Thermodynamics of saturated lanthanide nitrate-water systems

The thermodynamic properties of saturated aqueous lanthanide nitrate solutions were determined using recently published critically evaluated solubility and activity data. The variation of the thermodynamic functions and congruent melting points as a function of atomic number are interpreted in terms of changes in inner sphere coordination number in both the solid hexahydrates and in the aquo ions, and in terms of the double-double effect.Inconsistencies in experimental solubility data are generally caused by uncertainties in solid phase composition which is shown to be due to the very small Gibbs energies accompanying transitions from stable to metastable systems differing in the number of hydrating water molecules.Presentation to First International Symposium on Solubility Phenomena, University of Western Ontario, London, Ontario, August 21–23, 1984.     

Topological effect on MO energies,IV. The total π-electron energy ofS- andT-isomers

A novel general property of theS- andT-isomers (a concept which has been introduced and elaborated elsewhere^{1, 2}) of alternant hydrocarbons is demonstrated, namely that due to the HMO total -electron energy theS-isomer should always be more stable than theT-isomer. Some other classes of conjugated isomers are also constructed, for which similar inequalities are derived.

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Topologischer Effekt bei MO-Energien, 4. Mitt.: Die -Elektronen-Gesamtenergie vonS- undT-Isomeren

Zusammenfassung Es wird allgemein gezeigt, daß bei einemS-T-Isomerenpaar (beschrieben in^{1, 2}) eines alternierenden Kohlenwasserstoffes infolge der HMO -Elektronen-Gesamtenergie dasS-Isomere stets stabiler sein sollte als dasT-Isomere. Weitere Klassen konjugierter Isomere werden konstruiert und ähnliche Ungleichungen angegeben.

     

Accurate values for the nonrelativistic energies of the lowest singlet and triplet S-states of the4He-Isotop

Accurate lower and upper bounds for the nonrelativistic lowest energies¹ E ₀ and³ E ₀ of the singlet and triplet-system of the⁴He-Isotop are calculated with the linearized method of variance minimization. The same was done for¹ E ₁ the energy of the first excitedS-state 2¹ S. The results especially for¹ E ₀ and³ E ₀ in a.u. are −2.9033076997₅ ≤¹ E ₀ ≤ −2.9033076921₈ −2.1749324263₇ ≤³ E ₀ ≤ −2.1749324245₉ i.e. the values are determined with an absolute error smaller than 0.00167 cm⁻¹ for¹ E ₀ and 0.00039 cm⁻¹ for³ E ₀.     

Thermodynamic properties of alkali halides. V. Temperature and pressure dependence of excess free energies in water

A simple equation has been derived relating the temperature dependence of activity functions with excess enthalpies and excess heat capacities. Using experimentally determined parameters at 298.15°K, it is possible to predict osmotic coefficients and mean activity coefficients of alkali halides in water up to 1 m from 273°K to about 350°K. In general, the predicted functions agree with the measured values within the uncertainty of the activity data. An equation is also given for the pressure dependence of the excess free energies, but it was not possible to check the limitation of this equation due to lack of activity data at various pressures.To whom correspondence should be addressed.     

用~(13)C NMR弛豫研究星形聚苯乙烯在溶液中的分子运动(Ⅱ)

对不同支化度和不同支链链长的20％(W/V)星形聚苯乙烯溶液测定了~(13)C NMR弛豫参数,用1g-x~2分布、Cole-Cole分布和构象跳跃模型对主链的分子运动进行了分析讨论,并对芳环侧基的内旋转运动也进行了分析,求出了活化能和跳跃速率。结果表明,轻度化学交联对相关时间分布有一定影响,对链段运动的势垒没有明显影响。支链链长对~(13)C NMR弛豫的影响和对线形聚合物的影响是类似的。     

Conductance of tetraalkylammonium salts in 2-butanone from −45 to 25°C

Interactions of three types of tetraalkylammonium cations (tetrapropyltetrabutyl-and tri-isoamylbutyl- ammonium) with perchlorate and tetraphenylborate anions were studied by the conductivity method in 2-butanone from –45°C to 25°C. Conductance data obtained for diluted solutions (5×10^–5 – 2×10^–3 mol-dm^–3) were used to calculate the limiting molar conductivities and associationconstants. The conductance equation of Fuoss-Hsia including the Chen term and the chemical model assumption were applied. Limiting ion conductivities were calculated assuming equal limiting conductivities of the i-Am₃BuN⁺ and BPh ₄ ^– ions at all temperatures. Gibbs energies and entropies of ion pair formation, calculated from the dependence of association constants on temperature, are presented including the contributions due to short-range forces.     

Geometries, Electronic Structures, and Electron Detachment Energies of Small Boron Sulfide Anions： A Density Functional Theory Investigation

A density functional theory investigation on the geometries, electronic structures, and electron detachment energies of BS, BS2, B（BS）2 and B（BS）3 has been performed in this work. The linear ground-state structures of BS （C∞v, ^1∑^＋） and BS2^- （O∞h, ^1∑g^＋） prove to be similar to the previously reported BO and BO2 with systematically lower electron detachment energies. Small boron sulfide clusters are found to favor the formation of -B=S groups which function basically as a-radicals and dominate the ground-state structures of the systems. The perfect linear B（BS）2^-（D∞h, ^3∑g） and beautiful equilateral triangle B（BS）3^- （D3h,^2A1”） turn out to be analogous to the well-known C2v BH2 and O3h BH3, respectively. The electron affinities of BS, BS2, B（BS）2 and B（BS）3 are predicted to be 2.3, 3.69, 3.00 and 3.45 eV, respectively. The electron detachment energies calculated for BS^-, BS2^-, B（BS）2^-, and B（BS）3^- may facilitate future photoelectron spectroscopy measurements to characterize the geometrical and electronic structures of these anions.     

Doxorubicin Encapsulation in Carbon Nanotubes Having Haeckelite or Stone–Wales Defects as Drug Carriers: A Molecular Dynamics Approach

Doxorubicin (DOX), a recognized anticancer drug, forms stable associations with carbon nanotubes (CNTs). CNTs when properly functionalized have the ability to anchor directly in cancerous tumors where the release of the drug occurs thanks to the tumor slightly acidic pH. Herein, we study the armchair and zigzag CNTs with Stone–Wales (SW) defects to rank their ability to encapsulate DOX by determining the DOX-CNT binding free energies using the MM/PBSA and MM/GBSA methods implemented in AMBER16. We investigate also the chiral CNTs with haeckelite defects. Each haeckelite defect consists of a pair of square and octagonal rings. The armchair and zigzag CNT with SW defects and chiral nanotubes with haeckelite defects predict DOX-CNT interactions that depend on the length of the nanotube, the number of present defects and nitrogen doping. Chiral nanotubes having two haeckelite defects reveal a clear dependence on the nitrogen content with DOX-CNT interaction forces decreasing in the order 0N > 4N > 8N. These results contribute to a further understanding of drug-nanotube interactions and to the design of new drug delivery systems based on CNTs.     

Influence of temperature and alloying elements on the threshold displacement energies in concentrated Ni–Fe–Cr alloys

Concentrated solid-solution alloys(CSAs) have demonstrated promising irradiation resistance depending on their compositions. Under irradiation, various defects can be produced. One of the most important parameters characterizing the defect production and the resulting defect number is the threshold displacement energies(E_d). In this work, we report the results of E_dvalues in a series of Ni–Fe–Cr concentrated solid solution alloys through molecular dynamics(MD)simulations. Based on several different empirical potentials, we show that the differences in the E_dvalues and its angular dependence are mainly due to the stiffness of the potential in the intermediate regime. The influences of different alloying elements and temperatures on E_dvalues in different CSAs are further evaluated by calculating the defect production probabilities. Our results suggest a limited influence of alloying elements and temperature on E_dvalues in concentrated alloys. Finally, we discuss the relationship between the primary damage and E_dvalues in different alloys. Overall, this work presents a thorough study on the E_dvalues in concentrated alloys, including the influence of empirical potentials,their angular dependence, temperature dependence, and effects on primary defect production.     

Polymorphism of methyl 4‐amino‐3‐phenylisothiazole‐5‐carboxylate: an experimental and theoretical study

Being a close analogue of amflutizole, methyl 4‐amino‐3‐phenylisothiazole‐5‐carboxylate (C₁₁H₁₀N₂O₂S) was assumed to be capable of forming polymorphic structures. Noncentrosymmetric and centrosymmetric polymorphs have been obtained by crystallization from a series of more volatile solvents and from denser tetrachloromethane, respectively. Identical conformations of the molecule are found in both structures. The two polymorphs differ mainly in the intermolecular interactions formed by the amino group and in the type of stacking interactions between the π‐systems. The most effective method for revealing packing motifs in structures with intermolecular interactions of different types (hydrogen bonding, stacking, dispersion, etc.) is to study the pairwise interaction energies using quantum chemical calculations. Molecules form a column as the primary basic structural motif due to stacking interactions in both polymorphic structures under study. The character of a column (straight or zigzag) is determined by the orientations of the stacked molecules (in a `head‐to‐head' or `head‐to‐tail' manner). Columns bound by intermolecular N—H…O and N—H…N hydrogen bonds form a double column as the main structural motif in the noncentrosymmetric structure. Double columns in the noncentrosymmetric structure and columns in the centrosymmetric structure interact strongly within the ab crystallographic plane, forming a layer as a secondary basic structural motif. The noncentrosymmetric structure has a lower density and a lower (by 0.59 kJ mol^?1) lattice energy, calculated using periodic calculations, compared to the centrosymmetric structure.