QM-CSA: A Novel Quantum Mechanics-Based Protocol for Evaluation of the Carcinogen-Scavenging Activity of Polyphenolic Compounds.

In this study, a novel quantum mechanics-based protocol for the evaluation of carcinogen-scavenging activity (QM-CSA) is developed. The QM-CSA protocol represents a universal and quantitative approach to evaluate and compare the activation-free energies for alkylation reactions between individual polyphenolic compounds and chemical carcinogens of the epoxy type at physiological conditions by applying two scales: the absolute scale allowing for the comparison with guanine and the relative scale allowing the comparison with glutathione as a reference compound. The devised quantum mechanical methodology was validated by comparing the activation-free energies calculated with 14 DFT functionals in conjunction with two implicit solvation models (SMD and CPCM) and the experimental activation-free energies for reactions between nine investigated chemical carcinogens and guanine. According to the obtained results, the best agreement with experimental data was achieved by applying DFT functionals M11-L and MN12-L in conjunction with the flexible 6-311++G(d,p) basis set and implicit solvation model SMD, and the obtained uncertainties were proven to be similar to the experimental ones. To demonstrate the applicability of the QM-CSA protocol, functionals M11-L, and MN12-L in conjunction with the SMD implicit solvation model were applied to calculate activation-free energies for the reactions of nine investigated chemical carcinogens of the epoxy type with three catechins, namely EGCG, EGC, and (+)-catechin. The order of CSA in this series of catechins in comparison to guanine and glutathione was determined as (+)-catechin > EGC > EGCG. The obtained results, for the first time, demonstrated the evaluation and comparison of CSA in a series of selected catechins with respect to glutathione and guanine. Moreover, the presented results provide valuable insights into the reaction mechanisms and configurations of the corresponding transition states. The novel QM-CSA protocol is also expected to expand the kinetic data for alkylation reactions between various polyphenolic compounds and chemical carcinogens of the epoxy type, which is currently lacking in the scientific literature.

Lower Diffusion-Induced Stress in Nano-Crystallites of P2-Na2/3 Ni1/3 Mn1/2 Ti1/6 O2 Novel Cathode for High Energy Na-ion Batteries.

P2-type Na2/3 Ni1/3 Mn1/2 Ti1/6 O2 (NMTNO) cathode is a preeminent electrode material for Na-ion batteries owing to its open prismatic framework, air-moisture stability, inexpensiveness, appealing capacity, environmental benignity, and Co-free composition. However, the poor cycling stability, sluggish Na-ion kinetics induced in bulk-sized cathode particles, cracking, and exfoliation in the crystallites remain a setback. To outmaneuver these, a designing strategy of a mechanically robust, hexagonal nano-crystallites of P2-type Na2/3 Ni1/3 Mn1/2 Ti1/6 O2 (NMTNOnano ) electrode via quick, energy-efficient, and low-cost microwave-irradiated synthesis is proposed. For the first time, employing a unified experimental and theoretical approach with fracture mechanics analysis, the mechanism behind the enhanced performance, better structural stability, and lower diffusion-induced stress of NMTNOnano compared to micro-sized Na2/3 Ni1/3 Mn1/2 Ti1/6 O2 is unveiled and the electrochemical shock map is predicted. The NMTNOnano cathode provides 94.8% capacity retention after 100 cycles at 0.1 C with prolonged performance for 1000 cycles at 0.5 C. The practical viability of this cathode, tested in a full cell against a hard carbon anode delivered 85.48% capacity retention at 0.14 mA cm-2 after 200 cycles. This work bridges the gap in correlating the microstructural and electrochemical properties through experimental, theoretical (DFT), and fracture mechanics analysis, thereby tailoring efficient cathode with lower diffusion-induced stress for high-energy Na-ion batteries.

Large giraffids (Mammalia, Ruminantia) from the new late Miocene fossiliferous locality of Kemiklitepe-E (Western Anatolia, Turkey).

Kemiklitepe is a well-known locality with four recognised fossiliferous horizons, KTA to KTD, which have yielded a plethora of mammalian remains. Previous taxonomic studies indicate the presence of three giraffid taxa: Samotherium major and Palaeotragus rouenii from the uppermost three horizons, KTA, KTB and KTC, as well as Palaeotragus rouenii and Samotherium? sp. from the lowermost KTD horizon. In this study a new locality, Kemiklitepe-E, is presented for the first time. Kemiklitepe-E is located approximately 350 m NW of the classic Kemiklitepe locality. The fossiliferous sedimentary rocks at Kemiklitepe-E occur at the same stratigraphic level as localities KTA, KTB and KTC. The preliminary faunal list includes representatives of Proboscidea, Chalicotheriidae, Equidae, Bovidae and Giraffidae. Comprehensive descriptions and comparisons of the Kemiklitepe-E Giraffidae specimens suggest the co-occurrence of two large giraffids: Samotherium major and Helladotherium duvernoyi. Samotherium major, previously documented from this region, is the most common taxon at Kemiklitepe. Helladotherium duvernoyi is rare at Kemiklitepe and here reported for the first time. The two taxa coexisted during the middle Turolian in Greece and Western Anatolia. In addition, it is suggested that specimens of Samotherium? sp described from KTD possibly belong to Samotherium neumayri. Based on the stratigraphic position of fossiliferous rocks, as well as the faunal data presented herein, the newly discovered locality is considered to be of middle Turolian (MN12) age.

The Role of the -OH Groups within Mn12 Clusters in Electrocatalytic Water Oxidation.

The formidable reactivity of the oxygen-evolving center near photosystem II is largely based on its protein environment that stabilizes it during catalysis. Inspired by this concept, the water-soluble Mn12 clusters Mn12 O12 (O2 CC6 H3 (OH)2 )16 (H2 O)4 (3,5DHMn12 ) and Mn12 O12 (O2 CC6 H3 (OH)3 )16 (H2 O)4 (3,4,5THMn12 ) were developed as efficient electrocatalysts for water oxidation. In this work, the role of the -OH groups in the electrocatalytic process was explored by describing the structural and electrocatalytic properties of two new Mn12 clusters, 3,4DHMn12 and 2,3DHMn12 , having one -OH group in the meta position relative to the benzoate-Mn moiety, and one at the para or ortho position, respectively. The Mn centers in 3,4DHMn12 were discovered to have lower oxidation potential compared with those in 2,3DHMn12 , and thus, 3,4DHMn12 can catalyze water oxidation with higher rate and TON than 2,3DHMn12 . Hence, the role of the -OH groups in the electrocatalysis was established, being involved in electronic stabilization of the Mn centers or in proton shuttling.

Magnetic Behaviour of Mn12-Stearate Single-Molecule Magnets Immobilized on the Surface of 300 nm Spherical Silica Nanoparticles.

The magnetic behaviour of Mn 12 -stearate single-molecule magnets (SMMs) ([ Mn 12 O 12 ( CH 3 ( CH 2 ) 16 CO 2 ) 16 ] · 2 CH 3 COOH · 4 H 2 O ) on the surface of 300 nm spherical silica nanoparticles were investigated. The SMMs were bonded at the silica surface with the assumed number of anchoring points, which influenced on their degree of freedom and distribution. In order to check the properties of Mn 12 -stearate molecules separated on the silica surface, and check their interactions, the samples containing four different concentration of spacers per single anchoring unit and variously bonded Mn 12 -stearate particles were prepared. The materials have been examined using Raman spectroscopy, transmission electron microscopy, and SQUID magnetometry. The results of magnetic measurements showed a correlation between the way of single-molecule magnets immobilization onto the silica spheres and the magnetic properties of the obtained hybrid materials.

Eutectic Synthesis of the P2-Type NaxFe1/2Mn1/2O2 Cathode with Improved Cell Design for Sodium-Ion Batteries.

An engaging area of research in sodium-ion batteries (SIBs) has been focusing on discovery, design, and synthesis of high-capacity cathode materials in order to boost energy density to levels close enough to that of state-of-the-art lithium-ion batteries. Of particular interest, P2-type layered oxide, Na2/3Fe1/2Mn1/2O2, has been researched as a potential cathode in SIBs based on its high theoretical capacity of 260 mA h/g and use of noncritical materials. However, the reported synthesis methods are not only complex and energy-demanding but also often yield inhomogeneous and impure materials with capacities less than 200 mA h/g under impractical test conditions. Here, we report a novel synthesis route using low-temperature eutectic reaction to produce highly homogeneous, crystalline, and impurity-free P2-NaxFe1/2Mn1/2O2 with enhanced Na-ion diffusivity and kinetics. The overall electrochemical performances of the Na-ion cells have been improved by pairing the P2-cathode with presodiated hard carbon anodes, leading to reversible capacities in the range of 180 mA h/g. This new approach is a contribution toward the simplification of synthesis and scalability of sodium-based cathodes with high crystallinity and fine-tuned morphology and the realization of a sodium-ion battery system with lower cost and improved electrochemical performance.

How to Control the Distribution of Anchored, Mn12-Stearate, Single-Molecule Magnets.

Controlling the distribution of the Mn 12 -stearate, single-molecule magnets (SMMs) anchored on a select surface is expected to be a new method for tuning its interactions, and an investigation on the magnetic properties of separated magnetic molecules is also lacking. The anchoring of the SMMs at the surface with an assumed statistic distance between each other is not an easy task; nevertheless, in this work, we show a synthesis which allows for this in detail. The immobilization of the Mn 12 -stearate was demonstrated with the use of FTO glasses and spherical silica as substrates. Based on differential pulse anodic stripping voltammetry (DPASV) and transmission electron microscopy (TEM) observations, we proved the efficiency of the method proposed. We observed continuous decreasing the number of bonds, and afterward, decreasing in the number of immobilized molecules with an increasing the number of spacer units used for separation of the magnetic particles.

The Separation of the Mn12 Single-Molecule Magnets onto Spherical Silica Nanoparticles.

The Mn12 single-molecule magnets (SMMs) could be attached to the surface of spherical silica for the first time with a high probability. This allowed separation of the individual molecular magnets and direct microscopic observation of the SMMs. We described in detail how to fabricate such a composite material. The synthesis procedure proposed here is simple and efficient. We confirmed the efficiency of the method by transmission electron microscopy (TEM): single-molecule magnets were visible at the surface of a silica substrate. Based on TEM observation, we described how the molecules anchor to the surface of silica (the geometry of the magnetic molecule in regard to the surface of the substrate). The SQUID magnetometry showed that single-molecule magnet behaviour is kept intact after grafting. The attachment of the single-molecule magnets to the surface of silica allows to investigate their properties as separate molecules. This is particularly important in the analysis of magnetic properties such as magnetic states of the separated SMMs, their mutual interactions, and the influence of a silica support.

Enhanced Sodium Ion Storage Behavior of P2-Type Na(2/3)Fe(1/2)Mn(1/2)O2 Synthesized via a Chelating Agent Assisted Route.

On the basis of resource abundance and low cost, high capacity layered P2-type Na2/3Fe1/2Mn1/2O2 material is regarded as a potential cathode material for sodium-ion batteries but suffers from its unstable structure during cycling. In this work, P2-type Na2/3Fe1/2Mn1/2O2 layered materials were synthesized by a chelating agent assisted sol-gel method with NH3·H2O. With the addition of NH3·H2O and the control of the synthesis conditions, highly active material with a more stable structure and better electrochemical performance was obtained. Furthermore, the influences of structure changes during different voltage ranges (1.5-4.0 V and 1.5-4.3 V vs Na(+)/Na) on the Na(+) storage behaviors were also evaluated and compared. It is confirmed that, when being charged to 4.2 V, an OP4-type phase emerges, which can reduce the damage by the gilding of the MeO2 layers but leads to an unstable crystal structure. For long-term cycling, it is preferred to cut off at 4.0 V rather than at 4.3 V. For the optimized P2-type Na2/3Fe1/2Mn1/2O2 calcined at 900 °C, a discharge capacity of 92 mAh/g remains after 40 cycles in the voltage range of 1.5-4.0 V, and the Coulombic efficiency remains 100%.

[Mn12O12(O2CMe)12(NO3)4(H2O)4]: facile synthesis of a new type of Mn12 complex.

The title dodecanuclear Mn complex, namely dodeca-µ(2)-acetato-κ(24)O:O'-tetraaquatetra-µ(2)-nitrato-κ(8)O:O'-tetra-µ(4)-oxido-octa-µ(3)-oxido-tetramanganese(IV)octamanganese(III) nitromethane tetrasolvate, [Mn(12)(CH(3)COO)(12)(NO(3))(4)O(12)(H(2)O)(4)]·4CH(3)NO(2), was synthesized by the reaction of Mn(2+) and Ce(4+) sources in nitromethane with an excess of acetic acid. This compound is distinct from the previously known single-molecule magnet [Mn(12)O(12)(O(2)CMe)(16)(H(2)O)(4)], synthesized by Lis [Acta Cryst. (1980), B36, 2042-2044]. It is the first Mn(12)-type molecule containing nitrate ligands to be directly synthesized without the use of a preformed cluster. Additionally, this molecule is distinct from all other known Mn(12) complexes due to intermolecular hydrogen bonds between the nitrate and water ligands, which give rise to a three-dimensional network. The complex is compared to other known Mn(12) molecules in terms of its structural parameters and symmetry.