Biocentri-voltammetric biosensor for acetylcholine and choline

We report on the determination of choline and acetylcholine via biocentrivoltammetry. This method combines centrifugation and voltammetry and is based on a carbon paste electrode modified with acetylcholinesterase and choline oxidase. The electrode was placed at the bottom of a biocentrivoltammetric cell. Acetylcholine and choline are accumulated on the enzyme electrode via centrifugative forces, upon which a direct voltammetric scan is applied. Reaction time, pH values, quantities of enzyme and centrifugation parameters were optimized. A linear response is obtained in the 0.07 to 10?μM concentration range of acetylcholine, and a limit of detection as low as 0.5?μM. The linear range is between 0.1 and 500?μM for choline. The method was applied to the determination of acetylcholine and choline in spiked serum samples.

Material structure-composite morphology-photovoltaic performance relationship for organic bulk heterojunction solar cells

Conjugated PPV-PPE copolymer has been investigated in organic solar cells in combination with twelve different fullerene derivatives. It was shown that the length of solubilizing alkyl chains in the fullerene derivative structures correlates well with the performance of photovoltaic cells.     

Controlled formation of the two-dimensional TTBC J-aggregates in an aqueous solution

Strong experimental and theoretical evidence was provided on the controlled formation of the two-dimensional J-aggregates that were assembled in the herringbone morphology. The exciton-band structure formation of 1,1',3,3'-tetraethyl-5,5',6,6'-tetrachlorobenzimidazolocarbocyanine (TTBC) J-aggregates was investigated in ionic (NaOH) aqueous solution at room temperature. The control was achieved by changing the [TTBC] at a given [NaOH], or vice versa, and was monitored through the changes in the absorption, fluorescence excitation, and emission spectra. Specific attention was paid to expose the excited-state structure and dynamics through simulations of the excitonic properties, which included diagonal energetic disorder and phonon-assisted exciton relaxation. Aggregates were characterized by an asymmetrically split Davydov pair, an H-band (approximately 500 nm, 1300 cm(-1) wide, Lorentzian-like) and a J-band (approximately 590 nm, 235 cm(-1) wide, with a band shape typical of a one-dimensional J-aggregate), whose relative intensities showed a strong dependence on the [TTBC]/[NaOH]. The H-band is favored by high [TTBC] or high [NaOH]. An explanation of the control on the aggregate formation was given by correlating the changes in the absorption with the structural modifications and the subsequent changes in the dynamics, which were induced by variations in the dye and NaOH concentrations. The J-band shape/width was attributed to disorder and disorder-induced intraband phonon-assisted exciton relaxation. The intraband processes in both bands were estimated to occur in the same time scale (about a picosecond). It has been suggested that the wide energetic gap between the Davydov split bands (3000 cm(-1)) could get bridged by the excitonic states of the loosely coupled chains, in addition to the monomeric species at low [TTBC]. Phonon-assisted interband relaxation, through the band gap states and/or directly from the H- to the J-band, are suggested for accounting the difference between the bandwidths and shapes of the two bands. Energy transfer between the H-band and the monomeric species is suggested as crucial for tuning the relative strengths of the two bands.     

Long-lived photoinduced charges in donor-acceptor anthraquinone-substituted thiophene copolymers

The photoinduced charge-transfer properties of a series of polyalkylthiophene copolymers, carrying anthraquinone substituents covalently linked to the conjugated backbone, have been studied in the solid state by photoinduced absorption (PA) and light-induced electron spin resonance (LESR) spectroscopy. The measurements indicate the formation of metastable charges arising from the photoinduced electron transfer from the polythiophene backbone to the anthraquinone moieties. At low temperatures (below 200 K), long-lived persistent charges are formed, exhibiting lifetimes that extend for several minutes; their recombination kinetics has been studied by following the formation and decay of the PA and LESR signals. The results are rationalized using a model originally proposed to describe the low-temperature recombination kinetics of long-lived photoexcited carriers in amorphous inorganic semiconductors. It is clearly evidenced that, in these polymers, the number of acceptor substituents in the chain, easily tuned by chemical tailoring, plays a key role in the photoexcitation scenario.     

Photoinduced electron transfer in a new Bis(C60)-phthalocyanine triad

[Structure: see text] A novel covalently linked bis([60]fullerene)-phthalocyanine triad is reported, exhibiting long-lived photoinduced charge separation both in solution and in the solid state. The first demonstration of a working solar cell using triad 1 as the active material is also presented.     

Stabilization using fractional-order PI and PID controllers

This paper presents a solution to the problem of stabilizing a given fractional dynamic system using fractional-order PIλ and PI^λD^μ controllers. It is based on plotting the global stability region in the (k _p, k _i)-plane for the PI^λ controller and in the (k _p , k _i , k _d)-space for the PIλDμ controller. Analytical expressions are derived for the purpose of describing the stability domain boundaries which are described by real root boundary, infinite root boundary and complex root boundary. Thus, the complete set of stabilizing parameters of the fractional-order controller is obtained. The algorithm has a simple and reliable result which is illustrated by several examples, and hence is practically useful in the analysis and design of fractional-order control systems.     

Combined effects of conjugation pattern and alkoxy side chains on the photovoltaic properties of thiophene‐containing PPE‐PPVs

This contribution presents the synthesis and properties of four thiophene‐containing poly(‐p‐arylene‐ethynylene)/poly(‐p‐arylene‐vinylene)s, PIa‐b and PIIa‐b , whose repeating units (RU) consist either of 1:2 or 2:2 triple bond/double bond ratio, and which bear linear alkoxy side chains not longer than octyloxy and branched 2‐ethylhexyloxy. PIa‐b and PIIa‐b exhibit similar absorption and emission behaviour in dilute solution (λ_a = 483–486 nm, λ_e = 540 nm) as well as in solid state (λ_a = 500, 530 nm, λ_e = 560 nm), whereby slightly higher fluorescence quantum yields (Φ_f) were obtained for PI than for PII systems, as a result of higher number of thiophene units within the RU of PII . An enhancement of the Φ_f‐value from 0% to 3% is obtained after replacing linear octadecyloxy in PIIc‐e by bulky branched 2‐ethylhexyloxy in PIIa‐b . Nonoptimized solar cells of configuration ITO/PEDOT:PSS/polymer: PCBM (1:3 weight ratio)/LiF/Al show open circuit voltages as high as 900 mV for PIa‐b and 800 mV for PIIa‐b . Reducing the size of the side chain from R = 2‐ethylhexyl in PIa to R = methyl in PIb leads to a significant increase of the short circuit current, I _SC, from ca. 2.5 mA to ca. 3.7 mA and consequently to an enhancement of the energy conversion efficiency, η_AM1.5, from ca. 1.2% to ca. 1.7%. This is due to an extended donor‐acceptor interfacial area, as evidenced by AFM topology pictures showing smaller nanoscale clusters size in PIb than in PIa active layer. The same change led to minimal effect in PII systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1619–1631, 2007     

HPLC Separation of Different Groups of Small Polar Compounds on a Novel Amide-Embedded Stationary Phase

Retention behaviors of an amide-embedded silica base stationary phase, which was recently developed by our group, were studied by using six different groups of small polar compounds including phenolic compounds, substituted anilines, chlorinated herbicides, Sudan dyes and some nucleotides and nucleosides in HPLC. The chromatographic behaviors of the prepared stationary phase for these analytes were compared with those of a commercially available reversed-phase column ACE C18 under same conditions. Among the six groups of analytes studied, the amide-silica stationary phase showed enhanced selectivity towards phenolic compounds, substituted anilines, Sudan dyes and herbicides under reversed-phase conditions and satisfactory selectivity towards nucleosides and nucleotides which could not be separated with ACE C18 column under HILIC conditions. Experimental data provided some evidence that functional groups on the stationary phases might have certain degrees of influence on selectivity possibly through secondary interactions with the model compounds. The retentions of the moderately polar compounds such as phenolic acids, anilines and herbicides on the stationary phase are higher than highly polar compounds such as nucleotides and nucleosides due to both the hydrophobic and hydrophilic interactions between the stationary phase and analytes. The quantitative determination of Sudan dyes (I, II, III, and IV) in red chilli peppers was performed. Many red chilli peppers were screened and three of them contained Sudans dyes.