Electron-pair shell density approximation applied to inner and outer densities of atoms

The shell density approximation to the electron-pair radial density of atoms is applied to the inner $D_< (r)$ and outer $D_> (r)$ densities, which are two components of the single-electron density $D(r)$ . The inner and outer densities are found to be expressed by product sums of shell densities and shell distributions or their complements. The expressions clarify physical meaning of the two densities and give examples for constructing two-electron properties from single-electron properties. Examination of the 53 atoms He through Xe shows that the quantum similarity indices between the original and approximate densities, bounded by 0 (complete dissimilarity) and 1 (complete similarity), are never smaller than 0.99998 and 0.99987 for the inner and outer densities, respectively. The local nature of the shell density and the monotonically increasing property of the shell distribution are used to derive simple shellwise lower and upper bounds to $D_< (r)$ and $D_> (r)$ in terms of $D(r)$ and the numbers of shell electrons. Numerical tests of the bounds demonstrate their utility.     

On the inner and outer radial density functions

Starting from the two-electron radial density D ₂(r ₁,r ₂), a generalized partitioning of the one-electron radial density function D(r) into two component densities D _a (r) and D _b (r) is discussed for many-electron systems. The literature partitioning (Koga and Matsuyama Theor Chem Acc 115:59, 2006) of D(r) into the inner D _<(r) and outer D _>(r) radial densities is shown to minimize the average variance of the two component density functions D _a (r) and D _b (r). It is also found that the average radial separation halved, , constitutes a lower bound to the standard deviation σ of D(r).     

Thermoanalytical study of inner and outer residue of coffee harvest

The better use of agricultural residues is expected, when they are mostly disposed of improperly and it is often burned in the natural environment. This study of the thermal decomposition of residues was performed from the coffee crop for energy purposes and in this case was used thermal analysis techniques for such assessment. The TG/DTG and DSC curves showed that the thermal decomposition occurs in four consecutive events and it is predominantly exothermic. The first mass loss evidenced in TG/DTG curves has an endothermic peak in DSC curve, which it can be associated with the water liberation of the material. This first thermal event also can be related to the liberation of volatile compounds present in the sample, which is also corroborated by the endothermic peak. The other events of mass loss are related with the thermal decomposition of the material. This decomposition has an exothermic behavior, which is positively applied to the main aim of this scientific research: the coffee straw use like biomass energy font. The thermoanalytical techniques were satisfactory in the characterization of this material.     

Engineered lipids that cross-link the inner and outer leaflets of lipid bilayers

The application of supported lipid bilayer systems as molecular sensors, diagnostic devices, and medical implants is limited by their lack of stability. In an effort to enhance the stability of supported lipid bilayers, three pairs of phosphatidylcholine lipids were designed to cross-link at the termini of their 2-position acyl chain upon the formation of lipid bilayers. The cross-linked lipids span the lipid bilayer, resembling naturally occurring bolaamphiphiles that stabilize archaebacterial membranes against high temperatures. The three reactions investigated here include the acyl chain cross-linking between thiol and bromine groups, thiol and acryloyl groups, and cyclopentadiene and acryloyl groups. All three reactive lipid pairs were found to cross-link in liposomal membranes, as determined by thin-layer chromatography, ion-spray mass spectrometry, and 1H NMR. The monolayer film properties of the reactive amphiphiles were characterized by surface pressure-area isotherms and showed that stable monolayers formed at the air-water interface with limiting molecular areas comparable to that of pure saturated phosphatidylcholine lipids. Langmuir-Blodgett bilayers of dimyristoylphosphatidylcholine incorporating 15 mol % of the reactive thiol and acryloyl lipids had diffusion coefficients comparable with pure dimyristoylphosphatidylcholine, while bilayers with more than 25 mol % of the reactive lipids were immobile, suggesting that interleaflet cross-linking of the lipids inhibited membrane diffusion. Our results show that the reactive lipids can cross-link within a lipid bilayer and are suitable for assembling supported lipid bilayers using Langmuir-Blodgett deposition. By using terminally reactive amphiphiles to build up supported lipid bilayers with cross-linked leaflets, bolaamphiphiles can be incorporated into asymmetric solid supported membranes to increase their stability in biosensor and medical implant applications.     

Exploring long-range proton conduction,the conduction mechanism and inner hydration state of protein biopolymers

Proteins are the main proton mediators in various biological proton circuits. Using proteins for the formation of long-range proton conductors is offering a bioinspired approach for proton conductive polymers. One of the main challenges in the field of proton conductors is to explore the local environment within the polymers, along with deciphering the conduction mechanism. Here, we show that the protonic conductivity across a protein-based biopolymer can be hindered using straightforward chemical modifications, targeting carboxylate- or amine-terminated residues of the protein, as well as exploring the effect of surface hydrophobicity on proton conduction. We further use the natural tryptophan residue as a local fluorescent probe for the inner local hydration state of the protein surface and its tendency to form hydrogen bonds with nearby water molecules, along with the dynamicity of the process. Our electrical and spectroscopic measurements of the different chemically-modified protein materials as well as the material at different water–aprotic solvent mixtures result in our fundamental understanding of the proton mediators within the material and gaining important insights on the proton conduction mechanism. Our biopolymer can be used as an attractive platform for the study of bio-related protonic circuits as well as a proton conducting biopolymer for various applications, such as protonic transistors, ionic transducers and fuel cells.

Post formation modification of protein-based materials can attenuate the proton conduction efficiency resulting from change in conduction mechanism, charge carrier mobility, carrier concentrations and inner hydration layer.     

Playing with dye molecules at the inner and outer surface of zeolite L

Plants are masters of transforming sunlight into chemical energy. In the ingenious antenna system of the leaf, the energy of the sunlight is transported by chlorophyll molecules for the purpose of energy transformation. We have succeeded in reproducing a similar light transport in an artificial system on a nano scale. In this artificial system, zeolite L cylinders adopt the antenna function. The light transport is made possible by specifically organized dye molecules, which mimic the natural function of chlorophyll. Zeolites are crystalline materials with different cavity structures. Some of them occur in nature as a component of the soil. We are using zeolite L crystals of cylindrical morphology which consist of a continuous one-dimensional tube system and we have succeeded in filling each individual tube with chains of joined but noninteracting dye molecules. Light shining on the cylinder is first absorbed and the energy is then transported by the dye molecules inside the tubes to the cylinder ends. We expect that our system can contribute to a better understanding of the important light harvesting process which plants use for the photochemical transformation and storage of solar energy. We have synthesized nanocrystalline zeolite L cylinders ranging in length from 300 to 3000 nm. A cylinder of 800 nm diameter, e.g. consists of about 150 000 parallel tubes. Single red emitting dye molecules (oxonine) were put at each end of the tubes filled with a green emitting dye (pyronine). This arrangement made the experimental proof of efficient light transport possible. Light of appropriate wavelength shining on the cylinder is only absorbed by the pyronine and the energy moves along these molecules until it reaches the oxonine. The oxonine absorbs the energy by a radiationless energy transfer process, but it is not able to send it back to the pyronine. Instead it emits the energy in the form of red light. The artificial light harvesting system makes it possible to realize a device in which different dye molecules inside the tubes are arranged in such a way that the whole visible spectrum can be used by conducting light from blue to green to red without significant loss. Such a material could conceivably be used in a dye laser of extremely small size. The light harvesting nanocrystals are also investigated as probes in near-field microscopy, as materials for new imaging techniques and as luminescent probes in biological systems. The extremely fast energy migration, the pronounced anisotropy, the geometrical constraints and the high concentration of monomers which can be realized, have great potential in leading to new photophysical phenomena. Attempts are being made to use the efficient zeolite-based light harvesting system for the development of a new type of thin-layer solar cell in which the absorption of light and the creation of an electron-hole pair are spatially separated as in the natural antenna system of green plants. Synthesis, characterization and applications of an artificial antenna for light harvesting within a certain volume and transport of the electronic excitation energy to a specific place of molecular dimension has been the target of research in many laboratories in which different approaches have been followed. To our knowledge, the system developed by us is the first artificial antenna which works well enough to deserve this name. Many other highly organized dye–zeolite materials of this type can be prepared by similar methods and are expected to show a wide variety of remarkable properties. The largely improved chemical and photochemical stability of dye molecules inserted in an appropriate zeolite framework allows us to work with dyes which otherwise would be considered uninteresting because of their lack of stability. We have developed two methods for preparing well-defined dye–zeolite materials, one of them working at the solid–liquid and the other at the solid–gas interface. Different approaches for preparing similar materials are in situ synthesis (ship in a bottle) or different types of crystallization inclusion synthesis.     

The mechanism of boundary lubrication and the properties of the lubricating film: Short- and long-range action in the theory of boundary lubrication

Two versions of the blow-off method are described, by means of which the dependence of the viscosity of oils and other non-volatile fluids on the distance from the solid wall can be measured, and the viscosity localized with an accuracy of 10 Å.

In the case of non-polar specially purified vaseline oil the viscosity remains strictly constant to a distance of the order of 10⁻⁷ cm from the wall. The addition of polar additives causes changes in the viscosity near the wall. In a number of cases the viscosity changes discontinuously at some distances of the order of 10⁻⁶ to 10⁻⁵ cm from the wall. In the case of polar liquids the viscosity may rise or fall on approaching the wall, depending on the molecular structure.

The results obtained prove that the solid wall is capable of altering the orientation of the molecules in adjacent layers of the liquid up to 10⁻⁵ cm thick, and even up to 10⁻³ cm thick in the case of polymeric liquids. This effect plays a substantial part in the mechanism of boundary lubrication, since oiliness always disappears if it is absent.

In conclusion, an examination is made of the mechanical properties of the boundary lubrication layer which explain both the existence of static friction and the observation of the two-term friction law derived by from the molecular theory of friction.

The general conclusion is the impossibility of accounting for the phenomenon of boundary lubrication without taking into consideration the specific properties of the polymolecular boundary layers of liquids.

Zusammenfassung

Zwei verschiedene Varianten der sogenannten Abblas-methode werden beschrieben. Diesc erlauben es die Abhängigkeit der Zähigkeit von Ölen und anderen nicht-flüchtigen Flüssigkeiten als Funktion des Abstandes von der festen Wand zu messen und die Zähigkeit mit einer Genauigkeit bis auf 10 Å zu lokalisieren.

Für ein nichtpolares speziell gereinigtes Vaselinöl bleibt die Zähigkeit streng stabil bis zu einem Abstand von der Wand von der Grössenordnung 10⁻⁷ cm. Zufügung polarer Substanzen zu dem Öl hat eine Veränderung der Zähigkeit in der Nähe der Wand zur Folge. In einer Reihe von Fällen verändert sich die Zähigkeit sprungweise und zwar bei einem Abstand von der Wand von der Grössenordnung 10⁻⁶−10⁻⁵ cm. Für polare Flüssigkeiten kann die Zähigkeit abhängig von der Struktur von Molekülen, entweder zunehmen oder abnehmen.

Versuchsergebnisse zeigen, dass eine feste Wand die Orientierung der Moleküle von Flüssigkeitsschichten bis auf einen Abstand von 10⁻⁵ cm und für polymere Flüssigkeiten sogar bis auf 10⁻³ cm beeinflussen kann. Diese Erscheinung spielt eine bedeutende Rolle in dem Mechanismus der Grenzschmierung denn, wenn sie nicht auftritt verschwindet auch regelmässig die Schlüpfrigkeit.     

Bile acid-based cage compounds with lipophilic outer shells and inner cavities

The uniquely functionalized steroid-based cyclodimers 4, cis-5, and trans-5 have been synthesized and fully characterized.The cyclodimer 5, with a cis-trans ratio of 3:1, is obtained by coupling the terminal alkenes of two 4-pentenoate groups on a cyclodimer 4 via Grubbs' intramolecular ring-closing metathesis. The crystal structure shows cis-5 to be a cagelike cyclic oligomer bridged by the flexible oct-4-enedioate link.     

Lipid diffusion compared in outer and inner leaflets of planar supported bilayers

The translational diffusion coefficient (D) of lipids located in the outer and inner leaflets of planar supported DLPC (1,2-dilauroyl-sn-glycero-3-phosphocholine) bilayers in the fluid phase was measured using fluorescence correlation spectroscopy of dye-labeled lipids at the low concentration of 0.001% and using iodide quenching of dyes in the outer leaflet to distinguish diffusion in the inner leaflet from that in the outer leaflet. To confirm the generality of these findings, the bilayers were prepared not only by vesicle fusion but also by Langmuir-Blodgett deposition. We conclude that regardless of whether the bilayers were supported on quartz or on a polymer cushion, D in the inner and outer leaflets was the same within an experimental uncertainty of +/-10% but with a small systematic tendency to be slower (by <5%) within the inner leaflet.     

Gram-negative outer and inner membrane models: insertion of cyclic cationic lipopeptides

Most Gram-negative bacteria are susceptible to polymyxin B (PxB), and development of resistance to this cationic lipopeptide is very rare. PxB mechanism of action involves interaction with both the outer membrane (OM) and the inner membrane (IM) of bacteria. For the design of new antibiotics based on the structure of PxB and with improved therapeutic indexes, it is essential to establish the key features of PxB that are important for activity. We have used an approach based on mimicking the outer layers of the OM and the IM of Gram-negative bacteria using monolayers of lipopolysaccharide (LPS) or anionic 1-palmitoyl-2-oleoylglycero-sn-3-phosphoglycerol (POPG), respectively, and using a combination of penetration assay, analysis of pressure/area curves, and Brewster angle microscopy to monitor surface morphology changes. Synthetic analogue sp-B maintains the basic structural characteristics of the natural compound and interacts with the OM and the IM in a similar way. Analogue sp-C, with a mutation of the sequence [d-Phe6-Leu7] into [d-Phe6-Dab7], shows that this hydrophobic domain is involved in LPS binding. The significant role of the positive charges is demonstrated with sp-Dap analogue, where l-alpha,gamma-diaminobutyric acid residues Dab1 and Dab8 are replaced by l-alpha,gamma-diaminopropionic acid (Dap), resulting in lower degrees of insertion in both LPS and PG monolayers. The importance of the N-terminal acyl chain is demonstrated with polymyxin B nonapeptide (PxB-np). PxB-np shows lower affinity for LPS compared to PxB, sp-B, or sp-C, but it does not insert into PG monolayers, although it binds superficially to the anionic film. Since PxB microbial killing appears to be mediated by osmotic instability due to OM-IM phospholipid exchange, the ability of the different peptides to induce membrane-membrane lipid exchange has been studied by use of phospholipid unilamellar vesicles. Results indicate that cationic amphipathicity determines peptide activity.     

Application of perturbation theory to estimate inner and outer spherf ligand reactivities

As a mutual ligand reactivity index we proposed the stabilization energy E calculated by perturbation theory. For intermediate complexes from the oxidation reaction of phosphine and arsine with the halogenide Cu(II) we obtain a correlation between the size of E and the rate constant. The electronic properties of the complexes are calculated using the MWH method.Sokolskii Institute for Organic Catalysis and Electrochemistry, Kazakh Academy of Sciences, Alma-Ata. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 27, No. 6, pp. 653–658, November–December, 1991. Original article submitted March 3, 1987.     

Direct and exchange contributions to inner and outer radii in many-electron atoms

Within the Hartree-Fock framework, the spinless two-electron density function Γ (r ₁, r ₂) consists of direct Γ_di (r ₁, r ₂) and exchange Γ_ex (r ₁, r ₂) parts. Accordingly, the inner and outer radii in many-electron systems are rigorously separated into the direct and exchange contributions, i.e., and . It is generally shown that and , where is the usual average radius of an electron. Numerical examinations of the direct and exchange contributions for the 102 atoms from He to Lr in their ground states find that the electron exchange works to decrease and increase . However, the exchange parts are very small and the direct parts essentially govern the inner and outer radii.     

Constrained self-consistent-field wave functions with improved long-range behavior

The recent suggestion that the long-range behavior of energy-optimized Gaussian basis sets can be improved by augmenting them with a Gaussian chosen to satisfy a constraint involving a linearly averaged position moment is explored. Calculations indicate that the high-order moments 〈r^k〉, with k > 4, in He, Be, and Li^?, and 〈x^kz^L?k〉, with L > 4 and k ≤ L, in H₂ are improved by the constraint, but that lower-order moments and dipole polarizabilities are not. In H₂, the higher moments with a given L improve by different amounts for different k, and, hence, the multipole moments do not improve. The basis-set superposition error in He? He and Be? Be interaction energy calculations decreases if the internuclear distance is large enough. Thus, the constraint procedure improves the very long range behavior of the self-consistent-field wave functions. © 1992 John Wiley & Sons, Inc.     

Short- and long-range order balance in nanocrystalline Gd2Zr2O7 powders with a fluorite-pyrochlore structure

A series of nanocrystalline Gd₂Zr₂O₇ powders has been studied using a combination of X-ray diffraction and X-ray spectroscopy with synchrotron radiation. It has been shown that isothermal annealing of an X-ray amorphous mixed hydroxide first leads to the formation of an oxide nanomaterial with a defect fluorite structure and clearly pronounced nonequivalence of the local environment of the Gd³⁺ and Zr⁴⁺ ions. Increasing heat treatment temperature results in initiation and growth of nanodomains with pyrochlore-type superstructure ordering of cations inside bulkier crystallites of defect fluorite. To adequately describe the evolution of the real nanocrystalline structure of gadolinium zirconate, a combination of X-ray structural methods sensitive to the averaged crystal structure and local atomic structure should be used.     

Nanocellulose characteristics from the inner and outer layer of banana pseudo-stem prepared by TEMPO-mediated oxidation

Many tonnes of agricultural wastes are generated annually, which contains a relatively high amount of cellulose; banana pseudo-stem is one waste type that is a promising material for nanocellulose production. This research characterised nanocellulose from inner and outer layers of banana pseudo-stem as a preliminary research strategy for designing biodegradable packaging material from banana pseudo-stem nanocellulose. Nanocellulose was successfully prepared through TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl)-mediated oxidation. The extracted nanocellulose from both the inner and outer layers had observed widths of approximately 7–35 nm and long fibrillated fibre. They had high negative zeta potential (lower than ?33.6) that provided good colloidal stability. The purity of the nanocellulose was high as demonstrated by ¹³C solid-state NMR and Fourier transform infrared spectroscopy. Nanocellulose from both layers was significantly more crystalline than the raw materials. Thermal stability of nanocellulose sourced from inner and outer layers was relatively similar, with degradation temperature of approximately 220 °C, which was slightly lower than the degradation temperature of its native form (232 °C for inner layer and 261 °C for outer layer).     

Flexible inner and outer coordination of Zn(II) N-confused porphyrin complex

Tetra- and dinuclear Zn(II) N-confused porphyrin dimers (1, 2) and pyridine-coordinating Zn(II) monomer complex (3) were synthesized, and the ditopic, inner and outer coordination of Zn metal in the dimer complex (1) was demonstrated by X-ray analyses.