Removal of Co by carbonaceous material obtained through solution combustion of tamarind shell

New carbonaceous materials were obtained through solution combustion process of tamarind shell in the presence of urea and ammonium nitrate, and all of them were tested for Co removal. The effect of temperature (from 600 to 1000°C) and water volume on surface texture of carbonaceous material and its adsorptive capacity was evaluated. Scanning electron microscope, Fourier transform infrared spectroscopy, X-ray powder diffraction, and Brunauer–Emmett–Teller (BET) model were used to characterize the obtained carbonaceous material before applying for the removal of cobalt. The point of zero charge was also determined. The results indicate that BET-specific surface areas ranged from 6.40 to 216.72 m²g^?1 for the carbonaceous materials obtained at 600, 700, 800, 900, and 1000°C. The one obtained at 900°C (CombTSF₉₀₀) was found to be the most effective adsorbent for the removal of Co(II) ions from aqueous solutions, with a maximum sorption capacity (Q_max) of 43.56 mg/g. Carbonaceous material obtained through the solution combustion process improves morphological characteristics of adsorbent in a short time, and could be used as an alternative method for the removal of cobalt.     

A dye-sensitized solar cell driven electrochromic device.

A new dye-sensitized solar cell driven electrochromic device has been fabricated. The device consists of an electrochromic display and a solar cell in a single nanocrystalline film. The optimization of the electrochromic and the solar cell functions was carried out. An applied potential of 1.0 V was required for coloring and the best solar energy conversion efficiency 1.1% was achieved. The efficiency may be compared to an efficiency of 4.6% obtained in a similar dye-sensitized solar cell without the display property. Coloring and bleaching times of the device were less than one second and a transmittance change from 38.7% (bleached) to 15.9% (colored) at best was achieved. The optimization of the electrochromic property of the device lead to decreasing efficiency of the solar cell and vice versa.     

Electrochromic detection of a coherent component in the formation of the charge pair P(+)H(L)(-) in bacterial reaction centers

We demonstrate coupling of an intraprotein electron transfer reaction to coherent vibrational motions. The kinetics of charge separation toward the radical pair state P(+)H(L)(-) were studied in reaction centers of Rhodobacter sphaeroides at 15 K. The electrochromic shift of the bacteriochlorophyll monomers is the most prominent spectral feature associated with this charge displacement. The newly reported absolute absorption spectrum of the P(+)H(L)(-) state is discussed in terms of this shift. In wild-type reaction centers, the rise kinetics of the electrochromic shift display a small but significant 30 cm(-)(1) periodic modulation (period of approximately 1 ps). This modulation is also present in FL181Y mutant reaction centers, where overall charge separation is somewhat more rapid than in the wild-type reaction center. In contrast, in YM210L mutant reaction centers, where the charge separation is much slower, the modulation is absent. The conclusion that the motion along the reaction coordinate has a 30 cm(-)(1) coherent component is discussed in light of possible mechanisms of electron transfer.     

Light-induced conformational changes in photosynthetic reaction centers: dielectric relaxation in the vicinity of the dimer

Conformational changes near the bacteriochlorophyll dimer induced by continuous illumination were identified in the wild type and 11 different mutants of reaction centers from Rhodobacter sphaeroides. The properties of the bacteriochlorophyll dimer, which has a different hydrogen bonding pattern with the surrounding protein in each mutant, were characterized by steady-state and transient optical spectroscopy. After illumination for 1 min, in the absence of the secondary quinone, the recovery of the charge-separated states was nearly 1 order of magnitude slower in one group of mutants including the wild type than in the mutants carrying the Leu to His mutation at the L131 position. The slower recovery was accompanied by a substantial decrease in the electrochromic absorption changes associated with the Q(y) bands of the nearby monomers during the illumination. The other set of mutants containing the Leu L131 to His substitution exhibited slightly altered electrochromic changes that decreased only half as much during the illumination as in the other family of mutants. The correlation between the recovery of the charge-separated states in the light-induced conformation and the electrochromic absorption changes suggests a dielectric relaxation of the protein that stabilizes the charge on the dimer.     

Spectra, membrane binding, and potentiometric responses of new charge shift probes

The properties of a series of new potentiometric membrane probes have been explored. The probes all contain an (aminostyryl)pyridinium chromophore or a more highly conjugated analogue. The spectral properties of the dyes are discussed in terms of the excitation-induced charge shift from the pyridine to the aniline; this charge shift also provides the basis for the voltage dependence of the spectra according to an electrochromic mechanism. The spectral responses to a membrane potential on a hemispherical bilayer have been obtained and, grossly, are quite similar for all probes tested. The more subtle variations from dye to dye can be partially rationalized by consideration of binding parameters, the depth within the membrane, and structural factors. The most potential sensitive dye in this collection has been designated di-4-ANEPPS and has a 6-amino-2-naphthyl group in place of the p-anilino on the parent chromophore. Both the relative fluorescence emission and excitation responses have maxima of 8% per 100 mV, and these two spectra display a striking symmetry.     

Evidence for slow turnover in a fraction of Photosystem II complexes in thylakoid membranes

We used two different techniques to measure the recovery time of Photosystem II following the transfer of a single electron from P-680 to Q_A in thylakoid membranes isolated from spinach. Electron transfer in Photosystem II reaction centers was probed first by spectroscopic measurements of the electrochromic shift at 518 nm due to charge separation within the reaction centers. Using two short actinic flashes separated by a variable time interval we determined the time required after the first flash for the electrochromic shift at 518 nm to recover to the full extent on the second flash. In the second technique the redox state of Q_A at variable times after a saturating flash was monitored by measurement of the fluorescence induction in the absence of an inhibitor and in the presence of ferricyanide. The objective was to determine the time required after the actinic flash for the fluorescence induction to recover to the value observed after a 60 s dark period. Measurements were done under conditions in which (1) the electron donor for Photosystem II was water and the acceptor was the endogenous plastoquinone pool, and (2) Q₄₀₀, the Fe²⁺ near Q_A, remained reduced and therefore was not a participant in the flash-induced electron-transfer reactions. The electrochromic shift at 518 nm and the fluorescence induction revealed a prominent biphasic recovery time for Photosystem II reaction centers. The majority of the Photosystem II reaction centers recovered in less than 50 ms. However, approx. one-third of the Photosystem II reaction centers required a half-time of 2–3 s to recover. Our interpretation of these data is that Photosystem II reaction centers consist of at least two distinct populations. One population, typically 68% of the total amount of Photosystem II as determined by the electrochromic shift, has a steady-state turnover rate for the electron-transfer reaction from water to the plastoquinone pool of approx. 250 e⁻ / s, sufficiently rapid to account for measured rates of steady-state electron transport. The other population, typically 32%, has a turnover rate of approx. 0.2 e⁻ / s. Since this turnover rate is over 1000-times slower than normally active Photosystem II complexes, we conclude that the slowly turning over Photosystem II complexes are inconsequential in contributing to energy transduction. The slowly turning over Photosystem II complexes are able to transfer an electron from P-680 to Q_A rapidly, but the reoxidation of Q⁻_A is slow (t1/2 = 2 s). The fluorescence induction measurements lead us to conclude that there is significant overlap between the slowly turning over fraction of Photosystem II complexes and PS II_β reaction centers. One corollary of this conclusion is that electron transfer from P-680 to Q_A in PS II_β reaction centers results in charge separation across the membrane and gives rise to an electrochromic shift.     

The rate of Q(x)→Q(y) relaxation in bacteriochlorophylls of reaction centers from Rhodobacter sphaeroides determined by kinetics of the ultrafast carotenoid bandshift

Transient absorption changes induced by excitation of isolated reaction centers (RCs) from Rhodobacter sphaeroides with 600nm laser pulses of 20fs (full width at half maximum) were monitored in the wavelength region of 420-560nm. The spectral features of the spectrum obtained are characteristic for an electrochromic band shift of the single carotenoid (Car) molecule spheroidene, which is an integral constituent of these RCs. This effect is assigned to an electrochromic bandshift of Car due to the local electric field of the dipole moment formed by electronic excitation of bacteriochlorophyll (BChl) molecule(s) in the neighborhood of Car. Based on the known distances between the pigments, the monomeric BChl (B(B)) in the inactive B-branch is inferred to dominate this effect. The excitation of B(B) at 600nm leads to a transition into the S(2) state (Q(x) band), which is followed by rapid internal conversion to the S(1) state (Q(y) band), thus leading to a change of strength and orientation of the dipole moment, i.e., of the electric field acting on the Car molecule. Therefore, the time course of the electrochromic bandshift reflects the rate of the internal conversion from S(2) to S(1) of B(B). The evaluation of the kinetics leads to a value of 30fs for this relaxation process. This article is part of a Special Issue entitled: Photosynthesis Research for Sustainability: from Natural to Artificial.     

Electrochromic Smart Windows Can Achieve an Absolute Private State through Thermochromically Engineered Electrolyte

Smart windows regulate the indoor solar radiation by adjusting their optical transmissive properties, offering an efficient way toward energy‐saving buildings, vehicles, etc. Electrochromism is one of the most promising solutions due to its simple control, versatile colors. Yet, electrochromics cannot give zero‐transmission through the whole visible range, leading to the windows that can always be looked through and limited for applications in the public sector. In this work, poly(N‐isopropylacrylamide) (PNIPAm) hydrogel, which undergoes temperature‐stimulated phase transition from a highly transparent state to a highly scattered zero‐transmission state through the whole visible range is used in the electrolyte of the electrochromic devices without affecting their electrochromic performance. It can be universally applied to inorganic and organic electrochromic devices, and the phase transition temperature can be easily tuned by the ion concentration. Therefore, apart from its ion conductive function, the electrolyte performs the chromatic transition function as well, allowing the electrochromic devices to achieve a zero‐transmissive, absolute “private” state. This chromatic engineering of the electrolyte can significantly broaden the industrial market of electrochromic smart window applications from public to private circumstances and bring much more flexibility in building façades design, which is a remarkable pavement for further industrial applications.     

Continuous ECS-indicated recording of the proton-motive charge flux in leaves

Technical features and examples of application of a special emitter–detector module for highly sensitive measurements of the electrochromic pigment absorbance shift (ECS) via dual-wavelength (550–520 nm) transmittance changes (P515) are described. This device, which has been introduced as an accessory of the standard, commercially available Dual-PAM-100 measuring system, not only allows steady-state assessment of the proton motive force (pmf) and its partitioning into ΔpH and ΔΨ components, but also continuous recording of the overall charge flux driven by photosynthetic light reactions. The new approach employs a double-modulation technique to derive a continuous signal from the light/dark modulation amplitude of the P515 signal. This new, continuously measured signal primarily reflects the rate of proton efflux via the ATP synthase, which under quasi-stationary conditions corresponds to the overall rate of proton influx driven by coupled electron transport. Simultaneous measurements of charge flux and CO₂ uptake as a function of light intensity indicated a close to linear relationship in the light-limited range. A linear relationship between these two signals was also found for different internal CO₂ concentrations, except for very low CO₂, where the rate of charge flux distinctly exceeded the rate of CO₂ uptake. Parallel oscillations in CO₂ uptake and charge flux were induced by high CO₂ and O₂. The new device may contribute to the elucidation of complex regulatory mechanisms in intact leaves.     

Charge translocation by the Na,K-pump: I. Kinetics of local field changes studied by time-resolved fluorescence measurements

Summary Membrane fragments containing a high density of Na, K-ATPase can be noncovalently labeled with amphiphilic styryl dyes (e.g., RH 421). Phosphorylation of the Na,K-ATPase by ATP in the presence of Na⁺ and in the absence of K⁺ leads to a large increase of the fluorescence of RH 421 (up to 100%). In this paper evidence is presented that the styryl dye mainly responds to changes of the electric field strength in the membrane, resulting from charge movements during the pumping cycle: (i) The spectral characteristic of the ATP-induced dye response essentially agrees with the predictions for an electrochromic shift of the absorption peak. (ii) Adsorption of lipophilic anions to Na, K-ATPase membranes leads to an increase, adsorption of lipophilic cations to the decrease of dye fluorescence. These ions are known to bind to the hydrophobic interior of the membrane and to change the electric field strength in the boundary layer close to the interface. (iii) The fluorescence change that is normally observed upon phosphorylation by ATP is abolished at high concentrations of lipophilic ions. Lipophilic ions are thought to redistribute between the adsorption sites and water and to neutralize in this way the change of field strength caused by ion translocation in the pump protein. (iv) Changes of the fluorescence of RH 421 correlate with known electrogenic transitions in the pumping cycle, whereas transitions that are known to be electrically silent do not lead to fluorescence changes. The information obtained from experiments with amphiphilic styryl dyes is complementary to the results of electrophysiological investigations in which pump currents are measured as a function of transmembrane voltage. In particular, electrochromic dyes can be used for studying electrogenic processes in microsomal membrane preparations which are not amenable to electrophysiological techniques.Deceased (September 13, 1990).     

Recruitment of a foreign quinone into the A1 site of photosystem I. Altered kinetics of electron transfer in phylloquinone biosynthetic pathway mutants studied by time-resolved optical, EPR, and electrometric techniques

Interruption of the menA or menB gene in Synechocystis sp. PCC 6803 results in the incorporation of a foreign quinone, termed Q, into the A(1) site of photosystem I with a number of experimental indicators identifying Q as plastoquinone-9. A global multiexponential analysis of time-resolved optical spectra in the blue region shows the following three kinetic components: 1) a 3-ms lifetime in the absence of methyl viologen that represents charge recombination between P700(+) and an FeS(-) cluster; 2) a 750-microseconds lifetime that represents electron donation from an FeS(-) cluster to methyl viologen; and 3) an approximately 15-microseconds lifetime that represents an electrochromic shift of a carotenoid pigment. Room temperature direct detection transient EPR studies of forward electron transfer show a spectrum of P700(+) Q(-) during the lifetime of the spin polarization and give no evidence of a significant population of P700(+) FeS(-) for t 相似文献   

Measurements of the distribution of adenylate concentrations and adenylate energy charge across Pseudomonas aeruginosa biofilms.

Adenine nucleotide pools and adenylate energy charge distributions were determined by using a laboratory-generated quasi-steady-state Pseudomonas aeruginosa biofilm. The method used involved freezing and sectioning of the intact biofilm, followed by extraction and assay of the adenylates in the sectioned material. Results indicated an increase in adenylate energy charge of about 0.2 units from the bottom to the surface of the biofilm. However, energy charge values were generally low throughout the biofilm, reaching a maximum of only 0.6 units. Of the adenylates measured, AMP was the predominant nucleotide, especially in the deeper parts of the biofilm profile.     

Measurements of the distribution of adenylate concentrations and adenylate energy charge across Pseudomonas aeruginosa biofilms.

Adenine nucleotide pools and adenylate energy charge distributions were determined by using a laboratory-generated quasi-steady-state Pseudomonas aeruginosa biofilm. The method used involved freezing and sectioning of the intact biofilm, followed by extraction and assay of the adenylates in the sectioned material. Results indicated an increase in adenylate energy charge of about 0.2 units from the bottom to the surface of the biofilm. However, energy charge values were generally low throughout the biofilm, reaching a maximum of only 0.6 units. Of the adenylates measured, AMP was the predominant nucleotide, especially in the deeper parts of the biofilm profile.     

Electrochromic shift of chlorophyll absorption in photosystem I from Synechocystis sp. PCC 6803: a probe of optical and dielectric properties around the secondary electron acceptor

Nanosecond absorption dynamics at approximately 685 nm after excitation of photosystem I (PS I) from Synechocystis sp. PCC 6803 is consistent with electrochromic shift of absorption bands of the Chl a pigments in the vicinity of the secondary electron acceptor A(1). Based on experimental optical data and structure-based simulations, the effective local dielectric constant has been estimated to be between 3 and 20, which suggests that electron transfer in PS I is accompanied by considerable protein relaxation. Similar effective dielectric constant values have been previously observed for the bacterial photosynthetic reaction center and indicate that protein reorganization leading to effective charge screening may be a necessary structural property of proteins that facilitate the charge transfer function. The data presented here also argue against attributing redmost absorption in PS I to closely spaced antenna chlorophylls (Chls) A38 and A39, and suggest that optical transitions of these Chls, along with that of connecting chlorophyll (A40) lie in the range 680-695 nm.     

Chromatophore vesicles of Rhodobacter capsulatus contain on average one F(O)F(1)-ATP synthase each

ATP synthase is a unique rotary machine that uses the transmembrane electrochemical potential difference of proton (Delta(H(+))) to synthesize ATP from ADP and inorganic phosphate. Charge translocation by the enzyme can be most conveniently followed in chromatophores of phototrophic bacteria (vesicles derived from invaginations of the cytoplasmic membrane). Excitation of chromatophores by a short flash of light generates a step of the proton-motive force, and the charge transfer, which is coupled to ATP synthesis, can be spectrophotometrically monitored by electrochromic absorption transients of intrinsic carotenoids in the coupling membrane. We assessed the average number of functional enzyme molecules per chromatophore vesicle. Kinetic analysis of the electrochromic transients plus/minus specific ATP synthase inhibitors (efrapeptin and venturicidin) showed that the extent of the enzyme-related proton transfer dropped as a function of the inhibitor concentration, whereas the time constant of the proton transfer changed only marginally. Statistical analysis of the kinetic data revealed that the average number of proton-conducting F(O)F(1)-molecules per chromatophore was approximately one. Thereby chromatophores of Rhodobacter capsulatus provide a system where the coupling of proton transfer to ATP synthesis can be studied in a single enzyme/single vesicle mode.     

The rate of Qx→Qy relaxation in bacteriochlorophylls of reaction centers from Rhodobacter sphaeroides determined by kinetics of the ultrafast carotenoid bandshift

Transient absorption changes induced by excitation of isolated reaction centers (RCs) from Rhodobacter sphaeroides with 600 nm laser pulses of 20 fs (full width at half maximum) were monitored in the wavelength region of 420–560 nm. The spectral features of the spectrum obtained are characteristic for an electrochromic band shift of the single carotenoid (Car) molecule spheroidene, which is an integral constituent of these RCs. This effect is assigned to an electrochromic bandshift of Car due to the local electric field of the dipole moment formed by electronic excitation of bacteriochlorophyll (BChl) molecule(s) in the neighborhood of Car. Based on the known distances between the pigments, the monomeric BChl (B_B) in the inactive B-branch is inferred to dominate this effect. The excitation of B_B at 600 nm leads to a transition into the S₂ state (Q_x band), which is followed by rapid internal conversion to the S₁ state (Q_y band), thus leading to a change of strength and orientation of the dipole moment, i.e., of the electric field acting on the Car molecule. Therefore, the time course of the electrochromic bandshift reflects the rate of the internal conversion from S₂ to S₁ of B_B. The evaluation of the kinetics leads to a value of 30 fs for this relaxation process. This article is part of a Special Issue entitled: Photosynthesis Research for Sustainability: from Natural to Artificial.     

Excitation relaxation in the chemically modified photosynthetic reaction center from <Emphasis Type="Italic">Rhodobacter</Emphasis><Emphasis Type="Italic">sphaeroides</Emphasis> 601

The ultrafast excitation relaxation in the sodium borohydride-treated reaction center of Rhodobacter sphaeroides 601 was investigated with selective excitation. From the femtosecond pump-probe measurement at 790 nm, the excitation relaxation demonstrates a biexponential decay with time constants of about 200 fs and 1.4 ps. By comparison with the result from sodium ascorbate-pretreated modified RS601, it could be concluded that the dynamical trace at 790 nm mainly originates from the contribution of accessory bacteriochlorophyll in the active side, and the electrochromic shift arising from the induced positive charge on the special pair primarily affects the absorption band in the red region of the accessory bacteriochlorophyll in RS601. With direct excitation of the special pair, the charge separation and subsequent electron transfer were observed in borohydride-modified RS601. The 2.8 ps component was ascribed to the charge separation and electron transfer from P* to H(A). From the dynamical traces at 790, 800 and 818 nm, the ultrafast energy relaxation from the excited accessory bacteriochlorophyll in the active side is consistent with a two-step energy transfer mechanism. This dynamical observation in modified RS601 is of significance in understanding the physical mechanism of excitation relaxation and energy transfer in the photosynthetic primary process.     

Boosting the Charge Density of Triboelectric Nanogenerator by Suppressing Air Breakdown and Dielectric Charge Leakage

Charge generation and charge decay are two essential factors that determine the surface charge density of a triboelectric nanogenerator (TENG). However, research mainly focuses on boosting charge generation, and little attention is paid to suppressing charge decay. Here, a strategy of suppressing charge decay, including the air breakdown and dielectric charge leakage, of TENG with high surface charge density (HCD-TENG) is proposed by utilizing a dual dielectric layer. A series of parameters of different dielectric materials are tested with the assistance of a charge excitation TENG (CE-TENG) to reveal the relationships between charge generation, air breakdown, and dielectric charge leakage in the atmospheric environment. Further, the phenomenon of dielectric charge leakage limiting the maximum output of TENG prior to air breakdown is observed for the first time. With the simultaneous suppression of the air breakdown and dielectric charge leakage, the output of TENG is enhanced to 2.2 mC m⁻². This work not only provides new insight into the performance optimization and material selection of TENG, but also provides significant guidance for obtaining high-output TENG in the future.     

The relationship between Q gamma and Ca release from the sarcoplasmic reticulum in skeletal muscle

Asymmetric membrane currents and fluxes of Ca2+ release were determined in skeletal muscle fibers voltage clamped in a Vaseline-gap chamber. The conditioning pulse protocol 1 for suppressing Ca2+ release and the "hump" component of charge movement current (I gamma), described in the first paper of this series, was applied at different test pulse voltages. The amplitude of the current suppressed during the ON transient reached a maximum at slightly suprathreshold test voltages (-50 to -40 mV) and decayed at higher voltages. The component of charge movement current suppressed by 20 microM tetracaine also went through a maximum at low pulse voltages. This anomalous voltage dependence is thus a property of I gamma, defined by either the conditioning protocol or the tetracaine effect. A negative (inward-going) phase was often observed in the asymmetric current during the ON of depolarizing pulses. This inward phase was shown to be an intramembranous charge movement based on (a) its presence in the records of total membrane current, (b) its voltage dependence, with a maximum at slightly suprathreshold voltages, (c) its association with a "hump" in the asymmetric current, (d) its inhibition by interventions that reduce the "hump", (e) equality of ON and OFF areas in the records of asymmetric current presenting this inward phase, and (f) its kinetic relationship with the time derivative of Ca release flux. The nonmonotonic voltage dependence of the amplitude of the hump and the possibility of an inward phase of intramembranous charge movement are used as the main criteria in the quantitative testing of a specific model. According to this model, released Ca2+ binds to negatively charged sites on the myoplasmic face of the voltage sensor and increases the local transmembrane potential, thus driving additional charge movement (the hump). This model successfully predicts the anomalous voltage dependence and all the kinetic properties of I gamma described in the previous papers. It also accounts for the inward phase in total asymmetric current and in the current suppressed by protocol 1. According to this model, I gamma accompanies activating transitions at the same set of voltage sensors as I beta. Therefore it should open additional release channels, which in turn should cause more I gamma, providing a positive feedback mechanism in the regulation of calcium release.     

Fast Proton Insertion in Layered H2W2O7 via Selective Etching of an Aurivillius Phase

H₂W₂O₇, a metastable material synthesized via selective etching of the Aurivillius-related Bi₂W₂O₉, is demonstrated as an electrode for high power proton-based energy storage. Comprehensive structural characterization is performed to obtain a high-fidelity crystal structure of H₂W₂O₇ using an iterative approach that combines X-ray diffraction, neutron pair distribution function, scanning transmission electron microscopy, Raman spectroscopy, and density functional theory modeling. Electrochemical characterization shows a capacity retention of ≈80% at 1000 mV s^–1 (1.5-s charge/discharge time) as compared to 1 mV s^–1 (≈16-min charge/discharge time) with cyclability for over 100 000 cycles. Energetics from density functional theory calculations indicate that proton storage occurs at the terminal oxygen sites within the hydrated interlayer. Last, optical micrographs collected during in situ Raman spectroscopy show reversible, multicolor electrochromism, with color changes from pale yellow to blue, purple, and last, orange as a function of proton content. These results highlight the use of selective etching of layered perovskites for the synthesis of metastable transition metal oxide materials and the use of H₂W₂O₇ as an anode material for proton-based energy storage or electrochromic applications.