Theoretical design of alkaline earthides M+(36 adz) Be- (M+ = V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) with excellent nonlinear optical response and ultraviolet transparency.

A novel series of alkaline earthides containing eight complexes based upon 36adz complexant are designed by placing carefully transition metals (V-Zn) on inner side and alkaline earth metal outer side of the complexant i.e., M+(36adz) Be- (M+ = V, Cr, Mn, Fe, Co, Ni, Cu and Zn). All the designed compounds are electronically and thermodynamically stable as evaluated by their interaction energy and vertical ionization potential respectively. Moreover, the true nature of alkaline earthides is verified through NBOs and FMO study, showing negative charge and excess electrons on alkaline earth metal respectively. Furthermore, true alkaline earthides characteristics are evaluated graphically by spectra of partial density state (PDOS). The energy gap (HOMO -LUMO gap) is very small (ranging 2.95 eV-1.89 eV), when it is compared with pure cage 36adz HOMO-LUMO gap i.e., 8.50 eV. All the complexes show a very small value of transition energy ranging from 1.68eV to 0.89eV. Also, these possess higher hyper polarizability values up to 2.8 x 105au (for Co+(36adz) Be-). Furthermore, an increase in hyper polarizability was observed by applying external electric field on complexes. The remarkable increase of 100fold in hyper polarizability of Zn+(36adz) Be- complex is determined after application of external electric field i.e., from 1.7 x 104 au to 1.7 x 106 au when complex is subjected to external electric field of 0.001 au strength. So, when external electric field is applied on complexes it enhances the charge transfer, polarizability and hyper polarizability of complexes and proves to be effective for designing of true alkaline earthides with remarkable NLO response.

Navigating through the coordination preferences of heavy alkaline earth metals: Laying the foundations for 223Ra- and 131/135mBa-based targeted alpha therapy and theranostics of cancer.

The clinical success of [223Ra]RaCl2 (Xofigo®) for the palliative treatment of bone metastases in patients with prostate cancer has highlighted the therapeutic potential of α-particle emission. Expanding the applicability of radium-223 in Targeted Alpha Therapy of non-osseous tumors is followed up with significant interest, as it holds the potential to unveil novel treatment options in the comprehensive management of cancer. Moreover, the use of barium radionuclides, like barium-131 and -135m, is still unfamiliar in nuclear medicine applications, although they can be considered as radium-223 surrogates for imaging purposes. Enabling these applications requires the establishment of chelators able to form stable complexes with radium and barium radionuclides. Until now, only a limited number of ligands have been suggested and these molecules have been primarily inspired by existing structures known for their ability to complex large metal cations. However, a systematic inspection of chelators specifically tailored to Ra2+ and Ba2+ has yet to be conducted. This work delves into a comprehensive investigation of a series of small organic ligands, aiming to unveil the coordination preferences of both radium-223 and barium-131/135m. Electronic binding energies of both metal cations to each ligand were theoretically computed via Density Functional Theory calculations (COSMO-ZORA-PBE-D3/TZ2P), while thermodynamic stability constants were experimentally determined for Ba2+-ligand complexes by potentiometry, NMR and UV-Vis spectroscopies. The outcomes revealed malonate, 2-hydroxypyridine 1-oxide and picolinate as the most favorable building blocks to design multidentate chelators. These findings serve as foundation guidelines, propelling the development of cutting-edge radium-223- and barium-131/135m-based radiopharmaceuticals for Targeted Alpha Therapy and theranostics of cancer.

Structural insight and in silico prediction of the pharmacokinetic parameters and toxicity of alkaline earth metal compounds strontium and barium with the non-steroidal anti-inflammatory drug nimesulide.

In the crystals of alkaline earth metal compounds strontium and barium with the non-steroidal anti-inflammatory drug nimesulide, the strontium cation is nine-coordinated with a distorted tricapped trigonal prismatic geometry TCTPR-9, whereas the ten-coordinated barium ion exhibits a distorted tetracapped trigonal prismatic geometry TCTPR-10.

The unexplored role of alkali and alkaline earth elements (ALAEs) on the structure, processing, and biological effects of bioactive glasses.

Bioactive glass has been employed in several medical applications since its inception in 1969. The compositions of these materials have been investigated extensively with emphasis on glass network formers, therapeutic transition metals, and glass network modifiers. Through these experiments, several commercial and experimental compositions have been developed with varying chemical durability, induced physiological responses, and hydroxyapatite forming abilities. In many of these studies, the concentrations of each alkali and alkaline earth element have been altered to monitor changes in structure and biological response. This review aims to discuss the impact of each alkali and alkaline earth element on the structure, processing, and biological effects of bioactive glass. We explore critical questions regarding these elements from both a glass science and biological perspective. Should elements with little biological impact be included? Are alkali free bioactive glasses more promising for greater biological responses? Does this mixed alkali effect show increased degradation rates and should it be employed for optimized dissolution? Each of these questions along with others are evaluated comprehensively and discussed in the final section where guidance for compositional design is provided.

Organic small-molecule fluorescent probe-based detection for alkali and alkaline earth metal ions in biological systems.

Metal ions widely exist in biological systems and participate in many vital biochemical processes. Monitoring and analyzing metal ions in biological systems can help reveal physiological processes and understand disease causes. There are various detection methods for metal ions, among which organic small-molecule fluorescent probes have significant advantages, such as high fluorescence quantum yield, easy modification, good biocompatibility, high sensitivity, and fast real-time detection. This review presents recent studies on fluorescent probes for alkali and alkaline earth metal ions (including Na+, K+, Ca2+, and Mg2+) in biological systems. All the candidates are organized according to their structures, and the sensing mechanisms of fluorescent probes are also highly taken into account. Finally, the challenges, trends and prospects of fluorescent probes in metal ion detection are discussed. We hope that this review can provide guidance for the development of fluorescent molecular probe-based alkali and alkaline earth metal ion detection methods in the future.

A comprehensive study on the electronic structure, dielectric and optical properties of alkali-earth metals and transition metal hydroxides M(OH)2.

In the present work, the physical properties of alkali-earth metal and transition metal hydroxides are comprehensively investigated using the density functional theory. Here, the alkali-earth metals Ca, Mg, and transition metals Cd, Zn are considered from the II-A and II-B groups in the periodic table of elements. The first principle electronic structure calculations show that these bulk hydroxide materials are direct band gap material. Ca(OH)2 and Mg(OH)2 exhibit an insulating behavior with a very large band gap. However, Cd(OH)2 and Zn(OH)2 are found to be wide band gap semiconductors. The dielectric and optical studies reveal that these materials have a high degree of anisotropy. Hence, the light propagation in these materials behaves differently in the direction perpendicular and parallel to the optical axis, and exhibits birefringence. Therefore, these materials may be useful for optical communication. The calculated electron energy loss suggests that these materials can also be used for unwanted signal noise suppression. The wide band gap makes them useful for high-power applications. Moreover, Ca(OH)2 and Mg(OH)2 are found to be suitable for dielectric medium.

Reversible Assembly of an Artificial Protein Nanocage Using Alkaline Earth Metal Ions.

Protein nanocages are of increasing interest for use as drug capsules, but the encapsulation and release of drug molecules at appropriate times require the reversible association and dissociation of the nanocages. One promising approach to addressing this challenge is the design of metal-dependent associating proteins. Such designed proteins typically have Cys or His residues at the protein surface for connecting the associating proteins through metal-ion coordination. However, Cys and His residues favor interactions with soft and borderline metal ions, such as Au+ and Zn2+, classified by the hard and soft acids and bases concept, restricting the types of metal ions available to drive association. Here, we show the alkaline earth (AE) metal-dependent association of the recently designed artificial protein nanocage TIP60, which is composed of 60-mer fusion proteins. The introduction of a Glu (hard base) mutation to the fusion protein (K67E mutant) prevented the formation of the 60-mer but formed the expected cage structure in the presence of Ca, Sr, or Ba ions (hard acids). Cryogenic electron microscopy (cryo-EM) analysis indicated a Ba ion at the interface of the subunits. Furthermore, we demonstrated the encapsulation and release of single-stranded DNA molecules using this system. Our results provide insights into the design of AE metal-dependent association and dissociation mechanisms for proteins.

Stepwise dissociation of ion pairs by water molecules: cation-dependent separation mechanisms between carboxylate and alkali-earth metal ions.

Microhydrated H2-tagged ion pairs (Ca2+, AcO-)(H2O)n=0-8 and (Ba2+, AcO-)(H2O)n=0-5 are investigated by IR photodissociation laser spectroscopy and DFT-D frequency calculations. The detailed picture of the first steps of ion dissociation reveals two mechanisms, where water molecules promote dissociation either directly or indirectly depending on the nature of the cation.

Alkali /alkaline earth-based metal-organic frameworks for biomedical applications.

With the steady development of metal-organic framework (MOF) materials, this peculiar class of three-dimensional materials has found application prospects in a myriad of areas. The integration of different metals with various categories of ligands engendered a full gamut of frameworks, which of course are supplemented by diversified modification methods. Amongst many metal centers utilized to design and synthesize targeted MOFs, alkali/alkaline earth metal-based MOFs are gaining significant attention because these metal centers can be regarded as human endogenous metals. Numerous studies have shown that alkali/alkaline earth metal MOFs (A/A-E MOFs) tend to have better properties than other metals. This is because A/A-E MOFs offer better biocompatibility, so it is expected to be used in a broader field of biomedicine in the near future. This review mainly introduces the application of A/A-E MOF materials in drug delivery, sensing, and some materials with unique biomedical applications, and elaborates the challenges, obstacles and development of some A/A-E MOF materials in the biomedical field.

Alkali and Alkaline Earth Metal Complexes as Versatile Catalysts for Ring-Opening Polymerization of Cyclic Esters.

Biodegradable polyesters such as poly(ϵ-caprolactone) (PCL) and poly(lactic acid) (PLA) have been considered for use in several areas, such as drug delivery devices, sutures, tissue engineering, and GBR membranes, due to its bio-renewability, biodegradability, and biocompatibility. Several synthetic techniques for the preparation of polyesters have been reported in the literature, amongst which the ring-opening polymerization (ROP) of cyclic esters is the most efficient. A convenient approach to access iso-selective PLAs is polymerization of racemic lactide (rac-LA), which shows excellent stereoregularity without the need for costly chiral auxiliaries or ligands. In this personal account, we review a series of methods that have been practiced to the synthesis of biodegradable polyesters from various cyclic monomers using alkali and alkaline earth metal complexes as efficient catalysts.

Kinetic Process of an Alkaline Earth Metal Ion Transmembrane through ZIF-8.

The confinement effect of biological ion channels regulates the transport of molecules and ions due to angstrom-sized pores. The structure of the potassium channel has a selection region (3-4 Å), a cavity (10 Å), and a gated region, while ZIF-8 has intrinsic pores with a 3.4 Å aperture and an 11.6 Å cavity similar to those of the potassium channel. Inspired by this, we constructed the glass/ZIF-8 hybrid membrane through an electrochemical growth process to explore the kinetics of the ion transmembrane by I-V curves and electrochemical impedance spectroscopy. These complementary approaches yield highly correlated results that show that ion transportation of the ZIF-8 membrane follows Arrhenius behavior. The rates of ions are controlled by the transmembrane activation energy, in which the ionic charge and radius play an important role.

pH-dependent sedimentation of DNA in the presence of divalent, but not monovalent, metal ions.

Precipitation of DNA is performed frequently in molecular biology laboratories for the purpose of purification and concentration of samples and also for transfer of DNA into cells. Metal ions are used to facilitate these processes, though their precise functions are not well characterized. In the current study we have investigated the precipitation of double-stranded DNA by group 1 and group 2 metal ions. Double-stranded DNAs were not sedimented efficiently by metals alone, even at high concentrations. Increasing the pH to 11 or higher caused strong DNA precipitation in the presence of the divalent group 2 metals magnesium, calcium, strontium and barium, but not group 1 metals. Group 2 sedimentation profiles were distinctly different from that of the transition metal zinc, which caused precipitation at pH 8. Analysis of DNAs recovered from precipitates formed with calcium revealed that structural integrity was retained and that sedimentation efficiency was largely size-independent above 400 bp. Several tests supported a model whereby single-stranded DNA regions formed by denaturation at high pH became bound by the divalent metal cations. Neutralization of negative surface charges reduced the repulsive forces between molecules, leading to formation of insoluble aggregates that could be further stabilized by cation bridging (ionic crosslinking).

High Throughput Synthesis and Screening of Oxygen Reduction Catalysts in the MTiO3 (M = Ca, Sr, Ba) Perovskite Phase Diagram.

A library of 66 perovskite BaxSryCazTiO3 (x + y + z = 1) samples (ca. three grams per sample) was made in ca. 14 h using a high-throughput continuous hydrothermal flow synthesis system. The as-synthesized samples were collected from the outlet of the process and then cleaned and freeze-dried before being evaluated individually as oxygen reduction catalysts using a rotating disk electrode testing technique. To establish any correlations between physical and electrochemical characterization data, the as-synthesized samples were investigated using analytical methods including BET surface area, powder X-ray diffraction (PXRD) and in selected cases, transmission electron microscopy (TEM). The aforementioned approach was validated as being able to quickly identify oxygen reduction catalysts from new libraries of electrocatalysts.

Prospective and comparative Novel technique for evaluation the affinity of alginate for binding the alkaline-earth metal ions during formation the coordination biopolymer hydrogel complexes.

A prospective novel technique has been developed for evaluation the capacity of alginate as a natural polymer absorbent for binding Ca (II), Sr (II) and Ba(II) as alkaline earth metal ions for formation of coordination biopolymer hydrogel complexes. This method was based on avoiding the non-chelated metal-ions which may present free into the interstitial spaces of the spongy network of the alginate matrix. Neglecting of non-chelated metal ions in the various techniques will lead to miscalculation in the definite concentration of the binding metal ions. Hence, some uncertainty and dissimilarity were observed in the reported data with respect to the alginate capacity for binding the metal ions. Therefore, a novel technique for more precise determination was achieved by synthesis of coordination metal alginate gels of granule nature which are free from such non-chelated metal ions. Here, the true binding metal ions were eluted by addition of dilute HClO4 and the concentration of the metal ions into the effluent was determined, conductometrically. The experimental results indicated that the capacity of alginate was decreased in the order Ba2+ > Sr2+ > Ca2+ ions in good accord with their thermal stability. The factors affected the affinity of alginate for binding the metal ions were interpreted and discussed.

The remarkable effect of alkali earth metal ion on the catalytic activity of OMS-2 for benzene oxidation.

Cryptomelane-type octahedral molecular sieve (OMS-2) is one of the most promising catalysts for VOCs oxidation, and introduction of metal ions in OMS-2 tunnel is widely used for tailoring its catalytic activity. Here, different types of alkali earth metal ions with the same X/Mn atomic ratio of approximately 0.012 (X represents Mg2+, Ca2+, and Sr2+) were successfully introduced into OMS-2 tunnel by a one-step redox reaction. The catalytic test showed that introducing alkali earth metal ions into tunnels had a considerable effect on the catalytic performance of OMS-2 for benzene oxidation. The Sr2+ doped OMS-2 catalyst exhibited the better catalytic activity compared with those of Mg-OMS-2 and Ca-OMS-2 samples, and was also superior to a commercial 0.5% Pt/Al2O3 catalyst, as evidenced by its low reaction temperatures of T50 = 200 °C and T90 = 223 °C (corresponding to benzene conversions at 50% and 90%, respectively). The origin of the considerable effect of alkali earth metal doping on the catalytic activity of OMS-2 catalysts was experimentally and theoretically investigated by an 18O2 isotopic labeling experiment, CO temperature-programmed reduction, O2 temperature-programmed oxidation, and density functional theory calculations. The greatest catalytic activity of Sr-OMS-2 compared with those of Mg-OMS-2 and Ca-OMS-2 samples was attributed to its highest lattice oxygen activity as well as its largest surface area. By introducing alkali earth metal ions into the OMS-2 tunnel, we developed a low-cost and highly efficient catalyst that could be used as alternative to noble metal catalysts.

Molecular dynamics simulations of alkaline earth metal ions binding to DNA reveal ion size and hydration effects.

The identity of metal ions surrounding DNA is key to its biological function and materials applications. In this work, we compare atomistic molecular dynamics simulations of double strand DNA (dsDNA) with four alkaline earth metal ions (Mg2+, Ca2+, Sr2+, and Ba2+) to elucidate the physical interactions that govern DNA-ion binding. Simulations accurately model the ion-phosphate distance of Mg2+ and reproduce ion counting experiments for Ca2+, Sr2+, and Ba2+. Our analysis shows that alkaline earth metal ions prefer to bind at the phosphate backbone compared to the major groove and negligible binding occurs in the minor groove. Larger alkaline earth metal ions with variable first solvation shells (Ca2+, Sr2+, and Ba2+) show both direct and indirect binding, where indirect binding increases with ion size. Mg2+ does not fit this trend because the strength of its first solvation shell predicts indirect binding only. Ions bound to the phosphate backbone form fewer contacts per ion compared to the major groove. Within the major groove, metal ions preferentially bind to guanine-cystosine base pairs and form simultaneous contacts with the N7 and O6 atoms of guanine. Overall, we find that the interplay among ion size, DNA-ion interaction, and the size and flexibility of the first solvation shell are key to predicting how alkaline earth metal ions interact with DNA.

Photoluminescence and structural analysis of trivalent europium doped MLaAl3 O7 (M = Ba, Ca, Mg and Sr) nanophosphors.

The solution combustion technique was used to synthesize MLaAl3 O7 (M = Ba, Ca, Mg, and Sr) nanophosphors-doped with Eu3+ using metal nitrates as precursors. The photoluminescence (PL) emission spectra exhibited three peaks at 587-591, 610-616, and 653-654 corresponding to 5 D0 →7 F1 , 5 D0 →7 F2 , and 5 D0 →7 F3 transitions, respectively. Upon excitation at 254 nm, these nanophosphors displayed strong red emission with the dominant peak attributed to the 5 D0 →7 F2 transition of Eu3+ . The materials were further heated at 900 and 1050°C for 2 h to examine the consequence of temperature on crystal lattice and PL emission intensity. X-ray diffraction (XRD) analysis proved that all the synthesized materials were of a crystalline nature. CaLaAl3 O7 material has a tetragonal crystal structure with space group P421m. Scherer's equation was used to calculate the crystallite size of synthesized phosphors using XRD data. A Fourier transformation infrared study was used to observe the stretching vibrations of metal-oxygen bonds. Infrared peaks for stretching vibrations corresponding to lanthanum-oxygen and aluminium-oxygen bonds were found at 582 and 777 cm-1 respectively for CaLaAl3 O7 phosphor material. Transmission electron microscopy images were used to determine the size of particles (18-37 nm for the as-prepared materials) and also to analyze the three-dimensional view of these materials. The experimental data indicate that these materials may be promising red-emitting nanophosphors for use in white light-emitting diodes.

Alkali and Alkaline-Earth Cations in Complexes with Small Bioorganic Ligands: Ab†Initio Benchmark Calculations and Bond Energy Decomposition.

Herein, we report a computational database for the complexes of alkali [Li(I), Na(I), K(I)] and alkaline-earth [Be(II), Mg(II) and Ca(II)] cations with 25 small ligands with varying charge and donor atoms ("O", "N", and "S") that provides geometries and accurate bond energies useful to analyze metal-ligand interactions in proteins and nucleic acids. The role of the ligand→metal charge transfer, the equilibrium bond distance, the electronegativity of the donor atom, the ligand polarizability, and the relative stability of the complexes are discussed in detail. The interacting quantum atoms (IQA) method is used to decompose the binding energy into electrostatic and quantum mechanical contributions. In addition, bond energies are also estimated by means of multipolar electrostatic calculations. No simple correlation exists between bond energies and structural/electronic descriptors unless the data are segregated by the type of ligand or metal. The electrostatic attraction of some molecules (H2 O, NH3 , CH3 OH) towards the metal cations is well reproduced using their (unrelaxed) atomic multipoles, but the same comparison is much less satisfactory for other ligands (e. g. benzene, thiol/thiolate groups, etc.). Besides providing reference structures and bond energies, the database can contribute to validate molecular mechanics potentials capable of yielding a balanced description of alkali and alkaline-earth metals binding to biomolecules.

The Exchange Mechanism of Alkaline and Alkaline-Earth Ions in Zeolite N.

Zeolite N is a synthetic zeolite of the EDI framework family from the more than 200 known zeolite types. Previous experimental laboratory and field data show that zeolite N has a high capacity for exchange of ions. Computational modelling and simulation techniques are effective tools that help explain the atomic-scale behaviour of zeolites under different processing conditions and allow comparison with experiment. In this study, the ion exchange behaviour of synthetic zeolite N in an aqueous environment is investigated by molecular dynamics simulations. The exchange mechanism of K+ extra-framework cations with alkaline and alkaline-earth cations NH4+, Li+, Na+, Rb+, Cs+, Mg2+ and Ca2+ is explored in different crystallographic directions inside the zeolite N structure. Moreover, the effect of different framework partial charges on MD simulation results obtained from different DFT calculations are examined. The results show that the diffusion and exchange of cations in zeolite N are affected by shape and size of channels controlling the ion exchange flow as well as the nature of cation, ionic size and charge density.

Molecular Tweezers-like Calix[4]arene Based Alkaline Earth Metal Cation (Ca2+, Sr2+, and Ba2+) Chemosensor and Its Imaging in Living Cells and Zebrafish.

Although alkaline earth metal cations play an important role in our daily life, little attention has been paid to the field of fast quantitative analysis of their content due to a lack of satisfactory precision and a fast and convenient means of detection. In this study, we have designed a set of molecular tweezers based on the calix[4]arene chemosensor L, which was found to exhibit high selectivity and sensitivity toward Ca2+, Sr2+, and Ba2+ (by UV-vis and fluorescence methods) with low detection limits of the order of 10-7 to 10-8 M and high association constants (of the order of 106). More significantly, sensor L not only can recognize Ca2+, Sr2+, and Ba2+ but also can further discriminate between these three cations via the differing red shifts in their UV-vis spectra (560 nm for L·Ca2+, 570 nm for L·Sr2+, and 580 nm for L·Ba2+ complex) which is attributed to their different atomic radii. A rare synergistic effect for the recognition mechanism has been demonstrated by 1H NMR spectroscopic titration. Sensor L constructed a high shielding field by the cooperation of Tris with alkaline earth metal ion after complex. Additionally, the presence of acetoxymethyl group in sensor L results in enhancement of cell permeability, and as a consequence, sensor L exhibited excellent sensing and imaging (in vivo) in living cells and in zebrafish.