An automatic optosensing device for the simultaneous determination of resveratrol and piceid in wines

For the first time, a spectrofluorimetric method is reported for the simultaneous determination of resveratrol (RVT) and piceid (PCD), two stilbenes showing diverse interesting physiological and biochemical attributes, as well as a wide range of health benefits ranging from cardioprotection to chemoprevention. The method makes use of a multicommutated flow-through optosensor in which the resolution of RVT and PCD is accomplished by means the sequential arrival of their photoproducts, on-line generated by UV-irradiation, to the detection area. This is possible due to the different kinetic behaviour of these latter on a solid support (C₁₈ silica gel) filling a minicolumn placed before the detector. The measurement in solid-phase of the photochemically induced fluorescence of the photoproducts (λ_ex: 257 nm/λ_em: 382 nm) is used as analytical signal for monitoring both compounds. The method has been applied to the analysis of RVT and PCD in wines and requires a previous solid-phase extraction (SPE) using Bakerbond C₁₈ cartridges. This pretreatment and the use of a solid-support in both the minicolumn and the flow-cell of the detector allow the determination of RVT and PCD by external calibration. Detection limits (DLs) are 9.3 and 12.6 ng mL⁻¹ for RVT and PCD, respectively. Commercial red and white wine samples have been analysed and the results obtained have been satisfactorily validated by high-performance liquid chromatography (HPLC).     

微孔板发光二极管诱导荧光-表面活性剂增敏法测定盐酸小檗碱

研制了微孔板发光二极管诱导荧光分析仪,以发光二极管为激发光源,Y形光纤束传导激发光和荧光,采用平面型光敏二极管接收荧光.采用二维定位器移动微孔板,可实现对多个样品快速连续的测定.利用弱碱性介质中阴离子表面活性剂十二烷基苯磺酸钠(SDBS)对盐酸小檗碱荧光的增敏作用,在pH 9.0的Britton-Robinson缓冲溶...     

Self‐Regulation in Flow‐Induced Structure Formation of Polypropylene

Flow‐induced structure formation is investigated with in situ wide‐angle X‐ray diffraction with high acquisition rate (30 Hz) using isotactic polypropylene in a piston‐driven slit flow with high wall shear rates (up to ≈900 s⁻¹). We focus on crystallization within the shear layers that form in the high shear rate regions near the walls. Remarkably, the kinetics of the crystallization process show no dependence on either flow rate or flow time; the crystallization progresses identically regardless. Stronger or longer flows only increase the thickness of the layers. A conceptual model is proposed to explain the phenomenon. Above a certain threshold, the number of shish‐kebabs formed affects the rheology such that further structure formation is halted. The critical amount is reached already within 0.1 s under the current flow conditions. The change in rheology is hypothesized to be a consequence of the “hairy” nature of shish. Our results have large implications for process modelling, since they suggest that for injection molding type flows, crystallization kinetics can be considered independent of deformation history.

     

Study on the pressure induced charge transfer phase transition in (C5H11)4N(FeFe(C2O2S2)3) by means of μSR spectroscopy

We have investigated the magnetic properties of iron mixed-valence complexes, (n-C_nH_2n+1)₄N[Fe^IIFe^III(dto)₃] (dto = C₂O₂S₂, n = 3, 5), in which not only a ferromagnetic transition but also a novel charge transfer phase transition (CTPT) take place [1]. This CTPT can be observed under ambient pressure for n = 3, while it appears abruptly above 0.5 GPa for n = 5 [2]. Recently, we have measured the muon spin relaxation (μSR) for the CTPT of n = 3, which revealed the dynamical process of electron-transfer between Fe^II and Fe^III and its frequency was estimated at about 0.1 MHz [3]. To investigate the pressure induced CTPT for n = 5, we carried out the μSR measurement for n = 5 at 150 K between 0.30 and 0.64 GPa with the ⁴He gas-operated pressure system. The asymmetry of the muon spin relaxation for n = 5 with Cu-Be pressure cell was almost constant up to 0.55 GPa, while it rapidly decreased with increasing pressure above 0.60 GPa. This result shows that the applied pressure causes the spin fluctuation due to the CTPT, which induces the decrease of the asymmetry of muon spin relaxation. This experiment can correctly decide the phase transition pressure from the absence to the appearance of the CTPT for n = 5.     

Diagnosis of lubricating oil by evaluating cyanide and carbon molecular emission lines in laser induced breakdown spectra

To prevent engine failure it is essential to change lubricating oil regularly before it loses its protective properties. It is also necessary to monitor the physical and chemical conditions of the oil to reliably determine the optimum oil-change intervals. The present work focuses on studying evolution of the cyanide (CN) and carbon (C₂) molecular spectral emission lines in the laser induced breakdown spectra of lubricating oil as a function of its consumption. The intensities of these molecular bands have been taken as indicator of engine oil degradation at certain mileage. Furthermore, the percentage of decay of CN and C₂ integral intensity values at the corresponding mileage was calculated in order to relate it to the degree of consumption of the motor oil. Such percentage decay of the CN and C₂ integral intensities have been found to increase gradually with increasing mileage which is accompanied with increasing depletion of engine oil. The results of using LIBS technique in the present measurements proved that it is possible to have a direct, straightforward and easy method for prediction of lubricating oil degree of consumption. This may facilitate scheduling the proper time and/or mileage intervals for changing the oil to avoid any possibility of engine failure.     

Multiple Reaction Pathways Operating in the Mechanism of Vinylogous Mannich‐Type Reaction Activated by a Water Molecule

A systematic search for reaction pathways for the vinylogous Mannich‐type reaction was performed by the artificial force induced reaction method. This reaction affords δ‐amino‐γ‐butenolide in one pot by mixing 2‐trimethylsiloxyfuran, imine, and water under solvent‐free conditions. Surprisingly, the search identified as many as five working pathways. Among them, two concertedly produce anti and syn isomers of the product. Another two give an intermediate, which is a regioisomer of the main product. This intermediate can undergo a retro‐Mannich reaction to give a pair of intermediates: an imine and 2‐furanol. The remaining pathway directly generates this intermediate pair. The imine and 2‐furanol easily react with each other to afford the product. Thus, all of these stepwise pathways finally converge to give the main product. The rate‐determining step of all five (two concerted and three stepwise) pathways have a common mechanism: concerted Si? O bond formation through the nucleophilic attack of a water molecule on the silicon atom followed by proton transfer from the water molecule to the imine. Therefore, these five pathways have comparable barriers and compete with each other.     

Uncovering the Stoichiometry of Pyrococcus furiosus RNase P,a Multi‐Subunit Catalytic Ribonucleoprotein Complex,by Surface‐Induced Dissociation and Ion Mobility Mass Spectrometry

We demonstrate that surface‐induced dissociation (SID) coupled with ion mobility mass spectrometry (IM‐MS) is a powerful tool for determining the stoichiometry of a multi‐subunit ribonucleoprotein (RNP) complex assembled in a solution containing Mg²⁺. We investigated Pyrococcus furiosus (Pfu) RNase P, an archaeal RNP that catalyzes tRNA 5′ maturation. Previous step‐wise, Mg²⁺‐dependent reconstitutions of Pfu RNase P with its catalytic RNA subunit and two interacting protein cofactor pairs (RPP21?RPP29 and POP5?RPP30) revealed functional RNP intermediates en route to the RNase P enzyme, but provided no information on subunit stoichiometry. Our native MS studies with the proteins showed RPP21?RPP29 and (POP5?RPP30)₂ complexes, but indicated a 1:1 composition for all subunits when either one or both protein complexes bind the cognate RNA. These results highlight the utility of SID and IM‐MS in resolving conformational heterogeneity and yielding insights on RNP assembly.     

Liquid extraction surface analysis in-line coupled with capillary electrophoresis for direct analysis of a solid surface sample

A surface-sampling technique of liquid extraction surface analysis (LESA) was in-line coupled with capillary electrophoresis (CE) to expand the specimen types for CE to solid surfaces. The new direct surface analysis method of LESA–CE was applied to the determination of organophosphorus pesticides, including glufosinate-ammonium, aminomethylphosphonic acid, and glyphosate on the external surface of a fruit such as apple. Without any sample pretreatment, the analytes sprayed on the surface of a half apple were directly extracted into a liquid microjunction formed by dispensing the extractant from the inlet tip of a separation capillary. After extraction, the analytes were derivatized in-capillary with a fluorophore 4-fluoro-7-nitro-2,1,3-benzoxadiazole and analyzed with CE-laser induced fluorescence (LIF). The limits of detection for glufosinate-ammonium, aminomethylphosphonic acid, and glyphosate were 2.5, 1, and 10 ppb, respectively, which are at least 20 times lower than the tolerance limits established by the U.S. Environmental Protection Agency. Thus, we demonstrated that LESA–CE is a quite sensitive and convenient method to determine analytes on a solid surface avoiding the dilution from sample pretreatment procedures including homogenization of a bulk sample.     

Trace analysis of uranyl ion (UO2) in aqueous solution by fluorescence turn-on detection via aggregation induced emission enhancement effect

A sensitive fluorescence turn-on method for trace amounts of uranyl ion (UO₂²⁺) in solution has been developed in this study, based on aggregation induced emission enhancement (AIEE) characteristics of 4-pethoxycarboxyl salicylaldehyde azine (PCSA) induced by complex interaction between UO₂²⁺ and PCSA. Under optimized conditions, a fluorescence enhancement at 540 nm could be observed, which was linearly related to the concentration of UO₂²⁺ in the range of 1–25 ppb (part per billion). Analytical data showed that a detection limit of 0.2 ppb was achieved with the relative standard deviation (R.S.D.) 1.3% (n = 5). The proposed method was successfully utilized in quantifying UO₂²⁺ in fuel processing wastewaters.