Bead injection for surface enhanced Raman spectroscopy: automated on-line monitoring of substrate generation and application in quantitative analysis

The technique of bead injection has been adapted for surface enhanced Raman scattering (SERS) to substantially improve precision, long term stability and sensitivity of SERS detection in analytical chemistry. For this purpose a fully automated flow system comprising a dedicated flow-cell has been developed and tested. With the developed flow-cell, which contains two inlet and two outlet channels, it is possible to retain, perfuse and discharge minute amounts of polymer beads while monitoring all steps by Raman spectroscopy. First, beads carrying cation exchanger moieties were retained in the flow-cell and subsequently perfused with a silver nitrate and a hydroxylamine solution using one inlet of the flow cell. By this sequence homogeneous SERS active silver layers were formed on the beads. The uniformity of the achieved silver layer was studied by secondary electron microscopy. For measurement, the analyte was then introduced from the second inlet channel such that the interaction between the activated SERS beads and analyte occurred in close proximity and within the focus of the laser excitation beam. Due to the complete computer control of all experimental steps, including bead entrapment, SERS layer generation, sample introduction and final bead removal, highly reproducible conditions for SERS were achieved. The method was developed using 9-aminoacridine as a test molecule. Quantitative studies were carried out for 9-aminoacridine and acridine showing linear calibrations from 1-100 nmol l(-1) and 50-1,000 nmol l(-1), respectively, using a sample volume of 200 microl each. Typical relative standard deviations were 4.7% for 9-aminoacrine and 5.8% for acridine.     

Characterizations based on conditional expectations of the doubled truncated distribution

The expression of the continuous distribution function F(x) is obtained whenever % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiGc9yrFr0xXdbba91rFfpec8Eeeu0x% Xdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs% 0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaacaqabeaadaqaaqGaaO% qaaerbhv2BYDwAHbacfiGaa8xBaiaabIcacaWG4bGaaiilaiaadMha% caqGPaGaa8hiaiaab2dacaWFGaGaa8xraiaa-HcacaWFybGaa8hiai% aa-XhacaWFGaGaa8hEaiaa-bcacqGHKjYOcaWFGaGaa8hwaiaa-bca% cqGHKjYOcaWFGaGaa8xEaiaa-Lcaaaa!53EE!\[m{\rm{(}}x,y{\rm{)}} {\rm{ = }} E(X | x \le X \le y)\]is known. Moreover, we obtain the necessary and sufficient conditions so that any function m: ² is the conditional expectation % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiGc9yrFr0xXdbba91rFfpec8Eeeu0x% Xdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs% 0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaacaqabeaadaqaaqGaaO% qaaiaadweacaGGOaGaamiwaerbhv2BYDwAHbacfiGaa8hiaiaacYha% caWFGaGaa8hEaiaa-bcacqGHKjYOcaWFGaGaa8hwaiaa-bcacqGHKj% YOcaWFGaGaa8xEaiaacMcaaaa!4D0D!\[E(X | x \le X \le y)\]of a random variable X with continuous distribution function. Furthermore, we relate m(x,y) to order statistics.     

Simultaneous determination of propranolol and pindolol by synchronous spectrofluorimetry

A completely automated method to determine the most common parameters in cured meat products is proposed. The approach to full automation is based on the coupling of a robotic station for development of preliminary operations (namely weighing of the sample, grinding, leaching, filtration and transport to the aspiration zone) and a continuous unsegmented manifold for derivatisation and spectrophotometric monitoring of the reaction coloured products. This assembly works in an unattended fashion thus eliminating the bottleneck produced by the determination of these parameters in routine laboratories. The good agreement between results obtained by the proposed method and those from conventional methods for target analytes confirms its excellent performance and usefulness.     

Structure of a styrylbenzoselenazole platinum(II) complex: [NEt4][Pt(nsbse)Br3]

Tetraethylammonium tribromo[2-(2-chloro-5-nitrostyryl)benzoselenazole] platinate (II), [(C₂H₅)₄N][PtBr₃(C₁₅H₉ClN₂O₂Se)], is monoclinic, in space groupP2₁/c, witha=9.496(2),b=20.321(7),c=15.166(3)Å,=100.18(1)°,V=2880(2)ų,M _r =928.72,Z=4,D _x =2.141 g cm^–3, (MoK)=0.71073 Å,=104.1 cm^–1,F(000)=1752,T=298 K. The structure was solved by direct methods and refined toR=0.032 for 2626 unique observed reflections withI>3(I). The [Pt(nsbse)Br₃)] unit has square-planar geometry about the Pt atom, with the nsbse coordinated to the Pt through the N of the selenazole ring. The ligand molecule is non-planar, with a dihedral angle of 61.6(2)° between the benzoselenazole and phenyl rings. The dihedral angles between the PtBr₃ plane and the benzoselenazole and phenyl planes are 105.2(1) and 80.7(1)°, respectively.     

FeCp]+-induced hexafunctionalization of hexamethylbenzene with dendrons for the direct synthesis of redox-active iron-centered metallodendrimers

Phenol tri- and nonaallyl dendrons (3 and 7, respectively) were functionalized at the focal position to give the new triallyl dendrons 4 and 6 and the nonaallyl dendrons 11 and 13 that contain a iodoalkyl or a bromobenzyl termini. All these dendrons were used for the [FeCp]+-induced hexafunctionalization of hexamethylbenzene in [FeCp(eta6-C6Me6)][PF6] (1) under mild conditions in the presence of KOH. These reactions directly yielded the 18-allyl and 54-allyl dendrimers 9, 10, and 14 with a [FeCp(eta6-arene)]+ unit located at the dendrimer core. Cyclic voltammetry studies were recorded in THF and DMF with these metallodendrimers and compared with those of analogous dendrimers or complexes of smaller size that contain a [FeCp(eta6-arene)]+ unit at the core. The decreased rate of heterogeneous electron transfer when the dendritic size increases first disclosed by Diederich and Gross is confirmed. The variation of the redox potential of the Fe(II/I) redox system with increasing dendritic size is negligible even in a solvent of high dielectric constant such as DMF. This trend is attributed to fact that the involved "redox" orbital is buried on the metal center, well protected by the shell of alkyl chains (electron-reservoir nature), unlike in ferrocene. The chemical irreversibility increases in THF as the dendrimer size increases, due to more facile ligand substitution with THF at the 19-electron level when the chain bulk increases.