Ionic Size Difference Research Articles

α-D NUCLEOSIDE BASED SELF-HEALING SUPRAMOLECULAR HYDROGELS DERIVED FROM THE α-D ANOMERS OF 2'-DEOXYGUANOSINE AND FLUORESCENT 8-AZAPURINE 2'-DEOXYRIBOFURANOSIDES.

Self-assembly of α-D nucleosides to supramolecular hydrogels is described in detail. Hydrogel formation was studied on α-D 2'-deoxyguanosine (α-dG), and the fluorescent 8-azapurine α-D nucleosides 2-amino-8-aza-2'-deoxyadenosine (α-2-NH2-z8Ad) and 8-aza-2'-deoxyisoguanosine (α-z8iGd). These compounds were prepared from α-D 8-aza-2'-deoxyguanosine by an activation/amination protocol followed by deamination. Protonation and deprotonation pKa values of monomeric nucleosides were determined. Fluorescence measurements displayed the pH-dependent fluorescence intensity of α-D 8-azapurine nucleosides. α-dG and α-z8iGd self-assemble to gels that are selective for K+-ions. The α-dG gel is transparent and the α-z8iGd gel shows fluorescence. α-2-NH2-z8Ad forms fluorescent gels in the presence of alkali metal ions of different size. SEM images exposed a large condensed and flat structure for the α-dG gel, whereas the α-2-NH2-z8Ad gel consists of flakes that are connected to bundles. A porous structure generated by helical cylindric fibers was found for the α-z8iGd gel. All α-D hydrogels showed long-term lifetime stability. The α-z8iGd hydrogel in KCl solution has the highest Tgel value. The minimum gelation concentration of the hydrogels was 0.3-0.5 mg nucleoside/100 µL alkali ion solution. In periodical step-strain experiments, the hydrogels of α-dG and α-2-NH2-z8Adandα-z8iGddisplayed thixotropy. Based on their self-healing and shear-thinning properties thehydrogels are injectable.

Electrochemical Formation of Ionic Porous Organic Polymers Based on Viologen for Electrochromic Applications.

The systematic study of two ionic porous organic polymers (iPOPs) based on viologens and their first applications in the electrochromic field are reported. The viologen-based iPOPs are synthesized by electrochemical polymerization with cyano groups, providing a simple and controllable method for iPOPs that solves the film preparation problems common to viologens. After the characterization of these iPOPs, a detailed study of their electrochromic properties is conducted. The iPOP films based on viologens structure exhibit excellent electrochromic properties. In addition, the resulting iPOP films show high sensitivity to electrolyte ions of different sizes in the redox process. Electrochemical and electrochromic data of the iPOPs explain this phenomenon in detail. These results demonstrate that iPOPs of this type are ideal candidates as electrochromic materials due to their inherent porous structures and ion-rich properties.

Interface engineering for facile switching of bulk-strong polarization in Si-compatible vertical superlattices

Ferroelectric thin films incorporating different compositional layers have emerged as a promising approach for enhancing properties and performance of electronic devices. In recent years, superlattices utilizing various interactions between their constituent layers have been used to reveal unusual properties, such as improper ferroelectricity, charged domain walls, and negative capacitance in conventional ferroelectrics. Herein, we report a symmetry scheme based on the interface engineering in which the inherent cell-doubling symmetry allowed atomic distortions (phonons) in any vertically aligned superlattice activate novel interface couplings among atomic distortions of different symmetries and fundamentally improve the ferroelectric properties. In a materialized case, the ionic size difference between Hf4+ and Ce4+ in the HfO2/CeO2 (HCO) ferroelectric/paraelectric superlattice leads to these couplings. These couplings mitigate the phase boundary between polar and non-polar phases, and facilitate polarization switching with a remarkably low coercive field (Ec\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${E}_{c}$$\\end{document}) while preserving the original magnitude of the bulk HfO2 polarization and its scale-free ferroelectric characteristics. We show that the cell-doubled distortions present in any vertical superlattice have unique implications for designing low-voltage ferroelectric switching while retaining bulk-strong charge storing capacities in Si-compatible memory candidates.

Engineering soft nanochannels in isoporous block copolymer nanofiltration membranes for ion separation

Membranes with high ion selectivity are important for the separation of ionic species at the Ångstrom scale. Here, we report on positively charged isoporous block copolymer (BCP) nanofiltration membranes with designed soft nanochannels. The isoporous BCP membranes were obtained from the combination of BCP self-assembly and non-solvent-induced phase separation. The well-defined soft nanochannels were engineered via a versatile post-modification approach using a combination of di- and monofunctional alkyl halide. The water permeance and effective pore size of the membranes were fine-tuned within the nanofiltration regime. Both single- and binary-salt retentions demonstrate the capability of separating mono-/divalent cations based on the ionic size difference in Ångstrom scale, charge, and energy to strip away the hydration shells. Especially the real selectivity from the binary-salt systems is > 2 times higher than the selectivity obtained from the single-salt systems, e.g., the real selectivity of K+/Mg2+ is up to 15 for the 10 mM binary-salt mixture with a mole ratio of 1:1. Such enhancement arises from the competition effect regarding energy barrier, size of hydrated ion, and diffusivity. The Na+/Mg2+ binary-salt system with simulating the salt concentration ratio of the seawater illustrates the potential of the resulting membranes to recover the valuable ionic species from water, e.g. Mg, classified as a “critical raw material” in Europe. The Na+/Mg2+ real selectivity is up to 42 with a permeance of 15 L m−2 h−1 MPa−1 at a salt concentration of 10 mM.

Solvation of Nanoions in Aqueous Solutions.

In recent years it has been increasingly recognized that different classes of large ions with multiple valency have effects conceptually similar to weakly solvated ions in the Hofmeister series, also labeled by the term chaotropic. The term "superchaotropic effect" has been coined because these effects are much more strongly pronounced for nanometer-sized ions, whose adsorption properties often resemble typical surfactants. Despite this growing interest in these nanometer-sized ions, a simple conceptual extension of the Hofmeister series toward nanoions has not been achieved because an extrapolation of the one-dimensional surface charge density scale does not lead to the superchaotropic regime. In this work, we discuss a generic model that is broadly applicable to ions of nearly spherical shape and thus includes polyoxometalates and boron clusters. We present a qualitative classification scheme in which the ion size appears as a second dimension. Ions of different sizes but the same charge density differ in their bulk solvation free energy. As the ions grow bigger at constant surface charge density, they become more stable in solution, but the adsorption behavior is still governed by the surface charge density. A detailed molecular dynamics simulation study of large ions that is based on a shifted Lennard-Jones potential is presented that supports the presented classification scheme.

Defects mediated weak ferromagnetism in Zn1−yCyO (0.00 ≤ y ≤ 0.10) nanorods semiconductors for spintronics applications

A series of carbon-doped ZnO [Zn1−yCyO (0.00 ≤ y ≤ 0.10)] nanorods were synthesized using a cost-effective low-temperature (85 °C) dip coating technique. X-ray diffractometer scans of the samples revealed the hexagonal structure of the C-doped ZnO samples, except for y = 0.10. XRD analysis confirmed a decrease in the unit cell volume after doping C into the ZnO matrix, likely due to the incorporation of carbon at oxygen sites (CO defects) resulting from ionic size differences. The morphological analysis confirmed the presence of hexagonal-shaped nanorods. X-ray photoelectron spectroscopy identified C–Zn–C bonding, i.e., CO defects, Zn–O–C bond formation, O–C–O bonding, oxygen vacancies, and sp2-bonded carbon in the C-doped ZnO structure with different compositions. We analyzed the deconvoluted PL visible broadband emission through fitted Gaussian peaks to estimate various defects for electron transition within the bandgap. Raman spectroscopy confirmed the vibrational modes of each constituent. We observed a stronger room-temperature ferromagnetic nature in the y = 0.02 composition with a magnetization of 0.0018 emu/cc, corresponding to the highest CO defects concentration and the lowest measured bandgap (3.00 eV) compared to other samples. Partial density of states analysis demonstrated that magnetism from carbon is dominant due to its p-orbitals. We anticipate that if carbon substitutes oxygen sites in the ZnO structure, the C-2p orbitals become localized and create two holes at each site, leading to enhanced p–p type interactions and strong spin interactions between carbon atoms and carriers. This phenomenon can stabilize the long-range order of room-temperature ferromagnetism properties for spintronic applications.

Effects of lattice distortion and amount of d electrons on the pressure-driven structural phase transition in ZnO: A comparative study of V-, Mn-, and Co-doped ZnO

The pressure-driven phase transition from fourfold würtzite (B4) to sixfold coordinated rock salt (B1) structure in ZnO, in particular in transition metal (TM) doped ones, exhibited very scattered results and remained as an outstanding issue. The in situ angle-dispersive x-ray diffraction revealed that TM doping can result in significant reduction on the onset pressure at which the pressure-driven B4-to-B1 phase transition starts to emerge, albeit the transition path appeared to be very much dependent on the doping transition metal element. Systematic comparisons on a series of V-, Mn-, and Co-doped ZnO materials indicated that, in addition to ionic sized difference-induced lattice distortion, the amount of the 3d electrons carried by the doped TM atom may also play a prominent role in the underlying mechanism of the pressure-driven phase transition. Specifically, the existence of 3d electrons may have resulted in increased screening of the Coulomb forces between the cations at increasing pressure, leading to significant softening of the c44 and c66 elastic constants, which, in turn, lowers the onset pressure in triggering the B4-to-B1 phase transition in ZnO. Our results also indicate that the initial lattice distortion induced by the ionic size difference may change the landscape of energy barrier and alter the phase transition path.

Superhigh and Robust Ion Selectivity in Membranes Assembled with Monolayer Clay Nanosheets.

It is crucial to control the ion transport in membranes for various technological applications such as energy storage and conversion. The emerging functional two-dimensional (2D) nanosheets such as graphene oxide and MXenes show great potential for constructing ordered nanochannels, but the assembled membranes suffer from low ion selectivity and stability. Here a class of robust charge-selective membranes with superhigh cation/anion selectivity, which are assembled with monolayer nanosheets of cationic/anionic clays that inherently have permanent and uniform charges on each layer is reported. The transport number of cations/anions of cationic vermiculite nanosheet membranes (VNMs)/anionic Co-Al layered double hydroxide (CoAl-LDH) nanosheet membranes is over 0.90 in different NaCl concentration gradients, outperforming all the reported ion-selective membranes. Importantly, this excellent ion selectivity can persist at high-concentration salt solutions, under acidic and alkaline conditions, and for a wide range of ions of different sizes and charges. By coupling a pair of cation-selective vermiculite membrane and anion-selective CoAl-LDH membrane, a reverse electrodialysis device which shows an output power density of 0.7W m-2 and energy conversion efficiency of 45.5% is constructed. This work provides a new strategy to rationally design high-performance ion-selective membranes by using 2D nanosheets with inherent surface charges for controllable ion-transport applications.

Cellulose Nanocrystals (CNCs) and Cellulose Nanofibers (CNFs) as Adsorbents of Heavy Metal Ions

The isolation of nanocellulose has been extensively investigated due to the growing demand for sustainable green materials. Cellulose nanocrystals (CNCs) and cellulose nanofibers (CNFs), which have the same chemical composition but have different morphology, particle size, crystallinity, and other properties depending on the precursor and the synthesis method used. In comparison, CNC particles have a short rod-like shape and have smaller particle dimensions when compared to CNF particles in the form of fibers. CNC synthesis was carried out chemically (hydrolysis method), and CNF synthesis was carried out mechanically (homogenization, ball milling, and grinding), and both can be modified because they have a large surface area and are rich in hydroxyl groups. Modifications were made to increase the adsorption ability of heavy metal ions. The Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric (TG), and dynamic light scattering (DLS) can reveal the characteristics and morphology of CNCs and CNFs. The success and effectiveness of the heavy metal adsorption process are influenced by a few factors. These factors include adsorbent chemical structure changes, adsorbent surface area, the availability of active sites on the adsorbent’s surface, adsorption constants, heavy metal ionic size differences, pH, temperature, adsorbent dosage, and contact time during the adsorption process. In this review, we will discuss the characteristics of CNCs and CNFs synthesized from various precursors and methods, the modification methods, and the application of CNCs and CNFs as heavy metal ion adsorbents, which includes suitable isotherm and kinetics models and the effect of pH on the selectivity of various types of heavy metal ions.

Effect of High-Anisotropic Co2+ Substitution for Ni2+ on the Structural, Magnetic, and Magnetostrictive Properties of NiFe2O4: Implications for Sensor Applications.

This work reports on the effect of substituting a low-anisotropic and low-magnetic cation (Ni2+, 2μB) by a high-anisotropic and high-magnetic cation (Co2+, 3μB) on the crystal structure, phase, microstructure, magnetic properties, and magnetostrictive properties of NiFe2O4 (NFO). Co-substituted NFO (Ni1-xCoxFe2O4, NCFO, 0 ≤ x ≤ 1) nanomaterials were synthesized using glycine-nitrate autocombustion followed by postsynthesis annealing at 1200 °C. The X-ray diffraction measurements coupled with Rietveld refinement analyses indicate the significant effect of Co-substitution for Ni, where the lattice constant (a) exhibits a functional dependence on composition (x). The a-value increases from 8.3268 to 8.3751 Å (±0.0002 Å) with increasing the "x" value from 0 to 1 in NCFO. The a-x functional dependence is derived from the ionic-size difference between Co2+ and Ni2+, which also induces grain agglomeration, as evidenced in electron microscopy imaging. The chemical bonding of NCFO, as probed by Raman spectroscopy, reveals that Co(x)-substitution induced a red shift of the T2g(2) and A1g(1) modes, and it is attributed to the changes in the metal-oxygen bond length in the octahedral and tetrahedral sites in NCFO. X-ray photoelectron spectroscopy confirms the presence of Co2+, Ni2+, and Fe3+ chemical states in addition to the cation distribution upon Co-substitution in NFO. Chemical homogeneity and uniform distribution of Co, Ni, Fe, and O are confirmed by EDS. The magnetic parameters, saturation magnetization (MS), remnant magnetization (Mr), coercivity (HC), and anisotropy constant (K1) increased with increasing Co-content "x" in NCFO. The magnetostriction (λ) also follows a similar behavior and almost linearly varies from -33 ppm (x = 0) to -227 ppm (x = 1), which is primarily due to the high magnetocrystalline anisotropy contribution from Co2+ ions at the octahedral sites. The magnetic and magnetostriction measurements and analyses indicate the potential of NCFO for torque sensor applications. Efforts to optimize materials for sensor applications indicate that, among all of the NCFO materials, Co-substitution with x = 0.5 demonstrates high strain sensitivity (-2.3 × 10-9 m/A), which is nearly 2.5 times higher than that obtained for their intrinsic counterparts, namely, NiFe2O4 (x = 0) and CoFe2O4 (x = 1).

Magnetic field effects on the quantum spin liquid behaviors of NaYbS2

Spin-orbit coupling is an important ingredient to regulate the many-body physics, especially for many spin liquid candidate materials such as rare-earth magnets and Kitaev materials. The rare-earth chalcogenides (Ch = O, S, Se) is a congenital frustrating system to exhibit the intrinsic landmark of spin liquid by eliminating both the site disorders between and ions with the big ionic size difference and the Dzyaloshinskii-Moriya interaction with the perfect triangular lattice of the ions. The temperature versus magnetic-field phase diagram is established by the magnetization, specific heat, and neutron-scattering measurements. Notably, the neutron diffraction spectra and the magnetization curve might provide microscopic evidence for a series of spin configuration for in-plane fields, which include the disordered spin liquid state, 120° antiferromagnet, and one-half magnetization state. Furthermore, the ground state is suggested to be a gapless spin liquid from inelastic neutron scattering, and the magnetic field adjusts the spin orbit coupling. Therefore, the strong spin-orbit coupling in the frustrated quantum magnet substantially enriches low-energy spin physics. This rare-earth family could offer a good platform for exploring the quantum spin liquid ground state and quantum magnetic transitions.

Tunable physical properties of Ba doped BiFeO3 multiferroic nanoceramics for capacitor and memory storage devices

Recently, perovskite structured bismuth ferrite (BiFeO3) multiferroic material has been widely studied owing to its potential applications in various devices like spintronics, energy storage, sensors and photovoltaic devices. Interestingly, the presence of two or greater stable polarization states in this material and the ease of polarization switching by way of electric field exhibited high energy storage densities, making it appropriate for information storage devices. However, the large leakage current and weak magnetism associated with the material at 300 K hinders its usage in practical applications. It is noticed that the substitution of Bi by alkaline earth elements (Mg2+, Sr2+, Ca2+) could significantly enhance the physical properties of BiFeO3 ceramics. In this work, Bi1-xBaxFeO3 (x = 0.05–0.2 mol %) nanoceramics were prepared by adopting low temperature molten salt synthesis route using NaCl as flux. The X-ray diffraction studies revealed the formation of distorted perovskite structure of BiFeO3 phase in all the range of compositions studied. The FESEM analysis demonstrated the presence of nanosized grains of BiFeO3 and the average grain size decreases with an increase in Ba doping content. The X-ray photoelectron spectra revealed the existence of different valence states of the elements present in BiFeO3 nanoceramics. It is interesting to observe that the dielectric properties of Ba doped BiFeO3 ceramics are superior to the undoped samples, especially at the higher frequency range due to the ionic size difference of barium and bismuth ions in the crystal lattice of BiFeO3, which would significantly influence the energy storage capacity in the non-volatile random access memory storage devices.

Effects of Sr dopant and electric field poling on structural, thermal and dielectric properties of Ba1-x Sr x TiO3 ceramics (x = 0, 0.3, 0.4 and 0.45)

ABSTRACT The behavior of Ba1-x Sr x TiO3 ceramics (x = 0, 0.3, 0.4 and 0.45) in both unpoled and poled states was studied using XRD, SEM, DSC and dielectric methods. The ceramics exhibit pure perovskite structure with tetragonal symmetry for x = 0, 0.3 and 0.4 and pseudocubic for x = 0.45. It was found that the substitution of SrTiO3 to BaTiO3 significantly influences the properties under investigation, leading to a shift of phase transitions and weakness of the dielectric and ferroelectric properties. This suggests that the effects are mainly due to the differences in ionic size between dopant and host ions and to the more covalent nature of the A–O bond following Sr2+ addition and that the former effect is predominant. It was shown that prior electric field poling decreases the disorder introduced by Sr modification through reinforced domains/polar regions ordering.

Tailoring the critical temperature of Ca/K-1144 superconductors: the effect of aliovalent substitution on tetragonality

Among the iron-based superconductors, the so-called 1144 family has, in recent years, attracted significant interest due to its stoichiometric nature, with materials robust towards chemical inhomogeneities and characterized by a well-defined critical temperature. The most studied 1144 compounds are characterized by the A1AE1Fe4As4 chemical composition, where A and AE constitute an appropriate combination of alkaline and alkaline-earth metals, respectively. The 1144 structure is in fact formed only when the A and AE elements respect specific requirements in terms of relative size and parent compound structure. The stoichiometric aspect, one of their strong points, has represented, however, up to today a restriction, limiting the conceptualization of 1144 structures to quaternary compounds. In this work, we demonstrate that to obtain the 1144 crystalline phase it may be sufficient to maintain a 1:1 ratio between ions of different size that intercalate the Fe-As planes, and that in selected conditions an opportunely tailored cation substitution is possible. Using a simple mechanochemically assisted synthesis route 1144 compounds where Ca is substituted by Na, K by Ba, and both simultaneously, are obtained. We demonstrate that the critical temperature of doped compounds is not simply related to the substitution amount or to the resulting Fe valence. We show that the superconducting transition is in fact linked to the structural distortion induced by the chemical composition variation: by tailoring the chemical composition we obtain doubly substituted samples—with substitution levels up to 20%—characterized by a tetragonality ratio c/a similar to the pristine compound and critical temperatures of approximately 34 K.

Influence of anions on behavior of cationic polyelectrolyte poly(diallyldimethylammonium chloride) and its copolymer in aqueous solutions

Physicochemical properties of polyelectrolyte poly(diallyldimethylammonium chloride) (poly(DADMAC)) and the copolymer of DADMAC with zwitterionic monomer 2-(diallyl(methyl)ammonio) acetate (DAMA) containing equimolar amounts of DADMAC and DAMA units were studied in aqueous solutions in the presence of ions of different sizes (Cl, Br, and I). The solutions were investigated by viscometry, analytical ultracentrifugation (AUC), nuclear magnetic resonance (NMR), dynamic (DLS) and static (SLS) light scattering. It was shown that an increase in the halogen ion size facilitated condensation of bulky anions on the polyelectrolyte chain. Ultimately, this resulted in deterioration of the solvent quality and collapse of the poly(DADMAC) coil in aqueous solution in the presence of iodine ions. Introducing DAMA units into the polymer chain exerted a positive effect on solubility of the resulting copolymer (poly(DADMAC-co-DAMA)) in aqueous solutions containing iodine ions.

Grain boundary effect on the resistive switching characteristics of SrTi1-xFexO3 directly patterned via photochemical organic-metal deposition

Ionic memristors are a promising candidate for use in next-generation non-volatile memory and neuromorphic computing systems. To ensure that ionic memristors exhibit appropriate resistive switching characteristics, the precise control of oxygen vacancies is required. The ABO3 structure can accommodate various ions of different sizes in the A and B sites, and this flexibility allows for the accurate design of materials and for the oxygen defects to be controlled. This study systematically investigated the effect of Fe doping on the resistive switching characteristics of SrTi1-xFexO3 (x = 0, 0.05, 0.10, and 0.15) films fabricated using photochemical organic–metal deposition. The Fe dopant created oxygen vacancies via Schottky defects, especially at grain boundaries, with the space charge at the grain boundaries inhibiting grain growth and increased the number of defective grain boundaries. Since the defective grain boundary acts as a conducting path filament, an increase in the Fe content reduced the initial resistance of the films, and SrTi1-xFexO3 film optimized Fe content exhibited complementary resistive switching behavior without the need for a forming process. The Fe doping effects on the crystal and electronic structure were also analyzed using X-ray diffraction, valence band, O 1s X-ray absorption, and Raman spectra.

Machine learning-enabled prediction of chemical durability of A2B2O7 pyrochlore and fluorite

Pyrochlore-structure type and its derivative in a general formula A2B2O7 (A = rare earth elements and actinides; B = Ti, Sn, Zr, Hf, Pb, Si, etc.) display excellent structural flexibility and rich crystal chemistry as promising nuclear waste form materials capable of immobilizing actinides and fission products. It is essential to understand these materials’ chemical durability and element release of radionuclides in order to evaluate their performance in near-field environment. However, it is a formidable grand technological challenge to experimentally perform durability testing across hundreds of thousands of possibilities resulting from their extreme compositional complexities due to cation substitutions at both A and B-sites. In this work, we demonstrate a machine learning approach to determine the key materials parameters and structural characteristics governing the leaching behaviors from a small set of selected compositions as model systems, enabling a science-based prediction of their chemical durability that can be extended to a wide range of chemical compositions. The combination of four key structural characteristics and materials parameters, including ionic radius size difference rA-B, ionic potential difference EB-A, electronegativity difference χB-A, and lattice parameter α, creates features an optimized prediction of the chemical durability. Two machine learning models, linear regression and Kernel ridge regression models, are trained on the randomly-split training dataset derived from the experimentally-determined elemental release rates, and subsequently tested on the testing dataset. The predicted leaching rates from both machine learning models show an excellent agreement with the experimental data, demonstrating the feasibility of rapidly evaluating the material properties of new compositions. These results highlight the immense potential of synergizing informatics through machine learning-based models and well-controlled experiments of selected model systems to accelerate materials design and discovery with optimized compositions and performance of promising materials for effective nuclear waste management.

H2pyhox - Octadentate Bis(pyridyloxine).

A new versatile chelating ligand for intermediate size and softness radiometals [64Cu]Cu2+ and [111In]In3+, H2pyhox, was synthesized by introducing pyridine as a new donor moiety to complement 8-hydroxyquinoline on an ethylenediamine backbone. The combination of pyridine and oxine as donor sets was explored through structural analysis, and crystals of the three metal complexes with Cu2+, La3+, and In3+ demonstrate how the ligand adapts to accommodate metal ions of different sizes and charge. Exhaustive in-batch UV solution studies characterized the protonation constants of the free ligand as well as the formation constants of the metal complexes with Cu2+, In3+, and La3+. Preliminary concentration-dependent radiolabeling studies with [111In]In3+ and [64Cu]Cu2+ show the robustness of H2pyhox to successfully coordinate both radiometals under mild conditions (<15 min, room temperature, pH 6). H2pyhox is the first oxinate ligand to successfully radiolabel [225Ac]Ac3+, albeit only at high concentrations (0.1-1 mM) with gentle heating to 37 °C. Whole serum, protein, and ligand challenge assays further demonstrate the kinetic inertness of the [111In]In3+ and [64Cu]Cu2+ radiometal-ligand complexes, confirming H2pyhox to be a promising versatile radiopharmaceutical chelator.

Influence of tungsten substitution on structure, optical, vibrational and magnetic properties of hydrothermally prepared NiFe2O4

A series of single-phase NiFe2O4 powder with different W-doping (0.0 ≤ x ≤ 0.2) has been synthesized using hydrothermal processing route. The change in lattice parameter and magnetic properties with W-doping was correlated with the change in the occupancies of tetrahedral and octahedral sites with Fe(III) ions resulting from competence between Fe(III) and W(VI) ions. The total magnetic moment increases and the lattice parameter decreases with W-doping up to x = 0.1 (Ms = 49.0 emu/g). However, the lattice parameter increases and the total magnetic moment dramatically decreases to 27.0 emu/g with x = 0.2 doping. The microstrain (e) increases with increasing the level of W(VI) ion substitution. The e of pure NiFe2O4 sample is 3.5 × 10–3 and it increases to 9.7 × 10–3 for NiW0.2Fe1.6O4 (x = 0.2). The increase in e is due to the difference in ionic sizes of W(VI) an Fe(III) and the formation of cation vacancies. The latter is formed because W(VI) ion substituted for two Fe(III) ions, so that the produced ferrite will have the general formula; NiWxFe2-2xO4. The band gap slightly increases with increasing the increasing the level of W-doping.

Selectivity of ion transport in narrow carbon nanotubes depends on the driving force due to drag or drive nature of their active hydration shells.

Molecular dynamics simulations have revealed the important roles of hydration shells of ions transported through ultrathin carbon nanotubes (CNTs). In particular, ions driven by electric fields tend to drag their hydration shells behind them, while for ions transported by pressure, their hydration shells can actively drive them. Given the different binding strengths of hydration shells to ions of different sizes, these active roles of hydration shells affect the relative entry rates and driving speeds of ions in CNTs.