Mn Ions Research Articles

ATP-Responsive Manganese-Based Bacterial Materials Synergistically Activate the cGAS-STING Pathway for Tumor Immunotherapy.

Stimulating the cyclic guanosine monophophate(GMP)-adenosine monophosphate (AMP) synthase (cGAS)-stimulator of interferon genes (STING) pathway is a crucial strategy by which bacteria activate the tumor immune system. However, the limited stimulation capability poses significant challenges in advancing bacterial immunotherapy. Here, an adenosine 5'-triphosphate (ATP)-responsive manganese (Mn)-based bacterial material (E. coli@PDMC-PEG (polyethylene glycol)) is engineered successfully, which exhibits an exceptional ability to synergistically activate the cGAS-STING pathway. In the tumor microenvironment, which is characterized by elevated ATP levels, this biohybrid material degrades, resulting in the release of divalent manganese ions (Mn2+ ) and subsequent bacteria exposure. This combination synergistically activates the cGAS-STING pathway, as Mn2+ enhances the sensitivity of cGAS to the extracellular DNA (eDNA) secreted by the bacteria. The results of the in vivo experiments demonstrate that the biohybrid materials E. coli@PDMC-PEG and VNP20009@PDMC-PEG effectively inhibit the growth of subcutaneous melanoma in mice and in situ liver cancer in rabbits. Valuable insights for the development of bacteria-based tumor immunotherapy are provided here.

Acidity-activated degradable Mn-engineered silicon nanohybrids coordinated with iprodione for high-efficiency management of Sclerotinia sclerotiorum and nutrient enhancement to crops

Nanocarriers that respond to environmental stimuli are highly desirable in optimizing the bioavailability of pesticides while minimizing side effects. Manganese-engineered nanomaterials hold promising prospects in agriculture as versatile carriers for both intelligent controlled pesticide delivery and crop nutrient enhancement. Here, Mn-engineered hollow silicon nanospheres (Mn-HSNs) with a bubble-like structure were synthesized for encapsulating iprodione (IPR) to obtain IPR-loaded Mn-HSNs (IPR@Mn-HSNs). Due to its high surface area of 261.28 m2/g and surface-enriched active sites, Mn-HSNs demonstrated a commendable loading capacity of 56.4 % for IPR. Results indicated that the -Si-O-Mn- hybrid framework of IPR@Mn-HSNs not only facilitated acidity-triggered IPR release capability but also served as a plentiful source of Mn ion and orthosilicic acid (Si(OH)4) to promote crop growth. The release amount of IPR in an acidic environment generated by Sclerotinia sclerotiorum of oilseed rape was 3.14 times higher than that under neutral conditions. In vitro experiments demonstrated that the antibacterial activity of IPR@Mn-HSNs was about 1.2 times higher than that of commercial IPR suspension concentrate. Appreciably, IPR@Mn-HSNs could be effectively transported to different parts of rapeseed plants through foliar spray, thereby enhancing the effectiveness of pesticide utilization. More importantly, IPR@Mn-HSNs had no discernible impact on the survival of Harmonia axyridis and were relatively safe for HL-7702 and HK-2 cells. Therefore, this work offers valuable insights into the development of an efficient and environmentally friendly pesticide nanoformulation for sustainable and eco-friendly plant protection in agriculture.

Magnetically engineering enhanced EMA property through high entropy transition metal ions within all-inorganic perovskite

Addressing challenges such as signal interference and crosstalk requires the development of new materials capable of electromagnetic absorption (EMA). In this study, we explored magnetically high-entropy engineering by incorporating transition metal ions into the B sites of all-inorganic CsPbBr3 perovskite. This approach yielded excellent EMA properties, including a minimum reflection loss of 75 dB at 10.2 GHz with a thickness of 2.5 mm and an effective bandwidth of 8.8 GHz. Fe, Co, Ni, and Mn ions were successfully introduced into the CsPbBr3 lattice using high-energy ball milling and the combustion method. Through rigorous characterization techniques such as Rietveld refinement of X-ray diffraction and Grazing-Incidence Wide-Angle Scattering patterns, we confirmed the presence of high-entropy phases. Additionally, we conducted comprehensive studies using Vibrating-sample magnetometer, L2,3 edge XANES, and Mossbauer spectra to investigate the magnetic polarization, spin states, and dipolar exchanges of the transition metal ions. The observed synergistic effects among the magnetic permeability, polarization, and magnetic loss of these ions underscored their role in enhancing the EMA performance of CsPbBr3.

Doping Effects on the Multiferroic Properties of KNbO3 Nanoparticles

The magnetization, polarization, and band-gap energy in pure and ion-doped KNbO3 (KNO) bulk and nanoparticles (NPs) are investigated theoretically using a microscopic model and Green’s function theory. It is shown that KNO NPs are multiferroic. The size dependence of M and P is studied. The magnetization M increases with decreasing NP size, whereas the polarization P decreases slightly. The properties of KNO can be tuned by ion doping, for example, through the substitution of transition metal ions at the Nb site or Na ions at the K site. By ion doping, depending on the relation between the doping and host ion radii, different strains appear. They lead to changes in the exchange interaction constants, which are inversely proportional to the lattice parameters. So, we studied the macroscopic properties on a microscopic level. By doping with transition metal ions (Co, Mn, Cr) at the Nb site, M increases, whereas P decreases. Doped KNO NPs exhibit the same behavior as doped bulk KNO, but the values of the magnetization and polarization in KNO NPs are somewhat enhanced or reduced due to the size effects compared to the doped bulk KNO. In order to increase P, we substituted the K ions with Na ions. The polarization increases with increasing magnetic field, which is evidence of the multiferroic behavior of doped KNO bulk and NPs. The behavior of the band-gap energy Eg also depends on the dopants. Eg decreases with increasing Co, Mn, and Cr ion doping, whereas it increases with Zn doping. The results are compared with existing experimental data, showing good qualitative agreement.

Valence state conversion of Mn ions in Li2O–ZnO-GeO2 glass-ceramics: Spectral, structural, ESR and XRF studies

Lithium-zinc-germanate glass-ceramics doped with Mn ions are synthesized by volume crystallization method. Structural studies show nucleation of different forms of lithium germanate crystals depending on the isothermal treatment regime of the initial glass. With the increase of the heat treatment temperature and the lithium content in the initial glass, the [GeO4] /[GeO6] ratio in the nucleated crystalline phases increases. The initial distribution of Mn2+/Mn3+/Mn4+ is defined by the Li2O/ZnO ratio in the glass composition: the ratio growth increases the contribution of Mn4+ over the Mn2+ and Mn3+. Low-temperature heat treatment of initial glass leads to uprise of intense red emission of Mn4+ ions in the octahedral environment. High-temperature heat treatment leads to occurrence of intense green emission related to Mn2+ ions in a tetrahedral environment. Discussions on all transformations of symmetry, the crystal field strength of Mn ions’ environment and their valence state based on the results of optical spectroscopy, ESR and XRF studies are provided. The maximum quantum yield of red luminescence is 61%, and of green luminescence is 23%. The synthesized glass-ceramics can be used as a luminescent converter of the UV LED radiation with the maximum energy efficiency of 20%.

Synthesis, structural characterization and antitumor activities of manganese and cobalt isothiocyanate complexes with 2,2’-bipyridine

[Mn(SCN)2(2,2′-bipy)2] (1) and [Co(SCN)2(2,2′-bipy)2] (2) were synthesized at ambient temperature by adding aqueous solutions of manganese(II) or cobalt(II) chloride hydrate to aqueous acetonitrile solutions of 2,2′-bipyridine (2,2′-bipy) and potassium thiocyanate. Elemental analyses, FT-IR and UV–vis spectra were used to characterize 1 and 2. Single crystal X-ray diffraction was used to analyze the crystal structures of 1 and 2, revealing that the two are structurally similar. The molecular structures of 1 and 2 consist of Mn or Co ion chelated by two molecules of 2,2′-bipy through four nitrogen atoms and two NCS anions, giving distorted octahedral geometries. The isothiocyanate group is not bridging, instead, two ligands coordinate in a cis arrangement to the manganese or cobalt center by their nitrogen atoms while the sulfur atoms are free. Through hydrogen bonding and π–π stacking interactions, the discrete units of 1 and 2 extend to 3D supramolecular networks with flower and fishbone-like structures. The luminescence behavior of 2,2′-bipy, 1 and 2 were investigated. On HepG2 (liver) and MCF-7 (breast) cancer cells, the anticancer effects of 1 and 2 were evaluated. The activity of 1 and 2 on MCF-7 is more significant than that of HepG2. The IC50 of 1 was lower in HepG2 and MCF-7 cells than for 2.

Near-infrared light triggered upconversion nanocomposites with multifunction of enhanced antimicrobial photodynamic therapy and gas therapy for inflammation regulation

Antibacterial photodynamic therapy (aPDT) is highly effective in killing bacteria, while the problem of hypoxia and limited light penetration in deep tissue has not been properly solved. In addition, few aPDT works take into account the regulation of inflammation, which is an important regulatory process after antimicrobial therapy and the final purpose of treatment. In this work, to address the above isssues, we have designed a multi-functional composite UCNPs-Ce6-Mn(CO)5Br@Silane (referred to as UCM@Si), which consists of several key components: Up-conversion nanoparticles (UCNPs: NaErF4:Tm3+@NaYF4:Yb3+), Chlorin e6 (Ce6) and Manganese pentacarbonyl bromide (Mn(CO)5Br). When exposed to near-infrared (NIR) light (980 nm), the UCNPs can emit strong red light at 655 nm which further trigger the aPDT of Ce6. The generated reactive oxygen (ROS) subsequently break the metal carbonyl bond of Mn(CO)5Br, leading to the production of carbon monoxide (CO) molecules as well as manganese ions (Mn2+), which further decomposes hydrogen peroxide (H2O2) in the microenvironment to oxygen (O2). Therefore, this simple nanocomposite not only provides substantial self-oxygen replenishment for enhanced aPDT, but also facilitates effective inflammation regulation via CO across a wide range of deep infections. This approach leverages the unique properties of these materials to combat bacterial infections by simultaneously killing bacteria, regulating inflammation, and enhancing the oxygen levels in the affected microenvironment. This O2 and CO gas based aPDT treatment system offers a promising approach to comprehensively address microbial-induced infectious diseases, particularly deep infections, holding the potential clinical applications.

Effect of Auxiliary Ligands on the Architectures of Manganese Complexes Constructed by N-Heterocyclic Ligands: Syntheses, Structures, and Properties

Two manganese complexes based on N-heterocyclic ligands, [Mn(bqdca)(2,2'-bipy)(H2O)2]n (1), Mn0.5(4,4'-bipy) (H2O)2?0.5bqdca?2H2O (2) (H2bqdca = 2, 2'-biquinoline-4, 4'-dicarboxylic acid, 2, 2'-bipy = 2, 2'-bipyridine, 4, 4'-bipy = 4, 4'-bipyridine), have been synthesized by hydrothermal methods based on Pearson?s acid-base theory and structurally characterized. In Complex 1, the Mn ions are bridged by bqdca2- anions to form one-dimensional chains, which are further linked by hydrogen bonds to generate a two-dimensional layered structure. In Complex 2, each Mn ion was coordinated by 4, 4'-bipy and water molecules to generate a mononuclear structure accompanied by bqdca2- anion balancing valences. The intermolecular hydrogen bonds can link them to construct a three-dimensional supramolecular structure. The different structures of Complexes 1 and 2 illustrate the great influence of the N-heterocyclic auxiliary ligands on the self-assembly of coordination architectures. 2,2'- bipy and 4,4'-bipy ligands all act as terminal ligands. In addition, Complexes 1 and 2 exhibit the photoluminescent emission at 455 nm and 463 nm, and 455 nm and 465 nm in the solid state, respectively, which may be attributed to intraligand transitions. The redshifts of Complexes 1 and 2 may be due to the ligand-to-metal charge transfer, comparing to the H2bqdca ligand.. KEYWORDS :Crystal structure, Manganese complex, N-Heterocyclic ligand, Photoluminesce.

Novel yellowish-green single-phased spinel Mg1-xBaxAl2O4:Mn2+ phosphor(s) for color rendering white-light-emitting diodes.

For white light-rendering research activities, interpretation by using colored emitting materials is an alternative approach. But there are issues in designing the white color emitting materials. Particularly, differences in thermal and decay properties of discrete red, green, and blue emitting materials led to the quest for the search of a single-phased material, able to emit primary colors for white light generation. The current study is an effort to design a simple, single-phase, and cost-effective material with the tunable emission of primary colors by a series of Mg1-xBaxAl2O4:Mn2+ nanopowders. Doping of manganese ion (Mn2+) in the presence of the larger barium cation (Ba2+) at tetrahedral-sites of the spinel magnesium aluminate (MgAl2O4) structure led to the creation of antisite defects. Doped samples were found to have lower bandgaps compared with MgAl2O4, and hybridization of 3d-orbitals of Mn2+ with O(2p), Mg(2s)/Al(2s3p) was found to be responsible for narrowing the bandgap. The distribution of cations at various sites at random results in a variety of electronic transitions between the valance band and oxygen vacancies as well as electron traps produced the antisite defects. The suggested compositions might be used in white light applications since they have three emission bands with centers at 516 nm (green), 464 nm (blue) and 622 nm (red) at an excitation wavelength of 380 nm. A detailed discussion to analyze the effects of the larger cationic radius of Ba2+ on the lattice strain, unit cell parameters, and cell volumes using X-ray diffraction analysis is presented.

Stabilization of Li2MnO3 phase by Mg doping suppressing irreversible oxygen loss and Mn ions migration

Li-rich Mn-based oxide cathode material has attracted people’s attention in that their higher specific capacity, which is attributed to their unique biphasic structure. When the voltage is greater than 4.5V, the Li2MnO3 phase is activated to provide a high specific capacity. But during the cycling process, the Li2MnO3 phase is continuously activated. During this process, O2 will be released and transition metal (TM) ions will migrate, leading to structural phase transition, resulting in voltage decay and capacity loss. In this work, 2wt% Mg-doped Li1.18Mg0.02Mn0.54Co0.13Ni0.13O2 exhibits excellent electrochemical performance. After 100 cycles at 1C, the capacity retention rate is 87.83% By introducing Mg at the position of Li in the TM layer, a more stable Mg-O bond is introduced, in which the inert Mg is not involved in the redox reaction but is fixed in the TM layer. The Li2MnO3 phase is optimized by stabilizing the lattice oxygen to make the Li2MnO3 phase more stable, so as to suppress the irreversible oxygen loss and slow down the structural phase transition. Improved the issue of low initial Coulomb efficiency of materials, the voltage attenuation is alleviated, and the cycle stability is improved.

Optimization of energy storage performance in 0.8Na0.5Bi0.5TiO3-0.2Bi3.25La0.75Ti3O12 thin films via defect dipoles

Dielectric capacitors put forward higher requirements on the energy storage density, working stability and fatigue resistance of materials with the increasing shortage of energy. Herein, 0.8Na0.5Bi0.5TiO3-0.2Bi3.25La0.75Ti3O12-x%Mn (x = 0,2,4,6) thin film capacitors are designed to address above concern. The Mn ions inhibit the valence change of Ti ions and combine with oxygen vacancies to form defect dipoles, which improve breakdown strength and energy density of the films. As a result, high energy storage density of 92.7 J cm−3 and excellent efficiency of 70.2% are synchronously achieved for the 4% Mn-doped NBT-BLT film. Besides, outstanding stability of energy storage performance also exhibit over a wide range of temperature (25–200 °C) and cycle number (105). This result provides a novel strategy for the preparation of dielectric materials with high energy storage performance and high operational stability.

Synthesis, Structural Characterization, Reactivity and Bioactivity Studies of Some Binuclear Salen Type Schiff Base Complexes of Manganese(III)

Four new phenoxy bridged binuclear Salen type Schiff base complexes of manganese(III), [MnLX]2 with tetradentate Schiff base, H2L [H2L = N,N′-O-phenylene bis(salicylaldimine)] containing anionic co-ligands, X (X = benzoate, p-hydroxy benzoate, p-aminobenzoate, 3,5-dinitrobenzoate) have been synthesized from manganese(II) acetate, Schiff base (H2L) and the corresponding co-ligands in methanol medium. Schiff base ligand (H2L) was obtained in situ by condensation of salicylaldehyde and o-phenylenediamine in aqueous methanol. Elemental analyses, FT-IR, molar conductance, UV-visible spectroscopic studies and magnetic moment measurements at room temperature were used to characterize the binuclear Schiff base complexes. The IR spectra of [MnLX]2 (X = benzoate, p-hydroxy benzoate, p-aminobenzoate, 3,5-dinitrobenzoate) complexes showed the characteristic absorptions due to coordinated azomethine nitrogen and phenolic oxygen atoms of the Schiff base. In addition, IR spectra of the compounds also suggest coordination of the co-ligands namely benzoate, p-hydroxy benzoate, p-aminobenzoate, 3,5-dinitrobenzoate in the respective complexes. A consistent presence of a band at ca. 755 cm-1 in all the binuclear complexes arises due to (Mn-O-Mn) moiety originated from interactions of phenoxy oxygen and manganese atoms, resulted in dimeric structure of the compounds. The magnetic moment values ranging from 4.74-4.91 B.M. per manganese centre for the complexes suggest presence of Mn(III) ion in the complexes. The overall coordination geometry around the manganese centres is distorted octahedral. Redox behaviour of the synthesized complexes was ascertained from cyclic voltametric studies. The Schiff base complexes, [Mn(L)X]2 (X = p-aminobenzoate, 3,5-dinitrobenzoate) have demonstrated their catalytic potentials in oxidizing selective organic substrates namely cyclohexene and styrene by hydrogen peroxide as oxidant. The oxidized products were characterized as trans-cyclohexane 1,2-diol and styrene epoxide, respectively. Complex 4 demonstrated a considerable level of effectiveness against a wide variety of pathogenic microorganisms.

Wastewater Treatment Utilizing Industrial Waste Fly Ash as a Low-Cost Adsorbent for Heavy Metal Removal: Literature Review

Wastewater discharges from industrial processes typically include elevated concentrations of contaminants, which largely consist of potentially harmful chemicals such as heavy metals. These contaminants are characterized by their slow rate of decomposition. Hence, the removal of these metallic ions from effluents poses a challenge. Among different treatments, the adsorption approach has considerable potential due to its ability to effectively eliminate both soluble and insoluble pollutants from effluent, even at lower levels of concentration. Of various wastes, fly ash (FA) material has been the subject of attention because it is abundant, has favorable qualities, and contains a high percentage of minerals. This review investigates multiple facets, with a specific focus on the application of FA, an industrial byproduct, as an adsorbent in removing heavy metals. A comprehensive examination was conducted on a range of concerns pertaining to the pollution caused by metallic ions, including the underlying causes, levels of contamination, health implications of heavy metals, and removal methods. Multiple factors were found to affect the adsorption process. Of all the factors, the pH value considerably influences the elimination of heavy metals. An acidic pH range of 2.5–4.5 was found to be optimal for achieving the highest possible elimination of As(V), Cu(II), Hg(II), and Cr(VI). The latter elimination rate reached 89% at the optimal pH level. Most heavy metals’ adsorption isotherms conformed to the Langmuir or Freundlich models, while the pseudo-second-order kinetics provided a satisfactory match for their removal. Using a raw FA, adsorption capacities were achieved in the removal of metallic ions, Ni(II), Pb(II), and Cr(VI), that ranged from 14.0 to 23.9 mg g−1. Meanwhile, the FA-zeolite showed a remarkable capacity to adsorb ions Mn(II), Ni(II), Cd(II), Cu(II), and Pb(II), with values ranging from about 31 to 66 mg g−1. The cost analysis showed that the treatment of FA is economically advantageous and may result in significant cost reductions in comparison to commercial adsorbents. In summary, FA is an inexpensive waste material with potential for water treatment applications and several other purposes due to its excellent chemical and mineralogical composition.

Citric Acid as Multidentate Flexible Ligand for Multinuclear Late‐3 d‐Metal Complexes and Single‐Molecule Magnets

AbstractCitric acid (citH4) is a ubiquitous product in nature with an interesting chemistry owing to its three carboxy and one hydroxy groups, which can be deprotonated in a stepwise manner into six kinds of citrate anions involving two protonation isomers. Deprotonated citrates easily coordinate to late‐3d‐metal ions (Mn, Fe, Co, Ni, Cu, and Zn), affording complexes including mono‐, di‐, tri‐, tetra‐, hexa‐, hepta‐, octa‐, nona‐, and 21‐nuclear complexes with a variety of structures. Magnetic interactions between metal centers are mainly generated via superexchange through hydroxylate or carboxylate bridging, whereas weaker magnetic dipole interactions appear in the absence of superexchange interactions. In citrate complexes, both ferromagnetic and antiferromagnetic interactions have been found. Citrate has a great potential to serve as a bridge between spin quantum magnetism and green chemistry. In this review, the structures and magnetism of discrete citrate complexes of late‐3d‐metals, as well as their single‐molecule magnet properties are discussed.

Multi-color luminescent material with Mn2+/Mn4+ non-stoichiometric ratio doped octahedra and its anti-counterfeiting applications

Mn ions in different valence states can emit light of different colors in an octahedral coordination environment, which is conducive to the development of a single matrix with multi-color luminescence and applications in the field of anti-counterfeiting. The dual mode multi-color luminescent material CaSb2O6: Mn has been successfully synthesized using a single Mn source in the atmosphere. The CaSb2O6 matrix itself can also absorb 285 nm UV light, emit blue light, and show a long afterglow phenomenon. Both Mn4+ and Mn2+ ions will appear in the [SbO6] octahedra, whether the Mn source adopts MnCO3 or MnO2. The Mn4+ ion exhibits red emission upon UV excitation at 347 nm. The Mn2+ ion can emit a bright green light at 285 nm excitation while exhibiting a long afterglow phenomenon. In this study, the Mn2+ doped octahedron showed unique green emission and broadens the range of its photoluminescence (PL) wavelength. The performance of the material's long afterglow properties on the digital codes demonstrates its potential for dynamic anti-counterfeiting.

MnO2 doping enhances energy storage performances in lead-free BiFeO3-based ceramics

BiFeO3-based ferroelectric ceramics as promising candidates for energy storage devices have attracted a great deal of interest owing to the large ferroelectric polarization and high Curie temperature. However, the Bi volatilization induced oxygen vacancy and Fe2+/Fe3+ ionic hopping limit its energy storage performances (ESP). A charge compensated method by introducing multivalent oxide is proposed to inhibit the oxygen vacancy and Fe2+/Fe3+ ionic hopping, aiming to improve dielectric breakdown strength (BDS), polarization saturation and ESP. Here, we prepared a series of MnO2-modified Bi0.83Sm0.17Fe0.95Sc0.05O3-0.85BaTiO3-0.15Bi(Mg0.5Zr0.5)O3 [BSFS-BT-BMZ-x wt%MnO2] ceramics by traditional solid state sintering. It revealed that a large reversible energy storage density (Wrec) of ∼ 4.1 J/cm3 and a great efficiency (η) of ∼ 88% can be achieved at x = 2.1 ceramics. The improved ESP could be attributed mainly to the effective inhibition of Fe2+ by multi-fold valence states of Mn ions accompanying with the decreasing of oxygen vacancy and Fe3+/Fe2+ ionic hopping, leading to the refinement of grain size, and the enhancement of BDS and ferroelectric polarization. Moreover, the optimized ceramics exhibit the good frequency/thermal stability, excellent fatigue resistance and high powder density. These results demonstrate that a charge compensated method pays a route of improving ESP for dielectric ceramic capacitors.

Approaching the Curie temperature of ferromagnetic (Ga,Mn)P prepared by ion implantation and pulsed laser melting

This work aims to estimate the Curie temperature and critical exponents in the critical regime of III-V ferromagnetic semiconductor (FS) (Ga,Mn)P film using various methods, including Arrott and Kouvel-Fisher plots, as well as electrical transport measurements. The (Ga,Mn)P film was prepared by implanting Mn ions into an intrinsic (001) GaP wafer, followed by pulsed laser melting (PLM). The magnetic properties of the (Ga,Mn)P layer were systematically investigated. The study investigated the accuracy of four different methods in determining the critical behaviors for the magnetic properties close to TC. The results suggest that the critical exponents are similar to those of the mean-field model, as indicated by the modified Arrot plots and temperature dependent effective critical exponents. However, the accuracy of the temperature-dependent resistance Rxx(T) method and Kouvel-Fisher (K-F) analysis is limited due to the Gaussian distribution of Mn ions in the film.

4D-Printed Elution-Peak-Guided Dual-Responsive Monolithic Packing for the Solid-Phase Extraction of Metal Ions.

Four-dimensional printing (4DP) technologies are revolutionizing the fabrication of stimuli-responsive devices. To advance the analytical performance of conventional solid-phase extraction (SPE) devices using 4DP technology, in this study, we employed N-isopropylacrylamide (NIPAM)-incorporated photocurable resins and digital light processing three-dimensional printing to fabricate an SPE column with a [H+]/temperature dual-responsive monolithic packing stacked as interlacing cuboids to extract Mn, Co, Ni, Cu, Zn, Cd, and Pb ions. When these metal ions were eluted using 0.5% HNO3 solution as the eluent at a temperature below the lower critical solution temperature of polyNIPAM, the monolithic packing swelled owing to its hydrophilic/hydrophobic transition and electrostatic repulsion among the protonated units of polyNIPAM. These effects resulted in smaller interstitial volumes among these interlacing cuboids and improvements in the elution peak profiles of the metal ions, which, in turn, demonstrated the reduced method detection limits (MDLs; range, 0.2-7.2 ng L-1) during analysis using inductively coupled plasma mass spectrometry. We studied the effects of optimizing the elution peak profiles of the metal ions on the analytical performance of this method and validated its reliability and applicability by analyzing the metal ions in reference materials (CASS-4, SLRS-5, 1643f, and Seronorm Trace Elements Urine L-2) and performing spike analyses of seawater, groundwater, river water, and human urine samples. Our results suggest that this 4D-printed elution-peak-guided dual-responsive monolithic packing enables lower MDLs when packed in an SPE column to facilitate the analyses of the metal ions in complex real samples.

Synthesis, crystal structure, DFT calculations, and Hirshfeld surface analysis of a chlorido-bridged 1D manganese(II) coordination polymer

Abstract A novel 1D Mn(II) coordination polymer, namely, [Mn3(bpz)2(MeCN)2Cl6] n (1) was synthesized by a solvothermal method based on bpz and MnCl2, where bpz is di(1H-pyrazol-1-yl)methane. The X-ray diffraction data show that the crystal structure of complex 1 is a one-dimensional polymer with two different coordination modes of the Mn(II) ions. The structure was modelled with Density Functional Theory (DFT) calculations and the intermolecular interactions were analyzed using the Hirshfeld surface method.

Unlocking Precision Docking for Metalloproteins.

Metalloproteins play a fundamental role in molecular biology, contributing to various biological processes. However, the discovery of high-affinity ligands targeting metalloproteins has been delayed due, in part, to a lack of suitable tools and data. Molecular docking, a widely used technique for virtual screening of small-molecule ligand interactions with proteins, often faces challenges when applied to metalloproteins due to the particular nature of the ligand metal bond. To address these limitations associated with docking metalloproteins, we introduce a knowledge-driven docking approach known as "metalloprotein bias docking" (MBD), which extends the AutoDock Bias technique. We assembled a comprehensive data set of metalloprotein-ligand complexes from 15 different metalloprotein families, encompassing Ca, Co, Fe, Mg, Mn, and Zn metal ions. Subsequently, we conducted a performance analysis of our MBD method and compared it to the conventional docking (CD) program AutoDock4, applied to various metalloprotein targets within our data set. Our results demonstrate that MBD outperforms CD, significantly enhancing accuracy, selectivity, and precision in ligand pose prediction. Additionally, we observed a positive correlation between our predicted ligand free energies and the corresponding experimental values. These findings underscore the potential of MBD as a valuable tool for the effective exploration of metalloprotein-ligand interactions.