Thermal and electrochemically assisted Pd-Cl bond cleavage in the d9-d9 Pd2dppm2Cl2 complex by Pd3 dppm3COn+ clusters (n = 2, 1, 0)

A new aspect of reactivity of the cluster [Pd3(dppm)3(micro3-CO)]n+, ([Pd3]n+, n = 2, 1, 0) with the low-valent metal-metal-bonded Pd2(dppm)2Cl2 dimer (Pd2Cl2) was observed using electrochemical techniques. The direct reaction between [Pd3]2+ and Pd2Cl2 in THF at room temperature leads to the known [Pd3(dppm)3(micro3-CO)(Cl)]+ ([Pd3(Cl)]+) adduct and the monocationic species Pd2(dppm)2Cl+ (very likely as Pd2(dppm)2(Cl)(THF)+, [Pd2Cl]+) as unambiguously demonstrated by UV-vis and 31P NMR spectroscopy. In this case, [Pd3]2+ acts as a strong Lewis acid toward the labile Cl- ion, which weakly dissociates from Pd2Cl2 (i.e., dissociative mechanism). Host-guest interactions between [Pd3]2+ and Pd2Cl2 seem unlikely on the basis of computer modeling because of the strong screening of the Pd-Cl fragment by the Ph-dppm groups in Pd2Cl2. The electrogenerated clusters [Pd3]+ and [Pd3]0 also react with Pd2Cl2 to unexpectedly form the same oxidized adduct, [Pd3(Cl)]+, despite the known very low affinity of [Pd3]+ and [Pd3]0 toward Cl- ions. The reduced biproduct in this case is the highly reactive zerovalent species "Pd2(dppm)2" or "Pd(dppm)" as demonstrated by quenching with CDCl3 (forming the well-known complex Pd(dppm)Cl2) or in presence of dppm (forming the known Pd2(dppm)3 d10-d10 dimer). To bring these halide-electron exchange reactions to completion for [Pd3]+ and [Pd3]0, 0.5 and 1.0 equiv of Pd2Cl2 are necessary, respectively, accounting perfectly for the number of exchanged electrons. The presence of a partial dissociation of Pd2Cl2 into the Cl- ion and the monocation [Pd2Cl]+, which is easier to reduce than Pd2Cl2, is suggested to explain the overall electrochemical results. It is possible to regulate the nature of the species formed from Pd2Cl2 by changing the state of charge of the title cluster.     

Radical cations of branched alkanes as observed in irradiated solutions by the method of time-resolved magnetic field effect

Spin dynamics in radical ion pairs formed under ionizing irradiation of n-hexane solutions of two branched alkanes 2,3-dimethylbutane and 2,2,4-trimethylpentane has been studied by the method of time-resolved magnetic field effect in recombination fluorescence. Experimental curves of the magnetic field effect are satisfactorily described by assuming that the spin dynamics is determined by the hyperfine interactions in the radical cation (RC) of branched alkane under study with hyperfine coupling (HFC) constants averaged by internal rotations of RC fragments. The HFC constants determined from the magnetic field effect curves are close to those estimated within DFT B3LYP approach. Analysis of the results indicates that at room temperature the lifetimes of the RC of the studied branched alkanes amount to, at least, tens of nanoseconds.     

Adhesive properties of Staphylococcus epidermidis probed by atomic force microscopy

Mapping of the surface properties of Staphylococcus epidermidis and of biofilm forming bacteria in general is a key to understand their functions, particularly their adhesive properties. To gain a comprehensive view of the structural and chemical properties of S. epidermidis, four different strains (biofilm positive and biofilm negative strains) were analyzed using in situ atomic force microscopy (AFM). Force measurements performed using bare hydrophilic silicon nitride tips disclosed similar adhesive properties for each strain. However, use of hydrophobic tips showed that hydrophobic forces are not the driving forces for adhesion of the four strains. Rather, the observation of sawtooth force-distance patterns on the surface of biofilm positive strains documents the presence of modular proteins such as Aap that may mediate cell adhesion. Treatment of two biofilm positive strains with two chemical inhibitor compounds leads to a loss of adhesion, suggesting that AFM could be a valuable tool to screen for anti-adhesion molecules.     

Urinary peptides as a diagnostic tool for renal failure detected by matrix-assisted laser desorption/ionisation mass spectrometry: an evaluation of their clinical significance

The development of new analytical methodologies related to the proteome for the evaluation of renal physiology and pathology is surely of wide interest for physicians, giving them new tools for monitoring complications associated with diabetes, such as end-stage renal disease. In the present study, the clinical significance of the urinary abundance of two peptides, SGSVIDQSRVLNLGPITR (the uromodulin precursor, m/z 1912) and IGPHypGPHypGLMGPP [present in the collagen-α-5(IV) chain precursor, m/z 1219], detected by matrix- assisted laser desorption/ionisation mass spectrometry (MALDI/MS) in microalbuminuric or nephropathic diabetic patients and in non-diabetic nephropathic patients was evaluated. A progressive increase in the abundance of the ion at m/z 1219 and a decrease in the abundance of the ion at m/z 1912 have been found in diabetic microalbuminuric, diabetic-nephropathic and nephropathic patients. Linear correlations are present between serum creatinine values and the abundances of the ions at m/z 1219 (positive correlation, r=0.3645, P<0.0001) and at m/z 1912 (negative correlation, r=-0.3053, P<0.0005). Correlations between the MALDI data and the estimated glomerular filtration rate were also found, while relationships with urinary albumin excretion were found only in sub-sets of patients. Analysis of receiver operating characteristic curves showed a sensitivity up to 96% and a specificity of up to 84% for the two ionic species, or their ratio, for distinguishing diabetic patients with different degrees of nephropathy from healthy subjects, proving that the urinary abundance of the two peptides at m/z 1219 and m/z 1912, determined with MALDI/MS, may be considered as a possible diagnostic tool for the determination of progression toward renal failure, also with the aim of monitoring kidney function, in diabetic patients.     

The stained glass window of the southern transept of St. Anthony's Basilica (Padova, Italy): study of glasses and grisaille paint layers

This work reports results from a chemico-physical study of the stained glass window of the southern transept of St. Anthony's Basilica (Padova, Italy), dated to the late 19th century AD. Selected samples of glass with or without grisailles were characterised by means of various X-ray spectrometric techniques, such as wavelength dispersive X-ray fluorescence, electron microprobe, and scanning electron microscopy with energy dispersive X-ray microanalysis, coupled, in some cases, with X-ray powder diffraction. Integration of analytical results revealed many types of glass related to different phases of the “life” of stained glass, and the production technology of grisailles. In addition, the degree of damage undergone throughout the last century due to materials used in the production of windows was studied, to design and optimise a combined conservation and restoration strategy. Lastly, another important aim of the present study was to amplify the database on 19th-century stained glass windows, little documented in the literature.     

Radical cations of branched alkanes in solutions: time-resolved magnetic field effect and quantum chemical studies

Radical cations of heptane and octane isomers, as well as several longer branched alkanes, were detected in irradiated n-hexane solutions at room temperature by the method of time-resolved magnetic field effect (TR MFE). To identify radical cations, the hyperfine coupling constants as determined by simulation of the TR MFE curves were compared to the constants calculated using the density functional theory (DFT) approach. The g-values of the observed radical cations were close to that of the 2,2,3,3-tetramethylbutane radical cation studied earlier by optically detected electron spin resonance (ESR) and TR MFE techniques. No evidence of the decay of the radical cations of branched alkanes to produce olefin radical cations was found, which was further supported by the observation of positive charge transfer from the observed radical cations to cycloalkane molecules. The lifetimes of the radical cations of the branched alkanes were found to be longer than tens of nanoseconds.     

An interacting dark energy model in a non-flat universe

In this paper, an interacting dark energy model in a non-flat universe is studied, with taking interaction form $C=\alpha H\rho _{de}$ C = α H ρ d e . And in this study a property for the mysterious dark energy is aforehand assumed, i.e. its equation of state $w_{\Lambda }=-1$ w Λ = - 1 . After several derivations, a power-law form of dark energy density is obtained $\rho _{\Lambda } \propto a^{-\alpha }$ ρ Λ ∝ a - α , here $a$ a is the cosmic scale factor, $\alpha $ α is a constant parameter introducing to describe the interaction strength and the evolution of dark energy. By comparing with the current cosmic observations, the combined constraints on the parameter $\alpha $ α is investigated in a non-flat universe. For the used data they include: the Union2 data of type Ia supernova, the Hubble data at different redshifts including several new published datapoints, the baryon acoustic oscillation data, the cosmic microwave background data, and the observational data from cluster X-ray gas mass fraction. The constraint results on model parameters are $\Omega _{K}=0.0024\,(\pm 0.0053)^{+0.0052+0.0105}_{-0.0052-0.0103}, \alpha =-0.030\,(\pm 0.042)^{+0.041+0.079}_{-0.042-0.085}$ Ω K = 0.0024 ( ± 0.0053 ) - 0.0052 - 0.0103 + 0.0052 + 0.0105 , α = - 0.030 ( ± 0.042 ) - 0.042 - 0.085 + 0.041 + 0.079 and $\Omega _{0m}=0.282\,(\pm 0.011)^{+0.011+0.023}_{-0.011-0.022}$ Ω 0 m = 0.282 ( ± 0.011 ) - 0.011 - 0.022 + 0.011 + 0.023 . According to the constraint results, it is shown that small constraint values of $\alpha $ α indicate that the strength of interaction is weak, and at $1\sigma $ 1 σ confidence level the non-interacting cosmological constant model can not be excluded.     

Relative intensity noise and frequency noise of a compact Brillouin laser made of As38Se62 suspended-core chalcogenide fiber

Relative intensity noise and frequency noise have been measured for the first time for a single-frequency Brillouin chalcogenide As38Se62 fiber laser. This is also the first demonstration of a compact suspended-core fiber Brillouin laser, which exhibits a low threshold power of 22 mW and a slope efficiency of 26% for nonresonant pumping.     

Seed oil triglyceride profiling of thirty-two hybrid grape varieties

Triglyceride profile of seed oil samples from 32 hybrid grape varieties not studied before was investigated. A new method for the analysis of triacylglycerols (TAGs) has been developed based on the direct infusion in the electrospray ionization (ESI) source and employing tetrahydrofuran/methanol/water (85:10:5 v|v|v) as solvent; the formation of [M?+?Na](+) ions in high yield has been observed. TAGs were identified by ESI-tandem mass spectrometry analysis, and the matrix-assisted-laser-desorption-ionization and time-of-flight profile of samples was determined. Six were the principal TAGs identified in seed oil: trilinolein (LLL) was the most abundant (43%), followed by dilinoleoyl-oleoylglycerol (LOL, 23%), and dilinoleoyl-palmitoylglycerol (LPL, 15%). Compounds present in lower concentration were LSL and LOO (11%), LOP (6%), and LSP (2%). Compared with seed oils produced from V. Vinifera grapes, some significant differences in the relative abundances of TAGs were found, in particular hybrid grape seed oils showed higher LOL and lower LPL content, respectively. Among the samples studied, a particularly high content of LLL (rich in unsaturated fatty acids) was found in seed oils from two red varieties. Copyright ? 2012 John Wiley & Sons, Ltd.     

填充吸附剂微萃取技术及其在微小体积样品萃取应用中的研究进展

微萃取技术是分析化学领域发展迅速,且已经得到广泛应用的样品前处理技术.填充吸附剂微萃取(MEPS)是一种微量固相萃取技术,使用微量的吸附剂填充于微量注射器,通过反复抽推方式使样品多次流经吸附剂以完成样品吸附萃取过程,萃取后的样品可直接用于色谱分析.典型的MEPS萃取设备包括MEPS注射器和MEPS吸附床(BIN).ME...