materials are selected and recommended for the given target(s) to help facilitate their scalable applications under real-world conditions.


Subject(s)
Biosensing Techniques , Biosensing Techniques/methods , Food Contamination/analysis , Fluorescence , Environmental Pollutants/analysis , Spectrometry, Fluorescence , Fluorescent Dyes/chemistry , Ions/analysis , Ions/chemistry , Food Analysis/methods
17.
Nanoscale ; 16(34): 15984-15994, 2024 Aug 29.
Article in English | MEDLINE | ID: mdl-39141323

ABSTRACT

The presence of non-essential metals in the environment as contaminants is prone to cause hazardous health problems following accumulation in the human body and the ensuing toxic effects. This calls for continuous discovery and innovation in the realm of developing easy-to-operate, cheap and sensitive sensors. Herein, we describe the proof of concept approach for designing a molecular receptor-like, chimeric sensor based on the pore-forming peptide alamethicin (Alm), tethered via a linker with an ultrashort peptide nucleic acid (PNA) moiety, capable of generating functional ion channel oligomers in planar lipid membranes. The working principle of the sensor exploits the ability of Hg2+ ions to complex mismatching thymine-thymine sequences between the PNA receptor moiety on Alm oligomers and free, thymine-based, single-stranded DNAs (ssDNAs) in solution, thus creating a stable base pair at the oligomer entrance. This generates a transducing mechanism which converts the metal ion complexation into a specific electrical signature of the self-assembled Alm oligomers, enabling selective Hg2+ ion detection. The platform is programmable, whereby the simple exchange of the PNA sequence and its ssDNA counterpart in solution rendered the system selective for Cu2+ ion detection. With further optimization, the presented solution has the potential to translate into miniaturized, cost-effective biosensors suitable for the real-time, label-free and continuous detection of metal ions or other biomolecules.


Subject(s)
Copper , DNA, Single-Stranded , Mercury , Peptide Nucleic Acids , Mercury/analysis , Mercury/chemistry , Peptide Nucleic Acids/chemistry , Copper/chemistry , DNA, Single-Stranded/chemistry , Alamethicin/chemistry , Ion Channels/metabolism , Ion Channels/chemistry , Biosensing Techniques , Antimicrobial Peptides/chemistry , Antimicrobial Peptides/pharmacology , Ions/chemistry
18.
Luminescence ; 39(8): e4857, 2024 Aug.
Article in English | MEDLINE | ID: mdl-39129422

ABSTRACT

Copper (Cu2+) is a metal chemical element closely related to human life and is widely used in many fields. However, with the discharge of copper wastewater, the water quality will be seriously affected, leading to excessive intake of Cu2+ and a variety of diseases. Hence, there is a pressing need for an effective detection method for Cu2+ in aqueous environments. Leveraging the remarkable attributes of GFP chromophores and indenone derivatives, we have created a novel colorimetric fluorescent probe P-Cu2+, tailored for efficient copper ion detection. The addition of Cu2+ causes the solution to visibly change from colorless to a pronounced yellow, enabling naked-eye detection and offering promise for real sample analysis.


Subject(s)
Colorimetry , Copper , Fluorescent Dyes , Copper/chemistry , Copper/analysis , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Molecular Structure , Water Pollutants, Chemical/analysis , Water/chemistry , Indans/chemistry , Indans/analysis , Ions/analysis , Ions/chemistry , Spectrometry, Fluorescence
19.
Luminescence ; 39(8): e4856, 2024 Aug.
Article in English | MEDLINE | ID: mdl-39129424

ABSTRACT

Most nonconventional luminogens enjoy good water solubility and biocompatibility, showing unique application prospects in fields like biological imaging. Although clustering-triggered emission (CTE) mechanisms have been proposed to explain such emissions, the have not been thoroughly elucidated, which limits their development and application. Here, the photoluminescence properties of carboxymethyl ß-cyclodextrin (CM-ß-CD) aqueous solution are utilized to further investigate the effects of changes in concentration, in order to elucidate the emission mechanism through cryo-transmission electron microscopy (cryo-TEM), small-angle X-ray scattering (SAXS), molecular interaction analysis, and theoretical calculation. The results showed that the size distribution, morphology, and distance between water aggregates were successfully correlated with the cluster emission centers. The emission mechanism of nonconventional luminogen solutions was more clearly and intuitively elucidated, which has a promoting effect on the emission and application of this field. It is interesting that temperature-dependent emission spectra show the blue-shift phenomenon of PL with increasing excitation wavelengths. Moreover, due to its strong static quenching effect for Fe3+, CM-ß-CD can efficiently detect Fe3+ in mixed-ion aqueous solutions. It provides a strategy to clarify the CTE mechanism of nonconventional luminogen solutions more clearly and its application of mixed-ion detection.


Subject(s)
Water , beta-Cyclodextrins , beta-Cyclodextrins/chemistry , Water/chemistry , Luminescence , Ions/chemistry , Solutions , X-Ray Diffraction , Scattering, Small Angle , Molecular Structure , Ferric Compounds/chemistry
20.
Colloids Surf B Biointerfaces ; 243: 114131, 2024 Nov.
Article in English | MEDLINE | ID: mdl-39094211

ABSTRACT

Identifying the antibacterial mechanisms of elemental silver at the nanoscale remains a significant challenge due to the intertwining behaviors between the particles and their released ions. The open question is which of the above factor dominate the antibacterial behaviors when silver nanoparticles (Ag NPs) with different sizes. Considering the high reactivity of Ag NPs, prior research has primarily concentrated on coated particles, which inevitably hinder the release of Ag+ ions due to additional chemical agents. In this study, we synthesized various Ag NPs, both coated and uncoated, using the laser ablation in liquids (LAL) technique. By analyzing both the changes in particle size and Ag+ ions release, the impacts of various Ag NPs on the cellular activity and morphological changes of gram-negative (E. coil) and gram-positive (S. aureus) bacteria were evaluated. Our findings revealed that for uncoated Ag NPs, smaller particles exhibited greater ions release efficiency and enhanced antibacterial efficacy. Specifically, particles approximately 1.5 nm in size released up to 55 % of their Ag+ ions within 4 h, significantly inhibiting bacterial growth. Additionally, larger particles tended to aggregate on the bacterial cell membrane surface, whereas smaller particles were more likely to be internalized by the bacteria. Notably, treatment with smaller Ag NPs led to more pronounced bacterial morphological changes and elevated levels of intracellular reactive oxygen species (ROS). We proposed that the bactericidal activity of Ag NPs stems from the synergistic effect between particle-cell interaction and the ionic silver, which is dependent on the crucial parameter of particle size.


Subject(s)
Anti-Bacterial Agents , Ions , Lasers , Metal Nanoparticles , Microbial Sensitivity Tests , Particle Size , Silver , Staphylococcus aureus , Silver/chemistry , Silver/pharmacology , Metal Nanoparticles/chemistry , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/chemical synthesis , Staphylococcus aureus/drug effects , Ions/chemistry , Escherichia coli/drug effects , Surface Properties , Reactive Oxygen Species/metabolism
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