Kinetic and spectroscopic study of 1O2 generation from H2O2 catalyzed by LDH-MoO4(2-) (LDH=layered double hydroxide)

Layered double hydroxides (LDHs), exchanged with molybdate, decompose H2O2 to form one molecule of singlet-state dioxygen (1O2) from two molecules of H2O2. The dependence of the kinetics of H2O2 decomposition on Mo and H2O2 concentrations and on temperature has been related to structural characteristics of the material (X-ray diffraction (XRD), scanning electron microscopy (SEM), IR spectroscopy, N2 adsorption, thermogravimetry) and to molybdate speciation as revealed by in-situ studies in the presence of peroxide (FT Raman, diffuse reflectance UV/visible spectroscopy). The H2O2 decomposition rate is linearly correlated with the amount of LDH-exchanged molybdate, except when a considerable fraction of the molybdate occupies less accessible interlayer positions. A maximum in the H2O2 decomposition rate as the H2O2 concentration is increased is due to the successive formation of mono-, di-, tri-, and tetraperoxomolybdates. This behavior was modeled successfully by using the equilibrium constants for formation of the Mo-peroxo complexes, and the rate constants for decay of the peroxomolybdates with 1O2 liberation. Time-resolved diffuse reflectance and Raman observations of the various MoO4(2-)-peroxide adducts are in line with the proposed kinetic scheme. Of all the Mo-peroxo species on the LDH, the triperoxomolybdate has the highest rate for decay to 1O2. Comparison with the kinetics of dissolved molybdate shows that the monomolecular decay of all peroxomolybdate species proceeds much faster at the LDH surface than in solution. Consequently, maximal rates per Mo atom are at least twice as high for the heterogeneous LDH catalyst as for the homogeneous systems.     

高岭石吸附乙烯和苯的Delft分子力学研究

运用Ｄｅｌｆｔ分子力学（ＤＭＭ）程序及其粘土和共轭烯烃力场，计算研究了高岭石对乙烯和苯的吸附作用，探讨了吸附对粘土晶体和有机分子的结构、电荷分布和能量的影响，求得了高岭石吸附乙烯和苯的吸附热等重要物理量．     

Redox and spectroscopic orbitals in Ru(II) and Os(II) phenolate complexes

A detailed spectroscopic and electrochemical study of a series of novel phenolate bound complexes, of general formulas [M(L-L)(2)(box)](PF(6)), where M is Os and Ru, L-L is 2,2-bipyridine or 2,2-biquinoline, and box is 2-(2-hydroxyphenyl)benzoxazole, is presented. The objectives of this study were to probe the origin of the LUMOs and HOMOs in these complexes, to elucidate the impact of metal and counter ligand on the electronic properties of the complex, and to identify the extent of orbital mixing in comparison with considerably more frequently studied quinoid complexes. [M(L-L)(2)(box)](PF(6)) complexes exhibit a rich electronic spectroscopy extending into the near infrared region and good photostability, making them potentially useful as solar sensitizers. Electrochemistry and spectroscopy indicate that the first oxidation is metal based and is associated with the M(II)/(III) redox states. A second oxidative wave, which is irreversible at slow scan rates, is associated with the phenolate ligand. The stabilities of the oxidized complexes are assessed using dynamic electrochemistry and discussed from the perspective of metal and counter ligand (LL) identity and follow the order of increasing stability [Ru(biq)(2)(box)](+) < [Ru(bpy)(2)(box)](+) < [Os(bpy)(2)(box)](+). Electronic and resonance Raman spectroscopy indicate that the lowest energy optical transition for the ruthenium complexes is a phenolate (pi) to L-L (pi) interligand charge-transfer transition (ILCT) suggesting the HOMO is phenolate based whereas electrochemical data suggest that the HOMO is metal based. This unusual lack of correlation between redox and spectroscopically assigned orbitals is discussed in terms of metal-ligand orbital mixing which appears to be most significant in the biquinoline based complex.     

Preparation of conducting electrodes from biological samples for multi-element trace analysis by spark-source mass spectrometry or emission spectrometry

Four decomposition procedures frequently used for biological material (dry ashing, open wet digestion, wet digestion in a teflon bomb and low-temperature ashing) are optimized for the conversion of biological samples to conducting electrodes suitable for multi-element trace determinations by spark-source mass spectrometry or emission spectrometry. The optimized procedures are evaluated with respect to contamination, retention and preconcentration of the trace elements, homogeneity of the electrodes and precision of the final results. Both dry-ashing methods are prone to losses by volatilization; simple dry ashing suffers from contamination problems during electrode preparation. Wet digestion gives better precision; digestion with nitric/sulfuric acids in an open flask is the method of choice for most elements being simpler and giving lower blanks than the bomb method.     

Electronic energy transfer and collection in luminescent molecular rods containing ruthenium(II) and osmium(II) 2,2':6',2"-terpyridine complexes linked by thiophene-2,5-diyl spacers

The electronic absorption spectra, luminescence spectra and lifetimes (in MeCN at room temperature and in frozen n-C3H7CN at 77 K), and electrochemical potentials (in MeCN) of the novel dinuclear [(tpy)Ru(3)Os(tpy)]4+ and trinuclear [(tpy)Ru(3)Os(3)Ru(tpy)]6- complexes (3 = 2,5-bis(2,2':6',2'-terpyridin-4-yl)thiophene) have been obtained and are compared with those of model mononuclear complexes and homometallic [(tpy)Ru(3)Ru(tpy)]4+, [(tpy)Os(3)Os(tpy)]4+ and [(tpy)Ru(3)Ru(3)Ru(tpy)]6+ Complexes. The bridging ligand 3 is nearly planar in the complexes, as seen from a preliminary X-ray determination of [(tpy)Ru(3)Ru(tpy)][PF6]4, and confers a high degree of rigidity upon the polynuclear species. The trinuclear species are rod-shaped with a distance of about 3 nm between the terminal metal centres. For the polynuclear complexes, the spectroscopic and electrochemical data are in accord with a significant intermetal interaction. All of the complexes are luminescent (phi in the range 10(-4)-10(-2) and tau in the range 6-340 ns, at room temperature), and ruthenium- or osmium-based luminescence properties can be identified. Due to the excited state properties of the various components and to the geometric and electronic properties of the bridge, Ru --> Os directional transfer of excitation energy takes place in the complexes [(tpy)Ru(3)Os(tpy)]4+ (end-to-end) and [(tpy)Ru(3)Os(3)Ru(tpy)]6+ (periphery-to-centre). With respect to the homometallic case, for [(tpy)Ru(3)Os(3)Ru(tpy)]6+ excitation trapping at the central position is accompanied by a fivefold enhancement of luminescence intensity.     

The effects of different dietary fiber pectin structures on the gastrointestinal immune barrier: impact via gut microbiota and direct effects on immune cells

Pectins are dietary fibers with different structural characteristics. Specific pectin structures can influence the gastrointestinal immune barrier by directly interacting with immune cells or by impacting the intestinal microbiota. The impact of pectin strongly depends on the specific structural characteristics of pectin; for example, the degree of methyl-esterification, acetylation and rhamnogalacturonan I or rhamnogalacturonan II neutral side chains. Here, we review the interactions of specific pectin structures with the gastrointestinal immune barrier. The effects of pectin include strengthening the mucus layer, enhancing epithelial integrity, and activating or inhibiting dendritic cell and macrophage responses. The direct interaction of pectins with the gastrointestinal immune barrier may be governed through pattern recognition receptors, such as Toll-like receptors 2 and 4 or Galectin-3. In addition, specific pectins can stimulate the diversity and abundance of beneficial microbial communities. Furthermore, the gastrointestinal immune barrier may be enhanced by short-chain fatty acids. Moreover, pectins can enhance the intestinal immune barrier by favoring the adhesion of commensal bacteria and inhibiting the adhesion of pathogens to epithelial cells. Current data illustrate that pectin may be a powerful dietary fiber to manage and prevent several inflammatory conditions, but additional human studies with pectin molecules with well-defined structures are urgently needed.Subject terms: Mucosal immunology, Translational immunology     

Differential double-layer capacitance of a mercury-drop electrode attached to a platinum wire: Frequency dispersion due to the measuring bridge and to the geometry at pendant and sessile electrodes

The frequency dependence of the double-layer capacitance has been studied at the interface Hg/0.116 M KCl in water at ?1.200 V vs. a reversible calomel electrode at 25°C. Two drop electrodes attached to 0.1-mm platinum wire have been used, one sessile with a narrow wedge, the other pendant with a widely open wedge between drop surface and support. The operation of the a.c. resistor-ratio arms bridge has been analysed in a manner generally applicable to series-R, C measurements. On that basis the effect of stray capacitances could be compensated and the frequency dispersion due to the measuring system reduced to a minimum. Both electrodes show a low-frequency dispersion of the measured series capacitance C(ω) and resistance R(ω), ω being the angular frequency. This dispersion has been analysed with a simple R, C network. In series with the bulk resistance R₃ this network has two mutually parallel series R, C's: R₁, C₁ of the drop itself and R₂, C₂ of its edge (neck). From the actual C(ω), R(ω) data follow correct capacitance data C₁, while R₂ and C₂ show a relatively stronger dependence on frequency and kind of electrode (pendant or sessile). Moreover, a sessile electrode exhibits a wedge or shielding effect above a much smaller ω (=ω_h >ω₁, the frequency above which the edge effect becomes insignificant) than a pendant electrode. Conclusions drawn from this information are: in the frequency domain (ω_h?ω₁) diffusive mass transport may be studied without interference from any geometric effect, which is probably also true at small electrolyte concentrations. This study should be performed with a pendant electrode, since it has the largest (ω_h?ω₁) domain.