The active site of photosynthetic water oxidation by Photosystem II (PSII) is a manganese-calcium cluster (Mn(4)CaO(5)). A postulated catalytic base is assumed to be crucial. CP43-Arg357, which is a candidate for the identity of this base, is a second-sphere ligand of the Mn(4)-Ca cluster and is located near a putative proton exit pathway, which begins with residue D1-D61. Transient absorption spectroscopy and time-resolved O(2) polarography reveal that in the D1-D61N mutant, the transfer of an electron from the Mn(4)CaO(5) cluster to Y(Z)(OX) and O(2) release during the final step of the catalytic cycle, the S(3)-S(0) transition, proceed simultaneously but are more dramatically decelerated than previously thought (t(1/2) of up to ~50 ms vs a t(1/2) of 1.5 ms in the wild type). Using a bare platinum electrode to record the flash-dependent yields of O(2) from mutant and wild-type PSII has allowed the observation of the kinetics of release of O(2) from extracted thylakoid membranes at various pH values and in the presence of deuterated water. In the mutant, it was possible to resolve a clear lag phase prior to the appearance of O(2), indicating formation of an intermediate before the onset of O(2) formation. The lag phase and the photochemical miss factor were more sensitive to isotope substitution in the mutant, indicating that proton efflux in the mutant proceeds via an alternative pathway. The results are discussed in comparison with earlier results obtained from the substitution of CP43-Arg357 with lysine and in regard to hypotheses concerning the nature of the final steps in photosynthetic water oxidation. These considerations led to the conclusion that proton expulsion during the initial phase of the S(3)-S(0) transition starts with the deprotonation of the primary catalytic base, probably CP43-Arg357, followed by efficient proton egress involving the carboxyl group of D1-D61 in a process that constitutes the lag phase immediately prior to O(2) formation chemistry.

In the current X-ray crystallographic structural models of photosystem II, Glu354 of the CP43 polypeptide is the only amino acid ligand of the oxygen-evolving Mn4Ca cluster that is not provided by the D1 polypeptide. To further explore the influence of this structurally unique residue on the properties of the Mn4Ca cluster, the CP43-E354Q mutant of the cyanobacterium Synechocystis sp. PCC 6803 was characterized with a variety of biophysical and spectroscopic methods, including polarography, EPR, X-ray Absorption, FTIR, and mass spectrometry. The kinetics of oxygen release in the mutant were essentially unchanged from those in wild-type. In addition, the oxygen flash-yields exhibited normal period-four oscillations having normal S state parameters, although the yields were lower, correlating with the mutant’s lower steady-state rate (approx. 20% compared to wild-type). Experiments conducted with H218O showed that the fast and slow phases of substrate water exchange in CP43-E354Q thylakoid membranes were accelerated 8.5- and 1.8-fold, respectively, in the S3 state compared to wild-type. Purified oxygen-evolving CP43-E354Q PSII core complexes exhibited a slightly altered S1 state Mn-EXAFS spectrum, a slightly altered S2 state multiline EPR signal, a substantially altered S2-minus-S1 FTIR difference spectrum, and an unusually long lifetime for the S2 state (> 10 hours) in a substantial fraction of reaction centers. In contrast, the S2 state Mn-EXAFS spectrum was nearly indistinguishable from that of wild-type. The S2-minus-S1 FTIR difference spectrum showed alterations throughout the amide and carboxylate stretching regions. Global labeling with 15N and specific labeling with L-[1-13C]alanine revealed that the mutation perturbs both amide II and carboxylate stretching modes and shifts the symmetric carboxylate stretching modes of the α-COO− group of D1-Ala344 (the C-terminus of the D1 polypeptide) to higher frequencies by 3 – 4 cm−1 in both the S1 and S2 states. The EPR and FTIR data implied that 76 – 82 % of CP43-E354Q PSII centers can achieve the S2 state and that most of these can achieve the S3 state, but no evidence for advancement beyond the S3 state was observed in the FTIR data, at least not in a majority of PSII centers. Although the X-ray absorption and EPR data showed that the CP43-E354Q mutation only subtly perturbs the structure and spin state of the Mn4Ca cluster in the S2 state, the FTIR and H218O exchange data show that the mutation strongly influences other properties of the Mn4Ca cluster, altering the response of numerous carboxylate and amide groups to the increased positive charge that develops on the cluster during the S1 to S2 transition and weakening the binding of both substrate water molecules (or water derived ligands), especially the one that exchanges rapidly in the S3 state. The FTIR data provide evidence that CP43-Glu354 coordinates to the Mn4Ca cluster in the S1 state as a bridging ligand between two metal ions, but provide no compelling evidence that this residue changes its coordinat...

Electronic skin (E-skin) imitates human skin by converting external stimuli into electrical signals. E-skin requires high flexibility and a high level of device integration. Unlike conventional E-skin creation methods, a highly sensitive pressure sensor matrix (100 pixels cm −2 ) made of position-registered elastic conductive microparticles (MPs) is created. The MPs form a Schottky junction with the bottom electrode and the current through the junction is sensitive to external pressure, forming a simple one-selector two-terminal device array. The Schottky junction eliminates the electrical cross talks between the sensor pixels consisting of 64 MPs in each. The flexible pressure sensor matrix is used as an artificial fingertip for Braille reading and as an electronic scale based on detailed force distribution. This work opens up the possibility that assembled MPs, which have been a long-standing research topic in academia, can be used to make practical electronic devices.

Although solution processed metal nanowire (NW) percolation networks are a strong candidate to replace commercial indium tin oxide, their performance is limited in thin film device applications due to reduced effective electrical areas arising from the dimple structure and percolative voids that single size metal NW percolation networks inevitably possess. Here, we present a transparent electrode based on a dual-scale silver nanowire (AgNW) percolation network embedded in a flexible substrate to demonstrate a significant enhancement in the effective electrical area by filling the large percolative voids present in a long/thick AgNW network with short/thin AgNWs. As a proof of concept, the performance enhancement of a flexible phosphorescent OLED is demonstrated with the dual-scale AgNW percolation network compared to the previous mono-scale AgNWs. Moreover, we report that mechanical and oxidative robustness, which are critical for flexible OLEDs, are greatly increased by embedding the dual-scale AgNW network in a resin layer.

In the recent X-ray crystallographic structural models of photosystem II, Glu354 of the CP43 polypeptide is assigned as a ligand of the O 2 -evolving Mn 4 Ca cluster. In this communication, a preliminary characterization of the CP43-Glu354Gln mutant of the cyanobacterium Synechocystis sp. PCC 6803 is presented. The steady-state rate of O 2 evolution in the mutant cells is only approximately 20% compared with the wild-type, but the kinetics of O 2 release are essentially unchanged and the O 2 -flash yields show normal period-four oscillations, albeit with lower overall intensity. Purified PSII particles exhibit an essentially normal S 2 state multiline electron paramagnetic resonance (EPR) signal, but exhibit a substantially altered S 2 -minus-S 1 Fourier transform infrared (FTIR) difference spectrum. The intensities of the mutant EPR and FTIR difference spectra (above 75% compared with wild-type) are much greater than the O 2 signals and suggest that CP43-Glu354Gln PSII reaction centres are heterogeneous, with a minority fraction able to evolve O 2 with normal O 2 release kinetics and a majority fraction unable to advance beyond the S 2 or S 3 states. The S 2 -minus-S 1 FTIR difference spectrum of CP43-Glu354Gln PSII particles is altered in both the symmetric and asymmetric carboxylate stretching regions, implying either that CP43-Glu354 is exquisitely sensitive to the increased charge that develops on the Mn 4 Ca cluster during the S 1 /S 2 transition or that the CP43-Glu354Gln mutation changes the distribution of Mn(III ) and Mn(IV ) oxidation states within the Mn 4 Ca cluster in the S 1 and/or S 2 states.

In stretchable electronics, high-resolution stretchable interfacing at a mild temperature is considered as a great challenge and has not been achieved yet. This study presents a stretchable anisotropic conductive film (S-ACF) that can electrically connect high-resolution stretchable circuit lines to other electrodes whether they are rigid, flexible, or stretchable. The key concepts of this study are (i) high-resolution (~50 μm) but low–contact resistance (0.2 ohm in 0.25 mm2) interfacing by periodically embedding conductive microparticles in thermoplastic film, (ii) low-temperature interfacing through the formation of chemical bonds between the S-ACF and the substrates, (iii) economical interfacing by selectively patterning the S-ACF, and (iv) direct interfacing of chips by using the adhesion of the thermoplastic matrix. We integrate light-emitting diodes on the patterned S-ACF and demonstrate stable light operation at large biaxial areal stretching (εxy = 70%).

Basic amino acid side chains situated in active sites may mediate critical proton transfers during an enzymatic catalytic cycle. In the case of photosynthetic water oxidation, a strong base is postulated to facilitate the deprotonation of the active site Mn4-Ca cluster, thereby allowing the otherwise thermodynamically constrained transfer of an electron away from the Mn4-Ca cluster to the oxidized redox active tyrosine radical, YZ*, generated by photosynthetic charge separation. Arginine 357 of the CP43 polypeptide may be located in the second coordination shell of the O2-evolving Mn4-Ca cluster of photosystem II (PSII) according to current structural models. An ostensibly conservative substitution mutation, CP43-357K, was investigated using polarographic and fluorescence techniques in evaluating its potential impact on S-state cycling. Cells containing the CP43-357K mutation lost their capacity for autotrophic growth and exhibited a drastic reduction in O2 evolving activity ( approximately 15% of that of the wild type) despite the fact that mutant cells contained more than 80% of the concentration of charge-separating PSII reaction centers and more than half of these contained photooxidizable Mn. Fluorescence kinetics indicated that acceptor side electron transfer, dominated by the transfer of electrons from QA- to QB, was unaffected, but the fraction of centers containing Mn clusters capable of forming the S2 state was reduced to approximately 40% of that of the wild type. Analysis of O2 yields using a bare platinum electrode indicated a severe defect in the S-state cycling properties of the mutant H2O oxidation complexes. Although O2 evolution was delayed to the third flash during a train of single-turnover saturating flashes, the pattern of O2 emission did not exhibit a discernible periodicity indicating a very high miss factor, which was estimated to be approximately 45% compared to the wild-type value of approximately 10%. On the other hand, the multiflash fluorescence measurements indicate that the yield of formation of the S2 state from S1 is diminished by approximately 20%, although this latter estimate is complicated by the presence of damaged PSII centers. Taken together, the experiments indicate that the high miss factor observed during S-state cycling is likely due to a defect in the higher S-state transitions. These results are discussed in relation to the idea that CP43-R357 may serve as a ligand to bicarbonate or as the catalytic base proposed to mediate proton-coupled electron transfer (PCET) in the higher S states of the catalytic cycle of H2O oxidation.

This work introduces a robust means for excellent position registry of microparticles via a forced assembly technique on flexible or stretchable substrates. It is based on the dry powder rubbing process which allows assembly of a microparticle monolayer in a short time without requiring any solvent or thermal treatment. Elastic physical templates are used as substrates for the forced assembly in this study. Since the elastic templates can reduce the stress accumulation between the closely packed particles, they can minimize the defect formation in the particle assembly in large areas. The method can be used with powders comprising irregularly shaped particles with a relatively large size distribution that cannot be periodically ordered by conventional self-assembly. Furthermore, a non-closely packed particle array can be fabricated readily in large area, which is highly desirable for practical uses of the particle monolayers. The particle monolayers formed on the elastomer templates can be transferred to surfaces coated with thermoplastic block copolymers. Once transferred, the particle monolayers are flexible and stretchable over their entire surface. This work uses the particle monolayers on a large-area flexible substrate as photomasks to produce various photoresist patterns.