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1.
Anal Chem ; 96(21): 8518-8527, 2024 May 28.
Article in English | MEDLINE | ID: mdl-38711366

ABSTRACT

Accurate structural determination of proteins is critical to understanding their biological functions and the impact of structural disruption on disease progression. Gas-phase cross-linking mass spectrometry (XL-MS) via ion/ion reactions between multiply charged protein cations and singly charged cross-linker anions has previously been developed to obtain low-resolution structural information on proteins. This method significantly shortens experimental time relative to conventional solution-phase XL-MS but has several technical limitations: (1) the singly deprotonated N-hydroxysulfosuccinimide (sulfo-NHS)-based cross-linker anions are restricted to attachment at neutral amine groups of basic amino acid residues and (2) analyzing terminal cross-linked fragment ions is insufficient to unambiguously localize sites of linker attachment. Herein, we demonstrate enhanced structural information for alcohol-denatured A-state ubiquitin obtained from an alternative gas-phase XL-MS approach. Briefly, singly sodiated ethylene glycol bis(sulfosuccinimidyl succinate) (sulfo-EGS) cross-linker anions enable covalent cross-linking at both ammonium and amine groups. Additionally, covalently modified internal fragment ions, along with terminal b-/y-type counterparts, improve the determination of linker attachment sites. Molecular dynamics simulations validate experimentally obtained gas-phase conformations of denatured ubiquitin. This method has identified four cross-linking sites across 8+ ubiquitin, including two new sites in the N-terminal region of the protein that were originally inaccessible in prior gas-phase XL approaches. The two N-terminal cross-linking sites suggest that the N-terminal half of ubiquitin is more compact in gas-phase conformations. By comparison, the two C-terminal linker sites indicate the signature transformation of this region of the protein from a native to a denatured conformation. Overall, the results suggest that the solution-phase secondary structures of the A-state ubiquitin are conserved in the gas phase. This method also provides sufficient sensitivity to differentiate between two gas-phase conformers of the same charge state with subtle structural variations.


Subject(s)
Cross-Linking Reagents , Ubiquitin , Ubiquitin/chemistry , Cross-Linking Reagents/chemistry , Sodium/chemistry , Gases/chemistry , Cations/chemistry , Succinimides/chemistry , Mass Spectrometry , Ions/chemistry
2.
ACS Nano ; 18(21): 13794-13807, 2024 May 28.
Article in English | MEDLINE | ID: mdl-38741414

ABSTRACT

Gout flare-up, commonly resulting from monosodium urate monohydrate (MSUM) crystallization, has led to painful inflammatory arthritis among hundreds of millions of people. Herein, a kind of hydrogel nanoparticles (HNPs) with specific properties was developed, aimed at providing a promising pathway for MSUM crystallization control. The experimental and molecular dynamics simulation results synchronously indicate that the fabricated HNPs achieve efficient inhibition of MSUM crystallization governed by the mechanism of "host-guest interaction" even under very low-dose administration. HNPs as the host dispersed in the hyperuricemic model effectively lift the relative heterogeneous nucleation barrier of the MSUM crystal and hinder solute aggregation with strong electronegativity and hydrophobicity. The initial appearance of MSUM crystals was then delayed from 94 to 334 h. HNPs as the guest on the surface of the formed crystal can decelerate the growth rate by anchoring ions and occupying the active sites on the surface, and the terminal yield of the MSUM crystal declined to less than 1% of the control group. The good biocompatibility of HNPs (cell viability > 94%) renders it possible for future clinical applications. This study can guide the rational design of inhibitory nanomaterials and the development of their application in the control of relevant pathological crystallization.


Subject(s)
Crystallization , Hydrogels , Molecular Dynamics Simulation , Nanoparticles , Uric Acid , Uric Acid/chemistry , Hydrogels/chemistry , Nanoparticles/chemistry , Animals , Cell Survival/drug effects , Mice , Particle Size , Ions/chemistry , Surface Properties
3.
Water Sci Technol ; 89(9): 2429-2439, 2024 May.
Article in English | MEDLINE | ID: mdl-38747958

ABSTRACT

Sediment microbial fuel cells (SMFCs) represent a technology that can enhance sediment quality through processes such as nutrient suppression while simultaneously generating electricity from microorganisms. Despite its importance in elucidating the principles of nutrient suppression, the complex behavior of various ions within this context has been rarely explored. Herein, we applied an SMFC and systematically evaluated alterations in ion concentrations in interstitial and overlying waters. The SMFC deployment substantially decreased Na+ concentrations and increased Cl- levels in the interstitial water. This intriguing phenomenon was attributed to reactions driven by the electrodes. These reactions induced remarkable shifts in pH. Consequently, this pH shift triggered the leaching of heavy metals, particularly Fe, and decreased HCO3- concentrations within the interstitial water, thereby inducing the migration of other ions, including Na+ and Cl-, as compensation. Moreover, the PO43- concentration in interstitial water showed an increasing trend upon SMFC application, which contradicts the results of several previous reports. This increase was primarily attributed to the release of PO43-caused by the leaching of Fe salts, which was triggered by the pH shift. These findings provide new insights into sediment improvement research through SMFCs, enhancing our understanding of the fundamental principles and broadening the potential applications of this technology.


Subject(s)
Bioelectric Energy Sources , Geologic Sediments , Hydrogen-Ion Concentration , Geologic Sediments/chemistry , Ions/chemistry
4.
J Mass Spectrom ; 59(6): e5043, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38789127

ABSTRACT

The assignment of structure by tandem mass spectrometry (MS/MS) relies on the interpretation of the fragmentation behavior of gas-phase ions. Mass spectra were acquired for a series of heterocyclic mimetics of acidic amino acids and a related series of nitrile amino acids. All amino acids were readily protonated or deprotonated by electrospray ionization (ESI), and distinctive fragmentation processes were observed when the ions were subjected to collision-induced dissociation (CID). The deprotonated heterocycles showed bond cleavages of the 3-hydroxyfurazan ring with formation of oxoisocyanate and the complementary deprotonated nitrile amino acid. Further fragmentation of the deprotonated nitrile amino acids was greatly dependent on the length of the alkyl nitrile side chain. Competing losses of CO2 versus HCN occurred from α-cyanoglycinate (shortest chain), whereas water was lost from 2-amino-5-cyanopentanoate (longest chain). Interestingly, loss of acrylonitrile by a McLafferty-type fragmentation process was detected for 2-amino-4-cyanobutanoate, and several competing processes were observed for ß-cyanoalanate. In one process, cyanide ion was formed either by consecutive losses of ammonia, carbon dioxide, and acetylene or by a one-step decarboxylative elimination. In another, complementary ions were obtained from ß-cyanoalanate by loss of acetonitrile or HN=CHCO2H. Fragmentation of the protonated 3-hydroxyfurazan and nitrile amino acids resulted in the cumulative loss (H2O + CO), a loss that is commonly observed for protonated aliphatic α-amino acids. Overall, the distinct fragmentation behavior of the multifunctional 3-hydroxyfurazan amino acids correlated with the charged site, whereas fragmentations of the deprotonated nitrile amino acids showed cooperative interactions between the nitrile and the carboxylate groups.


Subject(s)
Amino Acids , Nitriles , Tandem Mass Spectrometry , Tandem Mass Spectrometry/methods , Nitriles/chemistry , Amino Acids/chemistry , Amino Acids/analysis , Spectrometry, Mass, Electrospray Ionization/methods , Ions/chemistry
5.
Anal Methods ; 16(20): 3202-3208, 2024 May 23.
Article in English | MEDLINE | ID: mdl-38742397

ABSTRACT

A sensitive photoelectrochemical (PEC) biosensor for silver ions (Ag+) was developed based on Zn-Co doped C and CdS quantum dot (CdS QD) nanomaterials. Hydrophobic modified sodium alginate (HMA), which could stabilize and improve the PEC performance of CdS QDs, was also used for the construction of PEC sensors. Especially, Zn-Co doped C, CdS QDs and HMA were sequentially modified onto an electrode surface via the drop-coating method, and a C base rich DNA strand was then immobilized onto the modified electrode. As the C base in DNA specifically recognized Ag+, it formed a C-Ag+-C complex in the presence of Ag+, which created a spatial steric hindrance, resulting in a reduced PEC response. The sensing platform is sensitive to Ag+ in the range of 10.0 fM to 0.10 µM, with a limit of detection of 3.99 fM. This work offers an ideal platform to determine trace heavy metal ions in environmental monitoring and bioanalysis.


Subject(s)
Biosensing Techniques , Cadmium Compounds , Electrochemical Techniques , Quantum Dots , Silver , Sulfides , Zinc , Silver/chemistry , Biosensing Techniques/methods , Quantum Dots/chemistry , Cadmium Compounds/chemistry , Sulfides/chemistry , Electrochemical Techniques/methods , Zinc/chemistry , Cobalt/chemistry , Carbon/chemistry , Ions/chemistry , Ions/analysis , Photochemical Processes , Limit of Detection
6.
J Am Chem Soc ; 146(20): 14307-14317, 2024 May 22.
Article in English | MEDLINE | ID: mdl-38722189

ABSTRACT

Biomolecules such as proteins and RNA could organize to form condensates with distinct microenvironments through liquid-liquid phase separation (LLPS). Recent works have demonstrated that the microenvironment of biomolecular condensates plays a crucial role in mediating biological activities, such as the partition of biomolecules, and the subphase organization of the multiphasic condensates. Ions could influence the phase transition point of LLPS, following the Hofmeister series. However, the ion-specific effect on the microenvironment of biomolecular condensates remains unknown. In this study, we utilized fluorescence lifetime imaging microscopy (FLIM), fluorescence recovery after photobleaching (FRAP), and microrheology techniques to investigate the ion effect on the microenvironment of condensates. We found that ions significantly affect the microenvironment of biomolecular condensates: salting-in ions increase micropolarity and reduce the microviscosity of the condensate, while salting-out ions induce opposing effects. Furthermore, we manipulate the miscibility and multilayering behavior of condensates through ion-specific effects. In summary, our work provides the first quantitative survey of the microenvironment of protein condensates in the presence of ions from the Hofmeister series, demonstrating how ions impact micropolarity, microviscosity, and viscoelasticity of condensates. Our results bear implications on how membrane-less organelles would exhibit varying microenvironments in the presence of continuously changing cellular conditions.


Subject(s)
Biomolecular Condensates , Biomolecular Condensates/chemistry , Ions/chemistry , Fluorescence Recovery After Photobleaching , Microscopy, Fluorescence , Proteins/chemistry , Proteins/metabolism
7.
Int J Mol Sci ; 25(9)2024 May 03.
Article in English | MEDLINE | ID: mdl-38732218

ABSTRACT

Boronate esters are a class of compounds containing a boron atom bonded to two oxygen atoms in an ester group, often being used as precursors in the synthesis of other materials. The characterization of the structure and properties of esters is usually carried out by UV-visible, infrared, and nuclear magnetic resonance (NMR) spectroscopic techniques. With the aim to better understand our experimental data, in this article, the density functional theory (DFT) is used to analyze the UV-visible and infrared spectra, as well as the isotropic shielding and chemical shifts of the hydrogen atoms 1H, carbon 13C and boron 11B in the compound 4-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)benzaldehyde. Furthermore, this study considers the change in its electronic and spectroscopic properties of this particular ester, when its boron atom is coordinated with a fluoride anion. The calculations were carried out using the LSDA and B3LYP functionals in Gaussian-16, and PBE in CASTEP. The results show that the B3LYP functional gives the best approximation to the experimental data. The formation of a coordinated covalent B-F bond highlights the remarkable sensitivity of the NMR chemical shifts of carbon, oxygen, and boron atoms and their surroundings. Furthermore, this bond also highlights the changes in the electron transitions bands n → π* and π → π* during the absorption and emission of a photon in the UV-vis, and in the stretching bands of the C=C bonds, and bending of BO2 in the infrared spectrum. This study not only contributes to the understanding of the properties of boronate esters but also provides important information on the interactions and responses optoelectronic of the compound when is bonded to a fluorine atom.


Subject(s)
Benzaldehydes , Benzaldehydes/chemistry , Magnetic Resonance Spectroscopy , Density Functional Theory , Fluorine/chemistry , Boron/chemistry , Models, Molecular , Esters/chemistry , Spectrophotometry, Infrared , Molecular Structure , Ions/chemistry
8.
Int J Nanomedicine ; 19: 4515-4531, 2024.
Article in English | MEDLINE | ID: mdl-38803996

ABSTRACT

Introduction: There is an ongoing need for improved healing response and expedited osseointegration on the Ti implants in acetabular fracture sites. To achieve adequate bonding and mechanical stability between the implant surface and the acetabular fracture, a new coating technology must be developed to promote bone integration and prevent bacterial growth. Methods: A cylindrical Ti substrate mounted on a rotating specimen holder was used to implant Ca2+, P2+, and Sr2+ ions at energies of 100 KeV, 75 KeV and 180 KeV, respectively, using a low-energy accelerator to synthesize strontium-substituted hydroxyapatite at varying conditions. Ag2+ ions of energy 100 KeV were subsequently implanted on the as-formed surface at the near-surface region to provide anti-bacterial properties to the as-formed specimen. Results: The properties of the as-formed ion-implanted specimen were compared with the SrHA-Ag synthesized specimens by cathodic deposition and low-temperature high-speed collision technique. The adhesion strength of the ion-implanted specimen was 43 ± 2.3 MPa, which is well above the ASTM standard for Ca-P coating on Ti. Live/dead cell analysis showed higher osteoblast activity on the ion-implanted specimen than the other two. Ag in the SrHA implanted Ti by ion implantation process showed superior antibacterial activity. Discussion: In the ion implantation technique, nano-topography patterned surfaces are not concealed after implantation, and their efficacy in interacting with the osteoblasts is retained. Although all three studies examined the antibacterial effects of Ag2+ ions and the ability to promote bone tissue formation by MC3T3-E1 cells on SrHA-Ag/Ti surfaces, ion implantation techniques demonstrated superior ability. The synthesized specimen can be used as an effective implant in acetabular fracture sites based on their mechanical and biological properties.


Subject(s)
Acetabulum , Anti-Bacterial Agents , Silver , Strontium , Titanium , Titanium/chemistry , Titanium/pharmacology , Silver/chemistry , Silver/pharmacology , Strontium/chemistry , Strontium/pharmacology , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Acetabulum/injuries , Animals , Coated Materials, Biocompatible/chemistry , Coated Materials, Biocompatible/pharmacology , Osseointegration/drug effects , Mice , Surface Properties , Fractures, Bone/therapy , Durapatite/chemistry , Durapatite/pharmacology , Osteoblasts/drug effects , Hydroxyapatites/chemistry , Hydroxyapatites/pharmacology , Prostheses and Implants , Ions/chemistry , Ions/pharmacology , Humans , Cell Line
9.
Food Chem ; 453: 139672, 2024 Sep 30.
Article in English | MEDLINE | ID: mdl-38805941

ABSTRACT

The structure and functional properties of protein fibrils are closely related to environmental factors in fibrillation. Herein, soy protein isolate fibrils (SPIFs, 22 mg/mL) were prepared under acid-heating conditions in the presence of 100 mM metal ions (K+, Na+, Ca2+, Mg2+, and Fe3+). Except for Fe3+, fibrillation and subsequent larger fibril aggregates were promoted, ultimately leading to gel formation. Compared with K+ or Na+, the addition of Ca2+ or Mg2+ resulted in more organized SPIF structures with increased ß-sheet contents and higher ThT fluorescence intensities. Furthermore, both of them resulted in longer fibrils with an average contour length of 700-800 nm, which significantly enhanced the storage modulus. However, the presence of Fe3+ accelerated protein hydrolysis and inhibited SPIF formation, resulting in samples consistently exhibited liquid behavior. These findings provide a foundation for understanding the influence of metal ions on regulating the fibrillation and gelling properties of SPIFs.


Subject(s)
Gels , Metals , Soybean Proteins , Soybean Proteins/chemistry , Gels/chemistry , Metals/chemistry , Ions/chemistry , Hydrolysis
10.
Chemosphere ; 359: 142260, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38735488

ABSTRACT

Human activity and industrial production have led to phenol becoming a significant risk factor. The proper treatment of phenol in wastewater is essential. In this study, the utilization of weak magnetic field (WMF) and zero-valent iron (ZVI) was proposed to activate H2O2 to degrade phenol contaminant. The results show that the weak magnetic field has greatly enhanced the reaction rate of ZVI/H2O2 removal of phenol. The removal rates of phenol by ZVI/H2O2/WMF generally decreased with increasing initial pH and phenol concentrations, and firstly increase and then decrease with increasing Fe0 or H2O2 dosage. When the initial pH is 5.0, ZVI concentration of 0.2 g L-1, H2O2 concentration of 6 mM, and phenol concentration of 100 mg L-1 were used, complete removal of phenol can be achieved within 180 min at 25 °C. The degradation process was consistent with the pseudo-first-order kinetic model when the experimental data was fitted. The ZVI/H2O2/WMF process exhibited a 1.05-2.66-fold enhancement in the removal rate of phenol under various conditions, surpassing its counterpart lacking WMF. It was noticed that the presence of 1-5 mM of Ca2+, Mg2+, Cl-, SO42- ions can significantly enhance the kinetics of phenol removal by ZVI/H2O2 system with or without WMF to 2.22-10.40-fold, but NO3-, CO32-, PO43- inhibited the reaction significantly in the following order: PO43- > CO32- > NO3-. Moreover, pre-magnetization for 3 min could enhance the ZVI/H2O2 process which was valuable in treatment of real wastewater. The hydroxyl radical has been identified as the primary radical species responsible for phenol degradation. The presence of WMF accelerates the corrosion rate of ZVI, thereby promoting the release of Fe2+ ions, which in turn induces an increased production of hydroxyl radicals and facilitates phenol degradation. The compounds hydroquinone, benzoquinone, catechol, maleic acid, and CO2 were identified using GC-MS, and degradation pathways were proposed. Employing WMF in combination with various ions like Ca2+, Mg2+, Cl-, SO42- is a novel method, which can enhance oxidation capacity of ZVI/H2O2 and may lead to economic benefit.


Subject(s)
Hydrogen Peroxide , Iron , Phenol , Wastewater , Water Pollutants, Chemical , Hydrogen Peroxide/chemistry , Phenol/chemistry , Wastewater/chemistry , Water Pollutants, Chemical/chemistry , Iron/chemistry , Kinetics , Magnetic Fields , Ions/chemistry , Hydrogen-Ion Concentration , Waste Disposal, Fluid/methods , Water Purification/methods
11.
Int J Biol Macromol ; 270(Pt 1): 132331, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38750843

ABSTRACT

Most of the transition metal ions and organic dyes are toxic in nature. Therefore, their removal from water is imperative for human health. For this purpose, various types of systems have been developed to tackle either transition metal ions or organic dyes individually. A core-shell microgel system is introduced which is capable of effectively removing both types (toxic organic dyes and transition metal ions) of pollutants. A long-rod-shaped silica@poly(chitosan-N-isopropylacrylamide-methacrylic acid) S@P(CS-NIPAM-MAA) S@P(CNM) core-shell microgel system was developed by free radical precipitation polymerization method (FRPPM). S@P(CNM) was utilized as an adsorbent for extracting palladium (II) (Pd (II)) ions from water under different concentrations of S@P(CNM), several agitation times, palladium (II) ion content, and pH levels. The adsorption data of Pd (II) ions on S@P(CNM) was evaluated by various adsorption isotherms. The kinetic study was investigated by employing pseudo-2nd order (Ps2O), Elovich model (ElM), intra-particle diffusion (IPDM), and pseudo-1st order (Ps1O). Additionally, palladium nanoparticles (Pd NPs) were generated via in-situ reduction of adsorbed Pd (II) ions within the P(CNM) shell region of S@P(CNM). The resulting Pd NPs loaded S@P(CNM) exhibited the capability to reduce organic pollutants like methyl orange (MeO), 4-nitrophenol (4NiP), methylene blue (MeB), and Rhodamine B (RhB) from aqueous medium. 0.766 min-1, 0.433 min-1, 0.682 min-1, and 1.140 min-1 were the values of pseudo 1st order rate constant (kobs) for catalytic reduction of MeB, 4NiP, MeO, and RhB respectively. The S@Pd-P(CNM) system exhibits significant catalytic potential for various organic transformations.


Subject(s)
Chitosan , Metal Nanoparticles , Palladium , Silicon Dioxide , Water Pollutants, Chemical , Palladium/chemistry , Chitosan/chemistry , Silicon Dioxide/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Adsorption , Metal Nanoparticles/chemistry , Kinetics , Acrylamides/chemistry , Gels/chemistry , Water Purification/methods , Hydrogen-Ion Concentration , Methacrylates/chemistry , Ions/chemistry
12.
Int J Biol Macromol ; 270(Pt 2): 132386, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38754671

ABSTRACT

Due to the high concentration of various toxic and dangerous pollutants, industrial effluents have imposed increasing threats. Among the various processes for wastewater treatment, adsorption is widely used due to its simplicity, good treatment efficiency, availability of a wide range of adsorbents, and cost-effectiveness. Chitosan (CS) has received great attention as a pollutant adsorbent due to its low cost and many -OH and -NH2 functional groups that can bind heavy metal ions. However, weaknesses such as sensitivity to pH, low thermal stability and low mechanical strength, limit the application of CS in wastewater treatment. The modification of these functional groups can improve its performance via cross-linking and grafting agents. The porosity and specific surface area of CS in powder form are not ideal, so physical modification of CS via integration with other materials (e.g., metal oxide, zeolite, clay, etc.) leads to the creation of composite materials with improved absorption performance. This review provides reports on the application of CS and its nanocomposites (NCs) for the removal of various heavy metal ions. Synthesis strategy, adsorption mechanism and influencing factors on sorbents for heavy metals are discussed in detail.


Subject(s)
Chitosan , Metals, Heavy , Nanocomposites , Water Pollutants, Chemical , Water Purification , Chitosan/chemistry , Metals, Heavy/chemistry , Metals, Heavy/isolation & purification , Adsorption , Nanocomposites/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Water Purification/methods , Wastewater/chemistry , Ions/chemistry
13.
Nat Commun ; 15(1): 4524, 2024 May 28.
Article in English | MEDLINE | ID: mdl-38806492

ABSTRACT

Membrane fusion, merging two lipid bilayers, is crucial for fabricating artificial membrane structures. Over the past 40 years, in contrast to precise and controllable membrane fusion in-vivo through specific molecules such as SNAREs, controlling the fusion in-vitro while fabricating artificial membrane structures in physiological ionic solutions without fusion proteins has been a challenge, becoming a significant obstacle to practical applications. We present an approach consisting of an electric field and a few kPa hydraulic pressure as an additional variable to physically control the fusion, enabling tuning of the shape and size of the 3D freestanding lipid bilayers in physiological ionic solutions. Mechanical model analysis reveals that pressure-induced parallel/normal tensions enhance fusion among membranes in the microwell. In-vitro peptide-membrane assay, mimicking vesicular transport via pressure-assisted fusion, and stability of 38 days with in-chip pressure control via pore size-regulated hydrogel highlight the potential for diverse biological applications.


Subject(s)
Lipid Bilayers , Membrane Fusion , Lipid Bilayers/chemistry , Lipid Bilayers/metabolism , Ions/chemistry , Membranes, Artificial , Hydrogels/chemistry , Pressure , Peptides/chemistry
14.
Molecules ; 29(10)2024 May 08.
Article in English | MEDLINE | ID: mdl-38792059

ABSTRACT

Bicyclic peptides have attracted the interest of pharmaceutical companies because of their remarkable properties, putting them on a new path in medicine. Their conformational rigidity improves proteolytic stability and leads to rapid penetration into tissues via any possible route of administration. Moreover, elimination of renal metabolism is of great importance, for example, for people with a history of liver diseases. In addition, each ring can function independently, making bicyclic peptides extremely versatile molecules for further optimization. In this paper, we compared the potentiometric and spectroscopic properties studied by UV-vis, MCD, and EPR of four synthetic analogues of the bi-cyclic peptide c(PKKHP-c(CFWKTC)-PKKH) (BCL). In particular, we correlated the structural and spectral properties of complexes with coordinating abilities toward Cu(II) ions of MCL1 (Ac-PKKHPc(CFWKTC)PKKH-NH2) that contains the unbinding cycle and N- and C-terminal linear parts with two histidine residues, one per part; two monocyclic ligands containing one histidine residue, both in the N-terminal position, i.e., MCL2 (Ac-PKKHPc(CFWKTC)PKKS-NH2) and in the C-terminal position, i.e., MCL3 (Ac-PKKSPc(CFWKTC)PKKH-NH2), respectively; and the linear structure LNL (Ac-PKKHPSFWKTSPKKH-NH2). Potentiometric results have shown that the bicyclic structure promotes the involvement of the side chain imidazole donors in Cu(II) binding. On the other hand, the results obtained for the mono-cyclic analogues lead to the conclusion that the coordination of the histidine moiety as an anchoring group is promoted by its location in the peptide sequence further from the nonbinding cycle, strongly influencing the involvement of the amide donors in Cu(II) coordination.


Subject(s)
Copper , Peptides, Cyclic , Copper/chemistry , Peptides, Cyclic/chemistry , Coordination Complexes/chemistry , Ligands , Ions/chemistry , Potentiometry
15.
Int J Biol Macromol ; 269(Pt 1): 131988, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38701999

ABSTRACT

The disposal of waste lithium batteries, especially waste separators, has always been a problem, incineration and burial will cause environmental pollution, therefore, the development of degradable and high-performance separators has become an important challenge. Herein, UiO-66-NH2 particles were successfully anchored onto bacterial cellulose (BC) separators by epichlorohydrin (ECH) as a crosslinker, then a BC/UiO-66-NH2 composite separator was prepared by vacuum filtration. The ammonia groups (-NH2) from UiO-66-NH2 can form hydrogen bonds with PF6- in the electrolyte, promoting lithium-ion transference. Additionally, UiO-66-NH2 can store the electrolyte and tune the porosity of the separator. The lithium ion migration number (0.62) of the battery assembled with BC/UiO-66-NH2 composite separator increased by 50 % compared to the battery assembled with commercial PP separator (0.45). The discharge specific capacity of the battery assembled with BC/UIO-66-NH2 composite separator after 50 charge and discharge cycles is 145.4 mAh/g, which is higher than the average discharge specific capacity of 114.3 mAh/g of the battery assembled with PP separator. When the current density is 2C, the minimum discharge capacity of the battery assembled with BC/UiO-66-NH2 composite separator is 85.3 mAh/g. The electrochemical performance of the BC/UiO-66-NH2 composite separator is significantly better than that of the commercial PP separator. In addition, -NH2 can offer a nitrogen source to facilitate degradation of the BC separators, whereby the BC/UiO-66-NH2 composite separator could be completely degraded in 15 days.


Subject(s)
Cellulose , Electric Power Supplies , Lithium , Lithium/chemistry , Cellulose/chemistry , Ions/chemistry , Biodegradation, Environmental
16.
Int J Biol Macromol ; 270(Pt 1): 132142, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38719005

ABSTRACT

The severe negative effects of impurities adhering to the external surface of wearable devices can significantly influence the signal transmission, performance, and lifespan of hydrogel sensors. Herein, we developed an ion-conducting hydrogel sensor with a strong adhesive side and a non-adhesive side, similar to a "semi-releasing material." This hydrogel, formulated using deep eutectic solvents obtained from choline chloride and acrylic acid, contained lignin. This versatile material, exhibiting properties similar to semi-releasing materials, was treated with an AlCl3 solution on one side. Additionally, the hydrogel was successfully used as a highly adhesive strain sensor for real-time monitoring of various human activity signals. Moreover, the hydrogel demonstrated excellent environmental tolerance and conductivity. Lignin extracted from wood flour endowed the hydrogel sensor with excellent adhesion energy (up to 427.1 J/m2) and UV resistance. Treatment of hydrogels with AlCl3 completely eliminated their adhesiveness, thereby enhancing fracture elongation and tensile strength. This improvement can be attributed to the absence of carboxyl groups and the formation of a metal-phenolic network. The implementation of this convenient and efficient strategy provides a more feasible approach to address challenges related to impurity adhesion and signal transmission in flexible wearable devices.


Subject(s)
Hydrogels , Lignin , Wearable Electronic Devices , Lignin/chemistry , Hydrogels/chemistry , Humans , Electric Conductivity , Tensile Strength , Aluminum Chloride/chemistry , Ions/chemistry
17.
Int J Biol Macromol ; 270(Pt 2): 132161, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38723810

ABSTRACT

A novel magnetic polyvinylpyrrolidone/chitosan-Schiff base/Fe2O3 (PVP/CS-SB/Fe2O3) adsorbent was prepared by one-pot facile co-precipitation route for adsorption of Pb(II) and Hg(II) ions from aqueous solution. Fourier transform infrared-spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscope (SEM), vibrating sample magnetometer (VSM) and Brunauer-Emmett-Teller (BET) were used to characterize the synthesized PVP/CS-SB/Fe2O3. The results predicted that the successfully synthesis of magnetic CSSB-PVP@Fe2O3. The effects of important factors such as pH solution, contact time, concentration of metal ions, adsorbent dose and co-existing ions on Pb(II) and Hg(II) adsorption were investigated. The maximum adsorption capacities of Pb(II) and Hg(II) ions at optimal conditions were 120 mg/g and 102.5 mg/g, respectively. The kinetic studies predicted that the adsorption followed the pseudo-second-order (PSO) model as chemisorption using the coordination of active sites of PVP/CS-SB/Fe2O3 with the metal ions and also n-π interactions. Reproducibility results predicted that the excellent regeneration ability after 6 adsorption cycles. According to the results of this work, the PVP/CS-SB/Fe2O3 nanocomposite is promising for Pb(II) and Hg(II) ions adsorption and can be potential as a simple, low-cost, high-efficient adsorbent for decontamination of other heavy metal ions from aqueous solution.


Subject(s)
Chitosan , Ferric Compounds , Lead , Mercury , Nanocomposites , Povidone , Schiff Bases , Water Pollutants, Chemical , Water Purification , Chitosan/chemistry , Nanocomposites/chemistry , Adsorption , Schiff Bases/chemistry , Lead/chemistry , Lead/isolation & purification , Mercury/chemistry , Mercury/isolation & purification , Povidone/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Ferric Compounds/chemistry , Hydrogen-Ion Concentration , Water Purification/methods , Kinetics , Solutions , Ions/chemistry , Water/chemistry , Spectroscopy, Fourier Transform Infrared
18.
Anal Chim Acta ; 1308: 342661, 2024 Jun 15.
Article in English | MEDLINE | ID: mdl-38740461

ABSTRACT

BACKGROUND: Timely diagnosis and prevention of diseases require rapid and sensitive detection of biomarkers from blood samples without external interference. Abnormal electrolyte ion levels in the blood are closely linked to various physiological disorders, including hypertension. Therefore, accurate, interference-free, and precise measurement of electrolyte ion concentrations in the blood is particularly important. RESULTS: In this work, a colorimetric sensor based on a biphasic microdroplet extraction is proposed for the detection of electrolyte ions in the blood. This sensor employs mini-pillar arrays to facilitate contact between adjacent blood microdroplets and organic microdroplets serving as sensing phases, with any color changes being monitored through a smartphone's colorimetric software. The sensor is highly resistant to interference and does not require pre-treatment of the blood samples. Remarkably, the sensor exhibits exceptional reliability and stability, allowing for rapid enrichment and detection of K+, Na+, and Cl- in the blood within 10 s (Cl-), 15 s (K+) and 40 s (Na+) respectively. SIGNIFICANCE: The colorimetric sensor based on biphasic microdroplet extraction offers portability due to its compact size and ease of operation without the need for large instruments. Additionally, it is location-independent, making it a promising tool for real-time biomarker detection in body fluids such as blood.


Subject(s)
Colorimetry , Electrolytes , Potassium , Colorimetry/methods , Electrolytes/chemistry , Humans , Potassium/blood , Sodium/blood , Chlorides/blood , Ions/chemistry
19.
J Phys Chem Lett ; 15(16): 4468-4476, 2024 Apr 25.
Article in English | MEDLINE | ID: mdl-38631022

ABSTRACT

The underlying mechanism and intermediate formation in the self-assembly of aromatic amino acids, peptides, and proteins remain elusive despite numerous reports. We, for the first time, report that one can stabilize the intermediates by tuning the metal ion-amino acid interaction. Microscopic and spectroscopic investigations of the self-assembly of carboxybenzyl (Z)-protected phenylalanine (ZF) reveal that the bivalent metal ions eventually lead to the formation of fibrillar networks similar to blank ZF whereas the trivalent ions develop vesicle-like intermediates that do not undergo fibrillation for a prolonged time. The time-lapse measurement of surface charge reveals that the surface charge of blank ZF and in the presence of bivalent metal ions changes from a negative value to zero, implying unstable intermediates leading to the fibril network. Strikingly, a prominent charge inversion from an initial negative value to a positive value in the presence of trivalent metal ions imparts unusual stability to the metastable intermediates.


Subject(s)
Phenylalanine , Phenylalanine/chemistry , Surface Properties , Ions/chemistry , Metals/chemistry
20.
J Chromatogr A ; 1722: 464903, 2024 May 10.
Article in English | MEDLINE | ID: mdl-38615559

ABSTRACT

High-Field Asymmetric Ion Mobility Spectrometry (FAIMS) is a technique for ion separation and detection based on ion mobility variation under high electronic field. While compensation voltage scanning speed is a fundamental parameter in FAIMS, its impact on spectra remains unclear. In this work, a function referred to as F-EMG is introduced to describe the impact of compensation voltage scanning speed on FAIMS spectra, and the properties of the function are studied. Theoretical analysis emphasizes the impact of the scanning speed on peak height, position, and symmetry, as well as the capability of the F-EMG function to progressively approach Gaussian function at lower scanning speeds. Furthermore, the function indicates that spectra obtained in positive and negative scanning modes exhibits symmetry. An experimental validation, conducted with a custom FAIMS setup and analyzing hydrogen sulfide, ethylbenzene, toluene, styrene, benzene and ammonia, confirms the model's influence on peak features, fitting accuracy, and exhibits a closer alignment with the Gaussian function at lower scanning speeds. Additionally, the experimental data indicate that the spectra show symmetry in positive and negative scanning models. This work not only improves understanding of FAIMS spectral analysis but also introduces a robust method for enhancing data accuracy across varying scanning speeds.


Subject(s)
Ion Mobility Spectrometry , Ion Mobility Spectrometry/methods , Models, Theoretical , Ions/chemistry , Ions/analysis
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