Sensitively probing the cofactor redox species and photo-induced electron transfer of wild-type and pheophytin-replaced photosynthetic proteins reconstituted in self-assembled monolayers

An ultrathin, ordered, and packed protein film, consisting of the 2-mercaptoacetic acid (MAA), polydimethyldiallylammonium chloride (PDDA), and wild-type (WT) photosynthetic reaction center (RC; termed as WT-RC) or its pheophytin (Phe)-replaced counterpart (termed as Phe-RC), was fabricated by self-assembling technique onto gold electrode for facilitating the electron transfer (ET) between RC and the electrode surface. Near-infrared (NIR)-visible (Vis) absorption and fluorescence (FL) emission spectra revealed the influence of pigment substitution on the cofactors arrangement and excitation relaxation of the proteins, respectively. Square wave voltammetry (SWV) and photoelectric tests were employed to systematically address the differences between the WT-RC films and mutant ones on the direct and photo-induced ET. The electrochemical results demonstrated that ET initiated by the oxidation of the primary donor (P) was obviously slowed down, and the formed P⁺ had more population as well as more positive redox potential in the Phe-RC films compared with those in the WT ones. The photoelectrochemical results displayed the dramatically enhanced photoelectric performances of the mutant ones, further suggesting the slow-down formation of final charge-separated state in Phe-RC. The functionalized protein films introduced in this paper provided an efficient approach to sensitively probe the redox cofactors and ET differences resulting from only minor changes in pigment arrangement in the pigment–protein complex. The favored ET process observed for the membrane proteins RC was potentially valuable for a deep understanding of the multi-step biological ET process and development of versatile bioelectronic devices.     

Developing a sequential injection-square wave voltammetry (SI-SWV) method for determination of atrazine using a hanging mercury drop electrode

This paper describes the development of a sequential injection analysis method to automate the determination of atrazine by square wave voltammetry exploiting the concept of monosegmented flow analysis to perform in-line sample conditioning and standard addition. To perform these tasks, an 800 μL monosegment is formed, composed by 400 μL of sample and 400 μL of buffer/standard solution. To obtain an efficient homogenization, the sample solution is divided in five zones intercalated by four zones of the Britton-Robinson buffer (pH 2.0) in presence of appropriate concentration of NaNO₃ and varying atrazine standard concentrations. This mixture zone is isolated from the carrier solution by two 100 μL air bubbles. After homogenization in an auxiliary reaction coil the mixture zone is injected toward the flow cell, which is adapted to the capillary of a hanging drop mercury electrode, at a flow rate of 50 μL s⁻¹. After a suitable delay time, the potential is scanned from −0.5 to −1.2 V versus Ag/AgCl using a frequency of 300 Hz and pulse height of 25 mV. The linear dynamic range is observed for atrazine concentrations between 1.16 × 10⁻⁷ and 2.32 × 10⁻⁶ mol L⁻¹, obeying the linear equation i_p = (−6.91 ± 0.07) × 10⁸[atrazine] + (4 ± 8), with r² = 0.9996, for which the slope is given in nA L mol⁻¹. The detection and quantification limits of the method are 2.1 × 10⁻⁸ and 7.0 × 10⁻⁸ mol L⁻¹, respectively. The sampling frequency is 37 h⁻¹, when the standard addition protocol is followed. This frequency can be increased to 42 h⁻¹ if the protocol to obtain in-line calibration curve is used for quantification. The method was applied for determination of atrazine in spiked river water samples and its accuracy was evaluated by comparison with the batch standard addition approach, which revealed that there is no evidence of statistically significant differences between the two methods.     

Nucleophilic Addition of Thiaproline to Electrochemically Derived o‐Quinone,Application to the Sensitive Voltammetric Detection of Thiaproline

The mechanism of electrochemical behavior of catechol in the presence of thiaproline is investigated by cyclic voltammetry, controlled‐potential coulometry and spectrophotometric tracing of the reaction coordinate. The results indicate that thiaproline participate in with an ECEC mechanism in a nucleophilic (Michael) addition to o‐quinone. Effect of pH of buffer solution on reaction pathway is studied and showed that addition of thiaproline to the o‐quinone is performed only in solutions with pHs higher than 5. These results indicate that the addition of thiaproline is occurred first from amine functional group. In the second step, the addition of carboxylate group of thiaproline to C‐5 of catechol results the final product with a lactone ring in its structure. Observation of two isosbestic point in absorption spectrum during the progress of the electrolysis together with the FT‐IR results for final product can be presented as evidence for two step addition of thiaproline to catechol. Final product, due to the electron donor property of thiaproline, more easily oxidized respect to the former catechol and as a result, a new redox couple is obtained for this compound in lower potentials. The easier anodic oxidation of addition product (relative to catechol) caused to an increase in anodic current for catechol, which is proportional to the thiaproline concentration. The differential pulse voltammetry (DPV) is applied as a sensitive voltammetric method for the detection of thiaproline. A linear range from 5×10^?8 to 5×10^?6 M with a detection limit of 1×10^?8 M is resulted for thiaproline. With respect to the reversibility of the electrochemical reactions in the mechanism, and also more facile oxidation of the addition products, the square‐wave voltammetry is presented as a method with considerably more sensitivity for the detection of sub‐micromolar amounts of thiaproline. The advantageous properties of the voltammetric method for thiaproline detection lie in its excellent catalytic activity, sensitivity and simplicity.     

Utilization of a Copper Solid Amalgam Electrode for the Analytical Determination of Atrazine

A copper solid amalgam electrode was prepared and used for the voltammetric determination of atrazine in natural water samples by square wave voltammetry. This electrode is a convenient substitute for the hanging mercury electrode since it is selective, sensitive, reliable and inexpensive and presents low toxicity characteristic. The detection limit of atrazine obtained in pure water (laboratory samples) was shown to be lower than the maximum limit of residue established for natural water by the Brazilian Environmental Agency. The relative standard deviation for 10 different measurements was found to be only 3.98% in solutions containing 8.16×10^?6 mol L^?1 of atrazine. In polluted stream water samples, the recovery measurements were approximately 70.00%, sustaining the applicability of the proposed methodology to the analysis of atrazine in such matrices.     

Acoustic absorbers at low frequency based on split-tube metamaterials

The remarkable properties of acoustic metamaterials have attracted massive researches and applications, especially on low-frequency sound absorptions. Currently, most of the acoustic metamaterial absorbers employ resonances in plastic cavities, and their structural strengths are important in many circumstances, especially in harsh environment. However, studies of metamaterials including this point are very scarce. Here, we propose an acoustic metamaterial for low-frequency (<500 Hz) absorptions, composed of three nested square split tubes with inverted opening directions. The efficiency of the absorber is investigated both numerically and experimentally, and absorptions at the peeks are found to exceed 90% and the frequency can be effectively adjusted by tuning its geometric parameters. We further test its yield strength under compression and confirm its buckling behavior happens from the outmost layer. This tunable acoustic metamaterial with a fairly good mechanical strength may lead to broad applications in noise reduction.     

Electroanalytical Determination of Cd(II) and Pb(II) in Bivalve Mollusks using Electrochemically Reduced Graphene Oxide‐based Electrode

An electrochemical sensor for the simultaneous determination of Cd(II) and Pb(II) by square wave anodic stripping voltammetry (SWASV) in bivalve mollusks using a glassy carbon electrode modified with electrochemically reduced graphene oxide has been developed. The modified surface was characterized by cyclic voltammetry, high resolution scanning electron microscopy (HR‐SEM), and Raman spectroscopy. The optimum conditions were optimized and a linear range was observed from 15–105 μg L^?1 with a limits of detection of 15 μg L^?1 for Cd(II) and Pb(II). The methodology was validated and applied in different samples of commercial bivalve mollusks with satisfactory results. The high conductivity and greater surface area of the modifying agent improves the preconcentration capacity of the electrochemical sensor, allowing to develop a simple, rapid and sensitive analysis in the detection of lead and cadmium in marine resources.     

A Facile Strategy for Construction of Sensor for Detection of Ondansetron and Investigation of its Redox Behavior and Thermodynamic Parameters

A sodium dodecylsulfate‐doped polypyrrole (SDS‐PPy) film was elaborated on glassy carbon electrode (GCE) by an electrodeposition method in phosphate buffer solution (pH 2.0) containing pyrrole (Py) and sodium dodecyl sulfate (SDS). SDS‐PPy/GCE was used for the construction of sensor, which showed excellent electrochemical response for the detection of ondansetron (OND) compared to conventional PPy. The application of the square wave (SW), with the adsorptive accumulation, indicates a maximum response at 1.33 V in H₂SO₄ (0.5 M). The influence of experimental parameters on determination of OND is discussed. The adsorptive stripping technique showed to be more sensitive, giving responses twice as big as those of non‐accumulated OND. The substantial improvement of response permits the development of an electroanalytical technique with a linear concentration in the range (1.0–80 μM), low detection (0.09 μM), and quantification limits (0.3 μM), and acceptable relative standard deviations of repeatability (0.59 %), and reproducibility (1.51 %). Consequently, this electrode is promising candidate for an accurate electroanalytical determination of OND in pharmaceutical samples with high sensitivity and selectivity, good accuracy and precision. The electrooxidation of OND at SDS‐PPy/GCE at various temperatures were studied by cyclic voltammetry to evaluate both the kinetic (k_s and E_a) and thermodynamic (ΔG*, ΔH* and ΔS*) parameters.     

斜入射角对二维正方形光子晶体带隙的影响

利用平面波法导出了光子晶体本征方程的矩阵形式,以此为基础计算了二维空气孔型正方形光子晶体在正入射时及斜入射时的带结构,并将带结构中混杂在一起的TE波和TM波的模式分离开来以分析斜入射角对带结构的影响.计算结果显示用电场E表示和用磁场H表示计算出来的结果完全一样,与电磁场是相互统一的结论完全吻合.研究还发现,TE波和TM波的第一带隙是完全分开的.随着波矢k的倾斜角度的增大,TE波的第一带隙逐渐减小并在波矢在（－1,0,1）平面内时完全消失.而TM波的带结构则随着波矢k的倾斜角的增大而变得平坦,带隙也是先随之增大,后又逐渐变小直至消失.     

正方形自聚焦透镜光线理论研究

针对正方形自聚焦透镜折射率分布特点,引入方向角概念,以平方律表征其折射率分布.从理论上研究了平方律折射率分布下正方形自聚焦透镜的光线轨迹方程,得到了子午光线表达式.结果表明,与传统径向自聚焦透镜相比,正方形自聚焦透镜的光线轨迹受光线入射方向角影响,会产生较大像差.得到了正方形自聚焦透镜数值孔径表达式,表明数值孔径并非常量,且与方向角密切相关.计算了中心轴上的最大数值孔径,方向角为0°时最小为0.405,方向角为45°时最大值0.5以上.     

Syntheses and structures of cobalt(II), nickel(II), and copper(II) complexes with N,N,N′,N′-tetraalkylpyridine-2,6-dicarboxamides (O-daap) containing nitrate as the counter ion

Reactions of M(NO₃)₂?·?xH₂O [M?=?Co(II), Ni(II), and Cu(II)] with N,N,N′,N′-tetraalkylpyridine-2,6-dicarboxamides(O-daap) in CH₃CN yield [Co(O-dmap)(NO₃)₂] (1), [Co(O-deap)(NO₃)₂] (2), [Co(O-dpap)(NO₃)₂] (3), [Ni(O-dmap)(H₂O)₃](NO₃)₂] (4), [Ni(O-deap)(H₂O)₂(NO₃)](NO₃)] (5), [Cu(O-deap)(NO₃)₂] (6), and [Cu(O-dpap)(NO₃)₂] (7). X-ray crystal structures of 1, 2, 4, 5, and 7 reveal that O-daap ligands coordinate tridentate to each metal, O–N–O, with nitrate playing a vital role in molecular and crystal structures of all the complexes. The coordination geometry in the two Co(II) complexes, 1 and 2, is approximately pentagonal bipyramidal with nitrate bonded in a slightly unsymmetrical bidentate chelating mode. [Ni(dmap)(H₂O)₃](NO₃)₂ (4) and [Ni(deap)(H₂O)₂(NO₃)](NO₃) (5) exhibit octahedral geometry, the former containing uncoordinated nitrate while the latter has one nitrate coordinated unidentate and the other nitrate outside the coordination sphere. The Cu(II) in [Cu(dpap)(NO₃)₂] (7) occupies a distorted square pyramidal geometry and is linked to two unidentate nitrates, although one nitrate is also involved in a weak interaction with the metal through its other oxygen. IR spectra and other physical studies are consistent with their crystal structural data. O-dmap?=?N,N,N′,N′-tetramethylpyridine-2,6-dicarboxamides; O-deap?=?N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamides; and O-dpap?=?N,N,N′,N′-tetraisopropylpyridine-2,6-dicarboxamides.