Monoolein cubic phase containing alginate/cystamine gel for controlled release of epidermal growth factor

Monoolein (MO) cubic phase including alginate and cystamine in its water channel controlled the release of epidermal growth factor (EGF) by responding to changes in pH value and the reductive conditions of the release medium. The crosslinking degree of alginate gel with cystamine and the complex coacervation of alginate and EGF were investigated by using light scattering. TEM micrographs of cubic phases revealed MO bilayers along with water channels. Differential scanning calorimetry indicated that the cubic-to-hexagonal phase transition took place at 60.2?°C. Additives such as stearyl trimethyl ammonium chloride and cystamine decreased the transition temperature by a few to more than 10?°C. The release of EGF loaded in cubic phases was completed in 5?h and, thereafter, no significant additional release was observed. The release % of EGF loaded in MO cubic phase containing alginate and cystamine increased not only with the increase of pH but also glutathione concentration. The MO cubic phase containing alginate/cystamine gel can be used as a carrier for the delivery of peptide and protein drugs.     

Time‐Resolved Phase Transitions of the Nanocrystalline Cubic to Submicron Monoclinic Phase in Mn2O3‐ZrO2

The nanocrystalline cubic phase of zirconia was found to be thermally stabilized by the addition of 3 to 40 mol % manganese. The nanocrystalline cubic, tetragonal and monoclinic phases of zirconia stabilized with manganese (III)oxide (Mn‐Stabilized Zirconia) were prepared by thermal decomposition of carbonate and hydroxide precursors. Both the crystallization and isothermal phase transitions associated with Mn‐SZ were studied using high temperature x‐ray diffraction and x‐ray diffraction of quenched samples. Cubic Mn‐SZ initially crystallized and progressively transformed to tetragonal, and monoclinic structures above 700°C. The nanocrystalline cubic Mn‐SZ containing 25 mol % Mn was found to have the greatest thermal stability, retaining its cubic form at temperatures as high as 800°C for periods up to 25 hours. Higher than 40 mol %, cubic Mn₂O₃ was found to coexist with cubic Mn‐SZ. The crystallite sizes observed for the cubic, tetragonal and monoclinic Mn‐SZ phases ranged from 50 to 137, 130 to 220, and 195 to 450 Å respectively, indicating, for ZrO₂, that particle size was a primary factor in determining its polymorphs. The classical Avrami equation for nucleation and growth was applied to the observed phase transformations.     

Time‐Resolved Phase Transitions of the Nanocrystalline Cubic to Submicron Monoclinic Phase in Zirconia

The nanocrystalline cubic, tetragonal, and submicron monoclinic phases of pure zirconia were prepared by thermal decomposition of carbonate and hydroxide precursors. The crystallization and isothermal phase transformations of the oxide were studied using high temperature X‐ray diffraction, X‐ray diffraction and Raman spectra of quenched samples. Cubic zirconia formed first, and then progressively transformed to tetragonal and monoclinic phases at temperatures as low as 320°C. The cubic, tetragonal, and monoclinic phases for ZrO₂ were found to be distinct functions of crystallite size, indicating the nanocrystalline nature of these phases. They were found to exist within critical size ranges of 50 to 140 Å, 100 to 220 Å and 190 to 420 Å (±5 Å), respectively. Thus, as the crystallites grow during annealing, they first transform from cubic to tetragonal and then from tetragonal to monoclinic at critical sizes. The classical Avrami equation for nucleation and growth was applied to the tetragonal to monoclinic phase transition.     

Kinetics of lamellar-to-cubic and intercubic phase transitions of pure and cytochrome c containing monoolein dispersions monitored by time-resolved small-angle X-ray diffraction

We investigated the effect of incorporation of a small aqueous peripheral membrane protein (cyt c) into the three-dimensional periodic nanochannel structures formed by the lipid monoolein (MO) on its rich phase behavior as a function of temperature, pressure, and protein concentration using synchrotron X-ray small-angle diffraction. By simultaneous use of the pressure-jump relaxation technique and time-resolved synchrotron X-ray diffraction, we also studied the kinetics of various lipid mesophase transformations of the system for understanding the mechanistic pathways of their formation influenced by the protein-lipid interactions. Cyt c incorporated into the bicontinuous cubic phase Ia3d of MO has a significant effect on the lipid structure and the pressure stability of the system already at low protein concentrations. Concentrations higher than 0.2 wt % of cyt c led to an increase in interfacial curvature due to interaction of the protein with the lipid headgroups. This promotes the formation of a new, probably partially micellar cubic phase of crystallographic space group P4(3)32. Upon pressurization, the P4(3)32 phase undergoes a phase transition to a cubic Pn3m phase with smaller partial specific volume. Increase in protein concentration increases the pressure stability of the P4(3)32 phase. The formation of this phase from the cubic phase Pn3m is a slow process taking many seconds and having a time lag in the beginning. It seems to occur as a two-state process without ordered intermediate states. At temperatures above 60 degrees C, the P4(3)32 phase is unable to accommodate the unfolded protein and transforms to a bicontinuous cubic Ia3d phase. Time-resolved small-angle X-ray scattering studies show that the L(alpha) --> Ia3d transition in pure MO dispersions under limited hydration conditions occurs within a time interval of 1 s at 35 degrees C preceded by a lag phase of 1.5 s. The Ia3d cubic phase initially forms with a much larger lattice constant due to hydration and experiences an initially lower curvature that relaxes within about 1 s. Interestingly, no other cubic phases are involved as intermediates in the transition, i.e., the gyroid cubic phase is able to form directly from the L(alpha) phase. The mechanism behind the L(alpha) --> Ia3d transition in pure MO dispersions has been discussed within the framework of recent stalk models for membrane fusion. In the presence of cyt c, the L(alpha) --> Ia3d transition is much slower. The rather long relaxation times of the order of seconds are probably due to a kinetic trapping of the system and limitation by the transport and redistribution of water and lipid in the evolving new lipid phases. We also studied the transition from the pure lamellar L(alpha) phase to the Ia3d-P4(3)32 two phase region and observed a rather complex transition behavior with transient lamellar and cubic intermediate states.     

In vitro skin permeation of cubosomes containing water soluble extracts of Korean barberry

The monoolein (MO) cubic phases containing water soluble extract (WSE) from Berberis koreana (Korean barberry) were prepared by hydrating the molten MO with aqueous solutions of WSE (0.5, 1.0, and 1.5%). The phase transition temperature of cubic phase containing WSE (∼70°C) was almost the same as that of WSE-free MO cubic phase that indicates that WSE was immobilized in the water channels of the cubic phase and did not affect its structure. The release of WSE from the cubic phase fits the first order process. The cubosomes were obtained by micronizing the cubic phase in a sonicator using Pluronic F127 as a dispersant. The cubosomes were stable in size at the ethanol concentration ≲16%. When compared with WSE solution in phosphate-buffered saline (10 mM, pH 7.4), in vitro skin permeation of WSE in the cubosomes was enhanced by about two times.     

Stimuli‐Responsive Lipidic Cubic Phase: Triggered Release and Sequestration of Guest Molecules

New stimuli‐responsive nanomaterials, made up of host–guest lipidic cubic phases (LCPs) are presented. These biocompatible, stable, transparent and water‐insoluble LCPs are composed of monoolein (MO) as a neutral host, and small amounts of one of three judiciously designed and synthesized designer lipids as guest that preserve the structure and stability of LCPs, but render them specific functionalities. Efficient pH‐ and light‐induced binding, release and sequestration of hydrophilic dyes are demonstrated. Significantly, these processes can be performed sequentially, thereby achieving both temporal and dosage control, opening up the possibility of using such LCPs as effective carriers to be used in drug delivery applications. Specifically, because of the inherent optical transparency and molecular isotropy of LCPs they can be envisaged as light‐induced drug carriers in ophthalmology. The results presented here demonstrate the potential of molecular design in creating new functional materials with predicted operating mode.     

Aqueous self-assembly of phytantriol in ternary systems: effect of monoolein, distearoylphosphatidylglycerol and three water-miscible solvents

The aqueous phase behavior of phytantriol (PT) in mixtures of monoolein (MO), distearoylphosphatidylglycerol (DSPG), propylene glycol (PG), polyethylene glycol 400 (PEG 400) and 2-methyl-2,4-pentanediol (MPD) was investigated by visual inspection, polarized light microscopy and small angle X-ray diffraction at room temperature. The phase diagrams of PT and MO in water are qualitatively very similar and PT/MO mixtures in excess water form one cubic phase of space group Pn3m irrespective of mixing ratio. The addition of the charged membrane lipid DSPG to the PT system gives rise to a considerable water swelling of the cubic phases as well as the occurrence of a cubic phase of space group Im3m. Whereas all three solvents studied give rise to a sponge (L3) phase in the MO-water system, this phase was only found when MPD was added to the PT-water system. The results are discussed with respect to the chemical differences between PT and MO.     

Thermo- and UV Photo-Triggerable Monoolein Cubic Phase Bearing Poly(Hydroxyethyl Acrylate-co-Coumaryl Acrylate-co-Octadecyl Acrylate)

Thermo- and UV photo-triggerable monoolein (MO) cubic phases were developed by incorporating poly(hydroxyethyl acrylate-co-coumaryl acrylate-co-octadecyl acrylate) (P(HEA-CA-ODA)) in the cubic phases. P(HEA-CA-ODA)s, for which the HEA/CA/ODA molar ratio was 98.6:0:1.4, 96.7:2.0:1.3, 96.2:2.6:1.2, 95:3.8:1.2, and 92.8:6.1:1.1, calculated on the ¹H NMR spectra, were prepared by a free radical reaction. The air–water interfacial tension was inversely proportional to the CA content of the copolymer. The copolymers for which the CA content was 2.6%, 3.8%, and 6.1% exhibited their phase transition temperature in an aqueous solution in the temperature range from 25°C to 40°C. As the CA content was more, the temperature sensitivity was higher and the phase transition temperature was lower. The UV light (254 nm, 6 W)-induced dimerization degree of CA was proportional to its content in the copolymers. The release of fluorescein isothiocyanate-dextran from cubic phases containing P(HEA/CA/ODA)s was promoted by UV light irradiation, possibly due to the photo-induced collapse of the copolymer chains. The release from cubic phases incorporating copolymers, for which the CA content was 3.8% and 6.1%, was enhanced by increasing the releasing medium temperature from 23°C to 37°C, possibly due to the thermal collapse of the copolymer chains.     

Time‐Resolved High and Low Temperature Phase Transitions of the Nanocrystalline Cubic Phase in the Y2O3‐ZrO2 and Fe2O3‐ZrO2 System

The nanocrystalline cubic Phase of zirconia was found to be thermally stabilized by the addition of 2.56 to 17.65 mol % Y₂O₃ (5.0 to 30.0 mol % Y, 95.0 to 70.0 mol % Zr cation content). The cubic phase of yttria stabilized zirconia was prepared by thermal decomposition of the hydroxides at 400°C for 1 hr. 2.56 mol % Y₂O₃‐ZrO₂ was stable up to 800°C in an argon atmosphere. The samples with 4.17 to 17.65 mol % Y₂O₃ were stable to 1200°C and higher. All samples at temperatures between 1450°C to 1700°C were cubic except the sample with 2.56 mol % Y₂O₃ which was tetragonal. The crystallite sizes observed for the cubic phase ranged from 50 to 150 Å at temperatures below 900°C and varied from 600 to 800 nm between 1450°C and 1700°C. Control of furnace atmosphere is the main factor for obtaining the cubic phase of Y‐SZ at higher temperature. Nanocrystalline cubic Fe‐SZ (Iron Stabilized Zirconia) with crystallite sizes from 70 to 137 Å was also prepared at 400°C. It transformed isothermally at temperatures above 800°C to the tetragonal Fe‐SZ and ultimately to the monoclinic phase at 900°C. The addition of up to 30 mol % Fe(III) thermally stabilized the cubic phase above 800°C in argon. Higher mol % resulted in a separation of Fe₂O₃. The nanocrystalline cubic Fe‐SZ containing a minimum 20 mol % Fe (III) was found to have the greatest thermal stability. The particle size was a primary factor in determining cubic or tetragonal formation. The oxidation state of Fe in zirconia remained Fe³⁺. Fe‐SZ lattice parameters and rate of particle growth were observed to decrease with higher iron content. The thermal stability of Fe‐SZ is comparable with that of Ca‐SZ, Mg‐SZ and Mn‐SZ prepared by this method.     

Effect of tris(hydroxymethyl) aminomethane on the phase behavior of poly(ethylene imine)/cinnamic acid conjugate and the release property of cubic phase containing the conjugate

The upper critical solution temperature (UCST) of poly(ethylene imine)/cinnamic acid (PEI/CA) conjugate decreased as the tris(hydroxymethyl) aminomethane (THMAM) concentration increased. On the optical micrographs of PEI/CA mixture solutions at 25°C, the microspheres were found when the THMAM concentration was 0?mM and 100?mM, but hardly found at 200?mM. Monoolein (MO) cubic phase containing PEI, CA, and THMAM exhibited a bilayer structure on the TEM micrograph. The release degree of methylene blue loaded in the cubic phase was not strongly dependent on THMAM concentration at 25°C and 37°C, but strongly dependent on the concentration at 50°C.     

Nanostructural studies on monoelaidin-water systems at low temperatures

In recent years, lipid based nanostructures have increasingly been used as model membranes to study various complex biological processes. For better understanding of such phenomena, it is essential to gain as much information as possible for model lipid structures under physiological conditions. In this paper, we focus on one of such lipids--monoelaidin (ME)--for its polymorphic nanostructures under varying conditions of temperature and water content. In the recent contribution (Soft Matter, 2010, 6, 3191), we have reported the phase diagram of ME above 30 °C and compared with the phase behavior of other lipids including monoolein (MO), monovaccenin (MV), and monolinolein (ML). Remarkable phase behavior of ME, stabilizing three bicontinuous cubic phases, motivates its study at low temperatures. Current studies concentrate on the low-temperature (<30 °C) behavior of ME and subsequent reconstruction of its phase diagram over the entire temperature-water composition space (temperature, 0-76 °C; and water content, 0-70%). The polymorphs found for the monoelaidin-water system include three bicontinuous cubic phases, i.e., Ia3d, Pn3m, and Im3m, and lamellar phases which exhibit two crystalline (L(c1) and L(c0)), two gel (L(β) and L(β*)), and a fluid lamellar (L(α)) states. The fluid isotropic phase (L(2)) was observed only for lower hydrations (<20%), whereas hexagonal phase (H(2)) was not found under studied conditions. Nanostructural parameters of these phases as a function of temperature and water content are presented together with some molecular level calculations. This study might be crucial for perception of the lyotropic phase behavior as well as for designing nanostructural assemblies for potential applications.     

Existiert eine Wurtzit‐Modifikation von Lithiumbromid? — Untersuchungen im System LiBr/LiI —

Is there a Wurtzite‐Modification of Lithium Bromide? — Studies on the System LiBr/LiI — Deposition of mixtures of LiBr/LiI (ratio: LiBr/LiI = 3:1, 2:1, 1:1, 1:2, 1:3, 1:4) and of pure LiI and LiBr from the gas phase onto a sapphire substrate at ‐196 °C in a high vacuum chamber were investigated by means of temperature‐dependent X‐ray diffraction. Below 0 °C LiI crystallizes in the hexagonal Wurtzite‐modification (β‐LiI) with a = 451.4(1) und c = 731.1(2) pm, which transforms into the cubic rock salt modification (α‐LiI, a = 602.57(3) pm) by heating up to room temperature. Co‐depositions of LiBr/LiI formed solid LiBr_1‐xI_x solutions that also crystallize in the Wurtzite‐modification, below room temperature. Compared to β‐LiI, these solid solutions are more stable and transform into the cubic phase at the significantly higher temperature of 80 °C. The lattice constants of LiBr_1‐xI_x with x ≈ 0.7 are a = 445.48(7), c = 719.1(1) pm and with x ≈ 0.4 are a = 431.50(5), c = 691.7(1) pm. The hexagonal phase LiBr_1‐xI_x is observed for the complete series of mixed crystals with 0.25 ≤ x ≤ 0.8. Both cubic phases, α‐LiI and LiBr, show solubilities of up to ca. 10 % of the respective other compound. In case of pure LiBr only the cubic modification (a = 551.54(2) pm, 25 °C) was observed in the complete temperature range (‐196 °C to 25 °C).     

Temperature‐Dependent Atomic Models of Detergent Micelles Refined against Small‐Angle X‐Ray Scattering Data

Surfactants have found a wide range of industrial and scientific applications. In particular, detergent micelles are used as lipid membrane mimics to solubilize membrane proteins for functional and structural characterization. However, an atomic‐level understanding of surfactants remains limited because many experiments provide only low‐resolution structural information on surfactant aggregates. In this work, small‐angle X‐ray scattering is combined with molecular dynamics simulations to derive fully atomic models of two maltoside micelles at temperatures between 10 °C and 70 °C. The micelles take the shape of general tri‐axial ellipsoids and decrease in size and aggregation number with increasing temperature. Density profiles of hydrophobic groups and water along the three principal axes reveal that the minor micelle axis closely mimics lipid membranes. The results suggest that coupling atomic simulations with low‐resolution data allows the structural characterization of surfactant aggregates.     

SAXS investigation of a cubic to a sponge (L3) phase transition in self-assembled lipid nanocarriers

The encapsulation and release of peptides, proteins, nucleic acids, and drugs in nanostructured lipid carriers depend on the type of the self-assembled liquid-crystalline organization and the structural dimensions of the aqueous and membraneous compartments, which can be tuned by the multicomponent composition of the systems. In this work, small-angle X-ray scattering (SAXS) investigation is performed on the 'melting' transition of the bicontinuous double diamond cubic phase, formed by pure glycerol monooleate (MO), upon progressive inclusion of varying fractions of pharmaceutical-grade glycerol monooleate (GO) in the hydrated system. The self-assembled MO/GO mixtures are found to form diamond (Pn3m) inverted cubic, inverted hexagonal (H(II)), and sponge (L(3)) phases at ambient temperature in excess of aqueous medium without heat treatment. Mixing of the inverted-cubic-phase-forming MO and the sponge-phase-forming GO components, in equivalent proportions (50/50 w/w), yields an inverted hexagonal (H(II)) phase nanostructured carrier. Scattering models are applied for fitting of the experimental SAXS patterns and identification of the structural changes in the aqueous and lipid bilayer subcompartments. The possibility of transforming, at ambient temperature (20 °C), the bicontinuous cubic nanostructures into inverted hexagonal (H(II)) or sponge (L(3)) mesophases may facilitate novel biomedical applications of the investigated liquid crystalline self-assemblies.     

On the microstructures of ethyl acetate/monoolein/water

A phase diagram, describing the behavior of the polar lipid monoolein (MO), water, and ethyl acetate (EtAc), is here presented as well as results from small angle X-ray scattering. MO is found to have a solubility of 60 wt.% in EtAc at 20 °C. No macroscopic aggregation of MO can, initially, be detected in the binary MO/EtAc solution even though MO forms solid crystals in concentrated samples when times goes by. In case of the ternary system small amounts of water, mainly bound to the lipid head groups, can be incorporated in the liquid EtAc/MO phase as water has a limited solubility in EtAc. For EtAc/water mass ratios below 2/3 EtAc is present into the reversed bicontinuous cubic and lamellar phases present in the binary MO/water system. To conclude, EtAc is mainly partitioned to the lipid membranes, with minor effects on spontaneous curvature. Hence, simple EtAc-addition has an effect similar to dehydration. For EtAc/water ratios above 2/3 the liquid crystalline phases dissolve. The phase behavior is here discussed in view of related phase behaviors for water-miscible solvent/MO/water systems. For instance, an interpretation of the swelling behavior of the sponge phase (L₃), present in the water-miscible solvent(s)/MO/water systems, shows that solvents partitioned to the polar domains strongly increases the spontaneous curvature of the MO-films. The reason is probably weaker hydrophobic interactions in interfacial regions. As expected, in case of water-miscible solvents, the ternary phase behaviors can be understood by consider water and water-miscible solvent as one “mixed solvent”.     

Monoolein cubic phases containing hydrogen peroxide

Monoolein (MO) cubic phases were prepared by hydrating MO using distilled water or 12 wt.% H₂O₂ solution so that the content of aqueous phase in the cubic phase is 30 wt.%. The thermal transition of the isotropic cubic phase to reversed hexagonal phase was observed on a polarizing photomicroscope and the transition temperature was found to be around 65 °C on a differential scanning calorimeter (DSC). Small-angle X-ray scattering (SAXS) patterns indicated the cubic phases had diamond surfaces. The cubic phase released H₂O₂ into an aqueous phase in a saturation manner so that approx. 50% of total loaded H₂O₂ release in the first 10 h and thereafter relatively slow was observed over 40 h. The cubic phase was stable at 45 °C for 56 days before it broke down into an oily phase and an aqueous phase in 70 days. According to ¹H NMR spectrum, glycerol moiety and ---CH₂=CH₂--- of the oily phase were detected less in number than those of intact MO. Therefore, the hydrolysis and the oxidation of MO would be responsible for the breakdown of the cubic phase. The tensile adhesive forces of the cubic phases were higher than a skin-adhesive patch prepared using polyacrylate. The cubic phase containing H₂O₂ could be used as a topical disinfected gel for a wounded skin.     

New mesogen with thermotropic cubic phase: 3,4,5‐tris‐(11,11,12,12,13,13,14,14,15,15,16,16,16‐tridecafluorohexadecyloxy)benzoic acid

A new mesogen, 3,4,5‐tris(11,11,12,12,13,13,14,14,15,15,16,16,16‐tridecafluoro‐hexadecyloxy)benzoic acid, with a thermotropic cubic phase was synthesized. The phase behaviour of the fluorinated compound and its corresponding non‐fluorinated analogue was investigated by differential scanning calorimetry, polarizing optical microscopy, and synchrotron small‐angle X‐ray diffraction. The fluorinated compound, which contains three partially perfluorinated alkoxy moieties and one carboxylic acid group capable of forming hydrogen bonding, exhibits a very interesting sequence of isotropic, cubic and hexagonal columnar phases, whereas its non‐fluorinated compound does not have a liquid crystalline phase. The cubic phase exists over a wide temperature range (from ～200°C to ～30°C on cooling) and is hence amenable to various physical measurements and potential applications. The ability to self‐assemble molecules into ordered superstructure via both partially perfluorinated chains and hydrogen bonding provides new insight for the development of novel liquid crystalline materials.     

Low-pH-induced transformation of bilayer membrane into bicontinuous cubic phase in dioleoylphosphatidylserine/monoolein membranes

Cubic biomembranes, nonbilayer membranes with connections in three-dimensional space that have a cubic symmetry, have been observed in various cells. Interconversion between the bilayer liquid-crystalline (L(alpha)) phase and cubic phases attracted much attention in terms of both biological and physicochemical aspects. Herein we report the pH effect on the phase and structure of dioleoylphosphatidylserine (DOPS)/monoolein (MO) membranes under a physiological ion concentration condition, which was revealed by small-angle X-ray scattering (SAXS) measurement. At neutral pH, DOPS/MO membranes containing high concentrations of DOPS were in the L(alpha) phase. First, the pH effect on the phase and structure of the multilamellar vesicles (MLVs) of the DOPS/MO membranes preformed at neutral pH was investigated by adding various low-pH buffers into the MLV suspension. For 20%-DOPS/80%-MO MLVs, at and below pH 2.9, a transition from the L(alpha) to cubic (Q(224)) phase occurred within 1 h. This phase transition was reversible; a subsequent increase in pH to a neutral one in the membrane suspension transformed the cubic phase into the original L(alpha) phase. Second, we found that a decrease in pH transformed large unilamellar vesicles of DOPS/MO membranes into the cubic phase under similar conditions. We have proposed the mechanism of the low-pH-induced phase transition and also made a quantitative analysis on the critical pH of the phase transition. This finding is the first demonstration that a change in pH can induce a reversible phase transition between the L(alpha) and cubic phases of lipid membranes within 1 h.     

Phase behaviour of the thermotropic cubic mesogen 1,2-bis-(4- n -octyloxybenzoyl)hydrazine under pressure

The phase transition behaviour of an optically isotropic, thermotropic cubic mesogen 1,2-bis-(4-n-octyloxybenzoyl)hydrazine, BABH(8), was investigated under pressures up to 200 MPa using a high pressure differential thermal analyser, wide-angle X-ray diffraction and a polarizing optical microscope equipped with a high pressure optical cell. The phase transition sequence, low temperature crystal (Cr₂)-high temperature crystal (Cr ₁)- cubic (Cub)-smectic C (SmC)-isotropic liquid (I) observed at atmospheric pressure, is seen in the low pressure region below about 30 MPa. The cubic phase disappears at high pressures above 30–40 MPa, in conjunction with the disappearance of the Cr₁ phase. The transition sequence changes to Cr₂-SmC-I in the high pressure region. Since only the Cub-SmC transition line among all the phase boundaries has a negative slope (dT/dP) in the temperature-pressure phase diagram, the temperature range for the cubic phase decreases rapidly with increasing pressure. As a result, a triple point was estimated approximately as 31.6 ±2.0 MPa, 147.0±1.0°C for the SmC, Cub and Cr₁ phases, indicating the upper limit of pressure for the observation of the cubic phase. Reversible changes in structure and optical texture between the Cub and SmC phases were observed from a spot-like X-ray pattern and dark field for the cubic phase to the Debye-Sherrer pattern and sand-like texture for the SmC phase both in isobaric and isothermal experiments.     

Facile synthesis of PbSe hollow nanostructure assemblies via a solid/liquid-phase chemical route and their electrogenerated chemiluminescence properties

Spherical PbSe hollow nanostructure assemblies (HNSAs) were synthesized by a simple one‐pot solid/liquid‐phase reaction in which solid KPbI₃ ? 2 H₂O and SeO₂ are heated in oleic acid/dodecylamine/1‐octadecene at 250 °C for 30 min. XRD analysis shows that the obtained product is cubic‐phase PbSe and well crystallized. FESEM and TEM images reveal that the obtained spherical PbSe assemblies are made up of small, irregular, and fused hollow nanostructure building blocks. On the basis of temperature‐ and time‐dependent investigations as well as control experiments, molten‐salt corrosion of solid PbSe nanocrystal aggregates formed in situ during the high‐temperature ripening stage is suggested to explain the formation of such novel assemblies. Moreover, when the reaction temperature is further increased to 280 or 320 °C with other conditions unchanged, cubic and orthorhombic mixed‐phase PbSe HNSAs is generated. The obtained PbSe HNSAs exhibit excellent electrogenerated chemiluminescence (ECL) performance. Two strong and stable emission peaks at about ?1.4 and +1.5 V (vs. Ag/AgCl) are observed. In particular, the ECL intensity is influenced by the crystal phase of PbSe.