Nanoscale heterogeneity in ceria zirconia with low-temperature redox properties

We have investigated nanoscale compositional and structural variations in Ce(0.5)Zr(0.5)O(2) samples with different redox properties. Different samples were prepared using a spray freezing technique, and the synthesis conditions were varied to yield materials with reduction temperatures in the range of 400-750 degrees C. X-ray diffraction and thermal gravimetric analysis were used to characterize the average structures and redox properties of these materials. The nanoscale structural and compositional variations in individual nanoparticles of high activity were determined with atomic-scale electron imaging and nanometer-resolution electron energy loss spectroscopy. During the early stage of particle formation, the crystallization process is initiated via the nucleation of ceria-rich nanodomains. This results in the formation of high-surface-area materials that exhibit nanoscale compositional heterogeneity consisting of Ce-rich cores surrounded by Zr-rich shells. The effect of high-temperature redox cycling on the nanoscale structure, composition, and low-temperature redox properties was also determined. Our analysis suggests that our most active material exhibits significant compositional and structural heterogeneity at the nanometer level.     

Kinetic gelation predictions of species aggregation in tetrafunctional monomer polymerizations

During the polymerization of tetrafunctional monomers, a heterogeneous distribution of species exists throughout the reaction mixture and dramatically complicates the network structural evolution. This work attempts to quantify this heterogeneity using kinetic gelation simulation predictions of a defining parameter called the heterogeneity index. The heterogeneity index directly measures how heterogeneous the polymerization is with respect to interactions of like species or pairs of species. Examples of the species are polymer segments, monomeric double bonds, pendant double bonds, initiator molecules, radicals, and free volume. By implementing this index, it is clear that the heterogeneity in the polymer network dramatically changes as a function of conversion and polymerization conditions. In particular, microgel formation and monomer pooling were characterized and quantified with the heterogeneity index. In addition to characterizing the structural heterogeneity, the influence of the heterogeneity on the initiator efficiency and trapping of free radicals was also studied and qualitatively compared to experimentally observed behavior. ©1995 John Wiley & Sons, Inc.     

Heterogeneity among multihollow polymer particles prepared by the alkali/cooling method under partial neutralization conditions

Heterogeneity in the formation of multihollow structure among styrene-methacrylic acid copolymer particles, which were produced by emulsion copolymerization, by the alkali/cooling method under partial neutralization conditions with potassium hydroxide was investigated. There was a threshold acid content to form the multihollow structure. The heterogeneity among the multihollow particles was based on the heterogeneity of acid contents among the original particles.     

Dielectric Study of Homogeneity in Some Binary Liquids in Their Supercooled State

In this work, we report a dielectric study of some binary mixtures in their supercooled region over a frequency range of 10⁶ to 10^–3 Hz. Differential scanning calorimetry measurements have been made above 100K. The samples studied here are DL-lactic acid (88% in aqueous solution), binary mixtures of dimethyl sulfoxide and acetic acid, of propylene glycol and cyclohexanol, and of 4-methyl-3-heptanol and tritolyl phosphate. The frequency dispersion of the relaxation spectra and the temperature dependence of the relaxation process have been critically examined for heterogeneity. The mixtures of dimethyl sulfoxide and acetic acid reveal a 1:1 complex formation. Some evidence of heterogeneity was found only in mixtures of 4-methyl-3-heptanol and tritolyl phosphate. For comparison, we have also studied liquid mixtures of isopropylbenzene with small quantities of acetone or fluorobenzene. These mixtures showed no signs of heterogeneity, although the relaxation spectra are broader than the spectrum of pure isopropylbenzene.     

Identification of Regions in Apomyoglobin that Form Intermolecular Interactions in Amyloid Aggregates Using High-Performance Mass Spectrometry

The formation of amyloid aggregates in human organs and tissues causes the development of incurable diseases. However, experimental studies of the mechanism of amyloid formation by proteins and the structural characteristics of amyloids are complicated because of the heterogeneity and high molecular weight of the aggregates. We used limited proteolysis and mass spectrometry for the identification of regions in the apomyoglobin polypeptide chain, which give rise to intermolecular interactions in amyloid structures. Tandem mass spectroscopy enabled the identification of regions in the myoglobin polypeptide chain, which form the core of amyloid structures. It was shown that the main structural elements for the formation of the core of amyloid fibrils in myoglobin were regions from 60 through 90 and from 97 through 124 amino acid residues. These regions coincide well with those theoretically predicted. This approach yielded important data on the structure of protein molecules in aggregates and on conformational rearrangements of apomyoglobin upon amyloid formation.     

Complexation and coacervation of polyelectrolytes with oppositely charged colloids

Polyelectrolyte-colloid coacervation could be viewed as a sub-category of complex coacervation, but is unique in (1) retaining the structure and properties of the colloid, and (2) reducing the heterogeneity and configurational complexity of polyelectrolyte-polyelectrolyte (PE-PE) systems. Interest in protein-polyelectrolyte coacervates arises from preservation of biofunctionality; in addition, the geometric and charge isotropy of micelles allows for better comparison with theory, taking into account the central role of colloid charge density. In the context of these two systems, we describe critical conditions for complex formation and for coacervation with regard to colloid and polyelectrolyte charge densities, ionic strength, PE molecular weight (MW), and stoichiometry; and effects of temperature and shear, which are unique to the PE-micelle systems. The coacervation process is discussed in terms of theoretical treatments and models, as supported by experimental findings. We point out how soluble aggregates, subject to various equilibria and disproportionation effects, can self-assemble leading to heterogeneity in macroscopically homogeneous coacervates, on multiple length scales.     

Esterification with orthophosphoric acid of cellulose samples with different extents of structural heterogeneity

Modification of cellulose samples with different extents of structural heterogeneity by esterification with orthophosphoric acid in the temperature range 140?C160??C was studied. The reaction yielded cellulose phosphates containing 3.2?C6.0 wt % P, with the ion-exchange capacity of 2.2?C3.0 mg-equiv g^?1. Introduction of phosphorus into cellulose leads to a slight decrease in the structural heterogeneity. The polymer with the lower ordering index is characterized by the higher phosphorus content, which suggests that the reaction mainly occurs in the amorphous part of the polymer.     

Interaction of long chain alkylammonium cations with reduced charge montmorillonite

Reduced charge montmorillonites (RCM) were prepared using lithium thermal treatment. The sorption of octylammonium (OA), dodecylammonium (DDA) and hexadecylammonium ions (HDA) on differently charged samples were studied. The amounts of DDA and HDA sorbed on each RCM exceed the cation exchange capacity (CEC) but that of OA exceeds only the CEC of samples with the lowest CEC. The sorption is affected not only by the layer charge but also by the formation of collapsed interlayer spaces in the lowest charged montmorillonites. X-ray measurements confirmed the decrease of the layer charge after lithium thermal treatment and the layer charge heterogeneity in RCMs.     

Formation of the surface NO during N2O interaction at low temperature with iron-containing ZSM-5

Interaction of N2O at low temperatures (473-603 K) with Fe-ZSM-5 zeolites (Fe, 0.01-2.1 wt %) activated by steaming and/or thermal treatment in He at 1323 K was studied by the transient response method and temperature-programmed desorption (TPD). Diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) of NO adsorbed at room temperature as a probe molecule indicated heterogeneity of surface Fe(II) sites. The most intensive bands were found at 1878 and 1891 cm(-1), characteristic of two types mononitrosyl species assigned to Fe2+(NO) involved in bi- and oligonuclear species. Fast loading of atomic oxygen from N2O on the surface and slower formation of adsorbed NO species were observed. The initial rate of adsorbed NO formation was linearly dependent on the concentration of active Fe sites assigned to bi- and oligonuclear species, evolving oxygen in the TPD at around 630-670 K. The maximal coverage of a zeolite surface by NO was estimated from the TPD of NO at approximately 700 K. This allowed the simulation of the dynamics of the adsorbed NO formation at 523 K, which was consistent with the experiments. The adsorbed NO facilitated the atomic oxygen recombination/desorption, the rate determining step during N2O decomposition to O2 and N2, taking place at temperatures > or =563 K.     

Two-dimension fluorescence correlation spectroscopy to characterize the binding of organic ligands with zinc in eutrophic lake

Metal binding of organic ligands can definitely affect its environmental behavior in waters, while information on the binding heterogeneity with different organic ligands is still lacked till now. In this study, the binding of zinc with organic matters associated with cyanobacterial blooms, including dissolved organic matters (DOM) and attached organic matters (AOM), were studied by using fluorescence quenching titration combined with two-dimensional correlation spectroscopy (2D-COS). Metal-induced fluorescent quenching was obviously observed both for DOM and AOM, indicating the formation of metal-ligand complexes. Compared with the one-dimensional spectra, 2D-COS revealed the sequences of metal-ligand interaction with the following orders: 276 nm > 232 nm for DOM and 232 nm > 276 nm for AOM. Furthermore, the modified Stern-Volmer model showed that the binding constant (log KM) of 276 nm in DOM was higher than that of 232 nm (4.93 vs. 4.51), while AOM was characterized with a high binding affinity for 232 nm (log KM: 4.83). The ranks of log KM values were consistent with the sequential orders derived from 2D-COS results both for the two samples. Fluorescence quenching titration combined with 2D-COS was an effective method to characterize the metal-ligand interaction.     

Polybithiophene Heterogeneity: A Differential Cyclic Voltabsorptometry Study

The redox behavior of polybithiophene in 0.1 M Bu₄NBF₄ solutions in acetonitrile is studied using cyclic voltammetry, potentiostatic spectroelectrochemical measurements, and differential cyclic voltabsorptometry. Comparing differential cyclic voltabsorptograms, obtained at wavelengths of 420, 475, and 520 nm for the undoped state and 720, 850, and 1050 nm for the doped state, with the cyclic voltammetry data reveals the polymer heterogeneity. The heterogeneity of the undoped polymer is ascribed to the formation of polymer chains of different lengths during the polybithiophene synthesis. The heterogeneity of the doped polymer is attributed to the existence of two types of an oxidized state. Both states presumably form as the result of the occurrence of two parallel processes. The first oxidized state is probably connected with the formation of a strong complex (associate) of positively charged fragments of a polymer chain with the dopant anion, while the second oxidized state is caused by a weak interaction between the dopant and the doped polymer.     

Spatial heterogeneity in a lyotropic liquid crystal with hexagonal phase

Non-ionic surfactant hexaethylene glycol, C(12)E(6), in water self-assembles into various kinds of mesophases by varying the surfactant concentration. A spatial heterogeneity was discussed on the basis of the diffusion of probe particles dispersed in the C(12)E(6)-water solution. Interestingly, at 50 wt% C(12)E(6) where the hexagonal structure was formed, two kinds of motion of probe particles were observed: some particles normally diffused while others were restricted, indicating the existence of a heterogeneity in the physical properties. Such heterogeneity can be explained in terms of heterogeneous structures composed of hexagonal domains with isotropic-like regions.     

A nanoengineering approach to regulate the lateral heterogeneity of self-assembled monolayers

Using a scanning probe lithography method known as nanografting in conjunction with knowledge of self-assembly chemistry, regulation of the heterogeneity of self-assembled monolayers (SAMs) is demonstrated. While nanografting in single-component thiols produces areas of SAMs with designed geometry and size, nanofabrication in mixed thiol solution yields segregated domains. The reaction mechanism in nanografting differs significantly from self-assembly in mix-and-grow methods, as proven in systematic studies reported in this article and a companion paper of theoretical calculations of the nanografting process. Knowledge of the reaction pathways enables development of methods for shifting the interplay between the kinetics and thermodynamics in SAM formation, and thus the heterogeneity of mixed SAMs. By varying fabrication parameters, such as shaving speed, and reaction conditions, such as concentration and ratio of the components, the lateral heterogeneity can be adjusted ranging from near molecular mixing to segregated domains of several to tens of nanometers.     

Heterogeneous copolymerization of acrylamide with maleic acid in dioxane

Heterogeneous copolymerization of acrylamide with maleic acid has been investigated. The process was carried out at 70°C in 1,4-dioxane. The polarographic method of analysis was applied. The analysis of the experimental and theoretical composition distribution curves has shown an anomalously large composition polydispersion for the experimental distribution curves. This is attributed to the heterogeneity of the copolymerization process.     

Evaluation of defect induced surface heterogeneity in Metal-Organic Framework materials with alkali dopants employing adsorption isotherm modelling

In this article, an assessment of surface structural heterogeneity in porous metal organic framework (MOF) structure has been demonstrated by employing the methane and carbon-dioxide adsorption isotherms data. The virgin MIL-101-(Cr) MOF was synthesized by the hydrothermal method and defects were induced in the MOF structure by doping with various alkali (K, Na, Li) cations. The synthesized MOFs were characterized by XRD, SEM, EDX and BET measurement techniques. In order to understand the defect induced surface heterogeneity by alkali cation dopants, the surface energy distributions for CH₄ and CO₂ adsorptions on MOFs were measured by Dubinin – Astakhov model equation. The surface heterogeneity is mainly controlled by the limiting uptakes of adsorbates, the polarizability of adsorbates and the adsorbate-adsorbent interaction energy.     

Dynamics and heterogeneity of Pb(II) binding by SiO2 nanoparticles in an aqueous dispersion

Pb(II) binding by SiO(2) nanoparticles in an aqueous dispersion was investigated under conditions where the concentrations of Pb(2+) ions and nanoparticles are of similar magnitude. Conditional stability constants (log K) obtained at different values of pH and ionic strength varied from 4.4 at pH 5.5 and I = 0.1 M to 6.4 at pH 6.5 and I = 0.0015 M. In the range of metal to nanoparticle ratios from 1.6 to 0.3, log K strongly increases, which is shown to be due to heterogeneity in Pb(II) binding. For an ionic strength of 0.1 M the Pb(2+)/SiO(2) nanoparticle system is labile, whereas for lower ionic strengths there is loss of lability with increasing pH and decreasing ionic strength. Theoretical calculations on the basis of Eigen-type complex formation kinetics seem to support the loss of lability. This is related to the nanoparticulate nature of the system, where complexation rate constants become increasingly diffusion controlled. The ion binding heterogeneity and chemodynamics of oxidic nanoparticles clearly need further detailed research.     

Radial structure and property relationship in the thermal stabilization of PAN precursor fibres

Here we report on the role of oxygen in the evolution of radial heterogeneity in the fibre structure and properties of PAN fibres stabilized in air and vacuum at different temperatures. Modulus mapping by Nano-indentation showed heterogeneous modulus distribution in the fibres treated in air, while no variation in modulus was observed in fibres processed in vacuum. Raman spectroscopy and elemental analysis revealed that the temperature dependent oxygen diffusion from skin to core of the fibres assisted in the evolution of higher extent of sp²-hybridized carbons in the skin compared to core of the air treated samples. Conversely, no radial structure variations were observed in the vacuum treated fibres. Higher modulus in the skin of air-treated fibres was due to the formation of compact structures which was associated with the enhanced intermolecular interactions facilitated by the formation of C=C bonds within the polymer backbone, promoted by oxidative-dehydrogenation reaction. Supporting these observations, the fracture morphology examined by SEM showed a brittle fracture in the skin and ductile fracture in the core.     

A comparative protein profiling of lymphocytes from blood of patients with chronic lymphoid leukemia by high-resolution mass-spectrometry in search of new markers for heterogeneity and disease prognosis

To find new markers of chronic lymphoid leukemia heterogeneity, a comparison of the proteomic profiles of pathologic and healthy lymphocytes from blood was carried out by high-resolution mass spectrometry and label-free quantitative analysis. A list of the most typical proteins for the two groups was obtained. The differences in the proteomic profiles within the pathologic group, which were consistent with the heterogeneity of clinical background, were found. Two subsets within the area of the pathologic cells were formed using statistical analysis; the list of characteristic proteins for each subset was obtained.     

Electrodeposition for obtaining homogeneous or heterogeneous cobalt-copper films

Direct electrodeposition of heterogeneous deposits may be an alternative method for preparing cobalt-copper coatings with magnetoresistive properties. Co-Cu electrodeposition was obtained in sulfate baths containing different citrate concentrations in order to prepare either homogeneous or heterogeneous Co-Cu deposits. X-ray diffraction (XRD) and voltammetric stripping analysis were used to study the kind of deposits formed. Citrate-free baths produced heterogeneous films, although dendritic growth was observed, thus increasing the deposit's thickness. Increasing the Cu(II)/Co(II) ratio in solution enabled the formation of smoother deposits. The presence of citrate at up to twice the total metallic concentration in the bath improved the morphological aspects of the deposits, their structural heterogeneity being maintained. Higher citrate concentrations induced the loss of heterogeneity, and both electrochemical and diffraction peaks tended towards single peaks. Homogeneous Co-Cu deposits, formed by a solid solution structure, were obtained in highly complexed citrate baths.     

Quantitative study of cellular heterogeneity in doxorubicin uptake and its pharmacological effect on cancer cells

Cellular heterogeneity in doxorubicin (DOX) uptake and its relationship with pharmacological effect on cancer cells were quantitatively investigated for the first time. An in vitro experimental model was established by treating human leukemia K562 and breast cancer MCF‐7 cells with different schedules of DOX with or without surface P‐glycoprotein (P‐gp) inhibitor verapamil (VER). The cellular heterogeneity in DOX uptake was quantitatively examined by single‐cell analysis using capillary electrophoresis coupled with laser‐induced fluorescence detection. The corresponding cytotoxic effect was tested by cellular morphology, 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl‐tetrazolium and flow cytometry assays. The expression of cellular membrane surface P‐gp was determined by flow cytometry. Results showed that the cellular heterogeneity exists in DOX uptake. The single‐high DOX schedule leads to lower uptake heterogeneity and higher mean drug uptake. The cellular heterogeneity in DOX uptake was found to be negatively correlated with drug cytotoxicity and surface P‐gp expression, with r = ?0.7680 to ~ ?0.9587. VER reduces the cellular variation in DOX uptake, suggesting that surface P‐gp may be one of the causes of the cellular heterogeneity in DOX uptake. This research demonstrates the importance of quantitative study of cellular heterogeneity in drug uptake and its potential application in drug schedule design, response prediction and therapy modulation. Copyright © 2014 John Wiley & Sons, Ltd.