Donor-acceptor concept of covalent interaction of substrate with catalysts

In terms of a unitary approach, the ability of complexes, clusters and metals of transition and nontransition elements for covalent interaction with reagents has been analyzed. the requirements for the catalysts to be efficient in the covalent activation of substrates have been formulated.

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Structural change of water by gelation of curdlan suspension

Phase transition of water restrained by curdlan suspension annealed at a temperature from 20 to 110°C was investigated by differential scanning calorimetry (DSC). The melting temperature of water restrained by annealed curdlan discontinuously decreased at around 60°C, while the amount of bound water calculated from enthalpy of melting increased at 60°C, regardless of water content. Using a highly sensitive DSC, curdlan suspension with various concentrations was studied. It was found that an endothermic transition was observed at ca. 58°C in a wide range of concentrations. The transition observed at 60°C is thermo-reversible and both temperature and transition enthalpy are constant even after gel formation. Well equilibrated suspension at a temperature lower than 60°C formed no gel.     

Research on radiation-induced color change of white topaz

In the present study, a method of producing sky blue topaz is studied. A 3–5 MeV scanning electron beam linear accelerator (which is currently used for processing semiconductor devices) was employed to change the color of white topaz under room-temperature conditions, together with a cooling device. A radiation-induced ion color center is formed in white topaz by an electron beam. To finish the irradiation, the total dose needs to be more than 5×10⁷–1×10⁸ Gy, the temperature of heat-treatment was between 180°C and 280°C in air conditions, after a while, a sky blue topaz was obtained.

There was a bright color and no radioactivity was formed in the sky blue topaz by this production method.     

Colorimetric and stochastic assessment of the visual limit of color perception for visual colorimetric analysis

Methods for evaluating the visual limit of color perception are proposed to create common rules for constructing color test scales in visual colorimetric assay using a probabilistic approach and instrumental measurements of the total color difference ΔE. Using a wealth of experimental data, we confirmed the previous idea that the minimum value of ΔE discernible by an average eye in 90% of cases may differ from the conventional criterion ΔE = 10. It has been shown that ΔE is not constant throughout the range corresponding to the visible spectral region and depends on the color tint of the scale. Using the dependence of the probability of color difference on the size of the scale step, a minimum step for each color tint is found. This makes possible the a priori selection of a step for constructing a calibration scale depending on its tint.     

Effect of sucrose on molecular and interaction parameters of sodium caseinate in aqueous solution: relationship to protein gelation

The effect of sucrose on molecular and interaction parameters of sodium caseinate in aqueous medium has been investigated using static and dynamic multi-angle laser light scattering over a wide range of sucrose concentration (from 10 to 78 w/v%) and pH values (from 7.0 to 3.5). Measurements have been made of the molar mass, the radius of gyration, the hydrodynamic radius, and the second virial coefficient of sodium caseinate in aqueous solution. Pronounced dissociation of sodium caseinate sub-micelles¹ was found in the presence of sucrose at a pH above the protein's isoelectric point. The effect of sucrose at a pH near the isoelectric point is very different. This is reflected in the pronounced increase in molar mass, radius of gyration, and the difference between the radius of gyration and the hydrodynamic radius. It was found that the extent of the protein association, caused by the presence of sucrose, is a key factor contributing to the hydrophobic–hydrophilic balance of the protein surface, and hence to the thermodynamic affinity of the caseinate sub-micelles for the aqueous medium and for each other. Analysis of light-scattering data using structure-sensitive plots shows a clear transition from Gaussian to wormlike chain/rod behaviour for sodium caseinate on pH lowering. Apparent relationships between the effects of sucrose on the self-association of sodium caseinate and a marked enhancement of the viscoelasticity of acid-induced casein gels have been revealed. Moreover, the dissociation of sodium caseinate sub-micelles is in excellent agreement with the more homogeneous microstructure of acid-induced protein gels in the presence of sucrose as detected by confocal laser scanning microscopy. We discuss likely molecular mechanisms underlying the observed effects of sucrose on the interactions and rheology in acidified caseinate systems.     

Columnar self-assembly of rhomboid macrocyclic molecules via step-like intermolecular interaction. Crystal formation and gelation

Two macrocyclic compounds with a rhomboid molecular shape, composed of a π-conjugated framework and an imine or amine functionality, were synthesized. The amine-containing macrocycle crystallizes with step-like interaction of each molecule, forming a columnar arrangement, although dispersion of the imine gelates upon ultrasonification.     

Synthesis of colorimetric receptors for dicarboxylate anions: a unique color change for malonate

Three new chromogenic receptors (1, 2, and 3) containing p-nitrophenyl or p-nitronaphthyl or methyl groups appended to the thiourea groups were synthesized and characterized. Upon addition of a series of dicarboxylate anions to receptor 1 in DMSO, only the appearance of the solution of receptor 1 with malonate showed a color change from blue to yellow which can be detected by the naked eye at parts per million. With the addition of the series of dicarboxylate anions to receptor 2, the solutions showed an indistinct intense dark-red color. Whereas the addition of the same dicarboxylate anions to receptor 3, the solutions did not induce any color change. Thus, for the unique color change, the receptor 1 can act as an optical chemosensor for the malonate anion even in the presence of other dicarboxylate anions.     

Direct visual observation of yeast deposition and removal during microfiltration

Periodic reverse flow through membranes is an effective technique to remove foulants from microfiltration (MF) membrane surfaces. This work explored direct visual observation (DVO) of yeast deposition and subsequent removal via backwashing and single backpulses using microvideo photography with cellulose-acetate (CA) and Anopore anodised-alumina (AN) MF membranes. Foulant deposited less uniformly on the surfaces of the CA membranes than on the AN membrane surfaces during forward filtration. Foulant cake layers of approximately 30 μm thickness formed on both membranes after forward filtration for 1–2 h, leading to fouled-membrane fluxes of only 15–25% of the clean-membrane fluxes.Foulant was removed by reverse flow from the CA membrane surfaces in clumps. The time constant for foulant removal was determined from photomicrographs to be approximately 0.2 s, and 95% of the membrane surface was cleaned within 1 s of backpulsing, resulting in 95% recovery of the initial flux. The foulant cake was also removed from the AN membranes in clumps, though much of the membrane remained covered in a monolayer of yeast. The flux through the membrane covered with a full monolayer was determined during forward filtration to be about 70% of the clean membrane flux.A model for flux recovery is proposed which takes into account the fraction of the membrane surface which is completely cleaned as well as the fraction which remains covered in a foulant monolayer. The predicted and experimentally-determined recovered fluxes as a function of backpulse duration are in very good agreement.     

Four-coordinate iron(II) porphyrinates: electronic configuration change by intermolecular interaction

The syntheses and structures of three four-coordinate iron(II) porphyrinates are reported. The three derivatives are tetraarylporphyrin species, where the aryl is either phenyl, p-methylphenyl, or p-methoxyphenyl. One of these derivatives, that of tetraphenylporphyrin, Fe(TPP), is a new crystalline phase that is distinct from the earlier reported phase (Collman, J. P.; et al. J. Am. Chem. Soc. 1975, 97, 2676). This new phase of Fe(TPP) has a very saddled porphyrin core; the prior phase was ruffled. The iron atom has close interactions (approximately 3.10 A) with two pyrrole Cb-Cb bonds above and below the porphyrin plane. M?ssbauer spectra and magnetic susceptibility measurements, different for the two phases, provide strong evidence that the two phases of Fe(TPP) have distinct electronic structures that originate from intermolecular interactions.     

Tetraarylethylene having two nitroxide groups: redox-switching of through-bond magnetic interaction by conformation change

Reversible redox-switching of through-bond magnetic interaction has been achieved by conformation change of the tetraarylethylene moiety upon redox input: intramolecular magnetic interaction between two nitroxide groups is dead after oxidation, whereas it was alive before.     

Phase change materials of n-alkane-containing microcapsules: observation of coexistence of ordered and rotator phases

In the present investigation, the crystallization and phase transition behaviours of normal alkane (n-docosane) in microcapsules with a mean diameter of 3.6 μm were studied by the combination of differential scanning calorimetry (DSC), temperature-dependent X-ray diffraction (XRD) and variable-temperature solid-state nuclear magnetic resonance (VT solid-state (13)C NMR). The DSC and VT solid-state (13)C NMR results reveal that a surface freezing monolayer is formed prior to the bulk crystallization of the microencapsulated n-docosane. More interestingly, it is confirmed that after the bulk crystallization, the ordered triclinic phase coexists with the rotator phase I (RI) for the microencapsulated n-docosane. We argue that the reduction of the free energy difference between the two phases, resulting from the microencapsulation process, leads to the coexistence of the ordered triclinic and rotator phases of the normal alkanes.     

Thermoreversible gelation of syndiotactic polystyrene: Effect of solvent type

The temperature-concentration phase diagrams of syndiotactic polystyrene (sPS)/benzene gels and sPS/toluene gels establish the existence of two polymer-solvent compounds in both systems. In particular it is found that the sto ichiometries of the compounds differ with the type of solvent: The stoichiometrics, expressed as solvent molecules/monomer are respectively for the benzene 4/1 and 1/1 and for the toluene 0.8/1 and 1/4. Neutron diffraction patterns allow us to confirm the existence of differents compounds in sPS/toluene gel and sPS/benzene gel.     

Donor-acceptor triazenes: synthesis, characterization, and study of their electronic and thermal properties

A new class of 1,3-disubstituted-triazenes were synthesized by coupling functionalized benzimidazol-2-ylidenes, as their free N-heterocyclic carbenes or generated in situ from their respective benzimidazolium precursors, to various aryl azides in modest to excellent isolated yields (36-99%). Electron delocalization between the two coupled components was studied using UV-vis spectroscopy, NMR spectroscopy, and X-ray crystallography. Depending on the complementarity of the functional groups on the N-heterocyclic carbenes and the organic azides, the respective triazenes were found to exhibit lambda(max) values ranging between 364 and 450 nm. X-ray crystallography revealed bond alteration patterns in a series of triazenes characteristic of donor-acceptor compounds. Triazene thermal stabilities were studied using thermogravimetric analysis and found to be strongly dependent on the sterics of the benzimidazol-2-ylidene component and the electronics of the azide component. Triazenes possessing bulky N-substituents (e.g., neo-pentyl, tert-butyl, etc.) were stable in the solid-state to temperatures exceeding 150 degrees C, whereas analogues with small N-substituents (e.g., methyl) were found to slowly decompose at room temperature. Triazenes featuring electron-rich phenyl azide components decomposed at higher temperatures than their electron-deficient analogues. Products of the thermally induced triazene decomposition reaction were identified as molecular nitrogen and the respective guanidine. Using an isotopically labeled triazene, the mechanism of the decomposition reaction was found to be analogous to the Staudinger reaction.     

A chromogenic macrocycle exhibiting cation-selective and anion-controlled color change: an approach to understanding structure-color relationships

[reaction: see text] A N-azo-coupled macrocycle (1) with a NO(2)S(2) donor set was synthesized as a chromoionophore and shown to exhibit Hg(2+) selectivity; anion control of the color of the Hg(2+) complex was observed. As a first approach, the nature of the color generation process was probed by determining the crystal structures of the two different colored species obtained with perchlorate and iodide anions. The results can be explained in terms of a "Push-n-Pull Process", which serves to illustrate how the coordinating ability of the anion controls the color change through formation of endo- or exo-metal complexes. The use of "simple" salts to induce color-switching of the above complex species was also reported.