Water-induced formation of an alkali-ion dimer in cryptomelane nanorods

Tunneled metal oxides such as α-Mn₈O₁₆ (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K⁺ ions (which act as structure-stabilizing dopants) and H₂O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K⁺-doped α-Mn₈O₁₆ (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H₂O displaces K⁺ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K²⁺ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li⁺/Na⁺ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.

Water displaces potassium ions and initiates the formation of a homonuclear dimer ion (K²⁺) in the tunnels of hollandite.     

Solid-phase approach towards the synthesis of functionalized imidazo[1,2-b]pyrazol-2-ones

The solid-phase synthesis of a series of imidazo[1,2-b]pyrazol-2-ones, an interesting 5,5-fused ring system, based on diverse set of hydrazine acids and malanonitriles is described. The method involves formation of 5-aminopyrazoles on solid support and subsequent cyclizative cleavage off the resin. Compounds were obtained in acceptable to excellent yields and are suitable for biological evaluation without further purification.     

Synthesis and characterization of isotopically enriched methylmercury (CH3201Hg+)

A simple procedure for the synthesis of an important standard, isotopically enriched methylmercury, which is not commercially available, has been established successfully. The isotopically enriched standard synthesized is utilized in conventional isotope dilution mass spectrometry (IDMS), as well as in speciated IDMS (SIDMS), for determination of the true concentration of methylmercury in environmental samples. The CH₃²⁰¹Hg⁺ standard has been synthesized from commercially available ²⁰¹HgO and tetramethyltin. The synthesis time required is 1 h at 60°C. The product is highly pure, yielding more than 90% as ²⁰¹Hg in CH₃²⁰¹Hg⁺. Hazardous dimethylmercury does not occur during this synthesis procedure. The product synthesized was analyzed using high‐performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (ICP‐MS) and ICP‐MS alone in order to determine its concentration, isotopic composition and purity. The stability of the product was also evaluated for over 6 months and found to be stable at 4°C in the dark. The isotopically enriched methylmercury synthesized can be used in SIDMS and IDMS analyses as a standard. Copyright © 2003 John Wiley & Sons, Ltd.     

How Focusing Phenomena in the Instructional Environment Support Individual Students' Generalizations

This article sets forth a way of connecting the classroom instructional environment with individual students' generalizations. To do so, we advance the notion of focusing phenomena, that is, regularities in the ways in which teachers, students, artifacts, and curricular materials act together to direct attention toward certain mathematical properties over others. The construct of focusing phenomena emerged from an empirical study conducted during a 5-week unit on slope and linear functions in a high school classroom using a reform curriculum. Qualitative evidence from interviews with 7 students revealed that students interpreted the m value in y = b + mx as a difference rather than a ratio as a result of counterproductive generalization afforded by focusing phenomena. Classroom analysis revealed 4 focusing phenomena, which regularly directed students' attention to various sets of differences rather than to the coordination of quantities.     

Dielectric properties of KDP-type ferroelectric crystals in the presence of external electric field

Considering external electric field as well as third- and fourth-order phonon anharmonic interaction terms in the pseudospin-lattice coupled mode (PLCM) model Hamiltonian for KDP-type ferroelectrics, expressions for field-dependent shift, width, renormalized soft mode frequency, Curie temperature, dielectric constant and dielectric loss are evaluated. For the calculation, method of statistical double-time temperature-dependent Green’s function has been used. By fitting model values of physical quantities, temperature and electric field dependences of soft mode frequency, dielectric constant and loss have been calculated which compare well with experimental results of Baumgartner [8] and Choi and Lockwood [9]. Both dielectric constant and loss decrease with electric field.     

HPTLC Determination of Swertiamarin and Amarogentin in Swertia Species from the Western Himalayas

JPC – Journal of Planar Chromatography – Modern TLC - A high-performance thin-layer chromatographic (HPTLC) method has been established for simple and rapid quantification of two...     

A facile approach to a d4 RuN: moiety

Replacement of chloride in (PNP)RuCl, PNP = (tBu2PCH2SiMe2)2N, by Me3SiN3 gives a pre-redox adduct that, already at -30 degrees C, releases N2 to produce the mononuclear nonplanar Ru(IV) nitride (PNP)RuN, characterized by spectroscopic and X-ray methods. DFT calculations show the planar structure to be only 1.6 kcal/mol less stable, which explains the time-averaged simplicity of the 1H NMR spectrum, as well as the large vibrational amplitude of the nitride ligand.     

Complexometric titration of total iron with o-mercaptobenzoic acid as indicator

The soluble deep blue complex of iron(II) with o-mercaptobenzoic acid in aqueous pyridine medium (pH 6.4-7.4) can be titrated with EDTA at room temperature with a sharp colour change from blue to light yellow. o-Mercaptobenzoic acid forms a 2:1 complex with iron(II), maximum absorption at 600 nm. Its stability constant was found to be log K = 7.7. With iron(III), a transient blue colour is first formed which soon becomes colourless and then on the addition of excess of reagent, the deep blue complex is formed on reduction of the iron(III). Iron can be titrated in the presence of copper, if the latter is masked with sodium thiosulphate. Cobalt and nickel interfere. Common anions such as chloride, tartrate, phosphate, oxalate, citrate and acetate have no interference.