Self-ordering process of phenanthrene polyesters observed by the simultaneous DSC-XRD method

Phase transition behavior of polyesters derived from 2,7-phenanthrene dicarbonic acid diethylester and alkanediols with even methylene carbon number was investigated by the simultaneous DSC-XRD method. The smectic A phase was observed on cooling from the molten state. The transition entropy from the isotropic state to the smectic A phase was about 9.0 J mol^-1 K^-1, which depended on the methylene carbon number. The linear expansion coefficients, based on the (001) spacing of the crystalline phase at room temperature, were 1.3·10^-4 K^-1 (crystalline phase), 5.7·10^-4 K^-1 (crystallization region), 1.7·10^-3 K^-1 (smectic A phase) during cooling, and 1.5·10^-4 K^-1 (crystalline phase), and 1.0·10^-3K^-1(melting region) on heating. This revised version was published online in July 2006 with corrections to the Cover Date.     

Phase Equilibria in the Fullerene C60-Fullerene C70-Hexane-o-Xylene-Dimethylformamide System

The phase diagram of the hexane-o-xylene-dimethylformamide ternary liquid system was studied at T= 298.15 K. The diagram contained the regions of homogeneous solutions and two-phase liquid systems (systems with stratification), phase I being enriched in dimethylformamide and phase II, in hexane. The distribution of fullerenes C⁶⁰ and C⁷⁰ was considered at various concentrations and simultaneous presence in sections at variable phase compositions. The extraction isotherms of fullerenes C⁶⁰ and C⁷⁰ under various conditions were found to be close to linear, and the C⁷⁰/C⁶⁰ separation factor depended on the composition of the coexisting phases and ranged from 1.25 to 1.8. Fullerene C⁷⁰ was predominantly distributed in phase I.     

Selective and efficient liquid membrane transport of gold as gold cyanide using an anion carrier

The facilitated transport of Au(III) from cyanide solutions through a bulk liquid membrane is reported. The organic phase consisted of a chloroform solution containing Victoria blue dye as the Au(CN)⁻₄ carrier. The effects of pH of source phase, potassium cyanide concentration in source phase, Victoria blue concentration in the organic phase and sodium hydroxide in the receiving phase on the efficiency of transport process were examined. Under optimum conditions the extent of Au(CN)⁻₄ transport across the liquid membrane was about 97% after 180 min. The carrier can selectively and efficiently transport Au(CN)⁻₄ ion from the aqueous solutions containing other cations such as alkali and alkaline earth, Zn²⁺, Pb²⁺, Cu²⁺, Cd²⁺, Hg²⁺, Ag⁺, Co²⁺, Fe²⁺, Pt²⁺, Pd²⁺ and Ni²⁺.     

Separation of no-carrier-added <Superscript>90</Superscript>Nb from proton induced natural zirconium target

Amongst various radionuclides of molybdenum, ⁹⁰Mo and ⁹⁹Mo have suitable β energy for clinical uses. In this paper we report separation of ⁹⁹Mo from ⁹⁹Mo-^99mTc equilibrium mixture. The liquid–liquid extraction technique has been employed using trioctylamine (TOA) diluted in cyclohexane as organic phase and HCl as aqueous phase. At 10⁻⁵ M HCl and 0.5 M TOA concentration ^99mTc quantitatively transferred to the organic phase leaving ⁹⁹Mo in the aqueous phase. The developed separation method is efficient and provides very high separation factor.     

Highly selective transport of silver ion through a supported liquid membrane using calix[4]pyrroles as suitable ion carriers

Facilitated transport of silver ion across a supported liquid membrane (SLM) by calix[4]pyrroles, as selective ion carriers, dissolved in kerosene has been investigated. The influences of fundamental parameters affecting the transport of silver ion including ion carrier concentration in the membrane phase, thiosulfate concentration in strip phase, picric acid concentration in the feed phase, stirring speed of aqueous phases, type of membrane solvent and time of transport have been studied. In the presence of thiosulfate as a suitable metal ion acceptor in the strip phase and picrate ion as ion pairing agent in the source phase, transport of silver occurs almost quantitatively after 75 min. The selectivity and efficiency of silver transport from aqueous solution containing Cu²⁺, Mg²⁺, Ni²⁺, Ca²⁺, Zn²⁺, Pb²⁺, Co²⁺, Al³⁺, Hg²⁺, Cd²⁺, Fe³⁺, Fe²⁺ and Cr³⁺ were investigated.     

Separation of yttrium from strontium in the aqueous phase of the water/nitrobenzene extraction system

A rapid separation for carrier-free ⁹⁰Y in the aqueous phase of the water/nitrobenzene extraction system from an ⁹⁰Y/⁹⁰Sr generator was proposed. After two-stage extraction separation, chemical yield of ⁹⁰Y in the final aqueous phase was roughly 80%, while ⁹⁰Sr radionuclide impurity in this phase containing carrier-free ⁹⁰Y was 10^-6%.     

Membrane Transport of Pb(II) with a Cooperative Carrier Composed of Dibenzyldiaza‐18‐Crown‐6 and Palmitic Acid

A chloroform membrane system containing a given mixture of dibenzyldiaza‐18‐crown‐6 and palmetic acid was applied for transport of Pb²⁺ ions. The transport was capable of moving metal ions “uphill”. Thus, it was possible to follow the transfer of Pb(II) from the aqueous source phase to the organic layer and from the organic layer to the receiving phase. The effects of thiosulfate concentration in the receiving phase, palmetic acid and dibenzyldiaza‐18‐crown‐6 concentration in the organic phase on the efficiency of the transport system were examined. By using S₂O₃^2? ion as metal ion acceptor in the receiving phase, the amount of lead ion transport across the liquid membrane after 150 minutes is 96 ± 1.5%. The selectivity and efficiency of lead transport from aqueous solution containing Cu²⁺, Tl⁺, Ag⁺, Co²⁺, Ni²⁺, Mg²⁺, Zn²⁺, Hg²⁺, Cd²⁺, Ca²⁺ were investigated. In the presence of thiosulfate as a suitable masking agent in the source phase, the interfering effects of Ag⁺ and Cu²⁺ were diminished drastically.     

Selective transport of copper(II) ions across a liquid membrane mediated by Piroxicam

Piroxicam was found to be a highly selective carrier for uphill transport of Cu²⁺ ions through a chloroform liquid membrane. The transport occurs via a counterflow of protons from the receiving phase to the source phase. The effects of several parameters on the transport of Cu²⁺ ions, such as the carrier concentration, pH of the source phase, composition of the receiving phase, and duration are described. A high transport efficiency (98±2%) was provided by the carrier for Cu²⁺ ions in a receiving phase of 0.01 mol l⁻¹ sulfuric acid after 4 h. Different metal ion transport experiments showed that Cu²⁺ ions were selectively transported over other ions, such as Co²⁺, Ni²⁺, Cd²⁺, Pb²⁺, Zn²⁺, UO₂²⁺ and ZrO₂²⁺. In the presence of fluoride ions (used as a suitable masking agent in the source phase), the interfering effects of UO₂²⁺ and ZrO₂²⁺ ions were eliminated. The applicability of the method was tested on a real sample, and the results obtained show that it is potentially useful for solvent extraction of copper.     

Mössbauer Spectroscopy and Preparation of Hg-1223, Tl-1223 and Tl-1212 Superconductors

Introduction of the Mössbauer nuclei ⁵⁷Fe into Hg-1223 phase and that of ⁵⁷Fe and ¹⁵¹Eu into Tl-1212 and Tl-1223 superconductors were investigated. Samples of high phase purity were obtained. Scanning electron microscopy and optical microscopy in normal and polarized light were employed to study the microstructure of the specimens. Energy dispersive X-ray analysis showed that ⁵⁷Fe in the Hg-based samples and ⁵⁷Fe as well as ¹⁵¹Eu in the Tl-based compounds, entered superconducting phases. Incorporation of Eu³⁺ into the superconducting phase favored the formation of the Tl-1212 phase. Mössbauer spectroscopy showed that Eu³⁺ entered the Ca-site. Two doublets found in the ⁵⁷Fe Mössbauer spectra in both the Hg-1223 and the Tl-1223 phase referred to two different micro-environments of Fe³⁺. The assignment of the ⁵⁷Fe Mössbauer spectra was made under the assumption that Fe favored the 1223 phase. Fe³⁺ may replace Cu in both the square pyramidal, five-fold oxygen coordinated Cu sites between the Ca and Ba-(Sr)-O layers, and in the square planar, four-fold oxygen coordinated Cu sites the Ca layers in the superconducting phases in both the Hg- and the Tl-based materials. From the relative areas of the two doublets, we concluded that the Fe³⁺ preferred the square planar Cu site.     

协同萃取液膜体系从Li+、Na+、K+混合溶液中提取Li+

从卤水、海水中提取Li是目前较为活跃的研究课题。用液膜法从Li~+、Na~+、K~+混合溶液中分离Li~+的报道很少。协同效应在乳状液型液膜中的应用还未见报道。本文采用噻吩甲酰三氟丙酮(HTTA)和磷酸三丁酯(TBP)作为混合载体的液膜体系,快速、高效地从Li~+、Na~+、K~+的混合溶液中分离、浓缩Li~+,为从卤水、海水中提取Li~+提供了重要的依据。     

Separation of yttrium from strontium in the aqueous phase of the water/nitrobenzene system

A rapid separation of carrier-free ⁹⁰Y in the aqueous phase of the water/nitrobenzene extraction system from an ⁹⁰Y/⁹⁰Sr generator is proposed. After a three-stage extraction, the chemical yield of ⁹⁰Y in the final aqueous phase was almost 90%, while the ⁹⁰Sr radionuclide impurity in this phase containing carrier-free ⁹⁰Y was about 10^–10%.     

Transitions de phases multiples et propriétés ferroïques de Pb5Al3F19

Pb₅Al₃F₁₉, a member of the isostructural Pb₅M₃F₁₉, family with M = Al, Ti, V, Cr, Fe and Ga, differs from the remaining members in having three additional phases between its ferroelectric phase V and its paraelectric phase I. Phase IV is shown to be antiferroelectric, phase III ferroelastic and phase II paraelastic. Each phase has been fully characterized. Formation of the three extra phases is attributed to interactions between the 6(sp)² lone electron pair of the Pb² ion and volume effects related to the small Al³⁺ ion.     

Synchrotron and neutron powder diffraction study of phase transition in weberite-type Nd3NbO7 and La3NbO7

La₃NbO₇ and Nd₃NbO₇ are insulating compounds that have an orthorhombic weberite-type crystal structure and undergo a phase transition at about 360 and 450 K, respectively. The nature of the phase transitions was investigated via heat capacity measurements, synchrotron X-ray and neutron diffraction experiments. It is here shown that above the phase transition temperature, the compounds possess a weberite-type structure described by space group Cmcm (No. 63). Below the phase transition, the high temperature phase transforms into a weberite-type structure with space group Pmcn (No. 62). The phase transformation primarily involves the off-center shifting of Nb⁵⁺ ions inside the NbO₆ octahedra, combined with shifts of one third of the Ln³⁺ (Ln³⁺=La³⁺ and Nd³⁺) ions at the center of the LnO₈ polyhedra towards off-center positions. The phase transition was also proven to have great impacts on the dielectric properties.     

Application of mercapto‐silica polymerized high internal phase emulsions for the solid‐phase extraction and preconcentration of trace lead(II)

A new class of solid‐phase extraction column prepared with grafted mercapto‐silica polymerized high internal phase emulsion particles was used for the preconcentration of trace lead. First, mercapto‐silica polymerized high internal phase emulsion particles were synthesized by using high internal phase emulsion polymerization and carefully assembled in a polyethylene syringe column. The influences of various parameters including adsorption pH value, adsorption and desorption solvents, flow rate of the adsorption and desorption procedure were optimized, respectively, and the suitable uploading sample volumes, adsorption capacity, and reusability of solid phase extraction column were also investigated. Under the optimum conditions, Pb²⁺ could be preconcentrated quantitatively over a wide pH range (2.0–5.0). In the presence of foreign ions, such as Na⁺, K⁺, Ca²⁺, Zn²⁺, Mg²⁺, Cu²⁺, Fe²⁺, Cd²⁺, Cl^? and NO₃^?, Pb²⁺ could be recovered successfully. The prepared solid‐phase extraction column performed with high stability and desirable durability, which allowed more than 100 replicate extractions without measurable changes of performance. The feasibility of the developed method was further validated by the extraction of Pb²⁺ in rice samples. At three spiked levels of 40.0, 200 and 800 μg/kg, the average recoveries for Pb²⁺ in rice samples ranged from 87.3 to 105.2%.     

Disorder in crystalline phases of chiral glass formers 5CB and 8OCB evidenced by the low temperature heat capacity

The heat capacity of two glass formers 5^*CB and 8^*OCB, each of which has two crystalline polymorphs (phases I and II) as well as a glass phase, was determined between 0.35 K and 20 K. The T-linear term of the heat capacity becomes significant below 1 K for both glasses. The glassy crystalline phase II of 5^*CB also shows such contribution, which is consistent with the existence of a residual entropy. Unexpectedly, however, the ‘stable’ phase II of 8^*OCB shows the similar contribution, indicating that this phase is disordered, whereas the glassy crystalline phase I shows no such contribution.     

Phase behavior and rheological properties of lecithin/TTAOH/H<Subscript>2</Subscript>O mixtures

The phase behavior, structures, and rheological properties of lecithin/tetradecyltrimethylammonium hydroxide (TTAOH)/water system were investigated by cryogenic transmission electron microscopy (cryo-TEM), polarization optical microscope, ¹H and ³¹P nuclear magnetic resonance (NMR) spectra, surface tension, and rheological measurements. With the variation of mixing molar ratios and concentrations of lecithin and TTAOH, the system exhibits the phase transition from micelles (L₁ phase) to vesicles (L_α phase) through a phase separation region. The rod-like micelles, uni- and multilamellar vesicles were determined by means of cryo-TEM observations. The surface tension and rheological measurements were performed to follow the phase transition. The samples of L₁ phase region behave as Newton fluids at low concentration of lecithin. With the increase of the lecithin concentration, a shear-thinning L₁ phase at the shearing rate 100 s⁻¹ was found. The samples of \textL_a {{\text{L}}_{\alpha }} phase region show viscoelastic properties of the typical vesicles. The interactions between lecithin and TTAOH were monitored by ¹H and ³¹P NMR spectra. These results could contribute towards the understanding of the basic function of lecithin in biological membranes and membranous organelles.     

Separation of Free Amiimo Acids on Reverse Stationary Phases Using an Alkyl Sulfonate Salt as a Mobile Phase Additive

Abstract

Alkylsulfonate (RSO₃ ^?) salts were evaluated as mobile phase additives for the separation of free amino acids on reverse stationary phases using an acidic mobile phase where the amino acids are cations. The enhanced amino acid retention is the result of two major interactions, one being retention of the RSO₃ ^? salt on the stationary phase and the other an ion exchange selectivity between the amino acid analyte cation and the RSO₃ ^? countercation, or other countercations in the mobile phase. Major mobile phase variables are: type and concentration of RSO₃ ^? salt (the studies focused on C₈SO₃ ^? salts), presence of organic modifier, type of countercation present, and mobile phase pH and ionic strength. Alkyl modified silica and polystyrenedivinyl-benzene copolymeric reverse stationary phases were compared. A mobile phase gradient, increasing per cent organic modifier was shown to be best, is necessary for separating complex mixtures of polar and nonpolar or basic amino acids. The procedure is applicable to the identification and/or determination of amino acids in mixtures or in peptides after hydrolysis.     

Cubic phases of binary systems of 4′-n-tetradecyloxy-3′-nitrobiphenyl-4-carboxylic acid (ANBC-14)-n-alkane

The phase behaviour of the binary systems 4′- ⁿ -tetradecyloxy-3′-nitrobiphenyl-4-carboxylic acid (ANBC-14)- ⁿ -alkane ( ⁿ -tetradecane or ⁿ -hexadecane) was investigated by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. The phase behaviour was a function of temperature ( ^T ) and the effective carbon number of the system ( ^n*), where ^n* involves carbon atoms both from the alkoxy group of ANBC-14 and from the ⁿ -alkane added. ANBC-14 shows no cubic phase, but the addition of ⁿ -alkane induced cubic phases when ^n*≧c. 15. An interesting point is that the type of cubic phase is ^Ia 3 ^d for 15^≦n*≦17, while an ^Im 3 ^m type is formed for 18^≦n*≦20. Furthermore, for ^n* = 22, two types of cubic phase, one with ^Im 3 ^m symmetry in the low temperature region and the other with ^Ia 3 ^d in the high temperature region, were observed both on heating and cooling. The phase diagram with respect to ^T and ^n* is very similar to that of pure one-component ANBC- ⁿ , which is a function of ^T and the number of carbon atoms in the alkoxy group ⁿ .     

Green and efficient extraction strategy to lithium isotope separation with double ionic liquids as the medium and ionic associated agent

The paper reported a green and efficient extraction strategy to lithium isotope separation. A 4-methyl-10-hydroxybenzoquinoline (ROH), hydrophobic ionic liquid—1,3-di(isooctyl)imidazolium hexafluorophosphate ([D(i-C₈)IM][PF₆]), and hydrophilic ionic liquid—1-butyl-3-methylimidazolium chloride (ILCl) were used as the chelating agent, extraction medium and ionic associated agent. Lithium ion (Li⁺) first reacted with ROH in strong alkali solution to produce a lithium complex anion. It then associated with IL⁺ to form the Li(RO)₂IL complex, which was rapidly extracted into the organic phase. Factors for effect on the lithium isotope separation were examined. To obtain high extraction efficiency, a saturated ROH in the [D(i-C₈)IM][PF₆] (0.3 mol l^?1), mixed aqueous solution containing 0.3 mol l^?1 lithium chloride, 1.6 mol l^?1 sodium hydroxide and 0.8 mol l^?1 ILCl and 3:1 were selected as the organic phase, aqueous phase and phase ratio (o/a). Under optimized conditions, the single-stage extraction efficiency was found to be 52 %. The saturated lithium concentration in the organic phase was up to 0.15 mol l^?1. The free energy change (ΔG), enthalpy change (ΔH) and entropy change (ΔS) of the extraction process were ?0.097 J mol^?1, ?14.70 J mol K^?1 and ?48.17 J mol^?1 K^?1, indicating a exothermic process. The partition coefficients of lithium will enhance with decrease of the temperature. Thus, a 25 °C of operating temperature was employed for total lithium isotope separation process. Lithium in Li(RO)₂IL was stripped by the sodium chloride of 5 mol l^?1 with a phase ratio (o/a) of 4. The lithium isotope exchange reaction in the interface between organic phase and aqueous phase reached the equilibrium within 1 min. The single-stage isotope separation factor of ⁷Li–⁶Li was up to 1.023 ± 0.002, indicating that ⁷Li was concentrated in organic phase and ⁶Li was concentrated in aqueous phase. All chemical reagents used can be well recycled. The extraction strategy offers green nature, low product cost, high efficiency and good application prospect to lithium isotope separation.     

Liquid-phase MnO<Subscript>2</Subscript>-modification of clinoptilolite

Formation mechanism of the MnO₂ phase in the reaction of heterogeneous synthesis between Mn²⁺ and MnO ₄ ^- ions on a solid aluminosilicate surface in aqueous solutions was studied. It was shown that, for lowsilica forms, the Mn²⁺ ion is oxidized by the MnO ₄ ^- ion uniformly across the grain depth to give the MnO₂ phase and manganese manganites. For high-silica materials, the MnO₂ phase is formed on the outer surface of grains, with the decomposition of the MnO ₄ ^- ion and formation of the MnO₂ phase and molecular oxygen. It was found that, for the clinoptilolite rock used as a solid support, the yield of the MnO₂ phase and its distribution over the particle volume depend on the penetration capacity of the MnO ₄ ^- ion into the porous structure of this rock, determined by its composition. It is shown that the amount of the MnO₂ phase grows with increasing concentration of the MnO ₄ ^- ion and treatment duration, with the phase thickness being 15–20 and 350–1050 μm for, respectively, high- and low-silica samples.