Molecular dynamics simulation of metastable ices IV and XII

The method of molecular dynamics with the use of Poltev-Malenkov potential is applied to simulate crystalline ices IV and XII, which do not have the regions of stability in the phase diagrams of H₂O and D₂O ices. Ice IV appears to undergo a partial destruction, whereas the ice XII structure is retained during the simulation. For different crystal types of water molecules in considered ices the mean square displacement of the center of mass of a water molecule with time is calculated together with the density of states of translational and librational vibrations.     

Molecular Dynamics Study of Structural and Transport Properties of Silver Iodide Using Effective Charges

The superionic conductor, solid state, and body-centered cubic structure, silver iodide at room temperature, has been studied via molecular dynamics simulations. The calculated results using pairwise Coulomb-Buckingham potential, zero pressure on the sample, a semi-rigid model system of 1000 Ag and 1000 I ions, (NVE) as a statistical ensemble, and an effective charge of Z=0.63 for the pairs Ag-Ag and I-I, were found to be consistent with experimental data and one study using Z=0.60, different potential, and simulation software. For the pair Ag-I, there is a discrepancy due to the high silver ion diffusion. The calculated value of the diffusion constant of the silver ion is greater than iodide ion. The dynamic transport properties (mean square displacement, velocity autocorrelation function) results indicated typical behavior reported by other authors, using different potentials in their DM simulations for iodine and silver ions.     

Quantum efficiency of the luminescence of Eu(III), Tb(III) and Dy(III) in aqueous solutions

Summary The luminescence quantum efficiency of Eu(III), Tb(III) and Dy(III) in chloride solutions as well as complexed by aminopolyacetic acids was determined. An interpretation of the observed dependences in the system investigated has been proposed.

---

Die Lumineszenz-Quantenausbeute von Eu(III), Tb(III) und Dy(III) in wäßrigen Lösungen

Zusammenfassung Die Lumineszenz-Quantenausbeute von Eu(III), Tb(III) und Dy(III) in Chloridlösung und in Komplexen mit Aminopolyessigsäuren wurde bestimmt. Eine Interpretation der beobachteten Abhängigkeiten im untersuchten System wurde vorgeschlagen.

     

All-Atom Molecular Dynamics of Pure Water–Methane Gas Hydrate Systems under Pre-Nucleation Conditions: A Direct Comparison between Experiments and Simulations of Transport Properties for the Tip4p/Ice Water Model

(1) Background: New technologies involving gas hydrates under pre-nucleation conditions such as gas separations and storage have become more prominent. This has necessitated the characterization and modeling of the transport properties of such systems. (2) Methodology: This work explored methane hydrate systems under pre-nucleation conditions. All-atom molecular dynamics simulations were used to quantify the performance of the TIP4P/2005 and TIP4P/Ice water models to predict the viscosity, diffusivity, and thermal conductivity using various formulations. (3) Results: Molecular simulation equilibrium was robustly demonstrated using various measures. The Green–Kubo estimation of viscosity outperformed other formulations when combined with TIP4P/Ice, and the same combination outperformed all TIP4P/2005 formulations. The Green–Kubo TIP4P/Ice estimation of viscosity overestimates (by 84% on average) the viscosity of methane hydrate systems under pre-nucleation conditions across all pressures considered (0–5 MPag). The presence of methane was found to increase the average number of hydrogen bonds over time (6.7–7.8%). TIP4P/Ice methane systems were also found to have 16–19% longer hydrogen bond lifetimes over pure water systems. (4) Conclusion: An inherent limitation in the current water force field for its application in the context of transport properties estimations for methane gas hydrate systems. A re-parametrization of the current force field is suggested as a starting point. Until then, this work may serve as a characterization of the deviance in viscosity prediction.     

Effects of Moisture on the Mechanical Properties of Microcrystalline Cellulose and the Mobility of the Water Molecules as Studied by the Hybrid Molecular Mechanics–Molecular Dynamics Simulation Method

A hybrid molecular mechanics–molecular dynamics simulation method has been performed to study the effects of moisture content on the mechanical properties of microcrystalline cellulose (MCC) and the mobility of the water molecules. The specific volume and diffusion coefficient of the water increase with increasing moisture content in the range studied of 1.8–25.5 w/w%, while the Young's modulus decreases. The simulation results are in close agreement with the published experimental data. Both the bound scission and free‐volume mechanisms contribute to the plasticization of MCC by water. The Voronoi volume increases with increasing moisture content. It is related to the free volume and the increase enhances the mobility of the water molecules and thus increases the coefficient of diffusion of the water. Moreover, with increasing moisture content, the hydrogen bonding per water molecule between MCC–water molecules decreases, thus increasing the water mobility and number of free water molecules. © 2019 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 454–464     

Comparison of the Non‐linear Spin Dynamics in Antiferromagnetic Chain Compounds Na2MnF5 and (ND4)2MnF5

Na₂Mn_0.98Fe_0.02F₅ and (ND₄)₂Mn_0.98Fe_0.02F₅ was studied with the aid of Mössbauer spectroscopy. These results were interpreted on the basis of classical soliton theory. In order to confirm this concept, we have performed neutron scattering experiments on large single crystals of the pure compounds. We discuss the results obtained on a thermal and cold three‐axis spectrometer, which probe the magnon spin wave excitations and the existence of the nonlinear excitations in the quasi 1‐d antiferromagnetic chains of Na₂MnF₅ and (ND₄)₂MnF₅, respectively. Additionally, we include elastic neutron diffraction and dc. single crystal susceptibility measurements to determine the magnetic structure. From the width of the quasielastic scattering signal the temperature dependence of the inverse magnetic correlation lengths was derived resulting in a soliton activation energy of E_s/k = 65(3) K and E_s/k = 81(3) K, respectively, which are in good agreement with the soliton energies obtained by our high resolution inelastic neutron scattering experiment. In contrast to these results the Mössbauer spectroscopy gives twice the value of the soliton energy caused by soliton pair or inter‐band excitations.     

Simulation Study on the Structure and Dynamics of Water in Sodium Tetrafluoroborate/Water

The microstructure, IR spectrum, as well as rotation dynamics of water molecule in sodium tetrafluoroborate （NaBF4）/water mixture at room temperatures were studied with molecular dynamics simulation. Different concentrations of water （6.25%, 25.0%, 50.0%, 75.0%, 90.0%, and 99.6%） in NaBF4/water mixture were simulated to understand the structure and dynamics. It was shown that water molecules tend to be isolated from each other in mixtures with more ions than water molecules in both liquids. With increase of the molar fraction of water in the mixture, the rotation bands and the bending bands of water display red shift whereas the O-H stretch bands show blue shift, and the decay of the reorientation correlation function becomes slower. This suggests that the molecules are hindered and their motions are difficult and slow, due to the hydrogen-bond interactions and the inharmonic interactions between the interor intra-molecular modes.     

Synthesis, Characterization, Thermal Decomposition Mechanism and Non-Isothermal Kinetics of the Pyruvic Acid-Salicylhydrazone and Its Complex of Praseodymium(III)

IntroductionHydrazonesactasherbicides,insecticides,nemato cides ,rodenticidesandplantgrowthregulators.Theyshowspasmolyticactivity ,hypotensiveactionandactivityagainstleukaemia,sarcomasandothermalignantneoplasm .1Rareearthelementshavestrongbiologicaleffectandmanycom plexesofrareearthshaveallkindofmedicinalactivities.2 Aseriesof 2 oxopropionyl(pyridine 4 fomyl)hydrazonewithrareearthscomplexeswassynthesizedbyYangandtheEucom plexshowedacertainanticanceractivity .3Therearethreeradicalsinthepyru…     

Directly light scattering imaging of the aggregations of biopolymer bound chromium(III) hydrolytic oligomers in aqueous phase and liquid/liquid interface

Investigations of inorganic oligomers are important in both chemistry and physiology. In this contribution, we propose a laser induced light scattering imaging (LSI) and a total internal reflected light scattering imaging (TIR-LSI) technique, and apply them to characterize the interactions of inorganic oligomers with biopolymer in aqueous phase and at liquid/liquid interface, respectively. In aqueous medium, synthetic chromium(III) hydrolytic oligomers (CrHO) react with DNA, and the resultant binary could be extracted into the H₂O/CCl₄ interface in the presence of triocyctyl phosphine oxide (TOPO), forming a DNA-CrHO-TOPO ternary amphipathic complex at the interface with the associate constant of 1.32 × 10³ mol⁻¹ dm⁴ for a given 1.0 × 10⁻⁴ mol l⁻¹ TOPO. Under the excitation of a 441-nm He-Cd laser light beam, the resultant light scattering and total internal reflected light scattering (TIR-LS) signals of the formed binary in aqueous phase and ternary at liquid/liquid interface could be easily captured using a common microscope coupled with a CCD camera. By digitally analyzing the CCD captures, we demonstrate that aggregations of the CrHO-DNA binary in aqueous phase and DNA-CrHO-TOPO ternary at liquid/liquid interface have occurred, respectively.     

Comparison of Various Analytical Methods in the Study of the Reaction Between Zinc Oxide and Fe(III) Oxide

The paper deals with the possible application of various methods to follow the course of reaction between zinc oxide and Fe(III) oxide with respect to various kinds of Fe(III) oxides used (Fe(III) pigments - red, yellow and black). Differential thermal analysis and chemical analysis can be recommended as the most suitable methods for following reactions leading to spinel formation. The possibilities of determining the activation energy of the studied processes are discussed. When Fe(III) red pigment is used as a reactant and therefore no reaction occurs except spinel formation, conductometric thermal analysis was found to be suitable and more sensitive for the evaluation of differences in reactivities. It has also been observed that the kind of Fe(III) pigment, due to its individual reactivity significantly affects the colouring properties of the final product (e.g., of the ceramic stain). This revised version was published online in July 2006 with corrections to the Cover Date.     

Rise of photoluminescence in the photolysis of EuIII complexes with copolymers of acrylic acid and butyl methacrylate

The luminescence and photochemical properties of Eu^III complexes with copolymers of acrylic acid and butyl methacrylate have been studied by luminescence, IR spectroscopy, and EXAFS.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 958–959, May, 1994.     

Effect of Water Microsolvation on the Excited-State Proton Transfer of 3-Hydroxyflavone Enclosed in γ-Cyclodextrin

The effect of microsolvation on excited-state proton transfer (ESPT) reaction of 3-hydroxyflavone (3HF) and its inclusion complex with γ-cyclodextrin (γ-CD) was studied using computational approaches. From molecular dynamics simulations, two possible inclusion complexes formed by the chromone ring (C-ring, Form I) and the phenyl ring (P-ring, Form II) of 3HF insertion to γ-CD were observed. Form II is likely more stable because of lower fluctuation of 3HF inside the hydrophobic cavity and lower water accessibility to the encapsulated 3HF. Next, the conformation analysis of these models in the ground (S₀) and the first excited (S₁) states was carried out by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, respectively, to reveal the photophysical properties of 3HF influenced by the γ-CD. The results show that the intermolecular hydrogen bonding (interHB) between 3HF and γ-CD, and intramolecular hydrogen bonding (intraHB) within 3HF are strengthened in the S₁ state confirmed by the shorter interHB and intraHB distances and the red-shift of O–H vibrational modes involving in the ESPT process. The simulated absorption and emission spectra are in good agreement with the experimental data. Significantly, in the S₁ state, the keto form of 3HF is stabilized by γ-CD, explaining the increased quantum yield of keto emission of 3HF when complexing with γ-CD in the experiment. In the other word, ESPT of 3HF is more favorable in the γ-CD hydrophobic cavity than in aqueous solution.     

The oxidation of carbohydrazide by the 12-tungstocobaltate(III) ion in acidic medium: Kinetics and mechanism

The redox reaction between the 12-tungstocobaltate(III) ion and carbohydrazide is first order with respect to both the oxidant and the substrate. The observed pseudo first-order rate constant, k_obs, is retarded by increasing the concentrations of H⁺ and alkali metal ion (Li⁺, Na⁺ and K⁺). There is a linear correlation between the k_obs and the concentrations of carbohydrazide and H⁺ ion, but the plots of k_obs against the concentrations of the alkali metal ions is non-linear. However, the same data is applicable to the Davies equation for the effect of the ionic strength on the k_obs.     

Synthesis and characterization of the complexes of lanthanide(III) chlorides and nitrates with the tetradentate schiff base diethyl(ethylenebis-β-aminocrotonate)

Summary The Schiff base ligand diethyl(ethylenebis--aminocrotonate) (LH₂) reacts with lanthanide(III) chlorides and nitrates in various solvents to give solid complexes of the stoichiometriesLn(LH₂)Cl₃ (Ln=La–Yb),Ln(LH₂)₂Cl₃ (Ln=La–Sm),Ln ₂(LH₂)₃Cl₆(Ln=Eu–Yb) andLn(LH₂)(NO₃)₃ (Ln=La–Yb). Properties, conductivity measurements, X-ray powder patterns, thermal data, magnetic moments and spectroscopic (IR,¹H-NMR, electronic diffuse reflectance and solid state emission f-f spectra) are discussed in terms of the nature of the bonding and the possible structural types.

---

Synthese und Charakterisierung der Komplexe von Lanthanid(III)chloriden und -nitraten mit der vierzähnigen Schiff-Base Diethyl(ethylenbis--aminocrotonat)

Zusammenfassung Der Schiffbasen-Ligand Diethyl(ethylenbis--aminocrotonat) reagiert mit Lanthanid(III)chloriden und -nitraten in verschiedenen Lösungsmitteln unter der Bildung von festen Komplexen der StöchiometrienLn(LH₂)Cl₃ (Ln = La – Yb),Ln(LH₂)₂Cl₃ (Ln = La – Sm),Ln(LH₂)₃Cl₆ (Ln = Eu – Yb) undLn(LH₂)(NO₃)₃ (Ln = La – Yb). Die allgemeinen Eigenschaften, Leitfähigkeitsmessungen, Röntgen-Pulverdiagramme, thermische Daten, magnetische Momente und spektroskopische Daten (IR,¹H-NMR, Elektronenreflexionsspektren und Festkörperemissions-f-f-Spektren) werden im Hinblick auf die Bildungsverhältnisse im Komplex und strukturelle Möglichkeiten diskutiert.

     

Chemical Speciation of Antimony(III and V) in Water by Adsorptive Cathodic Stripping Voltammetry Using the 4‐(2‐Thiazolylazo) – Resorcinol

A simple adsorptive cathodic stripping voltammetry method has been developed for antimony (III and V) speciation using 4‐(2‐thiazolylazo) – resorcinol (TAR). The methodology involves controlled preconcentration at pH 5, during which antimony(III) – TAR complex is adsorbed onto a hanging mercury drop electrode followed by measuring the cathodic peak current (I_p,c) at ?0.39 V versus Ag/AgCl electrode. The plot of I_p,c versus antimony(III) concentration was linear in the range 1.35×10^?9–9.53×10^?8 mol L^?1.The LOD and LOQ for Sb(III) were found 4.06×10^?10 and 1.35×10^?9 mol L^?1, respectively. Antimony(V) species after reduction to antimony(III) with Na₂SO₃ were also determined. Analysis of antimony in environment water samples was applied satisfactorily.     

Catalytic activity of Mn(III) and Fe(III) complexes of meso-tetra(n-propyl)porphyrin in oxidation of olefins: Meso-alkyl substituent in comparison with the alkenyl and aryl ones

Catalytic activity of Mn(III) and Fe(III) complexes of meso-tetra(n-propyl)porphyrin, MnT(n-Pr)P(X) and FeT(n-Pr)P(X) (X = Cl, SCN, OAc) in oxidation of olefins with tetra-n-butylammonium periodate at room temperature has been studied. The influence of different parameters including the molar ratio of catalyst to imidazole, type of counter ion (X) and oxidative stability of metalloporphyrins on the efficiency of the catalysts was investigated. The results of competitive oxidation of cis- and trans-stilbene suggest the presence of a high-valent Mn-oxo as the predominant oxidant species in equilibrium with a six coordinate complex, MnT(n-Pr)P(ImH)(IO₄) in the case of MnT(n-Pr)P(OAc). An unusual preference for trans-stilbene over cis-stilbene was observed in the reaction catalyzed by FeT(n-Pr)P(OAc). Control reaction indicated a significant cis- to trans-isomerization (81%) in oxidation of cis-stilbene catalyzed by FeT(n-Pr)P(OAc) which may explain the observed unusual cis to trans-stilbene oxide ratio. While oxidation of cyclooctene and styrene led to the exclusive formation of the corresponding epoxides, oxidation of cyclohexene gave 2-cyclohexe-1-ol and cyclohexene oxide as the products. However, the results of this study clearly demonstrate the key role played by the group substituted at the meso positions of metalloporphyrins on their catalytic activity, apart from the electron-donating or electron-withdrawing properties of the substituents.     

聚甲基三氟丙基硅氧烷固相微萃取涂层的制备及其对海水中酚类化合物的分析

采用溶胶-凝胶技术制备了聚甲基三氟丙基硅氧烷(PTFPMS)涂层,并将其作为萃取     

疏水性Cosalen/SBA-15的制备及在甲苯选择性氧化中的应用

以介孔分子筛SBA-15为载体, 先采用γ-氨丙基三乙氧基硅烷(APTES)进行氨基硅烷化修饰, 然后经甲基三乙氧基硅烷(MTES)疏水修饰后固载双水杨醛缩乙二胺合钴配合物(Cosalen). 采用傅里叶变换红外光谱、 紫外-可见漫反射光谱、 X射线光电子能谱、 元素分析、 等离子体发射光谱、 X射线衍射和氮气物理吸附等手段对制备的固载型催化剂Cosalen/SBA-15进行了物相结构和修饰程度的表征, 并考察了样品对甲苯、 苯甲醛和苯甲醇的吸附性能及在甲苯液相氧化反应中的催化性能. 结果表明, 固载型催化剂Cosalen/SBA-15的介孔结构和孔道有序性保持良好, Cosalen通过与氨基配位固载在修饰后的载体SBA-15上, 且高度分散, 氨基硅烷化和甲基修饰明显增强了其表面疏水性能, 对苯甲醛和苯甲醇的吸附量降低. 疏水性Cosalen/SBA-15协同N-羟基邻苯二甲酰亚胺(NHPI)催化甲苯液相分子氧氧化反应, 无溶剂体系在130 ℃下反应2 h, 甲苯转化率达到16.0%, 产物中苯甲醛和苯甲醇的总选择性为32.0%, 在一定程度上抑制了极性产物深度氧化为苯甲酸. 高温不利于苯甲醛和苯甲醇选择性的提高, 降低温度至110 ℃, 甲苯转化率达到12.9%时, 苯甲醛和苯甲醇的总选择性提高到43.9%.     

Reactions of co-ordinated ligands: Kinetics and mechanisms in the charge transfer interaction between dichloro or diaquo triethylene tetramine Co(III) and ferrocyanide

The cherry red-coloured solid state product obtained by the reaction ofcis-σ diaquo Co (III) triethylene tetramine with ferrocyanide was examined by thermogravimetric, infrared and M?ssbauer techniques. Its electronic spectrum in aqueous medium was interpreted to consist of charge transfer IT transition at 440 nm and a ligand field transition around 330 nm. The kinetics of formation of this 1:1 product in solution was also studied.     

Dynamics of liposomes in the fluid phase

We review the currently available material on the morphology and dynamics of phospholipids assembled into liposomes. Key information obtained from neutron scattering, nuclear magnetic resonance (NMR), and other techniques plays a crucial role in understanding the vital role of lipids in sustaining life in living organisms. We concentrate on the dynamics in the biologically important fluid phase in the time range from picoseconds to seconds, which includes a discussion of the center of mass diffusion of liposomes, membrane fluctuations; and lateral, rotational, and flip-flop motions of the lipids. We emphasize on the sensitivity of the dynamics on interactions with a variety of biologically relevant molecules such as cholesterol. By a comparison of data from literature, we witness a good agreement of the results from different techniques and studies.