Calculations of Avrami exponent and applicability of Johnson–Mehl–Avrami model on crystallization in Er:LiY(PO3)4 phosphate glass

Journal of Thermal Analysis and Calorimetry - Preparation and thermal properties of Er3+-doped lithium–yttrium meta-phosphate glasses with a nominal composition of Er:LiY(PO3)4 were studied...     

Anosov and expanding attractors

Science China Mathematics - An earlier conjecture is settled with an immersion of a 2-dimensional branched manifold. Possible obstructions in linear algebra and tiling theory are studied first.     

Cycloaddition Reactions of an Active Cyclic Phosphane/Borane Pair with Alkenes,Alkynes, and Carbon Dioxide

The active six-membered cyclo-FLP 6 undergoes a rapid P/B addition reaction to carbon dioxide. At elevated temperature, the resulting heterobicyclo[2.2.2]octane derived product 7 undergoes ring opening and equilibrates with the cyclotetramer (7)₄ . In the large macrocyclic structure, four monomeric six-membered cyclo-FLP units are connected by four CO₂ molecules to form the supramolecular ring system. The P/B cyclo-FLP 6 undergoes a variety of additional cycloaddition reactions.     

Spatiotemporal Studies of the One-Dimensional Coordination Polymer [Fe(ebtz)2(C2H5CN)2](BF4)2: Tug of War between the Nitrile Reorientation Versus Crystal Lattice as a Tool for Tuning the Spin Crossover Properties**

Reaction of 1,2-di(tetrazol-2-yl)ethane (ebtz) with Fe(BF₄)₂⋅6 H₂O in different nitriles yields one-dimensional coordination polymers [Fe(ebtz)₂(RCN)₂](BF₄)₂⋅nRCN (n=2 for R=CH₃ ( 1 ) and n=0 for R=C₂H₅ ( 2 ) C₃H₇ ( 3 ), C₃H₅ ( 4 ), CH₂Cl ( 5 )) exhibiting spin crossover (SCO). SCO in 1 and 3 – 5 is complete and occurs above 160 K. In 2 , it is shifted to lower temperatures and is accompanied by wide hysteresis (T_1/2^↓=78 K, T_1/2^↑=123 K) and proceeds extremely slowly. Isothermal (80 K) time-resolved single-crystal X-ray diffraction studies revealed a complex nature for the HS→LS transition in 2 . An initial, slow stage is associated with shrinkage of polymeric chains and with reduction of volume at 77 % (in relation to the difference between cell volumes V_HS−V_LS) whereas only 16 % of iron(II) ions change spin state. In the second stage, an abrupt SCO occurs, associated with breathing of the crystal lattice along the direction of the Fe–nitrile bonds, while the nitriles reorient. HS→LS switching triggered by light (808 nm) reveals the coupling of spin state and nitrile orientation. The importance of this coupling was confirmed by studies of [Fe(ebtz)₂(C₂H₅CN/C₃H₇CN)₂](BF₄)₂ mixed crystals ( 2 a , 2 b ), showing a shift of T_1/2 to higher values and narrowing of the hysteresis loop concomitant with an increase of the fraction of butyronitrile. This increase reduces the capability of nitrile molecules to reorient. Density functional theory (DFT) studies of models of 1 – 5 suggest a particular possibility of 2 to adopt a low (140–145°) value of its Fe-N-C(propionitrile) angle.     

Crossover mitigation strategies for redox-flow batteries

Redox-flow batteries can, in principle, use a wide range of active materials. However, a number of simultaneous requirements must be met to make a chemistry attractive. One of the most challenging requirements is minimizing transport of active species through the membrane separating the positive and negative electrodes, and the ensuing inefficiency and capacity loss. Developing technologies to mitigate crossover, and strategies for recovering from its consequences, will enable development of successful systems with new active materials. The rate and impact of crossover depend on the nature of the active materials and their fate after they transport across the separator. Accordingly, electrolyte solutions can be classified by what happens to the active species at the opposing electrolyte. This behavior also dictates what recovery strategies may be employed, and at what frequency. This review describes desirable attributes for active materials and separators that help diminish crossover, and strategies that can be used to recover from its effects for each of the different classes of electrolytes.     

A Micellar Mitotane Formulation with High Drug‐Loading and Solubility: Physico‐Chemical Characterization and Cytotoxicity Studies in 2D and 3D In Vitro Tumor Models

Adrenocortical carcinoma (ACC) is a rare tumor and prognosis is overall poor but heterogeneous. Mitotane (MT) has been used for treatment of ACC for decades, either alone or in combination with cytotoxic chemotherapy. Even at doses up to 6 g per day, more than half of the patients do not achieve targeted plasma concentration (14–20 mg L^?1) even after many months of treatment due to low water solubility, bioavailability, and unfavorable pharmacokinetic profile. Here a novel MT nanoformulation with very high MT concentrations in physiological aqueous media is reported. The MT‐loaded nanoformulations are characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, and powder X‐ray diffraction which confirms the amorphous nature of the drug. The polymer itself does not show any cytotoxicity in adrenal and liver cell lines. By using the ACC model cell line NCI‐H295 both in monolayers and tumor cell spheroids, micellar MT is demonstrated to exhibit comparable efficacy to its ethanol solution. It is postulated that this formulation will be suitable for i.v. application and rapid attainment of therapeutic plasma concentrations. In conclusion, the micellar formulation is considered a promising tool to alleviate major drawbacks of current MT treatment while retaining bioactivity toward ACC in vitro.     

Perimidine-based synthetic receptors for determination of copper(II) in water solution

Perimidine-based chelators 1 and 2 were prepared, and their structures were confirmed by ¹H and ¹³C NMR, MS spectroscopy and elemental analysis. These compounds were studied as specific synthetic receptors for the recognition of transition metal ions. They exhibited high affinity and selectivity towards Cu(II) ions. The conditional binding constants, linear dynamic range and detection limit were determined by UV–vis spectroscopy. These parameters demonstrated high potential of the prepared synthetic receptors for the recognition and determination of Cu(II) ions. The minimum detectable concentrations of Cu(II) ions for the synthetic receptors 1 and 2 were 270 and 75 nM (R ² = 0.9915 and 0.9964) in aqueous medium (water/DMSO; 99:1 (v/v)), respectively.     

Luminescence decay of distant donor-acceptor pairs in phosphorous-doped ZnTe

Luminescence decay of isolated donor-acceptor pairs has been measured over the range of pair distance R ～ 180 Å in phosphorous-doped ZnTe. Analysis of the recombination rate as a function of the pair distance suggests an asymptotic behaviour of the acceptor envelope function of the type exp(-r/a_A), with $\text{a}{}_{\mathrm{A}}\text{= 40 ± 10}\text{A}\text{?}$. This effective Bohr radius would correspond to an hydrogenic mass $\text{m}{}^1\text{= (0.13 ± 0.03)}\text{m}{}_{\mathrm{o}}$, which is close to the light hole mass as measured from cyclotron resonance experiments, $\text{m}{}^1\text{= (0.154 ± 0.005)}\text{m}{}_{\mathrm{o}}$. A discussion on the validity of the isolated donor-acceptor pair model is also given.     

The general relativistic hydrogen atom

The general relativistic Dirac equation is formulated in an arbitrary curved space-time using differential forms. These equations are applied to spherically symmetric systems with arbitrary charge and mass. For the case of a black hole (with event horizon) it is shown that the Dirac Hamiltonian is self-adjoint, has essential spectrum the whole real line and no bound states. Although rigorous results are obtained only for a spherically symmetric system, it is argued that, in the presence of any event horizon there will be no bound states. The case of a naked singularity is investigated with the results that the Dirac Hamiltonian is not self-adjoint. The self-adjoint extensions preserving angular momentum are studied and their spectrum is found to consist of an essential spectrum corresponding to that of a free electron plus eigenvalues in the gap (–mc ², +mc ²). It is shown that, for certain boundary conditions, neutrino bound states exist.Supported in part by the National Science Foundation